CN117677641A - Fluoroaryl sulfonic acid polymer compound and use thereof - Google Patents

Fluoroaryl sulfonic acid polymer compound and use thereof Download PDF

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CN117677641A
CN117677641A CN202280050329.1A CN202280050329A CN117677641A CN 117677641 A CN117677641 A CN 117677641A CN 202280050329 A CN202280050329 A CN 202280050329A CN 117677641 A CN117677641 A CN 117677641A
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group
charge
carbon atoms
transporting
sulfonic acid
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仓田阳介
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Nissan Chemical Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE

Abstract

A fluoroaryl sulfonic acid polymer compound containing a repeating unit represented by the following formula (1) is suitable as a dopant substance for use in an organic EL element or the like. [ formula, ar F Represents a fluoroalkylene group, X represents O, S, NH, CONH or NHCO, ar S Meaning having at least one SO on the ring 3 Aryl radicals of radicals R (R represents a hydrogen atom orAn alkali metal atom. ).]

Description

Fluoroaryl sulfonic acid polymer compound and use thereof
Technical Field
The present invention relates to fluoroaryl sulfonic acid polymer compounds and their use.
Background
In an organic electroluminescence (hereinafter referred to as organic EL) element, an organic functional film containing an organic compound is used as a light-emitting layer or a charge injection layer. In particular, the hole injection layer plays an important role in achieving low-voltage driving and high luminance of the organic EL element by taking charge transfer between the anode and the hole transport layer or the light-emitting layer.
Methods for forming the hole injection layer are roughly classified into a dry method typified by a vapor deposition method and a wet method typified by a spin coating method, and if these methods are compared, the wet method can produce a thin film having high flatness over a large area with high efficiency. Accordingly, in the current development of large-area organic EL displays, a hole injection layer that can be formed by a wet process is desired, and a technique related to a hole injection material that can be formed by a wet process has been reported (patent document 1).
In view of such practical situations, the present applicant has developed a charge transporting material which can be applied to various wet methods and which can form a thin film capable of achieving excellent EL element characteristics when applied to a hole injection layer of an organic EL element, and a compound which is suitable as a charge transporting material and a dopant which exhibit solubility to an organic solvent used therein (see patent documents 2 to 6).
Prior art literature
Patent literature
Patent document 1: international publication No. 2008/032616
Patent document 2: international publication No. 2008/129947
Patent document 3: international publication No. 2006/025342
Patent document 4: international publication No. 2010/058777
Patent document 5: international publication No. 2005/000832
Patent document 6: international publication No. 2009/096352
Disclosure of Invention
Problems to be solved by the invention
The present invention also aims to provide a fluorinated arylsulfonic acid polymer compound suitable as a dopant substance for use in an organic EL element or the like, similarly to the technology of the patent document developed so far.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, found that: the present invention has been completed by achieving a film excellent in charge transport properties when a predetermined fluoroaryl sulfonic acid polymer compound having a fluoroarylene group and an aryl group containing at least one sulfo group or a salt thereof is used as a dopant substance together with a charge transport substance.
Namely, the present invention provides:
1. a fluoroaryl sulfonic acid polymer compound comprising a repeating unit represented by the following formula (1),
[ chemical 1]
Wherein Ar is F Represents a fluoroalkylene group, X represents O, S, NH, CONH or NHCO, ar S Meaning having at least one SO on the ring 3 Aryl of the R group, R represents a hydrogen atom or an alkali metal atom.
2. The fluoroaryl sulfonic acid polymer compound according to 1, further comprising a repeating unit represented by the following formula (2),
[ chemical 2]
Wherein R' represents a 1-valent organic group.
3. The fluoroaryl sulfonic acid polymer compound of claim 2, wherein R' is a fluoroaryl group.
4. The fluoroaryl sulfonic acid polymer compound according to any one of claims 1 to 3, wherein the Ar F Is a perfluoroalkylene group.
5. The fluoroaryl sulfonic acid polymer compound of claim 4, wherein the Ar F Is tetrafluorophenylene.
6. The fluoroaryl sulfonic acid of any one of claims 1 to 5An acid polymer compound, wherein Ar is S To have more than 2 of said SOs on the ring 3 Aryl of R group.
7. The fluoroaryl sulfonic acid polymer compound of claim 6, wherein the Ar S To have more than 2 of said SOs on the ring 3 Naphthyl of R group.
8. The fluoroaryl sulfonic acid polymer compound according to any one of claims 1 to 7, wherein X is O.
9. A dopant substance composed of the fluoroaryl sulfonic acid polymer compound according to any one of 1 to 8.
10. A charge-transporting varnish comprising: a charge transporting material, a dopant material according to 9, and a solvent.
11. The charge-transporting varnish of claim 10, wherein the charge-transporting substance is an arylamine derivative or a thiophene derivative.
12. A charge-transporting film obtained from the charge-transporting varnish according to 10 or 11.
13. An electronic component comprising the charge transporting film according to 12.
14. An organic electroluminescent element comprising the charge transporting thin film according to 12.
15. The organic electroluminescent element according to claim 14, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.
ADVANTAGEOUS EFFECTS OF INVENTION
When the fluoroaryl sulfonic acid polymer compound of the present invention is used together with a charge transporting substance as a dopant substance, a charge transporting thin film having excellent electrical characteristics is formed, and an organic EL element having the thin film exhibits excellent characteristics and particularly has excellent lifetime performance.
In addition, the film containing the fluoroaryl sulfonic acid polymer compound of the present invention has good coating properties on the upper layer.
The fluoroaryl sulfonic acid polymer compound of the present invention having such characteristics can be suitably used as a dopant substance in the production of a thin film for electronic devices such as an organic EL device, in particular, a thin film for organic EL display.
Detailed Description
The present invention will be described in more detail below.
[1] Fluoroaryl sulfonic acid polymer compound
The fluoroaryl sulfonic acid polymer compound according to the present invention is characterized by comprising a repeating unit represented by the following formula (1).
[ chemical 3]
In the formula (1), ar F Represents a fluoroalkylene group.
Ar F The fluorinated arylene group of (2) is not particularly limited as long as at least one hydrogen atom on the arylene group is substituted with a fluorine atom, and it is preferable that at least one of the remaining hydrogen atoms is substituted with an electron withdrawing group other than a sulfo group.
Examples of the electron-withdrawing group include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; a nitro group; cyano group; an acyl group; a carboxyl group; a carboxylic acid ester group; acyl groups such as formyl and acetyl.
In particular Ar F The fluorinated arylene group of (2) is preferably an arylene group substituted with 2 or more fluorine atoms, and more preferably a perfluoroalkylene group.
To form Ar F The number of carbon atoms of the arylene group is not particularly limited, but is preferably 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, 7-naphthylene, 4' -biphenylene, anthracenyl and the like, preferably phenylene, more preferably 1, 4-phenylene.
Thus, as Ar F Tetrafluorophenylene is preferred, and 2,3,5, 6-tetrafluoro-1, 4-phenylene is more preferred.
X represents O, S, NH, CONH or NHCO, preferably O, S, more preferably O.
Examples of suitable fluoroaryl sulfonic acid polymer compounds of the present invention include compounds represented by the following formula (1-1).
[ chemical 4]
(wherein n1 represents an integer of 1 to 4.)
More preferable fluoroaryl sulfonic acid polymer compounds include compounds represented by the following formula (1-2).
[ chemical 5]
(wherein n1 represents an integer of 1 to 4.)
More preferable fluoroaryl sulfonic acid polymer compounds include compounds represented by the following formulas (1-3).
[ chemical 6]
Ar S Meaning having at least one SO on the ring 3 Aryl of R group, R represents a hydrogen atom or an alkali metal atom such as Li, na, K, etc., preferably a hydrogen atom.
To form Ar S The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still 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, 9-phenanthryl and the like, preferably naphthyl, more preferably 1-naphthyl.
In addition, ar S Having SO 3 The number of R groups is not less than 1, preferably 2 to 4, more preferably 2.
As a suitable Ar S Can be used forThe compound represented by the following formula (Ar) S -1)～(Ar S -6) a group as shown.
[ chemical 7]
( Wherein R represents the same as defined above. n represents an integer of 2 to 4. )
[ chemical 8]
(wherein R represents the same meaning as described above.)
[ chemical 9]
(wherein R represents the same meaning as described above.)
[ chemical 10]
(wherein R represents the same meaning as described above.)
The fluoroaryl sulfonic acid polymer compound of the present invention may be a polymer comprising only the repeating unit represented by the above formula (1), and preferably further comprises the repeating unit represented by the following formula (2) in view of improving the solubility in an organic solvent.
[ chemical 11]
In formula (2), R' represents a 1-valent organic group.
Examples of the 1-valent organic group include a 1-valent hydrocarbon group, a heteroaryl group, and a-COOR "group (R" represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
The number of carbon atoms of the 1-valent hydrocarbon group is not particularly limited, but is preferably 1 to 20 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.
Specific examples of the heteroaryl group include heteroaryl groups having 2 to 20 carbon atoms such as 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl and the like.
Examples of the alkyl group having 1 to 10 carbon atoms of R "include the same groups as those exemplified above, and among them, alkyl groups having 1 to 5 carbon atoms are preferable.
In the alkyl group having 1 to 10 carbon atoms of the above-mentioned 1-valent hydrocarbon group, heteroaryl group, and R ", a part or all of hydrogen atoms may be substituted with a substituent. Examples of such substituents include halogen atoms, cyano groups, nitro groups, carboxyl groups, sulfo groups, hydroxyl groups, and the like. The halogen atom may be the same as the above-exemplified atom.
Of these, R 'is considered to improve the element characteristics and lifetime characteristics of an organic EL element obtained by using the fluoroaryl sulfonic acid polymer compound of the present invention as a dopant substance'
Aryl substituted with a halogen atom is preferred, fluorinated aryl is more preferred, and perfluorinated aryl is still more preferred.
In particular, phenyl substituted with a halogen atom is preferable, fluorophenyl is more preferable, and perfluorophenyl is still more preferable.
In the case where the fluoroaryl sulfonic acid polymer compound of the present invention contains a repeating unit represented by formula (2), the content ratio of the unit of formula (1) to the unit of formula (2) is not particularly limited, and if considering improvement of the element characteristics when used as a dopant substance, the formula (1) is preferable in terms of molar ratio: formula (2) =10: 1 to 1:10, more preferably 5:1 to 1:5, further preferably 3:1 to 1:3, more preferably 1:1.
The molecular weight of the fluoroaryl sulfonic acid polymer compound of the present invention is not particularly limited, but from the viewpoints of improving the heat resistance and securing the solubility in a solvent, the weight average molecular weight Mw is preferably 1000 to 50000, more preferably 1500 to 10000, and still more preferably 2000 to 10000.
The molecular weight distribution (Mw/Mn) is preferably 1 to 3, more preferably 1 to 2.
The weight average molecular weight is a measurement value obtained by Gel Permeation Chromatography (GPC) using polyethylene oxide as a standard sample.
The fluorinated arylsulfonic acid polymer compound of the present invention can be obtained by polymerizing a monomer represented by the following formula (1A) and a monomer represented by the following formula (2A) which is used if necessary, in the presence of a solvent and a radical polymerization initiator by a known radical polymerization method.
In this case, 2 or more monomers represented by the formula (1A) may be used in combination, and 2 or more monomers represented by the formula (2A) may be used in combination.
[ chemical 12]
(wherein Ar is F 、Ar S X and R 1 The same meaning as described above is indicated. )
As the radical polymerization initiator, a known compound such as a radical thermal polymerization initiator or a radical photopolymerization initiator can be used.
The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. 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 (hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl cyclohexane, etc.), alkyl peresters (t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxy-2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile, etc.), and the like. The radical thermal polymerization initiator may be used alone in an amount of 1 or in an amount of 2 or more.
The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by irradiation with light. As such a radical photopolymerization initiator, examples thereof include benzophenone, michaelketone, 4' -bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4-diethyl thioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-2-methyl-4 ' -isopropyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2-diethoxy acetophenone, 2-dimethoxy-2-phenyl acetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4' -di (t-butylperoxycarbonyl) benzophenone, 3,4' -tri (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine 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 ' -pentyloxylstyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl) ] -2, 6-bis (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) benzothiazole, 2-mercaptobenzothiazole, 3' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole, 2' -bis (2, 4' -ethoxyphenyl) -2 ' -bisimidazole, 4-dichlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4', 5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4, 6-trichlorophenyl) -4,4', 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-cyclopenta-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3',4,4' -tetra (t-butylperoxycarbonyl) benzophenone, 3',4' -tetra (t-hexylperoxycarbonyl) benzophenone, 3' -di (methoxycarbonyl) -4,4' -di (t-butylperoxycarbonyl) benzophenone, 3,4' -di (methoxycarbonyl) -4,3' -di (t-butylperoxycarbonyl) benzophenone, 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. The radical photopolymerization initiator may be used alone or in combination of 1 or more than 2 kinds.
The solvent used in the polymerization reaction is not particularly limited as long as the polymer to be produced is dissolved. As specific examples thereof, water may be cited; n, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-epsilon-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentanone, methylnonone, methylethyl ketone, methylisopentyl ketone, methylisopropyl ketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate 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, ethylisobutyl 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, organic solvents such as ethyl acetate, N-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide.
The polymerization temperature in the radical polymerization can be any temperature selected from 30 to 150 ℃, and is preferably in the range of 50 to 100 ℃.
The monomer of formula (1A) can be produced by a known method disclosed in patent document 7 or the like, and can be obtained, for example, by reacting an aryl sulfonate having a hydroxyl group with a fluoroaryl compound in the presence of a base.
[2] Charge-transporting varnish
The charge-transporting varnish of the present invention comprises a dopant substance composed of the above-mentioned fluoroaryl sulfonic acid polymer compound, a charge-transporting substance, and a solvent.
In the present invention, charge transport property is synonymous with conductivity and hole transport property. The charge-transporting varnish may be a substance having charge-transporting property itself or a solid film obtained therefrom.
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 '-diarylbenzidine derivatives, and N, N' -tetraarylbenzidine derivatives; thiophene derivatives such as oligothiophene derivatives, thienothiophene derivatives, thienobenzothiophene derivatives, and the like; various charge-transporting compounds such as pyrrole derivatives such as oligopyrroles, charge-transporting oligomers, polythiophene derivatives, polyaniline derivatives, charge-transporting polymers such as polypyrrole derivatives, and the like, and among these, polythiophene derivatives and arylamine derivatives are preferable.
In addition, for example, from the viewpoint of producing a film having high flatness, a charge transporting compound (low molecular compound) or a charge transporting oligomer such as an arylamine compound represented by the formula (H2) or (H3) described later is preferably monodisperse (i.e., has a molecular weight distribution of 1). In this case, the molecular weight of the charge transporting substance is usually about 200 to 9000 from the viewpoint of producing a uniform varnish that forms a thin film with high flatness, preferably 300 or more, more preferably 400 or more from the viewpoint of obtaining a thin film with more excellent charge transporting property, and preferably 8000 or less, more preferably 7000 or less, more preferably 6000 or less, more preferably 5000 or less from the viewpoint of producing a uniform varnish that forms a thin film with high flatness with better reproducibility.
Examples of the charge-transporting substance include substances disclosed in Japanese patent application laid-open No. 2002-151272, international publication No. 2004/105446, international publication No. 2005/043962, international publication No. 2008/032517, international publication No. 2008/032516, international publication No. 2013/042623, international publication No. 2014/141998, international publication No. 2014/185208, international publication No. 2015/050253, international publication No. 2015/137391, international publication No. 2015/137395, international publication No. 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 or an amine adduct thereof including a repeating unit represented by formula (H1).
[ chemical 13]
Wherein R is 1’ And R is 2’ Each independently is 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, a fluoroalkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, -O- [ Z-O ]]h-R e Or sulfo, or R 1 And R is 2 The bond-formed-O-Y-O-, wherein 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 an alkylene group having 1 to 40 carbon atoms which may be substituted with a halogen atom, 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 any of a straight-chain, branched-chain, and cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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-eicosyl, docosyl, triacontyl, and forty-alkyl groups. In the present invention, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
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 replaced with a fluorine atom, examples thereof include fluoromethyl, difluoromethyl, perfluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1, 2-difluoroethyl, 1-difluoroethyl, 2-difluoroethyl, 1, 2-trifluoroethyl, 1, 2-trifluoroethyl, 2-trifluoroethyl, 1-difluoroethyl, 2-difluoroethyl, 1-trifluoroethyl, 1-difluoroethyl, 1-trifluoroethyl, 2-trifluoroethyl, and 1-trifluoroethyl 1, 2-tetrafluoroethyl, 1, 2-tetrafluoroethyl, perfluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1-difluoropropyl, 1, 2-difluoropropyl, 1, 3-difluoropropyl, 2-difluoropropyl 1, 2-tetrafluoroethyl, 1, 2-tetrafluoroethyl, perfluoroethyl, 1-fluoropropyl, 2-fluoropropyl 3-fluoropropyl group, 1-difluoropropyl group, 1, 2-difluoropropyl group, 1, 3-difluoropropyl group, 2-difluoropropyl group, 1, 3-pentafluoropropyl, 1,2, 3-pentafluoropropyl 2, 3-pentafluoropropyl, perfluoropropyl perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, and the like.
The alkoxy group having 1 to 40 carbon atoms may be any of a straight-chain, branched-chain and cyclic alkyl group, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, n-nonoxy group, n-decoxy group, n-undecoxy group, n-dodecoxy group, n-trideecoxy group, n-tetradecoxy group, n-pentadecoxy group, n-hexadecoxy group, n-heptadecoxy group, n-octadecyloxy group, n-nonadecoxy group and n-eicosoxy group.
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 replaced with a fluorine atom, examples thereof include fluoromethoxy, difluoromethoxy, perfluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 1, 2-difluoroethoxy, 1-difluoroethoxy, 2-difluoroethoxy, 1, 2-trifluoroethoxy, 1, 2-trifluoroethoxy, 2, 2-trifluoroethoxy, 1, 2-tetrafluoroethoxy, 1, 2-tetrafluoroethoxy, perfluoroethoxy, 1-fluoropropoxy, 2-fluoropropoxy, 3-fluoropropoxy, 1-difluoropropoxy, 1, 2-difluoropropoxy, 1, 3-difluoropropoxy 2, 2-trifluoroethoxy, 1, 2-tetrafluoroethoxy, perfluoroethoxy, 1-fluoropropoxy 2-fluoropropoxy, 3-fluoropropoxy, 1-difluoropropoxy, 1, 2-difluoropropoxy, 1, 3-difluoropropoxy, 1,2, 3-pentafluoropropoxy, 1,2, 3-pentafluoropropoxy 1, 3-pentafluoropropoxy 1,2, 3-pentafluoropropoxy, 2, 3-pentafluoropropoxy, perfluoropropoxy, and the like.
The alkylene group having 1 to 40 carbon atoms may be any of a linear, branched, and cyclic group, and specific examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and eicosylene.
Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, tolyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like, and phenyl group, tolyl group and naphthyl group are preferable.
Specific examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, anthracenoxy group, naphthyloxy group, phenanthryloxy group, fluorenyloxy group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the above formula (1), R is preferably 1 And R is 2 Each independently represents 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 sulfo, or R 1 And R is 2 -O-Y-O-formed by bonding.
R a ～R d Examples of the groups which independently represent 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 include the same groups as those listed above.
Among them, R is preferable a ～R d Each independently represents 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 The alkyl group having 1 to 8 carbon atoms, the fluoroalkyl group having 1 to 8 carbon atoms, or the phenyl group is 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, a C1-40 alkyl group, a C1-40 fluoroalkyl group or a C6-20 aryl group, preferably a hydrogen atom, a C1-8 alkyl group, a C1-8 fluoroalkyl group or a phenyl group, more preferably-CH 2 CF 3 。
R is as described above 1’ Preferably a hydrogen atom or a sulfo group, more preferably a sulfo group, and R 2’ Preferably of carbon number1-40 alkoxy or-O- [ Z-O ]] h -R e More preferably-O [ C (R) a R b )-C(R c R d )-O] h -R e OR-OR f Further preferably-O [ C (R) a R b )-C(R c R d )-O] h -R e 、-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 is 2 -O-Y-O-formed by bonding each other.
For example, the polythiophene derivative according to a preferred embodiment of the present invention contains R 1’ Is sulfo, R 2’ Is a repeating unit other than sulfo, or comprises R 1 And R is 2’ Bonding the formed repeating units of-O-Y-O-.
Preferably, the polythiophene derivative comprises R 1 Is sulfo, R 2’ Is an alkoxy group having 1 to 40 carbon atoms or-O- [ Z-O ]] h -R e Or comprises R 1’ And R is 2’ Bonding the formed repeating units of-O-Y-O-.
More preferably, the polythiophene derivative comprises R 1’ Is sulfo, R 2’ is-O [ C (R) a R b )-C(R c R d )-O] h -R e OR-OR f Is a repeating unit of (a).
Further preferably, the polythiophene derivative comprises R 1’ Is sulfo, R 2’ is-O [ C (R) a R b )-C(R c R d )-O] h -R e Or comprises R 1’ And R is 2’ Bonding the formed repeating units of-O-Y-O-.
Still more preferably, the polythiophene derivative comprises R 1’ Is sulfo, 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 Repeat unit of-OHA member, or comprise R 1’ And R is 2’ And repeating units bonded to each other and each being a group represented by the following formulas (Y1) and (Y2).
[ chemical 14]
As a preferred specific example of the polythiophene derivative, for example, polythiophenes containing at least one kind of repeating units represented by the following formulas (H1-1) to (H1-5) can be cited.
[ 15]
Examples of suitable structures of the polythiophene derivatives include polythiophene derivatives having a structure represented by the following formula (H1 a). In the following formula, each unit may be bonded randomly or may be bonded as a block polymer.
[ 16]
Wherein a to d represent the molar ratio of each unit, and satisfy 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.1, 0.ltoreq.a+b.ltoreq.1, 0.ltoreq.c.ltoreq.1, 0.ltoreq.d.ltoreq.1, a+b+c+d=1.
Furthermore, the polythiophene derivatives may be homopolymers or copolymers (statistically, including random, gradient, and block copolymers). As the polymer comprising the monomer A and the monomer B, the block copolymer comprises, for example, an A-B diblock copolymer, an A-B-A triblock copolymer, and (AB) k -multiblock copolymers. Polythiophenes can include repeat units derived from other types of monomers (e.g., thienothiophene, selenophene, pyrrole, furan, tellurothiophene, aniline, arylamine, and arylene groups (e.g., phenylene, phenylacetylene, fluorene, etc.), and the like).
The content of the repeating unit represented by the formula (H1) in the polythiophene derivative is preferably more than 50 mol%, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol% of all the repeating units contained in the polythiophene derivative.
The polythiophene derivative may contain a repeating unit derived from an impurity according to the purity of the initial monomer used in the polymerization. The term "homopolymer" as described above means a polymer comprising repeating units derived from one monomer, but may comprise repeating units derived from impurities. The polythiophene derivative is preferably a polymer in which substantially all of the repeating units are repeating units represented by the formula (H1), and more preferably a polymer including at least one of the repeating units represented by the formulas (H1-1) to (H1-5).
In the case where the polythiophene derivative contains a repeating unit having a sulfo group, the polythiophene derivative is preferably an amine adduct in which an amine compound is added to at least a part of the sulfo groups contained therein, from the viewpoint of further improving the solubility and dispersibility in an organic solvent.
Examples of amine compounds that can be used to form amine adducts include monoalkylamine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-dodecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, and n-eicosylamine; primary amine compounds such as monoarylamine compounds including aniline, toluidine, 1-naphthylamine, 2-naphthylamine, 1-anthracylamine, 2-anthracylamine, 9-anthracylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine, and 9-phenanthrylamine; n-ethylmethylamine, N-methyl-N-propylamine, N-methylisopropylamine, N-methyl-N-butylamine, N-methyl-sec-butylamine, N-methyl-tert-butylamine, N-methylisobutylamine, diethylamine, N-ethyl-N-propylamine, N-ethylisopropylamine, N-ethyl-N-butylamine, N-ethyl-sec-butylamine, dipropylamine, N-N-propylisopropylamine, N-N-propyl-N-butylamine, N-N-propyl-sec-butylamine, diisopropylamine, N-N-butylisopropylamine, N-tert-butylisopropylamine, di (N-butyl) amine, di (sec-butyl) amine, diisobutylamine, aziridine (ethyleneimine), 2-methylaziridine (propyleneimine), 2-dimethylaziridine, azetidine (trimethylene imine), 2-methylazetidine, pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 2, 5-dimethylpyrrolidine, piperidine, 2, 6-dimethylpiperidine, 3, 5-dimethylpiperidine, 2, 6-tetramethylpiperidine, hexamethyleneimine, octamethyleneimine, and the like; diarylamine compounds such as diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1' -naphthylamine, 2' -naphthylamine, 1,2' -naphthylamine, carbazole, 7H-benzo [ c ] carbazole, 11H-benzo [ a ] carbazole, 7H-dibenzo [ c, g ] carbazole, and 13H-dibenzo [ a, i ] carbazole; secondary amine compounds such as alkylaryl amine compounds including N-methylaniline, N-ethylaniline, N-N-propylaniline, N-isopropylaniline, N-N-butylaniline, N-sec-butylaniline, N-isobutylaniline, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, N-N-propyl-1-naphthylamine, indoline, isoindoline, 1,2,3, 4-tetrahydroquinoline, 1,2,3, 4-tetrahydroisoquinoline; n, N-dimethylethylamine, N-dimethyln-propylamine, N-dimethylisopropylamine, N-dimethyl N-butylamine, N-dimethyl sec-butylamine, N-dimethyl tert-butylamine, N, N-dimethylisobutylamine, N-diethylmethylamine, N-methyldi (N-propyl) amine, N-methyldiisopropylamine, N-methyldi (N-butyl) amine, N-methyldiisobutylamine, triethylamine, N, trialkylamine compounds such as N-diethyl-N-butylamine, N-diisopropylethylamine, N-di (N-butyl) ethylamine, tri (N-propyl) amine, tri (isopropyl) amine, tri (N-butyl) amine, tri (isobutyl) amine, 1-methylazetidine, 1-methylpyrrolidine, and 1-methylpiperidine; triarylamine compounds such as triphenylamine; alkyl diarylamine compounds such as N-methyl diphenylamine, N-ethyl diphenylamine, 9-methyl carbazole and 9-ethyl carbazole; tertiary amine compounds such as dialkylarylamine compounds, e.g., N-diethylaniline, N-di (N-propyl) aniline, N-di (isopropyl) aniline, and N, N-di (N-butyl) aniline, are preferable, tertiary amine compounds are more preferable, trialkylamine compounds are still more preferable, and triethylamine is still more preferable, in view of the balance of solubility of amine adducts, charge transport properties of the obtained organic functional film, and the like.
The amine adduct can be obtained by adding the polythiophene derivative to the amine itself or a solution thereof and sufficiently stirring the mixture.
In addition, the polythiophene derivative or the amine adduct thereof can be treated with a reducing agent.
In the polythiophene derivative or the amine adduct thereof, a part of the repeating units constituting the polythiophene derivative or the amine adduct may have an oxidized structure called "quinoid structure". The term "quinoid structure" is used with respect to the term "benzenoid structure", and the former means a structure in which a double bond in an aromatic ring moves outward (as a result of disappearance of the aromatic ring) and 2 exocyclic double bonds conjugated with other double bonds remaining in the ring are formed with respect to the latter as a structure including the aromatic ring. The relationship of these two structures can be readily understood by those skilled in the art from the relationship of the structures of benzoquinone and hydroquinone. The quinoid structure of the repeating units for various conjugated polymers is well known to those skilled in the art. As an example, a quinoid structure corresponding to a repeating unit of a polythiophene derivative including a repeating unit represented by the above formula (H1) is shown in the following formula (H1').
[ chemical 17]
(wherein R is 1 And R is 2 As defined in formula (H1) above. )
The quinoid structure is produced by a process in which a polythiophene derivative including a repeating unit represented by the above formula (H1) undergoes an oxidation reaction by a dopant, so-called doping reaction, and a part of structures called a "polaron structure" and a "dual-polaron structure" which impart charge transport property are produced in the polythiophene derivative. These structures are well known. In the production of an organic EL element, the introduction of a "polaron structure" and/or a "dual-polaron structure" is necessary, and in practice, the above-described doping reaction is intentionally caused to achieve the introduction at the time of firing a thin film formed of a charge-transporting varnish at the time of producing an organic EL element. The reason why the quinoid structure is contained in the polythiophene derivative before the doping reaction is considered to be that the polythiophene derivative undergoes an unintended oxidation reaction equivalent to the doping reaction in the production process (particularly, the sulfonation step thereof).
The amount of the quinoid structure contained in the polythiophene derivative has a correlation with the solubility and dispersibility of the polythiophene derivative in an organic solvent, and if the amount of the quinoid structure is increased, the solubility and dispersibility tend to be lowered. Therefore, the introduction of the quinoid structure after forming a thin film from the charge-transporting varnish does not cause any problem, and if the quinoid structure is excessively introduced into the polythiophene derivative by the above-mentioned unintended oxidation reaction, there is a case where the production of the charge-transporting varnish is hindered. Among polythiophene derivatives, it is known that there is a difference in solubility and dispersibility in an organic solvent, and one of the reasons for this is that the amount of the quinoid structure of polythiophene introduced by the above-described unintended oxidation reaction varies depending on the difference in production conditions of the respective polythiophene derivatives.
Therefore, if the polythiophene derivative is subjected to the reduction treatment using the reducing agent, even if the quinoid structure is excessively incorporated into the polythiophene derivative, the quinoid structure is reduced by the reduction, and the solubility and dispersibility of the polythiophene derivative in the organic solvent are improved, so that a good charge-transporting varnish that forms a thin film excellent in uniformity can be stably produced.
The conditions for the reduction treatment are not particularly limited as long as the conditions are such that the quinoid structure can be reduced to a non-oxidized structure, that is, the benzenoid structure (for example, in a polythiophene derivative containing a repeating unit represented by the formula (H1), the quinoid structure represented by the formula (H1') is converted to a structure represented by the formula (H1)), and the treatment can be performed, for example, by merely bringing a polythiophene derivative or an amine adduct into contact with a reducing agent in the presence or absence of an appropriate solvent.
Such a reducing agent is not particularly limited as long as it is appropriately reduced, and for example, ammonia water, hydrazine, and the like, which are easily available on the market, are suitable.
The amount of the reducing agent is not generally defined depending on the amount of the reducing agent used, and is usually 0.1 parts by mass or more based on 100 parts by mass of the polythiophene derivative or amine adduct to be treated, from the viewpoint of properly reducing, and 10 parts by mass or less from the viewpoint of not leaving an excessive amount of the reducing agent.
As an example of a specific method for the reduction treatment, the polythiophene derivative and the amine adduct were stirred in 28% aqueous ammonia at room temperature overnight. The solubility and dispersibility of the polythiophene derivative and the amine adduct in the organic solvent are sufficiently improved by the reduction treatment under such relatively mild conditions.
In the charge-transporting varnish of the present invention, in the case of using an amine adduct of a polythiophene derivative, the reduction treatment may be performed before or after the formation of the amine adduct.
In addition, the reduction treatment may change the solubility and dispersibility of the polythiophene derivative or amine adduct thereof in a solvent, and as a result, the polythiophene derivative or amine adduct thereof that was not dissolved in the reaction system at the beginning of the treatment may be dissolved at the end of the treatment. In such a case, an organic solvent (acetone, isopropyl alcohol, or the like in the case of sulfonated polythiophene) having incompatibility with the polythiophene derivative or the amine adduct thereof is added to the reaction system to form a precipitate of the polythiophene derivative or the amine adduct thereof, and the polythiophene derivative or the amine adduct thereof can be recovered by a method such as filtration.
The weight average molecular weight of the polythiophene derivative or the amine adduct thereof comprising the repeating unit represented by formula (H1) is preferably about 1000 to 1000000, more preferably about 5000 to 100000, still more preferably about 10000 to about 50000. When the weight average molecular weight is not less than the lower limit, good conductivity can be obtained with good reproducibility, and when the weight average molecular weight is not more than the upper limit, solubility in a solvent can be improved. The weight average molecular weight is a polystyrene equivalent using GPC.
The polythiophene derivative or amine adduct thereof contained in the charge transporting varnish used in the present invention may be 1 kind or 2 or more kinds of polythiophene derivatives or amine adducts thereof containing the repeating unit represented by the formula (H1).
In addition, the polythiophene derivative containing the repeating unit represented by the formula (H1) may be commercially available, or may be polymerized by a known method using a thiophene derivative or the like as a starting material, and in any case, a substance purified by a method such as reprecipitation or ion exchange is preferably used. By using the purified substance, the characteristics of the organic EL element having the thin film obtained from the charge-transporting varnish of the present invention can be further improved.
Sulfonated conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in U.S. patent No. 8017241 to Seshadri et al. Further, the sulfonated polythiophenes are described in International publication No. 2008/073149 and International publication No. 2016/171935.
At least a part of the polythiophene derivative or the amine adduct thereof including the repeating unit represented by the above formula (H1) is dissolved in a solvent described later.
In the present invention, when a polythiophene derivative or an amine adduct thereof containing a repeating unit represented by the formula (H1) is used, the polythiophene derivative or an amine adduct thereof and a charge transporting substance composed of a charge transporting compound other than the polythiophene derivative or the amine adduct thereof may be used together as the charge transporting substance, but it is preferable that the polythiophene derivative or the amine adduct thereof containing only the repeating unit represented by the formula (H1) is used.
When the polythiophene derivative or the amine adduct thereof containing the repeating unit represented by the formula (H1) is used, the content of the charge transporting substance in the charge transporting varnish is usually determined appropriately in the range of 0.05 to 40 mass%, preferably 0.1 to 35 mass% in the solid content in consideration of the desired film thickness, viscosity of the varnish, and the like.
As another preferable embodiment of the charge transporting substance, a substance represented by the following formulas (H2) and (H3) and the like can be given.
[ chemical 18]
The aniline derivative represented by the formula (H2) may be an oxidized aniline derivative (quinone diimine derivative) having a quinone diimine structure represented by the following formula in its molecule. Examples of the method for oxidizing the aniline derivative to produce the quinone diimine derivative include the methods described in international publication No. 2008/010474 and international publication No. 2014/119782.
[ chemical 19]
In the formula (H2), R 1 ～R 6 Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, and may be Z 1 Substituted, C1-20 alkyl, C2-20 alkenyl or C2-20 alkynyl, which may be substituted by Z 2 Substituted aryl with 6-20 carbon atoms or heteroaryl with 2-20 carbon atoms, -NHY 1 、-NY 2 Y 3 、-OY 4 or-SY 5 Radical, Y 1 ～Y 5 Each independently represents a group which can be Z 1 Substituted, C1-20 alkyl, C2-20 alkenyl or C2-20 alkynyl, or can be substituted by Z 2 Substituted aryl having 6 to 20 carbon atoms or heteroaryl having 2 to 20 carbon atoms, Z 1 Represents halogen atoms, nitro groups, cyano groups, amino groups, or can be substituted by Z 3 Substituted aryl having 6 to 20 carbon atoms or heteroaryl having 2 to 20 carbon atoms, Z 2 Represents halogen atoms, nitro groups, cyano groups, amino groups, or can be substituted by Z 3 Substituted, C1-20 alkyl, C2-20 alkenyl or C2-20 alkenylAlkynyl, Z 3 Represents a halogen atom, a nitro group, a cyano group, or an amino group, and k and l are each independently an integer of 1 to 5.
In the formula (H3), R 7 ～R 10 Each independently represents 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, or a group which may be substituted by Z 1 Substituted alkoxy having 1 to 20 carbon atoms, thioalkoxy having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms or alkynyl having 2 to 20 carbon atoms, which may be substituted by Z 2 Substituted aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or acyl group having 1 to 20 carbon atoms, R 11 ～R 14 Each independently represents a hydrogen atom, a phenyl group, a naphthyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a furyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a thienyl group (these groups may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphate group, a sulfo group, a carboxyl group, 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, a haloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 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 formula (H3 a) (wherein R 11 ～R 14 At least one of which is a hydrogen atom. ) M represents an integer of 2 to 5. Z is Z 1 And Z 2 The same meaning as described above is indicated.
[ chemical 20]
In the formula (H3 a), R 15 ～R 18 Each independently represents 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, or a group which may be substituted by Z 1 Substituted alkoxy having 1 to 20 carbon atoms, thioalkoxy having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms or alkynyl having 2 to 20 carbon atoms, which may be substituted by Z 2 Substituted aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or acyl group having 1 to 20 carbon atoms, R 19 And R is 20 Each independently represents a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a furyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, or a thienyl group (these groups may be bonded to each other to form a ring, and may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphate group, a sulfo group, a carboxyl group, 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, a haloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms). Z is Z 1 And Z 2 The same meaning as described above is indicated.
In the above formulae, examples of the halogen atom include 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 any of a linear, branched, and cyclic alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and a cyclic alkyl group having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, dicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, and the like.
Specific examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylvinyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl group, n-1-decenyl group, and n-1-eicosenyl group.
Specific examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, a n-1-propynyl group, a n-2-propynyl group, a n-1-butynyl group, a n-2-butynyl group, a n-3-butynyl group, a 1-methyl-2-propynyl group, a n-1-pentynyl group, a n-2-pentynyl group, a n-3-pentynyl group, a n-4-pentynyl group, a 1-methyl-n-butynyl group, a 2-methyl-n-butynyl group, a 3-methyl-n-butynyl group, a 1, 1-dimethyl-n-propynyl group, a n-1-hexynyl group, a n-1-decynyl group, a n-1-pentadecynyl group, a n-1-eicosynyl group and the like.
Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
Specific examples of the aralkyl group having 7 to 20 carbon atoms include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, naphthylpropyl and the like.
Specific examples of the heteroaryl group having 2 to 20 carbon atoms include a 2-thienyl group, a 3-thienyl group, a 2-furyl group, a 3-furyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, a 4-isoxazolyl group, a 5-isoxazolyl group, a 2-thiazolyl group, a 4-thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, a 5-isothiazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, and the like.
Examples of the haloalkyl group having 1 to 20 carbon atoms include a group in which at least one of hydrogen atoms of the alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and among these, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred.
As a specific example thereof, examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 2-trifluoroethyl, heptafluoropropyl 2, 3-pentafluoropropyl, 2, 3-tetrafluoropropyl, 2-trifluoro-1- (trifluoromethyl) ethyl, nonafluorobutyl 2, 3-pentafluoropropyl, 2, 3-tetrafluoropropyl 2, 2-trifluoro-1- (trifluoromethyl) ethyl, nonafluorobutyl.
Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, n-nonoxy group, n-decyloxy group, n-undecoxy group, n-dodecoxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosyloxy group and the like.
Specific examples of the thioalkoxy group (alkylthio group) having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group, n-nonadecylthio group, n-eicosylthio group and the like.
Specific examples of the acyl group having 1 to 20 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, isovaleryl, benzoyl and the like.
In the formula (H2), R 1 ～R 6 Preferably hydrogen atom, halogen atom, and optionally Z 1 Substituted C1-20 alkyl groups, optionally substituted by Z 2 Substituted aryl-NHY having 6 to 20 carbon atoms 1 、-NY 2 Y 3 、-OY 4 or-SY 5 In this case, Y 1 ～Y 5 Preferably can be Z 1 Substituted C1-10 alkyl or Z 2 Substituted aryl groups having 6 to 10 carbon atoms, more preferably optionally substituted by Z 1 Substituted C1-6 alkyl or Z 2 The substituted phenyl group is more preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
In particular, R 1 ～R 6 More preferably hydrogen atom, fluorine atom, methyl group, phenyl group or diphenyl groupBasic amino group (Y) 2 And Y 3 -NY being phenyl 2 Y 3 ) Further preferably R 1 ～R 4 Is a hydrogen atom, and R 5 And R is 6 And is simultaneously a hydrogen atom or a diphenylamino group.
In particular, at R 1 ～R 6 And Y 1 ～Y 5 Wherein Z is 1 Preferably halogen atoms or can be Z 3 Substituted aryl having 6 to 10 carbon atoms, more preferably a fluorine atom or phenyl group, still more preferably is absent (i.e., is an unsubstituted group), and Z 2 Preferably halogen atoms or can be Z 3 The substituted alkyl group having 1 to 10 carbon atoms, more preferably a fluorine atom or an alkyl group having 1 to 6 carbon atoms, and still more preferably is absent (i.e., is an unsubstituted group).
In addition, Z 3 Preferably a halogen atom, more preferably a fluorine atom, and even more preferably is absent (i.e., is an unsubstituted group).
From the viewpoint of improving the solubility of the aniline derivative represented by the formula (H2), k+l is preferably equal to or less than 8, and more preferably k+l is equal to or less than 5.
In formula (H3), R 7 ～R 10 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, more preferably a hydrogen atom.
In addition, if it is considered to improve the uniformity of the resulting film while improving the solubility of the aniline derivative represented by formula (H3) to a solvent, R is preferable 11 And R is 13 Are all hydrogen atoms.
In particular, R is preferably 11 And R is 13 Are all hydrogen atoms, R 12 And R is 14 Each independently is phenyl (the phenyl may be substituted with halogen atom, nitro group, cyano group, hydroxyl group, thiol group, phosphate group, sulfo group, carboxyl 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, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or acyl group having 1 to 20 carbon atoms). ) Or a group represented by the above formula (H3 a), more preferably R 11 And R is 13 Are all hydrogen atoms, R 12 And R is 14 Each independently is phenyl, or R 19’ And R is 20’ The groups each of which is phenyl are represented by the following formula (H3 a'), R being more preferable 11 And R is 13 Are all hydrogen atoms, R 12 And R is 14 Are all phenyl groups.
In addition, as m, if considering the ease of obtaining the compound, ease of manufacture, cost, etc., it is preferably 2 to 4, if considering the improvement of solubility in a solvent, it is more preferably 2 or 3, and if considering the balance of ease of obtaining the compound, ease of manufacture, manufacturing cost, solubility in a solvent, transparency of the obtained film, etc., it is most preferable that 2.
[ chemical 21]
The aniline derivatives represented by the formulae (H2) and (H3) may be commercially available ones or ones produced by a known method such as the method described in the above publications, but in either case, one purified by recrystallization, vapor deposition or the like before the preparation of the charge-transporting varnish is preferably used. By using the purified substance, the characteristics of the electronic component having a film obtained from the varnish can be further improved. In the case of purification by recrystallization, for example, 1, 4-dioxane, tetrahydrofuran, or the like can be used as the solvent.
In the present invention, as the charge transporting substance represented by the formulas (H2) and (H3), 1 compound selected from the compounds represented by the formulas (H2) and (H3) (i.e., the dispersity of the molecular weight distribution is 1) may be used alone, or 2 or more compounds may be used in combination.
Specific examples of the charge transporting materials represented by the formulas (H2) and (H3) that can be suitably used in the present invention include, but are not limited to, the following.
[ chemical 22]
[ chemical 23]
(wherein DPA represents a diphenylamino group.)
In the charge-transporting varnish of the present invention, the amount of the fluorinated arylsulfonic acid polymer compound as the dopant material to be used is preferably about 0.01 to 20.0, more preferably about 0.05 to 15, in terms of mass (molar) ratio, relative to the charge-transporting material 1 such as a polythiophene derivative or an arylamine derivative.
The charge transporting varnish of the present invention may contain a known organic dopant substance or inorganic dopant substance in addition to the fluorinated arylsulfonic acid polymer compound, but preferably does not contain any of these other dopant substances.
As the solvent used in the preparation of the charge transporting varnish of the present invention, a highly polar solvent that can satisfactorily dissolve the charge transporting substance, dopant substance, and the like used can be used. In addition, a low-polarity solvent may be used in terms of excellent process suitability as compared with a high-polarity solvent, if necessary. In the present invention, the low-polarity solvent is defined as a solvent having a relative dielectric constant of less than 7 at a frequency of 100kHz, and the high-polarity solvent is defined as a solvent having a relative dielectric constant of 7 or more at a frequency of 100 kHz.
Examples of the low-polarity solvent include
A chlorine-based solvent such as chloroform or chlorobenzene;
aromatic hydrocarbon solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene;
aliphatic alcohol solvents such as 1-octanol, 1-nonanol and 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, and triethylene glycol butyl methyl ether;
And ester solvents 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, and diethylene glycol monobutyl ether acetate.
In addition, examples of the highly polar solvent include
Amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-dimethylisobutyl amide, N-methylpyrrolidone, and 1, 3-dimethyl-2-imidazolidinone;
ketone solvents such as ethyl methyl ketone, isophorone and 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, and 2, 3-butanediol;
1-membered alcohol solvents 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, tetrahydrofurfuryl alcohol, and the like;
sulfoxide solvents such as dimethyl sulfoxide, and the like.
Further, the charge transporting varnish of the present invention may contain 1 or more kinds of metal oxide nanoparticles. The term nanoparticle means a fine particle having an average particle diameter of a primary particle of a nanometer order (typically 500nm or less). The metal oxide nanoparticle means a metal oxide formed into a nanoparticle.
The primary particle diameter of the metal oxide nanoparticles is not particularly limited as long as it is a nano-size, but is preferably 2 to 150nm, more preferably 3 to 100nm, and even more preferably 5 to 50nm. The particle size is a measured value based on the BET method using a nitrogen adsorption isotherm.
The metal constituting the metal oxide nanoparticles includes a semimetal in addition to a metal in a usual sense.
The metal in general is not particularly limited, and 1 or 2 or more kinds selected from tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (tungsten) are preferably used.
On the other hand, by semi-metal is meant an element whose chemical and/or physical properties are intermediate between metal and non-metal. The general definition of a semi-metal has not been established, and in the present invention, 6 elements in total, boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb) and tellurium (Te), are used As the semi-metal. These semi-metals may be used alone, or in combination of 2 or more kinds, or may be used in combination with metals in a usual sense.
In particular, the metal oxide nanoparticles preferably contain oxides of 1 or 2 or more metals selected from boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten). In the case where the metal is a combination of 2 or more kinds, the metal oxide may be a mixture of oxides of individual metals or may be a composite oxide containing a plurality of metals.
As specific examples of the metal oxide, B 2 O 3 、B 2 O、SiO 2 、SiO、GeO 2 、GeO、As 2 O 4 、As 2 O 3 、As 2 O 5 、Sb 2 O 3 、Sb 2 O 5 、TeO 2 、SnO 2 、ZrO 2 、Al 2 O 3 ZnO, etc., preferably B 2 O 3 、B 2 O、SiO 2 、SiO、GeO 2 、GeO、As 2 O 4 、As 2 O 3 、As 2 O 5 、SnO 2 、SnO、Sb 2 O 3 、TeO 2 And mixtures thereof, more preferably SiO 2 。
The amount of the metal oxide nanoparticles is not particularly limited, but the lower limit of the amount of the metal oxide nanoparticles in the solid content is usually 50% by mass, preferably 60% by mass, more preferably 65% by mass, and the upper limit of the amount of the metal oxide nanoparticles is usually 95% by mass, preferably 90% by mass, from the viewpoint of improving the transparency of the obtained thin film and the uniformity of the film.
In particular, in the present invention, as the metal oxide nanoparticles, siO is used 2 Silica sols in which the nanoparticles are dispersed in a dispersion medium are suitable.
The silica sol is not particularly limited, and may be appropriately selected from known silica sols.
Commercially available silica sols are generally in the form of dispersions. As a commercially available silica sol, siO may be mentioned 2 The nanoparticles are dispersed in various solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, ethyl acetate, toluene, propylene glycol monomethyl ether acetate, and the like.
Specific examples of the commercially available silica sol include water-dispersible silica sols such as SNOWTEX (registered trademark) ST-O, ST-OS, ST-O-40, ST-OL, and SILIDOL 20, 30, and 40 manufactured by Japanese chemical industries, ltd; examples of the silica sol include, but are not limited to, silica sols such as methanol silica sol, MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, and EG-ST manufactured by Nissan chemical Co., ltd.
The solid content concentration of the silica sol is not particularly limited, and is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 30% by mass.
The amount of the silica sol to be used is appropriately determined in consideration of the concentration thereof so that the amount of silica to be finally contained in the charge-transporting varnish becomes the amount of the metal oxide nanoparticles to be blended.
In addition, in the case where the obtained thin film is used as a hole injection layer of an organic EL element, the charge transporting varnish of the present invention may contain an organosilane compound for the purpose of improving the injection property into the hole injection layer, improving the lifetime characteristics of the element, and the like. The content thereof is usually about 1 to 30 mass% relative to the total mass of the charge transporting material and the dopant material.
Examples of the organosilane compound include a dialkoxysilane compound, a trialkoxysilane compound, and a tetraalkoxysilane compound.
The viscosity of the charge-transporting varnish is appropriately determined according to the thickness of the film to be produced, the solid content concentration, and the like, and is usually 1 to 50mpa·s at 25 ℃. In the present invention, the term "solid component" means a component other than the solvent contained in the charge-transporting varnish.
The solid content concentration of the charge-transporting varnish is usually about 0.1 to 10.0 mass% in view of the viscosity, surface tension, etc. of the varnish, and the thickness of the film to be produced, and is preferably about 0.5 to 5.0 mass% in view of improving the coatability of the varnish, and more preferably about 1.0 to 3.0 mass%.
The method for producing the charge-transporting varnish is not particularly limited, and examples thereof include a method of dissolving a charge-transporting substance and a dopant substance in a highly polar solvent, adding a low polar solvent thereto, and surface-treating metal oxide nanoparticles; a method of mixing a high-polarity solvent and a low-polarity solvent, dissolving a charge transporting substance and a dopant substance therein, and further adding surface-treated metal oxide nanoparticles, and the like.
In particular, in the production of a charge-transporting varnish, it is desirable to dissolve a charge-transporting substance, a dopant substance, or the like in an organic solvent, and then filter the solution with a submicron filter or the like, for the purpose of obtaining a film having higher flatness with good reproducibility.
The charge-transporting varnish described above can be used to easily produce a charge-transporting thin film, and therefore can be suitably used in the production of electronic devices, particularly organic EL devices.
In this case, the charge-transporting varnish can be applied to a substrate and baked to form a charge-transporting thin film.
The method of applying the varnish is not particularly limited, and examples thereof include dipping, spin coating, transfer printing, roll coating, brush coating, ink jet, spray coating, and slit coating, and the viscosity and surface tension of the varnish are preferably adjusted according to the application method.
The firing atmosphere of the charge-transporting varnish after application is not particularly limited, and a film having a uniform film formation surface and high charge-transporting property can be obtained not only in an atmosphere but also in an inert gas such as nitrogen or in vacuum, and a film having charge-transporting property may be obtained with good reproducibility by firing the varnish in an atmosphere according to the kind of dopant used.
The firing temperature is appropriately determined in the range of about 100 to 260 ℃ 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 of solvent, the boiling point, and the like, and for example, when the obtained thin film is used as a hole injection layer of an organic EL element, it is preferable that the temperature is about 140 to 250 ℃, and more preferably about 145 to 240 ℃, and when the above-mentioned arylamine compound is used as a charge transport substance, a thin film having good charge transport property can be obtained even by firing at a low temperature of 200 ℃.
In addition, in order to develop a higher uniform film formation property or to allow the reaction to proceed on the substrate during firing, a temperature change of 2 or more stages may be provided, and heating may be performed using an appropriate apparatus such as a hot plate or an oven.
The thickness of the charge transporting thin film is not particularly limited, and in the case of using the charge transporting thin film as 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, it is preferably 5 to 300nm. As a method for changing the film thickness, there are methods such as changing the concentration of a solid component in the varnish, and changing the amount of a solution on a substrate at the time of coating.
[3] Organic EL element
When the charge transporting thin film is applied to an organic EL element, the charge transporting thin film can be provided between a pair of electrodes constituting the organic EL element.
The following (a) to (f) are typical examples of the organic EL element, but are not limited thereto. In the following configuration, an electron blocking layer or the like may be provided between the light-emitting layer and the anode, and a hole (hole) blocking layer or the like may be provided between the light-emitting layer and the cathode, as necessary. In addition, 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 also function as a hole (hole) blocking layer or the like. Further, any functional layer may be provided between the layers 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/hole injection layer/hole transport layer/light emitting layer/cathode
(f) Anode/hole injection transport layer/light emitting layer/cathode
The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have a function of transporting holes from the anode to the light-emitting layer, and are "hole injection transport layers" when only 1 layer of a hole transport material is provided between the light-emitting layer and the anode, and are "hole injection layers" when 2 or more layers of a hole transport material are provided between the light-emitting layer and the anode, and are "hole transport layers" when the layers close to the anode are other layers. In particular, a thin film having excellent hole-injecting property to the hole-transporting (light-emitting) layer as well as excellent hole-accepting property from the anode is used for the hole-injecting (transporting) layer.
The "electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light-emitting layer, and are "electron injection transport layers" when only 1 layer of electron transport material is provided between the light-emitting layer and the cathode, and are "electron injection layers" when 2 or more layers of electron transport material are provided between the light-emitting layer and the cathode, and are "electron transport layers" when the other layers are "electron injection layers".
The "light-emitting layer" is an organic layer having a light-emitting function, and in the case of using a doping system, contains a host material and a dopant material. In this case, the host material mainly has a function of promoting recombination of electrons and holes and sealing excitons in the light-emitting layer, and the dopant material has a function of efficiently emitting excitons obtained by recombination. In the case of a phosphorescent element, the host material has a function of enclosing excitons mainly generated by a dopant in the light-emitting layer.
The charge transporting film of the present invention is useful as a functional layer provided between an anode and a light-emitting layer in an organic EL element, and is suitable as a hole injection layer, a hole transport layer, a hole injection layer or a hole transport layer, and a hole injection layer.
Examples of the materials and methods for producing an EL element using the charge-transporting varnish of the present invention include, but are not limited to, the following materials and methods.
An example of a method for producing an OLED element having a hole injection layer including a thin film obtained from the charge-transporting varnish of the present invention is as follows. The electrode is preferably cleaned with alcohol, pure water, or the like in advance in a range where the electrode is not adversely affected; surface treatment such as UV ozone treatment and oxygen-plasma treatment is used.
A hole injection layer including the charge transport film of the present invention was formed on the anode substrate by the method described above. The material is introduced into a vacuum evaporation device, and a hole transport layer, a luminescent layer, an electron transport layer/hole blocking layer, an electron injection layer and cathode metal are evaporated in sequence. Alternatively, in this method, instead of forming a hole transporting layer and a light emitting layer by vapor deposition, 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, and these layers are formed by a wet method. An electron blocking layer may be provided between the light emitting layer and the hole transporting layer, as needed.
Examples of the anode material include transparent electrodes represented by Indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO), metal anodes composed of metals represented by aluminum, alloys thereof, and the like, and the anode material subjected to the planarization treatment is preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
The other metal constituting the metal anode may be gold, silver, copper, indium, an alloy thereof, or the like, but is not limited thereto.
Examples of the material for forming the hole transporting layer include (triphenylamine) dimer derivatives, [ (triphenylamine) dimer ] spiro dimers, N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -benzidine (. Alpha. -NPD), 4', triarylamines such as 4 "-tris [ 3-methylphenyl (phenyl) amino ] triphenylamine (m-MTDATA), 4',4" -tris [ 1-naphthyl (phenyl) amino ] triphenylamine (1-TNATA), and 5,5 "-bis- {4- [ bis (4-methylphenyl) amino ] phenyl } -2,2': and oligothiophenes such as 5', 2' -terthiophene (BMA-3T).
Examples of the material for forming the light-emitting layer include low-molecular light-emitting materials such as metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo [ h ] quinoline, distyrylbenzene derivatives, distyrylarylene derivatives, (2-hydroxyphenyl) benzothiazole, and silole derivatives; examples of the polymer compound include, but are not limited to, a system in which a light-emitting material and an electron-transporting material are mixed with a polymer compound such as poly (p-phenylacetylene), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylacetylene ], poly (3-alkylthiophene), and polyvinylcarbazole.
In the case of forming the light-emitting layer by vapor deposition, the light-emitting layer may be co-vapor deposited with a light-emitting dopant, and as the light-emitting dopant, tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) Such as metal complexes, naphthacene derivatives such as rubrene, quinacridone derivatives, and fused polycyclic aromatic rings such as perylene, but are not limited thereto.
Examples of the material for forming the electron transport layer and the hole blocking layer include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like, but are not limited thereto.
As a material for forming the electron injection layer, lithium oxide (Li 2 O), magnesium oxide (MgO), aluminum oxide (Al 2 O 3 ) Metal fluorides such as metal oxides, lithium fluoride (LiF), and sodium fluoride (NaF), but are not limited thereto.
Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
Examples of the material for forming the electron blocking layer include tris (phenylpyrazole) iridium, but are not limited thereto.
Examples of the hole-transporting polymer 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 ] capped with polysilsesquioxane, and poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4, 4' - (N- (p-butylphenyl)) diphenylamine) ].
Examples of the light-emitting polymer include polyfluorene derivatives such as poly (9, 9-dialkylfluorene) (PDAF), polyphenylacetylene derivatives such as poly (2-methoxy-5- (2' -ethylhexyloxy) -1, 4-phenylacetylene) (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
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, or a hole injection transport layer of an organic EL element, and can be used for forming a charge transporting thin film in an electronic element such as an organic photoelectric conversion element, an organic thin film solar cell, an organic perovskite photoelectric conversion element, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light-emitting transistor, an organic optical inspector, an organic photoreceptor, an organic field extinction element, a light-emitting electron chemical cell, a quantum dot light-emitting diode, a quantum laser, an organic laser diode, or an organic plasmon light-emitting element.
Examples
The present invention will be described more specifically with reference to synthesis examples, production examples, examples and comparative examples, but the present invention is not limited to the examples described below. The following means were used.
(1) 1 H-NMR
Bruker Corp. Nuclear magnetic resonance spectrometer AVANCE III HD MHz
(2) Determination of weight average molecular weight (Mw) and number average molecular weight (Mn)
GPC apparatus Promince (column: TSKgel. Alpha. 2500+alpha. 3000+alpha. 4000, column temperature: 40 ℃, detector: UV detector (254 nm) and RI detector, eluent: meOH, liBr (10 mM), column flow rate: 1 mL/min), standard sample manufactured by Shimadzu corporation: polyethylene oxide
(condition B) GPC apparatus HLC-8320GPC (chromatographic column: shodex KD-805, column temperature: 50deg.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, manufactured by Tosoh Corp.). Polyethylene oxide
(3) Cleaning of substrates
Apparatus for cleaning substrate (reduced pressure plasma system) manufactured by Changzhou industries (ltd)
(4) Coating of charge-transporting varnishes
Spin coater MS-A100 manufactured by MIKASA
(5) Manufacture of organic EL elements
Multifunctional vapor deposition device system C-E2L1G1-N manufactured by Changzhou industries (Ltd.)
(6) Measurement of luminance and the like of organic EL element
Multi-channel IVL measuring device manufactured by EHC
(7) Measurement of contact angle of Charge-transporting film
DropMaster DM-700 of Confucius interface science (Inc.) contact angle meter
[1] Synthesis of raw Material Compound (monomer)
Synthesis example 1 Synthesis of Compound 1
[ chemical 24]
10.0g of sodium 1-naphthol-3, 6-disulfonate (manufactured by mountain land chemical industry Co., ltd.) and 18.4g of 2,3,4,5, 6-pentafluorostyrene (manufactured by tokyo chemical industry Co., ltd., hereinafter the same) and 5.02g of sodium carbonate (manufactured by Kato chemical industry Co., ltd.) were put into a three-necked flask, and 100g of dimethyl sulfoxide (manufactured by pure chemical industry Co., hereinafter the same) was further added thereto, and stirred under a nitrogen atmosphere at 80℃for 30 hours.
After cooling the reaction solution to room temperature, 200g of dimethyl sulfoxide was added thereto, and the mixture was stirred at room temperature for 3 hours to dissolve the precipitated product. After the obtained solution was filtered, the filtrate was depressurized to remove the solvent, to obtain a crude product. The obtained crude product was added to 900g of a mixed solvent (1/1 (w/w)) of 2-propanol (manufactured by pure chemical Co., ltd.) and ethyl acetate (manufactured by pure chemical Co., ltd., the same applies below), and stirred at room temperature for 1 hour. The precipitated solid was collected by filtration, and the obtained solid was dried under reduced pressure to obtain compound 1 (yield: 11.3g, yield: 76%).
The following shows compound 1 1 H-NMR spectrum.
1 H-NMR(500MHz、DMSO)：δ5.87(d，J＝11.5Hz，1H)，6.12(d，J＝18.0Hz，1H)，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 polymers
EXAMPLE 1-1 Synthesis of Polymer A
[ chemical 25]
Into a two-necked flask, 1.0 g of the compound obtained in Synthesis example 1 and 0.043g of ammonium persulfate (manufactured by Tokyo chemical industries, ltd.) were charged, and 10g of degassed ion-exchanged water was further added thereto, followed by stirring at 65℃for 20 hours under a nitrogen atmosphere. After cooling the reaction mixture to room temperature, 150g of methanol (manufactured by pure chemical Co., ltd., the same applies below) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. The precipitated solid was recovered by filtration, and the recovered solid was dried under reduced pressure. To the obtained dry solid, 5.5g of ion-exchanged water was added, and after dissolving, 20mL of cation-exchange resin (Dowex Monosphere650C, fuji photo-Tech., manufactured by Wako pure chemical industries, ltd., hereinafter) was added, followed by stirring at room temperature for 20 minutes, and then filtration was performed. The filtrate was depressurized and the solvent was removed to give polymer a (0.95 g).
Mw=2340, mn=2270, mw/mn=1.03 (GPC, condition a)
EXAMPLES 1-2 Synthesis of Polymer B
[ chemical 26]
Into a two-necked flask, 1.0 g of the compound obtained in Synthesis example 1, 0.74g of 2,3,4,5, 6-pentafluorostyrene, 0.14g of AIBN (manufactured by Fuji photo-Co., ltd.) and 20g of degassed dimethylformamide (manufactured by Chun chemical Co., ltd.) were charged, and the mixture was stirred under a nitrogen atmosphere at 80℃for 8 hours. After cooling the reaction solution to room temperature, it was added to 200g of a mixed solvent (1/3 (w/w)) of methanol and ethyl acetate, and stirred at room temperature for 1 hour. The precipitated solid was recovered by filtration, and the recovered solid was dried under reduced pressure. To the obtained dry solid, 10g of ion exchange water was added and dissolved, and then 20mL of cation exchange resin (Dowex Monosphere 650C) was added, followed by stirring at room temperature for 20 minutes and filtration. The filtrate was depressurized and the solvent was removed to give polymer B (1.59 g).
Mw=5150, mn=3550, mw/mn=1.23 (GPC, condition B)
[3] Synthesis of comparative Compounds
Comparative example 1-1 Synthesis of Compound 2
[ chemical 27]
To 1.3g of the compound 1 obtained in Synthesis example 1 was added 56.5g of ion-exchanged water, dissolved, and ion-exchanged by column chromatography using ion-exchanged water as an extraction solvent with 150mL of cation-exchange resin (Dowex Monosphere 650C). The fraction around pH1 was dried under reduced pressure to obtain Compound 2 (10.24 g, yield 98.8%).
[4] Preparation of composition for preparation of Charge-transporting varnish
[ preparation examples 1-1]
To 0.5g of an amine adduct of a polythiophene derivative which is a polymer having a repeating unit represented by the formula (H1 a) and was synthesized in the following manner according to the specification of U.S. Pat. No. 8017241 and the method described in International publication No. 2016/171935, 8.75g of 1, 3-dimethyl-2-imidazolidinone (manufactured by Kato chemical Co., ltd., hereinafter, the same) and 0.75g of n-butylamine (manufactured by Tokyo chemical industry Co., ltd.) were added, and the mixture was stirred at 80℃for 3 hours by using a hot stirrer to obtain a solution in which the polythiophene was dissolved.
[ chemical 28]
[ preparation examples 1-2]
100g of ST-OS (manufactured by Nissan chemical Co., ltd.) and dipropylene glycol monomethyl ether (manufactured by Kanto chemical Co., ltd., the same applies below) as water-dispersed silica sol were placed in an eggplant-shaped flask, and the water solvent contained in ST-OS was replaced with dipropylene glycol monomethyl ether using an evaporator to obtain dipropylene glycol monomethyl ether-dispersed silica sol (silica concentration 9.43%).
[ preparation examples 1-3]
A diethylene glycol (manufactured by Kato chemical Co., ltd., hereinafter) 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 ℃ for 1 hour using a hot stirrer.
[ preparation examples 1 to 4]
A1, 3-dimethyl-2-imidazolidinone solution containing 10 mass% of the polymer B obtained in example 1-2 was prepared. The above solution was prepared by stirring at 50 ℃ for 1 hour using a hot stirrer.
[ preparation examples 1 to 5]
A commercially available aqueous solution of D-66-20BS (manufactured by Solvay Co., ltd., AQUIVION) as a copolymer of tetrafluoroethylene and sulfonyl fluoride vinyl ether (Sulfonyl fluoride vinyl ether) was distilled off with an evaporator, and then dried with a reduced pressure dryer at 80℃for 1 hour to obtain a powder of D-66-20 BS. Then, a 1, 3-dimethyl-2-imidazolidinone solution containing 5 mass% of D-66-20BS was prepared. The above solution was prepared by stirring at 80℃for 2 hours using a hot stirrer.
[ preparation examples 1 to 6]
A diethylene glycol solution containing 10 mass% of the compound 2 obtained in comparative example 1-1 was prepared. The above solution was prepared by stirring at 50 ℃ for 1 hour using a hot stirrer.
[5] Preparation of a Charge-transporting varnish
Examples 2 to 1
1.723g of 1, 3-dimethyl-2-imidazolidinone, 3.537g of diethylene glycol and 2.927g of dipropylene glycol monomethyl ether were added to the sample tube, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 0.42g of the diethylene glycol solution of the polymer A obtained in preparation examples 1 to 3 was added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Next, 0.28g of the solution obtained in preparation 1-1 was added thereto, and the mixture was stirred at room temperature for 30 minutes. Further, 1.113g of the silica sol dispersed in dipropylene glycol monomethyl ether obtained in production example 1-2 was added thereto, and the mixture was stirred at room temperature for 30 minutes. The obtained mixed solution was filtered by a PP syringe filter having a pore size of 0.2 μm to obtain a charge-transporting varnish.
Examples 2 to 2
To the sample tube were added 2.524g of 1, 3-dimethyl-2-imidazolidinone, 3.451g of dipropylene glycol and 2.443g of dipropylene glycol monomethyl ether, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 0.21g of the 1, 3-dimethyl-2-imidazolidinone solution of the polymer B obtained in preparation examples 1-3 was added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Next, 0.28g of the solution obtained in preparation 1-1 was added thereto, and the mixture was stirred at room temperature for 30 minutes. Further, 1.113g of the silica sol dispersed in dipropylene glycol monomethyl ether obtained in production example 1-2 was added thereto, and the mixture was stirred at room temperature for 30 minutes. The obtained mixed solution was filtered by a PP syringe filter having a pore size of 0.2 μm to obtain a charge-transporting varnish.
Comparative examples 2 to 1
To the sample tube were added 2.308g of 1, 3-dimethyl-2-imidazolidinone, 3.444g of dipropylene glycol and 2.435g of dipropylene glycol monomethyl ether, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 0.42g of the 1, 3-dimethyl-2-imidazolidinone solution of D-66-20BS obtained in preparation examples 1-5 was added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Next, 0.28g of the solution obtained in preparation 1-1 was added thereto, and the mixture was stirred at room temperature for 30 minutes. Further, 1.113g of the silica sol dispersed in dipropylene glycol monomethyl ether obtained in production example 1-2 was added thereto, and the mixture was stirred at room temperature for 30 minutes. The obtained mixed solution was filtered by a PP syringe filter having a pore size of 0.2 μm to obtain a charge-transporting varnish.
Comparative examples 2 to 2
1.727g of 1, 3-dimethyl-2-imidazolidinone, 3.755g of diethylene glycol and 2.936g of dipropylene glycol monomethyl ether were added to the sample tube, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 0.21g of the diethylene glycol solution of the compound 2 obtained in production examples 1 to 6 was added, and stirred at room temperature for 30 minutes using a stirrer. Next, 0.28g of the solution obtained in preparation 1-1 was added thereto, and the mixture was stirred at room temperature for 30 minutes. Further, 1.113g of the silica sol dispersed in dipropylene glycol monomethyl ether obtained in production example 1-2 was added thereto, and the mixture was stirred at room temperature for 30 minutes. The obtained mixed solution was filtered by a PP syringe filter having a pore size of 0.2 μm to obtain a charge-transporting varnish.
[6] Evaluation of coating Property of upper layer
The charge-transporting varnishes obtained in example 2-1, example 2-2, comparative example 2-1 and comparative example 2-2 were applied to an ITO substrate using a spin coater, and then dried at 120℃for 1 minute under atmospheric pressure. Next, the dried ITO substrate was fired at 230 ℃ for 15 minutes under an atmospheric atmosphere to form a 30nm uniform charge-transporting thin film on the ITO substrate. As the ITO substrate, a glass substrate of 50mm×50mm×0.7t in which an ITO film of 50nm thickness was uniformly formed on the substrate surface was used, and O was used before use 2 The plasma cleaning device (150W, 30 seconds) removed impurities on the surface.
To each of the obtained films, 1. Mu.L of anisole (manufactured by Tokyo chemical industries, ltd.) was added dropwise, and the measurement results of the contact angle thereof are shown in Table 1.
TABLE 1
Anisole contact angle
Example 2-1 Less than 5 DEG
Example 2-2 Less than 5 DEG
Comparative example 2-1 21°
Comparative example 2-2 Less than 5 DEG
The charge transporting films obtained in example 2-1, example 2-2 and comparative example 2-2 were each composed of anisole with a contact angle of less than 5 °, and were excellent in wettability. The difference between the solid matters of the charge transporting varnishes of examples 2-1, 2-2, comparative example 2-1 and comparative example 2-2 was the kind of the fluorosulfonic acid compound, and it was confirmed that the wettability of the upper layer was excellent in the charge transporting film using the polymer a, the polymer B and the compound 2.
[7] Manufacture and property evaluation of organic EL element
Examples 3 to 1
The varnish obtained in example 2-1 was applied to the same ITO substrate from which impurities were removed using a spin coater, and then dried at 120 ℃ for 1 minute under the atmosphere. Next, the dried ITO substrate was fired at 230℃for 15 minutes under an atmospheric atmosphere to form a 30nm uniform thin film on the ITO substrate.
Next, an ITO substrate on which a thin film was formed was subjected to a vapor deposition apparatus (vacuum degree 1.0x10 -5 Pa), the α -NPD (N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine) was formed into a film at 0.2 nm/sec for 30nm. Next, an electron blocking material HTEB-01 manufactured by Kabushiki Kaisha was formed into a film of 10nm. Next, a light-emitting layer host material NS60 manufactured by new japanese iron-gold chemical corporation and a light-emitting layer dopant material Ir (ppy) 3 were co-evaporated. In the case of co-evaporation, the evaporation rate was controlled so that the concentration of Ir (ppy) 3 became 6%, and 40nm was stacked. Next, alq3, lithium fluoride, and aluminum thin films were sequentially stacked to obtain an organic EL element. At this time, the vapor deposition rates were set to 0.2 nm/sec for Alq3 and aluminum, and 0.02 nm/sec for lithium fluoride to give film thicknesses of 20nm, 0.5nm and 80nm, respectively.
In order to prevent deterioration of characteristics due to influence of oxygen, water, and the like in the air, the characteristics of the organic EL element were evaluated after the organic EL element was sealed with a sealing substrate. The sealing is performed by the following steps.
Organic EL elements are placed between sealing substrates in a nitrogen atmosphere having an oxygen concentration of 2ppm or less and a dew point of-76 ℃ or less, and the sealing substrates are bonded with an adhesive (manufactured by Moresco, MORESCO MOISTURE CUT WB US (P)). At this time, the water-trapping agent (HD-071010W-40 manufactured by Dynic Co., ltd.) was housed together with the organic EL element in the sealing substrate. UV light (wavelength: 365nm, irradiation amount: 6000 mJ/cm) was irradiated to the bonded sealing substrate 2 ) Thereafter, the adhesive was cured by annealing at 80℃for 1 hour.
Examples 3 to 2
The procedure of example 3-1 was repeated except that the varnish obtained in example 2-2 was used instead of the varnish obtained in example 2-1, to obtain an organic EL element.
Comparative example 3-1
The procedure of example 3-1 was repeated except that the varnish obtained in comparative example 2-2 was used instead of the varnish obtained in example 2-1, to obtain an organic EL element.
For each of the elements obtained in example 3-1, example 3-2 and comparative example 3-1, the measurement luminance was 10000cd/m 2 Driving voltage, current density and luminous efficiency at the time of driving, and half-life of luminance (initial luminance 10000 cd/m) 2 Half the time required). The results are shown in Table 2.
TABLE 2
As shown in Table 1, it was found that the organic EL elements produced in examples 3-1, 3-2 and 3-1 all exhibited good initial characteristics, and the element of example 3-1 using the polymer A and the element of example 3-2 using the polymer B exhibited superior life characteristics as compared with the element of comparative example 3-1 using the compound 2. This is presumably because the heat resistance of the compound is improved by the polymerization to increase the molecular weight.
In addition, it was found that the element of example 3-2 using the polymer B composed of the copolymer of the compound 1 and perfluorostyrene was excellent in element efficiency and life. This is presumably because the proportion of fluorine atoms in the polymer increases, and the surface modifying effect of the charge transporting thin film increases.

Claims (15)

1. A fluoroaryl sulfonic acid polymer compound comprising a repeating unit represented by the following formula (1),
[ chemical 1]
Wherein Ar is F Represents a fluoroalkylene group, X represents O, S, NH, CONH or NHCO, ar S Meaning having at least one SO on the ring 3 Aryl of the R group, R represents a hydrogen atom or an alkali metal atom.
2. The fluoroaryl sulfonic acid polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (2),
[ chemical 2]
Wherein R' represents a 1-valent organic group.
3. The fluoroaryl sulfonic acid polymer compound of claim 2 wherein R' is a fluoroaryl group.
4. A fluoroaryl sulfonic acid polymer compound according to any one of claims 1 to 3, wherein the Ar F Is a perfluoroalkylene group.
5. The fluoroaryl sulfonic acid polymer compound of claim 4 wherein Ar F Is tetrafluoro-subPhenyl.
6. The fluoroaryl sulfonic acid polymer compound of any one of claims 1-5, wherein the Ar S To have more than 2 of said SOs on the ring 3 Aryl of R group.
7. The fluoroaryl sulfonic acid polymer compound of claim 6 wherein Ar S To have more than 2 of said SOs on the ring 3 Naphthyl of R group.
8. The fluoroaryl sulfonic acid polymer compound of any one of claims 1-7, wherein the X is O.
9. A dopant species consisting of a fluoroaryl sulfonic acid polymer compound according to any one of claims 1 to 8.
10. A charge-transporting varnish comprising: a charge transporting material, a dopant material according to claim 9, and a solvent.
11. The charge-transporting varnish of claim 10 wherein the charge-transporting material is an arylamine derivative or a thiophene derivative.
12. A charge-transporting film obtained from the charge-transporting varnish according to claim 10 or 11.
13. An electronic component comprising the charge transporting film according to claim 12.
14. An organic electroluminescent element comprising the charge transporting thin film according to claim 12.
15. The organic electroluminescent element according to claim 14, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.
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