JP5879795B2 - ORGANIC ELECTRONIC ELECTRONIC MATERIAL, INK COMPOSITION, ORGANIC THIN FILM AND PROCESS FOR PRODUCING THE SAME, ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY ELEMENT, LIGHTING DEVICE, AND DISPLAY DEVICE - Google Patents

Description

  The present invention relates to an organic electronics material, an ink composition, an organic thin film and a method for producing the same, an organic electronics element, an organic electroluminescence element (hereinafter sometimes referred to as an organic EL element), 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, 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 proposes 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 electronic material using the ionic compound in the present invention.

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 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.

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. It is an object of the present invention to provide an organic electronic material useful for making it, an ink composition containing the organic electronic material, the organic electronic material, and an organic thin film formed from the ink composition.
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 containing a predetermined ionic compound, an ink composition containing the organic electronic material, and an organic material formed using the organic electronic material or the ink composition The thin film was found to be useful for improving the efficiency and life of organic EL devices, and this research was completed.
That is, the present invention is characterized by the following items (1) to (16).

(1) An organic electronic material comprising at least one ionic compound represented by the following general formula (1b).

(In the general formula (1b), Y represents a divalent linking group containing a carbon atom or a sulfur atom, and R represents an electron withdrawing group (which may further have a substituent or a hetero atom in these structures). L ⁺ represents a monovalent cation.)

(2) The organic electronic material as described in (1) above, which contains at least one charge transporting compound.

(3) The organic electronic material as described in (2) above, wherein the charge transporting compound has at least one polymerizable substituent.

(4) The organic electronic material according to any one of (1) to (3), wherein the ionic compound functions as a polymerization initiator.

(5) An ink composition comprising the organic electronic material according to any one of (1) to (4) and a solvent.

(6) The organic thin film formed using the organic electronics material in any one of said (1)-(4).

(7) An organic thin film formed using the ink composition according to (5).

(8) An organic electronic device comprising the organic thin film according to (6) or (7).

(9) An organic electroluminescent device comprising the organic thin film according to (6) or (7).

(10) The organic electroluminescent element as described in (9) above, wherein the organic thin film is a hole injection layer.

(11) The organic electroluminescent element as described in (9) above, wherein the organic thin film is a hole transport layer.

(12) The organic electroluminescent element according to any one of (9) to (11), wherein the substrate is a flexible substrate.

(13) The organic electroluminescent element according to any one of (9) to (12), wherein the substrate is a resin film.

(14) A display device comprising the organic electroluminescence device according to any one of (9) to (13).

(15) A lighting device comprising the organic electroluminescent element according to any one of (9) to (13).

(16) A display device comprising the illumination device according to (15) and a liquid crystal element as a display unit.

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 for improving the productivity of the organic EL element.
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. It is a figure which shows the relationship of the applied voltage-current density of the element produced in Example 4 and 5 and Comparative Example 5 and 6 with a graph.

<Organic electronics materials>
The organic electronic material of the present invention is characterized by containing at least one ionic compound represented by the following general formula (1b).

(In the formula, Y represents a divalent linking group containing a carbon atom or a sulfur atom, R represents an electron-withdrawing group (which may further have a substituent or a hetero atom in these structures), and L ⁺ represents a cation. Represents.)

[Ionic compounds]
Here, the “ionic compound” in the present invention will be described in detail. In the present invention, the ionic compound refers to a compound composed of a cation and an anion. No particular limitation is imposed on the type and valency of the ^{cation, Li +, Na +, K} +, Rb +, alkali metal ions such as ^{Cs +, Mg 2+, Ba 2+} , alkaline earth metal ions such as ^{Ca 2+, Al 3+,} Other metal ions such as Fe ³⁺ , Fe ²⁺ , Zn ²⁺ and Mn ²⁺ , inorganic cations represented by metal complex ions such as [Ag (NH ₃ ) ₂ ] ⁺ and [Zn (NH ₃ ) ₄ ] ²⁺ , H ⁺ , In addition to NH ₄ ⁺ , organic cations can be mentioned. In the case of an organic cation, the cation may be a polymer or oligomer, or may be an onium ion such as iodonium or phosphonium, a carbenium ion, an aminium ion, or the like. Further, when the cation is multivalent, it may be a composition having a balance between the monovalent anion and the charge. That is, in the case of an ionic compound having a divalent cation, it may be a composition containing two equivalents of monovalent anions with respect to one equivalent of divalent cations.

(Cation)
The cation in the ionic compound according to the present invention is preferably an organic cation from the viewpoint of the solubility of the compound. On the other hand, an ionic compound having an inorganic cation is generally difficult to dissolve in a low polarity organic solvent. Among organic cations, a cation having a structure represented by the following general formulas (2b) to (4b) is particularly preferable from the viewpoint of synthesis and availability.

^(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 above general formula are each independently an alkyl group, an alkenyl group, an alkynyl group, or an aromatic hydrocarbon group, from the viewpoint of stability of the compound and solubility in a solvent. Or it is preferable that it is an aromatic heterocyclic group.
In view of stability, synthesis and purification of the compound, A ¹ in the general formula (2b) is a bromine atom, an iodine atom or a carbon atom, and A ² in the general formula (3b) is an oxygen atom or a carbon atom. , A sulfur atom or a selenium atom, and A ³ in the general formula (4b) 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).

(Anion)
The anion in the present invention is not particularly limited as long as it is represented by the anion moiety of the general formula (1b). Specific examples of R as an electron withdrawing group 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 aryl having an aromatic hydrocarbon group or an aromatic heterocyclic group of 4 or more and 25 or less, preferably 15 or less The number of carbon atoms of an acyloxy group, alkyloxysulfonyl group, aryloxysulfonyl group, trifluoromethyl group, pentafluoroethyl group, etc., usually having 2 to 20 carbon atoms, such as xyloxycarbonyl and acetoxy, is usually 1 to 10, preferably Is a haloalkyl, haloalkenyl, haloalkynyl group, pentafluorophenyl group or the like having a halogen atom such as a fluorine atom or a chlorine atom 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 a negative charge, more preferably, a group obtained by substituting a part or all of hydrogen atoms of a group having a hydrogen atom among the above organic groups with a fluorine atom, for example, carbon A linear, branched or cyclic perfluoroalkyl group, perfluoroalkyloxy group, perfluoroaryl group, perfluoroaryloxy group, perfluoroacyl group, perfluoroalkoxy group, which may contain hetero atoms of 1 to 20 Group, perfluoroacyloxy group, perfluoroaryloxycarbonyl group, perfluoroalkenyl group, perfluoroalkynyl group, specifically represented by the following structural formula group (1), but limited thereto is not. Among these, those containing an aryl group are preferable, and an aryl group substituted with all fluorine is more preferable.

Structural formula group (1)

  Y in the general formula (1b) represents a divalent linking group and is preferably any one of the following general formulas (5b) to (11b).

(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) and (11b) are 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 has a negative charge mainly on the oxygen atom, more preferably has a —SO ₃ ^— or —CO ₂ ^— group, and most preferably the following general formula (16b), ( 17b).

(In the formula, R _f each independently represents an arbitrary electron-withdrawing group, and is exemplified by the structural formula group (1).)

[Charge transporting compound]
In addition, the present invention preferably includes the ionic compound and at least one charge transporting compound.

  Here, the “charge transporting compound” in the present invention will be described in detail. In the present invention, the charge transporting compound refers to a compound having a charge transporting unit.

  In the present invention, the “charge transporting unit” is an atomic group having the ability to transport holes or electrons, and 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. It is preferable to have a partial structure represented by 1) 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 following substituent group (A) to substituent group (N) Ar is independently an ant 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, and the like. -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, thi And diazole-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.

  The charge transporting compound in the present invention may be a low molecular compound or a high molecular compound such as a polymer or an oligomer. From the viewpoint of solubility in an organic solvent, a polymer compound such as a polymer or an oligomer is preferable, and from the viewpoint of easy purification by sublimation or recrystallization, a low molecular compound is preferable.

  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) from a viewpoint excellent in charge transport property.

  The charge transporting compound in the present invention preferably has at least one “polymerizable substituent” in order to produce a laminated structure of an organic thin film by changing 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 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)

In addition, the ionic compound according to the present invention can be used alone as a polymerization initiator. That is, the ionic compound represented by the general formula (1b) according to the present invention can function as a polymerization initiator. In other words, the ionic compound according to the present invention can be used as a polymerization initiator that imparts solvent resistance to the organic thin film by a polymerization reaction.
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 is at least the ionic compound represented by the general formula (1b) according to the present invention described above. It is characterized by including one kind.

When the solvent resistance is imparted to the organic thin film using the polymerization initiator, the condition for using the polymerization initiator is that the thin film is formed using 0.1 to 50% by mass of the polymerization initiator with respect to the charge transporting compound. After that, heating may be performed in a vacuum, in the air, or in a nitrogen atmosphere. When the amount is less than 0.1% by mass, the polymerization does not proceed efficiently and the solubility cannot be changed sufficiently. On the other hand, when the amount is more than 50% by mass, a large amount of the polymerization initiator and / or decomposition product remains, and the effect of washing becomes low.
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, when the ionic compound according to the present invention functions as a polymerization initiator, it may contain a sensitizer for improving photosensitivity and / or heat sensitivity in addition to the above polymerization initiator.

<Ink composition>
In addition, the ink composition of the present invention is characterized by containing the above-described organic electronic material of the present invention and a solvent, and other additives such as polymerization inhibitors, stabilizers, thickeners, gelling agents. , Flame retardants, antioxidants, anti-reducing agents, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, dispersants, surfactants, and the like. 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, organic electronics element, organic electroluminescence element>
The organic thin film of the present invention is formed using the organic electronic material or the ink composition.
Moreover, the organic electronics element or the organic electroluminescence element (organic EL element) of the present invention is characterized by including the organic thin film.
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 electronics element of the present invention is characterized by including the organic thin film of the present invention described above. 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 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 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.

<Preparation of Pd catalyst>
In a glove box under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature, anisole (15 ml) was added, and the mixture was stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed in a sample tube, anisole (5 ml) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to obtain a catalyst.

<Synthesis of charge transporting compound>
(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 a further prepared Pd catalyst solution (7.5 ml) ) Was added. After stirring for 30 minutes, 10% tetraethylammonium hydroxide aqueous solution (20 ml) was added. All solvents were used after 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 suction filtered, dissolved in toluene, triphenylphosphine, polymer-bound on styrene-divine benzene copolymer (200 mg from 100 mg of polymer, polymer), and stirred overnight. After completion of 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 1. 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 1]
Chlorobenzene (800 μL) was added to the polymer 1 obtained above (9.0 mg) and the following ionic compound 1 (1.0 mg) to prepare an ink composition containing the organic electronic material of the present invention. The polymer 1 and the ionic compound 1 did not remain dissolved, and a uniform solution was obtained.

[Comparative Example 1]
An ink composition was prepared in the same manner as in Example 1 except that the ionic compound 1 in Example 1 was replaced with tetraphenylphosphonium hexafluoroantimonate (Alfa Easer). However, undissolved residue is generated and a uniform solution cannot be obtained, and it is not suitable as a coating ink.

  Comparison between Example 1 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 2]
Polymer 1 (9.0 mg) obtained above, the ionic compound 1 (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%.

[Example 3]
A thin film was produced in the same manner as in Example 2 except that the ionic compound 1 in Example 2 was changed to the following ionic compound 2, and the residual film ratio was determined to be 99%.

[Comparative Example 2]
A thin film was prepared in the same manner as in Example 2 except that the ionic compound 1 in Example 2 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 as in Example 2 except that the ionic compound 1 in Example 2 was changed to triphenylsulfonium tetrafluoroborate (manufactured by Tokyo Chemical Industry). there were.

[Comparative Example 4]
A thin film was prepared in the same manner as in Example 2 except that the ionic compound 1 in Example 2 was changed to tropylium hexafluorophosphate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the residual film ratio was determined to be 13%. .

  Table 1 shows a comparison between the remaining film ratios of Examples 2 and 3 and the remaining film ratios of Comparative Examples 2 to 4.

Comparison between Examples 2 and 3 and Comparative Examples 2 to 4 shows that the organic electronic material of the present invention can exhibit sufficient solvent resistance upon curing.
Moreover, it turns out that the ionic compound of this invention functions as a polymerization initiator which can be hardened at low temperature.
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.

<Production of charge transportability evaluation element>
[Example 4]
A mixed solution of polymer 1 (100 mg), the ionic compound 1 (3.0 mg) and anisole (1.91 mL) was spin-coated at 3000 min ⁻¹ on a glass substrate patterned with ITO to a width of 1.6 mm, 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.

[Example 5]
A charge transportability evaluation element was produced in the same manner as in Example 4 except that the ionic compound 1 in Example 4 was changed to the ionic compound 2.

[Comparative Example 5]
A charge transportability evaluation element was produced in the same manner as in Example 4 except that the ionic compound 1 in Example 4 was changed to the following ionic compound A.

[Comparative Example 6]
A charge transportability evaluation element was produced in the same manner as in Example 4 except that the ionic compound 1 in Example 4 was changed to the following ionic compound B.

  FIG. 2 shows a graph of applied voltage-current density when voltage is applied using ITO as a positive electrode and aluminum as a cathode of these charge transportability evaluation elements. From FIG. 2, it can be seen that the devices of Examples 4 and 5 are much easier to flow the hole current than the devices of Comparative Examples 5 and 6.

<Production of organic EL element>
[Example 6]
A coating solution in which the polymer 1 (9.0 mg) obtained above, ionic compound 1 (1.0 mg), and chlorobenzene (800 μl) were mixed on a glass substrate obtained by patterning ITO to a width of 1.6 mm was 3000 min ^−. After spin coating at ¹ , the film was cured by heating at 180 ° C. for 10 minutes on a hot plate to form a hole injection layer (30 nm).

Next, in nitrogen, CDBP (15 mg), FIr (pic) (0.9 mg), Ir (ppy) 3 (0.9 mg), (btp) 2Ir (acac) (1.2 mg), dichlorobenzene (0. 5 mL) was spin-coated at 3000 rpm and then dried at 80 ° C. for 5 minutes to form a light emitting layer (40 nm). Further, BAlq (10 nm), Alq ₃ (30 nm), LiF (film thickness of 0.5 nm), and Al (film thickness of 100 nm) were vapor-deposited in this order, and sealed to produce an organic EL element and a lighting device.

  When voltage was applied to the white organic EL element and the lighting device, white light emission was observed at 3.5V.

[Comparative Example 7]
A white organic EL element and a lighting device were produced in the same manner as in Example 6 except that the ionic compound 1 was not added when forming the hole injection layer.

  When voltage was applied to the white organic EL element and the illuminating device, white light emission was observed at 10.0 V, but the light emission lifetime was 1/3 that of Example 6.

[Example 7]
A coating solution was prepared by mixing the polymer 1 (9.7 mg) obtained above, the ionic compound 1 (0.3 mg), and chlorobenzene (866 μL). After spin-coating the coating solution at 3000 min ⁻¹ in a nitrogen atmosphere on a glass substrate patterned with a width of 1.6 mm of ITO, the coating solution was heated and cured on a hot plate at 180 ° C. for 10 minutes to form a hole injection layer ( 30 nm).

Next, a mixture of the following yellow-green light emitting polymer (10 mg) and toluene (566 μL) was spin-coated at 4000 min ⁻¹ under a nitrogen atmosphere, and then dried at 80 ° C. for 5 minutes to form a light emitting layer (100 nm). Next, the obtained ITO glass substrate was transferred into a vacuum vapor deposition machine, and Ba (3 nm) and Al (100 nm) were vapor-deposited in this order.
After vapor deposition of Al, the substrate is moved into a dry nitrogen environment without opening to the atmosphere, and the sealing glass and ITO glass substrate in which 0.4 mm of counterbore is added to 0.7 mm non-alkali glass are used as a photocurable epoxy. Sealing was performed by bonding using a resin to produce an organic EL element.

When a voltage was applied to this organic EL element, yellow-green light emission was observed at 3.5 V, and the light emission lifetime at an initial luminance of 1000 cd / m ² was 676 hours.

[Example 8]
An organic EL device was prepared in the same manner as in Example 7 except that the ionic compound 1 in Example 7 was changed to the ionic compound 2, and when a voltage was applied, yellow-green light emission was observed at 3.5 V. The light emission lifetime at an initial luminance of 1000 cd / m ² was 541 hours.

[Comparative Example 8]
An organic EL device was prepared in the same manner as in Example 7 except that the ionic compound 1 in Example 7 was changed to the ionic compound A, and when a voltage was applied, yellow-green light emission was observed at 4.0 V. The light emission lifetime at an initial luminance of 1000 cd / m ² was 172 hours.

[Comparative Example 9]
An organic EL device was prepared in the same manner as in Example 7 except that the ionic compound 1 in Example 7 was changed to the ionic compound B, and when a voltage was applied, yellow-green light emission was observed at 4.0 V. The light emission lifetime at an initial luminance of 1000 cd / m ² was 93 hours.

[Comparative Example 10]
An organic EL device was produced in the same manner as in Example 7 except that the ionic compound 1 in Example 7 was changed to the following ionic compound C. When a voltage was applied, yellow-green light emission was observed at 4.0 V, The light emission lifetime at an initial luminance of 1000 cd / m ² was 93 hours.

  By comparing the above Example 6 with Comparative Example 7, Examples 7 and 8, and Comparative Examples 8-10, the charge transportability is improved by applying the organic electronics material of the present invention, and the organic EL element and illumination It can be seen that the device can be driven with low voltage and long life.

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 (16)

At least one including organic electronic material an ionic compound represented by the following general formula (1b).

(In General Formula (1b), Y represents a divalent linking group containing a carbon atom or a sulfur atom, R represents an aryl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. L ⁺ represents a monovalent group . Represents a cation.) The organic electronic material according to at least one charge-transporting compound including請 Motomeko 1. The organic electronic material according to 請 Motomeko 2 wherein the charge transporting compound that have a least one polymerizable substituent. The organic electronic material according to any one of 請 Motomeko 1-3 wherein the ionic compound that acts as a polymerization initiator.   An ink composition comprising the organic electronic material according to claim 1 and a solvent.   The organic thin film formed using the organic electronics material of any one of Claims 1-4.   An organic thin film formed using the ink composition according to claim 5. Including organic electronic devices the organic thin film according to claim 6 or 7. Including organic electroluminescent elements organic thin film according to claim 6 or 7. The organic electroluminescent element according to 請 Motomeko 9 wherein the organic thin film Ru HIL der. The organic electroluminescent element according to 請 Motomeko 9 wherein the organic thin film Ru hole transport layer der. Further comprising a substrate, said substrate is an organic electroluminescent element according to any one of 請 Motomeko 9-11 Ru flexible substrate der. Further comprising a substrate, said substrate is an organic electroluminescent element according to any one of Ru resin film der 請 Motomeko 9-12.   The display element provided with the organic electroluminescent element of any one of Claims 9-13.   The illuminating device provided with the organic electroluminescent element of any one of Claims 9-13.   A display device comprising the illumination device according to claim 15 and a liquid crystal element as a display means.