TWI791449B - Varnish for forming charge-transporting thin film - Google Patents

Abstract

The present invention provides a varnish for forming a charge-transporting thin film containing a pentavalent superatomic iodine compound, a charge-transporting substance, and an organic solvent.

Description

Varnish for forming charge-transporting thin film

The present invention relates to a varnish for forming a charge-transporting thin film.

In an organic electroluminescence (EL) device, a charge-transporting 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-transporting thin film is roughly divided into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. When comparing the dry process and the wet process, the wet process can more efficiently produce a thin film with high flatness on a large area. There are many cases where thin films are formed by conventional processes.

From this point of view, the inventors of the present invention have developed a varnish for forming a charge-transporting thin film that can be applied to various electronic devices by a wet process (such as Refer to Patent Document 1).

However, in the field of organic EL in recent years, there is a need to reduce the weight and thickness of components. In view of the trend of flexibility, substrates made of organic compounds have begun to be used instead of glass substrates. Therefore, it is possible to bake at a lower temperature than conventional products, and at this time, a varnish that imparts a thin film with good charge transport properties is expected.

[Prior Technical Literature] 〔Patent Document〕

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

The present invention is made in view of the foregoing, to provide a device that exhibits high charge transportability even when baked at a low temperature, and when used as a hole injection layer of an organic EL device, can achieve driving while maintaining the current efficiency of the device. The object is a varnish for forming a charge-transporting thin film containing a pentavalent superatomic iodine compound for reducing voltage or improving luminance characteristics. The present invention also aims at a method of reducing the driving voltage of an organic EL device, a method of improving luminance, and a method of improving luminance life using such a varnish for forming a charge transporting thin film.

The inventors of the present invention repeated detailed examinations in order to achieve the aforementioned object, and found that the pentavalent superatomic iodine compound has both excellent solubility in organic solvents and excellent oxidizing properties for charge transporting substances, which are combined with charge transporting properties. When the charge-transporting film obtained by dissolving the substance in a varnish prepared by an organic solvent is used as the hole injection layer of an organic EL element, even if the varnish is baked at a low temperature, it can reach the driving voltage without losing the current efficiency of the element. Reduction or improvement of luminance characteristics completes the present invention. In addition, in the present invention, "grilling at a low temperature" means "grilling at a temperature of 180° C. or less".

That is, the present invention provides the following: 1. A varnish for forming a charge-transporting thin film characterized by containing a pentavalent super-valent iodine compound, a charge-transporting substance, and an organic solvent; 2. The aforementioned pentavalent super-valent iodine compound is Dess-Martin Periodinane (Dess-Martin Periodinane), 2-Dioxyiodobenzoic acid, 2-Dioxyiodobenzenesulfonic acid, and compounds represented by the following formulas (X1) and (X2) are selected from the group One or more compositions for forming a charge-transporting thin film according to 1.;

3. The above-mentioned pentavalent superatomic iodine compound is a composition for forming a charge-transporting thin film of 2. of Dess-Martin periodinane; 4. The above-mentioned charge-transporting substance is a charge-transporting compound containing a molecular weight of 200 to 9,500 The varnish for forming a charge-transporting thin film according to any one of 1. to 3.; 5. The charge-transporting substance is a group consisting of arylamine derivatives and thiophene derivatives selected from molecular weights of 200 to 9,500. The varnish for forming a charge-transporting film according to any one of 1. to 4. characterized by at least one of them; 6. The charge-transporting film according to any one of 1. to 5. characterized by containing a blend Forming varnish; 7. The varnish for forming a charge-transporting thin film as in 6. characterized in that the aforementioned blend contains arylsulfonic acid; 8. Using the charge-transporting thin film according to any one of 1. to 7. A charge-transporting thin film made of a varnish for forming it; 9. An organic EL device having a charge-transporting thin film as described in 8.; 10. A charge-transporting film-forming varnish as in any one of 1. to 7. is used. A method for producing a characteristic charge transport film; 11. A method for producing an organic EL element characterized by using any of the varnishes for forming a charge transport film in 1. to 7.; A method for driving voltage of an organic EL element with a charge transporting thin film manufactured from a varnish for forming a charge transporting thin film, characterized in that as the varnish for forming a charge transporting thin film, a charge transporting thin film according to any one of 1. to 7. is used Forming varnish; 13. A method of improving the brightness of an organic EL element having a charge transporting thin film manufactured using a charge transporting thin film forming varnish, characterized in that as the aforementioned charge transporting thin film forming varnish, such as 1. ~7. Any one of the varnish for forming a charge transporting thin film; 14. A method of improving the luminance life of an organic EL element having a charge transporting thin film produced using a varnish for forming a charge transporting thin film, characterized by being As the varnish for forming a charge-transporting thin film, the varnish for forming a charge-transporting thin film according to any one of 1. to 7. is used.

By using the varnish for forming a charge-transporting thin film of the present invention, compared with a varnish not containing it or a varnish containing other organic oxidizing agents, the present invention shows high charge transport even when baked at a low temperature. Sexual charge transport film. And when this thin film is used as a hole injection layer, it is possible to reduce the driving voltage of the organic EL element or improve the luminance characteristics.

In addition, the thin film obtained from the varnish for forming a charge-transporting thin film of the present invention is also expected to be used as an antistatic film, a hole-trapping layer of an organic thin-film solar cell, and the like.

The varnish for forming a charge-transporting thin film according to the present invention contains a pentavalent superatomic iodine compound. In the present invention, the aforementioned 5-valent superatomic iodine compound is selected from Dess-Martin periodinane (1,1,1-acetyloxy-1,1-dihydro-1,2-Benzioodoxol-3-( 1H)-ketone), 2-dioxioiodobenzoic acid (IBX), 2-dioxoiodobenzenesulfonic acid (IBS), and one or more groups of compounds represented by the following formulas (X1) and (X2) Preferably, Dess-Martin periodinane is preferred.

The content of the pentavalent superatomic iodine compound in the varnish of the present invention is about 10 to 80 mass % with respect to the charge transporting substance (the charge transporting substance and the blend when it contains a blend), preferably 20% by mass. ~60% by mass.

As the charge-transporting substance containing the varnish for forming a charge-transporting thin film of the present invention, those used in the field of organic EL can also be used. Specific examples of this include arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, N,N,N',N'-tetraarylbenzidine derivatives, Various charge-transporting compounds such as oligothiophene derivatives, thienothiophene derivatives, thiophene derivatives such as thienothiophene derivatives, and pyrrole derivatives such as oligopyrrole. Among them, arylamine derivatives and thiophene derivatives are preferable, and arylamine derivatives are more preferable because of their excellent solubility in organic solvents.

The molecular weight of the aforementioned charge-transporting compound is generally about 200 to 9,500 from the viewpoint of preparing a uniform varnish that imparts a high flatness film, but it is preferably 300 or more from the viewpoint of obtaining a film with better charge-transporting properties , preferably 400 or more, from the viewpoint of preparing a uniform varnish that imparts high reproducibility to a film with high flatness, preferably 8,000 or less, more preferably 7,000 or less, still more preferably 6,000 or less, Less than 5,000 is better. Furthermore, from the viewpoint of preventing separation of the charge-transporting substance when forming a thin film, it is preferable that the charge-transporting compound has no molecular weight distribution (the degree of dispersion is 1) (that is, one having a single molecular weight is preferable).

Specific examples of arylamine derivatives include those represented by formula (1).

In formula (1), X ²⁰¹ represents -NY ²⁰¹ -, -O-, -S-, -(CR ²⁰⁷ R ²⁰⁸ ) _L - or a single bond, and when m ¹ or m ² is 0, it represents -NY ²⁰¹ -.

Y ²⁰¹ independently represents a hydrogen atom, an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons or an alkynyl group with 2 to ²⁰ carbons that can be replaced by Z 201, or a carbon that can be replaced by Z ²⁰² An aryl group with 6-20 carbon atoms or a heteroaryl group with 2-20 carbon atoms.

Specific examples of the alkyl group having 1 to 20 carbon atoms include linear, branched, and cyclic, such as methyl, ethyl, n-propyl, and isopropyl. , n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other carbon Straight-chain or branched-chain alkyl with a number of 1-20; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl , bicyclopentyl, bicyclohexyl, bicycloheptyl, bicycloctyl, bicyclononyl, bicyclodecyl and other cyclic alkyl groups with 3 to 20 carbon atoms, etc.

Specific examples of alkenyl groups having 2 to 20 carbon atoms include vinyl, n-1-propenyl, n-2-propenyl, 1-methylvinyl, n-1-butenyl, n- 2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl , 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n-1-eicosenyl, etc.

Specific examples of alkynyl groups having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl , n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl base, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n -1-hexynyl, n-1-decynyl, n-1-pentadeynyl, n-1-eicosynyl and the like.

Specific examples of aryl groups having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2- -Phenyl, 3-Phi, 4-Phi, 9-Phi, etc.

Specific examples of heteroaryl groups having 2 to 20 carbon atoms include 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5 -Oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-iso Thiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.

R ²⁰⁷ and R ²⁰⁸ independently represent 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 carboxyl group, and carbon numbers 1 to 20 that can be replaced by Z ²⁰¹ Alkyl with 2~20 carbons, alkenyl with 2~20 carbons or alkynyl with 2~20 carbons, aryl with 6~20 carbons or heteroaryl with 2~20 carbons which can be substituted by Z ²⁰² or -NHY ²⁰² , -NY ²⁰³ Y ²⁰⁴ , -C(O)Y ²⁰⁵ , -OY ²⁰⁶ , -SY ²⁰⁷ , -SO ₃ Y ²⁰⁸ , -C(O)OY ²⁰⁹ , -OC(O)Y ²¹⁰ , -C(O) NHY ²¹¹ or -C(O)NY ²¹² Y ²¹³ group.

Y ²⁰² ~ Y ²¹³ independently represent an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons or an alkynyl group with 2 to 20 carbons that can be replaced by Z ²⁰¹ , or a carbon number that can be replaced by Z ²⁰² An aryl group with 6-20 carbon atoms or a heteroaryl group with 2-20 carbon atoms.

Z ²⁰¹ represents an aryl group with 6 to 20 carbons or an aryl group with 2 to 20 carbons that can be substituted by a halogen atom, nitro, cyano, amine, aldehyde, hydroxyl, thiol, sulfonic acid, carboxyl or Z ²⁰³ The heteroaryl.

Z ²⁰² represents an alkyl group with 1 to 20 carbons, 2 to 20 carbons that can be substituted by a halogen atom, nitro, cyano, amine, aldehyde, hydroxyl, thiol, sulfonic acid, carboxyl or Z ²⁰³ alkenyl or alkynyl with 2 to 20 carbons.

Z ²⁰³ represents 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 carboxyl group.

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

Examples of the alkyl, alkenyl, alkynyl, aryl, and heteroaryl groups for R ²⁰⁷ to R ²⁰⁸ and Y ²⁰² to Y ²¹³ include the same ones as described above.

Among them, as R ²⁰⁷ and R ²⁰⁸ , a hydrogen atom or an alkyl group with 1 to 20 carbon atoms which may be substituted by Z ²⁰¹ is preferred, a hydrogen atom or a methyl group which may be substituted by Z ²⁰¹ is preferred, and hydrogen Atom is best.

L represents the number of divalent groups represented by -(CR ²⁰⁷ R ²⁰⁸ )-, although it is an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, and more preferably 1 to 2 , with 1 being the best. Moreover, when L is 2 or more, the plural R ²⁰⁷ may be the same or different from each other, and the plural R ²⁰⁸ may be the same or different from each other.

In other words, -NY ²⁰¹ - or a single bond is preferable as X ²⁰¹ . In addition, ^Y201 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbons which may be substituted by ^Z201 , preferably a hydrogen atom or a methyl group which may be substituted by ^Z201 , and most preferably a hydrogen atom.

R ²⁰¹ ~ R ²⁰⁶ independently represent 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 carboxyl group, and carbon numbers 1 to 20 that can be replaced by Z ²⁰¹ alkyl, alkenyl with 2 to 20 carbons or alkynyl with 2 to 20 carbons, aryl with 6 to 20 carbons or heteroaryl with 2 to 20 carbons which may be substituted by Z ²⁰² , or -NHY ²⁰² , -NY ²⁰³ Y ²⁰⁴ , -C(O)Y ²⁰⁵ , -OY ²⁰⁶ , -SY ²⁰⁷ , -SO ₃ Y ²⁰⁸ , -C(O)OY ²⁰⁹ , -OC(O)Y ²¹⁰ , -C(O ) NHY ²¹¹ or -C(O)NY ²¹² Y ²¹³ group (Y ²⁰² ~ Y ²¹³ represent the same meaning as above). Examples of these halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups and heteroaryl groups include the same ones as described above.

Especially for formula (1), as R ²⁰¹ ~ R ²⁰⁴ , a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons that can be replaced by Z ²⁰¹ , or an aryl group with 6 to 14 carbons that can be replaced by Z ²⁰² Preferably, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbons which may be substituted by a fluorine atom is more preferred, and the most preferred are all hydrogen atoms.

Also, as R ²⁰⁵ and R ²⁰⁶ , a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons that may be substituted by Z ²⁰¹ , an aryl group with 6 to 14 carbons that may be substituted by Z ²⁰² or an aryl group that may be substituted by Z ²⁰² Substituted diphenylamine groups (Y ²⁰³ and Y ²⁰⁴ are -NY ²⁰³ Y ²⁰⁴ groups of phenyl groups that can be substituted by Z ²⁰² ) are preferably hydrogen atoms, fluorine atoms or diphenylamines that can be substituted by fluorine atoms It is preferable to be a hydrogen atom or a diphenylamine group at the same time, which is more preferable.

Among them, R ²⁰¹ ~ R ²⁰⁴ are also hydrogen atoms, fluorine atoms, and alkyl groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, and R ²⁰⁵ and R ²⁰⁶ are hydrogen atoms, fluorine atoms, or alkyl groups that can be replaced by fluorine atoms. Substituted diphenylamino group, X ²⁰¹ is -NY ²⁰¹ - or a single bond, and Y ²⁰¹ is a combination of hydrogen atom or methyl group, R ²⁰¹ ~ R ²⁰⁴ are hydrogen atoms, R ²⁰⁵ and R ²⁰⁶ are at the same time is a hydrogen atom or a diphenylamine group, X ²⁰¹ is a combination of -NH- or a single bond is preferred.

Regarding formula (1), m ¹ and m ² are integers independently representing 0 or more, and satisfying 1≦m ¹ +m ² ≦20, if considering the charge transport property of the obtained film and the dissolution of the arylamine derivative Sexual balance, it is better to satisfy 2≦m ¹ +m ² ≦8, better to satisfy 2≦m ¹ +m ² ≦6, and better to satisfy 2≦m ¹ +m ² ≦4 .

For Y ²⁰¹ ~Y ²¹³ and R ²⁰¹ ~R ²⁰⁸ , Z ²⁰¹ is preferably an aryl group with 6-20 carbons that can be substituted by a halogen atom or Z ²⁰³ , and a phenyl group that can be substituted by a halogen atom or Z ²⁰³ is more preferred. Good, the one that does not exist (that is, the one that is not a substitute) is the best.

^Z202 is preferably an alkyl group with 1 to 20 carbons that can be substituted by a halogen atom or ^Z203 , preferably an alkyl group with 1 to 4 carbons that can be substituted by a halogen atom or ^Z203 . non-replacement) is the best.

Z ²⁰³ is preferably a halogen atom, more preferably fluorine, and most preferably present (ie non-substituted).

Among Y ²⁰¹ to Y ²¹³ and R ²⁰¹ to R ²⁰⁸ , the number of carbons in the alkyl group, alkenyl group and alkynyl group is preferably 10 or less, preferably 6 or less, further preferably 4 or less. Also, the number of carbon atoms in the aryl and heteroaryl groups is preferably 14 or less, preferably 10 or less, further preferably 6 or less.

The molecular weight of the arylamine derivative represented by the formula (1) is preferably 9,500 or less, more preferably 8,000 or less, further preferably 7,000 or less, and more preferably 7,000 or less from the viewpoint of ensuring solubility in organic solvents. 6,000 or less, more preferably 5,000 or less. Also, from the viewpoint of improving charge transportability, the molecular weight is preferably 300 or more, more preferably 400 or more. And, from the viewpoint of preventing separation of the charge-transporting substance when the film is thinned, it is preferable that the arylamine derivative represented by the formula (1) has no molecular weight distribution (the degree of dispersion is 1) (that is, a single Molecular weight is preferred).

Moreover, although it does not specifically limit as a synthesis method of an arylamine derivative, Bulletin of Chemical Society of Japan, 67, pp.1749-1752 (1994), Synthetic Metals, 84, pp.119-120 ( 1997), Thin Solid Films, 520(24), pp.7157-7163, (2012), International Publication No. 2008/032617, International Publication No. 2008/032616, International Publication No. 2008/129947, International Publication No. 2013 /084664 and other methods described.

Specific examples of the arylamine derivative represented by formula (1) include those represented by the following formula, but are not limited thereto.

(wherein, DPA represents diphenylamino group)

(In the formula, Ph represents phenyl, TPA represents p-(diphenylamino) phenyl)

Other specific examples of arylamine derivatives include those represented by formula (2) or (3).

In formula (3), R ¹ and R ² independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group with 1 to 20 carbons or an alkenyl group with 2 to 20 carbons that may be substituted by a halogen atom , an alkynyl group with 2 to 20 carbons, an aryl group with 6 to 20 carbons or a heteroaryl group with 2 to 20 carbons.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, among which a fluorine atom is preferred.

Examples of the alkyl group having 1 to 20 carbons, the alkenyl group having 2 to 20 carbons, the alkynyl group having 2 to 20 carbons, and the aryl group having 6 to 20 carbons include the same ones as above.

Specific examples of heteroaryl groups having 2 to 20 carbon atoms include 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, and 3-isoxazole 2-thienyl, 3-thienyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-iso Thiazolyl, 4-isothiazolyl, 5-isothiazolyl and other sulfur-containing heteroaryl groups; 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazine Base, 3-pyrazinyl, 5-pyrazinyl, 6-pyrazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl, 3-pyridazinyl, 4-pyridazine Base, 5-pyridazinyl, 6-pyridazinyl, 1,2,3-triazin-4-yl, 1,2,3-triazin-5-yl, 1,2,4-triazin-3 -yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl, 1,3,5-triazin-2-yl, 1,2,4,5- Tetrazin-3-yl, 1,2,3,4-tetrazin-5-yl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl Base, 7-quinolinyl, 8-quinolinyl, 1-isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7 -isoquinolinyl, 8-isoquinolinyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 5- Quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl and other nitrogen-containing heteroaryl groups, etc.

Among them, as R ¹ and R ² , a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom Or a heteroaryl group with 2 to 20 carbons that can be substituted by a halogen atom is preferred, a hydrogen atom, a fluorine atom, a cyano group, an alkyl group with 1 to 10 carbons that can be substituted by a halogen atom, or a heteroaryl group that can be substituted by a halogen atom A phenyl group is preferred, a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group is further preferred, and a hydrogen atom is most preferred.

In formulas (2) and (3), Ph ¹ represents a group represented by formula (P1).

In the formula, R ³ ~ R ⁶ independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons, or a carbon number that can be substituted by a halogen atom. Alkynyl with 2-20 carbons, aryl with 6-20 carbons or heteroaryl with 2-20 carbons. As these specific examples, the same ones as described above for R ¹ and R ² can be mentioned.

Especially as R ³ ~ R ⁶ , a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, or an aryl group which may be substituted by a halogen atom Heteroaryl groups with 2 to 20 carbon atoms substituted by atoms are preferred, such as hydrogen atoms, fluorine atoms, cyano groups, alkyl groups with 1 to 10 carbon atoms that may be substituted by halogen atoms, or phenyl groups that may be substituted by halogen atoms. Preferably, a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group is further preferred, and a hydrogen atom is most preferred.

Preferred specific examples of Ph ¹ are given below, but are not limited thereto.

In formula (2), Ar ¹ independently represents any of the groups shown in formulas (B1)~(B11), but any group shown in formulas (B1')~(B11') is particularly preferred.

In the formula, R ⁷ ~ R ²⁷ , R ³⁰ ~ R ⁵¹ and R ⁵³ ~ R ¹⁵⁴ independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group that may be substituted by a halogen atom, and the carbon number Alkyl with 1-20 carbons, alkenyl with 2-20 carbons, alkynyl with 2-20 carbons, aryl with 6-20 carbons or heteroaryl with 2-20 carbons. R ²⁸ and R ²⁹ independently represent an aryl group with 6 to 20 carbons or a heteroaryl group with 2 to 20 carbons which may be substituted by Z ¹ . R ⁵² represents a hydrogen atom, an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons or an alkynyl group with 2 to 20 carbons which may be substituted by Z ⁴ or a carbon number 6 to 20 which may be substituted by Z ¹ aryl or heteroaryl with 2 to 20 carbons.

Z ¹ represents an alkyl group having 1 to 20 carbons, an alkenyl group having 2 to 20 carbons, or an alkynyl group having 2 to 20 carbons which may be substituted by a halogen atom, a nitro group, a cyano group or Z ² . Z ² represents an aryl group with 6 to 20 carbons or a heteroaryl group with 2 to 20 carbons which may be substituted by a halogen atom, a nitro group, a cyano group, or a Z ³ . Z ³ represents a halogen atom, a nitro group or a cyano group.

Z ⁴ represents an aryl group with 6 to 20 carbons or a heteroaryl group with 2 to 20 carbons which may be substituted by a halogen atom, a nitro group, a cyano group or Z ⁵ . Z ⁵ represents an alkyl group having 1 to 20 carbons, an alkenyl group having 2 to 20 carbons, or an alkynyl group having 2 to 20 carbons which may be substituted by a halogen atom, a nitro group, a cyano group or Z ³ .

As these halogen atoms, alkyl groups having 1 to 20 carbons, alkenyl groups having 2 to 20 carbons, alkynyl groups having 2 to 20 carbons, aryl groups having 6 to 20 carbons and heteroaryl groups having 2 to 20 carbons Specific examples include the same ones as described above for R ¹ and R ² .

Especially as R ⁷ ~ R ²⁷ , R ³⁰ ~ R ⁵¹ and R ⁵³ ~ R ¹⁵⁴ , hydrogen atom, fluorine atom, cyano group, diphenylamino group which may be substituted by halogen atom, carbon number which may be substituted by halogen atom An alkyl group of 1 to 20, an aryl group with 6 to 20 carbons which may be substituted by a halogen atom, or a heteroaryl group with 2 to 20 carbons which may be substituted by a halogen atom is preferred, such as a hydrogen atom, a fluorine atom, a cyano group, An alkyl group with 1 to 10 carbon atoms which may be substituted by a halogen atom or a phenyl group which may be substituted by a halogen atom is preferred, a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group is further preferred, and a hydrogen atom is preferred optimal.

R ²⁸ and R ²⁹ are preferably an aryl group with 6 to 14 carbons that may be substituted by Z ¹ or a heteroaryl group with 2 to 14 carbons that may be substituted by Z ¹ , and the number of carbons that may be substituted by Z ¹ Aryl groups of 6 to 14 are preferred, and phenyl which may be substituted by Z ¹ , 1-naphthyl which may be substituted by Z ¹ or 2-naphthyl which may be substituted by Z ¹ are more preferred.

As R ⁵² , a hydrogen atom, an aryl group with 6 to 20 carbons which may be substituted by Z ¹ , a heteroaryl group with 2 to 20 carbons which may be substituted by Z ¹ , or a carbon number 1 to 20 which may be substituted by Z ⁴ The alkyl group is preferably a hydrogen atom, an aryl group with 6 to 14 carbons that can be substituted by Z ¹ , a heteroaryl group with 2 to 14 carbons that can be substituted by Z ¹ , or a carbon number 1 that can be substituted by Z ⁴ An alkyl group of ~10 is preferred, and a hydrogen atom, an aryl group with 6 to 14 carbons that can be substituted by Z ¹ , a nitrogen-containing heteroaryl group with 2 to 14 carbons that can be substituted by Z ¹ , or a nitrogen-containing heteroaryl group that can be substituted by Z ⁴ The substituted alkyl group with 1 to 10 carbon atoms is more preferably a hydrogen atom, a phenyl group which may be substituted by Z ¹ , a 1-naphthyl group which may be substituted by Z ¹ , a 2-naphthyl group which may be substituted by Z ¹ , 2-pyridyl which may be substituted by Z ¹ , 3-pyridyl which may be substituted by Z ¹ , 4-pyridyl which may be substituted by Z ¹ or methyl which may be substituted by Z ⁴ are more preferred.

Ar ⁴ is an aryl group with 6 to 20 carbons independently representing that each aryl group can be substituted by a diarylamine group with an aryl group with 6 to 20 carbons. Specific examples of the aryl group having 6 to 20 carbon atoms include the same ones described above for R ^{and R.} Specific examples of the aforementioned diarylamine group include diphenylamino, 1-naphthylphenylamino group, bis(1-naphthyl)amino group, 1-naphthalene-2-naphthylamino group, bis(2-naphthyl)amino group and the like.

As Ar ⁴ , phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4- Phenanthryl, 9-phenanthrenyl, p-(diphenylamino)phenyl, p-(1-naphthylphenylamino)phenyl, p-(two(1-naphthalene)amino)phenyl, p -(1-naphthalene-2-naphthylamino)phenyl, p-(di(2-naphthalene)amino)phenyl, etc. are preferred, and p-(diphenylamino)phenyl is more preferred.

Specific examples of preferred groups for Ar ¹ are given below, but are not limited thereto. In addition, in the following formulae, DPA and R ⁵² represent the same meanings as described above.

In the formula (2), Ar ² independently represents any one of the groups shown in the formulas (A1) to (A18), especially any one of the groups shown in the formulas (A1'-1) to (A18'-2) is good.

In the formula, R ¹⁵⁵ represents a hydrogen atom, an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons or an alkynyl group with 2 to 20 carbons that may be substituted by Z ⁴ , or a carbon that may be substituted by Z ¹ An aryl group with 6-20 carbon atoms or a heteroaryl group with 2-20 carbon atoms. R ¹⁵⁶ and R ¹⁵⁷ independently represent an aryl group with 6 to 20 carbons or a heteroaryl group with 2 to 20 carbons substituted by Z ¹ . DPA, Ar ⁴ , Z ¹ and Z ⁴ represent the same meanings as above. As these halogen atoms, alkyl groups having 1 to 20 carbons, alkenyl groups having 2 to 20 carbons, alkynyl groups having 2 to 20 carbons, aryl groups having 6 to 20 carbons and heteroaryl groups having 2 to 20 carbons Specific examples include the same ones described above for R ¹ and R ² .

Especially as R ¹⁵⁵ with a hydrogen atom, an aryl group with 6 to 20 carbons that can be substituted by Z ¹ , a heteroaryl group with 2 to 20 carbons that can be substituted by Z ¹ , or a carbon number 1 to 20 that can be substituted by Z ⁴ The alkyl group of 20 is preferably a hydrogen atom, an aryl group with 6 to 14 carbons that can be substituted by Z ¹ , a heteroaryl group with 2 to 14 carbons that can be substituted by Z ¹ , or a carbon that can be substituted by Z ⁴ An alkyl group with a number of 1 to 10 is preferred, a hydrogen atom, an aryl group with a carbon number of 6 to 14 that can be replaced by ^Z1 , a nitrogen-containing heteroaryl group with a carbon number of 2 to 14 that can be replaced by ^Z1 , or a nitrogen-containing heteroaryl group that can be replaced by Z1 An alkyl group with 1 to 10 carbon atoms substituted by Z ⁴ is further preferred, and it is further preferably a hydrogen atom, a phenyl group that may be substituted by Z ¹ , a 1-naphthyl group that may be substituted by Z ¹ , or a 2-naphthyl group that may be substituted by Z ¹ . Naphthyl, 2-pyridyl which may be substituted by Z ¹ , 3-pyridyl which may be substituted by Z ¹ , 4-pyridyl which may be substituted by Z ¹ , or methyl which may be substituted by Z ⁴ are more preferred.

R ¹⁵⁶ and R ¹⁵⁷ are preferably an aryl group with 6 to 14 carbons that may be substituted by Z ¹ , or a heteroaryl group with 2 to 14 carbons that may be substituted by Z ¹ , and the number of carbons that may be substituted by Z ¹ Aryl groups of 6-14 are preferred, phenyl substituted by Z ¹ , 1-naphthyl which may be substituted by Z ¹ , or 2-naphthyl which may be substituted by Z ¹ are further preferred.

Specific examples of preferred groups for Ar ² are listed below, but are not limited thereto. In addition, in the following formulae, R ¹⁵⁵ and DPA represent the same meanings as above.

For formula (2), if considering the ease of synthesis of the obtained arylamine derivatives, it is better to use all Ar ¹ as the same group, preferably all Ar ² as the same group, and take all Ar ¹ and Ar ² as the same group whichever is better. That is, the arylamine derivative represented by formula (2) is preferably represented by formula (2-1).

In formula (2-1), Ph ¹ represents the same meaning as above. x is described later. Although Ar ⁵ simultaneously represents any group shown in formulas (D1)~(D13), it is particularly preferred to be any group shown in formulas (D1')~(D13'). In addition, in the following formulae, R ²⁸ , R ²⁹ , R ⁵² , Ar ⁴ , and DPA represent the same meanings as above. Specific examples of Ar ⁵ include the same ones mentioned above as specific examples of preferred groups of Ar ¹ .

In addition, as the raw material compound described later, it can be synthesized relatively easily by using relatively cheap bis(4-aminophenyl)amine, and at the same time, it has excellent solubility in organic solvents for the obtained arylamine derivative, so the formula ( 2) The arylamine derivative shown in formula (2-2) is preferred.

In the formula, Ar ⁶ simultaneously represents any one of the groups shown in formulas (E1) to (E14). In addition, in the following formulae, R ⁵² represents the same meaning as above.

In formula (3), Ar ³ represents any one of formulas (C1)~(C8), especially any one of (C1')~(C8'). In addition, DPA in the following formula represents the same meaning as above.

In formula (2) and (2-1), x represents the integer of 1～10, but from the point of view of improving the dissolubility of compound to organic solvent, 1～5 is good, 1～3 is better, 1 or 2 is more preferable, and 1 is the best. In formula (3), y represents 1 or 2.

For R ²⁸ , R ²⁹ , R ⁵² and R ¹⁵⁵ ~R ¹⁵⁷ , Z ¹ is a halogen atom, a nitro group, a cyano group, an alkyl group with 1 to 10 carbons that can be substituted by Z ² , or a carbon that can be substituted by Z ² Alkenyl with 2-10 carbons, or alkynyl with 2-10 carbons which can be substituted by ^Z2 is preferred, halogen atom, nitro, cyano, alkyl with 1-3 carbons which can be substituted with ^Z2 , an alkenyl group with 2 to 3 carbons that can be substituted by Z ² , or an alkynyl group with 2 to 3 carbons that can be substituted by Z ² is preferred, with a fluorine atom, and a carbon number 1 to 3 that can be substituted by Z ² An alkyl group, an alkenyl group with 2 to 3 carbons which may be substituted by Z ² , or an alkynyl group with 2 to 3 carbons which may be substituted by Z ² are further preferred.

For R ²⁸ , R ²⁹ , R ⁵² and R ¹⁵⁵ ~R ¹⁵⁷ , Z ⁴ is preferably a halogen atom, nitro, cyano, or an aryl group with 6 to 14 carbons that can be substituted by Z ⁵ , and a halogen atom, A nitro group, a cyano group, or an aryl group with 6 to 10 carbons that can be substituted by ^Z5 is preferred, a fluorine atom, or an aryl group with 6 to 10 carbons that can be substituted by ^Z5 is more preferred, and A fluorine atom, or a phenyl group which may be substituted by Z ⁵ is more preferred.

For R ²⁸ , R ²⁹ , R ⁵² and R ¹⁵⁵ ~R ¹⁵⁷ , Z ² is preferably a halogen atom, nitro, cyano, or an aryl group with 6 to 14 carbons that can be substituted by Z ³ , and a halogen atom, A nitro group, a cyano group, or an aryl group with 6 to 10 carbons that can be substituted by ^Z3 is preferred, a fluorine atom, or an aryl group with 6 to 10 carbons that can be substituted by ^Z3 is more preferred, and A fluorine atom, or a phenyl group that may be substituted by Z ³ is more preferred

For R ²⁸ , R ²⁹ , R ⁵² and R ¹⁵⁵ ~R ¹⁵⁷ , Z ⁵ is a halogen atom, a nitro group, a cyano group, an alkyl group with 1 to 10 carbons that can be substituted by Z ³ , or a carbon that can be substituted by Z ³ Alkenyl with 2-10 carbons, or alkynyl with 2-10 carbons which can be substituted by Z ³ is preferred, halogen atom, nitro, cyano, alkyl with 1-3 carbons which can be substituted with Z ³ , an alkenyl group with 2 to 3 carbons that can be substituted by Z ³ , or an alkynyl group with 2 to 3 carbons that can be substituted by Z ³ is preferred, and a fluorine atom, a carbon number 1 to ³ that can be substituted by Z 3 An alkyl group, an alkenyl group with 2 to 3 carbons which may be substituted by Z ³ , or an alkynyl group with 2 to 3 carbons which may be substituted by Z ³ is more preferred.

For R ²⁸ , R ²⁹ , R ⁵² and R ¹⁵⁵ ~R ¹⁵⁷ , Z ³ is preferably a halogen atom, more preferably a fluorine atom.

For R ⁷ ~R ²⁷ , R ³⁰ ~R ⁵¹ and R ⁵³ ~R ¹⁵⁴ , Z ¹ is a halogen atom, nitro, cyano, an alkyl group with 1 to 3 carbons that can be replaced by Z ² , and can be replaced by Z ² A substituted alkenyl group with 2 to 3 carbons, or an alkynyl group with 2 to 3 carbons that can be substituted by Z ² is preferred, and a halogen atom, or an alkyl group with 1 to 3 carbons that can be substituted by Z ² is preferred Preferably, a fluorine atom, or a methyl group that may be substituted by Z ² is more preferred.

For R ⁷ ~ R ²⁷ , R ³⁰ ~ R ⁵¹ and R ⁵³ ~ R ¹⁵⁴ , Z ⁴ is preferably a halogen atom, nitro, cyano, or an aryl group with 6 to 10 carbons that can be substituted by Z ⁵ , with A halogen atom, or an aryl group having 6 to 10 carbon atoms that may be substituted by Z ⁵ is preferred, and a fluorine atom, or a phenyl group that may be substituted by Z ⁵ is further preferred.

For R ⁷ ~ R ²⁷ , R ³⁰ ~ R ⁵¹ and R ⁵³ ~ R ¹⁵⁴ , Z ² is preferably a halogen atom, nitro, cyano, or an aryl group with 6 to 10 carbons that can be substituted by Z ³ . A halogen atom, or an aryl group having 6 to 10 carbon atoms that may be substituted by Z ³ is preferred, and a fluorine atom, or a phenyl group that may be substituted by Z ³ is further preferred.

For R ⁷ ~R ²⁷ , R ³⁰ ~R ⁵¹ and R ⁵³ ~R ¹⁵⁴ , Z ⁵ is a halogen atom, nitro, cyano, an alkyl group with 1 to 3 carbons that can be replaced by Z ³ , and can be replaced by Z ³ A substituted alkenyl group with 2 to 3 carbons, or an alkynyl group with 2 to 3 carbons that can be substituted by Z ³ is preferred, and a halogen atom, or an alkyl group with 1 to 3 carbons that can be substituted by Z ³ is preferred Preferably, a fluorine atom, or a methyl group that may be substituted by Z ³ is more preferred.

For R ⁷ ~R ²⁷ , R ³⁰ ~R ⁵¹ and R ⁵³ ~R ¹⁵⁴ , Z ³ is preferably a halogen atom, more preferably a fluorine atom.

In the present invention, specific examples of preferred groups for R ⁵² and R ¹⁵⁵ include those shown below, but are not limited thereto.

In the present invention, the carbon number of the aforementioned alkyl, alkenyl and alkynyl groups is preferably 10 or less, more preferably 6 or less, further preferably 4 or less. Also, the number of carbon atoms in the aryl and heteroaryl groups is preferably 14 or less, preferably 10 or less, further preferably 6 or less.

The molecular weight of the arylamine derivative represented by the formula (2) and the arylamine derivative represented by the formula (3) is usually about 200 to 9,500 from the viewpoint of preparing a uniform varnish that imparts a high flatness film. However, from the viewpoint of preparing a uniform varnish with a high flatness film that provides better reproducibility, it is preferably 8,000 or less, more preferably 7,000 or less, still more preferably 6,000 or less, and more preferably 5,000 or less , is preferably 300 or more, and more preferably 400 or more, from the viewpoint of obtaining a thin film having more excellent charge transport properties. Furthermore, when thinning the compound, it is preferable that the charge-transporting compound has no molecular weight distribution (dispersion degree of 1) (that is, a single molecular weight is preferable) from the viewpoint of preventing separation of the charge-transporting substance.

The arylamine derivative represented by formula (2) and the arylamine derivative represented by formula (3) can be produced according to the method described in International Publication No. 2015/050253.

Specific examples of the arylamine derivative represented by the formula (2) or (3) are given below, but are not limited thereto. And, in the formula, "Me" represents a methyl group, "Et" represents an ethyl group, " ^Prn " represents an n-propyl group, "Pr ⁱ " represents an i-propyl group, "Bu ⁿ " represents an n-butyl group, " Bu ⁱ "means i-butyl, "Bu ^s " means s-butyl, "But ^t " means t-butyl, "DPA" means diphenylamine, "SBF" means 9,9'-spirodi [9H-fluorene]-2-yl.

The content of the charge-transporting substance in the varnish of the present invention can be appropriately set according to the viscosity and surface tension of the varnish, etc. or the thickness of the film to be produced, and is usually about 0.1 to 10.0% by mass in the varnish. The coatability is preferably about 0.5 to 5.0% by mass, more preferably about 1.0 to 3.0% by mass.

The varnish for forming a charge-transporting thin film of the present invention may contain a blend from the viewpoint of further improving the charge-transporting property of the obtained thin film. As a blend, although not particularly limited, arylsulfonic acid is preferred. One example thereof is arylsulfonic acid represented by formula (4) or (5).

In formula (4), A ¹ represents -O- or -S-, preferably -O-. Although A ² represents a naphthalene ring or an anthracene ring, a naphthalene ring is preferred. A ³ represents a 2-4 valent perfluorobiphenyl group, and j ¹ represents the number of bonds between A ¹ and A ³ , satisfying an integer of 2≦j ¹ ≦4, but when A ³ is a divalent perfluorobiphenyl group, And j ¹ is preferably 2. j ² represents the number of sulfonic acid groups bonded to A ² , and is an integer satisfying 1≦j ² ≦4, but preferably 2.

In formula (5), A ⁴ to A ⁸ independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group with 1 to 20 carbons, a halogenated alkyl group with 1 to 20 carbons, or an alkyl group with 2 to 20 carbons Halogenated alkenyl, but at least 3 of A ⁴ to A ⁸ are halogen atoms. k represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1≦k≦4, preferably 2~4, more preferably 2.

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

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

Among them, A ⁴ to A ⁸ are also hydrogen atoms, halogen atoms, cyano groups, alkyl groups with 1 to 10 carbons, halogenated alkyl groups with 1 to 10 carbons, or halogenated alkenes with 2 to 10 carbons group, and at least 3 of A ⁴ to A ⁸ are preferably fluorine atoms, hydrogen atoms, fluorine atoms, cyano groups, alkyl groups with 1 to 5 carbons, fluorinated alkyl groups with 1 to 5 carbons or carbon A fluorinated alkenyl group with a number of 2 to 5, and at least 3 of A ⁴ to A ⁸ are fluorine atoms, preferably a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group with a carbon number of 1 to 5, or a carbon number 1 to 5 perfluoroalkenyl groups, and A ⁴ , A ⁵ and A ⁸ are fluorine atoms are more preferable.

In addition, the term "perfluoroalkyl" means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms, and the term "perfluoroalkenyl" means a group in which all hydrogen atoms of an alkenyl group are substituted with fluorine atoms.

Although specific examples of the aforementioned arylsulfonic acid were given, it is not limited thereto.

The content of the blend in the varnish of the present invention can be appropriately set depending on the type or amount of the charge-transporting substance, and is usually about 0.5 to 10 in mass ratio to the charge-transporting substance.

In the varnish for forming a charge-transporting thin film of the present invention, for the purpose of adjusting the physical properties of the resulting charge-transporting thin film, etc., an organic silane compound such as trimethoxysilane or triethoxysilane or the hole injection of the film is improved. Other components such as oligoaniline derivatives containing fluorine atoms may be contained for the purpose of input and the like. The content of other components in the varnish for forming a charge-transporting thin film of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is determined based on the properties, functions, etc. of other components. The atomic oligoaniline derivative is usually about 5 to 50% by mass, preferably about 10 to 30% by mass for the charge transporting substance.

Preferable examples of the aforementioned fluorine atom-containing oligoaniline derivatives include those represented by formula (6).

In the formula, R ³⁰¹ represents a hydrogen atom, or an alkyl group with 1 to 20 carbons that may be substituted by Z. Z represents a halogen atom, a nitro group, a cyano group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxyl group, an aryl group with 6 to 20 carbons that can be replaced by Z', or a carbon number 2~ that can be replaced by Z' The heteroaryl group of 20, Z' 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 carboxyl group.

R ³⁰² ~ R ³¹⁰ independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons, an alkenyl group with 2 to 20 carbons substituted by a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a halogen atom Alkynyl, aryl with 6-20 carbons or heteroaryl with 2-20 carbons.

As a halogen atom, an alkyl group with 1 to 20 carbons, an alkenyl group with 2 to 20 carbons, an alkynyl group with 2 to 20 carbons, an aryl group with 6 to 20 carbons and a heteroaryl group with 2 to 20 carbons, The same thing as above can be mentioned.

Among them, as R ³⁰¹ , when considering the solubility of oligoaniline derivatives containing fluorine atoms in organic solvents, a hydrogen atom or an alkyl group with 1 to 10 carbons that may be substituted by Z is preferred, and hydrogen is preferred. Atoms, or alkyl groups with 1 to 4 carbons which may be substituted by Z are preferred, and hydrogen atoms are most preferred. Also, the plurality of R ³⁰¹ may be the same or different.

In addition, among them, as R ³⁰² ~ R ³¹⁰ , if considering the solubility of oligoaniline derivatives containing fluorine atoms in organic solvents, they are replaced by hydrogen atoms, halogen atoms, nitro groups, cyano groups, or halogen atoms An alkyl group with 1 to 10 carbons is preferred, a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons substituted by a halogen atom is preferred, and a hydrogen atom is most preferred. And, each of the plurality of R ³⁰² to R ³⁰⁵ may be the same or different.

In formula (6), A represents a fluoroalkyl group with 1 to 20 carbons, a carbon number 3 Fluorocycloalkyl with ~20 carbons, fluorobicycloalkyl with 4 to 20 carbons, fluoroalkenyl with 2 to 20 carbons or fluoroalkynyl with 2 to 20 carbons; can be composed of cyano group, chlorine atom, bromine atom, Iodine atom, nitro, alkyl with 1 to 20 carbons, fluoroalkyl with 1 to 20 carbons or fluoroaryl with 6 to 20 carbons substituted by fluoroalkoxy with 1 to 20 carbons; Fluoroalkyl with 1-20 carbons, fluorocycloalkyl with 3-20 carbons, fluorobicycloalkyl with 4-20 carbons, fluoroalkenyl with 2-20 carbons or fluoroalkyne with 2-20 carbons At the same time as substituted by a cyano group, a halogen atom or a fluoroalkoxy group with 1 to 20 carbons, an aryl group with 6 to 20 carbons can be substituted; a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro , fluoroalkoxy with 1 to 20 carbons, fluoroalkyl with 1 to 20 carbons, fluorocycloalkyl with 3 to 20 carbons, fluorobicycloalkyl with 4 to 20 carbons, 2 to 20 carbons A fluoroalkenyl group with 7 to 20 carbons substituted by a fluoroalkenyl group or a fluoroalkynyl group with 2 to 20 carbons; or a fluoroalkyl group with 1 to 20 carbons or a fluorocycloalkyl group with 3 to 20 carbons , a fluorobicycloalkyl group with 4 to 20 carbons, a fluoroalkenyl group with 2 to 20 carbons or a fluoroalkynyl group with 2 to 20 carbons may be replaced by a cyano group, a halogen atom or a cyano group with 1 to 20 carbons Aralkyl group with 7 to 20 carbon atoms substituted by fluoroalkoxy group.

The above-mentioned fluoroalkyl group is not particularly limited as long as at least one hydrogen atom on the carbon atom is replaced by a fluorine atom, and it is not particularly limited. Examples include fluoromethyl, difluoro Methyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,2-difluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 1,1 ,2-trifluoroethyl, 1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,2,2,2 -tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 1, 2-difluoropropyl, 1,3-difluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 3,3-difluoropropyl, 1,1,2-trifluoropropyl Fluoropropyl, 1,1,3-trifluoropropyl, 1,2,3-trifluoropropyl, 1,3,3-trifluoropropyl, 2,2,3-trifluoropropyl, 2, 3,3-trifluoropropyl, 3,3,3-trifluoropropyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,3-tetrafluoropropyl, 1,2, 2,3-tetrafluoropropyl, 1,3,3,3-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,3,3,3-tetrafluoropropyl, 1, 1,2,2,3-pentafluoropropyl, 1,2,2,3,3-pentafluoropropyl, 1,1,3,3,3-pentafluoropropyl, 1,2,3,3 , 3-pentafluoropropyl, 2,2,3,3,3-pentafluoropropyl, pentafluoropropyl, etc.

The aforementioned fluorocycloalkyl group is not particularly limited as long as at least one hydrogen atom on the carbon atom is replaced by a fluorine atom, and is not particularly limited, for example, 1-fluorocyclopropyl, 2-fluorocyclopropyl base, 2,2-difluorocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, pentafluorocyclopropyl, 2,2-difluorocyclobutyl, 2,2,3,3- Tetrafluorocyclobutyl, 2,2,3,3,4,4-hexafluorocyclobutyl, pentafluorocyclobutyl, 1-fluorocyclopentyl, 3-fluorocyclopentyl, 3,3-difluoro Cyclopentyl, 3,3,4,4-tetrafluorocyclopentyl, nonafluorocyclopentyl, 1-fluorocyclohexyl, 2-fluorocyclohexyl, 4-fluorocyclohexyl, 4,4-difluorocyclohexyl , 2,2,3,3-tetrafluorocyclohexyl, 2,3,4,5,6-pentafluorocyclohexyl, undecafluorocyclohexyl, etc.

The above-mentioned fluorobicycloalkyl group is not particularly limited as long as at least one hydrogen atom on the carbon atom is replaced by a fluorine atom, and is not particularly limited, for example, 3-fluorobicyclo[1.1.0] Butane-1-yl, 2,2,4,4-tetrafluorobicyclo[1.1.0]butane-1-yl, pentafluorobicyclo[1.1.0]butane-1-yl, 3-fluoro Bicyclo[1.1.1]pentan-1-yl, 2,2,4,4,5-pentafluorobicyclo[1.1.1]pentan-1-yl, 2,2,4,4,5, 5-Hexafluorobicyclo[1.1.1]pentane-1-yl, 5-fluorobicyclo[3.1.0]hexane-6-yl, 6-fluorobicyclo[3.1.0]hexane-6- Base, 6,6-difluorobicyclo[3.1.0]hexane-2-yl, 2,2,3,3,5,5,6,6-octafluorobicyclo[2.2.0]hexane- 1-yl, 1-fluorobicyclo[2.2.1]heptane-2-yl, 3-fluorobicyclo[2.2.1]heptane-2-yl, 4-fluorobicyclo[2.2.1]heptane -1-yl, 5-fluorobicyclo[3.1.1]heptane-1-yl, 1,3,3,4,5,5,6,6,7,7-decafluorobicyclo[2.2.1 ]Heptane-2-yl, undecafluorobicyclo[2.2.1]heptane-2-yl, 3-fluorobicyclo[2.2.2]octane-1-yl, 4-fluorobicyclo[2.2. 2) Octane-1-yl, etc.

The aforementioned fluoroalkenyl group is not particularly limited as long as at least one hydrogen atom on the carbon atom is substituted by a fluorine atom, and is not particularly limited, for example, 1-fluorovinyl, 2-fluorovinyl, 1, 2-difluorovinyl, 1,2,2-trifluorovinyl, 2,3,3-trifluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 2,3, 3,3-tetrafluoro-1-propenyl, pentafluoro-1-propenyl, 1-fluoro-2-propenyl, 1,1-difluoro-2-propenyl, 2,3-difluoro-2- propenyl, 3,3-difluoro-2-propenyl, 2,3,3-trifluoro-2-propenyl, 1,2,3,3-tetrafluoro-2-propenyl, pentafluoro-2- Acrylic etc.

The aforementioned fluoroalkynyl group is not particularly limited as long as it is an alkynyl group in which at least one hydrogen atom on a carbon atom is replaced by a fluorine atom, and examples thereof include fluoroethynyl, 3-fluoro-1-propynyl, 3,3-difluoro-1-propynyl, 3,3,3-trifluoro-1-propynyl, 1-fluoro-2-propynyl, 1,1-difluoro-2-propynyl wait.

The aforementioned fluoroaryl group is not particularly limited as long as it is an aryl group in which at least one hydrogen atom on a carbon atom is replaced by a fluorine atom, and examples thereof include 2-fluorophenyl, 3-fluorophenyl, 4- Fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3 ,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorobenzene base, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl, 4-fluoro-1-naphthyl, 6-fluoro-1 -Naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8- Difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, pentafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, pentafluoro-2-naphthyl and the like.

As the aforementioned fluoroaryl group, if considering the solubility of the oligoaniline derivatives containing fluorine atoms to organic solvents, the ease of obtaining raw materials for the oligoaniline derivatives containing fluorine atoms, etc., it can be a cyano group, a chlorine atom, Bromine atom, iodine atom, nitro group, alkyl group with 1 to 20 carbons, fluoroalkyl group with 1 to 20 carbons or fluoroalkoxy group with 1 to 20 carbons, replaced by 3 or more fluorine atoms Substituted phenyl groups are preferred.

The aforementioned fluoroalkoxy group is not particularly limited as long as it is an alkoxy group in which at least one hydrogen atom on a carbon atom is replaced by a fluorine atom, and examples thereof include fluoromethoxy, difluoromethoxy, and , Trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 1,2-difluoroethoxy, 1,1-difluoroethoxy, 2,2-difluoroethoxy , 1,1,2-trifluoroethoxy, 1,2,2-trifluoroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy , 1,2,2,2-tetrafluoroethoxy, 1,1,2,2,2-pentafluoroethoxy, 1-fluoropropoxy, 2-fluoropropoxy, 3-fluoropropoxy base, 1,1-difluoropropoxy, 1,2-difluoropropoxy, 1,3-difluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy 3,3-difluoropropoxy, 1,1,2-trifluoropropoxy, 1,1,3-trifluoropropoxy, 1,2,3-trifluoropropoxy, 1, 3,3-trifluoropropoxy, 2,2,3-trifluoropropoxy, 2,3,3-trifluoropropoxy, 3,3,3-trifluoropropoxy, 1,1, 2,2-tetrafluoropropoxy, 1,1,2,3-tetrafluoropropoxy, 1,2,2,3-tetrafluoropropoxy, 1,3,3,3-tetrafluoropropoxy 2,2,3,3-tetrafluoropropoxy, 2,3,3,3-tetrafluoropropoxy, 1,1,2,2,3-pentafluoropropoxy, 1,2, 2,3,3-pentafluoropropoxy, 1,1,3,3,3-pentafluoropropoxy, 1,2,3,3,3-pentafluoropropoxy, 2,2,3, 3,3-pentafluoropropoxy, pentafluoropropoxy, etc.

As the above-mentioned fluoroalkyl group with 1~20 carbons, fluorocycloalkyl group with 3~20 carbons, fluorobicycloalkyl group with 4~20 carbons, fluoroalkenyl group with 2~20 carbons or 2~20 carbons 20 fluoroalkynyl groups, and aryl groups with 6 to 20 carbons (hereinafter also referred to as substituted aryl groups) that can be substituted by cyano, halogen atoms or fluoroalkoxy groups with 1 to 20 carbons, if in At least one hydrogen atom on the carbon atom can be fluoroalkyl with 1-20 carbons, fluorocycloalkyl with 3-20 carbons, fluorobicycloalkyl with 4-20 carbons, fluorocycloalkyl with 2-20 carbons Aryl groups substituted with fluoroalkenyl groups or fluoroalkynyl groups having 2 to 20 carbon atoms are sufficient, and are not particularly limited, for example, 2-(trifluoromethyl)phenyl, 3-(trifluoromethyl)benzene Base, 4-(trifluoromethyl)phenyl, 4-ethoxy-3-(trifluoromethyl)phenyl, 3-fluoro-4-trifluoromethylphenyl, 4-fluoro-3-tri Fluoromethylphenyl, 4-fluoro-2-trifluoromethylphenyl, 2-fluoro-5-(trifluoromethyl)phenyl, 3-fluoro-5-(trifluoromethyl)phenyl, 3 ,5-bis(trifluoromethyl)phenyl, 2,4,6-tri(trifluoromethyl)phenyl, 4-(pentafluoroethyl)phenyl, 4-(3,3,3-tri Fluoropropyl)phenyl, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl, 4-(perfluorovinyl)phenyl, 4-(perfluoropropenyl)phenyl, 4 -(perfluorobutenyl)phenyl and the like.

As the aforementioned substituted aryl group, in consideration of the solubility of oligoaniline derivatives containing fluorine atoms in organic solvents and the ease of obtaining raw materials for oligoaniline derivatives containing fluorine atoms, etc., those with 3 to 20 carbon atoms Fluorocycloalkyl, fluorobicycloalkyl with 4-20 carbons, fluoroalkenyl with 2-20 carbons or fluoroalkynyl with 2-20 carbons may be substituted by cyano group, halogen atom or carbon number The phenyl group substituted with 1-20 fluoroalkoxy groups (hereinafter also referred to as substituted phenyl group) is preferred, the phenyl group substituted with 1-3 trifluoromethyl groups is preferred, and p-trifluoromethyl Phenyl is further preferred.

The aforementioned fluoroaralkyl group is not particularly limited as long as it is an aralkyl group in which at least one hydrogen atom on a carbon atom is replaced by a fluorine atom, and examples thereof include 2-fluorobenzyl, 3-fluoro Benzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl , 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6 -Trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4 ,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc.

As the above-mentioned fluoroalkyl group with 1~20 carbons, fluorocycloalkyl group with 3~20 carbons, fluorobicycloalkyl group with 4~20 carbons, fluoroalkenyl group with 2~20 carbons or 2~20 carbons While being substituted by 20 fluoroalkynyl groups, an aralkyl group having 7 to 20 carbons may be substituted by a cyano group, a halogen atom or a fluoroalkoxy group having 1 to 20 carbons, if at least one of the carbon atoms is present The hydrogen atom consists of fluoroalkyl group with 1~20 carbons, fluorocycloalkyl group with 3~20 carbons, fluorobicycloalkyl group with 4~20 carbons, fluoroalkenyl group with 2~20 carbons or 2~20 carbons Aralkyl groups substituted with 20 fluoroalkynyl groups are not particularly limited, and examples include 2-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzene Methyl, 2,4-bis(trifluoromethyl)benzyl, 2,5-bis(trifluoromethyl)benzyl, 2,6-bis(trifluoromethyl)benzyl, 3, 5-bis(trifluoromethyl)benzyl, 2,4,6-tris(trifluoromethyl)benzyl, etc.

Among them, A is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may be substituted by the aforementioned, a fluoroaryl group having 6 to 20 carbon atoms which may be substituted by the aforementioned substituted aryl group, or an aryl group which may be substituted by the aforementioned carbon atoms. The fluoroaryl group or the aforementioned substituted aryl group having a number of 6 to 20 is preferred, the fluorophenyl group or the aforementioned substituted phenyl group that may be substituted by the aforementioned group is further preferred, the trifluorophenyl group that may be substituted by the aforementioned group, the tetrafluorophenyl group that may be substituted by the aforementioned Fluorophenyl, pentafluorophenyl which can be substituted by the above or phenyl which can be substituted by 1~3 trifluoromethyl groups is more preferable

Specific examples of preferred groups of A are given below, but are not limited thereto.

Also, in the formula (6), although n ¹ is an integer of 1-20, preferably 2-10, more preferably 2-8, further preferably 3-5, more preferably 3-4.

The aforementioned oligoaniline derivatives containing fluorine atoms can be synthesized by reacting an amine compound represented by formula (7) with an acid halide compound containing fluorine atoms represented by formula (8) as shown in Scheme A below. In this case, for the purpose of allowing the reaction to proceed more efficiently, it is preferable to perform the reaction in the presence of a base.

(In the formula, R ³⁰¹ ~ R ³¹⁰ , A and n ¹ are the same as above. X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, but preferably a chlorine atom or a bromine atom)

Examples of the amine compound represented by the formula (7) include those represented by the following formula, but are not limited thereto.

As the acid halide containing fluorine atom represented by formula (8), 2-fluorobenzoyl chloride, 3-fluorobenzoyl chloride, 4-fluorobenzoyl chloride, 2-fluoro-4-methyl Benzoyl chloride, 2-fluoro-5-methylbenzoyl chloride, 3-fluoro-4-methylbenzoyl chloride, 3-fluoro-6-methylbenzoyl chloride, 4-fluoro-2- Methylbenzoyl chloride, 4-fluoro-3-methylbenzoyl chloride, 2,3-difluorobenzoyl chloride, 2,4-difluorobenzoyl chloride, 2,5-difluorobenzoyl chloride Acyl chloride, 2,6-difluorobenzoyl chloride, 3,4-difluorobenzoyl chloride, 3,5-difluorobenzoyl chloride, 3-chloro-2-fluorobenzoyl chloride, 4- Chloro-2-fluorobenzoyl chloride, 5-chloro-2-fluorobenzoyl chloride, 2-chloro-6-fluorobenzoyl chloride, 2-chloro-3-fluorobenzoyl chloride, 2-chloro- 4-fluorobenzoyl chloride, 2-chloro-5-fluorobenzoyl chloride, 3-chloro-4-fluorobenzoyl chloride, 3-chloro-5-fluorobenzoyl chloride, 3-bromo-2- Fluorobenzoyl chloride, 4-bromo-2-fluorobenzoyl chloride, 5-bromo-2-fluorobenzoyl chloride, 2-bromo-6-fluorobenzoyl chloride, 2-bromo-3-fluorobenzene Formyl chloride, 2-bromo-4-fluorobenzoyl chloride, 2-bromo-5-fluorobenzoyl chloride, 3-bromo-4-fluorobenzoyl chloride, 3-bromo-5-fluorobenzoyl chloride Chlorine, 2-fluoro-5-iodobenzoyl chloride, 2-fluoro-6-iodobenzoyl chloride, 2-fluoro-3-(trifluoromethyl)benzoyl chloride, 2-fluoro-5-( Trifluoromethyl)benzoyl chloride, 2-fluoro-6-(trifluoromethyl)benzoyl chloride, 3-fluoro-4-(trifluoromethyl)benzoyl chloride, 3-fluoro-5- (Trifluoromethyl)benzoyl chloride, 3-fluoro-6-(trifluoromethyl)benzoyl chloride, 4-fluoro-2-(trifluoromethyl)benzoyl chloride, 4-fluoro-3 -(trifluoromethyl)benzoyl chloride, 2-fluoro-4-nitrobenzoyl chloride, 2-fluoro-5-nitrobenzoyl chloride, 3-fluoro-2-nitrobenzoyl chloride , 3-fluoro-4-nitrobenzoyl chloride, 3-fluoro-6-nitrobenzoyl chloride, 4-fluoro-2-nitrobenzoyl chloride, 4-fluoro-3-nitrobenzoyl chloride Acyl chloride, 4-cyano-2-fluorobenzoyl chloride, 3-cyano-5-fluorobenzoyl chloride, 2,3,4-trifluorobenzoyl chloride, 2,3,5-trifluoro Benzoyl chloride, 2,3,6-trifluorobenzoyl chloride, 2,4,5-trifluorobenzoyl chloride, 2,4,6-trifluorobenzoyl chloride, 3,4,5- Trifluorobenzoyl chloride, 4-chloro-2,4-difluorobenzoyl chloride, 2,4-dichloro-5-fluoro-4-nitrobenzoyl chloride, 2,4,5-trifluoro -3-Methyl-6-nitrobenzoyl chloride, 2,3,4,5-tetrafluorobenzoyl chloride, 2,3,5,6-tetrafluorobenzoyl chloride, 2,3,5 ,6-tetrafluoro-4-methyl-benzoyl chloride, 2,3,4,5-tetrafluoro-6-nitrobenzoyl chloride, 2,3,4,5,6-pentafluorobenzyl chloride Acyl chloride, 2-(trifluoromethyl)benzoyl chloride, 3-(trifluoromethyl)benzoyl chloride, 4-(trifluoromethyl)benzoyl chloride, 3-trifluoromethyl-4 -Ethoxybenzoyl chloride, 3,5-bis(trifluoromethyl)benzoyl chloride, 2,4,6-para(trifluoromethyl)benzoyl chloride, 4-(pentafluoroethyl ) benzoyl chloride, 4-(3-tetrafluoropropyl) benzoyl chloride, 2,3,5,6-tetrafluoro-4-(trifluoromethyl) benzoyl chloride, 2,3,5 , 6-tetrafluoro-4-(trifluorovinyl)benzoyl chloride, 2,3,5,6-tetrafluoro-4-(pentafluoroallyl)benzoyl chloride, etc., but not limited to etc.

As the base, alkoxides such as t-butoxysodium (t-BuONa) and t-butoxypotassium; fluoride salts such as lithium fluoride, potassium fluoride, and cesium fluoride; sodium carbonate, Potassium carbonate, sodium bicarbonate, potassium bicarbonate and other carbonates; trimethylamine, triethylamine, diisopropylethylamine, tetramethylethylenediamine, pyridine, morpholine, N-methyl morphine Amines such as morphine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, and 4-dimethylaminopyridine are not particularly limited as long as they can be used for this type of reaction. In particular, triethylamine, pyridine, diisopropylethylamine, and the like are preferable from the standpoint of ease of handling.

The reaction solvent is preferably an aprotic polar organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3- Dimethyl-2-imidazolinone, dimethylsulfene, tetrahydrofuran, dioxane, etc. From the viewpoint of the ease of removal of the reaction solvent after the reaction, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, and the like are preferable.

The reaction temperature can be appropriately set in the range from the melting point to the boiling point of the solvent, usually at about 0-200°C, preferably at 20-150°C, in consideration of the type or amount of the raw material compound or catalyst used. In addition, since the reaction time is different depending on the type or amount of the raw material compound or catalyst used, the reaction temperature, etc., it cannot be definitively determined, but it is usually about 1 to 24 hours.

After completion of the reaction, post-treatment is carried out according to a conventional method to obtain the intended oligoaniline derivative containing fluorine atoms.

And, the acid halide compound that contains fluorine atom shown in formula (8) can be by the corresponding carboxylic acid that contains fluorine atom, for example with thionyl chloride or oxalyl chloride, phosphoryl chloride group, thionyl chloride, three Phosphorus chloride, phosphorus pentachloride and other electron-seeking halogenating agents are reacted. In addition, the corresponding carboxylic acid containing fluorine atoms can be commercially available, and can also be obtained by known methods (such as Japanese Patent Application Publication No. 9-67303, Japanese Patent Application Publication No. 9-67304, Japanese Patent Application Publication No. 2002-284733). Those synthesized by the methods described in publications, etc.).

Specific examples of the fluorine atom-containing oligoaniline derivative represented by formula (6) are given below, but are not limited thereto. In addition, "R ³⁰¹ ~ R ³¹⁰ ", "A" and "n ¹ " in the table represent those specified in the relevant formula (6) of each compound shown in each row, such as the compound shown in formula (E-1) and The compounds represented by the formula (E-138) are each shown below.

As the organic solvent used when preparing the varnish for forming a charge-transporting thin film, a good solvent capable of satisfactorily dissolving the charge-transporting substance and the blend can be used.

Such good solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylbutylamide, N,N-diethyl Butylamide, N,N-Methylethylbutylamide, N,N-Dimethylisobutylamide, N,N-Diethylisobutylamide, N-Ethyl-N - organic solvents such as methyl isobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone, but are not limited thereto. These solvents may be used alone or in combination of two or more. The usage-amount is 5-100 mass % in the solvent of a varnish.

Furthermore, it is preferable that the charge-transporting substance, the blend, and the like can be completely dissolved in the aforementioned solvent.

In addition, in the present invention, other organic solvents other than the aforementioned organic solvents may be contained for the purpose of improving the wettability of the substrate, adjusting the surface tension of the solvent, adjusting the polarity, and adjusting the boiling point. Examples of such other organic solvents include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-ethylene glycol (ethylene glycol), and 1,2-propanediol (propylene glycol). , 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-2,4 -Glycols such as pentanediol (hexanediol), 1,3-octanediol, 3,6-octanediol; triols such as glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl Ethylene glycol monoalkyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, etc. Propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monohexyl ether, etc. Alkanediol monoalkyl ethers such as ethylene glycol monophenyl ethers; ethylene glycol monoaryl ethers such as ethylene glycol monophenyl ethers; propylene glycol monoaryl ethers such as propylene glycol monophenyl ethers and other alkanediol monoaryl ethers; Ethylene glycol monoaralkyl ethers such as ethylene glycol monobenzyl ether, propylene glycol monoaralkyl ethers such as propylene glycol monoaralkyl ethers, etc., alkanediol monoaralkyl ethers; ethylene glycol butoxy Ethyl ether and other ethylene glycol alkoxyalkyl ethers, propylene glycol butoxy ethyl ether and other propylene glycol alkoxyalkyl ethers and other alkanediol alkoxyalkyl ethers; ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether and other ethylene glycol dialkyl ethers, propylene glycol dimethyl ether, propylene glycol Diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, etc., propylene glycol dialkyl ethers, such as alkanediol dialkyl ethers; ethylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, etc. Alkyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether ethyl Alkanediol monoalkyl ether acetates such as esters of propylene glycol monoalkyl ether acetates; ethylene glycol monoacetates such as ethylene glycol monoacetate; propylene glycol monoacetates such as propylene glycol monoacetate Alkanediol monoacetates such as alkanediol monoacetate; Alkanediol diacetate such as ethylene glycol diacetate, propylene glycol diacetate etc. Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether , Diethylene glycol monoalkyl ethers of diethylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol Dipropylene glycol monoalkyl ethers such as monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monohexyl ether, etc.; diethylene glycol monoalkyl ethers, etc.; diethylene glycol monophenyl ether, etc. Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoaryl ether, etc. Ethylene glycol dipropyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether and other diethylene glycol dialkyl ethers, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether , dipropylene glycol dipropyl ether, dipropylene glycol diisopropyl ether, dipropylene glycol dibutyl ether and other dipropylene glycol dialkyl ethers and other dialkyl glycol dialkyl ethers; diethylene glycol monomethyl ether Diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol monobutyl ether acetate Esters, diethylene glycol monoisobutyl ether acetate, diethylene glycol monoalkyl ether acetates of diethylene glycol monohexyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monoisobutyl ether acetate, Dipropylene glycol monohexyl ether acetate and other dipropylene glycol monoalkyl ether acetates and other dialkyl glycol monoalkyl ether acetates; triethylene glycol monomethyl ether and triethylene glycol monoethyl ether Tripropylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ethers, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Triethylene glycol dialkyl ethers such as triethylene glycol diethyl ether Tripropylene glycol dialkyl ethers such as tripropylene glycol dimethyl ether and tripropylene glycol diethyl ether Trialkylene glycol dialkyl ethers such as tripropylene glycol dialkyl ethers ;1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-nonanol, 1-decanol, 1-undecanol Alcohol, 1-dodecanol, 1-tetradecyl alcohol and other straight-chain aliphatic alcohols, cyclohexanol, 2-methylcyclohexanol and other cycloaliphatic alcohols and other aliphatic alcohols; phenols such as phenol; Aromatic alcohols such as benzyl alcohol; heterocyclic alcohols such as furfuryl alcohol; hydrogenated heterocyclic alcohols such as tetrahydrofurfuryl alcohol; diisopropyl ether, di-n-butyl ether, di-n -Dialkyl ethers such as hexyl ether; methyl phenyl ether, ethyl phenyl ether, n-butyl phenyl ether, benzyl (3-methyl butyl) ether, (2-methyl phenyl ) methyl ether, (3-methylphenyl) methyl ether, (4-methylphenyl) methyl ether and other alkyl aryl ethers; ethyl benzyl ether and other alkyl aralkyl ethers ; Cyclic alkyl monoethers such as 2-methylfuran, tetrahydrofuran and tetrahydropyran; Cyclic alkyl diethers such as 1,4-dioxane; Cyclic alkyl triethers such as trioxane; Diglycidyl ether and other diepoxyalkyl ethers; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate , s-butyl acetate, t-butyl acetate, n-pentyl acetate, (3-methylbutyl) acetate, n-hexyl acetate, (2-ethylbutyl straight-chain or branched-chain alkyl acetates such as (yl) acetate, (2-ethylhexyl) acetate, and cyclic alkyl groups such as cyclohexyl acetate and 2-methylcyclohexyl acetate Alkyl acetates such as acetates; ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, s-butyl Propionate, t-butylpropionate, n-pentylpropionate, (3-methylbutyl)propionate, n-hexylpropionate, (2-ethylbutyl)propionate , (2-ethylhexyl) propionate and other linear or branched alkyl propionate esters, cyclohexyl propionate, 2-methylcyclohexyl propionate and other cyclic alkyl propionate esters Isoalkyl propionates; ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, s-butyl butyrate ester, t-butyl butyrate, n-pentyl butyrate, (3-methylbutyl) butyrate, n-hexyl butyrate, (2-ethylbutyl) butyrate, ( Linear or branched alkyl butyrates such as 2-ethylhexyl) butyrate, cyclic alkyl butyrates such as cyclohexyl butyrate and 2-methylcyclohexyl butyrate Butyl butyrates; ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, s-butyl lactate, t-butyl lactate, n-pentyl lactate, (3-methylbutyl) lactate, n-hexyl lactate, (2-ethylbutyl) lactate, (2- Linear or branched alkyl lactate such as ethylhexyl) lactate, cyclic alkyl lactate such as cyclohexyl lactate, 2-methylcyclohexyl lactate, etc. Alkyl lactate Alkyl esters such as benzyl acetate; aralkyl acetates such as benzyl acetate, aralkyl propionates such as benzyl propionate, aralkyl butyrates such as benzyl butyrate, Aralkyl alkyl esters such as benzyl lactate and other aralkyl lactate; diethyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl n-propyl ketone, methyl n- -Dialkyl ketones such as butyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl n-hexyl ketone, ethyl n-butyl ketone, di-n-propyl ketone and other dialkyl ketones; Cyclic alkenyl ketones such as phorone; Cyclic alkyl ketones such as cyclohexanone; Hydroxy dialkyl ketones such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol); Furfural, etc. Heterocycles contain aldehydes; linear or branched alkanes such as heptane, octane, 2,2,3-trimethylhexane, decane, dodecane; toluene, xylene, o-xylene , m-xylene, p-xylene, trimethylbenzene, tetrahydronaphthalene, cyclohexylbenzene and other alkylbenzenes; cyclohexane, methylcyclohexane, ethylcyclohexane and other cyclic alkanes, etc., but Not limited to these. These solvents can be used individually by 1 type or in mixture of 2 or more types. The usage amount can be determined according to the amount of good solvent used at the same time. Furthermore, depending on the type of the charge transporting substance, the aforementioned other solvents may also function as good solvents.

Among them, other organic solvents other than good solvents include glycols, triols, alkanediol monoalkyl ethers, alkanediol dialkyl ethers, dioxanediol monoalkylethers, dioxane Glycol dialkyl ethers are preferred, those containing glycols, alkanediol monoalkyl ethers, and dioxanediol monoalkyl ethers are preferred, and those containing diethylene glycol, triethylene glycol alcohol, dipropylene glycol, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4- Butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monoisopropyl Ether, Propylene Glycol Monobutyl Ether, Propylene Glycol Monoisobutyl Ether Diethylene Glycol Monomethyl Ether, Diethyl Glycol monoethyl ether, diethylene glycol propyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monoisobutyl ether are further preferred, with diethylene glycol, three Ethylene glycol, dipropylene glycol, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1, 4-Butanediol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether are more preferable, if charge transporting substances or blending Varnishes having desired physical properties can be easily prepared by selecting the solvent used among these solvents according to the type or amount of the substance.

Although the viscosity of the varnish of the present invention is appropriately set according to the thickness of the film to be produced or the concentration of solid components, it is usually 1~50mPa at 25°C. s, the surface tension is usually 20~50mN/m.

The preparation method of the varnish for forming a charge-transporting thin film is not particularly limited, for example, a method of dissolving a charge-transporting substance in a solvent and then sequentially adding a blend and a pentavalent superatomic iodine compound, or adding a charge-transporting substance A method for dissolving a transport substance, admixture, or a mixture of pentavalent superatomic iodine compounds in a solvent can be mentioned.

In addition, when there are plural organic solvents, in a solvent that can dissolve the charge-transporting substance, the blend, and the pentavalent superatomic iodine compound well, these can be dissolved first, and other solvents can also be added here. In the mixed solvent of the organic solvent, the charge-transporting substance, the blend, and the pentavalent superatomic iodine compound are dissolved sequentially or simultaneously.

In the present invention, the varnish for forming a charge-transporting thin film is obtained by dissolving a charge-transporting substance, admixture, etc. in an organic solvent, and then filtering it with a submicron filter, etc. from the viewpoint of obtaining a highly flat film with excellent reproducibility better.

The charge-transporting film-forming varnish of the present invention is coated on a substrate and baked to form a charge-transporting film on the substrate.

Examples of coating methods for the varnish include, but are not limited to, dipping, spin coating, transfer printing, roll coating, brush coating, inkjet, spray, and slit coating. wait here. The coating method is preferably spin coating method, inkjet method, or spray method, considering that a charge transport film with high flatness can be obtained with good reproducibility. And corresponding to the coating method, it is better to adjust the viscosity and surface tension of the varnish.

In addition, when using the varnish of the present invention, when it is desired to obtain a film with a uniform film-forming surface and high charge transport properties, it is necessary to select the grilling environment in consideration of the charge transport properties contained in the present invention, blends, solvents, etc. (Under the atmosphere, under an inert gas such as nitrogen, under a vacuum, etc.), however, generally, a thin film with uniformity and excellent charge transport properties can be obtained after baking in an atmosphere.

The firing temperature can be set in the range of 100-260°C in consideration of the use of the obtained film, the degree of charge transport properties imparted to the obtained film, etc., but when used as the hole injection layer of an organic EL device, the The temperature is preferably 140~250℃, and the temperature is 150~230℃. In particular, the varnish of the present invention can be baked at a temperature of less than 200°C, especially because it can be baked at a low temperature of 150-190°C. Even when baked at a relatively low temperature, a film with excellent charge transport properties can be realized. In addition, at the time of baking, for the purpose of expressing high uniform film-forming property or reacting on the base material, it is possible to impart temperature changes in two or more stages. Moreover, heating can be performed using suitable apparatuses, such as a hotplate and an oven, for example.

The film thickness of the charge-transporting thin film is not particularly limited, but it is preferably 5 to 200 nm when used as a hole injection layer of an organic EL device. As a method of changing the film thickness, there are methods such as changing the concentration of a charge-transporting substance in the varnish, or changing the amount of the solution on the substrate during coating.

The charge-transporting thin film of the present invention is preferably used as a hole injection layer for an organic EL device, but can also be used as a charge-transporting functional layer such as a hole injection and transport layer.

The organic EL device of the present invention has a pair of electrodes, and the charge-transporting thin film of the present invention is provided between these electrodes.

The following (a)-(f) are mentioned as a typical structure of an organic EL element, However, It is not limited to these. In addition, in the following configuration, an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) blocking layer or the like may be provided between the light emitting layer and the cathode as necessary. Again, the hole injection layer, the hole transport layer or the hole injection transport layer can have functions such as an electron blocking layer, and the electron injection layer, the electron transport layer or the electron injection transport layer can also serve as a hole (hole) barrier layer, etc. Function.

(a) anode/hole injection layer/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode

(b) anode/hole injection layer/hole transport layer/luminescent layer/electron injection transport layer/cathode

(c) Anode/hole injection transport layer/luminescent layer/electron transport layer/electron injection layer/cathode

(d) anode/hole injection transport layer/luminescent layer/electron injection transport layer/cathode

(e) anode/hole injection layer/hole transport layer/luminescent layer/cathode

(f) anode/hole injection transport layer/luminescent layer/cathode

The so-called "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, which have the function of transporting holes from the anode to the light-emitting layer. When only one layer of the hole transport material layer is provided between the light emitting layer and the anode, this is called a "hole injection transport layer", and two layers of the hole transport material layer are provided between the light emitting layer and the anode In the above case, the layer close to the anode is the "hole injection layer", and the other layers are the "hole transport layer". In particular, the hole injection layer and the hole injection transport layer are not only capable of accepting holes from the anode, but thin films that are also excellent in hole injection properties to each of the hole transport layer and the light emitting layer are used.

The "electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light-emitting layer. When only one layer of the electron transport material is provided between the light emitting layer and the cathode, this is called an "electron injection and transport layer", and when two or more layers of the electron transport material are provided between the light emitting layer and the cathode , the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layer".

The so-called "light-emitting layer" refers to an organic layer with a light-emitting function, and when a doping system is used, it contains a host material and a blend material. At this time, the host material mainly promotes the recombination of electrons and holes, and has the function of sealing the excitons in the light-emitting layer, and the blend material has the function of enabling the recombined excitons to emit light efficiently. In the case of a phosphorescent device, the host material mainly has the function of confining the excitons generated in the blend in the light-emitting layer.

Examples of materials and production methods for producing an organic EL device using the varnish for forming a charge-transporting thin film of the present invention include the following, but are not limited thereto.

It is better to use the electrode substrate to be cleaned by washing with detergent, alcohol, pure water, etc. in advance to purify it. For example, the surface treatment such as UV ozone treatment and oxygen-plasma treatment can be carried out on the anode substrate before use. good. However, when the anode material has an organic substance as a main component, it is not necessary to perform surface treatment.

An example of the production method of the organic EL device of the present invention when the thin film obtained from the varnish for forming a charge transporting thin film of the present invention is a hole injection layer is shown below.

By the aforementioned method, the varnish for forming a charge transporting thin film of the present invention is coated on the anode substrate and baked to form a hole injection layer on the electrode. On the hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are arranged in sequence. The hole transport layer, light-emitting layer, electron transport layer, and electron injection layer may be formed by either evaporation method or coating method (wet process) in accordance with the properties of the materials used.

As the anode material, transparent electrodes represented by indium tin oxide (ITO) and indium zinc oxide (IZO) or metal anodes composed of metals represented by aluminum or these alloys can be mentioned, and planarized Those are also good. Polythiophene derivatives or polyaniline derivatives having high charge transportability can also be used.

Furthermore, examples of other metals constituting the metal anode include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, and cadmium. , indium, scandium, lanthanum, cerium, 鐠, neodymium, hook, samarium, europium, 釓, 鋱, dysprosium, ', erbium, 銩, ytterbium, hafnium, thallium, tungsten, rhenium, osmium, iridium, platinum, gold, titanium , lead, bismuth or these alloys, etc., but not limited to these.

As materials for forming the hole transport layer, (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimers, N,N'-bis(naphthalene-1 -yl)-N,N'-bis(phenyl)-benzidine (α-NPD), N,N'-bis(naphthalene-2-yl)-N,N'-bis(phenyl)-benzidine , N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N'- Bis(phenyl)-9,9-spirobifluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-spirobifluorene, N,N '-Bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(naphthalene-1-yl)-N,N '-Bis(phenyl)-9,9-dimethyl-fluorene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-diphenyl Base-fluorene, N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-9,9-diphenyl-fluorene, N,N'-bis(naphthalene-1- base)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine, 2,2',7,7'-tetra(N,N-diphenylamino)-9, 9-spirobifluorene, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-fluorene, 9,9-bis[4-(N ,N-bis-naphthalen-2-yl-amino)phenyl]-9H-fluorene, 9,9-bis[4-(N-naphthalen-1-yl-N-phenylamino)-phenyl] -9H-fluorene, 2,2',7,7'-tetra[N-naphthyl(phenyl)-amino]-9,9-spirobifluorene, N,N'-bis(phenanthrene-9-yl )-N,N'-bis(phenyl)-benzidine, 2,2'-bis[N,N-bis(biphenyl-4-yl)amino]-9,9-spirobifluorene, 2 ,2'-bis(N,N-diphenylamino)-9,9-spirobifluorene, bis-[4-(N,N-bis(p-tolyl)amino)-phenyl] ring Hexane, 2,2',7,7'-tetrakis(N,N-bis(p-tolyl)amino)-9,9-spirobifluorene, N,N,N',N'-tetrakis- Naphthalene-2-yl-benzidine, N,N,N',N'-tetrakis-(3-methylphenyl)-3,3'-dimethylbenzidine, N,N'-di(naphthyl )-N,N'-bis(naphthalene-2-yl)-benzidine, N,N,N',N'-tetrakis(naphthyl)-benzidine, N,N'-bis(naphthalene-2-yl )-N,N'-diphenylbenzidine-1,4-diamine, N ¹ ,N ⁴ -diphenyl-N ¹ ,N ⁴ -di(m-tolyl)benzene-1,4-di Amine, N ² , N ² , N ⁶ , N ⁶ -tetraphenylnaphthalene-2,6-diamine, reference (4-(quinolin-8-yl)phenyl)amine, 2,2'-bis( 3-(N,N-bis(p-tolyl)amino)phenyl)biphenyl, 4,4',4''-para[3-methylphenyl(phenyl)amino]triphenyl Triarylamine (m-MTDATA), 4,4',4''-reference [1-naphthalene(phenyl)amino]triphenylamine (1-TNATA), and other triarylamines, 5,5''- Bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2': 5',2''-trithiophene (BMA-3T) and other oligothiophene isoelectric hole transport low-molecular-weight materials, etc.

Examples of materials for forming the light-emitting layer include ginseng(8-quinolinolato)aluminum(III)(Alq ₃ ), bis(8-quinolinolato)zinc(II)(Znq ₂ ), bis(2-methylquinoline) -8-hydroxyquinoline)-4-(p-phenylphenol)aluminum(III)(BAlq), 4,4'-bis(2,2-diphenylvinyl)biphenyl, 9,10- Bis(naphthalene-2-yl)anthracene, 2-t-butyl-9,10-bis(naphthalene-2-yl)anthracene, 2,7-bis[9,9-bis(4-methylphenyl) -Fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene, 2-methyl-9,10-bis(naphthalene-2-yl)anthracene, 2-(9,9-spiro Bifluorene-2-yl)-9,9-spirobifluorene, 2,7-bis(9,9-spirobifluorene-2-yl)-9,9-spirobifluorene, 2-[9,9- Bis(4-methylphenyl)-fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene, 2,2'-dipyrenyl-9,9-spirobifluorene, 1 ,3,5-Pyrene-1-yl)benzene, 9,9-bis[4-(pyrenyl)phenyl]-9H-fluorene, 2,2'-bis(9,10-diphenylanthracene ), 2,7-bispyrenyl-9,9-spirobifluorene, 1,4-bis(pyren-1-yl)benzene, 1,3-bis(pyren-1-yl)benzene, 6,13- Bis(biphenyl-4-yl)pentaphenyl, 3,9-bis(naphthalene-2-yl)perylene, 3,10-bis(naphthalene-2-yl)perylene, reference [4-(pyrenyl)- Phenyl]amine, 10,10'-bis(biphenyl-4-yl)-9,9'-bisanthracene, N,N'-bis(naphthalene-1-yl)-N,N'-diphenyl Base-[1,1':4',1'':4'',1'''-quaternary phenyl]-4,4'''-diamine, 4,4'-bis[10-(naphthalene- 1-yl)anthracen-9-yl]biphenyl, dibenzo{[f,f']-4,4',7,7'-tetraphenyl}bisindeno[1,2,3-cd : 1',2',3'-lm] perylene, 1-(7-(9,9'-bisanthracene-10-yl)-9,9-dimethyl-9H-fluoren-2-yl)pyrene , 1-(7-(9,9'-bisanthracene-10-yl)-9,9-dihexyl-9H-fluoren-2-yl)pyrene, 1,3-bis(carbazol-9-yl) Benzene, 1,3,5- reference (carbazol-9-yl) benzene, 4,4', 4''- reference (carbazol-9-yl) triphenylamine, 4,4'- bis (carbazol-9-yl) triphenylamine, Azol-9-yl)biphenyl (CBP), 4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl, 2,7-bis(carbazole-9 -yl)-9,9-dimethylfluorene, 2,2',7,7'-tetra(carbazol-9-yl)-9,9-spirobifluorene, 2,7-bis(carbazole- 9-yl)-9,9-bis(p-tolyl)fluorene, 9,9-bis[4-(carbazol-9-yl)-phenyl]fluorene, 2,7-bis(carbazole-9 -yl)-9,9-spirobifluorene, 1,4-bis(triphenylsilyl)benzene, 1,3-bis(triphenylsilyl)benzene, bis(4-N,N-diethyl Amino-2-methylphenyl)-4-methylphenylmethane, 2,7-bis(carbazol-9-yl)-9,9-dioctylfluorene, 4,4''-di (Triphenylsilyl)-p-terphenyl, 4,4'-bis(triphenylsilyl)biphenyl, 9-(4-t-butylphenyl)-3,6-bis(triphenyl) Phenylsilyl)-9H-carbazole, 9-(4-t-butylphenyl)-3,6-bistrityl-9H-carbazole, 9-(4-t-butylphenyl )-3,6-bis(9-(4-methoxyphenyl)-9H-fluoren-9-yl)-9H-carbazole, 2,6-bis(3-(9H-carbazole-9- yl)phenyl)pyridine, triphenyl(4-(9-phenyl-9H-fluoren-9-yl)phenyl)silane, 9,9-dimethyl-N,N-diphenyl-7- (4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-9H-fluoren-2-amine, 3,5-bis(3-(9H-carbazole-9- base) phenyl) pyridine, 9,9-spirobifluoren-2-yl-diphenyl-phosphine oxide, 9,9'-(5-(triphenylsilyl)-1,3-phenylene ) bis(9H-carbazole), 3-(2,7-bis(diphenylphosphoryl)-9-phenyl-9H-fluoren-9-yl)-9-phenyl-9H-carbazole, 4,4,8,8,12,12-hexa(p-tolyl)-4H-8H-12H-12C-azadibenzo[cd,mn]pyrene, 4,7-bis(9H-carbazole -9-yl)-1,10-phenanthroline, 2,2'-bis(4-(carbazol-9-yl)phenyl)biphenyl, 2,8-bis(diphenylphosphoryl ) dibenzo[b,d]thiophene, bis(2-methylphenyl)diphenylsilane, bis[3,5-bis(9H-carbazol-9-yl)phenyl]diphenylsilane, 3,6-bis(carbazol-9-yl)-9-(2-ethyl-hexyl)-9H-carbazole, 3-(diphenylphosphoryl)-9-(4-(diphenyl Phosphoryl)phenyl)-9H-carbazole, 3,6-bis[(3,5-diphenyl)phenyl]-9-phenylcarbazole, etc. A light-emitting layer can be formed by co-evaporating these materials with a light-emitting blend.

Examples of luminescent blends include 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 2,3,6,7-tetrahydro-1,1,7 ,7-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinazino[9,9a,1gh]coumarin, quinacridone, N,N'-dimethyl -quinacridone, reference (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ), bis (2-phenylpyridine) (acetylpyruvate) iridium (III) (Ir (ppy) ₂ (acac)), reference [2-(p-tolyl)pyridine]iridium (III) (Ir(mppy) ₃ ), 9,10-bis[N,N-bis(p-tolyl)amino] Anthracene, 9,10-bis[phenyl(m-tolyl)amino]anthracene, bis[2-(2-hydroxyphenyl)benzothiazolate]zinc(II), N ¹⁰ , N ¹⁰ , N ¹⁰ ,N ¹⁰ -tetra(p-tolyl)-9,9'-bisanthracene-10,10'-diamine, N ¹⁰ ,N ¹⁰ ,N ¹⁰ ,N ¹⁰ -tetraphenyl-9,9'-bis Anthracene-10,10'-diamine, N ¹⁰ ,N ¹⁰ -diphenyl-N ¹⁰ ,N ¹⁰ -dinaphthyl-9,9'-bisanthracene-10,10'-diamine, 4,4'-bis(9-ethyl-3-carbazolovinyl)-1,1'-biphenyl, perylene, 2,5,8,11-tetra-t-butylperylene, 1,4-bis[ 2-(3-N-Ethylcarbazolyl)vinyl]benzene, 4,4'-bis[4-(di-p-tolylamino)styrene]biphenyl, 4-(di-p -tolylamino)-4'-[(di-p-tolylamino)styrene]stilbene, bis[3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxy Pyridyl)] iridium (III), 4,4'-bis[4-(diphenylamino)styrene]biphenyl, bis(2,4-difluorophenylpyrindinato)) (1-pyrazolyl)borate iridium(III), N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-para(9,9-dimethylfluorene) , 2,7-bis{2-[phenyl(m-tolyl)amino]-9,9-dimethyl-fluoren-7-yl}-9,9-dimethyl-fluorene, N-( 4-((E)-2-(6((E)-4-(Diphenylamino)styrene)naphthalene-2-yl)vinyl)phenyl)-N-phenylaniline, fac-iridium (III) ginseng (1-phenyl-3-methylbenzimidazolium-2-ylidene-C,C ² ), mer-iridium (III) ginseng (1-phenyl-3-methylbenzimidazole Line-2-ylidene-C,C ² ), 2,7-bis[4-(diphenylamino)styrene]-9,9-spirobifluorene, 6-methyl-2-(4- (9-(4-(6-methylbenzo[d]thiazol-2-yl)phenyl)anthracen-10-yl)phenyl)benzo[d]thiazole, 1,4-bis[4-( N,N-diphenyl)amino]styrene benzene, 1,4-bis(4-(9H-carbazol-9-yl)styrene)benzene, (E)-6-(4-(diphenyl Amino)-styrene)-N,N-diphenylnaphthalene-2-amine, bis(2,4-difluorophenylpyrindinato)(5-(pyridin-2-yl)-1H -tetrazole) iridium(III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazole)((2,4-difluorobenzyl)diphenylphosphonate)iridium( III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazole salt) (benzyl diphenylphosphonate) iridium(III), bis(1-(2,4-bis Fluorobenzyl)-3-methylbenzimidazolium)(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole)iridium(III), bis( 3-trifluoromethyl-5-(2-pyridyl)pyrazole salt)(4',6'-difluorophenylpyridinium salt)iridium(III), bis(4',6'-difluorophenyl Pyrindinato (pyrindinato) (3,5-bis(trifluoromethyl)-2-(2'-pyridyl)pyrrole salt) iridium(III), bis(4',6'-difluorophenylpyrrole Cetyl (pyrindinato)) (3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole) iridium (III), (Z)-6-trimethylphenyl-N -(6-tricresylquinolin-2(1H)-ylidene)quinolin-2-amine-BF ₂ , (E)-2-(2-(4-(dimethylamino)styrene) -6-methyl-4H-pyran-4-ylidene) malononitrile, 4-(dicyanomethyl)-2-methyl-6-julolidyl (Julolidyl)-9-enyl- 4H-pyran, 4-(dicyanomethyl)-2-methyl-6-(1,1,7,7-tetramethyljulolidyl (Julolidyl)-9-enyl)-4H- Pyran, 4-(dicyanomethyl)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidine (Julolidine)-4-yl-vinyl)- 4H-pyran, ginseng(dibenzoylmethane)phenanthroline europium(III), 5,6,11,12-tetraphenylnaphthonaphthalene, bis(2-benzo[b]thiophene-2- Base-pyridine) (acetylpyruvate) iridium (III), reference (1-phenylisoquinoline) iridium (III), bis (1-phenylisoquinoline) (acetylpyruvate) iridium ( III), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)-isoquinoline] (acetylpyruvate) iridium(III), bis[2-(9,9- Dimethyl-9H-fluoren-2-yl)quinoline](acetylpyruvate)iridium(III), reference[4,4'-di-t-butyl-(2,2')-bipyridine ] Ruthenium (III). Bis(hexafluorophosphate), ginseng(2-phenylquinoline)iridium(III), bis(2-phenylquinoline)(acetylpyruvate)iridium(III), 2,8-di-t -Butyl-5,11-bis(4-t-butylphenyl)-6,12-diphenyltetracene (tetracene), bis(2-phenylbenzothiazolium) (acetylpyruvate ) iridium(III), 5,10,15,20-tetraphenyltetrabenzoporphyrin platinum, osmium(II) bis(3-trifluoromethyl-5-(2-pyridine)-pyrazole salt) di Methylphenylphosphine, Osmium(II) bis(3-(trifluoromethyl)-5-(4-t-butylpyridyl)-1,2,4-triazole)diphenylmethylphosphine, Osmium(II)bis(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole)dimethylphenylphosphine, osmium(II)bis(3-(tri Fluoromethyl)-5-(4-t-butylpyridyl)-1,2,4-triazole)dimethylphenylphosphine, bis[2-(4-n-hexylphenyl)quinoline] (Acetylpyruvate) iridium (III), reference [2-(4-n-hexylphenyl) quinoline] iridium (III), reference [2-phenyl-4-methylquinoline] iridium (III) ), bis(2-phenylquinoline)(2-(3-methylphenyl)pyridinium salt) iridium(III), bis(2-(9,9-diethyl-fluoren-2-yl)- 1-phenyl-1H-benzo[d]imidazolato (imidazolato)) (acetylpyruvate) iridium (III), bis(2-phenylpyridine) (3-(pyridin-2-yl)-2H -Chromen-2-one-onyl iridium(III), bis(2-phenylquinoline)(2,2,6,6-tetramethylheptane-3,5-dionyl)iridium(III) , bis(phenylisoquinoline)(2,2,6,6-tetramethylheptane-3,5-diketonyl) iridium(III), iridium(III)bis(4-phenylthieno[ 3,2-c] pyrindinato (pyrindinato)-N,C ² ) acetylpyruvate, (E)-2-(2-t-butyl-6-(2-(2,6,6- Trimethyl-2,4,5,6-tetrahydro-1H-pyrrolo[3,2,1-ij]quinolin-8-yl)vinyl)-4H-pyran-4-ylidene)propane Dinitrile, bis(3-trifluoromethyl-5-(1-isoquinolyl)pyrazolium salt)(methyldiphenylphosphine)ruthenium, bis[(4-n-hexylphenyl)isoquinoline ] (acetylpyruvate) iridium(III), platinum(II) octaethylporphin (Porphin), bis(2-methyldibenzo[f,h]quinoxaline)(acetylpyruvate ) iridium (III), reference [(4-n-hexylphenyl) oxyquinoline] iridium (III), etc.

As materials for forming the electron transport layer, 8-hydroxyquinolinolato (quinolinolato)-lithium, 2,2',2''-(1,3,5-benzenetriyl)-paraffin (1-phenyl -1-H-benzimidazole), 2-(4-biphenyl) 5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,9-dimethyl- 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, bis(2-methyl-8-hydroxyquinolinolato (quinolinolato))- 4-(phenylphenate)aluminum, 1,3-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazol-5-yl]benzene, 6, 6'-bis[5-(biphenyl-4-yl)-1,3,4-oxadiazol-2-yl]-2,2'-bipyridine, 3-(4-biphenyl)- 4-phenyl-5-t-butylphenyl-1,2,4-triazole, 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-tri Azole, 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline, 2,7-bis[2-(2,2'-bipyridine-6- Base)-1,3,4-oxadiazol-5-yl]-9,9-dimethylfluorene, 1,3-bis[2-(4-t-butylphenyl)-1,3, 4-Oxadiazol-5-yl]benzene, ginseng(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane, 1-methyl-2-(4-( Naphthalene-2-yl)phenyl)-1H-imidazo[4,5f][1,10]phenanthroline, 2-(naphthalene-2-yl)-4,7-diphenyl-1,10- Phenanthroline, phenyl-dipyrenylphosphine oxide, 3,3',5,5'-tetrakis[(m-pyridyl)-phenyl-3-yl]biphenyl, 1,3,5- Refer to [(3-pyridyl)-phenyl-3-yl]benzene, 4,4'-bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl, 1,3-bis[3,5-bis(pyridin-3-yl)phenyl]benzene, bis(10-hydroxybenzo[h]quinolinate)beryllium, diphenylbis(4-(pyridine-3 -yl)phenyl)silane, 3,5-bis(pyrene-1-yl)pyridine, etc.

Examples of materials forming the electron injection layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), fluoride Magnesium (MgF ₂ ), Cesium Fluoride (CsF), Strontium Fluoride (SrF ₂ ), Molybdenum Trioxide (MoO ₃ ), Aluminum, Lithium Acetylpyruvate (Li(acac)), Lithium Acetate, Lithium Benzoate wait.

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

Further, another example of the method for producing the organic EL device of the present invention when the film obtained from the varnish for forming a charge transporting thin film of the present invention is a hole injection layer is shown below.

Also, for the aforementioned organic EL device manufacturing method, instead of performing 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 layer and the light-emitting layer can be formed sequentially to produce a product with An organic EL element of a charge transporting thin film formed with the varnish for forming a charge transporting thin film of the present invention. Specifically, by coating the varnish for forming a charge-transporting thin film of the present invention on the anode substrate, a hole injection layer is produced by the aforementioned method, and a hole-transporting layer and a light-emitting layer are sequentially formed on it, and the cathode material is further evaporated. Plating becomes an organic EL element.

As the cathode and anode materials used, the same ones as above can be used, and the same cleaning treatment and surface treatment can be performed.

As a method for forming the hole transport layer and the light emitting layer, a hole transport polymer material or a luminescent polymer material may be mentioned, or a solvent may be added to the material in which these materials are blended to dissolve or uniformly disperse them. A method of forming a film by firing after coating on each hole injection layer or hole transport layer.

Examples of hole-transporting polymer materials include 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]-terminated with polysilsesquioxane, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4, 4'-(N-(p-butylphenyl))diphenylamine)], etc.

Examples of light-emitting polymer materials include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2'-ethylhexyloxy) - Polyphenylene derivatives such as 1,4-phenylene vinylene (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), polyvinylcarbazole (PVCz), etc.

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

The coating method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a transfer printing method, a roll coating method, and brush coating. It is also preferable that the coating can be performed under an inert gas such as nitrogen or argon.

As a grilling method, the method of heating under an inert gas or vacuum, an oven, or a hot plate is mentioned.

An example of the production method of the organic EL device of the present invention when the thin film obtained from the varnish for forming a charge-transporting thin film of the present invention is a hole injection and transport layer is shown below.

A hole injection and transport layer is formed on the anode substrate, and a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially arranged on the hole injection and transport layer. The methods and specific examples for forming the light-emitting layer, the electron transport layer, and the electron injection layer include the same ones as described above.

Examples of the materials forming the anode material, light-emitting layer, light-emitting blend, electron transport layer, and electron blocking layer, and the cathode material include the same ones as described above.

In addition, a hole blocking layer, an electron blocking layer, and the like may be provided as necessary between the electrodes and any of the aforementioned layers. For example, para(phenylpyrazole)iridium etc. are mentioned as a material which forms an electron blocking layer.

The materials constituting the anode, the cathode, and the layers formed therebetween differ depending on whether or not a device having either a bottom emission structure or a top emission structure is produced, and an appropriate material is selected in consideration of this point.

Usually, in the element of the bottom emission structure, a transparent anode is used on the substrate side. For light extraction from the substrate side, in the element of the top emission structure, a reflective anode made of metal is used, and the transparent electrode opposite to the substrate ( Cathode) side extracts light. Therefore, for example, for anode materials, transparent anodes such as ITO are used when manufacturing elements with a bottom emission structure, and reflective anodes such as Al/Nd are used when manufacturing elements with a top emission structure.

The organic EL element of the present invention can be blocked simultaneously with a water-catching agent, etc., according to a certain method in order to prevent deterioration of characteristics.

[Example]

Examples and comparative examples are given below to describe the present invention more specifically, but the present invention is not limited to the following examples. In addition, the apparatuses used are as follows.

(1) Substrate cleaning: Substrate cleaning device manufactured by Changzhou Sangyo Co., Ltd. (decompression plasma method)

(2) Coating of varnish: spin coater MS-A100 manufactured by Mikasa Co., Ltd.

(3) Film thickness measurement: Micro shape measuring machine SurfcoderET-4000 manufactured by Kosaka Laboratory

(4) Production of organic EL elements: Multifunctional vapor deposition system C-E2L1G1-N manufactured by Changzhou Sangyo Co., Ltd.

(5) Measurement of brightness, etc. of organic EL elements: (existing) I-V-L measurement system manufactured by Tech World

(6) Lifetime measurement of organic EL elements (measurement of luminance half-life): PEL-105S organic EL luminance life evaluation system manufactured by Ecchsea Co., Ltd.

[1] Preparation of varnish for forming charge-transporting thin film [Example 1-1]

Dissolve 0.094 g of arylamine derivative shown in formula (f), 0.215 g of arylsulfonic acid shown in formula (b-1), and 0.031 g of Dess-Martin periodinane (manufactured by Tokyo Chemical Industry Co., Ltd.) in 1,3-Dimethyl-2-imidazolinone (DMI) 3.3 g. Here, 4 g of 2,3-butanediol (2,3-BD) and 2.7 g of dipropylene glycol monomethyl ether (DPM) were added and stirred, and the resulting solution was filtered using a PTFE filter with a pore size of 0.2 μm to obtain a varnish. The content of Dess-Martin periodinane in the obtained varnish was 10% by mass relative to the charge transporting substance. In addition, the aforementioned arylamine derivatives were synthesized according to the method described in International Publication No. 2015/050253, and the aforementioned arylsulfonic acids were synthesized according to the method described in International Publication No. 2006/025342.

[Example 1-2]

The same varnish as in Example 1-1 was obtained except that the content of Dess-Martin periodinane was changed to 20% by mass relative to the charge-transporting substance.

[Example 1-3]

The same varnish as in Example 1-1 was obtained except that the content of Dess-Martin periodinane was changed to 40% by mass relative to the charge-transporting substance.

[Example 1-4]

The same varnish as in Example 1-1 was obtained except that the content of Dess-Martin periodinane was changed to 60% by mass relative to the charge-transporting substance.

[Comparative Example 1-1]

0.094 g of an arylamine derivative represented by the formula (f) and 0.215 g of an arylsulfonic acid represented by the formula (b-1) were dissolved in 3.3 g of DMI. 4 g of 2,3-BD and 2.7 g of DPM were added and stirred here, and the resulting solution was filtered using a PTFE filter with a pore diameter of 0.2 μm to obtain a varnish.

〔2〕Fabrication and characteristic evaluation of single-layer components

For the following examples and comparative examples, as an ITO substrate, use ITO to form a glass substrate with a film thickness of 150nm on the surface of 25mm × 25mm × 0.7t, before use by _O2 plasma cleaning device (150W, 30 seconds ) to remove impurities on the surface.

[Example 2-1]

Apply the varnish obtained in Example 1-1 to the ITO substrate using a spin coater, dry it at 80°C for 1 minute in the atmosphere, and then bake it at 150°C for 15 minutes to form a 65nm varnish on the ITO substrate. film.

On top of this, a single-layer device in which an aluminum thin film was formed using a vapor deposition apparatus (vacuum degree 4.0×10 ^-5 Pa) was obtained. The vapor deposition was carried out under the condition of a vapor deposition rate of 0.2 nm/sec. The film thickness of the aluminum thin film was 80 nm.

Also, in order to prevent the deterioration of characteristics caused by the influence of oxygen and water in the air, single-layer devices are sealed with a sealing substrate, and then their characteristics are evaluated. Blocking is performed with the following procedure.

In a nitrogen environment with an oxygen concentration below 2ppm and a dew point below -85°C, the single-layer element is placed between the sealing substrates, and the sealing substrates are bonded with an adhesive (Moresco Moisture CutWB90US(P) manufactured by MORESCO) . At this time, a water-catching agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed in the sealing substrate together with the single-layer element. After the bonded sealing substrate was irradiated with UV light (wavelength 365 nm, irradiation dose 6,000 mJ/cm ² ), annealing was performed at 80° C. for 1 hour to harden the bonding material.

[Examples 2-2 to 2-4, Comparative Example 2-1]

Instead of the varnish obtained in Example 1-1, the varnish obtained in Examples 1-2 to 1-4 and Comparative Example 1-1 was used, and a single-layer device was produced by the same method as in Example 2-1.

The current density at a driving voltage of 3V was measured for each of the single-layer devices fabricated in the aforementioned Examples and Comparative Examples. The results are shown in Table 22.

[3] Manufacture and characteristic evaluation of organic EL elements

For the following examples and comparative examples, as the ITO substrate, as in the above [2], ITO was used to pattern the glass substrate with a film thickness of 150 nm on the surface of 25mm × 25mm × 0.7t, and before use, it was sprayed with _O2 plasma. Clean the device (150W, 30 seconds) to remove impurities on the surface.

[Example 3-1]

The varnish obtained in Example 1-1 was coated on an ITO substrate using a spin coater, dried at 80°C for 1 minute, and then baked at 150°C for 15 minutes in an atmospheric environment to form on the ITO substrate Uniform thin film of 65nm.

Next, on the ITO substrate on which the thin film was formed, α-NPD was formed into a 30 nm film at 0.2 nm/sec using a vapor deposition apparatus (vacuum degree: 1.0×10 ^-5 Pa). Second, CBP was co-evaporated with Ir(PPy) ₃ . Co-evaporation was carried out so that the deposition rate was controlled so that the concentration of Ir(PPy) ₃ became 6%, and 40 nm lamination was performed. Next, the organic EL element is obtained by sequentially laminating thin films of ginseng(8-quinolinolato)aluminum(III)(Alq ₃ ), lithium fluoride and aluminum. At this time, the vapor deposition rate was 0.2 nm/sec for Alq ₃ and aluminum, and 0.02 nm/sec for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm.

In addition, in order to prevent the deterioration of characteristics caused by the influence of oxygen and water in the air, organic EL elements are sealed with a sealing substrate, and then the characteristics are evaluated. The closure is carried out under the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2ppm or less and a dew point of -85°C or less, the organic EL element was retracted between the sealing substrates, and the sealing substrates were bonded together with an adhesive (XNR5516Z-B1 manufactured by Nagase Chemtex Co., Ltd.). At this time, a water-catching agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed in the sealing substrate together with the organic EL element. The sealed substrate to be bonded was irradiated with UV light (wavelength: 365 nm, irradiation dose: 6,000 mJ/cm ² ), and then annealed at 80° C. for 1 hour to harden the bonding material.

[Example 3-2~3-4, Comparative Example 3-1]

Instead of the varnish obtained in Example 1-1, an organic EL element was produced in the same manner as in Example 3-1, except that the varnish obtained in Examples 1-2 to 1-4 and Comparative Example 1-1 was used.

Evaluate the properties of fabricated components. Table 23 shows the driving voltage, current density, and current efficiency when the device was made to emit light at 5,000 cd/m ² . Table 24 shows the current density, luminance and current efficiency when the device is driven at 9V. Also, Table 25 shows the half-life of the luminance of the device (initial luminance: 5,000 cd/m ² ).

As shown in Tables 23 and 24, compared with the device (Comparative Example 3-1) having a thin film obtained from a varnish not containing a pentavalent superatomic iodine compound, the film obtained from a varnish containing a pentavalent superatomic iodine compound The thin-film element has a low driving voltage when emitting light at the same luminance, and improves luminance when emitting light at the same driving voltage. Also, as shown in Table 25, the durability of the element including the thin film obtained from the varnish containing the pentavalent superatomic iodine compound was also excellent.

Claims (12)

A varnish for forming a charge-transporting thin film, characterized in that it contains a pentavalent superatomic iodine compound, a charge-transporting substance, and an organic solvent, wherein the pentavalent superatomic iodine compound is selected from the group consisting of Dess-Martin periodinane, 2- Dioxyiodobenzoic acid, 2-dioxyliodobenzenesulfonic acid, and one or more of the compounds represented by the following formulas (X1) and (X2) in groups, the content of the aforementioned pentavalent superatomic valence iodine compound, relative to the charge 10 to 80% by mass of the transporting substance, the aforementioned charge transporting substance contains a charge transporting compound having a single molecular weight in the range of molecular weight 200 to 9,500,

The varnish for forming a charge-transporting thin film according to claim 1, wherein the pentavalent superatomic iodine compound is Dess-Martin periodinane. The varnish for forming a charge-transporting thin film according to claim 1 or 2, wherein the charge-transporting substance contains at least one member selected from the group consisting of arylamine derivatives and thiophene derivatives with a molecular weight of 200 to 9,500. The varnish for forming a charge-transporting thin film according to claim 1 or 2, further comprising a blend. The varnish for forming a charge-transporting thin film according to claim 4, wherein the blend contains arylsulfonic acid. A charge transport film characterized by being manufactured using the varnish for forming a charge transport film according to any one of Claims 1 to 5. An organic electroluminescent element, characterized by having the charge transporting thin film as claimed in claim 6. A method for producing a charge transporting thin film, characterized by using the varnish for forming a charge transporting thin film according to any one of Claims 1 to 5. A method of manufacturing an organic electroluminescent element, characterized by using the varnish for forming a charge-transporting thin film according to any one of claims 1 to 5. A method of reducing the driving voltage of an organic electroluminescent element having a charge transporting thin film manufactured using a varnish for forming a charge transporting thin film, characterized in that the varnish for forming a charge transporting thin film is used as in claims 1 to 5 Any one of the varnishes for forming a charge-transporting thin film. A method for improving the brightness of an organic electroluminescence element having a charge transport film produced by using a varnish for forming a charge transport film, characterized in that the varnish for forming a charge transport film is used as in Claims 1 to 5 The varnish for forming a charge-transporting thin film according to any one of the above items. A method for improving the luminance life of an organic electroluminescent element having a charge transporting thin film manufactured using a varnish for forming a charge transporting thin film, characterized in that as the varnish for forming a charge transporting thin film, the following claims 1 to 5 are used Any one of the varnishes for forming a charge-transporting thin film.