TW201529537A - Charge-transporting varnish, charge-transporting thin film, organic electroluminescent device, and manufacturing method for charge-transporting thin film - Google Patents

Abstract

This invention provides a charge-transporting varnish which is capable of being fired at low temperature under 200 DEG C, and thin films manufactured under such firing conditions have high flatness, high charging-transporting capacity, and demonstrate superior EL device characteristics when applied to organic EL devices. A charge-transporting varnish of this invention comprises a charge-transporting substance, dopants, and organic solvents, characterized in that the dopants contain heteropolyacid and at least one selected from halogenated tetracyanoquinonedimethane and halogenated or cyano-benzoquinone.

Description

Charge transporting varnish, charge transporting film, organic electroluminescent device, and method for producing charge transporting film

The present invention relates to a charge transporting varnish, a charge transporting film, an organic electroluminescence (hereinafter referred to as an organic EL) device, and a method for producing a charge transporting film.

In the organic EL device, a charge transporting film composed of an organic compound can be used as the light emitting layer or the charge injection layer. The method for forming the charge transporting film is roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. When the dry process is compared with the wet process, the wet process can efficiently produce a film having a large area and a high flatness. Therefore, in the field where a large area of a film of an organic EL or the like is desired, most of the film is formed by a wet process. .

In view of the above, the present inventors have developed a charge transporting varnish for producing a charge transporting film which can be applied to various electronic devices by a wet process (see, for example, Patent Document 1).

However, in recent years, in the field of organic EL, the use of substrates composed of organic compounds has been replaced by the trend of lighter or thinner components. Since the glass substrate is required to be calcined at a lower temperature than in the past, and in this case, a varnish having a film having good charge transportability can be provided.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-151272

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film which can be fired at a low temperature of less than 200 ° C, and which has high flatness and high charge transportability under the firing conditions. In the case of an organic EL device, a charge transporting varnish having excellent characteristics can be exhibited.

As a result of intensive studies in order to achieve the above object, the present inventors have found that a charge transport of a heteropoly acid and at least one selected from the group consisting of tetracyanoquinone dimethane halide and halogenated or benzoquinone cyanide is used as a dopant. The varnish is fired not only at a high temperature of 200 ° C or higher but also at a low temperature of less than 200 ° C, and the film produced under the firing conditions is amorphous, and has high flatness and high charge transportability. When the film is used in a hole injection layer, an organic EL device which can realize excellent luminance characteristics can be obtained, and the present invention has been completed.

In other words, the present invention provides a charge transporting varnish, a charge transporting film, an organic electroluminescent device, and a method for producing a charge transporting film.

A charge transporting varnish which is a charge transporting varnish containing a charge transporting substance, a dopant and an organic solvent, characterized in that the dopant is a heteropoly acid and a halogenated tetracyanoquinone At least one of methane and halogenated or cyanogenic benzoquinone.

2. The charge transporting varnish according to the above item 1, wherein the above-mentioned halogenated tetracyanoquinone dimethane comprises tetracyanoquinodimethane fluoride.

3. The charge transporting varnish according to the above item 1 or 2, wherein the above heteropoly acid comprises phosphotungstic acid.

4. The charge transporting varnish according to any one of the above items 1 to 3, wherein the charge transporting substance is an aniline derivative or a thiophene derivative.

A charge transporting film produced by using the charge transporting varnish according to any one of items 1 to 4 above.

An organic electroluminescence device comprising the charge transporting film according to the above fifth aspect.

7. The organic electroluminescence device according to item 6, wherein the charge transporting film is a hole injection layer or a hole transport layer.

A method for producing a charge transporting film, which is characterized in that the charge transporting varnish according to any one of the above items 1 to 4 is applied onto a substrate and fired at less than 200 °C.

A method of producing an organic electroluminescence device, characterized in that the charge transporting film according to the above fifth aspect is used.

A charge transporting material which is a charge transporting material composed of a charge transporting substance and a dopant, characterized in that the dopant is a heteropoly acid and is selected from a halogenated tetracyanobenzoquinone dimethane. And at least one of halogenated or cyanide benzoquinone.

A method for planarizing a charge transporting film, which is a planarization method using at least one charge transporting film selected from the group consisting of tetracyanoquinone dimethane halide and halogenated or cyanoquinone cyanide, characterized in that it contains A charge transporting substance, a dopant, and an organic solvent, wherein the dopant is a charge transporting varnish containing at least one selected from the group consisting of a heteropoly acid and a halogenated tetracyanoquinodimethane and a halogenated or cyanoquinone.

The use of the charge transporting varnish of the present invention comprising at least one selected from the group consisting of heteropolyacids and at least one selected from the group consisting of tetracyanoquinone dimethane halides and halogenated or cyanoquinones, not only at temperatures above 200 ° C In addition, it is also possible to obtain a film having excellent brightness characteristics when it is used in a hole injection layer of an organic EL device, and it can be obtained by firing at a low temperature of not lower than 200 ° C, and also having high flatness and high charge transportability. Although this reason has not been determined, it is presumed that a halogenated tetracyanoquinone dimethane having a high electron accepting capacity is used as a dopant together with a heteropoly acid, and it is possible to suppress crystallization or doping of a film caused by using only one of them. The reason for the lack of impurities.

In addition, by using the charge transporting varnish of the present invention, it is excellent in reproducibility, and excellent in charge transport property, even when various wet processes capable of forming a large area by a spin coating method or a slit coating method are used. Thin film, therefore, It can also fully cope with the progress in the field of organic EL components in recent years.

Further, the film obtained from the charge transporting varnish of the present invention can also be used as an antistatic film or an anode buffer layer of an organic thin film solar cell.

[Formation of the Invention] [charge transport varnish]

The charge transporting varnish of the present invention contains a charge transporting substance, a dopant, and an organic solvent, and the dopant comprises at least 1 selected from the group consisting of a heteropoly acid and a halogenated tetracyanoquinone dimethane and a halogenated or cyanoquinone. That is, at least one selected from the group consisting of tetracyanoquinone dimethane halide, phenyl halide, and benzoquinone.

[charge transporting substance]

The charge transporting substance contained in the charge transporting varnish of the present invention has a charge transporting property, that is, a conductive property, and may have charge transport property itself, or may have a charge when used together with a dopant. Conveying sex. In particular, a substance having a hole transporting property is preferred.

As such a charge transporting substance, a charge transporting compound used in the field of organic EL or the like can be used, and specific examples thereof include an aniline derivative, an N,N'-diarylbenzidine derivative, and N,N,N'. An arylamine derivative (aniline derivative) such as an N'-tetraarylbenzidine derivative, an oligothiophene derivative, a Thienothiophene derivative, a thiophenebenzothiophene derivative, or the like a thiophene derivative, a pyrrole derivative such as oligopyrrole or the like.

The aniline derivative is preferably a quinonediamine structure, that is, an aniline derivative which does not have a partial structure represented by the following formula.

Further, the benzoquinone diimine structure refers to a structure in which one of the double bonds in the carbocyclic ring of the aromatic compound is reduced by one, and instead has two outer double bonds in the para or ortho position (so-called fluorene structure), for example, The benzoquinone diimine structure having an aryldiamine compound having two amine groups in the opposite position has a structure represented by the following formula.

The molecular weight of the charge-transporting substance is not particularly limited as long as it is dissolved in the organic solvent used for the charge-transporting substance, and is approximately 200 to 10,000. From the viewpoint of obtaining a film having higher charge transportability from good reproducibility, It is preferably 300 or more, more preferably 400 or more, and is preferably 8,000 or less, more preferably 7,000 or less, still more preferably 6,000 or less, from the viewpoint of providing a uniform varnish of a film having high flatness with good modulation reproducibility. The best is 5,000 or less. Also, when thinning, prevent charge loss From the viewpoint of separating the transporting substances from each other, the charge transporting compound preferably has no molecular weight distribution (dispersion degree is 1) (that is, a single molecular weight is preferable).

[dopant]

The charge transporting varnish of the present invention contains at least one selected from the group consisting of a heteropoly acid as a first dopant and a tetrabasic benzoquinone dimethane and a halogenated or cyanoquinone as a second dopant. Hereinafter, these are collectively referred to as dopants.

The heteropolyacid of the first dopant is represented by a Keggin type represented by the formula (A1) or a chemical structure of the Dawson type represented by the formula (A2), having a structure in which a hetero atom is located at the center of the molecule, and vanadium ( V), molybdenum (Mo), tungsten (W), etc., an oxoacid isopoly acid, and a polyacid condensed with an oxoacid of a different element. The oxo acid of such a different element is mainly an oxo acid such as cerium (Si), phosphorus (P) or arsenic (As).

Specific examples of the heteropoly acid include phosphomolybdic acid, hydrazine molybdate, phosphotungstic acid, tungstic acid, phosphotungstic acid, and the like. These may be used alone or in combination of two or more. Further, the heteropoly acid used in the present invention can be obtained from a commercially available product, or can be synthesized by a conventional method.

In particular, when one type of heteropoly acid is used, the heteropoly acid is preferably phosphotungstic acid or phosphomolybdic acid, more preferably phosphotungstic acid. When two or more types of heteropolyacids are used, at least one of the two or more kinds of heteropoly acids is preferably phosphotungstic acid or phosphomolybdic acid, more preferably phosphotungstic acid.

Further, in the quantitative analysis of elemental analysis or the like, the heteropoly acid has a structure represented by a general formula, and even if the number of elements is large or small, it is suitably synthesized as a commercially available product or according to a conventional synthesis method. Both can be used in the present invention.

That is, for example, the general phosphotungstic acid is represented by the chemical formula H ₃ (PW ₁₂ O ₄₀ ) ‧nH ₂ O, and the phosphomolybdic acid is represented by the chemical formula H ₃ (PMo ₁₂ O ₄₀ )‧nH ₂ O, but in quantitative analysis Even if the amount of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in the formula is large or small, it is preferably obtained as a commercial product or according to a conventional synthesis method. Both of the synthesizers can be used in the present invention. In this case, the mass of the heteropoly acid specified in the present invention does not refer to the mass of the pure phosphotungstic acid (phosphoric acid content) in the composition or the commercial product, but refers to the form which can be obtained by the commercially available product and The form in which the conventional synthesis method can be separated includes the total mass of a state such as water of hydration or other impurities.

The halogenated tetracyanoquinone dimethane of the second dopant is represented by the formula (1).

In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or a halogen atom, but at least one of them is a halogen atom. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. Further, it is preferable that at least two of R ¹ to R ⁴ are a halogen atom, more preferably at least three are halogen atoms, and most preferably all are halogen atoms.

Tetracyanobenzoquinone dimethane, specifically, for example, tetrafluorotetracyanoquinodimethane (F4TCNQ), tetrachlorotetracyanoquinodimethane, 2-fluorotetracyanoquinodimethane, 2 - chlorotetracyanoquinone dimethane, 2,5-difluorotetracyanoquinodimethane, 2,5-dichlorotetracyanoquinodimethane, and the like. The tetracyanoquinone dimethane halide is particularly preferably F4TCNQ.

The halogenated or cyanated benzoquinone of the other second dopant is represented by the formula (2).

In the formula, R ⁵ to R ⁸ each independently represent a hydrogen atom, a halogen atom or a cyano group, but at least one of them is a halogen atom or a cyano group. The halogen atom is, for example, the same as the above, and is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. Further, it is preferred that at least two of R ⁵ to R ⁸ are a halogen atom or a cyano group, more preferably at least three are a halogen atom or a cyano group, and even more preferably a halogen atom or a cyano group.

Halogenated or cyanoquinone cyanide, for example, 2,3-dichloro- 5,6-dicyano-p-benzoquinone, trifluorophenylhydrazine, tetrafluorophenylhydrazine, tetrabromophenylhydrazine, tetracyanobenzoquinone, and the like. The halogenated or cyanoquinone is preferably 2,3-dichloro-5,6-dicyano-p-benzoquinone, trifluorophenylhydrazine, tetrafluorophenylhydrazine, tetracyanobenzoquinone, more preferably 2, 3-Dichloro-5,6-dicyano-p-benzoquinone, tetrafluorophenylhydrazine, tetracyanobenzoquinone, and more preferably 2,3-dichloro-5,6-dicyano-p- Benzoquinone.

The content of the dopant in the charge transporting varnish of the present invention is appropriately determined depending on the charge transporting substance.

When the thiophene derivative is used as a charge transporting substance, the content of the first dopant is expressed by a mass ratio of 0.01 to 100, more preferably 0.1 to 50, with respect to the charge transporting substance composed of the thiophene derivative. The degree is better than 1 to 10. The content of the second dopant is preferably from 0.1 to 100% by mass, more preferably from 1 to 50% by mass, even more preferably 5, based on the total solid content (the components contained in the varnish remaining after firing). ~30% by mass. Further, a compound in which a thiophene moiety and an aniline moiety coexist in a molecule is used as a thiophene derivative when the dopant/host ratio is calculated.

Further, when the aniline derivative is used as a charge transporting substance, the content of the first dopant is usually from 1 to 500% by mass, preferably from 10 to 200% by mass, more preferably 50%, based on the total solid content. ~150% by mass. Further, the content of the second dopant is expressed by an equivalent ratio with respect to the charge transporting substance composed of the aniline derivative, and is usually from 0.01 to 100, preferably from 0.1 to 50, more preferably from 1 to 10. degree.

Since the charge transporting varnish of the present invention contains the first and second dopants, it is not only fired at a high temperature of 200 ° C or higher, but also It is less than 200 ° C, and can be fired at a low temperature of 180 ° C or lower and 160 ° C or lower. It is excellent in brightness and the like, and is not only represented by indium tin oxide (ITO) or indium zinc oxide (IZO). The high hole of the transparent electrode is subjected to a capacitive energy, and also exhibits a film having excellent charge transportability from a high hole of a metal anode represented by aluminum.

[Organic solvents]

As the organic solvent used in the preparation of the charge transporting varnish, a highly soluble solvent which can dissolve the charge transporting substance, the dopant, and other components described later can be used.

As such a highly soluble solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazoline can be used. An organic solvent such as a ketone or diethylene glycol monomethyl ether. These solvents may be used singly or in combination of two or more kinds, and the amount thereof may be from 5 to 100% by mass based on the total amount of the solvent used in the varnish.

Further, it is preferable that the charge transporting substance and the dopant are completely dissolved in the above solvent.

Further, in the present invention, the varnish contains at least one kind of 10 to 200 mPa at 25 ° C. s, especially 35~150mPa. The viscosity of s, and the atmospheric viscosity (atmospheric pressure) of boiling point of 50 ~ 300 ° C, especially 150 ~ 250 ° C high viscosity of the solvent, the viscosity of the varnish adjustment is easy, as a result, good reproducibility provides flatness The high film can be used to prepare the varnish according to the coating method used.

The high-viscosity organic solvent is not particularly limited, and for example, a cyclohexane Alcohol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3- Butylene glycol, 1,4-butanediol, propylene glycol, hexanediol, and the like. These solvents may be used alone or in combination of two or more.

The addition ratio of the high-viscosity organic solvent to the entire solvent used in the varnish of the present invention is preferably in the range where the solid does not precipitate, and the addition ratio is preferably from 5 to 80% by mass in the range in which the solid does not precipitate.

Further, in order to improve the wettability of the substrate, adjust the surface tension of the solvent, adjust the polarity, adjust the boiling point, etc., it is preferable to mix 1 to 90% by mass, more preferably 1 to 1% of the solvent used for the varnish. 50% by mass of other solvents.

Such a solvent may, for example, be ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, or diethylene glycol alone. Butyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, γ-butyrolactone, ethyl lactate, n- Hexyl acetate, propylene glycol monomethyl ether, etc., but are not limited thereto. These solvents may be used alone or in combination of two or more.

The viscosity of the varnish of the present invention is suitable for setting the thickness of the film to be produced or the solid concentration, but is usually 1 to 50 mPa at 25 ° C. s.

In addition, the solid content concentration of the charge transporting varnish in the present invention is preferably set in consideration of the viscosity of the varnish, the surface tension, or the like, or the thickness of the produced film, but is usually about 0.1 to 10.0% by mass, and the varnish is considered to be considered. When the coatability is used, it is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass. %.

[other ingredients]

The charge transporting varnish of the present invention may comprise an organic decane compound. Specific examples of the organic decane compound include a dialkoxy decane compound, a trialkoxy decane compound, and a tetraalkoxy decane compound. These may be used alone or in combination of two or more.

In particular, the organic decane compound preferably contains one selected from a dialkoxy decane compound and a trialkoxy decane compound, and more preferably a trialkoxy decane compound.

The dialkoxy decane compound, the trialkoxy decane compound, and the tetraalkoxy decane compound may, for example, be represented by the formulae (B1) to (B3).

SiR' ₂ (OR) ₂ (B1)

SiR'(OR) ₃ (B2)

Si(OR) ₄ (B3)

In the formula, R each independently represents an alkyl group may be substituted with Z ¹⁰¹ of 1 to 20 carbon atoms, the sum Z ¹⁰¹ may be a substituted alkenyl group having a carbon number of 2 to 20, Z ¹⁰¹ may be substituted alkynyl of 2 to 20 carbon atoms of the a aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹⁰² or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ¹⁰² .

R 'each independently represent an alkyl group may be substituted with Z 1 of ¹⁰³ to 20 carbon atoms, the substituents Z may be the ¹⁰³ carbon atoms of the alkenyl group having 2 to 20, Z may be a substituted alkynyl group of ¹⁰³ carbon atoms of 2 to 20, the heteroaryl may be 2 to 20 substituted aryl group of Z ¹⁰⁴ carbon atoms, an aryl group of 6 to 20 may be substituted with Z ¹⁰⁴ or the number of carbon atoms.

Z ¹⁰¹ represents a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹⁰⁵ or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ¹⁰⁵ .

Z ¹⁰² represents a halogen atom, an alkyl group may be substituted by Z ¹⁰⁵ of 1 to 20 carbon atoms, the sum may be substituted with Z ¹⁰⁵ carbon atoms of the alkenyl group having 2 to 20 or ¹⁰⁵ may be substituted with Z alkynyl of 2 to 20 carbon atoms of the group .

Z ¹⁰³ represents a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹⁰⁵ , a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ¹⁰⁵ , an epoxycyclohexyl group, a glycidyloxy group, and a Alkyl methoxyoxy, acryloxy, ureido (-NHCONH ₂ ), thiol, isocyanate (-NCO), amine, -NHY ¹⁰¹ or -NY ¹⁰² Y ¹⁰³ .

Z ¹⁰⁴ represents a halogen atom, an alkyl group may be substituted with Z ¹⁰⁵ of 1 to 20 carbon atoms, the substituents Z may be the ¹⁰⁵ carbon atoms of the alkenyl group having 2 to 20, Z ¹⁰⁵ may be substituted alkynyl of 2 to 20 carbon atoms of the group , epoxycyclohexyl, glycidoxy, methacryloxy, propyleneoxy, ureido (-NHCONH ₂ ), thiol, isocyanate (-NCO), amine, -NHY ¹⁰¹ Base or -NY ¹⁰² Y ¹⁰³ base.

Y ¹⁰¹ ~ Y ¹⁰³ each independently represent an alkyl group may be substituted with Z ¹⁰⁵ of 1 to 20 carbon atoms, the sum may be substituted with Z ¹⁰⁵ carbon atoms of the alkenyl group having 2 to 20, carbon atoms can be substituted by Z 2 to 20 of the ¹⁰⁵ alkynyl group, Z ¹⁰⁵ may be a substituted aryl group of a carbon number of 6 to 20 aryl or heteroaryl group substituted by Z ¹⁰⁵ of the 2 to 20 carbon atoms.

Z ¹⁰⁵ represents a halogen atom, an amine group, a nitro group, a cyano group or a thiol group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group having 1 to 20 carbon atoms may be any of a linear chain, a branched chain, and a cyclic group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Carbon of n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, etc. a straight or branched chain alkyl group of 1 to 20; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, bicyclobutyl, bicyclo a cyclic alkyl group having 3 to 20 carbon atoms such as a pentyl group, a bicyclohexyl group, a bicycloheptyl group, a bicyclooctyl group, a bicyclononyl group or a bicycloindenyl group.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include, for example, a vinyl group, an n-1-propenyl group, an n-2-propenyl group, a 1-methylvinyl group, an n-1-butenyl group, and a n-2- Butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1 -Methyl-2-propenyl, n-1-pentenyl, n-1-nonenyl, n-1-icosyl, and the like.

Specific examples of the alkynyl group having 2 to 20 carbon atoms include, for example, an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group, an n-2-butynyl group, and n. 3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1 a hexynyl group, an n-1-decynyl group, an n-1-pentadecenyl group, an n-1-eicoyl group, and the like.

Specific examples of the aryl group having 6 to 20 carbon atoms include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, a 1-phenanthryl group, and a 2-phenanthrene group. Base, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and the like.

R is preferably an alkyl group may be substituted by the Z ¹⁰¹ of 1 to 20 carbon atoms, may be substituted with the group Z ¹⁰¹ carbon atoms, alkenyl of 2 to 20, or it may be substituted with Z ¹⁰² carbon atoms of the aryl group having 6 to 20, more Jia Z ¹⁰¹ is substituted it may be an alkyl group having 1 to 6 carbon atoms, the substituents may be the Z ¹⁰¹ carbon atoms of the alkenyl group having 2 to 6 or, more preferably and Z ¹⁰¹ may be substituted by a substituted phenyl group of Z ¹⁰² The alkyl group having 1 to 4 carbon atoms or the phenyl group which may be substituted by Z ¹⁰² is more preferably a methyl group or an ethyl group which may be substituted by Z ¹⁰¹ .

Further, R' is preferably an alkyl group having 1 to 20 carbon atoms which may be substituted by Z ¹⁰³ or an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹⁰⁴ , more preferably a carbon number 1 which may be substituted by Z ¹⁰³ An alkyl group of 10 or an aryl group having 6 to 14 carbon atoms which may be substituted by Z ¹⁰⁴ , more preferably an alkyl group having 1 to 6 carbon atoms which may be substituted by Z ¹⁰³ or a carbon number of 6 to 10 which may be substituted by Z ¹⁰⁴ The aryl group is more preferably an alkyl group having 1 to 4 carbon atoms which may be substituted by Z ¹⁰³ or a phenyl group which may be substituted by Z ¹⁰⁴ .

Further, the plural R's may all be the same or different, and the plural R' may all be the same or different.

Z ^{101 is} preferably a halogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹⁰⁵ , more preferably a fluorine atom or a phenyl group which may be substituted by Z ¹⁰⁵ , and is preferably absent (i.e., unsubstituted).

Further, Z ^{102 is} preferably a halogen atom or an alkyl group having 6 to 20 carbon atoms which may be substituted by Z ¹⁰⁵ , more preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by Z ¹⁰⁵ , and most preferably Exist (ie, non-substituted).

Further, Z ¹⁰³ is preferably a halogen atom, a phenyl group may be substituted by Z of ^{105, 105} may be substituted with Z of furanyl, epoxy cyclohexyl group, glycidoxy group, Bing Xixi methyl group, an oxygen Bing Xixi a ureido group, a ureido group, a thiol group, an isocyanate group, an amine group, a phenylamine group which may be substituted by Z ¹⁰⁵ or a diphenylamino group which may be substituted by Z ¹⁰⁴ , more preferably a halogen atom, more preferably a fluorine atom Or does not exist (ie, non-substitution).

And, Z ¹⁰⁴ is preferably a halogen atom, an alkyl group may be substituted by Z ¹⁰⁵ of 1 to 20 carbon atoms, the substituents Z may be the ¹⁰⁵ furanyl, epoxy cyclohexyl group, glycidoxy group, methyl Bing Xixi group, Bing Xixi group, a ureido group, a thiol group, isocyanate group, amino group, Z may be a substituted phenyl group of ¹⁰⁵ or ¹⁰⁵ may be substituted with Z bis phenyl group, more preferably a halogen atom, More preferably, it is a fluorine atom or is absent (i.e., non-substituted).

Further, Z ^{105 is} preferably a halogen atom, more preferably a fluorine atom or is absent (i.e., unsubstituted).

Specific examples of the organodecane compound which can be used in the present invention are listed below, but are not limited thereto.

Specific examples of the dialkoxy decane compound include, for example, dimethyldimethoxydecane, dimethyldiethoxydecane, methylethyldimethoxydecane, and diethyldimethoxydecane. Diethyldiethoxydecane, methylpropyldimethoxydecane, methylpropyldiethoxydecane, diisopropyldimethoxydecane, phenylmethyldimethoxydecane, ethylene Methyldimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-(3,4- Epoxycyclohexyl)ethylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxy Decane, 3-mercaptopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, N-(2-aminoethyl)aminopropylmethyldimethoxydecane , 3,3,3-trifluoropropylmethyldimethoxydecane, and the like.

Specific examples of the trialkoxydecane compound include, for example, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, and propyltrimethoxydecane. Propyl triethoxy decane, butyl trimethoxy decane, butyl triethoxy decane, pentyl tri Methoxy decane, pentyl triethoxy decane, heptyl trimethoxy decane, heptyl triethoxy decane, octyl trimethoxy decane, octyl triethoxy decane, dodecyl trimethoxy Decane, dodecyltriethoxydecane, hexadecyltrimethoxynonane, hexadecyltriethoxydecane,octadecyltrimethoxydecane,octadecyltriethoxydecane,phenyl Trimethoxy decane, phenyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropene醯oxypropyl triethoxy decane, triethoxy (4-(trifluoromethyl)phenyl) decane, dodecyl triethoxy decane, 3,3,3-trifluoropropyltrimethyl Oxydecane, (triethoxydecyl) cyclohexane, perfluorooctylethyltriethoxydecane, triethoxyfluorodecane, tridecafluoro-1,1,2,2-tetrahydroxin Triethoxy decane, pentafluorophenyl three Oxy decane, pentafluorophenyl triethoxy decane, 3-(heptafluoroisopropoxy)propyl triethoxy decane, heptafluoro-1,1,2,2-tetrahydroindenyl triethyl Oxydecane, triethoxy-2-thienyldecane, 3-(triethoxydecylalkyl)furan, and the like.

Specific examples of the tetraalkoxydecane compound include tetramethoxynonane, tetraethoxysilane, tetrapropoxydecane, and the like.

Among these, 3,3,3-trifluoropropylmethyldimethoxydecane, triethoxy(4-(trifluoromethyl)phenyl)decane, 3,3,3- are preferred. Trifluoropropyltrimethoxydecane, perfluorooctylethyltriethoxydecane, pentafluorophenyltrimethoxydecane, pentafluorophenyltriethoxydecane, and the like.

Organic decane compound in the charge transport varnish of the invention The content of the substance is usually about 0.1 to 50% by mass based on the total mass of the charge transporting substance and the dopant, but if the amount of the film obtained by the suppression is lowered, the charge transportability of the film is lowered, and the hole transport layer is improved. Or the opposite side of the anode of the light-emitting layer or the like, and the hole injection energy of the layer to be laminated in contact with the hole injection layer is preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and still more Good is about 1~20% by mass.

In the charge transporting varnish of the present invention, other known dopants may be used as long as the effects of the present invention are not impaired.

Other dopants include, for example, benzenesulfonic acid, tosic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid. (Sulfosalicylic Acid), p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid , dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonate Acid, hexylnaphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dimercapto-4-naphthalenesulfonic acid, diterpene Naphthalene disulfonic acid, 2,7-dimercapto-4,5-naphthalene disulfonic acid, 1,4-benzodioxane disulfonic acid compound described in International Publication No. 2005/000832, International Publication No. An arylsulfonic acid compound described in No. 2006/025342, an arylsulfonic acid compound described in International Publication No. 2009/096352, an arylsulfonium compound such as polystyrenesulfonic acid, or the like; Based on compounds and the like.

[Charge transport material]

The charge transporting material of the present invention contains a charge transporting substance, a dopant, and an organic solvent, and the dopant contains at least one selected from the group consisting of a heteropoly acid and a halogenated tetracyanoquinodimethane and a halogenated or cyanoquinone. That is, at least one selected from the group consisting of tetracyanoquinone dimethane halide, phenyl halide, and benzoquinone. Such a charge transporting material exhibits good solubility to an organic solvent, and as described above, a charge transporting varnish can be easily produced by dissolving the charge transporting material in an organic solvent.

[Charge transport film]

The charge transporting varnish of the present invention is applied onto a substrate and fired to form a charge transporting film on the substrate.

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 the like, and the coating method is used to adjust the varnish viscosity and surface tension. Preferably.

In addition, when the varnish of the present invention is used, the firing environment is not particularly limited, and a film having a uniform film formation surface and high charge transport property can be obtained not only in an atmosphere but also in an inert gas such as nitrogen or a vacuum. .

The varnish of the present invention is characterized in that it is fired not only at a high temperature of 200 ° C or higher but also at a low temperature of less than 200 ° C. The use of the film obtained by the calcination temperature, the degree of charge transport property of the obtained film, the type of the solvent, and the like can be suitably set within a range of from 100 ° C to less than 250 ° C, but the obtained film is used as an organic EL element. Hole When the transport layer or the hole injection layer is used, it is preferably from 130 to 245 ° C, more preferably from 140 to 240 ° C.

Further, at the time of firing, in order to exhibit higher uniform film forming properties or to carry out a reaction on a substrate, a temperature change of two or more stages can be applied. The heating can be carried out using a suitable machine such as a hot plate or an oven.

The film thickness of the charge transporting film is not particularly limited, and is preferably 5 to 200 nm when used as a hole injection layer in the organic EL device. The method of changing the film thickness may be, for example, a method of changing the concentration of the solid component in the varnish or changing the amount of the solution on the substrate during coating.

Since the charge transporting film of the present invention is produced by using the above-described charge transporting varnish of the present invention, it is excellent in not only charge transport property but also flatness.

[Organic EL Element]

The material to be used and the production method for producing the OLED element using the charge transporting varnish of the present invention are as follows, but are not limited thereto.

The electrode substrate to be used is preferably purified by washing with a liquid such as a lotion, alcohol or pure water in advance, for example, an anode substrate, and surface treatment such as UV ozone treatment or oxygen-plasma treatment before use is preferred. . However, when the anode material is mainly composed of an organic substance, surface treatment may not be performed.

An example of a method for producing an OLED element having a hole injection layer composed of a film obtained by the charge transporting varnish of the present invention is as follows.

The charge transporting varnish of the present invention is applied onto the anode substrate by the above method, and the hole injection layer is formed on the electrode by firing. This was introduced into a vacuum vapor deposition apparatus, and the hole transport layer, the light-emitting layer, the electron transport layer, the electron transport layer/hole barrier layer, the electron injection layer, and the cathode metal were sequentially deposited to form an OLED device. Further, an electron blocking layer may be provided between the light-emitting layer and the hole transport layer as necessary.

The anode material may, for example, be a transparent electrode represented by indium tin oxide (ITO), indium zinc oxide (IZO), or a metal anode composed of aluminum or an alloy thereof, and is preferably flat. Processor. A polythiophene derivative or a polyaniline derivative having high charge transportability can also be used.

Further, as other metals constituting the metal anode, there may be mentioned, for example, ruthenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, lanthanum, zirconium, hafnium, molybdenum, niobium, tantalum, palladium, cadmium, Indium, bismuth, antimony, bismuth, antimony, bismuth, giant, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, tungsten, antimony, bismuth, antimony, platinum, gold, titanium, Lead, antimony or alloys of these, etc., but are not limited thereto.

Examples of the material for forming the hole transport layer include (triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, and N, N'-bis (naphthalene-1-). -N,N'-bis(phenyl)-benzidine (α-NPD), N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'-double (phenyl)-9,9-spirobifluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-spirobifluorene, N,N' - bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-anthracene, N,N'-bis(naphthalen-1-yl)-N,N' -bis(phenyl)-9,9-dimethyl-anthracene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-diphenyl -茀,N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-diphenyl-indole, N,N'-bis(naphthalen-1-yl) )-N,N'-bis(phenyl)-2,2'-dimethylbenzidine, 2,2',7,7'-tetrakis(N,N-diphenylamino)-9,9 - Spirobiindole, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-indole, 9,9-bis[4-(N, N-bis-naphthalen-2-yl-amino)phenyl]-9H-indole, 9,9-bis[4-(N-naphthalen-1-yl-N-phenylamino)-phenyl]- 9H-茀, 2,2',7,7'-tetra[N-naphthyl(phenyl)-amino]-9,9-spirobifluorene, N,N'-bis(phenanthrene-9-yl) -N,N'-double ( Bis-benzidine, 2,2'-bis[N,N-bis(biphenyl-4-yl)amino]-9,9-spirobifluorene, 2,2'-bis(N,N- Diphenylamino)-9,9-spirobifluorene, bis-[4-(N,N-bis(p-tolyl)amino)-phenyl]cyclohexane, 2,2',7, 7'-tetrakis(N,N-bis(p-tolyl)amino)-9,9-spirobifluorene, N,N,N',N'-tetra-naphthalen-2-yl-benzidine, N ,N,N',N'-tetra-(3-methylphenyl)-3,3'-dimethylbenzidine, N,N'-di(naphthyl)-N,N'-di(naphthalene) -2-yl)-benzidine, N,N,N',N'-tetrakis(naphthyl)-benzidine, N,N'-di(naphthalen-2-yl)-N,N'-diphenyl Benzidine-1,4-diamine, N ¹ ,N ⁴ -diphenyl-N ¹ ,N ⁴ -di(m-tolyl)benzene-1,4-diamine, N ² ,N ² ,N ⁶ , N ⁶ -tetraphenylnaphthalene-2,6-diamine, tris(4-(quinolin-8-yl)phenyl)amine, 2,2'-bis(3-(N,N-di(p) -toluyl)amino)phenyl)biphenyl, 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4' , 4"-tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), etc., triarylamines, 5,5"-bis-{4-[bis(4-methyl) Oligothiophenes such as phenyl)amino]phenyl}-2,2':5',2"-trithiophene (BMA-3T).

Examples of the material for forming the light-emitting layer include ginseng (8-hydroxyquinoline) aluminum (III) (Alq ₃ ), bis(8-hydroxyquinoline) zinc (II) (Znq ₂ ), and bis(2-methyl-). 8-hydroxyquinoline)-4-(p-phenylphenolate) aluminum (III) (BAlq), 4,4'-bis(2,2-diphenylvinyl)biphenyl, 9,10-di (naphthalen-2-yl)anthracene, 2-t-butyl-9,10-di(naphthalen-2-yl)anthracene, 2,7-bis[9,9-bis(4-methylphenyl)- Ind-2-yl]-9,9-bis(4-methylphenyl)anthracene, 2-methyl-9,10-bis(naphthalen-2-yl)anthracene, 2-(9,9-ring Bis-indol-2-yl)-9,9-cyclocyclobiguanide, 2,7-bis(9,9-cyclocyclobiguanin-2-yl)-9,9-cyclohexane, 2-[9 ,9-bis(4-methylphenyl)-indol-2-yl]-9,9-bis(4-methylphenyl)anthracene, 2,2'-diindenyl-9,9-spin Biguanide, 1,3,5-gin (indol-1-yl)benzene, 9,9-bis[4-(indenyl)phenyl]-9H-indole, 2,2'-linked (9,10- Diphenyl hydrazine), 2,7-dimercapto-9,9-cyclobiguanide, 1,4-bis(indol-1-yl)benzene, 1,3-bis(indol-1-yl)benzene 6,6-bis(biphenyl-4-yl) fused pentabenzene, 3,9-di(naphthalen-2-yl)anthracene, 3,10-di(naphthalen-2-yl)anthracene, ginseng [4- (fluorenyl)-phenyl]amine, 10,10'-bis(biphenyl-4-yl)-9,9'-biguanide, N,N'-di(naphthalen-1-yl)-N,N '-Diphenyl-[1,1':4',1":4",1"'-tetraphenylene]-4,4"'- , 4,4'-bis[10-(naphthalen-1-yl)fluoren-9-yl]biphenyl, dibenzo{[f,f']-4,4',7,7'-tetraphenyl }Dimercapto[1,2,3-cd:1',2',3'-1m]苝, 1-(7-(9,9'-biguan-10-yl)-9,9-di Methyl-9H-indol-2-yl)indole, 1-(7-(9,9'-biguanide-10-yl)-9,9-dihexyl-9H-indol-2-yl)anthracene, 1 , 3-bis(carbazol-9-yl)benzene, 1,3,5-gin (carbazol-9-yl)benzene, 4,4',4"-gin (carbazol-9-yl)triphenyl Amine, 4,4'-bis(carbazol-9-yl)biphenyl (CBP), 4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl, 2 ,7-bis(carbazol-9-yl)-9,9-dimethylindole, 2,2',7,7'-indole (carbazol-9-yl)-9,9-cyclodane , 2,7-bis(carbazol-9-yl)-9,9-di(p-tolyl)anthracene, 9,9-bis[4-(carbazol-9-yl)-phenyl]anthracene, 2,7-bis(carbazol-9-yl)-9,9-cyclobiguanide, 1,4-bis(triphenyldecyl)benzene, 1,3-bis(triphenyldecyl)benzene , bis(4-N,N-diethylamino-2-methylphenyl)-4-methylphenylmethane, 2,7-bis(carbazol-9-yl)-9,9-di Octyl hydrazine, 4,4"-bis(triphenyldecyl)-p-terphenyl, 4,4'-bis(triphenyldecyl)biphenyl, 9-(4-t-butylphenyl -3,6-bis(triphenyldecyl)-9H-carbazole, 9-(4-t-butylphenyl)-3,6-di(trityl)-9H-indole Azole, 9-(4-t-butylphenyl)-3,6-bis(9-(4-methoxyphenyl)-9H-indol-9-yl)-9H-carbazole, 2,6 - bis(3-(9H-carbazol-9-yl)phenyl)pyridine, triphenyl(4-(9-phenyl-9H-fluoren-9-yl)phenyl)decane, 9,9-di Methyl-N,N-diphenyl-7-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-9H-indol-2-amine, 3,5 - bis(3-(9H-carbazol-9-yl)phenyl)pyridine, 9,9-cyclobiguanidin-2-yl-diphenyl-phosphine oxide, 9,9'-(5-( Triphenylsulfonyl)-1,3-phenylene bis(9H-carbazole), 3-(2,7-bis(diphenylphosphino)-9-phenyl-9H-fluorene-9 -yl)-9-phenyl-9H-carbazole, 4,4,8,8,12,12-hexa(p-tolyl)-4H-8H-12H-12C-azadibenzo[cd, Mn]芘,4,7-bis(9H-carbazol-9-yl)-1,10-morpholine, 2,2'-bis(4-(carbazol-9-yl)phenyl)biphenyl, 2,8-bis(diphenylphosphonium)dibenzo[b,d]thiophene, bis(2-methylphenyl)diphenylnonane, bis[3,5-di(9H-carbazole- 9-yl)phenyl]diphenylnonane, 3,6-bis(carbazol-9-yl)-9-(2-ethyl-hexyl)-9H-carbazole, 3-(diphenylphosphonium) 9-(4-(diphenylphosphonium)phenyl)-9H-carbazole, 3,6-bis[(3,5-diphenyl)phenyl]-9-phenylcarbazole Etc., and may also be shared with luminescent dopants Plating a light emitting layer.

The luminescent dopant may, for example, be 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 2,3,6,7-tetrahydro-1,1,7,7 -tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinolizino [9,9a,1gh]coumarin, quinacridone, N,N'-dimethyl Base-quinacridone, tris(2-phenylpyridine)ruthenium (III) (Ir(ppy) ₃ ), bis(2-phenylpyridine) (acetoxyacetone) (Acetylacetonate) ruthenium (III) (Ir ( Ppy) ₂ (acac)), tris[2-(p-tolyl)pyridine]ruthenium (III) (Ir(mppy) ₃ ), 9,10-bis[N,N-bis(p-tolyl)amine蒽, 9,10-bis[phenyl(m-tolyl)amino]indole, bis[2-(2-hydroxyphenyl)benzothiazole (thiazolato)]zinc(II), N ¹⁰ ,N ¹⁰ ,N ¹⁰ ,N ¹⁰ -tetrakis(p-tolyl)-9,9'-bithracene-10,10'-diamine, N ¹⁰ ,N ¹⁰ ,N ¹⁰ ,N ¹⁰ -tetraphenyl -9,9'-biindole-10,10'-diamine, N ¹⁰ ,N ¹⁰ -diphenyl-N ¹⁰ ,N ¹⁰ -dinaphthyl-9,9'-biindole-10,10'- Diamine, 4,4'-bis(9-ethyl-3-carbazolevinylidene)-1,1'-biphenyl, anthracene, 2,5,8,11-tetra-t-butylhydrazine, 1,4-bis[2-(3-N-ethylcarbazolyl)vinyl]benzene, 4,4'-bis[4-(di-p-tolylamino)styrene]biphenyl, 4-(di-p-tolylamino)-4'-[(di-p-toluene) Amino)styryl]indole, bis[3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)]ruthenium(III), 4,4'-bis[4 -(diphenylamino)styryl]biphenyl, bis(2,4-difluorophenylpyridine)tetrakis(1-pyrazolyl)borate ruthenium(III), N,N'-double ( Naphthalen-2-yl)-N,N'-bis(phenyl)-tris(9,9-dimethylexene), 2,7-bis{2-[phenyl(m-tolyl)amine ]]-9,9-dimethyl-indol-7-yl}-9,9-dimethyl-anthracene, N-(4-((E)-2-(6((E)-4-) Diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylaniline, fac-铱(III) ginseng (1-phenyl-3-methylbenzimidazoline) -2-subunit-C, C ² ), mer-铱(III) ginseng (1-phenyl-3-methylbenzimidazolidin-2-ylidene-C, C ² ), 2,7-double [4-(Diphenylamino)styryl]-9,9-cyclohexane, 6-methyl-2-(4-(9-(4-(6-methylbenzo[d]]] Thiazol-2-yl)phenyl)indole-10-yl)phenyl)benzo[d]thiazole, 1,4-bis[4-(N,N-diphenyl)amino]styrylbenzene, 1,4-bis(4-(9H-carbazol-9-yl)styryl)benzene, (E)-6-(4-(diphenylamino)styryl)-N,N-di Phenylnaphthalen-2-amine, bis(2,4-difluorophenylpyridine)(5-(pyridin-2-yl)-1H-tetrazole) ruthenium (III), bis(3-trifluoromethyl- 5-(2-pyridyl) (pyridazole) ((2,4-difluorobenzyl)diphenylphosphinate) ruthenium (III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazole) Benzyldiphenylphosphonite) ruthenium (III), bis(1-(2,4-difluorobenzyl)-3-methylbenzimidazolium) (3-(trifluoromethyl)-5 -(2-pyridyl)-1,2,4-triazole) ruthenium (III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazole) (4',6'-di Fluorophenylpyridine) ruthenium (III), bis(4',6'-difluorophenylpyridine) (3,5-bis(trifluoromethyl)-2-(2'-pyridyl)pyrrole) (III), bis(4',6'-difluorophenylpyridine)(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole) ruthenium(III) (Z)-6-Trimethylphenyl-N-(6-trimethyls(Mesityl)quinoline-2(1H)-ylidenequinolin-2-amine-BF ₂ , (E)-2-( 2-(4-(Dimethylamino)styryl)-6-methyl-4H-pyran-4-ylidene)malononitrile, 4-(dicyanomethylidene)-2-methyl Base-6-julonidine-9-alkenyl-4H-pyran, 4-(dicyanomethylidene)-2-methyl-6-(1,1,7,7-tetramethyl for a long time Lonidine-9-alkenyl)-4H-pyran, 4-(dicyanomethylidene)-2-t-butyl-6-(1,1,7,7-tetramethyljuloloni D--4-yl-vinyl)-4H-pyran, tris(diphenylmercaptomethane)phenanthroline iridium(III), 5,6,11,12-tetraphenyl Tetraphenyl, bis(2-benzo[b]thiophen-2-yl-pyridine) (acetamidine) ruthenium (III), tris(1-phenylisoquinoline) ruthenium (III), bis(1-benzene Isoquinoline)(acetonitrile) ruthenium(III), bis[1-(9,9-dimethyl-9H-indol-2-yl)-isoquinoline](acetamidineacetone) ruthenium(III) , bis[2-(9,9-dimethyl-9H-indol-2-yl)quinoline](acetamidineacetone) ruthenium(III), tris[4,4'-di-t-butyl-( 2,2')-dipyridine] ruthenium (III). Bis(hexafluorophosphate), tris(2-phenylquinoline)iridium(III), bis(2-phenylquinoline)(acetamidineacetone)ruthenium(III), 2,8-di-t-butyl -5,11-bis(4-t-butylphenyl)-6,12-diphenyltetracene, bis(2-phenylbenzothiazole) (acetamidine) ruthenium (III) ,5,10,15,20-tetraphenyltetrabenzoporphyrin platinum, ruthenium (II) bis(3-trifluoromethyl-5-(2-pyridine)-pyrazole) dimethylphenylphosphine , (II) bis(3-(trifluoromethyl)-5-(4-t-butylpyridyl)-1,2,4-triazole)diphenylmethylphosphine, ruthenium (II) double (3-(Trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole)dimethylphenylphosphine, ruthenium (II) bis(3-(trifluoromethyl)- 5-(4-t-butylpyridyl)-1,2,4-triazole)dimethylphenylphosphine, bis[2-(4-n-hexylphenyl)quinoline](acetonitrile)铱(III), tris[2-(4-n-hexylphenyl)quinoline]ruthenium(III), tris[2-phenyl-4-methylquinoline]ruthenium(III), bis(2-benzene (quinoquinoline) (2-(3-methylphenyl)pyridinyl) ruthenium (III), bis(2-(9,9-diethyl-indol-2-yl)-1-phenyl-1H- Benzo[d]imidazole (imidazolato) (acetamidine) ruthenium (III), bis(2-phenylpyridine) (3-(pyridin-2-yl)-2H-chromene-2-ione (onate) )) bismuth (III), bis(2-phenylquinoline) (2,2,6,6-tetramethylheptane) -3,5-dionis) ruthenium (III), bis(phenylisoquinoline) (2,2,6,6-tetramethylheptane-3,5-dioniin) ruthenium (III), Ruthenium (III) bis(4-phenylthieno[3,2-c]pyridine-N,C ² )acetamidineacetone, (E)-2-(2-t-butyl-6-(2-( 2,6,6-Trimethyl-2,4,5,6-tetrahydro-1H-pyrrolo[3,2,1-ij]quinolin-8-yl)vinyl)-4H-pyran- 4-subunit)malononitrile, bis(3-trifluoromethyl-5-(1-isoquinolinyl)pyrazole)(methyldiphenylphosphine)indole, bis[(4-n-hexylbenzene) (isoquinoline) (acetamidine) ruthenium (III), platinum (II) octaethyl porphin, bis(2-methyldibenzo[f,h]quinoxaline) (acetamidine) oxime (III), tris[(4-n-hexylphenyl)hydroxyquinoline]indole (III), and the like.

Examples of the material for forming the electron transport layer/hole barrier layer include, for example, 8-hydroxyquinoline-lithium, 2,2',2"-(1,3,5-benzyltolyl)-tris(1-phenyl). 1-H-benzimidazole), 2-(4-biphenyl)5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,9-dimethyl- 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl- 1,10-phenanthroline, bis(2-methyl-8-quinoline)-4-(phenylphenol)aluminum, 1,3-bis[2-(2,2'-bipyridine- 6-yl)-1,3,4-oxadiazol-5-yl]benzene, 6,6'-bis[5-(biphenyl-4-yl)-1,3,4-oxadiazole-2 -yl]-2,2'-bipyridine, 3-(4-biphenyl)-4-phenyl-5-t-butylphenyl-1,2,4-triazole, 4-(naphthalene- 1-yl)-3,5-diphenyl-4H-1,2,4-triazole, 2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthrene Rotunolin, 2,7-bis[2-(2,2'-dipyridin-6-yl)-1,3,4-oxadiazol-5-yl]-9,9-dimethylhydrazine, 1 ,3-bis[2-(4-t-butylphenyl)-1,3,4-oxadiazol-5-yl]benzene, tris(2,4,6-trimethyl-3-(pyridine) 3-yl)phenyl)borane, 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazole [4,5f][1,10]phenanthroline, 2 -(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline, phenyl-dimercaptophosphine oxide, 3,3',5,5'-tetra[(m- Pyridyl)-phenyl-3-yl]biphenyl, 1,3,5-tris[(3-pyridyl)-phenyl-3-yl]benzene, 4,4'-bis(4,6-diphenyl -1,3,5-triazin-2-yl)biphenyl, 1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene, bis(10-hydroxybenzo[h] Quinoline) oxime, diphenylbis(4-(pyridin-3-yl)phenyl)decane, 3,5-di(indol-1-yl)pyridine, and the like.

Examples of the material for forming the electron injecting layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), and fluorination. Magnesium (MgF ₂ ), cesium fluoride (CsF), strontium fluoride (SrF ₂ ), molybdenum trioxide (MoO ₃ ), aluminum, Li (acac), lithium acetate, lithium benzoate, and the like.

Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, rubidium, and the like.

The material forming the electron blocking layer may, for example, be tris(phenylpyrazole)fluorene or the like.

The method for producing the PLED element using the charge transporting varnish of the present invention is not particularly limited, and examples thereof include the following methods.

In the OLED element fabrication, instead of performing a vacuum vapor deposition operation of the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer, the hole transport polymer layer and the light-emitting polymer layer are sequentially formed. A PLED element having a charge transporting film formed of the charge transporting varnish of the present invention was produced.

Specifically, the charge transporting varnish of the present invention is applied onto an anode substrate, and a hole injection layer is formed by the above method, and a hole transporting polymer layer and a light emitting polymer layer are sequentially formed thereon, and then The cathode electrode was vapor-deposited to form a PLED element.

The cathode and anode materials used can be the same as those used in the production of the above OLED element, and can be subjected to the same cleaning treatment and surface treatment.

The method for forming the hole transporting polymer layer and the luminescent polymer layer may be, for example, adding a solvent to a hole transporting polymer material or a luminescent polymer material or a material to which a dopant is added. Or a method of uniformly dispersing and applying it to a hole injection layer or a hole transporting polymer layer, followed by firing to form a film.

The hole transporting polymer material may, for example, be poly[(9,9-dihexylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl]-1 ,4-diaminophenylene)], poly[(9,9-dioctylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1 , 1'-biphenyl-4,4-diamine)], poly[(9,9-bis{1'-pentene-5'-yl}茀-2,7-diyl)-co-( N,N'-bis{p-butylphenyl]-1,4-diaminophenylene)], Poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine], poly[(9,9-贰) terminated with polysesquioxanes Dioctylindole-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)] and the like.

The luminescent polymer material is, for example, a polyfluorene derivative such as poly(9,9-dialkylfluorene) (PDAF) or poly(2-methoxy-5-(2'-ethylhexyloxy)- a polyphenylene derivative such as 1,4-phenylene vinylene) (MEH-PPV), a polyphenylene derivative such as poly(3-alkylthiophene) (PAT), or a polyvinyl carbazole ( PVCz) and so on.

The solvent may, for example, be toluene, xylene, chloroform or the like. Examples of the dissolution or uniform dispersion method include stirring, heating and stirring, and ultrasonic dispersion.

The coating method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating method. Further, the coating is preferably carried out under an inert gas such as nitrogen or argon.

The firing method may, for example, be a method of heating in an oven or a hot plate under an inert gas or in a vacuum.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. Also, the device used is as follows.

(1) Substrate washing: Changzhou Industry Co., Ltd. Substrate cleaning device (decompression) Pulp method)

(2) Coating of varnish: Mikasa (share) Rotary coating machine MS-A100

(3) Measurement of film thickness: (s) 坂 坂 research institute Micro shape measuring machine SurfcorderET-4000

(4) Production of EL components: Changzhou Industry (stock) system Multi-function evaporation equipment system C-E2L1G1-N

(5) Measurement of brightness of EL element, etc.: (Yes) I-V-L measurement system manufactured by Tech world

(6) Life measurement of EL element (durability evaluation): (share) E etch Sea system Organic EL brightness life evaluation system PEL-105S

(7) NMR measurement: JNM-ECX300 FT NMR SYSTEM made by Nippon Electronics Co., Ltd.

(8) MS measurement: Bruker (automatic) autoflex III smartbem

[Synthesis Example 1] Synthesis of thiophene derivative 2

The thiophene derivative 2 (TP2) represented by the formula (X1) is synthesized by the following method.

Wear 2,3-dihydrothieno[3,4-b][1,4] in the flask 2.0 g of oxin and 150 mL of tetrahydrofuran were replaced with nitrogen, and then cooled to -78 °C. After dropping 10 mL of n-hexane solution of n-butyllithium (concentration: 1.64 mol/L), the mixture was stirred at -78 ° C for 30 minutes, and then heated to -40 ° C. After dropping 5 mL of tributylchlorostannane, the temperature was raised to room temperature. Stir for 16 hours.

After the completion of the stirring, the reaction mixture was concentrated, and the mixture was combined with n-hexane and filtered. Then, the obtained filtrate was concentrated to obtain 7.4 g of a mixture containing tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylstannane.

Next, 1.5 g of 5,5'-dibromo-2,2'-dithiophene and 0.27 g of tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) were placed in a separate flask to carry out nitrogen substitution. . 6.2 g of the above mixture containing tributyl (2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane and N,N-dimethylformamidine were added thereto. 20 mL of the amine was heated to 125 ° C and stirred for 2 hours.

After completion of the stirring, the mixture was cooled to room temperature, and n-hexane was added thereto to carry out liquid separation, and the obtained N,N-dimethylformamide layer was dropped into a mixed solution of ion-exchanged water and methanol to carry out reprecipitation.

Then, the precipitate was recovered by filtration, and dried to obtain TP2 (yield: 1.4 g, yield: 66%). The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCL ₃ ) δ: 7.11 (d, J = 4.2 Hz, 2H), 7.07 (d, J = 4.2 Hz, 2H), 6.23 (s, 2H), 4.37-4.33 (m, 4H), 4.28-4.24 (m, 4H).

[Synthesis Example 2] Synthesis of thiophene derivative 3 (1) Synthesis of 5-tributylstannyl-2,2'-dithiophene

4.0 g of 2,2'-bisthiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel, and after nitrogen substitution, 120 mL of tetrahydrofuran was added thereto, followed by cooling to -78 °C. While maintaining the temperature at -78 ° C, 14.7 mL of a n-hexane solution of n-butyllithium (concentration: 1.64 mol/L) was added, followed by stirring for 30 minutes. After dropping 7.8 mL (d1.20) of tri-n-butyl chlorostannane, the mixture was stirred for 10 minutes, and then the mixture was warmed to room temperature and stirred. After 6 hours, the reaction mixture was concentrated, and 50 ml of n-hexane was added to the residue, and the insoluble material was removed by filtration (cake washed: n-hexane 30 mL). The resulting filtrate was concentrated. After drying, 12.64 g of a dark red oil containing 5-tributylstannyl-2,2'-dithiophene was obtained. The purification was carried out without further purification. The yield of this step was 100% (theoretical yield: 10.96 g), and the purity (10.96 / 12.64 × 100 = 86.7%) was calculated and used as a raw material of the next step.

(2) Synthesis of thiophene derivative 3

The thiophene derivative 3 (TP3) represented by the formula (X4) is synthesized by the following method.

2.0 g of tributylphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.24 g of Pd(PPh ₃ ) _{4 were} placed in a reaction vessel, and after nitrogen substitution, 5-trimethyltin-tin synthesized by [1] was added. A solution of 7.8 g (purity of 86.7%) of alkyl-2,2'-dithiophene in dimethylformamide (DMF) was 100 mL. After stirring at 110 ° C for 2.5 hours, the reaction solution was reprecipitated with 1.5 L of methanol. After the slurry was stirred at room temperature for 15 hours, it was filtered, and 90 mL of toluene, 10 mL of ethanol, and 0.75 g of activated carbon were added to the obtained filtrate, and the mixture was stirred under reflux for 1 hour. Filtration was carried out while hot, and the obtained filtrate was cooled to 0 ° C under stirring, and stirring was continued at 0 ° C for 2 hours. The slurry was filtered, and the filtrate was dried (80 ° C, 2 hours) to give TP3 (yield: 1.4 g, yield 47%). The measurement results of ¹ H-NMR and TOF-MS are shown below.

¹ H-NMR (300 MHz, CDCl ₃ ) δ [ppm]: 7.51 (d, J = 8.4 Hz, 6H), 7.13 - 7.22 (m, 18H), 7.01 - 7.04 (m, 3H).

MALDI-TOF-MS m/Z found: 737.29 ([M] ⁺ calcd:737.05)

[Synthesis Example 3] Synthesis of thiophene derivative 4

The thiophene derivative 4 (TP4) represented by the formula (X2) was synthesized by the following method.

2.00 g of thienothiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 mL of dimethylformamide (DMF) were placed in a reaction vessel, and after stirring at room temperature to confirm dissolution, N-bromosuccinimide was added. (Bromosuccinimide: NBS) 6.10 g (2.4 eq) was put in a powder state. After confirming the disappearance of the raw materials, n-hexane and ion-exchanged water were added to the reaction liquid to carry out liquid separation. The organic layer was washed once with ion-exchanged water and saturated brine, and dried with Na ₂ SO ₄ . The solvent was distilled off under reduced pressure and dried to give 4.21 g (yield: 99%) of the desired thiophenethiophene dibromide.

Next, 1.93 g of thienothiophene dibromide, 0.75 g (10 mol%) of Pd(PPh ₃ ) ₄ , and pinacol ester (manufactured by Aldrich Co., Ltd.) of 4.00 g of thienothiophene dibromide were added under a nitrogen atmosphere. 43 mL of dimethoxyethane (DME) and 16.2 mL (5 eq) of a 2 mol/L K ₂ CO ₃ aqueous solution were stirred under heating and reflux for 5 hours to carry out a reaction. After the completion of the reaction, n-hexane was added thereto, and the mixture was stirred at room temperature for 30 minutes, and then the insoluble material was removed by filtration. The filtrate was washed twice with ion-exchanged water and once with saturated brine. After drying over Na ₂ SO ₄ , the solvent was evaporated under reduced pressure, and the residue was separated and purified by column chromatography to afford TP 4 (yield 85%). The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (300MHz, CDCl ₃ ) δ [ppm]: 7.24 (s, 2H), 7.21 (d, J = 5.1 Hz, 2H), 6.96 (d, J = 5.3 Hz, 2H), 2.79 (t, J = 7.4 Hz, 4H), 1.60-1.70 (m, 4H), 1.27-1.42 (m, 12H), 0.88 (t, J = 6.9 Hz, 6H).

[Synthesis Example 4] Synthesis of thiophene derivative 5

The thiophene derivative 5 (TP5) represented by the formula (X3) is synthesized by the following method.

Under a nitrogen atmosphere, 1.50 g of benzodithiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel, and 50 mL of tetrahydrofuran (THF) was added thereto, followed by cooling to -78 °C. After 19.2 mL of a n-hexane solution of n-butyllithium (concentration: 1.64 mol/L, 4 eq) was added thereto, the mixture was stirred for 1.5 hours. Further, 8.6 mL (4 eq) of tri-n-butyl chlorostannane was added dropwise thereto, and the reaction was further carried out at 1 hour to -78 ° C, then the cooling bath was removed and the mixture was warmed to room temperature. After reaching room temperature, the solvent was distilled off under reduced pressure, and the precipitate obtained in the obtained slurry was filtered and dried to obtain 11.84 g of a mixture containing the desired benzodithiophene bis stannyl. Further, without further purification, when the yield of this step was taken as 100% (theoretical yield: 6.07 g), the purity (6.07/11.84 × 100 = 51.3%) was calculated and used as a raw material of the next step.

Next, 5.92 g of a mixture containing the obtained benzodithiophene bisstannyl group and 2.25 g (2.2 eq) of 2-bromo-3-n-hexylthiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed under a nitrogen atmosphere. 25 mL of toluene and 0.230 g (5 mol%) of Pd(PPh ₃ ) _{4 were} placed in a reaction vessel, and the mixture was stirred under reflux for 4.5 hours to cause a reaction. After standing to cool to room temperature, chloroform and ion-exchanged water were added for liquid separation. The solvent of the obtained organic layer was distilled off under reduced pressure, and methanol was added to the obtained yellow slurry, and the insoluble matter was filtered off. After the activated carbon treatment of the filtrate, the solvent was distilled off under reduced pressure, and ethanol and toluene were added to the residue, and the mixture was stirred under heating and reflux to confirm complete dissolution, and then allowed to cool to room temperature. In this state, the mixture was stirred at room temperature for one night, and then filtered and dried to obtain TP5 (yield: 1.40 g, yield of a yield of 68%). The measurement results of ¹ H-NMR and TOF-MS are shown below.

¹ H-NMR (300MHz, CDCl ₃ ) δ [ppm]: 8.16 (s, 2H), 7.34 (s, 2H), 7.26 (d, J = 5.1 Hz, 2H), 6.98 (d, J = 5.1 Hz, 2H), 2.87 (t, J = 8.0 Hz, 4H), 1.63-1.74 (m, 4H), 1.30-1.42 (m, 12H), 0.88 (t, J = 6.6 Hz, 6H).

MALDI-TOF-MS m/Z found:521.87([M] ⁺ calcd:522.15)

[Synthesis Example 5] Synthesis of aniline derivative 1 (AN1)

The aniline derivative 1 (AN1) represented by the formula (X5) was synthesized by the following method.

2.00 g of N,N'-diphenylbenzidine, 4.25 g of 4-bromo-N,N-diphenylaniline, 68.4 mg of Pd(dba) ₂ and 1.49 g of ^t BuONa were placed in a reaction vessel to carry out nitrogen. After the substitution, 20 mL of toluene and 1.0 mL of a toluene solution of P( ^t Bu) ₃ prepared separately (concentration: 47.2 g/L) were added, and the mixture was stirred at 50 ° C for 7 hours to carry out a reaction. After cooling to room temperature, the reaction solution was filtered, and the obtained filtrate was washed with ion-exchanged water. Filtration was further carried out, and the obtained filtrate was dried to obtain AN1 (yield: 4.46 g, yield: 91%). The measurement results of TOF-MS are as follows.

MALDI-TOF-MS m/Z found: 822.25 ([M] ⁺ calcd: 822.37).

[Synthesis Example 6] Synthesis of aniline derivative 2 (AN2)

The aniline derivative 2 (AN2) represented by the formula (X6) was synthesized by the following method.

1.00 g of N,N'-diphenylbenzidine, 1.96 g of 3-bromo-9-ethylcarbazole, 34.7 mg of Pd(dba) _{2 and} 0.860 g of ^t BuONa were placed in a reaction vessel to carry out nitrogen substitution. , 15mL of toluene was added and separately prepared of P ^(t Bu) ₃ 0.51 mL of a toluene solution (concentration of 47.2g / L), stirred at 50 ℃ 6.5 hours the reaction. After cooling to room temperature, toluene and saturated brine were added for liquid separation. After the obtained organic layer was dried over Na ₂ SO ₄ , activated carbon was added and stirred at room temperature for 30 minutes. The activated carbon was removed by filtration and concentrated. The obtained concentrated liquid was dropped into a mixed solvent of MeOH-AcOEt, and stirred at room temperature. After the slurry solution was filtered and dried, the slurry was washed with a toluene-methanol mixed solvent. After filtration, the obtained powder was dried to obtain AN2 (yield: 1.87 g, yield: 87%). The measurement results of ¹ H-NMR are shown below.

^{1 H-NMR (300MHz, DMSO} -d6) δ [ppm]: 8.10 (d, J = 7.8Hz, 2H), 7.99 (d, J = 1.8Hz, 2H), 7.59-7.66 (m, 4H), 7.42 -7.51 (m, 6H), 7.23 - 7.29 (m, 7H), 6.94 - 7.18 (m, 11H).

[2] Modulation of charge transport varnish [Example 1-1]

3,3"'-dihexyl-2,2':5',2":5",2"'-tetrathiophene (manufactured by Sigma-Aldrich Co. LLC., hereinafter referred to as TP1) 0.050 g, phosphorus 0.250 g of tungstic acid (PTA, manufactured by Kanto Chemical Co., Ltd.) and 0.045 g of F4TCNQ (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 1,3-dimethyl-2-imidazolidinone (DMI) under nitrogen atmosphere 3.2g. To the resulting solution, 4.9 g of cyclohexanol (CHA) and 1.6 g of propylene glycol (PG) were added, and then a charge transporting varnish was prepared by stirring.

[Example 1-2]

TP1 (0.052 g), PTA (0.258 g) and F4TCNQ (0.031 g) were dissolved in DMI (2 g) under a nitrogen atmosphere. To the obtained solution, CHA (2 g) and 6 g of diethylene glycol dimethyl ether (Diglyme) were added, and the charge transport varnish was prepared by stirring.

[Example 1-3]

TP1 (0.052 g), PTA (0.258 g) and F4TCNQ (0.031 g) were dissolved in DMI (2 g) under a nitrogen atmosphere. To the obtained solution, 8 g of propylene glycol monomethyl ether (PGME) was added, and the charge transporting varnish was stirred and stirred.

[Example 1-4]

TP1 (0.052 g), PTA (0.258 g) and F4TCNQ (0.031 g) were dissolved in DMI (2 g) under a nitrogen atmosphere. To the obtained solution, PGME (8 g) was added, and after stirring, 0.031 g of pentafluorophenyltriethoxydecane was added, and the charge transporting varnish was further stirred.

[Example 1-5]

TP1 (0.017 g), PTA (0.083 g) and F4TCNQ (0.010 g) were dissolved in DMI (0.98 g) under a nitrogen atmosphere. To the obtained solution, 0.49 g of diethylene glycol monomethyl ether (DEGME) and PGME (3.43 g) were added, and after stirring, 0.001 g of 3,3,3-trifluoropropyltrimethoxydecane and phenyltrimethyl group were added. The oxydecane was 0.009 g, and the charge transporting varnish was further stirred.

[Example 1-6]

TP2 (0.052 g), PTA (0.258 g) and F4TCNQ (0.031 g) were dissolved in DMI (2 g) under a nitrogen atmosphere. To the obtained solution, CHA (2 g) and Diglyme (6 g) were added, and the charge transport varnish was prepared by stirring.

[Examples 1-7]

TP3 (0.062 g), PTA (0.309 g) and F4TCNQ (0.026 g) were dissolved in DMI (3.6 g) under a nitrogen atmosphere. 2.4 g of 1,3-butanediol and Diglyme (6.0 g) were added to the obtained solution, and the charge-transporting varnish was prepared by stirring.

[Examples 1-8]

TP4 (0.034 g), PTA (0.170 g) and F4TCNQ (0.020 g) were dissolved in DMI (2 g) under a nitrogen atmosphere. To the obtained solution, DEGME (1 g) and PGME (7 g) were added, and after stirring, 0.007 g of 3,3,3-trifluoropropyltrimethoxydecane and 0.014 g of phenyltrimethoxydecane were added, and the charge transport was carried out by stirring. Varnish.

[Examples 1-9]

TP5 (0.034 g), PTA (0.170 g) and F4TCNQ (0.031 g) were dissolved in DMI (2 g) under a nitrogen atmosphere. To the obtained solution, DEGME (1 g) and PGME (7 g) were added and stirred, and 0.007 g of 3,3,3-trifluoropropyltrimethoxydecane and 0.014 g of phenyltrimethoxydecane were added and stirred and stirred. Charge transport varnish.

[Example 1-10]

AN1 (0.046 g), PTA (0.202 g) and F4TCNQ (0.156 g) were dissolved in 20 g of cyclohexanone (CHN) under a nitrogen atmosphere. To the obtained solution, 0.007 g of 3,3,3-trifluoropropyltrimethoxydecane and 0.014 g of phenyltrimethoxydecane were added, and the charge transporting varnish was prepared by stirring.

[Examples 1-11]

AN2 (0.042 g), PTA (0.202 g) and F4TCNQ (0.160 g) were dissolved in CHN (20 g) under a nitrogen atmosphere. To the obtained solution, 0.007 g of 3,3,3-trifluoropropyltrimethoxydecane and 0.014 g of phenyltrimethoxydecane were added, and the charge transporting varnish was prepared by stirring.

[Comparative Example 1-1]

TP1 (0.124 g) and PTA (0.247 g) were dissolved in DMI (4 g) under a nitrogen atmosphere. To the obtained solution, CHA (6 g) and PG (2 g) were added, and the charge transport varnish was prepared by stirring.

[Comparative Example 1-2]

Try to modulate the charge by using TP1 (0.050g), PTA (0.250g) and tetracyanoquinodimethane 0.045g, and DMI (3.2g), CHA (4.9g) and PG (1.6g) under nitrogen atmosphere. Conveying varnish. However, the solid component is not dissolved, and it is impossible to obtain a uniform film which can be used for the organic EL element. Varnish.

[3] Manufacturing and characterization of organic EL components [Example 2-1]

The varnish obtained in Example 1-1 was applied onto an ITO substrate using a spin coater, and then dried at 50 ° C for 5 minutes, followed by firing at 150 ° C for 10 minutes in an atmosphere, and 30 nm was formed on the ITO substrate. Uniform film. The ITO substrate is a 25 mm × 25 mm × 0.7 t glass substrate having a thickness of 150 nm on the surface of the indium tin oxide (ITO), and the O ₂ plasma cleaning device (150 W, 30) is used before use. Seconds) remove impurities from the surface.

Next, a thin film of α-NPD, Alq ₃ , lithium fluoride, and aluminum was laminated on the ITO substrate on which the thin film was formed by using a vapor deposition apparatus (vacuum degree: 1.0 × 10 ^-5 Pa) to obtain an organic EL device. At this time, the vapor deposition rate was carried out under conditions of α-NPD, Alq ₃ and aluminum of 0.2 nm/sec and lithium fluoride of 0.02 nm/sec, and the film thicknesses were 30 nm, 40 nm, 0.5 nm and 120 nm, respectively.

Further, in order to prevent deterioration of characteristics due to the influence of oxygen, water, or the like in the air, the organic EL element is sealed by a sealing substrate, and its characteristics are evaluated. The sealing system is carried out in the following order. The organic EL device was housed between the sealing substrates in a nitrogen atmosphere having an oxygen concentration of 2 ppm or less and a dew point of -85 ° C or less, and the sealing substrate was bonded by a bonding material (XNR5516Z-B1 manufactured by Nagase Chemtex Co., Ltd.). At this time, a water-trapping agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was placed in the sealing substrate together with the organic EL element. The sealed substrate to which the bonding was applied was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6000 mJ/cm ² ), and then annealed at 80 ° C for 1 hour to cure the bonding material.

[Examples 2-2 to 2-7]

An organic EL device was produced in the same manner as in Example 2-1 except that the varnish obtained in Examples 1-2 to 1-7 was used instead of the varnish obtained in Example 1-1.

[Example 2-8~2-9]

The same varnish as in Example 2-1 was used except that the varnish obtained in Example 1-8 to 1-9 was used instead of the varnish obtained in Example 1-1, and firing was performed at 160 ° C instead of firing at 150 ° C. Method An organic EL element was produced.

[Comparative Example 2-1]

An organic EL device was produced in the same manner as in Example 2-1, except that the varnish obtained in Comparative Example 1-1 was used instead of the varnish obtained in Example 1-1.

[Example 2-10]

In place of the varnish obtained in Example 1-10, in place of the varnish obtained in Example 1-1, a film of CBP and Ir(PPy) ₃ and BAlq were sequentially formed using an evaporation apparatus (vacuum degree: 1.0 × 10 ^-5 Pa). An organic EL device was produced in the same manner as in Example 2-1 except that a 40 nm Alq ₃ film was formed using a vapor deposition apparatus (vacuum degree: 1.0 × 10 ^-5 Pa).

CBP and Ir (PPy) ₃ of the thin-film evaporation rate was controlled so that Ir (PPy) ₃ become 6% concentration, co-evaporation with CBP Ir (PPy) ₃ to form a film, a thickness of 40nm. Further, the vapor deposition rate of the film thickness of BAlq was 0.2 nm/second, and the film thickness was 20 nm.

[Embodiment 2-11]

An organic EL device was produced in the same manner as in Example 2-10, except that the varnish obtained in Example 1-11 was used instead of the varnish obtained in Example 1-10.

The luminances of the elements of Examples 2 to 2-9 when the driving voltage was 5 V and the luminance of the elements of Examples 2-10 to 2-11 when the driving current was 0.4 mA were measured. The results are shown in Tables 1 and 2.

As shown in Tables 1 and 2, the varnish of the present invention can realize an organic EL device having excellent luminance characteristics even when it is fired at a low temperature of less than 200 °C.

The durability of the elements obtained in Examples 2 to 8 was evaluated. The half life of the luminance (initial luminance: 5,000 cd/m ² ) is shown in Table 3.

As shown in Table 3, the organic EL device of the present invention is excellent in durability.

Claims (11)

A charge transporting varnish comprising a charge transporting substance, a dopant and an organic solvent, wherein the dopant comprises a heteropoly acid and a halogenated tetracyanoquinodimethane and At least one of halogenated or cyanide benzoquinone. The charge transporting varnish of claim 1, wherein the above-mentioned halogenated tetracyanoquinone dimethane comprises tetracyanoquinone dimethane. A charge transporting varnish according to claim 1 or 2, wherein the above heteropoly acid comprises phosphotungstic acid. The charge transporting varnish according to any one of claims 1 to 3, wherein the charge transporting substance is an aniline derivative or a thiophene derivative. A charge transporting film produced by using the charge transporting varnish according to any one of claims 1 to 4. An organic electroluminescence device characterized by having a charge transporting film according to item 5 of the patent application. The organic electroluminescence device of claim 6, wherein the charge transporting film is a hole injection layer or a hole transport layer. A method for producing a charge transporting film, which is characterized in that the charge transporting varnish according to any one of claims 1 to 4 is applied onto a substrate and fired at less than 200 °C. A method for producing an organic electroluminescence device characterized by using a charge transporting film according to item 5 of the patent application. A charge transporting material which is composed of a charge transporting substance and A charge transporting material composed of a dopant is characterized in that the dopant is at least one selected from the group consisting of a heteropoly acid and a halogenated tetracyanoquinone dimethane and a halogenated or benzoquinone cyanide. A method for planarizing a charge transporting film, which is a planarization method using at least one charge transporting film selected from the group consisting of tetracyanoquinone dimethane halide and halogenated or cyanoquinone cyanide, characterized in that it contains charge transporting The dopant, the dopant, and the organic solvent, wherein the dopant is a charge transporting varnish containing at least one selected from the group consisting of a heteropoly acid and a halogenated tetracyanoquinone dimethane and a halogenated or cyanoquinone.