JP2018181872A - Charge transport material, ink composition, and organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge transport material and an ink composition that allow production of a light-scattering organic layer.SOLUTION: The charge transport material contains a polymer having a structural unit having a hole transport property, and an ionic compound represented by the general formula (1) in the figure, where the polymer has a nonpolar moiety at an end thereof.SELECTED DRAWING: None

Description

  Embodiments of the present invention include charge transport materials, ink compositions, organic layers, organic electronic devices, organic electroluminescent devices (hereinafter, also referred to as organic EL devices), display devices, lighting devices, display devices, and The present invention relates to a method of producing an organic layer.

  Organic electronics elements are elements that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, flexibility, etc., and are noted as a technology to replace conventional inorganic semiconductors based mainly on silicon It is done.

  Examples of the organic electronic element include an organic EL element, an organic photoelectric conversion element, an organic transistor and the like.

  Among organic electronic devices, organic EL devices are attracting attention as large-area solid state light source applications, for example, as an alternative to incandescent lamps and gas-filled lamps. In addition, it is attracting attention as a leading self-luminous display to replace liquid crystal displays (LCDs) in the flat panel display (FPD) field, and its commercialization is in progress.

  Organic EL elements are roughly classified into low molecular weight organic EL elements and high molecular weight organic EL elements from the organic materials used. In a high molecular weight organic EL device, a high molecular weight material is used as an organic material, and in a low molecular weight organic EL device, a low molecular weight material is used (for example, Patent Document 1). High-molecular-weight organic EL elements can be easily formed by wet processes such as plate-less printing and plate-less printing such as inkjet printing, compared to low-molecular-weight organic EL elements in which film formation is mainly performed in a vacuum system. Because of that, it is expected as an indispensable element in future large screen organic EL display.

JP 2004-296429 A

  Since the organic EL device generally has a high refractive index of the organic layer including the light emitting layer and the transparent electrode, the amount of light extracted into the air remains at a part of the total light emission. Therefore, improvement of light extraction efficiency is required. As a method for improving the light extraction efficiency, it has been proposed to provide a region that causes disturbance in light reflection and scattering angle (for example, Patent Document 1).

  The embodiment of the present invention has been made in view of the above, and its object is to provide a charge transporting material and an ink composition which can produce an organic layer having light scattering properties. Another object of the present invention is to provide an organic layer having light scattering properties. Another object of the present invention is to provide an organic electronic device, an organic EL device, a display device, a lighting device and a display device provided with an organic layer having a light scattering property. Another object of the present invention is to provide a simple method for producing an organic layer having light scattering properties.

  As a result of intensive studies, the present inventors have found that an organic layer having a light scattering property can be produced by a charge transporting material containing a polymer having an end at a nonpolar site and an ionic compound. It came to complete.

［一般式（１）中、
Ｒ^ａ〜Ｒ^ｃは、それぞれ独立に、水素原子（Ｈ）、アルキル基、アルコキシアルキル基、アリールアルキル基、アリール基、又はヘテロアリール基を表し、Ｒ^ａ〜Ｒ^ｃから選ばれる少なくとも２つの基は、互いに連結して環を形成してもよい。ただし、Ｒ^ａ〜Ｒ^ｃの少なくとも１つは水素原子（Ｈ）、アルキル基、アルコキシアルキル基、及びアリールアルキル基からなる群から選択される。
Ａは、下記一般式（１Ａ）〜（５Ａ）のいずれかで表されるアニオンを表す。

（一般式（１Ａ）〜（５Ａ）中、
Ｙ^１〜Ｙ^６は、それぞれ独立に、単結合又は二価の連結基を表し、
Ｒ^１〜Ｒ^１６は、それぞれ独立に、電子求引性の１価の基を表す。Ｒ^２及びＲ^３、Ｒ^４〜Ｒ^６から選ばれる少なくとも２つの基、Ｒ^７〜Ｒ^１０から選ばれる少なくとも２つの基、及びＲ^１１〜Ｒ^１６から選ばれる少なくとも２つの基は、それぞれ、互いに結合して環を形成してもよい。
Ｅ^１は酸素原子、Ｅ^２は窒素原子、Ｅ^３は炭素原子、Ｅ^４はホウ素原子又はガリウム原子、Ｅ^５はリン原子又はアンチモン原子を表す。）］ One embodiment of the present invention includes a polymer having a structural unit having a hole transportability and having a nonpolar site at the end, and an ionic compound represented by the following general formula (1), and a charge It relates to transportable materials.

[In general formula (1),
R ^{a to} R ^c each independently represent a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, an arylalkyl group, an aryl group or a heteroaryl group, and at least two groups selected from R ^{a to} R ^c And may be linked to each other to form a ring. However, at least one of R ^{a to} R ^c is selected from the group consisting of a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, and an arylalkyl group.
A represents an anion represented by any of the following general formulas (1A) to (5A).

(In the general formulas (1A) to (5A),
Y ^{1 to} Y ⁶ each independently represent a single bond or a divalent linking group,
Each of R ^{1 to} R ¹⁶ independently represents an electron-withdrawing monovalent group. At least two groups selected from R ² and R ³ , R ^{4 to} R ⁶ , at least two groups selected from R ^{7 to} R ¹⁰ , and at least two groups selected from R ^{11 to} R ¹⁶ respectively are each other It may combine to form a ring.
E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom. )]

  In a preferred embodiment, the polymer has a branched structure.

  In a preferred embodiment, the structural unit having a hole transportability comprises at least one selected from the group consisting of an aromatic amine structure and a carbazole structure.

  In a preferred embodiment, the nonpolar moiety is selected from the group consisting of a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group.

  Another embodiment of the present invention relates to an ink composition containing the charge transporting material and a solvent.

  Another embodiment of the present invention relates to an organic layer formed using the charge transporting material or the ink composition.

  Another embodiment of the present invention relates to an organic electronic device comprising at least the organic layer.

  Another embodiment of the present invention relates to an organic electroluminescent device comprising at least the organic layer.

  In a preferred embodiment, the organic electroluminescent device further comprises a flexible substrate.

  In a preferred embodiment, the organic electroluminescent device further comprises a resin film substrate.

  Another embodiment of the present invention relates to a display device comprising the organic electroluminescent device.

  Another embodiment of the present invention relates to a lighting device comprising the organic electroluminescent element.

  Another embodiment of the present invention relates to a display device including the lighting device and a liquid crystal element as a display unit.

  Another embodiment of the present invention is a method of producing an organic layer, comprising the steps of applying the ink composition, and irradiating the applied ink composition with light or heating the applied ink composition. About.

  According to the embodiments of the present invention, it is possible to provide a charge transporting material and an ink composition capable of producing an organic layer having light scattering properties. According to another embodiment of the present invention, an organic layer having light scattering can be provided. According to another embodiment of the present invention, it is possible to provide an organic electronic device, an organic EL device, a display device, a lighting device, and a display device provided with an organic layer having a light scattering property. According to another embodiment of the present invention, a simple method of producing an organic layer having light scattering properties can be provided.

It is a cross-sectional schematic diagram which shows an example of the organic EL element which is embodiment of this invention.

Embodiments of the present invention will be described below. Embodiments of the present invention are not limited to the following.
<Charge transporting material>
A charge transporting material according to an embodiment of the present invention has a structural unit having a hole transporting property, and has a polymer having a nonpolar site at the end, and an ionic compound represented by the general formula (1) And. Hereinafter, the polymer which has a structural unit which has a hole transportability, and has a nonpolar site at the end may only be called "hole transportable polymer." Moreover, the ionic compound represented by General formula (1) may only be called an "ionic compound."

[Hole transportable polymer]
The hole transporting polymer has a structural unit having a hole transporting property. The hole transporting polymer has a nonpolar site at the end of the polymer chain.

Examples of the "nonpolar moiety" include monovalent nonpolar groups. The nonpolar moiety is preferably a monovalent hydrocarbon group, and examples thereof include a monovalent nonaromatic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a monovalent group formed by combining these. . Examples of non-aromatic hydrocarbon groups include saturated hydrocarbon groups and unsaturated hydrocarbon groups. The saturated hydrocarbon group may be linear, branched or cyclic. The unsaturated hydrocarbon group may be linear, branched or cyclic. Specific examples of the monovalent nonpolar group include an alkyl group, an alkenyl group, an aryl substituted alkyl group, an aryl substituted alkenyl group, an aryl group, an alkyl substituted aryl group, an alkenyl substituted aryl group and the like. The "alkyl" and "alkenyl" in the above specific examples may be linear, branched or cyclic. It is preferably a linear, branched or cyclic alkyl group, and a linear, branched or cyclic alkenyl group, more preferably a linear or branched alkyl group, and a linear or branched alkenyl group.
The carbon number of the nonaromatic hydrocarbon group is preferably 1 to 22, more preferably 2 to 12, and still more preferably 3 to 10. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 18.

  The hole transportable polymer has “a structural unit having a hole transportability”. The hole transporting polymer may be linear or may have a branched structure. The hole transporting polymer preferably includes at least a divalent structural unit D having a hole transporting property and a monovalent structural unit M constituting an end of a polymer chain, and a trivalent or higher constituting a branch. The structural unit T may be further included. That is, according to one embodiment, the hole transporting polymer has at least the structural unit D as the “structural unit having a hole transporting property”, and further, the structural unit M and / or the structural unit T is a hole. It may be a structural unit having transportability. The hole transportable polymer may contain only one type of each structural unit, or may contain a plurality of types of each structural unit. In the hole transporting polymer, the structural units are bonded to each other at the “monovalent” to “trivalent or higher” bonding sites.

  The structural unit having a hole transportability preferably contains at least one selected from the group consisting of an aromatic amine structure and a carbazole structure. More preferably, the hole transporting polymer is selected from the group consisting of a structural unit D comprising at least one selected from the group consisting of an aromatic amine structure and a carbazole structure, and / or an aromatic amine structure and a carbazole structure Structural unit T containing at least one of the The aromatic amine structure may be a substituted or unsubstituted aromatic amine structure, and the carbazole structure may be a substituted or unsubstituted carbazole structure. The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.

  As a form which a hole transportable polymer has a nonpolar site at the end, a form where a hole transportable polymer has structural unit M which has a nonpolar site is mentioned ("structural unit M having a nonpolar site" Sometimes referred to as “structural unit M1”. Therefore, the structural unit M at least includes the structural unit M1. The structural unit M may include a structural unit having no nonpolar site ("structural unit having no nonpolar site" may be referred to as "structural unit M2"). The structural unit M1 preferably does not have a polar site from the viewpoint of improving the light scattering property of the organic layer. A monovalent polar group is mentioned as an example of a "polar site." The monovalent polar group is, for example, a group containing a hetero atom such as an oxygen atom or a nitrogen atom.

(Construction)
The following is mentioned as an example of the partial structure contained in a hole transportable polymer. The hole transporting polymer is not limited to one having the following partial structure. In the partial structure, “D” represents a structural unit D, “M” represents a structural unit M, and “T” represents a structural unit T. In the following partial structures, a plurality of D may be identical structural units to one another or structural units different from one another. The same applies to M and T. As used herein, "*" represents a binding site to another structure.

Linear hole transporting polymer

Hole transporting polymer having branched structure

(Structural unit D)
The structural unit D is preferably a divalent structural unit having hole transportability. The divalent structural unit D having a hole transporting property may contain an atomic group having the ability to transport a hole, and is not particularly limited. For example, the structural unit D may be 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, benzo Thiophene structure, benzoxazole structure, benzoxadiazole structure, benzothiazole structure, benzothiadiazole structure, benzotriazole structure, and one of these or It is selected from a structure including more species. The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.

  In one embodiment, the structural unit D is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, or one of them, from the viewpoint of obtaining excellent hole transportability. Or preferably selected from structures containing two or more, more preferably selected from substituted or unsubstituted aromatic amine structures, carbazole structures, and structures containing one or more of them . In another embodiment, the structural unit D is a substituted or unsubstituted fluorene structure, a benzene structure, a phenanthrene structure, a pyridine structure, a quinoline structure, and one or two of them from the viewpoint of obtaining excellent electron transportability. It is preferable to select from the structure containing a species or more.

  Here, as the “substituent” in the case of “substituted or unsubstituted”, monovalent nonpolar groups and monovalent polar groups can be mentioned. The monovalent nonpolar group and the monovalent polar group are as described above. From the viewpoint of improving the light scattering properties of the organic layer, the “substituent” contained in the structural unit D is preferably a monovalent nonpolar group. In one embodiment, from the viewpoint of further improving the light scattering property of the organic layer, the structural unit D may not contain a monovalent polar group. Specific examples of the “substituent” include substituents in R described later.

  As specific examples of the structural unit D, the following may be mentioned. Structural unit D is not limited to the following.

Each R independently represents a hydrogen atom or a substituent. The substituent includes a monovalent nonpolar group and a monovalent polar group. The monovalent nonpolar group and the monovalent polar group are as described above. Specific examples of the substituted groups, -R ^1, (except where a hydrogen ^{atom.) - OR 2, -SR 3} , -OCOR 4, -COOR 5, -SiR 6 R 7 R 8, a halogen atom And, the group containing the below-mentioned polymerizable functional group is mentioned. Each of R ^{1 to} R ⁸ independently represents a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms; or an aryl or heteroaryl group having 2 to 30 carbon atoms. The alkyl group may be further substituted by an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group is further preferably a linear, branched or cyclic group having 1 to 22 carbon atoms. It may be substituted by an alkyl group. R is preferably a hydrogen atom, an alkyl group, an aryl group or an alkyl-substituted aryl group.
Ar represents an arylene group or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group.

  The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. Aromatic hydrocarbons include those having a fused ring. In addition, aromatic hydrocarbons include those in which two or more selected from independent single rings and condensed rings are directly bonded (single bond) or via a group such as vinylene. The heteroaryl group is an atomic group obtained by removing one hydrogen atom from a heteroaromatic ring having a hetero atom. The heteroarylene group is an atomic group obtained by removing 2 hydrogen atoms from an aromatic heterocycle having a hetero atom. The aromatic heterocycle includes those having a fused ring. Further, the aromatic heterocyclic ring includes one in which two or more members selected from independent single rings and fused rings are directly or linked via a group such as vinylene.

(Structural unit T)
The structural unit T is a trivalent or higher structural unit constituting a branched portion when the hole transporting polymer has a branched structure. The structural unit T is preferably hexavalent or less, more preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic device. The structural unit T is preferably a unit having a hole transportability. For example, the structural unit T may be a substituted or non-substituted triphenylamine structure, a carbazole structure, a fused polycyclic aromatic hydrocarbon structure, and one or two of them, from the viewpoint of improving the durability of the organic electronic device. It is selected from the structure including the species or more.

  As specific examples of the structural unit T, the following may be mentioned. Structural unit T is not limited to the following.

W represents a trivalent linking group, and represents, for example, an arenetriyl group having 2 to 30 carbon atoms or a heteroarenetriyl group. An arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. The heteroarene triyl group is an atomic group obtained by removing 3 hydrogen atoms from an aromatic heterocycle.
Ar each independently represents a divalent linking group, and each independently represents, for example, an arylene group or 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, for example, from R in the structural unit D (with the exception of the group containing a polymerizable functional group), a group having one or more hydrogen atoms, and one more hydrogen atom And divalent groups other than.
Z represents either a carbon atom, a silicon atom, or a phosphorus atom.
In the structural unit, the benzene ring and Ar may have a substituent, and examples of the substituent include a monovalent nonpolar group and a monovalent polar group. The monovalent nonpolar group and the monovalent polar group are as described above. As a specific example, R in the structural unit D can be mentioned.

(Structural unit M)
The structural unit M is a monovalent structural unit that constitutes an end of the hole transporting polymer. At least a part of the structural unit M is a structural unit M1 having a nonpolar site. The structural unit M is selected from, for example, a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure, and a structure containing one or more of them. In one embodiment, the structural unit M is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without reducing charge transportability, and is preferably a substituted or unsubstituted benzene It is more preferable that it is a structure or a substituted or unsubstituted fused polycyclic aromatic hydrocarbon structure, and it is still more preferable that it is a substituted or unsubstituted benzene structure. The number of benzene rings contained in the fused polycyclic aromatic hydrocarbon structure is preferably 2 to 10, more preferably 2 to 8, and still more preferably 3 to 5. For example, naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, triphenylene structure, perylene structure and the like can be mentioned.

  As specific examples of the structural unit M, the following may be mentioned. The structural unit M is not limited to the following.

Ar is an aromatic hydrocarbon structure, an aromatic heterocyclic structure, and a structure containing one or more of them.
Each R is independently a hydrogen atom or a substituent. The substituent is a monovalent nonpolar group or a monovalent polar group, and the monovalent nonpolar group and the monovalent polar group are as described above.
n is an integer of 1 or more. The upper limit of n is determined by the structure of Ar.

  Examples of the structural unit M include the following. The structural unit M is not limited to the following.

  Each R is independently a hydrogen atom or a substituent. The substituent is a monovalent nonpolar group or a monovalent polar group, and the monovalent nonpolar group and the monovalent polar group are as described above.

  Structural unit M includes at least structural unit M1. In the structural unit M1, R in the general formula (m1) and the general formula (m2) is each independently a hydrogen atom, a monovalent nonpolar group, or a monovalent polar group, and at least one of R Is a monovalent nonpolar group. R's are each independently preferably a hydrogen atom or a monovalent nonpolar group, and at least one of R's is a nonpolar group. Ar in General Formula (m1) is preferably an aromatic hydrocarbon structure.

  The structural unit M may include the structural unit M2. In the structural unit M2, R in the general formula (m1) and the general formula (m2) is each independently a hydrogen atom or a monovalent polar group. The monovalent polar group can be selected from R in the structural unit D. Ar in the general formula (m2) is preferably an aromatic hydrocarbon structure.

  The ratio of the structural unit M1 is preferably 80 mol% or more, more preferably 90 mol% or more, and 100% based on the entire structural unit M.

  The structural unit M1 may contain only one nonpolar group or may contain two or more nonpolar groups. When two or more nonpolar groups are included, the two or more nonpolar groups may be the same or different.

  In the structural unit M1, the number of nonpolar groups is not particularly limited. In addition, the position at which the nonpolar group is present is not particularly limited, and, for example, in the structural unit M, any of ortho position, meta position and para position relative to the binding site (*) with other structural unit Although it is good, it is preferably in the para position.

The combination with the ionic compound described later is not particularly limited, but as a preferred combination, for example, an ionic compound having a long-chain alkyl group having 13 to 24 carbon atoms as at least one of R ^{a to} R ^{c in} the general formula (1) And a combination of a hole transporting polymer having a structural unit M1 represented by General Formula (m1).

  The following is mentioned as a specific example of the unit structure M1. The structural unit M1 is not limited to the following.

(Polymerizable functional group)
In one embodiment, the hole transportable polymer may have a polymerizable functional group from the viewpoint of curing by polymerization reaction to change the solubility in a solvent. The "polymerizable functional group" refers to a functional group that can form a bond with each other by the addition of heat and / or light. It is also possible to select a monovalent nonpolar group and / or a monovalent polar group from the polymerizable functional groups.

  As the polymerizable functional group, a group having a carbon-carbon multiple bond (eg, vinyl group, styryl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group) , Methacryloyl amino group, vinyloxy group, vinyl amino group, benzocyclobutene group etc., group having a small ring (eg, cyclic alkyl group such as cyclopropyl group, cyclobutyl group etc .; epoxy group (oxiranyl group), oxetane group ( Cyclic ether group such as oxetanyl group); diketene group; episulfide group; lactone group; lactam group etc .; heterocyclic group (eg furan-yl group, pyrrol-yl group, thiophene-yl group, silole-yl group) etc. Can be mentioned. As the polymerizable functional group, in particular, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group and an oxetane group are preferable. From the viewpoint of the reactivity and the characteristics of the organic electronic device, a vinyl group, a styryl group, an acryloyl group, an acryloyloxy group Groups, methacryloyl groups, methacryloyloxy groups, benzocyclobutene groups, oxetane groups, or epoxy groups are more preferable.

  The polymerizable functional group may be introduced into the terminal portion (that is, structural unit M) of the hole-transporting polymer, or into a portion other than the terminal portion (that is, structural unit D or T). It may be introduced into both a part and a part other than the end. From the viewpoint of curability, it is preferably introduced to at least the terminal part, and from the viewpoint of achieving both curability and charge transportability, it is preferably introduced to only the terminal part. When the hole transporting polymer has a branched structure, the polymerizable functional group may be introduced into the main chain of the hole transporting polymer or may be introduced into the side chain, and the main chain and the side chain May be introduced to both. When the polymerizable functional group is a nonpolar group (for example, a vinyl group), the structural unit M having the polymerizable functional group corresponds to the structural unit M1.

  From the viewpoint of contributing to the change in solubility, the polymerizable functional group is preferably contained in a large amount in the hole transporting polymer. On the other hand, from the viewpoint of not interfering with the charge transportability, it is preferable that the amount contained in the hole transportable polymer be 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 hole transporting polymer is preferably 2 or more, and more preferably 3 or more from the viewpoint of obtaining sufficient change in solubility. The number of polymerizable functional groups is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of maintaining charge transportability.

The number of polymerizable functional groups per molecule of the hole transporting polymer is the amount of the polymerizable functional group (for example, the amount of the monomer having the polymerizable functional group), which was used to synthesize the hole transporting polymer. The amount of monomers corresponding to each structural unit, the weight average molecular weight of the hole transporting polymer, and the like can be used as the average value. Further, the number of polymerizable functional groups is the ratio of the integral value of the signal derived from the polymerizable functional group in the ¹ H NMR (nuclear magnetic resonance) spectrum of the hole transporting polymer to the integral value of the entire spectrum, hole transport It can be calculated as an average value using the weight average molecular weight and the like of the base polymer. In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

(Number average molecular weight)
The number average molecular weight of the hole transporting polymer can be appropriately adjusted in consideration of the solubility in a solvent, the film forming property, and the like. From the viewpoint of excellent hole transportability, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more. The number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. The following is more preferable.

(Weight average molecular weight)
The weight average molecular weight of the hole transporting polymer can be appropriately adjusted in consideration of the solubility in a solvent, the film forming property and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more from the viewpoint of excellent hole transportability. The weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. The following is more preferable.

  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.

  When the hole transporting polymer is a copolymer, the copolymer may be a random, block or graft copolymer, or a copolymer having an intermediate structure thereof, for example, a block property It may be a carried random copolymer. In one embodiment, the structural unit means a monomeric unit.

(Proportion of structural unit)
The proportion of the structural unit D contained in the hole transporting polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol based on all structural units from the viewpoint of obtaining sufficient hole transportability. % Or more is more preferable. Further, the ratio of the structural unit D is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less, in consideration of the structural unit M and the structural unit T introduced as necessary.

  The proportion of the structural unit M contained in the hole transportable polymer is the total structural unit from the viewpoint of improving the properties of the organic electronic device or from the viewpoint of suppressing the increase in viscosity and performing synthesis of the hole transportable polymer well. As a standard, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 15 mol% or more is still more preferable. The proportion of the structural unit M 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 sufficient hole transportability.

  When the hole transporting polymer contains the structural unit T, the proportion of the structural unit T is preferably 1 mol% or more, and 5 mol% or more based on the total structural units, from the viewpoint of improving the durability of the organic electronic device. More preferably, 10 mol% or more is more preferable. Further, the proportion of the structural unit T is preferably 50 mol% or less, 40 mol% or less, from the viewpoint of suppressing the increase in viscosity and favorably synthesizing the hole transporting polymer, or from the viewpoint of obtaining sufficient hole transporting property. % Or less is more preferable, and 30 mol% or less is more preferable.

  In consideration of the balance of hole transportability, durability, productivity, etc., the ratio (molar ratio) of the structural unit D and the structural unit M is preferably D: M = 100: 1 to 70, and 100: 3 to 50. More preferably, 100: 5 to 30 are more preferable. When the hole transporting polymer contains the structural unit T, the ratio (molar ratio) of the structural unit D, the structural unit M, and the structural unit T is D: M: T = 100: 10 to 200: 10 to 100. 100: 20 to 180: 20 to 90 are more preferable, and 100: 40 to 160: 30 to 80 are more preferable.

The proportion of structural units can be determined using the amount of monomer corresponding to each structural unit used to synthesize the hole transporting polymer. In addition, the ratio of structural units can be calculated as an average value using the integral value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the hole transporting polymer. In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

(Production method)
The hole transporting polymer can be produced by various synthesis methods and is not particularly limited. For example, known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, still coupling, Buchwald-Heartwig coupling can be used. The Suzuki coupling, for example, causes a Pd-catalyzed cross coupling reaction between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki coupling, a hole transportable 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. Alternatively, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like as a precursor with a phosphine ligand can also be used.

  The charge transporting material may contain only one or two or more hole transporting polymers. The content of the hole transportable polymer is 50% by mass or more based on the total mass of the charge transportable material from the viewpoint of obtaining good hole transportability and from the viewpoint of increasing the light scattering of the obtained organic layer. Is preferable, 70 mass% or more is more preferable, and 80 mass% or more is still more preferable. In addition, the content of the hole transporting polymer is preferably 99.9% by mass or less, in consideration of the content of the ionic compound.

[Ion compound]
The charge transportable material contains an ionic compound represented by the following general formula (1). The ionic compound is considered to have a doping function to the hole transporting polymer in the charge transporting material. Moreover, when a hole transportable polymer has a polymerizable functional group, it is estimated that it has a function which promotes a crosslinking reaction. When the charge transporting material contains the hole transporting polymer and the ionic compound, the light scattering properties of the organic layer are improved.

［一般式（１）中、
Ｒ^ａ〜Ｒ^ｃは、それぞれ独立に、水素原子（Ｈ）、アルキル基、アルコキシアルキル基、アリールアルキル基、アリール基、又はヘテロアリール基を表し、Ｒ^ａ〜Ｒ^ｃから選ばれる少なくとも２つの基は、互いに連結して環を形成してもよい。ただし、Ｒ^ａ〜Ｒ^ｃの少なくとも１つは水素原子（Ｈ）、アルキル基、アルコキシアルキル基、及びアリールアルキル基からなる群から選択される。
Ａは、下記一般式（１Ａ）〜（５Ａ）のいずれかで表されるアニオンを表す。

[In general formula (1),
R ^{a to} R ^c each independently represent a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, an arylalkyl group, an aryl group or a heteroaryl group, and at least two groups selected from R ^{a to} R ^c And may be linked to each other to form a ring. However, at least one of R ^{a to} R ^c is selected from the group consisting of a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, and an arylalkyl group.
A represents an anion represented by any of the following general formulas (1A) to (5A).

（一般式（１Ａ）〜（５Ａ）中、
Ｙ^１〜Ｙ^６は、それぞれ独立に単結合又は二価の連結基を表し、
Ｒ^１〜Ｒ^１６は、それぞれ独立に、電子求引性の１価の基を表す。Ｒ^２及びＲ^３、Ｒ^４〜Ｒ^６から選ばれる少なくとも２つの基、Ｒ^７〜Ｒ^１０から選ばれる少なくとも２つの基、及びＲ^１１〜Ｒ^１６から選ばれる少なくとも２つの基は、それぞれ、互いに結合して環を形成していてもよい。
Ｅ^１は酸素原子、Ｅ^２は窒素原子、Ｅ^３は炭素原子、Ｅ^４はホウ素原子又はガリウム原子、Ｅ^５はリン原子又はアンチモン原子を表す。）］

(In the general formulas (1A) to (5A),
Y ^{1 to} Y ⁶ each independently represent a single bond or a divalent linking group,
Each of R ^{1 to} R ¹⁶ independently represents an electron-withdrawing monovalent group. At least two groups selected from R ² and R ³ , R ^{4 to} R ⁶ , at least two groups selected from R ^{7 to} R ¹⁰ , and at least two groups selected from R ^{11 to} R ¹⁶ respectively are each other It may combine to form a ring.
E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom. )]

(Ammonia cation)
In the general formula (1), R ^{a to} R ^c each independently represent a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, an arylalkyl group, an aryl group or a heteroaryl group. From the viewpoint of solubility and reactivity, it is preferable that at least one of R ^{a to} R ^c be an alkyl group or an arylalkyl group. Note that all of R ^{a to} R ^c do not become an aryl group and / or a heteroaryl group.

The alkyl group represented by R ^a , R ^b or R ^c may be linear, branched or cyclic, and may have a substituent. The carbon number is, for example, 1 to 30, preferably 1 to 24, and more preferably 1 to 20. Examples of the substituent include halogen and the like. Specific examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl and 3,7- Examples thereof include dimethyl octyl, lauryl, a long chain alkyl group having 13 or more carbon atoms, trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl and the like. When two or more selected from R ^a , R ^b and R ^c are alkyl groups, the two or more alkyl groups may be the same or different. For example, the combination of 2 or more types chosen from a C1-C3 alkyl group, a C4-C12 alkyl group, and a C13-C24 alkyl group may be sufficient. In a preferred embodiment, the ammonium cation has a long-chain alkyl group having 13 to 24 carbon atoms as at least one of R ^{a to} R ^c . In this case, the other two are preferably alkyl groups having 1 to 3 carbon atoms.

The alkoxyalkyl group represented by R ^a , R ^b or R ^c is a group in which at least one of the hydrogen atoms of the alkyl group is substituted by an alkoxy group. The alkoxyalkyl group may have a substituent. Examples of the substituent include halogen and the like. As the alkyl group, the above-mentioned alkyl group is exemplified, and an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group and a propyl group are more preferable. As an alkoxy group, a C1-C30 alkoxy group is mentioned. From the viewpoint of solubility, an alkoxy group having 10 to 30 carbon atoms is preferable.

The arylalkyl group represented by R ^a , R ^b or R ^c is a group in which at least one of the hydrogen atoms of the alkyl group is substituted by an aryl group. As the alkyl group, the above-mentioned alkyl group is exemplified, and an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group and a propyl group are more preferable. As an aryl group, the below-mentioned aryl group is illustrated. The carbon number of the monovalent arylalkyl group in the unsubstituted state is preferably 7 to 19, and more preferably 7 to 13. The arylalkyl group may have a substituent. As a substituent, halogen, a C1-C5 alkyl group, etc. are mentioned. Specific examples thereof include a benzyl group, a fluorobenzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a diphenylmethyl group and the like, and a benzyl group and a fluorobenzyl group are preferable.

The aryl group represented by R ^a , R ^b or R ^c may have a substituent. As a substituent, halogen, an alkoxy group, an alkyl group etc. are mentioned. The carbon number of the monovalent aryl group in the unsubstituted state is preferably 6 to 60, more preferably 6 to 18, and still more preferably 6 to 12. Specifically, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, phenanthren-yl group, pyrene-yl group, perylene-yl group, pentafluoro A phenyl group etc. are illustrated.

The heteroaryl group represented by R ^a , R ^b or R ^c may have a substituent. As a substituent, the above-mentioned C1-C12 alkyl group etc. are mentioned. The carbon number of the unsubstituted monovalent heteroaryl group is preferably 4 to 60, more preferably 4 to 20, and still more preferably 4 to 10. Specific examples thereof include a thienyl group, a C _{1 to} C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, and a C _{1 to} C ₁₂ alkyl pyridyl group.

  Specific examples of the alkoxy group as a substituent include an alkoxy group having 1 to 12 carbon atoms, such as methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, Hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3, 7-dimethyloctyloxy, lauryloxy and the like.

  Specific examples of the alkyl group as a substituent include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl and cyclohexyl And heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3, 7-dimethyloctyl, lauryl and the like.

(Anion)
In formulas (1A) to (5A), R ^{1 to} R ¹⁶ each independently represent an electron-withdrawing monovalent group. The electron-withdrawing monovalent group refers to a substituent that is more likely to attract an electron from the side of the bonding atom than a hydrogen atom. R ^{1 to} R ¹⁶ are preferably organic groups. At least two groups selected from R ² and R ³ , R ^{4 to} R ^6, at least two groups selected from R ^{7 to} R ¹⁰ , and at least two groups selected from R ^{11 to} R ¹⁶ , May be coupled to each other. The bonded group may be cyclic.

  Examples of the electron-withdrawing monovalent group include halogen atoms such as fluorine atom, chlorine atom and bromine atom; cyano group; thiocyano group; nitro group; alkylsulfonyl group such as mesyl group (for example, having 1 to 12 carbon atoms) Preferably a carbon number of 1 to 6); an arylsulfonyl group such as a tosyl group (for example, a carbon number of 6 to 18, preferably a carbon number of 6 to 12); an alkyloxysulfonyl group such as a methoxysulfonyl group (for example, a carbon number of 1 to 12) Preferably a carbon number of 1 to 6); an aryloxysulfonyl group such as a phenoxysulfonyl group (for example, a carbon number of 6 to 18, preferably a carbon number of 6 to 12); an acyl group such as a formyl group, an acetyl group or a benzoyl group (for example 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms; acyloxy groups such as formyloxy and acetoxy groups (for example, 1 to 20 carbon atoms, preferably) Prime number 1 to 6); alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group (for example, 2 to 10 carbon atoms, preferably 2 to 7 carbon atoms); "aryloxycarbonyl group such as phenoxycarbonyl group and pyridyloxycarbonyl group Or heteroaryloxycarbonyl group "(for example, 4 to 25 carbon atoms, preferably 5 to 15 carbon atoms); linear, branched or cyclic" alkyl group, alkenyl group such as trifluoromethyl group, pentafluoroethyl group, etc. A haloalkyl group, a haloalkenyl group or a haloalkynyl group (for example, having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms) in which a halogen atom is substituted to a group or an alkynyl group (for example, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms); A haloaryl group substituted with an atom (eg, 6 to 20 carbon atoms, preferably C6-12); pentafluorophenyl halo arylalkyl group in which a halogen atom is substituted with an arylalkyl group such as a methyl group (for example, having a carbon number 7 to 19, and preferably the number 7 to 13) such as carbon.

  Furthermore, as an example of the electron withdrawing monovalent group, from the viewpoint of being able to delocalize the negative charge efficiently, among the examples of the electron withdrawing monovalent group, “an organic group having a hydrogen atom And groups in which part or all of the hydrogen atoms are substituted with halogen atoms are preferred. For example, perfluoroalkylsulfonyl group, perfluoroarylsulfonyl group, perfluoroalkyloxysulfonyl group, perfluoroaryloxysulfonyl group, perfluoroacyl group, perfluoroacyloxy group, perfluoroalkoxycarbonyl group, perfluoroaryloxycarbonyl group And perfluoroalkyl groups, perfluoroalkenyl groups, perfluoroalkynyl groups, perfluoroaryl groups, perfluoroarylalkyl groups and the like.

  Specific examples of the electron-withdrawing monovalent group include, in particular, a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms, a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, or carbon The number 6 to 18 perfluoroaryl group is preferable.

  The electron withdrawing monovalent group is not limited to these. The examples of the electron-withdrawing monovalent group shown above may have a substituent or may have a hetero atom.

  Specific examples of the electron-withdrawing monovalent group include groups exemplified as the following Substituent Group (1).

Substituent group (1)

In formulas (1A) to (5A), Y ^{1 to} Y ⁶ each independently represent a single bond or a divalent linking group. When Y ^{1 to} Y ⁶ is a single bond, it means that E and R are directly bonded. As a bivalent coupling group, the coupling group represented by either of following formula (1c)-(11c) is mentioned, for example.

［式中、Ｒは、それぞれ独立に水素原子又は１価の基を表す。］

[In formula, R respectively independently represents a hydrogen atom or monovalent group. ]

  R is preferably an organic group. R is more preferably independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group from the viewpoint of improving electron acceptability, solubility in a solvent, and the like. It is preferable that carbon number of an alkyl group, an alkenyl group, and an alkynyl group is 1-20, and it is still more preferable that it is 1-10. As the aryl group and the heteroaryl group, those exemplified in the description of the above ammonium cation can be mentioned. These groups may have a substituent or may have a hetero atom. R is preferably an electron-withdrawing monovalent group, and as the electron-withdrawing monovalent group, for example, an example of the electron-withdrawing monovalent group, the substituent group The group etc. shown in (1) can be mentioned.

  The charge transporting material may contain only one type of the above-described ionic compound or may contain two or more types. The content of the ionic compound represented by the general formula (1) is 0 for the hole transporting polymer from the viewpoint of the effect of improving the light scattering property of the organic layer and the doping effect on the hole transporting polymer. .01 mass% or more is preferable, 0.1 mass% or more is more preferable, 0.5 mass% or more is still more preferable. In addition, from the viewpoint of maintaining good film formability, 50% by mass or less is preferable, 30% by mass or less is more preferable, 20% by mass or less is more preferable, and 12% by mass or less is more preferable. preferable.

[Dopant]
The charge transporting material may further contain a dopant. The dopant is not particularly limited as long as it can be added to a hole transporting polymer to exhibit a doping effect and improve hole transportability. However, the dopant is a compound different from the ionic compound represented by the general formula (1). The dopants may be used alone or in combination of two or more.

The dopant used for the hole transporting polymer is preferably an electron accepting compound, and for example, a Lewis acid, a protonic acid, a transition metal compound, an ionic compound (however, the ionic compound represented by the general formula (1)) Ion compounds different from H), halogen compounds, π-conjugated compounds and the like. Specifically, as a Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SfF ₅ , BF ₅ , BCl ₃ , BBr ₃ etc .; As a protonic acid, HF, HCl, HBr, HNO ₅ , 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 camphor sulfonic acid; transition metal compounds such as FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , MoF ₅ ; ionic compounds such as tetrakis (pentafluoro acid) Phenyl) borate ion, tris (trifluoro) Methanesulfonyl) Mechidoion, bis (trifluoromethanesulfonyl) imide ion, hexafluoroantimonate ion, AsF ₆ ^- (hexafluoro arsenic acid ions), BF ₄ ^- (tetrafluoroborate), PF ₆ ^- (hexafluorophosphate) Salts with perfluorinated anions, salts with conjugated bases of the above-mentioned protonic acids as anions, etc .; halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF etc .; π-conjugated compounds Examples of TC include TCNE (tetracyanoethylene), TCNQ (tetracyanoquinodimethane), and the like. Moreover, it is also possible to use the electron-accepting compound as described in JP-A-2000-36390, JP-A-2005-75948, JP-A-2003-213002, and the like. Preferred are Lewis acids, ionic compounds, π-conjugated compounds and the like.

  When the hole transporting polymer has a polymerizable functional group, the dopant is preferably a compound having a function of promoting a crosslinking reaction.

  When the dopant is contained, the content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, with respect to the hole transporting polymer, from the viewpoint of improving the hole transporting property. 0.5 mass% or more is more preferable. Moreover, from a viewpoint of keeping film-forming property favorable, 50 mass% or less is preferable with respect to hole transportable polymer, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable.

  The charge transporting material is preferably used for forming an organic layer exhibiting a hole transporting property, such as a hole injecting layer, a hole transporting layer, a hole injecting and transporting layer and the like. By using a charge transporting material, an organic layer with a large haze can be formed. Furthermore, even in the case of using a wet process, multilayering of the organic layer can be easily performed. Therefore, the charge transporting material is suitable as a coating type hole transporting material, and suitable for an organic electronic device and an organic EL device multilayered by a coating method, and a display device, a lighting device and a display device using them. It can be used for

<Ink composition>
The ink composition which is an embodiment of the present invention contains the charge transporting material of the embodiment and an organic solvent capable of dissolving or dispersing the charge transporting material. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.

[Organic solvent]
The organic solvent is not particularly limited, and examples thereof include solvents generally used when applying a polymer. For example, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic ethers, aromatic ethers, aliphatic esters, aromatic esters, amides, sulfoxides, ketones, organic halogen compounds and the like can be mentioned.
The alcohol is preferably an alcohol having 1 to 6 carbon atoms, and examples thereof include methanol, ethanol, isopropyl alcohol and the like.
The aliphatic hydrocarbon is preferably an alkane having 5 to 10 carbon atoms or a cycloalkane having 5 to 10 carbon atoms, and examples thereof include pentane, hexane, octane, cyclohexane and the like.
The aromatic hydrocarbon is preferably an aromatic hydrocarbon having 6 to 13 carbon atoms, and examples thereof include benzene, toluene, xylene, mesitylene, tetralin, diphenylmethane and the like.
Examples of the aliphatic ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate and the like.
As the aromatic ether, for example, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2, 4-dimethyl anisole etc. are mentioned.
Examples of aliphatic esters include ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate and the like.
Examples of the aromatic ester include phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate and the like.
Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide and the like.
Examples of the sulfoxide include dimethyl sulfoxide, diethyl sulfoxide and the like.
Examples of the ketone include tetrahydrofuran, acetone and the like.
As an organic halogen compound, chloroform, a methylene chloride etc. are mentioned, for example.

  The content of the organic solvent in the ink composition can be determined in consideration of application to various coating methods. For example, the content of the organic solvent is preferably such that the ratio of the hole transporting polymer to the organic solvent is 0.1% by mass or more, and more preferably 0.2% by mass or more. It is more preferable that the amount is not less than mass%. In addition, the content of the organic solvent is preferably such an amount that the ratio of the hole transporting polymer to the organic solvent is 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less Is more preferred.

[Additive]
The ink composition may further contain an additive as an optional component. As the additive, for example, 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 antifoamer, Dispersants, surfactants and the like can be mentioned.

<Organic layer>
The organic layer which is one embodiment of the present invention is a layer formed using the charge transporting material or the ink composition of the above embodiment. By using the ink composition, an organic layer can be favorably formed by a coating method.

  Coating methods include, for example, spin coating method; cast method; immersion method; plate printing method such as letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reverse offset printing, screen printing, gravure printing, etc .; Known methods such as plateless printing can be mentioned. When forming an organic layer by the apply | coating method, the organic layer (application layer) obtained after application may be dried using a hotplate or oven, and a solvent may be removed.

  In a preferred embodiment, the organic layer is produced by a method including, for example, applying an ink composition, and irradiating the applied ink composition or heating the applied ink composition. be able to. In addition, the organic layer was prepared, for example, in the steps of preparing an ink composition containing the charge transporting material of the embodiment and a solvent, applying the ink composition on a substrate, and applying the ink composition on a substrate Irradiating the ink composition or heating the ink composition applied on the substrate.

  According to one embodiment, in the organic electronic device, in order to improve device characteristics such as lifetime and light emission efficiency, multilayering of the organic layers constituting the device is performed. In the vapor deposition method, multi-layering can be easily achieved by performing deposition while sequentially changing the compounds to be used. However, in order to form the organic layer into a multilayer using a wet process, a method that does not dissolve the lower layer when forming the upper layer is required.

  When the hole transporting polymer has a polymerizable functional group, the crosslinking reaction of the hole transporting polymer can be advanced to change the solubility of the organic layer by performing treatment such as heating and light irradiation. By laminating the organic layer of which the solubility is changed, it is possible to easily achieve multilayering of the organic electronic device by a wet process. Specifically, when an organic layer containing a crosslinked hole transporting polymer is used as a lower layer and the upper layer is formed by a coating method, the dissolution of the lower layer by the organic solvent can be suppressed, and the upper layer can be favorably formed.

  The crosslinking reaction can be carried out by heating, light irradiation or the like, and heating is preferred from the viewpoint of simplicity of the process. The heating temperature and time are not particularly limited as long as the crosslinking reaction can sufficiently proceed.

  For heating, a heater such as a hot plate or an oven can be used. The temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less, still more preferably 200 ° C. or less from the viewpoint of applying various substrates. Further, from the viewpoint of accelerating the crosslinking reaction, it is preferably 40 ° C. or more, more preferably 50 ° C. or more, and still more preferably 60 ° C. or more. The time is preferably 2 hours or less, more preferably 1 hour or less, and still more preferably 30 minutes or less from the viewpoint of improving the productivity. Also, from the viewpoint of completely advancing the crosslinking reaction, it is preferably 1 minute or more, more preferably 3 minutes or more, and still more preferably 5 minutes or more.

  For light irradiation, a light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a light emitting diode, or sunlight can be used.

  The thickness of the organic layer after removal of the solvent and / or treatment such as heating and light irradiation is preferably 0.1 nm or more, more preferably 1 nm, from the viewpoint of improving the efficiency of charge transport. Or more, more preferably 3 nm or more. 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 the electrical resistance.

  The organic layer is excellent in light scattering. By using a charge transporting material containing a hole transporting polymer and an ionic compound, it is possible to form an organic layer having light scattering properties and exhibiting charge transport properties. Although the reason for this is not clear, when the hole transporting polymer having a nonpolar site at the end and the ionic compound represented by the general formula (1) are used in combination, the hole transporting polymer and the ionic compound are compatible. It is guessed that it is difficult to do it. Note that this mechanism is inference and does not limit the present invention.

<Organic electronics device>
The organic electronic device which is an embodiment of the present invention has at least the organic layer of the above-mentioned embodiment. As an organic electronics element, an organic EL element, an organic photoelectric conversion element, an organic transistor etc. are mentioned, for example. The organic electronic device preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

<Organic EL element>
The organic EL element which is embodiment of this invention has the organic layer of the said embodiment at least. The organic EL device generally comprises a light emitting layer, an anode, a cathode, and a substrate, and as necessary, other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, etc. Have. Each layer may be formed by a vapor deposition method or may be formed by a coating method. The organic EL device preferably has an organic layer as a light emitting layer or another functional layer, more preferably as a functional layer, and still more preferably as at least one of a hole injection layer and a hole transport layer. When the organic layer is provided at least as a hole injection layer, the effect of improving the light extraction efficiency can be easily obtained. The organic layer can improve the light extraction efficiency without separately forming a new layer as a scattering layer in order to have both the functions as a hole injection layer, a hole transport layer, and the like and the function as a scattering layer.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of the organic EL element. The organic EL device of FIG. 1 is a device having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 and a hole transport layer 6 consisting of the organic layer of the embodiment, a light emitting layer 1, an electron transport layer 7, The electron injection layer 5 and the cathode 4 are provided in this order. Each layer will be described below.

[Emitting layer]
As materials used for the light emitting layer, light emitting materials such as low molecular weight compounds, polymers, and dendrimers can be used. The polymer is preferable because it has high solubility in a solvent and is suitable for a coating method. As the light emitting material, a fluorescent material, a phosphorescent material, a heat activated delayed fluorescent material (TADF) and the like can be mentioned.

  Fluorescent materials such as perylene, coumarin, rubrene, quinacdoline, stilbene, dyes for dye laser, aluminum complexes, low molecular weight compounds such as derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer And polymers such as fluorene-triphenylamine copolymer and derivatives thereof; and mixtures thereof.

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

  When the light emitting layer contains a phosphorescent material, it is preferable to further contain a host material in addition to the phosphorescent material. As a host material, a low molecular weight compound, a polymer or a dendrimer can be used. As low molecular weight compounds, 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), derivatives thereof and the like, as the polymer, the charge transporting material of the above embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof and the like It can be mentioned.

  As a heat activation delayed fluorescence material, for example, Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012) Appl. Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); Nature, 492, 234 (2012). Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. Chem. Chem. Phys., 15, 15850 (2013); Chem. Comm., 49, 10385 (2013); Chem. Lett., 43, 319 (2014) and the like.

[Hole transport layer, hole injection layer]
Examples of the material used for the hole transport layer and the hole injection layer include the charge transportable material of the above embodiment. In addition, it is also possible to use a hole transporting polymer having no polar site at the end. The hole transporting polymer having no polar site at the end can have the same structure as the hole transporting polymer having a polar site at the above end except that it does not have a polar site at the end. That is, the hole transporting polymer having no polar site at the end has, for example, structural unit D, structural unit M2, and / or structural unit T.

  Furthermore, as known materials, for example, aromatic amine compounds (for example, aromatic diamines such as N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine (α-NPD)) And phthalocyanine-based compounds (eg, thiophene-based conductive polymers such as poly (3,4-ethylenedioxythiophene): poly (4-styrene sulfonate) (PEDOT: PSS)).

[Electron transport layer, electron injection layer]
Materials used for the electron transport layer and the electron injection layer include, for example, phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, fused ring tetracarboxylic acid anhydrides such as naphthalene and perylene, carbodiimides And fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes and the like. In addition, the charge transporting material of the embodiment can also be used.

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

[anode]
As the anode material, for example, a metal (for example, Au) or another conductive material is used. Other materials include, for example, oxides (eg, ITO: indium oxide / tin oxide), 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 flexible. Quartz glass, a light transmitting resin film, etc. are preferably used.

  As the resin film, for example, a film composed of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, etc. It can be mentioned.

  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 permeation of water vapor, oxygen and the like.

[Emitting color]
The luminescent color of 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, in-car lighting, clocks, backlights of liquid crystals, and the like.

  As a method of forming a white organic EL element, it is possible to use a method in which a plurality of light emitting materials are used to simultaneously emit light of a plurality of light emitting colors for color mixing. The combination of plural emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, two emission maximum wavelengths such as blue and yellow, yellow green and orange, etc. The combination to contain is mentioned. Control of the luminescent color can be performed by adjusting the type and amount of the luminescent material.

<Display element, lighting device, display device>
The display element which is an embodiment of the present invention includes the organic EL element of the embodiment. 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 thin film transistors are arranged and driven in each element.

  Moreover, the illuminating device which is embodiment of this invention is equipped with the organic EL element of embodiment of this invention. Furthermore, 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 a lighting device which is an embodiment of the present invention as a backlight and a liquid crystal display device using a known liquid crystal element as a display means.

  Hereinafter, the embodiment of the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples.

<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 and anisole (15 ml) was added and stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, anisole (5 mL) was added and stirred for 5 minutes. The solutions were mixed and stirred at room temperature for 30 minutes to catalyze. All solvents were used after degassing with nitrogen bubbles for over 30 minutes.

<Synthesis of Hole Transportable Polymer 1 Having Polar Site at End>
The following monomer D1 (5.0 mmol), the following monomer T (2.0 mmol), the following monomer M1 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a Pd catalyst solution (7. 5 mL) was added. After stirring for 30 minutes, 10% aqueous tetraethylammonium hydroxide solution (20 mL) was added. All solvents were used after degassing with nitrogen bubble for more than 30 minutes. The mixture was heated to reflux for 2 hours. All operations up to this point were performed under a nitrogen stream.

  After 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 resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate is collected by suction filtration, dissolved in toluene, a metal adsorbent ("Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer" manufactured by Strem Chemicals, 200 mg per 100 mg of precipitate) is added, Stir overnight. After completion of the stirring, the metal adsorbent and the insoluble matter were removed by filtration, and the filtrate was concentrated by a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The resulting precipitate was dried under vacuum to obtain a hole transporting polymer 1. The number average molecular weight of the hole transportable polymer 1 was 7,800, and the weight average molecular weight was 31,000. The mixing ratio of the solvent is a volume ratio.

The number average molecular weight and the weight average molecular weight were measured by GPC (in terms of polystyrene) using tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.
Liquid transfer pump: L-6050 Hitachi High-Technologies Corporation UV-Vis Detector: L-3000 Hitachi High-Technologies Corporation Column: Gelpack (registered trademark) GL-A160S / GL-A150S Hitachi Chemical Co., Ltd.
Eluent: THF (for HPLC, without stabilizer) Wako Pure Chemical Industries, Ltd.
Flow rate: 1 mL / min
Column temperature: Room temperature molecular weight standard substance: Standard polystyrene

<Synthesis of Hole Transportable Polymer 2 Having Nonpolar Site at End>
The above monomer D1 (5.0 mmol), the monomer T (2.0 mmol), the following monomer M2 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and the Pd catalyst solution (7. 5 mL) was added. Thereafter, in the same manner as in the synthesis of the hole transporting polymer 1, a hole transporting polymer 2 was synthesized. The number average molecular weight of the obtained hole transporting polymer 2 was 15,800, and the weight average molecular weight was 141,100.

<Synthesis of Hole Transport Polymer 3 Having Nonpolar Site at End>
The above monomer D1 (5.0 mmol), the monomer T (2.0 mmol), the following monomer M3 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and the Pd catalyst solution (7. 5 mL) was added. The hole transporting polymer 3 was synthesized in the same manner as the synthesis of the hole transporting polymer 1 thereafter. The number average molecular weight of the obtained hole transporting polymer 3 was 18,900, and the weight average molecular weight was 49,100.

<Synthesis of Hole Transportable Polymer 4 Having Nonpolar Site at End>
In a three-necked round bottom flask, the monomer D1 (5.0 mmol), the monomer T (2.0 mmol), the following monomer M4 (4.0 mmol), and anisole (20 mL) were added, and the Pd catalyst solution (7. 5 mL) was added. Thereafter, in the same manner as in the synthesis of the hole transporting polymer 1, a hole transporting polymer 4 was synthesized. The number average molecular weight of the obtained hole transporting polymer 4 was 9,000, and the weight average molecular weight was 44,100.

<Synthesis of Hole-Transporting Polymer 5 Having Nonpolar Site at End>
The following monomer D2 (5.0 mmol), the monomer T (2.0 mmol), the monomer M2 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and the Pd catalyst solution (7. 5 mL) was added. The hole transporting polymer 5 was synthesized in the same manner as the synthesis of the hole transporting polymer 1 thereafter. The number average molecular weight of the obtained hole transporting polymer 5 was 13,600, and the weight average molecular weight was 60,000.

<Evaluation of organic thin film (organic layer)>
(Comparative example 1)
Hole transport polymer 1 (10.0 mg) was dissolved in 348 μL of toluene to obtain a polymer solution. In addition, the following ionic compound 1 (1.1 mg) was dissolved in 37 μL of toluene to obtain an ionic compound solution. The obtained polymer solution and the ionic compound solution were mixed to prepare a coating solution (ink composition). The coating solution was spin-coated on a quartz glass substrate at room temperature (25 ° C.) at a rotational speed of 3,000 min ⁻¹ to form an organic thin film (thickness: 40 nm). Next, the quartz glass substrate was heated at 220 ° C. for 10 minutes on a hot plate.

  The total light transmittance and the haze of the organic thin film were measured. For the measurement, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH-5000 (based on JIS K7105)) was used. The evaluation results are shown in Table 1.

(Examples 1 to 4)
In the same manner, organic thin films (Examples 1 to 4) using the hole transporting polymers 2 to 5 were prepared, and the total light transmittance and the haze were evaluated.

  The organic thin films of Examples 1 to 4 had large haze values and excellent light scattering properties. On the other hand, in the organic thin film of the comparative example, the haze value was small and the light scattering property was inferior. By using the charge transportable material containing the hole transportable polymer according to the embodiment of the present invention and the ionic compound, the light scattering property of the organic thin film can be improved.

<Fabrication of organic EL element>
(Comparative Example 2 and Examples 5 to 8)
Under the atmosphere, hole transporting polymer 1 (10.0 mg), ionic compound (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition for forming a hole injection layer. The ink composition is spin-coated at a rotational speed of 3,000 min- ¹ on a glass substrate patterned to a width of 1.6 mm of ITO, and then cured by heating at 220 ° C. for 10 minutes on a hot plate. A layer (25 nm) was formed.

The glass substrate obtained above is transferred into a vacuum deposition machine, and on the hole injection layer, α-NPD (20 nm), Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), TPBi (30 nm) ), LiF (0.8 nm), and Al (100 nm) were formed in this order by vapor deposition, and sealing treatment was performed to fabricate an organic EL element (Comparative Example 2).

  In the same manner, organic EL devices (Examples 5 to 8) using the hole transporting polymers 2 to 5 were produced.

  When voltage was applied to the organic EL elements obtained in Examples 5 to 8 and Comparative Example 1, green light emission was confirmed. For each element, the total luminous flux was measured by the following. As a result, Table 2 shows relative values when the total luminous flux of Comparative Example 2 is 1.

  An organic EL element was placed in an integrating sphere, light was emitted at a predetermined luminance, and emission was detected by a multi-channel spectroscope through an optical fiber connected to a port of the integrating sphere to obtain an emission spectrum. The total luminous flux was determined from the obtained emission spectrum by calibrating with a standard light source measured in advance.

  In the organic EL elements of Examples 5 to 8, the total luminous flux was improved. By using the charge transportable material containing the hole transportable polymer according to the embodiment of the present invention and the ionic compound, it is possible to improve the light extraction efficiency of the organic EL device.

  The effects of the present invention were shown by the above examples. In addition to the hole transporting polymer and the ionic compound used in the examples, the light transporting organic layer can be formed by using the hole transporting polymer and the ionic compound described above. The organic electronic device produced using the above organic layer exhibits the same excellent effect.

Reference Signs List 1 light emitting layer 2 anode 3 hole injecting layer 4 cathode 5 electron injecting layer 6 hole transporting layer 7 electron transporting layer 8 substrate

Claims (14)

A charge transportable material comprising a polymer having a structural unit having a hole transportability and having a nonpolar site at an end, and an ionic compound represented by the following general formula (1).

[In general formula (1),
R ^{a to} R ^c each independently represent a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, an arylalkyl group, an aryl group or a heteroaryl group, and at least two groups selected from R ^{a to} R ^c And may be linked to each other to form a ring. However, at least one of R ^{a to} R ^c is selected from the group consisting of a hydrogen atom (H), an alkyl group, an alkoxyalkyl group, and an arylalkyl group.
A represents an anion represented by any of the following general formulas (1A) to (5A).

(In the general formulas (1A) to (5A),
Y ^{1 to} Y ⁶ each independently represent a single bond or a divalent linking group,
Each of R ^{1 to} R ¹⁶ independently represents an electron-withdrawing monovalent group. At least two groups selected from R ² and R ³ , R ^{4 to} R ⁶ , at least two groups selected from R ^{7 to} R ¹⁰ , and at least two groups selected from R ^{11 to} R ¹⁶ respectively are each other It may combine to form a ring.
E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom. )]   The charge transportable material according to claim 1, wherein the polymer has a branched structure.   The charge transportable material according to claim 1 or 2, wherein the structural unit having a hole transportability comprises at least one selected from the group consisting of an aromatic amine structure and a carbazole structure.   The charge transporting material according to any one of claims 1 to 3, wherein the nonpolar site is selected from the group consisting of a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group.   An ink composition comprising the charge transporting material according to any one of claims 1 to 4 and a solvent.   An organic layer formed using the charge transporting material according to any one of claims 1 to 4 or the ink composition according to claim 5.   An organic electronic device comprising at least the organic layer according to claim 6.   An organic electroluminescent device comprising at least the organic layer according to claim 6.   The organic electroluminescent device according to claim 8, further comprising a flexible substrate.   The organic electroluminescent device according to claim 8, further comprising a resin film substrate.   A display device comprising the organic electroluminescent device according to any one of claims 8 to 10.   A lighting device comprising the organic electroluminescent device according to any one of claims 8 to 10.   A display device comprising the lighting device according to claim 12 and a liquid crystal element as display means. A method for producing an organic layer, comprising: applying the ink composition according to claim 5; and irradiating the applied ink composition with light or heating the applied ink composition.

Images