TW201024385A - Charge transporting material and charge transporting varnish - Google Patents

Abstract

Disclosed are a charge transporting material that contains a charge transporting substance, e.g., an oligoaniline compound, etc., and a heteropoly acid compound, e.g., phosphomolybdic acid, etc., as an electron-accepting dopant, and a charge transporting varnish that contains this charge transporting material and an organic solvent, wherein the charge transporting material is dissolved in the organic solvent. It is thus possible to provide a charge transporting material, which contains an electron-accepting dopant with high solubility in organic solvents, high oxidizing ability toward electron transporting host substances in a hole injection layer, and oxidizing ability toward hole transporting materials, and a charge transporting varnish, which contains this charge transporting material.

Description

201024385 VI. Description of the Invention: [Technical Field] The present invention relates to a charge transporting material, a charge transporting varnish, and more particularly to a charge transporting property of a heteropolyacid compound as an electron accepting dopant. Materials and charge transport varnishes. [Prior Art] φ In the past, it has been reported that a copper phthalocyanine (CuPC) layer is provided as a hole injection layer in a low molecular organic electroluminescence (hereinafter referred to as OLED) device, thereby achieving a driving voltage drop or an improvement in luminous efficiency. The improvement of the initial characteristics, and the improvement of the life characteristics (Non-Patent Document 1: Applied Physics Letters, 1996, 69, p. 2 1 60-2 1 62) ° Also, it has been reported that by making metals The oxide is vacuum-deposited and formed into a thin film, and the use as a hole injection layer can lower the driving voltage (Non-Patent Document 2: British Journal of Physics D: Applied Physics, 1996, vol. 29, p. 27 5 0- 275 3 ) ° On the other hand, an organic electroluminescence (hereinafter abbreviated as PLED) element using a polymer light-emitting material has been proposed by using a polyaniline-based material (Patent Document 1: Japanese Patent Publication No. Hei 3-273087) , Non-Patent Document 3: British Nature, 1992, Vol. 357, p477-479) or polythiophene-based materials (Non-Patent Document 4: US Applied Physics Letters, 1998, Vol. 72, p. 2660-2662) Film It is a hole transport layer, obtained with the same effect 0LED element. In recent years, it has been found that a highly transportable low molecular oligoaniline material 201024385 or an oligothiophene-based material can be used as a charge transport varnish which is completely soluble in a homogeneous solvent in an organic solvent. Therefore, it has been reported that by inserting a hole injection layer obtained from the varnish into an organic electroluminescence (hereinafter referred to as an organic EL) element, the planarization effect of the underlying substrate or the excellent EL element characteristics can be obtained (Patent Document 2: Japanese Patent Publication No. 2002-1551, No. 2, Patent Document 3: International Publication No. 2005/0 43962). Since the low molecular weight oligomer has a low viscosity and a general organic solvent, the process range in the film forming operation is narrow, and various coating methods such as spin coating φ, inkjet coating, and spray coating are used. In the case of various firing conditions, it is difficult to form a film having high uniformity. In this regard, it is possible to adjust the viscosity, the boiling point, and the vapor pressure by using various kinds of added solvents, and it is possible to obtain a film-forming surface having high uniformity in accordance with various coating methods (Patent Document 4: International Publication No. 2004/043) 1 1 No. 7 specification, Patent Document 5: International Publication No. 2005/1 073 3 5). However, in the face of the formal mass production of organic EL devices, it is required to further reduce the component drive voltage. On the other hand, in recent years, the hole injection layer using metal oxide has been re-examined, and it has been reported that the interface is oxidized on the hole transport layer by contacting the metal oxide forming the hole injection layer with the hole transport layer. A doping layer is formed to lower the driving voltage (Non-Patent Document 5: Applied Physics Letters, 2007, Vol. 91, p. 253504, Non-Patent Document 6: Applied Physics Letters, 2008, Vol. 93, p. 043308 ), but the coating material that is oxidizing for the hole transporting material does not have the example of _ 6 - 201024385, and requires the development of new materials. [PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT Patent Document 2: International Publication No. 2005-043962 2004/043 1 1 No. 7 Patent Document 5: International Publication No. 2 005/107335 Specification Non-Patent Document Non-Patent Document 1: American Applied Physics Letters, 1996, 69, p. 2160-2162 Non-Patent Document 2: British Journal of Physics D: Applied Physics, 1996, Vol. 29, ρ·2750-2753

Non-Patent Document 3: British Nature, 992, vol. 357, P477-479 Non-Patent Document 4: American Applied Physics Letters, 1998, Vol. 72, p. 2660-2662 Non-Patent Document 5: American Applied Physics Letters, 2007, Vol. 91, p. 2535 04 Non-Patent Document 6: Applied Physics Letters, 2008, Vol. 93, 043308 [Invention] The present invention is based on the above-mentioned problems. The object of the present invention is to provide an electron containing a high oxidizing property to a charge transporting host substance in a hole injection layer and having an oxidizing property to a hole transporting material. a charge transporting material of a capacitive dopant; and a charge transporting varnish comprising the charge transporting material. [Means for Solving the Problem] The present inventors have found that the heteropoly acid compound such as phosphomolybdic acid has high solubility in an organic solvent and is in the hole injection layer. The high oxidizability of the charge transporting host material is further oxidizing to the hole transporting material, and it is found that when the charge transporting film containing the heteropoly acid compound and the charge transporting substance is used as the hole injecting layer of the OLED element, it can be lowered. The voltage is driven and the life of the element is increased, thus completing the present invention. Further, a heteropoly acid compound such as phosphomolybdic acid is represented by a chemical group of Kggin type or Dawson type represented by Chemical Formula 2, that is, a structure having a hetero atom position at a molecular center. [Chemical 1]

-8 - 201024385 [Chemical 2]

By these special chemical structures, it is shown that there are significant differences in solubility characteristics or redox characteristics from isopolyacids or simple metal oxides composed only of oxyacids. This compound is known as a coloring reagent for a poly-φ catalyst or an organic compound, but there are not many examples of using it as a charge transporting substance. The present inventors have found that the heteropoly acid compound exhibits an effective hole injecting layer function as an extremely thin film forming layer in an organic EL device. That is, the present invention provides a charge transporting material characterized by comprising a charge transporting substance and a heteropoly acid compound as an electron accepting dopant. 2. The charge transporting material according to Item 1, wherein the heteropolyacidified φ compound is phosphomolybdic acid. 3. The charge transporting material according to Item 1 or 2, wherein the charge transporting substance is an aniline derivative compound. 4. The charge transporting material according to Item 3, wherein the charge transporting substance is an oligoaniline derivative represented by the following formula (1) or a quinone diimine derivative represented by the oxidized body of the formula (1): 3]

R1-A-NH-B--R3 (1) -9 - 201024385 [wherein, R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine group, a triol group, a thiol group' Base, dish acid group, dish ester group, ester group, thioester group, decylamino group, nitro group, monovalent hydrocarbon group, organooxy group, organic amine group, organic alkyl group, organic thio group, sulfhydryl group or sulfo group , A and B each independently represent a divalent group represented by the formula (2) or (3), [Chemical 4]

Base, stanol, thiol, carboxyl, phosphate, phosphate, ester, thioester, guanamine, nitro, monovalent, organooxy, organic amine, organoalkyl, organic The thio group, the fluorenyl group or the sulfo group), m and η are each independently an integer of 1 or more, and satisfy m + nS2 0]. 5. The charge transporting material according to item 4, wherein the charge transporting material is an aniline derivative represented by the formula (4) or a quinone diimine derivative of the oxidized body of the formula (4). 5]

R3 (4) (wherein R1 to R7, m and η have the same meanings as described above). 6. The charge transporting material according to item 4, wherein the aforementioned charge transporting-10-201024385 is a aniline derivative represented by the formula (5), or is derived from the quinone diimide of the formula (5) Object, [Chem. 6] R^7 »17

(wherein R2, R4 to R7, n and m have the same meanings as defined above, and R1 2 to R3 5 each independently represent a hydrogen atom, a hydroxy 'stanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate group, Ester group, thioester group, decylamino group, nitro group, substituted or unsubstituted one-valent hydrocarbon group, organic oxy group, organic amine group, organic decyl group, organic thio group, thiol group, sulfo group or halogen atom) . 7. A charge transporting varnish characterized by comprising a charge transporting material according to any one of the first to 61th stomachs and an organic solvent, and wherein said charge substance and a heteropoly acid compound are uniformly dissolved in said organic solvent . 8. The charge transporting varnish of item 7, wherein the organic content of the BU is a mixed solvent containing at least one good solvent. 9. The charge transporting varnish according to item 7 or 8, which comprises a solvent having a viscosity of from 10 to 200 mPa.s at 25 t. A charge transporting film comprising the charge transporting material according to any one of the first to any one of the preceding claims. A charge transporting film characterized by being produced by a charge transporting varnish according to any one of items 7 to 9. -11 - 201024385 12. An organic electroluminescence device characterized by comprising the charge transporting film of item 10 or 11. 13. The organic electroluminescence device according to item 12, wherein the charge transporting film constitutes a hole injection layer. [Effect of the Invention] The heteropolyacid compound contained in the charge transporting material and the varnish of the present invention has good solubility in an organic solvent for preparing a general charge transporting varnish, especially when dissolved in a good solvent, Various organic solvents typified by high viscosity solvents or low surface tension solvents also exhibit excellent solubility. Accordingly, a low-polarity organic solvent-based charge transporting varnish can be prepared by partially or almost entirely using a high viscosity solvent or a low surface tension solvent. The low-polarity organic solvent-based charge-transporting varnish can be applied not only to an inkjet coating device which is problematic in solvent resistance but also to a structure in which an insulating film or a separator has a solvent resistance. Under the circumstance, as a result, an amorphous solid film having high flatness can be produced without any problem. Further, since the obtained film exhibits high charge transportability, when used as a hole injection layer or a hole transport layer, the driving voltage of the organic EL element can be lowered and the life of the element can be extended. Therefore, since the heteropoly acid compound generally has a high refractive index, it is expected that the efficiency of light extraction can be improved by an effective optical design. Moreover, since the film has high flatness and high charge transportability, -12-201024385 can utilize this property to apply the film to a buffer layer or a hole transport layer of a solar cell, an electrode for a fuel cell, and a capacitor. Electrode protective film, antistatic film. [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The charge transporting material of the present invention is a heteropolyacid compound containing a charge transporting substance and an electron accepting dopant. The charge transporting substance and the electron-accepting dopant are also referred to as a charge transporting host substance when used. Herein, the charge transporting property is synonymous with conductivity, and means any one of hole transportability, electron transportability, hole, and electron two-charge transportability. The charge transporting material of the present invention may be one having charge transportability by itself, or may be one having a charge transport property in a solid film obtained therefrom. β The above-mentioned heteropoly acid compound is a polyacid obtained by condensing an isoxia of an oxo acid such as vanadium (V), molybdenum (Mo) or tungsten (W) with an oxyacid of a different element. In this case, as the oxyacid of the different element, oxo (Si), phosphorus (P), and arsenic (As) oxyacid are mainly exemplified. Specific examples of the heteropoly acid compound are, for example, phosphomolybdic acid, hydrazine molybdate, phosphotungstic acid, phosphotungstic acid, samarium tungstic acid, etc., but in the present invention, high solubility for an organic solvent and charge transporting substance From the viewpoint of high oxidizability and a reduction in driving voltage and life improvement when used in an organic EL device, -13-201024385 is preferably a phosphomolybdic acid, a phosphotungstic acid or a phosphotungstic acid, preferably a phosphomolybdic acid. Further, these heteropoly acid compounds are commercially available, for example, phosphomolybdic acid (phosphomolybdic acid hydrate, or 12 molybdenum(VI) phosphate η-hydrate, and the formula: Η3 (ΡΜ〇1204〇) · ηΗ20 ) It can be purchased from Kanto Chemical Co., Ltd., Wako Pure Chemical Co., Ltd., Japan Sigma-Aldrich Co., Ltd., etc. The charge transporting material which can be used in the charge transporting material of the present invention is not particularly limited as long as it is soluble in the organic solvent to be used. However, when it is used for organic EL applications, it is necessary to produce a highly uniform particle size of 1 〇〇 nm or less. Usually, an extremely thin film of about 20 to 50 nm, so that the charge transporting substance is preferably highly soluble, and the molecular weight distribution is not affected by the incorporation of the impurity component, especially the low molecular weight compound having a molecular weight of 200 to 2000. Preferably. Since the low molecular weight compound is often difficult to apply a highly uniform coating film because of its low viscosity, it is desirable to use a high viscosity solvent, and thus the 'charge transporting substance is preferably soluble in a high viscosity solvent. Specifically, an aniline derivative compound or a low molecular oligothiophene compound or the like which is a low molecular oligoaniline compound which has been used as a highly soluble material in the past can be used. Since the heteropoly acid compound contains a protonic acid and functions as a strong electron accepting substance for the charge transporting substance containing an NH group, the charge transporting substance is preferably an aniline derivative compound, and further considers a high electric charge. In terms of transportability, it is more preferably an aniline derivative compound having three or more aniline units. In other words, the heteropoly acid compound usually has two or more proton hydrogens and is formed into a pseudo-polymer of the oligoaniline derivative having a plurality of NH groups and an ionic pseudo-polymer, so that it is easily inhibited in the element in the driving. Transitional and life expectancy. Further, since the heteropoly acid compound described later is also oxidizing to the compound containing triphenylamine, when it is used in the hole injection layer, not only the charge transporting host substance in the hole injection layer can be oxidized. It is also possible to carry out cerium oxide on the material contained in the adjacent hole transport layer. In particular, since it exhibits high solubility and extremely high charge transportability, and also has an appropriate ionization potential, the following formula (1) can be suitably used. The oligoaniline derivative or the quinone diimine derivative of the oxide of the formula (1), and further, solubility, charge transportability, ionization potential (Ip), and the heteropoly acid compound of the present invention From the viewpoint of oxidizing properties, the aniline derivative represented by the formula (4) or (5) or the quinone diimine derivative of the oxidized body is most suitably used. [化7] .r

I 参 R1- Α—ΝΗ---Β—Ν—-R5 (1)

Jn I Jm [wherein R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine group 'stanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate group, an ester group, a thioester group, Amidino, nitro, monovalent hydrocarbon, organooxy, organic amine, organoalkyl, organothio, sulfhydryl or sulfo, each independently represented by formula (2) or (3) Divalent base, -15- 201024385 [Chem. 8]

(wherein R4 to R11 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine group, a stanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate group, an ester group, a thioester group, a decylamino group, a nitrate A group, a monovalent hydrocarbon group, an organic oxy group, an organic amine group, an organic decyl group, an organic thio group, a fluorenyl group or a sulfo group), m and η are each independently an integer of 1 or more, and satisfy m + nS20]. [Chemistry 9]

(4) (wherein R1 to R7, m and η have the same meanings as described above).

[化10]

(5) (wherein R2, R4 to R7, R12 to R35, η and m have the same meanings as described above). Further, the so-called quinone diimide means a compound having a partial structure represented by the following formula -16-201024385 in its skeleton. [化11]

(wherein R4 to R7 are the same as described above). Specific examples of the halogen atom in the above formulae such as fluorine, chlorine, bromine, or carboxylic acid group are exemplified by methyl, ethyl 'n-propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, An alkyl group such as n-octylhexyl or fluorenyl; a bicycloalkyl group such as a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a vinyl group, a 1-propenyl group, a 2-propenyl group, and a 1-methyl-2-propenyl group; Or an arylalkyl group such as 1 or 2 or 3 -butenyl, hexenylphenyl, xylyl, tolyl, biphenyl or naphthyl, phenylcyclohexyl or the like, or the like Some or all of the monovalent atoms are replaced by a halogen atom, a hydroxyl group, an alkoxy group or the like. Specific examples of the organooxy group are alkoxy groups, alkenyloxy groups, and the alkyl groups, alkenyl groups, and aryl groups are exemplified by the groups exemplified above. Specific examples of the organic amine group are exemplified by an anilamine such as an anilino group, a methylamino group, an propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a decylamino group or an undecylamino group. a dialkylamino iodine atom such as a dimethylamino group, a dipropylamino group, a dibutylamino group, a diamylamino group, a dihexylamino group, a dioctylamino group, a dinonylamino group or a diammonium group. Alkenyl group such as isopropyl group, isopropyl group, 2-ethyl group; dicyclohexylisopropenyl group; benzyl group, hydrocarbyl group, sulfonic acid aryloxy group and the like ethylamine group, amine group, hydrazine, diethylamine, Diheptylamine: cyclohexylamine-17- 201024385, morpholinyl and the like. Specific examples of the organic decyl group are exemplified by trimethyl decyl group, triethyl decyl group, tripropyl decyl group, tributyl decyl group, tripentyl decyl group, trihexyl decyl group, pentyl dimethyl decyl group. And hexyl dimethyl decyl, octyl dimethyl decyl, decyl dimethyl decyl and the like. Specific examples of the organic sulfur group are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, sulfonylthio, sulfonylthio, and eleven An alkylthio group such as an alkylthio group. Specific examples of the mercapto group are a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group and the like. The phosphate group is exemplified by -P(〇) ( OQ1 ) ( OQ 2 ). The ester group is exemplified by -C(O)OQ1, -OC(O)Q1. The thioester group is exemplified by -C(S)OQ1, -OC(S) Q1. The guanamine group is exemplified by -C ( Ο ) NHQ1, -NHC ( Ο ) Q1, -C ( 〇 ) NQ'Q2, -NQk ( Ο ) Q2. Wherein Q1 and Q2 represent an alkyl group, an alkenyl group or an aryl group, and examples of the group are the same as those exemplified in the above monovalent hydrocarbon group. The number of carbon atoms in the above-mentioned monovalent hydrocarbon group, organic oxy group, organic amine group, organic decyl group, organic thio group, thiol group, phosphate group, ester group, thioester group, and decylamino group is not particularly limited, but usually The carbon number is from 1 to 20, preferably from 1 to 8. Preferred substituents are exemplified by fluorine, sulfo group, organooxy group, alkyl group, organic decyl group and the like. Further, the 'substituent group also includes a moiety in which the substituents are bonded to each other to form a cyclic group -18- 201024385 In the general formulae (1), (4) and (5), m + n is a viewpoint of exhibiting good charge transportability. It is preferably 3 or more, and it is preferably 16 or less from the viewpoint of ensuring solubility in a solvent. Further, in the case of the oligoaniline derivatives of the formulae (1) and (4), in view of improving the solubility and making the charge transport property uniform, it is preferred that the molecular weight distribution is not obtained. In other words, the aniline derivative having a degree of dispersion of 1 is preferable. In order to suppress volatilization and display of the material and charge transportability, the molecular weight is usually 200 or more, preferably 3 or more, and in order to improve solubility, the upper limit is usually 5,000 or less, preferably 2,000 or less. These charge transporting substances may be used singly or in combination of two or more kinds. Specific examples of the compounds are exemplified by N,N,N',N'-tetraphenyl-p-C-aminopentaphenylamine represented by the following formula (6), and N-phenyl trisole represented by the formula (7). An aniline derivative which is soluble in an organic solvent such as aniline, N-phenyltetraphenylamine represented by the formula (8), tetraphenylamine (aniline tetramer), or octaphenylamine (aniline octamer). -19- (6)201024385 [Chem. 12]

(7)

(8)

Further, the synthesis method of the charge transporting substance is not particularly limited, but may be exemplified by the method described in the specification of International Publication No. 2008/1 29947, the oligoaniline synthesis method (refer to Bulletin of Chemical Society of Japan, 1994). , Vol. 67, p. 1 794-1752: Synthetic Metals, USA, 1977, Vol. 84, ρ·1 19-120), or oligothiophene synthesis (see eg Heterocycles, 1987, pp. 26, ρ.939-942; Heterocycles, 1 987, vol. 26, ρ.1 793-1 796). Further, a method of oxidizing the aniline derivative compound to a quinone diimine compound is exemplified by the method described in the specification of International Publication No. 2008/01 047. The charge transporting varnish of the present invention comprises a charge transporting material and an organic solvent comprising a heteropolyacid compound containing the above charge transporting substance and an electron accepting dopant, and the charge transporting substance and the heteropoly acid compound are uniform. Dissolved in organic solvents. -20- 201024385 The organic solvent used in the preparation of the charge transport varnish can be a good solvent having a charge transporting property and a solubility of a heteropoly acid compound. Among them, a good solvent means a solvent having a high polarity of a solvent molecule and a good solution of a highly polar compound. Examples of such good solvents are, for example, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone. , dimethyl sulfoxide, fluorene-cyclohexyl-2-pyrrolidone, and the like. These solvents may be used singly or in combination of two or more kinds, and the amount thereof may be 5 to 100% by mass based on the total amount of the solvent used in the varnish. Since the heteropoly acid compound used in the present invention is excellent in solubility in an organic solvent, it is also possible to use a high viscosity solvent and/or a low surface tension solvent together with the above good solvent. Good solvents, high viscosity solvents and low surface tension solvents can also have their own properties. The so-called 髙-viscosity solvent means a viscous film which is suitable for spraying or coating in various coating apparatuses and forms a uniform wet film, and suppresses the aggregation of the wet film or the occurrence of irregularities during firing to volatilize the solvent. A solvent having a film having a high film thickness uniformity can be formed. As for the high-viscosity solvent, it is exemplified by a viscosity of from 10 〇 to 200 mPa «s at 25 ° C, especially from 50 to 150 mPa · s. Specifically, cyclohexanol, ethylene glycol, 1,3-octanediol, diethylene glycol, a high viscosity solvent having a boiling point of 50 to 300 ° C, especially 150 to 250 ° C under normal pressure, Dipropylene glycol, triethylene glycol, tripropylene glycol '1,3-butanediol, 2,3·butanediol, 1,4-butanediol, propylene glycol, hexanediol, o-cresol, m-cresol Preferably, p-cresol or the like is used in the range of from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the total amount of the solvent in the varnish. The low surface tension solvent means improving the wettability to the substrate by lowering the surface tension, imparting volatility, etc., or imparting physical properties suitable for spraying or coating in various coating apparatuses, and reducing the coating apparatus. Corrosive solvent. Such low surface tension solvents are exemplified by, for example, benzene, toluene, ethylbenzene,

Aromatic hydrocarbons such as p-xylene, o-xylene, styrene; hydrocarbons such as n-pentane, Q-hexane, n-heptane, n-octane, n-decane, n-decane; acetone, methyl b Ketones such as ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethyl n-pentyl ketone; ethyl acetate, isopropyl acetate Ester, n-propyl acetate, isobutyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl hexanoate, 2-methylpentyl acetate, n-lactide, n-butyl lactate, etc. Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol Ether acetate © , propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethyl Glycol monomethyl ether 'dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate 'diethylene glycol and other glycol esters or two Ethers; methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-butanol ' 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-octanol, 1-methoxy-2-butanol, diacetone alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, benzene Alcohols such as methanol-22-201024385; ethers or carboxylic acids such as diethyl ether, di-n-propyl ether, diisopropyl ether, diisopropyl ether, 1,4-dioxane, acetic acid, and r-butyrolactone. When a good solvent and a high viscosity solvent and/or a low surface tension solvent are used, the ratio of use thereof is not particularly limited. However, when a high viscosity solvent or a low surface tension solvent is used in a large proportion, as described above, it is possible to impart an increased viscosity. The surface tension is lowered, the volatility is imparted, the coating property to the surface of the substrate is improved, and the new preferable physical properties such as coating, sprayability, and the like are improved. Further, as a result of the decrease in the polarity of the obtained varnish e, a coating apparatus or a substrate which can be used for solvent resistance is used, and the application range thereof is widened. When a low surface tension solvent is used, specifically, the ratio of the good solvent to the high viscosity solvent and/or the low surface tension solvent is preferably from about 9:1 to about 1:9, more preferably about 1:1 by mass ratio. ~ 1 : 4 or so. Further, when two or more solvents are used in combination, the boiling point of the good solvent is preferably equal to or higher than the other solvents. The preparation method of the charge transporting varnish is not particularly limited, and the components and the solvent may be mixed and prepared in any order, but once the above heteropoly acid compound is dissolved in a good solvent, it has a high viscosity solvent even if a lower polarity is added. And/or a low surface tension solvent is also less likely to cause precipitation properties. Therefore, it is added to a solution in which a charge transporting substance and a heteropoly acid compound are dissolved in a good solvent to add a high viscosity solvent and/or a low surface tension solvent. Modulation is preferred. When such methods are used, the ratio of high viscosity solvent or low surface tension solvent in the charge transport varnish can be increased. The solid concentration of the charge transporting varnish is not particularly limited, but is usually from about 0.01 to 50% by mass in the range of from -23 to 201024385, and preferably from 0.1 to 10% by mass, more preferably from 0.5 to 10% by weight. 5 mass%. Further, the mixing ratio of the charge transporting substance to the heteropolyacid compound is not particularly limited, but in consideration of further improving the charge transporting property of the obtained film, the mass-producing substance is preferably a charge-transporting substance: heteropoly acid compound = 1: 0.01. ~10.0, better for 1: 〇.〇5~4.0. The viscosity of the charge transporting varnish is not particularly limited, but it is preferably 25° when a film of _0.1 to 200 nm is formed by a spin coating method, an inkjet method or a spray method with high film thickness uniformity. The viscosity under C is 1 to 100 mPa·s, more preferably 3 to 30 mPa·s, and even more preferably 5 to 20 mPa. S ° The charge transporting varnish of the present invention may be used as opposed to the charge transporting substance as needed. The amount of addition of about 0.1 to 90% by mass is used to use a dopant other than the above heteropoly acid compound to improve the charge transport performance and the like. The dopant substance is preferably an electron-acceptable dopant having high electron acceptability. The solubility of the dopant substance is not particularly limited as long as it is at least one solvent which can be dissolved in the varnish @. Specific examples of the electron-accepting dopant are exemplified by inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid, and ortho-acid; aluminum (III) chloride (A1C13), titanium (IV) chloride (TiCl4), and boron tribromide (BBr3). ), boron trifluoride ether complex (BF3 · OEt2), iron (III) chloride (FeCl3), copper chloride (

II) (CuCl2), antimony pentachloride (V) (SbCl5), arsenic pentafluoride (V) (AsF5), phosphorus pentafluoride (PF5), ginseng (4-bromophenyl) aluminum hexachloroantimonate Lewis acid such as (TBPHA); benzenesulfonic acid, toluenesulfonic acid, camphor-24- 201024385 sulfonic acid, hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, polystyrenesulfonic acid, The 1,4-benzodioxane disulfonic acid derivative described in the specification of International Publication No. 2005/000832, the arylsulfonic acid derivative described in the specification of International Publication No. 2006/025342, JP-A-2005 - an organic strong acid such as a dinonylnaphthalenesulfonic acid derivative described in the publication No. 1 08 828; 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6 An organic or inorganic oxidizing agent such as dicyano-1,4-benzoquinone (DDQ) or iodine, but is not limited to φ. The most preferred electron-accepting dopants are exemplified by 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, polystyrenesulfonic acid, and 1,4 described in the specification of International Publication No. 2005/0008. a benzodioxane disulfonic acid derivative, an organic strong acid such as a dinonylnaphthalenesulfonic acid derivative described in JP-A No. 2 005 - 1 0882 8; International Publication No. 2006/02 5 3 42 The electron-acceptable dopant substance 〇Φ of an organic strong acid such as a naphthalene disulfonic acid derivative described above is applied to a substrate by applying the charge transporting varnish described above to a substrate, and evaporating the solvent to form a charge transport on the substrate Film. The coating method of the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, and a slit coating method. The evaporation method of the solvent is not particularly limited, for example, by using a hot plate or an oven to evaporate under a suitable atmosphere, that is, under an inert gas such as air or nitrogen, or a vacuum. According to this, a film having a uniform film formation surface can be obtained. -25- 201024385 The firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably carried out at 40 to 2 50 °C. In this case, in order to exhibit higher uniform film forming properties and to carry out a reaction on a substrate, temperature changes of two or more stages may be performed. The film thickness of the charge transporting film is not particularly limited. However, when it is used as a charge injection layer in the organic EL device, it is preferably from 0.1 to 200 nm, more preferably from 1 to 100 nm, still more preferably from 10 to 50 nm. The method of changing the film thickness has a method of changing the solid content concentration in the varnish, and changing the amount of the solution on the substrate during coating. The materials or production methods used in the production of the OLED device using the charge transporting varnish of the present invention are exemplified below, but are not limited thereto. The electrode substrate to be used is preferably liquid-washed in advance with a lotion, alcohol, pure water or the like. For example, the anode substrate is preferably subjected to surface treatment such as ozone treatment or oxygen-plasma treatment just before use. However, when the anode material is mainly composed of an organic substance, it may be left untreated. When a hole transporting varnish is used in the OLED element, the following methods can be mentioned. This hole-transporting varnish was applied onto an anode substrate, and was evaporated and fired by the above method, and a hole transporting film was formed on the electrode to form a hole injection layer or a hole transport layer. This was introduced into a vacuum vapor deposition apparatus, and the hole transport layer, the light-emitting layer, the electron transport layer, the electron injection layer, and the cathode metal were sequentially vapor-deposited to form an OLED element. Among them, it is also possible to remove any layer or a plurality of layers to fabricate components as needed. A carrier barrier layer may also be provided between any of the layers to control the field of illumination. -26- 201024385 The anode material is exemplified by a transparent electrode typified by indium tin oxide (ITO) or lanthanum lead oxide (IZO), and is preferably planarized. Polythiophene derivatives or polyaniline derivatives having high charge transportability can also be used. The material for forming the hole transport layer may be exemplified by (triphenylamine) dimer derivative (TPD), (α-naphthalene diphenylamine) dimer (a-NPD), [(triphenylamine). Dimer] snail dimer (spiro-TAD) and other triarylamine ginseng, 4,4',4",-gin[3-methylphenyl(phenyl)amino]triphenylamine (m_) MTDATA), 4,4',4",-[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), etc., Starburst Amine, 5,5, _ bis-{4-[bis(4-methylphenyl)amino]phenyl}_2,2,:5,,2,,_trithiophene (BMA-3T) and other oligothiophenes. The hole transporting material having a reducing property of the heteropoly acid compound used in the present invention is preferable from the viewpoint of lowering the driving voltage of the characteristics of the organic EL element. In particular, since triphenylamine, triarylamine or stellate amine is easily oxidized by the heteropoly acid compound used in the present invention, it is suitable to use a layer containing the compound as and containing the heteropoly acid compound. The hole injection layer is adjacent to the hole injection layer. The material for forming the light-emitting layer is exemplified by tris(8-hydroxyquinoline)aluminum (111) (Alq3), bis(8-hydroxyquinoline)zinc(n)(Znq2), bis(2-methyl-8·pyridinium Porphyrin) (p-phenylphenol) aluminum (ιπ) (8 八 ()) and 4,4'-bis(2,2-diphenylvinyl)biphenyl (DPvBi), etc., by co-evaporation The electron transporting material or the hole transporting material and the luminescent dopant may also form a light emitting layer. -27- 201024385 As for the electron transport materials listed as Alq3, BAlq, DPBVi, (2·(4-biphenyl)-5-(4·t-butylphenyl)·1,3,4·oxadiazole) ( PBD ), triazole derivative (ΤΑΖ), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), dihaloquinone (silole) ) derivatives and the like. Examples of luminescent dopants are quinacridone, rubrene, coumarin 540, 4-(dicyanomethylidene)-2-methyl-6-(p-dimethylaminobenzene) Vinyl)-4H- succinyl (DCM), ginseng (2-phenylpyridine _) ruthenium (III) ( Ir(ppy) 3), ( 1,1 0 -phenanthroline)-parameter (4,4, 4-Trifluoro-1-(2-thienyl)-butyl-1,3-diacid) ruthenium (III) (E u (TTA) 3 phe η ) and the like. The material forming the carrier barrier layer is exemplified by PBD, ruthenium, BCP, and the like. The material forming the electron injecting layer is exemplified by lithium oxide (Li 2 Ο ), magnesium oxide (MgO), aluminum oxide (Al 2 〇 3 ), lithium fluoride (LiF ), magnesium fluoride (MgF 2 ), strontium fluoride (SrF 2 ), Liq. , Li (acac), lithium acetate, lithium benzoate, and the like. The cathode material is exemplified by aluminum 'magnesium-silver alloy, aluminum lithium alloy, lithium, sodium, potassium, planer, and the like. Further, when an electron transporting varnish is used for the OLED element, the following methods can be mentioned. The electron transporting varnish is applied onto the cathode substrate to form an electron transporting film, which is introduced into a vacuum vapor deposition apparatus, and an electron transporting layer, a light emitting layer, a hole transporting layer, and a hole injection layer are formed using the same material as described above. After that, the anode material is formed into a OLED element by sputtering or the like. -28- 201024385 The method for producing a PLED element using the hole transporting varnish of the present invention is not particularly limited, but the following methods are listed. In the above OLED device manufacturing, by forming a luminescent charge transporting polymer layer instead of performing a vacuum vapor deposition operation on the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, the charge transport using the present invention can be produced. A PLED element of a charge transporting film formed by a varnish. Specifically, the charge transporting φ clearing group (hole transporting varnish) of the present invention is applied onto an anode substrate, and a hole transporting film is produced by the above method, and a luminescent charge transport property is formed in the upper portion thereof. The molecular layer is re-evaporated to form a PLED element. In order to improve luminous efficiency and device life, an intermediate layer may be provided between the hole transporting film and the light emitting polymer layer. As the cathode and anode materials to be used, the same materials as those used in the production of the above OLED elements can be used, and the same washing treatment and surface treatment can be carried out. Φ The method of forming the luminescent charge transporting polymer layer is exemplified by adding a solvent to the luminescent charge transporting polymer material or a material in which the luminescent dopant is added thereto, dissolving it, uniformly dispersing, and coating. After forming the electrode substrate of the hole injection layer, the film is formed by evaporation of a solvent. The luminescent charge transporting polymer material is exemplified by a polyfluorene derivative such as poly(9,9-dialkyln) (PDAF) or poly(2-methoxy-5-(2'-ethylhexyloxy). · 1,4-phenylphenylene vinylene) (MEH-PPV), such as poly(phenylene vinylene) derivatives, poly(3-alkoxythiophene) (PAT), etc. Poly-29-201024385 Thiophene derivatives , polyvinyl carbazole (PVCz) and the like. The solvent may be exemplified by toluene, xylene, chloroform, etc., and the dissolution or the uniform dispersion method is exemplified by stirring, heating and stirring, ultrasonic dispersion, and the like. The coating method is not particularly limited, and examples thereof include an inkjet method and a spray coating. Method, dipping method, spin coating method, slit coating method, transfer printing method, roll coating method, brush coating, and the like. Further, the coating is preferably carried out under an inert gas such as nitrogen or argon. The solvent evaporation method is exemplified by heating in an inert gas or in a vacuum in an oven or a hot plate. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. Further, since the correct amount of moisture in the heteropolyacid compound to be used is not clear, the concentration of the solid component described below is calculated by weighing the amount of water which is not deducted from the occasional amount. When the weighing is not carried out, the pretreatment such as removing moisture is used, and the purchased compound is directly used. Π] Preparation of charge transporting varnish and charge transporting film [Example 1] In a nitrogen atmosphere, 270 mg or more of the formula (6) is represented by >?chuan, :^,,:^-tetraphenyl- Adding 11.47 g of good solvent DMI to a mixture of -(:-aminopentaphenylamine (hereinafter referred to as Ding?man?8) and 540 mg of phosphomolybdic acid (hereinafter referred to as PMA) -30- 201024385 Solution: 5.73 g of propylene glycol and 17.20 g of cyclohexanol which had been heated to 40 ° C were added to the solution, and allowed to stand to cool to room temperature to obtain a transparent solution of greenish black. Using a pore size of 2.2μιη The resulting solution was filtered through a PTFE filter to obtain a green-black transparent charge transport varnish (solid content concentration: 2.3% by mass, viscosity at 25t: 1 ImPa · s). • The resulting varnish was applied to the warp by spin coating. Ozone was washed on an ITO substrate of 30 minutes φ, and baked on a hot plate at 220 ° C for 30 minutes in the air to form a charge transporting film. The obtained film was a uniform amorphous solid. 6) The TPAPA is in accordance with International Publication No. 2008/129 Synthesis of the method described in the specification No. 94 No. 7 [Example 2] A mixture of 270 mg or more of N-Φ phenyltetraphenylamine (hereinafter abbreviated as PTA) represented by the formula (8) and 540 mg of PMA in a nitrogen atmosphere 1 1.47 g of good solvent DMI was added and dissolved. 5.73 g of propylene glycol and 17.20 g of cyclohexanol which had been heated to 4 (TC melted) were added to the solution, and allowed to stand to cool to room temperature to obtain a green-black transparent solution. The resulting solution was filtered through a PTFE filter having a pore size of 2 μm to obtain a green-black transparent charge-transporting varnish (viscosity at 25 ° C llmPa • s ) ° The resulting varnish was applied to the ozone-washed by spin coating. On a 30-minute ITO substrate, and on a hot plate, it was baked at 30 ° C for 30 - 31 - 201024385 minutes in the atmosphere to form a charge transporting film. The obtained film was uniform and amorphous. (8) The PTA is synthesized according to the method described in Bulletin of Chemical Society of Japan, 1994, Vol. 67, p. 1749-1752. [Example 3] Under a nitrogen atmosphere, the following formula is 270 mg. (9) Representation, Ν, Ν', Ν'-four Add 1 1.47 g of good solvent DMI to the mixture of keto-p-C-aminotetraphenylamine (hereinafter referred to as ox-indole) and 540 mg of hydrazine. Dissolve 5.73 g of propylene glycol and 17.20 g of heat to 40 ° C. The cyclohexanol was added to the solution, and allowed to stand to cool to room temperature to obtain a green-black transparent solution. The obtained solution was filtered using a PTFE filter having a pore size of 22 μιη to obtain a green-black transparent charge transporting varnish (solid content concentration: 2.3% by mass, viscosity at 25 ° C, 1 1 mP a · s ). The obtained varnish was applied onto an ITO substrate which was washed with ozone for 30 minutes by a spin coating method, and baked on a hot plate at 220 ° C for 30 minutes in the air to form a charge transporting film. The resulting film was a homogeneous amorphous solid. Further, the ox-TPATA represented by the formula (9) is synthesized in accordance with the method described in the specification of International Publication No. 2008/1 29947 and International Publication No. 2008/01 047. -32- 201024385 [Chem. 13]

[Example 4] 13 DMF of 13.30 g of a good solvent was added to a mixture of 204 mg of NSO-2 and 204 mg of PMA in a nitrogen atmosphere and dissolved. 6.65 g of propylene glycol and 19.95 g of cyclohexanol which had been heated to 40 ° C were added to the solution, and the mixture was allowed to cool to room temperature, and a green-black transparent solution was obtained by filtration using a PTFE filter having a pore size of 2 μm. Solution, obtaining a green-black transparent charge-transporting varnish (viscosity at 25 ° C llmPa • S ) ° The resulting varnish was applied by spin coating to an ITO substrate cleaned by ozone for 30 minutes φ, and on a hot plate The film was fired at 220 ° C for 30 minutes in the atmosphere to form a charge transporting film. The resulting film was a homogeneous amorphous solid. Further, the NSO-2 represented by the following formula is synthesized in accordance with the specification of International Publication No. 2006/025342. [Chem. 14]

-33-201024385 [Example 5] To a mixture of 200 mg of hydrazine and 400 mg of PMA, DMI of 13.79 g of a good solvent was added and dissolved in a nitrogen atmosphere. 19.70 g of 2,3-butanediol and 5.91 g of n-hexyl acetate were added to the solution, and stirred at room temperature to obtain a green-black transparent solution. The resulting solution was filtered using a PTFE filter having a pore size of 22 μηι to obtain a green-black transparent charge-transporting varnish (viscosity at 25 ° C of 8 mPa·s). The obtained varnish was applied onto an ITO substrate which was washed with ozone for 30 minutes by a spray coating method using a spray coating apparatus (NVD200, manufactured by Fujimori Technology Research Institute Co., Ltd.), and on a hot plate. The film was fired at 220 ° C for 30 minutes in the atmosphere to form a charge transporting film. The resulting film was a homogeneous amorphous solid. [Comparative Example 1] To a mixture of 50 mg of PTA and 102 mg of NSO-2, 1 1.68 ml of DMI was added and dissolved in a nitrogen atmosphere. 0.85 ml of propylene glycol and 2.78 ml of cyclohexanol which had been heated to 40 ° C were added to the solution, and allowed to stand to cool to room temperature to obtain a green transparent solution. The obtained solution was filtered using a PTFE filter having a pore size of 22 μιη to obtain a green transparent charge transporting varnish (viscosity at 25 ° C of 11 mPa·s). The resulting varnish was applied to ozone by spray coating. The film was washed for 30 minutes on an ITO substrate, and fired at 220 ° C in the air for 30 - 34 - 2010 24385 minutes on a hot plate to form a charge transporting film. The resulting film was a homogeneous amorphous solid. [Comparative Example 2] PED〇T/PSS (manufactured by HC Starck Co., Ltd., grade name CH8000) was applied onto an ITO substrate by a spin coating method, and baked on a hot plate at 100 ° C for 60 minutes in the air. Forming a charge transporting film. The film obtained by G is a uniform amorphous solid. [Comparative Example 3] PTA was used as a charge transporting host material, and molybdenum oxide (manufactured by Kanto Chemical Co., Ltd., Mo03), molybdic acid (manufactured by Kanto Chemical Co., Ltd., Η2Μο04), ammonium molybdate (Kanto Chemical Co., Ltd.) was used. ), (ΝΗ4)6Μ〇7024), tungsten oxide (manufactured by Kanto Chemical Co., Ltd., W03), vanadium oxide (manufactured by Kanto Chemical Co., Ltd., V205), manganese oxide (manufactured by Kanto Φ Chemical Co., Ltd., Μη02) As the charge-accepting dopant substance, attempts have been made to prepare a charge transporting varnish, but since the solubility of each component with respect to the above-mentioned good solvent is extremely low, a uniform solution cannot be obtained. [Comparative Example 4] 5.70 g of DMI was added and dissolved in a mixture of 100 mg of PTA and 200 mg of manganese acetate (manufactured by Kanto Chemical Co., Ltd., Mn(OCOCH3)3) in a nitrogen atmosphere. The liquid in which the oxidation (dehydrogenation) reaction of PTA occurs is blackened, and a black solid precipitates. When using PMA, since there is no solid precipitation in the dehydrogenation reaction of PTA-35-201024385, it can be understood that the stability of the manganese acetate transport varnish is poor. Further, as shown in the specification of International Publication No. 2008/01047, the oxidized body (amine) of PTA is likely to cause solid precipitation due to low solubility, and therefore it is desirable to contain no oxidized body in the state of the varnish and at the time of coating. However, from the viewpoint of subsequent charge transportability, it is desirable to be fired in the atmosphere and to form an oxidized body. In N-phenyltriphenylamine and the like, it is difficult to produce solid precipitation due to desulfurization (dehydrogenation), and the amount thereof is reduced. Table 1 shows the varnish concentration, the film thickness of the film, and the ionization potential (Ip) of Example 1 and Comparative Examples 1 and 2. Further, the refractive indices of 450 nm and 650 nm of the film obtained in 2 are shown in Table 1. Further, the ionization potential was measured using a spectroscopic device AC-2 manufactured by a sputum counter. The film thickness is measured by the surface roughness measuring device Surfcorder ET-4000A manufactured by Xiaoyan Research Institute. The M-2000 manufactured by JA Woollam, Japan, is used for the charge-distribution of the second Asian-original transport, and the substrate is coated with oxygen. Therefore, the solidification example 1 is shown in the photoelectron (unit). Folding 201024385 [Table 1] Material film thickness Γηιηΐ Ip[eV] Refractive index (450 nm) Refractive index (650 nm) Example 1 TPAPA/PMA 30 5.4 1.86 1.74 Example 2 PTA/PMA 30 5.4 1.89 1.75 Example 3 οχ-ΤΡΑΤΑ /ΡΜΑ 30 5.4 • _ Example 4 PTA/(NSO-2+PMA) 30 5.6 - Example 5 TPATA/PMA (spray coating) 30 5.4 - Comparative Example 1 PTA/NSO-2 30 5.6 - Comparative Example 2 PEDOT/PSS 40 5.6 • [2] OLED device fabrication [Example 6] After forming a hole transporting film on an ITO substrate in the same manner as in Example 4, the substrate was introduced into a vacuum vapor deposition apparatus. The OLED element (light-emitting area: 4 mm 2 ) was fabricated by vapor-depositing a-NPD, Alq3, Alq3, LiF, and A1 having a volume ratio of 7% of rubrene. The film thickness was determined to be 3 Onm ' 30 nm '30 nm, 0.8 nm, 15 5 nm> and the evaporation operation was performed from 2 x 1 (pressure below T4 Pa. The evaporation rate was 0.1 in a-NPD and Alq3). 2.2nm/s, rubrene and LiF are 0.01 to 0.02iim/s, and A1 is 0.2 to 0.4nrn/s. The moving operation between vapor deposition operations is performed in vacuum [Comparative Example 5] Utilization and Comparative Example 1 In the same manner, after forming a charge transporting film on the ITO substrate, each film was deposited in the same manner as in Example 6 to prepare an OLED element (light emitting area: 4 mm 2 ) of -37-201024385. Using an organic EL luminous efficiency measuring device ( EL1003, manufactured by PRECISE GAUGES (manufactured by GA). The characteristics of the 0 LED elements obtained in Example 6 and Comparative Example 5 were measured. The measurement results are shown in Table 2. m 2] Material film thickness (nm) Current density (mA/cm 2 ) Voltage ( V) Brightness (cd/cm2) Luminance halving time (hr) Example 6 PTA/(NSO-2+PMA) 30 68 6.9 2000 2300 Comparative Example 5 PTA/NSO-2 30 61 6.6 2000 370

As shown in Table 2, it was found that the OLED characteristics obtained in Example 6 were significantly longer than those obtained in Comparative Example 5, and the luminance halving time was remarkably elongated, and the life characteristics were good. Moreover, it can be understood that the current density and the voltage are almost equal. [Examples 7 to 9] In the same manner as in Examples 1 to 3, a hole transporting film was formed on each of the ITO substrates, and then the substrate was introduced into a vacuum vapor deposition apparatus to sequentially evaporate a-NPD. Alq3, LiF, and A1 were used to fabricate an OLED device (light-emitting area: 100 mm 2 ). The film thicknesses were 40 nm' 60 nm, 〇.8 nm, and 150 nm, respectively, and vapor deposition was performed from 2x 1 (T4Pa or less). The vapor deposition rate was 〇.l~〇.2nm/s for a-NPD and Alq3, LiF It is 0.01 to 0.02 nm/s, and A1 is 0 · 2 to 0.4 nm/s. The moving operation of the vapor deposition operation is performed in a vacuum. -38 - 201024385 [Comparative Example 6] Except that the hole injection layer is not provided' The OLED element was produced in the same manner as in Example 7 except that the thickness of the α-NPD of the hole transport layer was changed to 7 〇 nm. [Comparative Example 7] PED〇T/PSS (manufactured by HC Starck Co., Ltd.) by spin coating method φ , grade name AI408 3 ) was applied onto an ITO substrate, and baked on a hot plate at atmospheric temperature for 60 minutes to form a charge transporting film. Except that the substrate was used, Example 7 was used. In general, an OLED device in which a hole injection layer was a PEDOT/PSS film was produced. The characteristics of the OLED devices obtained in Examples 7 to 9 and Comparative Example 6 '7 were measured, and the results are shown in Table 3. [Table 3] Material film thickness (nm Current density (mA/cm2) Voltage (V) Brightness (cd/cm2) Luminance halving time (hr) Example 7 TPAPA/PMA 30 10 5.7 250 290 Example 8 PTA/PMA 30 10 5.0 300 180 Example 9 οχ-ΤΡΑΡΑ/ΡΜΑ 30 10 6.2 250 770 Comparative Example 6 No HII - 10 21.9 230 <1 Comparative Example/2 PEDOT/PSS 40 10 4.8 270 150 *1 Initial brightness 1 500 cd/m2 *2 4mm2 of light-emitting surface (others are 100mm2) PEDOT/PSS: Since the characteristics of 100mm2 cannot be determined, the measurement of 4mm2-39-201024385 cannot be 4 Onm or more because the film thickness is not uniform, so it is set to 40nm. As shown in Table 3, the films constituting the hole injection layer in the elements of Examples 7 to 9 are extremely flat compared to the PEDOT/PSS film, so even under the light-emitting area of 1 〇〇 mm 2 There is a problem of characteristic stability. It can be understood that although the light-emitting area is large, the lifetime is still equal or higher, and in particular, by combining with a suitable host material, the life can be greatly improved. φ [3] Conductivity measurement [Example 10] The measurement was performed to carry out the conductivity measurement. The DMAc solution containing 30% by mass of PTA/PMA (mass ratio 1/2) was prepared as a charge transport varnish in the same manner as in Example 2 except that the solvent was changed to DM Ac. . Further, in the measurement of the conductivity, the resistance of the sample film itself must be sufficiently higher than the resistance of the measuring element, and it is necessary to form a thick film. Therefore, a high concentration varnish is prepared. φ The obtained varnish was applied onto an ITO substrate which was washed with ozone for 30 minutes by a spray coating method, and baked on a hot plate at 220 ° C for 30 minutes in the air to form a charge transporting property of a film thickness of 3 60 nm. film. The resulting film was a homogeneous amorphous solid. [Comparative Example 8] PEDOT/PSS (manufactured by HC Starck Co., Ltd., grade name CH8000) was applied onto an ITO substrate by a spin coating method, and fired at 100 ° C in a large -40-201024385 gas on a hot plate. After 60 minutes, a charge transporting film was formed. The resulting film was a homogeneous amorphous solid. The conductivity of the film obtained in the above Example 10 and Comparative Example 8 is shown in Table 4. Further, in the conductivity, each of the obtained substrates was introduced into a vacuum vapor deposition apparatus, and the sandwich type element (ITO/sample/A1 (150 nm)) which was deposited by depositing A1 of a thickness of 15 Onm in a vapor deposition cover was used for measurement (electrode area). 〇.2mm2 〇), current density 100mA/cm2). [Table 4] Conductivity voltage rS/cml m Example 1 〇PTA/PMA lxl〇·4 <0.1 Comparative Example 8 PEDOT/PSS 2x 1 0-7 4.1 As shown in Table 4, the PTA used in Example 10 /PMA Conductivity® has a small electric field dependency, exhibits good charge transportability under a weak voltage, and exhibits a sufficiently high conductivity as a material for the hole injection layer (generally required to be 10_7 S/cm or more). Further, the electric field from the electrode is injected into the material having a small barrier, and it is desired that the Ip値 is deeper than the crucible of the material to be transported, that is, deeper than about 5.4 eV, but the Ip is in an appropriate range. [4] Evaluation of oxidizing property of a material containing a triarylamine [Example 1 1] Now, a hole transporting layer which is laminated adjacent to a hole injection layer is used in a large amount of -41 - 201024385 to contain triphenylamine. The material is a triarylamine-containing material. In order to evaluate the oxidizing property of the heteropoly acid compound of the present invention for the triphenylamine-containing compound, the following experiment was conducted. Since the triphenylamine-containing compound is similar in physical properties to the other triarylamine-containing compound as the material of the hole transporting layer, the triarylamine-based hole transporting layer material can be evaluated for overall oxidative properties. The fact that the material of the hole transport layer is oxidizable means that an electrostatic carrier can be formed on one of the portions of the hole transport layer, whereby it is possible to reduce the driving voltage in the organic EL element. 7.05 g of DMI was added to 0.15 g of the triphenylamine dimer represented by the formula and 0.30 g of the above-mentioned ortho-molybdic acid (twice the weight ratio of triphenylamine dimer) in and at 60 ° Stir and stir under C and cool to room temperature to obtain a homogeneous solution. The resulting solution was passed through a PTFE filter having a pore size of 22 μιη to obtain a light brown transparent charge transporting varnish (solid content concentration: 6.0% by mass).所得 The obtained varnish was applied onto a quartz substrate which was washed with ozone for 30 minutes by a spin coating method, and baked on a hot plate at 150 ° C for 30 minutes in the air to form a charge transporting film. The resulting film was a homogeneous amorphous solid. After measuring the UV-VIS spectrum of the obtained film (measurement apparatus: UV-3100, manufactured by Shimadzu Corporation), a broad peak absorption peak appeared at 550 nm and 73 0 nm. -42- 201024385 [Chem. 15]

ρ b Since the film containing only the triphenylamine dimer and the film containing only the phosphomolybdic acid do not have such absorption peaks, the absorption peak is considered to be derived from the cation of the triphenylamine dimer or Dication. Further, the α-NPD of the triarylamine-based material was thoroughly studied using α-NPD, and it was found that the absorption peak of the cation system at 490 nm and 1330 nm, and the absorption peak was shifted to the cation derived by the action of the oxidizing agent. 610nm and 810nm. From the above results, it is understood that phosphomolybdic acid is oxidizing to triphenylamine dimer. Therefore, it is understood that the hole injection layer containing phosphomolybdic acid is oxidized at the contact interface and forms a dopant layer for a hole transport layer composed of a hole transport material containing triphenylamine or the like. The possibility, according to this, contributes to the possibility that the driving voltage of the organic EL element is lowered. [Comparative Example 9] A charge transporting film was formed in the same manner except that the phosphomolybdic acid (manufactured by Aldrich) of Example 5 was changed to dinonylnaphthalene disulfonic acid. After the UV-VIS spectrum of the obtained film was measured, a new absorption peak other than the absorption peak obtained by the individual monomer film did not appear. It was confirmed that 5-sulfosalicylic acid was not oxidizing to the triphenylamine dimer. -43-

Claims (1)

201024385 VII. Patent Application Range: 1. A charge transporting material characterized by a charge transporting substance and a heteropoly acid compound as an electron accepting dopant. 2. The charge transporting material according to claim 1, wherein the heteropoly acid compound is phosphomolybdic acid. 3. The charge transporting material according to claim 1 or 2, wherein the charge transporting substance is an aniline derivative compound. 4. The charge transporting material according to claim 3, wherein the charge transporting substance is an aniline derivative represented by the following formula (1), or a bisdiimine derivative of the oxidized body of the formula (1) : [Chemical Formula 1] "Γ Rzn R1-A-NH---B-il-Rs (X) . Jn L "m [wherein R1' R2 and R3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine Base, stanol, thiol, carboxyl, phosphate, phosphate, ester, thioester, decyl, nitro, monovalent, organooxy, organic amine, organoalkyl, organic a thio group, a thiol group or a sulfo group, and each of A and B independently represents a divalent group represented by the formula (2) or (3), [Chemical 2] (wherein R 4 to R 1 1 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amine 201024385 group, a stanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate group, an ester group, a thioester group, a decyl group. , nitro, monovalent hydrocarbon group, organooxy 'organic amine group, organodecyl group, organothio group, fluorenyl group or sulfo group), m and η are each independently an integer of 1 or more, and satisfy m + n$20]. 5. The charge transporting material according to claim 4, wherein the charge transporting substance is an aniline derivative represented by the formula (4) or a quinone diimine derivative of the oxidized form of the formula (4) , 〇[化3] (wherein R1 to R7, m and η have the same meanings as described above). 6. The charge transporting material according to item 4 of the patent application, wherein the charge transporting substance is derived from an oligoaniline derivative represented by the formula (5) or an oxidized body of the formula (5). Object '[4] (wherein R 2 , R 4 to R 7 , η and m have the same meanings as defined above, and R 12 to R 35 each independently represent a hydrogen atom, a hydroxyl group, a stanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate group, or an ester group. , thioester, guanamine, nitro-45- 201024385, substituted or unsubstituted one-valent hydrocarbon, organooxy, organic amine, organoalkyl, organothio, sulfhydryl, sulfo or halogen atom). 7. A charge transporting varnish comprising the charge transporting material according to any one of claims 1 to 6 and an organic solvent, wherein the charge transporting substance and the heteropolyacid compound are uniformly dissolved in the foregoing In organic solvents. 8. The charge transporting varnish of claim 7, wherein the organic solvent is a mixed solvent containing at least one good solvent. _ 9· A charge transporting varnish according to claim 7 or 8, which comprises a solvent having a viscosity of from 1 〇 to 200 mPa·s at 25 ° C. A charge transporting film characterized by comprising the charge transporting material according to any one of claims 1 to 6. A charge transporting film produced by the charge transporting varnish according to any one of claims 7 to 9. 12. An organic electroluminescence device characterized by having a charge transporting film of claim 10 or 11. The organic electroluminescence device of claim 12, wherein the charge transporting film constitutes a hole injection layer. -46 - 201024385 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: none -3- 201024385 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none