JP2017123362A - Organic electronics material and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an organic electronics material suitable for a wet process and also suitable for an improvement in life characteristics of an organic electronic element; an organic electroluminescent element including at least one organic layer containing the organic electronics material; a display device; and a lighting system.SOLUTION: An organic electronics material contains: a charge transport polymer or an oligomer having a structural unit with a triazine ring, at at least one terminal thereof.SELECTED DRAWING: None

Description

  Embodiments described herein relate generally to an organic electronics material, an ink composition, an organic layer, an organic electronics element, an organic electroluminescence element (also referred to as “organic EL element”), a display element, a lighting device, and a display device.

  Organic EL devices are attracting attention as large-area solid-state light source applications as alternatives to, for example, incandescent lamps and gas-filled lamps. 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, ie, low molecular organic EL elements using low molecular compounds and high molecular organic EL elements using high molecular compounds, depending on the organic materials used. The manufacturing method of the organic EL element includes a dry process in which film formation is mainly performed in a vacuum system and a wet process in which film formation is performed by plate printing such as letterpress printing and intaglio printing, and plateless printing such as inkjet. It is roughly divided into two. Since simple film formation is possible, the wet process is expected as an indispensable method for future large-screen organic EL displays (see, for example, Patent Document 1 and Non-Patent Document 1).

JP 2006-279007 A

Kengo Hirose, Daisuke Kumaki, Nobuaki Koike, Satoshi Kuriyama, Seiichiro Ikehata, Shizushi Tokito, 53rd Joint Physics Conference on Applied Physics, 26p-ZK-4 (2006)

  An organic EL element manufactured using a wet process has a feature that cost reduction and area increase are easy. However, regarding the characteristics of the organic EL element, further improvement is desired in the organic EL element including an organic layer manufactured by using a wet process.

  In view of the above, it is an object of an embodiment of the present invention to provide an organic electronics material and an ink composition that are suitable for a wet process and suitable for improving the lifetime characteristics of an organic electronics element. Another embodiment of the present invention provides an organic layer suitable for improving the lifetime characteristics of an organic electronics element, and further, an organic electronics element, an organic EL element, a display element, a lighting device, and a display having excellent lifetime characteristics It is an object to provide an apparatus.

Embodiments of the present invention relate to an organic electronic material comprising a charge transporting polymer or oligomer having a structural unit having a triazine ring at at least one terminal.
Another embodiment of the present invention relates to an ink composition comprising the organic electronic material and a solvent.
Another embodiment of the present invention relates to an organic layer formed using the organic electronics material or the ink composition.

Another embodiment of the present invention relates to an organic electronic device comprising at least one organic layer.
Other embodiment of this invention is related with an organic electroluminescent element provided with at least one said organic layer.

Other embodiment of this invention is related with the display element provided with the said organic electroluminescent element.
Other embodiment of this invention is related with the illuminating device provided with the said organic electroluminescent element.
Furthermore, another embodiment of the present invention relates to a display device comprising the illumination device and a liquid crystal element as display means.

  The organic electronics material and ink composition which are embodiments of the present invention are suitable for wet processes and for improving the lifetime characteristics of organic electronics elements. Moreover, the organic layer which is embodiment of this invention is suitable for the improvement of the lifetime characteristic of an organic electronics element. Furthermore, the organic electronics element, the organic EL element, the display element, the lighting device, and the display device according to the embodiment of the present invention have excellent life characteristics.

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

  Although embodiments of the present invention will be described, the present invention is not limited to these embodiments.

<Organic electronics materials>
The organic electronic material of this embodiment includes a charge transporting polymer or oligomer having a structural unit having a triazine ring at at least one terminal. The organic electronic material may contain only one kind or two or more kinds of charge transporting polymers or oligomers. The charge transporting polymer or oligomer is preferable in that the film forming property in the wet process is excellent as compared with the low molecular compound.

[Charge transporting polymer or oligomer]
The charge transporting polymer or oligomer (in the following description, the charge transporting polymer or oligomer is also collectively referred to as “charge transporting polymer”) is a polymer or oligomer having the ability to transport charge. The charge transporting polymer may be linear or have a branched structure. 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 a trivalent or higher structural unit B constituting a branched portion. Further, it 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”.

  As will be described later, the charge transporting polymer of the present embodiment has a characteristic structure including a structural unit having a triazine ring at at least one polymer terminal. That is, at least a part of the above-mentioned “monovalent structural unit T constituting the terminal portion” is a structural unit having a triazine ring. The structural unit having this triazine ring may exist other than the polymer terminal and is included as a substituent of the above-mentioned “divalent structural unit L” and / or “trivalent or higher structural unit B”. May be.

(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 the structural unit L, “T” represents the structural unit T, and “B” represents the structural unit B. In the present specification, “*” in the formula 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

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

  In one embodiment, the structural unit L includes 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, from the viewpoint of obtaining excellent electron transport properties, the structural unit L is a substituted or unsubstituted fluorene structure, benzene structure, phenanthrene structure, pyridine structure, quinoline structure, and one or two of these. It is preferably selected from structures containing more than one species.

Specific examples of the structural unit L include the following. The structural unit L 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. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. Ar is preferably an arylene group, more preferably a phenylene group.

(Structural unit T)
The structural unit T is a monovalent structural unit constituting the terminal portion of the charge transporting polymer. In other embodiments, 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, a polymerizable functional group such as a pyrrol-yl group, for example). ).

(Structural unit T1)
In the present embodiment, as described above, at least a part of the structural unit T is a structural unit having a triazine ring (hereinafter, also referred to as “structural unit T1”). The charge transporting polymer may have only one structural unit T1, or two or more structural units T1. It is considered that the electron transporting property is improved by including the structural unit T1 at the terminal of the charge transporting polymer. In particular, when the charge transporting polymer has a structural unit having a hole transporting property and a structural unit T1 at the terminal, the charge transporting polymer is stable against electrons while maintaining the hole transporting property. As a result, it is considered that high performance can be exhibited as an organic electronic material.

“Having a triazine ring” means a structural unit containing a triazine ring, which may be any of the three isomers having three different nitrogen positions in the triazine ring, or a mixture of these isomers. May be. In one embodiment, the structural unit having a triazine ring includes a structure of a 1,3,5-triazine ring represented by the following formula.

  In the structural unit T1 of the above formula, each R is independently a hydrogen atom, or a linear, cyclic, or branched alkyl group, alkenyl group, alkynyl group having 1 to 22 carbon atoms, and It is at least one selected from the group consisting of an alkoxy group and an aryl group and heteroaryl group having 2 to 30 carbon atoms. The aryl group and heteroaryl group may further have a substituent, and the substituent is preferably a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms. R is preferably a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted phenyl group or naphthyl. More preferred are groups. When the charge transporting polymer has a polymerizable functional group at the terminal portion, at least one of R may be a group containing a polymerizable functional group.

  In the structural unit T1 of the above formula, Ar is a substituted or unsubstituted arylene group or arenetriyl group having 6 to 40 carbon atoms, preferably a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. . The arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. Preferable substituents that can be substituted on the arylene group or arenetriyl group include the same substituents as those described above for the aryl group and heteroaryl group. The arylene group is preferably a phenylene group or a naphthylene group, and more preferably a 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.

Preferred specific examples of the structural unit T1 are listed below. The structural unit T1 is not limited to the following. As described above, the substituent R in the ring other than the triazine ring is preferably a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms.

  R and Ar may be bonded to the triazine ring via an amino group. That is, the substituent of the triazine ring is also preferably —NHR, —NHAr—, —NRR, —NRAr— or the like. R is a hydrogen atom as described above, or a linear, cyclic, or branched alkyl group, alkenyl group, alkynyl group, and alkoxy group having 1 to 22 carbon atoms, and the number of carbon atoms. It is at least one selected from the group consisting of 2 to 30 aryl groups and heteroaryl groups, and the aryl group and heteroaryl group may further have a substituent.

(Structural unit T2)
In one embodiment, the charge-transporting polymer includes, as the terminal structural unit T, in addition to the structural unit T1, a structural unit other than the structural unit T1, that is, a structural unit having no triazine ring (hereinafter referred to as “structural unit T2”). May also be included). The charge transporting polymer may have only one type of structural unit T2, or may have two or more types.

  The structural unit T2 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 T2 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 described later, when the charge transporting polymer has a polymerizable functional group at the terminal portion, the structural unit T2 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 unit L or may have a different structure.

Specific examples of the structural unit T2 include the following. The structural unit T2 is not limited to the following.

  In the structural unit T2 of the above formula, R is the same as R in the structural unit L (except that the heteroaryl group and the heteroarylene group include a triazine ring). 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.

  The proportion of the structural unit T1 at all terminals of the charge transporting polymer is 25% or more, more preferably 30% or more, more preferably 35% or more, based on the number of all terminals, from the viewpoint of improving the characteristics of the organic electronics element. . The upper limit is not particularly limited and is 100% or less. The ratio at all terminals can be determined by the charge ratio (molar ratio) of the monomer corresponding to the terminal structural unit used for synthesizing the charge transporting polymer.

  When the charge transporting polymer has the structural unit T2, the proportion of the structural unit T2 at all terminals is preferably 75% or less, more preferably 70%, based on the number of all terminals, from the viewpoint of improving the characteristics of the organic electronics element. Hereinafter, it is more preferably 65% or less. The lower limit is not particularly limited, but may be 5% or more, for example, in consideration of introduction of a polymerizable substituent described later, introduction of a substituent for improving film formability, wettability, and the like.

(Structural unit B)
The structural unit B 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 B 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 B is preferably a unit having charge transportability. For example, the structural unit B 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 B may have the same structure as the structural unit L or may have a different structure, may have the same structure as the structural unit T, or may have a different structure. You may have.

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

  W represents a trivalent linking group, for example, an arenetriyl group or a heteroarenetriyl group having 2 to 30 carbon atoms. As described above, 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 L (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 any of a carbon atom, a silicon atom, or a phosphorus atom. In the structural unit, the benzene ring and Ar may have a substituent, and examples of the substituent include R in the structural unit L.

(Polymerizable functional group)
In one embodiment, the charge transporting polymer preferably has at least one polymerizable functional group (also referred to as “polymerizable substituent”) 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. An oxetane group is preferred and the most preferred.

  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, for example, linear alkylene chains having 1 to 8 carbon atoms. It is preferable that it is connected. 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, and 300,000 or less is most 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 L contained in the charge transporting polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% or more based on the total structural unit from the viewpoint of obtaining sufficient charge transportability. 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.

  The proportion of the structural unit T (the total of the structural units T1 and T2) contained in the charge transporting polymer is the viewpoint of improving the characteristics of the organic electronics element, or suppressing the increase in viscosity, so that the charge transporting polymer is well synthesized. From the viewpoint, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 15 mol% or more is still more preferable based on the total structural unit. 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 the structural unit B, the proportion of the structural unit B is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total structural units, from the viewpoint of improving the durability of the organic electronics element. 10 mol% or more is 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.

  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.

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.

  In a particularly preferred embodiment, the charge transporting polymer is mainly composed of a structural unit having an aromatic amine structure and / or a structural unit having a carbazole structure from the viewpoint of having a high hole injection property, a hole transporting property, and the like. A compound having a unit (main skeleton) is preferred. The charge transporting polymer is preferably a compound having at least two polymerizable substituents from the viewpoint of easily multilayering. From the viewpoint of having excellent curability, the polymerizable substituent is preferably a group having a cyclic ether structure, a group having a carbon-carbon multiple bond, or the like.

(Production method)
The charge transporting polymer of this embodiment is preferably a copolymer of a monomer including at least a monomer including a structural unit having a hole transporting property and a monomer including a structural unit having a triazine ring. That is, one or more monomers including the structural unit L and one or more monomers including the structural unit T1, and optionally one or more other monomers (for example, a monomer including the structural unit T2 and / or the structure). By using a monomer mixture which may contain a monomer containing unit B), these monomers can be preferably copolymerized. The type of copolymerization may be an alternating, random, block or graft copolymer, or a copolymer having an intermediate structure thereof, for example, a random copolymer having a block property. .

  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.

[Dopant]
The organic electronic material may contain any additive, for example, may further contain a dopant. The dopant can be added to the organic electronic material to exhibit a doping effect and improve the charge transport property. There is no particular limitation. 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 in the organic electronic 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 easily change the solubility of the organic layer.

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

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

  When the dopant is contained, the content is preferably 0.01% by mass or more, and 0.1% by mass or more with respect to the total mass of the organic electronic material from the viewpoint of improving the charge transport property of the organic electronic material. More preferred is 0.5% by mass or more. Moreover, from a viewpoint of maintaining favorable film formability, 50 mass% or less is preferable with respect to the total mass of the organic electronic material, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable.

<Ink composition>
The ink composition which is an embodiment of the present invention contains the organic electronic 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 organic electronic material or ink composition of the above embodiment. By using the ink composition, the organic layer can be satisfactorily and easily 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 electronic device which is an embodiment of the present invention has at least one organic layer of the above-described embodiment. 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 an embodiment of the present invention has at least one organic layer of the above-described embodiment. 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 the 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, a light emitting layer 1, an electron transport layer 7, an electron injection layer 5, and a cathode 4. In this order. Hereinafter, each layer will be described.

[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 exemplified by the organic electronic materials, polyvinyl carbazole, polyphenylene, polyfluorene, derivatives thereof, and the like of the embodiment. It is done.

  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.

[Hole injection layer, hole transport layer]
The organic layer formed using the organic electronic material is preferably used as at least one of a hole injection layer and a hole transport layer, and more preferably at least as a hole transport layer. As described above, these layers can be easily formed by using an ink composition containing an organic electronic material.
When the organic EL element has an organic layer formed by using the organic electronic material as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. In addition, when the organic EL element has an organic layer formed using the organic electronic material as a hole injection layer and further has a hole transport layer, a known material can be used for the hole transport layer. .

  When a material made of triphenylamine is used for the hole injection layer, it is preferable to use the organic electronic material of the present embodiment for the hole transport layer from the viewpoint of energy level with respect to the movement of holes. In particular, when a hole-injecting layer contains a polymerization initiator and the hole-transporting layer uses a branched polymer having a polymerizable substituent as the charge transporting polymer, the hole-transporting layer can be cured, Therefore, a light emitting layer made of ink or the like can be further applied thereon.

[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. Moreover, the organic electronic material of the said 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 is preferably a flexible substrate having 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.

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

[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. A combination of a plurality of emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, a combination containing two emission maximum wavelengths of blue and yellow, yellow green and orange, etc. 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 can 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.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Unless otherwise specified, “%” means “mass%”.
<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. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes.

<Synthesis of Charge Transporting Polymer 1>
In a three-necked round bottom flask, the following monomer L-1 (5.0 mmol), the following monomer B-1 (2.0 mmol), the following monomer T2-1 (2.0 mmol), the following monomer T2-2 (2.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. After stirring for 30 minutes, 10% tetraethylammonium hydroxide aqueous solution (20 mL) was added. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes. The mixture was heated to reflux for 2 hours. All the operations so far were performed under a nitrogen stream.

  After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The resulting precipitate was collected by suction filtration, dissolved in toluene, and a metal adsorbent (“Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer” manufactured by Strem Chemicals, 200 mg for 100 mg of the precipitate) was added. Stir overnight. After completion of the stirring, the metal adsorbent and insoluble matter were removed by filtration, and the filtrate was concentrated with a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The 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 5,200, and the weight average molecular weight was 41,200. The charge transporting polymer 1 has a structural unit L-1, a structural unit B-1, a structural unit T2-2, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 18.2%, and 18.2%.

The number average molecular weight and the mass average molecular weight were measured by GPC (polystyrene conversion) using tetrahydrofuran (THF) as an eluent. The measurement conditions 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 (for HPLC, without stabilizer) Wako Pure Chemical Industries, Ltd.
Flow rate: 1 mL / min
Column temperature: Room temperature Molecular weight standard: Standard polystyrene

<Synthesis of charge transporting polymer 2>
In a three-necked round bottom flask, the monomer L-1 (5.0 mmol), the following monomer B-2 (2.0 mmol), the following monomer T1-1 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 2 was synthesized in the same manner as the synthesis of the charge transporting polymer 1.

  The number average molecular weight of the obtained charge transporting polymer 2 was 15,600, and the weight average molecular weight was 56,400. The charge transporting polymer 2 has a structural unit L-1, a structural unit B-2, a structural unit T1-1, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 3>
In a three-neck round bottom flask, the monomer L-1 (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-2 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 3 was synthesized in the same manner as the synthesis of the charge transporting polymer 1.

  The number average molecular weight of the obtained charge transporting polymer 3 was 14,600, and the weight average molecular weight was 52,900. The charge transporting polymer 3 has a structural unit L-1, a structural unit B-2, a structural unit T1-2, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 4>
In a three-necked round bottom flask, the monomer L-1 (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-3 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 4 was synthesized in the same manner as the charge transporting polymer 1 was synthesized.

  The number average molecular weight of the obtained charge transporting polymer 4 was 16,600, and the weight average molecular weight was 58,100. The charge transporting polymer 4 has a structural unit L-1, a structural unit B-2, a structural unit T1-3, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 5>
In a three-necked round bottom flask, the monomer L-1 (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-4 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 5 was synthesized in the same manner as the charge transporting polymer 1 was synthesized.

  The number average molecular weight of the obtained charge transporting polymer 5 was 14,500, and the weight average molecular weight was 64,000. The charge transporting polymer 5 has a structural unit L-1, a structural unit B-2, a structural unit T1-4, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 6>
In a three-necked round bottom flask, the monomer L-1 (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-5 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 6 was synthesized in the same manner as the charge transporting polymer 1 was synthesized.

  The resulting charge transporting polymer 6 had a number average molecular weight of 19,700 and a weight average molecular weight of 66,600. The charge transporting polymer 6 has a structural unit L-1, a structural unit B-2, a structural unit T1-5, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 7>
In a three-necked round bottom flask, the monomer L-1 (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T2-3 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 7 was synthesized in the same manner as the charge transporting polymer 1 was synthesized.

  The number average molecular weight of the obtained charge transporting polymer 7 was 15,300, and the weight average molecular weight was 112,600. The charge transporting polymer 7 has a structural unit L-1, a structural unit B-2, a structural unit T2-3, and a structural unit T2-1 having an oxetane group, and the ratio (molar ratio) of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 8>
In a three-necked round bottom flask, the monomer L-1 (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T2-4 (3.0 mmol), the monomer T2-1 (1.0 mmol), And anisole (20 mL) were added, and a further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 8 was synthesized in the same manner as the charge transporting polymer 1 was synthesized.

  The resulting charge transporting polymer 8 had a number average molecular weight of 14,500 and a weight average molecular weight of 53,900. The charge transporting polymer 8 has a structural unit L-1, a structural unit B-2, a structural unit T2-4 containing a thiophene structure, and a structural unit T2-1 having an oxetane group, and the proportion of each structural unit ( The molar ratio) was 45.5%, 18.2%, 27.3%, and 9.1%.

<Production of organic EL element>
[Examples 1-5 and Comparative Examples 1-2]
In a nitrogen atmosphere, charge transporting polymer 1 (10.0 mg), the following electron-accepting compound 1 (0.5 mg), and toluene (2.3 mL) are mixed to prepare an ink composition for forming a hole injection layer. Prepared. The ink composition is spin-coated on a glass substrate patterned with ITO to a width of 1.6 mm at a rotation speed of 3,000 min ⁻¹ and then cured by heating on a hot plate at 220 ° C. for 10 minutes to inject holes. A layer (25 nm) was formed.

Next, any one (10.0 mg) of charge transporting polymers 2 to 8 shown in Table 1 and toluene (1.15 mL) were mixed to prepare an ink composition for forming a hole transporting layer. The ink composition was spin-coated on the hole injection layer formed above at a rotation speed of 3,000 min ⁻¹ and then cured by heating on a hot plate at 200 ° C. for 10 minutes to form a hole transport layer ( 40 nm). In each Example and Comparative Example, the hole transport layer could be formed without dissolving the hole injection layer.

The substrate obtained above was transferred into a vacuum vapor deposition machine, and CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (0. 8 nm) and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to produce an organic EL element.

When voltage was applied to the organic EL elements obtained in Examples 1 to 5 and Comparative Examples 1 and 2, green light emission was confirmed. For each element, the luminescence was measured lifetime (luminance half-life) in the luminous efficiency, and initial luminance 5,000 cd / ^{m 2} in the emission luminance 1,000 cd / ^{m 2.} The measurement results are shown in Table 2.

  As shown in Table 2, from the comparison between Examples 1 to 5 and Comparative Examples 1 and 2, the organic electronics material according to the embodiment of the present invention is used for the hole transport layer, so that the light emission efficiency is high and the driving stability is high. Thus, an element having a long lifetime was obtained.

<Production of white organic EL element (lighting device)>
[Example 6]
In a nitrogen atmosphere, the charge transporting polymer 1 (10.0 mg), the electron accepting compound 1 (0.5 mg), and toluene (2.3 mL) are mixed to prepare an ink composition for forming a hole injection layer. Prepared. The ink composition is spin-coated on a glass substrate patterned with ITO to a width of 1.6 mm at a rotation speed of 3,000 min ⁻¹ and then cured by heating on a hot plate at 220 ° C. for 10 minutes to inject holes. A layer (25 nm) was formed.

Charge transporting polymer 2 (20 mg) and toluene (1.15 mL) were mixed to prepare an ink composition for forming a hole transporting layer. The ink composition is spin-coated on the hole injection layer at a rotation speed of 3,000 min ⁻¹ and then cured by heating on a hot plate at 200 ° C. for 10 minutes to form a hole transport layer (40 nm). did. The hole transport layer could be formed without dissolving the hole injection layer.

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) ) Were mixed to prepare an ink composition for forming a light emitting layer. The ink composition was spin-coated on the hole transport layer at a rotation speed of 3,000 min ⁻¹ and dried by heating at 80 ° C. for 5 minutes on a hot plate to form a light emitting layer (40 nm). The light emitting layer could be formed without dissolving the hole transport layer.

  A glass substrate in which a hole injection layer, a hole transport layer, and a light emitting layer are laminated in this order is transferred into a vacuum evaporation machine, and BAlq (10 nm), TPBi (30 nm), LiF (0.5 nm), And Al (100 nm) was formed into a film by the vapor deposition method in this order. Then, the sealing process was performed and the white organic EL element was produced. The obtained white organic EL element could be used as a lighting device.

[Comparative Example 3]
A white organic EL device was produced in the same manner as in Example 6 except that the charge transporting polymer 2 was changed to the charge transporting polymer 7. The light emitting layer could be formed without dissolving the hole transport layer. Moreover, the white organic EL element could be used as a lighting device.

A voltage was applied to the white organic EL elements obtained in Example 6 and Comparative Example 3, and the light emission lifetime (luminance half time) was measured with an initial luminance of 1,000 cd / m ² . When the light emission lifetime in Example 6 was 1, it was 0.23 in Comparative Example 3. Further, when the voltage at a luminance of 1,000 cd / m ² in Example 6 was 1, it was 1.09 in Comparative Example 3.
The white organic EL element of Example 6 exhibited excellent light emission lifetime and driving voltage.

  In the above, the effect of the embodiment of the present invention was shown using the example. In addition to the charge transporting polymer used in the examples, it is possible to obtain an organic EL device having a long lifetime by using the above-described charge transporting polymer containing a structural unit having a triazine ring at one end. In the same manner, it exhibits excellent effects.

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 (14)

  An organic electronic material comprising a charge transporting polymer or oligomer having a structural unit having a triazine ring at at least one terminal.   The organic electronic material according to claim 1, wherein the charge transporting polymer or oligomer has three or more terminals.   The organic electronic material according to claim 1 or 2, wherein the charge transporting polymer or oligomer has a structural unit having the triazine ring at a terminal of 25% or more based on the total number of terminals.   The charge transporting polymer or oligomer is a copolymer of a monomer containing at least a monomer containing a structural unit having a hole transporting property and a monomer containing a structural unit having a triazine ring. The organic electronics material according to claim 1.   The organic electronic material according to claim 1, wherein the charge transporting polymer or oligomer further has a polymerizable substituent.   An ink composition comprising the organic electronic material according to claim 1 and a solvent.   The organic layer formed using the organic electronics material of any one of Claims 1-5, or the ink composition of Claim 6.   An organic electronic device comprising at least one organic layer according to claim 7.   An organic electroluminescent device comprising at least one organic layer according to claim 7.   The organic electroluminescent element according to claim 9, further comprising a flexible substrate.   The organic electroluminescent element according to claim 9, further comprising a resin film substrate.   The display element provided with the organic electroluminescent element of any one of Claims 9-11.   The illuminating device provided with the organic electroluminescent element of any one of Claims 9-11.   A display device comprising the illumination device according to claim 13 and a liquid crystal element as a display means.

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