Organic electronics material, organic layer, and organic electronics element

Abstract

To provide an organic electronics material containing a charge-transporting polymer which can form an organic layer capable of improving characteristics such as conductivity and is obtained by a simple method using an inexpensive material.SOLUTION: The organic electronics material contains the charge-transporting polymer having a branched structure. The charge-transporting polymer contains a trivalent structural unit represented by the following formula (a) and a divalent structural unit represented by the following formula (b), has a structure represented by formula (I) formed by directly bonding at least one binding site in the trivalent structural unit and at least one binding site in the divalent structural unit, and has a weight average molecular weight of 2,000-500,000.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present invention relate to organic electronic materials, organic layers, and organic electronic devices. [Background technology]

[0002] Organic electronics elements are elements that use organic materials to perform electrical functions, and are expected to offer advantages such as energy savings, low cost, and flexibility. As such, they are attracting attention as a technology that can replace conventional silicon-based inorganic semiconductors.

[0003] Examples of organic electronic elements include organic electroluminescence elements (hereinafter referred to as organic EL elements), organic photoelectric conversion elements, and organic transistors. Among organic electronic elements, organic EL elements have been attracting attention as large-area solid-state light sources, for example, as replacements for incandescent lamps and gas-filled lamps. They have also been attracting attention as the most promising self-luminous displays to replace liquid crystal displays (LCDs) in the field of flat panel displays (FPDs), and commercialization is progressing.

[0004] Organic EL elements are broadly classified into low molecular weight organic EL elements and high molecular weight organic EL elements based on the organic materials that compose the element. Low molecular weight organic EL elements use low molecular weight compounds and require a dry process in which a film is formed under vacuum. In contrast, high molecular weight organic EL elements use high molecular weight compounds and can be easily formed into a film using wet processes such as plate printing, including letterpress printing and intaglio printing, and plateless printing, including inkjet printing.

[0005] For this reason, polymer-type organic EL elements that can be easily formed are expected to be essential elements for realizing large-screen organic EL displays in the future. For this reason, in recent years, the development of various charge-transporting polymers as polymer compounds that constitute polymer-type organic EL elements has been progressing. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2008 / 010487 Summary of the Invention [Problem to be solved by the invention]

[0007] As an example of a charge transporting polymer, an arylamine polymer is widely known, and efforts are being made to improve the properties of organic electroluminescence devices by molecular design of the polymer. For example, Patent Document 1 discloses an arylamine polymer containing a triphenylamine structure. However, in recent years, in the field of organic electronics such as organic electroluminescence devices, further improvements in properties such as electrical conductivity are required, and conventional arylamine polymers have room for improvement. In addition, in order to introduce a specific structure into an arylamine polymer, expensive materials or multiple steps are often required in the production of the polymer. Therefore, there is a demand for a charge-transporting polymer that can form an organic layer that can improve the properties of an organic electroluminescence device and can be obtained by a simple method using inexpensive materials.

[0008] Thus, one embodiment of the present invention provides an organic electronic material comprising a charge transporting polymer capable of forming an organic layer capable of improving electrical conductivity, and which can be obtained by a simple method using inexpensive materials. [Means for solving the problem]

[0009] The present inventors have conducted extensive research into charge transporting polymers having an arylamine structure and have found that polymers having a specific arylamine structure are suitable as organic electronics materials, thereby completing the present invention.

[0010] That is, the embodiments of the present invention relate to the following, but the present invention is not limited to the following embodiments and includes various embodiments.

[0011] <1> An organic electronics material comprising a charge-transporting polymer having a branched structure, the charge-transporting polymer comprising a trivalent structural unit represented by the following formula (a) and a divalent structural unit represented by the following formula (b), and having a structure represented by formula (I) formed by directly bonding at least one bonding site in the trivalent structural unit to at least one bonding site in the divalent structural unit, and having a weight-average molecular weight of 2,000 to 500,000.

[0012] [ka]

[0013] [ka]

[0014] In the formula, Ar 1 represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine; Ar 2 represents a monovalent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms and having an electron-withdrawing group or an electron-donating group, and * represents a bonding site with another structure.

[0015] <2> The structure represented by the above formula (I) includes a structure represented by the following formula (I-1) or the following formula (I-2): <1> The organic electronic material according to claim 1.

[0016] [ka]

[0017] In the formula, Ar 1 represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine; Ar 2 represents a monovalent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms and having an electron-withdrawing group or an electron-donating group, and * represents a bonding site with another structure.

[0018] <3> In the above formula (I), Ar 1 has a structure derived from triphenylamine or a structure derived from N-phenylcarbazole. <1> or <2> The organic electronic material according to claim 1.

[0019] <4> In the above formula (I), Ar 2 has a structure represented by the following formula (b-1): <1> or <2> The organic electronic material according to claim 1.

[0020] [ka]

[0021] In the formula, R 1 represents an electron-withdrawing group, an electron-donating group, or an alkyl group having 1 to 12 carbon atoms, at least one of which is an electron-withdrawing group or an electron-donating group; and a represents an integer of 1 to 5.

[0022] <5> In the above formula (b-1), R 1 is an electron-withdrawing group, a is an integer of 1 or 2, and the electron-withdrawing group is at least one selected from the group consisting of a halogen group, a halogen-substituted alkyl group, a nitro group, a cyano group, a sulfonic acid group, and a sulfoxide group. <4> The organic electronic material according to claim 1.

[0023] <6> The charge transport polymer further contains a monovalent structural unit represented by the following formula (c): <1> ~ <5> 13. The organic electronic material according to claim 12,

[0024] [ka]

[0025] In the formula, R 2 is an alkyl group having 1 to 8 carbon atoms, and b is an integer of 1 to 5.

[0026] <7> The above further contains a solvent. <1> ~ <6> 13. The organic electronic material according to claim 12,

[0027] <8> the above <7> 2. An organic layer formed using the organic electronic material according to claim 1.

[0028] <9> the above <8> 2. An organic electronic device comprising the organic layer according to claim 1.

[0029] <10> the above <8> 2. An organic electroluminescence device comprising the organic layer according to claim 1. Effect of the Invention

[0030] According to an embodiment of the present invention, it is possible to form an organic layer capable of improving electrical conductivity, and further to provide an organic electronic material including a charge transporting polymer which can be obtained by a simple method using inexpensive materials. [Brief description of the drawings]

[0031] [Figure 1] FIG. 1 is a cross-sectional view showing an example of an organic EL element according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] Hereinafter, an embodiment of the present invention will be described, however, the present invention is not limited to the embodiment described below. <Organic electronic materials> (Charge transport polymer) One embodiment relates to an organic electronic material, and the charge transporting polymer constituting the organic electronic material may have at least a branched structure represented by the following formula (I) and an electron-withdrawing group or an electron-donating group at a predetermined position. The electron-withdrawing group or the electron-donating group is represented by Ar 2 It is introduced as a substituent on the aromatic ring.

[0033] [ka]

[0034] More specifically, the charge transporting polymer of the present embodiment has charge transporting properties and contains at least a trivalent or higher structural unit B constituting a branched portion and a divalent structural unit L. The charge transporting polymer preferably further contains a monovalent structural unit T.

[0035] Charge transporting polymers having a branched structure have excellent heat resistance and can have many terminal groups introduced therein, and therefore exhibit good solubility and curability. The charge transporting polymer may contain only one type of each structural unit, or may contain multiple types of each structural unit. In the charge transporting polymer, each structural unit is bonded to each other at a "monovalent" to "trivalent or higher" bonding site.

[0036] Examples of partial structures contained in the charge transporting polymer include the following. However, the charge transporting polymer is not limited to polymers having the following partial structures. In the partial structures, "L" represents structural unit L, "T" represents structural unit T, and "B" represents structural unit B. In the following, "*" represents a bonding site with other structural units. In the following partial structures, multiple Ls may be the same structural unit or different structural units. The same applies to T and B.

[0037] (Partial structure of charge transport polymer having a branched structure) [ka]

[0038] The charge-transporting polymer of this embodiment preferably contains at least a trivalent structural unit represented by the following formula (a) as the structural unit B, and at least a divalent structural unit represented by the following formula (b) as the structural unit L, and contains a structure represented by the following formula (I) formed by directly bonding at least one bonding site in each structural unit.

[0039] [ka]

[0040] [ka]

[0041] In the formula, Ar 1 represents a trivalent organic group derived from an aromatic hydrocarbon, aromatic heterocycle, or triarylamine having 2 to 30 carbon atoms; Ar 2 represents a monovalent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms and having an electron-withdrawing group or an electron-donating group, and * represents a bonding site with other structures. 1 and Ar 2 Details will be provided later.

[0042] The charge transporting polymer preferably contains a structure represented by the following formula (I-1) or the following formula (I-2), and more preferably contains a structure represented by the following formula (I-2). 1 , Ar 2 , and * are the same as those explained above.

[0043] [ka]

[0044] The structural unit of the charge transporting polymer will be described in more detail below. (Structural unit B) The structural unit B is a trivalent or higher structural unit constituting a branched portion of a charge transporting polymer having a branched structure. From the viewpoint of improving the durability of an organic electronics element, the structural unit B is preferably hexavalent or lower, more preferably trivalent or tetravalent. The structural unit B preferably has charge transport properties. For example, the structural unit B may be an organic group derived from an aromatic hydrocarbon, an aromatic heterocycle, or a triarylamine. Among them, from the viewpoint of improving the durability of an organic electronics element, for example, a substituted or unsubstituted organic group (structure) derived from a triarylamine, carbazole, or a condensed polycyclic aromatic hydrocarbon can be preferably selected as the structural unit B.

[0045] The charge transporting polymer of this embodiment contains, as the structural unit B, at least a trivalent structural unit represented by the above formula (a) (hereinafter, also referred to as structural unit B1).

[0046] [ka]

[0047] In the formula, Ar 1 represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle, or a triarylamine. The trivalent organic group is also called an arenetriyl group or a heteroarenetriyl group. Ar 1 is an atomic group formed by removing three hydrogen atoms from an aromatic hydrocarbon or aromatic heterocycle, or from an aromatic ring in a triarylamine. In one embodiment, Ar 1 may be a trivalent organic group preferably derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms.

[0048] Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, triphenylene, pyrene, chrysene, perylene, triphenylene, pentacene, and benzopyrene.

[0049] 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, benzoxadiazole, benzothiadiazole, benzotriazole, and benzothiophene.

[0050] The aromatic hydrocarbon and aromatic heterocycle may be a single ring or a condensed ring. In addition, they may have a polycyclic structure in which two or more selected from the single ring and the condensed ring are bonded via a single bond. Examples of aromatic hydrocarbons having such a polycyclic structure include biphenyl, terphenyl, and triphenylbenzene.

[0051] In one embodiment, Ar 1 may be a trivalent organic group derived from triarylamine. Triarylamine means a tertiary aromatic amine in which three aryl groups (aromatic groups) are bonded to a nitrogen atom. Here, the aryl group is a monovalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms. The aromatic hydrocarbon and aromatic heterocycle may be specifically as described above. In triarylamine, specific examples of the aryl group derived from an aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a biphenyl group. Specific examples of the aryl group derived from an aromatic heterocycle group include a thienyl group, a furyl group, a pyrrolyl group, a pyridyl group, and an imidazolyl group. In one embodiment, the triarylamine is preferably triphenylamine.

[0052] The aromatic hydrocarbon and aromatic heterocycle contained in the monovalent organic group and the trivalent organic group may be unsubstituted or may have one or more substituents R. Each of the substituents R is independently -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R7 R 8 , a halogen atom, and a group containing a polymerizable functional group as described below. 1 It is more preferable that: R 1 ~R 8 each independently represents a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms (provided that R 1 is a hydrogen atom); or represents an aryl group or heteroaryl group having 2 to 30 carbon atoms. An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. The alkyl group may be further substituted with an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group may be further substituted with a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms.

[0053] Specific examples of the structural unit B1 include the structures shown below. Among these, structures derived from triarylamine and structures derived from N-arylcarbazole are preferred.

[0054] [ka]

[0055] In the formula, Ar each independently represents a divalent linking group, for example, each independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group.

[0056] In one embodiment, the structural unit B1 preferably includes at least one of a structural unit derived from a triphenylamine structure represented by the following formula (B1-1) and a structural unit derived from an N-phenylcarbazole structure represented by the following formula (B1-2).

[0057] [ka]

[0058] In the structural unit (B1-1), l, m, and n each independently represent an integer of 0 to 4, and each independently represent the number of substituents R. l, m, and n each independently represent an integer of 0 to 2, and more preferably an integer of 0 or 1. In one embodiment, the number of substituents in the structural unit (B1-1) is preferably 1 or 2. In another embodiment, the number of substituents in the structural unit (B1-1) is preferably 0.

[0059] In the structural unit (B1-2), l is an integer of 0 to 4, and m and n are each independently an integer of 0 to 3, each indicating the number of substituents R. l is preferably an integer of 0 to 2, more preferably an integer of 0 or 1. m and n are each independently an integer of 0 to 2, more preferably an integer of 0 or 1. In one embodiment, the number of substituents in the structural unit (B1-2) is preferably 1 or 2. In another embodiment, the number of substituents in the structural unit (B1-2) is preferably 0.

[0060] In each of the above structural units, "*" indicates a bonding site with other structures, and at least one of the bonding sites is bonded to a nitrogen atom (N). In the structural unit (B1-1) or (B1-2), it is preferable that two or three of the three bonding sites are bonded to a nitrogen atom. It is more preferable that all of the three bonding sites are bonded to a nitrogen atom. When the charge transport polymer contains an N-Ph bond, doping and conjugation become easy, and it tends to be easy to obtain better electrical conductivity. From this viewpoint, it is preferable that the structural unit B contains either the structural unit (B1-1) derived from triphenylamine and the structural unit (B1-2) derived from N-phenylcarbazole shown below. By containing these structural units, it is easy to obtain good electrical conductivity.

[0061] In the structural units (B1-1) and (B1-2), the substituent R is the same as the substituent R described above for the structure represented by formula (I). In one embodiment, when the structural unit B has the structural unit (B1-1) or (B1-2), the substituent R may have a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The aromatic ring in the aryl group may be further substituted with a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. In another embodiment, it is preferable that both of the structural units (B1-1) and (B1-2) are unsubstituted.

[0062] In one embodiment, the structural unit B may include a tetravalent or higher structural unit B2 in addition to the structural unit B1. For example, specific examples of the structural unit B2 include the following. Among them, a structure including a triarylamine structure and a structure including a carbazole structure are preferred.

[0063] [ka]

[0064] In the formula, each Ar independently represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group, and examples thereof include divalent groups obtained by removing one hydrogen atom from a group having one or more hydrogen atoms among R (excluding groups containing a polymerizable functional group) in the structural unit L described below. Z represents any one of a carbon atom, a silicon atom, and a phosphorus atom. In the structural unit, the benzene ring and Ar may have a substituent, and examples of the substituent include the substituent R in the structural unit B1 described above.

[0065] (Structural unit L) The structural unit L is a divalent structural unit having charge transportability, and is not particularly limited as long as it contains an atomic group having the ability to transport charge. From the viewpoint of directly bonding with the structural unit (a) described above to form a structure represented by formula (I), the structural unit L contains at least a divalent structural unit represented by the following formula (b) (hereinafter also referred to as structural unit L1).

[0066] [ka]

[0067] In the formula, Ar 2 is a monovalent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, which has an electron-withdrawing group or an electron-donating group, and is an atomic group obtained by removing one hydrogen atom from the aromatic ring of the aromatic hydrocarbon. 2 is also called an aryl group. 2 is an aryl group having 6 to 30 carbon atoms forming a ring, and has a structure in which at least one hydrogen atom of the aromatic ring in the aryl group is substituted with an electron-withdrawing group or an electron-donating group. 2 In the above formula, the number of carbon atoms forming the ring is more preferably 6 to 24.

[0068] Specific examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, biphenyl, terphenyl, triphenylbenzene, etc. Here, the aromatic ring in the aromatic hydrocarbon has one or more electron-withdrawing groups or electron-donating groups as substituents, and may further have other substituents as necessary.

[0069] In one embodiment, the Ar 2 may have a structure represented by the following formula (b-1): [ka] In the formula, R 1 is an electron-withdrawing group, an electron-donating group, or an alkyl group having 1 to 12 carbon atoms; a is an integer of 1 to 5; R 1At least one of the groups is an electron withdrawing group or an electron donating group. In one embodiment, a may be preferably 1 to 4, more preferably 1 to 3, and further preferably 1 or 2.

[0070] The above "electron-withdrawing group" refers to a substituent that is more likely to attract electrons from the bonding atom than a hydrogen atom. On the other hand, the above "electron-donating group" refers to a substituent that is more likely to donate electrons to the bonding atom than a hydrogen atom, and does not include alkyl groups. When a charge-transporting polymer contains a specific structure in which a hydrogen atom in an aromatic ring bonded to an N atom is replaced with an electron-withdrawing group or an electron-donating group, the HOMO level tends to be easily adjusted. For example, when an electron-withdrawing group is introduced into a specific portion of a charge-transporting polymer as described above, the HOMO level can be deepened. Also, when an electron-withdrawing group is introduced into a specific portion, the solubility of the charge-transporting polymer tends to be improved. From this viewpoint, in one embodiment, in a charge-transporting polymer having a structure of formula (I), Ar 2 It is preferred that the hydrogen atoms of the aromatic ring are substituted with electron-withdrawing groups.

[0071] The electron-withdrawing group is not particularly limited, and specific examples thereof include a halogen group, a halogen-substituted alkyl group, a nitro group, a cyano group, a sulfonic acid group, and a sulfoxide group. More specifically, examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodine group. The number of carbon atoms in the alkyl group in the halogen-substituted alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. From the viewpoint of the strength of the electron-withdrawing property, the halogen group is preferably a fluoro group, and the halogen-substituted alkyl group is preferably a fluoroalkyl group.

[0072] Considering the thermal stability of the charge transporting polymer, the electron-withdrawing group is preferably at least one selected from the group consisting of a fluoro group, a fluoroalkyl group, a nitro group, a cyano group, a sulfonic acid group, and a sulfoxide group. More preferably, it may be at least one selected from the group consisting of a fluoro group, a fluoroalkyl group, a sulfonic acid group, and a sulfoxide group. More preferably, it may be at least one of a fluoro group and a fluoroalkyl group. When the aryl group contains multiple electron-withdrawing groups, the multiple electron-withdrawing groups may be the same or different from each other.

[0073] In one embodiment, Ar in formula (I) 2 preferably has a structure represented by the following formula (b-1a) or (b-1b).

[0074] [ka]

[0075] In each formula, Ew represents an electron-withdrawing group. In the structure represented by the above formula (b-1a) or (b-1b), the electron-withdrawing group (Ew) is preferably a halogen atom or a halogen-substituted alkyl group. Among them, a fluorine atom (F) or trifluoromethane (CF3) is more preferable.

[0076] The electron donating group is not particularly limited, but specific examples include -OR, -OH, and -NR2. The alkyl group of the alkyloxy group (-OR) may have any of a linear, branched, or cyclic structure. The number of carbon atoms in the alkyl group may be preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0077] In one embodiment, Ar in formula (I) 2 preferably has a structure represented by the following formula (b-1c) or (b-1d).

[0078] [ka]

[0079] In each formula, Ea represents an electron-withdrawing group. In the structure represented by the above formula (b-1c) or (b-1d), the electron-withdrawing group (Ea) is preferably -OR, and more preferably a methoxy group.

[0080] As described above, the charge transport polymer having the structure represented by the above formula (I) is 2 In one embodiment, the charge transporting polymer may further have an alkyl group having 1 to 12 carbon atoms as the substituent, in addition to the at least one electron withdrawing group or electron donating group. The alkyl group having 1 to 12 carbon atoms may have any of a linear, branched, or cyclic structure. In one embodiment, the alkyl group preferably has a linear or branched structure. In one embodiment, in consideration of application to a wet process, R 1 is preferably an alkyl group having 2 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and further preferably an alkyl group having 4 to 12 carbon atoms.

[0081] In one embodiment, the structural unit L may further include a structural unit L2 having a structure different from the structural unit L1 in addition to the structural unit L1. The structural unit L2 is selected from a substituted or unsubstituted triarylamine structure, a carbazole structure, a thiophene structure, a bithiophene structure, a fluorene structure, a benzene structure, a biphenylene structure, a terphenylene structure, a naphthalene structure, an 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 diazaphenanthrene 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, an N-arylphenoxazine structure, and a structure including one or more of these. The triarylamine structure is more preferably a triphenylamine structure.

[0082] In one embodiment, from the viewpoint of obtaining excellent hole transport properties, the structural unit L2 preferably contains one or more structures selected from the group consisting of a substituted or unsubstituted triarylamine structure, a carbazole structure, a thiophene structure, a bithiophene structure, a benzene structure, a fluorene structure, and a pyrrole structure, and more preferably contains one or more structures selected from the group consisting of a substituted or unsubstituted triarylamine structure and a carbazole structure. In another embodiment, from the viewpoint of obtaining excellent electron transport properties, the structural unit L preferably contains one or more structures selected from the group consisting of a substituted or unsubstituted fluorene structure, a benzene structure, a phenanthrene structure, a pyridine structure, and a quinoline structure.

[0083] Specific examples of the structural unit L2 include the following: However, the structural unit L2 is not limited to the following.

[0084] [ka]

[0085] [ka]

[0086] Each R independently represents a hydrogen atom or a substituent. Preferably, each R independently represents -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 , a halogen atom, and a group containing a polymerizable functional group as described below. 1 It is more preferable that R 1 ~R 8 each independently represents a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms; or an aryl group or heteroaryl group having 2 to 30 carbon atoms. An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. The alkyl group may be further substituted with an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group may be further substituted with a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms. Ar represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. The heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. Ar is preferably an arylene group, and more preferably a phenylene group.

[0087] The aromatic hydrocarbon may be a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more rings selected from a monocyclic ring and a condensed ring are bonded via a single bond. The aromatic heterocyclic ring may be a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more rings selected from a monocyclic ring and a condensed ring are bonded via a single bond.

[0088] (Structural unit T) The structural unit T is a monovalent structural unit constituting the terminal portion of the charge transporting polymer. The structural unit T is not particularly limited, and is selected from, for example, a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure, and a structure containing one or more of these. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure, more preferably a substituted or unsubstituted benzene structure, from the viewpoint of imparting durability without reducing the charge transportability. The structural unit T may have the same structure as the structural unit L, except for the valence. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure, more preferably a substituted or unsubstituted benzene structure, from the viewpoint of imparting durability without reducing the charge transportability.

[0089] Specific examples of the structural unit T include the following: The structural unit T is not limited to the following.

[0090] [ka]

[0091] Each R independently represents a hydrogen atom or a substituent. The substituent is -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 , a halogen atom, and a polymerizable functional group described below. 1 ~R 8 is the R in the structural unit L explained above. 1 ~R 8 In one embodiment, the substituent is -R 1 It is preferable that:

[0092] In one embodiment, the charge transporting polymer preferably has a monovalent structural unit T1 represented by the following formula (c).

[0093] [ka]

[0094] In the formula, R 2 is an alkyl group having 1 to 8 carbon atoms, and b is an integer of 1 to 5. In one embodiment, R 2 is preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may have any of a linear, branched, or cyclic structure. In one embodiment, b is preferably 1 to 3, and more preferably 1 or 2.

[0095] (Polymerizable functional group) In one embodiment, the charge transport polymer may have a polymerizable functional group. The polymerizable functional group is a functional group that can form a bond with each other by applying heat and / or light. When the charge transport polymer contains a polymerizable functional group, an organic layer made of a cured film can be formed by curing a coating film formed using the charge transport polymer. The organic layer made of such a cured film has a solvent resistance required for further laminating an upper layer on the organic layer by a wet process. Therefore, when the charge transport polymer contains a polymerizable functional group, it is easy to form a multilayer by a wet process.

[0096] Examples of the polymerizable functional group include a group having a carbon-carbon multiple bond (e.g., a vinyl 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 (e.g., a cyclic alkyl group such as a cyclopropyl group or a cyclobutyl group; a cyclic ether group such as an epoxy group (oxiranyl group) or an oxetane group (oxetanyl group); a cyclic thioether group such as an episulfide group; a cyclic ester group such as a diketene group or a lactone group; a cyclic amide group such as a lactam group), a heterocyclic group (e.g., a furan-yl group, a pyrrol-yl group, a thiophen-yl group, a silol-yl group), a benzocyclobutene group, etc.

[0097] The polymerizable functional group preferably includes one or more selected from the group consisting of a group having a carbon-carbon multiple bond, a group having a small ring, and a heterocyclic group, and more preferably includes one or more selected from the group consisting of a group having a carbon-carbon double bond, a cyclic ether group, and a heterocyclic group. Specifically, the polymerizable functional group is preferably a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, an oxetane group, a pyrrolyl group, and a thiopheneyl group, and from the viewpoint of the solubility and curability of the charge transport polymer, the vinyl group, the oxetane group, and the thiopheneyl group are more preferable. The polymerizable functional group may be a substituted or unsubstituted polymerizable functional group. Examples of the substituent that the polymerizable functional group may have include alkyl groups having 1 to 6 carbon atoms, such as a methyl group and an ethyl group. The polymerizable functional group may be directly bonded to the aromatic ring, or may be bonded to the aromatic ring via a divalent group such as a linking group. Examples of the linking group include -O-, -(CH2) n -, -, and combinations thereof, where n may be an integer of 1 to 10.

[0098] In the charge transporting polymer, the polymerizable functional group is preferably introduced at least to the terminal portion (i.e., the structural unit T) of the charge transporting polymer. The polymerizable functional group may be introduced to a portion other than the terminal portion (i.e., the structural unit L or B), or may be introduced to both the terminal portion and the portion other than the terminal portion. From the viewpoint of achieving both curability and charge transportability, it is preferable that the polymerizable functional group is introduced only to the terminal portion. In addition, in the charge transporting polymer having a branched structure, the polymerizable functional group may be introduced to the main chain of the charge transporting polymer, may be introduced to the side chain, or may be introduced to both the main chain and the side chain.

[0099] For example, the number of polymerizable functional groups per molecule of the charge transporting polymer is preferably 2 or more, more preferably 3 or more, from the viewpoint of obtaining a sufficient change in solubility, and is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of maintaining the charge transporting property.

[0100] In addition, from the viewpoint of obtaining good curability, the ratio of polymerizable functional groups in the charge transporting polymer is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 3 mol% or more, based on the total structural units. In addition, from the viewpoint of obtaining good charge transportability, the ratio of polymerizable functional groups is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. Here, the "ratio of polymerizable functional groups" refers to the ratio of structural units having polymerizable functional groups.

[0101] The content and ratio of the polymerizable functional group per molecule of the charge transport polymer can be calculated as an average value using the amount of the polymerizable functional group used to synthesize the charge transport polymer (for example, the amount of the monomer having the polymerizable functional group multiplied by the number of polymerizable functional groups per monomer), the amount of the monomer corresponding to each structural unit, the weight average molecular weight of the charge transport polymer, etc. 1It can be calculated as an average value using the ratio of the integral value of the signal derived from the polymerizable functional group to the integral value of the entire spectrum in the H NMR (nuclear magnetic resonance) spectrum, the weight average molecular weight of the charge transport polymer, etc. When the amount of the charge is clear, it is preferable to use the value calculated using the amount of the charge, since it is simple.

[0102] (number average molecular weight) The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming property, etc. From the viewpoint of excellent charge transportability, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, even more preferably 2,000 or more, and even more preferably 5,000 or more. In addition, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of an ink composition, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less.

[0103] (Weight average molecular weight) The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming property, etc. From the viewpoint of excellent charge transportability, the weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and even more preferably 30,000 or more. In addition, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of an ink composition, the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, even more preferably 400,000 or less, and even more preferably 200,000 or less, and 100,000 or less, in this order. In one embodiment, the weight average molecular weight of the charge transporting polymer may be preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and further preferably 8,000 to 50,000.

[0104] 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.

[0105] (Structural unit ratio) The ratio of the structural unit B contained in the charge transporting polymer is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total structural units, from the viewpoint of improving the durability of the organic electronics element. In addition, the ratio of the structural unit B is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, from the viewpoint of suppressing an increase in viscosity and smoothly synthesizing the charge transporting polymer, or from the viewpoint of obtaining sufficient charge transportability. Here, the above ratio of the structural unit B means the total amount of the structural units B1 and B2. In one embodiment, the structural unit B may be composed of only the structural unit B1.

[0106] In the charge transporting polymer, the ratio of the structural unit L is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total structural units, from the viewpoint of obtaining sufficient charge transportability. In addition, the ratio of the structural unit L is preferably 97 mol% or less, more preferably 92 mol% or less, and even more preferably 85 mol% or less, taking into consideration the structural unit T and the structural unit B. Here, the above ratio of the structural unit L means the total amount of the structural units L1 and L2. In one embodiment, the structural unit L may be composed of only the structural unit L1.

[0107] The ratio of the structural unit T contained in the charge transporting polymer is preferably 3 mol% or more, more preferably 8 mol% or more, and even more preferably 15 mol% or more, based on the total structural units, from the viewpoint of solubility and curability. The above range is also preferred from the viewpoint of improving the characteristics of an organic electronic device, or from the viewpoint of suppressing an increase in viscosity and smoothly synthesizing the charge transporting polymer. Moreover, from the viewpoint of obtaining sufficient charge transportability, the ratio of the structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.

[0108] In consideration of the balance between charge transport properties, durability, productivity, and the like, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is preferably L:T:B=100:10 to 200:10 to 100, more preferably 100:20 to 180:20 to 90, and further preferably 100:40 to 160:30 to 80.

[0109] The ratio of the structural units can be determined by the amount of monomers corresponding to each structural unit used to synthesize the charge transporting polymer. 1 The average value can be calculated by using the integral value of the spectrum derived from each structural unit in the H NMR spectrum. When the amount of the charge is clear, the value calculated using the amount of the charge is preferably used because it is simple. The ratio of the terminal group described above can also be calculated in the same manner.

[0110] The degree of polymerization (the number of structural units) of the charge transporting polymer is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, from the viewpoint of stabilizing the film quality of the coating film. In addition, the degree of polymerization is preferably 1,000 or less, more preferably 700 or less, and even more preferably 500 or less, from the viewpoint of solubility in a solvent. 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 units, and the ratio of the structural units.

[0111] The charge transporting polymer of the above embodiment may have a structure in which a plurality of structural units B, and optionally structural units L2 and T, are bonded via the structural unit L1, and a charge transporting polymer containing an N-Ph bond in the molecule is formed by the structural unit L1. The charge transporting polymer containing an N-Ph bond tends to be easier to dope and conjugate than a charge transporting polymer containing a Ph-Ph bond formed by, for example, a method using Suzuki-Miyaura coupling. From this viewpoint, in one embodiment, the charge transporting polymer preferably has a partial structure represented by the following formula (i).

[0112] [ka]

[0113] From the viewpoint of easily introducing the partial structure represented by the above formula (i), it is preferable that the above structural unit B1 and the above structural unit L2 contain either a structure derived from a triphenylamine structure or a structure derived from an N-phenylcarbazole structure. In the above formula (i), n is an integer of 2 or more, and Ar 2 is as described above, and may preferably be a structure represented by the above formula (b-1). In one embodiment, n is preferably an integer of 3 or more, more preferably an integer of 4 or more, and even more preferably an integer of 6 or more. On the other hand, n may preferably be an integer of 3,000 or less, more preferably an integer of 1,500 or less, and even more preferably an integer of 500 or less.

[0114] In the charge transporting polymer, the content of N-Ph bonds formed by bonding each structural unit to each other may be preferably 10 to 80%, more preferably 20 to 70%, and further preferably 30 to 60%. Here, the above content is a value calculated from the amount of raw material monomer charged by performing NMR measurement, similar to the ratio of the structural units.

[0115] (Method of Manufacturing Charge-Transporting Polymer) The charge transporting polymer (I) having the structure represented by the above formula (I) can be prepared by using two or more aromatic compounds as raw material monomers and reacting these two or more raw material monomers according to a known method. For example, it can be prepared by using an aromatic compound having a reactive functional group (1) and an aromatic compound having a reactive functional group (2) capable of reacting with the reactive functional group (1) and performing a coupling reaction according to a known method. Examples of combinations of the reactive functional group (1) and the reactive functional group (2) include a halogen atom and an amino group, a triflate group and an amino group, and a halogen atom and a boronic acid group. The triflate group has a structure (CF3SO2-) in which one hydrogen atom has been removed from trifluoromethanesulfonic acid.

[0116] From the viewpoint of easily forming an N-Ph bond by a coupling reaction, the combination of the reactive functional groups (1) and (2) is preferably a halogen atom and an amino group, or a triflate group and an amino group, where the amino group is preferably a primary amino group.

[0117] From the above viewpoint, the Buchwald-Hartwig reaction can be preferably applied to produce a charge transporting polymer having a structure represented by the above formula (I). In the case of the Buchwald-Hartwig reaction, the combination of the reactive functional groups (1) and (2) may be a halogen atom and an amino group. The amino group is preferably a primary amino group. More specifically, a polymer having a desired structure can be obtained by reacting an aromatic compound having a halogen atom directly bonded to an aromatic ring with an aromatic compound having a primary amino group. Here, the halogen atom may be a chlorine atom, a bromine atom, or an iodine atom. Also, an aromatic compound having a triflate group instead of a halogen atom can be used.

[0118] In the Buchwald-Hartwig reaction, an aromatic compound (1) having two or more halogen atoms or triflate groups directly bonded to the aromatic ring and an aromatic compound (2) having a primary amino group are used to produce an arylamine polymer having one or more structural units derived from each of the aromatic compounds (1) and (2). From this perspective, by selecting the aromatic compound used as the raw material monomer, a charge transporting polymer having two or more of the desired structure (I) as represented by the following formula (IA) can be easily obtained.

[0119] [ka]

[0120] In the formula, Ar 1 and Ar 2is as described above, and n is an integer of 2 or more. n may be preferably 3 or more, more preferably 5 or more, and further preferably 10 or more. For example, n may be an integer that is appropriately set so that the weight average molecular weight (Mw) of the charge transporting polymer is in the range of 1,000 to 500,000, 2,000 to 500,000, 3,000 to 500,000, or 5,000 to 300,000.

[0121] In one embodiment, as a raw material monomer for producing a charge transporting polymer having the above structure (I), at least a triphenylamine having a halogen atom directly bonded to an aromatic ring and an aromatic primary amine having an electron withdrawing group or an electron donating group (hereinafter also referred to as an arylamine) can be used. In such an embodiment, the structure (I) in the charge transporting polymer preferably includes a structure represented by the following formula (I-1).

[0122] [ka]

[0123] In the formula, Ar 2 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and having an electron-withdrawing group or an electron-donating group, the details of which are as explained above. "*" represents a bonding site with another structure.

[0124] The structure (I) in the charge transporting polymer more preferably contains a structure represented by the following formula (I-2a) or formula (I-3a), and further preferably has a structure represented by the following formula (I-3a).

[0125] [ka]

[0126] From the viewpoint of obtaining a charge transporting polymer having a structure represented by the above formula (I-3a), in one embodiment, at least triphenylamine having three halogen atoms directly bonded to an aromatic ring and arylamine can be suitably used as raw material monomers. More specifically, a compound in which Ar is a phenylene group in the trivalent structural unit B1 represented by the above formula (a) and a halogen atom is directly bonded to each of the three bonding sites (*) can be preferably used. Also, a compound in which hydrogen is bonded to the two bonding sites (*) in the divalent structural unit L1 represented by the above formula (b) is an aromatic primary amine and has one or more electron-withdrawing or electron-donating groups in the aromatic ring can be preferably used.

[0127] In one embodiment, the charge transporting polymer preferably further comprises a monovalent structural unit T represented by the following formula (c): 2 and b are as explained above. In order to introduce the structural unit T into the charge transporting polymer, a compound in which a halogen atom is directly bonded to the bonding site (*) in the structure represented by the following formula (c) can be used as a raw material monomer.

[0128] [ka]

[0129] In one embodiment, the charge transporting polymer (I) includes the structural units B1, L1, and T. In another embodiment, the charge transporting polymer (I) may further include other structural units in addition to the structural units B1, L1, and T. For example, the structural units B2 and L2 described above may further be included. In this case, an aromatic compound having a structure capable of inducing the additional structural unit and having a halogen atom directly bonded to the aromatic ring or an aromatic compound having an amino group can be used as a raw material monomer. In this way, a charge transporting polymer having a desired structure can be easily obtained by arbitrarily combining the raw material monomers.

[0130] For example, in one embodiment, in order to introduce the structural unit B2 and the structural unit L2 exemplified above into the charge transporting polymer, a compound in which a halogen atom is directly bonded to the bonding site (*) in the structural unit B2 and the structural unit L2 can be used as a raw material monomer. In another embodiment, in order to introduce the structural unit L2, a compound having an -NH-Ar group at the bonding site (*) in the structural unit L2 can also be used as a raw material monomer (wherein, Ar each independently represents an aryl group or heteroaryl group having 2 to 30 carbon atoms).

[0131] The method for producing a charge-transporting polymer using the Buchwald-Hartwig reaction will now be described in more detail. (Buchwald-Hartwig reaction) The Buchwald-Hartwig reaction can be carried out according to conditions and methods well known to those skilled in the art. For example, the reaction can be carried out under an inert gas atmosphere such as nitrogen, using a compound containing a heavy metal such as palladium as a catalyst. It is preferable to use a catalyst and a base in combination during the reaction.

[0132] In the Buchwald-Hartwig reaction, a palladium-containing catalyst can be preferably used as a catalyst. In this specification, the term "palladium-containing catalyst" refers to a catalyst containing palladium and a ligand, and includes a complex compound or salt containing palladium and a ligand, or a combination of a precursor of the palladium-containing catalyst and a ligand or a ligand precursor.

[0133] The above-mentioned ligand is preferably one having a bulky structure, and specific examples thereof include phosphine ligands and Buchwald ligands. N-heterocyclic carbene (NHC) can also be used as the ligand. Among them, phosphine ligands such as tri-t-butylphosphine, tri-o-tolylphosphine, and triphenylphosphine are more preferred.

[0134] The palladium-containing catalyst may be a palladium(0) complex or a palladium(II) salt. Specific examples of palladium-containing catalysts include bis(tri-t-butylphosphine)palladium(0), tetrakis(triphenylphosphine)palladium(0), bis[1,2-bis(diphenylphosphino)ethane]palladium(0), dichlorobis(triphenylphosphine)palladium(II), dichlorobis(tri-o-tolylphosphine)palladium(II), bis[di-t-butyl(4-dimethylaminophenyl)phosphine]dichloropalladium(II), [1,1'-bis(di-t-butylphosphino)ferrocene]dichloropalladium(II), dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II), dichloro[1,2-bis(diphenylphosphino)ethane]palladium(II), and dichloro[1,3-bis(diphenylphosphino)propane]palladium(II), and Umicore CX31 and CX32 having NHC ligands. These compounds can also be used in combination with the ligands or ligand precursors described above.

[0135] Also, a precursor of a palladium-containing catalyst can be used to generate active palladium in the reaction system from the precursor, using organometallic reagents, phosphines, amines, and other components present in the reaction system. Examples of the precursor include bis(dibenzylideneacetone)palladium(0), palladium acetate(II), palladium chloride(II), di-μ-chlorobis[(η-allyl)palladium(II)], dichlorobis(acetonitrile)palladium(II), and dichlorobis(benzonitrile)palladium(II).

[0136] When using the precursor of the above-mentioned palladium-containing catalyst, it is preferable to use a precursor of a ligand such as a triphosphonium salt in combination. A specific example of the triphosphonium salt is tri-t-butylphosphonium tetrafluoroborate. This compound generates tri-t-butylphosphine in the system and functions as a ligand for palladium. Although not particularly limited, in one embodiment, it is preferable to use a combination of bis(tri-t-butylphosphine)palladium(0) and tri-t-butylphosphonium tetrafluoroborate as the palladium-containing catalyst.

[0137] In one embodiment, a palladium-containing catalyst having at least a structure represented by the following formula (1) can be suitably used as the catalyst. PdArBrP(t-Bu)3(1)

[0138] In the formula, Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Ar may be, for example, a substituted or unsubstituted phenyl group. At least one hydrogen atom in the aromatic ring of the aryl group may be substituted with an alkyl group having 1 to 12 carbon atoms.

[0139] A specific example of the palladium-containing catalyst having the above structure is the compound represented by the following formula (2): This compound can be produced, for example, by reacting tris(dibenzylideneacetone)dipalladium(0), o-bromotoluene, and tri-tert-butylphosphine.

[0140] [ka]

[0141] In another embodiment, a palladium-containing catalyst having at least a structure represented by the following formula (3) can be suitably used as the catalyst. [ka]

[0142] In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L represents a ligand. Z represents a leaving group. The leaving group may be one selected from the group consisting of a halogen atom, a methylsulfonyloxy group (-OSO2CH3), a tosyl group (-OSO2C6H5CH3), and a trifluoromethylsulfonyloxy group (-OSO2CH3).

[0143] Specific examples of the catalyst having the structure represented by the above formula (3) include the following. [ka]

[0144] In one embodiment, the palladium-containing catalyst that can be suitably used can be produced according to a method well known to those skilled in the art, but can also be obtained as a commercial product. For example, the XphosPd series manufactured by Aldrich Co., Ltd. can be used, and among them, the catalysts represented by the above formulas (3-1) to (3-4) can be obtained as XphosPd G1, XphosPd G2, XphosPd G3, and XphosPd G4. In one embodiment, the catalysts represented by the above formulas (3-2) and (3-4) can be more preferably used, and these can be obtained as XphosPd G2 and XphosPd G4, respectively.

[0145] The amount of the catalyst used is not particularly limited, but may typically be in the range of 0.1 mol% or more and 20 mol% or less with respect to the aromatic compound having an amino group used as the raw material monomer. By adjusting the amount of the catalyst used within the above range, it becomes easy to efficiently proceed with the reaction and to suppress the generation of by-products. In one embodiment, the amount of the catalyst used may be preferably 0.1 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, and even more preferably 0.1 mol% to 2 mol%, with respect to the aromatic compound having an amino group used as the raw material monomer. According to the production method of this embodiment, even if the amount of the catalyst used is reduced, it is possible to efficiently proceed with the reaction. Therefore, it becomes easy to reduce the amount of impurities derived from the catalyst in the polymer obtained by the reaction.

[0146] In one embodiment, the palladium-containing catalyst may further include an additive. The additive is preferably a compound that functions as a ligand for palladium metal. Specific examples of compounds that can be used as additives include P(t-Bu)3·HBF3, PCy3·HBF3, and Xphos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl). Among these, P(t-Bu)3·HBF3 is preferred. When such an additive is used, the reactivity of the palladium catalyst tends to be further improved.

[0147] The base is not particularly limited, and may be either an inorganic base or an organic base. In one embodiment, although not particularly limited, an organic base is preferred, and an organic alkali metal compound such as t-butoxy sodium or n-butyl lithium can be suitably used. The amount of the base used is not particularly limited, but may typically be in the range of 1.0 molar equivalent or more and 4 molar equivalent or less with respect to the number of moles of the aromatic compound having an amino group used as the raw material monomer. By adjusting the amount of the base used within the above range, the reaction can be efficiently carried out and the production of by-products can be easily suppressed.

[0148] The reaction is preferably carried out in the presence of an organic solvent. Examples of the organic solvent (reaction solvent) include aromatic hydrocarbons such as benzene and toluene, aliphatic ethers such as dioxane, tetrahydrofuran, and dimethoxyethane, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, and dimethylsulfoxide. Among them, in one embodiment, the reaction is preferably carried out in the presence of an aromatic hydrocarbon, and more preferably in the presence of toluene.

[0149] The reaction temperature is not particularly limited. For example, the reaction temperature may be in the range of 0 to 200° C. In one embodiment, the reaction temperature is preferably in the range of 80 to 180° C.

[0150] In the mixture of raw material monomers, the blending ratio of the aromatic compound having an amino group and the aromatic compound having a halogen atom is not particularly limited.However, if the unreacted raw material monomers remain in excess in the reaction system, undesirable side reactions may occur, so it is preferable to adjust the blending ratio appropriately.The blending ratio can be adjusted appropriately in consideration of the structure of the aromatic compound used as raw material monomer and the structure of the desired charge transport polymer.

[0151] In one embodiment, the following aromatic compounds can be suitably used as the raw material monomer. Thus, in one embodiment, the raw material monomer may be a mixture of a halogenated aromatic compound having one or more halogen atoms, including an aromatic compound represented by the following formula (A), and an arylamine, including an aromatic compound represented by the following formula (B). In the aromatic compound represented by the following formula (B), R 1 , a is as described above in the explanation of formula (b-1). That is, R 1 is an electron-withdrawing group, an electron-donating group, or an alkyl group having 1 to 12 carbon atoms; a is an integer of 1 to 5; R 1 At least one of R is an electron withdrawing group or an electron donating group. 1 is preferably an electron withdrawing group.

[0152] [ka]

[0153] In another embodiment, the mixture preferably further contains an aromatic compound represented by the following formula (C) as a halogenated aromatic compound having one or more halogen atoms. In the aromatic compound represented by the following formula (C), R 2 , b is as explained above in formula (c).

[0154] [ka]

[0155] In one embodiment, it is preferable to use an aromatic compound (A) represented by the above formula (A) and an aromatic compound (B) represented by the above formula (B) as the raw material monomers. The compounding ratio of the raw material monomers (A):(B) may be preferably 0.5 to 1.5:1.0, more preferably 0.6 to 1.4:1.0, as the ratio of the number of reaction points based on the amino group of the aromatic compound (B).

[0156] In one embodiment, it is preferable to use an aromatic compound (C) represented by the above formula (C) as the raw material monomer in addition to the aromatic compound (A) and aromatic compound (B). The compounding ratio of the raw material monomers (A):(B):(C) may be preferably 0.2-0.9:1.0:0.0-1.0, more preferably 0.3-0.7:1.0:0.1-0.9, and even more preferably 0.4-0.6:1.0:0.2-0.8, as the ratio of the number of reaction points based on the amino group of the aromatic compound (B).

[0157] In one embodiment, the charge transporting polymer may further include other structural units in addition to the structural units derived from the aromatic compounds (A), (B), and (C). For example, the charge transporting polymer may further include a divalent structural unit L2 having a structure different from the divalent structural unit L1 derived from the aromatic compound (B). The structural unit L2 may be introduced, for example, using a compound represented by the following formula: Q-L2―Q Ar 1 -NH-L2-NH-Ar 1 In the formula, Q represents a halogen atom and may be, for example, a chlorine atom, a bromine atom, or an iodine atom. L2 represents a divalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine. In one embodiment, L2 is preferably a divalent organic group derived from a triarylamine, and more preferably a divalent organic group derived from a triphenylamine. Ar 1 may be a monovalent organic group derived from an aromatic compound having 6 to 24 carbon atoms, and preferably has, for example, the structure represented by the above formula (b-1) explained above.

[0158] From the viewpoint of easily producing a preferred charge transporting polymer, it is preferable to use the aromatic compound (A), the aromatic compound (B), and the aromatic compound (C) as raw material monomers in the method for producing a charge transporting polymer, although this is not particularly limited. In one embodiment, the raw material monomer is preferably a mixture consisting of only the aromatic compound (A), the aromatic compound (B), and the aromatic compound (C). When such a mixture is used as the raw material monomer, -(NAr-Ph) is formed without forming a Ph-Ph bond in the molecule. n It becomes possible to easily form a polymer having a -(n is an integer of 2 or more) structure.

[0159] As shown above, -(NAr-Ph) nCharge transporting polymers having the structure of - can be easily synthesized according to the Buchwald-Hartwig reaction. On the other hand, impurities derived from the catalyst and raw monomers used in the reaction are likely to remain in the polymer obtained by the above reaction. Therefore, it is preferable to separate and purify the polymer after the above reaction. The separation and purification of the polymer can be performed by applying a method well known in the art. For example, a method can be applied in which water is added to the reaction solution after the coupling reaction and mixed, the mixture is separated into an organic phase and an aqueous phase, and the polymer is recovered from the organic phase.

[0160] In one embodiment, impurities derived from the catalyst and the like can be effectively removed by adding a heavy metal scavenger when the reaction solution and water are mixed. The heavy metal scavenger may be a compound capable of chelating and scavenging a heavy metal such as palladium used as a catalyst, or a compound capable of specifically binding to and adsorbing a heavy metal. For example, a dithiocarbamate can be used. In particular, an aqueous solution of an alkyldithiocarbamate having an alkyl group having 1 to 6 carbon atoms can be preferably used. In addition, the amount of impurities remaining in the polymer obtained by the above production method can be easily reduced by appropriately selecting an organic solvent used during separation and purification. For example, a water-soluble organic solvent such as methanol can be preferably used when the reaction solution and water are mixed.

[0161] When forming an organic electronic material containing a charge transporting polymer, the charge transporting polymer may contain impurities that are mixed in during the manufacturing process. However, since impurities are a cause of deterioration of the characteristics of an organic electronic element formed using an organic electronic material, it is desirable that the amount of impurities is as small as possible. In one embodiment, from the viewpoint of providing a charge transporting polymer that can be suitably used as an organic electronic material, the palladium content in the polymer is preferably 100 ppm or less, more preferably 80 ppm or less, and even more preferably 50 ppm or less. In addition, the content (total amount) of halogen atoms in the polymer is preferably 300 ppm or less, more preferably 100 ppm or less, and even more preferably 60 ppm or less. As described above, by performing separation and purification as necessary after the coupling reaction, a charge transporting polymer having a desired purity can be easily obtained.

[0162] The organic electronic material according to one embodiment of the present invention comprises at least one charge transporting polymer including the charge transporting polymer (I) having the structure (I). The content of the charge transporting polymer (I) in the organic electronic material may be preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the organic electronic material. When the content of the charge transporting polymer (I) is adjusted within the above range, excellent charge transportability can be easily obtained. In one embodiment, the content of the charge transporting polymer (I) may be 100% by mass.

[0163] In one embodiment, an additive such as a dopant may be added in order to improve the charge transportability of the organic electronic material. When an additive such as a dopant is used, the content of the charge transporting polymer based on the total mass of the organic electronic material may be 95% or less, or may be 90% or less by mass.

[0164] The content of the dopant is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the organic electronic material. On the other hand, from the viewpoint of maintaining good film formability, the content of the dopant is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the organic electronic material.

[0165] From the viewpoint of applying a wet process as a film formation method, the organic electronic material preferably further contains a solvent. The organic electronic material may be configured as an ink composition (polymer solution) containing a charge transporting polymer and a solvent. The solvent used may be capable of dissolving the charge transporting polymer. By using an ink composition in which a charge transporting polymer is dissolved in a solvent, an organic layer can be easily formed by a simple method such as a wet process.

[0166] (solvent) As the solvent, any solvent medium can be used, such as water, an organic solvent, or a mixture thereof. As the organic solvent, alcohols such as methanol, ethanol, isopropyl alcohol, etc.; alkanes such as pentane, hexane, octane, etc.; cyclic alkanes such as cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, diphenylmethane, etc.; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate, etc.; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methylphenyl ether, etc.; Examples of the solvent include aromatic ethers such as methoxytoluene, 4-methoxytoluene, 3-phenoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, and methylene chloride. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers, and more preferred are aromatic hydrocarbons.

[0167] The content of the solvent in the organic electronic material (ink composition) can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the charge transport polymer to the solvent is 0.1% by mass or more, more preferably such that the ratio is 0.2% by mass or more, and even more preferably such that the ratio is 0.5% by mass or more. The content of the solvent is preferably such that the ratio of the charge transport polymer to the solvent is 20% by mass or less, more preferably such that the ratio is 15% by mass or less, and even more preferably such that the ratio is 10% by mass or less.

[0168] In another embodiment, the organic electronic material may contain additives as optional components from the viewpoint of improving workability when forming an organic layer as an ink composition, further improving the function of the organic layer, etc. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reduction inhibitors, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, dispersants, surfactants, etc.

[0169] <Organic layer> One embodiment relates to an organic layer formed using the organic electronics material or the ink composition. The organic layer exhibits good charge transport properties. By using the ink composition, an organic layer can be formed well and easily by a coating method. Examples of the coating method include known methods such as spin coating; casting; immersion; plate-based printing methods such as letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reverse offset printing, screen printing, and gravure printing; and plateless printing methods such as inkjet printing. When the organic layer is formed by a coating method, the coating layer obtained after coating may be dried by heat treatment to remove the solvent.

[0170] The heat treatment can be carried out in an air atmosphere or an inert gas atmosphere. Examples of the inert gas include helium gas, argon gas, nitrogen gas, and mixtures thereof. The "inert gas atmosphere" is preferably an atmosphere 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.

[0171] The heat treatment can be carried out using a heater such as a hot plate, an oven, etc. To carry out the heat treatment in an inert gas atmosphere, for example, a hot plate is used in an inert gas atmosphere, or the inside of an oven is made to be under an inert gas atmosphere.

[0172] From the viewpoint of efficiently removing the solvent, the heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent. In addition, when the polymerization reaction of the charge transporting polymer is to proceed, the temperature at which the polymerization reaction proceeds efficiently is preferable. In one embodiment, the temperature of the heat treatment is preferably 140°C or higher, more preferably 180°C or higher, and even more preferably 190°C or higher. On the other hand, from the viewpoint of suppressing deterioration due to the heat treatment, the temperature is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 250°C or lower.

[0173] The thickness of the organic layer after drying is preferably 0.1 nm or more, more preferably 1 nm or more, and even more preferably 3 nm or more, from the viewpoint of improving the efficiency of charge transport, and is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less, from the viewpoint of reducing the electrical resistance.

[0174] <Organic electronics elements> One embodiment relates to an organic electronics element having at least one of the organic layers. Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, and an organic transistor. The organic electronics element preferably has a structure in which an organic layer is disposed between at least a pair of electrodes. The organic electronics element can be manufactured by a manufacturing method including forming an organic layer using the organic electronic material or the ink composition.

[0175] <Organic EL element> One embodiment relates to an organic EL device having at least one of the organic layers. The organic EL device usually includes a light-emitting layer, an anode, a cathode, and a substrate, and may include other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer, if necessary. Each layer may be formed by a deposition method or a coating method. The organic EL device preferably includes the organic layer as a light-emitting layer or other functional layer, more preferably as other functional layer, and further preferably as at least one of a hole injection layer and a hole transport layer.

[0176] Fig. 1 is a cross-sectional schematic diagram showing one embodiment of an organic EL element. The organic EL element in Fig. 1 has a multi-layer structure and includes a substrate 8, an anode 2, a hole injection layer 3, a hole transport layer 6, an emitting layer 1, an electron transport layer 7, an electron injection layer 5, and a cathode 4, in this order.

[0177] [Light-emitting layer] The light-emitting layer may be made of light-emitting materials such as low molecular weight compounds, polymers, and dendrimers. Polymers are preferred because they are highly soluble in solvents and suitable for coating methods. Light-emitting materials include fluorescent materials, phosphorescent materials, and thermally activated delayed fluorescent materials (TADF).

[0178] Examples of fluorescent materials include low molecular weight compounds such as perylene, coumarin, rubrene, quinacridone, stilbene, dyes for dye lasers, aluminum complexes, and derivatives thereof; polymers such as polyfluorene, polyphenylene, polyphenylenevinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, and derivatives thereof; and mixtures of these.

[0179] As the phosphorescent material, metal complexes containing metals such as Ir and Pt can be used. As an Ir complex, for example, FIr(pic) (iridium(III)bis[(4,6-difluorophenyl)-pyridinate-N,C], which emits blue light, can be used. 2 ]picolinate), which emits green light, Ir(ppy)3 (factris(2-phenylpyridine)iridium), which emits red light, and (btp)2Ir(acac) (bis[2-(2'-benzo[4,5-α]thienyl)pyridinato-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-phorphine platinum) which emits red light, etc.

[0180] When the light-emitting layer contains a phosphorescent material, it is preferable that the light-emitting layer further contains a host material in addition to the phosphorescent material. As the host material, a low molecular weight compound, a polymer, or a dendrimer can be used. As the low molecular weight compound, for example, CBP (4,4'-bis(9H-carbazol-9-yl)biphenyl), mCP (1,3-bis(9-carbazolyl)benzene), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), their derivatives, etc., and as the polymer, the organic electronic material, polyvinylcarbazole, polyphenylene, polyfluorene, their derivatives, etc. can be mentioned.

[0181] Examples of thermally activated delayed fluorescence materials 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), and CC2TA (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)), 4CzPN(3,4,5,6-tetra(9H-carbazol-9-yl)phthalonitrile), HAP-3TPA(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.

[0182] [Hole injection layer, hole transport layer] The organic layer is preferably 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 an ink composition containing an organic electronic material and a solvent.

[0183] When the organic EL element has the organic layer as a hole injection layer and further has a hole transport layer, a known material can be used for the hole transport layer. When the organic EL element has the organic layer as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. Both the hole injection layer and the hole transport layer may be the organic layer. Examples of known materials include aromatic amine compounds (e.g., aromatic diamines such as N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (α-NPD)), phthalocyanine compounds, and thiophene compounds (e.g., thiophene conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)).

[0184] When the hole transport layer is an organic layer with a changed solubility, it is possible to easily form a light emitting layer thereon by a wet process. In this case, the polymerization initiator may be contained in the organic layer that is the hole transport layer, or in the organic layer below the hole transport layer.

[0185] [Electron transport layer, electron injection layer] Examples of materials used for the electron transport layer and the electron injection layer include phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, condensed ring tetracarboxylic acid anhydrides such as naphthalene and perylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes, etc. The organic electronic materials described above can also be used.

[0186] [cathode] 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.

[0187] [anode] The anode material may be, for example, a metal (e.g., Au) or another material having electrical conductivity, such as an oxide (e.g., ITO: indium oxide / tin oxide) or a conductive polymer (e.g., polythiophene-polystyrene sulfonate mixture (PEDOT:PSS)).

[0188] [substrate] The substrate may be made of glass, plastic, etc. The substrate is preferably transparent and flexible. Quartz glass, resin film, etc. are preferably used.

[0189] The resin film is preferably a light-transmitting resin film, such as a film mainly composed of polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, or the like.

[0190] When a resin film is used, the resin film may be coated with an inorganic material such as silicon oxide or silicon nitride in order to suppress the transmission of water vapor, oxygen, and the like.

[0191] [Sealing] The organic EL element may be sealed in order to reduce the influence of the outside air and extend the life. Materials used for sealing include glass, epoxy resin, acrylic resin, plastic films such as polyethylene terephthalate and polyethylene naphthalate, and inorganic materials such as silicon oxide and silicon nitride, but are not limited thereto. The sealing method is also not particularly limited, and can be performed by a known method.

[0192] [Emission color] The color of the emitted light from the organic EL element is not particularly limited. A white organic EL element is preferable because it can be used in various lighting fixtures such as home lighting, car lighting, clocks, and liquid crystal backlights.

[0193] A method for forming a white organic EL element can be a method in which multiple luminescent materials are used to simultaneously emit multiple luminescent colors and mix the colors. The combination of multiple luminescent colors is not particularly limited, but includes a combination containing three luminescent maximum wavelengths of blue, green, and red, and a combination containing two luminescent maximum 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.

[0194] <Display elements, lighting devices, display devices> One embodiment relates to a display device including the organic EL element. For example, a color display device can be obtained by using organic EL elements as elements corresponding to each pixel of red, green, and blue (RGB). There are two methods for forming an image: a simple matrix type in which individual organic EL elements arranged on a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged in each element and driven.

[0195] One embodiment also relates to a lighting device including the organic EL element. Another embodiment also relates to a display device including the lighting device and a liquid crystal element as a display means. For example, the display device may be a display device using the lighting device as a backlight and a known liquid crystal element as a display means, i.e., a liquid crystal display device. EXAMPLES

[0196] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples and includes various embodiments.

[0197] <Synthesis of charge transporting polymer> The raw material monomers used in the following Examples and Comparative Examples are shown below.

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] Example 1 A reaction vessel equipped with a Dimroth condenser and a stirring function was prepared, and an oil bath was placed so that it could move forward and backward relative to the reaction vessel. The following components were added to the reaction vessel, whose atmosphere had been replaced with nitrogen, while nitrogen was injected, and a nitrogen gas supply device was connected to the tip of the Dimroth condenser to create a reaction environment in a nitrogen atmosphere. Starting monomers: Monomer A1 (1285 mg, 2.67 mmol), Monomer B2 (556 mg, 5.00 mmol), Monomer C1 (370 mg, 2.00 mmol) Organic solvent (toluene): Dehydrated toluene stored under nitrogen atmosphere, Fujifilm Wako Pure Chemical Industries, Ltd., 25.6 mL Base: sodium t-butoxide, manufactured by Tokyo Chemical Industry Co., Ltd., 1442 mg (3.0 equivalents based on the monomer B2 having an amino group) Catalyst: Xphos Pd G2 (chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl) [2-(2'-amino-1,1'-biphenyl)] palladium), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 20 mg (0.5 mol % based on the amount of monomer B2 having an amino group) Next, the reaction vessel was heated in an oil bath (bath temperature: 120° C.) to a temperature at which the organic solvent in the reaction vessel refluxed, and the reaction was carried out for 2 hours with stirring.

[0203] After the above reaction, the temperature of the reaction mixture in the reaction vessel was lowered to room temperature, and 10 mL of an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) adjusted to 0.1 mol / L was added and stirred. Methanol-water (9:1) was added to the resulting suspension to cause reprecipitation, and the resulting precipitate was suction filtered. Ethyl acetate was added to the obtained precipitate, and the mixture was stirred for 15 minutes while being heated to 60°C in an oil bath, and the precipitate was washed with ethyl acetate. The washed precipitate was then collected by suction filtration. The collected washed precipitate was washed once more with ethyl acetate in the same manner as above, and the remaining monomers and reactants soluble in ethyl acetate in the precipitate were removed. The precipitate washed with ethyl acetate was then dried under reduced pressure to obtain a polymer (light yellow powder).

[0204] Proton nuclear magnetic resonance of polymers ( 1 By measuring the H-NMR spectrum, it was confirmed that the polymer had a structure obtained by polycondensation of monomers A1, B1, and C1. The polymer yield was 55%, the weight average molecular weight (Mw) was 13,300, the number average molecular weight (Mn) was 7,300, and the molecular weight distribution Mw / Mn was 1.8.

[0205] In addition, 1 The H-NMR spectrum was measured using an AVANCE-600 NMR spectrometer manufactured by Bruker. The Mw and Mn were measured using a Prominence GPC system manufactured by Shimadzu Corporation. The Mw and Mn were measured by gel permeation chromatography (GPC) using a styrene gel column, calibrated with standard polystyrene at 40° C., and then tetrahydrofuran was used as the eluent. The measurement conditions were as follows. The same applies to the examples described below.

[0206] Liquid delivery pump: L-6050 Hitachi High-Technologies Corporation UV-Vis Detector: L-3000 Hitachi High-Technologies Corporation Column: Gelpack (registered trademark) GL-A160S / GL-A150S, Resonac Inc. Eluent: THF (for HPLC, no stabilizers) Wako Pure Chemical Industries, Ltd. Flow rate: 1ml / min Column temperature: room temperature Molecular weight standards: Standard polystyrene

[0207] (Examples 2 to 5) A polymer was prepared in the same manner as in Example 1, except that the raw material monomers, blend amounts, and catalysts were changed as shown in Table 1. Various measurements were carried out on the obtained polymer in the same manner as in Example 1. The results are shown in Table 1.

[0208] (Control Example 1) A polymer was prepared in the same manner as in Example 1, except that the raw material monomers, blend amounts, and catalysts were changed as shown in Table 1. Various measurements were carried out on the obtained polymer in the same manner as in Example 1. The results are shown in Table 1.

[0209] [Table 1]

[0210] <Evaluation of charge transport polymer> (Evaluation of HOMO levels) Ink compositions were prepared according to the method described below using each of the charge transporting polymers obtained in Examples 1 to 5 and Comparative Example 1. Furthermore, an organic layer was formed using the ink composition, and the HOMO level was evaluated. A polymer (50.0 mg) and the following ionic compound (1) (0.5 mg) were weighed out and placed in a 9 mL screw tube, and toluene (4949.5 mg) was added thereto to dissolve, thereby preparing an ink composition.

[0211] [ka]

[0212] The ink composition was then filtered using a PTFE filter (pore size 0.2 μm). The filtered ink composition was dropped onto a quartz substrate (length 22 mm × width 29 mm × thickness 0.7 mm) and formed into a film using a spin coater. The ink composition was then heated at 210° C. for 30 minutes in air to form an organic layer with a thickness of 30 nm on the quartz substrate.

[0213] The surface work function of the organic layer formed on the quartz substrate was measured in air using a photoelectron yield spectrometer (model AC-5) manufactured by Riken Keiki Co., Ltd. The HOMO levels determined from the surface work function values ​​are shown in Table 2.

[0214] [Table 2]

[0215] As shown in Table 2, the charge transporting polymers according to the present invention (Examples 1 to 5) have an electron-withdrawing group or an electron-donating group, which makes it possible to easily adjust the HOMO level of the charge transporting polymer (Comparative Example 1) that does not have these substituents. In particular, when the polymers have an electron-withdrawing group (Examples 1 to 3), it is found that a higher HOMO level can be easily obtained. When the HOMO level is made deeper, the difference in energy level between the charge transporting polymer and the adjacent hole transporting layer or light emitting layer becomes smaller, which is preferable from the viewpoint of low driving voltage and improved electrical conductivity. Therefore, by introducing an electron-withdrawing group or an electron-donating group into a specific position of the charge transporting polymer, it becomes easy to improve the properties such as electrical conductivity and driving voltage of the organic EL device. From the above, it can be seen that the present invention can provide an organic electronic material containing a charge transporting polymer that can easily form an organic layer that can improve properties such as electrical conductivity. [Explanation of symbols]

[0216] 1. Light-emitting layer 2 Anode 3. Hole injection layer 4 cathode 5 Electron injection layer 6. Hole transport layer 7 Electron transport layer 8 Substrate

Claims

1. An organic electronics material containing a charge-transporting polymer having a branched structure, comprising a trivalent structural unit represented by the following formula (a) and a divalent structural unit represented by the following formula (b), and having a structure represented by formula (I) formed by the direct bonding of at least one binding site in the trivalent structural unit and at least one binding site in the divalent structural unit, wherein the weight-average molecular weight is 2,000 to 500,000. 【Chemistry 1】 【Chemistry 2】 [In the formula, Ar １ Ar represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or from a triarylamine. ２ * represents a monovalent organic group derived from a C6-C30 aromatic hydrocarbon having an electron-withdrawing or electron-donating group, and * represents a bonding site with other structures.

2. The organic electronic material according to claim 1, wherein the structure represented by formula (I) includes a structure represented by the following formula (I-1) or the following formula (I-2). 【Transformation 3】 [In the formula, Ar １ Ar represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or from a triarylamine. ２ * represents a monovalent organic group derived from a C6-C30 aromatic hydrocarbon having an electron-withdrawing or electron-donating group, and * represents a bonding site with other structures.

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

4. In the above formula (I), Ar ２ The organic electronic material according to claim 1, wherein the structure is represented by the following formula (b-1). 【Chemistry 4】 [In the formula, R １ [where a is an electron-withdrawing group, an electron-donating group, or an alkyl group having 1 to 12 carbon atoms, with at least one being an electron-withdrawing group or an electron-donating group, and a is an integer from 1 to 5.]

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

6. The organic electronics material according to claim 1, wherein the charge-transporting polymer further comprises a monovalent structural unit represented by the following formula (c). 【Transformation 5】 [In the formula, R ２ is an alkyl group having 1 to 8 carbon atoms, and b is an integer of 1 to 5.]

7. The organic electronic material according to claim 1, further comprising a solvent.

8. An organic layer formed using the organic electronics material described in any one of claims 1 to 7.

9. An organic electronics element comprising an organic layer as described in claim 8.

10. An organic electroluminescent element comprising the organic layer described in claim 8.

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