JP6641845B2 - Charge transporting material, ink composition using the material, organic electronic device, organic electroluminescent device, display device, lighting device, and display device - Google Patents

Description

  Embodiments of the present invention relate to a charge transporting material and an ink composition using the material. Further, another embodiment of the present invention relates to an organic electronic element, an organic electroluminescent element, a display element, a lighting device, and a display device having an organic layer using the charge transporting material or the ink composition.

  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 replaces conventional silicon-based inorganic semiconductors. ing.

  Examples of the organic electronic element include an organic electroluminescent element (hereinafter, also referred to as an “organic EL element”), an organic photoelectric conversion element, an organic transistor, and the like.

  Among organic electronic elements, an organic EL element has been receiving attention as a large-area solid-state light source application, for example, as a substitute for an incandescent lamp or a gas-filled lamp. 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.

  Organic EL elements are roughly classified into two types, a low-molecular type organic EL element and a high-molecular type organic EL element, according to the organic material used. In the polymer-type organic EL device, a polymer material is used as an organic material, and in the low-molecular-weight organic EL device, a low-molecular material is used. The polymer organic EL element can be easily formed by a wet process such as printing or ink-jet, compared to a low-molecular organic EL element in which film formation is mainly performed in a vacuum system. It is expected as an indispensable element for EL displays.

  For this reason, materials suitable for wet processes are being developed. For example, studies as described in Patent Document 1 are being conducted.

JP 2006-279007 A

  In general, an organic EL device manufactured by a wet process using a polymer material has features that it is easy to reduce the cost and increase the area. However, it is desired that organic EL devices including a thin film manufactured using a conventional polymer material have further improved characteristics such as driving voltage, luminous efficiency, and luminescent lifetime.

  In view of the above, it is an object of an embodiment of the present invention to provide a charge transporting material including a charge transporting polymer that can be used for an organic electronic device, and an ink composition including the material. In another embodiment, an organic electronic element and an organic EL element which are excellent in luminous efficiency and luminous life using the charge transporting material or the ink composition, and a display element and a lighting device using the same are provided. , And a display device.

  The present inventors have conducted intensive studies and found that a charge transporting polymer having a specific structural unit is suitable as a charge transporting material constituting an organic layer of an organic electronic element. Reached.

  One embodiment of the present invention relates to a charge transporting material containing a charge transporting polymer containing at least one of a silicon-containing divalent structural unit L1 and a silicon-containing trivalent or higher valent structural unit B1.

  Here, the charge-transporting polymer includes a charge-transporting divalent structural unit L2 and a charge-transporting divalent structural unit L2 other than the silicon-containing divalent structural unit L1 and the silicon-containing trivalent or higher-valent structural unit B1. It is preferable to further include at least one of the trivalent or higher-valent structural units B2 having transportability. More preferably, the charge transporting polymer further includes a divalent structural unit L2 having a charge transporting property other than the silicon-containing divalent structural unit L1. The divalent structural unit L2 having a charge transporting property preferably includes a structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a bithiophene structure, a benzene structure, and a fluorene structure. The charge transporting polymer preferably has a structure branched in three or more directions. The charge transporting material is preferably used as a hole transporting material.

  One embodiment of the present invention relates to an ink composition including the charge transporting material of the above embodiment and a solvent.

  One embodiment of the present invention relates to an organic electronic device having an organic layer containing the charge transporting material of the above embodiment.

  One embodiment of the present invention relates to an organic electroluminescent device having an organic layer containing the charge transporting material of the above embodiment. Here, the organic electroluminescence element preferably further includes a flexible substrate, and the flexible substrate preferably includes a resin film.

  One embodiment of the present invention relates to a display device including the organic electroluminescent device of the above embodiment.

  One embodiment of the present invention relates to a lighting device provided with the organic electroluminescence element of the above embodiment.

  One embodiment of the present invention relates to a display device including the lighting device of the above embodiment and a liquid crystal element as display means.

  According to the embodiments of the present invention, an organic electronic element and an organic EL element having excellent durability, low driving voltage, and excellent luminous efficiency and luminous life, and a display element, a lighting device, and a display device using the same are provided. Can be provided.

FIG. 2 is a schematic cross-sectional view showing one embodiment of the organic EL device of the present invention.

Hereinafter, embodiments of the present invention will be described.
<Charge transporting material>
The charge transporting material according to the present invention comprises a charge transporting polymer having a structural unit containing silicon. The charge transporting polymer has the ability to transport charges. Hereinafter, the charge transporting polymer will be described in detail.

(Charge transport polymer)
In the present invention, the charge transporting polymer may be any as long as it contains a silicon-containing structural unit in the molecule and exhibits charge transportability. The charge transporting polymer may have a linear structure or may have a branched structure. More specifically, the charge-transporting polymer preferably contains at least a divalent structural unit L having a charge-transporting property and a monovalent structural unit T constituting a terminal portion, and further comprises 3 which constitutes a branched portion. It may contain a structural unit B having a valency or higher. The charge transporting polymer may include only one type of each structural unit, or may include a plurality of types of each structural unit. In the charge transporting polymer, the respective structural units are bonded to each other at “monovalent” to “trivalent or more” binding sites.

(Construction)
Examples of the partial structure contained in the charge transporting polymer include the following. The charge transporting polymer is not limited to those having the following partial structures. In the partial structure, “L” represents a structural unit L, “T” represents a structural unit T, and “B” represents a structural unit B. “*” Represents a binding site to another structural unit. 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.

Linear charge transport polymer

Charge transporting polymer having branched structure

In one embodiment, the charge transporting polymer includes at least one of a silicon-containing divalent structural unit L1 and a silicon-containing trivalent or higher valent structural unit B1 described below.
(Structural unit L1)
The silicon-containing divalent structural unit L1 is intended to have two bonding sites with other structural units as a whole, and preferably has a structure in which an arylene group or an arentolyl group is bonded to silicon. . Examples of the divalent structural unit L1 containing silicon include the following.

Here, in the formula, R is each independently a hydrogen atom or a linear, cyclic or branched alkyl group, alkenyl group, alkynyl group, and alkoxy group having 1 to 22 carbon atoms. And at least one selected from the group consisting of aryl groups and heteroaryl groups having 2 to 30 carbon atoms. The aryl group and the heteroaryl group may have a substituent. R is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted phenyl group or More preferably, it is a naphthyl group.
In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, preferably a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and more preferably a substituted or unsubstituted phenylene group. Or a naphthylene group, more preferably an unsubstituted phenylene group. The phenylene group may be any of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, but a 1,4-phenylene group is preferred. In the formula, “*” represents a binding site to another structural unit.

The following are specific examples of the structural unit L1. However, the structural unit L1 is not limited to the following.

ここで、式中、Ｒ及びＡｒは、それぞれ、先に２価の構造単位Ｌ１に記載したとおりである。 (Structural unit B1)
The structural unit B1 contains silicon and is intended to have three or more bonding sites with other structural units as a whole. The structural unit B1 is preferably hexavalent or less, more preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic element. That is, the structural unit B1 is preferably a trivalent or tetravalent structural unit containing silicon. Examples of the structural unit B1 include the following.

Here, in the formula, R and Ar are as described above for the divalent structural unit L1.

The following are specific examples of the structural unit B1. However, the structural unit B1 is not limited to the following.

  In one embodiment, the charge-transporting polymer further comprises a charge-transporting divalent structural unit L2 and a charge-transporting trivalent or higher-valent structural unit B2 other than the structural unit L1 and the structural unit B1. It is preferable to include at least one of the following. Specific examples are as follows.

(Structural unit L2)
The structural unit L2 is a divalent structural unit having a charge transporting property. The structural unit L2 is not particularly limited as long as the structural unit L2 includes an atomic group capable of transporting charges. For example, the structural unit L2 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 Thiophene structure, benzoxazole structure, benzoxadiazole structure, benzothiazole structure, benzothiadiazole structure, benzotriazole structure, and one or more of these It is selected from a structure containing two or more kinds. The aromatic amine structure is preferably a triarylamine structure, and more preferably a triphenylamine structure.

  In one embodiment, the structural unit L2 is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, and Is preferably selected from a structure containing one or more of the following, and is selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, and a structure containing one or more of these. Is more preferred. In another embodiment, the structural unit L2 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.

The following are specific examples of the structural unit L2. However, the structural unit L2 is not limited to the following.

R represents a hydrogen atom or a substituent each independently. Preferably, R independently represents -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , a halogen atom, and a polymerizable functional group described below. Selected from the group consisting of: R ^{1 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. An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic ring. The alkyl group may be further substituted with an aryl group or a heteroaryl group having 2 to 20 carbon atoms, and the aryl group or the heteroaryl group may further have a linear, cyclic or branched 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 having 2 to 30 carbon atoms or a heteroarylene group. Ar is preferably an arylene group, more preferably a phenylene group. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring. Ar is preferably an arylene group, more preferably a phenylene group.

  Examples of the aromatic hydrocarbon 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 single bond. Examples of the aromatic heterocyclic ring include 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 single bond.

(Structural unit B2)
When the charge transporting polymer has a branched structure, the structural unit B2 is a trivalent or higher valent structural unit constituting a branched portion. The structural unit B2 is preferably hexavalent or less, more preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic element. The structural unit B2 is preferably a unit having a charge transporting property. For example, the structural unit B2 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 structural unit B2 may have the same structure as the structural unit L2, or may have a different structure.

The following are specific examples of the structural unit B2. However, the structural unit B2 is not limited to the following.

  W represents a trivalent linking group, for example, an alentolyl group or a heteroarenetriyl group having 2 to 30 carbon atoms. The arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. A heteroarenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocyclic ring. Ar represents a divalent linking group each independently, for example, each independently represents an arylene group having 2 to 30 carbon atoms or a heteroarylene group. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group, for example, a group having at least one hydrogen atom in R (excluding a group including a polymerizable functional group) in the structural unit L2, and one more hydrogen atom And a divalent group excluding. Z represents either a carbon atom or 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 L2.

(Structural unit T)
In the charge transporting polymer, the structural unit T is a monovalent structural unit constituting a 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. 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 (that is, for example, a polymerizable functional group such as a pyrrol-yl group). Functional group). The structural unit T may have the same structure as the structural units L2 and / or B2, or may have a different structure.

The following are specific examples of the structural unit T. However, the structural unit T is not limited to the following.

  R is the same as R in the structural unit L2. When the charge transporting polymer has a polymerizable functional group at the terminal, preferably, at least one of R is a group containing a polymerizable functional group.

  In one embodiment, the charge-transporting polymer has at least one of a silicon-containing divalent structural unit L1 and a silicon-containing trivalent or higher valent structural unit B1, and further includes the divalent structural unit L1. It is preferable to include a divalent structural unit L2 having a charge transporting property other than the trivalent or higher structural unit B1. Here, the divalent structural unit L2 is preferably a structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a bithiophene structure, a benzene structure, and a fluorene structure. The aromatic amine structure is preferably a triarylamine structure, and more preferably a triphenylamine structure. The benzene structure is preferably a p-phenylene structure or an m-phenylene structure. In one embodiment, the divalent structural unit L2 is more preferably a triphenylamine structure or a carbazole structure.

  In one embodiment, it is preferable that the charge transporting polymer includes a trivalent or higher valent structural unit B1 and / or B2 and has a structure branched in three or more directions. The charge transporting polymer preferably contains at least a trivalent or higher-valent structural unit B1. “Structure branched in three or more directions” means that, among the various chains in one molecule of the charge transporting polymer, when the chain having the highest degree of polymerization is the main chain, the degree of polymerization is the same as the main chain. Or one or more side chains having a lower degree of polymerization. In the present invention, the degree of polymerization represents the number of units of a monomer used for synthesizing the charge transporting polymer per molecule of the charge transporting polymer. In the present invention, the side chain is a chain different from the main chain of the charge transporting polymer and has at least one or more structural units, and the other is regarded as a substituent instead of a side chain.

(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 and / or light.

  Examples of the polymerizable functional group include groups having a carbon-carbon multiple bond (for example, vinyl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group, methacryloylamino group). Groups, vinyloxy groups, vinylamino groups, etc.), groups having a small ring (eg, cyclic alkyl groups such as cyclopropyl group and cyclobutyl group; cyclic ether groups such as epoxy group (oxiranyl group) and oxetane group (oxetanyl group)) A diketene group; an episulfide group; a lactone group; a lactam group); and a heterocyclic group (eg, a furan-yl group, a pyrrole-yl group, a thiophen-yl group, a silole-yl group). As the polymerizable functional group, particularly, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are preferable, and from the viewpoint of reactivity and characteristics of the organic electronic element, a vinyl group, an oxetane group, or an epoxy group is more preferable. preferable.

  From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the polymerization reaction, the main skeleton of the charge transporting polymer and the polymerizable functional group are preferably connected by an alkylene chain. In addition, for example, when an organic layer is formed on an electrode, from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO, the organic layer may be connected by a hydrophilic chain such as an ethylene glycol chain or a diethylene glycol chain. preferable. Further, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group, the charge transporting polymer is used as the terminal portion of the alkylene chain and / or the hydrophilic chain, that is, the chain is polymerized with these chains. An ether bond or an ester bond may be present in the link between the functional group and / or the link between these chains and the skeleton of the charge transporting polymer. The above-mentioned “group containing a polymerizable functional group” means a polymerizable functional group itself or a group obtained by combining a polymerizable functional group with an alkylene chain or the like. As the group containing a polymerizable functional group, for example, a group exemplified in International Publication No. WO2010 / 140553 can be suitably used.

  The polymerizable functional group may be introduced into the terminal portion (ie, the structural unit T) of the charge transporting polymer, or may be introduced into a portion other than the terminal portion (ie, the structural unit L or B). And a moiety other than the terminal. 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, when the charge transporting polymer has a branched structure, the polymerizable functional group may be introduced into the main chain of the charge transporting polymer or may be introduced into the side chain. May be introduced.

  From the viewpoint of contributing to a change in solubility, it is preferable that the polymerizable functional group be 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. In addition, the number of polymerizable functional groups is preferably 1,000 or less, and more preferably 500 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. For simplicity, when the charged amount is clear, preferably, a value obtained using the charged amount is used.

(Number average molecular weight)
The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film formability, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more, from the viewpoint of excellent charge transportability. Further, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and 50,000 from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. The following are more preferred.

(Weight average molecular weight)
The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film formability, 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 charge transportability. Further, the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and 400,000, from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. The following are more preferred.

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

(Ratio of structural units)
The ratio of the structural unit containing silicon contained in the charge transporting polymer, that is, the ratio of the structural unit L1 and / or the structural unit B1 based on all the structural units is 1 mol from the viewpoint of obtaining excellent durability. % Or more, more preferably 3 mol% or more, and most preferably 5 mol% or more. On the other hand, from the viewpoint of further improving the charge transporting property of the charge transporting polymer, the charge transporting polymer preferably further includes a structural unit having a charge transporting property other than the structural unit L1 and / or the structural unit B1. From such a viewpoint, in one embodiment, the ratio of the structural unit L1 and / or the structural unit B1 is preferably 90 mol% or less, more preferably 80 mol% or less, and more preferably 70 mol% or less based on all the structural units. Is more preferable. In one embodiment, the proportion of the silicon-containing structural unit in the charge transporting polymer is preferably from 5 to 90 mol%, more preferably from 10 to 80 mol%, and still more preferably from 15 to 90 mol%, based on all structural units. It is in the range of 70 mol%. The above ratio is also preferable in that a charge transporting polymer having an appropriate molecular weight can be obtained as the charge transporting material.

  In the charge transporting polymer, the proportion of the divalent structural unit L 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 charge transportability. % Or more is more preferable. Further, in consideration of the structural unit T and the structural unit B introduced as necessary, the proportion of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and further preferably 85 mol% or less. Here, the structural unit L means the total of the structural unit L1 and the structural unit L2 introduced as needed. In light of exhibiting the effect of the silicon-containing structural unit, the ratio of the structural unit L1 to the total amount of L1 and L2 is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more. It is.

  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.

  When the charge transporting polymer contains a trivalent or higher valent structural unit B, the proportion of the structural unit B is preferably 1 mol% or more, preferably 5 mol%, based on all structural units, from the viewpoint of improving the durability of the organic electronic element. % Or more, more preferably 10 mol% or more. Further, the proportion of the structural unit B is preferably 50 mol% or less, and more preferably 40 mol% or less, from the viewpoint of suppressing an increase in viscosity and favorably synthesizing the charge transporting polymer, or from the viewpoint of obtaining a sufficient charge transporting property. Is more preferable, and 30 mol% or less is further preferable. Here, the structural unit B means the total of the structural unit B1 and the structural unit B2 introduced as needed. In light of exhibiting the effect of the silicon-containing structural unit, the ratio of the structural unit B1 to the total amount of B1 and B2 is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more. It is.

  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 of charge transportability, durability, productivity, and the like, the ratio (molar ratio) of the structural units L and T is preferably L: T = 100: 1 to 70, and more preferably 100: 3 to 50. Preferably, 100: 5-30 is more preferable. When the charge transporting polymer contains the structural unit B, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is L: T: B = 100: 10 to 200: 10 to 100. Preferably, 100: 20-180: 20-90 is more preferable, and 100: 40-160: 30-80 is still more preferable. Here, the structural unit L means the total of the structural unit L1 containing silicon and the structural unit L2 introduced as needed. Further, the structural unit B means the total of the structural unit B1 containing silicon and the structural unit B2 introduced as needed. Here, the ratio between the structural units L1 and L2 and the ratio between the structural units B1 and B2 are as described above.

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, known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Still 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 International Publication WO 2010/140553 can be referred to.

In the case of preparing a charge transporting polymer using the Suzuki coupling reaction, examples of combinations of monomer compounds that can be suitably used as raw materials are shown below. R described in the monomer (B) and the monomer (L) is the same as R described in the structural unit B1 and the structural units L1 and L2, respectively.

[Dopant]
When the organic electronic device is formed using the charge transporting material, the charge transporting material may further include an additive known as an organic electronic material. In one embodiment, the charge transporting material may further include a dopant. The dopant is not particularly limited as long as it can exert a doping effect by being added to the charge transporting material and improve the charge transporting property. 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 charge transporting material may be a dopant that exhibits any of p-type doping and n-type doping effects. 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 protonic acid, HF, HCl, HBr, HNO ₅ , H ₂ SO ₄ , inorganic acids such as HClO _4, benzenesulfonic acid, p- toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinyl sulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butane sulfonic acid, vinyl phenyl sulfonate , 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). Further, it is also possible to use the electron-accepting compounds 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.

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 capable of acting as a polymerization initiator for the polymerizable functional group as a dopant in order to easily change the solubility of the organic layer.

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

[Content]
The content of the charge transporting polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 80% by mass or more, based on the total mass of the charge transporting material, from the viewpoint of obtaining good charge transporting properties. More preferred. It can be 100% by mass.

  When a dopant is contained, the content is preferably 0.01% by mass or more, and more preferably 0.1% by mass, based on the total mass of the charge transporting material, from the viewpoint of improving the charge transporting property of the charge transporting material. More preferably, the content is 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 even more preferably 20% by mass or less based on the total mass of the charge transporting material.

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

[solvent]
As the solvent, 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 and 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, aromatic ethers and the like.

[Polymerization initiator]
When the charge transporting polymer has a polymerizable functional group, the ink 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 that the ink composition can be easily prepared, 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 described above.

[Additive]
The ink 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 ink composition can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the charge 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 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. 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 organic layer (coated layer) obtained after the coating may be dried using a hot plate or an oven to remove the solvent.

  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 organic layer can be changed. By stacking the organic layers having different solubilities, it is possible to easily achieve a multilayer structure of the organic electronic element. For the method of forming the organic layer, for example, the description in International Publication WO 2010/140553 can be referred to.

  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 the organic layer according to the above embodiment. 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.

[Organic EL device]
An organic EL device according to an embodiment of the present invention has at least the organic layer according to the above embodiment. 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 an organic layer as a light emitting layer or another functional layer, more preferably has a functional layer, and still more preferably has at least one of a hole injection layer and a hole transport layer.

  FIG. 1 is a schematic sectional view showing an embodiment of the organic EL device. 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, which are composed of the organic layers of the above embodiment, a light emitting layer 1, an electron transport layer 7, An electron injection layer 5 and a cathode 4 are provided in this order. Hereinafter, each layer will be described.

[Hole injection layer, hole transport layer]
In FIG. 1, the hole injection layer 3 and the hole transport layer 6 are organic layers formed using the charge transporting material or the ink composition, but the organic EL element is not limited to such a structure. Another organic layer may be a layer formed using the charge transporting material or the ink composition. It is preferable that at least one of the hole transport layer and the hole injection layer is an organic layer formed using the charge transporting material or the ink composition, and that at least the hole transport layer is the organic layer. preferable. For example, when the organic EL element has an organic layer formed using the charge transporting material or the ink composition as a hole transport layer, and further has a hole injection layer, a known hole injection layer is used. Material can be used. Further, for example, when the organic EL element has an organic layer formed using the charge transporting material or the ink composition as a hole injecting layer, and further has a hole transporting layer, the hole transporting layer Known materials can be used.

[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 compounds such as perylene, coumarin, rubrene, quinacdrine, stilbene, dyes for dye lasers, aluminum complexes, and derivatives thereof; polyfluorene, polyphenylene, polyphenylenevinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer , Fluorene-triphenylamine copolymers, and their derivatives; 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) (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate) that emits blue light and Ir (ppy) ₃ that 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)), Ir (piq) ₃ (tris (1-phenylisoquinoline) iridium) and the like. Examples of the Pt complex include PtOEP (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-forfin platinum) that emits red light.

  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 their derivatives. Examples of the polymer include the charge-transporting material of the above embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, and their derivatives. No.

  Examples of the thermally activated delayed fluorescent material include, 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).

[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, thiopyran dioxide 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. Further, the charge transporting material of the above embodiment 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, light transmissive resin film and the like are preferably used.

  As the resin film, for example, a film made of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, etc. No.

  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.

[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.

  As a method for forming a white organic EL element, a method in which a plurality of light-emitting colors are simultaneously emitted using a plurality of light-emitting materials to mix colors can be used. The combination of a plurality of emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, and two emission maximum wavelengths such as blue and yellow, yellow green and orange, etc. Combinations to be included. 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 according to 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 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 according to the embodiment of the present invention. Further, the display device according to the embodiment of the present invention includes a lighting device and a liquid crystal element as a display unit. For example, the display device can be a display device using a lighting device according to an embodiment of the present invention as a backlight and a known liquid crystal element as a display means, that is, a liquid crystal display device.

(Example)
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

<1> 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, anisole (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, anisole (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. In the preparation of the catalyst, all solvents were used after being degassed with nitrogen bubbles for 30 minutes or more.

(Preparation Example 1) Charge transporting polymer 1
The following monomer 1 (4.0 mmol), the following monomer 2 (5.0 mmol), the following monomer 3 (2.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a solution of a separately prepared Pd catalyst was further added. (7.5 mL) and stirred. After stirring for 30 minutes, a 10% aqueous solution of tetraethylammonium hydroxide (20 mL) was added into the flask. The mixture was heated and refluxed for 2 hours. Note that all operations up to this point were performed under a nitrogen stream. All solvents were used after degassing with nitrogen bubbles for 30 minutes or more.

After the completion of the reaction, the organic layer was washed with water. Then, the organic layer was poured into methanol-water (9: 1). The resulting precipitate was filtered by suction and washed with methanol-water (9: 1). The precipitate after washing was dissolved in toluene and reprecipitated from methanol. The resulting precipitate is suction-filtered, dissolved in toluene, and added with triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer (200 mg per 100 mg of polymer, Strem Chemicals, hereinafter referred to as “metal adsorbent”). Stirred overnight.
After completion of the stirring, the metal adsorbent and insolubles were removed by filtration, and the filtrate was concentrated using a rotary evaporator. After dissolving the concentrate in toluene, it was reprecipitated from methanol-acetone (8: 3). The resulting precipitate was suction filtered and washed with methanol-acetone (8: 3). The resulting precipitate was dried under vacuum to obtain a charge transporting polymer 1.
The number average molecular weight of the obtained charge transporting polymer 1 was 7,800, and the weight average molecular weight was 31,000. The molecular weight was measured by GPC (in terms of polystyrene) using THF as an eluent. The charge-transporting polymer 1 has a trivalent or higher valent structural unit B2 (derived from the monomer 3) containing no silicon, a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a polymerizable functional group. And a monovalent structural unit T (derived from monomer 1), and the ratio of each structural unit was 18.2%, 45.5%, and 36.4%, respectively.

The measurement conditions of the number average molecular weight and the weight average molecular weight are as follows.
Liquid 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 (manufactured by Wako Pure Chemical Industries, for HPLC, without stabilizer)
Flow rate: 1 mL / min
Column temperature: room temperature Molecular weight standard substance: standard polystyrene

(Preparation Example 2) Charge transporting polymer 2
Monomer 2 (5.0 mmol) and Monomer 3 (2.0 mmol) described in Preparation Example 1, Monomer 4 (4.0 mmol), and Anisole (20 mL) described in Preparation Example 1 were added to a three-necked round bottom flask, and further separately prepared. A solution of the Pd catalyst (7.5 mL) was added and stirred. Thereafter, the charge transporting polymer 2 was prepared in the same manner as in the method described in Preparation Example 1.
The number average molecular weight of the obtained charge transporting polymer 2 was 22,900, and the weight average molecular weight was 169,000. The charge transporting polymer 2 includes a trivalent or higher valent structural unit B2 (derived from the monomer 3) containing no silicon, a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a monovalent structural unit. Including T (derived from monomer 4), the ratio of each structural unit was 18.2%, 45.5%, and 36.4%, respectively.

(Preparation Example 3) Charge transporting polymer 3
In a three-necked round bottom flask, monomer 2 (5.0 mmol) described in Preparation Example 1 and monomer 4 (4.0 mmol) described in Preparation Example 2, the following monomer 5 (1.5 mmol), and anisole (20 mL) were added. Was added, and a separately prepared solution of a Pd catalyst (7.5 mL) was added, followed by stirring. Thereafter, the charge transporting polymer 3 was prepared in the same manner as in Preparation Example 1.
The number average molecular weight of the obtained charge transporting polymer 3 was 7,200, and the weight average molecular weight was 60,200. The charge-transporting polymer 3 is composed of a trivalent or higher-valent silicon-containing structural unit B1 (derived from the monomer 5), a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a monovalent structural unit T (Derived from monomer 4), and the ratio of each structural unit was 14.3%, 47.6%, and 38.1%, respectively.

(Preparation Example 4) Charge transporting polymer 4
Charge transportable polymer 4 was prepared in the same manner as in Preparation Example 3 except that monomer 6 was used instead of monomer 2.
The number average molecular weight of the obtained charge transporting polymer 4 was 3,300, and the weight average molecular weight was 25,700. The charge transporting polymer 4 includes a trivalent or higher valent silicon-containing structural unit B1 (derived from the monomer 5), a divalent silicon-free structural unit L2 (derived from the monomer 6), and a monovalent structural unit T (Derived from monomer 4), and the ratio of each structural unit was 14.3%, 47.6%, and 38.1%, respectively.

(Preparation Example 5) Charge transporting polymer 5
Charge transportable polymer 5 was prepared in the same manner as in Preparation Example 3, except that monomer 4 (4.0 mmol) was changed to monomer 4 (2.0 mmol) and monomer 1 (2.0 mmol).
The number average molecular weight of the obtained charge transporting polymer 5 was 6,500, and the weight average molecular weight was 50,700. The charge transporting polymer 5 includes a trivalent or higher-valent silicon-containing structural unit B1 (derived from the monomer 5), a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a monovalent structural unit T ( Monomer 4) and a monovalent structural unit T having a polymerizable functional group (derived from monomer 1), and the ratio of each structural unit is 14.3%, 47.6%, 19 0.1% and 19.1%.

(Preparation Example 6) Charge transporting polymer 6
In a three-necked round bottom flask, the monomer 2 (5.0 mmol) described in Preparation Example 1 and the monomer 4 (2.0 mmol) described in Preparation Example 2, the following monomer 7 (4.0 mmol), and anisole (20 mL) were added. Was added, and a separately prepared solution of a Pd catalyst (7.5 mL) was added, followed by stirring. Thereafter, the charge transporting polymer 6 was prepared in the same manner as in Preparation Example 1.
The number average molecular weight of the obtained charge transporting polymer 6 was 4,500, and the weight average molecular weight was 5,700. The charge transporting polymer 6 is composed of a silicon-containing divalent structural unit L1 (derived from the monomer 7), a silicon-free divalent structural unit L2 (derived from the monomer 2), and a monovalent structural unit T ( Monomer 4), and the proportion of each structural unit was 36.4%, 45.5%, and 18.2%, respectively.

(Preparation Example 7) Charge transporting polymer 7
Same as Preparation Example 3 except that monomer 5 (1.5 mmol) was changed to monomer 5 (0.75 mmol) and monomer 7 (3.0 mmol), monomer 2 was used 6.0 mmol, and monomer 4 was used 3.0 mmol. In the manner described above, the charge transporting polymer 7 was prepared.
The number average molecular weight of the obtained charge transporting polymer 7 was 5,300, and the weight average molecular weight was 35,700. The charge-transporting polymer 7 includes a silicon-containing trivalent or higher valent structural unit B1 (derived from the monomer 5), a silicon-containing divalent structural unit L1 (derived from the monomer 7), and a silicon-free divalent structure. It contains a unit L2 (derived from monomer 2) and a monovalent structural unit T (derived from monomer 4), and the ratio of each structural unit is 5.9%, 23.5%, 47.1% , And 23.5%.

(Preparation Example 8) Charge transporting polymer 8
Charge transportable polymer 8 was prepared in the same manner as in Preparation Example 3, except that monomer 8 (2.0 mmol) was used instead of monomer 5 (1.5 mmol).
The number average molecular weight of the obtained charge transporting polymer 8 was 3,300, and the weight average molecular weight was 25,700. The charge transporting polymer 8 includes a trivalent or higher valent structural unit B1 (derived from the monomer 8) containing silicon, a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a monovalent structural unit T (Derived from monomer 4), and the ratio of each structural unit was 18.2%, 45.5%, and 36.4%, respectively.

<2-1> Preparation of organic EL element (Example 1)
Under a nitrogen atmosphere, a charge-transporting polymer 1 (10.0 mg) obtained by synthesizing the above-described charge-transporting polymer, a ionic compound (0.5 mg) shown below, on a glass substrate on which ITO was patterned to a width of 1.6 mm, After spin coating at 3000 min ⁻¹ , the ink composition 1 composed of toluene and 2.3 mL of toluene was heated and cured on a hot plate at 220 ° C. for 10 minutes to form a hole injection layer (30 nm).

Next, on the hole injection layer obtained by the above operation, an ink composition 3 composed of the charge transporting polymer 3 (20 mg), the ionic compound (1.0 mg), and toluene (2.3 mL) was added. After spin coating at 3000 min ⁻¹ , the resultant was heated at 180 ° C. for 10 minutes on a hot plate and dried to form a hole transport layer (40 nm). The hole transport layer could be formed without dissolving the hole injection layer.

The substrate obtained above was transferred into a vacuum evaporation machine, and CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), Alq ₃ (30 nm), 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 element.

(Example 2)
In Example 1, an ink composition 4 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer in the organic EL element was changed to the above charge transporting polymer 4. An organic EL device was produced in the same manner as in Example 1 except that a hole transport layer was formed using this ink composition 4.

(Example 3)
In Example 1, an ink composition 5 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer in the organic EL element was changed to the charge transporting polymer 5. An organic EL device was produced in the same manner as in Example 1 except that a hole transport layer was formed using this ink composition 5.

(Example 4)
In Example 1, an ink composition 6 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer in the organic EL element was changed to the charge transporting polymer 6. An organic EL device was produced in the same manner as in Example 1 except that a hole transport layer was formed using this ink composition 6.

(Example 5)
In Example 1, an ink composition 7 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer in the organic EL element was changed to the above charge transporting polymer 7. An organic EL device was produced in the same manner as in Example 1 except that a hole transport layer was formed using this ink composition 7.

(Example 6)
In Example 1, an ink composition 8 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer in the organic EL element was changed to the above charge transporting polymer 8. An organic EL device was produced in the same manner as in Example 1 except that a hole transport layer was formed using this ink composition 8.

(Comparative Example 1)
In Example 1, an ink composition 2 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer in the organic EL element was changed to the charge transporting polymer 2. An organic EL device was produced in the same manner as in Example 1 except that a hole transport layer was formed using this ink composition 2.

<2-2> Evaluation of Organic EL Device When a voltage was applied to the organic EL devices obtained in Examples 1 to 6 and Comparative Example 1, green light emission was confirmed in each case. For each element, emission luminance 1000 cd / ^{m 2} at the drive voltage and luminous efficiency were measured emission lifetime (luminance half-life) in the initial luminance 3000 cd / ^{m 2.} Table 2 shows the measurement results.

  As shown in Table 2, the organic EL devices of Examples 1 to 6 exhibited lower driving voltage, higher luminous efficiency, and longer luminous life than Comparative Example 1. That is, from the viewpoint of the constituent material of the hole transporting layer, by using a charge transporting polymer having a structural unit containing silicon in the molecule as a charge transporting material, it is possible to improve luminous efficiency and luminous life. It can be seen that the effect can be obtained.

<3-1> Production of white organic EL element (illumination device) (Example 7)
In the same manner as in Example 1, under a nitrogen atmosphere, a charge transporting polymer 1 (10.0 mg), an ionic compound (0.5 mg), and toluene (2 .3 mL) was spin-coated at 3000 min ^-1 , and cured by heating at 220 ° C. for 10 minutes on a hot plate to form a hole injection layer (30 nm).

Next, similarly to Example 1, the charge transporting polymer 3 (20 mg), the ionic compound (1.0 mg), and toluene (2.3 mL) were formed on the hole injection layer obtained by the above operation. The ink composition 3 was spin-coated at 3000 min ^-1 and then cured by heating at 180 ° C. for 10 minutes on a hot plate to form a hole transport layer (40 nm). The hole transport layer could be formed without dissolving the hole injection layer.

Next, in nitrogen, CDBP (15 mg), FIr (pic) (0.9 mg), Ir (ppy) ₃ (0.9 mg), (btp) ₂ Ir (acac) (1.2 mg), and dichlorobenzene ( 0.5 mL) was spin-coated at 3000 min ^-1 and then dried at 80 ° C. for 5 minutes to form a light-emitting layer (40 nm). Further, BAlq (10 nm), Alq ₃ (30 nm), LiF (0.5 nm), and Al (100 nm) were deposited in this order, and sealing treatment was performed to produce a white organic EL device. The white organic EL element could be used as a lighting device. The light emitting layer could be formed without dissolving the hole transport layer.

(Example 8)
In Example 7, an ink composition 4 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer was changed to the charge transporting polymer 4. A white organic EL device was produced in the same manner as in Example 7, except that a hole transport layer was formed using this ink composition 4.

(Example 9)
In Example 7, an ink composition 5 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer was changed to the charge transporting polymer 5. A white organic EL device was produced in the same manner as in Example 7, except that a hole transport layer was formed using this ink composition 5.

(Example 10)
In Example 7, an ink composition 6 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer was changed to the charge transporting polymer 6. A white organic EL device was produced in the same manner as in Example 7, except that a hole transport layer was formed using this ink composition 6.

(Example 11)
In Example 7, an ink composition 7 was prepared in which the charge transport polymer 3 in the ink composition 3 used for forming the hole transport layer was changed to the charge transport polymer 7. A white organic EL device was produced in the same manner as in Example 7, except that a hole transport layer was formed using this ink composition 7.

(Example 12)
In Example 7, an ink composition 8 was prepared in which the charge transport polymer 3 in the ink composition 3 used for forming the hole transport layer was changed to the charge transport polymer 8. A white organic EL device was produced in the same manner as in Example 7, except that a hole transport layer was formed using this ink composition 8.

(Comparative Example 2)
In Example 7, an ink composition 2 was prepared in which the charge transporting polymer 3 in the ink composition 3 used for forming the hole transporting layer was changed to the charge transporting polymer 2. A white organic EL device was produced in the same manner as in Example 7, except that a hole transport layer was formed using this ink composition 2.

<3-2> Evaluation of White Organic EL Element (Illumination Device) A voltage was applied to the white organic EL elements obtained in Examples 7 to 12 and Comparative Example 2, and a drive voltage and light emission at an initial luminance of 1000 cd / m ² were applied. The efficiency and the luminescence lifetime were measured. Table 3 shows the driving voltages, luminous efficiencies, and luminous lives of Examples 7 to 12 when the driving voltage, the luminous efficiency, and the luminous life of Comparative Example 2 were each set to 1.

  As shown in Table 3, the white organic EL elements of Examples 7 to 12 are superior to the white organic EL element of Comparative Example 2 in luminous efficiency and luminous life. That is, from the viewpoint of the constituent material of the hole transporting layer, the use of the charge transporting polymer having the structural unit containing silicon as the charge transporting material has the effect of improving the luminous efficiency and the luminous life. It is understood that it can be done.

  As described above, the effects of the embodiment of the present invention are shown by the examples. However, according to the present invention, the charge transporting material is not limited to the charge transporting polymer used in the examples, and the charge transporting material may be constituted by using other charge transporting polymers without departing from the scope of the present invention. In the same manner, an organic electronic element can be obtained. The obtained organic electronic device has excellent effects as in the above embodiments.

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 (13)

A charge transporting material comprising a charge transporting polymer containing a silicon-containing trivalent or tetravalent structural unit B1 represented by the following formula.

[Wherein, R is a hydrogen atom or a linear, cyclic, or branched alkyl group, alkenyl group, alkynyl group, and alkoxy group having 1 to 22 carbon atoms, and 2 to 30 carbon atoms. And Ar is independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. ]   The charge transport material according to claim 1, wherein the charge transport polymer includes a tetravalent structural unit B1 in which each Ar is independently a substituted or unsubstituted phenylene group or naphthylene group. The charge-transporting polymer is a silicon-containing divalent structural unit L1 represented by the following formula:

[Wherein, R is each independently a hydrogen atom, or a linear, cyclic, or branched alkyl group, alkenyl group, alkynyl group, and alkoxy group having 1 to 22 carbon atoms, and Ar is selected from the group consisting of an aryl group and a heteroaryl group having 2 to 30 carbon atoms, and Ar is independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms . ]
And at least one of the divalent structural units L2 having charge transportability other than the silicon-containing divalent structural units L1,
The divalent structural units L2 is an aromatic amine structure, a carbazole structure, thiophene structure, having at least one structure selected from the group consisting of bithiophene structure, benzene structures, and fluorene structure, according to claim 1 or 2 Charge transporting materials. The charge transporting material according to claim 3 , wherein the divalent structural unit L2 having charge transporting property includes at least one structure 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 4, which is used as a hole transporting material.   An ink composition comprising the charge transporting material according to claim 1 and a solvent.   An organic electronic device having an organic layer containing the charge transporting material according to claim 1.   An organic electroluminescence device having an organic layer containing the charge transporting material according to claim 1.   The organic electroluminescence device according to claim 8, further comprising a flexible substrate.   The organic electroluminescence device according to claim 9, wherein the flexible substrate includes a resin film.   A display device comprising the organic electroluminescence device according to claim 8.   A lighting device comprising the organic electroluminescent element according to claim 8.   A display device comprising: the lighting device according to claim 12; and a liquid crystal element as a display unit.

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