JP6089389B2 - Electron-accepting compound and method for producing the same, polymerization initiator containing the compound, organic electronics material and organic thin film, organic electronics element, organic electroluminescence element, display element, lighting device, and display apparatus using the same - Google Patents

Description

  The present invention relates to an electron-accepting compound and a method for producing the same, a polymerization initiator containing the compound, an organic electronics material, an organic thin film using these, an organic electronics element, an organic electroluminescence element (hereinafter also referred to as an organic EL element). A display device, a lighting device, 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.

  Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, and an organic transistor.

  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.
Patent Document 4 discloses a composition comprising an ionic compound and a charge transporting compound as the charge transport film composition.

  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 the charge transporting compound and the electron accepting compound are mixed.

  However, these documents do not describe the electron-accepting compound of the present invention, the method for producing the electron-accepting compound, and the fact that the compound is used.

  In addition, there is no description of impurities resulting from the cationic compound and its decomposition products that would remain when a compound comprising a radical cation and a counter anion of the charge transporting compound is produced.

  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, it is an element having a two-layer structure of a water-soluble polythiophene: polystyrene sulfonic acid (PEDOT: PSS) hole injection layer and a light-emitting layer formed using an aromatic organic solvent such as toluene. 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.

Non-Patent Document 1 discloses an element having a three-layer structure using compounds having greatly different solubilities.
Patent Document 5 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 6, in order to overcome such a problem, the solubility of the compound is changed using a polymerization reaction of a siloxane compound, an oxetane group, a vinyl group, etc. 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 Literature 7, Patent Literature 8, and Patent Literature 9 disclose photoacid generators or initiators containing fluorine.
However, these documents do not describe an organic electronics material using a polymerization initiator containing the electron accepting compound of the present invention. Further, Patent Document 5 describes a compound similar to the present invention, but there is no description using the compound as a polymerization initiator.

Japanese Patent No. 3748491 Japanese Patent Laid-Open No. 11-251067 Japanese Patent No. 4023204 JP 2006-233162 A JP 2007-1119763 A International Publication No. 2008/010487 JP 2003-215791 A JP 2009-242391 A Japanese Patent No. 3985020

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 improve the charge transporting property of the charge transporting compound by adding an electron accepting compound to the charge transporting compound in order to reduce the driving voltage of the organic EL device, but the characteristics are still sufficient. It was not something.

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. Polymerization initiator, electron-accepting compound, organic electronics material and production method thereof, ink composition containing the organic electronics material, organic electronics material, and organic thin film formed from the ink composition The purpose is to provide.
Furthermore, an object of the present invention is to provide an organic thin film that is more excellent in charge transport than conventional ones, an organic electronics element and an organic EL element using the thin film, a lighting device, and a display element.

As a result of intensive studies, the inventors have made a production method including a step of mixing a charge transporting compound and an oxidizing agent in the presence of a predetermined anion, or a charge transporting compound and a) a predetermined silver salt, or b) It has been found that a method for producing an electron-accepting compound including a step of mixing silver nitrate and a predetermined anion is useful for easily producing a high-purity electron-accepting compound. Obtained electron-accepting compound, polymerization initiator containing the electron-accepting compound, and organic electronic material, ink composition containing the organic electronic material, and organic organic material or organic material formed using the ink composition The present inventors have found that the thin film has excellent charge transport properties that are important for improving the characteristics of the organic EL device, and have completed the present invention.
That is, the present invention is characterized by the following items (1) to (23).

(1) An electron-accepting compound comprising a cation and / or cation radical of a first charge transporting compound and at least one of anions represented by the following general formulas (1b) to (5b) .

(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)

(2) The electron-accepting compound as described in (1) above, wherein the first charge transporting compound is an aromatic amine, carbazole, or thiophene compound.

(3) The electron-accepting compound according to (1), wherein the first charge transporting compound is a polymer containing a repeating unit of an aromatic amine, carbazole, or thiophene compound.

(4) Production of an electron-accepting compound comprising a step of mixing a first charge transporting compound and an oxidizing agent in the presence of anions represented by the following general formulas (1b) to (5b) Method.

(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)

(5) A method for producing an electron-accepting compound, comprising a step of mixing the first charge transporting compound and at least one silver salt represented by the following general formula.

(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)

(6) A method for producing an electron-accepting compound, comprising a step of mixing a first charge transporting compound, silver nitrate, and at least one compound represented by the following general formula.

(In the formula, L represents a hydrogen atom or an element belonging to Group 1 or Group 2 of the long-period periodic table. Y ¹ to Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are , Each independently has an electron-withdrawing organic substituent (these structures may further have a substituent or a hetero atom, and R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer.) E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, E ⁵ represents a phosphorus atom or an antimony atom.)

(7) An electron-accepting compound produced by the production method according to any one of (4) to (6).

(8) A polymerization initiator comprising at least one of the electron-accepting compounds according to any one of (1) to (3) or (7).

(9) An organic electronic material comprising at least one of the electron-accepting compounds according to any one of (1) to (3) or (7).

(10) The organic electronic material as described in (9) above, further comprising at least one second charge transporting compound.

(11) The organic electronic material as described in (10) above, wherein the second charge transporting compound is an oligomer or a polymer.

(12) The organic electronic material as described in (10) or (11) above, wherein the second charge transporting compound has one or more polymerizable substituents.

(13) An organic thin film comprising the polymerization initiator according to (8) and / or at least one organic electronic material according to any of (9) to (12).

(14) An ink composition comprising the organic electronic material according to any one of (9) to (12) and a solvent.

(15) An organic electronic device comprising at least one organic thin film according to (13).

(16) An organic electroluminescent device comprising at least one organic thin film according to (13).

(17) The organic electroluminescent element as described in (16) above, wherein at least one of the organic thin films is a hole injection layer.

(18) The organic electroluminescent device as described in (16) or (17) above, wherein at least one of the organic thin films is a hole transport layer.

(19) The organic electroluminescent element according to any one of (16) to (18), wherein the substrate is a flexible substrate.

(20) The organic electroluminescent element according to any one of (16) to (19), wherein the substrate is a resin film.

(21) A display device comprising the organic electroluminescent device according to any one of (16) to (20).

(22) An illumination device comprising the organic electroluminescent element according to any one of (16) to (20).

(23) A display device comprising the illumination device according to (22) and a liquid crystal element as display means.

According to the present invention, an electron-accepting compound for improving charge transportability can be produced with high purity by a simple method. The electron-accepting compound can also be used as a highly active polymerization initiator. By using the polymerization initiator, a thin film can be formed stably and easily, and the organic thin film layer can be easily multi-layered. it can. Therefore, it is possible to provide an organic electronics material and an ink composition that are extremely useful for improving the productivity of organic electronics elements, particularly polymer type organic EL elements.
Furthermore, since the organic thin film formed of the organic electronic material and the ink composition does not contain impurities that hinder charge transportability, the organic thin film is excellent in charge transportability, and has high efficiency and long life. An EL element can be provided.

It is a schematic diagram which shows an example of the multilayered organic EL element. 2 is a graph showing an absorption spectrum of a toluene solution of N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine and an electron-accepting compound 5. FIG. It is a figure which shows the absorption spectrum in 0.003 mass% toluene of the polymer 1, the electron-accepting compound 8, and the electron-accepting compound 9. FIG.

<Method for producing electron-accepting compound>
According to the first aspect of the method for producing an electron-accepting compound of the present invention, the step of mixing the first charge transporting compound and the oxidizing agent in the presence of the anions of the general formulas (1b) to (5b). It is characterized by including.

(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)

The oxidizing agent is not particularly limited as long as it is a compound that can oxidize the first charge transporting compound. As a method of oxidizing the charge transporting compound using the oxidizing agent, a method of oxidizing the charge transporting compound with Cu ²⁺ (for example, JP-B-59-40825, JP-A-63-51462), Fe A method of oxidizing with ³⁺ (for example, JP-A No. 2-311447 and JP-A No. 11-315054), a method utilizing an oxidation reaction with a solid catalyst (for example, JP-A No. 5-98243), peroxodisulfate (Eg, JP 2003-55643 A), oxidation with silver hexafluoroantimonate (eg, Journal of Dispersion Science and Technology, Vol. 23, 555 (2002)) and An oxidation method using hypervalent iodine or the like can be given.

  In the first aspect, the cation and / or cation radical of the charge transport compound generated by oxidation of the first charge transport compound, and at least one of the anions of the general formulas (1b) to (5b) An electron accepting compound is obtained. In this embodiment, a wide range of charge transporting compounds can be used by selecting an appropriate oxidizing agent.

  According to the second aspect, the method for producing an electron-accepting compound of the present invention includes a step of mixing the first charge transporting compound and one of the silver salts represented by the following general formula. It is characterized by.

(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)

  According to the third aspect of the method for producing an electron-accepting compound of the present invention, the first charge transporting compound, silver nitrate, and one of the compounds represented by the following general formula are mixed. Including a process.

(In the formula, L represents a hydrogen atom or an element belonging to Group 1 or Group 2 of the long-period periodic table. Y ¹ to Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are , Each independently has an electron-withdrawing organic substituent (these structures may further have a substituent or a hetero atom, and R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer.) E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, E ⁵ represents a phosphorus atom or an antimony atom.)

  L represents a hydrogen atom or an element belonging to Group 1 or Group 2 of the long-period periodic table, among which sodium, potassium, calcium, and cesium are preferable.

In any embodiment of the electron-accepting compound of the present invention, examples of electron-withdrawing organic substituents in the general formula (R ^{1 to} R ¹⁶ in the above formula) include a fluorine atom, a chlorine atom, and a bromine atom. The halogen atom such as cyano group, thiocyano group, alkylsulfonyl group such as nitro group and mesyl group, arylsulfonyl group such as tosyl group, formyl group, acetyl group and benzoyl group usually has 1 to 12 carbon atoms, preferably The carbon number of 6 or less acyl group, methoxycarbonyl group, ethoxycarbonyl group and the like is usually 2 or more and 10 or less, preferably 7 or less, such as alkoxycarbonyl group, phenoxycarbonyl group and pyridyloxycarbonyl group, usually 3 or more. Preferably aryloxycarbo having 4 or more and 25 or less, preferably 15 or less aromatic hydrocarbon group or aromatic heterocyclic group The number of carbon atoms of the acyloxy group, alkyloxysulfonyl group, aryloxysulfonyl group, trifluoromethyl group, pentafluoroethyl group, etc. usually having 2 or more and 20 or less carbon atoms such as nyl group or acetoxy group is usually 1 or more and 10 or less, preferably Is a carbon number such as a haloalkyl, haloalkenyl, haloalkynyl group, pentafluorophenyl group or the like in which a halogen atom such as a fluorine atom or a chlorine atom is substituted on a linear, branched or cyclic alkyl, alkenyl or alkynyl group of 6 or less Is usually 6 to 20 haloaryl groups. Among these, from the viewpoint of efficiently delocalizing negative charges, more preferably, a group in which some or all of the hydrogen atoms of the group having a hydrogen atom in the organic group are substituted with a halogen atom such as fluorine, For example, a linear, branched or cyclic perfluoroalkyl group, perfluoroalkylsulfonyl group, perfluoroaryl group, perfluoroalkyloxysulfonyl group, perfluoroarylsulfonyl, which may contain a heteroatom having 1 to 20 carbon atoms Group, perfluoroaryloxysulfonyl group, perfluoroacyl group, perfluoroalkoxycarbonyl group, perfluoroacyloxy group, perfluoroaryloxycarbonyl group, perfluoroalkenyl group, perfluoroalkynyl group, and the following structural formula group (1 ), But limited to this Not intended to be. Among these, a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms, a cyclic perfluoroalkyl group having 3 to 6 carbon atoms, and a perfluoroaryl group having 6 to 18 carbon atoms are preferable.

Structural formula group (1)

Further, the ^Y 1 to Y ⁶ in the general formula is a divalent linking group is preferably any one of the following general formula (1c) ~ (11c).

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

  R in the general formulas (7c) to (11c) 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.

[Silver salt]
As the silver salt in the second embodiment of the production method of the present invention, the silver salt represented by the above general formula is used from the viewpoint of easy availability and easy production of the electron-accepting compound.

  These silver salts may be commercially available products, or silver nitrate and an inorganic salt having a counter anion in the silver salt represented by the above general formula are reacted in water, or silver oxide and the above general salt. It can be easily obtained by a known method in which an acid having a counter anion in a silver salt represented by the formula is reacted in an organic solvent such as methanol.

[Compound represented by the general formula]
The compound represented by the general formula in the third aspect of the production method of the present invention is a salt represented by the following general formula from the viewpoint of easy availability and easy production of an electron-accepting compound. preferable.

(In the formula, L represents a hydrogen atom or an element belonging to Group 1 or Group 2 of the long-period periodic table. Y ¹ to Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are , Each independently has an electron-withdrawing organic substituent (these structures may further have a substituent or a hetero atom, and R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer.) E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, E ⁵ represents a phosphorus atom or an antimony atom.)

[First charge transporting compound]
Next, the “first charge transporting compound” in the present invention will be described in detail. In the present invention, the first charge transporting compound may be a commercially available one, or one synthesized by a method known to those skilled in the art, and is not particularly limited. Moreover, it is sufficient to include an atomic group having a hole or electron transport capability, and is not particularly limited, but is preferably an amine having an aromatic ring (aromatic amine), carbazole, or thiophene compound. It is preferable to have a partial structure represented by the general formulas (1) to (58).

^(-R 1 wherein each E is ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8, a halogen atom, 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; a and b and c represents an integer greater than or equal to 1. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, which may have a substituent. An atomic group obtained by removing one hydrogen atom from an aromatic compound having a hetero atom, which may have a substituent.), Or represented by the following substituent group (A) to substituent group (N) Each represents a group represented by Ar. Represents an arylene group having 2 to 30 carbon atoms, or a heteroarylene group, which is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and may have a substituent. Examples include phenylene, biphenyl-diyl, terphenyl-diyl, naphthalene-diyl, anthracene-diyl, tetracene-diyl, fluorene-diyl, phenanthrene-diyl, etc. A heteroarylene group is a hydrogen atom from an aromatic compound having a heteroatom. An atomic group excluding two atoms and optionally having a substituent, such as pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, Pyrrole-diyl, thiophene-diyl, oxazole-diyl, o Sadiazole-diyl, thiadiazole-diyl, triazole-diyl, benzoxazole-diyl, benzooxadiazole-diyl, benzothiadiazole-diyl, benzotriazole-diyl, benzothiophene-diyl, etc. X and Z are each independently. There are no particular restrictions on the divalent linking group, but a group in which one hydrogen atom is further removed from a group having one or more hydrogen atoms in the R or a group exemplified by the linking group group (A) described later X is an integer of 0 to 2. Y is the trivalent linking group, and the R is a group obtained by removing two hydrogen atoms from a group having two or more hydrogen atoms.

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 the first aspect of the method for producing an electron-accepting compound of the present invention, in the presence of an anion represented by the general formulas (1b) to (5b), the first charge transporting compound and an oxidizing agent are used. An electron-accepting compound is obtained by a production method including a step of mixing. In the second aspect and the third aspect, the first charge transporting compound, a) a silver salt represented by the general formula, or b) silver nitrate and a compound represented by the general formula, An electron-accepting compound can be obtained by a production method including a step of mixing. In order to make mixing uniform, in the first embodiment, the anion, the first charge transporting compound, and the oxidizing agent are used. In the second and third embodiments, the first charge transporting compound is used. And a) a silver salt represented by the above general formula, or b) a silver nitrate and a compound represented by the above general formula are preferably dissolved in a solvent and mixed.

  The solvent is not particularly limited as long as each component is dissolved, but water, alcohols such as methanol, ethanol and isopropyl alcohol, alkanes such as pentane, hexane and octane, cyclic alkanes such as cyclohexane, benzene, toluene and xylene , Aromatic solvents such as mesitylene, tetralin and diphenylmethane, aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol-1-monomethyl ether acetate, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, Anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, aromatic ethers such as 2,4-dimethylanisole, ethyl acetate, n-acetate Aliphatic esters such as butyl, ethyl lactate, n-butyl lactate, phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate, N, N-dimethyl Examples include amide solvents such as formamide and N, N-dimethylacetamide, halogen solvents such as chloroform, methylene chloride, chlorobenzene, and o-dichlorobenzene, dimethyl sulfoxide, tetrahydrofuran, and acetone. You may use these in mixture of 2 or more types.

  It can also be mixed in two phases, an organic phase and an aqueous phase. The target electron-accepting compound can be easily obtained by dissolving the first charge transporting compound in the organic phase and dissolving and mixing silver nitrate and the compound represented by the general formula.

  After mixing, acid separation, alkali washing, neutralization, water washing, hot water washing, organic solvent washing, reprecipitation, centrifugation, extraction, column chromatography, dialysis and other conventional separation operations, purification operations, drying, metal It is preferable to remove the heavy metal by the scavenger and to perform purification by other operations in order to increase the efficiency and extend the life of the organic electronics element and the organic EL element.

In the first aspect of the production method of the present invention, when the first charge transporting compound and the oxidizing agent are mixed in the presence of the anion represented by the general formulas (1b) to (5b), It is preferable to mix the anion in an amount of 0.01 to 1000 mol% and an oxidant in an amount of 0.01 to 1000 mol% with respect to the charge transporting compound. It is -200 mol%, Most preferably, it is 0.1-150 mol%.
In the second embodiment of the production method of the present invention, when the first charge transporting compound and the silver salt represented by the general formula are mixed, the first charge transporting compound is represented by the general formula. It is preferable to mix 0.01 to 1000 mol% of the silver salt, more preferably 0.1 to 200 mol%, most preferably 0.1 to 150 mol%.
On the other hand, in the third aspect of the production method of the present invention, when the first charge transporting compound, silver nitrate, and the compound represented by the general formula are mixed, It is preferable to mix silver nitrate and the compound represented by the general formula at 0.01 to 1000 mol%, more preferably 0.1 to 200 mol%, most preferably 0.1 to 150 mol%. If the amount is 0.01 mol% or less, the reaction hardly proceeds, and if it is 1000 mol% or more, the side reaction tends to proceed.
On the other hand, from the charge transporting compound and the ionic compound obtained by adjusting the amount of silver salt used in the second aspect, and the amount of silver nitrate and the compound represented by the above general formula in the third aspect. It is possible to adjust the degree of doping of the charge transport material.
When the first charge transporting compound is an oligomer or polymer containing a charge transporting repeating unit, use of a compound represented by the general formula: silver salt or silver nitrate, based on the number of moles of the repeating unit of the first charge transporting compound If the amount is reduced, the doping can be reduced below 100%.

  In any embodiment of the production method of the present invention, the first charge transporting compound may partially remain unreacted. When the first charge transporting compound is a high molecular weight compound, only a part of the repeating units may have the electron accepting compound structure of the present invention. In addition, the first charge transporting compound may have two or more electrons oxidized or a mixture with a one-electron oxide.

  The reaction temperature is -30 to 250 ° C, preferably -10 to 250 ° C, more preferably 10 to 200 ° C. If the temperature is too low, the reaction does not proceed easily. If the temperature is too high, the yield decreases due to decomposition of the charge transporting compound.

  In the second and third aspects of the method for producing an electron-accepting compound of the present invention described above, it is only possible to produce an electron-accepting compound having an electron-accepting property necessary for improving charge transportability. Since Ag precipitates and can be easily removed by filtration, impurities that hinder charge transport are reduced, which is preferable.

<Electron-accepting compound>
The electron-accepting compound of the present invention is an electron-accepting compound that can be produced by the above-described method for producing an electron-accepting compound of the present invention. The cation and / or cation radical of the first charge-transporting compound, It consists of at least 1 type of the anion represented by General formula (1b)-(5b), It is characterized by the above-mentioned.

(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)

  The electron-accepting compound of the present invention is preferable because it not only has the electron-accepting property necessary for improving the charge transporting property, but also reduces impurities that hinder charge transporting.

  In the general formulas (1b) to (5b), the electron-withdrawing organic substituent and the divalent linking group are any one of the structural formula groups (1) and (1c) to (11c). It is preferable.

The cation radical may be composed of a low molecule having no repeating unit or may be composed of a polymer having a repeating unit, and is not particularly limited, but is represented by the general formulas (1) to (58). A structure in which one electron is removed from the structure of a low molecular weight aromatic amine, carbazole, thiophene compound, or a polymer aromatic amine, carbazole, or thiophene compound represented by the following general formulas (1a) to (84a): It is done. In addition, the number of cation radicals contained in one molecule of the electron-accepting compound, that is, aminium, carbazolium, thiophenium, etc. may be one or plural.
In addition, the cation includes a divalent cation structure in which one electron is further removed from the cation radical.

[Anion]
Next, the [anion] in the present invention will be described in detail below.
The anion according to the present invention is preferably an anion represented by the general formulas (1b) to (5b) from the viewpoint of availability and easy production of an electron-accepting compound.
Here, the general formula (1b) in ^{~ (5b) Y 1 ~Y 6} , R 1 ~R 16 is, ^Y 1 in the general formula in the silver salt represented by the general formula described above to Y ⁶ , R ^{1 to} R ¹⁶ , and specific examples and preferred examples are also the same.

  In addition, the anion in the present invention preferably has a negative charge mainly on an oxygen atom, nitrogen atom, carbon atom, boron atom or gallium atom, and is not particularly limited, but more preferably an oxygen atom, nitrogen atom, carbon atom, boron Most preferred are those represented by the following general formulas (12c), (13c), (14c), and (15c).

(In the formula, R _{F1 to} R _F10 are each independently an electron-withdrawing organic substituent (there may further have a substituent or a hetero atom in these structures, and R _{F1 to} R _F9 are bonded to each other). It may be cyclic or polymeric, and is not particularly limited, and examples thereof include groups represented by the structural formula group (1).)

<Polymerization initiator>
The polymerization initiator of the present invention is characterized by containing at least one electron-accepting compound of the present invention. In particular, the polymerization initiator of the present invention is effective not only in its function as a polymerization initiator but also in charge transport performance when used in an organic electronic material as described below.
The polymerization initiator of the present invention does not contain a cation that hinders the charge transport property, and has a high polymerization initiating activity. From the viewpoint of having a high polymerization initiating activity, an aminium cation radical, a carbazolium cation radical, or a thiophenium cation radical, It is particularly preferable to include an electron-accepting compound composed of any one of the counter anions represented by (1b) to (5b).

<Organic electronics materials>
The organic electronic material of the present invention is characterized by containing at least one electron-accepting compound of the present invention. The electron-accepting compound of the present invention functions as a polymerization initiator, and the polymerization-initiating ability is preferable in that a compound having a known polymerizable functional group can be polymerized. Also, by the function as an electron-accepting compound, This is preferable in that an ionic compound composed of a cation radical and a counter anion of the charge transporting compound can be generated to improve the charge transportability.

  The organic electronic material of the present invention preferably contains a charge transporting compound (second charge transporting compound) in addition to the electron accepting compound in order to generate an ionic compound having excellent charge transporting property. The second charge transporting compound here is not particularly limited, and examples thereof include compounds represented by the general formulas (1) to (58).

  Furthermore, from the viewpoints of solubility in a solvent and film formability, the second charge transporting compound is preferably a polymer or an oligomer.

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

  Further, when the second charge transporting compound is a polymer or 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.

  The second charge transporting compound preferably has one or more “polymerizable substituents” in order to change the solubility. Here, the “polymerizable substituent” means a substituent capable of forming a bond between two or more molecules by causing a polymerization reaction, and the 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, it is more preferable that the polymerizable substituent in the charge transporting compound is connected by an alkyl chain having 1 to 8 carbon atoms. 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. Further, from the viewpoint of facilitating the preparation of the corresponding compound, it may have an ether bond at the terminal part of the alkyl chain, that is, the connecting part with the polymerizable substituent and the connecting part with the charge transporting compound. More specifically, it is specifically represented by the substituent groups (A) to (C).

  Further, the polymer or oligomer in the present invention is represented by the following structural formula group (O) as the above arylene group and heteroarylene group in addition to the above repeating unit for the purpose of adjusting the solubility, heat resistance, and electrical characteristics. It may be a copolymer having a structure 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 (O)

  In the electron-accepting compound as a polymerization initiator according to the present invention, the trigger for initiating polymerization expresses the ability to polymerize a polymerizable substituent such as application of heat, light, microwave, radiation, electron beam, etc. There is no particular limitation as long as it is a material, but light irradiation and / or heating are preferable, and heating is most preferable from the viewpoint of easily performing the polymerization initiation step. That is, the electron-accepting compound of the present invention can be used as a thermal polymerization initiator.

  In the present invention, the conditions for using the electron-accepting compound as a polymerization initiator are such that a thin film is formed by using 0.1 to 50% by mass of a polymerization initiator based on the mass of the charge transporting compound having a polymerizable substituent. After that, 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.

  Further, the organic electronic material of the present invention may contain a sensitizer for improving photosensitivity and / or heat sensitivity in addition to the electron accepting compound.

<Organic thin film>
The organic thin film of the present invention is characterized by containing at least one of the above-described polymerization initiator of the present invention and / or the above-described organic electronic material of the present invention.
The organic thin film of the present invention can be cured at low temperature due to the excellent polymerization initiating ability of the polymerization initiator of the present invention, and can produce a laminated structure of the organic thin film, and the excellent electron transport property of the organic electronic material of the present invention Therefore, when applied to an organic EL element, the drive voltage can be lowered and the current density can be improved.

<Ink composition>
The ink composition of the present invention is characterized by including the organic electronic material of the present invention described above and a solvent. The ink composition of the present invention is useful for forming the above-described organic thin film of the present invention. For example, the organic thin film can be obtained by applying the ink composition to a substrate.
In addition to the above components, the ink composition of the present invention includes other additives such as polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reducing agents, oxidizing agents, reducing agents. , Surface modifiers, emulsifiers, antifoaming agents, dispersants, surfactants 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 relative to the solvent is preferably 0.1 to 30% by mass from the viewpoint of being applicable to various coating processes.

<Organic electronics devices, organic electroluminescence devices>
The organic electronic device of the present invention is characterized by including at least one organic thin film of the present invention described above.
Similarly, the organic electroluminescent element (organic EL element) of the present invention is characterized by including at least one organic thin film of the present invention described above.
Each element includes the organic thin film of the present invention as an organic thin film, and the organic thin film can be easily multilayered, and has excellent charge transport properties, and is a highly efficient and long-life element.
The EL element of the present invention will be described in detail below.

[Organic EL device]
The organic electronics element of the present invention is characterized by including an organic thin film made of an organic electronics material containing an electron-accepting 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. Low molecular weight compounds that utilize fluorescence include perylene, coumarin, rubrene, quinacridone, dye laser dyes (eg, rhodamine, DCM1, etc.), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq3) ), Stilbene, and derivatives thereof. Examples of 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, examples of the Ir complex include FIr (pic) that emits blue light [Iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C2] picolinate], Ir that emits green light. (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) 2Ir (acac) {bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C3] iridium (acetyl-acetonate) which emits red light as shown in 11,2001, 1622 }, 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, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimides, 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) (Alq3)) 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 is used, flexibility can be imparted to the organic EL element (that is, a flexible substrate), 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 a 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 electron-accepting compound>
[Example 1]
N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine (516.7 mg) and bis (trifluoromethanesulfonyl) imide silver (388.0 mg) in dimethylformamide in a three-necked flask (30 mL). The reaction was carried out for 2 hours while heating at 100 ° C. in an oil bath under stirring. Then, it cooled to room temperature and left at room temperature for 12 hours. Insoluble matter was filtered off with a PTFE filter having a pore size of 0.2 μm, water was added to the reaction solution, and the precipitated crystals were filtered, washed with methanol, and washed with water. The crystals were dissolved in toluene (50 mL) and washed with water using a separatory funnel. The organic phase was dried to obtain electron accepting compound 1 (681 mg). The reaction formula of the above reaction is shown below.

[Example 2]
Electron-accepting compound 2 (598 mg) was prepared in the same manner as in the synthesis of electron-accepting compound 1 except that bis (trifluoromethanesulfonyl) imide silver (388.0 mg) was changed to silver trifluoromethanesulfonate (256.9 mg). Got. The reaction formula of the above reaction is shown below.

[Example 3]
Lithium tetrakis (pentafluorophenyl) borate ethyl ether complex (1.0 g) was dissolved in water (4.0 mL), and silver nitrate (1.0 g) was added and stirred. The resulting precipitate was filtered, washed with water, and dried under reduced pressure to obtain a silver salt (0.82 g) of tetrakis (pentafluorophenyl) borate.
N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine (516.7 mg) and silver salt of tetrakis (pentafluorophenyl) borate (786.9 mg) in a three-necked flask Dissolved in dimethylformamide (30 mL). The reaction was carried out for 2 hours while heating at 100 ° C. in an oil bath under stirring. Then, it cooled to room temperature and left at room temperature for 12 hours. Insoluble matter was filtered off with a PTFE filter having a pore size of 0.2 μm, water was added to the reaction solution, and the precipitated crystals were filtered, washed with methanol, and washed with water. The crystals were dissolved in toluene (50 mL) and washed with water using a separatory funnel. The organic phase was dried to obtain electron accepting compound 3 (1095 mg). The reaction formula of the above reaction is shown below.

[Example 4]
N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine (516.7 mg) was dissolved in toluene (20 mL), and silver nitrate (169.9 mg) and potassium tris (trifluoromethanesulfonyl) methide ( 450.3 mg) was dissolved in water (15 mL) and stirred in a three neck flask. After reacting for 2 hours while heating at 90 ° C. in an oil bath, the mixture was cooled to room temperature and allowed to stand at room temperature for 12 hours. The organic phase was filtered off with a PTFE filter having a pore size of 0.2 μm, and then washed with a separatory funnel. The organic phase was dried to obtain electron accepting compound 4 (885 mg). The reaction formula of the above reaction is shown below.

[Example 5]
The electron-accepting compound 5 was prepared in the same manner as the electron-accepting compound 4 except that potassium tris (trifluoromethanesulfonyl) methide (450.3 mg) was changed to sodium tetrakis (pentafluorophenyl) borate (702.0 mg). (1012 mg) was obtained. The reaction formula of the above reaction is shown below.

  FIG. 2 shows an absorption spectrum of a toluene solution of N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine and the electron accepting compound 5. The vertical axis is normalized by the maximum absorption at 300-800 nm. It can be seen that the electron-accepting compound 5 exhibited maximum absorption at 489 nm in the raw material.

[Example 6]
N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine (516.7 mg) was converted to N, N ′-(4-methoxyphenyl) -N, N′-diphenyl-1,4-phenylene. An electron-accepting compound 6 (879 mg) was obtained in the same manner as the electron-accepting compound 5 except that the diamine (472.6 mg) was used. The reaction formula of the above reaction is shown below.

[Example 7]
4,4′-bis (9H-carbazol-9-yl) biphenyl (484.6 mg) was dissolved in chlorobenzene (30 mL), and silver nitrate (169.9 mg) and sodium tetrakis (pentafluorophenyl) borate (702.0 mg) Was dissolved in water (15 mL) and stirred in a three-necked flask. The reaction was carried out for 24 hours while heating at 100 ° C. in an oil bath, then cooled to room temperature and left at room temperature for 12 hours. The organic phase was filtered off with a PTFE filter having a pore size of 0.2 μm, and then washed with a separatory funnel. The organic phase was dried to obtain electron accepting compound 7 (348 mg). The reaction formula of the above reaction is shown below.

[Example 8]
The following polymer 1 (500 mg) was dissolved in toluene (30 mL), and silver nitrate (169.9 mg) and sodium tetrakis (pentafluorophenyl) borate (702.0 mg) were dissolved in water (15 mL). Stir at room temperature for 2 hours, stop stirring and let stand at room temperature for 12 hours. The organic phase was filtered off with a PTFE filter having a pore size of 0.2 μm, and then washed with a separatory funnel. The organic phase was dried, redissolved in toluene (4 mL), and acid-precipitated with methanol (200 mL) to obtain electron accepting compound 8 (442 mg). The reaction formula of the above reaction is shown below.

[Example 9]
The following polymer 1 (500 mg) was dissolved in toluene (30 mL), and silver nitrate (34.0 mg) and sodium tetrakis (pentafluorophenyl) borate (140.4 mg) were dissolved in water (15 mL). Stir at room temperature for 2 hours, stop stirring and let stand at room temperature for 12 hours. The organic phase was filtered off with a PTFE filter having a pore size of 0.2 μm, and then washed with a separatory funnel. The organic phase was dried, redissolved in toluene (4 mL), and acid-precipitated with methanol (200 mL) to obtain electron-accepting compound 9 (302 mg). The reaction formula of the above reaction is shown below.

[Example 10]
N, N′-bis (4-methylphenyl) -N, N′-diphenylbenzidine (517 mg), ferric chloride (162 mg), cesium tris (trifluoromethanesulfonyl) methide (540 mg) in acetonitrile (20 mL) ) And stirred at 25 ° C. for 6 hours in a three-necked flask. Toluene (5 mL) was added and further stirred for 12 hours. The solvent was removed by distillation under reduced pressure, toluene (20 mL) was added to extract the target product, and the mixture was washed with water using a separatory funnel. The toluene layer was filtered off with a PTFE filter having a pore size of 0.2 μm, and then toluene was removed to obtain an electron-accepting compound 10 (320 mg). The reaction formula of the above reaction is shown below.

  FIG. 3 shows absorption spectra of polymer 1, electron-accepting compound 8, and electron-accepting compound 9 in 0.003% by mass of toluene. It can be seen that the electron-accepting compound 8 and the electron-accepting compound 9 generated absorption having a maximum at 506 nm, which is not present in the raw material polymer 1.

<Synthesis of Second Charge Transporting Compound>
[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 Example 1)
The following monomer 1 (4.0 mmol), the following monomer 2 (5.0 mmol), the following monomer 3 (2.0 mmol), and anisole (20 ml) were added to a three-necked round bottom flask, and the 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 degassing with nitrogen bubble for more than 30 minutes. This 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 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 the stirring, triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer and insoluble matter were removed by filtration, and the filtrate was concentrated by a rotary evaporator. The residue was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was filtered by suction and washed with methanol-acetone (8: 3). The resulting precipitate was vacuum-dried to obtain polymer A. The molecular weight was measured by GPC (polystyrene conversion) using THF as an eluent. The number average molecular weight of the obtained polymer 1 was 7,800, and the weight average molecular weight was 31,000.

<Preparation of ink composition>
[Example 11]
Chlorobenzene (800 μL) was added to polymer A (9.0 mg) obtained above and electron accepting compound 5 (1.0 mg) to prepare an ink composition containing the organic electronic material of the present invention. The polymer A and the electron accepting compound 5 did not remain dissolved, and a uniform solution was obtained.

<Production of charge transportability evaluation element>
[Example 12]
On a glass substrate patterned with a width of 1.6 mm of ITO, a mixed solution of polymer A (100 mg), electron-accepting compound 5 (3.0 mg), and anisole (1.91 mL) was spin-coated at 3000 min ⁻¹ and hot A charge transport film (125 nm) was produced by heating at 180 ° C. for 10 minutes on the plate. Next, the obtained glass substrate was moved into a vacuum evaporation machine, and aluminum (film thickness 100 nm) was evaporated.
After vapor deposition of aluminum, 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 laminating using, to produce a charge transporting evaluation element.

[Examples 13 to 14]
Similarly to Example 12, charge transportability evaluation elements including electron-accepting compounds 4, 6, and 8 were prepared in Examples 13 to 14, respectively.

[Comparative Example 1]
A charge transportability evaluation element was produced in the same manner except that the mixed solution containing no electron accepting compound 5 in Example 12 was used.

Table 1 below shows the applied voltage (V) at the time of 10 mA / cm ² energization when a voltage is applied using ITO as a positive electrode and aluminum as a cathode of these charge transportability evaluation elements. From Table 1, in Examples 11-14, the applied voltage at the time of 10 mA / cm < ² > energization is very low, and it turns out that an applied voltage can be reduced significantly by adding the electron-accepting compound of this invention.

<Evaluation as a polymerization initiator>
[Example 16]
Polymer A (9.0 mg), electron accepting compound 5 (1.0 mg) and chlorobenzene (800 μL) were added to prepare an ink composition. This solution was spin-coated on a quartz glass plate 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: 30 nm). When this organic thin film was rinsed with toluene in a quartz glass plate in toluene, and the remaining 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 98%.

[Comparative Example 2]
An organic thin film was formed in the same manner as in Example 16 except that the electron accepting compound 5 was not added, and the remaining film ratio was determined. The remaining film ratio was 28%.

Comparison between Example 16 and Comparative Example 2 shows that the organic electronic material of the present invention can exhibit sufficient solvent resistance upon curing.
From the above, it can be seen that a laminated structure of an organic thin film can be produced by using the organic electronic material of the present invention.

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 (23)

An electron accepting compound comprising a cation and / or cation radical of a first charge transporting compound and at least one of anions represented by the following general formulas (1b) to (5b), An electron-accepting compound selected from the group consisting of compounds A, D, E and G.
(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)
The following electron-accepting compounds A to G including a step of mixing the first charge transporting compound and an oxidizing agent in the presence of at least one of the anions represented by the following general formulas (1b) to (5b) A method for producing an electron-accepting compound selected from the group consisting of :
(Wherein, Y ¹ to Y ⁶ each independently represent a divalent linking group, R ¹ to R ¹⁶ are each independently electron-withdrawing organic substituent (a substituent in these structures, the heteroatom And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)
An electron-accepting compound selected from the group consisting of the following electron-accepting compounds A to G , comprising a step of mixing the first charge-transporting compound and at least one silver salt represented by the following general formula: Production method.
(Wherein Y ^{1 to} Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are each independently an electron-withdrawing organic substituent (in these structures, further substituents, heteroatoms And R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer. ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, and E ⁵ represents a phosphorus atom or an antimony atom.)
An electron accepting property selected from the group consisting of the following electron accepting compounds A to G , comprising a step of mixing the first charge transporting compound, silver nitrate, and at least one compound represented by the following general formula: Compound production method.
(In the formula, L represents a hydrogen atom or an element belonging to Group 1 or Group 2 of the long-period periodic table. Y ¹ to Y ⁶ are each independently a divalent linking group, and R ^{1 to} R ¹⁶ are , Each independently has an electron-withdrawing organic substituent (these structures may further have a substituent or a hetero atom, and R ² and R ³ , R ^{4 to} R ⁶ , R ^{7 to} R ^10, or R ^{11 to} R ¹⁶ may be bonded to each other to form a ring or a polymer.) E ¹ represents an oxygen atom, E ² represents a nitrogen atom, E ³ represents a carbon atom, E ⁴ represents a boron atom or a gallium atom, E ⁵ represents a phosphorus atom or an antimony atom.)
A polymerization initiator comprising at least one electron-accepting compound selected from the group consisting of the following electron-accepting compounds A to G.
An organic electronic material comprising at least one electron-accepting compound according to claim 1 . The organic electronic material according to claim 6, further comprising at least one second charge transporting compound. The organic electronic material according to claim 7, wherein the second charge transporting compound is an oligomer or a polymer. The organic electronic material according to claim 7 or 8, wherein the second charge transporting compound has one or more polymerizable substituents. An organic thin film comprising the polymerization initiator according to claim 5 and / or at least one organic electronic material according to any one of claims 6 to 9 . An ink composition comprising the organic electronic material according to any one of claims 6 to 9 and a solvent. An organic electronic device comprising at least one organic thin film according to claim 10 . An organic electroluminescent device comprising at least one organic thin film according to claim 10 . 14. The organic electroluminescent device according to claim 13, wherein at least one of the organic thin films is a hole injection layer. The organic electroluminescent device according to claim 13 or 14 , wherein at least one of the organic thin films is a hole transport layer. The organic electroluminescent element according to any one of claims 13 to 15 , wherein the substrate is a flexible substrate. The organic electroluminescent element according to any one of claims 13 to 16 , wherein the substrate is a resin film. A display element comprising the organic electroluminescent element according to claim 13 . An illuminating device comprising the organic electroluminescent element according to any one of claims 13 to 17 . 20. A display device comprising: the lighting device according to claim 19; and a liquid crystal element as display means. A method for producing an electron-accepting compound comprising a step of mixing a first charge transporting compound and an oxidizing agent in the presence of at least one anion represented by the following general formulas (1b) to (5b). The first charge transporting compound is a carbazole compound, a thiophene compound, or a polymer compound containing a repeating unit of an aromatic amine, carbazole or thiophene compound.
(Where Y ¹ ~ Y ⁶ Are each independently a divalent linking group, R ¹ ~ R ¹⁶ Are each independently an electron-withdrawing organic substituent (which may further have a substituent or a heteroatom in these structures, and R ² And R ³ , R ⁴ ~ R ⁶ , R ⁷ ~ R ¹⁰ Or R ¹¹ ~ R ¹⁶ Each may be bonded to form a ring or a polymer. ). E ¹ Is an oxygen atom, E ² Is a nitrogen atom, E ³ Is a carbon atom, E ⁴ Is boron atom or gallium atom, E ⁵ Represents a phosphorus atom or an antimony atom. ) A method for producing an electron-accepting compound comprising a step of mixing a first charge-transporting compound and at least one silver salt represented by the following general formula, wherein the first charge-transporting compound comprises: The manufacturing method which is a high molecular compound containing the repeating unit of a carbazole compound, a thiophene compound, or an aromatic amine, a carbazole, or a thiophene compound.
(Where Y ¹ ~ Y ⁶ Are each independently a divalent linking group, R ¹ ~ R ¹⁶ Are each independently an electron-withdrawing organic substituent (which may further have a substituent or a heteroatom in these structures, and R ² And R ³ , R ⁴ ~ R ⁶ , R ⁷ ~ R ¹⁰ Or R ¹¹ ~ R ¹⁶ Each may be bonded to form a ring or a polymer. ). E ¹ Is an oxygen atom, E ² Is a nitrogen atom, E ³ Is a carbon atom, E ⁴ Is boron atom or gallium atom, E ⁵ Represents a phosphorus atom or an antimony atom. ) A method for producing an electron-accepting compound, comprising a step of mixing a first charge-transporting compound, silver nitrate, and at least one compound represented by the following general formula, wherein the first charge-transporting compound comprises: Is a polymer compound containing a repeating unit of a carbazole compound, a thiophene compound, or an aromatic amine, a carbazole or a thiophene compound.
(In the formula, L represents a hydrogen atom or an element belonging to Group 1 or Group 2 of the long-period periodic table. Y ¹ ~ Y ⁶ Are each independently a divalent linking group, R ¹ ~ R ¹⁶ Are each independently an electron-withdrawing organic substituent (which may further have a substituent or a heteroatom in these structures, and R ² And R ³ , R ⁴ ~ R ⁶ , R ⁷ ~ R ¹⁰ Or R ¹¹ ~ R ¹⁶ Each may be bonded to form a ring or a polymer. ). E ¹ Is an oxygen atom, E ² Is a nitrogen atom, E ³ Is a carbon atom, E ⁴ Is boron atom or gallium atom, E ⁵ Represents a phosphorus atom or an antimony atom. )