KR102270673B1 - Hole transporting varnish for metal positive electrodes and composite metal positive electrode - Google Patents

Abstract

(X¹은 -NY¹-, -O-, -S-, -(CR⁷R⁸)_l- 또는 단결합을 나타내고, Y¹은, 서로 독립하여, 수소 원자 등을 나타내고, R¹∼R⁸은, 서로 독립하여, 수소 원자, 할로젠 원자 등을 나타내고, m 및 n은, 서로 독립하여, 0 이상의 정수를 나타내고, 1≤m+n≤20을 충족시킨다. 단, m 또는 n이 0일 때는, X¹은 -NY¹-을 나타낸다.)For example, a hole-transporting varnish for a metal anode comprising a charge-transporting material comprising an aniline derivative represented by Formula (1), a dopant material comprising a heteropolyacid, and an organic solvent has excellent hole-accepting capacity from the metal anode, A thin film suitable for use as a hole injection layer formed on a metal anode is provided.

(X ¹ represents -NY ¹ -, -O-, -S-, -(CR ⁷ R ⁸ ) ₁ - or a single bond, Y ¹ represents, independently of each other, a hydrogen atom or the like, R ¹ to R ⁸ independently of each other represents a hydrogen atom, a halogen atom, etc., m and n independently represent an integer greater than or equal to 0, satisfying 1≤m+n≤20, provided that m or n is 0 When , X ¹ represents -NY ¹ -.)

Description

HOLE TRANSPORTING VARNISH FOR METAL POSITIVE ELECTRODES AND COMPOSITE METAL POSITIVE ELECTRODE

The present invention relates to a hole-transporting varnish for a metal anode and a composite metal anode, and more particularly, a hole-transporting varnish providing a thin film exhibiting high hole-accepting capacity from a metal anode by forming on a metal anode, and such a thin film and a metal It relates to a composite metal anode comprising a laminate of

In an organic electroluminescence (hereinafter referred to as organic EL) device, a charge-transporting thin film made of an organic compound is used as a light emitting layer or a charge injection layer. In particular, the hole injection layer is responsible for the exchange of charges between the anode and the hole transport layer or the light emitting layer, and performs an important function to achieve low voltage driving and high luminance.

The method of forming the hole injection layer is roughly divided into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. Comparing the dry process and the wet process, the wet process efficiently forms a thin film with high flatness over a large area. can be manufactured.

Therefore, in the field of organic EL where a large-area thin film is desired, a hole injection layer is formed by a wet process in many cases. In view of this situation, the present inventors applied to the hole injection layer of an organic EL element. In order to provide a thin film capable of realizing excellent EL device properties, materials applicable to various wet processes have been developed (see Patent Documents 1 to 3).

By the way, the structure of the organic EL device can be roughly divided into a bottom emission structure and a top emission structure. In a device of a bottom emission structure, a transparent anode is used on the substrate side, and light is extracted from the substrate side, whereas in an element of a top emission structure, a reflective anode made of metal is used and is located in the opposite direction to the substrate. Light is extracted from the transparent electrode (cathode) side.

Since the element of the top emission structure does not extract light from the substrate side as in the element of the bottom emission structure, there is no problem that the light from the light emitting layer is blocked by the TFT. Therefore, the element of the top emission structure There is an advantage that a high aperture ratio can be maintained. As a result, the light extraction efficiency is improved, and power consumption of the device can be reduced and the lifespan of the device can be increased. Therefore, in recent years, a device having a top emission structure is attracting attention.

In this top-emission device, the hole injection layer is formed directly on the metal. For varnishes usable in wet processes, which, when laminated directly on the metal, provide a thin film exhibiting excellent hole injection capability, so far, There is no specific report.

Japanese Patent Laid-Open No. 2002-151272 International Publication No. 2008/129947 International Publication No. 2010/058777

The present invention has been made in consideration of the above circumstances, and has excellent hole accepting capacity from a metal anode, and provides a thin film suitable for use as a hole injection layer formed on a metal anode, for the purpose of providing a hole transporting varnish for a metal anode do.

Further, in the present invention, the hole injection layer is a layer formed thereon so as to be in contact with the anode for the main purpose of increasing the efficiency of hole transport from the anode in the device. In the organic EL device, the light emitting layer may be formed directly on the hole injection layer, but other functional layers such as a hole transport layer may be formed between the light emitting layer and the hole injection layer.

As a result of repeated studies to achieve the above object, the present inventors have found that a thin film formed on a metal anode using a varnish containing a charge transporting material, a dopant material consisting of a heteropolyacid, and an organic solvent has high flatness and In addition, it was discovered that high hole solubility from a metal anode was found, and the present invention was completed.

That is, the present invention is

1. A hole transporting varnish for a metal anode for forming a thin film laminated on a metal anode and transporting holes received from the metal anode to a layer stacked on the opposite side of the metal anode, comprising a charge transporting material and a heteropoly acid A hole-transporting varnish for a metal anode comprising a dopant material and an organic solvent,

2. The hole transporting varnish for a metal anode of 1, wherein the charge transporting material is at least one selected from aniline derivatives and thiophene derivatives;

3. Hole-transporting varnish for a metal anode of 2, wherein the aniline derivative is represented by Formula (1);

(Wherein, X ¹ represents -NY ¹ -, -O-, -S-, -(CR ⁷ R ⁸ ) ₁ - or a single bond, and Y ¹ is, independently of each other, a hydrogen atom or Z ¹ . An optionally substituted C1-C20 alkyl group, a C2-C20 alkenyl group, or a C2-C20 alkynyl group, or a C6-C20 aryl group or a C2-C20 hetero which may be substituted with ^{Z 2 .} represents an aryl group, and R ¹ to ^{R 8} are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z ¹ 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, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 2} group, -NHY ^{2 , -NY 3} Y ⁴ , -C(O)Y ⁵ , -OY ^{6 , -SY 7} , -SO ₃ Y ⁸ , -C(O)OY ⁹ , -OC(O)Y ¹⁰ , -C(O)NHY ¹¹ , or -C(O)NY ¹² Y ¹³ group, and Y ^{2 to Y 13} are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with ^{Z 1 , an alkyl group having 2 to carbon atoms.} An alkenyl group having 20 or an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 2 , Z 1} is a halogen atom or a nitro group , a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with ^{Z 3 , Z 2} is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an alkyl group having 1 to 20 carbon atoms, which may be substituted with ^{Z 3 , an alkyl group having 2 to 20 carbon atoms} represents an alkenyl group or an alkynyl group having 2 to 20 carbon atoms, Z ³ is a halogen atom, a nitro group, represents a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, or a carboxylic acid group, l represents an integer from 1 to 20, m and n, independently of each other, represent an integer of 0 or more, and 1≤m +n≤20. However, when m or n is 0, X ¹ represents -NY ¹ -.)

4. Hole-transporting varnish for a metal anode of 2, wherein the thiophene derivative is represented by Formula (2);

(Wherein, R ¹¹ to ^{R 16} are each independently a hydrogen atom, 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, which may be substituted with ^{Z 9 , Z} an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with ^{10 , or -OY 17} , -SY ¹⁸ , -NHY ¹⁹ , ^{-NY 20} Y ²¹ or NHC(O)Y ²² R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, 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, which may be substituted with ^{Z 9 , Z 11} represents an optionally substituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, or ^{-OY 17} , -SY ¹⁸ , -NHY ¹⁹ , ^{-NY 20} Y ²¹ or NHC(O)Y ²² ; Y ^{17 to Y 22} each independently represent 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, which may be substituted with ^{Z 9} , or may be substituted with ^{Z 10 .} , an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, Z ⁹ is an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, Z ¹⁰ is an alkyl group having 1 to 20 carbon atoms, represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ¹¹ 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, di( represents an alkyl)amino group or a di(C6-C20 aryl)amino group, and n ^{1 to} n ³ independently represent a natural number, and satisfy ⁴ ≦n 1 +n ² +n ³ ≦20. In addition, when R ¹¹ to ^{R 16} are not hydrogen atoms, two groups on the thiophene ring above one may be bonded to each other to form a divalent group.)

5. The hole-transporting varnish for a metal anode according to any one of 1 to 4, wherein the metal anode is made of at least one metal selected from molybdenum, chromium, aluminum, silver, gold and platinum;

6. A composite metal anode comprising a metal anode and a hole injection layer laminated on its surface, wherein the hole injection layer is produced from the hole transporting varnish for a metal anode of any one of 1 to 5;

7. An organic electroluminescent device having a composite metal anode of 6,

8. Top emission type 7 organic electroluminescence device,

9. A method for manufacturing an organic electroluminescent device, comprising the step of applying the hole transporting varnish for a metal anode according to any one of 1 to 5 on the surface of the metal anode and drying it;

10. Method of manufacturing an organic electroluminescent device characterized in that using the composite metal anode of 6

provides

By using the hole-transporting varnish of the present invention, a thin film having high flatness can be formed even on the metal anode, and the obtained thin film is excellent in the hole-accepting capacity from the metal anode. The hole transporting varnish of the present invention can be suitably used for the organic EL device having the above-described top emission structure using a metal anode.

In addition, the hole-transporting varnish of the present invention can produce a thin film excellent in charge-transporting property with good reproducibility even when various wet processes capable of forming a film over a large area, such as spin coating or slit coating, are used. It can sufficiently respond to progress in

Hereinafter, the present invention will be described in more detail.

The hole transporting varnish for a metal anode according to the present invention is a hole transporting varnish for a metal anode for forming a thin film that is laminated on the metal anode and transports the holes received from the metal anode to the layer stacked on the opposite side of the metal anode , a charge-transporting material, a dopant material comprising a heteropolyacid, and an organic solvent.

In the present invention, charge-transporting property is synonymous with conductivity, and has the same meaning as hole-transporting property. A charge-transporting substance may have charge-transporting property by itself, and when it uses with a dopant substance, the thing which has charge-transporting property may be sufficient as it.

Further, the hole-transporting varnish may have charge-transporting properties in itself, or the solid film obtained therefrom may have charge-transporting properties.

In the present invention, for a metal anode means a hole-transporting varnish used to directly form a thin film on the anode of an electronic device, particularly, when the anode of an organic electroluminescent element is a metal.

In addition, the metal referred to herein is a single metal or an alloy, and does not include metal oxides or alloys of which most of metals such as ITO, IZO, IGZO, etc. are intentionally oxidized, but for example, to external factors such as oxygen in the air. Including those in which all or part of the surface of the metal is oxidized by

Metals constituting such a metal anode include aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, cadmium. , indium, scandium, lanthanum, cerium, praseodymium, neodymium, propetium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, thallium, tungsten, rhenium, osmium, iridium, osmium, iridium Silver, gold, titanium, lead, bismuth, etc. and alloys thereof are mentioned, As mentioned above, these may be used individually or may be used by an alloy, respectively.

Among these, the hole transporting varnish for a metal anode of the present invention forms a hole injection layer on an anode made of niobium, tantalum, molybdenum, chromium, aluminum, silver, gold, platinum, or an aluminum-neodymium (Al/Nd) alloy. Suitable.

In particular, when used as an anode of an organic EL device having a top emission structure, the metal is preferably a reflective metal having excellent light reflection ability. Examples of such metal include molybdenum, chromium, aluminum, silver, gold, platinum, and the like. can

The charge transport material used in the present invention is not particularly limited, but a varnish having excellent solubility in an organic solvent and providing a thin film excellent in flatness can be prepared, so a charge transporting substance composed of a charge transporting monomer or a charge transporting oligomer. This is preferable, and various hole-transporting substances, such as an aniline derivative, a thiophene derivative, and a pyrrole derivative, are mentioned, for example. In addition, these may be used independently or may be used in combination of 2 or more types.

Among them, aniline derivatives and thiophene derivatives are preferable.

Although it does not specifically limit as a charge-transporting substance which consists of an aniline derivative, The thing represented by Formula (1) is preferable.

In Formula (1), X ¹ represents -NY ¹ -, -O-, -S-, -(CR ⁷ R ⁸ ) ₁ - or a single bond, and when m or n is 0, it represents ^{-NY 1 -} .

Y ¹ is each independently a hydrogen atom, ^{an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1} , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, or Z ² may be substituted with , an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group , t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, such as a linear or branched alkyl group having 1 to 20 carbon atoms; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicyclohep and a cyclic alkyl group having 3 to 20 carbon atoms such as a tyl group, a bicyclooctyl group, a bicyclononyl group and a bicyclodecyl group.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include an ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2- A propenyl group, n-1-pentenyl group, n-1-decenyl group, n-1-eicosenyl group, etc. are mentioned.

Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentinyl group, n-2-pentinyl group, n-3-pentinyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2-methyl -n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group, n-1-pentadecinyl group, n-1-eicosinyl group; and the like.

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

Specific examples of the heteroaryl group having 2 to 20 carbon atoms include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group , 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-iso A thiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group etc. are mentioned.

R ⁷ and R ⁸ may be each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z ¹ ; 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, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 2 , -NHY 2} , -NY ³ Y ⁴ , -C(O)Y ⁵ , ^{-OY 6} , -SY ⁷ , -SO ³ Y ⁸ , -C(O)OY ⁹ , -OC(O)Y ¹⁰ , -C(O) ) NHY ¹¹ , or —C(O)NY ¹² Y ¹³ , and Y ^{2 to Y 13} are, each independently, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, which may be substituted with ^{Z 1 .} Alternatively, an alkynyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 2 is represented.}

A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom.

In addition, examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group of ^{R 7 to R 8} and Y ^{2 to Y 13 are the same as those described above.}

Among these, as R ⁷ and R ⁸ , a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may be substituted with ^{Z 1 is preferable, and a hydrogen atom or a methyl group which may be substituted with Z 1} is more preferable, and both are hydrogen. Atoms are optimal.

l represents the number of repeating units of the divalent alkylene group represented by -(CR ⁷ R ⁸ )- and is an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, and 1 or 2 Furthermore, it is more preferable, and 1 is optimal.

In addition, when l is 2 or more, some R<^7> may mutually be same or different, and some R<^{8> may} also mutually be same or different.

In particular, as X ¹ , -NY ¹ - or a single bond is preferable. Moreover, as Y<^1> , a hydrogen atom or a C1-C20 alkyl group which may be substituted with ^{Z<1> is preferable, A hydrogen atom or a methyl group which may be substituted with Z<1>} is more preferable, and a hydrogen atom is optimal.

R ¹ to ^{R 6} may each independently be substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z ^{1 ;} 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, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 2 , -NHY 2} , -NY ³ Y ⁴ , -C(O)Y ⁵ , ^{-OY 6} , -SY ⁷ , -SO ₃ Y ⁸ , -C(O)OY ⁹ , -OC(O)Y ¹⁰ , -C(O) ) NHY ¹¹ , or —C(O)NY ¹² Y ¹³ group (Y ^{2 to Y 13} has the same meaning as above), and these halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups and heteroaryl groups Examples of the group include those similar to those described above.

In particular, in Formula (1), as R ¹ to ^{R 4} , a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with ^{Z 1} , or an aryl group having 6 to 14 carbon atoms which may be substituted with ^{Z 2 .} Preferably, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is more preferable, and both are most preferably a hydrogen atom.

Also optionally substituted with R ⁵ and R ⁶ as aryl groups having 6 to 14 carbon atoms that may be substituted with an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a halogen atom, Z ¹ to, Z ^2, or Z ² A diphenylamino group (the ^{-NY 3} Y ^{4 group in which Y 3} and Y ⁴ is a phenyl group optionally substituted with ^{Z 2} ) is preferable, and a hydrogen atom, a fluorine atom, or a diphenylamino group optionally substituted with a fluorine atom is more preferable and at the same time, a hydrogen atom or a diphenylamino group is more preferable.

And, among these, R ¹ ~R ⁴ is an alkyl group of 1 to 10 carbon atoms that may be substituted with a hydrogen atom, a fluorine atom, a fluorine atom, R ⁵ and R ⁶ is diphenyl that may be substituted with a hydrogen atom, a fluorine atom, a fluorine atom A combination of an amino group, X ¹ is -NY ¹ - or a single bond, and Y ¹ is preferably a hydrogen atom or a methyl group, R ¹ to ^{R 4} are a hydrogen atom, R ⁵ and R ⁶ are simultaneously a hydrogen atom or a diphenylamino group , X ¹ is -NH- or a combination of a single bond is more preferable.

In the formula (1), m and n independently represent an integer of 0 or more and satisfy 1≤m+n≤20, but considering the balance between the charge transport properties of the resulting thin film and the solubility of the aniline derivative, 2 It is preferable to satisfy ? m+n ? 8, more preferably satisfy 2 ? m+n ? 6, and even more preferably satisfy 2 ? m+n ? 4.

In addition, the ^{alkyl group, alkenyl group and alkynyl group of Y 1 to Y 13} and R ¹ to ^{R 8} are halogen atom, nitro group, cyano group, amino group, aldehyde group, hydroxyl group, thiol group, sulfonic acid group, carboxylic acid group or being optionally substituted by a heterocyclic aryl group of the aryl group or Z ¹ of the 2 to 20 carbon atoms, 6 to 20 carbon atoms optionally substituted by Z ^3, said Y ¹ ~Y ¹³ and aryl group of R ¹ ~R ⁸ and The heteroaryl group is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an alkyl group having 1 to 20 carbon atoms, which may be substituted with ^{Z 3 , an alkyl group having 2 to carbon atoms It may be substituted with Z 2 which} is an alkenyl group having 20 or an alkynyl group having 2 to 20 carbon atoms, and these groups further include a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, or a carboxylic acid group (there may be mentioned as the halogen atom the same meanings as defined above.) may be substituted with Z ^3.

In particular, in Y ^{1 to Y 13} and R ¹ to ^{R 8} , the substituent Z ¹ is preferably a halogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with ^{Z 3 , and is a halogen atom or Z 3} . The phenyl group which may be substituted is more preferable, and the thing which does not exist (that is, unsubstituted thing) is optimal.

In addition, the substituent Z ² is a halogen atom, or an alkyl group of 1 to 20 carbon atoms that may be substituted with Z ³ is preferable, and a halogen atom, or an alkyl group having 1 to 4 carbon atoms that may be substituted with Z ³ more preferred, and Non-existent (ie, unsubstituted) is optimal.

And, as for Z ³ , a halogen atom is preferable, a fluorine atom is more preferable, and the thing which does not exist (that is, unsubstituted thing) is optimal.

Moreover, as an example of the charge-transporting substance which consists of a thiophene derivative, what is represented by Formula (2) is mentioned.

In formula (2), R ¹¹ to ^{R 16} are each independently a hydrogen atom, 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 which may be substituted with ^{Z 9 .} , Z ¹⁰ optionally substituted with an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, or ^{-OY 17} , -SY ¹⁸ , -NHY ¹⁹ , ^{-NY 20} Y ²¹ or NHC(O)Y ²² is shown.

In addition, when R ¹¹ to ^{R 16} are not hydrogen atoms, two groups on the thiophene ring above one (ie, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ and/or R ¹⁵ and R ¹⁶ ) are bonded to each other, You may form a bivalent group.

R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, ^{optionally substituted with Z 9} , 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 ¹¹ , optionally an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, or ^{-OY 17} , -SY ¹⁸ , -NHY ¹⁹ , ^{-NY 20} Y ²¹ or NHC(O)Y ²² .

Y ^{17 to Y 22} each independently represent 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, which may be substituted with ^{Z 9} , or may be substituted with ^{Z 10 .} , an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.

Z ⁹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, Z ¹⁰ 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 ¹¹ represents 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 di(C1-C20 alkyl)amino group, or a di(C6-C20 aryl)amino group.

Here, as a specific example of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the heteroaryl group, the thing similar to the group illustrated by Formula (1) is mentioned.

Equation (2), even as the R ¹¹ and R ¹² is an alkoxy group (i.e., Y ¹⁷ or 20 carbon atoms in the alkyl group of which may be substituted with hydrogen atoms, Z or ^9, having 1 to 20 carbon atoms substituted with Z ^{9 -OY 17} group) which is an alkyl group having 1 to 20 carbon atoms) is preferable, and a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms which may be substituted with ^{Z 9 is more preferable, a hydrogen atom;} Alternatively, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms which may be substituted with ^{Z 9 is further preferable, and a hydrogen atom is most preferable.}

Therefore, as a suitable thiophene derivative, the thing represented by Formula (3) is mentioned, for example.

(Wherein, R ^{13 to R 18} and n ^{1 to} n ³ have the same meanings as above.)

On the other hand, R ¹³ ~R ¹⁶ As the carbon number of which may have an alkoxy group (i.e., Y ¹⁷ or 20 carbon atoms in the alkyl group of 1 to 20 carbon atoms which may be substituted with a hydrogen atom, or Z is substituted with Z ^{9 9} 1~ ^{-OY 17} ) which is an alkyl group of 20 is preferable, a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms which may be substituted with ^{Z 9} is more preferable, and is substituted with a ^{hydrogen atom or Z 9 ,} A C1-C8 alkyl group or a C1-C8 alkoxy group which may exist is further more preferable. In particular, it is preferable that at least one of ^{R 13} and R ¹⁴ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms which may be substituted with ^{Z 9 .}

R ¹⁷ and R ^{18 are preferably a} hydrogen atom, -NY ²⁰ Y ²¹ , or an aryl group having 6 to 20 carbon atoms which may be substituted with a di(C1 to C20 alkyl)amino group or a di(C6 to C20 aryl)amino group. In this case, Y ²⁰ and Y ²¹ are preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with ^{Z 9} or an aryl group having 6 to ^{20 carbon atoms which may be substituted with Z 10} , and 1 to carbon atoms which may be substituted with ^{Z 9 .} group of 6 to 10 carbon atoms, aryl which may be substituted with an alkyl group or a Z 10 of ¹⁰ is more preferable.

Among these, R ¹⁷ and R ^{18 are} , in particular, a hydrogen atom, a ^{diarylamino group which is an aryl group having 6 to 10 carbon atoms which each aryl group may be substituted with Z 11} , or a phenyl group substituted with a di(C6-C20 aryl)amino group. is preferred, and a hydrogen atom or a 4-diphenylaminophenyl group is optimal.

Further, in R ¹¹ to ^{R 18} and Y ^{17 to Y 22} , the substituent Z ⁹ is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, and most preferably not present (that is, unsubstituted). .

Substituent Z ¹⁰ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, which does not exist. (ie, unsubstituted) is optimal.

Further, the substituent Z ¹¹ is preferably an alkyl group having 1 to 20 carbon atoms, a di(alkyl having 1 to 20 carbon atoms) amino group, or a di(aryl having 6 to 20 carbon atoms) amino group, an alkyl group having 1 to 10 carbon atoms, or di(alkyl having 1 to 10 carbon atoms). ) an amino group or a di(C6-C10 aryl)amino group, more preferably a C1-C8 alkyl group, a di(C1-8 alkyl)amino group, or a diphenylamino group, which does not exist (that is, unsubstituted) or a diphenylamino group is optimal.

In the formulas (2) and (3), n ^{1 to} n ³ independently represent a natural number and satisfy ⁴ ≦n 1 +n ² +n ³ ≦20. n ¹ is preferably 1 to 15, more preferably 1 to 10, further preferably 2 to 5, still more preferably 2 to 3. On the other hand, n ² and n ³ are, independently to each other, preferably 1 to 15, 1 to 10 and more preferably, is incidentally preferably 1 to 5, more preferably 1 to 3.

Further, in consideration of improving the solubility of the oligothiophene derivative in an organic solvent, n ¹ +n ² +n ³ is preferably 8 or less, more preferably 7 or less, even more preferably 6 or less, and 5 or less. It is optimal.

In the formulas (1) to (3), the carbon number of the alkyl group, the alkenyl group and the alkynyl group is preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less.

Further, the carbon number of the aryl group and the heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

The molecular weight of the charge-transporting monomer or charge-transporting oligomer used in the present invention is usually 300 to 8000, but from the viewpoint of improving solubility, it is preferably 5000 or less, more preferably 4000 or less, and further preferably 3000 or less, More preferably, it is 2000 or less.

In particular, the molecular weight of the aniline derivative and the thiophene derivative used in the present invention is usually 300 to 5000, but from the viewpoint of improving solubility, it is preferably 4000 or less, more preferably 3000 or less, and even more preferably 2000 or less. .

In addition, although it is not specifically limited as a synthesis method of the aniline derivative used in this invention, Bulletin of Chemical Society of Japan (1994, Vol. 67, p.1749-1752), Synthetic Synthetic Metals (1997, Vol. 84, p.119-120), Thin Solid Films (2012, 520(24) 7157-7163), International Publication No. 2008/032617, International Publication No. 2008- 032616, International Publication No. 2008-129947, etc. are mentioned.

The thiophene derivative may be synthesized by a known method (for example, the method described in Japanese Patent Application Laid-Open No. Hei 02-250881 or Chem. Eur. J. 2005, 11, pp. 3742-3752), or a commercially available product You may use it.

Hereinafter, although the specific example of a suitable aniline derivative is given, it is not limited to these.

Hereinafter, although the specific example of a suitable thiophene derivative is given, it is not limited to these.

(In the formula, n-Hex represents a normal hexyl group.)

The hole-transporting varnish of the present invention contains a heteropolyacid.

Heteropolyacid is typically represented by a Keggin type represented by formula (A) or a Dawson type chemical structure represented by formula (B), has a structure in which a hetero atom is located at the center of the molecule, vanadium (V), molybdenum It is a polyacid formed by condensing isopolyacid which is an oxygen acid, such as (Mo) and tungsten (W), and an oxygen acid of a different element. As the oxygen acid of such a heterogeneous element, the oxygen acid of silicon (Si), phosphorus (P), and arsenic (As) is mainly mentioned.

Specific examples of the heteropolyacid include phosphomolybdenic acid, silicomolybdenic acid, phosphotungstic acid, silicic tungstic acid, and phosphotungstomolybdenic acid, and these may be used alone or in combination of two or more. . In addition, the heteropolyacid used by this invention can be obtained as a commercial item, and can also be synthesize|combined by a well-known method.

In particular, when the dopant material is composed of one type of heteropolyacid alone, the one type of heteropolyacid is preferably phosphotungstic acid or phosphomolybdenic acid, and phosphotungstic acid is optimal. Further, when the dopant material is composed of two or more heteropolyacids, one of the two or more heteropolyacids is preferably phosphotungstic acid or phosphomolybdenic acid, and more preferably phosphotungstic acid.

In addition, in quantitative analysis such as elemental analysis, the heteropolyacid is obtained as a commercial product, even if the number of elements is large or small from the structure represented by the general formula, or appropriately synthesized according to a known synthesis method. As long as it is one, it can be used in the present invention.

That is, for example, in general, phosphotungstic acid is represented by the formula H ₃ (PW ₁₂ O ₄₀ )·nH ₂ O, and phosphomolybdenic acid is represented by the formula H ₃ (PMo ₁₂ O ₄₀ )·nH ₂ O, respectively, In quantitative analysis, even if the number of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product, or a known synthesis. As long as it is synthesized appropriately according to the method, it can be used in the present invention. In this case, the mass of heteropolyacid defined in the present invention is not the mass (phosphotungstic acid content) of pure phosphotungstic acid in a compound or a commercial product, but a commercially available form and a form that can be isolated by a known synthetic method, It refers to the total mass in a state including external impurities, etc.

In the present invention, heteropolyacid, preferably phosphotungstic acid, is about 1.0 to 11.0, preferably about 1.5 to 10.0, more preferably about 2.0 to 9.5, even more preferably about 2.5 to 6.5 with respect to charge-transporting substance 1 in a mass ratio of phosphotungstic acid. use to some extent.

That is, such a hole-transporting varnish ratio 1.0≤W _D / _H W ≤11.0, preferably 1.5≤W _D / W of the mass of the heteropolyacid on the weight of the charge-transporting material _{(W H) (W D)} H ≤10.0, More preferably, 2.0 ≤ _{W D} /W _H ≤ 9.5, _{and still more preferably 2.5 ≤ W D} /W _H ≤ 6.5.

In addition to the above-mentioned aniline derivatives, thiophene derivatives and heteropolyacids, other well-known charge-transporting substances and dopant substances can also be used for the hole-transporting varnish of the present invention.

Moreover, you may add an organosilane compound to the hole-transporting varnish for metal anodes of this invention. By adding the organosilane compound, it is possible to increase the hole injection capability into the layer laminated so as to be in contact with the hole injection layer on the opposite side to the metal anode such as the hole transport layer or the light emitting layer.

A dialkoxysilane compound, a trialkoxysilane compound, or a tetraalkoxysilane compound is mentioned as this organosilane compound, These may be used independently and may be used in combination of 2 or more types.

In particular, as an organosilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.

As a tetraalkoxysilane compound, a trialkoxysilane compound, and a dialkoxysilane compound, what is represented by Formula (4)-(6) is mentioned, for example.

Si(OR ⁹ ) ₄ (4)

SiR10(OR ⁹ ) ₃ (5)

Si(R10) ₂ (OR ⁹ ) ₂ (6)

Wherein, R ⁹ are, independently to each other, Z is ^{4-substituted} with an alkyl group of 1 to 20 carbon atoms that may be substituted, the alkynyl, or Z ⁵ of 2 to 20 carbon atoms or an alkenyl group of 2 to 20 carbon atoms which may and it represents an aryl group or a heteroaryl group of 2 to 20 carbon atoms having a carbon number of 6~20, R ¹⁰ are, each independently, optionally be substituted with Z ^6, an alkyl group of 1 to 20 carbon atoms, 2 to 20 carbon atoms in the alkenyl group, or that An alkynyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 7 is represented.}

Z ⁴ represents a halogen atom or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{a halogen atom or Z 8 , Z 5} is a halogen atom or may be substituted with ^{Z 8 .} , 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 ⁶ is a halogen atom, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with ^{a halogen atom, Z 8 , an epoxycyclohexyl group, a glycidoxy group, a methacryloxy group, an acryloxy group} , a ureido group (-NHCONH ₂ ), a thiol group, an isocyanate group (-NCO), an amino group, a -NHY ¹⁴ group, or a ^{-NY 15} Y ¹⁶ group, Z ⁷ is a halogen atom, Z ⁸ is substituted which may be 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, an epoxycyclohexyl group, a glycidoxy group, a methacryloxy group, an acryloxy group, a ureido group (-NHCONH ₂ ), a thiol group, an isocyanate group (-NCO), an amino group, a -NHY ¹⁴ group, or a ^{-NY 15} Y ¹⁶ group, and Y ^{14 to Y 16} are, independently of each other, optionally substituted with ^{Z 8 .} , 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, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.

Z ⁸ represents a halogen atom, an amino group, a nitro group, a cyano group, or a thiol group.

In the formulas (4) to (6), a halogen atom, 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, an aryl group having 6 to 20 carbon atoms and 2 to 20 carbon atoms Examples of the heteroaryl group include the same as those described above.

In R ⁹ and R ¹⁰ , the number of carbon atoms in the alkyl group, the alkenyl group and the alkynyl group is preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less.

Further, the carbon number of the aryl group and the heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

R ^{9 is} preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z ⁴ , or an aryl group having 6 to 20 carbon atoms which may be substituted with ^{Z 5} , and is preferably substituted with ^{Z 4 ,} An optionally substituted C1-C6 alkyl group or a C2-C6 alkenyl group, or a phenyl group optionally substituted with ^{Z 5} is more preferable, and an optionally substituted C1-C4 alkyl group with ^{Z 4 , or Z 5} a phenyl group that may be substituted, and preferably, incidentally, is a methyl group or an ethyl group which may be substituted with Z ⁴ is more preferred.

R ^{10 is} preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ⁶ or an aryl group having 6 to 20 carbon atoms which may be substituted with ^{Z 7} , an alkyl group having 1 to 10 carbon atoms which may be substituted with ^{Z 6 ;} Alternatively, an aryl group having 6 to 14 carbon atoms which may be substituted with ^{Z 7} is more preferable, an alkyl group having 1 to 6 carbon atoms which may be substituted with ^{Z 6} , or an aryl group having 6 to 10 carbon atoms which may be substituted with ^{Z 7 is even more preferable.} and an alkyl group having 1 to 4 carbon atoms which may be substituted with ^{Z 6} , or a phenyl group which may be substituted with ^{Z 7 is more preferable.}

Moreover, ^{all some R<9>} may be same or different, and some R<^{10> may} also be all same or different.

Z ⁴ is preferably a halogen atom or an aryl group having 6 to 20 carbon atoms optionally substituted with ^{Z 8 , more preferably a fluorine atom or a phenyl group optionally substituted with Z 8} , and does not exist (that is, no ring) is optimal.

Further, Z ⁵ is preferably a halogen atom or an alkyl group having 6 to 20 carbon atoms which may be substituted with ^{Z 8} , more preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with ^{Z 8 , and does not exist} (ie, unsubstituted) is optimal.

On the other hand, Z ⁶ as a halogen atom, Z ⁸ furan group, epoxy cyclohexyl group, articles that may be substituted with a phenyl group, Z ^8, which may be substituted with rayisi dock group, methacryloyl oxy group, acryloxy group, yureyi ceramics, thiol group, isocyanate group, an amino group, Z ⁸ is diphenyl amino group which may be substituted with a phenyl group, or Z ⁸ is optionally substituted preferably with, more preferably a halogen atom can, and a fluorine atom, or does not exist (that is, unsubstituted) is more preferable.

In addition, Z ⁷ as a halogen atom, Z ⁸ to 20 carbon atoms in the alkyl group which may be substituted with, a furan group, epoxy cycloalkyl that may be substituted with Z ⁸ hexyl, articles rayisi dock group, methacryloyl oxy group, acryloxy group , yureyi pottery, thiol group, isocyanate group, an amino group, Z ⁸ is diphenyl amino group which may be substituted with a phenyl group, or Z ⁸ is optionally substituted preferably with, more preferably a halogen atom can, and a fluorine atom, Or not present (ie, unsubstituted) is even more preferable.

And, Z ⁸ preferably a halogen atom to Examples, and more preferably (the words, Beach Whanin) does not seem to exist or fluorine atom.

Hereinafter, although the specific example of the organosilane compound which can be used by this invention is given, it is not limited to these.

Specific examples of the dialkoxysilane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyl Dimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Phosphorus, 3-glycidoxypropylmethyldiethoxysilane, 3-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-meth Cryloxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane etc. are mentioned.

Specific examples of the trialkoxysilane compound include methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, propyl trimethoxysilane, propyl triethoxysilane, Butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octylt Limethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrime oxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryl Oxypropyltriethoxysilane, triethoxy(4-(trifluoromethyl)phenyl)silane, dodecyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, ( Triethoxysilyl) cyclohexane, perfluorooctylethyltriethoxysilane, triethoxyfluorosilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane , pentafluorophenyl trimethoxysilane, pentafluorophenyl triethoxysilane, 3-(heptafluoroisopropoxy)propyltriethoxysilane, heptatecafluoro-1,1,2,2 -tetrahydrodecyltriethoxysilane, triethoxy-2-thienylsilane, 3-(triethoxysilyl)furan, etc. are mentioned.

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

Among these, 3,3,3-trifluoropropylmethyldimethoxysilane, triethoxy(4-(trifluoromethyl)phenyl)silane, 3,3,3-trifluoropropyl trimethoxy Silane, perfluorooctylethyltriethoxysilane, pentafluorophenyltrimethoxysilane, and pentafluorophenyltriethoxysilane are preferable.

The content of the organosilane compound in the hole-transporting varnish of the present invention is usually about 0.1 to 50% by mass relative to the total mass of the charge-transporting substance and the heteropolyacid, in consideration of maintaining the high charge-transporting property of the resulting thin film, but preferably Preferably it is about 0.5-40 mass %, More preferably, it is about 0.8-30 mass %, More preferably, it is 1-20 mass %.

As an organic solvent used when preparing the hole-transporting varnish for a metal anode of the present invention, a high-solubility solvent capable of dissolving a charge-transporting substance and a dopant substance satisfactorily can be used. Examples of such a highly soluble solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, di Organic solvents, such as ethylene glycol monomethyl ether, can be used. These solvents can be used individually by 1 type or in mixture of 2 or more types, The usage-amount can be 5-100 mass % with respect to the whole solvent used for a varnish.

In addition, it is preferable that both the charge-transporting material and the dopant material are completely dissolved in the solvent or are in a state in which they are uniformly dispersed.

In addition, in the hole-transporting varnish for a metal anode, 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 atmospheric pressure (atmospheric pressure) At least one type can be contained. By adding such a solvent, it becomes easy to adjust the viscosity of a varnish, and it becomes easy to prepare a varnish suitable for the application|coating method to be used which provides a thin film with high flatness with good reproducibility.

It does not specifically limit as a high viscosity organic solvent, For example, cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1, 3- octylene glycol, diethylene glycol, diethylene glycol, Propylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hex Silene glycol, etc. are mentioned. These solvents can be used individually by 1 type or in mixture of 2 or more types.

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 solids do not precipitate, and as long as solids do not precipitate, the addition ratio is preferably 5 to 80% by mass. .

In addition, for the purpose of improving the wettability to the metal anode, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., other solvents are added in an amount of 1 to 90% by mass, preferably based on the total amount of the solvent used in the varnish. may be mixed in a ratio of 1 to 50 mass %.

As such a solvent, for example, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene Glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone Alcohol, (gamma)-butyrolactone, ethyl lactate, n-hexyl acetate etc. are mentioned, However, It is not limited to these. These solvents can be used individually by 1 type or in mixture of 2 or more types.

Although the viscosity of the varnish of this invention is suitably set according to the thickness etc. of the layer to produce, and solid content concentration, it is 1-50 mPa*s at 25 degreeC normally.

In addition, the solid content concentration of the varnish of the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the layer to be produced, etc., but is usually about 0.1 to 10.0% by mass, improving the applicability of the varnish. Considering this, it is preferably 0.5 to 5.0 mass%, more preferably 1.0 to 3.5 mass%.

A hole-transporting thin film can be formed on the metal anode by applying the hole-transporting varnish for a metal anode described above on the metal anode and firing.

The method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a slit coating method, a transfer printing method, a roll coating method, a brushing method, an inkjet method, and a spraying method. It is desirable to control the viscosity and surface tension.

In addition, when the varnish of the present invention is used, the firing atmosphere is not particularly limited, and a thin film having a uniform film-forming surface can be obtained not only in an atmospheric atmosphere, but also in an inert gas such as nitrogen or in a vacuum. In order to obtain a thin film with excellent hole-accepting capacity with good reproducibility, an atmospheric atmosphere is preferable.

The firing temperature is appropriately set within the range of about 100 to 260°C in consideration of the purpose of the resulting thin film, the degree of charge transport properties imparted to the resulting thin film, and the like, but when used as a hole injection layer of an organic EL device, 140 About -250 degreeC is preferable, and about 150-230 degreeC is more preferable. In this case, for the purpose of expressing higher uniformity of film formation or advancing the reaction on the anode, two or more steps of temperature change may be applied, and heating is performed using an appropriate device such as a hot plate or oven, for example. and do it.

Although the film thickness can be usually set to about 5 to 200 nm, when used as a hole injection layer of an organic EL element, about 10 to 100 nm is preferable. As a method of changing a film thickness, there exist methods, such as changing the solid content concentration in a varnish, and changing the solution amount at the time of application|coating.

Although the following are mentioned as a material to be used in the case of producing an OLED element using the hole-transporting varnish for metal anodes of this invention, and a manufacturing method, It is not limited to these.

The metal anode to be used is preferably cleaned by performing liquid washing with detergent, alcohol, pure water, etc. in advance, for example, it is preferable to perform surface treatment such as UV ozone treatment or oxygen-plasma treatment immediately before use.

The example of the manufacturing method of the OLED element which has a hole injection layer obtained from the hole transporting varnish for metal anodes of this invention is as follows.

The hole transporting varnish for a metal anode of this invention is apply|coated on a metal anode, and it bakes by the said method, and produces a hole injection layer on an electrode. This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited to obtain an OLED device. In order to control the light emitting region, a carrier block layer may be formed between any layers other than between the metal anode and the hole injection layer.

Materials constituting the anode include aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, cadmium, and indium. , scandium, lanthanum, cerium, praseodymium, neodymium, propetium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, thallium, tungsten, rhenium, osmium, iridium, platinum metals such as titanium, lead, bismuth, and the like, and alloys thereof are mentioned, and a planarization treatment is preferable.

As a material for forming the hole transport layer, (triphenylamine)dimer derivative (TPD), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD), [(triphenylamine) ) Triarylamines such as dimer] spirodimer (Spiro-TAD), 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4 Starburst amines such as "-tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2 and oligothiophenes such as ,2':5',2"-terthiophene (BMA-3T).

As a material for forming the light emitting layer, tris(8-quinolinolate)aluminum(III)(Alq ₃ ), bis(8-quinolinolate)zinc(II)(Znq ₂ ), bis(2-methyl-8- quinolinolate) (p-phenylphenolate) aluminum (III) (BAlq) and 4,4'-bis (2,2-diphenylvinyl) biphenyl (DPVBi), and electron transporting material or A light emitting layer may be formed by co-evaporating a hole transport material and a light emitting dopant.

Examples of the electron transport material include Alq ₃ , BAlq, DPVBi, (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole) (PBD), triazole derivatives ( TAZ), Batocuproin (BCP), a silol derivative, etc. are mentioned.

As the luminescent dopant, quinacridone, rubrene, coumarin 540, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM), tris(2- Phenylpyridine) iridium (III) (Ir(ppy) ₃ ), (1,10-phenanthroline)-tris(4,4,4-trifluoro-1-(2-thienyl)-butane -1,3-dionate) europium (III) (Eu(TTA) ₃ phen) and the like.

PBD, TAZ, BCP, etc. are mentioned as a material which forms a carrier block layer.

Examples of the material for forming the electron injection layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ O ₃ ), lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), strontium fluoride (SrF ₂ ), Liq, Li(acac), lithium acetate, lithium benzoate, etc. are mentioned.

Examples of the negative electrode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, and cesium.

Although the manufacturing method of the PLED element using the hole-transporting varnish for metal anodes of this invention is not specifically limited, The following method is mentioned.

In manufacturing the OLED device, instead of performing vacuum deposition of the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, the hole transporting polymer layer and the light emitting polymer layer are sequentially formed by the hole transporting varnish for the metal anode of the present invention. A PLED device including a hole injection layer can be manufactured.

Specifically, the hole transporting varnish for a metal anode of the present invention is applied on the anode, a hole injection layer is prepared by the above method, a hole transporting polymer layer and a light emitting polymer layer are sequentially formed thereon, and a cathode electrode is deposited. PLED device.

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

As a method of forming the hole-transporting polymer layer and the light-emitting polymer layer, a solvent is added to a hole-transporting polymer material or a light-emitting polymer material, or a material added with a dopant material thereto, dissolved or uniformly dispersed, and a hole injection layer or a hole-transporting polymer layer After application|coating on top, the method of forming into a film by evaporation of each solvent is mentioned.

As the hole transporting polymer material, poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene) )], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4 ,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorenyl-2,7-diyl)-co-(N,N'-bis{p -Butylphenyl}-1,4-diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-end capd with polysilses Quoxane, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)], etc. can

Examples of the luminescent polymer material include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF) and poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinyl). and polyphenylenevinylene derivatives such as ene) (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

Toluene, xylene, chloroform, etc. are mentioned as a solvent, Methods, such as stirring, heating stirring, and ultrasonic dispersion, are mentioned as a dissolution or homogeneous dispersion method.

The coating method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a slit coating method, a transfer printing method, a roll coating method, and a brushing method. In addition, it is preferable to perform application|coating under inert gas, such as nitrogen and argon.

Examples of the solvent evaporation method include heating under an inert gas or vacuum, in an oven or on a hot plate.

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. In addition, the apparatus used is as follows.

(1) ¹ H-NMR measurement: Varian high-resolution nuclear magnetic resonance apparatus

(2) Anode cleaning: Choshu Sangyo Co., Ltd. substrate cleaning device (reduced plasma method)

(3) Varnish application: Spin coater MS-A100 manufactured by Mikasa Corporation

(4) Film thickness measurement: SURFCODA ET-4000, a fine shape measuring instrument manufactured by Kosaka Kenkyusho Co., Ltd.

(5) Fabrication of element: Choshu Sangyo Co., Ltd. multi-function vapor deposition system system C-E2L1G1-N

(6) Measurement of device current density, etc.: I-V-L measurement system manufactured by Tech World Co., Ltd.

[1] Synthesis of charge-transporting materials

[Synthesis Example 1] Synthesis of aniline derivative A

Aniline derivative A used in Examples was synthesized according to the following scheme.

In a mixed suspension of 4,4'-diaminodiphenylamine (10.00 g, 50.19 mmol) and 4-bromotriphenylamine (34.17 g, 105.40 mmol) in xylene (100 g), Pd (PPh) as a metal complex catalyst ₃ ) ₄ (0.5799 g, 0.5018 mmol) and t-BuONa (10.13 g, 105.40 mmol) as a base were added, and the reaction was stirred at 130° C. under nitrogen for 14 hours.

The cooled reaction mixture was filtered, saturated brine was added to the filtrate, and liquid separation was performed. Thereafter, the solvent was distilled off under reduced pressure, and then the target product was recrystallized from 1,4-dioxane to obtain an aniline derivative A (yield 65%).

[Synthesis Example 2] Synthesis of aniline derivative B

Aniline derivative B used in Examples was synthesized according to the following scheme.

Mixed suspension of N,N'-bis(4-aminophenyl)-p-phenylenediamine (5.00 g, 17.22 mmol) and 4-bromotriphenylamine (9.30 g, 28.70 mmol) in xylene (140 g) Then, Pd(PPh ₃ ) ₄ (0.33 g, 0.29 mmol) as a metal complex catalyst and t-BuONa (2.76 g, 28.70 mmol) as a base were added, and the reaction was stirred at 135° C. under nitrogen for 8 hours.

The cooled reaction mixture was filtered, and the solvent was distilled off under reduced pressure. Subsequently, the target product was recrystallized from 1,4-dioxane to obtain an aniline derivative B (yield 53%).

[Synthesis Example 3] Synthesis of arylsulfonic acid A

Arylsulfonic acid A used in Examples was synthesized according to the following scheme based on the description of International Publication No. 2006/025342.

To 11 g (31.59 mmol) of well-dried sodium 1-naphthol-3,6-disulfonate, under a nitrogen atmosphere, 4.797 g (14.36 mol) of perfluorobiphenyl, 4.167 g (30.15 mol) of potassium carbonate and N,N - 100 ml of dimethylformamide was sequentially added, and the reaction system was substituted with nitrogen, followed by stirring at an internal temperature of 100° C. for 6 hours.

After cooling to room temperature, in order to redissolve the arylsulfonic acid A precipitated after the reaction, 500 ml of N,N-dimethylformamide was further added, followed by stirring at room temperature for 90 minutes. After stirring at room temperature, the solution was filtered to remove the potassium carbonate residue, and concentrated under reduced pressure. Further, in order to remove the 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 to obtain a filtrate. 300 ml of ultrapure water was added to the filtrate to dissolve, and ion exchange was performed by column chromatography using a cation exchange resin Dow X650C (manufactured by Dow Chemical, about 200 ml of H type, effluent solvent: ultrapure water).

The fraction having a pH of 1 or less was concentrated to dryness under reduced pressure, and the residue was dried under reduced pressure to obtain 11 g of a yellow powder (yield 85%).

[Synthesis Example 4] Synthesis of thiophene derivative A

The thiophene derivative A used in Examples was synthesized according to the following scheme.

In a nitrogen atmosphere, 2.01 g of terthiophene and 50 mL of tetrahydrofuran were placed in a flask and cooled to -78°C. 19.6 mL of n-butyllithium normal hexane solution (1.64 M) was dripped there, and it stirred for 30 minutes at -78 degreeC, Then, it heated up to 0 degreeC, and stirred for 1 hour more.

Then, after cooling to -78 degreeC and stirring for 30 minutes, 8.8 mL of tributylchlorostannane was dripped and stirred for 10 minutes, Then, it heated up to 0 degreeC and stirred for 30 minutes further.

After stirring, the solvent was distilled off from the reaction mixture under reduced pressure, the obtained residue was added to toluene, insoluble matter was removed by filtration, and the solvent was distilled off from the obtained filtrate under reduced pressure to obtain the bisstannyl form of terthiophene. 12.88 g of an oily substance (purity of 51.91% of the bisstannyl compound) was obtained.

Then, in another flask under a nitrogen atmosphere, 6.44 g of an oily substance containing this terthiophenebisstanyl compound, 2.41 g of 2-bromo-3-normalhexylthiophene, 24 mL of toluene, and tetrakis(triphenylphosphine) ) 0.23 g of palladium was sequentially added, and the mixture was stirred under reflux conditions for 4.5 hours.

After allowing to cool to room temperature and distilling off the solvent under reduced pressure, insoluble matter was removed by filtration. The obtained filtrate was concentrated and purified by silica gel column chromatography to obtain a thiophene derivative A (yield: 1.29 g, yield: 55%, overall yield in two steps).

[2] Preparation of hole-transporting varnish for metal anode

[Example 1-1]

Bullentin of Chemical Society, 1994, vol. 67, pp. 0.122 g of an aniline derivative C represented by the following formula, prepared according to the method described in 1749-1752, and 0.367 g of phosphomolybdenic acid (manufactured by Kanto Chemical Co., Ltd., hereinafter the same.) were mixed with 1,3- It was dissolved in 8 g of dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI). To the obtained solution, 12 g of cyclohexanol (hereinafter, abbreviated as CHA) and 4 g of propylene glycol (hereinafter, abbreviated as PG) were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-2]

0.247 g of the aniline derivative A and 0.495 g of phosphomolybdenic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-3]

0.154 g of aniline derivative A, 0.423 g of phosphotungstic acid (manufactured by Kanto Chemical Co., Ltd., the same hereinafter) and 0.038 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and thereto, organosilane compound A (trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)/phenyltrimethoxysilane (Made by Shin-Etsu Chemical Co., Ltd.) = 1/2 (w/w) mixture, the same as follows.) 0.025 g was added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-4]

0.131 g of aniline derivative A, 0.261 g of phosphomolybdenic acid, and 0.098 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-5]

0.154 g of aniline derivative A, 0.385 g of phosphotungstic acid, and 0.077 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.025 g of organic silane compound A was added thereto and stirred to prepare a hole-transporting varnish for metal positive electrodes.

[Example 1-6]

0.186 g of the aniline derivative A and 0.557 g of phosphomolybdenic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-7]

0.186 g of the aniline derivative A and 0.557 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.03 g of the organosilane compound A was added thereto and stirred to prepare a hole-transporting varnish for metal positive electrodes.

[Example 1-8]

0.123 g of aniline derivative A, 0.369 g of phosphotungstic acid, and 0.123 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.025 g of organic silane compound A was added thereto and stirred to prepare a hole-transporting varnish for metal positive electrodes.

[Example 1-9]

0.148 g of aniline derivative B and 0.594 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-10]

0.124 g of the aniline derivative A and 0.619 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-11]

0.124 g of aniline derivative B and 0.619 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-12]

0.088 g of aniline derivative A, 0.440 g of phosphotungstic acid, and 0.088 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.062 g of the organosilane compound A was added thereto and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-13]

0.106 g of aniline derivative A and 0.636 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-14]

0.186 g of the aniline derivative A and 0.557 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.074 g of organosilane compound A was added thereto and stirred to prepare a hole-transporting varnish for metal positive electrodes.

[Example 1-15]

0.106 g of aniline derivative B and 0.636 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-16]

0.088 g of aniline derivative A, 0.484 g of phosphotungstic acid, and 0.044 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.062 g of the organosilane compound A was added thereto and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-17]

0.093 g of the aniline derivative B and 0.649 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-18]

0.148 g of N,N'-diphenylbenzidine (manufactured by Tokyo Chemical Industry Co., Ltd., the same applies hereinafter) and 0.594 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

Further, N,N'-diphenylbenzidine was recrystallized using 1,4-dioxane, and then dried well under reduced pressure before use (hereinafter the same.).

[Example 1-19]

0.124 g of N,N'-diphenylbenzidine and 0.619 g of phosphotungstic acid were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Example 1-20]

0.122 g of aniline derivative A, 0.103 g of phosphomolybdenic acid, 0.154 g of phosphotungstic acid, and 0.11 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.049 g of organosilane compound A was added thereto and stirred to prepare a hole-transporting varnish for metal positive electrodes.

[Example 1-21]

0.122 g of N,N'-diphenylbenzidine, 0.103 g of phosphomolybdenic acid, 0.154 g of phosphotungstic acid, and 0.11 g of arylsulfonic acid A were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred, and 0.049 g of organosilane compound A was added thereto and stirred to prepare a hole-transporting varnish for metal positive electrodes.

[Example 1-22]

0.116 g of a thiophene derivative A represented by the following formula and 0.348 g of phosphotungstic acid were dissolved in 10.5 g of DMI under a nitrogen atmosphere. To the obtained solution, 3 g of 2,3-butanediol and 1.5 g of propylene glycol monomethyl ether were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[Examples 1-23 to 1-24]

Example 1-22 and Example 1-22 except that the usage-amount of thiophene derivative A and the usage-amount of phosphotungstic acid were 0.093g and 0.371g (Example 1-23), 0.077g, and 0.387g (Example 1-24), respectively. In the same manner, a hole-transporting varnish for a metal anode was prepared.

[Comparative Example 1-1]

0.154 g of the aniline derivative A and 0.685 g of 5-salicylsulfonic acid dihydrate (manufactured by Sigma-Aldrich. Co) were dissolved in 8 g of DMI under a nitrogen atmosphere. To the obtained solution, 12 g of CHA and 4 g of PG were sequentially added and stirred to prepare a hole-transporting varnish for a metal positive electrode.

[3] Fabrication of devices

[Example 2-1]

The varnish obtained in Example 1-1 was applied to the Al/Nd anode using a spin coater, dried at 50° C. for 5 minutes, and then fired at 230° C. for 15 minutes to form a 30 nm uniform thin film on the Al/Nd anode. has formed In addition, the Al/Nd anode was produced by sputtering Al and Nd on a glass substrate.

Next, a thin film of N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD)) and aluminum was applied to the Al/Nd anode on which the thin film was formed, using a vapor deposition apparatus. were sequentially stacked to obtain a two-layer device. The film thicknesses were 30 nm and 100 nm, respectively, ^{and vapor deposition was performed under the conditions of a vacuum degree of 1.0×10 −5} Pa and a deposition rate of 0.2 nm/sec.

In addition, in order to prevent characteristic deterioration due to the influence of oxygen in the air, water, etc., the two-layer element was sealed with a sealing substrate, and then the characteristics were evaluated. Sealing was performed in the following procedure.

In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -85° C. or less, the two-layer element was placed between sealing substrates, and the sealing substrate was bonded with an adhesive. At this time, as a catcher, HD-071010W-40 manufactured by Dynic Co., Ltd. was put in the sealing substrate together with the two-layer element. As the adhesive material, XNR5516Z-B1 manufactured by Nagase Chemtex Co., Ltd. was used. After irradiating UV light (wavelength: 365 nm, irradiation amount: 6000 mJ/cm ² ) to the bonded sealing substrate, annealing treatment was performed at 80° C. for 1 hour to harden the adhesive material.

[Examples 2-2 to 2-24, Comparative Example 2-1]

An element was produced in the same manner as in Example 2-1 except that the varnish obtained in Examples 1-2 to 1-24 and Comparative Example 1-1 was used instead of the varnish obtained in Example 1-1, respectively.

[Comparative Example 2-2]

An element was produced in the same manner as in Example 2-1 except that PEDOT/PSS (AI4083 manufactured by H. C. Starck) was used instead of the varnish obtained in Example 1-1.

The current density was measured for each element. Table 1 shows the current density at a driving voltage of 5V.

Example 2-2 150 Example 2-3 432 Example 2-4 123 Example 2-5 486 Example 2-6 460 Example 2-7 494 Examples 2-8 114 Examples 2-9 236 Example 2-10 557 Example 2-11 411 Example 2-12 110 Examples 2-13 461 Examples 2-14 939 Examples 2-15 488 Examples 2-16 241 Example 2-17 233 Example 2-18 420 Examples 2-19 129 Examples 2-20 440 Example 2-21 580 Example 2-22 1280 Example 2-23 1420 Example 2-24 420 Comparative Example 2-1 2 Comparative Example 2-2 5

As shown in Table 1, the hole injection layer prepared by using the hole transporting varnish for a metal anode of the present invention containing a heteropoly acid showed high hole accepting capacity from the metal anode, whereas the generally known arylsulfonic acid type A thin film obtained from a material using only the dopant material of PEDOT/PSS, for example, had a low hole capacity from the metal anode.

From the above, it can be seen that the hole transporting varnish for a metal anode of the present invention comprising a charge transporting material such as an aniline derivative or a thiophene derivative and a heteropoly acid is particularly suitable for forming a hole injection layer on the metal anode.

Claims (10)

A hole-transporting varnish for a metal anode for forming a thin film laminated on a metal anode to transport holes received from the metal anode to a layer stacked on the opposite side of the metal anode,
A hole-transporting varnish for a metal anode, comprising a charge-transporting material comprising a thiophene derivative represented by Formula (3), a dopant material comprising a heteropolyacid, and an organic solvent.

(Wherein, R ¹³ to ^{R 16} each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms,
R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, a diarylamino group in which each aryl group is an aryl group having 6 to 10 carbon atoms, or a phenyl group substituted with a di(C 6 to C 20) arylamino group;
n ^{1 to} n ³ independently represent a natural number and satisfy 4≤n ¹ +n ² +n ³ ≤20.
Further, when R ¹³ to ^{R 16} are not hydrogen atoms, two groups on the thiophene ring above one may be bonded to each other to form a divalent group. However, the case where R ¹³ to ^{R 16} simultaneously becomes a hydrogen atom is excluded.) The method of claim 1,
A hole-transporting varnish for a metal anode, wherein the metal anode comprises at least one metal selected from molybdenum, chromium, aluminum, silver, gold, and platinum. Consists of a metal anode and a hole injection layer laminated on the surface,
The hole injection layer comprises a charge-transporting material comprising at least one of an aniline derivative represented by Formula (1) or a thiophene derivative represented by Formula (3), a dopant material comprising a heteropolyacid, and an organic solvent A composite metal anode, characterized in that it is produced from a hole-transporting varnish for a metal anode.

(Wherein, X ¹ represents -NH- or a single bond,
Y ¹ represents, independently of each other, a hydrogen atom or a methyl group,
R ¹ to ^{R 4} each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or a diphenylamino group optionally substituted with a fluorine atom,
l represents an integer of 1 to 20, m and n independently represent an integer of 0 or more, and satisfy 1≤m+n≤20. However, when m or n is 0, X ¹ represents -NH-.)

(Wherein, R ¹³ to ^{R 16} each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms,
R ¹⁷ and R ¹⁸ represent, independently of each other, a hydrogen atom, a diarylamino group in which each aryl group is an aryl group having 6 to 10 carbon atoms, or a phenyl group substituted with a di(C6 to C 20) arylamino group,
n ^{1 to} n ³ independently represent a natural number and satisfy 4≤n ¹ +n ² +n ³ ≤20.
Further, when R ¹³ to ^{R 16} are not hydrogen atoms, two groups on the thiophene ring above one may be bonded to each other to form a divalent group. However, the case where R ¹³ to ^{R 16} simultaneously becomes a hydrogen atom is excluded.) 4. The method of claim 3,
A composite metal anode, wherein the metal anode is made of at least one metal selected from molybdenum, chromium, aluminum, silver, gold, and platinum. 4. The method of claim 3,
^{X 1} of Formula (1) is -NH-, characterized in that the composite metal anode. The organic electroluminescent element which has the composite metal anode of Claim 3. 7. The method of claim 6,
An organic electroluminescence device characterized in that it is a top emission type. A method for manufacturing an organic electroluminescent device comprising the step of applying the hole-transporting varnish for a metal anode according to claim 1 or 2 to the surface of the metal anode and drying the metal anode. A method for manufacturing an organic electroluminescent device, comprising the use of the composite metal anode according to claim 3 . delete