WO2020067300A1

WO2020067300A1 - Organic electronic material and organic electronic element

Info

Publication number: WO2020067300A1
Application number: PCT/JP2019/037883
Authority: WO
Inventors: 和幸加茂; 伊織福島; 広貴佐久間; 石塚　健一; 智嗣杉岡; 涼本名; 児玉　俊輔; 知美内山
Original assignee: 日立化成株式会社
Priority date: 2018-09-28
Filing date: 2019-09-26
Publication date: 2020-04-02
Also published as: TW202026327A; JPWO2020067300A1; CN112771687A

Abstract

One embodiment of the present invention relates to an organic electronic material which contains a charge transport polymer, and which is configured such that: the charge transport polymer has a branched structure; the charge transport polymer has a weight average molecular weight of 20,000 or more; and if a solution that contains the charge transport polymer and toluene and has a concentration of the charge transport polymer of 10% by mass is prepared, the viscosity of the solution at room temperature is less than 3.0 mPa·s.

Description

Organic electronic materials and organic electronic devices

Embodiments of the present invention relate to an organic electronic material, a liquid composition, an organic layer, an organic electronic device, an organic electroluminescent device, a display device, a lighting device, a display device, and a method of manufacturing an organic electronic device.

Organic electronic devices are devices that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that can replace conventional silicon-based inorganic semiconductors. Have been. Examples of the organic electronic element include an organic electroluminescent element (organic EL element), an organic photoelectric conversion element, an organic transistor, and the like.

Organic EL devices are attracting attention, for example, as large-area solid-state light source applications that can replace incandescent lamps or gas-filled lamps. In addition, it is attracting attention as a leading self-luminous display replacing a liquid crystal display (LCD) in the field of a flat panel display (FPD), and its commercialization is progressing.

(4) The organic EL elements are roughly classified into two types, a low-molecular type organic EL element and a polymer type organic EL element, according to the organic material used. In the polymer type organic EL device, a polymer compound is used as an organic material, and in the low molecular weight organic EL device, a low molecular compound is used. On the other hand, a method of manufacturing an organic EL element includes a dry process in which film formation is mainly performed in a vacuum system, a wet process in which film formation is performed by plate printing such as letterpress printing, intaglio printing, and plateless printing such as inkjet printing. It is roughly divided into two. Since simple film formation is possible, a wet process is expected as an indispensable method for a large-screen organic EL display in the future.

For this reason, materials suitable for wet processes are being developed. For example, studies have been made to form a multilayer structure using a charge transporting compound having a polymerizable functional group (see Patent Document 1). .

JP 2006-279007 A

In the wet process, generally, a solution obtained by dissolving an organic material in a solvent is applied to form a coating layer, and then the organic layer is formed by drying the coating layer. Therefore, in order to form an organic layer having a sufficient thickness, it is preferable to use a high-concentration solution. However, in a solution containing a polymer compound, the viscosity tends to increase as the concentration increases. If the viscosity of the solution is high, it may be difficult to form an organic layer depending on the application method.

Accordingly, an object of the present invention is to provide an organic electronic material and a liquid composition that can form an organic layer having a sufficient thickness by a wet process. Another object of an embodiment of the present invention is to provide an organic layer which has a sufficient film thickness and can be easily formed by a wet process. Still another object of the embodiments of the present invention is to provide an organic electronic element, an organic EL element, a display element, a lighting device, and a display device having excellent characteristics.

The present invention includes various embodiments. An example of the embodiment will be described below. The present invention is not limited to the following embodiments.

One embodiment is an organic electronic material containing a charge transporting polymer, wherein the charge transporting polymer has a branched structure, and the weight average molecular weight of the charge transporting polymer is 20,000 or more; When a solution containing the charge-transporting polymer and toluene and the concentration of the charge-transporting polymer is 10% by mass is prepared, the viscosity of the solution at room temperature is less than 3.0 mPa · s. About the material.

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

Another embodiment relates to an organic layer formed using the organic electronic material or the liquid composition.

Another embodiment relates to an organic electronic device including the organic layer.

Another embodiment relates to an organic electroluminescence device including the organic layer.

Another embodiment relates to a display device including the organic electroluminescent element; a lighting device including the organic electroluminescent device; or a display device including the lighting device and a liquid crystal element as a display unit.

Still another embodiment relates to a method for manufacturing an organic electronic device, comprising forming an organic layer using the organic electronic material or the liquid composition.

According to the embodiment of the present invention, it is possible to provide an organic electronic material and a liquid composition capable of forming an organic layer having a sufficient thickness by a wet process. Further, according to the embodiment of the present invention, it is possible to provide an organic layer having a sufficient film thickness and which can be easily formed by a wet process. Furthermore, according to the embodiment of the present invention, it is possible to provide an organic electronic element, an organic EL element, a display element, a lighting device, and a display device having excellent characteristics.

FIG. 1 is a schematic sectional view showing an example of an organic EL device according to an embodiment of the present invention.

実施 An embodiment of the present invention will be described. The present invention is not limited to the following embodiments.

<Organic electronics materials>
An organic electronic material according to an embodiment of the present invention has a branched structure, a weight average molecular weight of 20,000 or more, and contains a charge transporting polymer satisfying the following.
When a solution containing the charge transporting polymer and toluene and having a charge transporting polymer concentration of 10% by mass is prepared, the viscosity of the solution at room temperature is less than 3.0 mPa · s.

[Charge transporting polymer]
The charge transporting polymer is a branched polymer and has a branched structure in the molecule. The structural unit constituting the charge transporting polymer includes at least a trivalent or higher valent structural unit B and a monovalent structural unit T, and may further include a divalent structural unit. The structural unit B is a structural unit forming a branch. The structural unit T is a structural unit constituting the terminal of the molecular chain. The structural unit L is preferably a structural unit having a charge transporting property.

The charge transporting polymer may include only one type of each structural unit, or may include a plurality of types. In the charge transporting polymer, each structural unit is bonded to each other at “one” to “three or more” bonding sites. Each structural unit will be described later.

(4) The weight average molecular weight of the charge transporting polymer is 20,000 or more. When the weight average molecular weight is 20,000 or more, an organic layer having excellent film forming properties, heat resistance, and stability can be formed. The weight average molecular weight is preferably 25,000 or more, more preferably 30,000 or more, and even more preferably 35,000 or more. On the other hand, the weight average molecular weight of the charge transporting polymer is preferably 1,000,000 or less, more preferably 700,000 or less, and still more preferably 400,000 or less. When it is 1,000,000 or less, good solubility in a solvent is maintained, and a liquid composition can be easily prepared. In particular, the weight average molecular weight of the charge transporting polymer is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. When it is 200,000 or less, an organic layer having a large thickness tends to be easily formed. The viscosity of the solution tends to increase as the weight average molecular weight of the charge transporting polymer increases, and the viscosity of the solution tends to decrease as the weight average molecular weight of the charge transporting polymer decreases.

数 The number average molecular weight of the charge transporting polymer is preferably 10,000 or more, more preferably 12,000 or more, and even more preferably 15,000 or more. When the number average molecular weight is 10,000 or more, an organic layer having excellent film forming properties, heat resistance, and stability can be formed. On the other hand, the number average molecular weight of the charge transporting polymer is preferably 500,000 or less, more preferably 100,000 or less. When it is 500,000 or less, good solubility in a solvent is maintained, and a liquid composition can be easily prepared. In particular, the number average molecular weight of the charge transporting polymer is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. When it is less than 50,000, an organic layer having a large thickness tends to be easily formed. The viscosity of the solution tends to increase as the number average molecular weight of the charge transporting polymer increases, and the viscosity of the solution tends to decrease as the number average molecular weight of the charge transporting polymer decreases.

The weight average molecular weight and the number average molecular weight can be measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

The GPC measurement conditions may be, for example, the following conditions.
Equipment: High-performance liquid chromatograph Prominence Shimadzu Corporation Liquid transfer pump (LC-20AD)
Deaeration unit (DGU-20A)
Autosampler (SIL-20AHT)
Column oven (CTO-20A)
PDA detector (SPD-M20A)
Differential refractive index detector (RID-20A)
Column: Gelpack (registered trademark)
GL-A160S (Production number: 686-1J27)
GL-A150S (Production number: 685-1J27) Hitachi Chemical Co., Ltd. Eluent: Tetrahydrofuran (THF) (for HPLC, containing stabilizer) Fujifilm Wako Pure Chemical Industries, Ltd. Flow rate: 1 mL / min
Column temperature: 40 ° C
Detection wavelength: 254 nm
Molecular weight standard substance: PStQuick A / B / C Tosoh Corporation

The charge transporting polymer is a polymer satisfying the following.
When a solution containing the charge transporting polymer and toluene and having a charge transporting polymer concentration of 10% by mass is prepared, the viscosity of the solution at room temperature is less than 3.0 mPa · s.

(4) The viscosity is measured at room temperature (25 ° C.). For the measurement of the viscosity, a solution whose temperature is adjusted to 25 ° C. is used. The concentration of the charge transporting polymer is a concentration based on the weight of the solution. For the measurement of the viscosity, for example, a measuring device utilizing a VROC technology (Viscometer / Rheometer-on-a-Chip (VROC (R)) technology) can be used. As an example of the measuring device, “microVISCO (registered trademark)” manufactured by RheoSense is mentioned. The measurement may be performed a plurality of times, and the average value of the measured values may be used as the viscosity value. Specifically, the solution for measurement can be prepared by the method described in Examples. Specifically, the viscosity of the solution can be measured by the method described in Examples.

場合 When the viscosity of the solution is less than 3.0 mPa · s, an organic layer having a sufficient film thickness can be easily formed using the charge transporting polymer. The viscosity of the solution is preferably less than 3.0 mPa · s, more preferably 2.8 mPa · s or less, and even more preferably 2.7 mPa · s or less. On the other hand, the lower limit of the viscosity is not particularly limited. As the viscosity is lower, an organic layer having a sufficient thickness tends to be easily formed. The viscosity of the solution is, for example, preferably 1.0 mPa · s or more, more preferably 1.5 mPa · s or more, and 2.0 mPa · s in consideration of workability in forming an organic layer. More preferably, it is the above.

粘度 The viscosity of the solution can be adjusted by changing the ratio of the structural units in the charge transporting polymer, the molecular weight of the charge transporting polymer, and the like.

If a charge transporting polymer having a viscosity of the toluene solution of less than 3.0 mPa · s is used, a high-concentration and low-viscosity liquid composition can be obtained. By applying a high-concentration and low-viscosity liquid composition to, for example, an inkjet method, an organic layer having a sufficient film thickness can be easily formed.

The charge transporting polymer is preferably a hole transporting polymer having the ability to transport holes. More preferably, the charge transporting polymer has at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure, and a phenoxazine structure. Including structural units. These structures can be substituted or unsubstituted. In addition, these structural units may be included as any of “monovalent” to “trivalent or more” structural units. That is, at least one of the structural unit B, the structural unit L, and the structural unit T is a substituted or unsubstituted, aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, aniline structure, and It is preferable to include a structural unit including at least one structure selected from the group consisting of phenoxazine structures. At least one of the structural unit B, the structural unit L, and the structural unit T is selected from the group consisting of a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, and a pyrrole structure. It is more preferable to include at least one structure selected from the group consisting of a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, and a pyrrole structure. It is more preferable to include a structural unit. The aromatic amine structure is preferably a structure selected from the group consisting of a diarylamine structure and a triarylamine structure, more preferably a triarylamine structure, and even more preferably a triphenylamine structure.

(Construction)
The charge transporting polymer is a branched polymer. According to the branched charge transporting polymer, an organic layer having a sufficient film thickness can be efficiently formed.

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

部分 Examples of the partial structure contained in the charge transporting polymer include the following. The charge transporting polymer is not limited to a polymer having the following partial structure. In the partial structure, “L” represents a structural unit L, “T” represents a structural unit T, and “B” represents a structural unit B. In the present specification, “*” represents a binding site to another structure. In the following partial structures, a plurality of Ls may be the same structural unit or different structural units. The same applies to T and B.

(Structural unit L)
The structural unit L is preferably a divalent structural unit having a charge transporting property. The structural unit L is not particularly limited as long as it contains an atomic group capable of transporting charges. For example, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, biphenylene structure, terphenylene structure, naphthalene structure, anthracene structure, tetracene structure, phenanthrene structure, dihydro Phenanthrene structure, pyridine structure, pyrazine structure, quinoline structure, isoquinoline structure, quinoxaline structure, acridine structure, diazaphenanthrene structure, furan structure, pyrrole structure, oxazole structure, oxadiazole structure, thiazole structure, thiadiazole structure, triazole structure, benzol A thiophene structure, a benzoxazole structure, a benzoxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, and one or a combination thereof It is selected from a structure including more species. The aromatic amine structure is preferably a structure selected from the group consisting of a diarylamine structure and a triarylamine structure, more preferably a triarylamine structure, and even more preferably a triphenylamine structure.

In one embodiment, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, benzene structure, pyrrole structure, aniline structure, from the viewpoint of obtaining excellent hole transporting properties. It is preferably selected from a phenoxazine structure and a structure containing one or more of these, and is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure. And more preferably selected from structures containing one or more of these, substituted or unsubstituted, aromatic amine structures, carbazole structures, thiophene structures, pyrrole structures, and one or more of these More preferably, it is selected from a structure containing two or more kinds, and a substituted or unsubstituted aromatic amine structure Carbazole structure, and it is particularly preferably selected from a structure comprising one or more of these. In another embodiment, the structural unit L is a substituted or unsubstituted fluorene structure, a benzene structure, a phenanthrene structure, a pyridine structure, a quinoline structure, and one or two of these, from the viewpoint of obtaining excellent electron transportability. Preferably, it is selected from a structure containing more than one species.

具体 Specific examples of the structural unit L include the following. The structural unit L is not limited to the following.

R represents a hydrogen atom or a substituent each independently. When R is a substituent, the substituents are preferably each independently —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , a halogen atom, And a group comprising a group containing a polymerizable functional group described below. R ¹ represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or heteroaryl group having 2 to 30 carbon atoms. R ² to R ⁸ each independently represent a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or a heteroaryl group having 2 to 30 carbon atoms. Alkyl, aryl, and heteroaryl groups can be substituted or unsubstituted. Examples of the substituent when the alkyl group, the aryl group, and the heteroaryl group further have a substituent include -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ^8, a halogen atom, and, include groups containing described later polymerizable functional groups, preferably -R ^1.
R is preferably a hydrogen atom, an alkyl group, an aryl group, an alkyl-substituted aryl group, a halogen atom, a halogen-substituted alkyl group, or the like.
Ar represents a divalent linking group each independently, for example, each independently represents an arylene group or a heteroarylene group. Ar is preferably an arylene group having 2 to 30 carbon atoms or a heteroarylene group, more preferably an arylene group having 2 to 30 carbon atoms, and further preferably a phenylene group.

The 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 heterocyclic compound. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocyclic compound.

As the aromatic hydrocarbon, a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more selected from a monocyclic ring and a condensed ring are bonded via a direct bond are exemplified. Examples of the aromatic heterocyclic compound include a single ring, a condensed ring, or a polycyclic ring in which two or more selected from a single ring and a condensed ring are bonded via a direct bond.

(Structural unit B)
When the charge transporting polymer has a branched structure, the structural unit B is a trivalent or higher valent structural unit constituting a branched portion. The structural unit B is preferably 6 or less, more preferably 5 or less, and still more preferably 4 or 3, from the viewpoint of improving the durability of the organic electronic element. The structural unit B is preferably a unit having a charge transporting property. For example, the structural unit B is a substituted or unsubstituted aromatic amine structure, a carbazole structure, a condensed polycyclic aromatic hydrocarbon structure, and one or two of these, from the viewpoint of improving the durability of the organic electronic element. It is selected from structures containing more than one species. The aromatic amine structure is preferably a structure selected from the group consisting of a diarylamine structure and a triarylamine structure, more preferably a triarylamine structure, and even more preferably a triphenylamine structure.

具体 Specific examples of the structural unit B include the following. The structural unit B is not limited to the following.

W represents a trivalent linking group, for example, an areentriyl group having 2 to 30 carbon atoms or a heteroarenetriyl group.
Ar represents a divalent linking group each independently, for example, each independently represents an arylene group or a heteroarylene group. Ar is preferably an arylene group having 2 to 30 carbon atoms or a heteroarylene group, more preferably an arylene group having 2 to 30 carbon atoms, and further preferably a phenylene group.
Y represents a direct bond or a divalent linking group, for example, a group having at least one hydrogen atom in R (excluding a group containing a polymerizable functional group) in the structural unit L, And a divalent group excluding one hydrogen atom.
Z represents any 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 R in the structural unit L.

Arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. The heteroarenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocyclic compound. The aromatic hydrocarbon and the aromatic heterocyclic compound are as described above.

(Structural unit T)
The structural unit T is a monovalent structural unit constituting the terminal 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. The structural unit T may have the same structure as the structural unit L. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without lowering the charge transportability, and is preferably a substituted or unsubstituted benzene. More preferably, it is a structure. In another embodiment, as described later, when the charge transporting polymer has a polymerizable functional group at a terminal portion, the structural unit T has a polymerizable structure (for example, a polymerizable functional group such as a pyrrol-yl group). ).

具体 Specific examples of the structural unit T include the following. The structural unit T is not limited to the following.

R is independently the same as R in the structural unit L. When the charge transporting polymer has a polymerizable functional group at the terminal, the structural unit T preferably includes a structural unit in which at least one of R in the above formula is a group containing a polymerizable functional group. In order to improve the solubility of the charge transporting polymer in the solvent, the structural unit T preferably includes a structural unit in which at least one of R in the above formula is an alkyl group or a fluoroalkyl group. Is preferred. The alkyl group is preferably a straight-chain alkyl group, more preferably a straight-chain alkyl group having 20 or less carbon atoms, and still more preferably a straight-chain alkyl group having 6 to 12 carbon atoms. The fluoroalkyl group is preferably a perfluoroalkyl group, more preferably a perfluoromethyl group or a perfluoroethyl group, and further preferably a perfluoromethyl group.

(Polymerizable functional group)
In one embodiment, the charge transporting polymer preferably has at least one polymerizable functional group from the viewpoint of curing by a polymerization reaction and changing the solubility in a solvent. “Polymerizable functional group” refers to a functional group capable of forming a bond with each other by applying heat, light, or the like.

As the polymerizable functional group, a substituted or unsubstituted group having a carbon-carbon multiple bond (for example, vinyl group, styryl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, A methacryloyl group, a methacryloyloxy group, a methacryloylamino group, a vinyloxy group, a vinylamino group, etc., a group having a small ring (for example, a cyclic alkyl group such as a cyclopropyl group, a benzocyclobutenyl group, a cyclobutyl group; an epoxy group ( Groups having a cyclic ether structure such as oxiranyl group), oxetane group (oxetanyl group); diketene group; episulfide group; lactone group; lactam group and the like); and heterocyclic groups (eg, furan-yl group, pyrrol-yl group, thiophene) -Yl group, silole-yl group) and the like.

置換 When these groups are substituted, the substituent is not particularly limited, and examples thereof include a linear, cyclic or branched alkyl group. The carbon number of the alkyl group is preferably 1 to 22, more preferably 1 to 10, and still more preferably 1 to 4.

As the polymerizable functional group, a substituted or unsubstituted group having a cyclic ether structure or a group having a carbon-carbon multiple bond is preferable, and a substituted or unsubstituted vinyl group, styryl group, acryloyl group, methacryloyl group, epoxy Groups or oxetane groups are more preferable, and a substituted or unsubstituted vinyl group or oxetane group is further preferable from the viewpoint of reactivity and characteristics of the organic electronic element.

From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the occurrence of the polymerization reaction, the skeleton structure of the charge transporting polymer and the polymerizable functional group are preferably formed of an alkylene chain (for example, a straight chain having 1 to 8 carbon atoms). And an alkylene chain). The solubility of the charge transporting polymer in a solvent tends to be improved by the alkylene chain. Further, for example, when an organic layer is formed on an electrode, from the viewpoint of improving affinity with a hydrophilic electrode such as ITO, the organic layer is bonded via a hydrophilic linking group such as an ethylene glycol chain or a diethylene glycol chain. You may. Further, from the viewpoint of facilitating the preparation of a monomer used for introducing a polymerizable functional group, one or more kinds selected from an ether bond, an ester bond, and the like are provided between the skeleton structure and the polymerizable functional group. May be included.

On the other hand, when a linking group such as an alkylene chain, an ethylene glycol chain, and a diethylene glycol chain is not included, the heat resistance of the organic layer tends to be improved.

Examples of the above-mentioned "group containing a polymerizable functional group" include "the polymerizable functional group" itself and "a group obtained by combining a polymerizable functional group with a linking group such as an alkylene chain or an ether bond". included. As the group containing a polymerizable functional group, for example, a group exemplified in WO 2010/140553 can be suitably used.

The polymerizable functional group may be introduced into the terminal (ie, the structural unit T) of the charge transporting polymer or may be introduced into a portion other than the terminal (ie, the structural unit B or L). And a part other than the terminal part. From the viewpoint of curability, it is preferably introduced at least at the terminal portion, and from the viewpoint of achieving both curability and charge transportability, it is preferably introduced only at the terminal portion. Further, the polymerizable functional group may be introduced into the main chain of the charge transporting polymer, into the side chain, or into both the main chain and the side chain.

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

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 facilitating multilayering. In addition, the number of polymerizable functional groups is preferably 1,000 or less, more preferably 500 or less, and still more preferably 300 or less, from the viewpoint of maintaining charge transportability.

The number of polymerizable functional groups per molecule of the charge transporting polymer is calculated based on the charged amount of the polymerizable functional group used for synthesizing the charge transporting polymer (for example, the charged amount of the monomer having the polymerizable functional group), and each structure. The average value can be determined using the charged amount of the monomer corresponding to the unit, the weight average molecular weight of the charge transporting polymer, and the like. The number of polymerizable functional groups is determined by the ratio of the integrated value of the signal derived from the polymerizable functional group in the ¹ H NMR (nuclear magnetic resonance) spectrum of the charge transporting polymer to the integrated value of the entire spectrum, the charge transporting polymer. Can be calculated as an average value using the weight average molecular weight and the like.

(Ratio of structural units)
From the viewpoint of suppressing the viscosity of the liquid composition and improving the durability of the organic electronic element, the proportion of the structural unit B contained in the charge transporting polymer is preferably 1 mol% or more based on all structural units. 5 mol% or more, more preferably 10 mol% or more. Further, the proportion of the structural unit B is preferably 17 mol% or less, more preferably 16 mol% or less, and preferably 15 mol% or less, from the viewpoint of suppressing the viscosity of the liquid composition to a low level and obtaining an organic layer having a sufficient film thickness. Is more preferred.

When the charge transporting polymer contains the structural unit L, the proportion of the structural unit L is preferably 10 mol% or more, more preferably 20 mol% or more based on all structural units, from the viewpoint of obtaining sufficient charge transportability. , 30 mol% or more is more preferable. Further, in consideration of the structural unit T and the structural unit B, the ratio of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

The ratio of the structural units T contained in the charge transporting polymer is based on all structural units, from the viewpoint of improving the characteristics of the organic electronic element, or suppressing the rise in viscosity and favorably synthesizing the charge transporting polymer. 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more. In addition, the proportion of the structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, and still more preferably 50 mol% or less, from the viewpoint of obtaining a sufficient charge transporting property.

For example, when the charge transporting polymer includes the structural unit L, the structural unit T, and the structural unit B, the ratio of the structural unit L, the structural unit T, and the structural unit B is L: T: B = (( 2x + 100) / 3): ((200-5x) / 3): x is preferably satisfied. x is a ratio (mol%) of the structural unit B based on all the structural units contained in the charge transporting polymer. x is preferably at least 1 mol%, more preferably at least 5 mol%, even more preferably at least 10 mol%. x is preferably 17 mol% or less, more preferably 16 mol% or less, and still more preferably 15 mol% or less. In general, it is considered that the larger the proportion of the structural unit B, the lower the viscosity of the solution. However, in order to make the above-mentioned viscosity less than 3.0 mPa · s, it is preferable that x is 17 mol% or less.

When the charge transporting polymer has a polymerizable functional group, the ratio of the polymerizable functional group is preferably 0.1 mol% or more based on all structural units from the viewpoint of efficiently curing the charge transporting polymer, 1 mol% or more is more preferable, and 3 mol% or more is further preferable. In addition, the proportion of the polymerizable functional group is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less, from the viewpoint of obtaining good charge transportability. Here, the “ratio of the polymerizable functional group” means the ratio of the structural unit having the polymerizable functional group.

In consideration of the balance between charge transportability, durability, productivity, and the like, the ratio (molar ratio) of the structural units L, T, and B is L: T: B = 100: 10 to 200: 10. 100 is preferable, 100: 20 to 180: 20 to 90 is more preferable, and 100: 40 to 160: 30 to 80 is further preferable.

The ratio of the structural units can be determined by using the charged amount of the monomer corresponding to each structural unit used for synthesizing the charge transporting polymer. Further, the ratio of the structural units can be calculated as an average value by using an integrated value of a spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge transporting polymer. For simplicity, when the charged amount is clear, preferably, a value obtained using the charged amount is used.

(Production method)
The charge transporting polymer can be produced by various synthetic methods and is not particularly limited. For example, a known coupling reaction such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Stille coupling, Buchwald-Hartwig coupling and the like can be used. Suzuki coupling causes a cross-coupling reaction using a Pd catalyst between an aromatic boronic acid derivative and an aromatic halide. According to the Suzuki coupling, a charge transporting polymer can be easily produced by bonding desired aromatic rings.

In the coupling reaction, for example, a Pd (0) compound, a Pd (II) compound, a Ni compound, or the like is used as a catalyst. Further, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like with a phosphine ligand can also be used. For the method of synthesizing the charge transporting polymer, for example, the description in WO 2010/140553 can be referred to.

[Dopant]
The organic electronic material may include any additives, for example, may further include a dopant. The dopant is not particularly limited as long as it is capable of exhibiting a doping effect and improving charge transportability by being added to the organic electronic material. There are two types of doping: p-type doping and n-type doping. In p-type doping, a substance that acts as an electron acceptor is used as a dopant, and in n-type doping, a substance that acts as an electron donor is used as a dopant. It is preferable to perform p-type doping for improving the hole transporting property and to perform n-type doping for improving the electron transporting property. The dopant used for the organic electronic material may be a dopant that exhibits either the p-type doping or the n-type doping effect. Further, one kind of dopant may be added alone, or a plurality of kinds of dopants may be mixed and added.

The dopant used for the p-type doping is an electron-accepting compound, and examples thereof include a Lewis acid, a proton acid, a transition metal compound, an ionic compound, a halogen compound, and a π-conjugated compound. Specifically, as the Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₃ , BBr ₃ or the like; As the protic acid, HF, HCl, HBr, HNO ₃ , H ₂ SO ₄ , Inorganic acids such as HClO ₄ , benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfonic acid, vinylphenylsulfonic acid , organic acids such as camphorsulfonic acid; the transition metal _{_{_{_{compound, FeOCl, TiCl 4, ZrCl 4}}}} , HfCl 4, NbF 5, AlCl 3, NbCl 5, TaCl 5, MoF 5; as ionic compounds include tetrakis (pentafluorophenyl Phenyl) borate ion, tris (trifluo) Methanesulfonyl) Mechidoion, bis (trifluoromethanesulfonyl) imide ion, hexafluoroantimonate ion, AsF ₆ ^- (hexafluoro arsenic acid ions), BF ₄ ^- (tetrafluoroborate), PF ₆ ^- (hexafluorophosphate) Such as salts having a perfluoroanion, such as a salt having a conjugate base of the above-mentioned protonic acid as an anion; and halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF, etc .; π-conjugated compounds Examples include TCNE (tetracyanoethylene) and TCNQ (tetracyanoquinodimethane). Known electron-accepting compounds other than those described above can also be used. Preferred are Lewis acids, ionic compounds, π-conjugated compounds and the like.

The dopant used for the n-type doping is an electron donating compound, for example, an alkali metal such as Li or Cs; an alkaline earth metal such as Mg or Ca; an alkali metal such as LiF or Cs ₂ CO ₃ and / or Alkaline earth metal salts; metal complexes; electron donating organic compounds, and the like.

When the charge transporting polymer has a polymerizable functional group, it is preferable to use a compound that can act as a polymerization initiator for the polymerizable functional group as a dopant in order to easily change the solubility due to curing of the organic layer.

[Other optional ingredients]
The organic electronic material may further contain a charge transporting low molecular compound, another polymer, and the like.

[Content]
The content of the charge transporting polymer in the organic electronic material is preferably 50% by mass or more, more preferably 70% by mass or more based on the total mass of the organic electronic material, from the viewpoint of obtaining good charge transportability. , 80% by mass or more is more preferable. The upper limit of the content of the charge transporting polymer is not particularly limited, and may be 100% by mass. In consideration of including additives such as dopants, the content of the charge transporting polymer may be set to, for example, 95% by mass or less or 90% by mass or less.

When a dopant is contained, the content is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more based on the total mass of the organic electronic material, from the viewpoint of improving the charge transportability of the organic electronic material. More preferably, the content is more preferably 0.5% by mass or more. In addition, from the viewpoint of maintaining good film formability, the amount is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on the total mass of the organic electronic material.

<Liquid composition>
A liquid composition according to an embodiment of the present invention contains the organic electronic material and a solvent. An organic layer can be easily formed by a simple method such as a coating method using a liquid composition containing a solvent. The liquid composition can be used as an ink composition.

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

[Polymerization initiator]
When the charge transporting polymer has a polymerizable functional group, the liquid composition preferably contains a polymerization initiator. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, and the like can be used. From the viewpoint of easily preparing a liquid composition, it is preferable to use a substance having both a function as a dopant and a function as a polymerization initiator. Such substances include, for example, the ionic compounds.

[Additive]
The liquid composition may further contain an additive as an optional component. Examples of the additives include a polymerization inhibitor, a stabilizer, a thickener, a gelling agent, a flame retardant, an antioxidant, a reduction inhibitor, an oxidizing agent, a reducing agent, a surface modifier, an emulsifier, an antifoaming agent, Dispersants, surfactants and the like can be mentioned.

[Content]
The content of the solvent in the liquid 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 transporting polymer to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Is more preferable. The content of the solvent is preferably such that the ratio of the charge transporting polymer to the solvent is 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. .

<Organic layer>
The organic layer according to the embodiment of the present invention is a layer formed using the organic electronic material or the liquid composition. The organic layer shows good charge transport properties. By using a liquid composition, an organic layer can be favorably and simply formed by a coating method. Examples of the coating method include a spin coating method; a casting method; an immersion method; a letterpress printing method such as letterpress printing, intaglio printing, offset printing, planographic printing, letterpress reverse offset printing, screen printing, gravure printing, and the like; A known method such as a plateless printing method may be used. When the organic layer is formed by a coating method, the coating layer obtained after the coating may be dried by a heat treatment to remove the solvent.

場合 When the charge transporting polymer has a polymerizable functional group, the polymerization reaction of the charge transporting polymer can be advanced by light irradiation, heat treatment, or the like, and the solubility of the coating layer can be changed. Heat treatment is preferred for simplicity. By laminating the organic layers obtained by changing the solubility of the coating layer, it is possible to easily achieve multilayering of the organic electronic element.

The heat treatment can be performed in an air atmosphere or an inert gas atmosphere. Examples of the inert gas include helium gas, argon gas, nitrogen gas, and a mixed gas 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 more preferably 99.99%. More preferably, the atmosphere is as described above.

The heat treatment can be performed using, for example, a heater such as a hot plate or an oven. In order to perform 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 set to an inert gas atmosphere.

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. When the polymerization reaction of the charge transporting polymer proceeds, a temperature at which the polymerization reaction efficiently proceeds is preferable. In one embodiment, the temperature of the heat treatment is preferably 140 ° C. or higher, more preferably 180 ° C. or higher, even more preferably 190 ° C. or higher. On the other hand, from the viewpoint of suppressing deterioration due to heat treatment, the temperature is preferably 300 ° C or lower, more preferably 280 ° C or lower, and further preferably 250 ° C or lower.

有機 The thickness of the organic layer after drying or after curing is preferably 0.1 nm or more, more preferably 1 nm or more, and still more preferably 3 nm or more, from the viewpoint of improving charge transport efficiency. The thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 100 nm or less, from the viewpoint of reducing electric resistance.

<Organic electronics device>
An organic electronic device according to an embodiment of the present invention has at least one of the organic layers. Examples of the organic electronic element include an organic EL element, an organic photoelectric conversion element, an organic transistor, and the like. The organic electronic element preferably has a structure in which an organic layer is disposed between at least a pair of electrodes. The organic electronic element can be manufactured by a manufacturing method including forming an organic layer using the organic electronic material or the liquid composition.

<Organic EL device>
An organic EL device according to an embodiment of the present invention has at least one organic layer. The organic EL device usually includes a light emitting layer, an anode, a cathode, and a substrate, and may further include, if necessary, other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. Have. Each layer may be formed by an evaporation method or a coating method. The organic EL device preferably has the organic layer as a light emitting layer or another functional layer, more preferably has the other functional layer, and still more preferably has at least one of a hole injection layer and a hole transport layer. Have.

FIG. 1 is a schematic cross-sectional view showing one embodiment of an organic EL device. The organic EL device shown in FIG. 1 is a device having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3, a hole transport layer 6, a light emitting layer 1, an electron transport layer 7, an electron injection layer 5, and a cathode 4. In this order.

[Light-emitting layer]
As a material used for the light emitting layer, a light emitting material such as a low molecular compound, a polymer, and a dendrimer can be used. Polymers are preferred because they have high solubility in solvents and are suitable for coating methods. Examples of the light emitting material include a fluorescent material, a phosphorescent material, and a thermally activated delayed fluorescent material (TADF).

As fluorescent materials, low molecular weight compounds such as perylene, coumarin, rubrene, quinacridone, stilbene, dyes for dye lasers, aluminum complexes and derivatives thereof; polyfluorene, polyphenylene, polyphenylenevinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer, Polymers such as fluorene-triphenylamine copolymers and derivatives thereof; and mixtures thereof.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. Examples of the Ir complex include FIr (pic) which emits blue light (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate) and Ir (ppy) _{3 which} emits green light. (Fact tris (2-phenylpyridine) iridium), emitting red light (btp) ₂ Ir (acac) (bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] Iridium (acetyl-acetonate)) and Ir (piq) ₃ (tris (1-phenylisoquinoline) iridium). Examples of the Pt complex include PtOEP (2,3,7,8,12,13,17,18-octaethyl-21H, 23H-formin platinum) that emits red light.

場合 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 compound, a polymer, or a dendrimer can be used. Examples of the low molecular weight compound include CBP (4,4′-bis (9H-carbazol-9-yl) biphenyl), mCP (1,3-bis (9-carbazolyl) benzene), and CDBP (4,4′- Examples of the polymer include bis (carbazol-9-yl) -2,2′-dimethylbiphenyl) and derivatives thereof. Examples of the polymer include the organic electronic materials, polyvinylcarbazole, polyphenylene, polyfluorene, and derivatives thereof.

Examples of the thermally activated delayed fluorescent material include PIC-TRZ (2-biphenyl-4,6-bis (12-phenylindolo [2,3-a] carbazol-11-yl) -1,3,5-triazine). , Spiro-CN (2 ', 7'-bis (di-P-tolylamino) -9,9'-spirobifluorene-s, 7-dicarbonitrile), CC2TA (2,4-bis {3- (9H-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)) And compounds such as 4CzIPN (1,2,3,5-tetrakis (carbazol-9-yl) -4,6-dicyanobenzene).

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

場合 When the organic EL device 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 device 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 layers. Known materials include, for example, aromatic amine compounds (eg, aromatic diamines such as N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine (α-NPD)), phthalocyanines And thiophene-based compounds (eg, poly (3,4-ethylenedioxythiophene): a thiophene-based conductive polymer such as poly (4-styrenesulfonate) (PEDOT: PSS)).

(4) When the hole transport layer is an organic layer whose solubility is changed by polymerization, the light emitting layer can be easily formed thereon by a wet process. In this case, the polymerization initiator may be contained in the organic layer which is the hole transport layer, or may be contained in the organic layer below the hole transport layer.

[Electron transport layer, electron injection layer]
Materials used for the electron transporting layer and the electron injecting layer include, for example, phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, naphthalene, condensed ring tetracarboxylic anhydrides such as perylene, carbodiimide Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes and the like. In addition, the organic electronic materials can also be used.

[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, and CsF is used.

[anode]
As the anode material, for example, a metal (for example, Au) or another material having conductivity is used. Other materials include, for example, oxides (eg, ITO: indium oxide / tin oxide) and conductive polymers (eg, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[substrate]
Glass, plastic, or the like can be used as the substrate. The substrate is preferably transparent and preferably has flexibility. Quartz glass, resin film and the like are preferably used.

光 As the resin film, a light-transmitting resin film is preferable. As the resin film, for example, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate and the like as a main component Film.

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

[Sealing]
The organic EL element may be sealed in order to reduce the influence of the outside air and extend the life. As a material used for sealing, glass, an epoxy resin, an acrylic resin, a plastic film such as polyethylene terephthalate or polyethylene naphthalate, or an inorganic substance such as silicon oxide or silicon nitride can be used, but is not limited thereto. There is no. The method of sealing is not particularly limited, and can be performed by a known method.

[Emission color]
The emission color of the organic EL element is not particularly limited. The white organic EL element is preferable because it can be used for various lighting devices such as home lighting, car lighting, a clock, and a liquid crystal backlight.

(4) As a method for forming a white organic EL element, a method in which a plurality of luminescent materials are simultaneously used to emit a plurality of luminescent colors to perform color mixing can be used. The combination of the plurality of emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, a combination containing two emission maximum wavelengths such as blue and yellow, yellow green and orange, and the like. Is mentioned. The emission color can be controlled by adjusting the type and amount of the emission material.

<Display element, lighting device, display device>
A display element according to an embodiment of the present invention includes the organic EL element. For example, a color display element can be obtained by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB). Image forming methods include a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which a thin film transistor is arranged and driven in each element.

The lighting device according to the embodiment of the present invention includes the organic EL element. Further, the display device according to the embodiment of the present invention includes a lighting device and a liquid crystal element as display means. For example, the display device can be a display device using the lighting device as a backlight and a known liquid crystal element as a display means, that is, a liquid crystal display device.

<Example of Embodiment>
Preferred examples of the embodiment of the present invention will be described below. Embodiments of the present invention are not limited to the following examples.

(1) An organic electronic material containing a charge transporting polymer,
The charge transporting polymer has a branched structure,
The charge transporting polymer has a weight average molecular weight of 20,000 or more,
When a solution containing the charge-transporting polymer and toluene and the concentration of the charge-transporting polymer is 10% by mass is prepared, the viscosity of the solution at room temperature is less than 3.0 mPa · s. material.

(2) The charge-transporting polymer according to (1), wherein the charge-transporting polymer contains a trivalent or higher-valent structural unit, and a content of the trivalent or higher-valent structural unit is 17 mol% or less based on all structural units. Organic electronics materials.

(3) The organic electronic material according to (2), wherein the charge transporting polymer further includes a divalent structural unit and a monovalent structural unit.

(4) The charge transporting polymer has at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure, and a phenoxazine structure. The organic electronic material according to any one of (1) to (3), including a structural unit including:

(5) The organic electronic material according to any one of (1) to (4), wherein the charge transporting polymer has at least one polymerizable functional group.

(6) The organic electronic material according to any of (1) to (5), wherein the charge transporting polymer is a hole transporting polymer.

(7) A liquid composition comprising the organic electronic material according to any one of (1) to (6) and a solvent.

(8) An organic layer formed using the organic electronic material according to any one of (1) to (6) or the liquid composition according to (7).

(9) An organic electronic device including the organic layer according to (8).

(10) An organic electroluminescence device including the organic layer according to (8).

(11) An organic electroluminescence device including the organic layer according to (8) as a hole injection layer or a hole transport layer.

(12) A display device including the organic electroluminescence device according to (10) or (11).

(13) A lighting device including the organic electroluminescent element according to (10) or (11).

(14) A display device including the lighting device according to (13) and a liquid crystal element as display means.

(15) Production of an organic electronic element, including forming an organic layer using the organic electronic material according to any one of (1) to (6) or the liquid composition according to (7). Method.

The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 2018-183978 filed on September 28, 2018, the entire disclosure of which is incorporated herein by reference.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.
<Preparation of charge transporting polymer>
[Preparation of Pd catalyst]
In a glove box under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature, toluene (15 mL) was added, and the mixture was stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, toluene (5 mL) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to obtain a catalyst solution (hereinafter, referred to as “Pd catalyst solution”). In preparing the Pd catalyst, all solvents were used after degassing with nitrogen bubbles for more than 30 minutes.

[Preparation of charge transporting polymer]
Charge transporting polymers 1 to 8 were prepared using the following monomers.

(Charge transporting polymer 1)
In a three-necked round bottom flask, 0.03 g of monomer A1 (3.0 mmol), monomer B1 (1.0 mmol), monomer C1 (3.0 mmol), methyltri-n-octylammonium chloride (Alliquat 336, manufactured by Alfa Aesar) ), Potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (15 mL), and the Pd catalyst solution (1.0 mL) was further added and mixed. The obtained mixture was heated under reflux for 2 hours. All the operations so far were performed under a nitrogen stream. All solvents were used after degassing with a nitrogen bubble for 30 minutes or more.

終了 After the completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The obtained precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was collected by suction filtration, dissolved in toluene, and a metal adsorbent ("Triphenylphosphine, polymer-bound styrene-divinylbenzene copolymer" manufactured by Strem Chemicals Co., 200 mg per 100 mg of the precipitate) was added thereto. Stirred at C for 2 hours. After completion of the stirring, the metal adsorbent and insolubles were removed by filtration, and then reprecipitation from methanol was performed. The resulting precipitate was collected by suction filtration and washed with methanol. The resulting precipitate was dried under vacuum to obtain a charge transporting polymer 1. The number average molecular weight of the charge transporting polymer 1 was 7,600, and the weight average molecular weight was 36,000.

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

(Charge transporting polymer 2)
In a three-necked round bottom flask, monomer A1 (3.0 mmol), monomer B1 (1.0 mmol), monomer C1 (1.5 mmol), monomer C2 (1.5 mmol), methyl tri-n-octyl ammonium chloride (Alfa Aesar, Inc.) Aliquot 336 ") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (17 mL), and a Pd catalyst solution (1.0 mL) was added and mixed. . Thereafter, the same operation as in the preparation of the charge transporting polymer 1 was performed to obtain a charge transporting polymer 2. The number average molecular weight of the charge transporting polymer 2 was 8,700, and the weight average molecular weight was 36,000.

(Charge transporting polymer 3)
In a three-necked round bottom flask, monomer A1 (3.0 mmol), monomer B1 (1.0 mmol), monomer C1 (1.5 mmol), monomer C3 (1.5 mmol), methyltri-n-octylammonium chloride (Alfa Aesar, Inc.) Aliquot 336 ") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (17 mL), and a Pd catalyst solution (1.0 mL) was added and mixed. . Thereafter, the same operation as that of the charge transporting polymer 1 was performed to obtain the charge transporting polymer 3. The number average molecular weight of the charge transporting polymer 3 was 12,200, and the weight average molecular weight was 40,000.

(Charge transporting polymer 4)
In a three-neck round bottom flask, 0.03 g of monomer A1 (3.0 mmol), monomer B1 (1.0 mmol), monomer C4 (3.0 mmol), methyltri-n-octylammonium chloride (Alliquat 336, manufactured by Alfa Aesar) ), Potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (17 mL), and a Pd catalyst solution (1.0 mL) was further added and mixed. Thereafter, the same operation as that of the charge transporting polymer 1 was performed to obtain the charge transporting polymer 4. The number average molecular weight of the charge transporting polymer 4 was 10,000 and the weight average molecular weight was 36,000.

(Charge transporting polymer 5)
In a three-necked round bottom flask, 0.03 g of monomer A1 (5.0 mmol), monomer B1 (2.0 mmol), monomer C1 (4.0 mmol), methyl tri-n-octyl ammonium chloride (Alliquot 336, manufactured by Alfa Aesar) ), Potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL), and a Pd catalyst solution (1.0 mL) was further added and mixed. Thereafter, the same operation as that of the charge transporting polymer 1 was performed to obtain a charge transporting polymer 5. The number average molecular weight of the charge transporting polymer 5 was 8,720 and the weight average molecular weight was 30,000.

(Charge transporting polymer 6)
In a three-necked round bottom flask, monomer A1 (5.0 mmol), monomer B1 (2.0 mmol), monomer C1 (2.0 mmol), monomer C2 (2.0 mmol), methyl tri-n-octyl ammonium chloride (Alfa Aesar, Inc.) Aliquot 336 ") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL), and a Pd catalyst solution (1.0 mL) was added and mixed. . Thereafter, the same operation as that of the charge transporting polymer 1 was performed to obtain the charge transporting polymer 6. The number average molecular weight of the charge transporting polymer 6 was 12,000, and the weight average molecular weight was 60,000.

(Charge transporting polymer 7)
In a three-necked round bottom flask, monomer A1 (5.0 mmol), monomer B1 (2.0 mmol), monomer C1 (2.0 mmol), monomer C3 (2.0 mmol), methyl tri-n-octyl ammonium chloride (Alfa Aesar, Inc.) Aliquot 336 ") (0.03 g), potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL), and a Pd catalyst solution (1.0 mL) was added and mixed. . Thereafter, the same operation as that of the charge transporting polymer 1 was performed to obtain the charge transporting polymer 7. The number average molecular weight of the charge transporting polymer 7 was 15,000, and the weight average molecular weight was 56,000.

(Charge transporting polymer 8)
In a three-neck round bottom flask, 0.03 g of monomer A1 (5.0 mmol), monomer B1 (2.0 mmol), monomer C4 (4.0 mmol), methyl tri-n-octyl ammonium chloride (Alliquat 336, manufactured by Alfa Aesar) ), Potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL), and a Pd catalyst solution (1.0 mL) was further added and mixed. Thereafter, the same operation as that of the charge transporting polymer 1 was performed to obtain a charge transporting polymer 8. The number average molecular weight of the charge transporting polymer 8 was 13,000, and the weight average molecular weight was 40,000.

[Measurement of viscosity]
A toluene solution was prepared using the charge transporting polymers 1 to 8, and the viscosity of the toluene solution was measured.

５０ 50 mg of each charge transporting polymer was weighed into a sample tube, and 520 μL of toluene was added. Then, the mixture was left at room temperature (25 ° C.) for 5 hours to dissolve the charge transporting polymer in toluene to obtain a solution for evaluation. The viscosity of the evaluation solution was measured using “microVISCO (registered trademark)” manufactured by RheoSense. The measurement was performed five times, and the average value of the five measured values was determined to be the viscosity of the evaluation solution. The viscosities are shown in Table 1.

By using an organic electronic material containing a charge-transporting polymer in which the viscosity of a 10% by mass toluene solution satisfies less than 3.0 mPa · s, a high-concentration and low-viscosity ink composition can be produced. When a high-concentration and low-viscosity ink composition is used, an organic layer having a large thickness can be easily obtained.

<Solubility evaluation of charge transporting polymer (organic electronics material)>
The solubility of the charge transporting polymers 1 to 8 in the solvent was evaluated.
10 mg of each charge transporting polymer was weighed into a sample tube (6 mL, manufactured by AS ONE Corporation). Thereafter, a stirrer was put in, 1,145 μL of toluene (25 ° C.) was added at room temperature (25 ° C.), and the mixture was stirred with a stirrer (revolution: 600 min ⁻¹ ). The dissolution time was visually observed, and the time (dissolution time) required immediately after the addition of toluene until the polymer mixture became transparent was measured. The solubility of the charge transporting polymer was evaluated according to the following criteria. Table 2 shows the dissolution time and the evaluation results.
A: Dissolution time is less than 5 minutes B: Dissolution time is more than 5 minutes

とおり As shown in Table 2, the charge transporting polymers 1 to 4 had a short dissolution time. It can be seen that the organic electronic material containing the charge transporting polymer that satisfies the viscosity of the 10% by mass toluene solution less than 3.0 mPa · s shows high solubility.

<Preparation and evaluation of organic EL element>
[Production of organic EL element]
(Organic EL element 1)
The charge transporting polymer 1 (10.0 mg) was dissolved in toluene (2,200 μL) to obtain a polymer solution. Further, the following onium salt (0.1 mg) was dissolved in toluene (100 μL) to obtain an onium salt solution. The obtained polymer solution and the onium salt solution were mixed to prepare an ink composition containing the charge transporting polymer 1. The ink composition was spin-coated at 3,000 min ^-1 on a glass substrate on which ITO was patterned to a width of 1.6 mm under air, and then heated on a hot plate at 200 ° C. for 30 minutes to form a hole injection layer ( 20 nm).

Thereafter, the glass substrate was transferred into a vacuum evaporation machine, and NPD (40 nm), CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), and Alq ₃ (30 nm) were placed on the hole injection layer. , LiF (0.8 nm), and Al (100 nm) in this order by a vapor deposition method, and a sealing treatment was performed to produce an organic EL device.

(Organic EL elements 2 to 8)
Organic EL devices 2 to 8 were produced in the same manner as in the organic EL device 1 except that the charge transporting polymer 1 was changed to the charge transporting polymers 2 to 8.

[Evaluation of organic EL element]
When voltage was applied to the organic EL device obtained above, green light emission was confirmed. For each element, emission luminance 1,000 cd / ^{m 2} at the drive voltage and luminous efficiency, as well as to measure the light emission life at an initial luminance 5,000 cd / ^{m 2} (luminance half-life). Table 3 shows the measurement results.

とおり As shown in Table 3, the organic EL devices prepared using the charge transporting polymers 1 to 8 exhibited the same driving voltage, luminous efficiency, and luminous life.

According to the above description, by using an organic electronic material containing a charge transporting polymer in which the viscosity of a 10% by mass toluene solution satisfying less than 3.0 mPa · s, an organic layer having a sufficient film thickness can be formed. Can be formed without affecting the characteristics of

Reference Signs List 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

An organic electronic material containing a charge transporting polymer,
The charge transporting polymer has a branched structure,
The charge transporting polymer has a weight average molecular weight of 20,000 or more,
When a solution containing the charge-transporting polymer and toluene and the concentration of the charge-transporting polymer is 10% by mass is prepared, the viscosity of the solution at room temperature is less than 3.0 mPa · s. material.
2. The organic electronic material according to claim 1, wherein the charge transporting polymer includes a trivalent or higher valent structural unit, and a content of the trivalent or higher valent structural unit is 17 mol% or less based on all structural units.
The organic electronic material according to claim 2, wherein the charge transporting polymer further includes a divalent structural unit and a monovalent structural unit.
A structural unit in which the charge-transporting polymer includes at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, an aniline structure, and a phenoxazine structure. The organic electronic material according to any one of claims 1 to 3, comprising:
(5) The organic electronic material according to any one of (1) to (4), wherein the charge transporting polymer has at least one polymerizable functional group.
(6) The organic electronic material according to any one of (1) to (5), wherein the charge transporting polymer is a hole transporting polymer.
(4) A liquid composition comprising the organic electronic material according to any one of (1) to (6) and a solvent.
(4) An organic layer formed using the organic electronic material according to any one of (1) to (6) or the liquid composition according to (7).
An organic electronic device comprising the organic layer according to claim 8.
An organic electroluminescence device comprising the organic layer according to claim 8.
An organic electroluminescence device comprising the organic layer according to claim 8 as a hole injection layer or a hole transport layer.
A display device comprising the organic electroluminescence device according to claim 10 or 11.
A lighting device comprising the organic electroluminescent element according to claim 10.
A display device, comprising: the lighting device according to claim 13; and a liquid crystal element as a display unit.
A method for producing an organic electronic device, comprising forming an organic layer using the organic electronic material according to any one of claims 1 to 6 or the liquid composition according to claim 7.