Organic electronic materials and their applications

Abstract

An organic electronic material and its use, the organic electronic material containing a charge transporting polymer, the charge transporting polymer having a branched structure and having a structural unit containing a structure represented by the following formula (1). #imgabs0#

Description

Technical Field

[0001] Embodiments of the present invention relate to an organic electronic material, a liquid composition, an organic layer, an organic electronic element, an organic electroluminescence element, a display element, a lighting device, a display device, and a method for producing an organic electronic element. Background Art

[0002] Organic electronic components are components that use organic matter to perform electrical operations. They are expected to have advantages such as energy saving, low price, and flexibility, and are attracting attention as a technology to replace existing inorganic semiconductors based on silicon. Examples of organic electronic components include organic electroluminescent components (organic EL components), organic photoelectric conversion components, and organic transistors.

[0003] Organic EL elements are attracting attention as large-area solid-state light sources that can be used as substitutes for incandescent lamps or gas-filled lamps. In addition, they are also attracting attention as the most powerful self-luminous display that can replace liquid crystal displays (LCDs) in the field of flat panel displays (FPDs), and are being promoted for commercialization.

[0004] Organic EL elements are roughly divided into two types, low-molecular organic EL elements and polymer organic EL elements, according to the organic materials used. Polymer compounds are used as organic materials in polymer organic EL elements, while low-molecular compounds are used in low-molecular organic EL elements. On the other hand, the manufacturing methods of organic EL elements are roughly divided into two types: dry processes that form films mainly in a vacuum system and wet processes that form films using plate printing such as relief printing and gravure printing, and plateless printing such as inkjet printing. Since it can achieve simple film formation, the wet process is expected to be an indispensable method for future large-screen organic EL displays.

[0005] Therefore, development of materials suitable for wet processes is being conducted, and for example, research is being conducted on forming a multilayer structure using a charge transporting compound having a polymerizable functional group (see Patent Document 1).

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] Patent Document 1: Japanese Patent Application Publication No. 2006-279007 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] Organic EL devices manufactured by wet processes have the advantages of being easy to achieve at low cost and large area. However, there is still room for improvement in terms of wet process efficiency and device characteristics.

[0011] Therefore, the subject of the embodiment of the present invention is to provide an organic electronic material having high solubility and capable of forming an organic layer with high charge transport. In addition, the subject of the embodiment of the present invention is to provide a liquid composition that can be easily prepared and can form an organic layer with high charge transport. In addition, the subject of the embodiment of the present invention is to provide an organic layer that can be efficiently formed by a wet process and has high charge transport. Furthermore, the subject of the embodiment of the present invention is to provide an organic electronic element, an organic EL element, a display element, a lighting device, and a display device having excellent life characteristics.

[0012] [Technical means to solve the problem]

[0013] The present invention includes various embodiments. Examples of the embodiments are listed below. The present invention is not limited to the following embodiments.

[0014] One embodiment relates to an organic electronic material including a charge-transporting polymer having a branched structure and having a structural unit including a structure represented by the following formula (1).

[0015]

[0016] (wherein, Ar each independently represents an aromatic ring group, Ra each independently represents a hydrogen atom, a substituent, or a bonding site with another structure, Rb each independently represents a substituent, and n each independently represents an integer greater than 0. At least one of Ra is a bonding site with another structure)

[0017] Another embodiment relates to a liquid composition containing the organic electronic material and a solvent.

[0018] Still another embodiment relates to an organic layer formed using the organic electronic material or the liquid composition.

[0019] Still another embodiment relates to an organic electronic device including the organic layer.

[0020] Still another embodiment relates to an organic electroluminescent element including the organic layer.

[0021] Still another embodiment relates to a display element including the organic electroluminescent element; a lighting device including the organic electroluminescent element; or a display device including the lighting device and a liquid crystal element as a display component.

[0022] Still another embodiment relates to a method for manufacturing an organic electronic element, comprising: forming an organic layer using the organic electronic material or the liquid composition.

[0023] [Effects of the Invention]

[0024] According to an embodiment of the present invention, an organic electronic material having high solubility and capable of forming an organic layer having high charge transport properties can be provided. In addition, according to an embodiment of the present invention, a liquid composition that can be easily prepared and capable of forming an organic layer having high charge transport properties can be provided. In addition, according to an embodiment of the present invention, an organic layer that can be efficiently formed by a wet process and has high charge transport properties can be provided. In addition, according to an embodiment of the present invention, an organic electronic element, an organic EL element, a display element, a lighting device, and a display device having excellent life characteristics can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic cross-sectional view showing an example of an organic EL element which is one embodiment of the present invention.

[0026] Figure 2 It is a schematic cross-sectional view showing a device for evaluation used in Examples.

[0027] [Explanation of Symbols]

[0028] 1: Luminous layer

[0029] 2: Anode

[0030] 3: Hole injection layer

[0031] 4: Cathode

[0032] 5: Electron injection layer

[0033] 6: Hole transport layer

[0034] 7: Electron transport layer

[0035] 8: Substrate

[0036] 11: Organic layer

[0037] 12: Anode

[0038] 13: Cathode

[0039] 14: Substrate DETAILED DESCRIPTION

[0040] The present invention is not limited to the following embodiments.

[0041] <Organic electronic materials>

[0042] The organic electronic material as an embodiment of the present invention contains a charge transporting polymer having a branched structure and a structural unit having a structure represented by the following formula (1). The organic electronic material may contain only one charge transporting polymer, or may contain two or more. Compared with low molecular weight compounds, charge transporting polymers are preferred in terms of excellent film forming properties in a wet process.

[0043]

[0044] In the formula, Ar each independently represents an aromatic ring group, Ra each independently represents a hydrogen atom, a substituent, or a bonding site with another structure, Rb each independently represents a substituent, and n each independently represents an integer greater than 0. At least one of Ra is a bonding site with another structure.

[0045] [Charge transport polymer]

[0046] The charge transporting polymer is a polymer capable of transporting charges, and preferably a hole transporting polymer capable of transporting holes. The charge transporting polymer has a branched structure branched in three or more directions, and has a structure represented by formula (1).

[0047] It is believed that the charge transporting polymer has a structure represented by formula (1), thereby improving the charge transporting property. In particular, when the charge transporting polymer has a structural unit comprising a structure represented by formula (1) and a structural unit having hole transporting property, a high hole transporting ability is shown. "Structural unit having hole transporting property" is a structural unit different from "structural unit comprising a structure represented by formula (1)". Furthermore, although the reason is not clear, the charge transporting polymer has a structure represented by formula (1), thereby improving the solubility in the solvent.

[0048] (Structural unit including the structure represented by formula (1))

[0049] The charge transporting polymer has a structural unit containing a structure represented by the following formula (1). In the following description, the "structure represented by formula (1)" is sometimes referred to as "structure (1)", and the "structural unit containing a structure represented by formula (1)" is sometimes referred to as "structural unit (1)". The charge transporting polymer may contain only one structural unit (1) or may contain two or more structural units (1).

[0050]

[0051] In the formula, Ar each independently represents an aromatic ring group, Ra each independently represents a hydrogen atom, a substituent, or a bonding site with another structure, Rb each independently represents a substituent, and n each independently represents an integer greater than 0. At least one of Ra is a bonding site with another structure.

[0052] The aromatic ring group is an atomic group obtained by removing one or more hydrogen atoms from an aromatic ring. The aromatic ring is preferably an aromatic ring having 2 to 30 carbon atoms. Examples of the aromatic ring include aromatic hydrocarbon rings and aromatic heterocyclic rings. In addition, examples of the aromatic ring include monocyclic rings and condensed rings. Examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, triphenylene, pyrene, Perylene, pentacene, benzopyrene, etc. Examples of the aromatic heterocycle include pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, carbazole, furan, benzofuran, dibenzofuran, pyrrole, thiophene, benzothiophene, dibenzothiophene, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzooxadiazole, benzothiadiazole, benzotriazole, benzothiophene, etc.

[0053] From the viewpoint of obtaining the effects of improving solubility and charge transport properties, the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, and further preferably benzene.

[0054] When Ra is a substituent, examples of the substituent include: 1 、-OR 2 、-SR 3 、-OCOR 4 、-COOR 5 、-SiR 6 R 7 R 8 A substituent selected from the group consisting of a halogen atom and a group including a polymerizable functional group described later (hereinafter, sometimes referred to as a "substituent X").

[0055] R 1 is selected from the group consisting of alkyl, aryl and heteroaryl. 2 ~R 10 are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group.

[0056] The alkyl group may be linear, branched or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 22. The number of carbon atoms in the aryl group is preferably 6 to 30. The number of carbon atoms in the heteroaryl group is preferably 2 to 30. The alkyl group, aryl group and heteroaryl group may be substituted or unsubstituted.

[0057] When the alkyl group, aryl group, or heteroaryl group further has a substituent, examples of the substituent include the substituent X described above, preferably -R 1 .

[0058] Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, 3,7-dimethyloctyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0059] In the present specification, an aryl group is an atomic group obtained by removing a hydrogen atom from an aromatic hydrocarbon, and a heteroaryl group is an atomic group obtained by removing a hydrogen atom from an aromatic heterocyclic compound.

[0060] As the aromatic hydrocarbons herein, monocyclic rings, condensed rings, or polycyclic rings in which two or more selected from monocyclic rings and condensed rings are bonded via direct bonds can be cited. As the aromatic heterocyclic compounds, monocyclic rings, condensed rings, or polycyclic rings in which two or more selected from monocyclic rings and condensed rings are bonded via direct bonds can be cited.

[0061] Examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, triphenylene, pyrene, Perylene, pentacene, benzopyrene, biphenyl, terphenyl, triphenylbenzene, etc. Examples of aromatic heterocyclic compounds include pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, carbazole, furan, benzofuran, dibenzofuran, pyrrole, thiophene, benzothiophene, dibenzothiophene, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzooxadiazole, benzothiadiazole, benzotriazole, benzothiophene, bithiophene, etc.

[0062] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. The halogen atom is preferably a fluorine atom.

[0063] When Ra has a substituent, the number of the substituent is 1 to 3, preferably 1 or 2. When a plurality of substituents in Ra are substituents, the plurality of substituents may be the same as or different from each other.

[0064] At least one of Ra is a bonding site with other structures. "Other structures" are structures other than hydrogen atoms and the substituents. When four of Ra are bonding sites, structure (1) is a tetravalent structure, when three of Ra are bonding sites, structure (1) is a trivalent structure, when two of Ra are bonding sites, structure (1) is a divalent structure, and when one of Ra is a bonding site, structure (1) is a monovalent structure. In terms of the effects of obtaining higher solubility improvement and charge transport improvement, the number of bonding sites is preferably 2 or 4. That is, structure (1) is preferably divalent or tetravalent.

[0065] Ra which is not a substituent or a bonding site is a hydrogen atom. The number of hydrogen atoms is zero to three. All Ra except the bonding site may be hydrogen atoms.

[0066] Rb represents a substituent. Examples of substituents include the substituent X. When structure (1) includes a plurality of Rb, the plurality of Rb may be the same as or different from each other. When structure (1) includes Rb and Ra as a substituent, Rb and Ra may be the same as or different from each other.

[0067] n represents the number of Rb. n is an integer greater than 0, and the upper limit of n can be determined according to the type of Ar. When Ar is a benzene ring group, the upper limit of n is 4, and when Ar is a naphthyl ring group, the upper limit of n is 6. If the influence of the substituent is considered, n can be 0.

[0068] Examples of structure (1) are listed below. Structure (1) is not limited to the structure represented by the following formula. In this specification, "*" indicates a bonding site with another structure.

[0069]

[0070] In the formula, Rc each independently represents a hydrogen atom or a substituent, Rb each independently represents a substituent, and n each independently represents an integer of 0 to 4.

[0071] When Rc is a substituent, examples of the substituent include the substituent X. In each structure, when Rc contains a substituent, the number of substituents is 1 to 3, preferably 1 or 2. When multiple Rc are substituents, the multiple substituents may be the same or different. In each structure, Rc that is not a substituent is a hydrogen atom. The number of hydrogen atoms is zero to three. All Rc may be hydrogen atoms.

[0072] Rb is a substituent, and examples of the substituent include the above-mentioned substituent X. In each structure, when there are multiple Rb, the multiple Rb may be the same or different from each other. In each structure, when there are Rb and Rc as a substituent, Rb and Rc may be the same or different from each other.

[0073] n represents the number of Rb. Each n is independently an integer of 0 to 4, and n may be 0 if the influence of the substituent is taken into consideration.

[0074] According to a preferred embodiment, the structure (1) preferably includes a structure represented by the formula (1B-1). In the formula (1B-1), n ​​is preferably independently 0 or 1, and more preferably all n are 0.

[0075] According to a preferred embodiment, structure (1) preferably includes at least one selected from the group consisting of the structure represented by the formula (1L-1) and the structure represented by the formula (1L-2), and more preferably includes the structure represented by the formula (1L-1). In each of the formulas (1L-1) and (1L-2), n is preferably 0 or 1 independently of each other, and more preferably all n are 0. Rc preferably represents a substituent independently of each other. According to a preferred embodiment, in each of the formulas (1L-1) and (1L-2), preferably two Rc are halogen atoms or alkyl groups substituted by halogen, more preferably halogen atoms, and further preferably fluorine atoms. According to another preferred embodiment, in each of the formulas (1L-1) and (1L-2), one Rc is preferably a halogen atom or an alkyl group substituted by halogen, more preferably a halogen atom, and further preferably a fluorine atom. The other Rc is preferably an alkyl group, more preferably a linear alkyl group, further preferably a linear alkyl group having 3 to 12 carbon atoms, and particularly preferably a linear alkyl group having 6 to 12 carbon atoms.

[0076] Preferred specific examples of the structure (1) are listed below. The structure (1) is not limited to the structure represented by the following formula.

[0077]

[0078] In the above formula, R represents an alkyl group. The alkyl group is preferably a linear alkyl group, more preferably a linear alkyl group having 3 to 12 carbon atoms, and still more preferably a linear alkyl group having 6 to 12 carbon atoms.

[0079] The structural unit (1) is a structural unit having at least one structure (1). The structural unit (1) is preferably monovalent to tetravalent, and is more preferably divalent or tetravalent in order to obtain a higher effect of improving the charge transport property.

[0080] Examples of the structural unit (1) are listed below. The structural unit (1) is not limited to the structural unit represented by the following formula.

[0081]

[0082] In the above formula, A each independently represents the structure (1), B each independently represents a structure containing an aromatic ring, and Y represents a direct bond or a divalent linking group.

[0083] The description of the aromatic ring in formula (1) can be applied to the aromatic ring included in B. For example, the divalent linking group is a divalent group obtained by removing one hydrogen atom from a group having one or more hydrogen atoms in the substituent X (excluding groups including polymerizable functional groups).

[0084] When the structure (1) is included in the charge transport polymer as a structural unit forming the skeleton structure of the molecular chain, there is a tendency to obtain a high charge transport improvement effect. From the above point of view, the structural unit (1) is preferably a structural unit represented by any one of the formulas (B1-1) to (B1-12), (L1-1) to (L1-5), and (T1-1) and (T1-2). In terms of the effect of obtaining a higher charge transport improvement, the structural unit (1) is more preferably a structural unit represented by any one of the formulas (B1-1), (B1-2), (L1-1) and (T1-1), more preferably a structural unit represented by any one of the formulas (B1-1), (L1-1) and (T1-1), and further preferably a structural unit represented by any one of the formulas (B1-1) and (L1-1). These units are also preferred units in terms of the tendency to easily synthesize the desired charge transport polymer.

[0085] Structure (1) may be included in the charge transporting polymer as a substituent that replaces the backbone structure of the molecular chain. When included as a substituent that replaces the backbone structure of the molecular chain, the structural unit (1) is, for example, a structural unit represented by any one of the formulas (L1-6) to (L1-8). As a specific example, there can be cited structural units that are the same as the structural units listed as specific examples in the description of the structural unit L2 described later, except that R' replaces R. R' represents a hydrogen atom or a substituent, and the substituent is preferably a substituent X or a group containing structure (1) independently of each other. Among them, in each structural unit, at least one of R' is a group containing structure (1).

[0086] (Structure of Charge Transporting Polymer)

[0087] The charge transporting polymer has a structural unit (1). The charge transporting polymer preferably also contains a structural unit having hole transport properties. The charge transporting polymer is a branched polymer having a branched structure in the molecule. The structural units constituting the charge transporting polymer include at least a trivalent or higher structural unit B and a monovalent structural unit T. The charge transporting polymer may also contain a divalent structural unit. The structural unit B is a structural unit constituting a branch portion. The structural unit T is a structural unit constituting the terminal portion of the molecular chain. The structural unit L is preferably a structural unit having charge transport properties.

[0088] The charge transporting polymer may contain only one type of each structural unit, or may contain a plurality of types of each structural unit. In the charge transporting polymer, each structural unit is bonded to each other at "one" to "three or more" bonding sites.

[0089] According to a preferred embodiment, the branch structure includes at least one structural unit B and three or more structural units L bonded to the one structural unit B. Preferably, the branch structure includes a multi-branch structure, wherein the multi-branch structure has one structural unit B and three or more structural units L bonded to the one structural unit B, and further, for each of the three or more structural units L, at least another structural unit B bonded to the structural unit L, and another two or more structural units L bonded to the another structural unit B.

[0090] The charge transporting polymer has at least one structural unit (1) as at least one selected from the group consisting of "structural unit B", "structural unit L" and "structural unit T". Preferred examples of the charge transporting polymer are listed below. In terms of the tendency to obtain a high charge transport improvement effect, the charge transporting polymer preferably satisfies at least one of (A), (B) and (D), and more preferably satisfies at least one of (B) and (D).

[0091] (A) a charge transporting polymer having at least a structural unit B and a structural unit T, wherein at least the structural unit B comprises the structural unit (1)

[0092] (B) a charge transporting polymer having structural units B, structural units L and structural units T, wherein at least structural unit B comprises structural unit (1)

[0093] (C) A charge transporting polymer having at least a structural unit B and a structural unit T, wherein at least the structural unit T comprises the structural unit (1)

[0094] (D) A charge transporting polymer having structural units B, structural units L and structural units T, wherein at least structural unit L comprises structural unit (1)

[0095] The charge transporting polymer having the structural unit (1) preferably also contains a structural unit having hole transporting properties. The structural unit having hole transporting properties is not particularly limited as long as it contains an atomic group having the ability to transport charge. The structural unit having hole transporting properties may be monovalent, divalent or trivalent or more. The structural unit having hole transporting properties is preferably hexavalent or less, more preferably tetravalent or less. For example, the charge transporting polymer contains at least one structural unit having hole transporting properties as at least one selected from the group consisting of "structural unit B", "structural unit L" and "structural unit T".

[0096] Preferred examples of charge transporting polymers containing structural units having hole transport properties are listed below. The following charge transporting polymers (a) to (d) also have structural unit (1). In terms of the tendency to obtain a high charge transport property improvement effect, the charge transporting polymer preferably satisfies at least one of (a) to (d).

[0097] (a) a charge transporting polymer having at least a structural unit B and a structural unit T, wherein at least the structural unit B includes a structural unit having a hole transporting property

[0098] (b) a charge transporting polymer having structural units B, structural units L and structural units T, wherein at least structural unit B includes a structural unit having hole transporting properties

[0099] (c) a charge transporting polymer having at least a structural unit B and a structural unit T, wherein at least the structural unit T includes a structural unit having a hole transporting property

[0100] (d) a charge transporting polymer having a structural unit B, a structural unit L and a structural unit T, wherein at least the structural unit L includes a structural unit having a hole transporting property

[0101] The charge transporting polymer containing the structural unit (1) and the structural unit having hole transport properties is preferably a charge transporting polymer that satisfies: at least one selected from the group consisting of (A) to (D) and at least one selected from the group consisting of (a) to (d). Specifically, it is preferably a charge transporting polymer that satisfies (B) and (d) or a charge transporting polymer that satisfies (D) and (b).

[0102] The structural unit having hole transport properties is preferably a structural unit containing at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure, and a phenoxazine structure. These structures may be substituted or unsubstituted. In terms of obtaining high hole injection properties, hole transport properties, etc., the structural unit having hole transport properties is more preferably a structural unit containing at least one structure selected from the group consisting of a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, and a pyrrole structure, and further preferably a structural unit containing at least one structure selected from the group consisting of a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, and a pyrrole structure, and particularly preferably a structural unit containing at least one structure selected from the group consisting of a substituted or unsubstituted aromatic amine structure and a substituted or unsubstituted carbazole structure. The aromatic amine structure is preferably a structure selected from the group consisting of a diarylamine structure and a triarylamine structure, more preferably a triarylamine structure, and further preferably a triphenylamine structure.

[0103] As examples of the structure contained in the charge transporting polymer, the following can be cited. In the structure, "B" represents the structural unit B, "L" represents the structural unit L, and "T" represents the structural unit T. In the following structure, multiple Bs may be structural units that are the same as each other, or structural units that are different from each other. The same is true for L and T. Furthermore, the charge transporting polymer is not limited to those having the following structure.

[0104]

[0105] (Structural unit B)

[0106] Structural unit B is a trivalent or higher structural unit constituting a branch portion when the charge transporting polymer has a branched structure. The charge transporting polymer may have only one structural unit B, or may have two or more structural units B. From the viewpoint of improving the durability of organic electronic components, structural unit B is preferably hexavalent or lower, more preferably trivalent or tetravalent. As examples of structural unit B, trivalent or higher structural units (1) (hereinafter, sometimes referred to as "structural unit B1") and structural units not containing structure (1) (hereinafter, sometimes referred to as "structural unit B2") can be cited.

[0107] The structural unit B2 is preferably a structural unit having charge transport properties, and more preferably a structural unit having hole transport properties. The structural unit B2 is not particularly limited, but for example, from the perspective of improving the durability of organic electronic devices, the structural unit B2 is selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, a condensed polycyclic aromatic hydrocarbon structure, and a structure containing one or more of these. The aromatic amine structure is preferably a structure selected from the group consisting of a diarylamine structure and a triarylamine structure, more preferably a triarylamine structure, and further preferably a triphenylamine structure.

[0108] Specific examples of the structural unit B2 include the following. The structural unit B2 is not limited to the following.

[0109]

[0110] W represents a trivalent linking group, for example, an arene triyl group or a heteroarene triyl group having 2 to 30 carbon atoms.

[0111] Ar each independently represents a divalent linking group, for example, each independently represents an arylene group or a heteroarylene group. Ar is preferably an arylene group or a heteroarylene group having 2 to 30 carbon atoms, more preferably an arylene group having 2 to 30 carbon atoms, and further preferably a phenylene group.

[0112] Y represents a direct bond or a divalent linking group, and examples thereof include a divalent group obtained by removing one hydrogen atom from a group having one or more hydrogen atoms in the substituent X described above (excluding groups containing a polymerizable functional group).

[0113] Z represents any one of a carbon atom, a silicon atom, or a phosphorus atom.

[0114] In the structural unit, W, the benzene ring and Ar may have a substituent, and examples of the substituent include the substituent X described above.

[0115] In this specification, an arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocyclic compound. An arene triyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. A heteroarene triyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocyclic compound. The description of the aromatic hydrocarbon and the aromatic heterocyclic compound in the aryl group and the heteroaryl group also applies to the aromatic hydrocarbon and the aromatic heterocyclic compound here.

[0116] (Structural unit L)

[0117] The structural unit L is a divalent structural unit. The charge transporting polymer may have only one structural unit L, or may have two or more structural units L. Examples of the structural unit L include a divalent structural unit (1) (hereinafter, sometimes referred to as "structural unit L1") and a structural unit not containing the structure (1) (hereinafter, sometimes referred to as "structural unit L2").

[0118] The structural unit L2 is preferably a structural unit with charge transport, and more preferably a structural unit with hole transport. The structural unit with charge transport is not particularly limited as long as it contains an atomic group with the ability to transport charge. For example, the structural unit L2 is selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a biphenyl structure, a terphenyl structure, a naphthalene structure, anthracene structure, a tetracene structure, a phenanthrene structure, a dihydrophenanthrene structure, a pyridine structure, a pyrazine structure, a quinoline structure, an isoquinoline structure, a quinoxaline structure, an acridine structure, a phenanthroline structure, a furan structure, a pyrrole structure, an oxazole structure, an oxadiazole structure, a thiazole structure, a thiadiazole structure, a triazole structure, a benzothiophene structure, a benzoxazole structure, a benzoxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, and one or more structures comprising these. The aromatic amine structure is preferably a structure selected from the group consisting of a diarylamine structure and a triarylamine structure, more preferably a triarylamine structure, and further preferably a triphenylamine structure. With respect to matters other than the valence number, the structural unit L2 may have the same structure as the structural unit B2, or may have a different structure from the structural unit B2.

[0119] In one embodiment, from the perspective of obtaining excellent hole transport properties, the structural unit L2 is preferably selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure, a phenoxazine structure, and one or more structures containing these, more preferably selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, and one or more structures containing these, further preferably selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a pyrrole structure, and one or more structures containing these, particularly preferably selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, and one or more structures containing these. In another embodiment, from the perspective of obtaining excellent electron transport properties, the structural unit L2 is preferably selected from a substituted or unsubstituted fluorene structure, a benzene structure, a phenanthrene structure, a pyridine structure, a quinoline structure, and one or more structures containing these.

[0120] Specific examples of the structural unit L2 include the following. The structural unit L2 is not limited to the following.

[0121]

[0122]

[0123] In the formula, R each independently represents a hydrogen atom or a substituent. Examples of substituents include the substituent X described above. R is preferably a hydrogen atom, an alkyl group, an aryl group, an aryl group substituted with an alkyl group, a halogen atom, an alkyl group substituted with a halogen, and the like.

[0124] Ar each independently represents a divalent linking group, for example, each independently represents an arylene group or a heteroarylene group. Ar is preferably an arylene group or a heteroarylene group having 2 to 30 carbon atoms, more preferably an arylene group having 2 to 30 carbon atoms, and further preferably a phenylene group.

[0125] (Structural unit T)

[0126] The structural unit T is a monovalent structural unit constituting the terminal portion of the charge transporting polymer. The charge transporting polymer may have only one structural unit T, or may have two or more structural units T. In the case where the charge transporting polymer has a polymerizable functional group at the terminal portion, the structural unit T has a group containing a polymerizable functional group. As examples of the structural unit T, a monovalent structural unit (1) (hereinafter, sometimes referred to as "structural unit T1") and a structural unit not containing structure (1) (hereinafter, sometimes referred to as "structural unit T2") can be cited.

[0127] The structural unit T2 is preferably a structural unit with charge transport properties, and more preferably a structural unit with hole transport properties. The structural unit T2 is not particularly limited, and is, for example, selected from a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure, and one or more structures containing these. From the perspective of imparting durability without reducing the transportability of the charge, the structural unit T2 is preferably a substituted or unsubstituted aromatic hydrocarbon structure, and more preferably a substituted or unsubstituted benzene structure. With respect to situations other than the valence number, the structural unit T2 may have the same structure as the structural unit L2, or it may have a different structure from the structural unit L2. With respect to situations other than the valence number, the structural unit T2 may have the same structure as the structural unit B2, or it may have a different structure from the structural unit B2.

[0128] Specific examples of the structural unit T2 include the following. The structural unit T2 is not limited to the following.

[0129]

[0130] In the formula, R each independently represents a hydrogen atom or a substituent. As examples of substituents, the substituent X described above can be cited. R is preferably a hydrogen atom, an alkyl group, an alkyl group substituted with a halogen, a group containing a polymerizable functional group, etc. In the case where the charge transporting polymer has a polymerizable functional group at the terminal portion, the structural unit T is preferably a structural unit comprising at least one of the R in the formula being a group containing a polymerizable functional group. In order to improve the solubility of the charge transporting polymer in the solvent and the charge transport property of the organic layer, the structural unit T is preferably a structural unit comprising at least one of the R in the formula being an alkyl group or a fluoroalkyl group. The alkyl group is preferably a straight-chain alkyl group, more preferably a straight-chain alkyl group having a carbon number of less than 20, and further preferably a straight-chain alkyl group having a carbon number of 6 to 12. The fluoroalkyl group is preferably a perfluoroalkyl group, more preferably a perfluoromethyl group or a perfluoroethyl group, and further preferably a perfluoromethyl group.

[0131] (Polymerizable functional group)

[0132] In one embodiment, from the viewpoint of curing by polymerization reaction and changing the solubility in the solvent, the charge transporting polymer preferably has at least one polymerizable functional group. The so-called "polymerizable functional group" refers to a functional group that can form a bond with each other by applying heat, light, etc. The polymerizable functional group may be contained in the structural unit (1) or in a structural unit other than the structural unit (1).

[0133] Examples of the polymerizable functional group include a substituted or unsubstituted group having a carbon-carbon multiple bond (e.g., a vinyl group, a styryl group, an allyl group, a butenyl group, an ethynyl group, an acryloyl group, an acryloyloxy group, an acryloylamino group, a methacryloyl group, a methacryloyloxy group, a methacryloylamino group, a vinyloxy group, a vinylamino group, etc.), a group having a small ring member (e.g., a cyclic alkyl group such as a cyclopropyl group, a benzocyclobutenyl group, a cyclobutyl group, etc.; a group having a cyclic ether structure such as an epoxy group (oxiranyl group), an oxetane group (oxetanyl group), etc.; a diketene group; an epithio group; a lactone group; a lactam group, etc.), a heterocyclic group (e.g., a furan-yl group, a pyrrol-yl group, a thien-yl group, a silol-yl group), etc.

[0134] When these groups are substituted, the substituent is not particularly limited, and examples thereof include linear, cyclic or branched alkyl groups. The alkyl group preferably has 1 to 22 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0135] The polymerizable functional group is preferably a substituted or unsubstituted group having a cyclic ether structure or a group having a carbon-carbon multiple bond, more preferably a substituted or unsubstituted vinyl group, a styryl group, an acryloyl group, a methacryloyl group, an epoxy group, or an oxetanyl group, and from the viewpoint of reactivity and the characteristics of the organic electronic device, a substituted or unsubstituted vinyl group, an oxetanyl group, and an epoxy group are further preferred.

[0136] From the perspective of increasing the degree of freedom of the polymerizable functional group and facilitating polymerization reaction, the backbone structure of the charge transporting polymer and the polymerizable functional group can be bonded via a linking group such as an alkylene chain (e.g., a linear alkylene chain having 1 to 8 carbon atoms). In the case of containing an alkylene chain, the solubility of the charge transporting polymer in the solvent also tends to increase. In addition, for example, in the case of forming an organic layer on an electrode, from the perspective of increasing the affinity with a hydrophilic electrode such as indium tin oxide (ITO), it can be bonded via a hydrophilic link such as an ethylene glycol chain or a diethylene glycol chain. Furthermore, from the perspective of facilitating the preparation of the monomer used to introduce the polymerizable functional group, there may also be a linking group comprising one or more selected from an ether bond, an ester bond, etc. between the backbone structure and the polymerizable functional group.

[0137] On the other hand, when no linking group such as an alkylene chain, an ethylene glycol chain, or a diethylene glycol chain is contained, the heat resistance of the organic layer tends to be improved.

[0138] Examples of the “group containing a polymerizable functional group” described above include the “polymerizable functional group” itself and “a group obtained by combining a polymerizable functional group and a linking group such as an alkylene chain or an ether bond”. As the group containing a polymerizable functional group, for example, the groups exemplified in International Publication No. 2010 / 140553 can be suitably used.

[0139] The polymerizable functional group can be introduced into the terminal portion (i.e., structural unit T) of the charge transporting polymer, or into the portion other than the terminal portion (i.e., structural unit B or structural unit L), or into both the terminal portion and the portion other than the terminal portion. From the perspective of hardenability, it is preferably introduced into at least the terminal portion, and from the perspective of achieving both hardenability and charge transportability, it is preferably introduced only into the terminal portion. In addition, the polymerizable functional group can be introduced into the main chain of the charge transporting polymer, or into the side chain, or into both the main chain and the side chain.

[0140] From the viewpoint of helping to change the solubility, the polymerizable functional group is preferably contained in a large amount in the charge transporting polymer. On the other hand, from the viewpoint of not hindering the charge transporting property, it is preferably contained in a small amount in the charge transporting polymer. The content of the polymerizable functional group can be appropriately set in consideration of these.

[0141] For example, from the viewpoint of being able to sufficiently change the solubility and facilitating multilayering, the number of polymerizable functional groups per molecule of the charge transporting polymer is preferably two or more, more preferably three or more. In addition, from the viewpoint of ensuring charge transportability, the number of polymerizable functional groups is preferably 1,000 or less, more preferably 500 or less, and further preferably 300 or less.

[0142] The number of polymerizable functional groups per molecule of the charge transporting polymer can be calculated as an average value using the amount of polymerizable functional groups added (e.g., the amount of monomers having polymerizable functional groups added) used to synthesize the charge transporting polymer, the amount of monomers added corresponding to each structural unit, the weight average molecular weight of the charge transporting polymer, and the like. 1 The ratio of the integrated value of the signal derived from the polymerizable functional group in the H nuclear magnetic resonance (NMR) spectrum to the integrated value of all spectra, the weight average molecular weight of the charge transporting polymer, and the like were calculated as average values.

[0143] (Number average molecular weight)

[0144] The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in the solvent, film-forming properties, etc. From the viewpoint of excellent charge transport, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, further preferably 2,000 or more, and particularly preferably 5,000 or more. In addition, from the viewpoint of maintaining good solubility in the solvent and facilitating the preparation of the liquid composition, 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 particularly preferably 30,000 or less.

[0145] (Weight average molecular weight)

[0146] The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in the solvent, film-forming properties, etc. From the viewpoint of excellent charge transport, the weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and further preferably 10,000 or more. In addition, from the viewpoint of maintaining good solubility in the solvent and facilitating the preparation of the liquid composition, 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 particularly preferably 100,000 or less.

[0147] The number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. Examples of the measurement conditions include those described in Examples.

[0148] (Ratio of structural units)

[0149] From the viewpoint of improving solubility and improving charge transportability, based on all structural units, the proportion of structural units (1) contained in the charge transport polymer is preferably 5 mol% or more, more preferably 7 mol% or more, and more preferably 10 mol% or more. The upper limit is not particularly limited and is 100 mol% or less. For example, in the case where the charge transport polymer also contains a structural unit having hole transportability, the proportion of structural units (1) is preferably 50 mol% or less, more preferably 30 mol% or less, and more preferably 20 mol% or less.

[0150] When the charge transport polymer contains a structural unit having hole transport properties, from the viewpoint of improving the hole transport properties of the organic layer, the proportion of the structural unit having hole transport properties is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more, based on all the structural units. The upper limit is less than 100 mol%.

[0151] From the viewpoint of improving the durability of organic electronic components, the proportion of structural unit B contained in the charge transporting polymer is preferably 1 mol% or more, more preferably 5 mol% or more, and more preferably 10 mol% or more, based on all structural units. In addition, from the viewpoint of suppressing the increase in viscosity, performing the synthesis of the charge transporting polymer well, or obtaining sufficient charge transportability, the proportion of structural unit B is preferably 50 mol% or less, more preferably 40 mol% or less, and more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

[0152] When the charge transport polymer contains a structural unit L, from the perspective of obtaining sufficient charge transport, the proportion of the structural unit L is preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more, based on all the structural units. In addition, considering the structural unit T and the structural unit B, the proportion of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and further preferably 85 mol% or less.

[0153] From the viewpoint of improving the characteristics of organic electronic components or suppressing the increase in viscosity and performing the synthesis of charge transport polymers well, the proportion of structural units T contained in the charge transport polymer is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 15 mol% or more, based on all structural units. In addition, from the viewpoint of obtaining sufficient charge transportability, the proportion of structural units T is preferably 60 mol% or less, more preferably 55 mol% or less, and more preferably 50 mol% or less.

[0154] In the case where the charge transport polymer has a polymerizable functional group, with respect to the viewpoint that the charge transport polymer is hardened efficiently, based on all structural units, the ratio of the polymerizable functional group is preferably 0.1 mol% or more, more preferably 1 mol% or more, and more preferably 3 mol% or more. In addition, with respect to the viewpoint of obtaining good charge transportability, the ratio of the polymerizable functional group is preferably 70 mol% or less, more preferably 60 mol% or less, and more preferably 50 mol% or less. Furthermore, the so-called "ratio of polymerizable functional groups" herein refers to the ratio of structural units having polymerizable functional groups.

[0155] In consideration of the balance among charge transport properties, durability, productivity, etc., the charge transport polymer preferably contains structural unit L, structural unit T, and structural unit B. The ratio (molar ratio) of structural unit L, structural unit T, and structural unit B is preferably L:T:B=100:10 to 400:10 to 300, more preferably 100:20 to 300:5 to 200, and even more preferably 100:40 to 200:10 to 100.

[0156] The ratio of the structural units can be determined by using the amount of monomers added to synthesize the charge transporting polymer corresponding to each structural unit. 1 The integrated value of the spectrum derived from each structural unit in the H NMR spectrum is calculated as an average value. For simplicity, when the amount of addition is clear, it is preferable to adopt the value obtained using the amount of addition.

[0157] Preferred examples of the charge transporting polymer are listed below. The charge transporting polymer preferably satisfies the following (1) or (2).

[0158] (1) A charge transporting polymer having at least structural unit B1, structural unit L2 and structural unit T2

[0159] (2) A charge transporting polymer having at least a structural unit B2, a structural unit L1 and a structural unit T2

[0160] (3) A charge transporting polymer having at least a structural unit B2, a structural unit L2 and a structural unit T1

[0161] In (1) to (3), the structural unit L2 and the structural unit B2 are preferably structural units independently having hole transport properties, and more preferably structural units containing at least one structure selected from the group consisting of a substituted or unsubstituted aromatic amine structure and a substituted or unsubstituted carbazole structure.

[0162] In (1) to (3), the structural unit T2 is preferably a structural unit containing a substituted or unsubstituted aromatic hydrocarbon structure, and more preferably a structural unit containing a substituted or unsubstituted benzene structure.

[0163] The degree of polymerization (number of units of the structural unit) of the charge transporting polymer is 2 or more, and from the viewpoint of stabilizing the film quality of the organic layer, it is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more. In addition, from the viewpoint of solubility in a solvent, the degree of polymerization is preferably 1,000 or less, more preferably 700 or less, and further preferably 500 or less.

[0164] The degree of polymerization can be determined as an average value using the weight average molecular weight of the charge transporting polymer, the molecular weight of the structural unit, and the ratio of the structural unit.

[0165] (Manufacturing method)

[0166] Charge transport polymers can be manufactured by various synthesis methods and are not particularly limited. For example, they can be manufactured by using monomers to form structural units possessed by charge transport polymers for polymerization reaction. The charge transport polymer is preferably a copolymer of the following monomer mixture, wherein the monomer mixture at least contains a monomer having structural unit (1) and a monomer containing a structural unit having hole transport properties. As examples of monomer mixtures, there can be cited: a monomer mixture containing a monomer having structural unit B1, a monomer having structural unit L2, and a monomer having structural unit T2; a monomer mixture containing a monomer having structural unit B2, a monomer having structural unit L1, and a monomer having structural unit T2, etc. The monomer mixture may also arbitrarily contain one or more monomers other than those described above.

[0167] From the viewpoint of improving the characteristics of organic electronic components, based on all monomers in the monomer mixture, the proportion of monomers having structural unit (1) in the monomer mixture is preferably 5 mol% or more, more preferably 7 mol% or more, and further preferably 10 mol% or more. The upper limit is not particularly limited and is 100 mol% or less. For example, when the monomer mixture also contains any one of a monomer having structural unit B2, a monomer having structural unit L2, and a monomer having structural unit T2, the proportion of structural unit (1) is preferably 50 mol% or less, more preferably 30 mol% or less, and further preferably 20 mol% or less.

[0168] When the monomer mixture contains the following monomers, that is, a monomer containing a structural unit having a hole transport property, from the viewpoint of improving the hole transport property of the organic layer, the ratio of the monomer containing the structural unit having a hole transport property is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more, based on all the monomers in the monomer mixture. The upper limit is not particularly limited and is less than 100 mol%.

[0169] When a monomer mixture is used, the charge transporting polymer can be easily produced by copolymerizing the monomers. The copolymerization form may be an alternating, random, block or graft copolymer, or a copolymer having an intermediate structure thereof, such as a random copolymer having block properties.

[0170] The polymerization reaction is preferably a coupling reaction. As a coupling reaction, for example, known reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Stille coupling, and Buchwald-Hartwig coupling can be used. Suzuki coupling causes a cross-coupling reaction using a Pd catalyst between an aromatic boronic acid compound and an aromatic halide. According to Suzuki coupling, a charge transporting polymer can be easily produced by bonding desired aromatic rings to each other.

[0171] In the coupling reaction, as a catalyst, for example, a Pd(0) compound, a Pd(II) compound, a Ni compound, etc. are used. In addition, a catalyst type produced by mixing tris(dibenzylideneacetone)dipalladium(0), palladium(II) acetate, etc. as a precursor with a phosphine ligand can also be used. For the synthesis method of the charge transporting polymer, for example, reference can be made to the description of International Publication No. 2010 / 140553.

[0172] Examples of monomers that can be used in the Suzuki coupling reaction include the following.

[0173] (Monomer B)

[0174]

[0175] (Monomer L)

[0176] R 2 -LR 2

[0177] (Monomer T)

[0178] TR 3

[0179] In the formula, B represents a trivalent or tetravalent structural unit, L represents a divalent structural unit, and T represents a monovalent structural unit. 1 ~R 3 represents a functional group capable of forming a bond with each other, for example, each independently represents any one selected from the group consisting of a boronic acid group, a borate ester group and a halogen group. The monomer used contains the structural unit (1) as at least any one of "B", "L" and "T".

[0180] These monomers can be synthesized by a known method and can be obtained from, for example, Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Associates, and the like.

[0181] [Dopant]

[0182] The organic electronic material may contain any additive, for example, it may also contain a dopant. The dopant is not particularly limited as long as it is a compound that shows a doping effect by adding to the organic electronic material and can improve the transportability of the charge. There are p-type doping and n-type doping. In p-type doping, the dopant uses a substance that acts as an electron acceptor, and in n-type doping, the dopant uses a substance that acts as an electron donor. In order to improve the hole transportability, it is preferably p-type doping, and in order to improve the electron transportability, it is preferably n-type doping. The dopant used in the organic electronic material may be a dopant that shows any effect of p-type doping or n-type doping. In addition, a dopant may be added alone, or a plurality of dopants may be added in a mixture.

[0183] The dopant used for p-type doping is an electron-accepting compound, and examples thereof include Lewis acids, protonic acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Specifically, as Lewis acids, FeCl3, PF5, AsF5, SbF5, BF5, BCl3, BBr3, etc. can be listed; as protonic acids, inorganic acids such as HF, HCl, HBr, HNO3, H2SO4, HClO4, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfonic acid, vinylphenylsulfonic acid, camphorsulfonic acid, etc. can be listed; as transition metal compounds, FeOCl, TiCl4, ZrCl4, HfCl4, NbF5, AlCl3, NbCl5, TaCl5, MoF5 can be listed; as ionic compounds, tetrakis(pentafluorophenyl)borate ion, tris(trifluoromethanesulfonyl)methide ion, bis(trifluoromethanesulfonyl)imide ion, hexafluoroantimonate ion, AsF6 can be listed. - (hexafluoroarsenate ion), BF4 - (tetrafluoroborate ion), PF6 - As halogen compounds, there can be cited Cl2, Br2, I2, ICl, ICl3, IBr, IF, etc.; as π-conjugated compounds, there can be cited TCNE (tetracyanoethylene) (tetracyanoethylene), TCNQ (tetracyanoquinodimethane) (tetracyanoquinodimethane), etc. Known electron-accepting compounds other than those mentioned above can also be used. Lewis acids, ionic compounds, π-conjugated compounds, etc. are preferred.

[0184] The dopant used in n-type doping is an electron-donating compound, for example, alkali metals such as Li and Cs; alkaline earth metals such as Mg and Ca; salts of alkali metals and / or alkaline earth metals such as LiF and Cs2CO3; metal complexes; electron-donating organic compounds, etc.

[0185] When the charge transporting polymer has a polymerizable functional group, it is preferred to use a compound that can function as a polymerization initiator for the polymerizable functional group as a dopant in order to easily change the solubility of the organic layer.

[0186] [Other optional ingredients]

[0187] The organic electronic material may further contain a charge transporting low molecular weight compound, other polymers, and the like.

[0188] [content]

[0189] From the viewpoint of obtaining good charge transportability, the content of the charge transporting polymer in the organic electronic material is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more, relative to the total mass of the organic electronic material. The upper limit of the content of the charge transporting polymer is not particularly limited, and can also be set to 100% by mass. It is also possible to consider including additives such as dopants, and the content of the charge transporting polymer is set to, for example, 95% by mass or less or 90% by mass or less.

[0190] In the case of containing a dopant, from the viewpoint of improving the charge transport property of the organic electronic material, the content of the dopant is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more, relative to the total mass of the organic electronic material. In addition, from the viewpoint of maintaining good film-forming properties, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, relative to the total mass of the organic electronic material.

[0191] <Liquid composition>

[0192] The liquid composition as an embodiment of the present invention contains the organic electronic material and a solvent. The liquid composition containing the solvent can be used to easily form an organic layer by a simple method such as a coating method. The liquid composition can be used as an ink composition.

[0193] [solvent]

[0194] As the solvent, any solvent such as water, an organic solvent, or a mixed solvent thereof can be used. Examples of the organic solvent include: alcohols such as methanol, ethanol, and isopropanol; alkanes such as pentane, hexane, and octane; cycloalkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, and diphenylmethane; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, Aromatic ethers such as 4-methoxytoluene, 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; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, and dichloromethane. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers, and more preferred are aromatic hydrocarbons.

[0195] [Polymerization initiator]

[0196] In the case where the charge transport polymer has a polymerizable functional group, the liquid composition preferably contains a polymerization initiator. As a polymerization initiator, known free radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, etc. can be used. From the perspective of being able to easily prepare a liquid composition, it is preferred to use a substance that has both the function of a dopant and the function of a polymerization initiator. As such a substance, for example, the ionic compound can be cited.

[0197] [additive]

[0198] The liquid composition may further contain additives as optional components. Examples of the additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reduction inhibitors, oxidants, reducing agents, surface modifiers, emulsifiers, defoamers, dispersants, surfactants, and the like.

[0199] [content]

[0200] The content of the solvent in the liquid composition can be determined by considering the application in various coating methods. For example, the content of the solvent is preferably an amount in which the ratio of the charge transporting polymer to the solvent is 0.1% by mass or more, more preferably an amount in which the ratio of the charge transporting polymer to the solvent is 0.2% by mass or more, and further preferably an amount in which the ratio of the charge transporting polymer to the solvent is 20% by mass or less, more preferably an amount in which the ratio of the charge transporting polymer to the solvent is 15% by mass or less, and further preferably an amount in which the ratio of the charge transporting polymer to the solvent is 10% by mass or less.

[0201] <Organic layer>

[0202] The organic layer as an embodiment of the present invention is a layer formed using the organic electronic material or liquid composition. The organic layer shows good charge transport properties. By using a liquid composition, an organic layer can be formed well and simply by a coating method. As a coating method, for example, spin coating; casting method; dipping method; plate printing methods such as relief printing, gravure printing, offset printing, lithography, relief reverse offset printing, screen printing, gravure printing; known methods such as inkjet printing and other plateless printing methods. In the case of forming an organic layer by a coating method, the coating layer obtained after coating can be dried by heat treatment to remove the solvent.

[0203] In the case where the charge transporting polymer has a polymerizable functional group, the polymerization reaction of the charge transporting polymer can be carried out by light irradiation, heat treatment, etc. to change the solubility of the coating layer. For simplicity, heat treatment is preferred. By stacking the organic layers obtained by changing the solubility of the coating layer, it is possible to easily realize the multilayering of the organic electronic element.

[0204] The heat treatment can be carried out in an atmospheric environment or in an inert gas environment. Examples of inert gases include helium, argon, nitrogen, and mixed gases thereof. The "inert gas environment" is preferably an environment in which the concentration of the inert gas is 99.5% or more by volume, more preferably 99.9% or more, and even more preferably 99.99% or more.

[0205] The heat treatment can be performed using a heater such as a hot plate or an oven. To perform the heat treatment in an inert gas atmosphere, for example, a hot plate is used in an inert gas atmosphere, or the interior of an oven is set in an inert gas atmosphere.

[0206] From the viewpoint of efficiently removing the solvent, the heat treatment is preferably carried out at a temperature above the boiling point of the solvent. In addition, when the polymerization reaction of the charge transporting polymer is carried out, it is preferably a temperature at which the polymerization reaction is carried out efficiently. In one embodiment, the temperature of the heat treatment is preferably 140°C or more, more preferably 180°C or more, and further preferably 190°C or more. On the other hand, from the viewpoint of suppressing the deterioration caused by the heat treatment, it is preferably 300°C or less, more preferably 280°C or less, and further preferably 250°C or less.

[0207] From the viewpoint of improving the efficiency of charge transfer, the thickness of the organic layer after drying or curing is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more. In addition, 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 further preferably 100 nm or less.

[0208] <Organic electronic components>

[0209] The organic electronic element as an embodiment of the present invention has at least one organic layer. As the organic electronic element, for example, an organic EL element, an organic photoelectric conversion element, an organic transistor, etc. can be cited. The organic electronic element preferably has a structure in which an organic layer is arranged between at least one pair of electrodes. The organic electronic element can be manufactured by the following manufacturing method, which includes using the organic electronic material or the liquid composition to form an organic layer.

[0210] <Organic EL devices>

[0211] The organic EL element as an embodiment of the present invention has at least one organic layer. The organic EL element generally includes a light-emitting layer, an anode, a cathode and a substrate, and optionally includes other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. Each layer can be formed by a vapor deposition method or by a coating method. The organic EL element preferably has the organic layer as a light-emitting layer or other functional layer, more preferably has the organic layer as another functional layer, and further preferably has the organic layer as at least one of a hole injection layer and a hole transport layer.

[0212] Figure 1 It is a schematic cross-sectional view showing one embodiment of an organic EL element. Figure 1 The organic EL element is a multi-layered element, which 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 in sequence.

[0213] [Luminous layer]

[0214] As the material used in the light-emitting layer, light-emitting materials such as low molecular weight compounds, polymers, and dendrimers can be used. Polymers have high solubility in solvents and are suitable for coating methods, so they are preferred. As light-emitting materials, fluorescent materials, phosphorescent materials, thermally activated delayed fluorescence materials (TADF), etc. can be listed.

[0215] Examples of fluorescent materials include low molecular weight compounds such as perylene, coumarin, rubrene, quinacridone, stilbene, dye laser pigments, aluminum complexes, and derivatives thereof; polymers such as polyfluorene, polyphenylene, polyphenylene vinylene, polyvinyl carbazole, fluorene-benzothiadiazole copolymers, fluorene-triphenylamine copolymers, and derivatives thereof; and mixtures thereof.

[0216] As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. Examples of the Ir complex include FIr(pic) (iridium(III)bis[(4,6-difluorophenyl)-pyridine-N,C 2 ] picolinic acid), green-emitting Ir(ppy)3(face-tri(2-phenylpyridine)iridium), red-emitting (btp)2Ir(acac)(bis[2-(2'-benzo[4,5-α]thienyl)pyridine-N,C 3〕iridium (acetylacetonate)), Ir(piq)3 (tris(1-phenylisoquinoline)iridium), etc. Examples of Pt complexes include PtOEP (2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum) which emits red light.

[0217] In the case where the light-emitting layer includes a phosphorescent material, it is preferred that it also includes a host material in addition to the phosphorescent material. As the host material, a low molecular weight compound, a polymer, or a dendritic polymer can be used. As a low molecular weight compound, for example, CBP (4,4'-bis (9H-carbazole-9-yl) biphenyl), mCP (1,3-bis (9-carbazole) benzene), CDBP (4,4'-bis (carbazole-9-yl) -2,2'- dimethylbiphenyl), derivatives thereof, etc., as a polymer, the organic electronic material, polyvinyl carbazole, polyphenylene, polyfluorene, derivatives thereof, etc. can be listed.

[0218] Examples of the thermally activated delayed fluorescent material include PIC-TRZ (2-biphenyl-4,6-bis(12-phenylindolo[2,3-a]carbazol-11-yl)-1,3,5-triazine), Spiro-CN (2',7'-bis(di-p-tolylamino)-9,9'-spirobifluorene-s,7-dicarbonitrile), CC2TA (2,4-bis{3-(9H-carbazole-9-yl)-9H-carbazole-9-yl}-6-phenyl-1,3,5 -triazine)(2,4-bis{3-(9H-carbazol-9-yl)-9H-carbazol-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))(9,9'-(4,4'-sulfonylbis(4,1-phenylene))bis(3,6-di-tert-butyl-9H-carbazole)), 4CzPN(3,4,5,6-tetra(9H-carbazol-9-yl)phthalonitrile), HAP-3TPA(4,4',4"-(1,3,3a 1,4,6,7,9-heptaazaphen-2,5,8-triyl)tris(N,N-bis(4-(tert-butyl)phenyl)aniline))(4,4',4"-(1,3,3a 1 ,4,6,7,9-heptaazaphenalene-2,5,8-triyl)tris(N,N-bis(4-(tert-butyl)phenyl)aniline)), 4CzIPN(1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) and other compounds.

[0219] [Hole injection layer, hole transport layer]

[0220] It is preferred that the organic layer be used as at least one of a hole injection layer and a hole transport layer. As described above, these layers can be easily formed by using a liquid composition containing an organic electronic material and a solvent.

[0221] When the organic EL element has the organic layer as a hole injection layer and also has a hole transport layer, a known material can be used for the hole transport layer. In addition, when the organic EL element has the organic layer as a hole transport layer and also has a hole injection layer, a known material can be used for the hole injection layer. The hole injection layer and the hole transport layer may both be the organic layer. As known materials, for example, aromatic amine compounds (for example, aromatic diamines such as N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (α-NPD)), phthalocyanine compounds, thiophene compounds (for example, thiophene conductive polymers such as poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene): Poly(sodium4-Styrenesulfonate), PEDOT: PSS)) and the like can be cited.

[0222] When the hole transport layer is an organic layer with changed solubility, a light emitting layer can be easily formed thereon by a wet process. In this case, the polymerization initiator may be contained in the organic layer serving as the hole transport layer or in an organic layer located below the hole transport layer.

[0223] [Electron transport layer, electron injection layer]

[0224] As materials used in the electron transport layer and the electron injection layer, for example, phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, dioxythiopyran derivatives, fused rings such as naphthalene and perylene, tetracarboxylic anhydride, carbodiimide, fluorenyl methane derivatives, anthraquinone dimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes, etc. In addition, the organic electronic materials described above can also be used.

[0225] [cathode]

[0226] As the cathode material, for example, a metal or a metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, or CsF can be used.

[0227] [anode]

[0228] As the anode material, for example, metal (such as Au) or other conductive materials can be used. Examples of other materials include oxides (such as ITO: indium oxide / tin oxide) and conductive polymers (such as polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[0229] [Substrate]

[0230] As the substrate, glass, plastic, etc. can be used. The substrate is preferably transparent and preferably flexible. Quartz glass, resin film, etc. can be preferably used.

[0231] The resin film is preferably a light-transmitting resin film. Examples of the resin film include films having polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, and the like as main components.

[0232] When a resin film is used, in order to suppress the permeation of water vapor, oxygen, etc., the resin film may be coated with an inorganic substance such as silicon oxide or silicon nitride before use.

[0233] [seal]

[0234] In order to reduce the influence of external gas and prolong the life, the organic EL element can be sealed. As the material used in the sealing, plastic films such as glass, epoxy resin, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, or inorganic substances such as silicon oxide and silicon nitride can be used, but it is not limited to these. The sealing method is also not particularly limited, and can be carried out using a known method.

[0235] [Emitting color]

[0236] The color of light emitted by the organic EL element is not particularly limited. White organic EL elements are preferably used in various lighting devices such as home lighting, interior lighting for cars, clocks, and backlights for liquid crystals.

[0237] As a method for forming a white organic EL element, a method of mixing colors by using multiple luminescent materials to emit multiple luminescent colors simultaneously can be used. The combination of multiple luminescent colors is not particularly limited, and examples thereof include: a combination containing three maximum luminescent wavelengths of blue, green, and red; a combination containing two maximum luminescent wavelengths of blue and yellow, yellow-green and orange, etc. The luminescent color can be controlled by adjusting the type and amount of the luminescent material.

[0238] <Display element, lighting device, display device>

[0239] The display element as an embodiment of the present invention includes the organic EL element. For example, by using the organic EL element as an element corresponding to each pixel of red, green and blue (RGB), a color display element can be obtained. The image forming method includes: a simple matrix type, which directly drives each organic EL element arranged on a flat panel using electrodes arranged in a matrix; and an active matrix type, which drives each element by configuring a thin film transistor.

[0240] In addition, a lighting device as an embodiment of the present invention includes the organic EL element. Furthermore, a display device as an embodiment of the present invention includes a lighting device and a liquid crystal element as a display component. For example, the display device can be a display device using the lighting device as a backlight and a well-known liquid crystal element as a display component, that is, a liquid crystal display device.

[0241] <Example of implementation>

[0242] The following are examples of preferred embodiments of the present invention. The embodiments of the present invention are not limited to the following examples.

[0243] [1] An organic electronic material comprising a charge transporting polymer having a branched structure and having a structural unit including a structure represented by the following formula (1).

[0244]

[0245] (wherein, Ar each independently represents an aromatic ring group, Ra each independently represents a hydrogen atom, a substituent, or a bonding site with another structure, Rb each independently represents a substituent, and n each independently represents an integer greater than 0. At least one of Ra is a bonding site with another structure)

[0246] [2] The organic electronic material according to [1], wherein the structure represented by the formula (1) includes at least one selected from the group consisting of the structure represented by the following formula (1B-1) and the structure represented by the following formula (1L-1).

[0247]

[0248] (wherein, * represents a bonding site with other structures, Rc each independently represents a hydrogen atom or a substituent, Rb each independently represents a substituent, and n each independently represents an integer of 0 to 4)

[0249] [3] An organic electronic material according to [1] or [2], wherein the charge transporting polymer further comprises a structural unit comprising at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure and a phenoxazine structure.

[0250] [4] The organic electronic material according to any one of [1] to [3], wherein the charge transporting polymer has at least one polymerizable functional group.

[0251] [5] The organic electronic material according to [4], further comprising a polymerization initiator.

[0252] [6] The organic electronic material according to any one of [1] to [5], wherein the charge transporting polymer is a hole transporting polymer.

[0253] [7] A liquid composition comprising: the organic electronic material according to any one of [1] to [6] above; and a solvent.

[0254] [8] An organic layer formed using the organic electronic material according to any one of [1] to [6] above or the liquid composition according to [7] above.

[0255] [9] An organic electronic device comprising the organic layer according to [8].

[0256]

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

[0257]

[11] An organic electroluminescent element comprising the organic layer according to [8] as a hole injection layer or a hole transport layer.

[0258]

[12] A display element comprising the organic electroluminescent element according to

[10] or

[11] .

[0259]

[13] A lighting device comprising the organic electroluminescent element according to

[10] or

[11] .

[0260]

[14] A display device comprising: the lighting device according to

[13] ; and a liquid crystal element as a display component.

[0261]

[15] A method for producing an organic electronic device, comprising: forming an organic layer using the organic electronic material according to any one of [1] to [6] or the liquid composition according to [7].

[0262] [Example]

[0263] The present invention will be described in more detail below by way of examples. However, the present invention is not limited to the following examples.

[0264] <Preparation of Charge Transporting Polymer>

[0265] [Preparation of Pd Catalyst]

[0266] In a glove box under a nitrogen environment, weigh tri(dibenzylideneacetone)dipalladium (73.2 mg, 80 μmol) into a sample tube at room temperature, add toluene (15 mL), and stir for 30 minutes. Similarly, weigh tri(tert-butyl)phosphine (129.6 mg, 640 μmol) into a sample tube, add toluene (5 mL), and stir for 5 minutes. Mix these solutions and stir at room temperature for 30 minutes to obtain a catalyst solution (hereinafter referred to as "Pd catalyst solution"). In the preparation of the Pd catalyst, all solvents are used after being degassed by nitrogen bubbling for more than 30 minutes.

[0267] [Preparation of Charge Transporting Polymer]

[0268] Charge-transporting polymers 1 to 14 were prepared as follows.

[0269] (Charge Transporting Polymer 1)

[0270] Monomer A1 (4.0 mmol), monomer B1 (1.0 mmol), monomer C1 (4.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (15 mL) were added to a three-necked round-bottom flask, and then the Pd catalyst solution (1.0 mL) was added for mixing. The resulting mixed solution was heated to reflux for 2 hours. All operations so far were performed under a nitrogen gas stream. In addition, all solvents were used after being degassed by nitrogen bubbling for more than 30 minutes.

[0271]

[0272] After the reaction is completed, the organic layer is washed with water and injected into methanol-water (9:1). The generated precipitate is recovered by suction filtration and washed with methanol-water (9:1). The obtained precipitate is dissolved in toluene and reprecipitated from methanol. The obtained precipitate is recovered by suction filtration and dissolved in toluene, and a metal adsorbent ("Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer" manufactured by Strem Chemicals, 200 mg relative to 100 mg of precipitate) is added, and stirred at 80°C for 2 hours. After the stirring is completed, the metal adsorbent and insoluble matter are removed by filtration, and then reprecipitated from methanol. The generated precipitate is recovered by suction filtration and washed with methanol. The obtained precipitate is vacuum dried to obtain a charge transporting polymer 1. The number average molecular weight of the charge transporting polymer 1 was 9,200, and the weight average molecular weight was 38,200.

[0273] The number average molecular weight and the weight average molecular weight were measured by GPC (polystyrene conversion) using tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.

[0274] Equipment: High Performance Liquid Chromatography Prominence Shimadzu Corporation

[0275] Liquid delivery pump (LC-20AD)

[0276] Degassing unit (DGU-20A)

[0277] Automatic Sampler (SIL-20AHT)

[0278] Column oven (CTO-20A)

[0279] Photodiode array (PDA) detector (SPD-M20A)

[0280] Differential Refractive Index Detector (RID-20A)

[0281] Column: Gelpack (registered trademark)

[0282] GL-A160S (Manufacturer No.: 686-1J27)

[0283] GL-A150S (Manufacturer No.: 685-1J27) Hitachi Chemical Co., Ltd.

[0284] Eluent: Tetrahydrofuran (THF) (for HPLC, containing stabilizer) Fujifilm Wako Pure Chemical Industries, Ltd.

[0285] Flow rate: 1mL / min

[0286] Column temperature: 40℃

[0287] Detection wavelength: 254nm

[0288] Molecular weight standard material: PStQuick A / B / C Tosoh Corporation

[0289] (Charge Transporting Polymer 2)

[0290] Monomer A2 (4.0 mmol), monomer B1 (1.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (17 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transporting polymer 1 was performed to obtain charge transporting polymer 2. The number average molecular weight of charge transporting polymer 2 was 12,100, and the weight average molecular weight was 49,000.

[0291]

[0292] (Charge Transporting Polymer 3)

[0293] Monomer A2 (4.0 mmol), monomer B1 (1.0 mmol), monomer C1 (2.0 mmol), monomer C3 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (17 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 3. The number average molecular weight of charge transport polymer 3 was 18,700, and the weight average molecular weight was 48,000.

[0294]

[0295] (Charge Transporting Polymer 4)

[0296] Monomer A2 (4.0 mmol), monomer B1 (1.0 mmol), monomer C2 (2.0 mmol), monomer C4 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (17 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 4. The number average molecular weight of charge transport polymer 4 was 12,100, and the weight average molecular weight was 48,600.

[0297]

[0298] (Charge Transporting Polymer 5)

[0299] Monomer A2 (4.0 mmol), monomer B1 (1.0 mmol), monomer C5 (4.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 5. The number average molecular weight of charge transport polymer 5 was 15,000, and the weight average molecular weight was 43,200.

[0300]

[0301] (Charge Transporting Polymer 6)

[0302] Monomer A1 (4.0 mmol), monomer B2 (1.0 mmol), monomer C1 (4.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 6. The number average molecular weight of charge transport polymer 6 was 17,700, and the weight average molecular weight was 59,000.

[0303]

[0304] (Charge Transporting Polymer 7)

[0305] Monomer A2 (4.0 mmol), monomer B2 (1.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 7. The number average molecular weight of charge transport polymer 7 was 12,100, and the weight average molecular weight was 63,900.

[0306]

[0307] (Charge Transporting Polymer 8)

[0308] Monomer A2 (4.0 mmol), monomer B2 (1.0 mmol), monomer C1 (2.0 mmol), monomer C3 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 8. The number average molecular weight of charge transport polymer 8 was 15,100, and the weight average molecular weight was 56,500.

[0309]

[0310] (Charge Transporting Polymer 9)

[0311] Monomer A2 (4.0 mmol), monomer B2 (1.0 mmol), monomer C2 (2.0 mmol), monomer C4 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 9. The number average molecular weight of the obtained charge transport polymer 9 was 13,700, and the weight average molecular weight was 60,800.

[0312]

[0313] (Charge Transporting Polymer 10)

[0314] Monomer A2 (4.0 mmol), monomer B2 (1.0 mmol), monomer C5 (4.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as in the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 10. The number average molecular weight of the obtained charge transport polymer 10 was 20,000, and the weight average molecular weight was 55,900.

[0315]

[0316] (Charge Transporting Polymer 11)

[0317] Monomer A3 (5.0 mmol), monomer B3 (2.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 11. The number average molecular weight of charge transport polymer 11 was 14,700, and the weight average molecular weight was 51,000.

[0318]

[0319] (Charge Transporting Polymer 12)

[0320] Monomer A4 (5.0 mmol), monomer B3 (2.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 12. The number average molecular weight of charge transport polymer 12 was 13,900, and the weight average molecular weight was 42,300.

[0321]

[0322] (Charge Transporting Polymer 13)

[0323] Monomer A5 (5.0 mmol), monomer B3 (2.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 13. The number average molecular weight of charge transport polymer 13 was 19,900, and the weight average molecular weight was 50,900.

[0324]

[0325] (Charge Transporting Polymer 14)

[0326] Monomer A6 (5.0 mmol), monomer B3 (2.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octylammonium chloride (Alfa Aesar "Aliquat 336") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL) and toluene (50 mL) were added to a three-necked round-bottom flask, and then Pd catalyst solution (1.0 mL) was added for mixing. Thereafter, the same operation as that for the preparation of charge transport polymer 1 was performed to obtain charge transport polymer 14. The number average molecular weight of charge transport polymer 14 was 14,700, and the weight average molecular weight was 61,600.

[0327]

[0328] <Solubility evaluation of charge transport polymers (organic electronic materials)>

[0329] The solubility of the charge-transporting polymers 1 to 14 in the solvent was evaluated.

[0330] 10 mg of each charge transporting polymer was weighed into a sample tube (manufactured by ASONE Co., Ltd., 6 mL). Then, a stirring blade was added, and 1,145 μL of toluene (25° C.) was added at room temperature (25° C.), and then stirred with a stirrer (speed 600 min / min). -1 ). The dissolution time was visually observed to measure the time required for the polymer mixture to become transparent immediately after the addition of toluene (dissolution time). The solubility of the charge transporting polymer was evaluated according to the following criteria. The dissolution time and evaluation results are shown in Table 1.

[0331] A: Dissolution time is less than 10 minutes

[0332] B: Dissolution time exceeds 10 minutes

[0333] [Table 1]

[0334] Table 1

[0335]

[0336]

[0337] As shown in Table 1, the solubility of charge transport polymers 1 to 5, 11 and 13 is improved compared with charge transport polymers 6 to 10, 12 and 14. It can be seen that the organic electronic material containing the charge transport polymer having structure (1) shows high solubility.

[0338] <Production and evaluation of organic layer>

[0339] Using the charge transporting polymers 1 to 14, a device for evaluation (organic hole-only device (HOD) (hereinafter referred to as "organic HOD")) was prepared, and the conductivity of the organic layer was evaluated. Figure 2 . Figure 2 11 denotes an organic layer, 12 denotes an anode, 13 denotes a cathode, and 14 denotes a substrate.

[0340] [Production of organic HOD]

[0341] (Organic HOD 1)

[0342] Charge transport polymer 1 (20.0 mg) was dissolved in toluene (647 μL) to obtain a polymer solution. In addition, the following onium salt (0.2 mg) was dissolved in toluene (101 μL) to obtain an onium salt solution. The obtained polymer solution and the onium salt solution were mixed to prepare an ink composition containing charge transport polymer 1.

[0343]

[0344] In the atmosphere, on a glass substrate with ITO patterned to a width of 1.6 mm, the -1 The ink composition was spin-coated, and then heated on a hot plate at 200° C. for 30 minutes in air to form an organic layer (100 nm).

[0345] Then, the glass substrate was moved to a vacuum deposition machine, and Al (100 nm) was formed into a film on the organic layer by a vapor deposition method to perform a sealing process, thereby manufacturing an organic HOD 1-A.

[0346] Organic HOD 1-B was produced in the same manner as organic HOD 1-A, except that the organic layer (100 nm) was formed by heating on a hot plate at 200° C. for 30 minutes in nitrogen after spin coating.

[0347] Organic HOD 1-C was prepared in the same manner as organic HOD 1-A except that the organic layer (100 nm) was formed by heating on a hot plate at 200° C. for 30 minutes in air after spin coating and then heating on a hot plate at 230° C. for 30 minutes in nitrogen.

[0348] (Organic HOD 2~Organic HOD 14)

[0349] Organic HOD 2-A to organic HOD 14-C were prepared in the same manner as organic HOD 1-A to organic HOD 1-C, except that charge-transporting polymers 2 to 14 were used instead of charge-transporting polymer 1.

[0350] [Evaluation of electrical conductivity]

[0351] A voltage was applied to the organic HOD obtained above, and the current density at 0.1 V was measured. Table 2 shows the measurement results.

[0352] [Table 2]

[0353] Table 2

[0354]

[0355] As shown in Table 2, the current density of organic HOD 1 to organic HOD 5, organic HOD 11 and organic HOD 13 was improved under all heating conditions compared with organic HOD 6 to organic HOD 10, organic HOD 12 and organic HOD 14. It can be seen that the organic layer formed using the organic electronic material containing the charge transporting polymer having the structure (1) exhibits high charge transport properties.

[0356] <Fabrication and evaluation of organic EL elements>

[0357] [Production of organic EL elements]

[0358] (Organic EL element 1)

[0359] The charge transporting polymer 1 (10.0 mg) was dissolved in toluene (2,200 μL) to obtain a polymer solution. In addition, the onium salt (0.2 mg) was dissolved in toluene (100 μL) to obtain an onium salt solution. The obtained polymer solution and the onium salt solution were mixed to prepare an ink composition containing the charge transporting polymer 1. In the atmosphere, on a glass substrate with ITO patterned to a width of 1.6 mm, the mixture was heated for 3,000 min. -1 After spin coating the ink composition, the ink was heated on a hot plate at 200° C. for 30 minutes in nitrogen to form a hole injection layer (20 nm).

[0360] Then, the glass substrate was moved to a vacuum evaporator, and NPD (40nm), CBP: Ir (ppy) 3 (94: 6, 30nm), BAlq (10nm), Alq3 (30nm), LiF (0.8nm) and Al (100nm) were formed on the hole injection layer by evaporation in the order of film, and then sealed to produce an organic EL element.

[0361] (Organic EL element 2 to organic EL element 14)

[0362] Organic EL elements 2 to 14 were produced in the same manner as in organic EL element 1 except that charge-transporting polymers 2 to 14 were used instead of charge-transporting polymer 1 .

[0363] [Evaluation of organic EL elements]

[0364] Voltage was applied to the organic EL device obtained above, and green light emission was confirmed. The light emission luminance of each device was measured at 1,000 cd / m 2 The driving voltage and luminous efficiency, as well as the initial brightness of 5,000cd / m 2 The measurement results are shown in Table 3.

[0365] [Table 3]

[0366] Table 3

[0367]

[0368]

[0369] As shown in Table 3, the emission lifetimes of organic EL elements 1 to 5, 11, and 13 are improved compared to organic EL elements 6 to 10, 12, and 14. It is known that the organic EL element formed using the organic electronic material containing the charge transporting polymer having the structure (1) exhibits a good emission lifetime.

Claims

1. An organic electronic material comprising a charge transporting polymer, wherein the charge transporting polymer has a branched structure and has a structural unit comprising at least one selected from the group consisting of a structure represented by the following formula (1B-1) and a structure represented by the following formula (1L-1), In the formula, * represents a bonding site with other structures, Rc each independently represents a hydrogen atom or a substituent, Rb each independently represents a substituent, and n each independently represents an integer of 0 to 4.

2. The organic electronic material according to claim 1, wherein the charge transporting polymer further has a structural unit comprising at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure and a phenoxazine structure. 3 . The organic electronic material according to claim 1 , wherein the charge transporting polymer has at least one polymerizable functional group. The organic electronic material according to claim 3 , further comprising a polymerization initiator. 5 . The organic electronic material according to claim 1 , wherein the charge transporting polymer is a hole transporting polymer. 6 . A liquid composition comprising: the organic electronic material according to claim 1 ; and a solvent. 7 . An organic layer formed using the organic electronic material according to claim 1 or the liquid composition according to claim 6 . An organic electronic component comprising the organic layer according to claim 7 . 9 . An organic electroluminescent element comprising the organic layer according to claim 7 . 10 . An organic electroluminescent element comprising the organic layer according to claim 7 as a hole injection layer or a hole transport layer.

11. A display element comprising the organic electroluminescent element according to claim 9 or 10.

12. A lighting device comprising the organic electroluminescent element according to claim 9 or 10.

13. A display device, comprising: The lighting device according to claim 12; And a liquid crystal element as a display member.

14. A method for manufacturing an organic electronic component, comprising: An organic layer is formed using the organic electronic material according to any one of claims 1 to 5 or the liquid composition according to claim 6.

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