JP2017059699A - Organic electronics material and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronics element suitable for reducing the driving voltage of an organic electronics element.SOLUTION: An organic electronics material comprises charge transporting polymer or oligomer having an arylamine structural unit having a substituent having 8 to 16 carbon atoms and a polymerizable substituent.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. High-molecular organic EL elements are composed of high-molecular materials, and simple film formation such as printing or inkjet is possible compared to low-molecular organic EL elements that require film formation in a vacuum system. Therefore, it is an indispensable element for future large-screen organic EL displays.

  Since the low molecular organic EL element is formed by vapor deposition, multilayering can be easily achieved by performing vapor deposition while sequentially changing the compounds to be used. On the other hand, since a polymer type organic EL element forms a film using a wet process such as printing or ink jetting, there is a problem that the lower layer dissolves when the upper layer is applied. For this reason, it is difficult to increase the number of polymer organic EL elements as compared with a low molecular organic EL element, and it has been a challenge to improve luminous efficiency and lifetime.

In order to cope with the above problem, several methods have been proposed so far. One is a method using a difference in solubility. For example, light emission formed using a water-soluble PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonic acid) hole injection layer using an aromatic organic solvent such as toluene. Devices with stacked layers are being studied. Non-Patent Document 1 discloses an element having a three-layer structure using compounds having greatly different solubilities.
On the other hand, in Non-Patent Documents 2 to 4 and Patent Document 1, in order to overcome such a problem, the solubility of the compound is changed using a polymerization reaction such as a siloxane compound, an oxetane group, or a vinyl group, and a thin film Discloses a method of insolubilizing the solvent with respect to a solvent.

International Publication No. 2008/010487

Y. Goto, T. Hayashida, M. Noto, IDW '04 Proceedings of The 11th International Display Workshop, 1343-1346 (2004) H. Yan, P. Lee, N. R. Armstrong, A. Graham, G. A. Evemenko, P. Dutta, T. J. Marks, J. Am. Chem. Soc., 127, 3172-3183 (2005) E. Bacher, M. Bayerl, P. Rudati, N. Reckfuss, C. David, K. Meerholz, O. Nuyken, Macromolecules, 38, 1640-1647 (2005) M. S. Liu, Y. H. Niu, J. W. Ka, H. L. Yip, F. Huang, J. Luo, T. D. Wong, A. K. Y. Jen, Macromolecules, 41, 9570-9580 (2008)

However, when water-soluble PEDOT: PSS is used, there is a problem that it is necessary to remove moisture remaining in the thin film. On the other hand, in addition to being unstable to moisture in the air, the siloxane compound has a problem that the device characteristics are not sufficient.
One of the required element characteristics is a reduction in driving voltage in order to further reduce power consumption and extend the life. In the prior art using the above materials, the drive voltage is reduced by adding a p-type dopant, such as PEDOT: PSS. However, it has been difficult to arbitrarily control the ratio of PEDOT molecules to PSS molecules.

  In view of the above, an embodiment of the present invention has an object to provide a material for organic electronics capable of reducing a driving voltage and an ink composition suitable for multilayering of an organic electronics element. Another embodiment of the present invention provides an organic layer capable of reducing the driving voltage of an organic electronics element, and further, an organic electronics element, an organic EL element, a display element, a lighting device, which can be driven at a low voltage, It is an object to provide a display device.

  Embodiments of the present invention relate to an organic electronic material including a charge transporting polymer or oligomer having an arylamine structural unit having a substituent having 8 to 16 carbon atoms and a polymerizable substituent.

Another embodiment of the present invention relates to an ink composition comprising the organic electronic material, a solvent, and a polymerization initiator.
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 electronic material which is embodiment of this invention can reduce the drive voltage of an organic electronics element. The ink composition according to an embodiment of the present invention is suitable for multilayering using a wet process. Moreover, the organic layer which is embodiment of this invention can reduce the drive voltage of an organic electronics element. Furthermore, the organic electronics element, the organic EL element, the display element, the illumination device, and the display device that are embodiments of the present invention can be driven at a low voltage.

It is a cross-sectional schematic diagram which shows an example of the organic EL element which is embodiment of this invention. It is the graph which showed the relationship of the applied voltage-current density in the hall | hole only element created in the Example and comparative example 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 the present embodiment includes a charge transporting polymer or oligomer having an arylamine structural unit having a substituent having 8 to 16 carbon atoms and a polymerizable substituent. 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”.

  In one embodiment, the charge transporting polymer is preferably a branched polymer (polymer or oligomer having a branched structure) having three or more terminals by including the structural unit B.

The charge transporting polymer of the present embodiment includes an arylamine structural unit having a substituent having 8 to 16 carbon atoms and one or more polymerizable substituents as a characteristic structure.
The “arylamine structural unit” may be included as at least a part of the above-mentioned “divalent structural unit L having charge transporting property” and / or “trivalent or higher structural unit B constituting a branched portion”. Preferably, it is more preferably at least part of the structural unit L. When the charge transporting polymer includes an arylamine structural unit having a substituent having 8 to 16 carbon atoms, the organic electronics element can be driven at a low voltage, thereby suppressing the decomposition of the organic material, thereby increasing the length of the element. It can contribute to life extension.
In addition, one or more polymerizable substituents (hereinafter also referred to as “polymerizable functional group”) may be contained in any one or more of the structural units L, T, and B. It is more preferable that it is contained in.

(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.

(Arylamine structural unit)
In the present embodiment, the structural unit L preferably includes an arylamine structural unit having a substituent having 8 to 16 carbon atoms (hereinafter also referred to as “structural unit L1”). The arylamine structural unit means an aromatic amine structural unit in which an aryl group is substituted on the nitrogen atom of the amine. The aromatic amine structure is preferably a diarylamine structure or a triarylamine structure, and the aryl group is preferably a phenyl group, and most preferably a triphenylamine structure.

As a triphenylamine structural unit, it is preferable to contain any one or more of the following, for example. In each structural formula, R ¹ represents a substituent having 8 to 16 carbon atoms. The position of the substituent on the aryl group may be any, but from the viewpoint of the effect of lowering the driving voltage, it is para-position, meta-position, and ortho-position on the basis of the bonding position to the nitrogen atom (in order below) Formulas (a1), (a2) and (a3)) are preferred in this order. It is also possible to combine two or more arylamines having different substituent substitution positions, such as a combination of formulas (a1) and (a2).

The number of carbon atoms of the substituent is preferably 8 or more from the viewpoint of reducing the driving voltage. Moreover, since the driving voltage tends to increase when the number of carbon atoms in the substituent R ¹ exceeds 16, the carbon number is preferably 16 or less, more preferably 14 or less, and 12 or less. More preferably it is.
The number of substituents having 8 to 16 carbon atoms in the arylamine structural unit is preferably one, but the aryl group may be other substituents R (—R ¹ , —OR ² , —SR ³ , ^{-OCOR 4, -COOR 5, -SiR 6} R 7 R 8, a halogen ^atom; R 1 to R ⁸ may include the same) and ^R 1 to R ⁸ of the substituents R.

More specifically, examples of the substituent having 8 to 16 carbon atoms include substituents represented by the following formulas (1) to (3). In formulas (1) to (3), n represents an integer of 7 to 15. From the viewpoint of the driving voltage lowering effect, the substituent of formula (1) is most preferable. As the structural unit L1, a plurality of arylamine structural units containing different substituents may be used in combination.

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

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

In the structural unit T of the above formula, R is the same as R in the structural unit L.
The structural unit T preferably has a polymerizable functional group. That is, at least one of R in the above formula is preferably a group containing a polymerizable functional group.

(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.

As the structural unit B, “an arylamine structural unit having a substituent having 8 to 16 carbon atoms” may be included. This arylamine structural unit is a divalent was above as a structural unit L1, if it contains the structural unit as a structural unit B, an aryl group containing in the formula (a1) ~ (a3), the substituents R ¹ However, what is necessary is just to become a trivalent structural unit by having the coupling | bond part with another structural unit.

(Polymerizable functional group)
The charge transporting polymer of this embodiment preferably has at least one polymerizable substituent (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. 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.

  When the structural unit L includes the specific arylamine structural unit L1, the ratio of the structural unit L1 in all the structural units L is preferably 10% or more from the viewpoint of lowering the driving voltage of the organic electronic element, More preferably, it is 20% or more, and further preferably 30% or more. The upper limit is not particularly limited and is 100% or less. The proportion of the structural unit L1 in the structural unit L can be determined by the charge ratio (molar ratio) of monomers corresponding to each structural unit used for synthesizing the charge transporting polymer.

  Moreover, it is preferable that the ratio of the arylamine structural unit containing a C8-16 substituent in a polymer is the range of 5-90 mol% in all the monomers which comprise a polymer, 15-75 mol%. More preferably, it is more preferably 30 to 60 mol%.

  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 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.

  From the viewpoint of efficiently curing the charge transporting polymer, the proportion of the polymerizable functional group contained in the charge transporting polymer is preferably 0.1 mol% or more, more preferably 1 mol% or more, based on the total structural unit. Preferably, 3 mol% or more is 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 containing at least a monomer containing an arylamine structural unit having a substituent having 8 to 16 carbon atoms and a monomer containing a polymerizable substituent. . For example, a monomer mixture including one or more monomers including the structural unit L and one or more monomers including the structural unit T, and may optionally include one or more other monomers (monomers including the structural unit B). Can be preferably produced by copolymerizing these monomers. Here, at least part or all of the monomer including the structural unit L is preferably one or more monomers including the structural unit L1, and at least part or all of the monomer including the structural unit T. Is preferably one or more monomers containing the polymerizable substituent.
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.

  Since the charge transporting polymer of the present embodiment 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-described embodiment, a solvent capable of dissolving or dispersing the material, and a polymerization initiator. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.
An ink composition which is another embodiment of the present invention contains the organic electronic material of the above embodiment and a solvent capable of dissolving or dispersing the material. For example, when using the ink composition of this embodiment that does not contain a polymerization initiator, it is preferable that the lower organic layer contains a polymerization initiator because the upper ink composition can be cured.

[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]
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. .

  When the ink composition contains a polymerization initiator, the content of the polymerization initiator is not particularly limited, and can be appropriately determined according to the type and amount of the polymerizable functional group contained in the charge transporting polymer. For example, the content of the polymerization initiator is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more with respect to the charge transporting polymer.

<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.

  Since the charge transporting polymer of this embodiment 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. Accordingly, a preferred embodiment of the organic EL device has the organic layer, the light emitting layer, and the cathode as an anode, a hole injection layer and / or a hole transport layer in this order, and an optional layer between these layers. You may have a layer of.

Particularly preferably, the organic layer is a hole injection layer or a transparent electrode.
When the organic electronic material of the above embodiment is used for the hole injection layer, the hole mobility is increased and the driving voltage of the device can be reduced. In particular, the hole injection layer can be cured by using this organic electronic material in combination with a polymerization initiator. As a result, it is possible to prevent the hole injection layer from being dissolved when a hole transport layer made of ink or the like is further applied thereon.

  When the organic electronic material of the above-described embodiment is used for the transparent electrode, it is possible to reduce the driving voltage of the device by reducing the injection barrier to the hole injection layer. In addition, since a flat surface can be obtained, a short circuit can be prevented and device yield is improved. Further, when a flexible substrate is used, it is excellent in flexibility, so that a bendable device can be manufactured.

  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 used as at least a hole injection 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 the hole injection layer contains a polymerization initiator and the hole transport layer uses a polymer having a polymerizable substituent as the charge transport polymer, the hole transport layer can be cured. Further, it becomes possible to apply a light emitting layer made of ink or the like on the upper layer. As the ink composition for forming the hole transport layer in this case, an ink composition containing no polymerization initiator can be used.

[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.

<Synthesis of charge transporting polymers 1 to 4>
[Example 1: Synthesis of charge transporting polymer 1]
The following monomer 1 (5.0 mmol), the following monomer 2 (2.0 mmol), the following monomer 3 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, 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 1.3 g of charge transporting polymer 1.

The number average molecular weight of the obtained charge transporting polymer 1 was 8,900, and the weight average molecular weight was 52,300.
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

[Example 2: Synthesis of charge transporting polymer 2]
A charge transporting polymer 2 was obtained in the same manner as in Example 1 except that the monomer 1 in Example 1 was changed to the following monomer 4. The number average molecular weight of the polymer 2 was 12,000, and the weight average molecular weight was 38,400.

[Example 3: Synthesis of charge transporting polymer 3]
A charge transporting polymer 3 was obtained in the same manner as in Example 1 except that the monomer 1 in Example 1 was changed to the following monomer 5. The number average molecular weight of the polymer 3 was 14,300, and the weight average molecular weight was 47,500.

[Comparative Example 1: Synthesis of charge transporting polymer 4]
A charge transporting polymer 4 was obtained in the same manner as in Example 1 except that the monomer 1 in Example 1 was changed to the following monomer 6. The number average molecular weight of the polymer 4 was 14,200, and the weight average molecular weight was 49,700.

<Evaluation of solvent resistance using ink composition>
[Example 4]
Ink composition 1 comprising charge transporting polymer 1 (10.0 mg), the following polymerization initiator (0.5 mg), and toluene (2.3 mL) was prepared. This ink composition 1 was spin-coated on a quartz plate at 3000 rpm to form an organic layer. Next, the obtained organic layer was heated on a hot plate at 180 ° C. for 10 minutes. The heated quartz plate was immersed in toluene for 1 minute for cleaning.

The UV-VIS (ultraviolet / visible) spectrum before and after washing with a toluene solvent was measured, and the ratio of the absorbance (Abs) of the absorption maximum (λmax) in the obtained spectrum (below) was measured.
Residual film rate (%) = Abs after cleaning / Abs before cleaning × 100
The UV-VIS spectrum was measured using U-3900H (Hitachi High Technologies) at a measurement wavelength of 250 nm to 600 nm and a scan speed of 600 nm / min.

[Example 5]
An organic layer was formed in the same manner as in Example 4 except that the charge transporting polymer 1 of the ink composition 1 in Example 4 was changed to the charge transporting polymer 2, and the remaining film ratio was measured.

[Example 6]
An organic layer was formed in the same manner as in Example 4 except that the charge transporting polymer 1 of the ink composition 1 in Example 4 was changed to the charge transporting polymer 3, and the remaining film ratio was measured.
[Example 7]
After the organic layer was formed in the same manner as in Example 4, the organic layer was laminated by spin-coating the ink composition 2 composed of the charge transporting polymer 1 (10.0 mg) and toluene (2.3 mL) at 3000 rpm. Then, it was heated on a hot plate at 180 ° C. for 10 minutes. Thereafter, the remaining film rate of the obtained organic layer was measured in the same manner as described above.

[Reference Example 1]
In the ink composition 1 of Example 4, an organic layer was formed in the same manner as in Example 4 except that the polymerization initiator was not added, and the remaining film ratio was measured.

  As shown in the above table, since the obtained organic layer is insolubilized in the examples, it can be seen that an arbitrary organic layer can be applied and laminated on the upper layer without dissolving the organic layer. According to Example 7, when a polymerization initiator is contained in the lower layer (for example, hole injection layer), it turns out that the layer (for example, hole transport layer) laminated | stacked on it becomes insoluble.

<Production of Hall-only device>
[Example 8]
On a glass substrate obtained by patterning ITO to a width of 1.6 mm under a nitrogen atmosphere, the charge transporting polymer 1 (30.0 mg), the polymerization initiator (1.5 mg), and toluene (2.3 mL) are formed. The ink composition was spin-coated 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 form a hole injection layer (90 nm).
The substrate obtained above was transferred into vacuum vapor deposition, and Al (100 nm) was deposited on the hole injection layer by vapor deposition, followed by sealing treatment to produce a hole-only device.

[Example 9]
A hole-only device was produced in the same manner as in Example 8 except that the charge-transporting polymer 1 of Example 8 was changed to the charge-transporting polymer 2.

[Example 10]
A hole-only device was produced in the same manner as in Example 8 except that the charge-transporting polymer 1 of Example 8 was changed to the charge-transporting polymer 3.

[Comparative Example 2]
A hole-only device was produced in the same manner as in Example 8 except that the charge-transporting polymer 1 of Example 8 was changed to the charge-transporting polymer 4.

  FIG. 2 shows a graph of applied voltage-current density when voltage is applied using ITO as a positive electrode and Al as a cathode of these hole-only elements. FIG. 2 shows that the driving voltage of the organic EL element can be lowered by using the organic electronic material and the ink composition of the present embodiment.

  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, the above-described charge transporting polymer containing an arylamine structural unit having a substituent having 8 to 16 carbon atoms is used to obtain an organic EL device having a low driving voltage. It is possible to achieve the same effect.

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)

  An organic electronic material comprising a charge transporting polymer or oligomer having an arylamine structural unit having a substituent having 8 to 16 carbon atoms and a polymerizable substituent.   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 substituent having 8 to 16 carbon atoms has a structure of any one of the following formulas (1) to (3).

[In formula (1)-(3), n shows the integer of 7-15. ]   An ink composition comprising the organic electronic material according to claim 1, a solvent, and a polymerization initiator.   The organic layer formed using the organic electronics material of any one of Claims 1-3, or the ink composition of Claim 4.   An organic electronic device comprising at least one organic layer according to claim 5.   An organic electroluminescence device comprising at least one organic layer according to claim 5.   The organic electroluminescent element according to claim 7, further comprising a resin film substrate.   The organic electroluminescent element according to claim 7 or 8, wherein the organic layer is a hole injection layer.   The organic electroluminescent element according to claim 7 or 8, wherein the organic layer is a transparent electrode.   The display element provided with the organic electroluminescent element of any one of Claims 7-10.   The illuminating device provided with the organic electroluminescent element of any one of Claims 7-10.   A display device comprising the illumination device according to claim 12 and a liquid crystal element as a display means.

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