Organic electronic material, organic layer, and organic electronic element

Abstract

An organic electronic material containing a charge-transporting polymer having a branched structure, the charge-transporting polymer including a trivalent structural unit represented by formula (a) and a divalent structural unit represented by formula (b), the charge-transporting polymer has a structure represented by formula (I) in which at least one bonding site in the trivalent structural unit and at least one bonding site in the divalent structural unit are directly bonded, the weight-average molecular weight of the charge-transporting polymer being 2,000-500,000 (in the formula, R1 represents a hydrogen atom or a hydrogen atom, and R2 represents a hydrogen atom or a hydrogen atom); ar1 represents a trivalent organic group derived from an aromatic hydrocarbon or an aromatic heterocyclic ring having 2-30 carbon atoms, or a triarylamine, and Ar2 represents a monovalent organic group derived from an aromatic hydrocarbon having 6-30 carbon atoms and having an electron withdrawing group or an electron donating group, and represents a bonding site with another structure.

Description

Technical Field

[0001] Embodiments of the present invention relate to organic electronic materials, organic layers, and organic electronic components. Background Technology

[0002] Organic electronic components are components that use organic materials to perform electrical operations. They are expected to leverage their advantages such as energy saving, low cost, and flexibility, and are attracting attention as a technology to replace the traditional silicon-based inorganic semiconductors.

[0003] Examples of organic electronic components include organic electroluminescent devices (hereinafter referred to as organic EL devices), organic photoelectric conversion devices, and organic transistors. Among organic electronic components, organic EL devices are attracting attention as a large-area solid-state light source, serving as a replacement for, for example, incandescent lamps and gas lamps. Furthermore, self-emissive displays, as the most promising alternative to liquid crystal displays (LCDs) in the field of flat panel displays (FPDs), are also receiving considerable attention, and their commercialization continues to advance.

[0004] Organic electroluminescent (EL) devices are broadly classified into low-molecular-weight organic EL devices and high-molecular-weight organic EL devices based on the organic materials they are composed of. Low-molecular-weight organic EL devices use low-molecular-weight compounds and require a dry film-forming process under vacuum. In contrast, high-molecular-weight organic EL devices use high-molecular-weight compounds and can be easily formed using wet processes such as letterpress printing, gravure printing, and inkjet printing.

[0005] Therefore, polymeric organic EL elements capable of simple film formation are highly anticipated and considered indispensable for the realization of future large-screen organic EL displays. Consequently, in recent years, various charge-transport polymers have been developed as the polymer compounds constituting polymeric organic EL elements.

[0006] Existing technical documents Patent documents Patent Document 1: International Publication No. 2008 / 010487 Summary of the Invention

[0007] The problem that the invention aims to solve As an example of charge-transporting polymers, arylamine polymers are widely known, and research is underway to improve the properties of organic EL devices through polymer molecular design. For example, Patent Document 1 discloses an arylamine polymer containing a triphenylamine structure.

[0008] However, in recent years, in the field of organic electronics such as organic EL devices, there has been a demand for further improvements in properties such as conductivity, and conventional arylamine polymers have room for improvement. Moreover, in order to introduce specific structures into arylamine polymers, the manufacturing process often requires expensive materials or multi-stage processes. Therefore, there is a need for charge-transport polymers that can form organic layers that improve the properties of organic EL devices and can be obtained using inexpensive materials and simple methods.

[0009] Therefore, one embodiment of the present invention provides an organic electronic material comprising a charge-transporting polymer, which can form an organic layer that improves conductivity, and can be obtained using inexpensive materials and in a simple manner.

[0010] Methods for solving problems The inventors conducted in-depth research on charge-transporting polymers with arylamine structures and discovered that polymers with specific arylamine structures are suitable as organic electronic materials, thus completing this invention.

[0011] That is, the embodiments of the present invention relate to the following, but the present invention is not limited to the following embodiments and includes various embodiments.

[0012] <1> An organic electronic material comprising a charge-transporting polymer with a branched structure, wherein the charge-transporting polymer comprises a trivalent structural unit as shown in formula (a) and a divalent structural unit as shown in formula (b), and has a structure as shown in formula (I) formed by direct bonding of at least one bonding site in the trivalent structural unit to at least one bonding site in the divalent structural unit, wherein the weight-average molecular weight of the charge-transporting polymer is 2,000 to 500,000.

[0013] [Chemical Formula 1] [Chemical Formula 2] In the formula, Ar 1 Ar represents an aromatic hydrocarbon or aromatic heterocycle with 2-30 carbon atoms, or a trivalent organic group derived from a triarylamine. 2 This refers to a monovalent organic group derived from an aromatic hydrocarbon with 6 to 30 carbon atoms that has an electron-withdrawing or electron-donating group. Indicates the bonding site with other structures.

[0014] <2> According to the above <1> The organic electronic material, wherein the structure shown in formula (I) above comprises the structure shown in formula (I-1) or formula (I-2) below.

[0015] [Chemical Formula 3] In the formula, Ar 1 Ar represents an aromatic hydrocarbon or aromatic heterocycle with 2-30 carbon atoms, or a trivalent organic group derived from a triarylamine. 2 This refers to a monovalent organic group derived from an aromatic hydrocarbon with 6 to 30 carbon atoms that has an electron-withdrawing or electron-donating group. Indicates the bonding site with other structures.

[0016] <3> According to the above <1> or <2> The organic electronic material, wherein, in the above formula (I), Ar 1 It has a structure derived from triphenylamine or from N-phenylcarbazole.

[0017] <4> According to the above <1> ~ <3> In any one of the organic electronic materials, wherein, in formula (I) above, Ar 2 It has the structure shown in the following formula (b-1).

[0018] [Chemical Formula 4] In the formula, R 1 It is an electron-withdrawing group, an electron-donating group, or an alkyl group having 1 to 12 carbon atoms, at least one of which is an electron-withdrawing group or an electron-donating group, and a is an integer from 1 to 5.

[0019] <5> According to the above <4> The organic electronic material, wherein, in the above formula (b-1), R 1 The electron-withdrawing group is a group where a is an integer of 1 or 2, and the electron-withdrawing group is selected from at least one of halogen groups, halogen-substituted alkyl groups, nitro groups, cyano groups, sulfonic acid groups, and sulfoxide groups.

[0020] <6> According to the above <1> ~ <5> The organic electronic material according to any one of the following methods, wherein the charge-transporting polymer further comprises a monovalent structural unit as shown in formula (c).

[0021] [Chemical Formula 5] In the formula, R 2 It is an alkyl group with 1 to 8 carbon atoms, and b is an integer from 1 to 5.

[0022] <7> According to the above <1> ~ <6> The organic electronic material described in any one of the above statements further comprises a solvent.

[0023] <8> An organic layer, which is used as described above <1> ~ <7> The organic electronic material described in any one of the above is formed.

[0024] <9> An organic electronic component comprising the above <8> The aforementioned organic layer.

[0025] <10> An organic electroluminescent element comprising the above-mentioned <8> The aforementioned organic layer.

[0026] The disclosure of this application is related to the subject matter described in Japanese Patent Application No. 2023-113252 filed on July 10, 2023, the entire disclosure of which is incorporated herein by reference.

[0027] Invention Effects According to embodiments of the present invention, organic electronic materials comprising charge-transporting polymers capable of forming an organic layer that improves conductivity and which can be obtained using inexpensive materials in a simple manner can be provided. Attached Figure Description

[0028] Figure 1 This is a cross-sectional schematic diagram showing an example of an organic EL element as an embodiment of the present invention. Detailed Implementation

[0029] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described below.

[0030] <Organic Electronic Materials> (charge transport polymers) One embodiment relates to an organic electronic material, wherein the charge-transporting polymer constituting the organic electronic material is only required to have a branched structure as shown in formula (I) below and to have electron-withdrawing or electron-donating groups at specified positions. Electron-withdrawing or electron-donating groups are described below as being for Ar... 2 It is introduced by substituents on the aromatic ring.

[0031] [Chemical Formula 6] More specifically, the charge-transporting polymer of this embodiment has charge-transporting properties and includes at least trivalent structural units B and divalent structural units L constituting the branched portion. Preferably, the charge-transporting polymer further includes a monovalent structural unit T.

[0032] Branched charge-transport polymers exhibit excellent heat resistance and can incorporate a large number of terminal groups, thus displaying good solubility and curability. Charge-transport polymers can contain only one type of structural unit or multiple types of structural units. In charge-transport polymers, the structural units are bonded to each other at bonding sites ranging from monovalent to trivalent or higher.

[0033] Examples of partial structures contained in charge-transporting polymers include the following partial structures. However, charge-transporting polymers are not limited to polymers having the following partial structures. In the partial structures, "L" represents structural unit L, "T" represents structural unit T, and "B" represents structural unit B. Hereinafter, "" indicates the bonding site with other structural units. In the following partial structures, multiple Ls can be the same structural unit or different structural units. The same applies to T and B.

[0034] (Partial structure of a charge-transporting polymer with a branched structure) [Chemical Formula 7] The charge transport polymer of this embodiment preferably includes at least a trivalent structural unit as shown in formula (a) as structural unit B and at least a divalent structural unit as shown in formula (b) as structural unit L, and includes a structure as shown in formula (I) formed by direct bonding of at least one bonding site in each structural unit to each other.

[0035] [Chemical Formula 8] [Chemical Formula 9] In the formula, Ar 1 Ar represents an aromatic hydrocarbon or aromatic heterocycle with 2-30 carbon atoms, or a trivalent organic group derived from a triarylamine. 2 This refers to a monovalent organic group derived from an aromatic hydrocarbon with 6 to 30 carbon atoms that has an electron-withdrawing or electron-donating group. Indicates the bonding site with other structures. Ar 1 and Ar 2 Details will be discussed later.

[0036] The charge-transporting polymer preferably comprises the structure shown in formula (I-1) or formula (I-2) below, and more preferably the structure shown in formula (I-2) below. In each formula, Ar 1 Ar 2 and The same as previously explained.

[0037] [Chemical Formula 10] The following section provides a more detailed explanation of the structural units of charge-transporting polymers.

[0038] (Structural Unit B) Structural unit B is a trivalent or higher structural unit constituting the branched portion of a charge-transporting polymer with a branched structure. From the viewpoint of improving the durability of organic electronic components, structural unit B is preferably hexavalent or lower, more preferably trivalent or tetravalent. Structural unit B preferably has charge-transporting properties. For example, structural unit B can be an organic group derived from aromatic hydrocarbons or aromatic heterocycles, or triarylamines. From the viewpoint of improving the durability of organic electronic components, as structural unit B, for example, an organic group (structure) derived from substituted or unsubstituted triarylamines, carbazoles, or fused polycyclic aromatic hydrocarbons can be preferably selected.

[0039] The charge-transporting polymer of this embodiment contains at least the trivalent structural unit shown in formula (a) above (hereinafter also referred to as structural unit B1) as the above structural unit B.

[0040] [Chemical Formula 11] In the formula, Ar 1 This indicates a trivalent organic group derived from aromatic hydrocarbons or aromatic heterocycles, or triarylamines. Trivalent organic groups are also called aromatic trimethylolpropionic acid or heteroarylolpropionic acid. 1 A radical is an atomic group obtained by removing three hydrogen atoms from the aromatic ring of an aromatic hydrocarbon, an aromatic heterocycle, or a triarylamine.

[0041] In one implementation, Ar 1 Preferably, it can be a trivalent organic group derived from an aromatic hydrocarbon or an aromatic heterocycle with 2 to 30 carbon atoms.

[0042] Examples of the aforementioned aromatic hydrocarbons include benzene, naphthalene, anthracene, tetraphenylene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, benzo[a]phenanthrene, pyrene, β-phenanthrene, perylene, benzo[a]phenanthrene, pentaphenylene, and benzo[a]pyrene.

[0043] Examples of the aforementioned aromatic heterocycles include pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthrene, carbazole, furan, benzofuran, dibenzofuran, pyrrole, thiophene, benzothiophene, dibenzothiophene, oxazole, oxadiazole, thiadiazole, triazole, benzooxazole, benzooxadiazole, benzothiadiazole, benzotriazole, benzothiophene, etc.

[0044] The aforementioned aromatic hydrocarbons and aromatic heterocycles can be monocyclic or fused rings. Additionally, they may have a polycyclic structure consisting of two or more single-bonded rings selected from monocyclic and fused rings. Examples of aromatic hydrocarbons with such polycyclic structures include biphenyl, terphenyl, and triphenylbenzene.

[0045] In one implementation, Ar 1The trivalent organic group can be derived from a triarylamine. A triarylamine is a tertiary aromatic amine formed by the bonding of three aryl groups (aromatic groups) to a nitrogen atom. Here, the aryl group is a monovalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle with 2 to 30 carbon atoms. The aromatic hydrocarbon and aromatic heterocycle can be as described above. Specific examples of aryl groups derived from aromatic hydrocarbon groups in triarylamines include phenyl, naphthyl, and biphenyl. Specific examples of aryl groups derived from aromatic heterocyclic groups include thiophene, furanyl, pyrrole, pyridinyl, and imidazolyl. In one embodiment, the triarylamine is preferably triphenylamine.

[0046] The aromatic hydrocarbons and aromatic heterocycles contained in the aforementioned monovalent and trivalent organic groups can be unsubstituted or have one or more substituents R. The substituents R are independently selected from -R. 1 -OR 2 -SR 3 -OCOR 4 -COOR 5 -SiR 6 R 7 R 8 Halogen atoms and groups comprising polymerizable functional groups described later. In one embodiment, R is more preferably -R 1 .

[0047] R 1 ~R 8 Each hydrogen atom is independently represented; a straight-chain, branched, or cyclic alkyl group having 1 to 22 carbon atoms (where R... 1 (Except in the case of hydrogen atoms); or aryl or heteroaryl groups with 2 to 30 carbon atoms. An aryl group is a group of atoms formed by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is a group of atoms formed by removing one hydrogen atom from an aromatic heterocycle. The alkyl group may be further substituted with aryl or heteroaryl groups with 2 to 20 carbon atoms, and the aryl or heteroaryl group may be further substituted with straight-chain, branched, or cyclic alkyl groups with 1 to 22 carbon atoms.

[0048] Specific examples of structural unit B1 include the structures shown below. Preferably, structures derived from triarylamines and structures derived from N-arylcarbazole are preferred.

[0049] [Chemical Formula 12] In the formula, Ar independently represents a divalent linking group, for example, an arylene or heteroarylene group with 2 to 30 carbon atoms. Ar is preferably arylene, and more preferably phenylene.

[0050] In one embodiment, structural unit B1 preferably comprises at least one of a structural unit derived from the triphenylamine structure shown in formula (B1-1) and a structural unit derived from the N-phenylcarbazole structure shown in formula (B1-2).

[0051] [Chemical Formula 13] In the above structural unit (B1-1), l, m, and n are each independently an integer from 0 to 4, representing the number of substituents R. l, m, and n are preferably independently integers from 0 to 2, more preferably integers of 0 or 1. In one embodiment, the number of substituents in the above structural unit (B1-1) is preferably 1 or 2. In another embodiment, the number of substituents in the above structural unit (B1-1) is preferably 0.

[0052] Furthermore, in the above structural unit (B1-2), l is an integer from 0 to 4, and m and n are each an independent integer from 0 to 3, representing the number of substituents R. l is preferably an integer from 0 to 2, more preferably an integer of 0 or 1. m and n are each an independent integer from 0 to 2, more preferably an integer of 0 or 1. In one embodiment, the number of substituents in the above structural unit (B1-2) is preferably 1 or 2. In another embodiment, the number of substituents in the above structural unit (B1-2) is preferably 0.

[0053] Among the above structural units, " "" indicates a bonding site with other structures, at least one of which is bonded to a nitrogen atom (N). In structural unit (B1-1) or (B1-2), it is preferable that two or three of the three bonding sites are bonded to nitrogen atoms respectively. More preferably, all three bonding sites are bonded to nitrogen atoms. In the case of charge-transporting polymers containing N-Ph bonds, there is a tendency for doping and conjugation to become easier, and for superior conductivity to be easily obtained. From this point of view, structural unit B preferably includes either the structural unit derived from triphenylamine (B1-1) or the structural unit derived from N-phenylcarbazole (B1-2) shown below. By including these structural units, excellent conductivity is easily obtained.

[0054] In the above structural units (B1-1) and (B1-2), the substituent R is the same as the substituent R previously described for the structure shown in formula (I). In one embodiment, when structural unit B has the above structural unit (B1-1) or (B1-2), the substituent R may be a straight-chain, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The aromatic ring in the aryl group may be further substituted with a straight-chain, branched, or cyclic alkyl group having 1 to 12 carbon atoms. In another embodiment, the above structural units (B1-1) or (B1-2) are preferably both unsubstituted.

[0055] In one embodiment, structural unit B may include structural unit B2 with a valence of four or more, in addition to structural unit B1 described above. For example, specific examples of structural unit B2 include the following structural units. Preferably, structures comprising a triarylamine structure and structures comprising a carbazole structure are preferred.

[0056] [Chemical Formula 14] In the formula, Ar independently represents an arylene or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably arylene, and more preferably phenylene. Y represents a divalent linking group, such as a divalent group obtained by further removing one hydrogen atom from a group having one or more hydrogen atoms in R (excluding groups containing polymerizable functional groups) in structural unit L described later. Z represents any one of carbon, silicon, or phosphorus atoms. In the structural unit, the benzene ring and Ar may have substituents; as an example of a substituent, the substituent R in structural unit B1 described earlier can be given.

[0057] (Structural Unit L) The structural unit L is a divalent structural unit with charge transport capability, and is not particularly limited as long as it contains atomic groups with the ability to transport charge. From the viewpoint that it forms the structure shown in formula (I) by directly bonding with the structural unit (a) described above, the structural unit L mentioned above shall at least contain the divalent structural unit shown in formula (b) below (hereinafter also referred to as structural unit L1).

[0058] [Chemical Formula 15] In the formula, Ar 2 Ar is a monovalent organic group derived from aromatic hydrocarbons with 6 to 30 carbon atoms that have electron-withdrawing or electron-donating groups. It is the atomic group obtained by removing one hydrogen atom from the aromatic ring of the aforementioned aromatic hydrocarbon. That is, Ar... 2 Also known as aryl. Ar 2A structure in which at least one hydrogen atom of the aromatic ring in an aryl group having 6 to 30 carbon atoms is substituted by an electron-withdrawing or electron-donating group. The above Ar 2 In this case, the number of carbon atoms forming the ring is more preferably 6 to 24.

[0059] Specific examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, tetraphenylene, fluorene, phenanthrene, biphenyl, terphenyl, and triphenylbenzene. Here, the aromatic ring in the aromatic hydrocarbon has one or more electron-withdrawing or electron-donating groups as substituents, and may further have other substituents as needed.

[0060] In one implementation, the aforementioned Ar 2 It can have the structure shown in equation (b-1) below.

[0061] [Chemical Formula 16] In the formula, R 1 It is an electron-withdrawing group, an electron-donating group, or an alkyl group with 1 to 12 carbon atoms, where a is an integer from 1 to 5, and R 1 At least one of them is an electron-withdrawing group or an electron-donating group.

[0062] In one embodiment, a is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0063] The aforementioned "electron-withdrawing group" refers to a substituent that readily attracts electrons from the bonding atom side compared to the hydrogen atom. Conversely, the aforementioned "electron-donating group" refers to a substituent that readily donates electrons to the bonding atom side compared to the hydrogen atom, excluding alkyl groups. Charge-transporting polymers, in specific structures containing hydrogen atoms in an aromatic ring bonded to the N atom that are replaced by electron-withdrawing or electron-donating groups, tend to exhibit a tendency to readily adjust their HOMO energy levels.

[0064] For example, by introducing electron-withdrawing groups to specific sites of the charge transport polymer as described above, the energy levels of the HOMO can be deepened. Furthermore, the introduction of electron-withdrawing groups to specific sites tends to increase the solubility of the charge transport polymer. From this viewpoint, in one embodiment, in a charge transport polymer having the structure of formula (I), Ar... 2 The hydrogen atoms in the aromatic ring are preferably replaced by electron-withdrawing groups.

[0065] The electron-withdrawing group is not particularly limited, but specific examples include halogen groups, halogen-substituted alkyl groups, nitro groups, cyano groups, sulfonic acid groups, and sulfoxide groups. More specifically, examples of halogen groups include fluorine groups, chloro groups, bromine groups, and iodo groups. The alkyl group in the halogen-substituted alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1. From the viewpoint of the strength of electron-withdrawing properties, the halogen group is preferably a fluorine group, and the halogen-substituted alkyl group is preferably a fluoroalkyl group.

[0066] Considering the thermal stability of charge-transporting polymers, the electron-withdrawing group is preferably selected from at least one of fluoro, fluoroalkyl, nitro, cyano, sulfonic acid, and sulfoxide groups. More preferably, it can be selected from at least one of fluoro, fluoroalkyl, sulfonic acid, and sulfoxide groups. More preferably, it can be at least one of fluoro and fluoroalkyl groups. When the aryl group contains multiple electron-withdrawing groups, the multiple electron-withdrawing groups can be the same or different from each other.

[0067] In one implementation, Ar in formula (I) 2 Preferably, it has the structure shown in formula (b-1a) or (b-1b).

[0068] [Chemical Formula 17] In each formula, Ew represents an electron-withdrawing group. In the structures shown in formulas (b-1a) or (b-1b) above, the electron-withdrawing group (Ew) is preferably a halogen atom or a halogen-substituted alkyl group. More preferably, it is a fluorine atom (F) or trifluoromethane (CF3).

[0069] The electron-donating group is not particularly limited; specific examples include -OR, -OH, and -NR2. The alkyl group of the alkoxy group (-OR) can have any of the following structures: straight-chain, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0070] In one implementation, Ar in formula (I) 2 Preferably, it has the structure shown in formula (b-1c) or (b-1d) below.

[0071] [Chemical Formula 18] In each formula, Ea represents an electron-donating group. In the structures shown in formulas (b-1c) or (b-1d) above, the electron-donating group (Ea) is preferably -OR, and particularly preferably methoxy.

[0072] As described above, charge-transporting polymers having the structure shown in formula (I) above are in Ar 2It contains at least one electron-withdrawing or electron-donating group as a substituent on the aromatic ring. In one embodiment, in the charge-transporting polymer, in addition to having at least one electron-withdrawing or electron-donating group, the substituent may further have an alkyl group having 1 to 12 carbon atoms.

[0073] The alkyl group having 1 to 12 carbon atoms can have any of the following structures: straight-chain, branched, or cyclic. In one embodiment, the alkyl group preferably has a straight-chain or branched structure. In one embodiment, considering its application in wet processes, and from the viewpoint of solubility in solvents, R... 1 Preferably, it can be an alkyl group having 2 to 12 carbon atoms; more preferably, it can be an alkyl group having 3 to 12 carbon atoms; and even more preferably, it can be an alkyl group having 4 to 12 carbon atoms.

[0074] In one embodiment, structural unit L may include, in addition to structural unit L1 described above, structural unit L2 having a structure different from that of structural unit L1. Structural unit L2 is selected from substituted or unsubstituted structures, including triarylamine structures, carbazole structures, thiophene structures, bithiophene structures, fluorene structures, benzene structures, biphenylene structures, triphenylene structures, naphthalene structures, anthracene structures, tetraphenylene structures, phenanthrene structures, dihydrophenanthrene structures, pyridine structures, pyrazine structures, quinoline structures, isoquinoline structures, quinoxaline structures, acridine structures, diazoxide structures, furan structures, pyrrole structures, oxazole structures, oxadiazole structures, thiazole structures, thiadiazole structures, triazole structures, benzothiophene structures, benzoxazole structures, benzoxadiazole structures, benzothiazole structures, benzothiadiazole structures, benzotriazole structures, N-arylphenoxazine structures, and structures comprising one or more of these. The triarylamine structure is more preferably a triphenylamine structure.

[0075] In one embodiment, from the viewpoint of obtaining excellent hole transport properties, structural unit L2 preferably comprises one or more structures selected from substituted or unsubstituted, triarylamine, carbazole, thiophene, bithiophene, benzene, fluorene, and pyrrole structures; more preferably, it comprises one or more structures selected from substituted or unsubstituted, triarylamine, and carbazole structures. In another embodiment, from the viewpoint of obtaining excellent electron transport properties, structural unit L preferably comprises one or more structures selected from substituted or unsubstituted, fluorene, benzene, phenanthrene, pyridine, and quinoline structures.

[0076] As specific examples of structural unit L2, the following structural units can be cited. However, structural unit L2 is not limited to the following.

[0077] [Chemical Formula 19] [Chemical Formula 20] R can independently represent either a hydrogen atom or a substituent. Preferably, R can independently be selected from -R. 1 -OR 2 -SR 3 -OCOR 4 -COOR 5 -SiR 6 R 7 R 8 Halogen atoms and groups comprising polymerizable functional groups described later. In one embodiment, R is more preferably -R 1 R 1 ~R 8 Each of these can be independently represented by a hydrogen atom; a straight-chain, branched, or cyclic alkyl group having 1 to 22 carbon atoms; or an aryl or heteroaryl group having 2 to 30 carbon atoms. An aryl group is a group of atoms formed by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is a group of atoms formed by removing one hydrogen atom from an aromatic heterocycle. Alkyl groups may be further substituted with aryl or heteroaryl groups having 2 to 20 carbon atoms, and aryl or heteroaryl groups may be further substituted with straight-chain, branched, or cyclic alkyl groups having 1 to 22 carbon atoms.

[0078] Ar represents an arylene or heteroarylene group with 2 to 30 carbon atoms. An arylene is a group of atoms formed by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene is a group of atoms formed by removing two hydrogen atoms from an aromatic heterocycle. Ar is preferably an arylene, and more preferably a phenylene.

[0079] Examples of aromatic hydrocarbons include monocyclic rings, fused rings, or polycyclic rings selected from monocyclic and fused rings formed by the bonding of two or more single bonds. Examples of aromatic heterocyclic rings include monocyclic rings, fused rings, or polycyclic rings selected from monocyclic and fused rings formed by the bonding of two or more single bonds.

[0080] (Structural unit T) Structural unit T is a monovalent structural unit constituting the terminal portion of the charge-transporting polymer. Structural unit T is not particularly limited, and may be selected from substituted or unsubstituted aromatic hydrocarbon structures, aromatic heterocyclic structures, and structures comprising one or more of these. In one embodiment, from the viewpoint of imparting durability without reducing charge transportability, structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure, more preferably a substituted or unsubstituted benzene structure. Except for valence, structural unit T may also have the same structure as structural unit L. In one embodiment, from the viewpoint of imparting durability without reducing charge transportability, structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure, more preferably a substituted or unsubstituted benzene structure.

[0081] As specific examples of structural element T, the following structural elements can be cited. Structural element T is not limited to the following.

[0082] [Chemical Formula 21] R can independently represent either a hydrogen atom or a substituent. The substituent is selected from -R. 1 -OR 2 -SR 3 -OCOR 4 -COOR 5 -SiR 6 R 7 R 8 Halogen atoms, and polymerizable functional groups (described later). R 1 ~R 8 R in the structural unit L described earlier 1 ~R 8 Same. In one embodiment, the substituent is preferably -R. 1 .

[0083] In one embodiment, the charge-transporting polymer preferably has a monovalent structural unit T1 as shown in formula (c).

[0084] [Chemical Formula 22] In the formula, R 2 R is an alkyl group having 1 to 8 carbon atoms, and b is an integer from 1 to 5. In one embodiment, R 2 Preferably, it can be an alkyl group having 1 to 7 carbon atoms; more preferably, it can be an alkyl group having 1 to 6 carbon atoms; and even more preferably, it can be an alkyl group having 1 to 5 carbon atoms. The aforementioned alkyl group can be any of the following structures: straight-chain, branched, or cyclic. In one embodiment, b is preferably 1 to 3, more preferably 1 or 2.

[0085] (aggregative functional groups) In one embodiment, the charge-transporting polymer may have polymerizable functional groups. Polymerizable functional groups are functional groups that can form bonds with each other by applying heat and / or light. When the charge-transporting polymer contains polymerizable functional groups, an organic layer consisting of a cured film can be formed by curing a coating film formed using the charge-transporting polymer. The organic layer consisting of such a cured film has the solvent resistance required for further layering using a wet process. Therefore, when the charge-transporting polymer contains polymerizable functional groups, multilayering using a wet process becomes easier.

[0086] Examples of polymerizable functional groups include groups with carbon-carbon multiple bonds (e.g., vinyl, allyl, butenyl, ethynyl, acryloyl, acryloyloxy, acryloylamino, methacryloyl, methacryloyloxy, methacryloylamino, vinyloxy, vinylamino, etc.), groups with small membered rings (e.g., cyclic alkyl groups such as cyclopropyl and cyclobutyl; cyclic ether groups such as epoxy (ethylene oxide) and oxetane (oxetane); cyclic thioether groups such as cyclic sulfide groups; cyclic ester groups such as diene group and lactone group; cyclic amide groups such as lactam group), heterocyclic groups (e.g., furanyl, pyrroleyl, thiophene, thiophene), benzocyclobutenyl, etc.

[0087] The polymerizable functional group preferably includes one or more selected from groups having carbon-carbon multiple bonds, groups having small membered rings, and heterocyclic groups; more preferably, it includes one or more selected from groups having carbon-carbon double bonds, cyclic ether groups, and heterocyclic groups. Specifically, vinyl, acryloyl, methacryl, epoxy, oxetyl, pyrrole, and thiophene groups are preferred as polymerizable functional groups. From the viewpoint of the solubility and curability of charge-transporting polymers, vinyl, oxetyl, and thiophene groups are more preferred.

[0088] The polymerizable functional group can be substituted or unsubstituted. Examples of substituents that can be present in the polymerizable functional group include alkyl groups with 1 to 6 carbon atoms, such as methyl and ethyl. The polymerizable functional group can be directly bonded to the aromatic ring, or it can be bonded to the aromatic ring via a divalent group such as a linking group. Examples of linking groups include -O- and -(CH2). n - and their combinations. Here, n can be an integer from 1 to 10.

[0089] In charge-transporting polymers, polymerizable functional groups are preferably introduced at least into the terminal portion (i.e., structural unit T) of the charge-transporting polymer. Polymerizable functional groups may also be introduced into portions other than the terminals (i.e., structural units L or B), or into both the terminal portion and portions other than the terminals. From the viewpoint of achieving both curability and charge transport properties, it is preferable to introduce them only into the terminal portion. Furthermore, in charge-transporting polymers with branched structures, polymerizable functional groups may be introduced into the main chain of the charge-transporting polymer, into the side chains, or into both the main chain and side chains.

[0090] For example, from the viewpoint of obtaining sufficient solubility change, the number of polymerizable functional groups per molecule of charge-transporting polymer is preferably 2 or more, more preferably 3 or more. Furthermore, from the viewpoint of maintaining charge transport, the number of polymerizable functional groups is preferably 1,000 or less, more preferably 500 or less.

[0091] Furthermore, from the viewpoint of obtaining good curability, based on all structural units, the proportion of polymerizable functional groups in the charge-transporting polymer is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 3 mol% or more. Furthermore, from the viewpoint of obtaining good charge transport properties, the proportion of polymerizable functional groups is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. In addition, the term "proportion of polymerizable functional groups" here refers to the proportion of structural units having polymerizable functional groups.

[0092] The content and proportion of polymeric functional groups per molecule of charge transport polymer can be calculated using averages of the amount of polymeric functional groups used in the synthesis of the charge transport polymer (e.g., the amount of monomers with polymeric functional groups × the number of polymeric functional groups per monomer), the amount of monomers corresponding to each structural unit, and the weight-average molecular weight of the charge transport polymer. Furthermore, the content of polymeric functional groups can be determined using the weight-average molecular weight of the charge transport polymer. 1 The value is calculated by averaging the ratio of the integral value of the signal originating from polymeric functional groups in the 1H NMR (nuclear magnetic resonance) spectrum to the integral value of the entire spectrum, and the weight-average molecular weight of the charge-transporting polymer. For simplicity, when the feed amount is known, it is preferable to use the value calculated using the feed amount.

[0093] (Number average molecular weight) The number-average molecular weight of the charge-transporting polymer can be appropriately adjusted considering factors such as solubility in solvents and film-forming properties. From the viewpoint of excellent charge transport properties, the number-average molecular weight is preferably 500 or more, more preferably 1,000 or more, further preferably 2,000 or more, and even more preferably 5,000 or more. Furthermore, from the viewpoint of maintaining good solubility in solvents and facilitating the preparation of ink compositions, the number-average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, further preferably 50,000 or less, and even more preferably 30,000 or less. In one embodiment, the number-average molecular weight can be 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000.

[0094] (weight-average molecular weight) The weight-average molecular weight of the charge-transporting polymer can be appropriately adjusted considering factors such as solubility in solvents and film-forming properties. From the viewpoint of excellent charge transport properties, the weight-average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, and even more preferably 30,000 or more. Furthermore, from the viewpoint of maintaining good solubility in solvents and facilitating the preparation of ink compositions, the weight-average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, further preferably 400,000 or less, and sequentially even more preferably 200,000 or less and 100,000 or less.

[0095] In one embodiment, the weight-average molecular weight of the charge-transporting polymer is preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and even more preferably 8,000 to 50,000.

[0096] Number-average molecular weight and weight-average molecular weight can be determined by gel permeation chromatography (GPC) using a standard curve of standard polystyrene.

[0097] (Proportion of structural units) From the viewpoint of improving the durability of organic electronic components, based on all structural units, the proportion of structural unit B in the charge-transporting polymer is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, from the viewpoint of suppressing viscosity increase, effectively synthesizing the charge-transporting polymer, or obtaining sufficient charge transport properties, the proportion of structural unit B is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less. Here, the above-mentioned proportion of structural unit B refers to the combined amount of structural units B1 and B2. In one embodiment, structural unit B may consist only of structural unit B1.

[0098] In charge-transporting polymers, from the viewpoint of obtaining sufficient charge transport, based on all structural units, the proportion of structural unit L is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Furthermore, considering structural units T and B, the proportion of structural unit L is preferably 97 mol% or less, more preferably 92 mol% or less, and even more preferably 85 mol% or less. Here, the above-mentioned proportion of structural unit L refers to the combined amount of structural units L1 and L2. In one embodiment, structural unit L may consist only of structural unit L1.

[0099] From the viewpoint of solubility and curability, based on all structural units, the proportion of structural unit T in the charge-transporting polymer is preferably 3 mol% or more, more preferably 8 mol% or more, and even more preferably 15 mol% or more. From the viewpoint of improving the properties of organic electronic components, or from the viewpoint of suppressing viscosity increases and efficiently synthesizing charge-transporting polymers, the above range is also preferred. Furthermore, from the viewpoint of obtaining sufficient charge transport properties, the proportion of structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.

[0100] Considering the balance of charge transport, durability, productivity, etc., the ratio (molar ratio) of structural unit L, structural unit T and structural unit B is preferably L:T:B=100:10~200:10~100, more preferably 100:20~180:20~90, and even more preferably 100:40~160:30~80.

[0101] The proportions of the structural units can be determined using the amount of monomers corresponding to each structural unit used in the synthesis of the charge-transporting polymer. Alternatively, the proportions of the structural units can be determined using the charge-transporting polymer... 1 The average value is calculated by integrating the spectra derived from each structural unit in the 1H NMR spectrum. For simplicity, when the feed amount is known, it is preferable to use the value obtained using the feed amount. Furthermore, the proportions related to the aforementioned end groups can also be obtained in the same way.

[0102] From the viewpoint of stabilizing the coating film, the degree of polymerization (number of structural units) of the charge-transporting polymer is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. Furthermore, from the viewpoint of solubility in solvents, the degree of polymerization is preferably 1,000 or less, more preferably 700 or less, and even more preferably 500 or less. The degree of polymerization can be determined by averaging the weight-average molecular weight of the charge-transporting polymer, the molecular weight of the structural units, and the proportion of the structural units.

[0103] The charge-transporting polymer described above can have a structure in which multiple structural units B are bonded to structural unit L1, and arbitrary structural units L2 and T are formed, thereby creating a charge-transporting polymer containing N-Ph (phenyl) bonds within the molecule through structural unit L1. Compared to charge-transporting polymers containing Ph-Ph bonds, such as those formed using the Suzuki-Miyaura coupling method, charge-transporting polymers containing N-Ph bonds tend to be easier to dopantize and conjugate. From this viewpoint, in one embodiment, the charge-transporting polymer preferably has a partial structure shown in formula (i) below.

[0104] [Chemical Formula 23] From the viewpoint that the partial structure shown in the above formula (i) can be easily imported, the above structural unit B1 and the above structural unit L2 preferably contain either a structure derived from the triphenylamine structure or a structure derived from the N-phenylcarbazole structure.

[0105] In the above formula (i), n is an integer greater than 2, and Ar 2 As previously explained, the structure is preferably as shown in formula (b-1) above. In one embodiment, n is preferably an integer of 3 or more, more preferably an integer of 4 or more, and even more preferably an integer of 6 or more. On the other hand, n is preferably an integer of 3,000 or less, more preferably an integer of 1,500 or less, and even more preferably an integer of 500 or less.

[0106] Furthermore, in charge-transporting polymers, the content of N-Ph bonds formed by the bonding of structural units is preferably 10-80%, more preferably 20-70%, and even more preferably 30-60%. Here, the above-mentioned content and the ratio of structural units are the same values ​​calculated from the amount of raw material monomers by NMR measurement.

[0107] (Method for manufacturing charge transport polymers) The charge-transport polymer (I) having the structure shown in formula (I) above can be prepared by a known method using two or more aromatic compounds as raw material monomers, through the reaction between these two or more raw material monomers. For example, it can be prepared by coupling an aromatic compound having a reactive functional group (1) and an aromatic compound having a reactive functional group (2) capable of reacting with the reactive functional group (1) according to a known method. Examples of combinations of reactive functional groups (1) and (2) include halogen atoms with amino groups, trifluoromethanesulfonate groups with amino groups, and halogen atoms with borate groups. The aforementioned trifluoromethanesulfonate group (CF3SO2-) is also called a trifluoromethanesulfonyl group.

[0108] From the viewpoint that N-Ph bonds can be easily formed through coupling reactions, the combination of the above-mentioned reactive functional groups (1) and (2) is preferably a halogen atom with an amino group, or a trifluoromethanesulfonate group with an amino group. Here, the amino group is preferably a primary amino group.

[0109] From the above perspective, the Bucnwald-Hartwig reaction is preferably used to produce charge-transporting polymers having the structure shown in formula (I). In the case of the Bucnwald-Hartwig reaction, the combination of reactive functional groups (1) and (2) can be a halogen atom and an amino group. The amino group is preferably a primary amino group. More specifically, by reacting an aromatic compound having a halogen atom directly bonded to an aromatic ring with an aromatic compound having a primary amino group, a polymer with the desired structure can be obtained. Here, the halogen atom can be a chlorine atom, a bromine atom, or an iodine atom. Alternatively, an aromatic compound having a trifluoromethanesulfonate group instead of a halogen atom can also be used.

[0110] In the Bucnwald-Hartwig reaction described above, by using an aromatic compound (1) having two or more halogen atoms or trifluoromethanesulfonate groups directly bonded to the aromatic ring and an aromatic compound (2) having a primary amino group, it is possible to produce an arylamine polymer derived from each of the aromatic compounds (1) and (2) having one or more structural units. From this point of view, by selecting aromatic compounds used as raw material monomers, it is possible to readily obtain charge-transporting polymers having two or more desired structures (I) as shown by the following formula (IA).

[0111] [Chemical Formula 24] In the formula, Ar 1 and Ar 2 As previously explained, n is an integer of 2 or more. n is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more. For example, n can be an integer appropriately set such that the weight-average molecular weight (Mw) of the charge-transporting polymer reaches the range of 1,000 or more and 500,000 or less, 2,000 or more and 500,000 or less, 3,000 or more and 500,000 or less, or 5,000 or more and 300,000 or less.

[0112] In one embodiment, as raw material monomers for manufacturing the charge-transporting polymer having the above-described structure (I), at least triphenylamine having a halogen atom directly bonded to an aromatic ring and aromatic primary amines (hereinafter also referred to as aryl amines) having electron-withdrawing or electron-donating groups can be used. In such an embodiment, structure (I) in the charge-transporting polymer preferably comprises the structure shown in the following formula (I-1).

[0113] [Chemical Formula 25] In the formula, Ar 2This refers to substituted or unsubstituted aryl groups with 6 to 30 carbon atoms, having either electron-withdrawing or electron-donating groups, as detailed previously. "" indicates the bonding site with other structures.

[0114] The structure (I) in the charge transport polymer more preferably includes the structure shown in formula (I-2a) or formula (I-3a) below, and even more preferably has the structure shown in formula (I-3a) below.

[0115] [Chemical Formula 26] From the viewpoint of obtaining a charge-transporting polymer having the structure shown in the above formula (I-3a), in one embodiment, at least as a raw material monomer, triphenylamine and arylamine having three halogen atoms directly bonded to the aromatic ring can preferably be used.

[0116] More specifically, it is preferable to use a trivalent structural unit B1 in formula (a) above where Ar is a phenylene oxide and at the three bonding sites ( Compounds in which halogen atoms are directly bonded to each other. Alternatively, it is preferable to use compounds at the two bonding sites of the divalent structural unit L1 shown in formula (b) above. Aromatic primary amines that have hydrogen atoms bonded to their aromatic rings and have one or more electron-withdrawing or electron-donating groups on the aromatic ring.

[0117] In one embodiment, the charge-transporting polymer preferably further comprises a monovalent structural unit T as shown in formula (c). Wherein, R 2 b, as previously explained. To introduce the aforementioned structural unit T into a charge-transporting polymer, the bonding sites in the structure shown in formula (c) below can be used as the starting monomer. Compounds in which halogen atoms are directly bonded.

[0118] [Chemical Formula 27] In one embodiment, the charge-transporting polymer (I) comprises the aforementioned structural units B1, L1, and T. In another embodiment, the charge-transporting polymer (I) may further comprise other structural units besides B1, L1, and T. For example, it may further comprise the previously described structural units B2 and L2. In this case, aromatic compounds having a structure capable of deriving the additional structural units and having halogen atoms directly bonded to the aromatic ring, or aromatic compounds having amino groups, can be used as raw material monomers. Thus, by arbitrarily combining raw material monomers, charge-transporting polymers with the desired structure can be readily obtained.

[0119] For example, in one embodiment, in order to introduce the previously illustrated structural units B2 and L2 into a charge-transporting polymer, the bonding sites in structural units B2 and L2 can be used as raw material monomers. Compounds with halogen atoms directly bonded to them. In another embodiment, in order to introduce structural unit L2 as a raw material monomer, the bonding sites in structural unit L2 can also be used. Compounds having -NH-Ar groups on each of the following (where Ar independently represents an aryl or heteroaryl group with 2 to 30 carbon atoms).

[0120] The following provides a more detailed explanation of the method for manufacturing charge-transporting polymers using the Bucnwald-Hartwig reaction.

[0121] (Bucnwald-Hartwig reaction) The Bucnwald-Hartwig reaction can be carried out under conditions and methods known to those skilled in the art. For example, the reaction can be carried out in an inert gaseous environment such as nitrogen using a compound containing a heavy metal such as palladium as a catalyst. Preferably, a catalyst and a base are used in conjunction with the reaction.

[0122] In the Bucnwald-Hartwig reaction described above, palladium-containing catalysts are typically preferred as catalysts. In this specification, "palladium-containing catalyst" refers to a catalyst comprising palladium and a ligand, including complex compounds or salts comprising palladium and a ligand, or a combination of a palladium-containing catalyst precursor and a ligand or a ligand precursor.

[0123] The aforementioned ligands preferably have a large volumetric structure; specific examples include phosphine ligands and Buchwald ligands. N-heterocyclic carbene (NHC) can also be used as ligands. More preferably, phosphine ligands include tri-tert-butylphosphine, tri-o-tolylphosphine, and triphenylphosphine.

[0124] Palladium-containing catalysts can be palladium (0) complexes or palladium (II) salts. Specific examples of palladium-containing catalysts include bis(tri-tert-butylphosphine)palladium (0), tetra(triphenylphosphine)palladium (0), bis[1,2-bis(diphenylphosphine)ethane]palladium (0), dichlorobis(triphenylphosphine)palladium (II), dichlorobis(tri-o-tolylphosphine)palladium (II), bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]dichloropalladium (II), [1,1'-bis(di-tert-butylphosphine)ferrocene]dichloropalladium (II), dichloro[1,1'-bis(diphenylphosphine)ferrocene]palladium (II), dichloro[1,2-bis(diphenylphosphine)ethane]palladium (II), and dichloro[1,3-bis(diphenylphosphine)propane]palladium (II), as well as Umicore CX31 and CX32 with NHC coordination groups. These compounds can also be used in combination with the aforementioned ligands or ligand precursors.

[0125] Alternatively, palladium-containing catalyst precursors can be used, utilizing organometallic reagents, phosphine, amines, and other components present in the reaction system to generate active palladium from the aforementioned precursors within the system. Examples of such precursors include bis(dibenzylacetone)palladium (0), palladium acetate (II), palladium chloride (II), di-μ-chlorobis[(n-allyl)palladium (II)], dichlorobis(acetonitrile)palladium (II), and dichlorobis(benzonitrile)palladium (II).

[0126] When using the aforementioned palladium-containing catalyst precursor, it is preferable to use a precursor with a ligand such as a triphosphonium salt. A specific example of a triphosphonium salt is tri-tert-butylphosphonium tetrafluoroborate. This compound generates tri-tert-butylphosphine in the system, which functions as a ligand targeting palladium.

[0127] Although not particularly limited, in one embodiment, bis(tri-tert-butylphosphine)palladium (0) and tri-tert-butylphosphonium tetrafluoroborate are preferably used as a palladium-containing catalyst in combination.

[0128] In one embodiment, as a catalyst, a palladium-containing catalyst having at least the structure shown in the following formula (1) can preferably be used.

[0129] In the formula, Ar is an aryl group with 6 to 30 carbon atoms, either substituted or unsubstituted. Ar can be, for example, a substituted or unsubstituted phenyl group. In the aromatic ring of the aryl group, at least one hydrogen atom can be substituted by an alkyl group with 1 to 12 carbon atoms.

[0130] As a specific example of a palladium-containing catalyst having the above structure, a compound represented by the following formula (2) can be cited. This compound can be produced, for example, by reacting tris(dibenzylacetone)dipalladium(0), o-bromotoluene, and tri-tert-butylphosphine.

[0131] [Chemical Formula 28] In another embodiment, as a catalyst, a palladium-containing catalyst having at least the structure shown in the following formula (3) can preferably be used.

[0132] [Chemical Formula 29] In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L represents a ligand. Z represents a leaving group. The leaving group can be one selected from halogen atoms, methanesulfonyloxy (-OSO2CH3), toluenesulfonyl (-OSO2C6H5CH3), and trifluoromethanesulfonyloxy (-OSO2CH3).

[0133] As a specific example of a catalyst having the structure shown in the above formula (3), the following catalysts can be cited.

[0134] [Chemical Formula 30] In one embodiment, the palladium-containing catalyst that can be preferably used can be manufactured according to methods known to those skilled in the art or can be obtained as a commercially available product. For example, the XphosPd series manufactured by Aldrich Corporation can be used, wherein the catalysts shown in formulas (3-1) to (3-4) above can be obtained as XphosPd G1, XphosPd G2, XphosPd G3, and XphosPd G4. In one embodiment, the catalysts shown in formulas (3-2) and (3-4) above can be more preferably used, which can be obtained as XphosPd G2 and XphosPd G4 respectively.

[0135] The amount of catalyst used is not particularly limited, but is typically in the range of 0.1 mol% to 20 mol% relative to the amino-containing aromatic compound used as a starting monomer. By adjusting the amount of catalyst used within the above range, the reaction can proceed efficiently, and the formation of byproducts can be easily suppressed. In one embodiment, the amount of catalyst used relative to the amino-containing aromatic compound used as a starting monomer is preferably 0.1 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, and even more preferably 0.1 mol% to 2 mol%. According to the manufacturing method of this embodiment, the reaction can proceed efficiently even when the amount of catalyst used is reduced. Therefore, the amount of impurities originating from the catalyst is easily reduced in the polymer obtained by the reaction.

[0136] In one embodiment, the palladium-containing catalyst may further comprise an additive. The additive is preferably a compound that functions as a palladium metal ligand. Specific examples of compounds that can be used as additives include P(t-Bu)3·HBF3, PCy3·HBF3, and Xphos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl). P(t-Bu)3·HBF3 is preferred. Using such an additive tends to further enhance the reactivity of the palladium catalyst.

[0137] The base is not particularly limited and can be either an inorganic or organic base. While not particularly limited, in one embodiment, an organic base is preferred, and organoalkali metal compounds such as sodium tert-butoxy or n-butyllithium are preferred. The amount of base used is not particularly limited, but representatively it can be between 1.0 molar equivalent and 4 molar equivalent relative to the molar number of the amino-containing aromatic compound used as a starting monomer. By adjusting the amount of base used within the above range, the reaction can proceed efficiently, and the formation of byproducts can be easily suppressed.

[0138] The reaction is preferably carried out in the presence of an organic solvent. Examples of organic solvents (reaction solvents) include aromatic hydrocarbons such as benzene and toluene, aliphatic ethers such as dioxane, tetrahydrofuran and dimethoxyethane, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, and dimethyl sulfoxide. In one embodiment, the reaction is preferably carried out in the presence of an aromatic hydrocarbon, and more preferably in the presence of toluene.

[0139] The reaction temperature is not particularly limited. For example, the reaction temperature can be in the range of 0 to 200°C. In one embodiment, the reaction temperature is preferably in the range of 80 to 180°C.

[0140] In the mixture of starting monomers, the ratio of aromatic compounds with amino groups to aromatic compounds with halogen atoms is not particularly limited. However, if unreacted starting monomers remain excessively in the reaction system, undesirable side reactions may sometimes occur; therefore, it is preferable to adjust the ratio appropriately. The ratio can be appropriately adjusted taking into account the structure of the aromatic compounds used as starting monomers and the structure of the desired charge-transporting polymer.

[0141] In one embodiment, the following aromatic compounds are preferably used as raw material monomers. Therefore, in one embodiment, the raw material monomer can be a mixture of a halogenated aromatic compound having one or more halogen atoms comprising an aromatic compound represented by formula (A) and an arylamine comprising an aromatic compound represented by formula (B). In the aromatic compound represented by formula (B), R... 1As stated in the explanation of equation (b-1) above, a is... 1 It is an electron-withdrawing group, an electron-donating group, or an alkyl group with 1 to 12 carbon atoms, where a is an integer from 1 to 5, and R 1 At least one of them is an electron-withdrawing group or an electron-donating group. In one embodiment, R 1 Preferably, it contains electron-withdrawing groups.

[0142] [Chemical Formula 31] In another embodiment, the mixture preferably further comprises an aromatic compound of formula (C) as a halogenated aromatic compound having one or more halogen atoms. In the aromatic compound of formula (C), R... 2 b is as previously explained in equation (c).

[0143] [Chemical Formula 32] In one embodiment, aromatic compound (A) represented by formula (A) and aromatic compound (B) represented by formula (B) are preferably used as the above-mentioned raw material monomers. The ratio of raw material monomers (A):(B) based on the number of reaction points of the above-mentioned aromatic compound (B) according to amino groups is preferably 0.5 to 1.5:1.0, more preferably 0.6 to 1.4:1.0.

[0144] In one embodiment, as a raw material monomer, it is preferable to use aromatic compound (C) represented by formula (C) in addition to the aromatic compound (A) and aromatic compound (B) described above. The ratio of raw material monomers (A):(B):(C) based on the number of reaction points of the aromatic compound (B) based on the amino group is preferably 0.2~0.9:1.0:0.0~1.0, more preferably 0.3~0.7:1.0:0.1~0.9, and even more preferably 0.4~0.6:1.0:0.2~0.8.

[0145] In one embodiment, the charge-transporting polymer may further include other structural units in addition to those derived from the aromatic compounds (A), (B), and (C) described above. For example, it may further include a divalent structural unit L2 having a different structure from the divalent structural unit L1 derived from the aromatic compound (B). Structural unit L2 may be introduced, for example, using compounds represented by the following formula.

[0146] In the formula, Q represents a halogen atom, which can be a chlorine atom, bromine atom, or iodine atom.

[0147] L2 represents a divalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle with 2 to 30 carbon atoms, or a triarylamine. In one embodiment, L2 is preferably a divalent organic group derived from a triarylamine, and more preferably a divalent organic group derived from triphenylamine.

[0148] Ar 1 It can be a monovalent organic group derived from an aromatic compound having 6 to 24 carbon atoms, preferably having the structure shown in the above formula (b-1) as previously described.

[0149] While not particularly limited, from the viewpoint of easily manufacturing preferred charge-transport polymers, the aromatic compounds (A), (B), and (C) described above are preferably used as raw material monomers in the method for manufacturing charge-transport polymers. In one embodiment, the raw material monomers are preferably a mixture consisting only of the aromatic compounds (A), (B), and (C) described above. When using such a mixture as the raw material monomers, it is possible to easily form a -(NAr-Ph) bond without forming Ph-Ph bonds within the molecule. n - Polymers with structures where n is an integer greater than or equal to 2.

[0150] Although not particularly limited, in one embodiment, the charge-transporting polymer (I) may be a polymer obtained by reacting monomer A1 used in the examples described later with monomers B2, B3, B4, B5 or B6 and monomer C1 in the presence of a catalyst.

[0151] As mentioned above, it has -(NAr-Ph) n Charge-transporting polymers with a -- structure can be readily synthesized via the Bucnwald-Hartwig reaction. However, impurities originating from components such as the catalyst and starting monomers used in the reaction are likely to remain in the polymer obtained by the above reaction. Therefore, it is preferable to perform polymer separation and purification after the above reaction. Polymer separation and purification can be performed using methods known in the art. For example, a method can be used that involves adding water to the reaction solution after the coupling reaction and mixing, separating the mixture into an organic phase and an aqueous phase, and recovering the polymer from the organic phase.

[0152] In one embodiment, by adding a heavy metal scavenger during the mixing of the above-described reaction solution and water, impurities originating from catalysts and the like can be removed more effectively. The heavy metal scavenger can be any compound capable of forming a chelate with heavy metals such as palladium used as a catalyst to capture them, or a compound capable of specifically binding to and adsorbing heavy metals. For example, dithiocarbamates can be used. Preferably, an aqueous solution of an alkyl dithiocarbamate having 1 to 6 carbon atoms can be used. Furthermore, by appropriately selecting the organic solvent used for separation and purification, the amount of residual impurities in the polymer obtained by the above-described manufacturing method can be easily reduced. For example, a water-soluble organic solvent such as methanol can preferably be used when mixing the reaction solution and water.

[0153] In the case of an organic electronic material comprising a charge-transporting polymer, the charge-transporting polymer may contain impurities introduced during the manufacturing process, etc. However, impurities can be a cause of reduced properties in organic electronic components formed using the organic electronic material, so it is preferable that the amount of impurities is as low as possible. In one embodiment, from the viewpoint of providing a charge-transporting polymer that can be preferably used as an organic electronic material, the palladium content in the polymer is preferably 100 ppm or less, more preferably 80 ppm or less, and even more preferably 50 ppm or less. In addition, the halogen atom content (total stoichiometry) in the polymer is preferably 300 ppm or less, more preferably 100 ppm or less, and even more preferably 60 ppm or less. By performing separation and purification as needed after the coupling reaction as described above, a charge-transporting polymer with the desired purity can be easily obtained.

[0154] As one embodiment of the present invention, the organic electronic material comprises at least one charge-transporting polymer containing a charge-transporting polymer (I) having the above-described structure (I). Based on the total mass of the organic electronic material, the content of the charge-transporting polymer (I) in the organic electronic material is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. When the content of the charge-transporting polymer (I) is adjusted to the above range, excellent charge transport properties can be easily obtained. In one embodiment, the content of the charge-transporting polymer (I) may be 100% by mass.

[0155] In one embodiment, from the viewpoint of improving the charge transport properties of organic electronic materials, additives such as dopants can be added. When using additives such as dopants, the content of the charge transport polymer, based on the total mass of the organic electronic material, can be 95% or less, or 90% or less by mass.

[0156] The content of the dopant relative to the total mass of the organic electronic material is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. On the other hand, from the viewpoint of maintaining good film-forming properties, the content of the dopant relative to the total mass of the organic electronic material is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0157] From the viewpoint of using a wet process as a film-forming method, organic electronic materials preferably further contain a solvent. Organic electronic materials can be configured as an ink composition (polymer solution) comprising a charge-transporting polymer and a solvent. The solvent used need only be able to dissolve the charge-transporting polymer. By using an ink composition formed by dissolving the charge-transporting polymer in a solvent, an organic layer can be easily formed using a simple wet process.

[0158] (solvent) As a solvent, any solvent medium such as water, organic solvents, or mixtures thereof can be used. Examples of organic solvents include alcohols such as methanol, ethanol, and isopropanol; alkanes such as pentane, hexane, and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetrahydronaphthalene, and diphenylmethane; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate; and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, and 4-methoxybenzene. Aromatic ethers such as methyltoluene, 3-phenoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, and dichloromethane. Preferably, they are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers, more preferably aromatic hydrocarbons.

[0159] The solvent content in the organic electronic material (ink composition) can be determined by considering various coating methods. For example, the solvent content is preferably 0.1% by mass or more relative to the solvent and charge-transporting polymer, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more. Furthermore, the solvent content is preferably 20% by mass or less relative to the solvent and charge-transporting polymer, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0160] In another embodiment, from the viewpoint of improving the operability of forming the organic layer when preparing the ink composition and further improving the function of the organic layer, organic electronic materials may contain additives as any component. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, anti-reduction agents, oxidants, reducing agents, surface modifiers, emulsifiers, defoamers, dispersants, surfactants, etc.

[0161] <Organic Layer> One embodiment relates to an organic layer formed using the aforementioned organic electronic material or the aforementioned ink composition. The organic layer exhibits good charge transport properties. By using the ink composition, the organic layer can be formed readily and easily via a coating method. Examples of coating methods include spin coating; casting; dipping; plate-printed methods such as letterpress printing, gravure printing, offset printing, lithography, letterpress-reverse offset printing, screen printing, and gravure printing; and plateless printing methods such as inkjet printing. When forming an organic layer by coating, the coated layer can be dried by heat treatment to remove the solvent.

[0162] The heat treatment can be carried out in an atmospheric gas environment or in an inert gas environment. Examples of inert gases include helium, argon, nitrogen, and mixtures thereof. The "inert gas environment" preferably has an inert gas concentration of 99.5% or more by volume, more preferably 99.9% or more, and even more preferably 99.99% or more.

[0163] Heating treatment can be performed using heaters such as hot plates or ovens. To perform heating treatment in an inert gas environment, for example, a hot plate can be used in an inert gas environment, or an oven can be placed inside an inert gas environment.

[0164] From the viewpoint of effectively removing the solvent, the heat treatment is preferably carried out at a temperature above the boiling point of the solvent. Furthermore, in the case of polymerization of charge-transporting polymers, a temperature at which the polymerization reaction proceeds efficiently is preferred. In one embodiment, the heat treatment temperature is preferably 140°C or higher, more preferably 180°C or higher, and even more preferably 190°C or higher. On the other hand, from the viewpoint of suppressing deterioration caused by the heat treatment, a temperature of 300°C or lower is preferred, more preferably 280°C or lower, and even more preferably 250°C or lower.

[0165] From the viewpoint of improving charge transport efficiency, the thickness of the dried organic layer is preferably 0.1 nm or more, more preferably 1 nm or more, and even more preferably 3 nm or more. Furthermore, from the viewpoint of reducing resistance, the thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.

[0166] <Organic Electronic Components> One embodiment relates to an organic electronic device having at least one of the aforementioned organic layers. Examples of organic electronic devices include organic EL devices, organic photoelectric conversion devices, and organic transistors. The organic electronic device preferably has a structure in which an organic layer is disposed between at least one pair of electrodes. The organic electronic device can be manufactured by a manufacturing method comprising the step of forming an organic layer using the aforementioned organic electronic material or the aforementioned ink composition.

[0167] <Organic EL Components> One embodiment relates to an organic EL device having at least one of the aforementioned organic layers. The organic EL device typically includes a light-emitting layer, an anode, a cathode, and a substrate, and may include other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer, as needed. Each layer can be formed by vapor deposition or by coating. Preferably, the organic EL device has the aforementioned organic layer as a light-emitting layer or other functional layer; more preferably, it has the aforementioned organic layer as another functional layer; and even more preferably, it has the aforementioned organic layer as at least one of a hole injection layer and a hole transport layer.

[0168] Figure 1 This is a cross-sectional schematic diagram illustrating one embodiment of an organic EL element. Figure 1 The organic EL element is a multilayer structure element, which sequentially includes a substrate 8, an anode 2, a hole injection layer 3, a hole transport layer 6, a light-emitting layer 1, an electron transport layer 7, an electron injection layer 5, and a cathode 4.

[0169] [Emitting Layer] Materials used in the luminescent layer can include low-molecular-weight compounds, polymers, dendritic macromolecules, and other luminescent materials. Polymers are preferred because they have high solubility in solvents and are suitable for coating methods. Examples of luminescent materials include fluorescent materials, phosphorescent materials, and thermally activated delayed fluorescence (TADF) materials.

[0170] Examples of fluorescent materials include low molecular weight compounds such as perylene, coumarin, rubrene, quinacridone, stilbene, pigments for lasers, aluminum complexes, and their derivatives; polymers such as polyfluorene, polyphenylene, polyphenylene ethylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, and their derivatives; and mixtures thereof.

[0171] As phosphorescent materials, metal complexes containing metals such as Ir and Pt can be used. For example, Fir(pic) (bis[(4,6-difluorophenyl)-pyridine-N,C)) exhibits blue luminescence and is an example of an Ir complex. 2 Ir(ppy)3(fac-tris(2-phenylpyridine)iridium) exhibits green luminescence, and (btp)2Ir(acac)(bis[2-(2'-benzo[4,5-α]thiophene)pyridine-N,C) exhibits red luminescence. 3 Examples of Pt complexes include iridium acetylacetonate (Ir(piq)3) (tris(1-phenylisoquinoline)iridium), etc. Examples of Pt complexes that exhibit red luminescence include PtOEP (2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum), etc.

[0172] When the luminescent layer contains a phosphorescent material, it is preferable to further include a host material in addition to the phosphorescent material. As the host material, low-molecular-weight compounds, polymers, or dendritic macromolecules can be used. Examples of low-molecular-weight compounds include CBP (4,4'-bis(9H-carbazole-9-yl)biphenyl), mCP (1,3-bis(9-carbazole-yl)benzene), CDBP (4,4'-bis(carbazole-9-yl)-2,2'-dimethylbiphenyl), and their derivatives. Examples of polymers include the aforementioned organic electronic materials, polyvinylcarbazole, polyphenylene, polyfluorene, and their derivatives.

[0173] Examples of thermally active delayed fluorescence materials include PIC-TRZ (2-biphenyl-4,6-bis(12-phenylindolo[2,3-a]carbazole-11-yl)-1,3,5-triazine), spiro-CN (2',7'-bis(di-p-tolylamino)-9,9'-spirodifluorene-s,7-dicarboxynitrile), CC2TA (2,4-bis{3-(9H-carbazole-9-yl)-9H-carbazole-9-yl}-6-phenyl-1,3,5-triazine), CZ-PS (9,9'-(4,4'-sulfonylbis(4,1-phenylene))bis(3,6-di-tert-butyl-9H-carbazole)), 4CzPN (3,4,5,6-tetra(9H-carbazole-9-yl)phthalonitrile), and HAP-3TPA (4,4',4''-(1,3,3a)... 1 Compounds such as 4,6,7,9-heptaazafinaene-2,5,8-triyl)tri(N,N-bis(4-(tert-butyl)phenyl)aniline) and 4CzIPN(1,2,3,5-tetra(carbazolyl-9-yl)-4,6-dicyanophenyl).

[0174] [Hole injection layer, hole transport layer] Preferably, the above-mentioned organic layer is used as at least one of the hole injection layer and the hole transport layer. As described above, these layers can be easily formed by using an ink composition containing organic electronic materials and solvents.

[0175] When an organic EL element has the aforementioned organic layer as a hole injection layer and further has a hole transport layer, the hole transport layer can be made of a known material. Similarly, when an organic EL element has the aforementioned organic layer as a hole transport layer and further has a hole injection layer, the hole injection layer can be made of a known material. Both the hole injection layer and the hole transport layer may also be the aforementioned organic layer. Examples of known materials include aromatic amine compounds (e.g., aromatic diamines such as N,N'-di(naphthyl-1-yl)-N,N'-diphenyl-benzidine (α-NPD), phthalocyanine compounds, and thiophene compounds (e.g., thiophene-based conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)).

[0176] When the hole transport layer is an organic layer whose solubility has changed, a light-emitting layer can be easily formed on top of it using a wet process. In this case, the polymerization initiator can be contained in the organic layer that serves as the hole transport layer, or it can be contained in the organic layer located below the hole transport layer.

[0177] [Electron transport layer, electron injection layer] Materials used in the electron transport and electron injection layers include, for example, phenanthrene derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiamethane dioxide derivatives, fused-ring tetracarboxylic anhydrides such as naphthalene and perylene, carbodiimide, fluorenemethane derivatives, anthraquinone dimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, and aluminum complexes. Additionally, the aforementioned organic electronic materials can also be used.

[0178] [cathode] For example, metals or metal alloys such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, and CsF can be used as cathode materials.

[0179] [anode] As an anode material, metals (e.g., Au) or other conductive materials can be used. Examples of other materials include oxides (e.g., ITO: indium oxide / tin oxide) and conductive polymers (e.g., polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[0180] [Substrate] Glass, plastic, etc., can be used as the substrate. The substrate is preferably transparent, and even more preferably flexible. Quartz glass, resin film, etc. are preferred.

[0181] As a resin film, a light-transmitting resin film is preferred. Examples of resin films include those with polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate as the main components.

[0182] In the case of using resin membranes, in order to suppress the permeation of water vapor, oxygen, etc., the resin membrane can also be coated with inorganic materials such as silicon oxide and silicon nitride.

[0183] [seal] Organic EL elements can also be sealed to reduce the influence of external gases and extend their lifespan. Materials used for sealing include, but are not limited to, plastic films such as glass, epoxy resin, acrylic resin, polyethylene terephthalate, and polyethylene naphthalate, or inorganic materials such as silicon dioxide and silicon nitride. The sealing method is also not particularly limited and can be performed using known methods.

[0184] [Luminous Color] There is no particular limitation on the emission color of organic EL elements. White organic EL elements are preferred as they can be used in various lighting fixtures such as home lighting, automotive lighting, clock or LCD backlights.

[0185] One method for forming white organic EL elements is to use multiple luminescent materials to simultaneously emit multiple colors, thus mixing colors. There are no particular limitations on the combination of multiple luminescent colors; examples include combinations containing the three maximum emission wavelengths of blue, green, and red, or combinations containing two maximum emission wavelengths such as blue and yellow, or yellow-green and orange. The color of the emitted light can be controlled by adjusting the type and amount of luminescent materials.

[0186] <Display elements, lighting devices, display devices> One embodiment relates to a display element having the aforementioned organic EL elements. For example, a color display element can be obtained by using organic EL elements as elements corresponding to each pixel of red, green, and blue (RGB). Among the image formation methods, there are simple matrix types that directly drive each organic EL element arranged on a panel using electrodes arranged in a matrix, and active matrix types that drive each element by arranging thin-film transistors on each element.

[0187] Additionally, one embodiment relates to a lighting device incorporating the aforementioned organic EL element. Furthermore, one embodiment relates to a display device incorporating a lighting device and a liquid crystal element as a display unit. For example, the display device may be a liquid crystal display device that uses the aforementioned lighting device as a backlight and a known liquid crystal element as a display unit.

[0188] Example The present invention will now be described in more detail through embodiments. However, the present invention is not limited to the embodiments described below, and includes various implementation methods.

[0189] Synthesis of Charge-Transporting Polymers The raw material monomers used in the following examples and comparative examples are shown below.

[0190] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] (Example 1) Prepare a reaction vessel equipped with a Dimroth condenser and stirring function, and then configure an oil bath in a manner that allows for relative movement within the reaction vessel. While injecting nitrogen into the nitrogen-purged reaction vessel, add the following components one by one. Connect a nitrogen supply device to the front end of the Dimroth condenser to create a nitrogen-environmental reaction environment.

[0191] Raw material monomers: Monomer A1 (1285 mg, 2.67 mmol), Monomer B2 (556 mg, 5.00 mmol), Monomer C1 (370 mg, 2.00 mmol) Organic solvent (toluene): Dehydrated toluene stored under a nitrogen atmosphere, manufactured by Fujifilm and Kojun Chemical Co., Ltd., 25.6 mL. Base: Sodium tert-butoxy, manufactured by Tokyo Chemical Industry Co., Ltd., 1442 mg (based on 3.0 equivalents of the amino-containing monomer B2). Catalyst: Xphos Pd G2 (chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium), manufactured by Fujifilm and Kohden Corporation, 20 mg (0.5 mol% based on the amino-containing monomer B2). Next, the mixture was heated to the temperature at which the organic solvent in the reaction vessel was refluxed using an oil bath (bath temperature 120°C) while being stirred for 2 hours to carry out the reaction.

[0192] After the above reaction, the temperature of the reaction mixture in the reaction vessel was lowered to room temperature, and 10 mL of an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm and Wakamitsu Chemical Co., Ltd.) adjusted to 0.1 mol / L was added and stirred. Methanol-water (9:1) was added to the resulting suspension for reprecipitation, and the resulting precipitate was filtered.

[0193] Ethyl acetate was added to the obtained precipitate, and the mixture was heated in an oil bath at 60°C with stirring for 15 minutes to wash the precipitate with ethyl acetate. The washed precipitate was then recovered by vacuum filtration. Using the recovered washed precipitate, a second washing with ethyl acetate was performed in the same manner as above to remove residual monomers and reactants soluble in ethyl acetate. The precipitate washed with ethyl acetate was then dried under reduced pressure to obtain the polymer (pale yellow powder).

[0194] By measuring the proton nuclear magnetic resonance of the polymer ( 1 ¹H-NMR spectroscopy confirmed that the polymer has a structure obtained by the condensation polymerization of monomers A1, B1, and C1. The polymer yield was 55%, with a weight-average molecular weight (Mw) of 13,300, a number-average molecular weight (Mn) of 7,300, and a molecular weight distribution Mw / Mn of 1.8.

[0195] also, 1 The 1H-NMR spectra were measured using a Bruker AVANCE-600NMR spectrometer. Mw and Mn were measured using a Shimadzu Prominence GPC system. In the determination of Mw and Mn, gel permeation chromatography (GPC) was performed using a styrene gel column, calibrated with standard polystyrene at 40°C, and tetrahydrofuran as the eluent. The measurement conditions are as follows. The same conditions apply in the examples described later.

[0196] Liquid delivery pump: L-6050, Hitachi High Technology Co., Ltd. UV-Vis detector: L-3000, Hitachi High Technology Co., Ltd. Column: Gelpack (registered trademark) GL-A160S / GL-A150S, Risennoko Co., Ltd. Eluent: THF (for HPLC, stabilizer-free) and Hikari Pure Chemical Industries, Ltd. Flow rate: 1 ml / min Column temperature: room temperature Molecular weight standard material: Standard polystyrene (Examples 2-5) Except for changes to the raw material monomers, formulation amounts, and catalysts as shown in Table 1, the polymers were prepared in the same manner as in Example 1. Various measurements were performed on the resulting polymers in the same manner as in Example 1. The results are shown in Table 1.

[0197] (Compare with Example 1) Except for changes to the raw material monomers, formulation amounts, and catalysts as shown in Table 1, the polymers were prepared in the same manner as in Example 1. Various measurements were performed on the resulting polymers in the same manner as in Example 1. The results are shown in Table 1.

[0198] <Evaluation of Charge Transport Polymers> (Evaluation of HOMO level) Ink compositions were prepared using the charge-transporting polymers obtained in Examples 1-5 and Comparative Example 1, according to the methods described below. An organic layer was then formed using the ink compositions, and the HOMO energy levels were evaluated.

[0199] The polymer (50.0 mg) and the following ionic compound (1) (0.5 mg) were measured in a 9 mL threaded tube and dissolved in toluene (4949.5 mg) to prepare the ink composition.

[0200] [Chemical Formula 37] Next, the ink composition was filtered using a PTFE filter (0.2 μm pore size). The filtered ink composition was then dropped onto a quartz substrate (22 mm x 29 mm x 0.7 mm) and spin-coated. Following this, the substrate was heated at 210°C for 30 minutes under atmospheric conditions to form an organic layer with a thickness of 30 nm on the quartz substrate.

[0201] In the atmosphere, the surface work function of the organic layer previously formed on a quartz substrate was measured using a photoelectro-electric yield spectrometer (model AC-5) manufactured by Riken Keiki Co., Ltd. The HOMO energy levels determined based on the surface work function values ​​are shown in Table 2.

[0202] As shown in Table 2, the HOMO energy level of the charge transport polymers according to the present invention (Examples 1-5) can be easily adjusted by having electron-withdrawing or electron-donating groups, even for charge transport polymers (Comparative Example 1) that do not have these substituents. In particular, it is evident that higher HOMO energy levels are readily obtained when electron-withdrawing groups are present (Examples 1-3).

[0203] By deepening the HOMO energy level, the energy difference between the charge-transporting polymer and the adjacent hole-transporting layer or light-emitting layer becomes smaller, which is preferable from the viewpoint of improving driving voltage and conductivity. Therefore, by introducing electron-withdrawing or electron-donating groups at specific positions in the charge-transporting polymer, it becomes easy to improve the conductivity and driving voltage of organic EL devices.

[0204] As can be seen from the above, according to the present invention, an organic electronic material comprising a charge-transporting polymer capable of readily forming an organic layer that improves properties such as conductivity can be provided.

[0205] Explanation of reference numerals in the attached figures 1. Emissive layer 2 Anode 3. Hole injection layer 4 Cathode 5 Electron Injection Layer 6. Hole transport layer 7. Electron Transport Layer 8 substrate

Claims

1. An organic electronic material containing a charge-transporting polymer having a branched structure, wherein, The charge transportable polymer contains a trivalent structural unit represented by the following formula (a) and a divalent structural unit represented by the following formula (b), and has a structure represented by the following formula (I) formed by directly bonding at least one bonding site in the trivalent structural unit to at least one bonding site in the divalent structural unit, the charge transportable polymer having a weight average molecular weight of 2,000 to 500,000, wherein Ar 1 represents a 3-valent organic group derived from an aromatic hydrocarbon or an aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine, Ar 2 represents a 1-valent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms having an electron-withdrawing group or an electron-donating group, represents a bonding site to other structures.

2. The organic electronic material according to claim 1, wherein The structure represented by the formula (I) contains a structure represented by the following formula (I-1) or the following formula (I-2), wherein Ar 1 represents a 3-valent organic group derived from an aromatic hydrocarbon or an aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine, Ar 2 represents a 1-valent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms having an electron-withdrawing group or an electron-donating group, represents a bonding site to other structures.

3. The organic electronic material according to claim 1 or 2, wherein In the formula (I), Ar 1 having a structure derived from triphenylamine or a structure derived from N-phenylcarbazole.

4. The organic electronic material according to any one of claims 1 to 3, wherein In the formula (I), Ar 2 having a structure represented by the following formula (b-1) In the formula, R 1 is an electron-withdrawing group, an electron-donating group, or an alkyl group having 1 to 12 carbon atoms, at least one of which is an electron-withdrawing group or an electron-donating group, and a is an integer of 1 to 5.

5. The organic electronic material according to claim 4, wherein In the formula (b-1), R 1 is an electron-withdrawing group, a is an integer of 1 or 2, and the electron-withdrawing group is at least one selected from a halogen group, a halogen-substituted alkyl group, a nitro group, a cyano group, a sulfonic acid group, and a sulfoxide group.

6. The organic electronic material according to any one of claims 1 to 5, wherein The charge transportable polymer further contains a monovalent structural unit represented by the following formula (c), In the formula, R 2 is an alkyl group having 1 to 8 carbon atoms, and b is an integer of 1 to 5.

7. The organic electronic material according to any one of claims 1 to 6, further comprising a solvent.

8. An organic layer formed using the organic electronic material according to any one of claims 1 to 7.

9. An organic electronic element comprising the organic layer according to claim 8.

10. An organic electroluminescent element comprising the organic layer according to claim 8.

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