JP2013229429A - Organic electronic material and manufacturing method thereof, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and manufacturing method thereof, organic electronic element, organic electroluminescence element, lighting system, display element, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for easily manufacturing an organic electronic material which enables stable and easy formation of a thin film or easy formation of a multilayered organic thin film and is useful in improving productivity of an organic electronic element.SOLUTION: A method of manufacturing an organic electronic material comprises: preparing an electrolyte containing a charge-transporting compound and an ionic compound containing any one of compounds represented by the general formulas (1c) to (4c); and applying a voltage to the electrolyte to react the ionic compound with the charge-transporting compound.

Description

  The present invention relates to an organic electronics material and a production method thereof, a polymerization initiator and a thermal polymerization initiator, an ink composition, an organic thin film and a production method thereof, an organic electronics element, an organic electroluminescence element (hereinafter also referred to as an organic EL element). A), a lighting device, a display element, and a display device.

  Organic electronics elements are elements that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that can replace conventional inorganic semiconductors based on silicon. ing.

  An organic EL element, an organic photoelectric conversion element, an organic transistor etc. are mentioned as an example of an organic electronics element.

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

  In recent years, attempts have been made to mix an electron-accepting compound with a charge-transporting compound for the purpose of improving the luminous efficiency and lifetime of an organic EL device.

  For example, Patent Document 1 discloses that tris (4-bromophenylaminium hexachloroantimonate) (TBPAH) is mixed as an electron-accepting compound with a hole-transporting polymer compound. It is disclosed that an organic electroluminescence device capable of being driven at a low voltage can be obtained.

Patent Document 2 discloses that iron (III) chloride (FeCl ₃ ) is mixed with a hole transporting compound as an electron accepting compound by a vacuum deposition method.

  In Patent Document 3, tris (pentafluorophenyl) borane (PPB) as an electron-accepting compound is mixed with a hole-transporting polymer compound by a wet film formation method to form holes. Forming an injection layer is disclosed.

  Thus, it is considered important to generate a compound composed of a radical cation and a counter anion of a charge transporting compound, which is generated when an electron accepting compound is mixed with the charge transporting compound.

  Patent Document 4 discloses a composition comprising a specific aminium cation radical as a composition for a charge transport film.

  However, these documents do not describe that the ionic compound according to the present invention is used as an electron-accepting compound.

  On the other hand, organic EL elements are roughly classified into two types, low molecular weight organic EL elements and high molecular weight organic EL elements, depending on the materials and film forming methods used. High-molecular organic EL elements are composed of high-molecular materials, and can be used for simple film formation such as printing and ink-jet compared to low-molecular organic EL elements that require vacuum-based film formation. Therefore, it is an indispensable element for future large-screen organic EL displays.

  Although research has been conducted energetically for both low-molecular organic EL elements and high-molecular organic EL elements, low luminous efficiency and short element lifetime are still serious problems. As one means for solving this problem, multilayering is performed in the low molecular organic EL element.

  FIG. 1 shows an example of a multilayered organic EL element. In FIG. 1, the layer responsible for light emission is described as the light emitting layer 1, and the layer in contact with the anode 2 is described as the hole injection layer 3, and the layer in contact with the cathode 4 is described as the electron injection layer 5. Furthermore, when a different layer exists between the light emitting layer 1 and the hole injection layer 3, it is described as a hole transport layer 6, and when a different layer exists between the light emitting layer 1 and the electron injection layer 5, an electron transport is described. It is described as layer 7. In FIG. 1, 8 is a substrate.

  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 inkjet, there arises a problem that the lower layer dissolves when the upper layer is applied. For this reason, it is difficult to make a polymer organic EL element multi-layered as compared to a low molecular organic EL element, and it has not been possible to obtain an effect of improving luminous efficiency and life.

To address this problem, several methods have been proposed so far. One is a method using a difference in solubility. For example, a device having a two-layer structure of a water-soluble polythiophene: polystyrene sulfonic acid (PEDOT: PSS) or a hole injection layer made of a polyaniline derivative, and a light emitting layer formed using an aromatic organic solvent such as toluene. It is. In this case, since the PEDOT: PSS layer is not dissolved in an aromatic solvent such as toluene, a two-layer structure can be produced. It is known that PEDOT is doped with PSS sulfonic acid to improve charge transportability. With respect to the polyaniline derivatives, counter anion polystyrene sulfonic acid, BF ₄ ^- and PF ₆ ^- are known to be by electrochemical doping with anions such is possible to improve the charge transportability. All of these are poorly soluble in organic solvents or aqueous solvents and are widely used as water-dispersed materials. Further, since the material is an aqueous dispersion, it is difficult to remove ionic impurities included in the synthesis.
Patent Document 5 discloses a technique of immersing and applying wet-coated polyaniline in a solution in which polystyrene sulfonate is dissolved.

  Non-Patent Document 1 proposes a device having a three-layer structure using compounds having greatly different solubilities.

  Patent Document 6 discloses an element having a three-layer structure in which a layer called an interlayer is introduced on PEDOT: PSS.

  Further, in Non-Patent Documents 2 to 4 and Patent Document 7, in order to overcome the problem of multilayering, the solubility of the compound is changed using a polymerization reaction such as a siloxane compound, an oxetane group, or a vinyl group, and the thin film is used as a solvent. A method of insolubilizing to is disclosed.

  These multi-layered methods are important. However, when water-soluble PEDOT: PSS is used, it is necessary to remove moisture remaining in the thin film, and the materials that can be used are limited in order to utilize the difference in solubility. In other words, the siloxane compound is unstable to moisture in the air and the device characteristics are not sufficient.

  In order to utilize the above polymerization reaction, it is necessary to add an appropriate polymerization initiator that reacts and decomposes by stimulation such as light and heat to generate acid, base, radical, and the like.

Patent Document 8, Patent Document 9, and Patent Document 10 disclose photoacid generators or initiators containing fluorine.
However, these documents do not describe organic electronic materials using photoacid generators or initiators containing fluorine.

Japanese Patent No. 3748491 Japanese Patent Laid-Open No. 11-251067 Japanese Patent No. 4023204 JP 2006-233162 A Japanese Patent Laid-Open No. 2001-217075 JP 2007-1119763 A 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, 3172-4183 (2005) E. Bacher, M. Bayerl, P. Rudati, N. Reckfuss, C. David, K. Meerholz, O. Nuyken, Macromolecules, 38, 1640 (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 (2008)

  In order to increase the efficiency and life of organic EL elements, it is desirable to divide the organic layers into layers and separate the functions of each layer. However, the organic layers can be formed using a wet process that is easy to form even in large areas. In order to increase the number of layers, as described above, it is necessary to prevent the lower layer from being dissolved when the upper layer is formed, and a change in solubility in a solvent utilizing a polymerization reaction has been used.

  In addition, attempts have been made to mix an electron-accepting compound with a charge-transporting compound in order to reduce the driving voltage of the organic EL device, but the characteristics have not been sufficient. Many of the electron-accepting compounds have low solubility in solvents and are difficult to handle.

In view of the above-described problems, the present invention can stably and easily form a thin film or easily form a multi-layered organic thin film layer to improve the productivity of organic electronics elements, particularly polymer type organic EL elements. Provided are an organic electronic material useful in manufacturing, a production method capable of easily producing the organic electronic material, an ink composition containing the organic electronic material, the organic electronic material, and an organic thin film formed from the ink composition For the purpose.
Furthermore, an object of the present invention is to provide an organic electronics element, an organic EL element, an illuminating device, and a display element that have a lower driving voltage than that of the prior art and have a long light emission lifetime.

  As a result of intensive studies, the present inventors have found that an organic electronic material as a charge transport material can be easily obtained by applying a voltage to an electrolyte solution containing a charge transport compound and an ionic compound, and the present invention has been completed. I came to let you. In addition, the organic electronic material, a polymerization initiator containing an ionic compound, an ink composition containing the organic electronic material, and an organic thin film formed using the organic electronic material or the ink composition, The present invention has been completed by finding that it is useful for increasing the efficiency and extending the life of organic EL elements.

That is, the present invention is characterized by the following items (1) to (28).
(1) a step of preparing an electrolytic solution containing an ionic compound containing any one of the compounds represented by the following general formulas (1c) to (4c) and a charge transporting compound;
Applying a voltage to the electrolytic solution to react the ionic compound with the charge transporting compound;
A method for producing an organic electronic material, comprising:

（式中、Ｙ^１〜Ｙ^６はそれぞれ独立に二価の連結基、Ｒ^１〜Ｒ^１０はそれぞれ独立に、電子求引性の有機置換基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよく、また、Ｒ^２及びＲ^３、Ｒ⁴〜Ｒ⁶、又はＲ^７〜Ｒ^１０はそれぞれが結合して環状あるいはポリマー状になってもよい。）を表す。Ｌ^＋は一価のカチオンを表す。）

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.)

(2) The method for producing an organic electronic material according to (1), wherein the ionic compound has a halogen atom.

(3) The ionic compound may be a linear, branched or cyclic perfluoroalkyl group, perfluoroalkylsulfonyl group, perfluoroalkyloxysulfonyl group, perfluoro group which may contain a hetero atom having 1 to 20 carbon atoms. Selected from the group consisting of fluoroarylsulfonyl group, perfluoroaryloxysulfonyl group, perfluoroacyl group, perfluoroalkoxycarbonyl group, perfluoroacyloxy group, perfluoroaryloxycarbonyl group, perfluoroalkenyl group, and perfluoroalkynyl group The method for producing an organic electronic material according to the above (1) or (2), wherein the organic electronic material has one kind.

(4) The organic electronic material according to any one of (1) to (3), wherein Y ^{1 to} Y ⁶ are any one of the following general formulas (4b) to (14b): Production method.

（式中、Ｒは任意の有機基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよい）を表す。）

(In the formula, R represents an arbitrary organic group (these structures may further have a substituent or a hetero atom).)

(5) L ⁺ in the general formulas (1c) to (4c) is an element belonging to Group 1 or Group 2 of the long-period periodic table, or a cation represented by General Formulas (15b) to (17b) below The method for producing an organic electronic material according to any one of (1) to (4), wherein the organic electronic material is any one of the above.

（式中、Ｒ^１１〜Ｒ^３４は、各々独立に、任意の有機基を表す。Ｒ^１１〜Ｒ^３４のうち隣接する２以上の基が、互いに連結して環を形成していてもよい。Ａ^１は長周期型周期表の第１７族または第１４族に属する元素を表し、Ａ^２は長周期型周期表の第１６族または第１４族に属する元素を表し、Ａ^３は長周期型周期表の第１５族に属する元素を表す。）

^(Wherein, R 11 ^{to R 34} each independently 2 or more neighboring groups of ^.R 11 ^{to R 34} represent any organic group may be bonded to each other to form a ring. A ¹ represents an element belonging to Group 17 or Group 14 of the long-period periodic table, A ² represents an element belonging to Group 16 or Group 14 of the long-period periodic table, and A ³ represents a long-period type (Represents elements belonging to Group 15 of the periodic table.)

(6) R ^{11 to} R ³⁴ in the general formulas (15b) to (17b) are each independently an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, or an aromatic heterocycle. It is a cyclic group, The manufacturing method of the organic electronics material as described in said (5) characterized by the above-mentioned.

(7) A ¹ in the general formula (15b) is a bromine atom, an iodine atom or a carbon atom; A ² in the general formula (16b) is an oxygen atom, a carbon atom, a sulfur atom or a selenium atom; a ³ is a nitrogen atom in the formula (17b), the method for producing an organic electronic material according to (5) or (6), wherein the phosphorus atom, arsenic atom or an antimony atom.

(8) The method for producing an organic electronic material according to any one of (1) to (7), wherein the charge transporting compound contains at least one aromatic amine, carbazole, or thiophene compound.

(9) The method for producing an organic electronic material as described in (8) above, wherein the aromatic amine, carbazole or thiophene compound is a polymer or an oligomer.

(10) The method for producing an organic electronic material as described in (9) above, wherein the number average molecular weight of the polymer or oligomer is 1,000 or more and 100,000 or less.

(11) The method for producing an organic electronic material as described in (9) or (10) above, wherein the polymer or oligomer has one or more polymerizable substituents.

(12) The method for producing an organic electronic material according to the above (11), wherein the polymerizable substituent is any one of an oxetane group, an epoxy group, a vinyl group, a vinyl ether group, an acrylate group, and a methacrylate group. .

(13) An organic electronic material produced by the method for producing an organic electronic material according to any one of (1) to (12).

(14) A polymerization initiator comprising at least an ionic compound represented by the following general formula (4c) among the ionic compounds represented by the following general formulas (1c) to (4c).

（式中、Ｙ^１〜Ｙ^６はそれぞれ独立に二価の連結基、Ｒ^１〜Ｒ^１０はそれぞれ独立に、電子求引性の有機置換基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよく、また、Ｒ^２及びＲ^３、Ｒ⁴〜Ｒ⁶、又はＲ^７〜Ｒ^１０はそれぞれが結合して環状あるいはポリマー状になってもよい。）を表す。Ｌ^＋は一価のカチオンを表す。）

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.)

(15) A thermal polymerization initiator comprising at least one ionic compound represented by the following general formulas (1c) to (4c).

（式中、Ｙ^１〜Ｙ^６はそれぞれ独立に二価の連結基、Ｒ^１〜Ｒ^１０はそれぞれ独立に、電子求引性の有機置換基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよく、また、Ｒ^２及びＲ^３、Ｒ⁴〜Ｒ⁶、又はＲ^７〜Ｒ^１０はそれぞれが結合して環状あるいはポリマー状になってもよい。）を表す。Ｌ^＋は一価のカチオンを表す。）

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.)

(16) A method for producing an organic thin film comprising a step of imparting solvent resistance to an organic thin film using the polymerization initiator according to (14) or the thermal polymerization initiator according to (15). .

(17) An ink composition comprising the organic electronic material according to (13) and a solvent.

(18) An organic thin film formed using the organic electronic material according to (13).

(19) An organic thin film formed using the ink composition according to (17).

(20) An organic electronic device comprising the organic thin film according to (18) or (19).

(21) An organic electroluminescent device comprising the organic thin film according to (18) or (19).

(22) The organic electroluminescent element as described in (21) above, wherein the organic thin film is a hole injection layer.

(23) The organic electroluminescent element as described in (21) above, wherein the organic thin film is a hole transport layer.

(24) The organic electroluminescent element according to any one of (21) to (23), wherein the substrate is a flexible substrate.

(25) The organic electroluminescent element according to any one of (21) to (23), wherein the substrate is a resin film.

(26) A display device comprising the organic electroluminescent device according to any one of (21) to (23).

(27) An illumination device comprising the organic electroluminescent element according to any one of (21) to (25).

(28) A display device comprising the illumination device according to (27) and a liquid crystal element as display means.

According to the present invention, a thin film can be formed stably and easily, and the solubility is changed by a polymerization reaction, so that an organic thin film layer can be easily formed in multiple layers. It is possible to provide an organic electronic material that is extremely useful in improving the productivity of the organic EL element and a manufacturing method that can easily manufacture the organic electronic material.
Furthermore, when the organic electronic material contains an ionic compound, it is possible to provide an organic electronic element and an organic EL element that have a lower driving voltage than conventional ones and have a long emission lifetime.

It is a schematic diagram which shows an example of the multilayered organic EL element. In Example 7 and Comparative Example 6, it is a figure which shows the relationship of the applied voltage-current density at the time of applying a voltage, using ITO of a hole only element as a positive electrode and Au as a cathode.

<Method for manufacturing organic electronics materials>
The method for producing an organic electronic material of the present invention prepares an electrolytic solution containing an ionic compound containing any one of the compounds represented by the following general formulas (1c) to (4c) and a charge transporting compound. And a step of reacting the ionic compound with the charge transporting compound by applying a voltage to the electrolytic solution.

（式中、Ｙ^１〜Ｙ^６はそれぞれ独立に二価の連結基、Ｒ^１〜Ｒ^１０はそれぞれ独立に、電子求引性の有機置換基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよく、また、Ｒ^２及びＲ^３、Ｒ⁴〜Ｒ⁶、又はＲ^７〜Ｒ^１０はそれぞれが結合して環状あるいはポリマー状になってもよい。）を表す。Ｌ^＋は一価のカチオンを表す。）

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.)

[Step of preparing electrolytic solution]
In the present invention, the electrolytic solution includes at least a charge transporting compound, an ionic compound, and a solvent.
The concentration of the charge transporting compound with respect to the electrolytic solution is preferably 0.001 to 40% by mass, and more preferably 0.1 to 30% by mass.
The concentration of the ionic compound with respect to the electrolytic solution is not particularly limited from the viewpoint of reaction as long as the molar ratio with the charge transporting compound is at least 1 or more, but is preferably 0.01 to 45% by mass, preferably 0.2 to More preferred is 40% by mass.

  As a solvent of the electrolytic solution used for electrolysis, there is no particular limitation as long as the charge transporting compound and the ionic compound do not react with the solvent and are stable under electrolytic conditions, and general solvents used for organic electrolysis can be used. It is. For example, formic acid, acetic acid, methanol, ethanol, propanol, methyl cellosolve, cellosolve, 1,4-dioxane, monoglyme (1,2-dimethoxyethane), acetone, 4-methyl-2-pentanone, acetylacetone, acetonitrile, propionitrile , Butyronitrile, isobutyronitrile, benzonitrile, ethylenediamine, pyridine, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, hexamethylphosphorus Acid triamide, N-methyl-2-pyrrolidone, 1,1,3,3-tetramethylurea, dimethyl sulfoxide, sulfolane, dimethylthioformamide, N-methylthiopyrrolidone, hexane, benzene, toluene, nitromethane, nitrobenzene, dichloromethane, 1 , 2- Chloromethane, .gamma.-butyrolactone, propylene carbonate, ethylene carbonate, methyl acetate, ethyl acetate, butyl acetate, chlorobenzene, dichlorobenzene, and the like. Of these, toluene, chlorobenzene, tetrahydrofuran, benzonitrile and the like are preferable from the viewpoints of the solubility of the charge transporting compound and the ionic compound and the stability to voltage.

In order to increase the conductivity of the electrolytic solution, a supporting electrolyte can be added to the electrolytic solution as necessary. Examples of the supporting electrolyte include tetraalkylammonium perchlorate (alkyl represents, for example, methyl, ethyl, propyl, butyl, isobutyl, hexyl, etc.), tetrafluoroboron tetraalkylammonium salt, hexafluoroline tetraalkylammonium salt trifluoromethanesulfone. Acid tetraalkylammonium salt, halogenated alkylammonium salt (halogenated as chloro, bromo, iodo, etc.), lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, sodium perchlorate, potassium perchlorate Etc. In particular, tetraalkylammonium salts are preferred from the viewpoints of solubility and reactivity. Moreover, since the ionic compound of this invention may improve the electrical conductivity of electrolyte solution, a supporting electrolyte may not necessarily be required.
In addition, an antioxidant or the like that suppresses side reactions can be added to the electrolytic solution as necessary.

[Step of reacting ionic compound and charge transporting compound by applying voltage to electrolyte]
As a method of forcibly applying a voltage with an electrolytic solution, there is a constant current or constant potential oxidation in an electrolytic cell in which at least an anode and a cathode are arranged, and it is easy to control a charge transport material obtained by electrolytic oxidation. From the viewpoint, constant potential oxidation is preferable.

  Examples of the electrolytic cell include a method in which the anode and the cathode are disposed in the same container, and a method in which the anode and the cathode are disposed in different containers and connected by liquid junction or the like. In addition, a plurality of anodes and cathodes may be disposed in the electrolytic cell as necessary. In addition, a bubbler for passing an inert gas (for example, argon, nitrogen, etc.), a stirrer, a reference electrode, and the like can be arranged as necessary.

  The anode and cathode are not particularly limited as long as they can withstand constant potential oxidation, but Pt, Au, and carbon electrodes are preferable from the viewpoint of durability. In particular, a Pt electrode is preferable from the viewpoint of durability and reactivity.

The potential set in the constant potential oxidation is preferably set to the oxidation potential of the charge transporting compound obtained from the cyclic voltagram. Since the oxidation potential here varies depending on the charge transporting compound, the solvent, the supporting electrolyte, the electrode material, and the like, it must be determined from the peak of the oxidation current with a cyclic voltammogram when setting. For example, when an Ag / Ag ⁺ electrode is used as a reference electrode and a triphenylamine derivative is used as a charge transporting compound, a first oxidation peak is obtained at 0.5 to 1.2 V.
In addition, when a plurality of oxidation peaks are obtained in the cyclic voltammogram, a charge transporting compound in any oxidation state can be obtained.

  The time for performing constant potential oxidation can be arbitrarily set. Usually, the time is adjusted in consideration of the oxidizable amount of charge transporting compound added to the electrolyte. The amount of electricity used for constant potential oxidation can be calculated by subtracting the Faraday current from the flowing current and multiplying it by the energized time. It is possible to adjust the doping degree of the charge transport material composed of the charge transport compound and the ionic compound obtained by adjusting the constant potential oxidation time.

(Ionic compounds)
In the present invention, the ionic compound includes any one of the compounds represented by the general formulas (1c) to (4c). More specifically, the “ionic compound” is a compound composed of a cation and an anion, and the anion contains an electron-withdrawing organic substituent (R ^{1 to} R ¹⁰ in the above formula), Examples thereof include halogen atoms such as fluorine atom, chlorine atom and bromine atom, alkylsulfonyl groups such as cyano group, thiocyano group, nitro group and mesyl group, arylsulfonyl groups such as tosyl group, formyl group, acetyl group and benzoyl. The number of carbon atoms of the group is usually 1 to 12, preferably 6 or less, and the number of carbon atoms of the acyl group, methoxycarbonyl group, ethoxycarbonyl group, etc. is usually 2 to 10, preferably 7 or less, preferably the alkoxycarbonyl group or phenoxycarbonyl group. An aromatic hydrocarbon having usually 3 or more, preferably 4 or more and 25 or less, preferably 15 or less carbon atoms such as a pyridyloxycarbonyl group. An aryloxycarbonyl group having an elementary group or an aromatic heterocyclic group, an acyloxy group having 2 to 20 carbon atoms, such as acetoxy, an alkyloxysulfonyl group, an aryloxysulfonyl group, a trifluoromethyl group, a pentafluoroethyl group, etc. Is usually a linear, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 10 carbon atoms, preferably a haloalkyl, haloalkenyl, halo or the like substituted with a halogen atom such as a fluorine atom or a chlorine atom. Examples thereof include haloaryl groups having 6 to 20 carbon atoms, such as alkynyl groups and pentafluorophenyl groups. Among these, from the viewpoint that the negative charge can be efficiently delocalized, more preferably, a group obtained by substituting a part or all of the hydrogen atoms of the group having a hydrogen atom with a halogen atom such as fluorine among the organic groups, For example, a linear, branched or cyclic perfluoroalkyl group, perfluoroalkylsulfonyl group, perfluoroalkyloxysulfonyl group, perfluoroarylsulfonyl group, perfluoroaryl, which may contain a heteroatom having 1 to 20 carbon atoms An oxysulfonyl group, a perfluoroacyl group, a perfluoroalkoxycarbonyl group, a perfluoroacyloxy group, a perfluoroaryloxycarbonyl group, a perfluoroalkenyl group, and a perfluoroalkynyl group, represented by the following structural formula group (1) However, the present invention is not limited to this.

Structural formula group (1)

Moreover, although Y < ¹ > -Y < ⁶ > in general formula (1c)-(4c) shows a bivalent coupling group, it is preferable that it is any one of the following general formula (4b)-(14b).

（式中、Ｒは任意の有機基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよい）を表す。）

(In the formula, R represents an arbitrary organic group (these structures may further have a substituent or a hetero atom).)

  R in the general formulas (10b) to (14b) is each independently an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, from the viewpoint of improving electron acceptability and solubility in a solvent. It is preferably a hydrocarbon group or an aromatic heterocyclic group, more preferably an organic group having an electron-withdrawing substituent among the substituents. For example, the group of the structural formula group (1) is Can be mentioned.

  The anion in the present invention preferably has a negative charge mainly on an oxygen atom, nitrogen atom, or carbon atom, and is not particularly limited, but more preferably has a negative charge on a nitrogen atom or carbon atom, most preferably. It is represented by the following general formulas (18b) and (19b).

（式中、Ｒ_Ｆ１〜Ｒ_Ｆ９はそれぞれ独立に電子求引性の有機置換基（これらの構造中にさらに置換基、ヘテロ原子をもっていてもよく、またＲ_Ｆ１〜Ｒ_Ｆ９はそれぞれが結合して環状あるいはポリマー状になってもよい。）を表し、特に限定されないが、例えば、前記構造式群（１）で示される基があげられる。）

(In the formula, R _{F1 to} R _F9 are each independently an electron-withdrawing organic substituent (these structures may further have a substituent or a heteroatom, and R _{F1 to} R _F9 are bonded to each other). (It may be cyclic or polymer.) And is not particularly limited, and examples thereof include groups represented by the structural formula group (1).

In addition, the cation of the ionic compound according to the present invention, that is, L ^{+ in the} general formulas (1c) to (4c) is a monovalent cation, and is not particularly limited. An element belonging to the genus or any one of the following general formulas (15b) to (17b) is preferable.

（式中、Ｒ^１１〜Ｒ^３４は、各々独立に、任意の有機基を表す。Ｒ^１１〜Ｒ^３４のうち隣接する２以上の基が、互いに連結して環を形成していてもよい。Ａ^１は長周期型周期表の第１７族または第１４族に属する元素を表し、Ａ^２は長周期型周期表の第１６族または第１４族に属する元素を表し、Ａ^３は長周期型周期表の第１５族に属する元素を表す。）

^(Wherein, R 11 ^{to R 34} each independently 2 or more neighboring groups of ^.R 11 ^{to R 34} represent any organic group may be bonded to each other to form a ring. A ¹ represents an element belonging to Group 17 or Group 14 of the long-period periodic table, A ² represents an element belonging to Group 16 or Group 14 of the long-period periodic table, and A ³ represents a long-period type (Represents elements belonging to Group 15 of the periodic table.)

R ^{11 to} R ³⁴ in the general formulas (15b) to (17b) are each independently an alkyl group, an alkenyl group, or an alkynyl group, from the viewpoint of compound stability and solubility in a solvent. An aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
In view of stability of the compound, ease of synthesis and purification, A ¹ in the general formula (15b) is a bromine atom, iodine atom or carbon atom, and A ² in the general formula (16b) is an oxygen atom or carbon atom. , A sulfur atom or a selenium atom, and A ³ in the general formula (17b) is preferably a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom.
That is, the cation of the ionic compound in the present invention is more preferably iodonium, sulfonium, phosphonium, carbenium (trityl), anilinium, bismuthonium, ammonium, selenium, pyridinium, imidazolium, oxonium, quinolinium, pyrrolidinium, aminium, imonium, Such as tropylium.

  For example, as sulfonium, triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluoro Phenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] Sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4 -Methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-Benzoylphenylthio) phenylbis (4-fluoro Phenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9 -Oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- ( 4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio)] phenyldi-p- Tolylsulfonium, 4- [4- (Benzoylph Enylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2, Triarylsulfonium such as 4,6-trimethylphenyl) thiaanthrhenium; diarylsulfonium such as diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenyl Methylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethyl N-disulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacyl Monoarylsulfonium such as sulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyl Trialkylsulfonium such as tetrahydrothiophenium and octadecylmethylphenacylsulfonium These are described in the following documents.

  Regarding triarylsulfonium, U.S. Pat. No. 4,231,951, U.S. Pat. No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922, JP-A-8- 27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, JP-A-10-287463. JP-A-10-245378, JP-A-8-157510, JP-A-10-204083, JP-A-8-245656, JP-A-8-157451, JP-A-7-324069, JP-A-9-268205. JP, 9-278935, JP 2001-288205, JP 11-80118, JP JP-A-10-182825, JP-A-10-330353, JP-A-10-152495, JP-A-5-239213, JP-A-7-333834, JP-A-9-12537, JP-A-8-325259, JP-A-8-160606. JP, 2000-186071 (US Pat. No. 6,368,769), etc .; Regarding diarylsulfonium, JP-A-7-300504, JP-A-64-45357, JP-A-64-29419, etc .; Monoarylsulfonium JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6,097,753), JP-A-2-196812, JP-A-2-1470, and JP-A-2-196812. JP-A-3-237107, JP-A-3-17101, JP-A-6-22 No. 086, JP-A-10-152469, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; regarding trialkylsulfonium, JP-A-4-308563, JP-A-5-140210, JP-A-5-140209, JP-A-5-230189, JP-A-6-271532, JP-A-58-37003, JP-A-2-178303, JP-A-10-338688, JP-A-9-328506, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, US Pat. It is done.

  Examples of the iodonium ions include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxyphenyl). ) Iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, and the like, which are listed in Macromolecules, 10, 1307 ( 1977), JP-A-6-184170, US Pat. No. 4,256,828, US Pat. No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117, JP-A-2001-139539. issue, Open No. 2000-510516, disclosed in such as JP-2000-119306.

  Selenium ions include triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium, tri-1 -Triaryl selenium such as naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyldiphenyl selenium, 4- (p-tolylthio) phenyldi-p-tolyl selenium; diphenylphena Diaryl selenium such as silselenium, diphenylbenzyl selenium, diphenylmethyl selenium; phenylmethyl benzyl selenium, 4-hydroxyphenylmethyl benzyl selenium, phenyl selenium Monoaryl selenium such as ruphenacyl selenium, 4-hydroxyphenylmethyl phenacyl selenium, 4-methoxyphenyl methyl phenacyl selenium; dimethyl phenacyl selenium, phenacyl tetrahydroselenophenium, dimethylbenzyl selenium, benzyl tetrahydroselenophenium, octadecyl Examples thereof include trialkyl selenium such as methylphenacyl selenium, and these are described in JP-A-50-151997, JP-A-50-151976, JP-A-53-22597, and the like.

  Examples of ammonium ions include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, trimethyl- tetraalkylammonium such as t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium, methyltriisopropylammonium; N, N-dimethylpyrrolidinium, N-ethyl Pyrrolidinium such as N-methylpyrrolidinium, N, N-diethylpyrrolidinium; N, N′-dimethylimidazolinium, N, N′-diethylimidazolinium, N-ethyl-N′-methylimidazolinium 1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4-methylimidazolinium, , 2,3,4-tetramethylimidazolinium and the like; N, N′-dimethyltetrahydropyrimidinium, N, N′-diethyltetrahydropyrimidinium, N-ethyl-N′-methyltetrahydropyrim Tetrahydropyrimidinium such as midinium, 1,2,3-trimethyltetrahydropyrimidinium; N, N′-dimethyl Morpholinium such as morpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium; N, N-dimethylpiperidinium, N-ethyl-N′-methylpiperidinium, N, N ′ -Piperidinium such as diethylpiperidinium; N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, N-isopropylpyridinium, Nn-butylpyridinium, N-benzylpyridinium, N-phenacylpyridinium, etc. N, N'-dimethylimidazolium, N-ethyl-N-methylimidazolium, N, N'-diethylimidazolium, 1,2-diethyl-3-methylimidazolium, 1,3-diethyl-2 -Methylimidazolium, 1-methyl-3-n-propyl-2,4- Imidazoliums such as methylimidazolium; N-methylquinolium, N-ethylquinolium, Nn-propylquinolium, N-isopropylquinolium, Nn-butylquinolium, N-benzylquinolium, N- Quinolium such as phenacylquinolium; N-methylisoquinolium, N-ethylisoquinolium, Nn-propylisoquinolium, N-isopropylisoquinolium, Nn-butylisoquinolium, N-benzyl Isoquinolium such as isoquinolium and N-phenacylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridium such as benzylacridium and phenacylacridium.

  These include US Pat. No. 4069055, Japanese Patent No. 2519480, Japanese Patent Laid-Open No. 5-222112, Japanese Patent Laid-Open No. 5-222111, Japanese Patent Laid-Open No. 5-262613, Japanese Patent Laid-Open No. 5-255256, Japanese Patent Laid-Open No. 7-109303, Kaihei 10-101718, JP-A-2-268173, JP-A-9-328507, JP-A-5-132461, JP-A-9-221652, JP-A-7-43854, JP-A-7-43901, JP-A-7-43901 No. 5-26213, JP-A-4-327574, JP-A-2-43202, JP-A-60-203628, JP-A-57-209931, JP-A-9-221652, and the like.

  Examples of the phosphonium ion include tetraarylphosphonium such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, tetrakis (4-methoxyphenyl) phosphonium; Triarylphosphonium such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium; triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, Tetraalkyl such as tributylphenacylphosphonium Suhoniumu and the like. These are described in JP-A-6-157624, JP-A-5-105692, JP-A-7-82283, JP-A-9-202873, and the like.

  Examples of the oxonium ion include trimethyloxonium, triethyloxonium, tripropyloxonium, tributyloxonium, trihexyloxonium, triphenyloxonium, pyririnium, chromenilium, and xanthylium.

  Examples of bismuthonium ions are described in JP-A-2008-214330.

  Examples of tropylium ions include J.I. Polym. Sci. Part A; Polym. Chem. 42, 2166 (2004).

(Charge transporting compound)
In the present invention, the “charge transporting compound” refers to a compound having a charge transporting unit. Here, the “charge transporting unit” in the present invention is an atomic group having the ability to transport holes or electrons, and the details thereof will be described below.

  The charge transporting unit is not particularly limited as long as it has an ability to transport holes or electrons, and is preferably an amine having an aromatic ring, carbazole, or thiophene. ) To (58).

(-R ¹ wherein each E is ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8 or the general formula (59) - (61) (wherein, R ^{1 to} R ¹¹ represent 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, and a and b and c are 1 The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and may have a substituent, and the heteroaryl group has a heteroatom. An atomic group obtained by removing one hydrogen atom from an aromatic compound, which may have a substituent.), Or any of the groups represented by the substituent group (A) to the substituent group (N) Ar represents each independently an aryl having 2 to 30 carbon atoms. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon and may have a substituent, such as phenylene, biphenyl-diyl, terphenyl -Diyl, naphthalene-diyl, anthracene-diyl, tetracene-diyl, fluorene-diyl, phenanthrene-diyl, etc. A heteroaryl group is an atomic group obtained by removing two hydrogen atoms from an aromatic compound having a heteroatom. And may have a substituent, for example, pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl, Oxazole-diyl, oxadiazole-diyl, thiadi Zol-diyl, triazole-diyl, benzoxazole-diyl, benzooxadiazole-diyl, benzothiadiazole-diyl, benzotriazole-diyl, benzothiophene-diyl, etc. X and Z are each independently a divalent linkage. The group is not particularly limited, but is preferably a group obtained by removing one hydrogen atom from a group having one or more hydrogen atoms in the R or a group exemplified by the linking group group (A) described below, where x is Represents an integer of 0 to 2. Y is the trivalent linking group, and represents a group obtained by removing two hydrogen atoms from a group having two or more hydrogen atoms in R.

Substituent group (A)

Substituent group (B)

Substituent group (C)

Substituent group (D)

Substituent group (E)

Substituent group (F)

Substituent group (G)

Substituent group (H)

Substituent group (I)

Substituent group (J)

Substituent group (K)

Substituent group (L)

Substituent group (M)

Substituent group (N)

Linking group (A)

  In addition, the charge transporting compound in the present invention may be a commercially available one, or one synthesized by a method known to those skilled in the art, and is not particularly limited.

  In addition, the ionic compound in the present invention is preferably a metal salt or an onium salt from the viewpoint of improving charge transportability.

Here, the metal salt in the present invention refers to a compound comprising a cation of sodium ion, potassium ion, rubidium ion, cesium ion, francium ion and a counter anion, for example. Examples of anions include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ^−. , Sulfonate ions such as CF ₃ SO ₃ ^— , sulfate ions such as HSO ₄ ⁻ , SO ₄ ²⁻ ; carbonate ions such as HCO ₃ ⁻ , CO ₃ ²⁻ ; H ₂ PO ₄ ⁻ , HPO ₄ ^{2. -,} phosphate ion such as _{^{PO 4 3-; PF 6 -,}} PF 5 OH - fluorophosphate ions such _{^{as; BF 4 -, B (C}} 6 F 5) 4-, B (C 6 H 4 CF ₃₎ ^4-boric acid ion such _{^{as; AlCl 4 -; BiF 6 -}} ; SbF 6 -, SbF 5 OH - fluoro antimonate ion such _{^{as; AsF 6 -, AsF 5 OH}} - fluoroarsenate periodate ions, such as And the like.

The onium salt refers to a compound composed of a cation such as a sulfonium ion, an iodonium ion, a selenium ion, an ammonium ion, a phosphonium ion, an oxonium ion, a bismuthonium ion, and a counter anion. Examples of anions include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ^−. , CF ₃ SO ₃ ^- sulfonate ion such as; HSO ₄ ^-, SO ₄ ^2- sulfate ions such as; HCO ₃ ^-, carbonate ions such as _{^{CO 3 2-; H 2 PO 4}} -, HPO 4 2 ^-, phosphate ion such as _{^{PO 4 3-; PF 6 -,}} PF 5 OH - fluorophosphate ions such ^{_{as; BF 4 -, B (C}} 6 F 5) 4 -, B (C 6 H 4 CF ₃ ) borate ions such as ₄ ⁻ ; AlCl ₄ ⁻ ; BiF ₆ ⁻ ; fluoroantimonate ions such as SbF ₆ ⁻ and SbF ₅ OH ⁻ ; fluoroarsenate ions such as AsF ₆ ⁻ and AsF ₅ OH ⁻ Etc.
Examples of the cation are the same as those exemplified in the above-described formulas (8b) to (10b).

In the present invention, the charge transporting compound preferably contains at least one aromatic amine, carbazole or thiophene compound for highly efficient charge transporting.
Moreover, in this invention, it is preferable that these charge transportable compounds are a polymer or an oligomer from a viewpoint of solubility and film formability, or contain a polymer or an oligomer.
When the charge transporting compound is a polymer or an oligomer, the number average molecular weight is preferably 1,000 or more and 1,000,000 or less from the viewpoint of solubility in a solvent and film formability. More preferably, it is 2,000 or more and 900,000 or less, and further preferably 3,000 or more and 800,000 or less. If it is less than 1,000, the compound is easily crystallized, resulting in poor film-forming properties. On the other hand, if it is larger than 1,000,000, the solubility in a solvent is lowered, making it difficult to produce a coating solution or a coating ink.

  Moreover, it is preferable that the said polymer or oligomer contains the repeating unit represented by the following general formula (1a)-(84a).

  It is preferable to use the above polymer or oligomer having one or more “polymerizable substituents”. Here, the “polymerizable substituent” means a substituent capable of forming a bond between two or more molecules by causing a polymerization reaction, and details thereof will be described below.

  Examples of the polymerizable substituent include a group having a carbon-carbon multiple bond (for example, vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, arene group). , Allyl group, vinyl ether group, vinylamino group, furyl group, pyrrole group, thiophene group, silole group, etc.), a group having a small ring (for example, cyclopropyl group, cyclobutyl group, epoxy group, oxetane group) , Diketene groups, episulfide groups, etc.), lactone groups, lactam groups, or groups containing siloxane derivatives. In addition to the above groups, combinations of groups capable of forming an ester bond or an amide bond can also be used. For example, a combination of an ester group and an amino group, an ester group and a hydroxyl group, or the like. As the polymerizable substituent, an oxetane group, an epoxy group, a vinyl group, a vinyl ether group, an acrylate group, and a methacrylate group are particularly preferable from the viewpoint of reactivity, and an oxetane group is most preferable. From the viewpoint of increasing the degree of freedom of the polymerizable substituent and facilitating the occurrence of a curing reaction, the polymer or oligomer main chain and the polymerizable substituent are more preferably linked by an alkyl chain having 1 to 8 carbon atoms. preferable. From the viewpoint of increasing the affinity with a hydrophilic electrode such as ITO, the alkyl chain is more preferably a hydrophilic group such as ethylene glycol or diethylene glycol. From the viewpoint of facilitating the preparation of the corresponding monomer, it has an ether bond at the terminal part of the alkyl chain, that is, the connecting part with the polymerizable substituent, or the connecting part with the polymer or oligomer main chain. Specifically, it is represented by the substituent groups (A) to (C).

  In addition, the polymer or oligomer in the present invention has a structure represented by the following structural group (X) as the above arylene group or heteroarylene group in addition to the above repeating unit in order to adjust solubility, heat resistance, and electrical characteristics. May be a copolymer having as a copolymer repeating unit. In this case, the copolymer may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. In addition, the polymer or oligomer used in the present invention may have branching in the main chain and may have three or more terminals.

Structural formula group (X)

<Polymerization initiator, thermal polymerization initiator>
In addition, the ionic compound according to the present invention can be used alone as a polymerization initiator. That is, the polymerization initiator of the present invention is an ionic compound represented by at least the following general formula (4c) among the ionic compounds represented by the general formulas (1c) to (4c) according to the present invention. It is characterized by including.

  The trigger for initiating polymerization is not particularly limited as long as it exhibits the ability to polymerize a polymerizable substituent by application of heat, light, microwave, radiation, electron beam, etc. It is preferable that the polymerization is initiated by heating, and heating is most preferable. That is, the ionic compound according to the present invention can be used as a thermal polymerization initiator, and the thermal polymerization initiator of the present invention is represented by the general formulas (1c) to (4c) according to the present invention described above. It contains at least one kind of ionic compound.

<Method for producing organic thin film>
The ionic compound according to the present invention can also be used as a polymerization initiator that imparts solvent resistance to the organic thin film by a polymerization reaction.
The method for producing an organic thin film of the present invention applies the action of this polymerization initiator to the method for producing an organic thin film. That is, the manufacturing method of the organic thin film of this invention is characterized by including the process of providing solvent resistance to an organic thin film using the polymerization initiator of the above-mentioned this invention.
In the method for producing an organic thin film of the present invention, when the solvent resistance is imparted to the organic thin film using the polymerization initiator of the present invention, the conditions for using the polymerization initiator are 0.01-50 for the charge transporting compound. After forming a thin film using a mass% polymerization initiator, heating may be performed in a vacuum, in the air, or in a nitrogen atmosphere. The heating temperature and time are not particularly limited as long as the polymerization reaction can be sufficiently advanced. However, the temperature is preferably 300 ° C. or less, more preferably 200 ° C. or less, more preferably, since various substrates can be applied. Is 150 ° C. or lower. From the viewpoint of increasing productivity, the time is preferably 2 hours or less, more preferably 1 hour or less, and even more preferably 30 minutes or less.

  The organic electronic material of the present invention preferably contains a polymerization initiator in order to utilize the difference in solubility due to the polymerization reaction.

  The polymerization initiator is not particularly limited as long as it exhibits the ability to polymerize a polymerizable substituent by application of heat, light, microwave, radiation, electron beam, and the like. Or it is preferable to start polymerization by heating.

  The ratio of the polymerization initiator in the charge transport film in the present invention is not particularly limited as long as the polymerization is sufficiently advanced, and is preferably 0.1% by mass to 50% by mass. When the amount is less than this, polymerization does not proceed efficiently, and the solubility cannot be changed sufficiently. On the other hand, when the amount is larger than this, a large amount of the polymerization initiator and / or decomposition product remains, and the effect of washing becomes low.

  Moreover, the polymerization initiator of this invention may contain the sensitizer for improving photosensitivity and / or heat sensitivity other than the said polymerization initiator.

  Further, from the viewpoint of imparting a charge transportability improving function and a polymerization initiating function, the polymerization initiator in the present invention is preferably the above ionic compound.

<Ink composition>
The ink composition of the present invention is characterized by containing the organic electronic material of the present invention described above and a solvent, and other additives such as polymerization inhibitors, stabilizers, thickeners, gelling agents, A flame retardant, an antioxidant, a reduction inhibitor, an oxidant, a reducing agent, a surface modifier, an emulsifier, an antifoaming agent, a dispersant, a surfactant, and the like may be included. Examples of the solvent include water, alcohols such as methanol, ethanol and isopropyl alcohol, alkanes such as pentane, hexane and octane, cyclic alkanes such as cyclohexane, aromatic solvents such as benzene, toluene, xylene, mesitylene, tetralin and diphenylmethane, ethylene Aliphatic ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene , 4-methoxytoluene, 2,3-dimethylanisole, aromatic ethers such as 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, others, dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like can be mentioned, but preferably aromatic solvents, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers can be used. .
In the ink composition of the present invention, the content of the organic electronic material with respect to the solvent is preferably 0.1 to 30% by mass from the viewpoint of being applicable to various coating processes.

<Organic thin film>
Furthermore, the organic electronic element of the present invention includes an organic thin film formed from the organic electronic material and / or the ink composition.
Similarly, the organic electroluminescent element (organic EL element) of the present invention includes an organic thin film formed from the organic electronic material and / or the ink composition.
Each element includes an excellent organic thin film formed using the organic electronic material of the present invention as the organic thin film, has a lower driving voltage than the conventional one, and has a long light emission lifetime.
The EL element of the present invention will be described in detail below.

<Organic EL device>
The organic electronic device of the present invention is characterized by including an organic thin film made of an organic electronic material including a charge transporting material made of a charge transporting compound and an ionic compound. The organic EL device of the present invention is not particularly limited as long as it includes a light emitting layer, a polymerized layer, an anode, a cathode, and a substrate. Other elements such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer are used. It may have a layer. Moreover, it is preferable to apply the organic thin film of this invention to a positive hole injection layer or a positive hole transport layer.
Hereinafter, each layer will be described in detail.

[Light emitting layer]
The material used for the light emitting layer may be a low molecular compound, a polymer or an oligomer, and a dendrimer or the like can also be used. Examples of low molecular weight compounds that utilize fluorescence include perylene, coumarin, rubrene, quinacrine, dye laser dyes (eg, rhodamine, DCM1, etc.), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq ₃ )), Stilbene, and derivatives thereof. Polymers or oligomers that utilize fluorescence include polyfluorene, polyphenylene, polyphenylene vinylene (PPV), polyvinyl carbazole (PVK), fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, and derivatives thereof. And a mixture can be suitably used.

  On the other hand, in recent years, phosphorescent organic EL devices have been actively developed in order to increase the efficiency of organic EL devices. In the phosphorescent organic EL element, not only singlet state energy but also triplet state energy can be used, and the internal quantum yield can be increased to 100% in principle. In a phosphorescent organic EL device, phosphorescence is extracted by doping a host material with a metal complex phosphorescent material containing a heavy metal such as platinum or iridium as a phosphorescent dopant (MABaldo et al., Nature, vol. 395). , p. 151 (1998), MABaldo et al., Applied Physics Letters, vol. 75, p. 4 (1999), MABaldo et al., Nature, vol. 403, p. 750 (2000)). .

Also in the organic EL device of the present invention, it is preferable to use a phosphorescent material for the light emitting layer from the viewpoint of high efficiency. As the phosphorescent material, a metal complex containing a central metal such as Ir or Pt can be preferably used. Specifically, as an Ir complex, for example, FIr (pic) that emits blue light [iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate], green light is emitted. Ir (ppy) ₃ [Factris (2-phenylpyridine) iridium] (see MABaldo et al., Nature, vol. 403, p. 750 (2000)) or Adachi et al. , Appl. Phys. Lett. 78no. (Btp) ₂ Ir (acac) {bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C3] iridium (acetyl-acetonate) )}, Ir (piq) ₃ [Tris (1-phenylisoquinoline) iridium] and the like.

Examples of the Pt complex include 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-forminplatinum (PtOEP) that emits red light.
The phosphorescent material can be a small molecule or a dendrite species, such as an iridium nucleus dendrimer. Moreover, these derivatives can also be used conveniently.

Further, in the case where a phosphorescent material is included in the light emitting layer, it is preferable that a host material is included in addition to the phosphorescent material.
The host material may be a low molecular compound or a high molecular compound, and a dendrimer or the like can also be used.

  Examples of the low molecular weight compound include CBP (4,4′-Bis (Carbazol-9-yl) -biphenyl), mCP (1,3-bis (9-carbazolyl) benzene), CDBP (4,4′-Bis). (Carbazol-9-yl) -2,2′-dimethylbiphenyl) and the like, for example, polyvinyl carbazole, polyphenylene, polyfluorene, etc. can be used as the polymer compound, and derivatives thereof can also be used.

The light emitting layer may be formed by a vapor deposition method or a coating method.
When forming by the apply | coating method, an organic EL element can be manufactured cheaply and it is more preferable. In order to form a light emitting layer by a coating method, a solution containing a phosphorescent material and, if necessary, a host material is used, for example, an ink jet method, a casting method, a dipping method, a relief printing, an intaglio printing, an offset printing, a flat printing, a relief printing. It can be carried out by applying on a desired substrate by a known method such as a printing method such as reverse offset printing, screen printing or gravure printing, or spin coating method.

[cathode]
The cathode material is preferably a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, and CsF.

[anode]
As the anode, a metal (for example, Au) or other material having metal conductivity, for example, an oxide (for example, ITO: indium oxide / tin oxide), a conductive polymer (for example, a polythiophene-polystyrene sulfonic acid mixture (for example, PEDOT: PSS)) can also be used.

[Electron transport layer, electron injection layer]
Examples of the electron transport layer and the electron injection layer include phenanthroline derivatives (for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)), bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives. , Thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives (2- (4-Biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)), aluminum complexes (for example, Tris (8-hydroxyquinolinato) aluminum (III) (Alq ₃ )) and the like. Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can be used.

[substrate]
As the substrate that can be used in the organic EL device of the present invention, the kind of glass, plastic and the like is not particularly limited, and is not particularly limited as long as it is transparent, but glass, quartz, light transmissive A resin film or the like is preferably used. When a resin film (flexible substrate) is used, it is possible to give flexibility to the organic EL element, which is particularly preferable.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. Examples thereof include films made of (TAC), cellulose acetate propionate (CAP) and the like.

  Moreover, 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 silicon nitride, on a resin film.

[Luminescent color]
The emission color in the organic EL device of the present invention is not particularly limited, but the white light-emitting device is preferable because it can be used for various lighting devices such as home lighting, interior lighting, clocks, and liquid crystal backlights.

  As a method of forming a white light emitting element, since it is currently difficult to show white light emission with a single material, a plurality of light emitting colors can be simultaneously emitted and mixed using a plurality of light emitting materials. White luminescence is obtained. A combination of a plurality of emission colors is not particularly limited. However, a combination of three emission maximum wavelengths of blue, green, and red, a complementary color relationship such as blue and yellow, yellow green and orange is used. The thing containing two light emission maximum wavelengths is mentioned. The emission color can be controlled by adjusting the type and amount of the phosphorescent material.

<Display element, lighting device, display device>
The display element of the present invention is characterized by including the above-described organic EL element of the present invention.
For example, a color display element can be obtained by using the organic EL element of the present invention as an element corresponding to each pixel of red, green, and blue (RGB).
Image formation includes a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged and driven in each element. The former is simple in structure but has a limit on the number of vertical pixels and is used for displaying characters. The latter is used for high-quality displays because the drive voltage is low and the current is small, and a bright high-definition image is obtained.

  The illumination device of the present invention is characterized by including the organic EL element of the present invention described above. Furthermore, the display device of the present invention is characterized by including a lighting device and a liquid crystal element as a display means. The illumination device of the present invention described above may be used as a backlight (white light source), and a display device using a liquid crystal element as a display unit, that is, a liquid crystal display device may be used. This configuration is a configuration in which only the backlight is replaced with the illumination device of the present invention in a known liquid crystal display device, and a known technique can be diverted to the liquid crystal element portion.

  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.

<Synthesis of a monomer having a polymerizable substituent>
(Monomer Synthesis Example 1)
In a round bottom flask, p-bromobenzyl alcohol (16.4 g, 0.088 mol) and 3- (6-bromohexyloxymethyl) -3-ethyloxetane (22.2 g, 0.080 mol) are dissolved in 320 mL of n-hexane. Heterobutylammonium bromide (1.29 g, 4.0 mmol) and 80 g of 45% aqueous sodium hydroxide solution were added, and the mixture was heated to reflux for 9 hours. After completion of the reaction, 200 mL of water was added to separate the organic layer and dried over anhydrous sodium sulfate. The solvent was distilled off with a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (filler: Wakogel (registered trademark) C-300HG, moving bed: n-hexane: ethyl acetate = 4: 1). Thus, a colorless oily monomer A having a polymerizable substituent was obtained (18.4 g, yield 60.2% by mass). ^{When 1} H NMR was measured, the following results were obtained.
¹ H NMR (300MHz, CDCl ₃ , dppm); 0.88 (t, 3H), 1.37 (m, 4H), 1.59 (m, 4H), 1.74 (q, 2H)
The reaction formula of the above reaction is shown below.

<Synthesis of charge transporting compound>
(Oligomer synthesis example 1)
<Synthesis of charge transporting oligomers having polymerizable substituents>
To a three-necked flask equipped with a Dimroth condenser and a three-way cock, 4, -n-butyltriphenylamine-4,4′-dibronic acid bis (pinacol) ester (18.2 mmol), 4,4′- Dibromo-4′-n-butyltriphenylamine (14.5 mmol), monomer A having a polymerizable substituent (7.3 mmol), Tris (dibenzylideneacetone) -dipalladium (0) (0.125 mmol), tri-t- Butylphosphine (0.200 mmol), 10% tetraethylammonium hydroxide solution (100 mL) and anisole (60 mL) were added, and the mixture was heated and stirred at 90 ° C. for 2 hours under a nitrogen atmosphere.

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 suction filtered and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was filtered with suction, dissolved in toluene, triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer (200 mg per 100 mg of polymer from Strem Chemicals) was added and stirred overnight. After stirring, triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer and insoluble matter were removed by filtration, and the resulting solution was added dropwise to methanol to obtain a precipitate. The charge transporting oligomer A having a polymerizable substituent was obtained by repeatedly performing the reprecipitation four times and purifying. The number average molecular weight of the obtained oligomer A was 8300 in terms of polystyrene.
The reaction formula of the above reaction is shown below.

(Oligomer synthesis example 2)
Oligomer B was synthesized in the same manner as in Oligomer Synthesis Example 1 except that monomer A having a polymerizable substituent was changed to 4-octylbromobenzene. The weight average molecular weight of the obtained oligomer B was 2700 in terms of polystyrene.

(Oligomer synthesis example 3)
4, -n-butyltriphenylamine-4,4′-dibronic acid bis (pinacol) ester (5 mmol), tris (4-bromophenyl) amine (2 mmol), polymerizable in the same manner as in oligomer synthesis example 1. Monomer A having various substituents (4 mmol), Tris (dibenzylideneacetone) -dipalladium (0) (0.125 mmol), tri-t-butylphosphine (0.200 mmol), 10% tetraethylammonium hydroxide solution (100 mL), anisole (60 mL) was added, and the mixture was heated and stirred at 90 ° C. for 2 hours under a nitrogen atmosphere. 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 suction filtered and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was filtered by suction, dissolved in toluene, triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer (200 mg for 100 mg of polymer from Strem chemicals) was added and stirred overnight. After stirring, triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer and insoluble matter were removed by filtration, and the resulting solution was added dropwise to methanol to obtain a precipitate. The re-precipitation was repeated 4 times and purified to obtain a charge transporting oligomer C having a polymerizable substituent. The number average molecular weight of the obtained oligomer C was 24,000 in terms of polystyrene.

<Preparation of electrolyte>
(Electrolytic solution 1)
20 g of bistetrafluoroimide lithium (manufactured by Aldrich) was dissolved in 50 mL of benzonitrile to prepare a bistetrafluoroimide lithium saturated solution. 100 mg of the oligomer A obtained in Synthesis Example 1 was dissolved in 20 mL of the saturated solution to obtain an electrolytic solution 1.

(Electrolyte 2)
An electrolytic solution 2 was obtained in the same manner as the electrolytic solution 1 except that benzonitrile was changed to chlorobenzene and bistetrafluoroimide lithium was changed to WPI-169 (manufactured by Wako Pure Chemical Industries, Ltd.).

(Electrolytic solution 3)
An electrolytic solution 3 was obtained in the same manner as the electrolytic solution 1 except that bistetrafluoroimide lithium was changed to cesium tetrafluoromethide (manufactured by Mitsubishi Materials Electronic Chemicals).

(Electrolyte 4)
An electrolytic solution 4 was obtained in the same manner as the electrolytic solution 3 except that the oligomer A was changed to the oligomer B.

<Constant potential oxidation>
[Example 1]
20 mL of electrolyte solution 1 was added to an electrolytic cell in which a 2 cm square Pt electrode, a bubbler (pastool pipette), and a magnetic stirrer were placed in a 30 mL glass container, and nitrogen was bubbled for 30 minutes.
Thereafter, using a potentio / galvanostat (1280Z, manufactured by solartron), cyclic voltammogram measurement was performed under the conditions of a stamping speed of 100 mV / sec and a stamping range of 0-2 V, and an oxidation peak was obtained at 1.8 V. . While the electrolytic solution 1 was bubbled with nitrogen, a voltage was applied to 1.8 V, and constant current oxidation was performed for 4 hours. After constant potential oxidation, the color of the electrolyte changed from yellow to black brown.
The electrolytic solution 1 after the constant potential oxidation was concentrated with a rotary evaporator and extracted with 100 mL of toluene. 50 mL of water was added to the extracted toluene, followed by liquid separation washing. After separating and washing four times, the organic layer was dried to dryness using a rotary evaporator. A charge transport material 1 was obtained.

[Example 2]
A charge transport material 2 was obtained in the same manner as in Example 1 except that the electrolytic solution 1 was changed to the electrolytic solution 2.

[Example 3]
A charge transport material 3 was obtained in the same manner as in Example 1 except that the electrolytic solution 1 was changed to the electrolytic solution 3.

[Example 4]
A charge transport material 4 was obtained in the same manner as in Example 1 except that the electrolytic solution 1 was changed to the electrolytic solution 4.

<Preparation of ink composition>
[Example 5]
The charge transport material 1 (4.5 mg) obtained in Example 1 was dissolved in toluene (465 μL) to prepare an ink composition containing the organic electronic material of the present invention.

[Comparative Example 1]
The oligomer A (4.5 mg) obtained in Synthesis Example 1 was dissolved in toluene (400 μL), and bistetrafluoromethanesulfonylimide lithium (0.5 mg) was added to prepare an ink composition. However, undissolved residue is generated and a uniform solution cannot be obtained, and it is not suitable as a coating ink.

  A comparison between Example 5 and Comparative Example 1 shows that the organic electronic material of the present invention has a high solubility in a solvent and can prepare a uniform solution and ink composition.

<Preparation of solvent-resistant organic thin film>
[Example 6]
Using the ink composition obtained in Example 5, spin-coating on a quartz glass plate at 3000 min ⁻¹ and heating and curing on a hot plate at 180 ° C. for 10 minutes to form an organic thin film (film thickness: 60 nm) did. When this organic thin film was rinsed with toluene in a quartz glass plate in toluene and the residual ratio (remaining film ratio) of the thin film was determined from the ratio of the absorbance of the thin film before and after rinsing, the remaining film ratio was 88%.

[Comparative Example 2]
A thin film was prepared in the same manner except that the bistetrafluoromethanesulfonylimide lithium in Comparative Example 1 was changed to diphenyliodonium hexafluorophosphate (manufactured by Aldrich), and the residual film ratio was determined to be 10%.

[Comparative Example 3]
A thin film was prepared in the same manner except that the bistetrafluoromethanesulfonylimide lithium in Comparative Example 1 was changed to triphenylsulfonium tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the residual film ratio was determined to be 8%. It was.

[Comparative Example 4]
A thin film was prepared in the same manner except that bistetrafluoromethanesulfonylimide lithium in Comparative Example 1 was changed to tropylium hexafluorophosphate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the residual film ratio was determined to be 13%.

[Comparative Example 5]
Oligomer A (4.5 mg) obtained in Synthesis Example 1 was dissolved in toluene (400 μL), and an ionic compound (BBI-103: manufactured by Midori Chemical Co., Ltd., 0.5 mg) was added. This solution was not oxidized at a constant potential and purified in the same manner as in Example 1 to obtain a charge transport material. An ink composition was prepared by dissolving 4.5 mg of this charge transport material in 400 μL of toluene. The ink composition was dropped onto a quartz glass plate, spin-coated at 3000 min-1, and cured by heating at 180 ° C. for 10 minutes on a hot plate to form an organic thin film (film thickness: 60 nm). When the organic thin film was rinsed with toluene in a quartz glass plate in toluene, and the residual ratio (remaining film ratio) of the thin film was determined from the ratio of the absorbance of the thin film before and after rinsing, the remaining film ratio was 80%.

  By comparing Example 6 and Comparative Examples 2 to 4, the organic electronic material of the present invention can exhibit solvent resistance by curing. Moreover, it turns out that the ionic compound of this invention functions as a polymerization initiator which can be hardened at low temperature. Further, it can be seen that a laminated structure of organic thin films can be produced.

<Production of Hall-only device>
[Example 7]
The ink composition obtained in Example 5 was spin-coated at 2000 min ⁻¹ on a glass substrate on which ITO was patterned to a width of 1.6 mm, and heated on a hot plate at 180 ° C. for 10 minutes. Next, the obtained glass substrate was transferred into a vacuum evaporation machine, and gold (film thickness 30 nm) was evaporated.

  After depositing gold, the substrate is moved into a dry nitrogen environment without opening to the atmosphere, and the sealing glass and ITO substrate in which 0.4 mm of counterbore is put into 0.7 mm non-alkali glass are used as a photocurable epoxy resin. Sealing was performed by bonding together to produce a hole-only element.

[Comparative Example 6]
Using the ink composition obtained in Comparative Example 5, a hole-only device was produced in the same manner as in Example 7. Subsequent experiments were performed in the atmosphere at room temperature (25 ° C.).

  FIG. 2 shows a graph of applied voltage-current density when a voltage is applied using ITO as a positive electrode and Au as a cathode of these hole-only elements. From FIG. 2, it can be seen that the hole current significantly flows in the element of Example 7 as compared with the element of Comparative Example 6.

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 (28)

A step of preparing an electrolytic solution containing an ionic compound containing any one of the compounds represented by the following general formulas (1c) to (4c), and a charge transporting compound;
Applying a voltage to the electrolytic solution to react the ionic compound with the charge transporting compound;
A method for producing an organic electronic material, comprising:

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.)   The method for producing an organic electronic material according to claim 1, wherein the ionic compound has a halogen atom.   The ionic compound may be a linear, branched or cyclic perfluoroalkyl group, perfluoroalkylsulfonyl group, perfluoroalkyloxysulfonyl group, perfluoroarylsulfonyl, which may contain a hetero atom having 1 to 20 carbon atoms. 1 selected from the group consisting of a group, a perfluoroaryloxysulfonyl group, a perfluoroacyl group, a perfluoroalkoxycarbonyl group, a perfluoroacyloxy group, a perfluoroaryloxycarbonyl group, a perfluoroalkenyl group, and a perfluoroalkynyl group It has a seed, The manufacturing method of the organic electronics material of Claim 1 or 2 characterized by the above-mentioned. 4. The method for producing an organic electronic material according to claim 1, wherein Y ^{1 to} Y ⁶ are any one of the following general formulas (4b) to (14b).

(In the formula, R represents an arbitrary organic group (these structures may further have a substituent or a hetero atom).) In the general formulas (1c) to (4c), L ⁺ is an element belonging to the first genus or the second genus of the long-period periodic table, or a cation represented by the following general formulas (15b) to (17b) It is any 1 type, The manufacturing method of the organic electronics material of any one of Claims 1-4 characterized by the above-mentioned.

^(Wherein, R 11 ^{to R 34} each independently 2 or more neighboring groups of ^.R 11 ^{to R 34} represent any organic group may be bonded to each other to form a ring. A ¹ represents an element belonging to Group 17 or Group 14 of the long-period periodic table, A ² represents an element belonging to Group 16 or Group 14 of the long-period periodic table, and A ³ represents a long-period type (Represents elements belonging to Group 15 of the periodic table.) R ^{11 to} R ³⁴ in the general formulas (15b) to (17b) are each independently an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, which may be substituted. 6. The method for producing an organic electronic material according to claim 5, wherein the organic electronic material is produced. A ¹ in the general formula (15b) is a bromine atom, iodine atom or carbon atom, A ² in the general formula (16b) is an oxygen atom, carbon atom, sulfur atom or selenium atom, and the general formula (17b a ³ is a nitrogen atom in), phosphorus atom, method for producing an organic electronic material according to claim 5 or 6, wherein the arsenic atom or an antimony atom.   The method for producing an organic electronic material according to claim 1, wherein the charge transporting compound contains at least one aromatic amine, carbazole, or thiophene compound.   The method for producing an organic electronic material according to claim 8, wherein the aromatic amine, carbazole, or thiophene compound is a polymer or an oligomer.   The number average molecular weight of the said polymer or oligomer is 1,000 or more and 100,000 or less, The manufacturing method of the organic electronics material of Claim 9 characterized by the above-mentioned.   The method for producing an organic electronic material according to claim 9 or 10, wherein the polymer or oligomer has one or more polymerizable substituents.   The method for producing an organic electronic material according to claim 11, wherein the polymerizable substituent is any one of an oxetane group, an epoxy group, a vinyl group, a vinyl ether group, an acrylate group, and a methacrylate group.   The organic electronics material manufactured by the manufacturing method of the organic electronics material of any one of Claims 1-12. A polymerization initiator comprising at least an ionic compound represented by the following general formula (4c) among the ionic compounds represented by the following general formulas (1c) to (4c).

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.) A thermal polymerization initiator comprising at least one ionic compound represented by the following general formulas (1c) to (4c).

(In the formula, Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁰ are each independently an electron-withdrawing organic substituent (with further substituents and heteroatoms in these structures). R ² and R ³ , R ^{4 to} R ⁶ , or R ^{7 to} R ¹⁰ may be bonded to each other to form a ring or a polymer.) L ⁺ represents a monovalent group. Represents a cation.)   The manufacturing method of the organic thin film characterized by including the process of providing solvent resistance to an organic thin film using the polymerization initiator of Claim 14, or the thermal polymerization initiator of Claim 15.   An ink composition comprising the organic electronic material according to claim 13 and a solvent.   An organic thin film formed using the organic electronic material according to claim 13.   An organic thin film formed using the ink composition according to claim 17.   An organic electronic device comprising the organic thin film according to claim 18 or 19.   An organic electroluminescent device comprising the organic thin film according to claim 18.   The organic electroluminescent device according to claim 21, wherein the organic thin film is a hole injection layer.   The organic electroluminescent device according to claim 21, wherein the organic thin film is a hole transport layer.   The organic electroluminescent element according to any one of claims 21 to 23, wherein the substrate is a flexible substrate.   The organic electroluminescent element according to any one of claims 21 to 23, wherein the substrate is a resin film.   The display element provided with the organic electroluminescent element of any one of Claims 21-23.   The illuminating device provided with the organic electroluminescent element of any one of Claims 21-25.   A display device comprising: the lighting device according to claim 27; and a liquid crystal element as display means.

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