WO2023008176A1

WO2023008176A1 - Fluorinated arylsulfonate polymer compound and use thereof

Info

Publication number: WO2023008176A1
Application number: PCT/JP2022/027373
Authority: WO
Inventors: 陽介倉田
Original assignee: 日産化学株式会社
Priority date: 2021-07-26
Filing date: 2022-07-12
Publication date: 2023-02-02
Also published as: CN117677641A; TW202319408A; JPWO2023008176A1; KR20240036640A

Abstract

This fluorinated arylsulfonate polymer compound comprises repeating units represented by formula (1), and is suitable as a dopant substance for use in organic EL elements and the like. (In the formula, ArF represents a fluorinated arylene group, X represents O, S, NH, CONH or NHCO, and ArS represents an aryl group having, on a ring, at least one SO3R group (where R represents a hydrogen atom or an alkali metal atom)).

Description

Fluorinated arylsulfonic acid polymer compound and use thereof

The present invention relates to a fluorinated arylsulfonic acid polymer compound and its use.

Organic functional films made of organic compounds are used as light-emitting layers and charge injection layers in organic electroluminescence (hereinafter referred to as organic EL) devices. In particular, the hole-injecting layer carries out charge transfer between the anode and the hole-transporting layer or the light-emitting layer, and plays an important role in achieving low-voltage driving and high luminance of the organic EL device.
The method of forming the hole injection layer is broadly divided into a dry process typified by vapor deposition and a wet process typified by spin coating. It is possible to efficiently manufacture a thin film with high resistance. Therefore, at present, where organic EL displays are becoming larger in area, there is a demand for a hole injection layer that can be formed by a wet process, and a technology related to a hole injection material that can be formed by a wet process has been reported. (Patent Document 1).

In view of such circumstances, the present applicant has developed a charge-transporting material that is applicable to various wet processes and that provides a thin film capable of realizing excellent EL device characteristics when applied to the hole injection layer of an organic EL device. In addition, we have developed charge-transporting substances exhibiting solubility in organic solvents used therein and compounds suitable as dopants (see Patent Documents 2 to 6).

WO2008/032616 WO2008/129947 WO2006/025342 WO2010/058777 WO2005/000832 WO2009/096352

The object of the present invention is to provide a fluorinated arylsulfonic acid polymer compound suitable as a dopant substance for use in organic EL devices and the like, in the same manner as the technologies in the above patent documents that have been developed so far.

As a result of intensive studies to solve the above problems, the present inventors have found that a predetermined fluorinated arylsulfonic acid polymer compound having a fluorinated arylene group and an aryl group containing at least one sulfo group or a salt thereof is used as a dopant. The present inventors have found that a thin film having excellent charge transport properties can be realized when used together with a charge transport material as a substance, and have completed the present invention.

That is, the present invention
1. a fluorinated arylsulfonic acid polymer compound comprising a repeating unit represented by the following formula (1);

[wherein Ar _F represents a fluorinated arylene group, X represents O, S, NH, CONH or NHCO, and Ar _S represents an aryl group having at least one SO ₃ R group on the ring (R represents a hydrogen atom or an alkali metal atom.). ]
2. Furthermore, one fluorinated arylsulfonic acid polymer compound containing a repeating unit represented by the following formula (2),

(In the formula, R' represents a monovalent organic group.)
3. 2 fluorinated arylsulfonic acid polymer compound, wherein R′ is a fluorinated aryl group;
4. The fluorinated arylsulfonic acid polymer compound according to any one of 1 to 3, wherein the Ar _F is a perfluoroarylene group;
5. The fluorinated arylsulfonic acid polymer compound of 4, wherein said Ar _F is a tetrafluorophenylene group;
6. The fluorinated arylsulfonic acid polymer compound of any one of 1 to 5, wherein said Ar _S is an aryl group having two or more said SO ₃ R groups on the ring;
7. The fluorinated arylsulfonic acid polymer compound of 6, wherein said Ar _S is a naphthyl group having two or more said SO ₃ R groups on the ring;
8. The fluorinated arylsulfonic acid polymer compound according to any one of 1 to 7, wherein X is O;
9. a dopant substance comprising a fluorinated arylsulfonic acid polymer compound according to any one of 1 to 8;
10. a charge-transporting varnish comprising a charge-transporting substance, nine dopant substances, and a solvent;
11. 10 charge-transporting varnishes, wherein the charge-transporting substance is an arylamine derivative or a thiophene derivative;
12. a charge-transporting thin film obtained from the charge-transporting varnish of 10 or 11;
13. an electronic device comprising 12 charge-transporting thin films;
14. an organic electroluminescence device comprising 12 charge-transporting thin films;
15. Provide 14 organic electroluminescent devices wherein the charge-transporting thin film is a hole-injecting layer or a hole-transporting layer.

When the fluorinated arylsulfonic acid polymer compound of the present invention is used together with a charge-transporting substance as a dopant substance, it provides a charge-transporting thin film with excellent electrical characteristics, and an organic EL device provided with the thin film exhibits excellent characteristics. In particular, it has excellent life performance.
In addition, the thin film containing the fluorinated arylsulfonic acid polymer compound of the present invention has good upper layer coatability.
The fluorinated arylsulfonic acid polymer compound of the present invention having such properties can be suitably used as a dopant substance in the production of thin films for electronic devices such as organic EL devices, particularly thin films for organic EL displays. .

The present invention will be described in more detail below.
[1] Fluorinated Arylsulfonic Acid Polymer Compound The fluorinated arylsulfonic acid polymer compound according to the present invention is characterized by containing a repeating unit represented by the following formula (1).

In Formula (1), Ar _F represents a fluorinated arylene group.
The fluorinated arylene group of Ar _F is not particularly limited as long as at least one hydrogen atom on the arylene group is substituted with a fluorine atom, but at least one of the remaining hydrogen atoms is an electron-withdrawing group other than a sulfo group. is preferably substituted with
Examples of electron-withdrawing groups include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; nitro group; cyano group; acyl group; carboxy group; mentioned.
In particular, the fluorinated arylene group of Ar _F is preferably an arylene group substituted with two or more fluorine atoms, more preferably a perfluoroarylene group.

Although the number of carbon atoms in the arylene group constituting Ar _F is not particularly limited, it preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms. Specific examples thereof include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2, Examples include 7-naphthylene, 4,4'-biphenylylene, anthracenyl group and the like, with phenylene group being preferred, and 1,4-phenylene group being more preferred.
Therefore, Ar _F is preferably a tetrafluorophenylene group, more preferably a 2,3,5,6-tetrafluoro-1,4-phenylene group.

X represents O, S, NH, CONH or NHCO, preferably O or S, more preferably O.

Suitable fluorinated arylsulfonic acid polymer compounds of the present invention include those represented by the following formula (1-1).

(In the formula, n1 represents an integer of 1 to 4.)

More suitable fluorinated arylsulfonic acid polymer compounds include those represented by the following formula (1-2).

(In the formula, n1 represents an integer of 1 to 4.)
More preferred fluorinated arylsulfonic acid polymer compounds include those represented by the following formula (1-3).

Ar _S represents an aryl group having at least one SO ₃ R group on the ring, and R represents a hydrogen atom or an alkali metal atom such as Li, Na, K, etc., preferably a hydrogen atom.
Although the number of carbon atoms in the aryl group constituting Ar _S is not particularly limited, it preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. Specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl groups. Among them, a naphthyl group is preferred, and a 1-naphthyl group is more preferred.
The number of SO ₃ R groups possessed by Ar _S may be 1 or more, preferably 2 to 4, more preferably 2.
Suitable Ar _s include those represented by the following formulas (Ar _s -1) to (Ar _s -6).

(Wherein, R represents the same meaning as above. n represents an integer of 2 to 4.)

(Wherein, R represents the same meaning as above.)

(Wherein, R represents the same meaning as above.)

(Wherein, R represents the same meaning as above.)

The fluorinated arylsulfonic acid polymer compound of the present invention may be a polymer containing only repeating units represented by the above formula (1). Polymers containing repeating units are preferred.

In formula (2), R' represents a monovalent organic group.
Examples of the monovalent organic group include a monovalent hydrocarbon group, a heteroaryl group, a —COOR″ group (R″ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and the like.
Although the number of carbon atoms in the monovalent hydrocarbon group is not particularly limited, it preferably has 1 to 20 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, Alkyl groups such as n-nonyl and n-decyl groups; , aryl groups such as 9-phenanthryl group.

Specific examples of heteroaryl groups include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2 - Thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl groups with 2 to 20 carbon atoms and the like.

Examples of the alkyl group having 1 to 10 carbon atoms for R″ include the same groups as those exemplified above, and among them, an alkyl group having 1 to 5 carbon atoms is preferable.

Some or all of the hydrogen atoms in the monovalent hydrocarbon group, the heteroaryl group, and the alkyl group having 1 to 10 carbon atoms of R″ may be substituted with a substituent. Examples include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, a hydroxyl group, etc. Examples of the halogen atom include the same atoms as those exemplified above.

Among these, in consideration of improving the device characteristics and life characteristics of an organic EL device obtained by using the fluorinated arylsulfonic acid polymer compound of the present invention as a dopant substance, R′ is an aryl substituted with a halogen atom. groups are preferred, fluorinated aryl groups are more preferred, and perfluoroaryl groups are even more preferred.
In particular, a phenyl group substituted with a halogen atom is preferred, a fluorinated phenyl group is more preferred, and a perfluorophenyl group is even more preferred.

When the fluorinated arylsulfonic acid polymer compound of the present invention contains repeating units represented by formula (2), the content ratio of the units of formula (1) to the units of formula (2) is not particularly limited. However, in consideration of improving the device characteristics when used as a dopant substance, the molar ratio of formula (1): formula (2) = 10: 1 to 1: 10 is preferable, and 5: 1 to 1: 5 is more preferred, 3:1 to 1:3 is even more preferred, and 1:1 is even more preferred.

The molecular weight of the fluorinated arylsulfonic acid polymer compound of the present invention is not particularly limited, but from the viewpoint of improving heat resistance and ensuring solubility in solvents, the weight average molecular weight Mw is preferably 1000 to 50000, more preferably 1500 to 10000. Preferably, 2000 to 10000 is even more preferable.
Further, the molecular weight distribution (Mw/Mn) is preferably 1-3, more preferably 1-2.
The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polyethylene oxide as a standard sample.

The fluorinated arylsulfonic acid polymer compound of the present invention is prepared by reacting a monomer represented by the following formula (1A) and optionally a monomer represented by the following formula (2A) in the presence of a solvent and a radical polymerization initiator to form a known radical It can be obtained by polymerizing by a polymerization method.
At this time, two or more monomers represented by formula (1A) may be used in combination, and two or more monomers represented by formula (2A) may be used in combination.

(In the formula, Ar _F , Ar _S , X and R ¹ have the same meanings as above.)

As the radical polymerization initiator, known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used.
A radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane etc.), alkyl peresters (peroxyneodecanoic acid -tert-butyl ester, peroxypivalic acid -tert-butyl ester, peroxy 2-ethylcyclohexanoic acid -tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.), and the like. The radical thermal polymerization initiator may be used singly or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate isoamyl, 4,4′-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4′-tri( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3' ,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(2'-Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4- [p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2′-chlorophenyl)-s- triazine, 1,3-bis(trichloromethyl)-5-(4′-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole, 2,2′-bis(2,4- dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl -1,2′-biimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 3-( 2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4- Cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3′,4,4′-tetra(t-butylperoxycarbonyl) benzophenone, 3,3′,4,4′-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3′-di(methoxycarbonyl)-4,4′-di(t-butylperoxycarbonyl)benzophenone, 3, 4'-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1 -(2-benzoyl)ethanone and the like. A radical photoinitiator may be used individually by 1 type, and may be used in mixture of 2 or more types.

The solvent used for the polymerization reaction is not particularly limited as long as it dissolves the polymer produced. Specific examples include water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, tetra Methylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, Methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol - tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene , amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3 - methoxypropion ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N -dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide.

The polymerization temperature during radical polymerization can be selected from any temperature in the range of 30 to 150°C, preferably in the range of 50 to 100°C.

The monomer of formula (1A) can be produced by a known method disclosed in Patent Document 7, for example, by reacting an arylsulfonate having a hydroxyl group with a fluoroaryl compound in the presence of a base. be able to.

[2] Charge-Transporting Varnish The charge-transporting varnish of the present invention contains a dopant substance comprising the fluorinated arylsulfonic acid polymer compound described above, a charge-transporting substance, and a solvent.
In the present invention, the term "charge-transporting property" has the same meaning as conductivity and the same meaning as hole-transporting property. The charge-transporting varnish may itself have charge-transporting properties, or the solid film obtained therefrom may have charge-transporting properties.

The charge-transporting substance is not particularly limited, and can be appropriately selected from charge-transporting compounds, charge-transporting oligomers, charge-transporting polymers, and the like used in the field of organic EL and the like.
Specific examples thereof include arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, N,N,N',N'-tetraarylbenzidine derivatives; oligothiophene derivatives, thienothiophene derivatives, and thienobenzothiophene. Thiophene derivatives such as derivatives; various charge-transporting compounds such as pyrrole derivatives such as oligopyrrole; charge-transporting polymers such as charge-transporting oligomers, polythiophene derivatives, polyaniline derivatives, and polypyrrole derivatives; Derivatives, arylamine derivatives are preferred.

Further, for example, a charge-transporting compound (low-molecular-weight compound) such as an arylamine compound represented by formula (H2) or (H3) described later or a charge-transporting oligomer is used from the viewpoint of producing a thin film with high flatness. Therefore, it is preferably monodisperse (that is, has a molecular weight distribution of 1). In this case, the molecular weight of the charge-transporting substance is usually about 200 to 9,000 from the viewpoint of preparing a uniform varnish that provides a thin film with high flatness. It is preferably 300 or more, more preferably 400 or more, and from the viewpoint of preparing a uniform varnish that gives a highly flat thin film with good reproducibility, it is preferably 8,000 or less, more preferably 7,000 or less, and 6,000 or less. is more preferred, and 5,000 or less is even more preferred.

Charge-transporting substances include, for example, JP-A-2002-151272, WO2004/105446, WO2005/043962, WO2008/032617, WO2008/032616, Publication No. 2013/042623, WO 2014/141998, WO 2014/185208, WO 2015/050253, WO 2015/137391, WO 2015/137395, WO 2015/146912, International Publication No. 2015/146965, International Publication No. 2016/190326, International Publication No. 2016/136544, International Publication No. 2016/204079 and the like.

In a preferred embodiment, the charge-transporting substance is a polythiophene derivative containing a repeating unit represented by formula (H1) or an amine adduct thereof.

In the formula, R ¹ ' and R ² ' are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or 1 carbon atom. ~40 fluoroalkoxy group, C6-C20 aryloxy group, -O-[Z-O] _h -R ^e , or sulfo group, or R ¹ and R ² are combined to form - O—Y—O—, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfo group, Z is substituted with a halogen atom is an alkylene group having 1 to 40 carbon atoms, p is an integer of 1 or more, R ^e is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 40 carbon atoms may be linear, branched or cyclic, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl. , t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n -hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl, behenyl, triacontyl, tetracontyl groups and the like. In the present invention, an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

The fluoroalkyl group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 40 carbon atoms in which at least one hydrogen atom on the carbon atoms is substituted with a fluorine atom. Examples include fluoromethyl, difluoromethyl, perfluoromethyl, 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, per fluoroethyl, 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, 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-tetrafluoro propyl, 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, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl groups and the like. .

As the alkoxy group having 1 to 40 carbon atoms, the alkyl group therein may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, c -propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy , n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosanyl An oxy group can be mentioned.

The fluoroalkoxy group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkoxy group having 1 to 40 carbon atoms in which at least one hydrogen atom on the carbon atoms is substituted with a fluorine atom. Examples include fluoromethoxy, difluoromethoxy, perfluoromethoxy, 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, per fluoroethoxy, 1-fluoropropoxy, 2-fluoropropoxy, 3-fluoropropoxy, 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-tetrafluoro propoxy, 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, perfluoropropoxy groups and the like.

The alkylene group having 1 to 40 carbon atoms may be linear, branched or cyclic, and specific examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and heptamethylene. , octamethylene, nonamethylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and eicosanylene groups.

Specific examples of aryl groups having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, Examples include 4-phenanthryl and 9-phenanthryl groups, with phenyl, tolyl and naphthyl being preferred.
Specific examples of aryloxy groups having 6 to 20 carbon atoms include phenoxy, anthracenoxy, naphthoxy, phenanthreoxy and fluorenoxy groups.
Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, —O[C(R ^a R ^b ) —C(R ^c R ^d )—O] _h —R ^e , —OR ^f , or —O—Y—O— which is a sulfo group or formed by combining R ¹ and R ² is preferred.
Each of R ^a to R ^d independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Examples include those similar to those listed above.
Among them, R ^a to R ^d are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group.
R ^e is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms or a phenyl group, preferably a hydrogen atom, a methyl group, a propyl group or a butyl group.
h is preferably an integer of 1 to 5, more preferably 1, 2 or 3.

R ^f is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 20 carbon atoms, but a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, A fluoroalkyl group having 1 to 8 carbon atoms or a phenyl group is preferred, and -CH ₂ CF ₃ is more preferred.

R ¹ ' is preferably a hydrogen atom or a sulfo group, more preferably a sulfo group, and R ² ' is preferably an alkoxy group having 1 to 40 carbon atoms or -O-[ZO] _h - R ^e , more preferably -O[C(R ^a R ^b )-C(R ^c R ^d )-O] _h -R ^e or -OR ^f , even more preferably -O[C(R ^a R ^b ) -C( ^RcRd )-O] _h -Re, -O- ^CH2CH2 -O _- ^CH2CH2 _- O _- _CH3 , -O _- _CH2CH2 _- O _- _CH2CH2 --OH or --O--CH ₂ CH ₂ --OH, or --O--Y--O-- formed by combining R ¹ and R ² together.

For example, the polythiophene derivative according to a preferred embodiment of the present invention includes repeating units in which R ¹ ' is a sulfo group and R ² ' is other than a sulfo group, or R ¹ and R ² ' are linked. It contains repeating units that are —O—Y—O— formed by
Preferably, the polythiophene derivative contains a repeating unit in which R ¹ is a sulfo group and R ² ' is an alkoxy group having 1 to 40 carbon atoms or -O-[ZO] _h -R ^e , or a repeating unit in which R ¹ ' and R ² ' are joined to form -O-Y-O-.
More preferably, in the above polythiophene derivative, R ¹ ' is a sulfo group and R ² ' is -O[C(R ^a R ^b )-C(R ^c R ^d )-O] _h -R ^e or -OR ^f .
Even more preferably, in the above polythiophene derivative, R ¹ ' is a sulfo group and R ² ' is -O[C(R ^a R ^b )-C(R ^c R ^d )-O] _h -R ^e or -O-Y-O- formed by combining R ¹ ' and R ² '.
More preferably, in the above polythiophene derivative, R ¹ ' is a sulfo group and R ² ' is -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ --O--CH ₂ CH ₂ --OH or --O--CH ₂ CH ₂ --OH, or R ¹ ' and R ² ' are bonded to each other, and the following formulas (Y1) and ( It contains a repeating unit which is a group represented by Y2).

Preferable specific examples of the above polythiophene derivatives include polythiophenes containing at least one repeating unit represented by the following formulas (H1-1) to (H1-5).

Suitable structures of the above polythiophene derivatives include, for example, polythiophene derivatives having a structure represented by the following formula (H1a). In addition, in the following formula, each unit may be combined randomly or may be combined as a block polymer.

In the formula, a to d represent the molar ratio of each unit, and 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 < a + b ≤ 1, 0 ≤ c < 1, 0 ≤ d < 1, a + b + c + d = 1 Be satisfied.

Additionally, the polythiophene derivatives may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers). As polymers comprising monomer A and monomer B, block copolymers include, for example, AB diblock copolymers, ABA triblock copolymers, and (AB) _k -multiblock copolymers. Polythiophenes contain repeat units derived from other types of monomers such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes such as phenylenes, phenylene vinylenes, and fluorenes. may contain.

The content of the repeating unit represented by formula (H1) in the polythiophene derivative is preferably more than 50 mol%, more preferably 80 mol% or more, and more preferably 90 mol% or more of all repeating units contained in the polythiophene derivative. It is more preferably 95 mol % or more, and most preferably 100 mol %.

The above polythiophene derivative may contain repeating units derived from impurities, depending on the purity of the starting monomers used for polymerization. The term "homopolymer" is intended to mean a polymer containing repeat units derived from one type of monomer, but may contain repeat units derived from impurities. The above polythiophene derivative is preferably a polymer in which basically all repeating units are repeating units represented by the above formula (H1), and is represented by the above formulas (H1-1) to (H1-5). More preferably, the polymer contains at least one repeating unit having

When the polythiophene derivative contains a repeating unit having a sulfo group, the polythiophene derivative has an amine compound added to at least a part of the sulfo group contained therein from the viewpoint of further improving the solubility and dispersibility in an organic solvent. Amine adducts are preferred.

Amine compounds that can be used to form amine adducts include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, n-hexylamine. , n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-penta Monoalkylamine compounds such as decylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosanylamine; aniline, tolylamine, 1-naphthylamine, 2-naphthylamine, 1- anthrylamine, 2-anthrylamine, 9-anthrylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine, 9-phenanthrylamine Primary amine compounds such as monoarylamine compounds such as; N-ethylmethylamine, N-methyl-n-propylamine, N-methylisopropylamine, N-methyl-n-butylamine, N-methyl-s-butylamine, N -methyl-t-butylamine, N-methylisobutylamine, diethylamine, N-ethyl-n-propylamine, N-ethylisopropylamine, N-ethyl-n-butylamine, N-ethyl-s-butylamine, N-ethyl- t-butylamine, dipropylamine, Nn-propylisopropylamine, Nn-propyl-n-butylamine, Nn-propyl-s-butylamine, diisopropylamine, Nn-butylisopropylamine, Nt -butylisopropylamine, di(n-butyl)amine, di(s-butyl)amine, diisobutylamine, aziridine (ethyleneimine), 2-methylaziridine (propyleneimine), 2,2-dimethylaziridine, azetidine (trimethylene imine), 2-methylazetidine, pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 2,2,6, Dialkylamine compounds such as 6-tetramethylpiperidine, hexamethyleneimine, heptamethyleneimine, octamethyleneimine; phenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1,1′-dinaphthylamine, 2,2′-dinaphthylamine, 1,2′-dinaphthylamine, carbazole, 7H-benzo[c] Diarylamine compounds such as carbazole, 11H-benzo[a]carbazole, 7H-dibenzo[c,g]carbazole, 13H-dibenzo[a,i]carbazole; N-methylaniline, N-ethylaniline, Nn-propyl Aniline, N-isopropylaniline, Nn-butylaniline, Ns-butylaniline, N-isobutylaniline, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, Nn-propyl-1- secondary amine compounds such as alkylarylamine compounds such as naphthylamine, indoline, isoindoline, 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroisoquinoline; N,N-dimethylethylamine, N, N-dimethyl-n-propylamine, N,N-dimethylisopropylamine, N,N-dimethyl-n-butylamine, N,N-dimethyl-s-butylamine, N,N-dimethyl-t-butylamine, N,N -dimethylisobutylamine, N,N-diethylmethylamine, N-methyldi(n-propyl)amine, N-methyldiisopropylamine, N-methyldi(n-butyl)amine, N-methyldiisobutylamine, triethylamine, N,N - diethyl-n-butylamine, N,N-diisopropylethylamine, N,N-di(n-butyl)ethylamine, tri(n-propyl)amine, tri(i-propyl)amine, tri(n-butyl)amine, Trialkylamine compounds such as tri(i-butyl)amine, 1-methylacetidine, 1-methylpyrrolidine, and 1-methylpiperidine; triarylamine compounds such as triphenylamine; N-methyldiphenylamine, N-ethyldiphenylamine, Alkyldiarylamine compounds such as 9-methylcarbazole and 9-ethylcarbazole; N,N-diethylaniline, N,N-di(n-propyl)aniline, N,N-di(i-propyl)aniline, N,N -tertiary amine compounds such as dialkylarylamine compounds such as di(n-butyl)aniline; Amine compounds are preferred. More preferred are trialkylamine compounds, and even more preferred is triethylamine.
The amine adduct can be obtained by adding the polythiophene derivative to the amine itself or its solution and stirring well.

In addition, the above polythiophene derivative or its amine adduct may be treated with a reducing agent before use.
In polythiophene derivatives or their amine adducts, some of the repeating units constituting them may have an oxidized chemical structure called a "quinoid structure". The term "quinoid structure" is used for the term "benzenoid structure", the latter being a structure containing an aromatic ring, whereas the former is a structure in which the double bond within the aromatic ring moves out of the ring (the As a result, the aromatic ring disappears), meaning a structure in which two exocyclic double bonds conjugated with other double bonds remaining in the ring are formed. For those skilled in the art, the relationship between these two structures can be readily understood from the relationship between the structures of benzoquinone and hydroquinone. Quinoid structures for repeating units of various conjugated polymers are well known to those skilled in the art. As an example, the quinoid structure corresponding to the repeating unit of the polythiophene derivative containing the repeating unit represented by the above formula (H1) is shown in the following formula (H1').

(Wherein, R ¹ and R ² are as defined in formula (H1) above.)

This quinoid structure is generated by a process in which the polythiophene derivative containing the repeating unit represented by the above formula (H1) undergoes an oxidation reaction by a dopant, a so-called doping reaction, and imparts charge transport properties to the polythiophene derivative. It forms part of a structure called "bipolaron structure". These structures are known. Introduction of a "polaron structure" and/or a "bipolaron structure" is essential in the production of organic EL elements. This is achieved by intentionally causing the doping reaction described above. The reason why the quinoid structure is included in the polythiophene derivative before the doping reaction is that the polythiophene derivative undergoes an unintended oxidation reaction equivalent to the doping reaction during the manufacturing process (especially the sulfonation step therein). This is thought to be due to the

There is a correlation between the amount of the quinoid structure contained in the polythiophene derivative and the solubility and dispersibility of the polythiophene derivative in organic solvents. be. Therefore, the introduction of the quinoid structure after the thin film is formed from the charge-transporting varnish does not cause any problems, but if the quinoid structure is excessively introduced into the polythiophene derivative due to the above unintended oxidation reaction, the charge May interfere with production of transportable varnishes. Polythiophene derivatives are known to vary in solubility and dispersibility in organic solvents. It is considered that it fluctuates according to the difference in the production conditions of each polythiophene derivative.
Therefore, when the polythiophene derivative is subjected to a reduction treatment using a reducing agent, even if the quinoid structure is excessively introduced into the polythiophene derivative, the quinoid structure is reduced by the reduction, and the solubility and dispersibility of the polythiophene derivative in an organic solvent are improved. is improved, it becomes possible to stably produce a good charge-transporting varnish that gives a thin film with excellent uniformity.

The conditions for the reduction treatment are such that the quinoid structure is reduced to appropriately convert to the non-oxidized structure, that is, the benzenoid structure (for example, in the polythiophene derivative containing the repeating unit represented by the above formula (H1), The quinoid structure represented by the above formula (H1′) is not particularly limited as long as it can be converted to the structure represented by the above formula (H1), for example, in the presence of an appropriate solvent or This treatment can be carried out simply by contacting the polythiophene derivative or amine adduct with a reducing agent in the absence thereof.
Such a reducing agent is not particularly limited as long as the reduction is performed properly, but suitable examples include aqueous ammonia, hydrazine, etc., which are readily available on the market.
In addition, the amount of the reducing agent varies depending on the amount of the reducing agent to be used, and cannot be categorically defined. It is 0.1 parts by mass or more and 10 parts by mass or less from the viewpoint of preventing excess reducing agent from remaining.

As an example of a specific reduction treatment method, a polythiophene derivative or an amine adduct is stirred overnight at room temperature in 28% ammonia water. The reduction treatment under such relatively mild conditions sufficiently improves the solubility and dispersibility of the polythiophene derivatives and amine adducts in organic solvents.

When an amine adduct of a polythiophene derivative is used in the charge-transporting varnish of the present invention, the reduction treatment may be performed before or after forming the amine adduct.

As a result of this reduction treatment, the solubility and dispersibility of the polythiophene derivative or its amine adduct in the solvent change, and as a result, the polythiophene derivative or its amine adduct, which was not dissolved in the reaction system at the start of the treatment, will be removed after the treatment is completed. Sometimes dissolved. In such a case, an organic solvent (acetone, isopropyl alcohol, etc. in the case of sulfonated polythiophene) incompatible with the polythiophene derivative or its amine adduct is added to the reaction system to obtain the polythiophene derivative or its amine adduct. The polythiophene derivative or its amine adduct can be recovered by a method such as causing precipitation and filtering.

The weight-average molecular weight of the polythiophene derivative containing the repeating unit represented by formula (H1) or its amine adduct is preferably about 1,000 to 1,000,000, more preferably about 5,000 to 100,000, About 10,000 to about 50,000 is even more preferred. By setting the weight average molecular weight to the lower limit or more, good conductivity can be obtained with good reproducibility, and by setting the weight average molecular weight to the upper limit or less, the solubility in a solvent is improved. In addition, this weight average molecular weight is a polystyrene conversion value by GPC.

The polythiophene derivative or its amine adduct contained in the charge-transporting varnish used in the present invention may be only one type of polythiophene derivative or its amine adduct containing a repeating unit represented by formula (H1), or two types. or more.
In addition, as the polythiophene derivative containing a repeating unit represented by formula (H1), a commercially available product or a product obtained by polymerizing a thiophene derivative or the like as a starting material by a known method may be used. It is also preferable to use those purified by methods such as reprecipitation and ion exchange. By using the purified varnish, the characteristics of the organic EL device provided with the thin film obtained from the charge-transporting varnish of the present invention can be further enhanced.

The sulfonation of conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in US Pat. No. 8,017,241 to Seshadri et al. Sulfonated polythiophenes are also described in WO2008/073149 and WO2016/171935.

At least part of the polythiophene derivative containing the repeating unit represented by formula (H1) or its amine adduct is dissolved in the solvent described below.

In the present invention, when a polythiophene derivative or its amine adduct containing a repeating unit represented by formula (H1) is used, the polythiophene derivative or its amine adduct and other charge-transporting compounds are used as charge-transporting substances. may be used in combination with a charge-transporting substance, but it is preferable that only a polythiophene derivative containing a repeating unit represented by formula (H1) or an amine adduct thereof is contained.

When a polythiophene derivative containing a repeating unit represented by the formula (H1) or an amine adduct thereof is used, the content of the charge-transporting substance in the charge-transporting varnish usually depends on the desired film thickness, viscosity of the varnish, and the like. Taking this into account, it is appropriately determined in the range of 0.05 to 40% by mass, preferably 0.1 to 35% by mass, based on the solid content.

Another preferred embodiment of the charge-transporting substance includes those represented by the following formulas (H2) and (H3).

The aniline derivative represented by formula (H2) may be an oxidized aniline derivative (quinonediimine derivative) having a quinonediimine structure represented by the following formula in its molecule. Examples of the method of oxidizing an aniline derivative to obtain a quinonediimine derivative include the methods described in International Publication Nos. 2008/010474 and 2014/119782.

In formula (H2), R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an alkyl having 1 to 20 carbon atoms which may be substituted with Z ¹ an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ² , - NHY ¹ , -NY ² Y ³ , -OY ⁴ or -SY ⁵ group, wherein Y ¹ to Y ⁵ are each independently alkyl having 1 to 20 carbon atoms optionally substituted by Z ¹ group, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ² wherein Z ¹ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group, a cyano group, an amino group, or Z ³ ; Z ² is a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, which may be substituted with Z ³ . is an alkynyl group, Z ³ is a halogen atom, a nitro group, a cyano group, or an amino group, and k and l are each independently an integer of 1-5.

In formula (H3), R ⁷ to R ¹⁰ are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfo group, a carboxyl group, and Z ¹ an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be , Z ² represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and R ¹¹ to R ¹⁴ are each independently a hydrogen atom, a phenyl group, a naphthyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a furanyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, and a thienyl group (these groups are halogen atoms, nitro groups, cyano group, hydroxyl group, thiol group, phosphate group, sulfo group, carboxy group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms a haloalkyl group having 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms; optionally substituted), or a group represented by the formula (H3a) (provided that at least one of R ¹¹ to R ¹⁴ is a hydrogen atom), m is an integer of 2 to 5 show. Z ¹ and Z ² have the same meanings as above.

In formula (H3a), R ¹⁵ to R ¹⁸ are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphate group, a sulfo group, a carboxyl group, and Z ¹ an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be , Z represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, which may be substituted with Z ² , and R ¹⁹ and R ²⁰ are each independently phenyl, naphthyl, anthryl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, and thienyl groups (these groups are bonded together to form a ring). Halogen atom, nitro group, cyano group, hydroxyl group, thiol group, phosphoric acid group, sulfo group, carboxy group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms , C1-20 alkyl group, C1-20 haloalkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C6-20 aryl group, C7- may be substituted with an aralkyl group having 20 carbon atoms or an acyl group having 1 to 20 carbon atoms). Z ¹ and Z ² have the same meanings as above.

In each formula above, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl. , n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, linear or branched alkyl groups having 1 to 20 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl groups.

Specific examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n- 1-eicosenyl group and the like.

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, 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-pentadecynyl, n-1-eicosinyl groups and the like.

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

Specific examples of aralkyl groups having 7 to 20 carbon atoms include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl and naphthylpropyl groups.

Specific examples of heteroaryl groups having 2 to 20 carbon atoms include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl and 4-isoxazolyl. , 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl groups, etc. is mentioned.

Examples of the haloalkyl group having 1 to 20 carbon atoms include those obtained by substituting at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms with a halogen atom. Alkyl groups are more preferred.
Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2, 2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, nonafluorobutyl, 4,4,4-trifluorobutyl, undecafluoropentyl, 2,2 , 3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2,3, 3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3, 4,4,5,5,6,6,6-nonafluorohexyl group and the like.

Specific examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy , n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy and n-eicosanyloxy groups.

Specific examples of thioalkoxy (alkylthio) groups having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, n- hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio, Examples include n-octadecylthio, n-nonadecylthio, n-eicosanylthio groups and the like.

Specific examples of acyl groups having 1 to 20 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and benzoyl groups.

In formula (H2), R ¹ to R ⁶ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms optionally substituted by Z ¹ , and an alkyl group having 6 to 20 carbon atoms optionally substituted by Z ² . 20 aryl groups, -NHY ¹ , -NY ² Y ³ , -OY ⁴ or -SY ⁵ are preferred, and in this case Y ¹ to Y ⁵ have 1 to 5 carbon atoms optionally substituted by Z ¹ An alkyl group having 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted with Z ² is preferred, and an alkyl group having 1 to 6 carbon atoms which may be substituted with Z ¹ or an aryl group having 1 to 6 carbon atoms which may be substituted with Z ² A phenyl group having a low molecular weight is more preferred, and an alkyl group having 1 to 6 carbon atoms or a phenyl group is even more preferred.
In particular, R ¹ to R ⁶ are more preferably a hydrogen atom, a fluorine atom, a methyl group, a phenyl group or a diphenylamino group (-NY ² Y ³ in which Y ² and Y ³ are phenyl groups), and R ¹ to R ⁴ is a hydrogen atom, and R ⁵ and R ⁶ are more preferably both a hydrogen atom or a diphenylamino group.

In particular, in R ¹ to R ⁶ and Y ¹ to Y ⁵ , Z ¹ is preferably a halogen atom or an aryl group having 6 to 10 carbon atoms optionally substituted by Z ³ , more preferably a fluorine atom or a phenyl group. preferably not present (that is, an unsubstituted group), and Z ² is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms optionally substituted by Z ³ , A fluorine atom or an alkyl group having 1 to 6 carbon atoms is more preferable, and its absence (that is, an unsubstituted group) is even more preferable.
Z ³ is preferably a halogen atom, more preferably a fluorine atom, and more preferably absent (that is, an unsubstituted group).
From the viewpoint of increasing the solubility of the aniline derivative represented by formula (H2), k and l are preferably k+l≦8, more preferably k+l≦5.

In formula (H3), R ⁷ to R ¹⁰ are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, A hydrogen atom is more preferred.
Moreover, both R ¹¹ and R ¹³ are preferably hydrogen atoms in consideration of increasing the solubility of the aniline derivative represented by formula (H3) in solvents and improving the uniformity of the resulting thin film.
In particular, both R ¹¹ and R ¹³ are hydrogen atoms, and R ¹² and R ¹⁴ are each independently a phenyl group (the phenyl group is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, sulfo group, carboxy group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms.), or a group represented by the above formula (H3a), wherein R ¹¹ and R ¹³ are both hydrogen atoms, R ¹² and R ¹⁴ are each independently a phenyl group, or R ^19' and more preferably a group represented by the following formula (H3a') in which both R ^20' are phenyl groups, both R ¹¹ and R ¹³ are hydrogen atoms, and both R ¹² and R ¹⁴ are phenyl groups; is even more preferable.
In addition, m is preferably 2 to 4 in consideration of the availability of the compound, ease of production, cost, etc., and more preferably 2 or 3 in consideration of increasing the solubility in the solvent. Considering the balance among availability, ease of production, production cost, solubility in solvents, transparency of the resulting thin film, etc., 2 is the most suitable.

The aniline derivatives represented by formulas (H2) and (H3) may be commercially available products or those produced by known methods such as those described in the above publications. In any case, it is preferable to use a material purified by recrystallization or vapor deposition before preparing the charge-transporting varnish. By using a purified varnish, the characteristics of an electronic device having a thin film obtained from the varnish can be further enhanced. When purifying by recrystallization, for example, 1,4-dioxane, tetrahydrofuran, or the like can be used as a solvent.

In the present invention, the charge-transporting substance represented by the formulas (H2) and (H3) is one compound selected from the compounds represented by the formulas (H2) and (H3) (i.e., the dispersity of the molecular weight distribution 1) may be used alone, or two or more compounds may be used in combination.

Specific examples of charge-transporting substances represented by formulas (H2) and (H3) that can be suitably used in the present invention include, but are not limited to, the following.

(In the formula, DPA represents a diphenylamino group.)

In the charge-transporting varnish of the present invention, the amount of the fluorinated arylsulfonic acid polymer compound used as the dopant substance is, in terms of the substance amount (mole) ratio, with respect to 1 charge-transporting substance such as a polythiophene derivative or an arylamine derivative: It is preferably about 0.01 to 20.0, more preferably about 0.05 to 15.
The charge-transporting varnish of the present invention may contain known organic dopant substances and inorganic dopant substances in addition to the fluorinated arylsulfonic acid polymer compound, but should not contain other dopant substances. is preferred.

As the solvent used for preparing the charge-transporting varnish of the present invention, a highly polar solvent capable of dissolving the charge-transporting substance, dopant substance, and the like to be used can be used. Also, if desired, less polar solvents may be used because they are more process compatible than highly polar solvents. In the present invention, a low polarity solvent is defined as having a dielectric constant of less than 7 at a frequency of 100 kHz, and a high polarity solvent is defined as having a dielectric constant of 7 or more at a frequency of 100 kHz.

Examples of low-polarity solvents include
Chlorinated solvents such as chloroform and chlorobenzene;
aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene;
Aliphatic alcohol solvents such as 1-octanol, 1-nonanol, 1-decanol;
Ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether;
Esters such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. A solvent etc. are mentioned.

In addition, as a highly polar solvent, for example,
Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone;
Ketone solvents such as ethyl methyl ketone, isophorone, cyclohexanone;
Cyano solvents such as acetonitrile and 3-methoxypropionitrile;
Polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol;
Other than aliphatic alcohols such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol and tetrahydrofurfuryl alcohol A monohydric alcohol solvent of;
Sulfoxide solvents such as dimethylsulfoxide and the like are included.

Furthermore, the charge-transporting varnish of the present invention may contain one or more metal oxide nanoparticles. A nanoparticle means a fine particle having an average primary particle size of the order of nanometers (typically 500 nm or less). Metal oxide nanoparticles refer to metal oxides shaped into nanoparticles.
The primary particle size of the metal oxide nanoparticles is not particularly limited as long as it is nano-sized, but is preferably 2 to 150 nm, more preferably 3 to 100 nm, and even more preferably 5 to 50 nm. The particle size is a measured value using a nitrogen adsorption isotherm by the BET method.

The metals constituting the metal oxide nanoparticles include not only metals in the usual sense, but also semimetals.
Metals in the usual sense include, but are not limited to, tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum ( It is preferable to use one or more selected from the group consisting of Ta) and W (tungsten).
On the other hand, metalloids refer to elements whose chemical and/or physical properties are intermediate between those of metals and nonmetals. A universal definition of metalloids has not been established, but in the present invention, a total of six Let the elements be semimetals. These semimetals may be used alone or in combination of two or more, and may also be used in combination with metals in the usual sense.

In particular, metal oxide nanoparticles include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum It preferably contains one or more metal oxides selected from (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (tungsten). In addition, when the metal is a combination of two or more kinds, the metal oxide may be a mixture of oxides of individual single metals, or a composite oxide containing a plurality of metals.

Specific examples of metal oxides include _B2O3 _, _B2O , _SiO2 , SiO, _GeO2 , _GeO _, _As2O4 , _As2O3 _, _As2O5 , _Sb2O3 , _Sb2 _. O5, TeO2, _SnO2 , _ZrO2 , _Al2O3 _, ZnO and the like, but also _B2O3 _, _B2O , _SiO2 , _SiO , _GeO2 , _GeO , _As2O4 , _As2 _. O3 _, _As2O5 _, _SnO2 , SnO, Sb2O3, _TeO2 , and mixtures thereof _are preferred, with _SiO2 being _more preferred.

The amount of metal oxide nanoparticles is not particularly limited, but from the viewpoint of improving the transparency of the resulting thin film, improving the uniformity of the film, etc., the lower limit is usually 50 in the solid content. % by mass, preferably 60% by mass, more preferably 65% by mass, and the upper limit is usually 95% by mass, preferably 90% by mass.

In particular, in the present invention, it is preferable to use silica sol in which SiO ₂ nanoparticles are dispersed in a dispersion medium as the metal oxide nanoparticles.
The silica sol is not particularly limited, and can be appropriately selected from known silica sols and used.
Commercially available silica sols are usually in the form of dispersions. As commercially available silica sols, _SiO2 nanoparticles are mixed with various solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, acetic acid. Examples include those dispersed in ethyl, toluene, propylene glycol monomethyl ether acetate, and the like.

Specific examples of commercially available silica sols include Snowtex (registered trademark) ST-O, ST-OS, ST-O-40 and ST-OL manufactured by Nissan Chemical Industries, Ltd., and Silidol 20 manufactured by Nippon Chemical Industries Co., Ltd. , 30, 40, etc.; methanol silica sol manufactured by Nissan Chemical Co., Ltd., MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, EG- Examples include, but are not limited to, organosilica sols such as ST.
The solid content concentration of the silica sol is also not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 30% by mass.

The amount of silica sol to be used is appropriately determined in consideration of its concentration so that the final amount of silica contained in the charge-transporting varnish is the amount of the metal oxide nanoparticles described above.

When the resulting thin film is used as a hole injection layer of an organic EL device, the charge-transporting varnish of the present invention is used for the purpose of improving the injection properties into the hole-transporting layer and improving the life characteristics of the device. It may contain a silane compound. Its content is usually about 1 to 30% by mass with respect to the total mass of the charge-transporting substance and the dopant substance.
Examples of organic silane compounds include dialkoxysilane compounds, trialkoxysilane compounds, and tetraalkoxysilane compounds.

The viscosity of the charge-transporting varnish is determined appropriately according to the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa·s at 25°C. In the present invention, the solid content means components other than the solvent contained in the charge-transporting varnish.
The solid content concentration of the charge-transporting varnish is appropriately determined in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc., but is usually 0.1 to 10.0 mass. %, preferably about 0.5 to 5.0% by mass, more preferably about 1.0 to 3.0% by mass, in consideration of improving the coatability of the varnish.

The method for preparing the charge-transporting varnish is not particularly limited. For example, a charge-transporting substance and a dopant substance are dissolved in a highly polar solvent, and then a low-polarity solvent and surface-treated metal oxide nanoparticles are added thereto. or a method of mixing a high-polarity solvent and a low-polarity solvent, dissolving the charge-transporting substance and the dopant substance therein, and then adding the surface-treated metal oxide nanoparticles.

In particular, when preparing a charge-transporting varnish, from the viewpoint of obtaining a flatter thin film with good reproducibility, after dissolving a charge-transporting substance, a dopant substance, etc. in an organic solvent, a submicrometer-order filter, etc. is applied. It is desirable to use it after filtering using it.

Since the charge-transporting varnish described above can be used to easily produce a charge-transporting thin film, it can be suitably used in the production of electronic devices, particularly organic EL devices.
In this case, the charge-transporting thin film can be formed by coating the above-described charge-transporting varnish on the base material and baking it.
The method of applying the varnish is not particularly limited, and includes dipping, spin coating, transfer printing, roll coating, brush coating, inkjet, spraying, slit coating, and the like. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.

In addition, the firing atmosphere of the charge-transporting varnish after application is not particularly limited. However, depending on the type of dopant substance used, a thin film having charge-transporting properties may be obtained with good reproducibility by baking the varnish in an air atmosphere.

The firing temperature is appropriately determined within a range of about 100 to 260° C. in consideration of the use of the obtained thin film, the degree of charge transport property to be imparted to the obtained thin film, the type and boiling point of the solvent, etc. For example, the obtained thin film is is used as a hole injection layer of an organic EL device, the temperature is preferably about 140 to 250°C, more preferably about 145 to 240°C. A thin film with good charge transport properties can also be obtained by calcination.
It should be noted that, during the firing, the temperature may be changed in two or more stages for the purpose of expressing a higher uniform film-forming property or promoting the reaction on the substrate. Suitable equipment such as an oven may be used.

The thickness of the charge-transporting thin film is not particularly limited, but when it is used as a functional layer provided between the anode and the light-emitting layer, such as a hole injection layer, a hole transport layer, and a hole injection transport layer of an organic EL device. , 5 to 300 nm. As a method for changing the film thickness, there are methods such as changing the solid content concentration in the varnish and changing the amount of the solution on the substrate during coating.

[3] Organic EL element When the charge-transporting thin film is applied to an organic EL element, the charge-transporting thin film may be provided between a pair of electrodes constituting the organic EL element.
Typical structures of the organic EL element include (a) to (f) below, but are not limited to these. In the following structure, an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a hole blocking layer or the like may be provided between the light emitting layer and the cathode, if necessary. Further, the hole injection layer, the hole transport layer or the hole injection transport layer may also function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may contain holes (holes). It may also have a function as a block layer or the like. Furthermore, it is also possible to provide arbitrary functional layers between each layer as needed.
(a) anode/hole-injection layer/hole-transport layer/light-emitting layer/electron-transport layer/electron-injection layer/cathode (b) anode/hole-injection layer/hole-transport layer/light-emitting layer/electron-injection-transport layer/ Cathode (c) anode/hole injection transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (d) anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode (e) anode/positive Hole-injection layer/hole-transport layer/light-emitting layer/cathode (f) Anode/hole-injection-transport layer/light-emitting layer/cathode

"Hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between a light-emitting layer and an anode that transport holes from the anode to the light-emitting layer. When only one layer of a hole-transporting material is provided between the light-emitting layer and the anode, it is a "hole-injection-transport layer", and between the light-emitting layer and the anode, When two or more layers of hole-transporting material are provided, the layer close to the anode is the "hole-injecting layer" and the other layer is the "hole-transporting layer". In particular, the hole-injecting (transporting) layer is a thin film that is excellent not only in the ability to accept holes from the anode but also in the ability to inject holes into the hole-transporting (light-emitting) layer.
"Electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between a light-emitting layer and a cathode, and have the function of transporting electrons from the cathode to the light-emitting layer. and when only one layer of the electron-transporting material is provided between the light-emitting layer and the cathode, it is the "electron-injection-transporting layer", and a layer of the electron-transporting material is provided between the light-emitting layer and the cathode When two or more layers are provided, the layer close to the cathode is the "electron injection layer" and the other layer is the "electron transport layer".
A "light-emitting layer" is an organic layer having a light-emitting function, and includes a host material and a dopant material when a doping system is employed. At this time, the host material mainly promotes recombination of electrons and holes and has the function of confining excitons in the light-emitting layer, and the dopant material efficiently emits the excitons obtained by recombination. have a function. In the case of a phosphorescent device, the host material mainly functions to confine excitons generated by the dopant within the light-emitting layer.

The charge-transporting thin film of the present invention can be used as a functional layer provided between an anode and a light-emitting layer in an organic EL device, and is suitable as a hole-injecting layer, a hole-transporting layer, and a hole-injecting-transporting layer. , more suitable as a hole injection layer or a hole transport layer, and even more suitable as a hole injection layer.

Examples of the materials to be used and the manufacturing method for manufacturing an EL device using the charge-transporting varnish of the present invention include, but are not limited to, the following.
An example of a method for producing an OLED device having a hole injection layer made of a thin film obtained from the charge-transporting varnish of the present invention is as follows. The electrodes are preferably cleaned with alcohol, pure water, or the like, or surface-treated with UV ozone treatment, oxygen-plasma treatment, or the like in advance, as long as the electrodes are not adversely affected.
A hole injection layer comprising the charge-transporting thin film of the present invention is formed on the anode substrate by the method described above. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron transport layer/hole blocking layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited. Alternatively, instead of forming the hole-transporting layer and the light-emitting layer by vapor deposition in the method, a composition for forming a hole-transporting layer containing a hole-transporting polymer and a composition for forming a light-emitting layer containing a light-emitting polymer are used. are used to form these layers by a wet process. An electron blocking layer may be provided between the light-emitting layer and the hole-transporting layer, if necessary.

Anode materials include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes composed of metals typified by aluminum and alloys thereof. It is preferable to have undergone a heat treatment. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
Other metals constituting the metal anode include gold, silver, copper, indium, and alloys thereof, but are not limited to these.

Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, N,N'-bis(naphthalene-1-yl)-N,N'-bis (Phenyl)-benzidine (α-NPD), 4,4′,4″-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4′,4″-tris[1 -triarylamines such as naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5″-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2′: oligothiophenes such as 5′,2″-terthiophene (BMA-3T);

Materials for forming the light-emitting layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, (2-hydroxyphenyl)benzo Low-molecular light-emitting materials such as thiazole metal complexes and silol derivatives; poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkyl thiophene), polyvinyl carbazole, etc., mixed with a light-emitting material and an electron transfer material, but not limited to these.
Further, when the light-emitting layer is formed by vapor deposition, it may be co-deposited with a light _- emitting dopant. , naphthacene derivatives such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, and the like, but are not limited thereto.

Materials for forming the electron-transporting layer/hole-blocking layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like.

Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ O ₃ ), lithium fluoride (LiF), and sodium fluoride (NaF). metal fluorides of, but are not limited to:
Cathode materials include, but are not limited to, aluminum, magnesium-silver alloys, aluminum-lithium alloys, and the like.
Materials for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole) iridium.

Examples of hole-transporting polymers 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]-endcapped with polysilsiquinoxane, poly[(9,9- didioctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(p-butylphenyl))diphenylamine)] and the like.

Examples of light-emitting polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene) (MEH- PPV) and other polyphenylene vinylene derivatives, poly(3-alkylthiophene) (PAT) and other polythiophene derivatives, and polyvinylcarbazole (PVCz).

As described above, the charge-transporting varnish of the present invention is suitable for forming a functional layer provided between an anode and a light-emitting layer, such as a hole-injection layer, a hole-transport layer, and a hole-injection-transport layer of an organic EL element. In addition, organic photoelectric conversion elements, organic thin film solar cells, organic perovskite photoelectric conversion elements, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic optical inspectors, organic photoreceptors, organic It can also be used to form charge-transporting thin films in electronic devices such as electric field quenching devices, light-emitting electrochemical cells, quantum dot light-emitting diodes, quantum lasers, organic laser diodes and organic plasmon light-emitting devices.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the used apparatus is as follows.
( ¹ ) 1H-NMR
Bruker nuclear magnetic resonance spectrometer AVANCE III HD500MHz
(2) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) (Condition A) Shimadzu Corporation GPC apparatus Prominence (column: TSKgel α2500 + α3000 + α4000, column temperature: 40 ° C., detector: UV detector (254 nm) ) and RI detector, eluent: MeOH, LiBr (10 mM), column flow rate: 1 mL / min), standard sample: polyethylene oxide (condition B) Tosoh Corporation GPC device HLC-8320GPC (column: Shodex KD-805 , column temperature: 50 ° C., detector: UV detector (254 nm) and RI detector, eluent: DMF, LiBr (30 mM), phosphoric acid (30 mM) THF (1%), column flow rate: 1 mL / min), Standard sample: Cleaning of polyethylene oxide (3) substrate Choshu Sangyo Co., Ltd., substrate cleaning device (low pressure plasma method)
(4) Application of charge-transporting varnish Spin coater MS-A100 manufactured by Mikasa Co., Ltd.
(5) Preparation of organic EL element Multifunctional vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
(6) Measurement of luminance etc. of organic EL element Multi-channel IVL measuring device manufactured by EHC Co., Ltd. (7) Measurement of contact angle of charge-transporting thin film Kyowa Interface Science Co., Ltd. Contact angle meter DropMaster DM-700

[1] Synthesis of raw material compound (monomer) [Synthesis example 1] Synthesis of compound 1

In a three-necked flask, 10.0 g of sodium 1-naphthol-3,6-disulfonate (manufactured by Yamada Chemical Industry Co., Ltd.) and 2,3,4,5,6-pentafluorostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) , the same applies hereinafter) and 5.02 g of sodium carbonate (manufactured by Kanto Kagaku Co., Ltd.) are added, and 100 g of dimethyl sulfoxide (manufactured by Junsei Chemical Co., Ltd.; the same applies hereinafter) are added thereto. and stirred for 30 hours.
After the reaction solution was cooled to room temperature, 200 g of dimethylsulfoxide was added and stirred at room temperature for 3 hours to dissolve the precipitated product. After filtering the resulting solution, the filtrate was decompressed to remove the solvent to obtain a crude product. The resulting crude product was added to 900 g of a mixed solvent (1/1 (w/w)) of 2-propanol (manufactured by Junsei Chemical Co., Ltd.) and ethyl acetate (manufactured by Junsei Chemical Co., Ltd.; and stirred for 1 hour. The precipitated solid was collected by filtration, and the resulting solid was dried under reduced pressure to obtain compound 1 (yield: 11.3 g, yield: 76%).
The ¹ H-NMR spectrum of compound 1 is shown below.

¹ H-NMR (500 MHz, DMSO): δ 5.87 (d, J=11.5 Hz, 1 H), 6.12 (d, J=18.0 Hz, 1 H), 6.72 (dd, J=18. 0, 11.5Hz, 1H), 6.99 (s, 1H), 7.88 (dd, J = 8.5, 1.5Hz, 1H), 7.97 (s, 1H), 8.21 ( s, 1H), 8.25 (d, J=8.5Hz, 1H).

[2] Synthesis of polymer [Example 1-1] Synthesis of polymer A

In a two-necked flask, 2.0 g of the compound 1 obtained in Synthesis Example 1 and 0.043 g of ammonium persulfate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added, and 10 g of degassed ion-exchanged water was added thereto. The mixture was stirred at 65° C. for 20 hours in an atmosphere. After the reaction solution was cooled to room temperature, it was added dropwise to 150 g of methanol (manufactured by Junsei Chemical Co., Ltd., the same shall apply hereinafter) and stirred at room temperature for 1 hour. The precipitated solid was recovered by filtration, and the recovered solid was dried under reduced pressure. After adding and dissolving 5.5 g of ion-exchanged water to the obtained dried product, 20 mL of a cation exchange resin (Dowex Monosphere 650C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) was added and left at room temperature for 20 minutes. After stirring, it was filtered. The filtrate was decompressed to remove the solvent to give polymer A (0.95 g).
Mw=2340, Mn=2270, Mw/Mn=1.03 (GPC, condition A)

[Example 1-2] Synthesis of polymer B

In a two-necked flask, 2.0 g of Compound 1 obtained in Synthesis Example 1, 0.74 g of 2,3,4,5,6-pentafluorostyrene, AIBN (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 0.2 g of AIBN were placed. Then, 20 g of degassed dimethylformamide (manufactured by Junsei Chemical Co., Ltd.) was added thereto, and the mixture was stirred at 80° C. for 8 hours in a nitrogen atmosphere. After the reaction solution was cooled to room temperature, it was added to 200 g of a mixed solvent of methanol and ethyl acetate (1/3 (w/w)) and stirred at room temperature for 1 hour. The precipitated solid was recovered by filtration, and the recovered solid was dried under reduced pressure. After adding and dissolving 10 g of ion-exchanged water to the resulting dried product, 20 mL of a cation exchange resin (Dowex Monosphere 650C) was added, and the mixture was stirred at room temperature for 20 minutes and then filtered. The filtrate was decompressed to remove the solvent to give polymer B (1.59 g).
Mw=5150, Mn=3550, Mw/Mn=1.23 (GPC, condition B)

[3] Synthesis of Comparative Compound [Comparative Example 1-1] Synthesis of Compound 2

To 1.3 g of the compound 1 obtained in Synthesis Example 1, 56.5 g of ion-exchanged water was added and dissolved, and by column chromatography using 150 mL of a cation exchange resin (Dowex Monosphere 650C) and ion-exchanged water as an extraction solvent, Ion exchange was performed. Fractions around pH 1 were dried under reduced pressure to give compound 2 (10.24 g, 98.8% yield).

[4] Preparation of composition for preparing charge-transporting varnish [Preparation Example 1-1]
To 0.5 g of an amine adduct of a polythiophene derivative, which is a polymer containing a repeating unit represented by formula (H1a), synthesized sequentially according to the methods described in U.S. Pat. No. 8,017,241 and WO 2016/171935, Add 8.75 g of 1,3-dimethyl-2-imidazolidinone (manufactured by Kanto Kagaku Co., Ltd., the same shall apply hereinafter) and 0.75 g of n-butylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and add 80 g using a hot stirrer. C. for 3 hours to obtain a solution in which polythiophene was dissolved.

[Preparation Example 1-2]
100 g of ST-OS (manufactured by Nissan Chemical Co., Ltd.), which is a water-dispersed silica sol, and dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd., hereinafter the same) are placed in an eggplant flask, and the ST-OS is evaporated using an evaporator. The water contained in the solution was solvent-substituted with dipropylene glycol monomethyl ether to obtain a dipropylene glycol monomethyl ether-dispersed silica sol (silica concentration: 9.43%).

[Preparation Example 1-3]
A diethylene glycol (manufactured by Kanto Kagaku Co., Ltd., hereinafter the same) solution containing 5.0% by mass of the polymer A obtained in Example 1-1 was prepared. The above solution was prepared by stirring at 50° C. for 1 hour using a hot stirrer.

[Preparation Example 1-4]
A 1,3-dimethyl-2-imidazolidinone solution containing 10% by mass of Polymer B obtained in Example 1-2 was prepared. The above solution was prepared by stirring at 50° C. for 1 hour using a hot stirrer.

[Preparation Example 1-5]
A commercially available D-66-20BS aqueous solution (manufactured by Solvay, AQUIVION), which is a copolymer of tetrafluoroethylene and fluorinated sulfone vinyl ether, was distilled with an evaporator to remove water, and then dried at 80°C with a vacuum dryer. ℃ for 1 hour to obtain a powder of D-66-20BS. After that, a 1,3-dimethyl-2-imidazolidinone solution containing 5% by mass of D-66-20BS was prepared. The above solution was prepared by stirring at 80° C. for 2 hours using a hot stirrer.

[Preparation Example 1-6]
A diethylene glycol solution containing 10% by mass of Compound 2 obtained in Comparative Example 1-1 was prepared. The above solution was prepared by stirring at 50° C. for 1 hour using a hot stirrer.

[5] Preparation of charge-transporting varnish [Example 2-1]
1.723 g of 1,3-dimethyl-2-imidazolidinone, 3.537 g of diethylene glycol and 2.927 g of dipropylene glycol monomethyl ether were added to the sample tube and stirred at room temperature for 30 minutes using a stirrer. After that, 0.42 g of the diethylene glycol solution of polymer A obtained in Preparation Example 1-3 was added and stirred at room temperature for 30 minutes using a stirrer. Then, 0.28 g of the solution obtained in Preparation Example 1-1 was added and intermittently stirred at room temperature for 30 minutes. Further, 1.113 g of the dipropylene glycol monomethyl ether-dispersed silica sol obtained in Preparation Example 1-2 was added and stirred at room temperature for 30 minutes. The resulting mixed solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting varnish.

[Example 2-2]
2.524 g of 1,3-dimethyl-2-imidazolidinone, 3.451 g of dipropylene glycol and 2.443 g of dipropylene glycol monomethyl ether were added to the sample tube and stirred at room temperature for 30 minutes using a stirrer. After that, 0.21 g of the 1,3-dimethyl-2-imidazolidinone solution of polymer B obtained in Preparation Example 1-3 was added, and stirred at room temperature for 30 minutes using a stirrer. Then, 0.28 g of the solution obtained in Preparation Example 1-1 was added and stirred at room temperature for 30 minutes. Further, 1.113 g of the dipropylene glycol monomethyl ether-dispersed silica sol obtained in Preparation Example 1-2 was added and stirred at room temperature for 30 minutes. The resulting mixed solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting varnish.

[Comparative Example 2-1]
2.308 g of 1,3-dimethyl-2-imidazolidinone, 3.444 g of dipropylene glycol and 2.435 g of dipropylene glycol monomethyl ether were added to the sample tube and stirred at room temperature for 30 minutes using a stirrer. After that, 0.42 g of the 1,3-dimethyl-2-imidazolidinone solution of D-66-20BS obtained in Preparation Example 1-5 was added and stirred at room temperature for 30 minutes using a stirrer. Then, 0.28 g of the solution obtained in Preparation Example 1-1 was added and stirred at room temperature for 30 minutes. Further, 1.113 g of the dipropylene glycol monomethyl ether-dispersed silica sol obtained in Preparation Example 1-2 was added and stirred at room temperature for 30 minutes. The resulting mixed solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting varnish.

[Comparative Example 2-2]
1.727 g of 1,3-dimethyl-2-imidazolidinone, 3.755 g of diethylene glycol and 2.936 g of dipropylene glycol monomethyl ether were added to the sample tube and stirred at room temperature for 30 minutes using a stirrer. After that, 0.21 g of the diethylene glycol solution of compound 2 obtained in Preparation Example 1-6 was added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 0.28 g of the solution obtained in Preparation Example 1-1 was added and stirred at room temperature for 30 minutes. Further, 1.113 g of the dipropylene glycol monomethyl ether-dispersed silica sol obtained in Preparation Example 1-2 was added and stirred at room temperature for 30 minutes. The resulting mixed solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting varnish.

[6] Evaluation of Upper Layer Coatability The charge-transporting varnishes obtained in Examples 2-1, 2-2, and Comparative Examples 2-1 and 2-2 were coated on an ITO substrate using a spin coater. After coating, the coating was dried at 120° C. for 1 minute in the atmosphere. Next, the dried ITO substrate was baked at 230° C. for 15 minutes in an air atmosphere to form a uniform charge-transporting thin film of 30 nm on the ITO substrate. As the ITO substrate, a glass substrate of 50 mm × 50 mm × 0.7 _t , on which an ITO film with a thickness of 50 nm is uniformly formed, was used. remove impurities from above.
1 μL of anisole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dropped on each of the obtained thin films, and the contact angle was measured. Table 1 shows the results.

All of the charge-transporting thin films obtained in Examples 2-1, 2-2, and Comparative Example 2-2 had a contact angle of anisole of less than 5° and had good wettability. The difference in the solids of the charge-transporting varnishes of Examples 2-1, 2-2, Comparative Examples 2-1 and 2-2 is the type of the fluorinated sulfonic acid compound. and the charge-transporting thin film using compound 2, it was confirmed that the wettability of the upper layer was excellent.

[7] Preparation and property evaluation of organic EL device [Example 3-1]
The varnish obtained in Example 2-1 was applied to the same ITO substrate as described above from which impurities had been removed using a spin coater, and then dried in the air at 120° C. for 1 minute. Next, the dried ITO substrate was baked at 230° C. for 15 minutes in an air atmosphere to form a uniform thin film of 30 nm on the ITO substrate.
Next, α-NPD(N,N'-di(1-naphthyl)-N, ^N'- diphenylbenzidine) was deposited at a rate of 0.2 nm/second to a thickness of 30 nm. Next, an electronic block material HTEB-01 manufactured by Kanto Kagaku Co., Ltd. was deposited to a thickness of 10 nm. Next, a light-emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and a light-emitting layer dopant material Ir(ppy) ₃ were co-evaporated. In the co-evaporation, the deposition rate was controlled so that the concentration of Ir(ppy) ₃ was 6%, and the layers were deposited to a thickness of 40 nm. Then, thin films of Alq ₃ , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL device. 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, respectively, and the film thicknesses were 20 nm, 0.5 nm and 80 nm, respectively.

In order to prevent deterioration of characteristics due to the influence of oxygen, water, etc. in the air, the characteristics of the organic EL element were evaluated after being sealed with a sealing substrate. Sealing was performed by the following procedure.
In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of −76° C. or less, the organic EL element was placed between the sealing substrates, and the sealing substrates were coated with an adhesive (manufactured by MORESCO Co., Ltd., MORESCO Moisture Cut WB90US (P)). pasted together by At this time, a water capturing agent (HD-071010W-40 manufactured by Dainic Co., Ltd.) was placed in the sealing substrate together with the organic EL element. The bonded sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm ² ) and then annealed at 80° C. for 1 hour to cure the adhesive.

[Example 3-2]
An organic EL device was obtained by repeating the procedure of Example 3-1 except that the varnish obtained in Example 2-2 was used instead of the varnish obtained in Example 2-1.

[Comparative Example 3-1]
An organic EL device was obtained by repeating the procedure of Example 3-1 except that the varnish obtained in Comparative Example 2-2 was used in place of the varnish obtained in Example 2-1.

Driving voltage, current density, luminous efficiency, and luminance half reduction when driven at a luminance of 10,000 cd/m ² for each of the devices obtained in Example 3-1, Example 3-2, and Comparative Example 3-1 The period (the time required for the initial luminance of 10,000 cd/m ² to reach half) was measured. Table 2 shows the results.

As shown in Table 1, the organic EL devices produced in Examples 3-1, 3-2, and Comparative Example 3-1 all exhibit good initial characteristics. It can be seen that the device of Example 3-1 and the device of Example 3-2 using polymer B exhibit better life characteristics than the device of Comparative Example 3-1 using compound 2. It is presumed that this is because the heat resistance of the compound was improved due to the increase in molecular weight due to the polymerization.
It is also found that the element of Example 3-2 using polymer B, which is a copolymer of compound 1 and perfluorostyrene, is excellent in element efficiency and life. It is presumed that this is because the ratio of fluorine atoms in the polymer was increased, and the effect of modifying the surface of the charge-transporting thin film was enhanced.

Claims

A fluorinated arylsulfonic acid polymer compound comprising a repeating unit represented by the following formula (1).

[wherein Ar F represents a fluorinated arylene group, X represents O, S, NH, CONH or NHCO, and Ar S represents an aryl group having at least one SO 3 R group on the ring (R represents a hydrogen atom or an alkali metal atom.). ]
2. The fluorinated arylsulfonic acid polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (2).

(In the formula, R' represents a monovalent organic group.)
The fluorinated arylsulfonic acid polymer compound according to claim 2, wherein said R' is a fluorinated aryl group.
The fluorinated arylsulfonic acid polymer compound according to any one of claims 1 to 3, wherein said Ar F is a perfluoroarylene group.
5. The fluorinated arylsulfonic acid polymer compound of claim 4, wherein said Ar F is a tetrafluorophenylene group.
The fluorinated arylsulfonic acid polymer compound according to any one of claims 1 to 5, wherein said Ar S is an aryl group having two or more said SO 3 R groups on the ring.
7. The fluorinated arylsulfonic acid polymer compound of claim 6, wherein said ArS is a naphthyl group having two or more said SO3R groups on the ring.
The fluorinated arylsulfonic acid polymer compound according to any one of claims 1 to 7, wherein said X is O.
A dopant substance comprising the fluorinated arylsulfonic acid polymer compound according to any one of claims 1 to 8.
A charge-transporting varnish containing a charge-transporting substance, the dopant substance according to claim 9, and a solvent.
The charge-transporting varnish according to claim 10, wherein the charge-transporting substance is an arylamine derivative or a thiophene derivative.
A charge-transporting thin film obtained from the charge-transporting varnish according to claim 10 or 11.
An electronic device comprising the charge-transporting thin film according to claim 12.
An organic electroluminescence device comprising the charge-transporting thin film according to claim 12.
The organic electroluminescence device according to claim 14, wherein the charge-transporting thin film is a hole injection layer or a hole transport layer.