KR20150040216A - Charge-transporting varnish, charge-transporting thin film, and organic electroluminescent device - Google Patents

Abstract

Provided is a charge-transporting varnish which is capable of being fired at low temperature under 200°C, and thin films manufactured under such firing conditions have high flatness, high charging-transporting capacity, and demonstrate superior luminance characteristics when applied to organic EL devices. A charge-transporting varnish comprises: a charge-transporting material consisting of oligothiophene derivatives represented by formula 1, dopants, organic silane compounds, and organic solvents. In the above formula, R^1 to R^8, independently, represent hydrogen, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, -0Y^1 group, -SY^2 group, -NHY^3 group, -NY^4Y^5 group, or -NHC(O)Y^6 group; and n^1 to n^3, independently, represent natural numbers, and satisfy 4<=n^1+n^2+n^3<=20.

Description

CHARGE-TRANSPORTING VARNISH, CHARGE-TRANSPORTING THIN FILM, AND ORGANIC ELECTROLUMINESCENT DEVICE [0001] The present invention relates to a charge transporting varnish, a charge transporting thin film and an organic electroluminescence element,

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

As the organic EL element, a charge transport thin film made of an organic compound is used as a light emitting layer or a charge injection layer. The method of forming the charge transport thin film is largely classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. In comparison with dry process and wet process, wet process can efficiently produce a thin film having high flatness in a large area. In the field where a large-sized thin film such as organic EL is desired, In many cases.

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

However, in the field of organic EL in recent years, a substrate made of an organic compound is used instead of a glass substrate from a lightweight and thin type of device, so that it can be fired at a lower temperature than the conventional one, A varnish for imparting a thin film having transportability is also required.

Japanese Laid-Open Patent Publication No. 2002-151272

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a thin film produced under such a firing condition that can be fired at a low temperature of less than 200 캜, has high flatness and high charge transportability, And an object of the present invention is to provide a charge transport varnish which can be exerted.

As a result of intensive investigations to achieve the above object, the present inventors have found that by using a charge-transporting varnish comprising an oligothiophene derivative, a dopant, an organosilane compound and an organic solvent, , And that the thin film produced under such firing conditions has high flatness and high charge transportability and that an organic EL device capable of realizing excellent luminance characteristics when the thin film is applied to the hole injection layer is obtained , Thereby completing the present invention.

Further, Patent Document 1 does not specifically disclose a varnish using an oligothiophene derivative, a dopant and an organosilane compound.

That is, the present invention provides the following charge transporting varnish and organic EL device.

1. A charge-transporting varnish comprising a charge-transporting material comprising an oligothiophene derivative represented by the formula (1), a dopant, an organosilane compound, and an organic solvent.

(Wherein, R ¹ ~ R ⁶ is substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, are each independently a heteroaryl group, is optionally -0Y of 2 to 20 carbon atoms and an alkynyl group, an aryl group having from 6 to 20 carbon atoms which may be substituted with Z ^2, 2 to 20 carbon atoms which may be substituted with Z ² of the ^first group, -SY ² group, -NHY ³ group, -NY ⁴ Y ⁵ group, or a -NHC (O) Y represents a ^6, again, R ¹ ~ R ⁶ is a, R ¹ and R ^2, R ³ is not a hydrogen atom and R ⁴ and / Or R ⁵ and R ⁶ may be bonded to each other to form a divalent group,

R ⁷ and R ⁸ are carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, independently each An alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms which may be substituted with Z ³ , a heteroaryl group of 2 to 20 carbon atoms which may be substituted with Z ³ , a -OY ¹ group, a -SY ² group, ³ group, -NY ⁴ Y ⁵ group or -NHC (O) Y ⁶ group,

Y ^l ~ Y ⁶ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms which may be substituted with, Z ¹ are each independently the alkynyl group, which may be substituted with Z ² represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group, or Z ² of 6 to 20 carbon atoms,

Z ¹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms,

Z ² represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms,

Z ³ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, &Lt; / RTI &gt;&lt; RTI ID = 0.0 &gt;

n ¹ to n ³ independently represent a natural number, and 4? n ¹ + n ² + n ³ ? 20).

2. The charge transporting varnish of 1 wherein the dopant comprises a heteropoly acid.

3. The charge transporting varnish of 2 wherein said heteropoly acid comprises tungstic acid.

4. The charge-transporting varnish of any one of 1 to 3, wherein the oligothiophene derivative is represented by formula (2).

(Wherein R ³ to R ⁸ and n ¹ to n ³ are as defined above)

5. The charge-transporting varnish of any one of 1 to 4, wherein the organosilane compound comprises at least one member selected from the group consisting of a dialkoxysilane compound, a trialkoxysilane compound and a tetraalkoxysilane compound.

6. The charge-transporting varnish of any one of 1 to 5, which further comprises a tetracyanoquinodimethane compound represented by the formula (12).

(Wherein R ¹⁰¹ to R ¹⁰⁴ each independently represent a hydrogen atom or a halogen atom, and at least one of them is a halogen atom.)

7. The charge-transporting varnish of any one of 1 to 6, wherein the charge-transporting varnish further comprises a dopant comprising an aryl sulfonic acid compound.

8. A charge-transporting thin film produced by using any one of the charge-transporting varnishes 1 to 7.

9. An organic electroluminescent device having a charge transporting thin film.

10. The organic electroluminescent device according to 9, wherein the charge transport thin film is a hole injection layer or a hole transport layer.

11. A method for producing a charge-transporting thin film, characterized in that any one of the charge-transporting varnishes 1 to 7 is coated on a substrate and baked.

12. The method of manufacturing an organic electroluminescent device according to claim 1, wherein a charge transporting thin film is used.

13. A charge-transporting material comprising a charge-transporting material comprising an oligothiophene derivative represented by the formula (1) and a dopant.

(Wherein, R ¹ ~ R ⁶ is substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, are each independently a heteroaryl group, is optionally -0Y of 2 to 20 carbon atoms and an alkynyl group, an aryl group having from 6 to 20 carbon atoms which may be substituted with Z ^2, 2 to 20 carbon atoms which may be substituted with Z ² of the ^first group, -SY ² group, -NHY ³ group, -NY ⁴ Y ⁵ group, or a -NHC (O) Y represents a ^6, again, R ¹ ~ R ⁶ is a, R ¹ and R ^2, R ³ is not a hydrogen atom and R ⁴ and / Or R ⁵ and R ⁶ may be bonded to each other to form a divalent group,

R ⁷ and R ⁸ are carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, independently each An alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ³ , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ³ , a -0Y ¹ group, a -SY ² group, ³ group, -NY ⁴ Y ⁵ group or -NHC (O) Y ⁶ group,

Y ¹ ~ Y ⁶ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms which may be substituted with, Z ¹ are each independently the alkynyl group, which may be substituted with Z ² represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group, or Z ² of 6 to 20 carbon atoms,

Z ¹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms,

Z ² represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms,

Z ³ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, &Lt; / RTI &gt;&lt; RTI ID = 0.0 &gt;

n ¹ to n ³ independently represent a natural number, and 4? n ¹ + n ² + n ³ ? 20).

By using the charge-transporting varnish of the present invention, it is possible to obtain an organic EL device having high flatness and high charge transportability and excellent luminance characteristics when applied to a hole injection layer of an organic EL device, when baked at a relatively low temperature of about 150 to 230 DEG C at a high temperature A thin film which can be realized can be obtained.

By using the charge transporting varnish of the present invention, a thin film having excellent charge transportability can be produced with high reproducibility even when various wet processes capable of forming a large-area film such as a spin coat method and a slit coat method are used, It can sufficiently cope with the progress in the field of the EL element.

The thin film obtained from the charge transporting varnish of the present invention can also be used as an antistatic film or a positive electrode buffer layer of an organic thin film solar cell.

[Oligothiophene derivatives]

The charge transporting varnish according to the present invention includes a charge-transporting material comprising an oligothiophene derivative represented by formula (1).

Further, in the present invention, the charge transportability agrees with the conductivity, and the hole transportability agrees. The charge-transporting material may have a charge-transporting property per se, or may have charge-transporting property when used together with an electron-accepting material. The charge transporting varnish may have a charge transporting property itself, and the solid film obtained thereby may have charge transporting property.

Wherein, R ¹ ~ R ⁶ is substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, are each independently An aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ² , a -OY ¹ group, a -SY ² group , -NHY ³ group, -NY ⁴ Y ⁵ group or -NHC (O) Y ⁶ group. When R ¹ to R ⁶ are not hydrogen atoms, R ¹ and R ² , R ³ and R ⁴ and / or R ⁵ and R ⁶ may be bonded to each other to form a divalent group.

R ⁷ and R ⁸ are carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, independently each An alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms which may be substituted with Z ³ , a heteroaryl group of 2 to 20 carbon atoms which may be substituted with Z ³ , a -OY ¹ group, a -SY ² group, ³ group, -NY ⁴ Y ⁵ group or -NHC (O) Y ⁶ group.

Y ¹ ~ Y ⁶ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms which may be substituted with, Z ¹ are each independently the alkynyl group, represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group, or Z ² of 6 to 20 carbon atoms which may be substituted with Z ^2.

Z ¹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.

Z ² represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms.

Z ³ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, &Lt; / RTI &gt;

The alkyl group having 1 to 20 carbon atoms may be any of linear, branched and cyclic, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, , a straight chain or branched alkyl group having 1 to 20 carbon atoms such as a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, A cyclohexyl group, a bicyclohexyl group, a bicyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclopentyl group, A cyclic alkyl group having 3 to 20 carbon atoms such as a t-butyl group, a bicyclooctyl group, a bicyclononyl group, and a bicyclo-decyl group.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include an ethenyl group, an n-1-propenyl group, an n-2-propenyl group, a 1-methylethenyl group, Methyl-1-propenyl group, a 1-methyl-2-propenyl group, a n-propyl group, 1-pentenyl group, n-1-decenyl group, n-1-eicosinyl group and the like.

Specific examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, Methyl-n-propyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, N-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, n-1-pentynyl, And an eicosinyl group.

Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, Group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

Specific examples of the heteroaryl group having 2 to 20 carbon atoms include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, Isothiazolyl group, 4-isothiazolyl group, 4-isothiazolyl group, 4-isothiazolyl group, 4-isothiazolyl group, An imidazolyl group, a 5-isothiazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group.

In the formula (1), the alkoxy group (i.e., Y ¹ of 1 to 20 carbon atoms which may Examples of R ¹ and R ² are substituted with an alkyl group or Z ¹ of 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ¹ an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ -OY ¹ group) are preferable, and carbon atoms that may be substituted with an alkyl group or Z ¹ of 1 to 10 carbon atoms that may be substituted with hydrogen atoms, Z ¹ ~ 1 10 alkoxy group is more preferred, and a hydrogen atom, Z ¹ group having 1 to 8 carbon atoms that may be substituted with an alkyl group or Z ¹ group having 1 to 8 carbon atoms optionally substituted alkoxy, and even more preferably a hydrogen atom is optimal.

Therefore, suitable oligothiophene derivatives include, for example, those represented by the formula (2).

(Wherein R ³ to R ⁸ are as defined above)

On the other hand, R ³ ~ R ⁶ As the alkoxy group (i.e., Y ¹ of 1 to 20 carbon atoms that may be substituted with an alkyl group or Z ¹ of 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ¹ is substituted with Z ¹ is optionally an alkyl group having 1 to 20 carbon atoms that is -OY ¹ group) is preferable, and more groups are hydrogen atoms, alkoxy of 1 to 10 carbon atoms that may be substituted with an alkyl group or Z ¹ of 1 to 10 carbon atoms which may be substituted with Z ¹ It preferred, and even more preferably an alkoxy group of a hydrogen atom, Z 1 carbon atoms which may be substituted with ^1-8 group having 1 to 8 carbon atoms that may be substituted with an alkyl group or Z ¹ of the. In addition, R ³ and R ⁴ at least one of the alkoxy group having 1 to 8 carbon atoms that may be substituted with an alkyl group or Z ¹ group having 1 to 8 carbon atoms which may be substituted with Z ^1, it is more preferable.

R ⁷ and R ⁸ are each a hydrogen atom, -NY ⁴ Y ⁵ group, or a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, or a diarylamino group in which each aryl group is an aryl group having 6 to 20 carbon atoms Is preferably an aryl group having 6 to 20 carbon atoms. At this time, Y ⁴ and Y ⁵ carbon atoms which may aryl of 6 to 20 carbon atoms that may be substituted with an alkyl group or Z ¹ of 1 to 20 carbon atoms which may be substituted with Z ¹ group is preferred, and is substituted with Z ¹ 1 ~ More preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted with Z &^lt; ^{1 &} gt ;.

Of these, R ⁷ and R ⁸ are preferably a hydrogen atom, a diarylamino group in which each aryl group is substituted with Z ² , or an aryl group having 6 to 10 carbon atoms, or a diarylamino group in which each aryl group is an aryl group having 6 to 20 carbon atoms Is preferable, and a hydrogen atom or a 4-diphenylaminophenyl group is most preferable.

In R ¹ to R ⁸ and Y ¹ to Y ⁶ , Z ¹ is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, and is absent (that is, unsubstituted). Z ² is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, (That is, an unsub) is optimal. Z ³ is an alkyl group having 1 to 20 carbon atoms, a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, or a diarylamino group in which each aryl group is an aryl group having 6 to 20 carbon atoms, , A dialkylamino group in which each alkyl group is an alkyl group having 1 to 10 carbon atoms or a diarylamino group in which each aryl group is an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, More preferably a dialkylamino group or a diphenylamino group which is an alkyl group having 1 to 8 carbon atoms, and is not present (i.e., is unsubstituted) or a diphenylamino group.

In the formulas (1) and (2), n ¹ to n ³ independently represent a natural number, and 4? N ¹ + n ² + n ³ ? n ¹ is preferably 1 to 15, more preferably 1 to 10, still more preferably 2 to 5, still more preferably 2 to 3. On the other hand, n ² and n ³ are preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 5, still more preferably 1 to 3.

From the viewpoint of improving the solubility of the oligothiophene derivative in an organic solvent, n ¹ to n ³ are preferably n ¹ + n ² + n ³ ≦ 8, more preferably n ¹ + n ² + n ³ ? 7, still more preferably n ¹ + n ² + n ^3? 6, more preferably n ¹ + n ² + n ³ ? 5.

Specific examples of the oligothiophene derivatives represented by the formula (1) are shown below, but are not limited thereto. In the formula, "Me" represents a methyl group, "Et" represents an ethyl group, "n-Pr" represents an n-propyl group, "i- N-Pen "represents an n-pentyl group," n-Hex "represents an isobutyl group," s-Bu "represents an s-butyl group, N-Oct "represents an n-octyl group," Ph "represents a phenyl group, and" Ar ¹ "represents a 4- (diphenylamino) phenyl group Respectively.

The oligothiophene derivative used in the present invention may be synthesized by a known method (for example, a method described in JP-A No. 02-250881 or Chem. Eur. J. 2005, 11, pp. 377-3752) Or a commercially available product may be used.

Specifically, the oligothiophene derivative used in the present invention can be synthesized, for example, according to the reaction scheme shown in Scheme 1 or 2 below. In particular, the oligothiophene derivative having an alkyl group, alkenyl group, alkynyl group, The oligothiophene derivative (formula (1 ')) having an aryl group or a heteroaryl group can be synthesized according to the reaction formula shown in scheme 3 below.

(Wherein Hal represents a halogen atom or a similar halogen group, R ¹ to R ⁸ and n ¹ to n ³ have the same meanings as defined above, and ⁿ Bu represents an n-butyl group.)

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

Examples of the similar halogen group include a (fluoro) alkylsulfonyloxy group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a nonafluorobutainesulfonyloxy group; And aromatic sulfonyloxy groups such as benzenesulfonyloxy group and toluenesulfonyloxy group.

R ⁹ and R ¹⁰ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms which may be substituted with, Z ¹ are each independently An aryl group having 6 to 20 carbon atoms which may be substituted with Z ³ , and a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ^3. Specific examples thereof include the same ones as described above. The substituents Z ¹ and Z ³ have the same meanings as described above.

In Scheme 1, the introduction ratio of the thiophene derivatives represented by the formulas (3) to (5) is usually such that the thiophene derivative represented by the formula (3), the thiophene derivative represented by the formula ) Is about 0.5 to about 1.5 equivalents, preferably about 0.9 to about 1.3 equivalents.

In Scheme 2, the introduction ratio of the thiophene derivatives represented by the formulas (6) to (8) is generally such that the thiophene derivative represented by the formula (6) 8) is about 0.5 to about 1.5 equivalents, preferably about 0.9 to about 1.3 equivalents.

The introduction ratio of the thiophene derivative represented by the formula (9) and the compound represented by the formulas (10) to (11) in Scheme 3 can be obtained by subjecting the thiophene derivative represented by the formula (9) And the compound represented by the formula (11) are each in the range of about 0.5 to 1.5 equivalents, preferably about 0.9 to 1.3 equivalents.

Examples of the catalyst used in the reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; (Triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), bis (triphenylphosphine) dichloropalladium (Pd (PPh ₃ ) ₂ Cl ₂ ), bis (benzylideneacetone) palladium ) _2), tris (dibenzylidene acetone) dipalladium (Pd ₂ (dba) _3), bis (tri -t- butylphosphine) palladium (Pd (Pt-Bu _{3) 2),} and the like palladium catalysts, such as have. These catalysts may be used singly or in combination of two or more. These catalysts may be used together with any known ligands.

The amount of the catalyst to be used is usually about 0.01 to 0.2 mol, preferably about 0.05 mol, per 1 mol of the compound represented by the formula (4), (7) or (9).

When a ligand is used, the amount of the ligand to be used is about 0.1 to 5 equivalents relative to the metal complex to be used, but about 1 to about 4 equivalents are suitable.

The reaction may be carried out in a solvent. When a solvent is used, the kind thereof is not particularly limited as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons such as pentane, n-hexane, n-octane, n-decane and decalin, halogenated aliphatic hydrocarbons such as chloroform, dichloromethane, dichloroethane and carbon tetrachloride, aromatic hydrocarbons such as benzene Xylene, mesylenes, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, (N, N-dimethylformamide, N, N-dimethylacetoamide, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, Etc.), lactam and lactones (N-methylpyrrolidone,? -Butyrolactone, etc.), urea compounds (N, N-dimethylacetamide Etc.), sulfoxides (such as dimethyl sulfoxide and sulfolane), nitriles (such as acetonitrile, propionitrile, and butyronitrile), and the like. These solvents may be used alone or in combination of two or more.

The reaction temperature may be appropriately set in the range from the melting point of the solvent to the boiling point, but is preferably about 0 to 200 占 폚, and more preferably 20 to 150 占 폚.

After completion of the reaction, post treatment is conducted according to the conventional method to obtain the oligothiophene derivative represented by the formula (1) or (1 ').

The compounds represented by the formulas (4), (6), (8), and (9) used in the above reaction can be produced by reacting a compound represented by the following general formula with a suitable base such as n-butyllithium, Can be obtained by using a suitable tin compound and introducing a tributyltin group at both ends of a thiophene compound having a structure corresponding to each compound. The compound represented by the formula (9) can also be obtained by introducing a tributyltin group at both ends of the oligothiophene derivative obtained according to Scheme 1 or 2.

The compounds represented by the formulas (3), (5), (7), (10) and (11) may be commercially available products, Can be obtained by halogenating or pseudohalizing alkanes, alkenes, alkynes, arenes or heteroarenes (except thiophenes).

[Dopant]

The charge transport varnish of the present invention comprises a dopant. The dopant is not particularly limited, and organic-based dopants and inorganic-based dopants can be used.

As the most preferable embodiment among them, the charge-transporting varnish of the present invention contains heteropoly acid as a dopant, and accordingly, it is possible to use not only high-hole capacity from a transparent electrode typified by indium tin oxide (ITO) or indium zinc oxide (IZO) It is possible to obtain a thin film having excellent charge transportability and exhibiting high hole-hole capacity from a representative metal anode.

The heteropoly acid typically has a structure in which a hetero atom is located at the center of a molecule, represented by Keggin type represented by the formula (A1) or Dawson type represented by the formula (A2), and vanadium (V), molybdenum ), Tungsten (W) and the like, and a polyacid obtained by condensation of oxoacid of a different element. As the oxo acid of such a different element, oxo acid of mainly silicon (Si), phosphorus (P) and arsenic (As) can be mentioned.

Specific examples of the heteropoly acid include phosphoromolybdic acid, silicomolybdic acid, tungstic acid, tungstic acid, and tungstomolybdic acid. These may be used singly or in combination of two or more kinds. In addition, the heteropoly acid used in the present invention is available as a commercial product, and may be synthesized by a known method.

In particular, when the dopant is composed of one kind of heteropoly acid, the one kind of heteropoly acid is preferably tungstic acid or phosphomolybdic acid, more preferably tungstic acid. In the case where the dopant is composed of two or more heteropoly acids, at least one of the two or more heteropoly acids is preferably tungstic acid or phosphomolybdic acid, more preferably tungstic acid.

In quantitative analysis such as elemental analysis, the heteropoly acid may be either a product having a large number or a small number of elements from a structure represented by a general formula, a product obtained as a commercial product thereof, or a product synthesized appropriately according to a known synthesis method However, it can be used in the present invention.

That is, for example, in general, tungstic acid is represented by the formula H ₃ (PW ₁₂ O ₄₀ ) .nH ₂ O and the molybdic acid is represented by the formula H ₃ (PMo ₁₂ O ₄₀ ) .nH ₂ O, And the number of P (phosphorus), O (oxygen), W (tungsten) or Mo (molybdenum) in this equation may be large or small, and it may be a product obtained as a commercial product, It can be used in the present invention. In this case, the mass of the heteropoly acid specified in the present invention is not a mass of pure tungstic acid (synthetic tungstic acid content) in a composite or a commercial product, but is in a form obtainable as a commercially available product and in a form which can be isolated by a known synthetic method, Means the total mass in a state including water or other impurities.

The amount of the heteropoly acid contained in the charge transporting varnish of the present invention may be about 1.0 to about 70.0, preferably about 2.0 to about 60.0, more preferably about 2.5 to about 55.0, and still more preferably about 2.5 ~ 25.0.

[Organosilane compound]

The organosilane compound included in the charge transporting varnish of the present invention includes a dialkoxysilane compound, a trialkoxysilane compound, or a tetraalkoxysilane compound. These may be used singly or in combination of two or more kinds.

In particular, the organosilane compound preferably contains one kind 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 those represented by the formulas (B1) to (B3).

SiR ' ₂ (OR) ₂ (B1)

SiR ' (OR) ₃ (B2)

Si (OR) ₄ (B3)

Wherein, R is a 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹⁰¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹⁰¹ of 1 to 20 carbon atoms which may be substituted with a independently, Z ¹⁰¹ alkynyl group, optionally substituted by an aryl group, or Z ¹⁰² of 6 to 20 carbon atoms which may be substituted with Z ¹⁰² may indicate that a heteroaryl group having 2 to 20 carbon atoms.

R 'are each independently, an alkynyl group of 2 to 20 carbon atoms substituted with Z ¹⁰³ as an alkyl group having 1 to 20 carbon atoms that may be substituted, an alkenyl group of 2 to 20 carbon atoms that may be substituted with Z ^103, Z ^103, which may represents a heteroaryl group having from 6 to 20 carbon atoms or aryl group having 2 to 20 carbon atoms which may be substituted with Z ¹⁰⁴ of which may be substituted with Z ^104.

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

Z ^1O2 is a halogen atom, Z is substituted with ¹⁰⁵ may be 1 to 20 carbon atoms an alkyl group, Z is substituted with ¹⁰⁵ may be 2 to 20 carbon atoms in the alkenyl group or Z ¹⁰⁵ to alkynyl groups having from 2 to 20 carbon atoms that may be substituted for .

Z ¹⁰³ represents a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹⁰⁵ , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹⁰⁵ , an epoxy cyclohexyl group, a glycidoxy group, represents a group, acrylic lock time, oil-laid group (-NHCONH _2), thiol group, isocyanate group (-NCO), amino group, or a group -NHY ¹⁰¹ -NY ¹⁰² Y ^1O3.

Z ¹⁰⁴ is of 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹⁰⁵ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹⁰⁵ of 1 to 20 carbon atoms that may be substituted with a halogen atom, Z ¹⁰⁵ alkynyl group, (-NHCONH ₂ ), a thiol group, an isocyanate group (-NCO), an amino group, an -NHY ¹⁰¹ group or -NY ¹⁰² Y group, a glycidoxy group, a methacryloxy group, an acryloyl group, ¹⁰³ groups.

Y ¹⁰¹ ~ Y ¹⁰³ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹⁰⁵ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹⁰⁵ of 1 to 20 carbon atoms which may be substituted with, Z ¹⁰⁵ are each independently a represents an alkynyl group, a heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group, or Z ¹⁰⁵ of 6 to 20 carbon atoms which may be substituted with Z ^105.

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

Examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, the alkynyl group having 2 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms in the formulas (B1) to (B3) .

Examples of R alkyl group of 1 to 20 carbon atoms which may be substituted with Z ^101, of 2 to 20 carbon atoms which may be substituted with Z ^1O1 alkenyl group or Z ¹⁰² an aryl group having from 6 to 20 carbon atoms that may be substituted preferably by and, Z ¹⁰¹ carbon atoms which may have a phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms that may be substituted, an alkenyl group, or Z ¹⁰² having a carbon number of 2-6 that may be substituted with Z ¹⁰¹ is substituted with more preferred, and Z ¹⁰¹ to 1 to More preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group optionally substituted with Z ¹⁰² , and still more preferably a methyl group or ethyl group which may be substituted with Z ¹⁰¹ .

As R ', an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹⁰³ , or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹⁰⁴ is preferable, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z ¹⁰³ , More preferably an aryl group having 6 to 14 carbon atoms which may be substituted with Z ¹⁰⁴ , still more preferably an alkyl group having 1 to 6 carbon atoms which may be substituted with Z ¹⁰³ or an aryl group having 6 to 10 carbon atoms which may be substituted with Z ¹⁰⁴ , An alkyl group having 1 to 4 carbon atoms which may be substituted with Z ¹⁰³ , or a phenyl group optionally substituted with Z ¹⁰⁴ .

The plurality of Rs may be the same or different, and a plurality of R 's may all be the same or different.

Z ¹⁰¹ As will halogen atoms or Z ¹⁰⁵ an aryl group having from 6 to 20 carbon atoms that may be substituted preferably with, and that is a phenyl group which may be substituted with a fluorine atom or Z ¹⁰⁵ no more present preferred, and (i. E., Beach Whanin) Is optimal.

In addition, Z ¹⁰² as an alkyl group having from 6 to 20 carbon atoms that may be substituted with a halogen atom or Z ¹⁰⁵ preferred, and a fluorine atom or having 1 to 10 carbon atoms which may be substituted with Z ¹⁰⁵ alkyl, and more preferably, does not exist will (I. E., An unsigned one) is optimal.

On the other hand, Z ¹⁰³ As the halogen atom, Z ¹⁰⁵ phenyl group which may be substituted with, furanoid group, epoxy cyclohexyl that may be substituted with Z ¹⁰⁵ group, an article rayisi dock timing, methacrylic lock time, acrylic lock time, oil-laid group, A halogen atom, a thiol group, an isocyanate group, an amino group, a phenylamino group which may be substituted with Z ¹⁰⁵ or a diphenylamino group which may be substituted with Z ¹⁰⁴ , more preferably a halogen atom, ) Is more preferable.

In addition, Z ¹⁰⁴ As the halogen atom, Z ¹⁰⁵ alkyl group having 1 to 20 carbon atoms which may be substituted with, furanoid group, epoxy cyclohexyl that may be substituted with Z ¹⁰⁵ group, an article rayisi dock timing, methacrylic lock time, acrylic lock time , oil-laid group, a thiol group, an isocyanate group, an amino group, Z ¹⁰⁵ is diphenyl amino group that may be substituted by phenyl group or Z ¹⁰⁵ is optionally substituted preferably with, more preferably a halogen atom, and a fluorine atom, or does not exist (I. E., An unsubstituted one) is even more preferred.

As Z ¹⁰⁵ , a halogen atom is preferable, and a fluorine atom or a non-fluorine atom (that is, an unsubstituted one) is more preferable.

Specific examples of the organosilane compound usable in the present invention are shown below, but the present invention is not limited thereto.

Specific examples of the dialkoxysilane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, But are not limited to, dimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3,3,3-Trifluoropropylmethyldimethoxysilane There may be mentioned, such as Sicily lane.

Specific examples of the trialkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, pentyltrimethoxysilane, heptyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, Hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethane, octadecyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, 3-Aminov 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri But are not limited to, ethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, dodecyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, (triethoxy Silyl) cyclohexane, perfluorooctylethyltriethoxysilane, triethoxyfluorosilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, pentafluoro (Heptafluoroisopropoxy) propyltriethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrofuran-1, 2, 2-tetrahydrothiophene, Decyl triethoxy silane, triethoxy-2-thienyl silane, 3- The silyl ethoxy), and the like THF.

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

Among them, 3,3,3-trifluoropropylmethyldimethoxysilane, triethoxy (4- (trifluoromethyl) phenyl) silane, 3,3,3-trifluoropropyltrimethoxysilane Perfluorooctylethyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, and the like are preferable.

The content of the organosilane compound in the charge transporting varnish of the present invention is usually about 0.1 to 50 mass% with respect to the total mass of the charge-transporting material and the dopant. The content of the organosilane compound in the charge- It is preferably about 0.5 to about 40 mass%, more preferably about 0.8 to about 30 mass%, more preferably about 0.5 to about 30 mass%, in consideration of enhancing the hole injecting ability with respect to the layer stacked to be in contact with the hole injection layer on the side opposite to the anode such as the light- More preferably about 1 to 20% by mass.

[Organic solvents]

As the organic solvent used for preparing the charge transporting varnish, a solvent capable of dissolving a charge-transporting substance, a dopant and an organosilane compound can be used.

Examples of such a solubilizing solvent include N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, And an organic solvent such as ethylene glycol monomethyl ether can be used. These solvents may be used singly or in combination of two or more, and the amount thereof may be 5 to 100% by weight based on the total solvent used in the varnish.

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

In the present invention, a high viscosity organic solvent having a viscosity of 10 to 200 mPa · s, particularly 35 to 150 mPa · s at 25 ° C. and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure) The inclusion of at least one kind makes it easy to adjust the viscosity of the varnish. As a result, a thin film with high flatness can be imparted with good reproducibility and varnish preparation according to the application method to be used becomes possible.

The high viscosity organic solvent is not particularly limited and includes, for example, cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octyleneglycol, diethylene glycol, di Propylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hex And cyanuric glycol. 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 within a range in which no solid is precipitated, and the addition ratio is preferably from 5 to 80 mass% unless a solid is precipitated.

For the purpose of improving the wettability with respect to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, and adjusting the boiling point, other solvents may be used in an amount of 1 to 90% by mass, preferably 1 By mass to 50% by mass.

Examples of such a solvent include ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol,? -Butyrolactone, ethyl lactate,? -Butyrolactone,? -Butyrolactone, , n-hexyl acetate, propylene glycol monomethyl ether, and the like, but are not limited thereto. These solvents may be used singly or in combination of two or more.

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

The solid concentration of the charge transporting varnish in the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, and the like, but is usually about 0.1 to 10.0 mass% It is preferably about 0.5 to 5.0 mass%, and more preferably about 1.0 to 3.0 mass%.

[Tetracyanoquinodimethane compound]

The charge transporting varnish of the present invention preferably contains the tetracyanoquinodimethane compound represented by formula (12). By including the tetracyanoquinodimethane compound, the lifetime of the device is improved and the characteristics such as brightness are further improved when the obtained thin film is used as the hole injection layer. In addition, even when the varnish is baked at low temperature, a thin film having high flatness and high charge transportability can be produced with good reproducibility.

In the formulas, R ¹⁰¹ to R ¹⁰⁴ independently represent a hydrogen atom or a halogen atom, and at least one of them is a halogen atom. Examples of the halogen atom include the same ones as described above, and a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable. At least two of R ¹⁰¹ to R ¹⁰⁴ are preferably a halogen atom, more preferably at least three of them are halogen atoms, and most preferably all of them are halogen atoms.

Specific examples of the tetracyanoquinodimethane compound include tetrafluorotetracycyanoidime methane (F4TCNQ), tetrachlorotetracycyanoidime methane, 2-fluorotetracyanoquinodimethane, 2- 2,5-dichlorotetracyanoquinodimethane, 2,5-dichlorotetracyanoquinodimethane, 2,5-dichlorotetracyanoquinodimethane, 2,5-dichlorotetracyanoquinodimethane, and the like. As the tetracyanoquinodimethane compound, F4TCNQ is particularly preferable.

The content of the tetracyanoquinodimethane compound in the charge transporting varnish of the present invention is preferably 0.0001 to 1 equivalent, more preferably 0.001 to 0.5 equivalent, still more preferably 0.01 to 0.2 equivalent to be.

[Other components]

The charge transporting varnish of the present invention may contain, in addition to the above-described oligothiophene derivatives, other charge-transporting materials as long as the effects of the present invention are not hindered. The charge transporting varnish of the present invention may contain other substances instead of the above-described heteropolyacid as a dopant.

Examples of other charge-transporting materials include oligoaniline derivatives described in JP 2002-151272 A, oligoaniline compounds described in WO 2004/105446, 1,4- Ditine ring, oligoaniline compounds described in International Publication No. 2008-032617, oligoaniline compounds disclosed in International Publication No. 2008/032616, and aryldiamine compounds described in International Publication No. 2013/042623 .

In particular, an aniline derivative is preferable as the other charge-transporting substance, and the molecular weight thereof is preferably 4,000 or less, more preferably 3,000 or less, still more preferably 2,000 or less in consideration of solubility in an organic solvent.

In the present invention, examples of the aniline derivatives which can be suitably used as other charge-transporting materials include those represented by the formula (13).

B ¹ represents a single bond, -NH-, -CH ₂ -, -S- or -O-, with a single bond or -NH- being preferred.

R ²⁰¹ ~ R ²⁰⁶ is substituted with independently, a hydrogen atom, a halogen atom, an alkenyl group, Z ²⁰¹ of 1 to 20 carbon atoms an alkyl group, having 2 to 20 carbon atoms which may be substituted with Z ²⁰¹ of which may be substituted with Z ²⁰¹ each the optionally 2 to 20 carbon atoms alkynyl group, optionally substituted by Z ²⁰² 6 to 20 carbon atoms an aryl group, having from 2 to 20 carbon atoms which may be substituted with Z is of the ²⁰² of the heteroaryl group, a -OY group ^201, group ²⁰² -SY , -NHY ²⁰³ , -NY ²⁰⁴ Y ²⁰⁵ group or -NHC (O) Y ² O ⁶ group. Y ²⁰¹ ~ Y ²⁰⁶ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ²⁰¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ²⁰¹ of 1 to 20 carbon atoms which may be substituted with, Z ²⁰¹ are each independently a represents an alkynyl group, a heteroaryl group having from 6 to 20 carbon atoms or aryl group having 2 to 20 carbon atoms which may be substituted with Z ²⁰² of which may be substituted with Z ^202. Specific examples of such a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heteroaryl group include the same ones as described above.

Z ²⁰¹ is optionally substituted with a halogen atom, a group, a cyano group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, an aryl group, or Z ²⁰³ of 6 to 20 carbon atoms that may be substituted with Z ²⁰³ nitro, And a heteroaryl group having 2 to 20 carbon atoms.

Z ²⁰² carbon atoms that may be substituted with a halogen atom, a nitro group, a cyano group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, an alkyl group, Z ²⁰³ of 1 to 20 carbon atoms that may be substituted with Z ²⁰³ An alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms which may be substituted with Z ²⁰³ .

Z ²⁰³ represents a halogen atom, a nitro group, a cyano group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group or a carboxylic acid group.

R ²⁰¹ ~ R ²⁰⁴ as the number of carbon atoms that may be substituted with an aryl group, Z ²⁰¹ of 6 to 20 carbon atoms that may be substituted with an alkyl group, Z ²⁰² of 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a halogen atom, Z ²⁰¹ 1 (-0Y ²⁰¹ group in which Y ²⁰¹ is an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ²⁰¹ ), more preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ²⁰¹ , More preferably an alkyl group having 1 to 10 carbon atoms which may be substituted with Z ²⁰² , an aryl group having 6 to 14 carbon atoms which may be substituted with Z ²⁰² , or an alkoxy group having 1 to 10 carbon atoms which may be substituted with Z ²⁰¹ , of 1 to 6 carbon atoms alkyl group, Z 6 ~ 10 aryl group are ²⁰² substituted with optionally, 1 to 6 carbon atoms which may be substituted with Z ²⁰¹ of the alkoxy group, and more preferably, is substituted by a hydrogen atom, a fluorine atom, Z ²⁰¹ Having 1 to 6 carbon atoms Group group, an alkoxy group having 1 to 6 carbon atoms which may be substituted with Z ²⁰¹ more preferred, and a hydrogen atom is optimal.

On the other hand, as R ²⁰⁵ and R ^{206, there may} be mentioned a hydrogen atom, a halogen atom, a dialkylamino group whose alkyl group has 1 to 20 carbon atoms and in which each alkyl group may be substituted with Z ²⁰¹ (that is, Y ²⁰⁴ and Y ²⁰⁵ are substituted with Z ²⁰¹ carbon number of 1 to 20 alkyl group -NY ²⁰⁴ Y ²⁰⁵ group), or a Z ²⁰¹ each aryl group is Z ²⁰² is substituted by the aryl group having from 6 to 20 carbon atoms which may diaryl amino groups (i.e., Y ²⁰⁴ and Y ²⁰⁵ of the A -NY ²⁰⁴ Y ²⁰⁵ group which may be substituted), a dialkylamino group which is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms in which each alkyl group may be substituted with Z ²⁰¹ , or an aryl group having from 6 to 20 carbon atoms which each aryl group is an aryl group diaryl amino group having from 6 to 20 carbon atoms which may be substituted with Z ²⁰² more preferred, and may be groups a hydrogen atom, each of the aryl substituted with Z ²⁰² diarylamino Amino Is the more preferable, and at the same time, an aryl group diaryl amino group having from 6 to 20 carbon atoms which may group a hydrogen atom or each aryl substituted by Z ²⁰² is more preferred.

P and q each independently represent an integer of 0 or more and satisfy 2? P + q? 20, preferably 2? P + q? 8, more preferably 2? P + q? 6, and even more preferably 2? p + q? 4.

In particular, in the R ²⁰¹ ~ R ²⁰⁶ and Y ²⁰¹ ~ Y ^206, Z ²⁰¹ is not preferred group of 6 to 20 carbon atoms aryl, and a phenyl group are more preferred, and there is optimal (i.e., Beach Whanin). Z ²⁰² is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, (That is, an unsub) is optimal.

Specific examples of aniline derivatives suitable as other charge-transporting materials in the present invention include, but are not limited to, the following.

On the other hand, examples of other dopant materials include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, Dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecylbenzenesulfonic acid, 2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, hexyl-1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, , 6-hexyl-2-naphthalenesulfonic acid, dynonylnaphthalenesulfonic acid, 2,7-dionyl-4-naphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, 2,7- Sulfonic acid, the 1,4-benzodioxane disulfonic acid compound described in WO 2005/000832, the arylsulfone compound described in WO 2006/025342 Aryl sulfonic acid compounds, such as compound, aryl sulfonate compounds, polystyrene sulfonic acid described in International Publication No. 2009/096352 call; Nonarylsulfone compounds such as 10-camphorsulfonic acid; Organic oxidizing agents such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) have.

Of these, arylsulfonic acid compounds are preferable as other dopants, and in view of the solubility in an organic solvent, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.

Examples of the arylsulfonic acid compound which can be suitably used as a dopant in the present invention include those represented by the formula (14) or (15).

In the formula (14), A ¹ represents -O- or -S-, preferably -O-. A ² represents a naphthalene ring or an anthracene ring, and a naphthalene ring is preferable. A ³ is a perfluorobiphenyl group having 2 to 4 valences, j is an integer satisfying 2? J? 4, which represents the number of bonds between A ¹ and A ³ , A ³ is a divalent perfluorobiphenyl group, Preferably perfluorobiphenyl-4,4-diyl, and j is preferably 2. m is a number of sulfonic acid groups bonded to A ² , and is an integer satisfying ^1? m? ⁴ , and 2 is suitable.

In formula (15), A ⁴ to A ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms , And at least three of A ⁴ to A ⁸ are halogen atoms. k represents a sulfonic acid group bonded to a naphthalene ring and is an integer satisfying 1? k? 4, preferably 2 to 4, more preferably 2.

Examples of the halogenated alkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3-trifluoropropyl group , 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3 , 3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4 , 4-nonafluorobutyl group, and the like. Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include a perfluorovinyl group, a 1-perfluoropropenyl group, a perfluoroallyl group, and a perfluorobutenyl group.

Examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same ones as described above. As the halogen atom, a fluorine atom is preferable.

Among these, A ⁴ ~ A ⁸ is a halogenated alkenyl group of a hydrogen atom, a halogen atom, a cyano group, 1 to 10 carbon atoms in the alkyl group, having 1 to 10 carbon atoms, a halogenated alkyl group or 2 to 10 carbon atoms of, and A ⁴ ~ A ⁸ of A fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, an alkyl fluoride group having 1 to 5 carbon atoms, or an alkenyl fluoride group having 2 to 5 carbon atoms, and at least one of A ^4, At least three of A ⁸ are more preferably a fluorine atom and are a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkenyl group having 1 to 5 carbon atoms, and A ⁴ , A &lt; ⁵ &gt; and A &lt; ⁸ &gt; are fluorine atoms.

The perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all the hydrogen atoms of the alkenyl group are substituted with fluorine atoms.

Specific examples of the arylsulfonic acid compound suitable as the dopant in the present invention include, but are not limited to, the following.

[Charge transporting material]

The charge-transporting material of the present invention includes a charge-transporting material comprising an oligothiophene derivative represented by the formula (1) and a dopant. Such a charge-transporting material exhibits good solubility in 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 transporting thin film]

The charge transporting thin film can be formed on the substrate by applying the charge transporting varnish of the present invention to the substrate and then firing it.

The varnish is not particularly limited, and examples of the varnish include dip coating, spin coating, transfer printing, roll coating, brushing, ink jet coating and spray coating. The varnish viscosity and surface tension can be controlled .

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

The firing temperature is suitably set in the range of about 100 to 260 DEG C in consideration of the use of the thin film to be obtained and the degree of charge transportability imparted to the resulting thin film. When the resulting thin film is used as the hole injection layer of the organic EL device , Preferably about 140 to 250 캜, and more preferably about 145 to 240 캜.

One of the features of the varnish of the present invention is that it can be fired at a low temperature of less than 200 DEG C, and even a thin film produced under such a firing condition has high planarity and high charge transportability.

Further, a temperature change of two or more stages may be provided for the purpose of exhibiting a higher uniform film-forming property at the time of baking, or to promote the reaction on the substrate. Heating may be performed using a suitable device such as, for example, a hot plate or an oven.

Although the film thickness of the charge transporting thin film is not particularly limited, it is preferably 5 to 200 nm when used as the hole injection layer in the organic EL device. As a method for changing the film thickness, there is a method of changing the solid content concentration in the varnish or changing the amount of solution on the substrate at the time of coating.

[Organic EL device]

Materials and methods for producing OLED devices using the charge-transporting varnish of the present invention include, but are not limited to, the following materials.

It is preferable that the electrode substrate to be used is cleaned beforehand by liquid cleaning with detergent, alcohol, pure water or the like. For example, in the case of the positive electrode substrate, it is preferable to perform surface treatment such as UV ozone treatment or oxygen- Do. However, in the case where the anode material is composed mainly of an organic material, the surface treatment need not be performed.

An example of a method for manufacturing an OLED element having a hole injection layer made of a thin film obtained from the charge transporting varnish of the present invention is as follows.

By the above method, the charge-transporting varnish of the present invention is coated on the anode substrate and baked, and a hole injection layer is formed on the electrode. This is introduced into a vacuum deposition apparatus, and a hole transporting layer, a light emitting layer, an electron transporting layer, an electron transporting layer / hole blocking layer, an electron injecting layer and a cathode metal are sequentially deposited to form an OLED device. In addition, an electronic block layer may be provided between the light emitting layer and the hole transporting layer as necessary.

As the anode material, a metal anode composed of a transparent electrode typified by indium tin oxide (ITO) or indium zinc oxide (IZO), a metal typified by aluminum, an alloy thereof, or the like can be used and it is preferable to perform the planarization treatment . A polythiophene derivative or a polyaniline derivative having high charge transportability may be used.

Examples of other metals constituting the metal anode include metals such as scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, A metal selected from the group consisting of lanthanum, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, thallium, tungsten, rhenium, osmium, iridium, Lead, bismuth, alloys thereof, and the like.

(Triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, and N, N'-bis (naphthalen-1-yl) -N, N'- Benzidine (? -NPD), N, N'-bis (naphthalene-2-yl) -N, N'- N, N'-bis (phenyl) -benzidine, N, N'-bis (3-methylphenyl) -N, N'- ), N, N'-bis (phenyl) -9,9-dimethylbiphenyl, N, N'- Fluorene, N, N'-bis (3-methylphenyl) -N (N'- (Phenyl) -9,9-diphenyl-fluorene, N, N'-bis (naphthalen-1-yl) -N, N'- N, N'-bis (phenyl) -2,2'-dimethylbenzidine, 2,2 ', 7,7'-tetrakis (N , N-diphenylamino) -9,9-spirobifluorene, 9,9- Bis [4- (N, N-bis-naphthalen-2-yl-amino) phenyl] -9H-fluorene, Phenyl] -9H-fluorene, 2,2 ', 7,7'-fluorene, 9,9-bis [4- (N-naphthalen- N, N'-bis (phenyl) -benzidine (phenyl) -amino] -9,9-spirobifluorene, N, N'-bis (phenanthrene- (N, N-diphenylamino) -9 (4-hydroxyphenyl) amino] -9,9-spirobifluorene, 2,2'-bis , 9- spirobifluorene, di- [4- (N, N-di (p-tolyl) amino) -phenyl] cyclohexane, 2,2 ', 7,7'- (p-tolyl)) amino-9,9-spirobifluorene, N, N, N ', N'-tetra-naphthalen- N, N ', N', N'-di (naphthalen-2-yl) -benzidine, N, N'-dicyclohexylcarbodiimide -Tetra (naphthalenyl) -benzidine, N, N'-di (naphthalen-2-yl) -N, N'-diphenylbenzidine- 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 - tetra Diamine, tris (4- (quinolin-8-yl) phenyl) amine, 2,2'-bis (Phenyl) amino] triphenylamine (m-MTDATA), 4,4 ', 4 "-tris [1-naphthyl (1-TNATA), triarylamines such as 5,5-bis- {4- [bis (4-methylphenyl) amino] phenyl} -2,2 ' 3T), and the like.

As the material for forming the light emitting layer, tris (8-quinolinolato) aluminum (III) (Alq ₃ ), bis (8-quinolinolato) zinc (II) (Znq ₂ ) Quinolinolato) -4- (p-phenylphenolato) aluminum (III) (BAlq), 4,4'-bis (2,2-diphenylvinyl) biphenyl, 9,10- Di (naphthalen-2-yl) anthracene, 2,7-bis [9,9-di (4-methylphenyl) 9,9-di (4-methylphenyl) fluorene, 2-methyl-9,10-bis (naphthalene- Spirobifluorene, 2- [9,9-di (4-methylphenyl) - 9,9-spirobifluorene, 2,7- (4-methylphenyl) fluorene, 2,2'-dipyrenyl-9,9-spirobifluorene, 1,3,5-tris (pyrene- Benzene, 9,9-bis [4- (pyrenyl) phenyl] -9H-fluorene, 2,2'-bya (9,10- diphenylanthracene), 2,7- 1,3-di (pyrene-1-yl) benzene, 6,13-di (biphenyl-4-yl) (Naphthalene-2-yl) perylene, tris [4- (pyrenyl) -phenyl] amine, 10 Di (biphenyl-4-yl) -9,9'-bianthracene, N, N'-di (naphthalen- 4'-di [10- (naphthalen-1-yl) anthracene-9-yl] biphenyl] -4,4'- Phenyl, dibenzo {[f, f '] - 4,4', 7,7'-tetraphenyl} diindeno [1,2,3-cd: (9,9'-bianthracene-10-yl) -9,9-dimethyl-9H-fluoren-2-yl) pyrene, 1- (7- (Carbazol-9-yl) benzene, 1,3,5-tris (bicyclopentadienyl) (Carbazol-9-yl) benzene, 4,4 ', 4 "-tris (carbazol-9-yl) triphenylamine, 4,4'- 4,4'-bis (carbazol-9-yl) -2,2'-dimeth- (Carbazol-9-yl) -9,9-dimethylfluorene, 2,2 ', 7,7'-tetrakis (carbazol-9-yl) -9, (Carbazol-9-yl) -9,9-di (p-tolyl) fluorene, 9,9-bis [4- (Phenyl) fluorene, 2,7-bis (carbazol-9-yl) -9,9-spirobifluorene, 1,4-bis (triphenylsilyl) benzene, ) Benzene, bis (4-N, N-diethylamino-2-methylphenyl) -4-methylphenylmethane, 2,7-bis (carbazol- , 4 "-di (triphenylsilyl) -p-terphenyl, 4,4'-di (triphenylsilyl) biphenyl, 9- ) -9H-carbazole, 9- (4-t-butylphenyl) -3,6-ditolyl-9H-carbazole, 9- Carbazole, 2,6-bis (3- (9H-carbazol-9-yl) phenyl) pyridine, triphenyl (4-methoxyphenyl) -9H-fluorene- - (9-phenyl-9H-fluoren-9-yl) phenyl) silane, 9,9- Phenyl) -9H-fluorene-2-amine, 3,5-bis (3- (9H-carbamoyl) 9,9 '- (5- (triphenylsilyl) -1,3-phenyl) -pyridine, 9,9-spirobifluorene- (9H-carbazole), 3- (2,7-bis (diphenylphosphoryl) -9-phenyl-9H-fluoren- (Cd, mn) pyrene, 4,7-di (9H-carbazol-9-yl) -hexahydro-4H-8H-12H- Bis (diphenylphosphoryl) dibenzo [b, d] azepin-2-yl) -1,10-phenanthroline, 2,2'- (9H-carbazol-9-yl) phenyl] diphenylsilane, 3,6-bis (carbazol-9-yl ) -9- (4- (diphenylphosphoryl) phenyl) -9H-carbazole, 3,6-bis [(3,5-diphenyl) phenyl] -9-phenylcarbazole, and the like. The luminescent dopant and the co- It may be formed by a light-emitting layer.

Examples of the luminescent dopant include 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, N, N'-dimethyl-quinacridone, tris (2-phenylpyridine) iridium (III) (prepared by reacting 10- (2-benzothiazolyl) quinolizino [9,9a, 1gh] coumarin, quinacridone, Ir (ppy) _3), bis (2-phenyl Charmander Dean) (acetylacetonate) iridium (III) (Ir (ppy) ₂ (acac)), tris [2- (p- tolyl) Charmander Dean] iridium (III ) (Ir (mppy) ₃ ), 9,10-bis [N, N-di (p- tolyl) amino] anthracene, 9,10- 2-hydroxyphenyl) benzothiazole Jolla Sat] zinc ^{(II), N 10, N} 10, N 10, N 10 - tetra (p- tolyl) -9,9'- bi-anthracene -10,10'- diamine ^{, N 10, N 10, N} 10, N 10 - tetraphenyl -9,9'- bi anthracene -10,10'- diamine, N ^10, N ¹⁰ - diphenyl -N ^10, N ¹⁰ - die-naphthalenol 9,9'-bianthracene-10,10'-diamine, 4,4'-bis (9-ethyl-3-carbazovinylene) -1,1'- Vinylene] benzene, 4,4'-bis [4- (di (tert-butyldimethylsilyl) (di-p-tolylamino) stilyl] stilbene, bis [3,5-difluoro 4- (diphenylamino) styryl] biphenyl, bis (2,4-dihydroxypyridyl) N, N'-bis (phenyl) -tris (III), N, N'-bis (naphthalen- , 9-dimethylfluorenylene), 2,7-bis {2- [phenyl (m-tolyl) amino] -9,9- Yl) vinyl) phenyl) -N-phenylbenzene amine, fac (phenylenediamine), and the like. Iridium (III) tris (1-phenyl-3-methylbenzimidazoline-2-ylidene-C, C ² ), mer- 2-Iridene -C, C ^2), 2,7- bis [4- (diphenylamino) styryl] 9,9-spiro-by-fluoren-6-methyl-2- (4- (9- (4- (6 Yl) phenyl) anthracene-10-yl) phenyl) benzo [d] thiazole, 1,4-di [4- (N, N- diphenyl) amino] Benzene, 1,4-bis (4- (9H-carbazol-9-yl) styryl) benzene, (E) -6- (4- (diphenylamino) Amide, bis (2,4-difluorophenylpyridinato) (5- (pyridin-2-yl) -1H-tetrazolate) iridium (III) -5- (2-pyridyl) pyrazole) ((2,4-difluorobenzyl) diphenylphosphinate) iridium (III), bis (3- trifluoromethyl- (Benzyl diphenylphosphinate) iridium (III), bis (1- (2,4-difluorobenzyl) -3-methylbenzimidazolium) (3- (trifluoromethyl) Methyl) -5- (2-pyridyl) -1,2,4-triazolate) iridium (III), bis (3-trifluoromethyl- (4 ', 6'-difluorophenylpyridinate) (iridium (III), bis (4', 6'-difluorophenylpyridinate) (Trifluoromethyl) -2- (2'-pyridyl) pyrollate) iridium (III), bis (4 ', 6'-difluorophenylpyridinato) Iridium (III), (Z) -6-mesityl-N- (6-mesitylquinolin-2 (1H) quinolin-2-amine _{-BF 2, (E) -2- (} 2- (4- ( dimethylamino) styryl) -6-methyl-4-ylidene -4H- Failan) words no nitrile, 4 (Dicyanomethylene) -2-methyl-6- (1, 1, 7, 7-tetra 9-enyl) -4H-pyran, 4- (dicyanomethylene) -2-t-butyl-6- (1,1,7,7-tetramethyljulolidin- Vinyl) -4H-pyran, tris (dibenzoylmethane) phenanthroline europium (III), 5,6,11,12-tetraphenylnaphthacene, bis Thiophen-2-yl-pyridine) (acetylacetonate) iridium (III), tris (1-phenylisoquinoline) iridium (III), bis (1-phenylisoquinoline) ), Bis [1- (9,9-dimethyl-9H-fluoren-2-yl) -isoquinoline] (acetylacetonate) iridium (III) (III), tris [4,4'-di-tert-butyl- (2,2 ') - bipyridine] ruthenium (III) (2-phenylquinoline) iridium (III), bis (2-phenylquinoline) (acetylacetonate) iridium (III), 2,8- Bis (4-t-butylphenyl) -6,12-diphenyltetracene, bis (2-phenylbenzothiazolato) (acetylacetonate) iridium (III), 5,10,15,20- Benzoporphyrin platinum, osmium (II) bis (3-trifluoromethyl-5- (2-pyridine) -pyrazolate) dimethylphenylphosphine, (II) bis (3- (trifluoromethyl) -5- (4-t-butylpyridyl) -1,2,4-triazolate) diphenylmethylphosphine, osmium (II) bis (2-pyridyl) -1,2,4-triazole) dimethylphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (4-n-hexylphenyl) quinoline] (acetylacetonate) iridium (III), tris (2-methylphenyl) - (4-n-hexylphenyl) quinoline] iridium (III), tris [2-phenyl-4-methylquinoline] iridium (III) ) Iridium (III), bis (2- (9,9-diethyl-fluoren-2-yl) -1-phenyl-1H- benzo [d] imidazolato) (acetylacetonate) iridium (III) Iridium (III), bis (2-phenylquinoline) (2,2,6,6-tetrahydronaphthalene-2- 6-tetramethylheptane-3,5-dionate) iridium (III), bis (phenyl (2,2,6,6-tetramethylheptane-3,5-dionate) iridium (III), iridium (III) bis (4-phenylthieno [3,2- c] pyridinate -N, C ² ) acetylacetonate, (E) -2- (2-t-butyl-6- (2- (2,6,6- Yl) vinyl] -4H-pyran-4-ylidene) malononitrile, bis (3-trifluoromethyl-5- (Methyldiphenylphosphine) ruthenium, bis [(4-n-hexylphenyl) isoquinoline] (acetylacetonate) iridium (III), platinum (II) octaethylpoppine, bis Iridium (III) 2-methyldibenzo [f, h] quinoxaline) (acetylacetonate) iridium (III) and tris [(4-n-hexylphenyl) quinoquinoline] iridium (III).

Examples of the material for forming the electron transporting layer / hole blocking layer include 8-hydroxyquinolinolato-lithium, 2,2 ', 2 "- (1,3,5-benzyltolyl) Benzimidazole), 2- (4-biphenyl) 5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,9- Bis (2-methyl-8-quinolinolato) -4- (phenylphenolato) aluminum, 1,3-bis [2 - (2,2'-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] benzene, 6,6'- Yl] -2,2'-bipyridine, 3- (4-biphenyl) -4-phenyl-5-t-butylphenyl- Triazole, 4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole, 2,9- -1,10-phenanthroline, 2,7-bis [2- (2,2'-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] -Dimethylfluorene, 1,3-bis [2- (4-t-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene, tris Methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4,5f] [1,10] phenan- Phenyl-dipyranylphosphine oxide, 3,3 ', 5,5'-tetra [((naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline, (3-pyridyl) -phen-3-yl] benzene, 4,4'-bis (4,6-di Bis (3,5-di (pyridin-3-yl) phenyl] benzene, bis (10-hydroxybenzo [h ] Quinolinato) beryllium, diphenylbis (4- (pyridin-3-yl) phenyl) silane and 3,5-di (pyrene-1-yl) pyridine.

Oxide as the material forming the electron injection layer of lithium (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ 0 _3), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF _2), fluoride Cesium (CsF), strontium fluoride (SrF ₂ ), molybdenum trioxide (MoO ₃ ), aluminum, Li (acac), lithium acetate and lithium benzoate.

Examples of the anode material include aluminum, a magnesium-silver alloy, an aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.

Examples of the material for forming the electron block layer include tris (phenylpyrazole) iridium and the like.

The method of producing the PLED device using the charge transporting varnish of the present invention is not particularly limited, but the following methods can be used.

In the production of the OLED device, instead of conducting the vacuum evaporation 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 luminescent polymer layer are sequentially formed to form the charge transporting varnish A PLED device having a transport thin film can be manufactured.

Specifically, the hole transporting varnish of the present invention is coated on the anode substrate to prepare a hole injecting layer by the above method, a hole transporting polymer layer and a luminescent polymer layer are sequentially formed thereon, and a cathode electrode is deposited to form a PLED Device.

As the anode and cathode materials to be used, the same materials as in the production of the OLED device can be used, and the same cleaning treatment and surface treatment can be performed.

The hole-transporting polymer layer and the light-emitting polymer layer may be formed by dissolving or uniformly dispersing a solvent in a hole-transporting polymeric material or a luminescent polymeric material or a material to which a dopant is added to the hole-transporting polymeric material or the luminescent polymeric material, A method of forming a film by coating each film after the coating, and the like.

As the hole-transporting polymer material, poly [(9,9-diahexylfluorenyl-2,7-diyl) -co- (N, N'-bis {p- ), Poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (N, N'-bis {p-butylphenyl} -1,1'- Diamine)], poly [(9,9-bis {1'-pentene-5'-yl} fluorenyl-2,7-diyl) -co- (N, N'- -Butylphenyl} -1,4-diaminophenylene), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (4,4 '- (N- (p-butylphenyl) diphenylamine)] and the like, .

Examples of the luminescent polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), and polyfluorene derivatives such as poly (2-methoxy-5- (2'-ethylhexoxy) (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

Examples of the solvent include toluene, xylene, and chloroform. Examples of the dissolution or uniform dispersion method include stirring, heating stirring, and ultrasonic dispersion.

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

As the firing method, a method of heating in an oven or a hot plate under an inert gas or in a vacuum may be mentioned.

(Example)

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

(1) ¹ H-NMR: JNM-ECX300 FT NMR system manufactured by Nihon Denshi Co., Ltd.

(2) Substrate cleaning: Substrate cleaning apparatus (reduced pressure plasma system) manufactured by Joshu Sangyo Co.,

(3) Application of Varnish: Spin Coater MS-A1O0 manufactured by Mikasa Co., Ltd.

(4) Measurement of Film Thickness: Kokusakusa Kosaka Co., Ltd. Fine shape measuring instrument Surfcoder ET-4000

(5) Fabrication of EL device: Multifunctional deposition apparatus system C-E2L1G1-N manufactured by Joshu Sangyo Co., Ltd.

(6) Measurement of luminance etc. of EL element: (I) Tech World I-V-L measurement system

[1] Synthesis of Compound

[Synthesis Example 1]

The oligothiophene derivative 2 (TP2) represented by the formula (a-58) was synthesized by the following method.

In a flask, 3,3 "-dihexyl-2,2 ': 5', 2 &quot;: 5 ", 2" -quaterthiophene (hereinafter referred to as TP1) g, and the mixture was purged with nitrogen. Then, 6.5 mL of tetrahydrofuran was added, and the mixture was cooled to -78 ° C. 1.85 mL (concentration: 1.64 mol / L) of n-hexyltin solution of n-butyllithium was added thereto, followed by stirring for 30 minutes. Then, 1.1 mL of tributylchlorostarch was added dropwise thereto, and then the mixture was heated to room temperature and stirred for 3 hours.

After stirring, ion-exchanged water and n-hexane were added to separate the layers, and the obtained organic layer was further washed with ion-exchanged water twice, and then dried using sodium sulfate.

Then, the solvent was distilled off to obtain (3,3 "-dihexyl- [2,2 '; 5', 2 ": 5 &quot;, 2" -quaterthiophene] A mixture (1.7 g) containing bis (tributylstarchane) was obtained.

Next, 1.48 g of the obtained mixture and 0.46 g of 2-bromo-3-hexylthiophene were placed in a separate flask, and the mixture was purged with nitrogen. Then, 15 mL of toluene and 0.05 g of tetrakis (triphenylphosphine) palladium were sequentially added, And the mixture was stirred under reflux conditions for 4 hours.

After stirring, the mixture was cooled to room temperature, and n-hexane, toluene and ion-exchanged water were added thereto for liquid separation. The obtained organic layer was further washed with ion-exchanged water and dried using sodium sulfate.

Then, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain TP2 (yield: 0.38 g, yield: 53%, yield in two steps). The measurement results of ¹ H-NMR are shown below.

_{^{1 H-NMR (CDCl 3)}} : δ 7.16-7.13 (m, 4H), 7.04 (d, J = 3.9Hz, 2H), 6.94 (s, 4H), 6.92 (d, J = 5.4Hz, 2H), 2.78 (m, 8H), 1.74-1.58 (m, 8H), 1.44-1.31 (m, 24H), 0.95-0.87 (m, 12H).

[Synthesis Example 2]

The oligothiophene derivative 3 (TP3) represented by the formula (a-144) was synthesized by the following method.

2.0 g of 2,3-dihydrothieno [3,4-b] [1,4] dioxane and 150 mL of tetrahydrofuran were placed in a flask, and the flask was purged with nitrogen and cooled to -78 ° C. Thereafter, 10 mL of n-hexylamine solution (concentration: 1.64 mol / L) of n-butyllithium was added dropwise and stirred for 30 minutes at -78 캜. Then, the temperature was raised to -40 캜 and 5 mL of tributylchlorostannane was added dropwise , The mixture was heated to room temperature and stirred for 16 hours.

After completion of the stirring, the reaction mixture was concentrated, and the concentrate and n-hexane were mixed and filtered. The resulting 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.

Subsequently, 1.5 g of 5,5'-dibromo-2,2'-bithiophene and 0.27 g of tetrakis (triphenylphosphine) palladium were placed in a separate flask and replaced with nitrogen. Thereafter, 6.2 g of the above mixture containing tributyl (2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) stannane and 20 ml of N, N-dimethylformamide And the mixture was heated to 125 DEG C and stirred for 2 hours.

After completion of the stirring, the mixture was cooled to room temperature, n-hexane was added thereto to separate the layers, and the obtained N, N-dimethylformamide layer was dropped into a mixture of ion-exchanged water and methanol to effect reprecipitation.

The precipitate was recovered by filtration and dried to obtain TP3 (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 = 4.2Hz, 2H), 7.07 (d, J = 4.2Hz, 2H), 6.23 (s, 2H), 4.37-4.33 (m, 4H), 4.28-4.24 (m, 4H).

[Synthesis Example 3]

The oligothiophene derivative 4 (TP4) represented by the formula (a-306) was synthesized by the following method.

1.00 g of TP1 was placed in the flask, and after replacing with nitrogen, 13 mL of tetrahydrofuran was added and the mixture was cooled to -78 ° C. 3.7 mL (concentration: 1.64 mol / L) of n-hexyltin solution of n-butyllithium was added dropwise thereto, followed by stirring for 30 minutes. Further, 2.2 mL of tributyl chloro stannane was added dropwise thereto, and then the mixture was heated to room temperature and stirred for 3 hours.

After stirring, ion-exchanged water and n-hexane were added to separate the layers, and the obtained organic layer was further washed with ion-exchanged water twice, and then dried using sodium sulfate.

Then, the solvent was distilled off to obtain (3,3 "-dihexyl- [2,2 ': 5', 2 &quot;: 5 ", 2" -quaterthiophene] A mixture (3.45 g) containing bis (tributylstarch) was obtained.

Next, 3.0 g of the resulting mixture and 1.2-bromo-N, N-diphenyl aniline were placed in a separate flask and purged with nitrogen. Then, 45 mL of toluene and 0.10 g of tetrakis (triphenylphosphine) And the mixture was stirred under refluxing conditions for 8 hours.

After stirring, the mixture was allowed to cool to room temperature, and chloroform and ion exchange water were added thereto for liquid separation. The obtained organic layer was further washed with ion-exchanged water and dried using sodium sulfate.

The solvent was distilled off, and the residue was purified by column chromatography to obtain TP4 (yield: 0.76 g, yield: 44%, yield in two steps). The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ):? 7.44 (4H, d, J = 8.9 Hz), 7.28-7.23 (m, 8H), 7.12-7.10 (t, J = 7.4 Hz, 4H), 1.69 (quint, J = 7.4 Hz, 4H), 1.44-1.30 (m, 12H), 0.89 (m, 6H).

[Synthesis Example 4]

The aniline derivative 1 (AN1) represented by the formula (b-8) was synthesized by the following method.

To a mixed suspension of 10.00 g (50.19 mmol) of 4,4'-diaminodiphenylamine, 34.17 g (105.40 mmol) of 4-bromotriphenylamine and 100 g of xylene was added tetrakis (triphenylphosphine) palladium And 10.13 g (105.40 mmol) of t-butoxysodium were added, and the mixture was stirred at 130 占 폚 under nitrogen for 14 hours.

Thereafter, the reaction mixture was filtered, the filtrate was subjected to liquid separation treatment with saturated brine, and the solvent was distilled off from the organic layer. The obtained solid was recrystallized using 1,4-dioxane to obtain AN1 (yield: 22 g, yield: 65%). The measurement results of ¹ H-NMR are shown below.

_{^{1 H-NMR (CDCl 3)}} : δ 7.83 (S, 2H), 7.68 (S, 1H), 7.26-7.20 (m, 8H), 7.01-6.89 (m, 28H).

[Synthesis Example 5]

The arylsulfonic acid compound 1 (SA1) represented by the formula (c-1) was synthesized by the following method.

(14.36 mmol) of perfluorobiphenyl, 4.167 g (30.15 mmol) of potassium carbonate and 10.0 g of N, N-diisopropylethylamine were added to 11 g (31.59 mmol) of sodium 1-naphthol- Methylformamide were sequentially added, the reaction system was purged with nitrogen, and the mixture was stirred at an inner temperature of 100 占 폚 for 6 hours.

After cooling to room temperature, another 500 mL of N, N-dimethylformamide was added to redissolve SA1 precipitated after the reaction, followed by stirring at room temperature for 90 minutes. After stirring at room temperature, this solution was filtered to remove the potassium carbonate residue, and the filtrate was concentrated under reduced pressure. Further, in order to remove remaining impurities, 100 mL of methanol was added to the residue, and the mixture was stirred at room temperature. After stirring at room temperature for 30 minutes, the suspension solution was filtered, and the filtrate was taken by filtration. 300 ml of ultrapure water was added to the filtrate, and the solution was ion-exchanged by column chromatography using cation exchange resin Dowex 650C (manufactured by Dow Chemical Co., H type, about 200 ml, effluent solvent: ultrapure water).

The fraction having a pH of not more than 1 was concentrated to dryness under reduced pressure, and the residue was solidified by drying under reduced pressure to obtain SA1 (11 g, yield 85%). The measurement results of ¹ H-NMR are shown below.

^{1 H-NMR (DMSO-d6} ): δ 7.18 (1H, s, Ar-H), 7.89 (1H, d, Ar-H), 8.01 (1H, s, Ar-H), 8.23 (1H, s, Ar-H), 8.28 (1H, d, Ar-H).

[Synthesis Example 6]

The oligothiophene derivative 5 (TP5) represented by the formula (a-34) was synthesized by the following method.

2.01 g of terthiophene and 50 mL of tetrahydrofuran were placed in a flask under a nitrogen atmosphere, and the mixture was cooled to -78 ° C. To this was added 19.6 mL of a normal hexane solution of n-butyllithium (1.64 mol / L), and the mixture was stirred at -78 ° C for 30 minutes. Then, the mixture was heated to 0 ° C and further stirred for 1 hour.

Thereafter, the mixture was cooled to -78 deg. C again and stirred for 30 minutes. Then 8.8 ml of tributylchlorostannane was added dropwise, and the mixture was stirred for 10 minutes, then heated to 0 deg. C and stirred for further 30 minutes.

After stirring, the solvent was distilled off from the reaction mixture under reduced pressure, and the resulting residue was added to toluene. The insoluble matter was removed by filtration, the solvent was distilled off under reduced pressure from the obtained filtrate, and a solution containing a bisteniyl compound of terthiophene 12.88 g of an oily product (purity of this bistranyl complex of 51.91%) was obtained.

Next, in a separate flask, under an atmosphere of nitrogen, 6.44 g of an oily product containing the terthiophene bisteniyl compound, 2.41 g of 2-bromo-3-nonohexylthiophene, 24 mL of toluene, and tetrakis (triphenylphosphine ) Palladium (0.23 g) were successively added thereto, and the mixture was stirred under reflux for 4.5 hours.

After cooling to room temperature, the solvent was distilled off under reduced pressure, and insolubles were removed by filtration. The obtained filtrate was concentrated and purified by silica gel column chromatography to obtain TP5 (yield: 1.29 g, yield: 55%, yield in two stages).

_{^{1 H-NMR (CDCl 3)}} : δ 7.17 (d, J = 5.1Hz, 2H), 7.12 (d, J = 3.9Hz, 2H), 7.09 (s, 2H), 7.01 (d, J = 3.9Hz, 2H), 6.93 (d, J = 5.1 Hz, 2H), 2.78 (t, J = 7.7 Hz, 4H), 1.54-1.70 (m, 4H), 1.28-1.41 = 7.0 Hz, 6H).

[2] preparation of charge transport varnish

[Example 1-1]

0.035 g of TP1 and 0.210 g of tungstic acid (PTA, manufactured by Kanto Kagaku) were dissolved in 4.0 g of 1,3-dimethyl-2-imidazolidinone (DMI) under a nitrogen atmosphere. To the obtained solution, 6.0 g of cyclohexanol (CHA) and 2.0 g of propylene glycol (PG) were added and stirred, and 0.024 g of pentafluorophenyltriethoxysilane (hereinafter referred to as Silane A) And further stirred to prepare a charge transporting varnish.

[Examples 1-2 to 1-26, 1-35 to 1-37]

A varnish was prepared in the same manner as in Example 1-1 except that the charge-transporting material, the dopant, the organosilane compound, the organic solvent, and the amount of the charge-transporting material, the organic solvent and the amount thereof were changed in accordance with Table 1.

[Comparative Example 1-1]

0.053 g of TP1 and 0.318 g of PTA O were dissolved in 4.0 g of DMI under a nitrogen atmosphere. To the obtained solution, 6.0 g of CHA and 2.0 g of PG were added and stirred to prepare a charge-transporting varnish.

[Examples 1-27]

0.052 g of TP1 and 0.258 g of PTA were dissolved in 2.0 g of DMI under a nitrogen atmosphere. To the obtained solution, 8.0 g of PGME was added and stirred. To this solution, 0.031 g of Silane A and 0.031 g of F4TCNQ (manufactured by Tokyo Kasei Kogyo K.K.) were further added and stirred to prepare a charge transporting varnish.

[Examples 1-28 to 1-34, 1-38]

A varnish was prepared in the same manner as in Example 1-27 except that the charge-transporting material, the dopant, the organosilane compound, the organic solvent, and the amount of the charge-transporting material, the organic solvent and the amount thereof were changed in accordance with Table 2.

In Table 1 and 2, "Silane B" represents 3,3,3-trifluoropropyltrimethoxysilane, "Silane C" represents phenyltrimethoxysilane, "PGME" represents propylene glycol "DEGME" represents diethylene glycol monomethylether, "2,3-BD" represents 2,3-butanediol, each number in parentheses represents the amount (unit: g).

[3] Manufacturing and Characterization of Organic EL Device

[Example 2-1]

The varnish obtained in Example 1-1 was applied to an ITO substrate using a spin coater, followed by drying at 50 ° C for 5 minutes and further baking at 150 ° C for 10 minutes in an air atmosphere. A thin film was formed. As the ITO substrate, a glass substrate of 25 mm x 25 mm x 0.7 t in which indium tin oxide (ITO) was patterned on the surface with a film thickness of 150 nm was used and impurities on the surface were removed by an O ₂ plasma cleaning apparatus (150 W, 30 seconds) .

Next, with respect to a IT0 substrate to form a thin film, the deposition device (degree of vacuum of 1.0 × 10 ^-5 Pa) by using the α-NPD, Alq _3, sequentially stacking the lithium fluoride and an aluminum thin film, and an organic EL element was completed. At this time, the deposition rate was 0.2 nm / sec for α-NPD, Alq ₃ and aluminum, and 0.02 nm / sec for lithium fluoride, respectively, 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 and the like in the air, the organic EL devices were sealed with a sealing substrate, and then their properties were evaluated. The encapsulation was carried out in the following order. The organic EL device was housed between the sealing substrates in an atmosphere of oxygen at a concentration of 2 ppm or less and at a dew point of -85 占 폚 or less and the sealing substrate was bonded by an adhesive (XNR5516Z-B1, manufactured by Nagase Chemtech Co., Ltd.). At this time, a catcher (HD-071010W-40, manufactured by Dainichick) was accommodated together with the organic EL device in the encapsulation substrate. The bonded sealant substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6.000 mJ / cm ² ) and annealed at 80 캜 for 1 hour to cure the adhesive.

[Examples 2-2 to 2-26]

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 1-26 was used instead of the varnish obtained in Example 1-1.

[Examples 2-27 to 2-29]

The device was fabricated in the same manner as in Example 2-10 except that the firing temperatures were 170 캜, 190 캜, and 210 캜, respectively.

[Examples 2-30 to 2-33]

An element was produced in the same manner as in Examples 2-14 to 2-16 and 2-20, except that the firing temperature was set to 230 캜.

[Comparative Example 2-1]

A device was fabricated 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.

[Examples 2-34 to 2-36]

An organic EL device was fabricated in the same manner as in Example 2-1 except that the varnish obtained in Examples 1-27 to 1-29 was used instead of the varnish obtained in Example 1-1.

[Examples 2-37 to 2-39]

An organic EL device was fabricated in the same manner as in Examples 2-34 to 2-36 except that the firing temperature was set to 230 캜.

[Examples 2-40 to 2-44]

An organic EL device was fabricated in the same manner as in Example 2-1 except that the varnish obtained in Examples 1-30 to 1-34 was used instead of the varnish obtained in Example 1-1.

[Examples 2-45 to 2-47]

An organic EL device was fabricated in the same manner as in Example 2-1 except that the varnish obtained in Examples 1-35 to 1-37 was used instead of the varnish obtained in Example 1-1.

[Examples 2-48 to 2-51]

A varnish obtained in Example 1-38 was used in place of the varnish obtained in Example 1-1, and the same procedure as in Example 2-1 was carried out except that the baking temperatures were changed to 150 ° C, 160 ° C, 170 ° C and 180 ° C, respectively To prepare an organic EL device.

And the current density and luminance at a driving voltage of 5 V of each device were measured. The results are shown in Tables 3 and 4. The half-life (initial luminance of 5000 cd / m ² ) of luminance of the devices of Examples 2-34, 2-35 and 2-40 to 2-48 was measured. The results are shown in Table 5.

As shown in Tables 3 and 4, when the charge-transporting varnish of the present invention is used, not only when a thin film baked at 230 DEG C is used but also when a thin film baked at a low temperature of 150 DEG C is used, An organic EL device was obtained. Further, as shown in Table 5, when a varnish containing F4TCNQ was used, a high number of devices were obtained.

Claims (13)

A charge-transporting varnish comprising a charge-transporting material comprising an oligothiophene derivative represented by formula (1), a dopant, an organosilane compound, and an organic solvent.

(Wherein, R ¹ ~ R ⁶ is substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, are each independently a heteroaryl group, is optionally -0Y of 2 to 20 carbon atoms and an alkynyl group, an aryl group having from 6 to 20 carbon atoms which may be substituted with Z ^2, 2 to 20 carbon atoms which may be substituted with Z ² of the ^first group, -SY ² group, -NHY ³ group, -NY ⁴ Y ⁵ group, or a -NHC (O) Y represents a ^6, again, R ¹ ~ R ⁶ is a, R ¹ and R ^2, R ³ is not a hydrogen atom and R ⁴ and / Or R ⁵ and R ⁶ may be bonded to each other to form a divalent group,
R ⁷ and R ⁸ are carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, independently each An alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms which may be substituted with Z ³ , a heteroaryl group of 2 to 20 carbon atoms which may be substituted with Z ³ , a -OY ¹ group, a -SY ² group, ³ group, -NY ⁴ Y ⁵ group or -NHC (O) Y ⁶ group,
Y ^l ~ Y ⁶ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms which may be substituted with, Z ¹ are each independently the alkynyl group, which may be substituted with Z ² represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group, or Z ² of 6 to 20 carbon atoms,
Z ¹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms,
Z ² represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms,
Z ³ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, &Lt; / RTI &gt;&lt; RTI ID = 0.0 &gt;
n ¹ to n ³ independently represent a natural number, and 4? n ¹ + n ² + n ³ ? 20). The charge transporting varnish of claim 1, wherein the dopant comprises a heteropoly acid. 3. The charge transporting varnish of claim 2, wherein the heteropoly acid comprises tungstic acid. 4. The charge-transporting varnish according to any one of claims 1 to 3, wherein the oligothiophene derivative is represented by formula (2).

(Wherein R ³ to R ⁸ and n ¹ to n ³ are as defined above) The method according to any one of claims 1 to 4, wherein the organosilane compound comprises at least one member selected from the group consisting of a dialkoxysilane compound, a trialkoxysilane compound and a tetraalkoxysilane compound Charge transport varnish. The charge transporting varnish according to any one of claims 1 to 5, further comprising a tetracyanoquinodimethane compound represented by the formula (12).

(Wherein R ¹⁰¹ to R ¹⁰⁴ each independently represent a hydrogen atom or a halogen atom, and at least one of them is a halogen atom.) The charge transporting varnish according to any one of claims 1 to 6, further comprising a dopant comprising an aryl sulfonic acid compound. A charge transport thin film produced using the charge transporting varnish according to any one of claims 1 to 7. An organic electro-luminescence device having the charge transporting thin film according to claim 8. The organic electro luminescence device according to claim 9, wherein the charge transport thin film is a hole injection layer or a hole transport layer. A process for producing a charge-transporting thin film, characterized in that the charge-transporting varnish according to any one of claims 1 to 7 is applied to a substrate and baked. A method for producing an organic electroluminescence element, characterized by using the charge transporting thin film according to claim 8. A charge-transporting material comprising a charge-transporting material comprising an oligothiophene derivative represented by the formula (1) and a dopant.

(Wherein, R ¹ ~ R ⁶ is substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, are each independently a heteroaryl group, is optionally -0Y of 2 to 20 carbon atoms and an alkynyl group, an aryl group having from 6 to 20 carbon atoms which may be substituted with Z ^2, 2 to 20 carbon atoms which may be substituted with Z ² of the ^first group, -SY ² group, -NHY ³ group, -NY ⁴ Y ⁵ group, or a -NHC (O) Y represents a ^6, again, R ¹ ~ R ⁶ is a, R ¹ and R ^2, R ³ is not a hydrogen atom and R ⁴ and / Or R ⁵ and R ⁶ may be bonded to each other to form a divalent group,
R ⁷ and R ⁸ are carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms that may be substituted with hydrogen atoms, Z ^1, independently each An alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ³ , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ³ , a -0Y ¹ group, a -SY ² group, ³ group, -NY ⁴ Y ⁵ group or -NHC (O) Y ⁶ group,
Y ¹ ~ Y ⁶ is 2 to 20 carbon atoms which may be substituted with an alkenyl group, Z ¹ of 2 to 20 carbon atoms that may be substituted with an alkyl group, Z ¹ group having from 1 to 20 carbon atoms which may be substituted with, Z ¹ are each independently the alkynyl group, which may be substituted with Z ² represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group, or Z ² of 6 to 20 carbon atoms,
Z ¹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms,
Z ² represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms,
Z ³ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dialkylamino group in which each alkyl group is an alkyl group having 1 to 20 carbon atoms, &Lt; / RTI &gt;&lt; RTI ID = 0.0 &gt;
n ¹ to n ³ independently represent a natural number, and 4? n ¹ + n ² + n ³ ? 20).