TWI630193B - Charge-transporting varnish, charge-transporting film, organic electroluminescence element, and method for manufacturing charge-transporting film - Google Patents

Abstract

The present invention provides a film that can be fired at a low temperature of less than 200 ° C. At the same time, the film produced under such firing conditions has high flatness and high charge transport properties. When applied to organic EL elements, it can exhibit excellent EL Element-specific charge-transporting varnish.

The charge-transporting varnish of the present invention is a charge-transporting varnish containing a charge-transporting substance, a dopant, and an organic solvent, and is characterized in that the dopant includes a heteropolyacid and a compound selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and At least one kind of halogenated or cyanoquinone (benzoquinone).

Description

Charge-transporting varnish, charge-transporting film, organic electroluminescence element, and method for manufacturing charge-transporting film

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

In the organic EL device, a charge-transporting thin film made of an organic compound can be used as a light-emitting layer or a charge-injection layer. The method for forming the charge transporting film is roughly divided 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 more efficiently produce a thin film having a large area and a high flatness. Therefore, in the field where a large area of a film such as an organic EL film is desired, most of the films are formed by the wet process. .

In view of this, the present inventors have developed a charge-transporting varnish for producing a charge-transporting film applicable to various electronic devices by a wet process (see, for example, Patent Document 1).

However, in recent years, in the field of organic EL, a substrate made of an organic compound has been used instead of a lighter or thinner element. Glass substrates are therefore required to be sintered at a lower temperature than in the past, and in this case, a varnish having a thin film having good charge transportability is also required.

[Prior technical literature] [Patent Literature]

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

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

As a result of careful research in order to achieve the above-mentioned object, the present inventors have found that a heteropoly acid and at least one selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and a halogenated or cyanobenzoquinone are used in combination as a charge transporter The varnish can be fired not only at a high temperature above 200 ° C, but also at a low temperature below 200 ° C. At the same time, the thin film produced under this firing condition is amorphous, and has high flatness and high charge transportability. When the thin film is used in a hole injection layer, an organic EL device capable of achieving excellent brightness characteristics can be obtained, and the present invention has been completed.

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

A charge-transporting varnish comprising a charge-transporting substance, a dopant, and an organic solvent, wherein the dopant comprises a heteropoly acid and a compound selected from the group consisting of a tetracyanobenzohalide halide. At least one of methane and halogenated or cyanobenzoquinone.

2. The charge-transporting varnish according to the aforementioned item 1, wherein the halogenated tetracyanobenzoquinone dimethane comprises a tetrafluorinated benzoquinone dimethane.

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

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

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

6. An organic electroluminescence device, comprising the charge-transporting film according to item 5 above.

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

8. A method for manufacturing a charge-transporting film, characterized in that the charge-transporting varnish according to any one of the foregoing items 1 to 4 is coated on a substrate and fired at a temperature of less than 200 ° C.

9. A method for manufacturing an organic electroluminescence device, characterized by using the charge-transporting film as described in item 5 above.

10. A charge-transporting material, which is a charge-transporting material composed of a charge-transporting substance and a dopant, characterized in that the above-mentioned dopant includes a heteropoly acid and is selected from a halogenated tetracyanobenzoquinone dimethane And at least one of halogenated or cyanobenzoquinone.

11. A method for planarizing a charge-transporting film, which is a method for planarizing a charge-transporting film using at least one selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and a halogenated or cyanobenzoquinone, characterized in that A charge-transporting substance, a dopant, and an organic solvent. The dopant is a charge-transporting varnish containing a heteropoly acid and at least one selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and a halogenated or cyanated benzoquinone.

By using the charge-transporting varnish of the present invention containing a heteropoly acid and at least one selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and a halogenated or cyanobenzoquinone as a dopant, not only at a high temperature of 200 ° C or higher It can also be fired at a low temperature of less than 200 ° C. It can also be amorphous, with high flatness and high charge transportability. When used in the hole injection layer of an organic EL device, it can achieve a thin film with excellent brightness characteristics. The reason has not been determined, but it is speculated that the use of halogenated tetracyanobenzoquinone dimethane and the like with a heteropolyacid as a dopant with high electron capacity can suppress the crystallization or doping of the thin film caused by using only either Miscellaneous insufficient sake's sake.

In addition, by using the charge-transporting varnish of the present invention, even when various wet processes capable of forming a large-area film are used, such as a spin coating method or a slit coating method, a reproducible film having excellent charge-transporting properties can be produced. Film, so It can also fully respond to the recent progress in the field of organic EL elements.

In addition, 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.

[Mode for Carrying Out the Invention] [Charge-transporting varnish]

The charge-transporting varnish of the present invention contains a charge-transporting substance, a dopant, and an organic solvent. The dopant includes a heteropolyacid and at least 1 selected from the group consisting of halogenated tetracyanobenzoquinone dimethane and halogenated or cyanobenzoquinone. Species, that is, at least one selected from the group consisting of halogenated tetracyanobenzoquinone dimethane, halogenated benzoquinone, and cyanobenzoquinone.

[Charge-transporting substance]

The charge-transporting substance contained in the charge-transporting varnish of the present invention is a substance having a charge-transporting property, that is, a conductive material, and may also have a charge-transporting property itself, or may have a charge when used together with a dopant. Transporters. Particularly, a substance having hole transport properties is preferred.

As such a charge-transporting substance, charge-transporting compounds used in the field of organic EL and the like can be used, and specific examples thereof include oligoaniline derivatives, N, N'-diarylbenzidine derivatives, N, N, N ', N'-tetraarylbenzidine derivatives, such as arylamine derivatives (aniline derivatives), oligothiophene derivatives, thienothiophene derivatives, thiophenobenzothiophene derivatives, etc. Thiophene derivatives, azole derivatives and the like.

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

In addition, the benzoquinone diimine structure refers to a structure in which the double bond in the carbocyclic ring of an aromatic compound is reduced by one, and instead, it has a structure with two extra-ring double bonds in the para or ortho position (so-called quinone structure). The benzoquinone diimide structure of an aryl diamine compound having two amine groups in the para position to each other is 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 an organic solvent used for the charge-transporting substance, and is about 200 to 10,000. From the viewpoint of obtaining a film with a higher charge-transporting property, the reproducibility is good, It is preferably 300 or more, more preferably 400 or more, and from the viewpoint of providing a uniform varnish with good modulation reproducibility and a highly flat film, it is preferably 8,000 or less, more preferably 7,000 or less, still more preferably 6,000 or less, and more It is preferably below 5,000. In addition, during film formation, charge transport is prevented. From the standpoint of separation of the transmissive substances from each other, the charge-transporting compound preferably has no molecular weight distribution (the degree of dispersion is 1) (that is, a single molecular weight is preferred).

[Dopant]

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

The heteropoly acid of the first dopant means a chemical structure represented by a Keggin type represented by the formula (A1) or a Dawson type represented by the formula (A2), having a structure in which a heteroatom is located at the center of the molecule, and vanadium ( V), molybdenum (Mo), tungsten (W) and other oxoacid oxoacid isopoly acid (isopoly acid) polycondensation with oxoacid of different elements and polyacids. The oxyacids of such heterogeneous elements include, for example, oxyacids of silicon (Si), phosphorus (P), and arsenic (As).

Specific examples of the heteropoly acid include, for example, phosphomolybdic acid, silomomolybdic acid, phosphotungstic acid, silototungstic acid, phosphotungstic molybdic acid, and the like. These can be used alone or in combination of two or more. The heteropolyacid used in the present invention can be obtained from a commercially available product, and can also 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, and more preferably phosphotungstic acid. When two or more kinds of heteropoly acids are used, at least one of the two or more kinds of heteropoly acids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.

In addition, in the quantitative analysis of elemental analysis such as heteropoly acid, the structure represented by the general formula is used, and even if the number of elements is large or small, as long as it is obtained from a commercially available product, or it is appropriately synthesized according to a conventional synthesis method In either case, it 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 the quantitative analysis , Even if the amount of P (phosphorus), O (oxygen), W (tungsten), or Mo (molybdenum) in this formula is more or less, as long as it is obtained from a commercially available product, or according to a conventional synthesis method, it is appropriate All synthesizers can be used in the present invention. At this time, the mass of the heteropolyacid specified in the present invention does not refer to the mass of pure phosphotungstic acid (phosphotungstic acid content) in the composition or the commercially available product, but refers to the form and commercially available product. In the form that can be separated by the conventional synthesis method, it contains the full mass of hydrated water or other impurities.

The halogenated tetracyanobenzoquinone dimethane of the second dopant is represented by 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. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred. Further, it is preferred that at least two of R ¹ to R ⁴ are halogen atoms, more preferably at least three are halogen atoms, and most preferably all of them are halogen atoms.

Specific examples of the halogenated tetracyanobenzoquinone dimethane include tetrafluorotetracyanobenzoquinone dimethane (F4TCNQ), tetrachlorotetracyanobenzoquinone dimethane, 2-fluorotetracyanobenzoquinone dimethane, 2 -Chlorotetracyanobenzoquinone dimethane, 2,5-difluorotetracyanobenzoquinone dimethane, 2,5-dichlorotetracyanobenzoquinone dimethane, and the like. Tetracyanobenzoquinone dimethane is particularly preferred as F4TCNQ.

The halogenated or cyanated benzoquinone of the other second dopant is represented by 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 described above, preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom. Further, it is preferred that at least two of R ⁵ to R ⁸ are halogen atoms or cyano groups, more preferably at least three are halogen atoms or cyano groups, and still more preferably all of them are halogen atoms or cyano groups.

Specific examples of halogenated or cyanobenzoquinone are 2,3-dichloro- 5,6-dicyano-p-benzoquinone, trifluorobenzoquinone, tetrafluorobenzoquinone, tetrabromobenzoquinone, tetracyanobenzoquinone, and the like. The halogenated or cyanobenzoquinone is preferably 2,3-dichloro-5,6-dicyano-p-benzoquinone, trifluorobenzoquinone, tetrafluorobenzoquinone, tetracyanobenzoquinone, more preferably 2, 3-dichloro-5,6-dicyano-p-benzoquinone, tetrafluorobenzoquinone, 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 a thiophene derivative is used as a charge transporting substance, the content of the first dopant is a mass ratio of the charge transporting substance composed of the thiophene derivative, which is usually about 0.01 to 100, and more preferably 0.1 to 50. The degree is more preferably 1 to 10. The content of the second dopant means the total solid content (the components contained in the varnish remaining after firing. The same applies hereinafter), about 0.1 to 100% by mass, more preferably 1 to 50% by mass, and even more preferably 5 ~ 30% by mass. A compound in which a thiophene site and an aniline site coexist in the molecule is regarded as a thiophene derivative when the dopant / host ratio is calculated.

When the aniline derivative is used as a charge-transporting substance, the content of the first dopant is in the total solid content, usually about 1 to 500% by mass, preferably about 10 to 200% by mass, and more preferably 50. ~ 150% by mass. The content of the second dopant is expressed in terms of an equivalent ratio to a charge-transporting substance composed of an aniline derivative, and is usually about 0.01 to 100, preferably about 0.1 to 50, and more preferably 1 to 10 degree.

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

[Organic solvents]

As the organic solvent used in the preparation of the charge-transporting varnish, a highly soluble solvent that can well 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. Organic solvents such as ketones and diethylene glycol monomethyl ether. These solvents can be used singly or in combination of two or more kinds. The amount of the solvent used is 5 to 100% by mass based on the entire solvent used in the varnish.

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

In the present invention, the varnish is contained in at least one kind and has 10 to 200 mPa at 25 ° C. s, especially 35 ~ 150mPa. s viscosity, and a high viscosity organic solvent with a boiling point of 50 ~ 300 ° C, especially 150 ~ 250 ° C under normal pressure (atmospheric pressure), it is easy to adjust the viscosity of the varnish. As a result, it has good reproducibility and provides flatness. High film, it can be prepared according to the coating method used.

The high-viscosity organic solvent is not particularly limited, and examples thereof include cyclohexyl Alcohol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3- Butanediol, 1,4-butanediol, propylene glycol, hexanediol, and the like. These solvents can be used singly 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 a range where solids do not precipitate, and in a range where solids do not precipitate, the addition ratio is preferably 5 to 80% by mass.

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

Examples of such a solvent include ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether. 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, and the like, but are not limited thereto. These solvents can be used alone or in combination of two or more.

The viscosity of the varnish of the present invention is suitably set according to the thickness of the film to be produced or the solid content concentration, but it is usually 1 to 50 mPa at 25 ° C. s.

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

[Other ingredients]

The charge-transporting varnish of the present invention may contain an organosilane compound. Specific examples of the organic silane compound include a dialkoxysilane compound, a trialkoxysilane compound, and a tetraalkoxysilane compound. These can be used individually by 1 type or in combination of 2 or more types.

In particular, the organic silane compound preferably contains one selected from a dialkoxysilane compound and a trialkoxysilane compound, and more preferably contains a trialkoxysilane compound.

Examples of the dialkoxysilane compound, trialkoxysilane compound, and tetraalkoxysilane compound include formulas (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 carbon atoms of 1 to 20, the sum may be substituted with Z ¹⁰¹ carbon atoms, alkenyl having 2 to 20, the sum may be substituted with Z ¹⁰¹ carbon atoms, alkynyl of 2 to 20 Group, an 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 with Z ¹⁰⁵ or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 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 can be substituted by Z ¹⁰⁵ , a heteroaryl group having 2 to 20 carbon atoms which can be substituted by Z ¹⁰⁵ , epoxycyclohexyl, glycidyloxy, methyl Propylene fluorenyloxy, propylene fluorenyloxy, 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, glycidyloxy, 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 linear, branched, and cyclic groups, and examples include methyl, ethyl, n-propyl, isopropyl, Carbon of n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Linear or branched alkyl groups of 1 to 20; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclic Amyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, etc. cyclic alkyl groups having 3 to 20 carbon atoms.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, n-1-propenyl, n-2-propenyl, 1-methylvinyl, n-1-butenyl, and 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-decenyl, n-1-icosenyl, and the like.

Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, 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 -Hexynyl, n-1-decynyl, n-1-pentadeynyl, n-1-icosynyl and the like.

Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, and 2-phenanthrene Radical, 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 An alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with Z ¹⁰² , and more preferably a methyl group or ethyl group which may be substituted with Z ¹⁰¹ .

Further, R ′ is preferably an alkyl group having 1 to 20 carbon atoms that can be substituted by Z ¹⁰³ or an aryl group having 6 to 20 carbon atoms that can be substituted by Z ¹⁰⁴ , and more preferably 1 to 20 carbon atoms that can be substituted by Z ¹⁰³ . An alkyl group of 10 or an aryl group having 6 to 14 carbon atoms that can be substituted by Z ¹⁰⁴ , and an alkyl group of 1 to 6 carbon atoms that can be substituted by Z ¹⁰³ or 6 to 10 carbon atoms that can 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 .

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

Z ^{101 is} preferably a halogen atom or an aryl group having 6 to 20 carbon atoms which can be substituted by Z ¹⁰⁵ , more preferably a fluorine atom or a phenyl group which can be substituted by Z ¹⁰⁵ , and most preferably is absent (ie, non-substituted).

In addition, Z ^{102 is} preferably a halogen atom or an alkyl group having 6 to 20 carbon atoms which may be substituted with Z ¹⁰⁵ , more preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z ¹⁰⁵ , and most preferably not Exists (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 Group, urea group, thiol group, isocyanate group, amine group, phenylamino group which can be substituted by Z ¹⁰⁵ or diphenylamino group which can be substituted by Z ¹⁰⁴ , more preferably a halogen atom, and more preferably a fluorine atom Or does not exist (ie, non-substituted).

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, Still more preferably, a fluorine atom is absent (ie, non-substituted).

Further, Z ^{105 is} preferably a halogen atom, more preferably a fluorine atom or is absent (ie, non-substituted).

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

Specific examples of the dialkoxysilane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, ethylene Methylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (3,4- (Epoxycyclohexyl) ethylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane , 3,3,3-trifluoropropylmethyldimethoxysilane.

Specific examples of the trialkoxysilane compound include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, Propyltriethoxysilane, butyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane Methoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxy Silane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropylene Ethoxypropyltriethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, dodecyltriethoxysilane, 3,3,3-trifluoropropyltrimethyl Oxysilane, (triethoxysilyl) cyclohexane, perfluorooctylethyltriethoxysilane, triethoxyfluorosilane, tridecyl-1,1,2,2-tetrahydrooctyl Triethoxysilane, pentafluorophenyltris Oxysilane, pentafluorophenyltriethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, heptafluoro-1,1,2,2-tetrahydrodecyltriethyl Oxysilane, triethoxy-2-thienylsilane, 3- (triethoxysilyl) furan, and the like.

Specific examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

Among these, 3,3,3-trifluoropropylmethyldimethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, and 3,3,3- Trifluoropropyltrimethoxysilane, perfluorooctylethyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, etc.

Organic silane compound in the charge-transporting varnish of the present invention The content of the substance is generally about 0.1 to 50% by mass relative to the total mass of the charge-transporting substance and the dopant, but if the reduction of the charge-transporting property of the obtained thin film is considered to be suppressed, and the effect on the hole-transporting layer is improved When the hole injection energy of the layer laminated on the opposite side of the anode such as the light emitting layer and the hole injection layer is preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and more It is preferably about 1 to 20% by mass.

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

Other dopants include 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-naphthalenesulfonic acid Acid, hexylnaphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonyl Naphthalene disulfonic acid, 2,7-dinonyl-4,5-naphthalenedisulfonic acid, 1,4-benzodioxane disulfonic acid compound described in International Publication No. 2005/000832, International Publication No. Arylsulfonic acid compounds described in 2006/025342, arylsulfonic acid compounds described in International Publication No. 2009/096352, and arylfluorene compounds such as polystyrenesulfonic acid; non-aromatic compounds such as 10-camphorsulfonic acid Based compounds

[Charge-transporting material]

The charge-transporting material of the present invention contains a charge-transporting substance, a dopant, and an organic solvent. The dopant contains a heteropoly acid and at least one selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and a halogenated or cyanobenzoquinone. That is, at least one selected from the group consisting of halogenated tetracyanobenzoquinone dimethane, halogenated benzoquinone, and cyanobenzoquinone. Such a charge-transporting material exhibits good solubility in an organic solvent. As described above, by dissolving this charge-transporting material in an organic solvent, a charge-transporting varnish can be easily produced.

[Charge Transporting Film]

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

The coating method of the varnish is not particularly limited. For example, there are a dipping method, a spin coating method, a transfer printing method, a roll coating method, a bristle coating method, an inkjet method, and a spray method. Better.

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

The varnish of the present invention has the feature that it can be fired not only at a high temperature of 200 ° C or higher, but also at a low temperature of less than 200 ° C. The application of the obtained film in consideration of the firing temperature, the degree of charge transport properties imparted to the obtained film, and the type of solvent can be appropriately set within a range of 100 ° C to 250 ° C, but the obtained film is used as an organic EL device. Electric hole When the transport layer or hole injection layer is used, the temperature is preferably about 130 to 245 ° C, and more preferably about 140 to 240 ° C.

In addition, during firing, a temperature change of two or more stages may be applied for the purpose of exhibiting a higher uniform film-forming property or allowing a reaction to proceed on the substrate. The heating may be performed using a suitable device such as a hot plate or an oven.

The film thickness of the charge-transporting thin film is not particularly limited. When it is used as a hole injection layer in an organic EL device, it is preferably 5 to 200 nm. The method of changing the film thickness includes, for example, a method of changing the solid content concentration in the varnish, or changing the amount of the solution on the substrate during coating.

The charge-transporting film of the present invention is produced using the above-described charge-transporting varnish of the present invention. Therefore, it is not only a charge-transporting film but also a flatness.

[Organic EL element]

Examples of the materials or manufacturing methods used in the production of OLED elements using the charge-transporting varnish of the present invention include the following, but are not limited thereto.

The electrode substrate used is preferably cleaned by washing with liquid such as lotion, alcohol, pure water in advance. For example, the anode substrate is preferably surface treated with UV ozone treatment, oxygen-plasma treatment, etc. before use. . However, when the anode material is mainly composed of organic matter, the surface treatment may not be performed.

An example of a method for manufacturing an OLED device having a hole injection layer composed of a thin film obtained from the charge-transporting varnish of the present invention is shown below.

According to the method described above, the charge-transporting varnish of the present invention is coated on the anode substrate, and a hole injection layer is formed on the electrode after firing. This was introduced into a vacuum evaporation device, and a hole transporting layer, a light emitting layer, an electron transporting layer, an electron transporting layer / hole blocking layer, an electron injection layer, and a cathode metal were sequentially vapor-deposited to form an OLED element. In addition, if necessary, an electron blocking layer may be provided between the light emitting layer and the hole transporting layer.

Examples of the anode material include metal anodes composed of transparent electrodes represented by indium tin oxide (ITO), indium zinc oxide (IZO), metals represented by aluminum, or alloys thereof, and the like is preferred.化 Processor. It is also possible to use a polythiophene derivative or a polyaniline derivative having a high charge-transporting property.

In addition, other metals constituting the metal anode include rhenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, cadmium, Indium, thallium, lanthanum, cerium, praseodymium, neodymium, giant, thorium, thorium, thorium, thorium, thorium, ', thorium, thorium, thorium, thorium, thorium, tungsten, thallium, thallium, thallium, iridium, platinum, gold, titanium, Lead, bismuth, or the like, but not limited thereto.

Examples of the material forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimers, and N, N'-bis (naphthalene-1- Group) -N, N'-bis (phenyl) -benzidine (α-NPD), N, N'-bis (naphthalene-2-yl) -N, N'-bis (phenyl) -benzidine, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -benzidine, N, N'-bis (3-methylphenyl) -N, N'-bis (Phenyl) -9,9-spirobifluorene, N, N'-bis (naphthalene-1-yl) -N, N'-bis (phenyl) -9,9-spirobifluorene, N, N ' -Bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9-dimethyl-fluorene, N, N'-bis (naphthalene-1-yl) -N, N ' -Bis (phenyl) -9,9-dimethyl-fluorene, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9-diphenyl -Fluorene, N, N'-bis (naphthalene-1-yl) -N, N'-bis (phenyl) -9,9-diphenyl-fluorene, N, N'-bis (naphthalene-1-yl) ) -N, N'-bis (phenyl) -2,2'-dimethylbenzidine, 2,2 ', 7,7'-tetra (N, N-diphenylamino) -9,9 -Spirobifluorene, 9,9-bis [4- (N, N-bis-biphenyl-4-yl-amino) phenyl] -9H-fluorene, 9,9-bis [4- (N, N-bis-naphthalene-2-yl-amino) phenyl] -9H-fluorene, 9,9-bis [4- (N-naphthalene-1-yl-N-phenylamino) -phenyl]- 9H-fluorene, 2,2 ', 7,7'-tetrakis [N-naphthyl (phenyl) -amino] -9,9-spirobifluorene, N, N'-bis (phenanthrene-9-yl) -N, N'-double ( ) -Benzidine, 2,2'-bis [N, N-bis (biphenyl-4-yl) amino] -9,9-spirobifluorene, 2,2'-bis (N, N- Diphenylamino) -9,9-spirobifluorene, di- [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'-bis (naphthyl) -N, N'-bis (naphthalene -2-yl) -benzidine, N, N, N ', N'-tetrakis (naphthyl) -benzidine, N, N'-bis (naphthalene-2-yl) -N, N'-diphenyl Benzidine-1,4-diamine, N ¹ , N ⁴ -diphenyl-N ¹ , N ⁴ -bis (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-bis (p -Tolyl) amino) phenyl) biphenyl, 4,4 ', 4 "-tri [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4' Triarylamines such as 4,4 "-tri [1-naphthyl (phenyl) amino] triphenylamine (1-TNATA), 5,5" -bis- {4- [bis (4-methyl Phenyl) amino] phenyl} -2,2 ': 5', 2 "-triptythiophene (BMA-3T) and the like.

Materials 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-bis (Naphthalene-2-yl) anthracene, 2-t-butyl-9,10-bis (naphthalene-2-yl) anthracene, 2,7-bis [9,9-bis (4-methylphenyl)- Fluoren-2-yl] -9,9-bis (4-methylphenyl) fluorene, 2-methyl-9,10-bis (naphthalene-2-yl) anthracene, 2- (9,9-cyclocyclo Bis (fluoren-2-yl) -9,9-cyclocyclobifluorene, 2,7-bis (9,9-cyclocyclobifluoren-2-yl) -9,9-cyclocyclobifluorene, 2- (9 , 9-bis (4-methylphenyl) -fluoren-2-yl] -9,9-bis (4-methylphenyl) fluorene, 2,2'-difluorenyl-9,9-cyclo Bispyrene, 1,3,5-ginsyl (fluoren-1-yl) benzene, 9,9-bis [4- (fluorenyl) phenyl] -9H-fluorene, 2,2'-bi (9,10- (Diphenylanthracene), 2,7-difluorenyl-9,9-cyclobifluorene, 1,4-bis (fluoren-1-yl) benzene, 1,3-bis (fluoren-1-yl) benzene , 6,13-bis (biphenyl-4-yl) fused pentabenzene, 3,9-bis (naphthalene-2-yl) fluorene, 3,10-bis (naphthalene-2-yl) fluorene, reference [4- (Fluorenyl) -phenyl] amine, 10,10'-bis (biphenyl-4-yl) -9,9'-bisanthracene, N, N'-bis (naphthalene-1-yl) -N, N '-Diphenyl- [1,1': 4 ', 1 ”: 4”, 1 ”'-Tetraphenyl] -4,4” '-Di , 4,4'-bis [10- (naphthalene-1-yl) anthracene-9-yl] biphenyl, dibenzo {[f, f ']-4,4', 7,7'-tetraphenyl } Diindenyl [1,2,3-cd: 1 ', 2', 3'-1m] fluorene, 1- (7- (9,9'-bisanthracene-10-yl) -9,9-di Methyl-9H-fluoren-2-yl) fluorene, 1- (7- (9,9'-bisanthracene-10-yl) -9,9-dihexyl-9H-fluoren-2-yl) fluorene, 1 , 3-Bis (carbazole-9-yl) benzene, 1,3,5-gins (carbazole-9-yl) benzene, 4,4 ', 4 "-syn (carbazole-9-yl) tribenzene Amine, 4,4'-bis (carbazole-9-yl) biphenyl (CBP), 4,4'-bis (carbazole-9-yl) -2,2'-dimethylbiphenyl, 2 , 7-bis (carbazole-9-yl) -9,9-dimethylfluorene, 2,2 ', 7,7'-(carbazole-9-yl) -9,9-cyclobicyclofluorene , 2,7-bis (carbazole-9-yl) -9,9-bis (p-tolyl) fluorene, 9,9-bis [4- (carbazole-9-yl) -phenyl] fluorene, 2,7-bis (carbazol-9-yl) -9,9-cyclobifluorene, 1,4-bis (triphenylsilyl) benzene, 1,3-bis (triphenylsilyl) benzene Bis (4-N, N-diethylamino-2-methylphenyl) -4-methylphenylmethane, 2,7-bis (carbazole-9-yl) -9,9-di Octylfluorene, 4,4 "-bis (triphenylsilyl) -p-terphenyl, 4,4'-bis (triphenylsilyl) biphenyl, 9- (4-t-butylphenyl ) -3,6-bis (triphenylsilyl) -9H-carbazole, 9- (4-t-butylphenyl) -3,6-bis (trityl) -9H-carb Azole, 9- (4-t-butylphenyl) -3,6-bis (9- (4-methoxyphenyl) -9H-fluoren-9-yl) -9H-carbazole, 2,6 -Bis (3- (9H-carbazole-9-yl) phenyl) pyridine, triphenyl (4- (9-phenyl-9H-fluoren-9-yl) phenyl) silane, 9,9-di Methyl-N, N-diphenyl-7- (4- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -9H-fluoren-2-amine, 3,5 -Bis (3- (9H-carbazole-9-yl) phenyl) pyridine, 9,9-cyclobifluoren-2-yl-diphenyl-phosphine oxide, 9,9 '-(5- ( Triphenylsilyl) -1,3-phenylene) bis (9H-carbazole), 3- (2,7-bis (diphenylphosphonium) -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) pyrene, 4,7-bis (9H-carbazole-9-yl) -1,10-morpholine, 2,2'-bis (4- (carbazole-9-yl) phenyl) biphenyl, 2,8-bis (diphenylphosphoranyl) dibenzo [b, d] thiophene, bis (2-methylphenyl) diphenylsilane, bis [3,5-bis (9H-carbazole- 9-yl) phenyl] diphenylsilane, 3,6-bis (carbazole-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 also by co- Plating a light emitting layer.

Examples of the light-emitting dopant include 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7 -Tetramethyl-1H, 5H, 11H-10- (2-benzothiazolyl) quinazino (9,9a, 1gh) coumarin, quinacridone, N, N'-dimethyl -Quinacridone, tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ), bis (2-phenylpyridine) (acetylacetonate) iridium (III) (Ir ( ppy) ₂ (acac)), tris [2- (p-tolyl) pyridine] iridium (III) (Ir (mppy) ₃ ), 9,10-bis [N, N-bis (p-tolyl) amine Yl] anthracene, 9,10-bis [phenyl (m-tolyl) amino] anthracene, bis [2- (2-hydroxyphenyl) thiazolato] zinc (II), N ¹⁰ , N ¹⁰ , N ¹⁰ , N ¹⁰ -tetra (p-tolyl) -9,9'-bianthracene-10,10'-diamine, N ¹⁰ , N ¹⁰ , N ¹⁰ , N ¹⁰ -tetraphenyl -9,9'-bianthracene-10,10'-diamine, N ¹⁰ , N ¹⁰ -diphenyl-N ¹⁰ , N ¹⁰ -dinaphthyl-9,9'-bianthryl-10,10'- Diamine, 4,4'-bis (9-ethyl-3-carbazole vinylidene) -1,1'-biphenyl, fluorene, 2,5,8,11-tetra-t-butylfluorene, 1,4-bis [2- (3-N-ethylcarbazolyl) vinyl] benzene, 4,4'-bis [4- (di-p-tolylamino) styryl] biphenyl, 4- (di-p-tolylamino) -4 '-[(di-p-toluene Amine) styryl] fluorene, bis [3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl)] iridium (III), 4,4'-bis [4 -(Diphenylamino) styryl] biphenyl, bis (2,4-difluorophenylpyridine) tetra (1-pyrazolyl) borate iridium (III), N, N'-bis ( Naphthalene-2-yl) -N, N'-bis (phenyl) -tris (9,9-dimethylarylene), 2,7-bis {2- [phenyl (m-tolyl) amine Yl] -9,9-dimethyl-fluoren-7-yl} -9,9-dimethyl-fluorene, N- (4-((E) -2- (6 ((E) -4- ( Diphenylamino) styryl) naphthalene-2-yl) vinyl) phenyl) -N-phenylaniline, fac-iridium (III), (1-phenyl-3-methylbenzimidazoline) -2-Subunit-C, C ² ), mer-iridium (III) ginseng (1-phenyl-3-methylbenzimidazoline-2-subunit-C, C ² ), 2,7-bis [4- (diphenylamino) styryl] -9,9-cyclodifluorene, 6-methyl-2- (4- (9- (4- (6-methylbenzo [d] Thiazol-2-yl) phenyl) anthracene-10-yl) phenyl) benzo [d] thiazole, 1,4-bis [4- (N, N-diphenyl) amino] styrylbenzene, 1,4-bis (4- (9H-carbazole-9-yl) styryl) benzene, (E) -6- (4- (diphenylamino) styryl) -N, N-di Phenylnaphthalene-2-amine, bis (2,4-difluorophenylpyridine) (5- (pyridin-2-yl) -1H-tetrazole) iridium (III), bis (3-trifluoromethyl- 5- (2-pyridine (Yl) pyrazole) ((2,4-difluorobenzyl) diphenylphosphinate) iridium (III), bis (3-trifluoromethyl-5- (2-pyridyl) pyrazole) ( Benzyl diphenyl phosphinate) iridium (III), bis (1- (2,4-difluorobenzyl) -3-methylbenzimidazolium) (3- (trifluoromethyl) -5 -(2-pyridyl) -1,2,4-triazole) iridium (III), bis (3-trifluoromethyl-5- (2-pyridyl) pyrazole) (4 ', 6'-di Fluorophenylpyridine ester) iridium (III), bis (4 ', 6'-difluorophenylpyridine) (3,5-bis (trifluoromethyl) -2- (2'-pyridyl) pyrrole) iridium (III), bis (4 ', 6'-difluorophenylpyridine) (3- (trifluoromethyl) -5- (2-pyridyl) -1,2,4-triazole) iridium (III) (Z) -6-Trisyl-N- (6-trisyl (Mesityl) quinoline-2 (1H) -subunit) quinoline-2-amine-BF ₂ , (E) -2- ( 2- (4- (dimethylamino) styryl) -6-methyl-4H-pyran-4-ylidene) malononitrile, 4- (dicyanomethylene) -2-methyl -6-giuronidin-9-alkenyl-4H-pyran, 4- (dicyanomethylene) -2-methyl-6- (1,1,7,7-tetramethyljiu Lonidinyl-9-alkenyl) -4H-pyran, 4- (dicyanomethylene) -2-t-butyl-6- (1,1,7,7-tetramethyljurone N-A-4-yl-vinyl) -4H-pyran, tris (dibenzylidenemethane) phenanthroline hydrazone (III), 5,6,11,12-tetraphenyl Tetrabenzene, bis (2-benzo [b] thiophen-2-yl-pyridine) (acetamidineacetone) iridium (III), tris (1-phenylisoquinoline) iridium (III), bis (1-benzene Isoquinoline) (Ethylacetone) Iridium (III), Bis [1- (9,9-dimethyl-9H-fluoren-2-yl) -isoquinoline] (Ethylacetone) Iridium (III) , Bis [2- (9,9-dimethyl-9H-fluoren-2-yl) quinoline] (acetamidineacetone) iridium (III), tris [4,4'-di-t-butyl- ( 2,2 ')-dipyridine] ruthenium (III). Bis (hexafluorophosphate), tris (2-phenylquinoline) iridium (III), bis (2-phenylquinoline) (acetamidineacetone) iridium (III), 2,8-di-t-butyl -5,11-bis (4-t-butylphenyl) -6,12-diphenyltetrane (tetracene), bis (2-phenylbenzothiazole) (ethylacetoacetone) iridium (III ), 5,10,15,20-tetraphenyltetrabenzoporphyrin platinum, pyrene (II) bis (3-trifluoromethyl-5- (2-pyridine) -pyrazole) dimethylphenylphosphine锇 (II) bis (3- (trifluoromethyl) -5- (4-t-butylpyridyl) -1,2,4-triazole) diphenylmethylphosphine, 锇 (II) bis (3- (trifluoromethyl) -5- (2-pyridyl) -1,2,4-triazole) dimethylphenylphosphine, fluorene (II) bis (3- (trifluoromethyl)- 5- (4-t-butylpyridyl) -1,2,4-triazole) dimethylphenylphosphine, bis [2- (4-n-hexylphenyl) quinoline] (acetamidine) Iridium (III), tris [2- (4-n-hexylphenyl) quinoline] iridium (III), tris [2-phenyl-4-methylquinoline] iridium (III), bis (2-benzene Quinoline) (2- (3-methylphenyl) pyridine ester) iridium (III), bis (2- (9,9-diethyl-fluoren-2-yl) -1-phenyl-1H- Benzo [d] imidazolato) (Ethylacetone) Iridium (III), Bis (2-phenylpyridine) (3- (pyridin-2-yl) -2H-chromene-2-onine (onate )) Iridium (III), bis (2-phenylquinoline) (2,2,6,6-tetramethylheptane -3,5-dionitri) iridium (III), bis (phenylisoquinoline) (2,2,6,6-tetramethylheptane-3,5-dionitri) iridium (III), Iridium (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) ruthenium, bis [(4-n-hexylbenzene Base) isoquinoline] (acetamidineacetone) iridium (III), platinum (II) octaethylporphine, bis (2-methyldibenzo [f, h] quinoxaline) (acetamidineacetone) iridium (III), tris [(4-n-hexylphenyl) hydroxyquinoline] iridium (III), and the like.

Examples of the material forming the electron transporting layer / hole blocking layer include 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'-dipyridine- 6-yl) -1,3,4-oxadiazol-5-yl] benzene, 6,6'-bis [5- (biphenyl-4-yl) -1,3,4-oxadiazole-2 -Yl] -2,2'-dipyridine, 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 (naphthalene-2-yl) -4,7-diphenyl-1,10-phenanthrene Ringoline, 2,7-bis [2- (2,2'-dipyridin-6-yl) -1,3,4-oxadiazol-5-yl] -9,9-dimethylfluorene, 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- (naphthalene-2-yl) phenyl) -1H-imidazole [4,5f] [1,10] phenanthroline, 2 -(Naphthalene-2-yl) -4,7-diphenyl-1,10-phenanthroline, phenyl-diamidinophosphine oxide, 3,3 ', 5,5'-tetra [(m- Pyridyl) -phenyl-3-yl] biphenyl, 1,3,5-tri [(3-pyridyl) -phenyl-3-yl] benzene, 4,4'-bis (4,6-diphenyl -1,3,5-triazin-2-yl) biphenyl, 1,3-bis [3,5-bis (pyridin-3-yl) phenyl] benzene, bis (10-hydroxybenzo [h] Quinoline) beryllium, diphenylbis (4- (pyridin-3-yl) phenyl) silane, 3,5-bis (fluoren-1-yl) pyridine, and the like.

Examples of the material for forming the electron injection layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), and fluoride 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, and cesium.

Examples of the material forming the electron blocking layer include tris (phenylpyrazole) iridium.

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 above-mentioned OLED device manufacturing, instead of performing a vacuum evaporation operation of a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injection layer, by sequentially forming a hole transporting polymer layer and a light emitting polymer layer, A PLED element having a charge-transporting film formed of the charge-transporting varnish of the present invention is produced.

Specifically, an anode substrate is coated with the charge-transporting varnish of the present invention, a hole injection layer is prepared by the above method, and a hole-transporting polymer layer and a light-emitting polymer layer are sequentially formed thereon, and then A cathode electrode was evaporated 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 elements, and can perform the same cleaning treatment and surface treatment.

Methods for forming the hole-transporting polymer layer and the light-emitting polymer layer include, for example, adding a solvent to the hole-transporting polymer material or the light-emitting polymer material, or adding a dopant to the solvent to dissolve the material. Or a method of uniformly dispersing and coating on a hole injection layer or a hole-transporting polymer layer, and then firing to form a film.

Examples of hole-transporting polymer materials include 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'-biphenylene-4,4-diamine)], poly [(9,9-bis {1'-pentene-5'-yl} fluorene-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) Dioctylfluorene-2,7-diyl) -co- (4,4 '-(N- (p-butylphenyl)) diphenylamine)] and the like.

Light-emitting polymer materials include, for example, polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), and poly (2-methoxy-5- (2'-ethylhexyloxy)- Polyphenylene vinylene derivatives such as 1,4-phenylene vinylene (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), polyvinylcarbazole ( PVCz) and so on.

Examples of the solvent include toluene, xylene, and chloroform. Examples of the dissolution or uniform dispersion method include methods such as 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 bristle coating method. The coating is preferably performed under an inert gas such as nitrogen or argon.

Examples of the firing method include a method of heating in an oven or a hot plate under an inert gas or in a vacuum.

[Example]

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The equipment used is as follows.

(1) Substrate cleaning: substrate cleaning equipment (reduced voltage Pulp method)

(2) Coating of varnish: Mikasa's spin coater MS-A100

(3) Measurement of film thickness: Surfcorder ET-4000, a micro shape measuring machine manufactured by Kosaka Laboratory

(4) Production of EL elements: Multi-function vapor deposition system C-E2L1G1-N made by Changzhou Industry Co., Ltd.

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

(6) Lifetime measurement (durability evaluation) of EL element: Organic EL brightness life evaluation system PEL-105S made by Eetch Sea

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

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

[Synthesis Example 1] Synthesis of thiophene derivative 2

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

Put 2,3-dihydrothieno [3,4-b] [1,4] in the flask 2.0 g of aoxin and 150 mL of tetrahydrofuran were nitrogen-substituted and then cooled to -78 ° C. Among them, 10 mL of n-butyl lithium n-hexane solution (concentration 1.64 mol / L) was dropped, followed by stirring at -78 ° C for 30 minutes, and then the temperature was raised to -40 ° C. After 5 mL of tributylchlorostannane was dropped, the temperature was raised to room temperature and Stir for 16 hours.

After the stirring was completed, the reaction mixture was concentrated, and the concentrated solution was mixed 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-yl) stannane.

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

After the stirring was completed, the mixture was left to cool to room temperature, and n-hexane was added for liquid separation. The obtained N, N-dimethylformamide layer was dropped into a mixed solution of ion-exchanged water and methanol, and reprecipitated.

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'-bisthiophene

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 and cooled to -78 ° C. While maintaining -78 ° C, 14.7 mL (concentration 1.64 mol / L) of n-hexane solution of n-butyllithium was dropped, followed by stirring for 30 minutes. 7.8 mL (d1.20) of tri-n-butylchlorostannane was dropped into the solution, and after stirring for 10 minutes, the temperature was raised to room temperature and stirred. After 6 hours, the reaction solution was concentrated, and 50 mL of n-hexane was added to the obtained residue, and insoluble matter was removed by filtration (cake washing: 30 mL of n-hexane). The resulting filtrate was concentrated. After drying, 12.64 g of a dark red oil containing 5-tributylstannyl-2,2'-bisthiophene was obtained. Without further purification, the yield in this step was 100% (theoretical yield 10.96 g), and the purity (10.96 / 12.64 × 100 = 86.7%) was calculated and used as the raw material in the next step.

(2) Synthesis of thiophene derivative 3

The thiophene derivative 3 (TP3) represented by the formula (X4) was 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-tributylmethyltin synthesized in [1] was added. 100 mL of a dimethylformamide (DMF) solution of 7.8 g (purity 86.7%) of alkyl-2,2'-bisthiophene. After stirring at 110 ° C for 2.5 hours, the reaction solution was reprecipitated with 1.5 L of methanol. The slurry was stirred at room temperature for 15 hours, and then filtered. 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 performed while hot, and the obtained filtrate was cooled to 0 ° C with 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 obtain 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 (Bromosuccinimide: NBS) 6.10 g (2.4 eq) was charged in a powder state. After confirming the disappearance of the raw materials, n-hexane and ion-exchanged water were added to the reaction solution, and liquid separation was performed. The organic layer was washed once with ion-exchanged water and saturated brine, and then dried with Na ₂ SO ₄ . The solvent was distilled off under reduced pressure and dried to obtain 4.21 g of the intended thienothiophene dibromide (yield: 99%).

Next, under a nitrogen environment, 1.93 g of thienothiophene dibromide, Pd (PPh ₃ ) ₄ 0.75 g (10 mol%), 3-hexylthiophene borate pinacol ester (manufactured by Aldrich) 4.00 g, 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 reflux for 5 hours to react. After the reaction was completed, n-hexane was added, and after stirring at room temperature for 30 minutes, insoluble matters were removed by filtration, and the filtrate was washed twice with ion-exchanged water and once with saturated saline. After drying with Na ₂ SO ₄ , the solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography to obtain TP4 (yield: 85%). The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (300 MHz, 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 = 7.4Hz, 4H), 1.60-1.70 (m, 4H), 1.27-1.42 (m, 12H), 0.88 (t, J = 6.9Hz, 6H).

[Synthesis Example 4] Synthesis of thiophene derivative 5

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

Under a nitrogen environment, 1.50 g of benzodithiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel, 50 mL of tetrahydrofuran (THF) was added, and then cooled to -78 ° C. Then, 19.2 mL of an n-hexane solution of n-butyllithium (concentration of 1.64 mol / L, 4 eq) was dropped, and then stirred for 1.5 hours. Then, 8.6 mL (4 eq) of tri-n-butylchlorostannane was dropped, and after reacting at -78 ° C for 1 hour, the cooling bath was removed and the temperature was raised to room temperature. After reaching room temperature, the solvent was distilled off under reduced pressure. The precipitate in the obtained slurry was filtered and obtained, and dried to obtain 11.84 g of a mixture containing the intended benzodithiophene bistinyl body. In addition, no further purification was performed. When the yield of this step was 100% (theoretical yield 6.07 g), the calculated purity (6.07 / 11.84 × 100 = 51.3%) was used as the raw material for the next step.

Next, under a nitrogen environment, 5.92 g of the mixture containing the obtained benzodithiophene dimethylstannyl body and 2.15 g (2.2 eq) of 2-bromo-3-n-hexylthiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) 25 mL of toluene and 0.230 g (5 mol%) of Pd (PPh ₃ ) _{4 were} placed in a reaction vessel, and the reaction was stirred for 4.5 hours under heating and refluxing conditions. After leaving 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. After adding methanol to the obtained yellow slurry, insoluble matters were filtered off. After the filtrate was subjected to activated carbon treatment, the solvent was distilled off under reduced pressure. Ethanol and toluene were added to the residue, and the mixture was stirred under heating and refluxing conditions. After confirming complete dissolution, it was allowed to cool to room temperature. After stirring at room temperature for one night in this state, TP5 was obtained by filtration and drying (yield: 1.40 g, two-stage yield: 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 = 5.1Hz, 2H), 6.98 (d, J = 5.1Hz, 2H), 2.87 (t, J = 8.0Hz, 4H), 1.63-1.74 (m, 4H), 1.30-1.42 (m, 12H), 0.88 (t, J = 6.6Hz, 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.

The N, N'- diphenyl benzidine 2.00g, 4- bromo -N, N- diphenylaniline _{4.25g, Pd (dba) 2 68.4mg} , and ^t BuONa 1.49g into a reaction vessel, with nitrogen after the substitution, 20mL of toluene was added and separately prepared of P ^(t Bu) ₃ of a toluene solution of 1.0 mL (concentration of 47.2g / L), stirred at 50 ℃ 7 hours the reaction. After cooling to room temperature, the reaction solution was filtered, and the obtained filtrate was washed with ion-exchanged water. After filtration, the obtained filtrate was dried to obtain AN1 (yield: 4.46 g, yield: 91%). The measurement results of TOF-MS are shown below.

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, and nitrogen substitution was performed. 15 mL of toluene and 0.51 mL (concentration 47.2 g / L) of a toluene solution of P ( ^t Bu) ₃ separately were added, and the mixture was stirred at 50 ° C. for 6.5 hours to react. After cooling to room temperature, toluene and saturated brine were added for liquid separation. The obtained organic layer was dried over Na ₂ SO ₄ , and activated carbon was added thereto, followed by stirring at room temperature for 30 minutes. The activated carbon was removed by filtration and concentrated. The obtained concentrated liquid was dropped into a MeOH-AcOEt mixed solvent, 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 = 7.8 Hz, 2H), 7.99 (d, J = 1.8 Hz, 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-transporting varnish [Example 1-1]

0.050 g of 3,3 "'-dihexyl-2,2': 5 ', 2": 5 ", 2"'-tetrathiophene (manufactured by Sigma-Aldrich Co. LLC, hereinafter referred to as TP1), phosphorus 0.250 g of tungstic acid (PTA, manufactured by Kanto Chemical Co., Ltd.) and 0.045 g of F4TCNQ (made by Tokyo Chemical Industry Co., Ltd.), dissolved in 1,3-dimethyl-2-imidazolinone (DMI) under a nitrogen environment 3.2g. To the obtained 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 (0.052g), PTA (0.258g) and F4TCNQ (0.031g) were dissolved in DMI (2g) under a nitrogen environment. CHA (2g) and 6 g of diethylene glycol dimethyl ether (Diglyme) were added to the obtained solution, and it stirred and prepared the charge-transporting varnish.

[Example 1-3]

TP1 (0.052g), PTA (0.258g) and F4TCNQ (0.031g) were dissolved in DMI (2g) under a nitrogen environment. 8 g of propylene glycol monomethyl ether (PGME) was added to the obtained solution, and the charge-transporting varnish was prepared by stirring.

[Example 1-4]

TP1 (0.052g), PTA (0.258g) and F4TCNQ (0.031g) were dissolved in DMI (2g) under a nitrogen environment. PGME (8 g) was added to the obtained solution, and after stirring, 0.031 g of pentafluorophenyltriethoxysilane was added, followed by stirring to prepare a charge-transporting varnish.

[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 environment. 0.49 g of diethylene glycol monomethyl ether (DEGME) and PGME (3.43 g) were added to the obtained solution, and after stirring, 0.001 g of 3,3,3-trifluoropropyltrimethoxysilane and phenyltrimethyl ether were added. 0.009 g of oxysilane, and then stirred to prepare a charge-transporting varnish.

[Example 1-6]

TP2 (0.052g), PTA (0.258g) and F4TCNQ (0.031g) were dissolved in DMI (2g) under a nitrogen environment. CHA (2g) and Diglyme (6g) were added to the obtained solution, and it stirred and prepared the charge-transporting varnish.

[Example 1-7]

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

[Example 1-8]

TP4 (0.034g), PTA (0.170g) and F4TCNQ (0.020g) were dissolved in DMI (2g) under a nitrogen environment. DEGME (1g) and PGME (7g) were added to the obtained solution, and after stirring, 0.007g of 3,3,3-trifluoropropyltrimethoxysilane and 0.014g of phenyltrimethoxysilane were added, and stirring was performed to adjust the charge transport. Sexual varnish.

[Example 1-9]

TP5 (0.034g), PTA (0.170g) and F4TCNQ (0.031g) were dissolved in DMI (2g) under a nitrogen environment. DEGME (1g) and PGME (7g) were added to the obtained solution and stirred, and 0.007g of 3,3,3-trifluoropropyltrimethoxysilane and 0.014g of phenyltrimethoxysilane were added and stirred. Charge-transporting 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 environment. To the obtained solution, 0.007 g of 3,3,3-trifluoropropyltrimethoxysilane and 0.014 g of phenyltrimethoxysilane were added, and the charge-transporting varnish was prepared by stirring.

[Example 1-11]

AN2 (0.042g), PTA (0.202g) and F4TCNQ (0.160g) were dissolved in CHN (20g) under a nitrogen environment. To the obtained solution, 0.007 g of 3,3,3-trifluoropropyltrimethoxysilane and 0.014 g of phenyltrimethoxysilane 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 environment. CHA (6g) and PG (2g) were added to the obtained solution, and it stirred and prepared the charge-transporting varnish.

[Comparative Example 1-2]

In a nitrogen environment, try to modulate the charge using TP1 (0.050g), PTA (0.250g) and 0.045g of tetracyanobenzoquinone dimethane, and DMI (3.2g), CHA (4.9g) and PG (1.6g) Conveying varnish. However, the solid content does not dissolve, and it is not possible to obtain a uniform film that can be used in organic EL devices. Varnish.

[3] Manufacturing and characteristic evaluation of organic EL elements [Example 2-1]

After applying the varnish obtained in Example 1-1 on an ITO substrate using a spin coater, it was dried at 50 ° C for 5 minutes, and then fired at 150 ° C for 10 minutes in an atmospheric environment to form 30 nm on the ITO substrate. A uniform film. The ITO substrate is a glass substrate of 25mm × 25mm × 0.7t after patterning with an indium tin oxide (ITO) film thickness of 150nm on the surface. Before use, it is cleaned by an O ₂ plasma cleaning device (150W, 30 Seconds) to remove impurities from the surface.

Next, using an evaporation device (vacuity degree: 1.0 × 10 ^-5 Pa), on the ITO substrate on which the thin film was formed, thin films of α-NPD, Alq ₃ , lithium fluoride, and aluminum were sequentially laminated to obtain an organic EL device. At this time, regarding the evaporation rate, α-NPD, Alq _3, and aluminum were performed at 0.2 nm / sec, and lithium fluoride was performed at 0.02 nm / sec. The film thicknesses were 30 nm, 40 nm, 0.5 nm, and 120 nm, respectively.

In addition, in order to prevent deterioration of characteristics due to the influence of oxygen, water, and the like in the air, the organic EL element is sealed with a sealing substrate, and its characteristics are evaluated. Sealing is performed in the following order. In a nitrogen environment with an oxygen concentration of 2 ppm or less and a dew point of -85 ° C or less, an organic EL element is housed between the sealing substrates, and the sealing substrate is bonded with an adhesive material (XNR5516Z-B1 made by Nagase Chemtex). At this time, a water-capturing agent (HD-071010W-40, manufactured by Dynac Co., Ltd.) was housed in a sealed substrate together with the organic EL element. The bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6000 mJ / cm ² ), and then annealed at 80 ° C. for 1 hour to harden the adhesive material.

[Examples 2-2 to 2-7]

An organic EL device was fabricated 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.

[Examples 2-8 to 2-9]

The varnishes obtained in Examples 1-8 to 1-9 were used instead of the varnishes obtained in Example 1-1, and were fired at 160 ° C instead of 150 ° C, respectively. Method: An organic EL device was fabricated.

[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]

Instead of using the varnish obtained in Example 1-10 instead of the varnish obtained in Example 1-1, a vapor deposition device (vacuity 1.0 × 10 ^-5 Pa) was used to sequentially form a thin film of CBP and Ir (PPy) ₃ and BAlq. An organic EL device was fabricated in the same manner as in Example 2-1 except that the Alq ₃ film was formed at a thickness of 40 nm using a vapor deposition apparatus (vacuity degree 1.0 × 10 ^-5 Pa).

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

[Example 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 brightness of the elements of Examples 2-1 to 2-9 at a driving voltage of 5V and the brightness of the elements of Examples 2-10 to 2-11 at a driving current of 0.4 mA were measured. The results are shown in Tables 1 and 2.

As shown in Tables 1 and 2, with the varnish of the present invention, an organic EL element having excellent brightness characteristics can be realized even when firing at a low temperature of less than 200C.

The durability of the elements obtained in Examples 2 to 8 was evaluated. The half-life of 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 (14)

A charge-transporting varnish, which is a charge-transporting varnish containing a charge-transporting substance, a dopant, and an organic solvent. At least one halogenated or cyanobenzoquinone. For example, the charge-transporting varnish according to item 1 of the patent application range, wherein the halogenated tetracyanobenzoquinone dimethane comprises tetrafluorinated benzoquinone dimethane. For example, the charge-transporting varnish according to item 1 or 2 of the application, wherein the heteropoly acid includes phosphotungstic acid. For example, the charge-transporting varnish according to item 3 of the application, wherein the charge-transporting substance is an aniline derivative or a thiophene derivative. For example, the charge-transporting varnish according to item 1 of the patent application scope, wherein the organic solvent only contains a member selected from N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1 A highly soluble solvent of at least one of 1,3-dimethyl-2-imidazolinone and diethylene glycol monomethyl ether, if necessary, selected from cyclohexanol, ethylene glycol, and ethylene glycol diglycidyl Ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, High viscosity organic solvent of at least one of propylene glycol and hexanediol, and if necessary, selected from ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, Other solvents of at least one of γ-butyrolactone, ethyl lactate, n-hexyl acetate, and propylene glycol monomethyl ether. For example, the charge-transporting varnish according to item 1 of the patent application range further includes a dialkoxysilane compound represented by the following formula (B1), a trialkoxysilane compound represented by the following formula (B2), and Said at least one type of tetraalkoxysilane compound represented by formula (B3), SiR ' ₂ (OR) ₂ (B1) SiR' (OR) ₃ (B2) Si (OR) ₄ (B3) [wherein, R each independently represents an alkyl group may be substituted with Z ¹⁰¹ carbon atoms of 1 to 20, the sum may be substituted with Z ¹⁰¹ carbon atoms, alkenyl having 2 to 20, the sum Z ¹⁰¹ may be a substituted alkynyl group having a carbon number of 2 to 20, may be Z ¹⁰² substituted aryl groups having 6 to 20 carbon atoms or Z ¹⁰² substituted aryl groups having 2 to 20 carbon atoms. R 'each independently represents an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z ¹⁰³ . by the Z substituent of ¹⁰³ carbon atoms, an alkenyl group having 2 to 20, the may be Z ¹⁰³ substituted with the carbon number of an alkynyl group having 2 to 20, the may be substituted with the Z ¹⁰⁴ carbon atoms, an aryl group having 6 to 20 in or may be substituted with the via Z ¹⁰⁴ A heteroaryl group having 2 to 20 carbon atoms, Z ¹⁰¹ represents a halogen atom, an aryl group having 6 to 20 carbon atoms that can be substituted with Z ¹⁰⁵ or a heteroaryl group having 2 to 20 carbon atoms that can be substituted with Z ¹⁰⁵ , and Z ¹⁰² represents a halogen atom, an alkyl group may be substituted with Z ¹⁰⁵ of 1 to 20 carbon atoms, the alkenyl group may be substituted with Z, or may be of 2 to ¹⁰⁵ carbon atoms of 20 Z ¹⁰⁵ is an alkynyl group having 2 to 20 carbon atoms, Z ¹⁰³ represents a halogen atom, aryl group having 6 to 20 carbon atoms that can be substituted by Z ¹⁰⁵ , and heteroaryl group having 2 to 20 carbon atoms that can be substituted by Z ¹⁰⁵ , Epoxycyclohexyl, glycidyloxy, methacryloxy, propyleneoxy, ureido (-NHCONH ₂ ), thiol, isocyanate (-NCO), amine, -NHY ¹⁰¹ group or a group -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 alkenyl group may be substituted by Z ¹⁰⁵ of the 2 to 20 carbon atoms, may be substituted with Z ¹⁰⁵ Alkynyl, epoxycyclohexyl, glycidyloxy, methacryloxy, propyleneoxy, ureido (-NHCONH ₂ ), thiol, isocyanate (- the NCO), amino, -NHY ¹⁰¹ yl group or -NY ¹⁰² Y ^103, Y ¹⁰¹ ~ Y ¹⁰³ each independently represents an alkyl group substituted by Z ¹⁰⁵ of 1 to 20 carbon atoms, the carbon atoms may be substituted by Z ^105. 2 ~ alkenyl group 20, the may be Z ¹⁰⁵ substituted with the carbon number of an alkynyl group having 2 to 20, the can heteroaryl via Z ¹⁰⁵ substitution of carbon atoms an aryl group having 6 to 20 in or may be substituted with Z ¹⁰⁵ of carbon number 2 to 20 of the Z ¹⁰⁵ represents a halogen atom, an amine group, a nitro group, a cyano group, or a thiol group. For example, the charge-transporting varnish according to item 1 or 2 of the application, wherein the charge-transporting substance is an aniline derivative or a thiophene derivative. A charge-transporting film characterized by using a charge-transporting varnish according to any one of claims 1 to 7 of the scope of patent application. An organic electroluminescence device, which is characterized by having a charge-transporting film as described in item 8 of the patent application. For example, the organic electroluminescence device according to item 9 of the application, wherein the above-mentioned charge transporting film is a hole injection layer or a hole transport layer. A method for manufacturing a charge-transporting film, which is characterized in that a charge-transporting varnish according to any one of claims 1 to 7 is applied to a substrate and fired at a temperature of less than 200 ° C. A method for manufacturing an organic electroluminescence device, which is characterized by using a charge-transporting film such as the item No. 8 in the scope of patent application. A charge-transporting material, which is a charge-transporting material composed of a charge-transporting substance and a dopant, characterized in that the above-mentioned dopant includes a heteropoly acid and is selected from a halogenated tetracyanobenzoquinone dimethane and a halogenation Or at least one kind of cyanobenzoquinone. A method for planarizing a charge-transporting film, which is a method for planarizing a charge-transporting film using at least one type selected from the group consisting of a tetracyanohalogenated dichloromethane and a halogenated or cyanobenzoquinone. And a dopant, which is a charge-transporting varnish containing a heteropolyacid and at least one selected from the group consisting of a halogenated tetracyanobenzoquinone dimethane and a halogenated or cyanobenzoquinone.