JP2017066289A - Charge transporting material, ink composition using the material, organic electronics element, organic electroluminescent element, display element, lighting device and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge transporting material containing a charge transporting polymer which can be applied for organic electronics elements, and an ink composition containing the material, and provide an organic electronics element excellent in luminous efficiency and emission lifetime and an organic EL element, and a display element, a lighting device, and a display device using them.SOLUTION: A charge transporting polymer comprising at least one of a silicon-comprising divalent structural unit L1 and a silicon-comprising trivalent or more structural unit B1 is used as a charge transporting material.SELECTED DRAWING: None

Description

  Embodiments described herein relate generally to a charge transport material and an ink composition using the material. In addition, another embodiment of the present invention relates to an organic electronics element, an organic electroluminescence 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 electronics elements are elements that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that can replace conventional inorganic semiconductors based on silicon. ing.

  Examples of organic electronics elements include organic electroluminescence elements (hereinafter also referred to as “organic EL elements”), organic photoelectric conversion elements, organic transistors, and the like.

  Among organic electronics elements, organic EL elements are attracting attention as applications for large-area solid-state light sources as an alternative to incandescent lamps and gas-filled lamps, for example. It is also attracting attention as the most powerful self-luminous display that can replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and its commercialization is progressing.

  Organic EL elements are roughly classified into two types, low molecular organic EL elements and polymer organic EL elements, from the organic materials used. In the polymer organic EL element, a polymer material is used as an organic material, and in the low molecular organic EL element, a low molecular material is used. Compared with low-molecular-weight organic EL devices, which are mainly formed in a vacuum system, polymer-type organic EL devices can be easily formed by wet processes such as printing and ink-jet. It is expected as an indispensable element for EL displays.

  For this reason, development of a material suitable for a wet process is underway, and for example, studies as described in Patent Document 1 are being performed.

JP 2006-279007 A

  In general, an organic EL device manufactured by a wet process using a polymer material has a feature that it is easy to reduce the cost and increase the area. However, an organic EL element including a thin film manufactured using a conventional polymer material is desired to be further improved in characteristics of the organic EL element such as driving voltage, light emission efficiency, and light emission lifetime.

  In view of the above, an object of one embodiment of the present invention is to provide a charge transporting material containing a charge transporting polymer that can be used in an organic electronic device, and an ink composition containing the material. In another embodiment, an organic electronics element, an organic EL element, and a display element and an illuminating device using the charge transporting material or the ink composition are excellent in luminous efficiency and luminous lifetime. And a display device.

  As a result of intensive studies, the present inventors have 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 electronics element, and to complete the present invention. It came.

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

  Here, the charge transporting polymer includes the divalent structural unit L2 having charge transporting property and the charge other than the divalent structural unit L1 containing silicon and the trivalent or higher structural unit B1 containing silicon. It is preferable that at least one of trivalent or higher structural units B2 having transportability is further included. More preferably, the charge transporting polymer further includes a divalent structural unit L2 having charge transporting properties other than the divalent structural unit L1 containing silicon. The divalent structural unit L2 having charge transporting properties 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 comprising 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 transport material of the above embodiment.

  One embodiment of the present invention relates to an organic electroluminescent device having an organic layer containing the charge transport material of the above-described 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 comprising the organic electroluminescence device of the above embodiment.

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

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

  According to the embodiments of the present invention, an organic electronics element, an organic EL element, and a display element, an illumination device, and a display device that use the organic electronic element and the organic EL element that have excellent durability, low driving voltage, and excellent emission efficiency and lifetime. Can be provided.

It is typical sectional drawing which shows one Embodiment of the organic EL element of this invention.

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

(Charge transporting polymer)
In the present invention, the charge transporting polymer may be any polymer that includes a structural unit containing silicon in the molecule and exhibits charge transporting properties. The charge transporting polymer may have a linear structure or a branched structure. More specifically, the charge transporting polymer preferably includes at least a divalent structural unit L having charge transporting properties and a monovalent structural unit T constituting a terminal portion, and further constitutes a branched portion. A structural unit B having a valence or higher may be included. The charge transporting polymer may contain only one type of each structural unit, or may contain a plurality of types. In the charge transporting polymer, each structural unit is bonded to each other at a binding site of “monovalent” to “trivalent or higher”.

(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 structure. In the partial structure, “L” represents the structural unit L, “T” represents the structural unit T, and “B” represents the structural unit B. “*” Represents a binding site with another structural unit. In the following partial structures, a plurality of L may be the same structural unit or different structural units. The same applies to T and B.

Linear charge transporting polymer

Charge transporting polymer having a branched structure

In one embodiment, the charge transporting polymer includes at least one of a divalent structural unit L1 containing silicon and a trivalent or higher structural unit B1 containing silicon described below.
(Structural unit L1)
The divalent structural unit L1 containing silicon 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 arenetriyl group is bonded to silicon. . Examples of the divalent structural unit L1 containing silicon include the following.

Here, in the formula, each R is 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 an aryl group and a heteroaryl group having 2 to 30 carbon atoms. The aryl group and 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, a substituted or unsubstituted phenyl group or More preferred 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, more preferably a substituted or unsubstituted phenylene group. Or it is a naphthylene group, More preferably, it is an unsubstituted phenylene group. The phenylene group may be any of 1,2-phenylene group, 1,3-phenylene group, and 1,4-phenylene group, but 1,4-phenylene group is preferable. In the formula, “*” represents a binding site with another structural unit.

Specific examples of the structural unit L1 include the following. 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 includes 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 respectively as described in the divalent structural unit L1.

Specific examples of the structural unit B1 include the following. However, the structural unit B1 is not limited to the following.

  In one embodiment, the charge transporting polymer further includes a divalent structural unit L2 having charge transporting property and a trivalent or higher structural unit B2 having charge transporting property other than the structural unit L1 and the structural unit B1. It is preferable that at least one of these is included. Specific examples are as follows.

(Structural unit L2)
The structural unit L2 is a divalent structural unit having charge transportability. The structural unit L2 is not particularly limited as long as it includes an atomic group having the ability to transport charges. For example, the structural unit L2 includes 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, benzo A thiophene structure, a benzoxazole structure, a benzooxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, and one of these It is selected from a structure containing two or more kinds. The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.

  In one embodiment, the structural unit L2 has a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, and these from the viewpoint of obtaining excellent hole transport properties. Preferably, it is selected from a structure containing one or more of these, and is selected from a substituted or unsubstituted aromatic amine structure, carbazole structure, and a structure containing one or more of these Is more preferable. In another embodiment, the structural unit L2 has a substituted or unsubstituted fluorene structure, benzene structure, phenanthrene structure, pyridine structure, quinoline structure, and one or two of these from the viewpoint of obtaining excellent electron transport properties. It is preferably selected from structures containing more than one species.

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

Each R independently represents a hydrogen atom or a substituent. Preferably, each R independently represents —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , a halogen atom, and a polymerizable functional group described later. Selected from the group consisting of containing groups. R ^{1 to} R ⁸ each independently represents a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or heteroaryl group having 2 to 30 carbon atoms. The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic ring. 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 linear, cyclic or branched having 1 to 22 carbon atoms. It may be substituted with 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. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. 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 polycycle in which two or more selected from a single ring and a condensed ring are bonded via a single bond. Examples of the aromatic heterocycle include a single ring, a condensed ring, or a polycycle in which two or more selected from a monocycle and a condensed ring are bonded via a single bond.

(Structural unit B2)
The structural unit B2 is a trivalent or higher-valent structural unit that constitutes a branched portion when the charge transporting polymer has a branched structure. 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, carbazole structure, condensed polycyclic aromatic hydrocarbon structure, and one or two of these from the viewpoint of improving the durability of the organic electronic device. 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.

Specific examples of the structural unit B2 include the following. However, the structural unit B2 is not limited to the following.

  W represents a trivalent linking group, for example, an arenetriyl 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. The heteroarene triyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocyclic ring. Ar each independently represents a divalent linking group, for example, each independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group. For example, one R atom in the structural unit L2 (excluding a group containing a polymerizable functional group) has one more hydrogen atom from a group having one or more hydrogen atoms. And divalent groups 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 the terminal portion of the charge transporting polymer. The structural unit T is not particularly limited, and is selected from, for example, a substituted or unsubstituted aromatic hydrocarbon structure, aromatic heterocyclic structure, and a structure including 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 deteriorating charge transportability, and is preferably a substituted or unsubstituted benzene structure. A structure is more preferable. In another embodiment, as will be described later, when the charge transporting polymer has a polymerizable functional group at the terminal portion, the structural unit T has a polymerizable structure (that is, polymerizable such as a pyrrole-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.

Specific examples of the structural unit T include the following. 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 portion, 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 divalent structural unit L1 containing silicon and a trivalent or higher structural unit B1 containing silicon, and the divalent structural unit L1 In addition, it is preferable to include a divalent structural unit L2 having charge transporting properties 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, the charge-transporting polymer preferably includes a tri- 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 structural unit B1. “A structure branched in three or more directions” means that the main chain has the same degree of polymerization when the main chain has the highest degree of polymerization among various chains in one molecule of the charge transporting polymer. Or it means that one or more side chains having a smaller degree of polymerization are present. In the present invention, the degree of polymerization indicates how many monomer units 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 structural unit. Other than that, the side chain 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. The “polymerizable functional group” refers to a functional group that can form a bond with each other by applying heat and / or light.

  The polymerizable functional group includes a group 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 groups, cyclobutyl groups; cyclic ether groups such as epoxy groups (oxiranyl groups), oxetane groups (oxetanyl groups), etc. Diketene group; episulfide group; lactone group; lactam group, etc.), heterocyclic group (for example, furan-yl group, pyrrol-yl group, thiophen-yl group, silole-yl group) and the like. As the polymerizable functional group, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are particularly preferable, and from the viewpoint of reactivity and characteristics of the organic electronics 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, it is preferable that the main skeleton of the charge transporting polymer and the polymerizable functional group are connected by an alkylene chain. In addition, for example, when an organic layer is formed on an electrode, it is connected with a hydrophilic chain such as an ethylene glycol chain or a diethylene glycol chain from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO. preferable. Further, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group, the charge transporting polymer is polymerized with the end of the alkylene chain and / or the hydrophilic chain, that is, with these chains. An ether bond or an ester bond may be present at the connecting portion with the functional group and / or the connecting portion 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 part (that is, the structural unit T) of the charge transporting polymer, or may be introduced into a part other than the terminal part (that is, the structural unit L or B). And may be introduced into both of the portions other than the terminal. From the viewpoint of curability, it is preferably introduced at least at the end portion, and from the viewpoint of achieving both curability and charge transportability, it is preferably introduced only at the end portion. 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 into the side chain, and both the main chain and the side chain may be introduced. May be introduced.

  It is preferable that a large amount of the polymerizable functional group is contained in the charge transporting polymer from the viewpoint of contributing to the change in solubility. On the other hand, from the viewpoint of not impeding charge transportability, it is preferable that the amount contained in the charge transport 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 solubility change. 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 charge transporting polymer is the amount of the polymerizable functional group used to synthesize the charge transporting polymer (for example, the amount of the monomer having a polymerizable functional group), each structure The average value can be obtained by using the monomer charge corresponding to the unit and the weight average molecular weight of the charge transporting polymer. The number of polymerizable functional groups is the ratio between the integral value of the signal derived from the polymerizable functional group and the integral value of the entire spectrum in the ¹ H NMR (nuclear magnetic resonance) spectrum of the charge transporting polymer, the charge transporting polymer The weight average molecular weight can be used to calculate the average value. Since it is simple, when the preparation amount is clear, a value obtained by using the preparation amount is preferably adopted.

(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. The number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and more preferably 50,000 from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of an ink composition. The following is more preferable.

(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 more preferably 400,000 from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of an 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 standard polystyrene calibration curve.

(Percentage of structural units)
The proportion of the structural unit containing silicon contained in the charge transporting polymer, that is, the proportion of the structural unit L1 and / or the structural unit B1 based on the total structural unit 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 transport property of the charge transport polymer, the charge transport polymer preferably further includes a structural unit having a charge transport 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 70 mol% or less, based on all structural units. More preferably. In one embodiment, the proportion of the structural unit containing silicon in the charge transporting polymer is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and still more preferably 15 to 15 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 a 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, more preferably 30 mol based on the total structural unit from the viewpoint of obtaining sufficient charge transportability. % Or more is more preferable. Further, the ratio of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less in consideration of the structural unit T and the structural unit B introduced as necessary. Here, the structural unit L means the sum of the structural unit L1 and the structural unit L2 introduced as necessary. From the viewpoint of expressing the effect of the structural unit containing silicon, 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 even more preferably 5 mol% or more. It is.

  The proportion of the structural unit T contained in the charge transporting polymer is based on the total structural unit from the viewpoint of improving the characteristics of the organic electronics element or suppressing the increase in the viscosity and satisfactorily synthesizing the charge transporting polymer. 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 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 sufficient charge transport properties.

  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 based on the total structural unit from the viewpoint of improving the durability of the organic electronics element. % Or more is more preferable, and 10 mol% or more is still more preferable. The proportion of the structural unit B is preferably 50 mol% or less, preferably 40 mol% or less, from the viewpoint of suppressing the increase in viscosity and satisfactorily synthesizing the charge transporting polymer or obtaining sufficient charge transportability. Is more preferable, and 30 mol% or less is still more preferable. Here, the structural unit B means the sum of the structural unit B1 and the structural unit B2 introduced as necessary. From the viewpoint of expressing the effect of the structural unit containing silicon, 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 even more preferably 5 mol% or more. It is.

  When the charge transporting polymer has a polymerizable functional group, the proportion of the polymerizable functional group is preferably 0.1 mol% or more based on the total structural unit from the viewpoint of efficiently curing the charge transporting polymer, 1 mol% or more is more preferable, and 3 mol% or more is still more preferable. 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. The “ratio of polymerizable functional groups” here refers to the ratio of structural units having a polymerizable functional group.

  Considering the balance of charge transportability, durability, productivity, etc., the ratio (molar ratio) of the structural unit L and the structural unit T is preferably L: T = 100: 1 to 70, more preferably 100: 3 to 50. Preferably, 100: 5-30 is more preferable. When the charge transporting polymer includes 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 are more preferable, and 100: 40-160: 30-80 are 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 necessary. Moreover, the said structural unit B means the sum total of the structural unit B1 containing silicon, and the structural unit B2 introduce | transduced 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 proportion of the structural unit can be determined by using the charged amount of the monomer corresponding to each structural unit used for synthesizing the charge transporting polymer. Moreover, the ratio of the structural unit can be calculated as an average value using an integrated value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge transporting polymer. Since it is simple, when the preparation amount is clear, a value obtained by using the preparation amount is preferably adopted.

(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, Stille coupling, Buchwald-Hartwig coupling and the like can be used. Suzuki coupling causes a cross coupling reaction using a Pd catalyst between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki coupling, a charge transporting polymer can be easily produced by bonding desired aromatic rings together.

  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. In addition, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate and the like with a phosphine ligand can also be used. For the method for synthesizing the charge transporting polymer, for example, the description of International Publication No. WO2010 / 140553 can be referred to.

An example of a combination of monomer compounds that can be suitably used as a raw material when preparing a charge transporting polymer using the Suzuki coupling reaction is shown below. R described in the monomer (B) and the monomer (L) is the same as R described above for the structural unit B1 and the structural units L1 and L2, respectively.

[Dopant]
When an organic electronic element is constituted using a charge transporting material, the charge transporting material may further contain an additive known as an organic electronic material. In one embodiment, the charge transport material may further contain a dopant. The dopant is not particularly limited as long as it can be added to the charge transporting material to develop a doping effect and improve the charge transporting property. Doping includes p-type doping and n-type doping. In p-type doping, a substance serving as an electron acceptor is used as a dopant, and in n-type doping, a substance serving as an electron donor is used as a dopant. It is preferable to perform p-type doping for improving hole transportability and n-type doping for improving electron transportability. The dopant used for the charge transporting material may be a dopant that exhibits any effect of p-type doping or n-type doping. Further, one kind of dopant may be added alone, or plural kinds of dopants may be mixed and added.

The dopant used for p-type doping is an electron-accepting compound, and examples thereof include Lewis acids, proton acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Specifically, as the Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₃ , BBr _{3 and the} like; as the protonic acid, HF, HCl, HBr, HNO ₅ , H ₂ SO ₄ , HClO _{4 and} other inorganic acids, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfonic acid, vinylphenylsulfonic acid Organic acids such as camphorsulfonic acid; transition metal compounds include FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , MoF ₅ ; 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) A salt having a perfluoroanion such as a salt, a salt having a conjugate base of the protonic acid as an anion; halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr and IF; π-conjugated compounds Examples thereof include TCNE (tetracyanoethylene), TCNQ (tetracyanoquinodimethane) and the like. Moreover, it is also possible to use the electron-accepting compounds described in JP 2000-36390 A, JP 2005-75948 A, JP 2003-213002 A, and the like. Preferred are Lewis acids, ionic compounds, π-conjugated compounds and the like.

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

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

[Other optional ingredients]
The charge transporting material may further contain a charge transporting low molecular weight compound, other polymers, and the like.

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

  When the dopant is contained, the content thereof is preferably 0.01% by mass or more, and 0.1% by mass with respect to the total mass of the charge transporting material, from the viewpoint of improving the charge transporting property of the charge transporting material. The above is more preferable, and 0.5% by mass or more is still more preferable. Further, from the viewpoint of maintaining good film formability, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less with respect to the total mass of the charge transporting material.

<Ink composition>
The ink composition which is an embodiment of the present invention contains the charge transport material of the above 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. Organic solvents 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; ethylene glycol Aliphatic ethers such as dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, Aromatic ethers such as 4-methoxytoluene, 2,3-dimethylanisole, 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, n-butyl benzoate; N, N-dimethylformamide, N, N-dimethylacetamide, etc. Amide solvents; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like can be mentioned. 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 of easily preparing the ink composition, it is preferable to use a substance having both a function as a dopant and a function as a polymerization initiator. As such a substance, the said ionic compound is mentioned, for example.

[Additive]
The ink composition may further contain an additive as an optional component. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, antioxidants, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, Examples thereof include a dispersant and a surfactant.

[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 0.5% by mass or more. More preferred is an amount of 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 which is an embodiment of the present invention is a layer formed using the charge transporting material or ink composition of the above embodiment. By using the ink composition, the organic layer can be favorably formed by a coating method. Examples of the coating method include spin coating method; casting method; dipping method; letterpress printing, intaglio printing, offset printing, planographic printing, letterpress inversion offset printing, screen printing, gravure printing and other plate printing methods; ink jet method, etc. 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 (coating 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 solubility of the organic layer can be changed by advancing the polymerization reaction of the charge transporting polymer by light irradiation, heat treatment or the like. By laminating organic layers with different solubility, it is possible to easily increase the number of organic electronics elements. For the method of forming the organic layer, for example, the description of International Publication No. WO2010 / 140553 can be referred to.

  From the viewpoint of improving the efficiency of charge transport, the thickness of the organic layer after drying or curing is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more. In addition, 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 electrical resistance.

<Organic electronics elements>
The organic electronics element which is embodiment of this invention has the organic layer of the said embodiment at least. Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, and an organic transistor. 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]
The organic EL element which is embodiment of this invention has an organic layer of the said embodiment at least. The organic EL element usually includes a light emitting layer, an anode, a cathode, and a substrate, and other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer are provided as necessary. I have. Each layer may be formed by a vapor deposition method or a coating method. The organic EL element preferably has an organic layer as a light emitting layer or other 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.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic EL element. The organic EL element of FIG. 1 is an element having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 and a hole transport layer 6 made of the organic layer of the above 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. 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 transport material or the ink composition, but the organic EL element is not limited to such a structure. The other 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 transport material or the ink composition, and at least the hole transport layer is the organic layer. preferable. For example, when the organic EL element has an organic layer formed by using the charge transporting material or ink composition as a hole transport layer and further has a hole injection layer, the hole injection layer has a known Material can be used. For example, when the organic EL element has an organic layer formed using the charge transporting material or ink composition as a hole injection layer and further has a hole transport layer, the hole transport layer includes 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, or a dendrimer can be used. A polymer is preferable because it has high solubility in a solvent and is suitable for a coating method. Examples of the light emitting material include a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescent material (TADF), and the like.

  Low molecular weight compounds such as perylene, coumarin, rubrene, quinacdrine, stilbene, dye laser dyes, aluminum complexes, and derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinyl carbazole, fluorene-benzothiadiazole copolymer , Fluorene-triphenylamine copolymers, polymers thereof such as derivatives thereof; mixtures thereof and the like.

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) that emits blue light (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate), Ir (ppy) ₃ that emits green light. (Factris (2-phenylpyridine) iridium), which emits 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-formin platinum) that emits red light.

  When the light emitting layer includes a phosphorescent material, it is preferable that a host material is further included 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), CDBP (4,4′- Bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), derivatives thereof, and the like are polymers such as the charge transport material of the above embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof, and the like. Can be mentioned.

  Examples of thermally activated delayed fluorescent materials include 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.

[Electron transport layer, electron injection layer]
Examples of materials used for the electron transport layer and the electron injection layer include phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, condensed ring tetracarboxylic anhydrides such as naphthalene and perylene, and carbodiimides. Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes, and the like. In addition, the charge transport 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. Examples of other materials include oxides (for example, ITO: indium oxide / tin oxide) and conductive polymers (for example, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

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

  Examples of the resin film include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Can be mentioned.

  When using a resin film, in order to suppress permeation | transmission of water vapor | steam, oxygen, etc., you may coat and use inorganic substances, such as a silicon oxide and a silicon nitride, on a resin film.

[Luminescent 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, interior lighting, a clock, or a liquid crystal backlight.

  As a method of forming a white organic EL element, a method of simultaneously emitting light of a plurality of emission colors using a plurality of light emitting materials and mixing the colors can be used. The combination of a plurality of emission colors is not particularly limited, but includes 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. The combination to contain is mentioned. The emission color can be controlled by adjusting the type and amount of the light emitting material.

<Display element, lighting device, display device>
The display element which is embodiment of this invention is equipped with the organic EL element of the said 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.

  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 apparatus which is embodiment of this invention is equipped with the illuminating device and the liquid crystal element as a display means. For example, the display device may be a display device using a known liquid crystal element as a display unit, that is, a liquid crystal display device, using the illumination device according to the embodiment of the present invention as a backlight.

(Example)
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<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 in 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 preparing the catalyst, all solvents were used after degassing 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 separately prepared Pd catalyst solution (7.5 mL) was added and stirred. After stirring for 30 minutes, a 10% tetraethylammonium hydroxide aqueous solution (20 mL) was added to the flask. The mixture was heated to reflux for 2 hours. All the operations so far were performed under a nitrogen stream. All the solvents were used after deaeration with nitrogen bubbles for 30 minutes or more.

After completion of the reaction, the organic layer was washed with water. The organic layer was then poured into methanol-water (9: 1). The resulting precipitate was suction filtered and washed with methanol-water (9: 1). The washed precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was filtered by suction, dissolved in toluene, and added with triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer (Strem Chemicals, 200 mg per 100 mg of polymer, hereinafter referred to as “metal adsorbent”). Stir overnight.
After completion of the stirring, the metal adsorbent and insoluble matter were removed by filtration, and the filtrate was concentrated using a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was filtered by suction and washed with methanol-acetone (8: 3). The obtained precipitate was vacuum-dried 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 (polystyrene conversion) using THF as an eluent. The charge transporting polymer 1 includes a trivalent or higher valent structural unit B2 (derived from the monomer 3) not containing silicon, a divalent structural unit L2 (derived from the monomer 2) not containing silicon, and a polymerizable functional group. The proportion of each structural unit was 18.2%, 45.5%, and 36.4% in order.

The measurement conditions for the number average molecular weight and the weight average molecular weight are as follows.
Liquid feed 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, HPLC, without stabilizer)
Flow rate: 1 mL / min
Column temperature: Room temperature Molecular weight standard: Standard polystyrene

(Preparation Example 2) Charge transporting polymer 2
To a three-necked round bottom flask, add monomer 2 (5.0 mmol) and monomer 3 (2.0 mmol) described in Preparation Example 1, monomer 4 (4.0 mmol) below, and anisole (20 mL), and prepare separately. The Pd catalyst solution (7.5 mL) was added and stirred. Thereafter, the charge transporting polymer 2 was prepared in the same manner as 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 structural unit B2 not containing silicon (derived from the monomer 3), a divalent structural unit L2 not containing silicon (derived from the monomer 2), and a monovalent structural unit. Including T (derived from monomer 4), the proportion of each structural unit was 18.2%, 45.5%, and 36.4% in order.

(Preparation Example 3) Charge transporting polymer 3
In a three-necked round bottom flask, monomer 2 (5.0 mmol) described in Preparation Example 1, monomer 4 (4.0 mmol) described in Preparation Example 2, monomer 5 (1.5 mmol) below, anisole (20 mL), and And a separately prepared Pd catalyst solution (7.5 mL) was added and stirred. Thereafter, the charge transporting polymer 3 was prepared in the same manner as described 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 includes a trivalent or higher structural unit B1 containing silicon (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 proportion of each structural unit was 14.3%, 47.6%, and 38.1%, respectively.

(Preparation Example 4) Charge transporting polymer 4
A charge transporting 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 structural unit B1 containing silicon (derived from the monomer 5), a divalent structural unit L2 containing no silicon (derived from the monomer 6), and a monovalent structural unit T. (Derived from monomer 4), and the proportion of each structural unit was 14.3%, 47.6%, and 38.1%, respectively.

(Preparation Example 5) Charge transporting polymer 5
A charge transporting polymer 5 was prepared in the same manner as in Preparation Example 3 except that the monomer 4 (4.0 mmol) was changed to the monomer 4 (2.0 mmol) and the 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 structural unit B1 containing silicon (derived from the monomer 5), a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a monovalent structural unit T ( And a monovalent structural unit T (derived from monomer 1) having a polymerizable functional group, and the proportion 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, monomer 2 (5.0 mmol) described in Preparation Example 1, monomer 4 (2.0 mmol) described in Preparation Example 2, monomer 7 (4.0 mmol) below, anisole (20 mL), And a separately prepared Pd catalyst solution (7.5 mL) was added and stirred. Thereafter, charge transporting polymer 6 was prepared in the same manner as described 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 includes a divalent structural unit L1 containing silicon (derived from the monomer 7), a divalent structural unit L2 containing no silicon (derived from the monomer 2), and a monovalent structural unit T ( The ratio of each structural unit was 36.4%, 45.5%, and 18.2% in order.

(Preparation Example 7) Charge transporting polymer 7
Monomer 5 (1.5 mmol) was changed to Monomer 5 (0.75 mmol) and Monomer 7 (3.0 mmol), and the same as Preparation Example 3 except that Monomer 2 was 6.0 mmol and Monomer 4 was 3.0 mmol The charge transporting polymer 7 was prepared by the method described above.
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 trivalent or higher structural unit B1 containing silicon (derived from the monomer 5), a divalent structural unit L1 containing silicon (derived from the monomer 7), and a divalent structure containing no silicon. Including the unit L2 (derived from the monomer 2) and the monovalent structural unit T (derived from the monomer 4), the proportion of each structural unit is 5.9%, 23.5%, 47.1% in order. And 23.5%.

(Preparation Example 8) Charge transporting polymer 8
Charge transporting 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 containing silicon (derived from the monomer 8), a divalent structural unit L2 not containing silicon (derived from the monomer 2), and a monovalent structural unit T. (Derived from monomer 4), and the proportion of each structural unit was 18.2%, 45.5%, and 36.4% in this order.

<2-1> Preparation of organic EL element (Example 1)
On a glass substrate obtained by patterning ITO to a width of 1.6 mm under a nitrogen atmosphere, charge transporting polymer 1 (10.0 mg) obtained by synthesis of the above charge transporting polymer, the following ionic compound (0.5 mg), Ink composition 1 consisting of toluene and 2.3 mL was spin-coated at 3000 min ⁻¹ and then cured by heating 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), After spin coating at 3000 min ⁻¹ , the film was dried 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.

The substrate obtained above was transferred into a vacuum evaporator, 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 were formed by vapor deposition, followed by sealing treatment to produce an organic EL device.

(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 device was replaced with the charge transporting polymer 4 described above. An organic EL device was produced in the same manner as in Example 1 except that this ink composition 4 was used to form a hole transport layer.

(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 device was changed to the charge transporting polymer 5 described above. An organic EL device was produced in the same manner as in Example 1 except that this ink composition 5 was used to form a hole transport layer.

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 device was changed to the charge transporting polymer 6 described above. An organic EL device was produced in the same manner as in Example 1 except that this ink composition 6 was used to form a hole transport layer.

(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 device was replaced with the charge transporting polymer 7. An organic EL device was produced in the same manner as in Example 1 except that this ink composition 7 was used to form a hole transport layer.

(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 device was replaced with the charge transporting polymer 8 described above. An organic EL device was produced in the same manner as in Example 1 except that this ink composition 8 was used to form a hole transport layer.

(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 device was changed to the charge transporting polymer 2 described above. An organic EL device was produced in the same manner as in Example 1 except that this ink composition 2 was used to form a hole transport layer.

<2-2> Evaluation of organic EL element When a voltage was applied to the organic EL elements obtained in Examples 1 to 6 and Comparative Example 1, green light emission was confirmed. 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.} The measurement results are shown in Table 2.

  As shown in Table 2, the organic EL elements of Examples 1 to 6 had a drive voltage lower than that of Comparative Example 1, excellent luminous efficiency, and a long luminous lifetime. That is, from the viewpoint of the constituent material of the hole transport layer, the use of a charge transporting polymer having a structural unit containing silicon in the molecule as the charge transporting material improves the light emission efficiency and the light emission lifetime. It turns out that an effect is acquired.

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

Next, as in Example 1, the charge transporting polymer 3 (20 mg), the ionic compound (1.0 mg), and toluene (2.3 mL) are 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 vapor-deposited in this order and sealed 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 a charge transporting polymer 4. A white organic EL device was produced in the same manner as in Example 7 except that this ink composition 4 was used to form a hole transport layer.

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 a charge transporting polymer 5. A white organic EL device was produced in the same manner as in Example 7 except that this ink composition 5 was used to form a hole transport layer.

(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 a charge transporting polymer 6. A white organic EL device was produced in the same manner as in Example 7 except that this ink composition 6 was used to form a hole transport layer.

(Example 11)
In Example 7, 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 was changed to the charge transporting polymer 7. A white organic EL device was produced in the same manner as in Example 7 except that this ink composition 7 was used to form a hole transport layer.

(Example 12)
In Example 7, 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 was changed to a charge transporting polymer 8. A white organic EL device was produced in the same manner as in Example 7 except that this ink composition 8 was used to form a hole transport layer.

(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 this ink composition 2 was used to form a hole transport layer.

<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 to drive voltage and light emission at an initial luminance of 1000 cd / m ^2. Efficiency and luminescence lifetime were measured. Table 3 shows the drive voltage, light emission efficiency, and light emission life of Examples 7 to 12 when the drive voltage, light emission efficiency, and light emission life of Comparative Example 2 are each 1.

  As shown in Table 3, the white organic EL elements of Examples 7 to 12 are superior in luminous efficiency and luminous lifetime as compared with the white organic EL element of Comparative Example 2. That is, from the viewpoint of the constituent material of the hole transport layer, by using a charge transporting polymer having a structural unit containing silicon as the charge transporting material, an effect of improving the light emission efficiency and the light emission lifetime is obtained. You can see that

  As described above, the effects of the embodiments 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 other charge transporting polymers are used as long as they do not depart from the scope of the present invention. In the same manner, an organic electronic device can be obtained. The obtained organic electronics element has excellent effects as in the previous examples.

DESCRIPTION OF SYMBOLS 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 comprising at least one of a divalent structural unit L1 containing silicon and a trivalent or higher structural unit B1 containing silicon.   The charge transporting polymer has a charge transporting property and a divalent structural unit L2 other than the divalent structural unit L1 containing silicon and the trivalent or higher structural unit B1 containing silicon. The charge transporting material according to claim 1, further comprising at least one of structural units B2 having a valence of 2 or more.   The charge transporting polymer further includes a divalent structural unit L2 having charge transporting properties other than the divalent structural unit L1 containing silicon, and the divalent structural unit is an aromatic amine structure, carbazole. The charge transport material according to claim 1, which has at least one structure selected from the group consisting of a structure, a thiophene structure, a bithiophene structure, a benzene structure, and a fluorene structure.   The charge transport material according to claim 1, wherein the charge transport polymer has a structure branched in three or more directions.   The charge transport material according to any one of claims 1 to 4, which is used as a hole transport material.   An ink composition comprising the charge transporting material according to claim 1 and a solvent.   The organic electronics element which has an organic layer containing the electric charge transport material of any one of Claims 1-5.   The organic electroluminescent element which has an organic layer containing the electric charge transport material of any one of Claims 1-5.   The organic electroluminescent element according to claim 8, further comprising a flexible substrate.   The organic electroluminescent element of Claim 9 in which the said flexible substrate contains a resin film.   The display element provided with the organic electroluminescent element of any one of Claims 8-10.   The illuminating device provided with the organic electroluminescent element of any one of Claims 8-10.   A display device comprising the illumination device according to claim 12 and a liquid crystal element as display means.

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