WO2019049867A1 - Ink composition - Google Patents

Ink composition Download PDF

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Publication number
WO2019049867A1
WO2019049867A1 PCT/JP2018/032787 JP2018032787W WO2019049867A1 WO 2019049867 A1 WO2019049867 A1 WO 2019049867A1 JP 2018032787 W JP2018032787 W JP 2018032787W WO 2019049867 A1 WO2019049867 A1 WO 2019049867A1
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Prior art keywords
group
ink composition
composition according
alkyl
carbon atoms
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PCT/JP2018/032787
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French (fr)
Japanese (ja)
Inventor
前田　大輔
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日産化学株式会社
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Priority to JP2019540969A priority Critical patent/JP7120242B2/en
Publication of WO2019049867A1 publication Critical patent/WO2019049867A1/en
Priority to JP2022088852A priority patent/JP7327580B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • C09D11/00—Inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources

Definitions

  • the present invention relates to an ink composition comprising a polythiophene compound, an onium borate salt and a liquid carrier.
  • the present disclosure also relates to a charge transporting thin film formed from an ink composition, and an organic electroluminescent device having the charge transporting thin film.
  • organic electroluminescent hereinafter referred to as organic EL
  • a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injecting layer.
  • the hole injection layer is responsible for charge transfer between the anode and the hole transport layer or the light emitting layer, and plays an important function to achieve low voltage drive and high luminance of the organic EL element.
  • the formation method of the hole injection layer is roughly divided into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method, and when these processes are compared, the wet process has a larger area Can efficiently produce thin films with high Therefore, as the area of the organic EL display is increased, a hole injection layer that can be formed by a wet process is desired at present.
  • the present inventors are applicable to various wet processes and charge transportability giving a thin film which can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element. Compounds having good solubility in materials and organic solvents used therefor have been developed (Patent Documents 1 and 2).
  • an ink composition for organic electronic devices Patent Document 3
  • OLED organic light emitting diode
  • the problem to be solved by the present invention is to provide an ink composition that is applicable to various wet processes and has excellent charge transportability.
  • ink compositions comprising a polythiophene compound having a specific structure, an onium borate salt having a specific structure, and a liquid carrier are applicable to various wet processes and have charge transportability.
  • the inventors have found that excellent charge transporting thin films can be formed, and completed the present invention.
  • the present invention provides the following inventions.
  • R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e
  • R 1 and R 2 together form —O—Z—O— (wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium
  • Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, Alkyl, fluoroalkyl or ary
  • the counter cation is represented by formulas (c1) to (c5):
  • R 1 and R 2 are each independently H, fluoroalkyl, -SO 3 M, -O [C (R a R b ) -C (R c R d ) -O] p -R e , Or -OR f , or R 1 and R 2 together are -O- (CH 2 ) q -O- (wherein (CH 2 ) q is optionally substituted by Y
  • M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and each of R a , R b , R c and R d is Independently H, halogen, alkyl, fluoroalkyl or aryl; R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; R f is alkyl , Fluoroalkyl Q is 1, 2, or 3; and Y is a linear or branche
  • R 1 and R 2 are each independently —O [C (R a R b ) —C (R c R d ) —O] p —R e or —OR f , or The ink composition according to (9), wherein R 1 and R 2 together form —O— (CH 2 ) q —O—.
  • each of R a , R b , R c and R d independently represents H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl;
  • the component (A) has the following formula: A repeating unit selected from the group consisting of a group represented by: wherein M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and combinations thereof, The ink composition according to any one of (1) to (12).
  • the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine and ethylenediamine (wherein 19)
  • the ink composition described above is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine and ethylenediamine (wherein 19) The ink composition described above.
  • a method of producing a charge transporting thin film comprising applying the ink composition according to any one of (1) to (23) onto a substrate and evaporating the solvent.
  • R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e
  • R 1 and R 2 together form —O—Z—O— (wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium
  • Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, Alkyl, fluoroalkyl
  • an ink composition that is applicable to various wet processes and that is excellent in charge transportability.
  • FIG. 1 shows the shape of the cross section of the charge transporting thin film of Example 3 and Comparative Example 2.
  • the noun described in the singular or the noun described without distin- guishing the singular or plural refers to "one (one) or more” or “at least one (1) unless otherwise noted. Means ").
  • the term “comprises” includes “consisting essentially of” and “consisting of.”
  • the term “comprising” includes “consisting essentially of” and “consisting of.”
  • (C x -C y) (wherein, x and y are each an integer) with respect to the organic group as used herein refers to the group, the carbon atom to one of the groups It means that x to y carbon atoms may be included.
  • alkyl refers to a monovalent linear or branched saturated hydrocarbon group, more typically a monovalent linear or branched saturated (C 1 -C 40 A hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, triacontyl, tetracontyl etc. Do.
  • fluoroalkyl one or more fluorine atoms are substituted with, herein synonymous with alkyl groups, more typically (C 1 -C 40 ) Means an alkyl group.
  • fluoroalkyl groups include, for example, difluoromethyl, trifluoromethyl, perfluoroalkyl, 1H, 1H, 2H, 2H-perfluorooctyl, perfluoroethyl, and —CH 2 CF 3 .
  • hydrocarbylene hydrocarbon typically divalent formed by removing two hydrogen atoms from (C 1 -C 40) hydrocarbon Means a group.
  • the hydrocarbylene group may be linear, branched or cyclic and may be saturated or unsaturated.
  • hydrocarbylene groups are methylene, ethylene, 1-methylethylene, 1-phenylethylene, propylene, butylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene and 2,6-naphthylene Including, but not limited to.
  • alkoxy refers to a monovalent group designated as -O-alkyl, wherein the alkyl group is as defined herein.
  • alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy.
  • aryl refers to a monovalent unsaturated bond containing one or more 6-membered carbocyclic rings (the unsaturation of which is represented by three conjugated double bonds). It means a hydrocarbon group.
  • Aryl groups include monocyclic aryl and polycyclic aryl.
  • Polycyclic aryl is a monovalent unsaturated hydrocarbon group containing two or more 6-membered carbocyclic rings (the unsaturation of which is represented by three conjugated double bonds), which are adjacent to each other Ring refers to a group linked to each other by one or more bonds or divalent bridging groups, or fused together.
  • Examples of aryl groups include, but are not limited to, phenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl and pyrenyl.
  • aryloxy refers to a monovalent group designated as -O-aryl, wherein the aryl group is as defined herein.
  • aryloxy groups include, but are not limited to phenoxy, anthracenoxy, naphthoxy, phenanthrenoxy and fluorenoxy.
  • any substituent or group described herein may be optionally substituted at one or more carbon atoms with one or more same or different substituents described herein.
  • the hydrocarbylene group may be further substituted with an aryl group or an alkyl group.
  • Any substituent or group described herein is also, at one or more carbon atoms, a halogen such as, for example, F, Cl, Br and I; nitro (NO 2 ), cyano (CN), and It may be optionally substituted by one or more substituents selected from the group consisting of hydroxy (OH).
  • charge transportability is synonymous with conductivity and is also synonymous with hole transportability.
  • the ink composition of the present invention may have charge transportability by itself, or may have charge transportability in a solid film obtained by using the ink composition.
  • a "hole carrier compound” can facilitate the movement of holes (i.e., positive charge carriers) and / or move electrons, for example, in an electronic device. Refers to any compound that can be blocked.
  • Hole carrier compounds are typically used in the hole transport layer (HTL), hole injection layer (HIL) and electron blocking layer (EBL) of electronic devices, typically organic electronic devices such as organic light emitting devices etc. Contains useful compounds.
  • the term “doped” with respect to a hole carrier compound, such as polythiophene refers to a chemical transformation, typically oxidation or reduction, in which the hole carrier compound is promoted by a dopant. It means that the reaction, more typically, it has undergone an oxidation reaction.
  • the term “dopant” refers to a hole carrier compound, eg, a substance that oxidizes, or reduces, typically polythiophene.
  • a process in which a hole carrier compound is subjected to a chemical conversion, typically an oxidation or reduction reaction, more typically an oxidation reaction, promoted by a dopant is a "doping reaction” or simply “doping” It is called Doping alters the properties of polythiophene, which may include, but is not limited to, electrical properties (such as resistivity and work function), mechanical properties, and optical properties.
  • Doping alters the properties of polythiophene, which may include, but is not limited to, electrical properties (such as resistivity and work function), mechanical properties, and optical properties.
  • the hole carrier compound is charged and the dopant becomes a counterion counter-charged to the doped hole carrier compound as a result of the doping reaction.
  • a substance must be chemically reacted, oxidized or reduced, typically oxidized, to be referred to as a dopant.
  • Substances that do not react with the hole carrier compound but can act as counterions are not considered dopants in the present disclosure.
  • the term "undoped" with respect to a hole carrier compound, such as polythiophene means that the hole carrier compound has not undergone the doping reaction described herein.
  • pile-up refers to the phenomenon where the ink composition crawls the sides of the bank.
  • various methods for applying the ink composition are known, an example of such a method is an inkjet method in which the ink composition is ejected as fine droplets from a nozzle and adhered to an object to be coated (droplets Discharge method) can be mentioned.
  • the charge transporting thin film formed in this manner preferably has a uniform thickness throughout the entire thin film.
  • the charge transport thin film may be in a non-uniform thickness state particularly when formed by the above-described bank method.
  • a state is a state in which the thickness of the peripheral portion of the formed charge transporting thin film increases along the direction from the center to the edge of the thin film. This is because the ink composition applied in the film forming area crawls up the side of the bank, so that the thickness around the coating film formed is the center to the edge of the coating film (in other words, the coating film)
  • the charge transportable thin film formed from the coating film in this state is uneven in thickness as described above, due to the state in which the It will be in the state.
  • such a phenomenon in which the ink composition crawls the side of the bank is referred to as "pile-up phenomenon" or simply "pile-up".
  • the ink composition of the present disclosure may be non-aqueous or may contain water, but is preferably non-aqueous from the viewpoint of process compatibility in ink jet coating and storage stability of the ink.
  • non-aqueous means that the total amount of water in the ink composition of the present disclosure is 0 to 2% by weight with respect to the total amount of the ink composition.
  • the total amount of water in the ink composition is 0 to 1% by weight, more typically 0 to 0.5% by weight, based on the total amount of the ink composition.
  • the ink composition of the present disclosure is substantially free of water.
  • the component (A) is represented by formula (I): [Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or alternatively, R 1 and R 2 together form —O—Z—O—, where M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium And Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, And R 14 is a polythiophen
  • R 1 and R 2 are each independently H, fluoroalkyl, -SO 3 M, -O [C (R a R b ) -C (R c R d ) -O] p -R e or -OR f , or alternatively, R 1 and R 2 are taken together -O- (CH 2 ) q -O- (wherein (CH 2 ) q is optionally substituted by Y
  • M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and each R a , R b , R c and R d are , Each independently H, halogen, alkyl, fluoroalkyl or aryl; R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; R f is , Alkyl, Q is 1, 2, or 3, and Y is a linear or branched
  • R 1 is H and R 2 is other than H.
  • the repeat unit is derived from a 3-substituted thiophene.
  • the polythiophenes may be regiorandom or regioregular compounds. Because of its asymmetric structure, polymerization of 3-substituted thiophenes produces a mixture of polythiophene structures containing three possible regiochemical bonds between repeat units. The three orientations available when the two thiophene rings are attached are 2,2 ', 2,5', and 5,5 'couplings. The 2, 2 '(or head-to-head) and 5, 5' (or tail-to-tail) couplings are referred to as regiorandom couplings. In contrast, a 2, 5 '(or head-to-tail) coupling is referred to as a regioregular coupling.
  • the degree of regioregularity may be, for example, about 0-100%, or about 25-99.9%, or about 50-98%.
  • Regioregularity can be determined by standard methods known to those skilled in the art, such as, for example, using NMR spectroscopy.
  • the polythiophene is regioregular.
  • the regioregularity of the polythiophene can be at least about 85%, typically at least about 95%, and more typically at least about 98%.
  • the degree of regioregularity may be at least about 70%, typically at least about 80%.
  • the regioregular polythiophene has a degree of regioregularity of at least about 90%, and typically a degree of regioregularity of at least about 98%.
  • the 3-substituted thiophene monomers are commercially available or can be prepared by methods known to those skilled in the art. Synthetic methods, doping methods, and polymer characterizations involving regioregular polythiophenes with pendant groups are described, for example, in US Pat. Nos. 6,602,974 to McCullough et al. And US Pat. No. 6,166,172 to McCullough et al. Provided to
  • R 1 and R 2 are both other than H.
  • the repeat unit is derived from a 3,4-disubstituted thiophene.
  • R 1 and R 2 are each independently —O [C (R a R b ) —C (R c R d ) —O] p —R e or —OR f
  • R 1 and R 2 together form -O- (CH 2 ) q -O-.
  • R 1 and R 2 are both —O [C (R a R b ) -C (R c R d ) -O] p -R e .
  • R 1 and R 2 may be the same or different.
  • each R a , R b , R c and R d is independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
  • R e is (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
  • R 1 and R 2 are each —O [CH 2 —CH 2 —O] p —R e . In one embodiment, R 1 and R 2 are each —O [CH (CH 3 ) —CH 2 —O] p —R e .
  • R e is methyl, propyl or butyl.
  • q is 2.
  • -O- (CH 2 ) q -O- is substituted at one or more positions with Y. In one embodiment, -O- (CH 2 ) q -O- is substituted at one position with Y.
  • q is 2 and Y is 3-sulfobutoxymethyl.
  • the —O— (CH 2 ) 2 —O— group is preferably substituted at one position with a 3-sulfobutoxymethyl group.
  • the polythiophene has the following formula: And a repeating unit selected from the group consisting of H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and combinations thereof.
  • the repeating unit represented by is of the following formula: 3- (2- (2-Methoxyethoxy) ethoxy) thiophene [referred to herein as 3-MEET] Derived from a monomer represented by the structure shown in The repeating unit represented by is of the following formula: (Wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium) Sulfonated 3- (2- (2-methoxyethoxy) ethoxy) thiophene [referred to herein as sulfonated 3-MEET] Derived from a monomer represented by the structure shown in The repeating unit represented by is of the following formula: 3,4-bis (2- (2-butoxyethoxy) ethoxy) thiophene (referred to herein as 3,4-di BEET) Derived from a monomer represented by the structure shown in The repeating unit represented by is of the following formula:
  • the 3,4-disubstituted thiophene monomers are commercially available or can be prepared by methods known to those skilled in the art.
  • the 3,4-disubstituted thiophene monomer is a 3,4-dibromothiophene, a compound of the formula: HO- [Z-O] p -R e or HOR f , wherein Z, R e , R f and p are , As defined herein, can be generated by reaction with a metal salt of a compound given by the formula, typically a sodium salt.
  • the polymerization of the 3,4-disubstituted thiophene monomer first brominates the 2 and 5 positions of the 3,4-disubstituted thiophene monomer to give the corresponding 2,5-dibromo derivative of the 3,4-disubstituted thiophene monomer It is carried out by forming.
  • the polymer can then be obtained by GRIM (Grignard metathesis) polymerization of a 2,5-dibromo derivative of 3,4-disubstituted thiophene in the presence of a nickel catalyst.
  • GRIM Garnier metathesis
  • metal free organic oxidizing agents such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as the oxidizing agent, or
  • DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
  • transition metal halides such as iron (III) chloride, molybdenum (V) chloride, and ruthenium (III) chloride.
  • polythiophenes having repeat units of formula (I) of the present disclosure can be further modified following their formation by polymerization.
  • hydrogen may be substituted by a substituent such as a sulfonic acid group (—SO 3 H) by sulfonation; It may have a part of
  • the term "sulfonated" in the context of polythiophene means that the polythiophene contains one or more sulfonic acid groups (-SO 3 H).
  • the said polythiophene is also called “sulfonated polythiophene”.
  • the sulfur atom of the —SO 3 H group is attached directly to the basic backbone of the polythiophene and not attached to the side groups.
  • side groups are monovalent groups that do not shrink the length of the polymer chain, even though it is theoretically or actually removed from the polymer.
  • Sulfonated polythiophene polymers and / or copolymers can be prepared using any method known to those skilled in the art.
  • polythiophene can be sulfonated by reaction with a sulfonation reagent such as, for example, oleum, acetyl sulfate, pyridine SO 3 and the like.
  • a sulfonation reagent such as, for example, oleum, acetyl sulfate, pyridine SO 3 and the like.
  • the monomers can be sulfonated using a sulfonation reagent and then polymerized by known methods and / or methods described herein.
  • the sulfonic acid groups can be basic compounds such as alkali metal hydroxides, ammonia and alkylamines such as mono-, di- and trialkylamines such as triethylamine etc. In the presence, this may result in the formation of the corresponding salt or adduct.
  • sulfonated in relation to polythiophene means that this polythiophene is one or more -SO 3 M groups, where M is an alkali metal ion (eg Na + , Li + , K + , Rb It includes the meaning that it may include + , Cs + and the like), ammonium (NH 4 + ), mono-, di- and trialkylammonium (which may be triethylammonium and the like).
  • M is an alkali metal ion (eg Na + , Li + , K + , Rb It includes the meaning that it may include + , Cs + and the like), ammonium (NH 4 + ), mono-, di- and trialkylammonium (which may be triethylammonium and the like).
  • Sulfonated and sulfonated conjugated polymers of conjugated polymers are described in Seshadri et al., US Pat. No. 8,017,241, which is incorporated herein by reference in its entirety Be Also, sulfonated polythiophenes are described in WO 2008/073149 and WO 2016/171935, which are incorporated herein by reference in their entirety.
  • the polythiophene is sulfonated.
  • the sulfonated polythiophenes have the formula (I): [Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, or —O— [Z—O] p —R e wherein Z is An optionally halogenated hydrocarbylene group, p is an integer greater than or equal to 1 and R e is H, alkyl, fluoroalkyl or aryl). However, any one of R 1 and R 2 is —SO 3 M (M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium). ] And a repeating unit represented by
  • the sulfonated polythiophene is represented by formula (I): wherein each of R 1 and R 2 is independently H, fluoroalkyl, —O [C (R a R b ) —C (R c R d ) -O] p -R e or -OR f ; wherein each of R a , R b , R c and R d is independently H, halogen, alkyl, fluoroalkyl R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; and R f is alkyl, fluoroalkyl or aryl.
  • any one of R 1 and R 2 is —SO 3 M (M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium).
  • M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl am
  • R 1 is —SO 3 M, wherein M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and R 2 is —SO 3 Other than M.
  • M is preferably monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, more preferably trialkyl ammonium.
  • R 1 is —SO 3 M
  • R 2 is —O [C (R a R b ) —C (R c R d ) —O] p —R e , or —OR f .
  • R 1 is —SO 3 M and R 2 is —O [C (R a R b ) -C (R c R d ) -O] p -R e .
  • R 1 is —SO 3 M and R 2 is —O—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 3 .
  • the sulfonated polythiophenes have the formula (I): [Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, or —O— [Z—O] p —R e wherein Z is An optionally halogenated hydrocarbylene group, p is an integer of 1 or more, and R e is H, alkyl, fluoroalkyl or aryl) It is obtained by sulfonation of polythiophene containing a repeating unit represented by
  • the sulfonated polythiophene is represented by formula (I) wherein R 1 and R 2 are each independently H, fluoroalkyl, —O [C (R a R b ) -C (R c R d ) -O] p- R e or -OR f ; wherein each of R a , R b , R c and R d is independently H, halogen, alkyl, fluoroalkyl or R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; and R f is alkyl, fluoroalkyl or aryl] Are obtained by sulfonation of polythiophene containing a repeating unit.
  • R 1 and R 2 are each independently H, fluoroalkyl, —O [C (R a R b ) -C (R c R d ) -O] p- R e or -OR
  • R 1 is H and R 2 is other than H.
  • the repeat unit is derived from a 3-substituted thiophene.
  • the sulfonated polythiophenes are obtained from polythiophenes which may be regiorandom or regioregular compounds. Because of its asymmetric structure, polymerization of 3-substituted thiophenes produces a mixture of polythiophene structures containing three possible regiochemical bonds between repeat units. The three orientations available when the two thiophene rings are attached are 2,2 ', 2,5', and 5,5 'couplings. The 2, 2 '(or head-to-head) and 5, 5' (or tail-to-tail) couplings are referred to as regiorandom couplings.
  • a 2, 5 '(or head-to-tail) coupling is referred to as a regioregular coupling.
  • the degree of regioregularity may be, for example, about 0-100%, or about 25-99.9%, or about 50-98%.
  • Regioregularity can be determined by standard methods known to those skilled in the art, such as, for example, using NMR spectroscopy.
  • the 3-substituted thiophene monomers are commercially available or can be prepared by methods known to those skilled in the art. Synthetic methods, doping methods, and polymer characterizations involving regioregular polythiophenes with pendant groups are described, for example, in US Pat. Nos. 6,602,974 to McCullough et al. And US Pat. No. 6,166,172 to McCullough et al. Provided to Sulfonated conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in Seshadri et al., US Pat. No. 8,017,241.
  • R 1 is H and R 2 is -O [C (R a R b ) -C (R c R d ) -O] p -R e , or -OR f .
  • R 1 is H and R 2 is —O [C (R a R b ) -C (R c R d ) -O] p -R e .
  • each R a , R b , R c and R d is independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
  • R e and R f are each independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
  • R 2 is —O [CH 2 —CH 2 —O] p —R e . In certain embodiments, R 2 is -OR f .
  • Examples of compounds having the formula HO [C (R a R b ) -C (R c R d ) -O] p -R e or HOR f include trifluoroethanol, ethylene glycol monohexyl ether (hexyl cellosolve) Propylene glycol monobutyl ether (Dowanol (trademark) PnB), diethylene glycol monoethylether (ethyl carbitol), dipropylene glycol n-butylether (Dowanol (trademark) DPnB), diethylene glycol monophenyl ether (phenyl carbitol), ethylene glycol mono Butyl ether ( Tyr cellosolve), diethylene glycol monobuty
  • R e is H, methyl, propyl or butyl. In one embodiment, R f is CH 2 CF 3 .
  • the sulfonated polythiophene has the following formula: It is obtained by sulfonation of the polythiophene containing the repeating unit shown by these.
  • the repeating unit represented by is of the following formula: 3- (2- (2-Methoxyethoxy) ethoxy) thiophene [referred to herein as 3-MEET] It derives from the monomer represented by the structure shown by
  • the polythiophene is sulfonated poly (3-MEET).
  • the polythiophenes used in the present disclosure may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers).
  • the block copolymer includes, for example, an AB diblock copolymer, an ABA triblock copolymer, and an (AB) k -multiblock copolymer.
  • Polythiophenes are repeating units derived from other types of monomers (eg, thienothiophene, selenophene, pyrrole, furan, tellurophene, aniline, arylamines, and arylene (eg, phenylene, phenylene vinylene, fluorene, etc.), etc.) May be included.
  • the polythiophene comprises more than 50% by weight, typically more than 80% by weight, more typically 90% by weight of recurring units of the formula (I) based on the total weight of the recurring units. It is included in an amount of more than wt%, still more typically more than 95 wt%.
  • the polymer formed may contain repeat units derived from impurities.
  • the term "homopolymer” is intended to mean a polymer comprising repeat units derived from one type of monomer, but containing repeat units derived from impurities It is also good.
  • the polythiophene is a homopolymer, wherein essentially all repeating units are repeating units of formula (I).
  • Polythiophenes typically have a number average molecular weight between about 1,000 and 1,000,000 g / mol. More typically, the conjugated polymer has a number average molecular weight between about 5,000 and 100,000 g / mol, and even more typically between about 10,000 and about 50,000 g / mol.
  • the number average molecular weight can be determined by methods known to those skilled in the art, such as, for example, gel permeation chromatography.
  • the polythiophene may be used after being treated with a reducing agent.
  • the chemical structure of some of the repeating units constituting them may be an oxidized type structure called "quinoid structure".
  • quinoid structure is used with respect to the term “benzenoid structure”, and the latter, which is a structure containing an aromatic ring, causes the double bond in the aromatic ring to move out of the ring ( As a result, the aromatic ring disappears), which means a structure in which two exocyclic double bonds to be coupled to other double bonds remaining in the ring are formed.
  • This quinoid structure is a part of a structure called “polaron structure” or “bipolaron structure” which is generated by the above-mentioned doping reaction and imparts charge transportability to polythiophene.
  • polaron structure or "bipolaron structure” which is generated by the above-mentioned doping reaction and imparts charge transportability to polythiophene.
  • These structures are known. Introduction of a “polaron structure” and / or a “bipolaron structure” is essential in the preparation of an organic EL device, and in fact, when an organic EL device is prepared, a charge transportable thin film formed of a charge transporting varnish is fired Sometimes this is achieved by intentionally causing the doping reaction described above.
  • the polythiophene before the occurrence of this doping reaction contains a quinoid structure, because polythiophene is equivalent to the doping reaction in its production process (in the case of sulfonated polythiophene, in particular, the sulfonation step therein), It is considered to be because an unintended oxidation reaction occurred.
  • the reducing agent used for this reduction treatment reduces the quinoid structure to convert it to a non-oxidized structure, ie, the benzenoid structure (for example, in the polythiophene represented by the formula (I), the formula (I).
  • the quinoid structure represented by ' can be converted to the structure represented by the above formula (I).
  • the amount of reducing agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polythiophene to be treated.
  • this treatment can be performed simply by contacting the polythiophene with a reducing agent in the presence or absence of a suitable solvent.
  • reduction treatment under relatively mild conditions such as stirring polythiophene in 28% ammonia water (for example, overnight at room temperature) sufficiently improves the dispersibility of polythiophene in an organic solvent.
  • the sulfonated polythiophene may be converted to a corresponding ammonium salt, for example, a trialkyl ammonium salt (sulfonated polythiophene amine adduct) and then subjected to a reduction treatment.
  • the polythiophene which was not dissolved in the reaction system at the start of the treatment may be dissolved at the completion of the treatment.
  • an organic solvent incompatible with polythiophene acetone, isopropyl alcohol, etc. in the case of sulfonated polythiophene
  • Polythiophene can be recovered.
  • the ink composition may further contain a hole carrier compound other than the component (A) in some cases, as long as the effects of the present invention are not impaired.
  • Optional hole carrier compounds include, for example, low molecular weight compounds or high molecular weight compounds.
  • the optional hole carrier compound may be non-polymeric or polymeric.
  • Non-polymeric hole carrier compounds include, but are not limited to, crosslinkable small molecules and non-crosslinked small molecules.
  • non-polymeric hole carrier compounds are N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) benzidine (CAS # 65181-78-4); N, N'-bis ( 4-Methylphenyl) -N, N'-bis (phenyl) benzidine; N, N'-bis (2-naphthalenyl) -N, N'-bis (phenylbenzidine) (CAS # 139255-17-1); 1 , 3,5-tris (N, N-bis (3-methylphenyl) amino) benzene (also called m-MTDAB); N, N'-bis (1-naphthalenyl) -N, N'-bis (phenyl) Benzidine (CAS # 123847-85-8, NPB); 4,4 ', 4 "-tris (N, N-phenyl-3-methylphenylamino) triphenylamine (also called m-MTDATA, CAS # 124729-98 -2); 4,4
  • the optional polymeric hole carrier compound is poly [(9,9-dihexylfluorenyl-2,7-diyl) -alt-co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,4 Diaminophenylene)]; poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,1'-biphenylene-4 , 4'-diamine)]; poly (9,9-dioctylfluorene-co-N- (4-butylphenyl) diphenylamine) (also called TFB) and poly [N, N'-bis (4-butylphenyl)- N, N'-bis (phenyl) -benzidine] (generally referred to as poly-TPD), but is not limited thereto.
  • poly-TPD poly [(9,
  • the component (B) is an onium borate salt, which is represented by the formula (a1): And the anion represented by and the formula (a2): A monovalent or divalent anion represented by the formula: wherein Ar is each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent; An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a fluoroaralkyl group having 7 to 10 carbon atoms , L represents an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -, and an onium borate salt composed of at least one anion selected from the group consisting of: It is a neutral salt).
  • the component (B) functions as a dopant which oxidizes the polythiophene of the component (A) and improves the electrical properties (such as resistivity and work function).
  • an onium borate salt composed of an anion represented by the formula (a1) or (a2) and a counter cation is used as a dopant as the component (B)
  • the electrical properties of the polythiophene can be greatly improved, and It can be set as the ink composition excellent in transportability.
  • each Ar is independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
  • aryl group examples include aryl groups having 6 to 20 carbon atoms. Specific examples thereof 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 And 4-phenanthryl group, 9-phenanthryl group and the like, and a phenyl group, a tolyl group and a naphthyl group are preferable.
  • the heteroaryl group preferably includes heteroaryl groups having 2 to 20 carbon atoms. Specific examples thereof include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group And sulfur-containing heteroaryl groups such as oxygen-containing heteroaryl groups such as 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, etc.
  • substituents examples include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms.
  • a fluorine atom As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, A fluorine atom is preferable.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group.
  • An alkyl group of 1 to 18 is preferable, and an alkyl group of 1 to 8 carbon atoms is more preferable.
  • alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- 1-pentenyl group, n-1-decenyl group, n-1-eicosenyl group etc. are mentioned.
  • alkynyl group having 2 to 20 carbon atoms include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, n-3-butynyl group Group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2- Methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group, n-1-pentadecynyl group, n- 1-Eicosinyl group etc. are mentioned.
  • Ar is preferably an aryl group having one or more electron withdrawing substituents. It is preferable that Ar is an aryl group having an electron withdrawing substituent from the viewpoint of improving the Lewis acidity.
  • the electron withdrawing group include a halogen atom, a nitro group, a cyano group and the like, a halogen atom is preferable, and a fluorine atom is particularly preferable.
  • Ar is particularly preferably a pentafluorophenyl group.
  • the component (B) is an onium borate salt comprising an anion represented by the formula (a1) and a counter cation
  • the formula (a4) Particularly preferred is an onium borate salt comprising an anion represented by and a counter cation.
  • R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or 7 carbon atoms And a fluoroaralkyl group of -10.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s -C1-C10 linear or branched, such as -butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl Examples thereof include chain alkyl groups and the like, and alkyl groups having 1 to 8 carbon atoms are preferable, and alkyl groups having 1 to 6 carbon atoms are more preferable.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group
  • a cyclic alkyl group having a carbon number of 3 to 20 such as bicycloheptyl group, bicyclooctyl group, bicyclononyl group and bicyclodecyl group.
  • fluoroalkyl group having 1 to 10 carbon atoms include groups in which at least one hydrogen atom of the alkyl group having 1 to 10 carbon atoms is substituted with a fluorine atom.
  • Examples of the aralkyl group having 7 to 10 carbon atoms include groups in which at least one hydrogen atom of an alkyl group is substituted with an aryl group, and examples thereof include benzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, phenylethyl group Groups, 1-naphthylethyl group, 2-naphthylmethyl group and the like can be mentioned, but an aralkyl group having 7 to 9 carbon atoms is preferable.
  • fluoroaralkyl group having 7 to 10 carbon atoms include groups in which at least one hydrogen atom of the aralkyl group having 7 to 10 carbon atoms is substituted with a fluorine atom.
  • fluorine atom include perfluorobenzyl group, pentafluorophenylmethyl group, heptafluoro-1-naphthylmethyl group, heptafluoro-2-naphthylmethyl group, heptafluoro-1-naphthylethyl group, heptafluoro-2-naphthyl group Ethyl group etc. are mentioned.
  • R in the formula (a1) is preferably an alkyl group having 1 to 6 carbon atoms.
  • R in the formula (a1) which can be used suitably by this invention, although what is represented by a following formula is mentioned, it is not limited to this.
  • L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -.
  • the alkylene group may be linear, branched or cyclic, and includes an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include methylene group, methyl methylene group, dimethyl methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like.
  • L is particularly preferably -CN + -.
  • the component (B) is an onium borate salt comprising an anion represented by the formula (a2) and a counter cation
  • the formula (a3) Particularly preferred is an onium borate salt comprising an anion represented by and a counter cation.
  • the counter cation of the component (B) is not particularly limited, but a cation containing an element belonging to Groups 15 to 17 is preferable, and a cation containing sulfur is more preferable.
  • the counter cation of component (B) is represented by formulas (c1) to (c5): Preferably it is selected from the group consisting of Among them, cations having a counter cation represented by (c1) are particularly preferable.
  • the component (B) has the following formula: Particularly preferred is an onium borate salt represented by
  • the component (B) may be used alone or in combination of two or more. Moreover, you may use together well-known other onium borate salt as needed.
  • the component (B) can be synthesized, for example, with reference to a known method described in JP-A-2005-314682 or the like.
  • the component (B) may be previously dissolved in an organic solvent constituting the liquid carrier (C) described later in order to facilitate the dissolution in the ink composition.
  • organic solvents carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene Glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether or tri Polyhydric alcohols such as ethylene glycol dimethyl ether and the like Derivatives; Cyclic ethers such as dioxane; e
  • the ink composition may contain a dopant other than the component (B) as long as the object of the present application is not hindered.
  • Dopants are known in the art. See, for example, U.S. Patent No. 7,070,867; U.S. Patent Application Publication No. 2005/0123793; and U.S. Patent Application Publication No. 2004/0113127.
  • the dopant may be an ionic compound.
  • the dopant can include a cation and an anion.
  • the cation of the ionic compound is, for example, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, or It may be Au.
  • the cations of the ionic compounds may be, for example, gold, molybdenum, rhenium, iron and silver cations.
  • the dopant may include sulfonates or carboxylates, including alkyl, aryl, and heteroaryl sulfonates or carboxylates.
  • sulfonate refers to a —SO 3 M 1 group, where M 1 is H + or an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + etc); or ammonium (NH 4 + )).
  • carboxylate refers to a —CO 2 M 1 group, where M 1 is H + or an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + and the like); or ammonium (NH 4 + )).
  • alkali metal ion eg, Na + , Li + , K + , Rb + , Cs + and the like
  • ammonium NH 4 +
  • sulfonate and carboxylate dopants include benzoate compounds, heptafluorobutyrate, methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, pentafluoropropionate, and polymeric sulfonates, perfluorosulfonate-containing ionomers And the like, but is not limited thereto.
  • the dopant does not include sulfonate or carboxylate.
  • the dopant is a sulfonylimide (eg, bis (trifluoromethanesulfonyl) imide, etc.); an antimonate (eg, hexafluoroantimonate, etc.); an arsenate (eg, hexafluoroarsenate, etc.); a phosphorus compound And borate (eg, tetrafluoroborate, tetraarylborate, and trifluoroborate etc.) excluding the (B) component.
  • a sulfonylimide eg, bis (trifluoromethanesulfonyl) imide, etc.
  • an antimonate eg, hexafluoroantimonate, etc.
  • an arsenate eg, hexafluoroarsenate, etc.
  • a phosphorus compound And borate eg, tetrafluoroborate, tetraarylborate, and trifluorobo
  • tetraaryl borates include, but are not limited to, halogenated tetraaryl borates such as tetrakis pentafluorophenyl borate (TPFB).
  • TPFB tetrakis pentafluorophenyl borate
  • trifluoroborates are (2-nitrophenyl) trifluoroborate, benzofurazan-5-trifluoroborate, pyrimidine-5-trifluoroborate, pyridine-3-trifluoroborate, and 2, 5-dimethylthiophene This includes, but is not limited to, 3-trifluoroborate.
  • the dopant may be, for example, a material from which doped polythiophene is produced by undergoing, for example, one or more electron transfer reactions with a conjugated polymer.
  • the dopant can be selected to provide a suitable charge balanced counter anion.
  • the reaction may occur by mixing the polythiophene and the dopant, as known in the art.
  • the dopant can undergo spontaneous electron transfer from the polymer to a cation-anion dopant (such as a metal salt) to leave the conjugated polymer with the free metal in the form of its oxidized form with which the anion is associated. See, for example, Lebedev et al. Chem. Mater., 1998, 10, 156-163.
  • polythiophene and dopant may refer to components that react to form a doped polymer.
  • the doping reaction may be a charge transfer reaction in which charge carriers are generated, which reaction may be reversible or irreversible.
  • silver ions can undergo electron transfer to or from silver metal and doped polymers.
  • the composition may be distinct from the combination of the original components (ie the polythiophene and / or the dopant may or may not be present in the final composition in the same form as before mixing Also good).
  • the dopant an inorganic acid, an organic acid, an organic or inorganic oxidizing agent or the like is used.
  • the organic acid a polymeric organic acid and / or a low molecular organic acid (nonpolymeric organic acid) is used.
  • the organic acid is a sulfonic acid and its salt (—SO 3 M 2, where M 2 is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs +, etc.) And ammonium (NH 4 + ), mono-, di-, and trialkyl ammonium (such as triethyl ammonium))
  • M 2 is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs +, etc.)
  • ammonium NH 4 +
  • aryl sulfonic acids are preferred.
  • specific examples of the dopant include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum (III) chloride (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), Boron Bromide (BBr 3 ), Boron Trifluoride Ether Complex (BF 3 ⁇ OEt 2 ), Iron (III) Chloride (FeCl 3 ), Copper (II) Chloride (CuCl 2 ), Antimony Pentachloride (V) (SbCl 5 ) Lewis acids such as arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); polymers such as polystyrene sulfonic acid Acid; benzenesulfonic acid, tosyl acid, camphorsulfonic
  • the dopant comprises at least one selected from the group consisting of an aryl sulfonic acid compound, a heteropoly acid compound, and an ionic compound comprising an element belonging to group 13 or 15 of the long period periodic table .
  • Particularly preferable dopants include polymer organic acids such as polystyrene sulfonic acid, 5-sulfosalicylic acid, dodecylbenzene sulfonic acid, 1,4-benzodioxane disulfonic acid derivatives described in WO 2005/000832, JP-A No.
  • non-polymeric organic acids such as dinonylnaphthalene sulfonic acid derivatives described in JP-108828.
  • the sulfonic acid derivative shown by following formula (2) can also be used suitably.
  • X 1 represents O, S or NH
  • A represents a naphthalene ring or an anthracene ring which may have a substituent other than X 1 and c (SO 3 H) groups
  • T is an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group, or an unsubstituted or substituted formula (3) or (4):
  • W 1 and W 2 are each independently O, S, S (O), S (O 2 ), or N, Si, to which is not substituted or substituted.
  • W 1 may be a single bond
  • R 46 to R 59 each independently represent a hydrogen atom or a halogen atom
  • c represents the number of sulfonic acid groups bonded to A Is an integer that satisfies 1 ⁇ c ⁇ 4
  • d is an integer that satisfies 1 ⁇ d, indicating the number of combinations of T and X 1 .
  • R 46 to R 59 in the formula (3) or (4) are preferably fluorine atoms, and more preferably all fluorine atoms.
  • W 1 in formula (3) is preferably a single bond. Most preferably, W 1 in the formula (3) is a single bond, and all of R 46 to R 53 are fluorine atoms.
  • arylsulfonic acid compound according to the present invention one represented by the following formula (5) can also be used.
  • X 1 represents O, S or NH
  • Ar 5 represents an aryl group
  • c represents the number of sulfonic acid groups, and is an integer satisfying 1 to 4)
  • X 1 represents O, S or NH, but O is particularly preferable because of easy synthesis.
  • a compound represented by the following formula (6) is preferable. (Wherein, Ar 5 represents an aryl group)
  • Examples of the aryl group in the formulas (5) and (6) include aryl groups such as phenyl group, xylyl group, tolyl group, biphenyl group and naphthyl group, and these aryl groups may have a substituent. Good.
  • this substituent examples include a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, a cyano group and a monovalent hydrocarbon group
  • an organo oxy group, an organo amino group, an organo silyl group, an organo thio group, an acyl group, a sulfone group, a halogen atom etc. are mentioned, it is not limited to these.
  • an aryl group represented by the following formula (7) is particularly preferably used.
  • R 60 to R 64 each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 2 to 10 carbon atoms Represents a halogenated alkenyl group of
  • any of chlorine, bromine, fluorine and iodine atoms may be used, but in the present invention, a fluorine atom is particularly preferable.
  • the alkyl group having 1 to 10 carbon atoms methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group Groups, n-heptyl group, n-octyl group, n-nonyl group, 2-ethylhexyl group, n-decyl group, cyclopentyl group, cyclohexyl group and the like.
  • halogenated alkyl group having 1 to 10 carbon atoms a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3- Trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4 And 4-nonafluorobutyl group.
  • halogenated alkenyl group having 2 to 10 carbon atoms examples include a perfluorovinyl group, a perfluoropropenyl group (allyl group), and a perfluorobutenyl group.
  • aryl group represented by the following formula (8) wherein, R 62 represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms.
  • R 62 is particularly preferably a halogenated alkyl group, a halogenated alkenyl group or a nitro group, and more preferably a trifluoromethyl group, a perfluoropropenyl group or a nitro group.
  • the ionic compound which consists of an anion represented by a following formula (a5), and its counter cation can also be used suitably as a dopant.
  • E represents an element belonging to Group 13 or Group 15 of the long period periodic table
  • Ar each independently has an aryl group which may have a substituent or a substituent Also represents a heteroaryl group which may be
  • E is preferably boron, gallium, phosphorus or antimony, more preferably boron.
  • examples of the aryl group and the heteroaryl group include monovalent groups derived from 5- or 6-membered monocyclic or 2-4 condensed rings.
  • a monovalent group derived from a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring and an isoquinoline ring is preferable.
  • at least one group of Ar has one or more fluorine atoms or chlorine atoms as a substituent.
  • a perfluoroaryl group in which all hydrogen atoms of Ar are substituted with fluorine atoms is most preferable.
  • Specific examples of the perfluoroaryl group include pentafluorophenyl group, heptafluoro-2-naphthyl group, tetrafluoro-4-pyridyl group and the like.
  • Heteropoly acid compounds are also particularly preferred as dopants.
  • the heteropoly acid compound has a structure in which the hetero atom is located at the center of the molecule, represented by the chemical structure of the Keggin type represented by the formula (A) or the Dawson type represented by the formula (B).
  • oxygen acids of different elements mainly include oxygen acids of silicon (Si), phosphorus (P) and arsenic (As).
  • heteropoly acid compounds include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, lintungstomolybdic acid, silicotungstic acid, etc.
  • Phosphormolybdic acid, phosphotungstic acid and silicotungstic acid are preferred, and phosphotungstic acid is more preferred.
  • These heteropoly acid compounds may be synthesized and used according to known synthetic methods, but are also available as commercial products.
  • phosphotungstic acid hydrate or 12-Tungstophosphoric acid n-hydrate (chemical formula: H 3 (PW 12 O 40 ) ⁇ nH 2 O), phosphomolybdic acid hydrate or 12-Molybdo (VI ) Phosphoric acid n-hydrate, chemical formula: H 3 (PMo 12 O 40 ), nH 2 O (n ⁇ 30)), Kanto Chemical Co., Ltd., Wako Pure Chemical Industries, Ltd., Sigma-Aldrich Japan Co., Ltd., Japan They are available from manufacturers such as Inorganic Chemical Industry Co., Ltd., Nippon Shin Metal Co., Ltd., and the like.
  • reaction byproducts may be removed from the doping process.
  • metals such as silver can be removed by filtration.
  • the material can be purified to remove halogens and metals.
  • Halogen includes, for example, chloride, bromide and iodide.
  • the metal includes, for example, the cation of the dopant (including the reduced form of the cation of the dopant) or the metal left from the catalyst or initiator residue.
  • Metals include, for example, silver, nickel and magnesium. The amount may be, for example, less than 100 ppm, or less than 10 ppm, or less than 1 ppm.
  • the metal content including the silver content, can be measured by ICP-MS, especially at concentrations above 50 ppm.
  • the doped polymer composition is formed by mixing the polythiophene and the dopant.
  • the mixing may be accomplished using any method known to one skilled in the art.
  • a solution containing polythiophene can be mixed with another solution containing a dopant.
  • the solvent used to dissolve the polythiophene and the dopant is one or more organic solvents constituting the liquid carrier (C) described below.
  • the reaction may occur by mixing the polythiophene and the dopant, as known in the art.
  • the resulting doped polythiophene composition comprises, based on the composition, about 40% to 75% by weight of polymer and about 25% to 55% by weight of dopant.
  • the doped polythiophene composition comprises about 50 wt% to 65 wt% polythiophene and about 35 wt% to 50 wt% dopant based on the composition.
  • the weight of the polythiophene is greater than the weight of the dopant.
  • the dopant may be a silver salt such as silver tetrakis (pentafluorophenyl) borate in an amount of about 0.25 to 0.5 m / ru, where m is the mole of silver salt Amount, and ru is the molar amount of polymer repeat units).
  • the doped polythiophene is isolated by methods known to those skilled in the art (eg, by rotary evaporation of the solvent, etc.) to obtain a dry or substantially dry material (powder, etc.).
  • the amount of residual solvent may be, for example, 10 wt% or less, or 5 wt% or less, or 1 wt% or less based on dry or substantially dry material.
  • the dry or substantially dry powder can be redispersed or redissolved in one or more fresh solvents.
  • the component (C) is a liquid carrier containing an organic solvent.
  • the component (C) dissolves the components (A) and (B) well, and is a component necessary for uniformly mixing the components (A) and (B) into an ink composition. .
  • the components (A) and / or (B) may be partially solubilized to adjust the ink properties such as wettability, viscosity, and shape control of the ink composition, or You may contain the organic solvent made to swell.
  • Component (C) may further contain one or more organic solvents that act as non-solvents for component (A).
  • the component (C) may be used alone or in combination of two or more.
  • Component (C) may be a solvent mixture comprising two or more organic solvents adapted for use and processing with other layers in the device such as the anode or light emitting layer.
  • organic solvents may be used in various proportions in the component (C) to improve ink properties such as substrate wettability, ease of solvent removal, viscosity, surface tension and ejection. it can.
  • glycocol system solvent As a component (C), "glycol system solvent (s1)" can be illustrated, for example.
  • the term “glycol solvent” refers to the formula R h —O— (R g —O) n —R i , wherein each R g is independently a linear or branched C 2 -C 4 non- R h and R i each independently represent a hydrogen atom, a linear, branched or cyclic C 1 -C 8 unsubstituted alkyl group, or a linear or branched C 1 -C 8 non-substituted alkyl group; An organic solvent not having one or more aromatic structures, which is a substituted aliphatic acyl group, and n is an integer of 1 to 6; glycol monoethers; glycol diethers Glycol ester ethers; glycol monoesters; glycol diesters; and glycols and the like.
  • the R g is particularly preferably a C 2 or C 3 unsubstituted alkylene group.
  • n is particularly preferably an integer of 1 to 4.
  • the alkyl group a linear, branched or cyclic C 1 -C 6 unsubstituted alkyl group is preferable, a linear C 1 -C 4 unsubstituted alkyl group is more preferable, and a methyl group and an n-butyl group are preferable. Particularly preferred.
  • acyl group a linear or branched C 2 -C 6 non-substituted aliphatic acyl group is preferable, a linear C 2 -C 4 non-substituted acyl group is more preferable, and an acetyl group and a propionyl group are particularly preferable .
  • the component (s1) in the component (C) includes, for example, the following solvents.
  • component (C) contains at least one selected from the group consisting of glycol monoethers, glycol diethers and glycols, and the total of the glycol monoethers, glycol diethers and glycols.
  • the solubility of the ink solid can be maintained at the time of film formation by ink jet coating, and the ink composition will be described later (E
  • metal oxide nanoparticles it is preferable because aggregation of the component (E) can be appropriately controlled to form a flatter film.
  • the total content of glycol monoethers, glycol diethers and glycols is more preferably 60% by weight or more based on the total weight of component (C), still more preferably 75% by weight or more, particularly preferably Is 90% by weight or more.
  • the upper limit of the content ratio of glycol monoethers, glycol diethers and glycols is 100% by weight.
  • the component (s1) in the component (C) may be mixed.
  • examples include, but are not limited to, mixing glycol diethers and glycols. Specific examples thereof include glycol diethers and glycols described later, but preferably, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether as glycol diethers, ethylene glycol as glycols, Diethylene glycol is mentioned.
  • glycol monoethers examples include alkylene glycol monoethers (glycol monoethers).
  • suitable glycol monoethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether (hexyl cellosolve), propylene glycol monobutyl ether (Dowanol® PnB), diethylene glycol monoethyl ether (ethyl carbitol) ), Dipropylene glycol n-butyl ether (Dowanol (registered trademark) DPnB), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol (registered trademark) DPM), propylene glycol monopropyl Ether (Dowanol (TM) PnP), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol Mono
  • glycol diethers are, for example, ethylene glycol diethers (1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane etc.); diethylene glycol diethers (diethylene glycol dimethyl ether and diethylene glycol diethyl ether) Etc.); propylene glycol diethers (propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether etc); dipropylene glycol diethers (dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol dibutyl ether etc); Higher order ethylene glycol and propylene glycol ether mentioned herein Analogs (i.e., tri - analogs such as triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether - and tetra) a.
  • glycols examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like.
  • Component (s1) in component (C) may further include ethylene glycol monoether acetate and propylene glycol monoether acetate etc. (glycol ester ethers), wherein the ether is, for example, methyl, ethyl , N-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl and cyclohexyl. Also included are the higher glycol ether analogs (di-, tri- and tetra- etc) of the above list.
  • Examples include, but are not limited to, propylene glycol methyl ether acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate.
  • Component (s1) in component (C) may further include ethylene glycol diacetates (glycol diesters), and higher glycol ether analogues (di-, tri- and tetra-). Etc.). Examples include, but are not limited to, ethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate.
  • organic solvents (s2) other than glycol solvents can be further considered.
  • the component (s2) may be used alone or in combination of two or more.
  • the component (s2) is, for example, organic sulfur solvents such as aliphatic and aromatic ketones, dimethyl sulfoxide (DMSO) and 2,3,4,5-tetrahydrothiophene-1,1-dioxide (tetramethylene sulfone; sulfolane)
  • Aromatic hydrocarbons such as tetrahydrofuran (THF), tetrahydropyran (THP), tetramethylurea (TMU), N, N'-dimethylpropyleneurea; alkylated benzenes (xylene and its isomers etc.), halogenation Benzenes, N-methylpyrrolidinone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dichloromethane, dioxanes, ethyl acetate
  • the component (s2) is preferably a nitrile, an alcohol, an aromatic ether or an aromatic hydrocarbon.
  • examples include, but are not limited to, as nitriles, methoxypropionitrile, ethoxypropionitrile, as alcohols benzyl alcohol, 2- (benzyloxy) ethanol, as aromatic ethers methylanisole, dimethylanisole, ethylanisole Butyl phenyl ether, butyl anisole, pentyl anisole, hexyl anisole, heptyl anisole, octyl anisole, phenoxytoluene, as aromatic hydrocarbons such as pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, cyclohexylbenzene or tetralin It can be mentioned. Among these, alcohols are more preferable, and among the alcohols, 2- (benzyl
  • Aliphatic and aromatic ketones include acetone, acetonylacetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl isobutenyl ketone, 2-hexanone, 2-pentanone, acetophenone, ethylphenyl ketone, cyclohexanone, and cyclopentanone Including, but not limited to.
  • ketones having a proton on carbon located alpha to the ketone such as cyclohexanone, methyl ethyl ketone and acetone, are avoided.
  • non-protonic non-polar solvents can provide the added benefit of extending the lifetime of devices (eg, PHOLEDs, etc.) comprising emitter technology that is sensitive to protons.
  • the component (C) comprises dimethyl sulfoxide, ethylene glycol (glycols), tetramethyl urea or a mixture thereof.
  • suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, dipropylene glycol, polypropylene glycol, propylene glycol, triethylene glycol and the like.
  • the content of the component (s1): wts1 (by weight) and the content of the component (s2): wts2 (by weight) can be represented by the formula It is preferable to satisfy 1-1), more preferably to satisfy the formula (1-2), and most preferably to satisfy the formula (1-3).
  • wts1 shows the total content (weight) of (s1) components
  • wts2 is (s2) ) Indicates the total content (weight) of the components.
  • the aggregation of the (E) component is more appropriately controlled during film formation by inkjet coating, and a flatter film is formed. It is preferable because it can be done.
  • the amount of component (C) is about 50% to about 99% by weight, typically about 75% to about 98% by weight, and more typically about 90% by weight, based on the total weight of the ink composition. To about 95% by weight.
  • the ink composition can further contain (D) an amine compound.
  • the component (D) includes, but is not limited to, ethanolamine compounds and alkylamine compounds.
  • the component (D) may be used alone or in combination of two or more.
  • Suitable ethanolamine compounds are dimethylethanolamine [(CH 3 ) 2 NCH 2 CH 2 OH], triethanolamine [N (CH 2 CH 2 OH) 3 ], and N-tert-butyldiethanolamine [t- containing C 4 H 9 N (CH 2 CH 2 OH) 2].
  • Alkylamine compounds include primary, secondary and tertiary alkylamine compounds.
  • primary alkylamine compounds are, for example, ethylamine [C 2 H 5 NH 2 ], n-butylamine [C 4 H 9 NH 2 ], t-butylamine [C 4 H 9 NH 2 ], 2-ethylhexylamine , N-hexylamine [C 6 H 13 NH 2 ], n-decylamine [C 10 H 21 NH 2 ], and ethylenediamine [H 2 NCH 2 CH 2 NH 2 ].
  • Examples of secondary alkylamine compounds include diethylamine [(C 2 H 5 ) 2 NH], di (n-propylamine) [(n-C 3 H 9 ) 2 NH], di (isopropylamine) [(i -C 3 H 9 ) 2 NH], and dimethylethylenediamine [CH 3 NHCH 2 CH 2 NHCH 3 ].
  • Examples of tertiary alkylamine compounds include trimethylamine [(CH 3 ) 3 N], triethylamine [(C 2 H 5 ) 3 N], tri (n-butyl) amine [(C 4 H 9 ) 3 N], and tetramethylethylenediamine [(CH 3) 2 NCH 2 CH 2 N (CH 3) 2].
  • component (D) contains (D1) a tertiary alkylamine compound and (D2) an amine compound other than the tertiary alkylamine compound.
  • the component (D1) is used to enhance the solubility or dispersibility of the component (A). It is preferable to pretreat the component (A) with the component (D1) before the production of the ink composition, because the solubility or dispersibility of the component (A) in the component (C) is enhanced.
  • the component (A) is usually obtained as an aqueous dispersion, and thus the aqueous dispersion is dried to form a powder as the component (C). It is dissolved or dispersed to make an ink composition.
  • the solubility and dispersibility of the component (A) in the component (C) improve. ,preferable.
  • the component (D1) is preferably triethylamine.
  • Component (D2) is preferably a primary alkylamine compound.
  • the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine and ethylenediamine (A ) Preferred in view of the solubility or dispersibility of the components.
  • the component (D2) is more preferably n-butylamine or 2-ethylhexylamine, particularly preferably n-butylamine.
  • the amount of component (D) can be adjusted and measured as a weight percentage to the total amount of the ink composition.
  • the amount of component (D) is at least 0.01% by weight, at least 0.10% by weight, at least 1.00% by weight, at least 1.50% by weight, based on the total weight of the ink composition. Or at least 2.00% by weight.
  • the amount of component (D) is about 0.01 wt% to about 2.00 wt%, typically about 0.05 wt% to about 1.50 wt%, based on the total weight of the ink composition. % By weight, more typically about 0.1% by weight to about 1.00% by weight.
  • a sulfonated polythiophene is used as the component (A)
  • at least a portion of the component (D) is present in the form of an ammonium salt with a sulfonated conjugated polymer, for example, a trialkylammonium salt (sulfonated polythiophene amine adduct) May be
  • the ink composition can further include (E) metal oxide nanoparticles.
  • the ink composition contains the component (E)
  • the transparency of the charge transporting thin film obtained using the ink composition can be increased, and the absorbance of the visible spectrum can be lowered.
  • the component (E) may be used alone or in combination of two or more.
  • metal refers to an element having properties of an intermediate or mixture of chemical and / or physical properties of metals and non-metals.
  • metal refers to boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).
  • metal oxide means tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (W) It refers to an oxide of one or more combinations of metals such as tungsten) and the above-mentioned semimetals.
  • nanoparticles refers to nanoscale particles, wherein the number average diameter of the primary particles is typically 500 nm or less.
  • the average diameter of the primary particles can be, for example, transmission electron microscopy (TEM), a method of converting from the specific surface area by BET method, or the like.
  • TEM transmission electron microscopy
  • TEM particle size measurement image processing software is used to process the projected image of the nanoparticles and then the area equivalent diameter (which is defined as the diameter of a circle with the same area as the nanoparticles)
  • the particle size can be measured by the method.
  • the projection image is produced using image processing software created by the TEM manufacturer, provided with the TEM (eg, transmission electron microscope HT 7700 (available from Hitachi High-Technologies Corporation)). Do the processing.
  • the average particle diameter can be determined as a number average of circle equivalent diameters.
  • the number average particle size of primary particles of the component (E) is 500 nm or less; 250 nm or less; 100 nm or less; or 50 nm or less; or 25 nm or less.
  • the (E) component has a number average particle size of about 1 nm to about 100 nm, more typically about 2 nm to about 30 nm.
  • metal oxides boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum (Al) And oxides such as zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (tungsten), or mixed oxides containing these.
  • Non-limiting specific examples of suitable metal oxide nanoparticles are 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 and mixtures thereof, including, but not limited to, nanoparticles.
  • the ink composition is 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. It includes one or more metal oxide nanoparticles including 2 O 3 , TeO 2 , or a mixture thereof.
  • the ink composition comprises one or more metal oxide nanoparticles comprising SiO 2 .
  • the charge transportable thin film obtained using the ink composition can be made more transparent and the absorbance of the visible spectrum can be made lower. It is preferable because the current efficiency, the external quantum efficiency, and the luminance half life of the organic EL device manufactured using the charge transporting thin film can be further improved.
  • the metal oxide nanoparticles may comprise one or more organic capping groups.
  • organic capping groups may be reactive or non-reactive.
  • Reactive organic capping groups are, for example, organic capping groups that can be crosslinked in the presence of UV radiation or radical initiators.
  • the metal oxide nanoparticles comprise one or more organic capping groups.
  • suitable metal oxide nanoparticles are various solvents (eg, methyl ethyl ketone, methyl isobutyl ketone, dimethyl acetamide, ethylene glycol, isopropanol, methanol, sold by Nissan Chemical Industries, Ltd. as ORGANOSILICASOLTM). And SiO 2 nanoparticles that can be used as dispersions in ethylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, and the like.
  • solvents eg, methyl ethyl ketone, methyl isobutyl ketone, dimethyl acetamide, ethylene glycol, isopropanol, methanol, sold by Nissan Chemical Industries, Ltd. as ORGANOSILICASOLTM.
  • SiO 2 nanoparticles that can be used as dispersions in ethylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, and the like.
  • the amount of component (E) in the ink composition can be adjusted and measured as a percentage by weight of the combined weight of components (A) and (B) and optional components (D) to (F).
  • the amount of component (E) is typically 1% to 98% by weight, based on the combined weight of components (A) and (B) and optional components (D) to (F). Is about 2% to about 95% by weight, more typically about 5% to about 90% by weight, and even more typically about 10% to about 90% by weight.
  • the amount of component (E) is about 20% to about 98% by weight, based on the combined weight of components (A) and (B) and optional components (D) to (F). Typically from about 25% to about 95% by weight.
  • the ink composition can further comprise one or more (F) matrix compounds known to be useful in the hole injection layer (HIL) or the hole transport layer (HTL).
  • the component (F) is a compound capable of improving the buildup during thin film formation and making the thickness uniform and flat, and any material having such a function can be used without particular limitation.
  • An organic EL device having a charge transportable thin film produced using an ink composition further comprising the component (F) also improves the uniformity of the thickness of the light emitting layer and the like formed on the upper layer side of the charge transport thin film Therefore, there is no light emission unevenness and the like, and the device characteristics can be improved.
  • the component (F) may be used alone or in combination of two or more.
  • Component (F) may be a low molecular weight or high molecular weight compound and is different from the polythiophenes described herein.
  • the matrix compound may, for example, be a synthetic polymer. See, eg, US Patent Publication No. 2006/0175582 published Aug. 10, 2006.
  • Synthetic polymers can, for example, comprise a carbon backbone. In some embodiments, the synthetic polymer has at least one polymer side group comprising an oxygen atom or a nitrogen atom.
  • the synthetic polymer may be a Lewis base.
  • synthetic polymers contain a carbon backbone and have a glass transition temperature above 25 ° C.
  • Synthetic polymers may also be semi-crystalline or crystalline polymers, having a glass transition temperature of 25 ° C. or less and / or a melting point above 25 ° C.
  • Synthetic polymers may contain one or more acidic groups, such as sulfonic acid groups.
  • the synthetic polymer which is the component (F) is at least one alkyl or alkoxy group substituted by at least one fluorine atom and at least one sulfonic acid (—SO 3 H) residue.
  • a polymeric acid comprising one or more repeating units, optionally comprising an alkyl or alkoxy group interrupted by at least one ether linkage (—O—) group.
  • the polymeric acid comprises recurring units according to formula (II) and recurring units according to formula (III): [Wherein each R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are independently H, halogen, fluoroalkyl or perfluoroalkyl; and X is [OC (R j R k ) -C (R l R m )] r -O- [CR n R o ] z -SO 3 H, and each R j , R k , R l , R m , R n and R o are independently H, halogen, fluoroalkyl or perfluoroalkyl; r is 0-10; and z is 1-5.
  • each R 5 , R 6 , R 7 , and R 8 is independently Cl or F. In certain embodiments, each R 5 , R 7 , and R 8 is F and R 6 is Cl. In certain embodiments, each R 5 , R 6 , R 7 , and R 8 is F.
  • each R 9 , R 10 , and R 11 is F.
  • each R j , R k , R l , R m , R n, and R o is independently F, (C 1 -C 8 ) fluoroalkyl, or (C 1 -C 8 ) perfluoro It is an alkyl.
  • each R n and R o is F; r is 0; and z is 2.
  • each R 5 , R 7 , and R 8 is F and R 6 is Cl; and each R n and R o is F; r is 0 And z is 2.
  • each R 5 , R 6 , R 7 , and R 8 is F; and each R n and R o is F; r is 0; and z is 2
  • the ratio of the number of repeating units according to formula (II) (“n1”) to the number of repeating units according to formula (III) (“n2”) is not particularly limited.
  • the n1: n2 ratio is typically 9: 1 to 1: 9, more typically 8: 2 to 2: 8. In one embodiment, the n1: n2 ratio is 9: 1. In one embodiment, the n1: n2 ratio is 8: 2.
  • polymers suitable for use in the present disclosure may be synthesized using methods known to those skilled in the art or may be obtained from commercial sources.
  • a polymer comprising a repeating unit according to formula (II) and a repeating unit according to formula (III) comprises a monomer represented by formula (IIa), a monomer represented by formula (IIIa):
  • R 5 to R 11 are as defined above, and Z 1 is-[OC (R j R k ) -C (R l R m )] r -O- [CR n R o ] z a -SO 2 F, R j, R k, R l, R m, R n and R o, r, and z, and herein is synonymous with, copolymerized by a known polymerization method Followed by hydrolysis to the sulfonic acid group by hydrolysis of the sulfonyl fluoride group.
  • TFE tetrafluoroethylene
  • CTFE chlorotrifluoroethylene
  • F 2 C CF-O -CF 2 -CF 2 -SO 2 F
  • F 2 C CF-OCF 2 -CF 2 -CF 2 -CF 2 -SO (2 F etc.
  • the equivalent weight of polymeric acid is defined as the weight (grams) of polymeric acid per mole of acid group present in the polymeric acid.
  • the equivalent weight of the polymeric acid is about 400 to about 15,000 g polymer / mol acid, typically about 500 to about 10,000 g polymer / mol acid, more typically about 500 to 8,000 g polymer / mol acid, Still more typically about 500 to 2,000 g polymer / mol acid, even more typically about 600 to about 1,700 g polymer / mol acid.
  • Such polymeric acids are, for example, those sold under the trade name NAFION® by EI DuPont, those sold under the trade name AQUIVION® by Solvay Specialty Polymers, or AGC It is sold under the trade name FLEMON® by the Corporation.
  • the synthetic polymer that is component (F) is a polyether sulfone comprising one or more repeating units comprising at least one sulfonic acid (—SO 3 H) residue.
  • the polyether sulfone is a compound of formula (IV): A repeating unit according to formula (V), a repeating unit according to formula (V) and a repeating unit according to formula (VI): [Wherein, R 12 to R 20 are each independently H, halogen, alkyl or SO 3 H, provided that at least one of R 12 to R 20 is SO 3 H; 21 to R 28 are each independently H, halogen, alkyl or SO 3 H, provided that at least one of R 21 to R 28 is SO 3 H, and R 29 and R 30 are , Each of which is H or alkyl].
  • R 29 and R 30 are each alkyl. In one embodiment, R 29 and R 30 are each methyl.
  • R 12 -R 17 , R 19 and R 20 are each H and R 18 is SO 3 H.
  • R 21 -R 25 , R 27 and R 28 are each H and R 26 is SO 3 H.
  • the polyethersulfone is of the formula (VII): Where a is from 0.7 to 0.9 and b is from 0.1 to 0.3.
  • the polyether sulfone may further comprise other repeating units which may or may not be sulfonated.
  • polyether sulfone is a compound of formula (VIII): [Wherein, R 31 and R 32 are each independently H or alkyl] may contain a repeating unit.
  • any two or more repeat units described herein may be taken together to form a repeat unit, and the polyether sulfone may comprise such repeat units.
  • a repeat unit according to formula (IV) is combined with a repeat unit according to formula (VI) to give a compound of formula (IX):
  • a repeat unit according to formula (IV) is combined with a repeat unit according to formula (VIII) to give a compound of formula (X):
  • the polyether sulfone is a compound of formula (XI): Where a is from 0.7 to 0.9 and b is from 0.1 to 0.3.
  • Polyether sulfones comprising one or more repeating units comprising at least one sulfonic acid (—SO 3 H) residue are commercially available, for example sulfonated polyether sulfones -Sold as PES.
  • the synthetic polymer that is component (F) has the following formula (XII): It is a vinyl aromatic polymer containing the repeating unit shown by these.
  • Ar ' is an aromatic ring which may be substituted, and 2 or more types may be sufficient as it.
  • Ar ′ an optionally substituted phenyl group, an optionally substituted naphthyl group and the like can be mentioned.
  • the synthetic polymer which is the component (F) is a vinyl aromatic polymer (for example, poly (styrene) or a derivative thereof (except polystyrene sulfonic acid)); poly (vinyl acetate) or a derivative thereof; (Ethylene-co-vinyl acetate) or a derivative thereof; poly (pyrrolidone) or a derivative thereof (eg, poly (1-vinylpyrrolidone-co-vinyl acetate)); poly (vinyl pyridine) or a derivative thereof; poly (methyl methacrylate) Or derivatives thereof; poly (aryl ether ketones) or derivatives thereof; poly (aryl sulfones) or derivatives thereof; poly (esters) or derivatives thereof; combinations thereof, etc. It contains a polymer or an oligomer. These polymers or oligomers are preferred in terms of the improvement of the buildup during thin film formation.
  • the component (F) is preferably a vinyl aromatic polymer or a derivative thereof because this further improves the buildup during thin film formation. More preferably, it is a homopolymer or copolymer synthesized from one or more substituted or unsubstituted styrene or a derivative thereof, and particularly preferably a copolymer synthesized from at least styrene and 4-hydroxystyrene or a derivative thereof. Furthermore, the use of a vinyl aromatic polymer or a derivative thereof as the component (F) is preferable because it makes it easy to increase the transparency of the charge transportable thin film obtained from the ink composition and to lower the absorbance in the visible spectrum. As a result, it is possible to improve the current efficiency, the external quantum efficiency, and the luminance half life of the organic EL device manufactured using the charge transporting thin film.
  • the vinyl aromatic polymer or the derivative thereof is a copolymer or homopolymer which may contain a monomer component forming a repeating unit other than the repeating unit represented by the formula (XII), and is represented by the formula (XII) in the entire monomer component It refers to a copolymer or homopolymer in which the proportion of monomers forming the indicated repeat unit is 50% by weight or more.
  • the proportion of the monomer forming the repeating unit represented by the formula (XII) in the entire monomer component is preferably 70% by weight or more, more preferably 80% by weight or more, and in one embodiment, 100%.
  • the matrix compound which is the component (F) may be composed of, for example, at least one semiconductor matrix compound component. This semiconductor matrix compound component is different from the component (A) described herein.
  • the semiconducting matrix compound component may be a semiconducting small molecule or semiconducting polymer, typically consisting of repeating units comprising hole transporting units in the main chain and / or in the side chain.
  • the semiconductor matrix compound component may be neutral or doped and typically is an organic solvent (eg, toluene, chloroform, acetonitrile, cyclohexanone, anisole, chlorobenzene, o-dichlorobenzene, benzoic acid Soluble and / or dispersible in ethyl and mixtures thereof etc.
  • the amount of component (F) in the ink composition is 5% by weight to 95% by weight based on the total weight of components (A) and (B) and optional components (D) to (F). Is more preferably 50% by weight to 90% by weight, particularly preferably 60% by weight to 80% by weight. When the amount of the component (F) is in the above range, the buildup can be further improved.
  • the present application is further an ink composition, wherein (A) Formula (I): [Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or alternatively, R 1 and R 2 together form —O—Z—O— (wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium And Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, Alkyl, fluor
  • the ink composition can be prepared by any suitable method known to those skilled in the art.
  • the first aqueous mixture is mixed with the dispersion of polythiophene described herein, optionally with an aqueous dispersion of a matrix compound such as a polymeric acid, and optionally with an additional solvent
  • a matrix compound such as a polymeric acid
  • an additional solvent Prepared by The solvent containing water in the mixture is then typically removed by evaporation.
  • the resulting dry product is dissolved or dispersed in one or more organic solvents such as dimethylsulfoxide, glycol based solvents and filtered under pressure to form a non-aqueous mixture.
  • the final ink composition is prepared by mixing such a non-aqueous mixture with an onium borate salt or a solution or dispersion thereof, optionally an amine compound, a dispersion of metal oxide nanoparticles and a matrix compound or a dispersion or solution thereof. Objects can be manufactured.
  • the order of addition of these components is not particularly limited, and the ink composition can be produced in any order of addition.
  • the ink composition described herein can be prepared from a stock solution.
  • a stock solution of polythiophene as described herein can be prepared by isolating polythiophene from an aqueous dispersion in the dry state, typically by evaporation.
  • the dried polythiophene is then combined with one or more organic solvents and, optionally, an amine compound.
  • Stock solutions of onium borate salts can be prepared by dissolution with an organic solvent.
  • Stock solutions of matrix compounds can be prepared by isolating the polymeric acid from the aqueous dispersion in the dry state, typically by evaporation, when the matrix compound is a polymeric acid.
  • the dried polymeric acid is then combined with one or more organic solvents.
  • Stock solutions of other matrix compounds can be prepared similarly.
  • the stock solution of metal oxide nanoparticles is a commercially available dispersion, which may be one or more organic solvents, which may be the same or different from the solvent or solvents contained in the commercially available dispersion. It can be produced by dilution with a good organic solvent. The desired amounts of each stock solution are then combined to form the ink composition of the present disclosure.
  • the ink composition described herein isolates individual components in the dry state as described herein, but instead of preparing a stock solution, the dry components are combined It can then be prepared by providing the NQ ink composition by subsequent dissolution in one or more organic solvents.
  • the amine compound is generally added at the final preparation of the ink composition, but may be previously added before that point.
  • a sulfonated polythiophene is used as the component (A), as described above, an amine compound is added to the sulfonated polythiophene to form a corresponding ammonium salt, for example, a trialkyl ammonium salt (sulfonated polythiophene amine adduct) May be converted to If necessary, this ammonium salt may be subjected to reduction treatment, or an amine compound (eg triethylamine) is added to the solution of reduction treated sulfonated polythiophene to give ammonium salt of sulfonated polythiophene (eg triethyl ammonium) It may be precipitated in the form of a powder as a salt) and recovered.
  • a solution obtained by adding water and triethylamine to a reduction treated sulfonated polythiophene to dissolve it and stirring it under heating (eg 60 ° C.) Isopropyl alcohol and acetone may be added thereto to precipitate the sulfonated conjugated polymer triethylammonium salt, which may be filtered and recovered.
  • the total solids content (% TS) in the ink composition is about 0.1 wt% to about 50 wt%, typically about 0.3 wt% to about 40 wt%, based on the total weight of the ink composition. More typically from about 0.5% to about 15% by weight, even more typically from about 1% to about 5% by weight.
  • the charge transporting thin film can be produced by applying the ink composition on a substrate and evaporating the solvent.
  • the charge transporting thin film is preferably a hole transporting thin film.
  • the ink compositions of the present disclosure can be cast and annealed as thin films on a substrate.
  • the present disclosure is also a method of forming a hole transport thin film, 1) coating a substrate with the ink composition disclosed herein; and 2) forming a hole transporting thin film by annealing the coating on the substrate.
  • the coating of the ink composition on the substrate is, for example, for spin casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, doctor blade method, and for example for the preparation of organic electronic devices. It can be carried out by methods known in the art, including any other methods known in the art of
  • the substrate may be flexible or rigid, organic or inorganic.
  • Suitable substrate compounds include, for example, glass (including, for example, display glass), ceramics, metals, and plastic thin films.
  • annealing refers to any common process for forming a cured layer, typically a thin film, on a substrate coated with the ink composition of the present disclosure.
  • General annealing processes are known to those skilled in the art.
  • the solvent is removed from the substrate coated with the ink composition.
  • the removal of the solvent is carried out, for example, by subjecting the coated substrate to a pressure less than atmospheric pressure, and / or heating the coating deposited on the substrate to a certain temperature (annealing temperature), and this temperature is maintained for a certain period (annealing time) B) maintaining and then achieving by slowly cooling the resulting layer, typically a thin film, to room temperature.
  • the step of annealing can be carried out by heating the substrate coated with the ink composition by any method known to the person skilled in the art, for example by heating in an oven or on a hot plate .
  • Annealing can be performed under an inert environment, such as a nitrogen atmosphere or a noble gas (eg, argon gas, etc.) atmosphere.
  • the annealing may be performed in an air atmosphere.
  • the annealing temperature is about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C., more typically about 200 ° C. to about 300 ° C., still more typically about 230 ° C. It is about 300 ° C.
  • Annealing time is the time during which the annealing temperature is maintained.
  • the annealing time is about 3 to about 40 minutes, typically about 15 to about 30 minutes.
  • the annealing temperature is about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C., more typically about 200 ° C. to about 300 ° C., still more typically about 250 to about 300 ° C.
  • the temperature is about 300 ° C.
  • the annealing time is about 3 to about 40 minutes, typically about 15 to about 30 minutes.
  • the present disclosure relates to hole transporting thin films formed by the methods described herein.
  • Visible light transmission is important, and good transmission (low light absorption) where the film thickness is large is particularly important.
  • thin films produced by the methods of the present disclosure have a transmission of at least about 85%, typically at least 90% (typically with the substrate) of light having a wavelength of about 380-800 nm. Can be shown. In one embodiment, the transmission is at least about 90%.
  • thin films produced by the methods of the present disclosure have a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm.
  • thin films produced by the methods of the present disclosure exhibit transmission of at least about 90%, and about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm. It has a thickness of ⁇ 120 nm. In certain embodiments, thin films produced by the methods of the present disclosure exhibit a transmission (% T) of at least about 90% and have a thickness of about 50 nm to 120 nm.
  • Thin films produced by the methods of the present disclosure can be produced on substrates optionally containing electrodes or additional layers used to improve the electronic properties of the final device.
  • the resulting thin film may be resistant to one or more organic solvents, which are then used as liquid carriers in the ink for layers to be coated or deposited during fabrication of the device.
  • the thin film is, for example, resistant to toluene, which can then be the solvent in the ink for the layer to be coated or deposited during fabrication of the device.
  • Organic EL device comprising a thin film prepared by the method described herein.
  • the devices described herein can be manufactured by methods known in the art, including, for example, dissolution methods.
  • the ink can be applied by standard methods and the solvent can be removed.
  • the thin film prepared by the methods described herein may be the HIL and / or HTL layers in the device.
  • OLEDs Organic light emitting diodes
  • Conducting polymers that emit light are described, for example, in US Pat. Nos. 5,247,190 and 5,401,827 (Cambridge Display Technologies).
  • Device architecture, physical principles, dissolution methods, layering, mixing, and compound synthesis and formulation can be found in Kraft et al., "Electroluminescent Conjugated Polymers-Seeing Polymers in a New Light," Angew. Chem. Int. Ed., 1998, 37, 402-428, which is incorporated herein by reference in its entirety.
  • Luminescent materials known in the art and commercially available that contain polymers as well as organic molecules can be used.
  • organic electroluminescent compounds include: (I) poly (p-phenylenevinylene) and its derivatives substituted at various positions on the phenylene residue; (Ii) poly (p-phenylenevinylene) and derivatives thereof substituted at various positions on the vinylene residue; (Iii) Poly (p-phenylenevinylene) and its derivatives which are substituted at various positions on the phenylene residue and also at various positions on the vinylene residue; (Iv) a poly (arylene vinylene), wherein the arylene may be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole etc; (V) a derivative of poly (arylene vinylene), wherein the arylene may be the same as in (iv) above, and further having substituents at various positions on the arylene; (Vi) a derivative of poly (arylene vinylene), wherein the arylene may be the same as in (ii)
  • Preferred organic light emitting polymers include SUMATION's light emitting polymers ("LEP”) or families thereof, copolymers, derivatives, or mixtures thereof that emit green, red, blue, or white light; Is available from Sumation KK.
  • Other polymers include polyspirofluorene-like polymers available from Covion Organic Semiconductors GmbH, Frankfurt, Germany® (now owned by Merck®).
  • organic electroluminescent layer small organic molecules that emit fluorescence or phosphorescence can be used as the organic electroluminescent layer.
  • organic electroluminescent compounds are (i) tris (8-hydroxyquinolinato) aluminum (Alq); (ii) 1,3-bis (N, N-dimethylaminophenyl) -1,3,4 -Oxadiazole (OXD-8); (iii) oxo-bis (2-methyl-8-quinolinato) aluminum; (iv) bis (2-methyl-8-hydroxyquinolinato) aluminum; (v) bis (hydroxy) Benzoquinolinato) beryllium (BeQ 2 ); (vi) bis (diphenylvinyl) biphenylene (DPVBI); and arylamine substituted distyrylarylene (DSA amine).
  • Devices can often be made using multilayer structures that can be prepared, for example, by dissolution or vacuum methods, as well as printing and patterning methods.
  • HIL hole injection layer
  • the embodiments described herein for the hole injection layer (HIL), which are effectively incorporated into the composition for use as a hole injection layer, are effective. Can be performed.
  • HIL in the device examples include: 1) Hole injection in OLEDs, including PLEDs and SMOLEDs; for example, HIL in PLEDs can use all classes of conjugated polymer light emitters, where the conjugation entraps carbon or silicon atoms.
  • HILs in SMOLEDs the following are examples: SMOLEDs containing fluorescent emitters; SMOLEDs containing phosphorescent emitters; SMOLEDs containing one or more organic layers in addition to the HIL layer; Or SMOLED being treated from an aerosol spray or by any other treatment method.
  • HILs in OLEDs of the dendrimer or oligomeric organic semiconductor system include: HILs in OLEDs of the dendrimer or oligomeric organic semiconductor system; bipolar light emitting FETs, wherein HILs are used to regulate charge injection or in FETs used as electrodes ; 2) Hole extraction layer in OPV; 3) channel material in transistor; 4) channel materials in circuits including combinations of transistors, such as logic gates; 5) electrode material in transistor; 6) Gate layer in capacitor; 7) A chemical sensor, wherein modulation of the doping level is achieved by the relationship between the species to be sensed and the conducting polymer; 8) Electrode or electrolyte material in the battery.
  • Photoactive layers can be used in OPV devices.
  • Photovoltaic devices are described, for example, in US Pat. Nos. 5,454,880; 6,812,399; and 6,933,436, for example, fullerene derivatives mixed with conductive polymers
  • the photoactive layer can comprise a mixture of conducting polymers, a mixture of conducting polymers and semiconducting nanoparticles, and small molecule bilayers such as phthalocyanines, fullerenes, and porphyrins.
  • Common electrode compounds and substrates and also encapsulation compounds can be used.
  • the cathode comprises Au, Ca, Al, Ag, or a combination thereof.
  • the anode comprises indium tin oxide.
  • the light emitting layer comprises at least one organic compound.
  • interface modification layers such as interlayers, and optical spacer layers can be used.
  • An electron transport layer can be used.
  • the present disclosure also relates to methods of manufacturing the devices described herein.
  • a method of manufacturing the device comprises: providing a substrate; for example, laminating a transparent conductor such as indium tin oxide on the substrate; an ink composition as described herein Providing: forming a hole injection layer or a hole transport layer by laminating an ink composition on a transparent conductor; laminating an active layer on a hole injection layer or a hole transport layer (HTL) And laminating the cathode on the active layer.
  • a transparent conductor such as indium tin oxide
  • the substrate may be flexible or rigid, organic or inorganic.
  • Suitable substrate compounds include, for example, glass, ceramic, metal and plastic thin films.
  • a method of manufacturing the device comprises: an ink composition as described herein, an OLED, a photovoltaic device, an ESD, a SMOLED, a PLED, a sensor, a supercapacitor, a cation converter, a drug delivery device, an electro Application as part of a HIL or HTL layer in a chromic element, a transistor, a field effect transistor, an electrode modifier, an electrode modifier for an organic field transistor, an actuator, or a transparent electrode.
  • Lamination of the ink composition to form the HIL or HTL layer can be carried out by methods known in the art (eg, spin casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, doctoring Can be carried out by the blade method, and including, for example, any other method known in the art for the production of organic electronic devices.
  • the HIL layer is thermally annealed. In one embodiment, the HIL layer is thermally annealed at a temperature of about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C. In one embodiment, the HIL layer is heated at a temperature of about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C., for about 3 to about 40 minutes, typically about 15 to about 30 minutes. Annealing.
  • a HIL or HTL capable of exhibiting at least about 85%, and typically at least about 90% transmission of light having a wavelength of about 380-800 nm (typically with the substrate) Can be prepared. In one embodiment, the transmission is at least about 90%.
  • the HIL layer has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm.
  • the HIL layer exhibits a transmission of at least about 90% and has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm. . In one embodiment, the HIL layer exhibits a transmission (% T) of at least about 90% and has a thickness of about 50 nm to 120 nm.
  • the ether layer was concentrated by an evaporator at 40-45 ° C., and then dried under reduced pressure for 20 hours to obtain 24.000 g of the desired product as a pale yellow solid.
  • the obtained target substance was identified by 1 H-NMR and LDI-MS.
  • 1 H-NMR 300 MHz, DMSO-d6): ⁇ 7.40 to 7.80 (19 H, m)
  • LDI-MS m / Z found: 371.04 ([M] + calcd: 371.09).
  • Example 1-1 0.125 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3 is 2.28 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt
  • Embodiment 1-2 0.025 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3, 2.35 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt
  • Embodiment 1-3 0.025 g of the charge transport material S-poly (3-MEET) -A obtained in Synthesis Example 3, 1.53 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt
  • Embodiment 1-4 0.025 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3, 2.35 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt
  • S-poly (3-MEET) -A obtained in Synthesis Example 3 is 1.20 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 1.95 g (manufactured by KK), 4.88 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.98 g of 2- (benzyloxy) ethanol (manufactured by Kanto Chemical Co., Ltd.) and n-butylamine (Tokyo) It was made to melt
  • ITO substrate As an ITO substrate, a glass substrate of 25 mm ⁇ 25 mm ⁇ 0.7 t in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and by O 2 plasma cleaning device (150 W, 30 seconds) before use The impurities on the surface were removed.
  • ITO indium tin oxide
  • ⁇ -NPD N, N′-di (1-) is used as a hole transport layer using a vapor deposition apparatus (vacuum degree 1.0 ⁇ 10 ⁇ 5 Pa).
  • Naphthyl) -N, N'-diphenylbenzidine was deposited to a thickness of 30 nm at 0.2 nm / sec.
  • 10 nm of electron block material HTEB-01 manufactured by Kanto Chemical Co., Ltd. was formed as a hole transport layer.
  • a light emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • a light emitting layer dopant material Ir (PPy) 3 were co-deposited as a light emitting layer.
  • the deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and 40 nm was laminated.
  • thin films of Alq 3 as an electron transport layer, lithium fluoride as an electron injection layer, and aluminum as a cathode layer were sequentially laminated to obtain an organic EL element.
  • the deposition rate was 0.2 nm / sec for Alq 3 and aluminum and 0.02 nm / sec for lithium fluoride, and the film thickness was 20 nm, 0.5 nm and 80 nm, respectively.
  • the characteristic was evaluated. Sealing was performed in the following procedure.
  • the organic EL element is housed between the sealing substrate in a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76 ° C. or less, and the sealing substrate is an adhesive (Moresco Co., Ltd., Mores moisture cut WB90US (P)) Bonded together.
  • a water-capturing agent manufactured by Dynik Co., Ltd., HD-071010W-40 was placed in the sealing substrate together with the organic EL element.
  • the sealing substrate thus bonded was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.
  • the luminance, driving voltage, current density, current efficiency, and external quantum efficiency were measured with a multi-channel IVL measuring device manufactured by E-Hetchsee.
  • the luminance half life was measured by an organic EL luminance life evaluation system PEL-105S manufactured by E-HC.
  • Examples 2-1 to 2-4 (A) a polythiophene containing a repeating unit represented by the formula (I), (B) an anion represented by the formula (a1) or (a2) and a counter cation
  • An ink composition comprising a liquid carrier containing an onium borate salt comprising the compound and an organic solvent is applicable to a wet process, and a hole injection layer formed from the composition is well driven as an organic EL element.
  • the number average molecular weight and weight average molecular weight of the copolymer obtained according to the following synthesis example were determined using a GPC apparatus (Shodex column KD 800 and TOSOH column TSK-GEL) manufactured by Tosoh Corp. Elution condition by flowing formamide (10 mmol / L (liter) mixture of lithium bromide-hydrate (LiBr ⁇ H 2 O) as an additive) at a flow rate of 1 ml / min into the column (column temperature 40 ° C.) It measured by.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Synthesis Example 4 Dissolve 10.0 g of MMA, 12.5 g of HEMA, 20.0 g of CHMI, 2.50 g of HPMA, 5.00 g of MAA and 3.20 g of AIBN in 79.8 g of PGME and react at 60 ° C. to 100 ° C. for 20 hours Thus, an acrylic polymer solution (solid content concentration 40 wt%) was obtained (P3). Mn of the obtained acrylic polymer P3 was 3,700, and Mw was 6,100.
  • Synthesis Example 5 Acrylic by dissolving HPA-QD 2.50 g, PFHMA 7.84 g, MAA 0.70 g, CHMI 1.46 g and AIBN 0.33 g in 51.3 g of CHN and agitating at 110 ° C. for 20 hours A polymer solution (solid content concentration 20 wt%) was obtained (P4). Mn of the obtained acrylic polymer P4 was 4,300, and Mw was 6,300.
  • a positive photosensitive resin composition was prepared by preparing a homogeneous solution.
  • the thin film was developed by immersing the thin film in a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) for 20 seconds, and then the thin film was washed with running ultrapure water for 20 seconds. Then, the thin film on which the rectangular pattern was formed was subjected to post-baking (heating at a temperature of 230 ° C. for 30 minutes) to be cured, thereby producing a banked substrate.
  • TMAH tetramethylammonium hydroxide
  • Example 3 Evaluation of cross-sectional shape of charge transporting thin film [Example 3] and [Comparative Example 2] It is obtained in Example 1-5 and Comparative Example 1 using Inkjet Designer manufactured by Cluster Technology Inc. in the rectangular opening (film formation region) on the banked substrate obtained in the step [6].
  • the resulting ink composition is discharged, and the resulting coated film is dried under reduced pressure at a reduced pressure (vacuum degree) of 10 Pa or less for 15 minutes, and then dried on a hot plate at 230 ° C. for 30 minutes.
  • the charge transporting thin film of Comparative Example 2 was formed.
  • the shape of the cross section of the charge transporting thin film of Example 3 and Comparative Example 2 was measured with a fine shape measuring machine ET4000A (manufactured by Kosaka Laboratory). The obtained result is shown in FIG.
  • the ink composition of the present invention can be used as a charge transporting thin film material of an organic electroluminescent device.

Abstract

Provided is an ink composition that can be applied to various wet processes and is excellent in charge transportability. The ink composition comprises (A) polythiophene, (B) an onium borate salt and (C) a liquid carrier that includes an organic solvent.

Description

インク組成物Ink composition
　本発明は、ポリチオフェン化合物、オニウムボレート塩及び液体担体を含む、インク組成物に関する。また、本開示は、インク組成物から形成された電荷輸送性薄膜、及び該電荷輸送性薄膜を有する有機エレクトロルミネッセンス素子に関する。 The present invention relates to an ink composition comprising a polythiophene compound, an onium borate salt and a liquid carrier. The present disclosure also relates to a charge transporting thin film formed from an ink composition, and an organic electroluminescent device having the charge transporting thin film.
　有機エレクトロルミネッセンス（以下、有機ＥＬという）素子には、発光層や電荷注入層として、有機化合物からなる電荷輸送性薄膜が用いられる。特に、正孔注入層は、陽極と、正孔輸送層あるいは発光層との電荷の授受を担い、有機ＥＬ素子の低電圧駆動及び高輝度を達成するために重要な機能を果たす。
　正孔注入層の形成方法は、蒸着法に代表されるドライプロセスと、スピンコート法に代表されるウェットプロセスとに大別され、これら各プロセスを比べると、ウェットプロセスの方が大面積に平坦性の高い薄膜を効率的に製造できる。それゆえ、有機ＥＬディスプレイの大面積化が進められている現在、ウェットプロセスで形成可能な正孔注入層が望まれている。
　このような事情に鑑み、本発明者らは、各種ウェットプロセスに適用可能であるとともに、有機ＥＬ素子の正孔注入層に適用した場合に優れたＥＬ素子特性を実現できる薄膜を与える電荷輸送性材料や、それに用いる有機溶媒に対する溶解性の良好な化合物を開発してきている（特許文献１及び２）。 In an organic electroluminescent (hereinafter referred to as organic EL) device, a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injecting layer. In particular, the hole injection layer is responsible for charge transfer between the anode and the hole transport layer or the light emitting layer, and plays an important function to achieve low voltage drive and high luminance of the organic EL element.
The formation method of the hole injection layer is roughly divided into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method, and when these processes are compared, the wet process has a larger area Can efficiently produce thin films with high Therefore, as the area of the organic EL display is increased, a hole injection layer that can be formed by a wet process is desired at present.
In view of such circumstances, the present inventors are applicable to various wet processes and charge transportability giving a thin film which can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element. Compounds having good solubility in materials and organic solvents used therefor have been developed (Patent Documents 1 and 2).
　一方、有機電子デバイス用インク組成物として、スルホン化共役ポリマー、アミン化合物等を含む組成物が知られている（特許文献３）。該インク組成物中のアミン化合物の存在は、良好な貯蔵寿命と安定性を有するインク組成物を提供するだけでなく、該インク組成物から形成される薄膜は、優れた均質性を示す。しかしながら、該インク組成物から形成される正孔注入層を含む有機発光ダイオード（ＯＬＥＤ）デバイスの電荷輸送性は、依然として改善の余地がある。 On the other hand, a composition containing a sulfonated conjugated polymer, an amine compound and the like is known as an ink composition for organic electronic devices (Patent Document 3). The presence of an amine compound in the ink composition not only provides the ink composition with good shelf life and stability, but the thin film formed from the ink composition exhibits excellent homogeneity. However, the charge transport properties of organic light emitting diode (OLED) devices that include a hole injection layer formed from the ink composition still have room for improvement.
国際公開第２００８／０３２６１６号International Publication No. 2008/032616 国際公開第２００８／１２９９４７号WO 2008/129947 国際公開第２０１６／１７１９３５号International Publication No. 2016/171935
　本発明が解決しようとする課題は、各種ウェットプロセスに適用可能であり、電荷輸送性に優れたインク組成物を提供することである。 The problem to be solved by the present invention is to provide an ink composition that is applicable to various wet processes and has excellent charge transportability.
　本発明者らは、鋭意研究を行った結果、特定構造を有するポリチオフェン化合物、特定構造を有するオニウムボレート塩及び液体担体を含むインク組成物は、各種ウェットプロセスに適用可能であり、電荷輸送性に優れた電荷輸送性薄膜を形成できることを見出し、本発明を完成させた。 As a result of intensive studies, the inventors of the present invention have found that ink compositions comprising a polythiophene compound having a specific structure, an onium borate salt having a specific structure, and a liquid carrier are applicable to various wet processes and have charge transportability. The inventors have found that excellent charge transporting thin films can be formed, and completed the present invention.
　すなわち、本発明は、下記の発明を提供する。 That is, the present invention provides the following inventions.
（１）インク組成物であって、
　（Ａ）式（Ｉ）：
Figure JPOXMLDOC01-appb-C000012
［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、－ＳＯ３Ｍ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－Ｚ－Ｏ－を形成する
（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、Ｚは、場合によりハロゲン又はＹで置換されているヒドロカルビレン基（ここで、Ｙは、炭素数１～１０の直鎖又は分岐鎖のアルキル基又はアルコキシアルキル基であり、該アルキル基又はアルコキシアルキル基は、任意の位置がスルホン酸基で置換されていてもよい）であり、ｐは、１以上の整数であり、そして、Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）］で表される繰り返し単位を含むポリチオフェン；
　（Ｂ）オニウムボレート塩であって、式（ａ１）：
Figure JPOXMLDOC01-appb-C000013
で表されるアニオン、及び式（ａ２）：
Figure JPOXMLDOC01-appb-C000014
で表される１価又は２価のアニオン
［式中、Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基であり、Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－である］からなる群より選択される少なくとも１種のアニオンと対カチオンとからなるオニウムボレート塩（ただし、電気的中性な塩である）；及び
　（Ｃ）有機溶媒を含む液体担体
を含む組成物。 (1) an ink composition,
(A) Formula (I):
Figure JPOXMLDOC01-appb-C000012
[Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or alternatively, R 1 and R 2 together form —O—Z—O— (wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium And Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, Alkyl, fluoroalkyl or aryl) is a polythiophene containing a repeating unit represented by
(B) an onium borate salt, which is represented by the formula (a1):
Figure JPOXMLDOC01-appb-C000013
And the anion represented by and the formula (a2):
Figure JPOXMLDOC01-appb-C000014
A monovalent or divalent anion represented by the formula: wherein Ar is each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent; An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a fluoroaralkyl group having 7 to 10 carbon atoms , L represents an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -, and an onium borate salt composed of at least one anion selected from the group consisting of: A composition comprising a liquid carrier comprising a neutral salt); and (C) an organic solvent.
（２）Ａｒが、１又は２以上の電子吸引性置換基を有するアリール基である、（１）記載のインク組成物。 (2) The ink composition according to (1), wherein Ar is an aryl group having one or more electron withdrawing substituents.
（３）電子吸引性置換基が、ハロゲン原子である、（２）記載のインク組成物。 (3) The ink composition according to (2), wherein the electron withdrawing substituent is a halogen atom.
（４）前記アニオンが、式（ａ３）で表される、（１）～（３）のいずれか一つに記載のインク組成物。
Figure JPOXMLDOC01-appb-C000015
 (4) The ink composition according to any one of (1) to (3), wherein the anion is represented by the formula (a3).
Figure JPOXMLDOC01-appb-C000015
（５）対カチオンが、式（ｃ１）～（ｃ５）：
Figure JPOXMLDOC01-appb-C000016
からなる群より選択される、（１）～（４）のいずれか一つに記載のインク組成物。 (5) The counter cation is represented by formulas (c1) to (c5):
Figure JPOXMLDOC01-appb-C000016
The ink composition according to any one of (1) to (4), which is selected from the group consisting of
（６）（Ｂ）成分が下記式で表される、（１）～（５）のいずれか一つに記載のインク組成物。
Figure JPOXMLDOC01-appb-C000017
 (6) The ink composition according to any one of (1) to (5), wherein the component (B) is represented by the following formula.
Figure JPOXMLDOC01-appb-C000017
（７）Ｒ１及びＲ２が、それぞれ独立に、Ｈ、フルオロアルキル、－ＳＯ３Ｍ、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－（ＣＨ２）ｑ－Ｏ－（ここで、（ＣＨ２）ｑは、場合によりＹで置換されている）を形成し；ここで、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄが、それぞれ独立に、Ｈ、ハロゲン、アルキル、フルオロアルキル、又はアリールであり；Ｒｅが、Ｈ、アルキル、フルオロアルキル、又はアリールであり；ｐが、１、２、又は３であり；Ｒｆが、アルキル、フルオロアルキル、又はアリールであり；ｑが、１、２、又は３であり；そしてＹが、炭素数１～１０の直鎖又は分岐鎖のアルコキシアルキル基であり、該アルコキシアルキル基は任意の位置がスルホン酸基で置換されていてもよい、（１）～（６）のいずれか一つに記載のインク組成物。 (7) R 1 and R 2 are each independently H, fluoroalkyl, -SO 3 M, -O [C (R a R b ) -C (R c R d ) -O] p -R e , Or -OR f , or R 1 and R 2 together are -O- (CH 2 ) q -O- (wherein (CH 2 ) q is optionally substituted by Y Where M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and each of R a , R b , R c and R d is Independently H, halogen, alkyl, fluoroalkyl or aryl; R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; R f is alkyl , Fluoroalkyl Q is 1, 2, or 3; and Y is a linear or branched alkoxyalkyl group having 1 to 10 carbon atoms, and the alkoxyalkyl group is a sulfonic acid at any position. The ink composition according to any one of (1) to (6), which may be substituted with a group.
（８）Ｒ１が、Ｈであり、そしてＲ２が、Ｈ以外である、（１）～（７）のいずれか一つに記載のインク組成物。 (8) The ink composition according to any one of (1) to (7), wherein R 1 is H and R 2 is other than H.
（９）Ｒ１及びＲ２が、両方ともＨ以外である、（１）～（７）のいずれか一つに記載のインク組成物。 (9) The ink composition according to any one of (1) to (7), wherein R 1 and R 2 are both other than H.
（１０）Ｒ１及びＲ２が、それぞれ独立に、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－（ＣＨ２）ｑ－Ｏ－を形成する、（９）記載のインク組成物。 (10) R 1 and R 2 are each independently —O [C (R a R b ) —C (R c R d ) —O] p —R e or —OR f , or The ink composition according to (9), wherein R 1 and R 2 together form —O— (CH 2 ) q —O—.
（１１）Ｒ１及びＲ２が、両方とも－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅである、（９）記載のインク組成物。 (11) The ink composition according to (9), wherein R 1 and R 2 are both —O [C (R a R b ) -C (R c R d ) -O] p -R e .
（１２）各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄが、それぞれ独立に、Ｈ、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルであり；そしてＲｅが、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルである、（７）～（１１）のいずれか一つに記載のインク組成物。 (12) each of R a , R b , R c and R d independently represents H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl; The ink composition according to any one of (7) to (11), wherein R e is (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl, or phenyl.
（１３）（Ａ）成分が、下記式：
Figure JPOXMLDOC01-appb-C000018
で表される基（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである）、及びこれらの組合せからなる群より選択される繰り返し単位を含む、（１）～（１２）のいずれか一つに記載のインク組成物。 (13) The component (A) has the following formula:
Figure JPOXMLDOC01-appb-C000018
A repeating unit selected from the group consisting of a group represented by: wherein M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and combinations thereof, The ink composition according to any one of (1) to (12).
（１４）（Ａ）成分が、スルホン化ポリ（３－ＭＥＥＴ）である、（１）～（１３）のいずれか一つに記載のインク組成物。 (14) The ink composition according to any one of (1) to (13), wherein the component (A) is a sulfonated poly (3-MEET).
（１５）（Ａ）成分が、式（Ｉ）で表される繰り返し単位を、繰り返し単位の総重量に基づいて５０重量％より多い量で含む、（１）～（１４）のいずれか一つに記載のインク組成物。 (15) Any one of (1) to (14), wherein the component (A) contains the repeating unit represented by the formula (I) in an amount of more than 50% by weight based on the total weight of the repeating units The ink composition as described in.
（１６）（Ｃ）成分が、グリコールモノエーテル類、グリコールジエーテル類及びグリコール類からなる群より選択される少なくとも１種を含む、（１）～（１５）のいずれか一つに記載のインク組成物。 (16) The ink according to any one of (1) to (15), wherein the component (C) contains at least one selected from the group consisting of glycol monoethers, glycol diethers and glycols Composition.
（１７）更に、（Ｄ）アミン化合物を含む、（１）～（１６）のいずれか一つに記載のインク組成物。 (17) The ink composition according to any one of (1) to (16), further comprising (D) an amine compound.
（１８）（Ｄ）成分が、（Ｄ１）第三級アルキルアミン化合物と、（Ｄ２）第三級アルキルアミン化合物以外のアミン化合物とを含む、（１７）記載のインク組成物。 (18) The ink composition according to (17), wherein the component (D) comprises (D1) a tertiary alkylamine compound and (D2) an amine compound other than a tertiary alkylamine compound.
（１９）（Ｄ２）成分が、第一級アルキルアミン化合物である、（１８）記載のインク組成物。 (19) The ink composition according to (18), wherein the component (D2) is a primary alkylamine compound.
（２０）第一級アルキルアミン化合物が、エチルアミン、ｎ－ブチルアミン、ｔ－ブチルアミン、２－エチルヘキシルアミン、ｎ－ヘキシルアミン、ｎ－デシルアミン及びエチレンジアミンからなる群より選択される少なくとも１種である、（１９）記載のインク組成物。 (20) The primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine and ethylenediamine (wherein 19) The ink composition described above.
（２１）第一級アルキルアミン化合物が、ｎ－ブチルアミンである、（１９）又は（２０）記載のインク組成物。 (21) The ink composition according to (19) or (20), wherein the primary alkylamine compound is n-butylamine.
（２２）更に、（Ｅ）金属酸化物ナノ粒子を含む、（１）～（２１）のいずれか一つに記載に記載のインク組成物。 (22) The ink composition according to any one of (1) to (21), further comprising (E) metal oxide nanoparticles.
（２３）更に、（Ｆ）マトリックス化合物を含む、（１）～（２２）のいずれか一つに記載のインク組成物。 (23) The ink composition according to any one of (1) to (22), further comprising (F) a matrix compound.
（２４）（１）～（２３）のいずれか一つに記載のインク組成物から形成された電荷輸送性薄膜。 (24) A charge transporting thin film formed from the ink composition according to any one of (1) to (23).
（２５）（２４）記載の電荷輸送性薄膜を有する有機エレクトロルミネッセンス素子。 (25) An organic electroluminescent device having the charge transporting thin film according to (24).
（２６）（１）～（２３）のいずれか一つに記載のインク組成物を基材上に塗布し、溶媒を蒸発させることを特徴とする電荷輸送性薄膜の製造方法。 (26) A method of producing a charge transporting thin film, comprising applying the ink composition according to any one of (1) to (23) onto a substrate and evaporating the solvent.
（２７）インク組成物であって、
　（Ａ）式（Ｉ）：
Figure JPOXMLDOC01-appb-C000019
［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、－ＳＯ３Ｍ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－Ｚ－Ｏ－を形成する
（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、Ｚは、場合によりハロゲン又はＹで置換されているヒドロカルビレン基（ここで、Ｙは、炭素数１～１０の直鎖又は分岐鎖のアルキル基又はアルコキシアルキル基であり、該アルキル基又はアルコキシアルキル基は、任意の位置がスルホン酸基で置換されていてもよい）であり、ｐは、１以上の整数であり、そして、Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）］で表される繰り返し単位を含むポリチオフェン；
　（Ｂ）オニウムボレート塩であって、式（ａ１）：
Figure JPOXMLDOC01-appb-C000020
で表されるアニオン、式（ａ２）：
Figure JPOXMLDOC01-appb-C000021
で表される１価又は２価のアニオン、及び（ａ５）
Figure JPOXMLDOC01-appb-C000022
で表されるアニオン
［式中、Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基であり、Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－であり、Ｅは長周期型周期表の第１３族又は第１５族に属する元素を表す］からなる群より選択される少なくとも１種のアニオンと対カチオンとからなるオニウムボレート塩（ただし、電気的中性な塩である）；
　（Ｃ）有機溶媒を含む液体担体；及び
　（Ｆ）マトリックス化合物
を含む組成物。 (27) It is an ink composition,
(A) Formula (I):
Figure JPOXMLDOC01-appb-C000019
[Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or alternatively, R 1 and R 2 together form —O—Z—O— (wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium And Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, Alkyl, fluoroalkyl or aryl) is a polythiophene containing a repeating unit represented by
(B) an onium borate salt, which is represented by the formula (a1):
Figure JPOXMLDOC01-appb-C000020
Anion represented by the formula (a2):
Figure JPOXMLDOC01-appb-C000021
And a monovalent or divalent anion represented by and (a5)
Figure JPOXMLDOC01-appb-C000022
Wherein Ar is each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and R is 1 to 10 carbon atoms Alkyl group, cycloalkyl group having 3 to 20 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms or fluoroaralkyl group having 7 to 10 carbon atoms, and L is an alkylene group , -NH-, an oxygen atom, a sulfur atom or -CN + -, and E represents an element belonging to Group 13 or 15 of the long periodic table, at least one selected from the group consisting of An onium borate salt consisting of an anion and a counter cation (however, an electrically neutral salt);
A composition comprising (C) a liquid carrier comprising an organic solvent; and (F) a matrix compound.
　本発明により、各種ウェットプロセスに適用可能であり、電荷輸送性に優れたインク組成物を提供することができる。 According to the present invention, it is possible to provide an ink composition that is applicable to various wet processes and that is excellent in charge transportability.
図１は、実施例３及び比較例２の電荷輸送性薄膜の断面の形状を表す。FIG. 1 shows the shape of the cross section of the charge transporting thin film of Example 3 and Comparative Example 2.
　本明細書に使用されるとき、単数で記載された名詞又は単数・複数を区別せずに記載された名詞は、特に断りない限り「１つ（１個）以上」又は「少なくとも１つ（１個）」を意味する。 As used herein, the noun described in the singular or the noun described without distin- guishing the singular or plural refers to "one (one) or more" or "at least one (1) unless otherwise noted. Means ")."
　本明細書に使用されるとき、「～を含む（comprises）」という用語は、「本質的に～からなる」及び「～からなる」を包含する。「～を含む（comprising）」という用語は、「本質的に～からなる」及び「～からなる」を包含する。 As used herein, the term "comprises" includes "consisting essentially of" and "consisting of." The term "comprising" includes "consisting essentially of" and "consisting of."
　「～がない（free of）」という句は、この句により修飾される材料の外部添加がないこと、及び当業者には公知の分析手法（例えば、ガス又は液体クロマトグラフィー、分光光度法、光学顕微鏡法等）により観測できる検出可能な量のこの材料が存在しないことを意味する。 The phrase "free of" means that there is no external addition of the material modified by this phrase, and analytical techniques known to the person skilled in the art (eg gas or liquid chromatography, spectrophotometry, optical This means that there is no detectable amount of this material observable by microscopy etc.).
　本開示を通して、種々の刊行物が参照により取り込まれる。参照により本明細書に取り込まれる該刊行物における任意の言語の意味が、本開示の言語の意味と矛盾するならば、特に断りない限り、本開示の言語の意味が優先するものである。 Various publications are incorporated by reference through the present disclosure. Unless the meaning of any language in the publication, which is incorporated herein by reference, contradicts the meaning of the language of the present disclosure, the meaning of the language of the present disclosure prevails unless otherwise noted.
　本明細書に使用されるとき、有機基に関して「（Ｃｘ－Ｃｙ）」（ここで、ｘ及びｙは、それぞれ整数である）という用語は、この基が、１個の基に炭素原子ｘ個から炭素原子ｙ個までを含んでよいことを意味する。 As used herein, "(C x -C y)" (wherein, x and y are each an integer) with respect to the organic group as used herein refers to the group, the carbon atom to one of the groups It means that x to y carbon atoms may be included.
　本明細書に使用されるとき、「アルキル」という用語は、一価の直鎖又は分岐の飽和炭化水素基、更に典型的には、一価の直鎖又は分岐の飽和（Ｃ１－Ｃ４０）炭化水素基、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、tert－ブチル、ヘキシル、２－エチルヘキシル、オクチル、ヘキサデシル、オクタデシル、エイコシル、ベヘニル、トリアコンチル、及びテトラコンチル等を意味する。 As used herein, the term "alkyl" refers to a monovalent linear or branched saturated hydrocarbon group, more typically a monovalent linear or branched saturated (C 1 -C 40 A hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, triacontyl, tetracontyl etc. Do.
　本明細書に使用されるとき、「フルオロアルキル」という用語は、１個以上のフッ素原子で置換されている、本明細書中と同義のアルキル基、更に典型的には（Ｃ１－Ｃ４０）アルキル基を意味する。フルオロアルキル基の例は、例えば、ジフルオロメチル、トリフルオロメチル、ペルフルオロアルキル、１Ｈ，１Ｈ，２Ｈ，２Ｈ－ペルフルオロオクチル、ペルフルオロエチル、及び－ＣＨ２ＣＦ３を含む。 As used herein, the term "fluoroalkyl", one or more fluorine atoms are substituted with, herein synonymous with alkyl groups, more typically (C 1 -C 40 ) Means an alkyl group. Examples of fluoroalkyl groups include, for example, difluoromethyl, trifluoromethyl, perfluoroalkyl, 1H, 1H, 2H, 2H-perfluorooctyl, perfluoroethyl, and —CH 2 CF 3 .
　本明細書に使用されるとき、「ヒドロカルビレン」という用語は、炭化水素、典型的には（Ｃ１－Ｃ４０）炭化水素から２個の水素原子を除去することにより形成される二価基を意味する。ヒドロカルビレン基は、直鎖、分岐又は環状であってよく、そして飽和又は不飽和であってよい。ヒドロカルビレン基の例は、メチレン、エチレン、１－メチルエチレン、１－フェニルエチレン、プロピレン、ブチレン、１，２－フェニレン、１，３－フェニレン、１，４－フェニレン、及び２，６－ナフチレンを含むが、これらに限定されない。 As used herein, the term "hydrocarbylene" hydrocarbon, typically divalent formed by removing two hydrogen atoms from (C 1 -C 40) hydrocarbon Means a group. The hydrocarbylene group may be linear, branched or cyclic and may be saturated or unsaturated. Examples of hydrocarbylene groups are methylene, ethylene, 1-methylethylene, 1-phenylethylene, propylene, butylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene and 2,6-naphthylene Including, but not limited to.
　本明細書に使用されるとき、「アルコキシ」という用語は、－Ｏ－アルキル（ここで、アルキル基は、本明細書中と同義である）として示される一価基を意味する。アルコキシ基の例は、メトキシ、エトキシ、ｎ－プロポキシ、イソプロポキシ、ｎ－ブトキシ、イソブトキシ、及びtert－ブトキシを含むが、これらに限定されない。 As used herein, the term "alkoxy" refers to a monovalent group designated as -O-alkyl, wherein the alkyl group is as defined herein. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy.
　本明細書に使用されるとき、「アリール」という用語は、１個以上の６員炭素環（その不飽和が、３個の共役二重結合により表される）を含有する一価の不飽和炭化水素基を意味する。アリール基は、単環式アリール及び多環式アリールを含む。多環式アリールとは、２個以上の６員炭素環（その不飽和が、３個の共役二重結合により表される）を含有する一価の不飽和炭化水素基であって、隣接する環が、１個以上の結合若しくは二価の架橋基により相互に結合しているか、又は一緒になって縮合している基のことをいう。アリール基の例は、フェニル、アントラセニル、ナフチル、フェナントレニル、フルオレニル、及びピレニルを含むが、これらに限定されない。 As used herein, the term "aryl" refers to a monovalent unsaturated bond containing one or more 6-membered carbocyclic rings (the unsaturation of which is represented by three conjugated double bonds). It means a hydrocarbon group. Aryl groups include monocyclic aryl and polycyclic aryl. Polycyclic aryl is a monovalent unsaturated hydrocarbon group containing two or more 6-membered carbocyclic rings (the unsaturation of which is represented by three conjugated double bonds), which are adjacent to each other Ring refers to a group linked to each other by one or more bonds or divalent bridging groups, or fused together. Examples of aryl groups include, but are not limited to, phenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl and pyrenyl.
　本明細書に使用されるとき、「アリールオキシ」という用語は、－Ｏ－アリール（ここで、アリール基は、本明細書中と同義である）として示される一価基を意味する。アリールオキシ基の例は、フェノキシ、アントラセノキシ、ナフトキシ、フェナントレノキシ、及びフルオレノキシを含むが、これらに限定されない。 As used herein, the term "aryloxy" refers to a monovalent group designated as -O-aryl, wherein the aryl group is as defined herein. Examples of aryloxy groups include, but are not limited to phenoxy, anthracenoxy, naphthoxy, phenanthrenoxy and fluorenoxy.
　本明細書に記載の任意の置換基又は基は、１個以上の炭素原子で、１個以上の同じか又は異なる本明細書に記載の置換基によって、場合により置換されていてもよい。例えば、ヒドロカルビレン基は、アリール基又はアルキル基で更に置換されていてもよい。本明細書に記載の任意の置換基又は基はまた、１個以上の炭素原子で、例えば、Ｆ、Ｃｌ、Ｂｒ、及びＩのようなハロゲン；ニトロ（ＮＯ２）、シアノ（ＣＮ）、並びにヒドロキシ（ＯＨ）からなる群より選択される１個以上の置換基によって、場合により置換されていてもよい。 Any substituent or group described herein may be optionally substituted at one or more carbon atoms with one or more same or different substituents described herein. For example, the hydrocarbylene group may be further substituted with an aryl group or an alkyl group. Any substituent or group described herein is also, at one or more carbon atoms, a halogen such as, for example, F, Cl, Br and I; nitro (NO 2 ), cyano (CN), and It may be optionally substituted by one or more substituents selected from the group consisting of hydroxy (OH).
　本明細書に使用されるとき、電荷輸送性とは、導電性と同義であり、正孔輸送性とも同義である。また、本発明のインク組成物は、それ自体に電荷輸送性があるものでもよく、インク組成物を使用して得られる固体膜に電荷輸送性があるものでもよい。 As used herein, charge transportability is synonymous with conductivity and is also synonymous with hole transportability. In addition, the ink composition of the present invention may have charge transportability by itself, or may have charge transportability in a solid film obtained by using the ink composition.
　本明細書に使用されるとき、「正孔キャリア化合物」とは、正孔の移動を容易にすることができる（即ち、正電荷キャリア）か、かつ／又は例えば、電子デバイスにおいて電子の移動をブロックできる任意の化合物のことをいう。正孔キャリア化合物は、電子デバイスの、典型的には有機電子デバイス（例えば、有機発光デバイス等）の正孔輸送層（ＨＴＬ）、正孔注入層（ＨＩＬ）及び電子ブロック層（ＥＢＬ）中で有用な化合物を含む。 As used herein, a "hole carrier compound" can facilitate the movement of holes (i.e., positive charge carriers) and / or move electrons, for example, in an electronic device. Refers to any compound that can be blocked. Hole carrier compounds are typically used in the hole transport layer (HTL), hole injection layer (HIL) and electron blocking layer (EBL) of electronic devices, typically organic electronic devices such as organic light emitting devices etc. Contains useful compounds.
　本明細書に使用されるとき、正孔キャリア化合物、例えば、ポリチオフェンに関する「ドープされた」という用語は、この正孔キャリア化合物が、ドーパントにより促進される、化学変換、典型的には酸化又は還元反応、更に典型的には酸化反応を受けたことを意味する。本明細書に使用されるとき、「ドーパント」という用語は、正孔キャリア化合物、例えば、ポリチオフェンを酸化又は還元する、典型的には酸化する物質のことをいう。本明細書で、正孔キャリア化合物が、ドーパントにより促進される、化学変換、典型的には酸化又は還元反応、更に典型的には酸化反応を受けるプロセスは、「ドーピング反応」又は単純に「ドーピング」と呼ばれる。ドーピングは、ポリチオフェンの特性を変えるが、この特性は、電気的特性（抵抗率及び仕事関数等）、機械的特性、及び光学的特性を含んでよいが、これらに限定されない。ドーピング反応の過程で、正孔キャリア化合物は、帯電し、そしてドーパントは、ドーピング反応の結果として、ドープされた正孔キャリア化合物に対して逆荷電した対イオンになる。本明細書に使用されるとき、物質は、ドーパントと称されるためには、正孔キャリア化合物を化学反応させるか、酸化するか、又は還元し、典型的には酸化しなければならない。正孔キャリア化合物と反応しないが、対イオンとして作用しうる物質は、本開示ではドーパントとはみなされない。したがって、正孔キャリア化合物、例えば、ポリチオフェンに関する「ドープされていない」という用語は、この正孔キャリア化合物が、本明細書に記載のドーピング反応を受けていないことを意味する。 As used herein, the term "doped" with respect to a hole carrier compound, such as polythiophene, refers to a chemical transformation, typically oxidation or reduction, in which the hole carrier compound is promoted by a dopant. It means that the reaction, more typically, it has undergone an oxidation reaction. As used herein, the term "dopant" refers to a hole carrier compound, eg, a substance that oxidizes, or reduces, typically polythiophene. As used herein, a process in which a hole carrier compound is subjected to a chemical conversion, typically an oxidation or reduction reaction, more typically an oxidation reaction, promoted by a dopant is a "doping reaction" or simply "doping" It is called Doping alters the properties of polythiophene, which may include, but is not limited to, electrical properties (such as resistivity and work function), mechanical properties, and optical properties. In the course of the doping reaction, the hole carrier compound is charged and the dopant becomes a counterion counter-charged to the doped hole carrier compound as a result of the doping reaction. As used herein, a substance must be chemically reacted, oxidized or reduced, typically oxidized, to be referred to as a dopant. Substances that do not react with the hole carrier compound but can act as counterions are not considered dopants in the present disclosure. Thus, the term "undoped" with respect to a hole carrier compound, such as polythiophene, means that the hole carrier compound has not undergone the doping reaction described herein.
　本明細書に使用されるとき、「パイルアップ」とはインク組成物がバンクの側面を這い上がる現象を意味する。
　インク組成物を塗布するための方法は種々知られているが、そのような方法の一例として、インク組成物を微小な液滴としてノズルから吐出させ、被塗布物に付着させるインクジェット法（液滴吐出法）を挙げることができる。有機ＥＬ素子の製造を目的として、インクジェット法を用いて電荷輸送性薄膜を基板上に形成する場合、基板上に形成された薄膜電極（多くの場合、パターニングされた薄膜電極）上にバンク（隔壁）を形成して、薄膜電極上の必要な領域が、バンクで囲まれた膜形成領域となるようにし、その膜形成領域のみに、インクジェット法によりインク組成物を塗布して電荷輸送性薄膜を形成する、という方法がしばしば採用される。 As used herein, "pile-up" refers to the phenomenon where the ink composition crawls the sides of the bank.
Although various methods for applying the ink composition are known, an example of such a method is an inkjet method in which the ink composition is ejected as fine droplets from a nozzle and adhered to an object to be coated (droplets Discharge method) can be mentioned. In the case of forming a charge transporting thin film on a substrate using an inkjet method for the purpose of manufacturing an organic EL element, banks (partition walls) are formed on thin film electrodes (in many cases, patterned thin film electrodes) formed on a substrate To form a film formation region surrounded by a bank, and apply the ink composition by an ink jet method only to the film formation region to form a charge transport thin film. The method of forming is often employed.
　このようにして形成される電荷輸送性薄膜は、その厚さが薄膜全体にわたって均一な状態であることが好ましい。しかし現実には、特に上記のようなバンクを用いる方法により形成された場合、電荷輸送性薄膜が厚さの不均一な状態となることがある。そのような状態の一例として、形成された電荷輸送性薄膜の周辺部の厚さが、薄膜の中央から端に向かう方向に沿って増大した状態を挙げることができる。これは、前記膜形成領域内に塗布されたインク組成物がバンクの側面を這い上がることにより、形成される塗膜の周囲の厚さが、塗膜の中央から端（換言すれば、塗膜がバンクの側面と接触する部分）に向かう方向に沿って増大した状態になることに起因し、この状態にある塗膜から形成された電荷輸送性薄膜は、前記の如く厚さの不均一な状態になる。本明細書では、このようにインク組成物がバンクの側面を這い上がる現象を「パイルアップ現象」又は単に「パイルアップ」と称する。 The charge transporting thin film formed in this manner preferably has a uniform thickness throughout the entire thin film. However, in reality, the charge transport thin film may be in a non-uniform thickness state particularly when formed by the above-described bank method. One example of such a state is a state in which the thickness of the peripheral portion of the formed charge transporting thin film increases along the direction from the center to the edge of the thin film. This is because the ink composition applied in the film forming area crawls up the side of the bank, so that the thickness around the coating film formed is the center to the edge of the coating film (in other words, the coating film) The charge transportable thin film formed from the coating film in this state is uneven in thickness as described above, due to the state in which the It will be in the state. In this specification, such a phenomenon in which the ink composition crawls the side of the bank is referred to as "pile-up phenomenon" or simply "pile-up".
　本開示のインク組成物は、非水系でもよく水が含まれていても良いが、インクジェット塗布におけるプロセス適合性とインクの保存安定性の観点で、非水系であることが好ましい。本明細書に使用されるとき、「非水系」は、本開示のインク組成物中の水の総量が、インク組成物の総量に対して０～２重量％であることを意味する。典型的には、インク組成物中の水の総量は、インク組成物の総量に対して０～１重量％、更に典型的には０～０．５重量％である。ある実施態様において、本開示のインク組成物には水が実質的に存在しない。 The ink composition of the present disclosure may be non-aqueous or may contain water, but is preferably non-aqueous from the viewpoint of process compatibility in ink jet coating and storage stability of the ink. As used herein, "non-aqueous" means that the total amount of water in the ink composition of the present disclosure is 0 to 2% by weight with respect to the total amount of the ink composition. Typically, the total amount of water in the ink composition is 0 to 1% by weight, more typically 0 to 0.5% by weight, based on the total amount of the ink composition. In one embodiment, the ink composition of the present disclosure is substantially free of water.
［（Ａ）成分］
　（Ａ）成分は、式（Ｉ）：
Figure JPOXMLDOC01-appb-C000023
　［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、－ＳＯ３Ｍ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－Ｚ－Ｏ－を形成し、ここで、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、Ｚは、場合によりハロゲン又はＹで置換されているヒドロカルビレン基（ここで、Ｙは、炭素数１～１０の直鎖又は分岐鎖のアルキル基又はアルコキシアルキル基であり、該アルキル基又はアルコキシアルキル基は、任意の位置がスルホン酸基で置換されていてもよい）であり、ｐは、１以上の整数であり、そしてＲｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである］で表される繰り返し単位を含む、ポリチオフェンである。（Ａ）成分は、単独でも、二種以上を併用してもよい。 [(A) component]
The component (A) is represented by formula (I):
Figure JPOXMLDOC01-appb-C000023
[Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or alternatively, R 1 and R 2 together form —O—Z—O—, where M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium And Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, And R 14 is a polythiophene containing a repeating unit represented by The component (A) may be used alone or in combination of two or more.
　ある実施態様において、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、フルオロアルキル、－ＳＯ３Ｍ、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－（ＣＨ２）ｑ－Ｏ－（ここで、（ＣＨ２）ｑは、場合によりＹで置換されている）を形成し；ここで、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄは、それぞれ独立に、Ｈ、ハロゲン、アルキル、フルオロアルキル、又はアリールであり；Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールであり；ｐは、１、２、又は３であり；Ｒｆは、アルキル、フルオロアルキル、又はアリールであり；ｑは、１、２、又は３であり、そしてＹは、炭素数１～１０の直鎖又は分岐鎖のアルコキシアルキル基であり、該アルコキシアルキル基は任意の位置がスルホン酸基で置換されていてもよい。 In one embodiment, R 1 and R 2 are each independently H, fluoroalkyl, -SO 3 M, -O [C (R a R b ) -C (R c R d ) -O] p -R e or -OR f , or alternatively, R 1 and R 2 are taken together -O- (CH 2 ) q -O- (wherein (CH 2 ) q is optionally substituted by Y Where M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and each R a , R b , R c and R d are , Each independently H, halogen, alkyl, fluoroalkyl or aryl; R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; R f is , Alkyl, Q is 1, 2, or 3, and Y is a linear or branched alkoxyalkyl group having 1 to 10 carbon atoms, and the alkoxyalkyl group may be any position It may be substituted by a sulfonic acid group.
　ある実施態様において、Ｒ１は、Ｈであり、そしてＲ２は、Ｈ以外である。このような実施態様において、繰り返し単位は、３－置換チオフェンから誘導される。 In certain embodiments, R 1 is H and R 2 is other than H. In such embodiments, the repeat unit is derived from a 3-substituted thiophene.
　ポリチオフェンは、レジオランダム型又はレジオレギュラー型化合物であってよい。その非対称構造のため、３－置換チオフェンの重合から、繰り返し単位間の３種の可能性がある位置化学結合を含有するポリチオフェン構造の混合物が生成する。２個のチオフェン環が結合するとき利用可能なこの３種の配向は、２，２’、２，５’、及び５，５’カップリングである。２，２’（即ち、頭－頭）カップリング及び５，５’（即ち、尾－尾）カップリングは、レジオランダム型カップリングと呼ばれる。対照的に、２，５’（即ち、頭－尾）カップリングは、レジオレギュラー型カップリングと呼ばれる。位置規則性（regioregularity）の程度は、例えば、約０～１００％、又は約２５～９９．９％、又は約５０～９８％でありうる。位置規則性は、例えば、ＮＭＲ分光法を用いる等の、当業者には公知の標準法により決定することができる。 The polythiophenes may be regiorandom or regioregular compounds. Because of its asymmetric structure, polymerization of 3-substituted thiophenes produces a mixture of polythiophene structures containing three possible regiochemical bonds between repeat units. The three orientations available when the two thiophene rings are attached are 2,2 ', 2,5', and 5,5 'couplings. The 2, 2 '(or head-to-head) and 5, 5' (or tail-to-tail) couplings are referred to as regiorandom couplings. In contrast, a 2, 5 '(or head-to-tail) coupling is referred to as a regioregular coupling. The degree of regioregularity may be, for example, about 0-100%, or about 25-99.9%, or about 50-98%. Regioregularity can be determined by standard methods known to those skilled in the art, such as, for example, using NMR spectroscopy.
　ある実施態様において、ポリチオフェンは、レジオレギュラー型である。幾つかの実施態様において、ポリチオフェンの位置規則性は、少なくとも約８５％、典型的には少なくとも約９５％、更に典型的には少なくとも約９８％であってよい。幾つかの実施態様において、位置規則性の程度は、少なくとも約７０％、典型的には少なくとも約８０％であってよい。更に他の実施態様において、レジオレギュラー型ポリチオフェンは、少なくとも約９０％の位置規則性の程度を、典型的には少なくとも約９８％の位置規則性の程度を有する。 In one embodiment, the polythiophene is regioregular. In some embodiments, the regioregularity of the polythiophene can be at least about 85%, typically at least about 95%, and more typically at least about 98%. In some embodiments, the degree of regioregularity may be at least about 70%, typically at least about 80%. In still other embodiments, the regioregular polythiophene has a degree of regioregularity of at least about 90%, and typically a degree of regioregularity of at least about 98%.
　３－置換チオフェンモノマー（該モノマーから誘導されるポリマーを含む）は、市販されているか、又は当業者には公知の方法により製造することができる。側基を持つレジオレギュラー型ポリチオフェンを含む、合成方法、ドーピング法、及びポリマー特性評価は、例えば、McCulloughらの米国特許第６，６０２，９７４号及びMcCulloughらの米国特許第６，１６６，１７２号に提供される。 The 3-substituted thiophene monomers (including polymers derived from said monomers) are commercially available or can be prepared by methods known to those skilled in the art. Synthetic methods, doping methods, and polymer characterizations involving regioregular polythiophenes with pendant groups are described, for example, in US Pat. Nos. 6,602,974 to McCullough et al. And US Pat. No. 6,166,172 to McCullough et al. Provided to
　別の実施態様において、Ｒ１及びＲ２は、両方ともＨ以外である。このような実施態様において、繰り返し単位は、３，４－二置換チオフェンから誘導される。 In another embodiment, R 1 and R 2 are both other than H. In such embodiments, the repeat unit is derived from a 3,4-disubstituted thiophene.
　ある実施態様において、Ｒ１及びＲ２は、それぞれ独立に、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－（ＣＨ２）ｑ－Ｏ－を形成する。ある実施態様において、Ｒ１及びＲ２は、両方とも－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅである。Ｒ１及びＲ２は、同一であっても異なっていてもよい。 In one embodiment, R 1 and R 2 are each independently —O [C (R a R b ) —C (R c R d ) —O] p —R e or —OR f Alternatively, R 1 and R 2 together form -O- (CH 2 ) q -O-. In one embodiment, R 1 and R 2 are both —O [C (R a R b ) -C (R c R d ) -O] p -R e . R 1 and R 2 may be the same or different.
　ある実施態様において、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄは、それぞれ独立に、Ｈ、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルであり；そしてＲｅは、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルである。 In certain embodiments, each R a , R b , R c and R d is independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl. And R e is (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
　ある実施態様において、Ｒ１及びＲ２は、それぞれ－Ｏ［ＣＨ２－ＣＨ２－Ｏ］ｐ－Ｒｅである。ある実施態様において、Ｒ１及びＲ２は、それぞれ－Ｏ［ＣＨ（ＣＨ３）－ＣＨ２－Ｏ］ｐ－Ｒｅである。 In one embodiment, R 1 and R 2 are each —O [CH 2 —CH 2 —O] p —R e . In one embodiment, R 1 and R 2 are each —O [CH (CH 3 ) —CH 2 —O] p —R e .
　ある実施態様において、Ｒｅは、メチル、プロピル、又はブチルである。 In certain embodiments, R e is methyl, propyl or butyl.
　ある実施態様において、ｑは、２である。 In one embodiment, q is 2.
　ある実施態様において、－Ｏ－（ＣＨ２）ｑ－Ｏ－は、１つ以上の位置がＹで置換されている。ある実施態様において、－Ｏ－（ＣＨ２）ｑ－Ｏ－は、１つの位置がＹで置換されている。 In certain embodiments, -O- (CH 2 ) q -O- is substituted at one or more positions with Y. In one embodiment, -O- (CH 2 ) q -O- is substituted at one position with Y.
　ある実施態様において、ｑは、２であり、Ｙは、３－スルホブトキシメチル基である。この場合、－Ｏ－（ＣＨ２）２－Ｏ－基は、１つの位置が３－スルホブトキシメチル基で置換されていると、好ましい。 In one embodiment, q is 2 and Y is 3-sulfobutoxymethyl. In this case, the —O— (CH 2 ) 2 —O— group is preferably substituted at one position with a 3-sulfobutoxymethyl group.
　ある実施態様において、ポリチオフェンは、下記式：
Figure JPOXMLDOC01-appb-C000024
で表される基（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである）、及びこれらの組合せからなる群より選択される繰り返し単位を含む。 In one embodiment, the polythiophene has the following formula:
Figure JPOXMLDOC01-appb-C000024
And a repeating unit selected from the group consisting of H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and combinations thereof.
　当業者には明らかであろうが、下記式：
Figure JPOXMLDOC01-appb-C000025
で示される繰り返し単位は、下記式：
Figure JPOXMLDOC01-appb-C000026
３－（２－（２－メトキシエトキシ）エトキシ）チオフェン［本明細書では３－ＭＥＥＴと呼ばれる］
で示される構造により表されるモノマーから誘導され；下記式：
Figure JPOXMLDOC01-appb-C000027
で示される繰り返し単位は、下記式：
Figure JPOXMLDOC01-appb-C000028
（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである）
スルホン化３－（２－（２－メトキシエトキシ）エトキシ）チオフェン［本明細書ではスルホン化３－ＭＥＥＴと呼ばれる］
で示される構造により表されるモノマーから誘導され；下記式：
Figure JPOXMLDOC01-appb-C000029
で示される繰り返し単位は、下記式：
Figure JPOXMLDOC01-appb-C000030
３，４－ビス（２－（２－ブトキシエトキシ）エトキシ）チオフェン［本明細書では３，４－ジＢＥＥＴと呼ばれる］
で示される構造により表されるモノマーから誘導され；下記式：
Figure JPOXMLDOC01-appb-C000031
で示される繰り返し単位は、下記式：
Figure JPOXMLDOC01-appb-C000032
３，４－ビス（（１－プロポキシプロパン－２－イル）オキシ）チオフェン［本明細書では３，４－ジＰＰＴと呼ばれる］
で示される構造により表されるモノマーから誘導され、そして下記式：
Figure JPOXMLDOC01-appb-C000033
で示される繰り返し単位は、下記式：
Figure JPOXMLDOC01-appb-C000034
３，４－エチレンジオキシチオフェン
で示される構造により表されるモノマーから誘導される。 As would be apparent to one skilled in the art, the following formula:
Figure JPOXMLDOC01-appb-C000025
The repeating unit represented by is of the following formula:
Figure JPOXMLDOC01-appb-C000026
3- (2- (2-Methoxyethoxy) ethoxy) thiophene [referred to herein as 3-MEET]
Derived from a monomer represented by the structure shown in
Figure JPOXMLDOC01-appb-C000027
The repeating unit represented by is of the following formula:
Figure JPOXMLDOC01-appb-C000028
(Wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium)
Sulfonated 3- (2- (2-methoxyethoxy) ethoxy) thiophene [referred to herein as sulfonated 3-MEET]
Derived from a monomer represented by the structure shown in
Figure JPOXMLDOC01-appb-C000029
The repeating unit represented by is of the following formula:
Figure JPOXMLDOC01-appb-C000030
3,4-bis (2- (2-butoxyethoxy) ethoxy) thiophene (referred to herein as 3,4-di BEET)
Derived from a monomer represented by the structure shown in
Figure JPOXMLDOC01-appb-C000031
The repeating unit represented by is of the following formula:
Figure JPOXMLDOC01-appb-C000032
3,4-Bis ((1-propoxypropan-2-yl) oxy) thiophene [referred to herein as 3,4-di PPT]
Is derived from a monomer represented by the structure shown below and:
Figure JPOXMLDOC01-appb-C000033
The repeating unit represented by is of the following formula:
Figure JPOXMLDOC01-appb-C000034
It is derived from a monomer represented by the structure represented by 3,4-ethylenedioxythiophene.
　３，４－二置換チオフェンモノマー（該モノマーから誘導されるポリマーを含む）は、市販されているか、又は当業者には公知の方法により製造することができる。例えば、３，４－二置換チオフェンモノマーは、３，４－ジブロモチオフェンを、式：ＨＯ－［Ｚ－Ｏ］ｐ－Ｒｅ又はＨＯＲｆ［式中、Ｚ、Ｒｅ、Ｒｆ及びｐは、本明細書中と同義である］で与えられる化合物の金属塩、典型的にはナトリウム塩と反応させることにより生成させることができる。 The 3,4-disubstituted thiophene monomers (including polymers derived from said monomers) are commercially available or can be prepared by methods known to those skilled in the art. For example, the 3,4-disubstituted thiophene monomer is a 3,4-dibromothiophene, a compound of the formula: HO- [Z-O] p -R e or HOR f , wherein Z, R e , R f and p are , As defined herein, can be generated by reaction with a metal salt of a compound given by the formula, typically a sodium salt.
　３，４－二置換チオフェンモノマーの重合は、最初に３，４－二置換チオフェンモノマーの２及び５位を臭素化して、対応する３，４－二置換チオフェンモノマーの２，５－ジブロモ誘導体を形成することにより実施される。次にニッケル触媒の存在下での３，４－二置換チオフェンの２，５－ジブロモ誘導体のＧＲＩＭ（グリニャールメタセシス）重合により、ポリマーを得ることができる。このような方法は、例えば、米国特許第８，８６５，０２５号に記載されており、これは、その全体が参照により本明細書に取り込まれる。チオフェンモノマーを重合する別の既知の方法は、酸化剤として、２，３－ジクロロ－５，６－ジシアノ－１，４－ベンゾキノン（ＤＤＱ）のような金属非含有有機酸化剤を用いるか、又は、例えば塩化鉄（ＩＩＩ）、塩化モリブデン（Ｖ）、及び塩化ルテニウム（ＩＩＩ）のような遷移金属ハロゲン化物を用いる、酸化重合によるものである。 The polymerization of the 3,4-disubstituted thiophene monomer first brominates the 2 and 5 positions of the 3,4-disubstituted thiophene monomer to give the corresponding 2,5-dibromo derivative of the 3,4-disubstituted thiophene monomer It is carried out by forming. The polymer can then be obtained by GRIM (Grignard metathesis) polymerization of a 2,5-dibromo derivative of 3,4-disubstituted thiophene in the presence of a nickel catalyst. Such methods are described, for example, in US Pat. No. 8,865,025, which is incorporated herein by reference in its entirety. Another known method of polymerizing thiophene monomers uses metal free organic oxidizing agents such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as the oxidizing agent, or For example, by oxidative polymerization using transition metal halides such as iron (III) chloride, molybdenum (V) chloride, and ruthenium (III) chloride.
　金属塩、典型的にはナトリウム塩に変換され、そして３，４－二置換チオフェンモノマーを生成させるのに使用されうる、式：ＨＯ－［Ｚ－Ｏ］ｐ－Ｒｅ又はＨＯＲｆを有する化合物の例は、トリフルオロエタノール、エチレングリコールモノヘキシルエーテル（ヘキシルセロソルブ）、プロピレングリコールモノブチルエーテル（Dowanol（商標） PnB）、ジエチレングリコールモノエチルエーテル（エチルカルビトール）、ジプロピレングリコールｎ－ブチルエーテル（Dowanol（商標） DPnB）、ジエチレングリコールモノフェニルエーテル（フェニルカルビトール）、エチレングリコールモノブチルエーテル（ブチルセロソルブ）、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）、ジプロピレングリコールモノメチルエーテル（Dowanol（商標） DPM）、ジイソブチルカルビノール、２－エチルヘキシルアルコール、メチルイソブチルカルビノール、エチレングリコールモノフェニルエーテル（Dowanol（商標） Eph）、プロピレングリコールモノプロピルエーテル（Dowanol（商標） PnP）、プロピレングリコールモノフェニルエーテル（Dowanol（商標） PPh）、ジエチレングリコールモノプロピルエーテル（プロピルカルビトール）、ジエチレングリコールモノヘキシルエーテル（ヘキシルカルビトール）、２－エチルヘキシルカルビトール、ジプロピレングリコールモノプロピルエーテル（Dowanol（商標） DPnP）、トリプロピレングリコールモノメチルエーテル（Dowanol（商標） TPM）、ジエチレングリコールモノメチルエーテル（メチルカルビトール）、及びトリプロピレングリコールモノブチルエーテル（Dowanol（商標） TPnB）を含むが、これらに限定されない。 Compounds having the formula: HO- [Z-O] p- R e or HOR f that can be converted to metal salts, typically sodium salts, and used to generate 3,4-disubstituted thiophene monomers Examples of trifluoroethanol, ethylene glycol monohexyl ether (hexyl cellosolve), propylene glycol monobutyl ether (Dowanol (trademark) PnB), diethylene glycol monoethyl ether (ethyl carbitol), dipropylene glycol n-butyl ether (Dowanol (trade mark) ) DPnB), diethylene glycol monophenyl ether (phenyl carbitol), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol (TM) DPM), diisobutyl carbinol, 2-ethylhexyl alcohol, methyl isobutyl carbinol, ethylene glycol monophenyl ether (Dowanol (TM) Eph), propylene glycol monopropyl ether (Dowanol (TM) PnP), propylene Glycol monophenyl ether (Dowanol (TM) PPh), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether (Dowanol (TM) DPnP ), Tripropylene glycol monomethyl ether (DowanolTM TPM), diethylene glycol monomethyl ether (methyl carbitol), and tripropylene glycol). Including glycol monomethyl ether (Dowanol (TM) TPnB), but are not limited to.
　本開示の式（Ｉ）で表される繰り返し単位を有するポリチオフェンは、重合によるその形成に続いて、更に修飾することができる。例えば、３－置換チオフェンモノマーから誘導される１種以上の繰り返し単位を有するポリチオフェンは、水素が、スルホン化によるスルホン酸基（－ＳＯ３Ｈ）のような置換基によって置換されうる、１個以上の部位を有していてもよい。 The polythiophenes having repeat units of formula (I) of the present disclosure can be further modified following their formation by polymerization. For example, in polythiophenes having one or more types of repeating units derived from 3-substituted thiophene monomers, hydrogen may be substituted by a substituent such as a sulfonic acid group (—SO 3 H) by sulfonation; It may have a part of
　本明細書に使用されるとき、ポリチオフェンに関連する「スルホン化」という用語は、そのポリチオフェンが、１個以上のスルホン酸基（－ＳＯ３Ｈ）を含むことを意味する。（当該ポリチオフェンは、「スルホン化ポリチオフェン」とも言う。）
　典型的には、－ＳＯ３Ｈ基の硫黄原子は、ポリチオフェンの基本骨格に直接結合しており、側基には結合していない。本開示の目的には、側基は、理論的に又は実際にポリマーから脱離されても、ポリマー鎖の長さを縮めない一価基である。スルホン化ポリチオフェンポリマー及び／又はコポリマーは、当業者には公知の任意の方法を用いて製造することができる。例えば、ポリチオフェンを、例えば、発煙硫酸、硫酸アセチル、ピリジンＳＯ３等のような、スルホン化試薬と反応させることによりスルホン化することができる。別の例では、モノマーをスルホン化試薬を用いてスルホン化し、次に既知の方法及び／又は本明細書に記載の方法により重合することができる。当業者には明らかであろうが、スルホン酸基は、塩基性化合物、例えば、アルカリ金属水酸化物、アンモニア及びアルキルアミン（例えば、モノ－、ジ－及びトリアルキルアミン、例えば、トリエチルアミン等）の存在下で、対応する塩又は付加体の形成をもたらし得る。よって、ポリチオフェンに関連する「スルホン化」という用語は、このポリチオフェンが、１個以上の－ＳＯ３Ｍ基（ここで、Ｍは、アルカリ金属イオン（例えば、Ｎａ＋、Ｌｉ＋、Ｋ＋、Ｒｂ＋、Ｃｓ＋等）、アンモニウム（ＮＨ４ ＋）、モノ－、ジ－、及びトリアルキルアンモニウム（トリエチルアンモニウム等）であってよい）を含んでもよいという意味を含む。 As used herein, the term "sulfonated" in the context of polythiophene means that the polythiophene contains one or more sulfonic acid groups (-SO 3 H). (The said polythiophene is also called "sulfonated polythiophene".)
Typically, the sulfur atom of the —SO 3 H group is attached directly to the basic backbone of the polythiophene and not attached to the side groups. For the purposes of the present disclosure, side groups are monovalent groups that do not shrink the length of the polymer chain, even though it is theoretically or actually removed from the polymer. Sulfonated polythiophene polymers and / or copolymers can be prepared using any method known to those skilled in the art. For example, polythiophene can be sulfonated by reaction with a sulfonation reagent such as, for example, oleum, acetyl sulfate, pyridine SO 3 and the like. In another example, the monomers can be sulfonated using a sulfonation reagent and then polymerized by known methods and / or methods described herein. As will be apparent to those skilled in the art, the sulfonic acid groups can be basic compounds such as alkali metal hydroxides, ammonia and alkylamines such as mono-, di- and trialkylamines such as triethylamine etc. In the presence, this may result in the formation of the corresponding salt or adduct. Thus, the term "sulfonated" in relation to polythiophene means that this polythiophene is one or more -SO 3 M groups, where M is an alkali metal ion (eg Na + , Li + , K + , Rb It includes the meaning that it may include + , Cs + and the like), ammonium (NH 4 + ), mono-, di- and trialkylammonium (which may be triethylammonium and the like).
　共役ポリマーのスルホン化及びスルホン化共役ポリマー（スルホン化ポリチオフェンを含む）は、Seshadriらの米国特許第８，０１７，２４１号に記載されており、これは、その全体が参照により本明細書に取り込まれる。
　また、スルホン化ポリチオフェンについては、国際公開第２００８／０７３１４９号及び国際公開第２０１６／１７１９３５号に記載されており、これは、その全体が参照により本明細書に取り込まれる。 Sulfonated and sulfonated conjugated polymers of conjugated polymers, including sulfonated polythiophenes, are described in Seshadri et al., US Pat. No. 8,017,241, which is incorporated herein by reference in its entirety Be
Also, sulfonated polythiophenes are described in WO 2008/073149 and WO 2016/171935, which are incorporated herein by reference in their entirety.
　ある実施態様において、ポリチオフェンは、スルホン化されている。 In one embodiment, the polythiophene is sulfonated.
　ある実施態様において、スルホン化ポリチオフェンは、式（Ｉ）：
Figure JPOXMLDOC01-appb-C000035
［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅ（式中、Ｚは、場合によりハロゲン化されているヒドロカルビレン基であり、ｐは、１以上の整数であり、そして、Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）である。
　但し、Ｒ１及びＲ２のいずれかは、－ＳＯ３Ｍ（Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである。）である。］
で表される繰り返し単位を含む。 In certain embodiments, the sulfonated polythiophenes have the formula (I):
Figure JPOXMLDOC01-appb-C000035
[Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, or —O— [Z—O] p —R e wherein Z is An optionally halogenated hydrocarbylene group, p is an integer greater than or equal to 1 and R e is H, alkyl, fluoroalkyl or aryl).
However, any one of R 1 and R 2 is —SO 3 M (M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium). ]
And a repeating unit represented by
　ある実施態様において、スルホン化ポリチオフェンは、式（Ｉ）［式中、各々のＲ１及びＲ２が、それぞれ独立に、Ｈ、フルオロアルキル、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであり；ここで、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄは、それぞれ独立に、Ｈ、ハロゲン、アルキル、フルオロアルキル、又はアリールであり；Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールであり；ｐは、１、２、又は３であり；そしてＲｆは、アルキル、フルオロアルキル、又はアリールである。
　但し、Ｒ１及びＲ２のいずれかは、－ＳＯ３Ｍ（Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである。）である。］
で表される繰り返し単位を含む。 In one embodiment, the sulfonated polythiophene is represented by formula (I): wherein each of R 1 and R 2 is independently H, fluoroalkyl, —O [C (R a R b ) —C (R c R d ) -O] p -R e or -OR f ; wherein each of R a , R b , R c and R d is independently H, halogen, alkyl, fluoroalkyl R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; and R f is alkyl, fluoroalkyl or aryl.
However, any one of R 1 and R 2 is —SO 3 M (M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium). ]
And a repeating unit represented by
　ある実施態様において、Ｒ１が、－ＳＯ３Ｍ（Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである。）であり、そしてＲ２が、－ＳＯ３Ｍ以外である。Ｍは、好ましくは、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、より好ましくはトリアルキルアンモニウムである。 In certain embodiments, R 1 is —SO 3 M, wherein M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and R 2 is —SO 3 Other than M. M is preferably monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, more preferably trialkyl ammonium.
　ある実施態様において、Ｒ１が、－ＳＯ３Ｍであり、そしてＲ２が、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆである。 In certain embodiments, R 1 is —SO 3 M, and R 2 is —O [C (R a R b ) —C (R c R d ) —O] p —R e , or —OR f .
　ある実施態様において、Ｒ１が、－ＳＯ３Ｍであり、そしてＲ２が、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅである。 In one embodiment, R 1 is —SO 3 M and R 2 is —O [C (R a R b ) -C (R c R d ) -O] p -R e .
　ある実施態様において、Ｒ１が、－ＳＯ３Ｍであり、そしてＲ２が、－Ｏ－ＣＨ２ＣＨ２－Ｏ－ＣＨ２ＣＨ２－Ｏ－ＣＨ３である。 In one embodiment, R 1 is —SO 3 M and R 2 is —O—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 3 .
　ある実施態様において、スルホン化ポリチオフェンは、式（Ｉ）：
Figure JPOXMLDOC01-appb-C000036
［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅ（式中、Ｚは、場合によりハロゲン化されているヒドロカルビレン基であり、ｐは、１以上の整数であり、そして、Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）である］
で表される繰り返し単位を含むポリチオフェンのスルホン化により得られる。 In certain embodiments, the sulfonated polythiophenes have the formula (I):
Figure JPOXMLDOC01-appb-C000036
[Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, or —O— [Z—O] p —R e wherein Z is An optionally halogenated hydrocarbylene group, p is an integer of 1 or more, and R e is H, alkyl, fluoroalkyl or aryl)
It is obtained by sulfonation of polythiophene containing a repeating unit represented by
　ある実施態様において、スルホン化ポリチオフェンは、式（Ｉ）［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、フルオロアルキル、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであり；ここで、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄは、それぞれ独立に、Ｈ、ハロゲン、アルキル、フルオロアルキル、又はアリールであり；Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールであり；ｐは、１、２、又は３であり；そしてＲｆは、アルキル、フルオロアルキル、又はアリールである］で表される繰り返し単位を含むポリチオフェンのスルホン化により得られる。 In one embodiment, the sulfonated polythiophene is represented by formula (I) wherein R 1 and R 2 are each independently H, fluoroalkyl, —O [C (R a R b ) -C (R c R d ) -O] p- R e or -OR f ; wherein each of R a , R b , R c and R d is independently H, halogen, alkyl, fluoroalkyl or R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; and R f is alkyl, fluoroalkyl or aryl] Are obtained by sulfonation of polythiophene containing a repeating unit.
　ある実施態様において、Ｒ１は、Ｈであり、そしてＲ２は、Ｈ以外である。このような実施態様において、繰り返し単位は、３－置換チオフェンから誘導される。 In certain embodiments, R 1 is H and R 2 is other than H. In such embodiments, the repeat unit is derived from a 3-substituted thiophene.
　スルホン化ポリチオフェンは、レジオランダム型又はレジオレギュラー型化合物でありうるポリチオフェンから得られる。その非対称構造のため、３－置換チオフェンの重合から、繰り返し単位間の３種の可能性がある位置化学結合を含有するポリチオフェン構造の混合物が生成する。２個のチオフェン環が結合するとき利用可能なこの３種の配向は、２，２’、２，５’、及び５，５’カップリングである。２，２’（即ち、頭－頭）カップリング及び５，５’（即ち、尾－尾）カップリングは、レジオランダム型カップリングと呼ばれる。対照的に、２，５’（即ち、頭－尾）カップリングは、レジオレギュラー型カップリングと呼ばれる。位置規則性（regioregularity）の程度は、例えば、約０～１００％、又は約２５～９９．９％、又は約５０～９８％でありうる。位置規則性は、例えば、ＮＭＲ分光法を用いる等の、当業者には公知の標準法により決定することができる。 The sulfonated polythiophenes are obtained from polythiophenes which may be regiorandom or regioregular compounds. Because of its asymmetric structure, polymerization of 3-substituted thiophenes produces a mixture of polythiophene structures containing three possible regiochemical bonds between repeat units. The three orientations available when the two thiophene rings are attached are 2,2 ', 2,5', and 5,5 'couplings. The 2, 2 '(or head-to-head) and 5, 5' (or tail-to-tail) couplings are referred to as regiorandom couplings. In contrast, a 2, 5 '(or head-to-tail) coupling is referred to as a regioregular coupling. The degree of regioregularity may be, for example, about 0-100%, or about 25-99.9%, or about 50-98%. Regioregularity can be determined by standard methods known to those skilled in the art, such as, for example, using NMR spectroscopy.
　３－置換チオフェンモノマー（該モノマーから誘導されるポリマーを含む）は、市販されているか、又は当業者には公知の方法により製造することができる。側基を持つレジオレギュラー型ポリチオフェンを含む、合成方法、ドーピング法、及びポリマー特性評価は、例えば、McCulloughらの米国特許第６，６０２，９７４号及びMcCulloughらの米国特許第６，１６６，１７２号に提供される。共役ポリマーのスルホン化及びスルホン化共役ポリマー（スルホン化ポリチオフェンを含む）は、Seshadriらの米国特許第８，０１７，２４１号に記載されている。 The 3-substituted thiophene monomers (including polymers derived from said monomers) are commercially available or can be prepared by methods known to those skilled in the art. Synthetic methods, doping methods, and polymer characterizations involving regioregular polythiophenes with pendant groups are described, for example, in US Pat. Nos. 6,602,974 to McCullough et al. And US Pat. No. 6,166,172 to McCullough et al. Provided to Sulfonated conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in Seshadri et al., US Pat. No. 8,017,241.
　ある実施態様において、Ｒ１は、Ｈであり、そしてＲ２は、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆである。ある実施態様において、Ｒ１は、Ｈであり、そしてＲ２は、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅである。 In certain embodiments, R 1 is H and R 2 is -O [C (R a R b ) -C (R c R d ) -O] p -R e , or -OR f . In certain embodiments, R 1 is H and R 2 is —O [C (R a R b ) -C (R c R d ) -O] p -R e .
　ある実施態様において、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄは、それぞれ独立に、Ｈ、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルであり；Ｒｅ及びＲｆは、それぞれ独立に、Ｈ、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルである。 In certain embodiments, each R a , R b , R c and R d is independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl. R e and R f are each independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
　ある実施態様において、Ｒ２は、－Ｏ［ＣＨ２－ＣＨ２－Ｏ］ｐ－Ｒｅである。ある実施態様において、Ｒ２は、－ＯＲｆである。 In one embodiment, R 2 is —O [CH 2 —CH 2 —O] p —R e . In certain embodiments, R 2 is -OR f .
　金属塩、典型的にはナトリウム塩に変換することができ、そしてチオフェンモノマーに結合して３－置換チオフェン（次にこれを使用して、スルホン化すべきポリチオフェンを生成させる）を形成させることができる、式：ＨＯ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ又はＨＯＲｆを有する化合物の例は、トリフルオロエタノール、エチレングリコールモノヘキシルエーテル（ヘキシルセロソルブ）、プロピレングリコールモノブチルエーテル（Dowanol（商標） PnB）、ジエチレングリコールモノエチルエーテル（エチルカルビトール）、ジプロピレングリコールｎ－ブチルエーテル（Dowanol（商標） DPnB）、ジエチレングリコールモノフェニルエーテル（フェニルカルビトール）、エチレングリコールモノブチルエーテル（ブチルセロソルブ）、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）、ジプロピレングリコールモノメチルエーテル（Dowanol（商標） DPM）、ジイソブチルカルビノール、２－エチルヘキシルアルコール、メチルイソブチルカルビノール、エチレングリコールモノフェニルエーテル（Dowanol（商標） Eph）、プロピレングリコールモノプロピルエーテル（Dowanol（商標） PnP）、プロピレングリコールモノフェニルエーテル（Dowanol（商標） PPh）、ジエチレングリコールモノプロピルエーテル（プロピルカルビトール）、ジエチレングリコールモノヘキシルエーテル（ヘキシルカルビトール）、２－エチルヘキシルカルビトール、ジプロピレングリコールモノプロピルエーテル（Dowanol（商標） DPnP）、トリプロピレングリコールモノメチルエーテル（Dowanol（商標） TPM）、ジエチレングリコールモノメチルエーテル（メチルカルビトール）、及びトリプロピレングリコールモノブチルエーテル（Dowanol（商標） TPnB）を含むが、これらに限定されない。 It can be converted to a metal salt, typically a sodium salt, and can be attached to a thiophene monomer to form a 3-substituted thiophene, which is then used to form the polythiophene to be sulfonated Examples of compounds having the formula HO [C (R a R b ) -C (R c R d ) -O] p -R e or HOR f include trifluoroethanol, ethylene glycol monohexyl ether (hexyl cellosolve) Propylene glycol monobutyl ether (Dowanol (trademark) PnB), diethylene glycol monoethylether (ethyl carbitol), dipropylene glycol n-butylether (Dowanol (trademark) DPnB), diethylene glycol monophenyl ether (phenyl carbitol), ethylene glycol mono Butyl ether ( Tyr cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol (registered trademark) DPM), diisobutyl carbinol, 2-ethylhexyl alcohol, methyl isobutyl carbinol, ethylene glycol monophenyl ether (Dowanol (trade name) Eph), Propylene glycol monopropyl ether (Dowanol (TM) PnP), Propylene glycol monophenyl ether (Dowanol (TM) PPh), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2 -Ethylhexyl carbitol, dipropylene glycol monopropyl ether (Dowanol (TM) DPnP), tripropylene glycol mono Chirueteru (Dowanol (TM) TPM), diethylene glycol monomethyl ether (methyl carbitol), and tripropylene glycol monobutyl ether (Dowanol (TM) TPnB), but are not limited to.
　ある実施態様において、Ｒｅは、Ｈ、メチル、プロピル、又はブチルである。ある実施態様において、Ｒｆは、ＣＨ２ＣＦ３である。 In certain embodiments, R e is H, methyl, propyl or butyl. In one embodiment, R f is CH 2 CF 3 .
　ある実施態様において、スルホン化ポリチオフェンは、下記式：
Figure JPOXMLDOC01-appb-C000037
で示される繰り返し単位を含むポリチオフェンをスルホン化することにより得られる。 In one embodiment, the sulfonated polythiophene has the following formula:
Figure JPOXMLDOC01-appb-C000037
It is obtained by sulfonation of the polythiophene containing the repeating unit shown by these.
　当業者には明らかであろうが、下記式：
Figure JPOXMLDOC01-appb-C000038
で示される繰り返し単位は、下記式：
Figure JPOXMLDOC01-appb-C000039
３－（２－（２－メトキシエトキシ）エトキシ）チオフェン［本明細書では３－ＭＥＥＴと呼ばれる］
で示される構造により表されるモノマーから誘導される。 As would be apparent to one skilled in the art, the following formula:
Figure JPOXMLDOC01-appb-C000038
The repeating unit represented by is of the following formula:
Figure JPOXMLDOC01-appb-C000039
3- (2- (2-Methoxyethoxy) ethoxy) thiophene [referred to herein as 3-MEET]
It derives from the monomer represented by the structure shown by
　したがって、下記式：
Figure JPOXMLDOC01-appb-C000040
で示される繰り返し単位を含むポリチオフェンのスルホン化により、スルホン化ポリ（３－ＭＥＥＴ）が生じる。 Therefore, the following formula:
Figure JPOXMLDOC01-appb-C000040
Sulfonation of the polythiophene containing the repeat unit shown in Figure gives a sulfonated poly (3-MEET).
　ある実施態様において、ポリチオフェンは、スルホン化ポリ（３－ＭＥＥＴ）である。 In one embodiment, the polythiophene is sulfonated poly (3-MEET).
　本開示に使用されるポリチオフェンは、ホモポリマー又はコポリマー（統計的、ランダム、勾配、及びブロックコポリマーを含む）であってよい。モノマーＡ及びモノマーＢを含むポリマーとしては、ブロックコポリマーは、例えば、Ａ－Ｂジブロックコポリマー、Ａ－Ｂ－Ａトリブロックコポリマー、及び－（ＡＢ）ｋ－マルチブロックコポリマーを含む。ポリチオフェンは、他のタイプのモノマー（例えば、チエノチオフェン、セレノフェン、ピロール、フラン、テルロフェン、アニリン、アリールアミン、及びアリーレン（例えば、フェニレン、フェニレンビニレン、及びフルオレン等）等）から誘導される繰り返し単位を含んでもよい。 The polythiophenes used in the present disclosure may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers). As a polymer containing the monomer A and the monomer B, the block copolymer includes, for example, an AB diblock copolymer, an ABA triblock copolymer, and an (AB) k -multiblock copolymer. Polythiophenes are repeating units derived from other types of monomers (eg, thienothiophene, selenophene, pyrrole, furan, tellurophene, aniline, arylamines, and arylene (eg, phenylene, phenylene vinylene, fluorene, etc.), etc.) May be included.
　ある実施態様において、ポリチオフェンは、式（Ｉ）で表される繰り返し単位を、繰り返し単位の総重量に基づいて５０重量％より多い、典型的には８０重量％より多い、更に典型的には９０重量％より多い、更になお典型的には９５重量％より多い量で含む。 In one embodiment, the polythiophene comprises more than 50% by weight, typically more than 80% by weight, more typically 90% by weight of recurring units of the formula (I) based on the total weight of the recurring units. It is included in an amount of more than wt%, still more typically more than 95 wt%.
　当業者には明らかであろうが、重合に使用される出発モノマー化合物の純度に応じて、形成されるポリマーは、不純物から誘導される繰り返し単位を含有してもよい。本明細書に使用されるとき、「ホモポリマー」という用語は、１つのタイプのモノマーから誘導される繰り返し単位を含むポリマーを意味するものであるが、不純物から誘導される繰り返し単位を含有してもよい。ある実施態様において、ポリチオフェンは、基本的に全ての繰り返し単位が、式（Ｉ）で表される繰り返し単位である、ホモポリマーである。 As will be apparent to those skilled in the art, depending on the purity of the starting monomeric compound used for polymerization, the polymer formed may contain repeat units derived from impurities. As used herein, the term "homopolymer" is intended to mean a polymer comprising repeat units derived from one type of monomer, but containing repeat units derived from impurities It is also good. In one embodiment, the polythiophene is a homopolymer, wherein essentially all repeating units are repeating units of formula (I).
　ポリチオフェンは、典型的には約１，０００～１，０００，０００g/molの間の数平均分子量を有する。更に典型的には、この共役ポリマーは、約５，０００～１００，０００g/molの、更になお典型的には約１０，０００～約５０，０００g/molの間の数平均分子量を有する。数平均分子量は、例えば、ゲル透過クロマトグラフィーのような、当業者に公知の方法により決定することができる。 Polythiophenes typically have a number average molecular weight between about 1,000 and 1,000,000 g / mol. More typically, the conjugated polymer has a number average molecular weight between about 5,000 and 100,000 g / mol, and even more typically between about 10,000 and about 50,000 g / mol. The number average molecular weight can be determined by methods known to those skilled in the art, such as, for example, gel permeation chromatography.
　本発明においては、前記のポリチオフェンを還元剤で処理した後に用いてもよい。
　ポリチオフェンでは、それらを構成する繰り返し単位の一部において、その化学構造が「キノイド構造」と呼ばれる酸化型の構造となっている場合がある。用語「キノイド構造」は、用語「ベンゼノイド構造」に対して用いられるもので、芳香環を含む構造である後者に対し、前者は、その芳香環内の二重結合が環外に移動し（その結果、芳香環は消失する）、環内に残る他の二重結合と共役する２つの環外二重結合が形成された構造を意味する。当業者にとって、これらの両構造の関係は、ベンゾキノンとヒドロキノンの構造の関係から容易に理解できるものである。種々の共役ポリマーの繰り返し単位についてのキノイド構造は、当業者にとって周知である。一例として、前記式（Ｉ）で表されるポリチオフェンの繰り返し単位に対応するキノイド構造を、下記式（Ｉ’）に示す。
Figure JPOXMLDOC01-appb-C000041
［式中、Ｒ１及びＲ２は、式（Ｉ）において定義された通りである。］ In the present invention, the polythiophene may be used after being treated with a reducing agent.
In polythiophenes, the chemical structure of some of the repeating units constituting them may be an oxidized type structure called "quinoid structure". The term "quinoid structure" is used with respect to the term "benzenoid structure", and the latter, which is a structure containing an aromatic ring, causes the double bond in the aromatic ring to move out of the ring ( As a result, the aromatic ring disappears), which means a structure in which two exocyclic double bonds to be coupled to other double bonds remaining in the ring are formed. Those skilled in the art can easily understand the relationship between these two structures from the relationship between the structures of benzoquinone and hydroquinone. Quinoid structures for the repeating units of various conjugated polymers are well known to those skilled in the art. As an example, the quinoid structure corresponding to the repeating unit of the polythiophene represented by said Formula (I) is shown to following formula (I ').
Figure JPOXMLDOC01-appb-C000041
[Wherein, R 1 and R 2 are as defined in the formula (I). ]
　このキノイド構造は、前記のドーピング反応によって生じ、ポリチオフェンに電荷輸送性を付与する「ポーラロン構造」及び「バイポーラロン構造」と称される構造の一部を成すものである。これらの構造は公知である。有機ＥＬ素子の作成において、「ポーラロン構造」及び／又は「バイポーラロン構造」の導入は必須であり、実際、有機ＥＬ素子作成時、電荷輸送性ワニスから形成された電荷輸送性薄膜を焼成処理するときに、前記のドーピング反応を意図的に起こさせて、これを達成している。このドーピング反応を起こさせる前のポリチオフェンにキノイド構造が含まれているのは、ポリチオフェンが、その製造過程（スルホン化ポリチオフェンの場合、特に、その中のスルホン化工程）において、ドーピング反応と同等の、意図しない酸化反応を起こしたためと考えられる。 This quinoid structure is a part of a structure called "polaron structure" or "bipolaron structure" which is generated by the above-mentioned doping reaction and imparts charge transportability to polythiophene. These structures are known. Introduction of a "polaron structure" and / or a "bipolaron structure" is essential in the preparation of an organic EL device, and in fact, when an organic EL device is prepared, a charge transportable thin film formed of a charge transporting varnish is fired Sometimes this is achieved by intentionally causing the doping reaction described above. The polythiophene before the occurrence of this doping reaction contains a quinoid structure, because polythiophene is equivalent to the doping reaction in its production process (in the case of sulfonated polythiophene, in particular, the sulfonation step therein), It is considered to be because an unintended oxidation reaction occurred.
　ポリチオフェンに含まれるキノイド構造の量と、ポリチオフェンの有機溶媒に対する分散性の間には相関があり、キノイド構造の量が多くなると、分散性は低下する。このため、インク組成物から電荷輸送性薄膜が形成された後でのキノイド構造の導入は問題を生じないが、前記の意図しない酸化反応により、ポリチオフェンにキノイド構造が過剰に導入されていると、インク組成物の製造に支障をきたす。ポリチオフェンにおいては、有機溶媒に対する分散性にばらつきがあることが知られているが、その原因の１つは、前記の意図しない酸化反応によりポリチオフェンに導入されたキノイド構造の量が、各々のポリチオフェンの製造条件の差に応じて変動することであると考えられる。
　そこで、ポリチオフェンを、還元剤を用いる還元処理に付すと、ポリチオフェンにキノイド構造が過剰に導入されていても、還元によりキノイド構造が減少し、ポリチオフェンの有機溶媒に対する分散性が向上するため、均質性に優れた電荷輸送性薄膜を与える良好なインク組成物を、安定的に製造することが可能になる。 There is a correlation between the amount of quinoid structure contained in polythiophene and the dispersibility of polythiophene in an organic solvent, and the dispersibility decreases as the amount of quinoid structure increases. For this reason, the introduction of the quinoid structure after the charge transportable thin film is formed from the ink composition does not cause a problem, but when the quinoid structure is excessively introduced to the polythiophene by the unintended oxidation reaction, It interferes with the production of the ink composition. In polythiophenes, it is known that the dispersibility in organic solvents varies, but one of the causes is that the amount of the quinoid structure introduced into polythiophene by the above-mentioned unintended oxidation reaction is the same as that of each polythiophene. It is considered to be variable according to the difference in manufacturing conditions.
Therefore, when the polythiophene is subjected to a reduction treatment using a reducing agent, the quinoid structure is reduced by the reduction even if the quinoid structure is introduced in excess to the polythiophene, and the dispersibility of the polythiophene in the organic solvent is improved. It is possible to stably manufacture a good ink composition which gives an excellent charge transporting thin film.
　この還元処理に用いる還元剤は、前記キノイド構造を還元して非酸化型の構造、即ち、前記ベンゼノイド構造に変換する（例えば、前記式（Ｉ）で表されるポリチオフェンにおいては、前記式（Ｉ’）で表されるキノイド構造を、前記式（Ｉ）で表される構造に変換する）ことができるものである限り特に制限はなく、例えば、アンモニア水、ヒドラジン等を使用することが好ましい。還元剤の量は、処理すべきポリチオフェン１００重量部に対し、通常０．１～１０重量部、好ましくは０．５～２重量部である。 The reducing agent used for this reduction treatment reduces the quinoid structure to convert it to a non-oxidized structure, ie, the benzenoid structure (for example, in the polythiophene represented by the formula (I), the formula (I There is no particular limitation as long as the quinoid structure represented by ') can be converted to the structure represented by the above formula (I). For example, it is preferable to use aqueous ammonia, hydrazine or the like. The amount of reducing agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polythiophene to be treated.
　還元処理の方法及び条件に特に制限はない。例えば、適当な溶媒の存在下又は非存在下、単にポリチオフェンを還元剤と接触させることにより、この処理を行うことができる。通常、ポリチオフェンを２８％アンモニア水中で撹拌する（例えば、室温にて終夜）等の、比較的温和な条件下での還元処理により、ポリチオフェンの有機溶媒に対する分散性は十分に向上する。
　スルホン化ポリチオフェンの場合、必要であれば、スルホン化ポリチオフェンを対応するアンモニウム塩、例えばトリアルキルアンモニウム塩（スルホン化ポリチオフェンアミン付加体）に変換した後に、還元処理に付してもよい。 There are no particular limitations on the method and conditions of the reduction treatment. For example, this treatment can be performed simply by contacting the polythiophene with a reducing agent in the presence or absence of a suitable solvent. In general, reduction treatment under relatively mild conditions such as stirring polythiophene in 28% ammonia water (for example, overnight at room temperature) sufficiently improves the dispersibility of polythiophene in an organic solvent.
In the case of a sulfonated polythiophene, if necessary, the sulfonated polythiophene may be converted to a corresponding ammonium salt, for example, a trialkyl ammonium salt (sulfonated polythiophene amine adduct) and then subjected to a reduction treatment.
　なお、この還元処理によりポリチオフェンの溶媒に対する分散性が変化する結果、処理の開始時には反応系に溶解していなかったポリチオフェンが、処理の完了時には溶解している場合がある。そのような場合には、ポリチオフェンと非相溶性の有機溶剤（スルホン化ポリチオフェンの場合、アセトン，イソプロピルアルコール等）を反応系に添加して、ポリチオフェンの沈殿を生じさせ、濾過する等の方法により、ポリチオフェンを回収することができる。 In addition, as a result of the dispersibility of the polythiophene in the solvent being changed by the reduction treatment, the polythiophene which was not dissolved in the reaction system at the start of the treatment may be dissolved at the completion of the treatment. In such a case, an organic solvent incompatible with polythiophene (acetone, isopropyl alcohol, etc. in the case of sulfonated polythiophene) is added to the reaction system to cause precipitation of polythiophene, followed by filtration, etc. Polythiophene can be recovered.
　インク組成物は、本発明の効果を損なわない範囲で、場合により（Ａ）成分以外の正孔キャリア化合物を更に含んでいてもよい。 The ink composition may further contain a hole carrier compound other than the component (A) in some cases, as long as the effects of the present invention are not impaired.
　オプションの正孔キャリア化合物は、例えば、低分子量化合物又は高分子量化合物を含む。オプションの正孔キャリア化合物は、非ポリマーであってもポリマーであってもよい。非ポリマー正孔キャリア化合物は、架橋性低分子及び架橋していない低分子を含むが、これらに限定されない。非ポリマー正孔キャリア化合物の例は、Ｎ，Ｎ’－ビス（３－メチルフェニル）－Ｎ，Ｎ’－ビス（フェニル）ベンジジン（CAS # 65181-78-4）；Ｎ，Ｎ’－ビス（４－メチルフェニル）－Ｎ，Ｎ’－ビス（フェニル）ベンジジン；Ｎ，Ｎ’－ビス（２－ナフタレニル）－Ｎ，Ｎ’－ビス（フェニルベンジジン）（CAS # 139255-17-1）；１，３，５－トリス（Ｎ，Ｎ－ビス（３－メチルフェニル）アミノ）ベンゼン（ｍ－ＭＴＤＡＢとも呼ばれる）；Ｎ，Ｎ’－ビス（１－ナフタレニル）－Ｎ，Ｎ’－ビス（フェニル）ベンジジン（CAS # 123847-85-8、ＮＰＢ）；４，４’，４”－トリス（Ｎ，Ｎ－フェニル－３－メチルフェニルアミノ）トリフェニルアミン（ｍ－ＭＴＤＡＴＡとも呼ばれる、CAS # 124729-98-2）；４，４’－ビス（カルバゾール－９－イル）ビフェニル（ＣＢＰとも呼ばれる、CAS # 58328-31-7）；１，３，５－トリス（ジフェニルアミノ）ベンゼン；１，３，５－トリス（２－（９－エチルカルバジル－３）エチレン）ベンゼン；１，３，５－トリス［（３－メチルフェニル）フェニルアミノ］ベンゼン；１，３－ビス（Ｎ－カルバゾリル）ベンゼン；１，４－ビス（ジフェニルアミノ）ベンゼン；４，４’－ビス（Ｎ－カルバゾリル）－１，１’－ビフェニル；４－（ジベンジルアミノ）ベンズアルデヒド－Ｎ，Ｎ－ジフェニルヒドラゾン；４－（ジエチルアミノ）ベンズアルデヒド ジフェニルヒドラゾン；４－（ジメチルアミノ）ベンズアルデヒド ジフェニルヒドラゾン；４－（ジフェニルアミノ）ベンズアルデヒド ジフェニルヒドラゾン；９－エチル－３－カルバゾールカルボキシアルデヒド ジフェニルヒドラゾン；銅（ＩＩ）フタロシアニン；Ｎ，Ｎ’－ビス（３－メチルフェニル）－Ｎ，Ｎ’－ジフェニルベンジジン；Ｎ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニル－１，１’－ビフェニル－４，４’－ジアミン；Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ジ－ｐ－トリルベンゼン－１，４－ジアミン；テトラ－Ｎ－フェニルベンジジン；チタニル フタロシアニン；トリ－ｐ－トリルアミン；トリス（４－カルバゾール－９－イルフェニル）アミン；及びトリス［４－（ジエチルアミノ）フェニル］アミンを含むが、これらに限定されない。 Optional hole carrier compounds include, for example, low molecular weight compounds or high molecular weight compounds. The optional hole carrier compound may be non-polymeric or polymeric. Non-polymeric hole carrier compounds include, but are not limited to, crosslinkable small molecules and non-crosslinked small molecules. Examples of non-polymeric hole carrier compounds are N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) benzidine (CAS # 65181-78-4); N, N'-bis ( 4-Methylphenyl) -N, N'-bis (phenyl) benzidine; N, N'-bis (2-naphthalenyl) -N, N'-bis (phenylbenzidine) (CAS # 139255-17-1); 1 , 3,5-tris (N, N-bis (3-methylphenyl) amino) benzene (also called m-MTDAB); N, N'-bis (1-naphthalenyl) -N, N'-bis (phenyl) Benzidine (CAS # 123847-85-8, NPB); 4,4 ', 4 "-tris (N, N-phenyl-3-methylphenylamino) triphenylamine (also called m-MTDATA, CAS # 124729-98 -2); 4,4'-bis (carbazole-9-i) ) Biphenyl (also called CBP, CAS # 58328-31-7); 1,3,5-tris (diphenylamino) benzene; 1,3,5-tris (2- (9-ethylcarbaline-3) ethylene) Benzene; 1,3,5-tris [(3-methylphenyl) phenylamino] benzene; 1,3-bis (N-carbazolyl) benzene; 1,4-bis (diphenylamino) benzene; 4,4′-bis (N-carbazolyl) -1,1'-biphenyl; 4- (dibenzylamino) benzaldehyde-N, N-diphenylhydrazone; 4- (diethylamino) benzaldehyde diphenylhydrazone; 4- (dimethylamino) benzaldehyde diphenylhydrazone; 4- (Diphenylamino) benzaldehyde diphenyl hydrazone; 9-ethyl-3-carbazo Carboxaldehyde Diphenylhydrazone; Copper (II) Phthalocyanine; N, N'-Bis (3-methylphenyl) -N, N'-diphenylbenzidine; N, N'-Di (1-naphthyl) -N, N'-diphenyl -1,1'-biphenyl-4,4'-diamine; N, N'-diphenyl-N, N'-di-p-tolylbenzene-1,4-diamine; tetra-N-phenylbenzidine; titanyl phthalocyanine; Includes, but is not limited to, tri-p-tolylamine; tris (4-carbazol-9-ylphenyl) amine; and tris [4- (diethylamino) phenyl] amine.
　オプションのポリマー正孔キャリア化合物は、ポリ［（９，９－ジヘキシルフルオレニル－２，７－ジイル）－alt－co－（Ｎ，Ｎ’－ビス｛ｐ－ブチルフェニル｝－１，４－ジアミノフェニレン）］；ポリ［（９，９－ジオクチルフルオレニル－２，７－ジイル）－alt－co－（Ｎ，Ｎ’－ビス｛ｐ－ブチルフェニル｝－１，１’－ビフェニレン－４，４’－ジアミン）］；ポリ（９，９－ジオクチルフルオレン－co－Ｎ－（４－ブチルフェニル）ジフェニルアミン）（ＴＦＢとも呼ばれる）及びポリ［Ｎ，Ｎ’－ビス（４－ブチルフェニル）－Ｎ，Ｎ’－ビス（フェニル）－ベンジジン］（一般にポリ－ＴＰＤと呼ばれる）を含むが、これらに限定されない。 The optional polymeric hole carrier compound is poly [(9,9-dihexylfluorenyl-2,7-diyl) -alt-co- (N, N'-bis {p-butylphenyl} -1,4 Diaminophenylene)]; poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (N, N'-bis {p-butylphenyl} -1,1'-biphenylene-4 , 4'-diamine)]; poly (9,9-dioctylfluorene-co-N- (4-butylphenyl) diphenylamine) (also called TFB) and poly [N, N'-bis (4-butylphenyl)- N, N'-bis (phenyl) -benzidine] (generally referred to as poly-TPD), but is not limited thereto.
　他のオプションの正孔キャリア化合物は、例えば、２０１０年１１月１８日に公開の米国特許出願公開第２０１０／０２９２３９９号；２０１０年５月６日に公開の米国特許出願公開第２０１０／０１０９０００号；及び２０１０年５月６日に公開の米国特許出願公開２０１０／０１０８９５４号に記載されている。本明細書に記載のオプションの正孔キャリア化合物は、当該分野において公知であり、そして市販されている。 Other optional hole carrier compounds are described, for example, US Patent Application Publication No. 2010/0292399 published Nov. 18, 2010; US Patent Application Publication No. 2010/0109000 published May 6, 2010; And U.S. Patent Application Publication 2010/0108954 published May 6, 2010. Optional hole carrier compounds described herein are known in the art and are commercially available.
［（Ｂ）成分］
　（Ｂ）成分は、オニウムボレート塩であって、式（ａ１）：
Figure JPOXMLDOC01-appb-C000042
で表されるアニオン、及び式（ａ２）：
Figure JPOXMLDOC01-appb-C000043
で表される１価又は２価のアニオン
　［式中、Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基であり、Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－である］からなる群より選択される少なくとも１種のアニオンと対カチオンとからなるオニウムボレート塩（ただし、電気的中性な塩である）である。 [(B) component]
The component (B) is an onium borate salt, which is represented by the formula (a1):
Figure JPOXMLDOC01-appb-C000042
And the anion represented by and the formula (a2):
Figure JPOXMLDOC01-appb-C000043
A monovalent or divalent anion represented by the formula: wherein Ar is each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent; An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a fluoroaralkyl group having 7 to 10 carbon atoms , L represents an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -, and an onium borate salt composed of at least one anion selected from the group consisting of: It is a neutral salt).
　（Ｂ）成分は、（Ａ）成分のポリチオフェンを酸化し、電気的特性（抵抗率及び仕事関数等）を改善するドーパントとして機能する。（Ｂ）成分のように、式（ａ１）又は（ａ２）で表されるアニオンと対カチオンとからなるオニウムボレート塩をドーパントとして用いると、ポリチオフェンの電気的特性を大きく改善することができ、電荷輸送性に優れたインク組成物とすることができる。 The component (B) functions as a dopant which oxidizes the polythiophene of the component (A) and improves the electrical properties (such as resistivity and work function). When an onium borate salt composed of an anion represented by the formula (a1) or (a2) and a counter cation is used as a dopant as the component (B), the electrical properties of the polythiophene can be greatly improved, and It can be set as the ink composition excellent in transportability.
　式（ａ１）及び（ａ２）において、Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基である。 In formulas (a1) and (a2), each Ar is independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
　アリール基としては、炭素数６～２０のアリール基等が挙げられる。その具体例としては、フェニル基、トリル基、１－ナフチル基、２－ナフチル基、１－アントリル基、２－アントリル基、９－アントリル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、４－フェナントリル基、９－フェナントリル基等が挙げられ、フェニル基、トリル基及びナフチル基が好ましい。 Examples of the aryl group include aryl groups having 6 to 20 carbon atoms. Specific examples thereof 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 And 4-phenanthryl group, 9-phenanthryl group and the like, and a phenyl group, a tolyl group and a naphthyl group are preferable.
　ヘテロアリール基としては、好ましくは炭素数２～２０のヘテロアリール基が挙げられる。その具体例としては、２－チエニル基、３－チエニル基、２－フラニル基、３－フラニル基、２－オキサゾリル基、４－オキサゾリル基、５－オキサゾリル基、３－イソオキサゾリル基、４－イソオキサゾリル基、５－イソオキサゾリル基等の含酸素ヘテロアリール基、２－チアゾリル基、４－チアゾリル基、５－チアゾリル基、３－イソチアゾリル基、４－イソチアゾリル基、５－イソチアゾリル基等の含硫黄ヘテロアリール基、２－イミダゾリル基、４－イミダゾリル基、２－ピリジル基、３－ピリジル基、４－ピリジル基、２－ピラジル基、３－ピラジル基、５－ピラジル基、６－ピラジル基、２－ピリミジル基、４－ピリミジル基、５－ピリミジル基、６－ピリミジル基、３－ピリダジル基、４－ピリダジル基、５－ピリダジル基、６－ピリダジル基、１，２，３－トリアジン－４－イル基、１，２，３－トリアジン－５－イル基、１，２，４－トリアジン－３－イル基、１，２，４－トリアジン－５－イル基、１，２，４－トリアジン－６－イル基、１，３，５－トリアジン－２－イル基、１，２，４，５－テトラジン－３－イル基、１，２，３，４－テトラジン－５－イル基、２－キノリニル基、３－キノリニル基、４－キノリニル基、５－キノリニル基、６－キノリニル基、７－キノリニル基、８－キノリニル基、１－イソキノリニル基、３－イソキノリニル基、４－イソキノリニル基、５－イソキノリニル基、６－イソキノリニル基、７－イソキノリニル基、８－イソキノリニル基、２－キノキサニル基、５－キノキサニル基、６－キノキサニル基、２－キナゾリニル基、４－キナゾリニル基、５－キナゾリニル基、６－キナゾリニル基、７－キナゾリニル基、８－キナゾリニル基、３－シンノリニル基、４－シンノリニル基、５－シンノリニル基、６－シンノリニル基、７－シンノリニル基、８－シンノリニル基等の含窒素ヘテロアリール基等が挙げられる。 The heteroaryl group preferably includes heteroaryl groups having 2 to 20 carbon atoms. Specific examples thereof include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group And sulfur-containing heteroaryl groups such as oxygen-containing heteroaryl groups such as 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, etc. 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 3-pyrazinyl group, 5-pyrazinyl group, 5-pyrazinyl group, 6-pyrazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 6-pyrimidyl group, 3-pyridazyl group, 4-pyridazyl group, 5-pyridazyl group -Pyridazyl group, 1,2,3-triazin-4-yl group, 1,2,3-triazin-5-yl group, 1,2,4-triazin-3-yl group, 1,2,4-triazine -5-yl group, 1,2,4-triazin-6-yl group, 1,3,5-triazin-2-yl group, 1,2,4,5-tetrazine-3-yl group, 1,2 , 3,4-tetrazine-5-yl group, 2-quinolinyl group, 3-quinolinyl group, 4-quinolinyl group, 5-quinolinyl group, 6-quinolinyl group, 7-quinolinyl group, 8-quinolinyl group, 1-isoquinolinyl Group, 3-isoquinolinyl group, 4-isoquinolinyl group, 5-isoquinolinyl group, 6-isoquinolinyl group, 7-isoquinolinyl group, 8-isoquinolinyl group, 2-quinoxanyl group, 5-quinoxanyl group, 6-quinoxanyl group, 2-quinazolyl Groups, 4-quinazolinyl groups, 5-quinazolinyl groups, 6-quinazolinyl groups, 7-quinazolinyl groups, 8-quinazolinyl groups, 3-cinnolinyl groups, 4-cinnolinyl groups, 5-cinnolinyl groups, 6-cinnolinyl groups, 7- And nitrogen-containing heteroaryl groups such as cinnolinyl group and 8-cinnolinyl group.
　前記置換基としては、ハロゲン原子、ニトロ基、シアノ基、炭素数１～２０のアルキル基、炭素数２～２０のアルケニル基及び炭素数２～２０のアルキニル基等が挙げられる。 Examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms.
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。 As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, A fluorine atom is preferable.
　炭素数１～２０のアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、その具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－ノナデシル基、ｎ－エイコサニル基等が挙げられるが、炭素数１～１８のアルキル基が好ましく、炭素数１～８のアルキル基がより好ましい。 The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n- Examples include a dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, etc. An alkyl group of 1 to 18 is preferable, and an alkyl group of 1 to 8 carbon atoms is more preferable.
　炭素数２～２０のアルケニル基の具体例としては、エテニル基、ｎ－１－プロペニル基、ｎ－２－プロペニル基、１－メチルエテニル基、ｎ－１－ブテニル基、ｎ－２－ブテニル基、ｎ－３－ブテニル基、２－メチル－１－プロペニル基、２－メチル－２－プロペニル基、１－エチルエテニル基、１－メチル－１－プロペニル基、１－メチル－２－プロペニル基、ｎ－１－ペンテニル基、ｎ－１－デセニル基、ｎ－１－エイコセニル基等が挙げられる。 Specific examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- 1-pentenyl group, n-1-decenyl group, n-1-eicosenyl group etc. are mentioned.
　炭素数２～２０のアルキニル基の具体例としては、エチニル基、ｎ－１－プロピニル基、ｎ－２－プロピニル基、ｎ－１－ブチニル基、ｎ－２－ブチニル基、ｎ－３－ブチニル基、１－メチル－２－プロピニル基、ｎ－１－ペンチニル基、ｎ－２－ペンチニル基、ｎ－３－ペンチニル基、ｎ－４－ペンチニル基、１－メチル－ｎ－ブチニル基、２－メチル－ｎ－ブチニル基、３－メチル－ｎ－ブチニル基、１，１－ジメチル－ｎ－プロピニル基、ｎ－１－ヘキシニル基、ｎ－１－デシニル基、ｎ－１－ペンタデシニル基、ｎ－１－エイコシニル基等が挙げられる。 Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, n-3-butynyl group Group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2- Methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group, n-1-pentadecynyl group, n- 1-Eicosinyl group etc. are mentioned.
　Ａｒは、好ましくは、１又は２以上の電子吸引性置換基を有するアリール基である。Ａｒが電子吸引性置換基を有するアリール基であると、ルイス酸性が向上する点で好ましい。前記電子吸引性基としては、ハロゲン原子、ニトロ基、シアノ基等が挙げられ、ハロゲン原子が好ましく、フッ素原子が特に好ましい。Ａｒは、特に好ましくは、ペンタフルオロフェニル基である。 Ar is preferably an aryl group having one or more electron withdrawing substituents. It is preferable that Ar is an aryl group having an electron withdrawing substituent from the viewpoint of improving the Lewis acidity. Examples of the electron withdrawing group include a halogen atom, a nitro group, a cyano group and the like, a halogen atom is preferable, and a fluorine atom is particularly preferable. Ar is particularly preferably a pentafluorophenyl group.
　（Ｂ）成分が式（ａ１）で表されるアニオンと対カチオンとからなるオニウムボレート塩である場合、式（ａ４）：
Figure JPOXMLDOC01-appb-C000044
で表されるアニオンと対カチオンとからなるオニウムボレート塩が、特に好ましい。 When the component (B) is an onium borate salt comprising an anion represented by the formula (a1) and a counter cation, the formula (a4):
Figure JPOXMLDOC01-appb-C000044
Particularly preferred is an onium borate salt comprising an anion represented by and a counter cation.
　式（ａ１）において、Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基である。 In formula (a1), R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or 7 carbon atoms And a fluoroaralkyl group of -10.
　炭素数１～１０のアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の炭素数１～１０の直鎖又は分岐鎖状アルキル基等が挙げられるが、炭素数１～８のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。 The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s -C1-C10 linear or branched, such as -butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl Examples thereof include chain alkyl groups and the like, and alkyl groups having 1 to 8 carbon atoms are preferable, and alkyl groups having 1 to 6 carbon atoms are more preferable.
　炭素数３～２０のシクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等の炭素数３～２０の環状アルキル基が挙げられる。 Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group And a cyclic alkyl group having a carbon number of 3 to 20 such as bicycloheptyl group, bicyclooctyl group, bicyclononyl group and bicyclodecyl group.
　炭素数１～１０のフルオロアルキル基の具体例としては、炭素数１～１０のアルキル基の水素原子の少なくとも１つをフッ素原子で置換した基が挙げられる。
　その具体例としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、２，２，２－トリフルオロエチル基、ヘプタフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、２，２，３，３－テトラフルオロプロピル基、２，２，２－トリフルオロ－１－（トリフルオロメチル）エチル基、ノナフルオロブチル基、４，４，４－トリフルオロブチル基、ウンデカフルオロペンチル基、２，２，３，３，４，４，５，５，５－ノナフルオロペンチル基、２，２，３，３，４，４，５，５－オクタフルオロペンチル基、トリデカフルオロヘキシル基、２，２，３，３，４，４，５，５，６，６，６－ウンデカフロオロヘキシル基、２，２，３，３，４，４，５，５，６，６－デカフルオロヘキシル基、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル基等が挙げられる。 Specific examples of the fluoroalkyl group having 1 to 10 carbon atoms include groups in which at least one hydrogen atom of the alkyl group having 1 to 10 carbon atoms is substituted with a fluorine atom.
Specific examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 2,2,3,3,3- Pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, nonafluorobutyl group, 4,4,4-trifluoro Butyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoro group Pentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,6 5,5,6,6-decafluo Hexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.
　炭素数７～１０のアラルキル基としては、アルキル基の水素原子の少なくとも１つをアリール基で置換した基が挙げられ、例えば、ベンジル基、１－ナフチルメチル基、２－ナフチルメチル基、フェニルエチル基、１－ナフチルエチル基、２－ナフチルメチル基等が挙げられるが、炭素数７～９のアラルキル基が好ましい。 Examples of the aralkyl group having 7 to 10 carbon atoms include groups in which at least one hydrogen atom of an alkyl group is substituted with an aryl group, and examples thereof include benzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, phenylethyl group Groups, 1-naphthylethyl group, 2-naphthylmethyl group and the like can be mentioned, but an aralkyl group having 7 to 9 carbon atoms is preferable.
　炭素数７～１０のフルオロアラルキル基の具体例としては、炭素数７～１０のアラルキル基の水素原子の少なくとも１つをフッ素原子で置換した基が挙げられる。
　その具体例としては、パーフルオロベンジル基、ペンタフルオロフェニルメチル基、ヘプタフルオロ－１－ナフチルメチル基、ヘプタフルオロ－２－ナフチルメチル基、ヘプタフルオロ－１－ナフチルエチル基、ヘプタフルオロ－２－ナフチルエチル基等が挙げられる。 Specific examples of the fluoroaralkyl group having 7 to 10 carbon atoms include groups in which at least one hydrogen atom of the aralkyl group having 7 to 10 carbon atoms is substituted with a fluorine atom.
Specific examples thereof include perfluorobenzyl group, pentafluorophenylmethyl group, heptafluoro-1-naphthylmethyl group, heptafluoro-2-naphthylmethyl group, heptafluoro-1-naphthylethyl group, heptafluoro-2-naphthyl group Ethyl group etc. are mentioned.
　これらの中でも、式（ａ１）におけるＲは、炭素数１～６のアルキル基が好ましい。本発明で好適に用いることのできる式（ａ１）で表されるアニオンとしては下記式で表されるものが挙げられるが、これに限定されるものではない。 Among these, R in the formula (a1) is preferably an alkyl group having 1 to 6 carbon atoms. As an anion represented by a formula (a1) which can be used suitably by this invention, although what is represented by a following formula is mentioned, it is not limited to this.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　式（ａ２）において、Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－である。アルキレン基としては、直鎖、分岐、環状のいずれでもよく、炭素数１～２０、好ましくは炭素数１～１０のアルキレン基が挙げられる。その具体例としては、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が挙げられる。 In formula (a2), L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -. The alkylene group may be linear, branched or cyclic, and includes an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include methylene group, methyl methylene group, dimethyl methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like.
　Ｌは、－ＣＮ+－であると、特に好ましい。 L is particularly preferably -CN + -.
　（Ｂ）成分が式（ａ２）で表されるアニオンと対カチオンとからなるオニウムボレート塩である場合、式（ａ３）：
Figure JPOXMLDOC01-appb-C000046
で表されるアニオンと対カチオンとからなるオニウムボレート塩が、特に好ましい。 When the component (B) is an onium borate salt comprising an anion represented by the formula (a2) and a counter cation, the formula (a3):
Figure JPOXMLDOC01-appb-C000046
Particularly preferred is an onium borate salt comprising an anion represented by and a counter cation.
　（Ｂ）成分の対カチオンは、特に限定されるものではないが、１５～１７族に属する元素を含むカチオンが好ましく、硫黄を含むカチオンがより好ましい。 The counter cation of the component (B) is not particularly limited, but a cation containing an element belonging to Groups 15 to 17 is preferable, and a cation containing sulfur is more preferable.
　（Ｂ）成分の対カチオンは、式（ｃ１）～（ｃ５）：
Figure JPOXMLDOC01-appb-C000047
からなる群より選択されることが好ましい。中でも、対カチオンが（ｃ１）で表されるカチオンは、特に好ましい。 The counter cation of component (B) is represented by formulas (c1) to (c5):
Figure JPOXMLDOC01-appb-C000047
Preferably it is selected from the group consisting of Among them, cations having a counter cation represented by (c1) are particularly preferable.
　（Ｂ）成分は、下記式：
Figure JPOXMLDOC01-appb-C000048
で表されるオニウムボレート塩であることが特に好ましい。 The component (B) has the following formula:
Figure JPOXMLDOC01-appb-C000048
Particularly preferred is an onium borate salt represented by
　（Ｂ）成分は、１種単独で用いても、２種以上組み合わせて用いてもよい。また、必要に応じて公知のその他のオニウムボレート塩を併用してもよい。なお、（Ｂ）成分は、例えば、特開２００５－３１４６８２号公報等に記載された公知の方法を参考に合成することができる。 The component (B) may be used alone or in combination of two or more. Moreover, you may use together well-known other onium borate salt as needed. The component (B) can be synthesized, for example, with reference to a known method described in JP-A-2005-314682 or the like.
　（Ａ）成分と（Ｂ）成分との比率は、物質量（モル）比で、（Ａ）成分：（Ｂ）成分＝１：０．０１～１５とすることができ、好ましくは、１：０．１～１０、より好ましくは、１：０．５～５である。（Ａ）成分と（Ｂ）成分との比率がこの範囲であると、素子特性の観点から、好ましい。 The ratio of component (A) to component (B) can be (A) component: (B) component = 1: 0.01 to 15 in terms of substance (mole) ratio, and preferably 1: 0.1 to 10, and more preferably 1: 0.5 to 5. It is preferable from the viewpoint of element characteristics that the ratio of the component (A) to the component (B) is in this range.
　（Ｂ）成分は、インク組成物への溶解を容易にするため、あらかじめ後述する（Ｃ）液体担体を構成する有機溶媒に溶かしておいてもよい。
　このような有機溶媒としては、プロピレンカーボネート、エチレンカーボネート、１，２－ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート等のカーボネート類；アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソアミルケトン、２－ヘプタノン等のケトン類；エチレングリコール、エチレングリコールモノアセテート、ジエチレングリコール、ジエチレングリコールモノアセテート、プロピレングリコール、プロピレングリコールモノアセテート、ジプロピレングリコール、ジプロピレングリコールモノアセテートのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテル、モノフェニルエーテル又はトリエチレングリコールジメチルエーテル等の多価アルコール及びその誘導体類；ジオキサン等の環式エーテル類；蟻酸エチル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、アセト酢酸メチル、アセト酢酸エチル、ピルビン酸エチル、エトキシ酢酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、２－ヒドロキシプロピオン酸メチル、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート等のエステル類；トルエン、キシレン、３－フェノキシトルエン、４－メトキシトルエン、安息香酸メチル、シクロヘキシルベンゼン、テトラリン、イソホロン等の芳香族炭化水素類等が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。
　有機溶媒を使用する場合、その使用割合は、（Ｂ）成分１００重量部に対して、１５～１，０００重量部が好ましく、３０～５００重量部がより好ましい。 The component (B) may be previously dissolved in an organic solvent constituting the liquid carrier (C) described later in order to facilitate the dissolution in the ink composition.
As such organic solvents, carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene Glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether or tri Polyhydric alcohols such as ethylene glycol dimethyl ether and the like Derivatives; Cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methoxy Methyl propionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, Esters such as 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene, xylene, 3-phenoxytoluene, 4-methoxytoluene, methyl benzoate, cyclohexylbenzene, tetralin, isophorone and the like. These can be used singly or may be used in combination of two or more.
When an organic solvent is used, its use ratio is preferably 15 to 1,000 parts by weight, and more preferably 30 to 500 parts by weight with respect to 100 parts by weight of the component (B).
　本願の目的を妨げない範囲で、インク組成物は、（Ｂ）成分以外のドーパントを含有してもよい。ドーパントは当該分野において公知である。例えば、米国特許第７，０７０，８６７号；米国特許出願公開第２００５／０１２３７９３号；及び米国特許出願公開第２００４／０１１３１２７号を参照のこと。ドーパントは、イオン性化合物であってもよい。ドーパントは、カチオン及びアニオンを含むことができる。 The ink composition may contain a dopant other than the component (B) as long as the object of the present application is not hindered. Dopants are known in the art. See, for example, U.S. Patent No. 7,070,867; U.S. Patent Application Publication No. 2005/0123793; and U.S. Patent Application Publication No. 2004/0113127. The dopant may be an ionic compound. The dopant can include a cation and an anion.
　イオン性化合物のカチオンは、例えば、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、又はＡｕであってよい。 The cation of the ionic compound is, for example, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, or It may be Au.
　イオン性化合物のカチオンは、例えば、金、モリブデン、レニウム、鉄、及び銀カチオンであってよい。 The cations of the ionic compounds may be, for example, gold, molybdenum, rhenium, iron and silver cations.
　幾つかの実施態様において、ドーパントは、アルキル、アリール、及びヘテロアリールスルホナート又はカルボキシラートを含む、スルホナート又はカルボキシラートを含んでもよい。本明細書に使用されるとき、「スルホナート」とは、－ＳＯ３Ｍ１基（ここで、Ｍ１は、Ｈ＋又はアルカリ金属イオン（例えば、Ｎａ＋、Ｌｉ＋、Ｋ＋、Ｒｂ＋、Ｃｓ＋等）；又はアンモニウム（ＮＨ４ ＋）であってよい）のことをいう。本明細書に使用されるとき、「カルボキシラート」とは、－ＣＯ２Ｍ１基（ここで、Ｍ１は、Ｈ＋又はアルカリ金属イオン（例えば、Ｎａ＋、Ｌｉ＋、Ｋ＋、Ｒｂ＋、Ｃｓ＋等）；又はアンモニウム（ＮＨ４ ＋）であってよい）のことをいう。スルホナート及びカルボキシラートドーパントの例は、ベンゾアート化合物、ヘプタフルオロブチラート、メタンスルホナート、トリフルオロメタンスルホナート、ｐ－トルエンスルホナート、ペンタフルオロプロピオナート、及びポリマースルホナート類、ペルフルオロスルホナート含有アイオノマー類等を含むが、これらに限定されない。 In some embodiments, the dopant may include sulfonates or carboxylates, including alkyl, aryl, and heteroaryl sulfonates or carboxylates. As used herein, “sulfonate” refers to a —SO 3 M 1 group, where M 1 is H + or an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + etc); or ammonium (NH 4 + )). As used herein, “carboxylate” refers to a —CO 2 M 1 group, where M 1 is H + or an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + and the like); or ammonium (NH 4 + )). Examples of sulfonate and carboxylate dopants include benzoate compounds, heptafluorobutyrate, methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, pentafluoropropionate, and polymeric sulfonates, perfluorosulfonate-containing ionomers And the like, but is not limited thereto.
　幾つかの実施態様において、ドーパントは、スルホナートもカルボキシラートも含まない。 In some embodiments, the dopant does not include sulfonate or carboxylate.
　幾つかの実施態様において、ドーパントは、スルホニルイミド（例えば、ビス（トリフルオロメタンスルホニル）イミド等）；アンチモナート（例えば、ヘキサフルオロアンチモナート等）；アルセナート（例えば、ヘキサフルオロアルセナート等）；リン化合物（例えば、ヘキサフルオロホスファート等）；及び（Ｂ）成分を除くボレート（例えば、テトラフルオロボレート、テトラアリールボレート、及びトリフルオロボレート等）を含んでよい。テトラアリールボレート類の例は、テトラキスペンタフルオロフェニルボレート（ＴＰＦＢ）のようなハロゲン化テトラアリールボレート類を含むが、これらに限定されない。トリフルオロボレート類の例は、（２－ニトロフェニル）トリフルオロボレート、ベンゾフラザン－５－トリフルオロボレート、ピリミジン－５－トリフルオロボレート、ピリジン－３－トリフルオロボレート、及び２，５－ジメチルチオフェン－３－トリフルオロボレートを含むが、これらに限定されない。 In some embodiments, the dopant is a sulfonylimide (eg, bis (trifluoromethanesulfonyl) imide, etc.); an antimonate (eg, hexafluoroantimonate, etc.); an arsenate (eg, hexafluoroarsenate, etc.); a phosphorus compound And borate (eg, tetrafluoroborate, tetraarylborate, and trifluoroborate etc.) excluding the (B) component. Examples of tetraaryl borates include, but are not limited to, halogenated tetraaryl borates such as tetrakis pentafluorophenyl borate (TPFB). Examples of trifluoroborates are (2-nitrophenyl) trifluoroborate, benzofurazan-5-trifluoroborate, pyrimidine-5-trifluoroborate, pyridine-3-trifluoroborate, and 2, 5-dimethylthiophene This includes, but is not limited to, 3-trifluoroborate.
　ドーパントは、例えば、共役ポリマーとの、例えば、１つ以上の電子移動反応を受けることによって、ドープされたポリチオフェンが生成する材料であってよい。ドーパントは、適切な電荷均衡する対アニオンを提供するように選択することができる。反応は、当該分野において公知のとおり、ポリチオフェンとドーパントの混合により起こり得る。例えば、ドーパントは、ポリマーからカチオン－アニオンドーパント（金属塩等）への自発電子移動を受けて、共役ポリマーを、アニオンが会合しているその酸化型の形態で、遊離金属と共に残すことができる。例えば、LebedevらのChem. Mater., 1998, 10, 156-163を参照のこと。本明細書に開示されるとおり、ポリチオフェン及びドーパントとは、反応することによりドープされたポリマーを形成する成分のことをいう場合がある。ドーピング反応は、電荷キャリアが生成される電荷移動反応であってよく、この反応は、可逆的であっても不可逆的であってもよい。幾つかの実施態様において、銀イオンは、銀金属及びドープされたポリマーへの又はこれらからの電子移動を受けることができる。 The dopant may be, for example, a material from which doped polythiophene is produced by undergoing, for example, one or more electron transfer reactions with a conjugated polymer. The dopant can be selected to provide a suitable charge balanced counter anion. The reaction may occur by mixing the polythiophene and the dopant, as known in the art. For example, the dopant can undergo spontaneous electron transfer from the polymer to a cation-anion dopant (such as a metal salt) to leave the conjugated polymer with the free metal in the form of its oxidized form with which the anion is associated. See, for example, Lebedev et al. Chem. Mater., 1998, 10, 156-163. As disclosed herein, polythiophene and dopant may refer to components that react to form a doped polymer. The doping reaction may be a charge transfer reaction in which charge carriers are generated, which reaction may be reversible or irreversible. In some embodiments, silver ions can undergo electron transfer to or from silver metal and doped polymers.
　最終配合物において、組成物は、元の成分の組合せとは明確に異なるものであってよい（即ち、ポリチオフェン及び／又はドーパントは、混合前と同じ形態で最終組成物中に存在してもしなくともよい）。
　ドーパントとしては、無機酸、有機酸、有機又は無機酸化剤等が用いられる。有機酸としては、ポリマー有機酸及び／又は低分子有機酸（非ポリマー有機酸）が用いられる。
　一実施形態では、有機酸はスルホン酸であり、その塩（－ＳＯ３Ｍ２（ここで、Ｍ２は、アルカリ金属イオン（例えば、Ｎａ＋、Ｌｉ＋、Ｋ＋、Ｒｂ＋、Ｃｓ＋等）、アンモニウム（ＮＨ４ ＋）、モノ－、ジ－、及びトリアルキルアンモニウム（トリエチルアンモニウム等））でもよい。該スルホン酸のなかでも、アリールスルホン酸が好ましい。 In the final formulation, the composition may be distinct from the combination of the original components (ie the polythiophene and / or the dopant may or may not be present in the final composition in the same form as before mixing Also good).
As the dopant, an inorganic acid, an organic acid, an organic or inorganic oxidizing agent or the like is used. As the organic acid, a polymeric organic acid and / or a low molecular organic acid (nonpolymeric organic acid) is used.
In one embodiment, the organic acid is a sulfonic acid and its salt (—SO 3 M 2, where M 2 is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs +, etc.) And ammonium (NH 4 + ), mono-, di-, and trialkyl ammonium (such as triethyl ammonium)) Among the sulfonic acids, aryl sulfonic acids are preferred.
　幾つかの実施態様において、ドーパントの具体例としては、塩化水素、硫酸、硝酸、リン酸等の無機強酸；塩化アルミニウム（ＩＩＩ）（ＡｌＣｌ３）、四塩化チタン（ＩＶ）（ＴｉＣｌ４）、三臭化ホウ素（ＢＢｒ３）、三フッ化ホウ素エーテル錯体（ＢＦ３・ＯＥｔ２）、塩化鉄（ＩＩＩ）（ＦｅＣｌ３）、塩化銅（ＩＩ）（ＣｕＣｌ２）、五塩化アンチモン（Ｖ）（ＳｂＣｌ５）、五フッ化砒素（Ｖ）（ＡｓＦ５）、五フッ化リン（ＰＦ５）、トリス（４－ブロモフェニル）アルミニウムヘキサクロロアンチモナート（ＴＢＰＡＨ）等のルイス酸；ポリスチレンスルホン酸等のポリマー有機酸；ベンゼンスルホン酸、トシル酸、カンファースルホン酸、ヒドロキシベンゼンスルホン酸、５－スルホサリチル酸、ドデシルベンゼンスルホン酸、国際公開第２００５／０００８３２号に記載されている１，４－ベンゾジオキサンジスルホン酸誘導体、国際公開第２００６／０２５３４２号に記載されているアリールスルホン酸誘導体、特開２００５－１０８８２８号公報に記載されているジノニルナフタレンスルホン酸誘導体等の低分子有機酸（非ポリマー有機酸）；７，７，８，８－テトラシアノキノジメタン（ＴＣＮＱ）、２，３－ジクロロ－５，６－ジシアノ－１，４－ベンゾキノン（ＤＤＱ）、ヨウ素、ヘテロポリ酸化合物等の有機又は無機酸化剤を挙げることができるが、これらに限定されるものではない。 In some embodiments, specific examples of the dopant include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum (III) chloride (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), Boron Bromide (BBr 3 ), Boron Trifluoride Ether Complex (BF 3 · OEt 2 ), Iron (III) Chloride (FeCl 3 ), Copper (II) Chloride (CuCl 2 ), Antimony Pentachloride (V) (SbCl 5 ) Lewis acids such as arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); polymers such as polystyrene sulfonic acid Acid; benzenesulfonic acid, tosyl acid, camphorsulfonic acid, hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecyl ether Nzensulfonic acid, 1,4-benzodioxane disulfonic acid derivative described in WO 2005/000832, aryl sulfonic acid derivative described in WO 2006/025342, JP 2005-108828 A Low-molecular organic acids (non-polymer organic acids) such as dinonyl naphthalene sulfonic acid derivatives described in the following; 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6 Mention may be made, without limitation, of organic or inorganic oxidizing agents such as dicyano-1,4-benzoquinone (DDQ), iodine, heteropolyacid compounds and the like.
　幾つかの実施態様において、ドーパントは、アリールスルホン酸化合物、ヘテロポリ酸化合物、長周期型周期表の第１３族又は１５族に属する元素を含むイオン化合物からなる群より選択される少なくとも１種を含む。
　特に好ましいドーパントとしては、ポリスチレンスルホン酸等のポリマー有機酸、５－スルホサリチル酸、ドデシルベンゼンスルホン酸、国際公開第２００５／０００８３２号に記載されている１，４－ベンゾジオキサンジスルホン酸誘導体、特開２００５－１０８８２８号公報に記載されているジノニルナフタレンスルホン酸誘導体等の低分子有機酸（非ポリマー有機酸）を挙げることができる。また、下記式（２）で示されるスルホン酸誘導体も、好適に用いることができる。 In some embodiments, the dopant comprises at least one selected from the group consisting of an aryl sulfonic acid compound, a heteropoly acid compound, and an ionic compound comprising an element belonging to group 13 or 15 of the long period periodic table .
Particularly preferable dopants include polymer organic acids such as polystyrene sulfonic acid, 5-sulfosalicylic acid, dodecylbenzene sulfonic acid, 1,4-benzodioxane disulfonic acid derivatives described in WO 2005/000832, JP-A No. 2005 Mention may be made of low molecular weight organic acids (non-polymeric organic acids) such as dinonylnaphthalene sulfonic acid derivatives described in JP-108828. Moreover, the sulfonic acid derivative shown by following formula (2) can also be used suitably.
Figure JPOXMLDOC01-appb-C000049
〔式中、Ｘ１は、Ｏ、Ｓ又はＮＨを表し、Ａは、Ｘ１及びｃ個の（ＳＯ３Ｈ）基以外の置換基を有していてもよいナフタレン環又はアントラセン環を表し、Ｔは、非置換若しくは置換の炭化水素基、１，３，５－トリアジン基、又は非置換若しくは置換の下記式（３）若しくは（４）：
Figure JPOXMLDOC01-appb-C000050
で示される基（式中、Ｗ１及びＷ２は、それぞれ独立して、Ｏ、Ｓ、Ｓ（Ｏ）基、Ｓ（Ｏ２）基、又は非置換若しくは置換基が結合したＮ、Ｓｉ、Ｐ、Ｐ（Ｏ）基を示す。Ｗ１は単結合でもよい。Ｒ４６～Ｒ５９はそれぞれ独立して水素原子又はハロゲン原子を表す。）を表し、ｃは、Ａに結合するスルホン酸基数を表し、１≦ｃ≦４を満たす整数であり、ｄは、ＴとＸ１との結合数を示し、１≦ｄを満たす整数である。〕
Figure JPOXMLDOC01-appb-C000049
[Wherein, X 1 represents O, S or NH, and A represents a naphthalene ring or an anthracene ring which may have a substituent other than X 1 and c (SO 3 H) groups, T is an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group, or an unsubstituted or substituted formula (3) or (4):
Figure JPOXMLDOC01-appb-C000050
Wherein W 1 and W 2 are each independently O, S, S (O), S (O 2 ), or N, Si, to which is not substituted or substituted. P and P (O) groups are shown, W 1 may be a single bond, R 46 to R 59 each independently represent a hydrogen atom or a halogen atom), c represents the number of sulfonic acid groups bonded to A Is an integer that satisfies 1 ≦ c ≦ 4, and d is an integer that satisfies 1 ≦ d, indicating the number of combinations of T and X 1 . ]
　式（３）又は（４）のＲ４６～Ｒ５９は好ましくはフッ素原子であり、全てフッ素原子であることがより好ましい。式（３）のＷ１は単結合が好ましい。最も好ましいのは式（３）におけるＷ１が単結合であり、Ｒ４６～Ｒ５３が全てフッ素原子である。 R 46 to R 59 in the formula (3) or (4) are preferably fluorine atoms, and more preferably all fluorine atoms. W 1 in formula (3) is preferably a single bond. Most preferably, W 1 in the formula (3) is a single bond, and all of R 46 to R 53 are fluorine atoms.
　本発明に係るアリールスルホン酸化合物は、更に下記式（５）で示されるものを用いることもできる。
Figure JPOXMLDOC01-appb-C000051
（式中、Ｘ１は、Ｏ、Ｓ又はＮＨを表し、Ａｒ５は、アリール基を表し、ｃは、スルホン酸基数を表し、１～４を満たす整数である。） As the arylsulfonic acid compound according to the present invention, one represented by the following formula (5) can also be used.
Figure JPOXMLDOC01-appb-C000051
(Wherein, X 1 represents O, S or NH, Ar 5 represents an aryl group, c represents the number of sulfonic acid groups, and is an integer satisfying 1 to 4)
　前記式（５）中、Ｘ１は、Ｏ、Ｓ又はＮＨを表すが、合成が容易であることから、特に、Ｏが好ましい。
　ｃは、ナフタレン環に結合するスルホン酸基数を表し、１～４を満たす整数であるが、当該化合物に高電子受容性及び高溶解性を付与することを考慮すると、ｃ＝１又は２が好ましい。中でも、下記式（６）で示される化合物が、好適である。
Figure JPOXMLDOC01-appb-C000052
（式中、Ａｒ５は、アリール基を表す。） In the above formula (5), X 1 represents O, S or NH, but O is particularly preferable because of easy synthesis.
c represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1 to 4, but preferably c = 1 or 2 in consideration of giving high electron acceptability and high solubility to the compound . Among them, a compound represented by the following formula (6) is preferable.
Figure JPOXMLDOC01-appb-C000052
(Wherein, Ar 5 represents an aryl group)
　式（５）及び式（６）におけるアリール基としては、フェニル基、キシリル基、トリル基、ビフェニル基、ナフチル基等のアリール基が挙げられ、これらのアリール基は置換基を有していてもよい。
　この置換基としては、水酸基、アミノ基、シラノール基、チオール基、カルボキシル基、リン酸基、リン酸エステル基、エステル基、チオエステル基、アミド基、ニトロ基、シアノ基、一価炭化水素基、オルガノオキシ基、オルガノアミノ基、オルガノシリル基、オルガノチオ基、アシル基、スルホン基、ハロゲン原子等が挙げられるが、これらに限定されるものではない。
　これらのアリール基の中でも特に下記式（７）で示されるアリール基が好適に用いられる。
Figure JPOXMLDOC01-appb-C000053
（式中、Ｒ６０～Ｒ６４は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、炭素数１～１０のアルキル基、炭素数１～１０のハロゲン化アルキル基、炭素数２～１０のハロゲン化アルケニル基を示す。） Examples of the aryl group in the formulas (5) and (6) include aryl groups such as phenyl group, xylyl group, tolyl group, biphenyl group and naphthyl group, and these aryl groups may have a substituent. Good.
Examples of this substituent include a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, a cyano group and a monovalent hydrocarbon group Although an organo oxy group, an organo amino group, an organo silyl group, an organo thio group, an acyl group, a sulfone group, a halogen atom etc. are mentioned, it is not limited to these.
Among these aryl groups, an aryl group represented by the following formula (7) is particularly preferably used.
Figure JPOXMLDOC01-appb-C000053
(Wherein, R 60 to R 64 each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 2 to 10 carbon atoms Represents a halogenated alkenyl group of
　式（７）中、ハロゲン原子としては、塩素、臭素、フッ素、ヨウ素原子のいずれでもよいが、本発明においては、特にフッ素原子が好適である。
　炭素数１～１０のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、２－エチルヘキシル基、ｎ－デシル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
　炭素数１～１０のハロゲン化アルキル基としては、トリフルオロメチル基、２，２，２－トリフルオロエチル基、１，１，２，２，２－ペンタフルオロエチル基、３，３，３－トリフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、１，１，２，２，３，３，３－ヘプタフルオロプロピル基、４，４，４－トリフルオロブチル基、３，３，４，４，４－ペンタフルオロブチル基、２，２，３，３，４，４，４－ヘプタフルオロブチル基、１，１，２，２，３，３，４，４，４－ノナフルオロブチル基等が挙げられる。
　炭素数２～１０のハロゲン化アルケニル基としては、パーフルオロビニル基、パーフルオロプロペニル基（アリル基）、パーフルオロブテニル基等が挙げられる。
　これらの中でも、有機溶剤に対する溶解性をより高めることを考慮すると、特に、下記式（８）で示されるアリール基を用いることが好ましい。
Figure JPOXMLDOC01-appb-C000054
（式中、Ｒ６２は、水素原子、ハロゲン原子、ニトロ基、炭素数１～１０のアルキル基、炭素数１～１０のハロゲン化アルキル基、炭素数２～１０のハロゲン化アルケニル基を示す。） In the formula (7), as a halogen atom, any of chlorine, bromine, fluorine and iodine atoms may be used, but in the present invention, a fluorine atom is particularly preferable.
As the alkyl group having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group Groups, n-heptyl group, n-octyl group, n-nonyl group, 2-ethylhexyl group, n-decyl group, cyclopentyl group, cyclohexyl group and the like.
As the halogenated alkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3- Trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4 And 4-nonafluorobutyl group.
Examples of the halogenated alkenyl group having 2 to 10 carbon atoms include a perfluorovinyl group, a perfluoropropenyl group (allyl group), and a perfluorobutenyl group.
Among these, in consideration of enhancing the solubility in organic solvents, it is particularly preferable to use an aryl group represented by the following formula (8).
Figure JPOXMLDOC01-appb-C000054
(Wherein, R 62 represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms. )
　式（８）中、Ｒ６２は特に、ハロゲン化アルキル基、ハロゲン化アルケニル基、ニトロ基が好ましく、トリフルオロメチル基、パーフルオロプロペニル基、ニトロ基がより好ましい。 In the formula (8), R 62 is particularly preferably a halogenated alkyl group, a halogenated alkenyl group or a nitro group, and more preferably a trifluoromethyl group, a perfluoropropenyl group or a nitro group.
　更に、後述する（Ｆ）マトリックス化合物を添加した場合は、下記式（ａ５）で表されるアニオンとその対カチオンとからなるイオン化合物も、ドーパントとして好適に用いることができる。
Figure JPOXMLDOC01-appb-C000055
（式中、Ｅは長周期型周期表の第１３族又は第１５族に属する元素を表し、Ａｒは、各々独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基を表わす。） Furthermore, when (F) matrix compound mentioned later is added, the ionic compound which consists of an anion represented by a following formula (a5), and its counter cation can also be used suitably as a dopant.
Figure JPOXMLDOC01-appb-C000055
(Wherein, E represents an element belonging to Group 13 or Group 15 of the long period periodic table, and Ar each independently has an aryl group which may have a substituent or a substituent Also represents a heteroaryl group which may be
　式（ａ５）中、Ｅは長周期型周期表の第１３族又は第１５族に属する元素の中でもホウ素、ガリウム、リン、アンチモンが好ましく、ホウ素がより好ましい。 In the formula (a5), among the elements belonging to Group 13 or Group 15 of the long period periodic table, E is preferably boron, gallium, phosphorus or antimony, more preferably boron.
　式（ａ５）中、アリール基、ヘテロアリール基の例示としては、５又は６員環の単環又は２～４縮合環由来の１価の基が挙げられる。中でも、化合物の安定性、耐熱性の点から、ベンゼン環、ナフタレン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環由来の１価の基が好ましい。
　更に、Ａｒのうち少なくとも１つの基が、フッ素原子又は塩素原子を置換基として１つ又は２つ以上有することがより好ましい。特に、Ａｒの水素原子がすべてフッ素原子で置換されたパーフルオロアリール基であることが最も好ましい。パーフルオロアリール基の具体例としては、ペンタフルオロフェニル基、ヘプタフルオロ－２－ナフチル基、テトラフルオロ－４－ピリジル基等が挙げられる。 In the formula (a5), examples of the aryl group and the heteroaryl group include monovalent groups derived from 5- or 6-membered monocyclic or 2-4 condensed rings. Among them, from the viewpoint of the stability of the compound and heat resistance, a monovalent group derived from a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring and an isoquinoline ring is preferable.
Furthermore, it is more preferable that at least one group of Ar has one or more fluorine atoms or chlorine atoms as a substituent. In particular, a perfluoroaryl group in which all hydrogen atoms of Ar are substituted with fluorine atoms is most preferable. Specific examples of the perfluoroaryl group include pentafluorophenyl group, heptafluoro-2-naphthyl group, tetrafluoro-4-pyridyl group and the like.
　上述した中でも、下記式（１０）、（１１）：
Figure JPOXMLDOC01-appb-C000056
で示されるアニオンとカチオンの組合せであるイオン化合物（特許第５３８１９３１号を参照）を好適に用いることができる。 Among the above-mentioned, the following formulas (10) and (11):
Figure JPOXMLDOC01-appb-C000056
An ionic compound (see Patent No. 5381931) which is a combination of an anion and a cation represented by the following can be suitably used.
　また、ヘテロポリ酸化合物も、ドーパントとして特に好ましい。ヘテロポリ酸化合物は、代表的に式（Ａ）で示されるＫｅｇｇｉｎ型あるいは式（Ｂ）で示されるＤａｗｓｏｎ型の化学構造で示される、ヘテロ原子が分子の中心に位置する構造を有し、バナジウム（Ｖ）、モリブデン（Ｍｏ）、タングステン（Ｗ）等の酸素酸であるイソポリ酸と、異種元素の酸素酸とが縮合してなるポリ酸である。このような異種元素の酸素酸としては、主にケイ素（Ｓｉ）、リン（Ｐ）、ヒ素（Ａｓ）の酸素酸が挙げられる。
Figure JPOXMLDOC01-appb-C000057
 Heteropoly acid compounds are also particularly preferred as dopants. The heteropoly acid compound has a structure in which the hetero atom is located at the center of the molecule, represented by the chemical structure of the Keggin type represented by the formula (A) or the Dawson type represented by the formula (B). V) A polyacid formed by condensation of an isopolyacid which is an oxygen acid such as molybdenum (Mo) or tungsten (W) and an oxygen acid of a different element. Such oxygen acids of different elements mainly include oxygen acids of silicon (Si), phosphorus (P) and arsenic (As).
Figure JPOXMLDOC01-appb-C000057
　ヘテロポリ酸化合物の具体例としては、リンモリブデン酸、ケイモリブデン酸、リンタングステン酸、リンタングストモリブデン酸、ケイタングステン酸等が挙げられるが、得られる薄膜を備えた有機ＥＬ素子の特性を考慮すると、リンモリブデン酸、リンタングステン酸、ケイタングステン酸が好適であり、リンタングステン酸がより好ましい。
　なお、これらのヘテロポリ酸化合物は、公知の合成法によって合成して用いてもよいが、市販品としても入手可能である。例えば、リンタングステン酸（Phosphotungstic acid hydrate、又は12-Tungstophosphoric acid n-hydrate，化学式：Ｈ３（ＰＷ１２Ｏ４０）・ｎＨ２Ｏ）や、リンモリブデン酸（Phosphomolybdic acid hydrate、又は12-Molybdo(VI)phosphoric acid n-hydrate，化学式：Ｈ３（ＰＭｏ１２Ｏ４０）・ｎＨ２Ｏ（ｎ≒３０））は、関東化学（株）、和光純薬（株）、シグマアルドリッチジャパン（株）、日本無機化学工業（株）、日本新金属（株）等のメーカーから入手可能である。 Specific examples of heteropoly acid compounds include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, lintungstomolybdic acid, silicotungstic acid, etc. In consideration of the characteristics of the organic EL device provided with the obtained thin film, Phosphormolybdic acid, phosphotungstic acid and silicotungstic acid are preferred, and phosphotungstic acid is more preferred.
These heteropoly acid compounds may be synthesized and used according to known synthetic methods, but are also available as commercial products. For example, phosphotungstic acid hydrate or 12-Tungstophosphoric acid n-hydrate (chemical formula: H 3 (PW 12 O 40 ) · nH 2 O), phosphomolybdic acid hydrate or 12-Molybdo (VI ) Phosphoric acid n-hydrate, chemical formula: H 3 (PMo 12 O 40 ), nH 2 O (n ≒ 30)), Kanto Chemical Co., Ltd., Wako Pure Chemical Industries, Ltd., Sigma-Aldrich Japan Co., Ltd., Japan They are available from manufacturers such as Inorganic Chemical Industry Co., Ltd., Nippon Shin Metal Co., Ltd., and the like.
　幾つかの実施態様では、ドーピングプロセスから反応副産物を除去してもよい。例えば、銀のような金属は、濾過によって除去することができる。 In some embodiments, reaction byproducts may be removed from the doping process. For example, metals such as silver can be removed by filtration.
　例えば、ハロゲン及び金属を除去するために、材料を精製することができる。ハロゲンは、例えば、塩化物、臭化物及びヨウ化物を含む。金属は、例えば、ドーパントのカチオン（ドーパントのカチオンの還元型を含む）、又は触媒若しくは開始剤残留物から残された金属を含む。金属は、例えば、銀、ニッケル、及びマグネシウムを含む。量は、例えば、１００ppm未満、又は１０ppm未満、又は１ppm未満であってよい。 For example, the material can be purified to remove halogens and metals. Halogen includes, for example, chloride, bromide and iodide. The metal includes, for example, the cation of the dopant (including the reduced form of the cation of the dopant) or the metal left from the catalyst or initiator residue. Metals include, for example, silver, nickel and magnesium. The amount may be, for example, less than 100 ppm, or less than 10 ppm, or less than 1 ppm.
　銀含量を含む金属含量は、特に５０ppmを超える濃度では、ＩＣＰ－ＭＳにより測定することができる。 The metal content, including the silver content, can be measured by ICP-MS, especially at concentrations above 50 ppm.
　ある実施態様において、ポリチオフェンが（Ｂ）成分を含むドーパントでドープされるとき、ポリチオフェンとドーパントを混合することにより、ドープされたポリマー組成物が形成される。混合は、当業者には公知の任意の方法を用いて達成されうる。例えば、ポリチオフェンを含む溶液を、ドーパントを含む別の溶液と混合することができる。ポリチオフェン及びドーパントを溶解するのに使用される溶媒は、後述の（Ｃ）液体担体を構成する１種以上有機溶媒である。反応は、当該分野において公知のとおり、ポリチオフェンとドーパントの混合により起こり得る。生じるドープされたポリチオフェン組成物は、組成物に基づいて、約４０重量％～７５重量％のポリマー及び約２５重量％～５５重量％のドーパントを含む。別の実施態様において、ドープされたポリチオフェン組成物は、組成物に基づいて、約５０重量％～６５重量％のポリチオフェン及び約３５重量％～５０重量％のドーパントを含む。典型的には、ポリチオフェンの重量は、ドーパントの重量よりも大きい。典型的には、ドーパントは、約０．２５～０．５m/ruの量のテトラキス（ペンタフルオロフェニル）ホウ酸銀のような銀塩であってよい（ここで、ｍは、銀塩のモル量であり、そしてruは、ポリマー繰り返し単位のモル量である）。 In one embodiment, when the polythiophene is doped with the dopant containing the component (B), the doped polymer composition is formed by mixing the polythiophene and the dopant. The mixing may be accomplished using any method known to one skilled in the art. For example, a solution containing polythiophene can be mixed with another solution containing a dopant. The solvent used to dissolve the polythiophene and the dopant is one or more organic solvents constituting the liquid carrier (C) described below. The reaction may occur by mixing the polythiophene and the dopant, as known in the art. The resulting doped polythiophene composition comprises, based on the composition, about 40% to 75% by weight of polymer and about 25% to 55% by weight of dopant. In another embodiment, the doped polythiophene composition comprises about 50 wt% to 65 wt% polythiophene and about 35 wt% to 50 wt% dopant based on the composition. Typically, the weight of the polythiophene is greater than the weight of the dopant. Typically, the dopant may be a silver salt such as silver tetrakis (pentafluorophenyl) borate in an amount of about 0.25 to 0.5 m / ru, where m is the mole of silver salt Amount, and ru is the molar amount of polymer repeat units).
　ドープされたポリチオフェンは、当業者には公知の方法により（例えば、溶媒の回転蒸発等により）単離されて、乾燥又は実質乾燥材料（粉末等）が得られる。残留溶媒の量は、乾燥又は実質乾燥材料に基づいて、例えば、１０重量％以下、又は５重量％以下、又は１重量％以下であってよい。乾燥又は実質乾燥粉末は、１種以上の新しい溶媒に再分散又は再溶解することができる。 The doped polythiophene is isolated by methods known to those skilled in the art (eg, by rotary evaporation of the solvent, etc.) to obtain a dry or substantially dry material (powder, etc.). The amount of residual solvent may be, for example, 10 wt% or less, or 5 wt% or less, or 1 wt% or less based on dry or substantially dry material. The dry or substantially dry powder can be redispersed or redissolved in one or more fresh solvents.
［（Ｃ）成分］
　（Ｃ）成分は、有機溶媒を含む液体担体である。（Ｃ）成分は、（Ａ）成分及び（Ｂ）成分を良好に溶解し、かつ、（Ａ）成分と（Ｂ）成分を均一に混合してインク組成物とするために必要な成分である。（Ｃ）成分としては、インク組成物の湿潤性、粘度、形態制御のようなインク特性を調節するために、（Ａ）成分及び／又は（Ｂ）成分を部分的に可溶化するか、又は膨潤させる有機溶媒を含有してもよい。また、（Ｃ）成分は、（Ａ）成分の非溶媒として作用する１種以上の有機溶媒を更に含んでもよい。 [(C) ingredient]
The component (C) is a liquid carrier containing an organic solvent. The component (C) dissolves the components (A) and (B) well, and is a component necessary for uniformly mixing the components (A) and (B) into an ink composition. . As the component (C), the components (A) and / or (B) may be partially solubilized to adjust the ink properties such as wettability, viscosity, and shape control of the ink composition, or You may contain the organic solvent made to swell. Component (C) may further contain one or more organic solvents that act as non-solvents for component (A).
　（Ｃ）成分は、単独でも、二種以上を併用してもよい。（Ｃ）成分は、アノード又は発光層のようなデバイス中の他の層との使用及び加工に適応させた二種以上の有機溶媒を含む溶媒混合物であってもよい。また、有機溶媒は、例えば、基板湿潤性、溶媒除去の容易性、粘性、表面張力及び出射性等のインク特性を改善するために、（Ｃ）成分中に種々の割合で使用されることができる。 The component (C) may be used alone or in combination of two or more. Component (C) may be a solvent mixture comprising two or more organic solvents adapted for use and processing with other layers in the device such as the anode or light emitting layer. In addition, organic solvents may be used in various proportions in the component (C) to improve ink properties such as substrate wettability, ease of solvent removal, viscosity, surface tension and ejection. it can.
　（Ｃ）成分としては、例えば、「グリコール系溶媒（ｓ１）」を例示することができる。「グリコール系溶媒」とは、式Ｒｈ－Ｏ－（Ｒｇ－Ｏ）ｎ－Ｒｉ（式中、それぞれのＲｇは、各々独立に、直鎖状又は分岐状Ｃ２－Ｃ４非置換アルキレン基であり、Ｒｈ及びＲｉは、各々独立に、水素原子、直鎖状、分岐状又は環状Ｃ１－Ｃ８非置換アルキル基或いは直鎖状又は分岐状Ｃ１－Ｃ８非置換脂肪族アシル基であり、ｎは、１～６の整数である）で表される、１種以上の芳香族構造を有していない有機溶媒であり、グリコールモノエーテル類；グリコールジエーテル類；グリコールエステルエーテル類；グリコールモノエステル類；グリコールジエステル類；及びグリコール類等を例示することができる。前記Ｒｇは、Ｃ２又はＣ３非置換アルキレン基であることが特に好ましい。また前記ｎは、１～４の整数であることが特に好ましい。前記アルキル基としては、直鎖状、分岐状又は環状Ｃ１－Ｃ６非置換アルキル基が好ましく、直鎖状Ｃ１－Ｃ４非置換アルキル基がより好ましく、メチル基及びｎ－ブチル基が特に好ましい。前記アシル基としては、直鎖状又は分岐状Ｃ２－Ｃ６非置換脂肪族アシル基が好ましく、直鎖状Ｃ２－Ｃ４非置換アシル基がより好ましく、アセチル基及びプロピオニル基が特に好ましい。 As a component (C), "glycol system solvent (s1)" can be illustrated, for example. The term “glycol solvent” refers to the formula R h —O— (R g —O) n —R i , wherein each R g is independently a linear or branched C 2 -C 4 non- R h and R i each independently represent a hydrogen atom, a linear, branched or cyclic C 1 -C 8 unsubstituted alkyl group, or a linear or branched C 1 -C 8 non-substituted alkyl group; An organic solvent not having one or more aromatic structures, which is a substituted aliphatic acyl group, and n is an integer of 1 to 6; glycol monoethers; glycol diethers Glycol ester ethers; glycol monoesters; glycol diesters; and glycols and the like. The R g is particularly preferably a C 2 or C 3 unsubstituted alkylene group. Further, n is particularly preferably an integer of 1 to 4. As the alkyl group, a linear, branched or cyclic C 1 -C 6 unsubstituted alkyl group is preferable, a linear C 1 -C 4 unsubstituted alkyl group is more preferable, and a methyl group and an n-butyl group are preferable. Particularly preferred. As the acyl group, a linear or branched C 2 -C 6 non-substituted aliphatic acyl group is preferable, a linear C 2 -C 4 non-substituted acyl group is more preferable, and an acetyl group and a propionyl group are particularly preferable .
　（Ｃ）成分中の（ｓ１）成分は、例えば以下の溶媒を包含する。
・エチレングリコール、プロピレングリコールであるグリコール類又はそのオリゴマー（２量体～４量体、例えばジエチレングリコール）であるグリコール類
・前記グリコール類のモノアルキルエーテルであるグリコールモノエーテル類
・前記グリコール類のジアルキルエーテルであるグリコールジエーテル類
・前記グリコール類の脂肪族カルボン酸モノエステルであるグリコールモノエステル類
・前記グリコール類の脂肪族カルボン酸ジエステルであるグリコールジエステル類
・前記グリコールモノエーテル類の脂肪族カルボン酸モノエステルであるグリコールエステルエーテル類 The component (s1) in the component (C) includes, for example, the following solvents.
· Ethylene glycol, glycols that are propylene glycol or glycols thereof (dimer to tetramer such as diethylene glycol) glycol monoethers that are monoalkyl ethers of the glycols · dialkyl ethers of the glycols Glycol diethers, glycol monoesters which are aliphatic carboxylic acid monoesters of the glycols, glycol diesters which are aliphatic carboxylic acid diesters of the glycols, aliphatic carboxylic acid monoesters of the glycol monoethers Glycol ester ethers that are esters
　これらの中でも、（Ｃ）成分が、グリコールモノエーテル類、グリコールジエーテル類及びグリコール類からなる群より選択される少なくとも１種を含み、該グリコールモノエーテル類、グリコールジエーテル類及びグリコール類の総含有量が、（Ｃ）成分の総重量に基づいて５０重量％より多いと、インクジェット塗布による成膜時に、インク固形分の溶解性を保つことができ、かつ、インク組成物が後述する（Ｅ）金属酸化物ナノ粒子を含有する場合、（Ｅ）成分の凝集を適切に制御し、より平坦な膜を形成することができるため、好ましい。グリコールモノエーテル類、グリコールジエーテル類及びグリコール類の総含有量は、（Ｃ）成分の総重量に基づいて６０重量％以上であることがより好ましく、更により好ましくは７５重量％以上、特に好ましくは９０重量％以上である。グリコールモノエーテル類、グリコールジエーテル類及びグリコール類の含有比率の上限は１００重量％である。 Among these, component (C) contains at least one selected from the group consisting of glycol monoethers, glycol diethers and glycols, and the total of the glycol monoethers, glycol diethers and glycols. When the content is more than 50% by weight based on the total weight of the component (C), the solubility of the ink solid can be maintained at the time of film formation by ink jet coating, and the ink composition will be described later (E When metal oxide nanoparticles are contained, it is preferable because aggregation of the component (E) can be appropriately controlled to form a flatter film. The total content of glycol monoethers, glycol diethers and glycols is more preferably 60% by weight or more based on the total weight of component (C), still more preferably 75% by weight or more, particularly preferably Is 90% by weight or more. The upper limit of the content ratio of glycol monoethers, glycol diethers and glycols is 100% by weight.
　（Ｃ）成分中の（ｓ１）成分は混合しても良い。例は限定されないが、グリコールジエーテル類とグリコール類を混合させることが挙げられる。具体例としては、後述するグリコールジエーテル類及びグリコール類の具体例が挙げられるが、好ましくは、グリコールジエーテル類として、トリエチレングリコールジメチルエーテル、トリエチレングリコールブチルメチルエーテル、グリコール類として、エチレングリコール、ジエチレングリコールが挙げられる。 The component (s1) in the component (C) may be mixed. Examples include, but are not limited to, mixing glycol diethers and glycols. Specific examples thereof include glycol diethers and glycols described later, but preferably, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether as glycol diethers, ethylene glycol as glycols, Diethylene glycol is mentioned.
　グリコールモノエーテル類の例は、アルキレングリコールモノエーテル（グリコールモノエーテル類）を含む。好適なグリコールモノエーテル類の例は、限定されないが、エチレングリコールモノプロピルエーテル、エチレングリコールモノヘキシルエーテル（ヘキシルセロソルブ）、プロピレングリコールモノブチルエーテル（Dowanol（商標） PnB）、ジエチレングリコールモノエチルエーテル（エチルカルビトール）、ジプロピレングリコールｎ－ブチルエーテル（Dowanol（商標） DPnB）、エチレングリコールモノブチルエーテル（ブチルセロソルブ）、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）、ジプロピレングリコールモノメチルエーテル（Dowanol（商標） DPM）、プロピレングリコールモノプロピルエーテル（Dowanol（商標） PnP）、ジエチレングリコールモノプロピルエーテル（プロピルカルビトール）、ジエチレングリコールモノヘキシルエーテル（ヘキシルカルビトール）、２－エチルヘキシルカルビトール、ジプロピレングリコールモノプロピルエーテル（Dowanol（商標） DPnP）、トリプロピレングリコールモノメチルエーテル（Dowanol（商標） TPM）、ジエチレングリコールモノメチルエーテル（メチルカルビトール）及びトリプロピレングリコールモノブチルエーテル（Dowanol（商標） TPnB）を含む。 Examples of glycol monoethers include alkylene glycol monoethers (glycol monoethers). Examples of suitable glycol monoethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether (hexyl cellosolve), propylene glycol monobutyl ether (Dowanol® PnB), diethylene glycol monoethyl ether (ethyl carbitol) ), Dipropylene glycol n-butyl ether (Dowanol (registered trademark) DPnB), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol (registered trademark) DPM), propylene glycol monopropyl Ether (Dowanol (TM) PnP), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol Monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether (Dowanol (TM) DPnP), tripropylene glycol monomethyl ether (Dowanol (TM) TPM), diethylene glycol monomethyl ether (methyl carbitol) And tripropylene glycol monobutyl ether (Dowanol (TM) TPnB).
　グリコールジエーテル類の例は、例えば、エチレングリコールジエーテル（１，２－ジメトキシエタン、１，２－ジエトキシエタン及び１，２－ジブトキシエタン等）；ジエチレングリコールジエーテル（ジエチレングリコールジメチルエーテル及びジエチレングリコールジエチルエーテル等）；プロピレングリコールジエーテル（プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル及びプロピレングリコールジブチルエーテル等）；ジプロピレングリコールジエーテル（ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル及びジプロピレングリコールジブチルエーテル等）；並びに本明細書に言及されるエチレングリコール及びプロピレングリコールエーテルのより高次の類似体（すなわち、トリ－及びテトラ－類似体、例えば、トリエチレングリコールジメチルエーテル、トリエチレングリコールブチルメチルエーテル、テトラエチレングリコールジメチルエーテル等）を含む。 Examples of glycol diethers are, for example, ethylene glycol diethers (1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane etc.); diethylene glycol diethers (diethylene glycol dimethyl ether and diethylene glycol diethyl ether) Etc.); propylene glycol diethers (propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether etc); dipropylene glycol diethers (dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol dibutyl ether etc); Higher order ethylene glycol and propylene glycol ether mentioned herein Analogs (i.e., tri - analogs such as triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether - and tetra) a.
　グリコール類の例は、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等を含む。　 Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like.
　（Ｃ）成分中の（ｓ１）成分は、更に、エチレングリコールモノエーテルアセテート及びプロピレングリコールモノエーテルアセテート等（グリコールエステルエーテル類）を考慮することができ、ここで、エーテルは、例えば、メチル、エチル、ｎ－プロピル、イソ－プロピル、ｎ－ブチル、sec－ブチル、tert－ブチル及びシクロヘキシルから選択されることができる。また、上記リストのより高次のグリコールエーテル類似体（ジ－、トリ－及びテトラ－等）を含む。
　例は、限定されないが、プロピレングリコールメチルエーテルアセテート、２－エトキシエチルアセテート、２－ブトキシエチルアセテート、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテートを含む。 Component (s1) in component (C) may further include ethylene glycol monoether acetate and propylene glycol monoether acetate etc. (glycol ester ethers), wherein the ether is, for example, methyl, ethyl , N-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl and cyclohexyl. Also included are the higher glycol ether analogs (di-, tri- and tetra- etc) of the above list.
Examples include, but are not limited to, propylene glycol methyl ether acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate.
　（Ｃ）成分中の（ｓ１）成分は、更に、エチレングリコールジアセテート等（グリコールジエステル類）を考慮することができ、また、より高次のグリコールエーテル類似体（ジ－、トリ－及びテトラ－等）を含む。
　例は、限定されないが、エチレングリコールジアセテート、トリエチレングリコールジアセテート、プロピレングリコールジアセテートを含む。 Component (s1) in component (C) may further include ethylene glycol diacetates (glycol diesters), and higher glycol ether analogues (di-, tri- and tetra-). Etc.).
Examples include, but are not limited to, ethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate.
　（Ｃ）成分は、更に、グリコール系溶媒を除く有機溶媒（ｓ２）を考慮することができる。（ｓ２）成分は、単独でも、二種以上を併用してもよい。（ｓ２）成分は例えば、脂肪族及び芳香族ケトン類、ジメチルスルホキシド（ＤＭＳＯ）及び２，３，４，５－テトラヒドロチオフェン－１，１－ジオキシド（テトラメチレンスルホン；スルホラン）のような有機硫黄溶媒；テトラヒドロフラン（ＴＨＦ）、テトラヒドロピラン（ＴＨＰ）、テトラメチル尿素（ＴＭＵ）、Ｎ，Ｎ’－ジメチルプロピレン尿素；アルキル化ベンゼン類（キシレン及びその異性体等）等の芳香族炭化水素類、ハロゲン化ベンゼン類、Ｎ－メチルピロリジノン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）、ジクロロメタン、ジオキサン類、酢酸エチル、安息香酸エチル、安息香酸メチル、炭酸ジメチル、炭酸エチレン、炭酸プロピレン；アセトニトリル、３－メトキシプロピオニトリル、３－エトキシプロピオニトリル等のニトリル類；、アニソール、エトキシベンゼン、ジメトキシベンゼン等の芳香族エーテル類；メタノール、エタノール、トリフルオロエタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、ｔ－ブタノール、２－エチルヘキシルアルコール、２－（ベンジルオキシ）エタノール、ジイソブチルカルビノール、メチルイソブチルカルビノール等のアルコール類、又はこれらの組合せを含むが、これらに限定されない。 As the component (C), organic solvents (s2) other than glycol solvents can be further considered. The component (s2) may be used alone or in combination of two or more. The component (s2) is, for example, organic sulfur solvents such as aliphatic and aromatic ketones, dimethyl sulfoxide (DMSO) and 2,3,4,5-tetrahydrothiophene-1,1-dioxide (tetramethylene sulfone; sulfolane) Aromatic hydrocarbons such as tetrahydrofuran (THF), tetrahydropyran (THP), tetramethylurea (TMU), N, N'-dimethylpropyleneurea; alkylated benzenes (xylene and its isomers etc.), halogenation Benzenes, N-methylpyrrolidinone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dichloromethane, dioxanes, ethyl acetate, ethyl benzoate, methyl benzoate, dimethyl carbonate, ethylene carbonate, propylene carbonate; acetonitrile, 3-Methoxypro Nitriles such as nitrile and 3-ethoxypropionitrile; aromatic ethers such as anisole, ethoxybenzene and dimethoxybenzene; methanol, ethanol, trifluoroethanol, n-propanol, isopropanol, n-butanol, t-butanol, Alcohols such as 2-ethylhexyl alcohol, 2- (benzyloxy) ethanol, diisobutyl carbinol, methyl isobutyl carbinol, or combinations thereof, but is not limited thereto.
　（ｓ２）成分は、ニトリル類、アルコール類、芳香族エーテル類又は芳香族炭化水素類が好ましい。
　例は、限定されないが、ニトリル類として、メトキシプロピオニトリル、エトキシプロピオニトリル、アルコール類として、ベンジルアルコール、２－（ベンジルオキシ）エタノール、芳香族エーテル類として、メチルアニソール、ジメチルアニソール、エチルアニソール、ブチルフェニルエーテル、ブチルアニソール、ペンチルアニソール、ヘキシルアニソール、ヘプチルアニソール、オクチルアニソール、フェノキシトルエン、芳香族炭化水素類として、ペンチルベンゼン、ヘキシルベンゼン、ヘプチルベンゼン、オクチルベンゼン、ノニルベンゼン、シクロヘキシルベンゼン又はテトラリンが挙げられる。
　これらの中でも、アルコール類がより好ましく、アルコール類の中でも２－（ベンジルオキシ）エタノールがより好ましい。 The component (s2) is preferably a nitrile, an alcohol, an aromatic ether or an aromatic hydrocarbon.
Examples include, but are not limited to, as nitriles, methoxypropionitrile, ethoxypropionitrile, as alcohols benzyl alcohol, 2- (benzyloxy) ethanol, as aromatic ethers methylanisole, dimethylanisole, ethylanisole Butyl phenyl ether, butyl anisole, pentyl anisole, hexyl anisole, heptyl anisole, octyl anisole, phenoxytoluene, as aromatic hydrocarbons such as pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, cyclohexylbenzene or tetralin It can be mentioned.
Among these, alcohols are more preferable, and among the alcohols, 2- (benzyloxy) ethanol is more preferable.
　（ｓ２）成分のその他の例としては、脂肪族及び芳香族ケトン類が挙げられる。脂肪族及び芳香族ケトン類は、アセトン、アセトニルアセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン、メチルイソブテニルケトン、２－ヘキサノン、２－ペンタノン、アセトフェノン、エチルフェニルケトン、シクロヘキサノン、及びシクロペンタノンを含むが、これらに限定されない。幾つかの実施態様において、シクロヘキサノン、メチルエチルケトン、及びアセトンのような、ケトンに対してα位に位置する炭素上にプロトンを有するケトン類は回避される。 Other examples of the component (s2) include aliphatic and aromatic ketones. Aliphatic and aromatic ketones include acetone, acetonylacetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl isobutenyl ketone, 2-hexanone, 2-pentanone, acetophenone, ethylphenyl ketone, cyclohexanone, and cyclopentanone Including, but not limited to. In some embodiments, ketones having a proton on carbon located alpha to the ketone, such as cyclohexanone, methyl ethyl ketone and acetone, are avoided.
　いくつかの実施態様において、非プロトン非極性溶媒の使用は、プロトンに感受性であるエミッター技術を備えるデバイス（例えば、ＰＨＯＬＥＤ等）の寿命を延ばす追加の利益を提供することができる。 In some embodiments, the use of non-protonic non-polar solvents can provide the added benefit of extending the lifetime of devices (eg, PHOLEDs, etc.) comprising emitter technology that is sensitive to protons.
　ある実施態様において、（Ｃ）成分は、ジメチルスルホキシド、エチレングリコール（グリコール類）、テトラメチル尿素又はそれらの混合物を含む。
　好適なグリコール類の例は、限定されないが、エチレングリコール、ジエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、プロピレングリコール、トリエチレングリコール等が挙げられる。 In one embodiment, the component (C) comprises dimethyl sulfoxide, ethylene glycol (glycols), tetramethyl urea or a mixture thereof.
Examples of suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, dipropylene glycol, polypropylene glycol, propylene glycol, triethylene glycol and the like.
　（Ｃ）成分が（ｓ１）成分と（ｓ２）成分とを含む場合、（ｓ１）成分の含有量：ｗｔｓ１（重量）と、（ｓ２）成分の含有量：ｗｔｓ２（重量）とが、式（１－１）を満たすことが好ましく、式（１－２）を満たすことがより好ましく、式（１－３）を満たすことが最も好ましい。
　０．０５≦ｗｔｓ２／（ｗｔｓ１＋ｗｔｓ２）≦０．５０　　（１－１）
　０．１０≦ｗｔｓ２／（ｗｔｓ１＋ｗｔｓ２）≦０．４０　　（１－２）
　０．１５≦ｗｔｓ２／（ｗｔｓ１＋ｗｔｓ２）≦０．３０　　（１－３）
　なお、（ｓ１）成分が２種以上含有されている場合、ｗｔｓ１は（ｓ１）成分の合計含有量（重量）を示し、（ｓ２）成分が２種以上含有されている場合、ｗｔｓ２は（ｓ２）成分の合計含有量（重量）を示す。
　ある態様において、（ｓ１）成分と（ｓ２）成分の含有量が上記関係を満たすと、インクジェット塗布による成膜時に、（Ｅ）成分の凝集をよりいっそう適切に制御し、より平坦な膜を形成することができるため、好ましい。 When the component (C) contains the components (s1) and (s2), the content of the component (s1): wts1 (by weight) and the content of the component (s2): wts2 (by weight) can be represented by the formula It is preferable to satisfy 1-1), more preferably to satisfy the formula (1-2), and most preferably to satisfy the formula (1-3).
0.05 ≦ wts2 / (wts1 + wts2) ≦ 0.50 (1-1)
0.10 ≦ wts2 / (wts1 + wts2) ≦ 0.40 (1-2)
0.15 ≦ wts2 / (wts1 + wts2) ≦ 0.30 (1-3)
In addition, when 2 or more types of (s1) components are contained, wts1 shows the total content (weight) of (s1) components, and when 2 or more types of (s2) components are contained, wts2 is (s2) ) Indicates the total content (weight) of the components.
In one aspect, when the contents of the (s1) component and the (s2) component satisfy the above relationship, the aggregation of the (E) component is more appropriately controlled during film formation by inkjet coating, and a flatter film is formed. It is preferable because it can be done.
　（Ｃ）成分の量は、インク組成物の総量に対して、約５０重量％～約９９重量％、典型的には約７５重量％～約９８重量％、更に典型的には約９０重量％～約９５重量％である。 The amount of component (C) is about 50% to about 99% by weight, typically about 75% to about 98% by weight, and more typically about 90% by weight, based on the total weight of the ink composition. To about 95% by weight.
［（Ｄ）成分］
　インク組成物は、更に（Ｄ）アミン化合物を含むことができる。（Ｄ）成分を添加することにより、（Ａ）成分の（Ｃ）成分に対する分散性を向上させることができる。（Ｄ）成分は、エタノールアミン化合物及びアルキルアミン化合物を含むが、これらに限定されない。（Ｄ）成分は、単独でも、二種以上を併用してもよい。 [(D) component]
The ink composition can further contain (D) an amine compound. By adding the component (D), the dispersibility of the component (A) in the component (C) can be improved. The component (D) includes, but is not limited to, ethanolamine compounds and alkylamine compounds. The component (D) may be used alone or in combination of two or more.
　適切なエタノールアミン化合物の例は、ジメチルエタノールアミン［（ＣＨ３）２ＮＣＨ２ＣＨ２ＯＨ］、トリエタノールアミン［Ｎ（ＣＨ２ＣＨ２ＯＨ）３］、及びＮ－tert－ブチルジエタノールアミン［ｔ－Ｃ４Ｈ９Ｎ（ＣＨ２ＣＨ２ＯＨ）２］を含む。 Examples of suitable ethanolamine compounds are dimethylethanolamine [(CH 3 ) 2 NCH 2 CH 2 OH], triethanolamine [N (CH 2 CH 2 OH) 3 ], and N-tert-butyldiethanolamine [t- containing C 4 H 9 N (CH 2 CH 2 OH) 2].
　アルキルアミン化合物は、第１級、第２級、及び第３級アルキルアミン化合物を含む。第１級アルキルアミン化合物の例は、例えば、エチルアミン［Ｃ２Ｈ５ＮＨ２］、ｎ－ブチルアミン［Ｃ４Ｈ９ＮＨ２］、ｔ－ブチルアミン［Ｃ４Ｈ９ＮＨ２］、２－エチルヘキシルアミン、ｎ－ヘキシルアミン［Ｃ６Ｈ１３ＮＨ２］、ｎ－デシルアミン［Ｃ１０Ｈ２１ＮＨ２］、及びエチレンジアミン［Ｈ２ＮＣＨ２ＣＨ２ＮＨ２］を含む。第２級アルキルアミン化合物は、例えば、ジエチルアミン［（Ｃ２Ｈ５）２ＮＨ］、ジ（ｎ－プロピルアミン）［（ｎ－Ｃ３Ｈ９）２ＮＨ］、ジ（イソプロピルアミン）［（ｉ－Ｃ３Ｈ９）２ＮＨ］、及びジメチルエチレンジアミン［ＣＨ３ＮＨＣＨ２ＣＨ２ＮＨＣＨ３］を含む。第３級アルキルアミン化合物は、例えば、トリメチルアミン［（ＣＨ３）３Ｎ］、トリエチルアミン［（Ｃ２Ｈ５）３Ｎ］、トリ（ｎ－ブチル）アミン［（Ｃ４Ｈ９）３Ｎ］、及びテトラメチルエチレンジアミン［（ＣＨ３）２ＮＣＨ２ＣＨ２Ｎ（ＣＨ３）２］を含む。 Alkylamine compounds include primary, secondary and tertiary alkylamine compounds. Examples of primary alkylamine compounds are, for example, ethylamine [C 2 H 5 NH 2 ], n-butylamine [C 4 H 9 NH 2 ], t-butylamine [C 4 H 9 NH 2 ], 2-ethylhexylamine , N-hexylamine [C 6 H 13 NH 2 ], n-decylamine [C 10 H 21 NH 2 ], and ethylenediamine [H 2 NCH 2 CH 2 NH 2 ]. Examples of secondary alkylamine compounds include diethylamine [(C 2 H 5 ) 2 NH], di (n-propylamine) [(n-C 3 H 9 ) 2 NH], di (isopropylamine) [(i -C 3 H 9 ) 2 NH], and dimethylethylenediamine [CH 3 NHCH 2 CH 2 NHCH 3 ]. Examples of tertiary alkylamine compounds include trimethylamine [(CH 3 ) 3 N], triethylamine [(C 2 H 5 ) 3 N], tri (n-butyl) amine [(C 4 H 9 ) 3 N], and tetramethylethylenediamine [(CH 3) 2 NCH 2 CH 2 N (CH 3) 2].
　（Ｄ）成分が、（Ｄ１）第三級アルキルアミン化合物と、（Ｄ２）第三級アルキルアミン化合物以外のアミン化合物とを含むと、溶解性又は分散性の観点で好ましい。 It is preferable from the viewpoint of solubility or dispersibility that the component (D) contains (D1) a tertiary alkylamine compound and (D2) an amine compound other than the tertiary alkylamine compound.
　（Ｄ１）成分は、（Ａ）成分の溶解性又は分散性を高めるために使用される。インク組成物の製造前に、（Ａ）成分を（Ｄ１）成分で前処理すると、（Ａ）成分の（Ｃ）成分への溶解性又は分散性が高められるため、好ましい。本願のインク組成物を非水系インク組成物とする場合、（Ａ）成分は通常、水性分散液で得られるため、該水性分散液を乾燥させて、粉末状としたものを（Ｃ）成分に溶解又は分散させて、インク組成物とする。この場合、（Ａ）成分の水性分散液に（Ｄ１）成分を添加・混合後、乾燥させたものを用いると、（Ａ）成分の（Ｃ）成分への溶解性・分散性が向上するため、好ましい。（Ｄ１）成分は、トリエチルアミンが好ましい。 The component (D1) is used to enhance the solubility or dispersibility of the component (A). It is preferable to pretreat the component (A) with the component (D1) before the production of the ink composition, because the solubility or dispersibility of the component (A) in the component (C) is enhanced. When the ink composition of the present invention is used as a non-aqueous ink composition, the component (A) is usually obtained as an aqueous dispersion, and thus the aqueous dispersion is dried to form a powder as the component (C). It is dissolved or dispersed to make an ink composition. In this case, when the aqueous dispersion liquid of the component (A) is added and mixed with the component (D1) and then dried, the solubility and dispersibility of the component (A) in the component (C) improve. ,preferable. The component (D1) is preferably triethylamine.
　（Ｄ２）成分は、第一級アルキルアミン化合物であると好ましい。該第一級アルキルアミン化合物が、エチルアミン、ｎ－ブチルアミン、ｔ－ブチルアミン、２－エチルヘキシルアミン、ｎ－ヘキシルアミン、ｎ－デシルアミン及びエチレンジアミンからなる群より選択される少なくとも１種であると、（Ａ）成分の溶解性又は分散性の観点で好ましい。（Ｄ２）成分は、より好ましくは、ｎ－ブチルアミン又は２－エチルヘキシルアミンであり、特に好ましくはｎ－ブチルアミンである。 Component (D2) is preferably a primary alkylamine compound. When the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine and ethylenediamine (A ) Preferred in view of the solubility or dispersibility of the components. The component (D2) is more preferably n-butylamine or 2-ethylhexylamine, particularly preferably n-butylamine.
　（Ｄ）成分の量は、インク組成物の総量に対する重量百分率として調節及び測定することができる。ある実施態様において、（Ｄ）成分の量は、インク組成物の総量に対して、少なくとも０．０１重量％、少なくとも０．１０重量％、少なくとも１．００重量％、少なくとも１．５０重量％、又は少なくとも２．００重量％である。ある実施態様において、（Ｄ）成分の量は、インク組成物の総量に対して、約０．０１重量～約２．００重量％、典型的には約０．０５重量％～約１．５０重量％、更に典型的には約０．１重量％～約１．００重量％である。（Ａ）成分としてスルホン化ポリチオフェンを用いる場合、（Ｄ）成分の少なくとも一部が、スルホン化共役ポリマーとのアンモニウム塩、例えばトリアルキルアンモニウム塩（スルホン化ポリチオフェンアミン付加体）の形態で存在していてもよい。 The amount of component (D) can be adjusted and measured as a weight percentage to the total amount of the ink composition. In one embodiment, the amount of component (D) is at least 0.01% by weight, at least 0.10% by weight, at least 1.00% by weight, at least 1.50% by weight, based on the total weight of the ink composition. Or at least 2.00% by weight. In one embodiment, the amount of component (D) is about 0.01 wt% to about 2.00 wt%, typically about 0.05 wt% to about 1.50 wt%, based on the total weight of the ink composition. % By weight, more typically about 0.1% by weight to about 1.00% by weight. When a sulfonated polythiophene is used as the component (A), at least a portion of the component (D) is present in the form of an ammonium salt with a sulfonated conjugated polymer, for example, a trialkylammonium salt (sulfonated polythiophene amine adduct) May be
　（Ｄ１）成分と（Ｄ２）成分との比率は、特に限定されないが、物質量（モル）比で、（Ｄ２）成分：（Ｄ１）成分＝３：１～１５：１とすることができ、好ましくは、５：１～１０：１である。 The ratio of the (D1) component to the (D2) component is not particularly limited, but it can be (D2) component: (D1) component = 3: 1 to 15: 1 in terms of substance (molar) ratio. Preferably, it is 5: 1 to 10: 1.
［（Ｅ）成分］
　インク組成物は、更に（Ｅ）金属酸化物ナノ粒子を含むことができる。インク組成物に（Ｅ）成分を含有させると、インク組成物を使用して得られる電荷輸送性薄膜の透明性を高く、かつ、可視スペクトルの吸光度を低くすることができる。その結果、該電荷輸送性薄膜を用いて作製された有機ＥＬ素子の電流効率、外部量子効率及び輝度半減期を向上させることができる。（Ｅ）成分は、単独でも、二種以上を併用してもよい。 [(E) ingredient]
The ink composition can further include (E) metal oxide nanoparticles. When the ink composition contains the component (E), the transparency of the charge transporting thin film obtained using the ink composition can be increased, and the absorbance of the visible spectrum can be lowered. As a result, it is possible to improve the current efficiency, the external quantum efficiency, and the luminance half life of the organic EL device manufactured using the charge transporting thin film. The component (E) may be used alone or in combination of two or more.
　本明細書に使用されるとき、「半金属」という用語は、金属と非金属との化学的及び／又は物理的性質の中間の又は混合物の性質を有する元素のことをいう。本明細書において、「半金属」という用語は、ホウ素（Ｂ）、ケイ素（Ｓｉ）、ゲルマニウム（Ｇｅ）、ヒ素（Ａｓ）、アンチモン（Ｓｂ）、及びテルル（Ｔｅ）のことをいう。
　本明細書において、「金属酸化物」とは、スズ（Ｓｎ）、チタン（Ｔｉ）、アルミニウム（Ａｌ）、ジルコニウム（Ｚｒ）、亜鉛（Ｚｎ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）及びＷ（タングステン）等の金属及び上述した半金属のうち１種又は２種以上の組み合わせの酸化物のことをいう。 As used herein, the term "metalloid" refers to an element having properties of an intermediate or mixture of chemical and / or physical properties of metals and non-metals. As used herein, the term "metalloid" refers to boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).
In the present specification, “metal oxide” means tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (W) It refers to an oxide of one or more combinations of metals such as tungsten) and the above-mentioned semimetals.
　本明細書に使用されるとき、「ナノ粒子」という用語は、ナノスケールの粒子であって、その一次粒子の数平均径が、典型的には５００ｎｍ以下である粒子のことをいう。一次粒子の平均径は、例えば、透過電子顕微鏡法（ＴＥＭ）や、ＢＥＴ法による比表面積から換算する方法等を利用することができる。 As used herein, the term "nanoparticles" refers to nanoscale particles, wherein the number average diameter of the primary particles is typically 500 nm or less. The average diameter of the primary particles can be, for example, transmission electron microscopy (TEM), a method of converting from the specific surface area by BET method, or the like.
　ＴＥＭによる粒子径の測定法では、画像処理ソフトウェアを用いてナノ粒子の投影画像を処理してから、面積相当径（これは、ナノ粒子と同じ面積を持つ円の直径として定義される）を求める方法で、粒子径を測定することができる。典型的には、ＴＥＭ（例えば、透過型電子顕微鏡ＨＴ７７００（株式会社日立ハイテクノロジーズより入手可能））と共に提供される、ＴＥＭの製造販売元が作成した画像処理ソフトウェアを用いて、前記の投影画像の処理を行う。平均粒子径は、円相当径の数平均として求める事ができる。 In TEM particle size measurement, image processing software is used to process the projected image of the nanoparticles and then the area equivalent diameter (which is defined as the diameter of a circle with the same area as the nanoparticles) The particle size can be measured by the method. Typically, the projection image is produced using image processing software created by the TEM manufacturer, provided with the TEM (eg, transmission electron microscope HT 7700 (available from Hitachi High-Technologies Corporation)). Do the processing. The average particle diameter can be determined as a number average of circle equivalent diameters.
　（Ｅ）成分の一次粒子の数平均粒径は、５００ｎｍ以下；２５０ｎｍ以下；１００ｎｍ以下；又は５０ｎｍ以下；又は２５ｎｍ以下である。典型的には、（Ｅ）成分は、約１ｎｍ～約１００ｎｍ、更に典型的には約２ｎｍ～約３０ｎｍの数平均粒径を有する。 The number average particle size of primary particles of the component (E) is 500 nm or less; 250 nm or less; 100 nm or less; or 50 nm or less; or 25 nm or less. Typically, the (E) component has a number average particle size of about 1 nm to about 100 nm, more typically about 2 nm to about 30 nm.
　金属酸化物としては、ホウ素（Ｂ）、ケイ素（Ｓｉ）、ゲルマニウム（Ｇｅ）、ヒ素（Ａｓ）、アンチモン（Ｓｂ）、テルル（Ｔｅ）、スズ（Ｓｎ）、チタン（Ｔｉ）、アルミニウム（Ａｌ）、ジルコニウム（Ｚｒ）、亜鉛（Ｚｎ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）及びＷ（タングステン）等の酸化物、又はこれらを含む混合酸化物が挙げられる。適切な金属酸化物ナノ粒子の非限定的な特定の例は、Ｂ２Ｏ３、Ｂ２Ｏ、ＳｉＯ２、ＳｉＯ、ＧｅＯ２、ＧｅＯ、Ａｓ２Ｏ４、Ａｓ２Ｏ３、Ａｓ２Ｏ５、Ｓｂ２Ｏ３、Ｓｂ２Ｏ５、ＴｅＯ２、ＳｎＯ２、ＺｒＯ２、Ａｌ２Ｏ３、ＺｎＯ及びこれらの混合物を含むナノ粒子を含むが、これらに限定されない。 As metal oxides, boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum (Al) And oxides such as zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (tungsten), or mixed oxides containing these. Non-limiting specific examples of suitable metal oxide nanoparticles are 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 and mixtures thereof, including, but not limited to, nanoparticles.
　ある実施態様において、インク組成物は、Ｂ２Ｏ３、Ｂ２Ｏ、ＳｉＯ２、ＳｉＯ、ＧｅＯ２、ＧｅＯ、Ａｓ２Ｏ４、Ａｓ２Ｏ３、Ａｓ２Ｏ５、ＳｎＯ２、ＳｎＯ、Ｓｂ２Ｏ３、ＴｅＯ２、又はこれらの混合物を含む１種以上の金属酸化物ナノ粒子を含む。 In an embodiment, the ink composition is 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. It includes one or more metal oxide nanoparticles including 2 O 3 , TeO 2 , or a mixture thereof.
　ある実施態様において、インク組成物は、ＳｉＯ２を含む１種以上の金属酸化物ナノ粒子を含む。（Ｅ）成分が、ＳｉＯ２を含む金属酸化物ナノ粒子であると、インク組成物を使用して得られる電荷輸送性薄膜の透明性をより高く、かつ、可視スペクトルの吸光度をより低くでき、該電荷輸送性薄膜を用いて作製された有機ＥＬ素子の電流効率、外部量子効率及び輝度半減期をよりいっそう向上させることができるため、好ましい。 In one embodiment, the ink composition comprises one or more metal oxide nanoparticles comprising SiO 2 . When the component (E) is a metal oxide nanoparticle containing SiO 2 , the charge transportable thin film obtained using the ink composition can be made more transparent and the absorbance of the visible spectrum can be made lower. It is preferable because the current efficiency, the external quantum efficiency, and the luminance half life of the organic EL device manufactured using the charge transporting thin film can be further improved.
　金属酸化物ナノ粒子は、１種以上の有機キャッピング基を含んでもよい。このような有機キャッピング基は、反応性であっても非反応性であってもよい。反応性有機キャッピング基は、例えば、ＵＶ線又はラジカル開始剤の存在下で、架橋できる有機キャッピング基である。 The metal oxide nanoparticles may comprise one or more organic capping groups. Such organic capping groups may be reactive or non-reactive. Reactive organic capping groups are, for example, organic capping groups that can be crosslinked in the presence of UV radiation or radical initiators.
　ある実施態様において、金属酸化物ナノ粒子は、１種以上の有機キャッピング基を含む。 In certain embodiments, the metal oxide nanoparticles comprise one or more organic capping groups.
　適切な金属酸化物ナノ粒子の例は、日産化学工業（株）によりORGANOSILICASOL（商標）として販売されている、種々の溶媒（例えば、メチルエチルケトン、メチルイソブチルケトン、ジメチルアセトアミド、エチレングリコール、イソプロパノール、メタノール、エチレングリコールモノプロピルエーテル、及びプロピレングリコールモノメチルエーテルアセテート等）中の分散液として利用できるＳｉＯ２ナノ粒子を含む。 Examples of suitable metal oxide nanoparticles are various solvents (eg, methyl ethyl ketone, methyl isobutyl ketone, dimethyl acetamide, ethylene glycol, isopropanol, methanol, sold by Nissan Chemical Industries, Ltd. as ORGANOSILICASOLTM). And SiO 2 nanoparticles that can be used as dispersions in ethylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, and the like.
　インク組成物中の（Ｅ）成分の量は、（Ａ）及び（Ｂ）成分並びに任意の（Ｄ）～（Ｆ）成分を合わせた重量に対する重量百分率として、調節及び測定することができる。ある実施態様において、（Ｅ）成分の量は、（Ａ）及び（Ｂ）成分並びに任意の（Ｄ）～（Ｆ）成分を合わせた重量に対して、１重量％～９８重量％、典型的には約２重量％～約９５重量％、更に典型的には約５重量％～約９０重量％、更になお典型的には約１０重量％～約９０重量％である。ある実施態様において、（Ｅ）成分の量は、（Ａ）及び（Ｂ）成分並びに任意の（Ｄ）～（Ｆ）成分を合わせた重量に対して、約２０重量％～約９８重量％、典型的には約２５重量％～約９５重量％である。 The amount of component (E) in the ink composition can be adjusted and measured as a percentage by weight of the combined weight of components (A) and (B) and optional components (D) to (F). In one embodiment, the amount of component (E) is typically 1% to 98% by weight, based on the combined weight of components (A) and (B) and optional components (D) to (F). Is about 2% to about 95% by weight, more typically about 5% to about 90% by weight, and even more typically about 10% to about 90% by weight. In one embodiment, the amount of component (E) is about 20% to about 98% by weight, based on the combined weight of components (A) and (B) and optional components (D) to (F). Typically from about 25% to about 95% by weight.
［（Ｆ）成分］
　インク組成物は、正孔注入層（ＨＩＬ）又は正孔輸送層（ＨＴＬ）中で有用であることが知られている１種以上の（Ｆ）マトリックス化合物を更に含むことができる。（Ｆ）成分は薄膜作製時のバイルアップを改善し、厚さを均一かつ平坦にするすることができる化合物であり、こうした機能を有する材料であれば、特に限定されず使用できる。（Ｆ）成分を更に含むインク組成物を用いて作製された電荷輸送性薄膜を有する有機ＥＬ素子は、電荷輸送性薄膜の上層側に形成される発光層等の厚みの均一性も改善されるため、発光ムラ等がなく、素子特性を改善することができる。（Ｆ）成分は、単独でも、二種以上を併用してもよい。 [(F) component]
The ink composition can further comprise one or more (F) matrix compounds known to be useful in the hole injection layer (HIL) or the hole transport layer (HTL). The component (F) is a compound capable of improving the buildup during thin film formation and making the thickness uniform and flat, and any material having such a function can be used without particular limitation. An organic EL device having a charge transportable thin film produced using an ink composition further comprising the component (F) also improves the uniformity of the thickness of the light emitting layer and the like formed on the upper layer side of the charge transport thin film Therefore, there is no light emission unevenness and the like, and the device characteristics can be improved. The component (F) may be used alone or in combination of two or more.
　（Ｆ）成分は、低分子量又は高分子量化合物であってよく、そして本明細書に記載のポリチオフェンとは異なる。マトリックス化合物は、例えば、合成ポリマーであってよい。例えば、２００６年８月１０日に公開の米国特許公開２００６／０１７５５８２号を参照のこと。合成ポリマーは、例えば、炭素基本骨格を含むことができる。幾つかの実施態様において、合成ポリマーは、酸素原子又は窒素原子を含む少なくとも１個のポリマー側基を有する。合成ポリマーは、ルイス塩基であってもよい。典型的には、合成ポリマーは、炭素基本骨格を含み、そして２５℃を超えるガラス転移点を有する。合成ポリマーはまた、２５℃以下のガラス転移点及び／又は２５℃を超える融点を有する、半結晶性又は結晶性ポリマーであってもよい。合成ポリマーは、１種以上の酸性基、例えば、スルホン酸基を含んでもよい。 Component (F) may be a low molecular weight or high molecular weight compound and is different from the polythiophenes described herein. The matrix compound may, for example, be a synthetic polymer. See, eg, US Patent Publication No. 2006/0175582 published Aug. 10, 2006. Synthetic polymers can, for example, comprise a carbon backbone. In some embodiments, the synthetic polymer has at least one polymer side group comprising an oxygen atom or a nitrogen atom. The synthetic polymer may be a Lewis base. Typically, synthetic polymers contain a carbon backbone and have a glass transition temperature above 25 ° C. Synthetic polymers may also be semi-crystalline or crystalline polymers, having a glass transition temperature of 25 ° C. or less and / or a melting point above 25 ° C. Synthetic polymers may contain one or more acidic groups, such as sulfonic acid groups.
　ある実施態様において、（Ｆ）成分である合成ポリマーは、少なくとも１個のフッ素原子及び少なくとも１個のスルホン酸（－ＳＯ３Ｈ）残基により置換されている、少なくとも１個のアルキル又はアルコキシ基であって、場合により少なくとも１個のエーテル結合（－Ｏ－）基により中断されているアルキル又はアルコキシ基を含む、１個以上の繰り返し単位を含むポリマー酸である。 In one embodiment, the synthetic polymer which is the component (F) is at least one alkyl or alkoxy group substituted by at least one fluorine atom and at least one sulfonic acid (—SO 3 H) residue. A polymeric acid comprising one or more repeating units, optionally comprising an alkyl or alkoxy group interrupted by at least one ether linkage (—O—) group.
　ある実施態様において、ポリマー酸は、式（ＩＩ）に従う繰り返し単位及び式（ＩＩＩ）に従う繰り返し単位：
Figure JPOXMLDOC01-appb-C000058
［式中、各々のＲ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、及びＲ１１は、独立に、Ｈ、ハロゲン、フルオロアルキル、又はペルフルオロアルキルであり；そしてＸは、－［ＯＣ（ＲｊＲｋ）－Ｃ（ＲｌＲｍ）］ｒ－Ｏ－［ＣＲｎＲｏ］ｚ－ＳＯ３Ｈであって、各々のＲｊ、Ｒｋ、Ｒｌ、Ｒｍ、Ｒｎ及びＲｏは、独立に、Ｈ、ハロゲン、フルオロアルキル、又はペルフルオロアルキルであり；ｒは、０～１０であり；そしてｚは、１～５である］を含む。 In one embodiment, the polymeric acid comprises recurring units according to formula (II) and recurring units according to formula (III):
Figure JPOXMLDOC01-appb-C000058
[Wherein each R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are independently H, halogen, fluoroalkyl or perfluoroalkyl; and X is [OC (R j R k ) -C (R l R m )] r -O- [CR n R o ] z -SO 3 H, and each R j , R k , R l , R m , R n and R o are independently H, halogen, fluoroalkyl or perfluoroalkyl; r is 0-10; and z is 1-5.
　ある実施態様において、各々のＲ５、Ｒ６、Ｒ７、及びＲ８は、独立に、Ｃｌ又はＦである。ある実施態様において、各々のＲ５、Ｒ７、及びＲ８は、Ｆであり、そしてＲ６は、Ｃｌである。ある実施態様において、各々のＲ５、Ｒ６、Ｒ７、及びＲ８は、Ｆである。 In certain embodiments, each R 5 , R 6 , R 7 , and R 8 is independently Cl or F. In certain embodiments, each R 5 , R 7 , and R 8 is F and R 6 is Cl. In certain embodiments, each R 5 , R 6 , R 7 , and R 8 is F.
　ある実施態様において、各々のＲ９、Ｒ１０、及びＲ１１は、Ｆである。 In certain embodiments, each R 9 , R 10 , and R 11 is F.
　ある実施態様において、各々のＲｊ、Ｒｋ、Ｒｌ、Ｒｍ、Ｒｎ及びＲｏは、独立に、Ｆ、（Ｃ１－Ｃ８）フルオロアルキル、又は（Ｃ１－Ｃ８）ペルフルオロアルキルである。 In certain embodiments, each R j , R k , R l , R m , R n, and R o is independently F, (C 1 -C 8 ) fluoroalkyl, or (C 1 -C 8 ) perfluoro It is an alkyl.
　ある実施態様において、各々のＲｎ及びＲｏは、Ｆであり；ｒは、０であり；そしてｚは、２である。 In certain embodiments, each R n and R o is F; r is 0; and z is 2.
　ある実施態様において、各々のＲ５、Ｒ７、及びＲ８は、Ｆであり、そしてＲ６は、Ｃｌであり；そして各々のＲｎ及びＲｏは、Ｆであり；ｒは、０であり；そしてｚは、２である。 In certain embodiments, each R 5 , R 7 , and R 8 is F and R 6 is Cl; and each R n and R o is F; r is 0 And z is 2.
　ある実施態様において、各々のＲ５、Ｒ６、Ｒ７、及びＲ８は、Ｆであり；そして各々のＲｎ及びＲｏは、Ｆであり；ｒは、０であり；そしてｚは、２である。 In certain embodiments, each R 5 , R 6 , R 7 , and R 8 is F; and each R n and R o is F; r is 0; and z is 2
　式（ＩＩ）に従う繰り返し単位の数（「ｎ１」）対式（ＩＩＩ）に従う繰り返し単位の数（「ｎ２」）の比は、特に限定されない。ｎ１：ｎ２比は、典型的には９：１～１：９、更に典型的には８：２～２：８である。ある実施態様において、ｎ１：ｎ２比は、９：１である。ある実施態様において、ｎ１：ｎ２比は、８：２である。 The ratio of the number of repeating units according to formula (II) (“n1”) to the number of repeating units according to formula (III) (“n2”) is not particularly limited. The n1: n2 ratio is typically 9: 1 to 1: 9, more typically 8: 2 to 2: 8. In one embodiment, the n1: n2 ratio is 9: 1. In one embodiment, the n1: n2 ratio is 8: 2.
　本開示の使用に適したポリマー酸は、当業者には公知の方法を用いて合成されるか、又は商業的供給元から得られる。例えば、式（ＩＩ）に従う繰り返し単位及び式（ＩＩＩ）に従う繰り返し単位を含むポリマーは、式（ＩＩａ）により表されるモノマーを式（ＩＩＩａ）により表されるモノマー： Polymeric acids suitable for use in the present disclosure may be synthesized using methods known to those skilled in the art or may be obtained from commercial sources. For example, a polymer comprising a repeating unit according to formula (II) and a repeating unit according to formula (III) comprises a monomer represented by formula (IIa), a monomer represented by formula (IIIa):
Figure JPOXMLDOC01-appb-C000059
［式中、Ｒ５～Ｒ１１は、上記と同義であり、Ｚ１は、－［ＯＣ（ＲｊＲｋ）－Ｃ（ＲｌＲｍ）］ｒ－Ｏ－［ＣＲｎＲｏ］ｚ－ＳＯ２Ｆであって、Ｒｊ、Ｒｋ、Ｒｌ、Ｒｍ、Ｒｎ及びＲｏ、ｒ、及びｚは、本明細書中と同義である］と、公知の重合方法により共重合し、続いてスルホニルフルオリド基の加水分解によりスルホン酸基に変換することによって製造されうる。
Figure JPOXMLDOC01-appb-C000059
[Wherein, R 5 to R 11 are as defined above, and Z 1 is-[OC (R j R k ) -C (R l R m )] r -O- [CR n R o ] z a -SO 2 F, R j, R k, R l, R m, R n and R o, r, and z, and herein is synonymous with, copolymerized by a known polymerization method Followed by hydrolysis to the sulfonic acid group by hydrolysis of the sulfonyl fluoride group.
　例えば、テトラフルオロエチレン（ＴＦＥ）又はクロロトリフルオロエチレン（ＣＴＦＥ）は、スルホン酸の前駆体基を含む１種以上のフッ素化モノマー（例えば、Ｆ２Ｃ＝ＣＦ－Ｏ－ＣＦ２－ＣＦ２－ＳＯ２Ｆ；Ｆ２Ｃ＝ＣＦ－［Ｏ－ＣＦ２－ＣＲｐＦ－Ｏ］ｑ１－ＣＦ２－ＣＦ２－ＳＯ２Ｆ（ここで、Ｒｐは、Ｆ又はＣＦ３であり、そしてｑ１は、１～１０である）；Ｆ２Ｃ＝ＣＦ－Ｏ－ＣＦ２－ＣＦ２－ＣＦ２－ＳＯ２Ｆ；及びＦ２Ｃ＝ＣＦ－ＯＣＦ２－ＣＦ２－ＣＦ２－ＣＦ２－ＳＯ２Ｆ等）と共重合されうる。 For example, tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTFE), the one or more fluorinated monomers containing precursor groups of sulfonic acid (e.g., F 2 C = CF-O -CF 2 -CF 2 - SO 2 F; F 2 C = CF- [O-CF 2 -CR p F-O] q1 -CF 2 -CF 2 -SO 2 F ( wherein, R p is F or CF 3, and q1 is 1 ~ 10); F 2 C = CF-OCF 2 -CF 2 -CF 2 -SO 2 F; and F 2 C = CF-OCF 2 -CF 2 -CF 2 -CF 2 -SO (2 F etc.) can be copolymerized.
　ポリマー酸の当量は、ポリマー酸に存在する酸基１モル当たりのポリマー酸の質量（グラム）として定義される。ポリマー酸の当量は、約４００～約１５，０００ｇポリマー/mol酸、典型的には約５００～約１０，０００ｇポリマー/mol酸、更に典型的には約５００～８，０００ｇポリマー/mol酸、更になお典型的には約５００～２，０００ｇポリマー/mol酸、更にいっそう典型的には約６００～約１，７００ｇポリマー/mol酸である。 The equivalent weight of polymeric acid is defined as the weight (grams) of polymeric acid per mole of acid group present in the polymeric acid. The equivalent weight of the polymeric acid is about 400 to about 15,000 g polymer / mol acid, typically about 500 to about 10,000 g polymer / mol acid, more typically about 500 to 8,000 g polymer / mol acid, Still more typically about 500 to 2,000 g polymer / mol acid, even more typically about 600 to about 1,700 g polymer / mol acid.
　このようなポリマー酸は、例えば、E.I. DuPontにより商品名 NAFION（登録商標）の下で販売されているもの、Solvay Specialty Polymersにより商品名 AQUIVION（登録商標）の下で販売されているもの、又はＡＧＣ株式会社により商品名 FLEMION（登録商標）の下で販売されているものである。 Such polymeric acids are, for example, those sold under the trade name NAFION® by EI DuPont, those sold under the trade name AQUIVION® by Solvay Specialty Polymers, or AGC It is sold under the trade name FLEMON® by the Corporation.
　ある実施態様において、（Ｆ）成分である合成ポリマーは、少なくとも１個のスルホン酸（－ＳＯ３Ｈ）残基を含む１個以上の繰り返し単位を含むポリエーテルスルホンである。 In one embodiment, the synthetic polymer that is component (F) is a polyether sulfone comprising one or more repeating units comprising at least one sulfonic acid (—SO 3 H) residue.
　ある実施態様において、ポリエーテルスルホンは、式（ＩＶ）：
Figure JPOXMLDOC01-appb-C000060
に従う繰り返し単位、並びに式（Ｖ）に従う繰り返し単位及び式（VI）に従う繰り返し単位：
Figure JPOXMLDOC01-appb-C000061
［式中、Ｒ１２～Ｒ２０は、それぞれ独立に、Ｈ、ハロゲン、アルキル、又はＳＯ３Ｈであるが、ただし、Ｒ１２～Ｒ２０の少なくとも１個は、ＳＯ３Ｈであり；そしてＲ２１～Ｒ２８は、それぞれ独立に、Ｈ、ハロゲン、アルキル、又はＳＯ３Ｈであるが、ただし、Ｒ２１～Ｒ２８の少なくとも１個は、ＳＯ３Ｈであり、そしてＲ２９及びＲ３０は、それぞれＨ又はアルキルである］からなる群より選択される繰り返し単位を含む。 In certain embodiments, the polyether sulfone is a compound of formula (IV):
Figure JPOXMLDOC01-appb-C000060
A repeating unit according to formula (V), a repeating unit according to formula (V) and a repeating unit according to formula (VI):
Figure JPOXMLDOC01-appb-C000061
[Wherein, R 12 to R 20 are each independently H, halogen, alkyl or SO 3 H, provided that at least one of R 12 to R 20 is SO 3 H; 21 to R 28 are each independently H, halogen, alkyl or SO 3 H, provided that at least one of R 21 to R 28 is SO 3 H, and R 29 and R 30 are , Each of which is H or alkyl].
　ある実施態様において、Ｒ２９及びＲ３０は、それぞれアルキルである。ある実施態様において、Ｒ２９及びＲ３０は、それぞれメチルである。 In certain embodiments, R 29 and R 30 are each alkyl. In one embodiment, R 29 and R 30 are each methyl.
　ある実施態様において、Ｒ１２～Ｒ１７、Ｒ１９、及びＲ２０は、それぞれＨであり、そしてＲ１８は、ＳＯ３Ｈである。 In one embodiment, R 12 -R 17 , R 19 and R 20 are each H and R 18 is SO 3 H.
　ある実施態様において、Ｒ２１～Ｒ２５、Ｒ２７、及びＲ２８は、それぞれＨであり、そしてＲ２６は、ＳＯ３Ｈである。 In one embodiment, R 21 -R 25 , R 27 and R 28 are each H and R 26 is SO 3 H.
　ある実施態様において、ポリエーテルスルホンは、式（ＶＩＩ）：
Figure JPOXMLDOC01-appb-C000062
［式中、ａは、０．７～０．９であり、そしてｂは、０．１～０．３である］により表される。 In one embodiment, the polyethersulfone is of the formula (VII):
Figure JPOXMLDOC01-appb-C000062
Where a is from 0.7 to 0.9 and b is from 0.1 to 0.3.
　ポリエーテルスルホンは、スルホン化されていてもいなくともよい、他の繰り返し単位を更に含んでもよい。 The polyether sulfone may further comprise other repeating units which may or may not be sulfonated.
　例えば、ポリエーテルスルホンは、式（ＶＩＩＩ）：
Figure JPOXMLDOC01-appb-C000063
［式中、Ｒ３１及びＲ３２は、それぞれ独立に、Ｈ又はアルキルである］で示される繰り返し単位を含んでもよい。 For example, polyether sulfone is a compound of formula (VIII):
Figure JPOXMLDOC01-appb-C000063
[Wherein, R 31 and R 32 are each independently H or alkyl] may contain a repeating unit.
　本明細書に記載の任意の２個以上の繰り返し単位は、一緒になって繰り返し単位を形成することができ、そしてポリエーテルスルホンは、このような繰り返し単位を含んでもよい。例えば、式（ＩＶ）に従う繰り返し単位は、式（ＶＩ）に従う繰り返し単位と合わせられて、式（ＩＸ）：
Figure JPOXMLDOC01-appb-C000064
に従う繰り返し単位を与えうる。 Any two or more repeat units described herein may be taken together to form a repeat unit, and the polyether sulfone may comprise such repeat units. For example, a repeat unit according to formula (IV) is combined with a repeat unit according to formula (VI) to give a compound of formula (IX):
Figure JPOXMLDOC01-appb-C000064
Can give a repeating unit according to
　同様に、例えば、式（ＩＶ）に従う繰り返し単位は、式（ＶＩＩＩ）に従う繰り返し単位と合わせられて、式（Ｘ）：
Figure JPOXMLDOC01-appb-C000065
に従う繰り返し単位を与えうる。 Similarly, for example, a repeat unit according to formula (IV) is combined with a repeat unit according to formula (VIII) to give a compound of formula (X):
Figure JPOXMLDOC01-appb-C000065
Can give a repeating unit according to
　ある実施態様において、ポリエーテルスルホンは、式（ＸＩ）：
Figure JPOXMLDOC01-appb-C000066
［式中、ａは、０．７～０．９であり、そしてｂは、０．１～０．３である］により表される。 In certain embodiments, the polyether sulfone is a compound of formula (XI):
Figure JPOXMLDOC01-appb-C000066
Where a is from 0.7 to 0.9 and b is from 0.1 to 0.3.
　少なくとも１個のスルホン酸（－ＳＯ３Ｈ）残基を含む１個以上の繰り返し単位を含むポリエーテルスルホンは、市販されており、例えば、スルホン化ポリエーテルスルホンは、小西化学工業株式会社によりＳ－ＰＥＳとして販売されている。 Polyether sulfones comprising one or more repeating units comprising at least one sulfonic acid (—SO 3 H) residue are commercially available, for example sulfonated polyether sulfones -Sold as PES.
　ある態様において、（Ｆ）成分である合成ポリマーは、下記式（ＸＩＩ）：
Figure JPOXMLDOC01-appb-C000067
で示される繰り返し単位を含む、ビニル芳香族重合体である。式中、Ａｒ’は、置換されていてもよい芳香環であり、２種類以上でもよい。Ａｒ’としては置換されていてもよいフェニル基、置換されていてもよいナフチル基等が挙げられる。 In one embodiment, the synthetic polymer that is component (F) has the following formula (XII):
Figure JPOXMLDOC01-appb-C000067
It is a vinyl aromatic polymer containing the repeating unit shown by these. In formula, Ar 'is an aromatic ring which may be substituted, and 2 or more types may be sufficient as it. As Ar ′, an optionally substituted phenyl group, an optionally substituted naphthyl group and the like can be mentioned.
　ある態様において、（Ｆ）成分である合成ポリマーは、ビニル芳香族重合体（例えば、ポリ（スチレン）又はその誘導体（但し、ポリスチレンスルホン酸を除く））；ポリ（酢酸ビニル）又はその誘導体；ポリ（エチレン－co－酢酸ビニル）又はその誘導体；ポリ（ピロリドン）又はその誘導体（例えば、ポリ（１－ビニルピロリドン－co－酢酸ビニル））；ポリ（ビニルピリジン）又はその誘導体；ポリ（メタクリル酸メチル）又はその誘導体；ポリ（アクリル酸ブチル）又はその誘導体；ポリ（アリールエーテルケトン）又はその誘導体；ポリ（アリールスルホン）又はその誘導体；ポリ（エステル）又はその誘導体；あるいはこれらの組合せ等のようなポリマー又はオリゴマーを含む。これらのポリマー又はオリゴマーは、薄膜作製時のバイルアップの改善の点で好ましい。 In one embodiment, the synthetic polymer which is the component (F) is a vinyl aromatic polymer (for example, poly (styrene) or a derivative thereof (except polystyrene sulfonic acid)); poly (vinyl acetate) or a derivative thereof; (Ethylene-co-vinyl acetate) or a derivative thereof; poly (pyrrolidone) or a derivative thereof (eg, poly (1-vinylpyrrolidone-co-vinyl acetate)); poly (vinyl pyridine) or a derivative thereof; poly (methyl methacrylate) Or derivatives thereof; poly (aryl ether ketones) or derivatives thereof; poly (aryl sulfones) or derivatives thereof; poly (esters) or derivatives thereof; combinations thereof, etc. It contains a polymer or an oligomer. These polymers or oligomers are preferred in terms of the improvement of the buildup during thin film formation.
　中でも、（Ｆ）成分は、ビニル芳香族重合体又はその誘導体であると、薄膜作製時のバイルアップがよりいっそう改善するため、好ましい。より好ましくは、１種以上の置換若しくは非置換のスチレンから合成されるホモポリマー若しくはコポリマー又はその誘導体であり、特に好ましくは、少なくともスチレン及び４－ヒドロキシスチレンから合成されるコポリマー又はその誘導体である。更に、（Ｆ）成分としてビニル芳香族重合体又はその誘導体を使用すると、インク組成物から得られる電荷輸送性薄膜の透明性を高く、かつ、可視スペクトルの吸光度を低くしやすくなるため、好ましい。その結果、該電荷輸送性薄膜を用いて作製された有機ＥＬ素子の電流効率、外部量子効率及び輝度半減期を向上させることができる。 Among them, the component (F) is preferably a vinyl aromatic polymer or a derivative thereof because this further improves the buildup during thin film formation. More preferably, it is a homopolymer or copolymer synthesized from one or more substituted or unsubstituted styrene or a derivative thereof, and particularly preferably a copolymer synthesized from at least styrene and 4-hydroxystyrene or a derivative thereof. Furthermore, the use of a vinyl aromatic polymer or a derivative thereof as the component (F) is preferable because it makes it easy to increase the transparency of the charge transportable thin film obtained from the ink composition and to lower the absorbance in the visible spectrum. As a result, it is possible to improve the current efficiency, the external quantum efficiency, and the luminance half life of the organic EL device manufactured using the charge transporting thin film.
　ビニル芳香族重合体又はその誘導体は、式（ＸＩＩ）で示される繰り返し単位以外の繰り返し単位を形成するモノマー成分を含んでも良い、コポリマー又はホモポリマーであり、モノマー成分全体に占める式（ＸＩＩ）で示される繰り返し単位を形成するモノマーの割合が５０重量％以上のコポリマー又はホモポリマーを指す。モノマー成分全体に占める式（ＸＩＩ）で示される繰り返し単位を形成するモノマーの割合は、好ましくは７０重量％以上、より好ましくは８０重量％以上であり、ある態様においては１００％である。 The vinyl aromatic polymer or the derivative thereof is a copolymer or homopolymer which may contain a monomer component forming a repeating unit other than the repeating unit represented by the formula (XII), and is represented by the formula (XII) in the entire monomer component It refers to a copolymer or homopolymer in which the proportion of monomers forming the indicated repeat unit is 50% by weight or more. The proportion of the monomer forming the repeating unit represented by the formula (XII) in the entire monomer component is preferably 70% by weight or more, more preferably 80% by weight or more, and in one embodiment, 100%.
　（Ｆ）成分であるマトリックス化合物は、例えば、少なくとも１種の半導体マトリックス化合物成分からなっていてよい。この半導体マトリックス化合物成分は、本明細書に記載の（Ａ）成分とは異なる。半導体マトリックス化合物成分は、典型的には主鎖及び／又は側鎖に正孔運搬単位を含む繰り返し単位からなる、半導体低分子又は半導体ポリマーであってよい。半導体マトリックス化合物成分は、中性型であっても、又はドープされていてもよく、典型的には有機溶媒（例えば、トルエン、クロロホルム、アセトニトリル、シクロヘキサノン、アニソール、クロロベンゼン、ｏ－ジクロロベンゼン、安息香酸エチル及びこれらの混合物等）に可溶性及び／又は分散性である。 The matrix compound which is the component (F) may be composed of, for example, at least one semiconductor matrix compound component. This semiconductor matrix compound component is different from the component (A) described herein. The semiconducting matrix compound component may be a semiconducting small molecule or semiconducting polymer, typically consisting of repeating units comprising hole transporting units in the main chain and / or in the side chain. The semiconductor matrix compound component may be neutral or doped and typically is an organic solvent (eg, toluene, chloroform, acetonitrile, cyclohexanone, anisole, chlorobenzene, o-dichlorobenzene, benzoic acid Soluble and / or dispersible in ethyl and mixtures thereof etc.
　ある態様においては、フッ素化されたポリマー酸とその他のマトリックス化合物とは成膜性の観点から混合しないほうが好ましい場合がある。 In some embodiments, it may be preferable not to mix the fluorinated polymer acid and the other matrix compound from the viewpoint of film forming property.
　インク組成物中の（Ｆ）成分の量は、（Ａ）及び（Ｂ）成分並びに任意の（Ｄ）～（Ｆ）成分を合わせた重量に対して、５重量％～９５重量％であることが好ましく、より好ましくは５０重量％～９０重量％、特に好ましくは６０重量％～８０量％である。（Ｆ）成分の量が上記範囲であると、バイルアップをよりいっそう改善することができる。 The amount of component (F) in the ink composition is 5% by weight to 95% by weight based on the total weight of components (A) and (B) and optional components (D) to (F). Is more preferably 50% by weight to 90% by weight, particularly preferably 60% by weight to 80% by weight. When the amount of the component (F) is in the above range, the buildup can be further improved.
　本願は、更に、インク組成物であって、
　（Ａ）式（Ｉ）：
Figure JPOXMLDOC01-appb-C000068
［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、－ＳＯ３Ｍ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－Ｚ－Ｏ－を形成する
（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、Ｚは、場合によりハロゲン又はＹで置換されているヒドロカルビレン基（ここで、Ｙは、炭素数１～１０の直鎖又は分岐鎖のアルキル基又はアルコキシアルキル基であり、該アルキル基又はアルコキシアルキル基は、任意の位置がスルホン酸基で置換されていてもよい）であり、ｐは、１以上の整数であり、そして、Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）］で表される繰り返し単位を含むポリチオフェン；
　（Ｂ）オニウムボレート塩であって、式（ａ１）：
Figure JPOXMLDOC01-appb-C000069
で表されるアニオン、式（ａ２）：
Figure JPOXMLDOC01-appb-C000070
で表される１価又は２価のアニオン、及び（ａ５）
Figure JPOXMLDOC01-appb-C000071
で表されるアニオン
［式中、Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基であり、Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－であり、Ｅは長周期型周期表の第１３族又は第１５族に属する元素を表す］からなる群より選択される少なくとも１種のアニオンと対カチオンとからなるオニウムボレート塩（ただし、電気的中性な塩である）；
　（Ｃ）有機溶媒を含む液体担体；及び
　（Ｆ）マトリックス化合物
を含む組成物を提供する。本構成のインク組成物を使用すると、薄膜作製時のバイルアップがいっそう改善され、厚さが均一で電荷輸送性に優れた電荷輸送性薄膜とすることができる。 The present application is further an ink composition, wherein
(A) Formula (I):
Figure JPOXMLDOC01-appb-C000068
[Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or alternatively, R 1 and R 2 together form —O—Z—O— (wherein, M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium, or trialkyl ammonium And Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl being Group or alkoxyalkyl group may be substituted at any position with a sulfonic acid group, p is an integer of 1 or more, and R e is H, Alkyl, fluoroalkyl or aryl) is a polythiophene containing a repeating unit represented by
(B) an onium borate salt, which is represented by the formula (a1):
Figure JPOXMLDOC01-appb-C000069
Anion represented by the formula (a2):
Figure JPOXMLDOC01-appb-C000070
And a monovalent or divalent anion represented by and (a5)
Figure JPOXMLDOC01-appb-C000071
Wherein Ar is each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and R is 1 to 10 carbon atoms Alkyl group, cycloalkyl group having 3 to 20 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms or fluoroaralkyl group having 7 to 10 carbon atoms, and L is an alkylene group , -NH-, an oxygen atom, a sulfur atom or -CN + -, and E represents an element belonging to Group 13 or 15 of the long periodic table, at least one selected from the group consisting of An onium borate salt consisting of an anion and a counter cation (however, an electrically neutral salt);
Provided is a composition comprising (C) a liquid carrier comprising an organic solvent; and (F) a matrix compound. By using the ink composition of this configuration, the buildup during film formation is further improved, and a charge transportable thin film having uniform thickness and excellent charge transportability can be obtained.
［インク組成物］ [Ink composition]
　インク組成物は、当業者には公知の任意の適切な方法により調製することができる。例えば、１つの方法において、最初の水性混合物は、本明細書に記載のポリチオフェンの分散液を、必要に応じてポリマー酸等のマトリックス化合物の水性分散液、及び必要に応じて追加の溶媒と混合することにより調製される。混合物中の水を含む溶媒を、典型的には蒸発により次に除去する。生じる乾燥生成物を、ジメチルスルホキシド、グリコール系溶媒のような１種以上の有機溶媒に溶解又は分散させ、加圧下で濾過することにより、非水性混合物が生成する。このような非水性混合物に、オニウムボレート塩又はその溶液若しくは分散液、場合によりアミン化合物、金属酸化物ナノ粒子の分散液及びマトリックス化合物又はその分散液若しくは溶液と混合することにより、最終のインク組成物を製造することができる。これらの成分の添加順は、特に限定されず、任意の添加順でインク組成物を製造することができる。 The ink composition can be prepared by any suitable method known to those skilled in the art. For example, in one method, the first aqueous mixture is mixed with the dispersion of polythiophene described herein, optionally with an aqueous dispersion of a matrix compound such as a polymeric acid, and optionally with an additional solvent Prepared by The solvent containing water in the mixture is then typically removed by evaporation. The resulting dry product is dissolved or dispersed in one or more organic solvents such as dimethylsulfoxide, glycol based solvents and filtered under pressure to form a non-aqueous mixture. The final ink composition is prepared by mixing such a non-aqueous mixture with an onium borate salt or a solution or dispersion thereof, optionally an amine compound, a dispersion of metal oxide nanoparticles and a matrix compound or a dispersion or solution thereof. Objects can be manufactured. The order of addition of these components is not particularly limited, and the ink composition can be produced in any order of addition.
　別の方法において、本明細書に記載のインク組成物は、ストック溶液から調製することができる。例えば、本明細書に記載のポリチオフェンのストック溶液は、水性分散液からポリチオフェンを乾燥状態で、典型的には蒸発により単離することによって調製することができる。乾燥されたポリチオフェンは、次に１種以上の有機溶媒、及び場合によりアミン化合物と合わせられる。オニウムボレート塩のストック溶液は、有機溶媒で溶解することにより、製造することができる。マトリックス化合物のストック溶液は、マトリックス化合物がポリマー酸の場合、水性分散液からポリマー酸を乾燥状態で、典型的には蒸発により単離することによって調製することができる。乾燥されたポリマー酸は、次に１種以上の有機溶媒と合わせられる。他のマトリックス化合物のストック溶液は、同様に製造することができる。金属酸化物ナノ粒子のストック溶液は、例えば、市販の分散液を１種以上の有機溶媒であって、市販の分散液に含まれる溶媒（単数又は複数）と同一であっても異なっていてもよい有機溶媒で希釈することにより、製造することができる。各ストック溶液の所望の量を次に合わせることにより、本開示のインク組成物を形成する。 In another method, the ink composition described herein can be prepared from a stock solution. For example, a stock solution of polythiophene as described herein can be prepared by isolating polythiophene from an aqueous dispersion in the dry state, typically by evaporation. The dried polythiophene is then combined with one or more organic solvents and, optionally, an amine compound. Stock solutions of onium borate salts can be prepared by dissolution with an organic solvent. Stock solutions of matrix compounds can be prepared by isolating the polymeric acid from the aqueous dispersion in the dry state, typically by evaporation, when the matrix compound is a polymeric acid. The dried polymeric acid is then combined with one or more organic solvents. Stock solutions of other matrix compounds can be prepared similarly. For example, the stock solution of metal oxide nanoparticles is a commercially available dispersion, which may be one or more organic solvents, which may be the same or different from the solvent or solvents contained in the commercially available dispersion. It can be produced by dilution with a good organic solvent. The desired amounts of each stock solution are then combined to form the ink composition of the present disclosure.
　更に別の方法において、本明細書に記載のインク組成物は、本明細書に記載のとおり乾燥状態で個々の成分を単離するが、ストック溶液を調製する代わりに、乾燥状態の成分を合わせて、次に１種以上の有機溶媒に溶解することによりＮＱインク組成物を提供することによって、調製することができる。 In yet another method, the ink composition described herein isolates individual components in the dry state as described herein, but instead of preparing a stock solution, the dry components are combined It can then be prepared by providing the NQ ink composition by subsequent dissolution in one or more organic solvents.
　なお、アミン化合物は通常、最終的にインク組成物を調製する際に添加するが、それ以前の時点で予め添加しておいてもよい。例えば、（Ａ）成分としてスルホン化ポリチオフェンを用いる場合、先に述べたように、スルホン化ポリチオフェンにアミン化合物を添加して、対応するアンモニウム塩、例えばトリアルキルアンモニウム塩（スルホン化ポリチオフェンアミン付加体）に変換してもよい。必要であれば、このアンモニウム塩を還元処理に付してもよいし、還元処理されたスルホン化ポリチオフェンの溶液にアミン化合物（例えばトリエチルアミン）を添加して、スルホン化ポリチオフェンをアンモニウム塩（例えばトリエチルアンモニウム塩）として、粉末の形態で沈殿させ、これを回収してもよい。
　このような処理の方法に特に制限はないが、例えば、還元処理されたスルホン化ポリチオフェンに水及びトリエチルアミンを加えて溶解し、これを加熱下（例えば６０℃）に撹拌した後、得られた溶液にイソプロピルアルコール及びアセトンを添加して、スルホン化共役ポリマーのトリエチルアンモニウム塩の沈殿を生じさせ、これを濾過して回収する等の方法を採用し得る。 The amine compound is generally added at the final preparation of the ink composition, but may be previously added before that point. For example, when a sulfonated polythiophene is used as the component (A), as described above, an amine compound is added to the sulfonated polythiophene to form a corresponding ammonium salt, for example, a trialkyl ammonium salt (sulfonated polythiophene amine adduct) May be converted to If necessary, this ammonium salt may be subjected to reduction treatment, or an amine compound (eg triethylamine) is added to the solution of reduction treated sulfonated polythiophene to give ammonium salt of sulfonated polythiophene (eg triethyl ammonium) It may be precipitated in the form of a powder as a salt) and recovered.
Although there is no particular limitation on the method of such treatment, for example, a solution obtained by adding water and triethylamine to a reduction treated sulfonated polythiophene to dissolve it and stirring it under heating (eg 60 ° C.) Isopropyl alcohol and acetone may be added thereto to precipitate the sulfonated conjugated polymer triethylammonium salt, which may be filtered and recovered.
　インク組成物中の全固形分（％ＴＳ）は、インク組成物の総量に対して、約０．１重量％～約５０重量％、典型的には約０．３重量％～約４０重量％、更に典型的には約０．５重量％～約１５重量％、更になお典型的には約１重量％～約５重量％である。 The total solids content (% TS) in the ink composition is about 0.1 wt% to about 50 wt%, typically about 0.3 wt% to about 40 wt%, based on the total weight of the ink composition. More typically from about 0.5% to about 15% by weight, even more typically from about 1% to about 5% by weight.
［電荷輸送性薄膜を形成する方法］
　電荷輸送性薄膜は、インク組成物を基材上に塗布し、溶媒を蒸発させることにより製造することができる。電荷輸送性薄膜は、正孔運搬薄膜であることが好ましい。
　本開示のインク組成物は、基板上の薄膜として注型及びアニーリングすることができる。 [Method of forming charge transporting thin film]
The charge transporting thin film can be produced by applying the ink composition on a substrate and evaporating the solvent. The charge transporting thin film is preferably a hole transporting thin film.
The ink compositions of the present disclosure can be cast and annealed as thin films on a substrate.
　よって、本開示はまた、正孔運搬薄膜の形成方法であって、
　１）基板を本明細書に開示のインク組成物でコーティングすること；及び
　２）基板上のコーティングをアニーリングすることにより、正孔運搬薄膜を形成すること
を含む方法に関する。 Thus, the present disclosure is also a method of forming a hole transport thin film,
1) coating a substrate with the ink composition disclosed herein; and 2) forming a hole transporting thin film by annealing the coating on the substrate.
　基板上のインク組成物のコーティングは、例えば、回転注型、スピンコーティング、ディップ注型、ディップコーティング、スロットダイコーティング、インクジェット印刷、グラビアコーティング、ドクターブレード法、及び例えば、有機電子デバイスの作製のための当該分野において公知の任意の他の方法を含む、当該分野において公知の方法によって実行することができる。 The coating of the ink composition on the substrate is, for example, for spin casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, doctor blade method, and for example for the preparation of organic electronic devices. It can be carried out by methods known in the art, including any other methods known in the art of
　基板は、可撓性であっても剛性であっても、有機であっても無機であってもよい。適切な基板化合物は、例えば、ガラス（例えば、ディスプレイガラスを含む）、セラミック、金属、及びプラスチック薄膜を含む。 The substrate may be flexible or rigid, organic or inorganic. Suitable substrate compounds include, for example, glass (including, for example, display glass), ceramics, metals, and plastic thin films.
　本明細書に使用されるとき、「アニーリング」という用語は、本開示のインク組成物でコーティングされた基板上に硬化層、典型的には薄膜を形成するための任意の一般的プロセスのことをいう。一般的アニーリングプロセスは、当業者には公知である。典型的には、インク組成物でコーティングされた基板から溶媒を除去する。溶媒の除去は、例えば、大気圧未満の圧力にコーティングされた基板を付すことにより、かつ／又は基板に積層されたコーティングをある温度（アニーリング温度）まで加熱し、この温度をある期間（アニーリング時間）維持し、そして次に生じた層、典型的には薄膜をゆっくり室温まで冷却させることにより達成できる。 As used herein, the term "annealing" refers to any common process for forming a cured layer, typically a thin film, on a substrate coated with the ink composition of the present disclosure. Say. General annealing processes are known to those skilled in the art. Typically, the solvent is removed from the substrate coated with the ink composition. The removal of the solvent is carried out, for example, by subjecting the coated substrate to a pressure less than atmospheric pressure, and / or heating the coating deposited on the substrate to a certain temperature (annealing temperature), and this temperature is maintained for a certain period (annealing time) B) maintaining and then achieving by slowly cooling the resulting layer, typically a thin film, to room temperature.
　アニーリングの工程は、インク組成物でコーティングされた基板を、当業者には公知の任意の方法を用いて加熱することにより、例えば、オーブン中又はホットプレート上で加熱することにより実行することができる。アニーリングは、不活性環境、例えば、窒素雰囲気又は希ガス（例えば、アルゴンガス等）雰囲気下で実行することができる。アニーリングは、空気雰囲気で実行してもよい。 The step of annealing can be carried out by heating the substrate coated with the ink composition by any method known to the person skilled in the art, for example by heating in an oven or on a hot plate . Annealing can be performed under an inert environment, such as a nitrogen atmosphere or a noble gas (eg, argon gas, etc.) atmosphere. The annealing may be performed in an air atmosphere.
　ある実施態様において、アニーリング温度は、約２５℃～約３５０℃、典型的には１５０℃～約３２５℃、更に典型的には約２００℃～約３００℃、更になお典型的には約２３０～約３００℃である。 In one embodiment, the annealing temperature is about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C., more typically about 200 ° C. to about 300 ° C., still more typically about 230 ° C. It is about 300 ° C.
　アニーリング時間は、アニーリング温度が維持される時間である。アニーリング時間は、約３～約４０分間、典型的には約１５～約３０分間である。 Annealing time is the time during which the annealing temperature is maintained. The annealing time is about 3 to about 40 minutes, typically about 15 to about 30 minutes.
　ある実施態様において、アニーリング温度は、約２５℃～約３５０℃、典型的には１５０℃～約３２５℃、更に典型的には約２００℃～約３００℃、更になお典型的には約２５０～約３００℃であり、そしてアニーリング時間は、約３～約４０分間、典型的には約１５～約３０分間である。 In one embodiment, the annealing temperature is about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C., more typically about 200 ° C. to about 300 ° C., still more typically about 250 to about 300 ° C. The temperature is about 300 ° C., and the annealing time is about 3 to about 40 minutes, typically about 15 to about 30 minutes.
　本開示は、本明細書に記載の方法により形成される正孔運搬薄膜に関する。 The present disclosure relates to hole transporting thin films formed by the methods described herein.
　可視光の透過は重要であり、そして薄膜の厚さが大きいところでの良好な透過（低い吸光）は特に重要である。例えば、本開示の方法により製造された薄膜は、約３８０～８００ｎｍの波長を有する光の、少なくとも約８５％、典型的には少なくとも９０％の透過率（典型的には、基板を伴う）を示すことができる。ある実施態様において、透過率は少なくとも約９０％である。 Visible light transmission is important, and good transmission (low light absorption) where the film thickness is large is particularly important. For example, thin films produced by the methods of the present disclosure have a transmission of at least about 85%, typically at least 90% (typically with the substrate) of light having a wavelength of about 380-800 nm. Can be shown. In one embodiment, the transmission is at least about 90%.
　１つの実施態様において、本開示の方法により製造された薄膜は、約５ｎｍ～約５００ｎｍ、典型的には約５ｎｍ～約１５０ｎｍ、更に典型的には約５０ｎｍ～１２０ｎｍの厚さを有する。 In one embodiment, thin films produced by the methods of the present disclosure have a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm.
　ある実施態様において、本開示の方法により製造された薄膜は、少なくとも約９０％の透過率を示し、そして約５ｎｍ～約５００ｎｍ、典型的には約５ｎｍ～約１５０ｎｍ、更に典型的には約５０ｎｍ～１２０ｎｍの厚さを有する。ある実施態様において、本開示の方法により製造された薄膜は、少なくとも約９０％の透過率（％Ｔ）を示し、そして約５０ｎｍ～１２０ｎｍの厚さを有する。 In certain embodiments, thin films produced by the methods of the present disclosure exhibit transmission of at least about 90%, and about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm. It has a thickness of ̃120 nm. In certain embodiments, thin films produced by the methods of the present disclosure exhibit a transmission (% T) of at least about 90% and have a thickness of about 50 nm to 120 nm.
　本開示の方法により製造された薄膜は、最終デバイスの電子的特性を向上させるのに使用される電極又は追加の層を場合により含有する基板上に製造することができる。得られる薄膜は、１種以上の有機溶媒に対して抵抗性である場合が有り、これらの溶媒は、その後デバイスの作製中にコーティング又は堆積される層のための、インク中の液体担体として使用される溶媒になり得る。薄膜は、例えば、トルエンに対して抵抗性であり、トルエンは、その後デバイスの作製中にコーティング又は堆積される層のためのインク中の溶媒になり得る。 Thin films produced by the methods of the present disclosure can be produced on substrates optionally containing electrodes or additional layers used to improve the electronic properties of the final device. The resulting thin film may be resistant to one or more organic solvents, which are then used as liquid carriers in the ink for layers to be coated or deposited during fabrication of the device. Can be a solvent. The thin film is, for example, resistant to toluene, which can then be the solvent in the ink for the layer to be coated or deposited during fabrication of the device.
［有機ＥＬデバイス］
　本開示はまた、本明細書に記載の方法により調製される薄膜を含む有機エレクトロルミネッセンス素子（デバイス）に関する。本明細書に記載のデバイスは、例えば、溶解法を含む当該分野において公知の方法により製造することができる。標準法によりインクを適用し、そして溶媒を除去することができる。本明細書に記載の方法により調製される薄膜は、デバイス中のＨＩＬ及び／又はＨＴＬ層であってよい。 [Organic EL device]
The present disclosure also relates to an organic electroluminescent device (device) comprising a thin film prepared by the method described herein. The devices described herein can be manufactured by methods known in the art, including, for example, dissolution methods. The ink can be applied by standard methods and the solvent can be removed. The thin film prepared by the methods described herein may be the HIL and / or HTL layers in the device.
　方法は、当該分野において公知であり、そして例えば、ＯＬＥＤ及びＯＰＶデバイスを含む、有機電子デバイスを作製するために利用することができる。当該分野において公知の方法は、輝度、効率、及び寿命を測定するために利用することができる。有機発光ダイオード（ＯＬＥＤ）は、例えば、米国特許第４，３５６，４２９号及び４，５３９，５０７号（Kodak）に記載されている。発光する導電性ポリマーは、例えば、米国特許第５，２４７，１９０号及び５，４０１，８２７号（Cambridge Display Technologies）に記載されている。デバイスアーキテクチャ、物理的原理、溶解法、多層化、混合、並びに化合物の合成及び配合は、Kraftら、“Electroluminescent Conjugated Polymers-Seeing Polymers in a New Light,” Angew. Chem. Int. Ed., 1998, 37, 402-428に記載されており、その全体が参照により本明細書に取り込まれる。 Methods are known in the art and can be utilized to make organic electronic devices, including, for example, OLED and OPV devices. Methods known in the art can be used to measure brightness, efficiency, and lifetime. Organic light emitting diodes (OLEDs) are described, for example, in U.S. Patent Nos. 4,356,429 and 4,539,507 (Kodak). Conducting polymers that emit light are described, for example, in US Pat. Nos. 5,247,190 and 5,401,827 (Cambridge Display Technologies). Device architecture, physical principles, dissolution methods, layering, mixing, and compound synthesis and formulation can be found in Kraft et al., "Electroluminescent Conjugated Polymers-Seeing Polymers in a New Light," Angew. Chem. Int. Ed., 1998, 37, 402-428, which is incorporated herein by reference in its entirety.
　Sumationから入手できる化合物、Merck Yellow、Merck Blue、American Dye Sources (ADS)から、Kodak（例えば、A1Q3等）から、及び実にAldrichから入手できる化合物（BEHP-PPV等）のような、種々の導電性ポリマー、更には有機分子を含む、当該分野において公知であり、かつ市販されている発光体を使用することができる。このような有機エレクトロルミネセント化合物の例は、以下を含む：
（ｉ）ポリ（ｐ－フェニレンビニレン）及びフェニレン残基上の種々の位置で置換されているその誘導体；
（ii）ポリ（ｐ－フェニレンビニレン）及びビニレン残基上の種々の位置で置換されているその誘導体；
（iii）ポリ（ｐ－フェニレンビニレン）及びフェニレン残基上の種々の位置で置換されており、そしてまたビニレン残基上の種々の位置で置換されているその誘導体；
（iv）ポリ（アリーレンビニレン）であって、アリーレンが、ナフタレン、アントラセン、フリレン、チエニレン、オキサジアゾール等のような残基であってよい、ポリ（アリーレンビニレン）；
（ｖ）ポリ（アリーレンビニレン）の誘導体であって、アリーレンが、上記（iv）中と同様であってよく、そして更にアリーレン上の種々の位置に置換基を有する、誘導体；
（vi）ポリ（アリーレンビニレン）の誘導体であって、アリーレンが、上記（iv）中と同様であってよく、そして更にビニレン上の種々の位置に置換基を有する、誘導体；
（vii）ポリ（アリーレンビニレン）の誘導体であって、アリーレンが、上記（iv）中と同様であってよく、そして更にアリーレン上の種々の位置に置換基を、及びビニレン上の種々の位置に置換基を有する、誘導体；
（viii）（iv）、（ｖ）、（vi）、及び（vii）中の化合物のような、アリーレンビニレンオリゴマーと非共役オリゴマーとのコポリマー；並びに
（ix）ポリ（ｐ－フェニレン）及びフェニレン残基上の種々の位置で置換されているその誘導体（ポリ（９，９－ジアルキルフルオレン）等のようなラダーポリマー誘導体を含む）；
（ｘ）ポリ（アリーレン）であって、アリーレンが、ナフタレン、アントラセン、フリレン、チエニレン、オキサジアゾール等のような残基であってよい、ポリ（アリーレン）；及びアリーレン残基上の種々の位置で置換されているその誘導体；
（xi）（ｘ）中の化合物のようなオリゴアリーレンと非共役オリゴマーとのコポリマー；
（xii）ポリキノリン及びその誘導体；
（xiii）ポリキノリンと、可溶性を提供するために、フェニレン上で例えば、アルキル又はアルコキシ基により置換されているｐ－フェニレンとのコポリマー；
（xiv）ポリ（ｐ－フェニレン－２，６－ベンゾビスチアゾール）、ポリ（ｐ－フェニレン－２，６－ベンゾビスオキサゾール）、ポリ（ｐ－フェニレン－２，６－ベンゾイミダゾール）、及びその誘導体のような、リジッドロッドポリマー、並びにその誘導体；
（xv）ポリフルオレン単位を持つポリフルオレンポリマー及びコポリマー。 Various conductivity properties, such as compounds available from Sumation, Merck Yellow, Merck Blue, from American Dye Sources (ADS), from Kodak (eg A1Q3 etc), and indeed from Aldrich (BEHP-PPV etc) Luminescent materials known in the art and commercially available that contain polymers as well as organic molecules can be used. Examples of such organic electroluminescent compounds include:
(I) poly (p-phenylenevinylene) and its derivatives substituted at various positions on the phenylene residue;
(Ii) poly (p-phenylenevinylene) and derivatives thereof substituted at various positions on the vinylene residue;
(Iii) Poly (p-phenylenevinylene) and its derivatives which are substituted at various positions on the phenylene residue and also at various positions on the vinylene residue;
(Iv) a poly (arylene vinylene), wherein the arylene may be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole etc;
(V) a derivative of poly (arylene vinylene), wherein the arylene may be the same as in (iv) above, and further having substituents at various positions on the arylene;
(Vi) a derivative of poly (arylene vinylene), wherein the arylene may be the same as in (iv) above and further having substituents at various positions on vinylene;
(Vii) derivatives of poly (arylene vinylene) s, wherein the arylene may be as in (iv) above, and additionally at various positions on the arylene and at various positions on the vinylene A derivative having a substituent;
(Viii) copolymers of arylene vinylene oligomers and non-conjugated oligomers, such as compounds in (iv), (v), (vi), and (vii); and (ix) poly (p-phenylene) and phenylene residues Derivatives thereof substituted at various positions on the group, including ladder polymer derivatives such as poly (9,9-dialkylfluorene) etc .;
(X) poly (arylene), wherein the arylene may be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole etc., poly (arylene); and various positions on the arylene residue Its derivative being substituted with;
(Xi) a copolymer of an oligoarylene such as a compound in (x) and a nonconjugated oligomer;
(Xii) polyquinoline and its derivatives;
(Xiii) a copolymer of polyquinoline and p-phenylene which is substituted, for example, by alkyl or alkoxy groups on phenylene to provide solubility;
(Xiv) poly (p-phenylene-2,6-benzobisthiazole), poly (p-phenylene-2,6-benzobisoxazole), poly (p-phenylene-2,6-benzoimidazole), and derivatives thereof Such as, rigid rod polymers, as well as their derivatives;
(Xv) polyfluorene polymers and copolymers with polyfluorene units.
　好ましい有機発光ポリマーは、緑色、赤色、青色、若しくは白色光を放射するSUMATIONの発光ポリマー（Light Emitting Polymers）（「ＬＥＰ」）又はそのファミリー、コポリマー、誘導体、又はこれらの混合物を含み；SUMATIONのＬＥＰは、Sumation KKから入手できる。他のポリマーは、Covion Organic Semiconductors GmbH, Frankfurt, Germany（今やMerck（登録商標）に所有されている）から入手できるポリスピロフルオレン様ポリマーを含む。 Preferred organic light emitting polymers include SUMATION's light emitting polymers ("LEP") or families thereof, copolymers, derivatives, or mixtures thereof that emit green, red, blue, or white light; Is available from Sumation KK. Other polymers include polyspirofluorene-like polymers available from Covion Organic Semiconductors GmbH, Frankfurt, Germany® (now owned by Merck®).
　あるいは、ポリマーよりむしろ、蛍光又は燐光を放射する有機低分子が有機エレクトロルミネセント層として使える。低分子有機エレクトロルミネセント化合物の例は、（ｉ）トリス（８－ヒドロキシキノリナト）アルミニウム（Ａｌｑ）；（ii）１，３－ビス（Ｎ，Ｎ－ジメチルアミノフェニル）－１，３，４－オキサジアゾール（ＯＸＤ－８）；（iii）オキソ－ビス（２－メチル－８－キノリナト）アルミニウム；（iv）ビス（２－メチル－８－ヒドロキシキノリナト）アルミニウム；（ｖ）ビス（ヒドロキシベンゾキノリナト）ベリリウム（ＢｅＱ２）；（vi）ビス（ジフェニルビニル）ビフェニレン（ＤＰＶＢＩ）；及びアリールアミン置換ジスチリルアリーレン（ＤＳＡアミン）を含む。 Alternatively, rather than polymers, small organic molecules that emit fluorescence or phosphorescence can be used as the organic electroluminescent layer. Examples of low molecular weight organic electroluminescent compounds are (i) tris (8-hydroxyquinolinato) aluminum (Alq); (ii) 1,3-bis (N, N-dimethylaminophenyl) -1,3,4 -Oxadiazole (OXD-8); (iii) oxo-bis (2-methyl-8-quinolinato) aluminum; (iv) bis (2-methyl-8-hydroxyquinolinato) aluminum; (v) bis (hydroxy) Benzoquinolinato) beryllium (BeQ 2 ); (vi) bis (diphenylvinyl) biphenylene (DPVBI); and arylamine substituted distyrylarylene (DSA amine).
　このようなポリマー及び低分子化合物は、当該分野において周知であり、そして例えば、米国特許第５，０４７，６８７号に記載されている。 Such polymers and low molecular weight compounds are well known in the art and are described, for example, in US Pat. No. 5,047,687.
　デバイスは、多くの場合、例えば、溶解法又は真空法、更には印刷法及びパターン形成法により調製できる多層構造を用いて作製することができる。詳しくは、正孔注入層（ＨＩＬ）のための本明細書に記載の実施態様であって、正孔注入層としての使用のために本組成物が配合される実施態様の利用を、効果的に実行することができる。 Devices can often be made using multilayer structures that can be prepared, for example, by dissolution or vacuum methods, as well as printing and patterning methods. In particular, the embodiments described herein for the hole injection layer (HIL), which are effectively incorporated into the composition for use as a hole injection layer, are effective. Can be performed.
　デバイス中のＨＩＬの例は以下を含む：
１）ＰＬＥＤ及びＳＭＯＬＥＤを含むＯＬＥＤ中の正孔注入；例えば、ＰＬＥＤ中のＨＩＬには、共役が炭素又はケイ素原子を巻き込む、全ての分類の共役ポリマー発光体を使用することができる。ＳＭＯＬＥＤ中のＨＩＬでは、以下が例である：蛍光発光体を含有するＳＭＯＬＥＤ；燐光発光体を含有するＳＭＯＬＥＤ；ＨＩＬ層に加えて１種以上の有機層を含むＳＭＯＬＥＤ；及び低分子層が、溶液若しくはエアゾール噴霧から、又は任意の他の処理方法により処理されているＳＭＯＬＥＤ。更に、他の例は、以下を含む：デンドリマー又はオリゴマー有機半導体系のＯＬＥＤ中のＨＩＬ；両極性発光ＦＥＴであって、ＨＩＬが、電荷注入を調節するため又は電極として使用されるＦＥＴ中のＨＩＬ；
２）ＯＰＶ中の正孔抽出層；
３）トランジスタ中のチャネル材料；
４）論理ゲートのような、トランジスタの組合せを含む回路中のチャネル材料；
５）トランジスタ中の電極材料；
６）コンデンサ中のゲート層；
７）化学センサーであって、ドーピングレベルの調節が、感知すべき種と導電性ポリマーとの関係により達成されるセンサー；
８）バッテリー中の電極又は電解質材料。 Examples of HIL in the device include:
1) Hole injection in OLEDs, including PLEDs and SMOLEDs; for example, HIL in PLEDs can use all classes of conjugated polymer light emitters, where the conjugation entraps carbon or silicon atoms. For HILs in SMOLEDs, the following are examples: SMOLEDs containing fluorescent emitters; SMOLEDs containing phosphorescent emitters; SMOLEDs containing one or more organic layers in addition to the HIL layer; Or SMOLED being treated from an aerosol spray or by any other treatment method. Furthermore, other examples include: HILs in OLEDs of the dendrimer or oligomeric organic semiconductor system; bipolar light emitting FETs, wherein HILs are used to regulate charge injection or in FETs used as electrodes ;
2) Hole extraction layer in OPV;
3) channel material in transistor;
4) channel materials in circuits including combinations of transistors, such as logic gates;
5) electrode material in transistor;
6) Gate layer in capacitor;
7) A chemical sensor, wherein modulation of the doping level is achieved by the relationship between the species to be sensed and the conducting polymer;
8) Electrode or electrolyte material in the battery.
　種々の光活性層をＯＰＶデバイスに使用することができる。光起電デバイスは、例えば、米国特許第５，４５４，８８０号；６，８１２，３９９号；及び６，９３３，４３６号に記載されるような、例えば、導電性ポリマーと混合されたフラーレン誘導体を含む光活性層により調製することができる。光活性層は、導電性ポリマーの混合物、導電性ポリマーと半導体ナノ粒子との混合物、及びフタロシアニン、フラーレン、及びポルフィリンのような低分子の二重層を含むことができる。 Various photoactive layers can be used in OPV devices. Photovoltaic devices are described, for example, in US Pat. Nos. 5,454,880; 6,812,399; and 6,933,436, for example, fullerene derivatives mixed with conductive polymers Can be prepared by the photoactive layer containing The photoactive layer can comprise a mixture of conducting polymers, a mixture of conducting polymers and semiconducting nanoparticles, and small molecule bilayers such as phthalocyanines, fullerenes, and porphyrins.
　一般的電極化合物及び基板、更には封入化合物を使用することができる。 Common electrode compounds and substrates and also encapsulation compounds can be used.
　１つの実施態様において、カソードは、Ａｕ、Ｃａ、Ａｌ、Ａｇ、又はこれらの組合せを含む。１つの実施態様において、アノードは、酸化インジウムスズを含む。１つの実施態様において、発光層は、少なくとも１種の有機化合物を含む。 In one embodiment, the cathode comprises Au, Ca, Al, Ag, or a combination thereof. In one embodiment, the anode comprises indium tin oxide. In one embodiment, the light emitting layer comprises at least one organic compound.
　例えば、中間層のような界面修飾層、及び光学スペーサー層を使用することができる。 For example, interface modification layers such as interlayers, and optical spacer layers can be used.
　電子輸送層を使用することができる。 An electron transport layer can be used.
　本開示はまた、本明細書に記載のデバイスの製造方法に関する。 The present disclosure also relates to methods of manufacturing the devices described herein.
　ある実施態様において、デバイスの製造方法は、以下を含む：基板を提供すること；例えば、酸化インジウムスズのような透明導電体を基板上に積層すること；本明細書に記載のインク組成物を提供すること；透明導電体上にインク組成物を積層することにより、正孔注入層又は正孔輸送層を形成すること；正孔注入層又は正孔輸送層（ＨＴＬ）上に活性層を積層すること；及び活性層上にカソードを積層すること。 In one embodiment, a method of manufacturing the device comprises: providing a substrate; for example, laminating a transparent conductor such as indium tin oxide on the substrate; an ink composition as described herein Providing: forming a hole injection layer or a hole transport layer by laminating an ink composition on a transparent conductor; laminating an active layer on a hole injection layer or a hole transport layer (HTL) And laminating the cathode on the active layer.
　本明細書に記載されるとおり、基板は、可撓性であっても剛性であっても、有機であっても無機であってもよい。適切な基板化合物は、例えば、ガラス、セラミック、金属、及びプラスチック薄膜を含む。 As described herein, the substrate may be flexible or rigid, organic or inorganic. Suitable substrate compounds include, for example, glass, ceramic, metal and plastic thin films.
　別の実施態様において、デバイスの製造方法は、本明細書に記載のインク組成物を、ＯＬＥＤ、光起電デバイス、ＥＳＤ、ＳＭＯＬＥＤ、ＰＬＥＤ、センサー、超コンデンサ、カチオン変換器、薬物放出デバイス、エレクトロクロミック素子、トランジスタ、電界効果トランジスタ、電極モディファイア、有機電界トランジスタ用の電極モディファイア、アクチュエータ、又は透明電極中の、ＨＩＬ又はＨＴＬ層の一部として適用することを含む。 In another embodiment, a method of manufacturing the device comprises: an ink composition as described herein, an OLED, a photovoltaic device, an ESD, a SMOLED, a PLED, a sensor, a supercapacitor, a cation converter, a drug delivery device, an electro Application as part of a HIL or HTL layer in a chromic element, a transistor, a field effect transistor, an electrode modifier, an electrode modifier for an organic field transistor, an actuator, or a transparent electrode.
　ＨＩＬ又はＨＴＬ層を形成するためのインク組成物の積層は、当該分野において公知の方法（例えば、回転注型、スピンコーティング、ディップ注型、ディップコーティング、スロットダイコーティング、インクジェット印刷、グラビアコーティング、ドクターブレード法、及び例えば、有機電子デバイスの作製のための当該分野において公知の任意の他の方法を含む）により実行することができる。 Lamination of the ink composition to form the HIL or HTL layer can be carried out by methods known in the art (eg, spin casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, doctoring Can be carried out by the blade method, and including, for example, any other method known in the art for the production of organic electronic devices.
　１つの実施態様において、ＨＩＬ層は、熱的にアニーリングされる。１つの実施態様において、ＨＩＬ層は、約２５℃～約３５０℃、典型的には１５０℃～約３２５℃の温度で熱的にアニーリングされる。１つの実施態様において、ＨＩＬ層は、約２５℃～約３５０℃、典型的には１５０℃～約３２５℃の温度で、約３～約４０分間、典型的には約１５～約３０分間熱的にアニーリングされる。 In one embodiment, the HIL layer is thermally annealed. In one embodiment, the HIL layer is thermally annealed at a temperature of about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C. In one embodiment, the HIL layer is heated at a temperature of about 25 ° C. to about 350 ° C., typically 150 ° C. to about 325 ° C., for about 3 to about 40 minutes, typically about 15 to about 30 minutes. Annealing.
　本開示により、約３８０～８００ｎｍの波長を有する光の、少なくとも約８５％、典型的には少なくとも約９０％の透過率（典型的には、基板を伴う）を示すことができる、ＨＩＬ又はＨＴＬを調製することができる。ある実施態様において、透過率は少なくとも約９０％である。 In accordance with the present disclosure, a HIL or HTL capable of exhibiting at least about 85%, and typically at least about 90% transmission of light having a wavelength of about 380-800 nm (typically with the substrate) Can be prepared. In one embodiment, the transmission is at least about 90%.
　１つの実施態様において、ＨＩＬ層は、約５ｎｍ～約５００ｎｍ、典型的には約５ｎｍ～約１５０ｎｍ、更に典型的には約５０ｎｍ～１２０ｎｍの厚さを有する。 In one embodiment, the HIL layer has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm.
　ある実施態様において、ＨＩＬ層は、少なくとも約９０％の透過率を示し、そして約５ｎｍ～約５００ｎｍ、典型的には約５ｎｍ～約１５０ｎｍ、更に典型的には約５０ｎｍ～１２０ｎｍの厚さを有する。ある実施態様において、ＨＩＬ層は、少なくとも約９０％の透過率（％Ｔ）を示し、そして約５０ｎｍ～１２０ｎｍの厚さを有する。 In certain embodiments, the HIL layer exhibits a transmission of at least about 90% and has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm. . In one embodiment, the HIL layer exhibits a transmission (% T) of at least about 90% and has a thickness of about 50 nm to 120 nm.
　本開示のインク、方法及びプロセス、薄膜、並びにデバイスは、以下の非限定例により更に説明される。 The inks, methods and processes, films, and devices of the present disclosure are further illustrated by the following non-limiting examples.
［１］オニウムボレート塩の合成
［合成例１］オニウムボレート塩（Ｐ－１）の合成
　下式で示されるＰ－１は、以下の方法で合成した。
Figure JPOXMLDOC01-appb-C000072
 [1] Synthesis of Onium Bolate Salt [Synthesis Example 1] Synthesis of Onium Bolate Salt (P-1) P-1 represented by the following formula was synthesized by the following method.
Figure JPOXMLDOC01-appb-C000072
　１０Ｌ四ツ口フラスコに、ジエチルエーテル６，０６８ｍＬ、下記式（Ｑ－１）で表される化合物１５１．７ｇ、ＫＣＮ９．４ｇを仕込み、３４～３６℃で３時間反応させた。反応後、常圧濃縮を行い、２６７．２ｇの褐色液体を得た。得られた褐色液体を、５５℃でエバポレーターにて濃縮後、３５℃で１６時間減圧乾燥し、１５７．７ｇの薄い茶色の固体である式（Ｑ－２）で表される中間体を得た。得られた中間体（Ｑ－２）は、ＬＤＩ－ＭＳにて同定した。
ＬＤＩ－ＭＳ ｍ／Ｚ　ｆｏｕｎｄ：１０５０．１２（［Ｍ］-ｃａｌｃｄ：
１０４９．９７）．
Figure JPOXMLDOC01-appb-C000073
 In a 10 L four-necked flask, 6,068 mL of diethyl ether, 151.7 g of a compound represented by the following formula (Q-1), and 9.4 g of KCN were charged, and reacted at 34 to 36 ° C. for 3 hours. After the reaction, atmospheric pressure concentration was performed to obtain 267.2 g of a brown liquid. The obtained brown liquid was concentrated by an evaporator at 55 ° C., and then dried under reduced pressure at 35 ° C. for 16 hours to obtain 157.7 g of a light brown solid intermediate represented by formula (Q-2) . The resulting intermediate (Q-2) was identified by LDI-MS.
LDI-MS m / Z found: 1050.12 ([M] - calcd:
1049.97).
Figure JPOXMLDOC01-appb-C000073
　３００ｍＬ三角フラスコに、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムトリフルオロメタンスルホナート１１．０４３ｇ、中間体（Ｑ－２）２２．０００ｇ、イオン交換水１１０ｍＬ、ジエチルエーテル１１０ｍＬを仕込み、２５℃で１６時間反応させた。反応後のフラスコ内容物を３００ｍＬ分液ロートに移し、水層を分離した。イオン交換水１００ｍＬでエーテル層を５回洗浄した。エーテル層を４０～４５℃でエバポレーターにて濃縮後、２０時間減圧乾燥し、２４．０００ｇの淡黄色の固体である目的物を得た。得られた目的物は、1Ｈ－ＮＭＲ及びＬＤＩ－ＭＳにて同定した。
1Ｈ－ＮＭＲ（３００ＭＨｚ、ＤＭＳＯ－ｄ６）：δ７．４０～７．８０（１９Ｈ，ｍ）
ＬＤＩ－ＭＳ ｍ／Ｚ　ｆｏｕｎｄ：３７１．０４（［Ｍ］+ｃａｌｃｄ：
３７１．０９）．
ＬＤＩ－ＭＳ ｍ／Ｚ　ｆｏｕｎｄ：１０５０．１１（［Ｍ］-ｃａｌｃｄ：
１０４９．９７）． In a 300 mL Erlenmeyer flask, 11.043 g of diphenyl [4- (phenylthio) phenyl] sulfonium trifluoromethanesulfonate, 22.000 g of intermediate (Q-2), 110 mL of ion exchanged water, and 110 mL of diethyl ether are charged, and it is kept at 25 ° C for 16 hours It was made to react. The contents of the flask after reaction were transferred to a 300 mL separatory funnel, and the aqueous layer was separated. The ether layer was washed five times with 100 mL of deionized water. The ether layer was concentrated by an evaporator at 40-45 ° C., and then dried under reduced pressure for 20 hours to obtain 24.000 g of the desired product as a pale yellow solid. The obtained target substance was identified by 1 H-NMR and LDI-MS.
1 H-NMR (300 MHz, DMSO-d6): δ 7.40 to 7.80 (19 H, m)
LDI-MS m / Z found: 371.04 ([M] + calcd:
371.09).
LDI-MS m / Z found: 1050.11 ([M] - calcd:
1049.97).
［合成例２］オニウムボレート塩（Ｐ－２）の合成
　下式で示されるＰ－２は、以下の方法で合成した。
Figure JPOXMLDOC01-appb-C000074
 Synthesis Example 2 Synthesis of Onium Bolate Salt (P-2) P-2 represented by the following formula was synthesized by the following method.
Figure JPOXMLDOC01-appb-C000074
　トリス（ペンタフルオロフェニル）ボラン（東京化成工業（株）製）３８．１ｇ、ペンタン１２００ｇを反応容器に仕込み、撹拌下、室温にてｎ－ブチルリチウムのヘキサン溶液（１．６Ｍ）３８．８ｇを滴下し、室温で３時間反応してスラリー状の反応液を得た。
　反応液をろ過して得られた結晶物をペンタンにてかけ洗いし、６０℃で減圧乾燥して中間体であるリチウム　ｎ－ブチルトリス（ペンタフルオロフェニル）ボレート３８．１ｇを得た（収率８９％）。 38.1 g of tris (pentafluorophenyl) borane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1200 g of pentane are charged in a reaction vessel, and 38.8 g of a hexane solution (1.6 M) of n-butyllithium is charged at room temperature under stirring. The reaction solution was dropped and reacted at room temperature for 3 hours to obtain a slurry-like reaction solution.
The reaction mixture was filtered and the crystals obtained were washed with pentane and dried under reduced pressure at 60 ° C. to obtain 38.1 g of lithium n-butyltris (pentafluorophenyl) borate as an intermediate (yield 89). %).
　続いて、（４－フェニルチオフェニル）ジフェニルスルホニウムヘキサフルオロホスファート（サンアプロ（株）製）２２．５ｇをジクロロメタン５３０ｇに溶解させた溶液に、上記で得られたボレート３０ｇをイオン交換水４００ｇに溶解させた水溶液を加え、撹拌下で１時間混合した。混合後、静置して水層を除き、ジクロロメタン溶液をイオン交換水４００ｇで５回洗浄した。水洗後のジクロロメタン溶液を減圧下、脱溶媒し、目的物である（４－フェニルチオフェニル）ジフェニルスルホニウム　ｎ－ブチルトリス（ペンタフルオロフェニル）ボレート塩の淡黄色固体４０ｇを得た（収率９７％）。得られた目的物は、1Ｈ－ＮＭＲ及び19Ｆ－ＮＭＲにて同定した。
1Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６）：δ　７．６～７．８（１２Ｈ，ｍ），７．４～７．５（５Ｈ，ｍ），７．３（２Ｈ，ｄ），１．０～１．２（４Ｈ，ｍ），０．６～０．８（５Ｈ，ｍ）ｐｐｍ．
19Ｆ－ＮＭＲ（ＤＭＳＯ－ｄ６）：δ　－１３２（６Ｆ，ｄ），－１５９．５（３Ｆ，ｔ），－１６３（６Ｆ，ｔ）ｐｐｍ． Subsequently, 30 g of the borate obtained above is dissolved in 400 g of ion-exchanged water in a solution of 22.5 g of (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate (manufactured by San Apro Co., Ltd.) dissolved in 530 g of dichloromethane The allowed aqueous solution was added and mixed under stirring for 1 hour. After mixing, the mixture was allowed to stand to remove the aqueous layer, and the dichloromethane solution was washed five times with 400 g of deionized water. The dichloromethane solution after water washing was desolvated under reduced pressure to obtain 40 g of a light yellow solid of the objective substance (4-phenylthiophenyl) diphenylsulfonium n-butyltris (pentafluorophenyl) borate salt (yield: 97%) . The obtained target substance was identified by 1 H-NMR and 19 F-NMR.
1 H-NMR (DMSO-d6): δ 7.6 to 7.8 (12 H, m), 7.4 to 7.5 (5 H, m), 7.3 (2 H, d), 1.0 to 1.2 (4 H, m), 0.6 to 0.8 (5 H, m) ppm.
19 F-NMR (DMSO-d6): δ -132 (6F, d), -159.5 (3F, t), -163 (6F, t) ppm.
［２］電荷輸送性物質の調整
［合成例３］スルホン化ポリ（３－ＭＥＥＴ）（以下、Ｓ－ポリ（３－ＭＥＥＴ）ともいう）アミン付加物の調製
　Ｓ－ポリ（３－ＭＥＥＴ）の水性分散液（水中０．５９８％固形物）５００ｇをトリエチルアミン（東京化成工業（株）製） ０．８５８ｇと混合することにより調製した。生じた混合物を回転蒸発により乾固し、そして次に、真空オーブンにて５０℃で一晩更に乾燥した。黒色の粉末３．８ｇとして生成物を単離した。
　電荷輸送性物質であるＳ－ポリ（３－ＭＥＥＴ）２．００ｇを２８％アンモニア水（純正化学（株）製）１００ｍＬに溶解させ、室温にて終夜撹拌させた。反応液は、アセトン１５００ｍＬにて再沈殿し、析出物をろ過にて回収した。得られた析出物は、再度、水２０ｍＬ及びトリエチルアミン（東京化成工業（株）製）７．５９ｇにて溶解させ、６０℃、１時間撹拌した。反応液を冷却後、イソプロピルアルコール１０００ｍＬ，及びアセトン５００ｍＬの混合溶媒にて再沈殿し、析出物をろ過にて回収した。得られた析出物は、０ｍｍＨｇ、５０℃にて１時間真空乾燥し、アンモニア水で処理したＳ－ポリ（３－ＭＥＥＴ）－Ａ　１．３０ｇを得た。 [2] Preparation of Charge-Transporting Substances [Synthesis Example 3] Preparation of Sulfonated Poly (3-MEET) (hereinafter also referred to as S-Poly (3-MEET)) Amine Adducts S-Poly (3-MEET) The dispersion was prepared by mixing 500 g of an aqueous dispersion (0.598% solids in water) with 0.858 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.). The resulting mixture was rotary evaporated to dryness and then further dried in a vacuum oven at 50 ° C. overnight. The product was isolated as 3.8 g of a black powder.
In 100 mL of 28% aqueous ammonia (manufactured by Junsei Chemical Co., Ltd.) was dissolved 2.00 g of a charge transporting substance S-poly (3-MEET), and the mixture was stirred overnight at room temperature. The reaction solution was reprecipitated with 1500 mL of acetone, and the precipitate was collected by filtration. The obtained precipitate was again dissolved in 20 mL of water and 7.59 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 60 ° C. for 1 hour. After cooling the reaction solution, it was reprecipitated with a mixed solvent of 1000 mL of isopropyl alcohol and 500 mL of acetone, and the precipitate was collected by filtration. The obtained precipitate was vacuum dried at 0 mmHg and 50 ° C. for 1 hour to obtain 1.30 g of S-poly (3-MEET) -A treated with aqueous ammonia.
［３］インク組成物の調製
［実施例１－１］
　合成例３にて得た電荷輸送性物質であるＳ－ポリ（３－ＭＥＥＴ）－Ａ　０．１２５ｇを、エチレングリコール（関東化学（株）製）２．２８ｇ、ジエチレングリコール（関東化学（株）製）２．２８ｇ、及びｎ－ブチルアミン（東京化成工業（株）製）０．２０ｇに溶解させた。溶液の調整はホットスターラーを用い、８０℃で１時間撹拌させた。次いで、トリエチレングリコールジメチルエーテル（東京化成工業（株）製）１．２５ｇを加え、ホットスターラーを用い、４００rpm、８０℃で１時間撹拌させた。最後に、Ｐ－１を０．１２５ｇ加え、ホットスターラーを用い、４００rpm、４０℃で１０分間撹拌させ、得られた溶液を、孔径０．２μｍのＰＰシリンジフィルターでろ過して４ｗｔ％のインク組成物を得た。 [3] Preparation of Ink Composition [Example 1-1]
0.125 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3 is 2.28 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt | dissolve in 2.28 g and n-butylamine (made by Tokyo Chemical Industry Co., Ltd. product) 0.20 g. The solution was adjusted using a hot stirrer at 80 ° C. for 1 hour. Next, 1.25 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 400 rpm and 80 ° C. for 1 hour using a hot stirrer. Finally, 0.125 g of P-1 was added, the solution was stirred at 400 rpm and 40 ° C. for 10 minutes using a hot stirrer, and the resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain 4 wt% ink composition I got a thing.
［実施例１－２］
　合成例３にて得た電荷輸送性物質であるＳ－ポリ（３－ＭＥＥＴ）－Ａ　０．０２５ｇを、エチレングリコール（関東化学（株）製）２．３５ｇ、ジエチレングリコール（関東化学（株）製）２．３５ｇ、及びｎ－ブチルアミン（東京化成工業（株）製）０．０４ｇに溶解させた。溶液の調整はホットスターラーを用い、８０℃で１時間撹拌させた。次いで、トリエチレングリコールジメチルエーテル（東京化成工業（株）製）１．２５ｇを加え、ホットスターラーを用い、４００rpm、８０℃で１時間撹拌させた。放冷後、Ｐ－１を０．０１３ｇ、（Ｆ）成分として粉末状の４－ヒドロキシスチレン／スチレン＝７０／３０の共重合体（マルカリンカーＣＳＴ７０３０（丸善石油化学（株）製））を０．２１３ｇ加え、ホットスターラーを用い、４００rpm、４０℃で３０分間撹拌させた。得られた溶液を、孔径０．２μｍのＰＰシリンジフィルターでろ過して４ｗｔ％のインク組成物を得た。 Embodiment 1-2
0.025 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3, 2.35 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt | dissolve in 2.35g and n-butylamine (Tokyo Chemical Industry Co., Ltd. product made) 0.04g. The solution was adjusted using a hot stirrer at 80 ° C. for 1 hour. Next, 1.25 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 400 rpm and 80 ° C. for 1 hour using a hot stirrer. After leaving to cool, 0.013 g of P-1 and 0 as a component (F), a powdery 4-hydroxystyrene / styrene = 70/30 copolymer (Marcalinker CST7030 (manufactured by Maruzen Petrochemical Co., Ltd.)) 0 After adding .213 g, the mixture was stirred at 400 rpm and 40 ° C. for 30 minutes using a hot stirrer. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a 4 wt% ink composition.
［実施例１－３］
　合成例３にて得た電荷輸送性物質であるＳ－ポリ（３－ＭＥＥＴ）－Ａ　０．０２５ｇを、エチレングリコール（関東化学（株）製）１．５３ｇ、ジエチレングリコール（関東化学（株）製）２．３５ｇ、及びｎ－ブチルアミン（東京化成工業（株）製）０．０４ｇに溶解させた。溶液の調整はホットスターラーを用い、８０℃で１時間撹拌させた。次いで、トリエチレングリコールジメチルエーテル（東京化成工業（株）製）１．２５ｇを加え、ホットスターラーを用い、４００rpm、８０℃で１時間撹拌させた。放冷後、Ｐ－１を０．０１３ｇ、オルガノシリカゾル（ＥＧ－ＳＴ（日産化学工業（株）製）、平均粒子径：１２ｎｍ、固形分濃度：２０～２１ｗｔ％、分散媒：エチレングリコール）を１．０４ｇ加え、ホットスターラーを用い、４００rpm、４０℃で３０分間撹拌させた。得られた溶液を、孔径０．２μｍのＰＰシリンジフィルターでろ過して４ｗｔ％のインク組成物を得た。 Embodiment 1-3
0.025 g of the charge transport material S-poly (3-MEET) -A obtained in Synthesis Example 3, 1.53 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt | dissolve in 2.35g and n-butylamine (Tokyo Chemical Industry Co., Ltd. product made) 0.04g. The solution was adjusted using a hot stirrer at 80 ° C. for 1 hour. Next, 1.25 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 400 rpm and 80 ° C. for 1 hour using a hot stirrer. After standing to cool, 0.013 g of P-1, organosilica sol (EG-ST (manufactured by Nissan Chemical Industries, Ltd.), average particle size: 12 nm, solid content concentration: 20 to 21 wt%, dispersion medium: ethylene glycol) After adding 1.04 g, the mixture was stirred at 400 rpm and 40 ° C. for 30 minutes using a hot stirrer. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a 4 wt% ink composition.
［実施例１－４］
　合成例３にて得た電荷輸送性物質であるＳ－ポリ（３－ＭＥＥＴ）－Ａ　０．０２５ｇを、エチレングリコール（関東化学（株）製）２．３５ｇ、ジエチレングリコール（関東化学（株）製）２．３５ｇ、及びｎ－ブチルアミン（東京化成工業（株）製）０．０４ｇに溶解させた。溶液の調整はホットスターラーを用い、８０℃で１時間撹拌させた。次いで、トリエチレングリコールジメチルエーテル（東京化成工業（株）製）１．２５ｇを加え、ホットスターラーを用い、４００rpm、８０℃で１時間撹拌させた。放冷後、Ｐ－２を０．０１３ｇ、（Ｆ）成分として粉末状の４－ヒドロキシスチレン／スチレン＝７０／３０の共重合体（マルカリンカーＣＳＴ７０３０（丸善石油化学（株）製））を０．２１３ｇ加え、ホットスターラーを用い、４００rpm、４０℃で３０分間撹拌させた。得られた溶液を、孔径０．２μｍのＰＰシリンジフィルターでろ過して４ｗｔ％のインク組成物を得た。 Embodiment 1-4
0.025 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3, 2.35 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 2.) It was made to melt | dissolve in 2.35g and n-butylamine (Tokyo Chemical Industry Co., Ltd. product made) 0.04g. The solution was adjusted using a hot stirrer at 80 ° C. for 1 hour. Next, 1.25 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 400 rpm and 80 ° C. for 1 hour using a hot stirrer. After leaving to cool, 0.013 g of P-2 and 0- 30/40 powdered powdery 4-hydroxystyrene / styrene copolymer (Marcalinker CST 7030 (manufactured by Maruzen Petrochemical Co., Ltd.)) as component (F) were added. After adding .213 g, the mixture was stirred at 400 rpm and 40 ° C. for 30 minutes using a hot stirrer. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a 4 wt% ink composition.
［実施例１－５］
　合成例３にて得た電荷輸送性物質であるＳ－ポリ（３－ＭＥＥＴ）－Ａ　０．０２５ｇを、エチレングリコール（関東化学（株）製）４．７０ｇ、ジエチレングリコール（関東化学（株）製）４．７０ｇ、及びｎ－ブチルアミン（東京化成工業（株）製）０．０４ｇに溶解させた。溶液の調整はホットスターラーを用い、８０℃で１時間撹拌させた。次いで、トリエチレングリコールジメチルエーテル（東京化成工業（株）製）２．５０ｇを加え、ホットスターラーを用い、４００rpm、８０℃で１時間撹拌させた。放冷後、Ｐ－１を０．０１３ｇ、（Ｆ）成分として粉末状の４－ヒドロキシスチレン／スチレン＝７０／３０の共重合体（マルカリンカーＣＳＴ７０３０（丸善石油化学（株）製））を０．２１３ｇ加え、ホットスターラーを用い、４００rpm、４０℃で３０分間撹拌させた。得られた溶液を、孔径０．２μｍのＰＰシリンジフィルターでろ過して２ｗｔ％のインク組成物を得た。 [Example 1-5]
0.025 g of the charge transporting substance S-poly (3-MEET) -A obtained in Synthesis Example 3, 4.70 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (manufactured by Kanto Chemical Co., Ltd.) 4.) It was made to melt | dissolve in 4.70 g and n-butylamine (made by Tokyo Chemical Industry Co., Ltd. product) 0.04g. The solution was adjusted using a hot stirrer at 80 ° C. for 1 hour. Next, 2.50 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 400 rpm and 80 ° C. for 1 hour using a hot stirrer. After leaving to cool, 0.013 g of P-1 and 0 as a component (F), a powdery 4-hydroxystyrene / styrene = 70/30 copolymer (Marcalinker CST7030 (manufactured by Maruzen Petrochemical Co., Ltd.)) 0 After adding .213 g, the mixture was stirred at 400 rpm and 40 ° C. for 30 minutes using a hot stirrer. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a 2 wt% ink composition.
［比較例１］
　初めに、ＡＱＵＩＶＩＯＮ　Ｄ６６－２０ＢＳ水溶液（Ｓｏｌｖａｙ社製、テトラフルオロエチレン／ペルフルオロ－２－（ビニルオキシ）エタン－１－スルホン酸コポリマー、６７６ｇポリマー／酸１モルの当量）の溶媒をエバボレーターにて留去し、得られた残留物を減圧乾燥機にて８０℃で１時間減圧乾燥させ、Ｄ６６－２０ＢＳの粉末を得た。得られた粉末を用いて、Ｄ６６－２０ＢＳの１０ｗｔ％エチレングリコール溶液を作製した。溶液の調製は、ホットスターラーを用い、４００rpm、９０℃で１時間撹拌することにより行った。
　次に、別の容器を用意し、合成例３にて得たＳ－ポリ（３－ＭＥＥＴ）－Ａ ０．０２０ｇを、エチレングリコール（関東化学（株）製）１．２０ｇ、ジエチレングリコール（関東化学（株）製）１．９５ｇ、トリエチレングリコールジメチルエーテル（東京化成工業（株）製）４．８８ｇ、２－（ベンジルオキシ）エタノール（関東化学（株）製）０．９８ｇ及びｎ－ブチルアミン（東京化成工業（株）製）０．０３２ｇに溶解させた。溶液の調製は、ホットスターラーを用い、８０℃で１時間撹拌することにより行った。次いで、得られた溶液に、Ｄ６６－２０ＢＳの１０ｗｔ％エチレングリコール溶液を０．１０ｇ加え、得られた混合物を、ホットスターラーを用いて４００rpm、８０℃で１時間撹拌した。最後に、オルガノシリカゾル（ＥＧ－ＳＴ（日産化学工業（株）製）、平均粒子径：１２ｎｍ、固形分濃度：２０～２１ｗｔ％、分散媒：エチレングリコール）を０．８３ｇ加え、得られた混合物を、ホットスターラーを用いて４００rpm、８０℃で１０分間撹拌し、得られた分散液を孔径０．２μｍのＰＰシリンジフィルターでろ過して２ｗｔ％のインク組成物を得た。 Comparative Example 1
First, the solvent of the aqueous solution of AQUIVION D66-20BS (Solvay, tetrafluoroethylene / perfluoro-2- (vinyloxy) ethane-1-sulfonic acid copolymer, equivalent of 676 g polymer / 1 mole of acid) is distilled off with an evaporator. The obtained residue was dried under reduced pressure at 80 ° C. for 1 hour in a reduced pressure drier to obtain a powder of D66-20BS. The obtained powder was used to prepare a 10 wt% ethylene glycol solution of D66-20BS. Preparation of the solution was performed by stirring at 400 rpm and 90 ° C. for 1 hour using a hot stirrer.
Next, another container is prepared, and 0.020 g of S-poly (3-MEET) -A obtained in Synthesis Example 3 is 1.20 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 1.95 g (manufactured by KK), 4.88 g of triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.98 g of 2- (benzyloxy) ethanol (manufactured by Kanto Chemical Co., Ltd.) and n-butylamine (Tokyo) It was made to melt | dissolve in 0.032 g of chemical conversion industry (made). The solution was prepared by stirring at 80 ° C. for 1 hour using a hot stirrer. Next, 0.10 g of a 10 wt% ethylene glycol solution of D66-20BS was added to the obtained solution, and the obtained mixture was stirred at 400 rpm and 80 ° C. for 1 hour using a hot stirrer. Finally, 0.83 g of organosilica sol (EG-ST (manufactured by Nissan Chemical Industries, Ltd.), average particle size: 12 nm, solid content concentration: 20 to 21 wt%, dispersion medium: ethylene glycol) was added, and the obtained mixture The mixture was stirred at 400 rpm and 80 ° C. for 10 minutes using a hot stirrer, and the obtained dispersion was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a 2 wt% ink composition.
［４］有機ＥＬ素子の作製及び特性評価
［実施例２－１～２－４］
　実施例１－１～１－４で得られたインク組成物を用いて、以下の手順により実施例２－１～２－４の有機ＥＬ素子を作製した。
　実施例１－１から１－４で得られた組成物を、それぞれ、スピンコーターを用いてＩＴＯ基板に塗布した後、真空乾燥機にて１５分間乾燥した。次に、乾燥させた各ＩＴＯ基板をグローブボックス内に挿入し、窒素下、２３０℃で３０分間焼成し、ＩＴＯ基板上に厚さ５０ｎｍの正孔注入層を形成した。ＩＴＯ基板としては、酸化インジウムスズ（ＩＴＯ）が表面上に膜厚１５０ｎｍでパターニングされた２５ｍｍ×２５ｍｍ×０．７ｔのガラス基板を用い、使用前にＯ2プラズマ洗浄装置（１５０Ｗ、３０秒間）によって表面上の不純物を除去した。 [4] Preparation of organic EL element and characteristic evaluation [Examples 2-1 to 2-4]
Using the ink compositions obtained in Examples 1-1 to 1-4, the organic EL elements of Examples 2-1 to 2-4 were produced according to the following procedure.
The compositions obtained in Examples 1-1 to 1-4 were each applied to an ITO substrate using a spin coater, and then dried for 15 minutes in a vacuum dryer. Next, each dried ITO substrate was inserted into a glove box, and baked under nitrogen at 230 ° C. for 30 minutes to form a 50 nm-thick hole injection layer on the ITO substrate. As an ITO substrate, a glass substrate of 25 mm × 25 mm × 0.7 t in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and by O 2 plasma cleaning device (150 W, 30 seconds) before use The impurities on the surface were removed.
　次いで、正孔注入層を形成したＩＴＯ基板に対し、蒸着装置（真空度１．０×１０-5Ｐａ）を用いて、正孔輸送層としてα－ＮＰＤ（Ｎ，Ｎ'－ジ（１－ナフチル）－Ｎ，Ｎ'－ジフェニルベンジジン）を０．２ｎｍ／秒にて３０ｎｍ成膜した。次に、正孔輸送層として関東化学（株）製の電子ブロック材料ＨＴＥＢ－０１を１０ｎｍ成膜した。次いで、発光層として新日鉄住金化学（株）製の発光層ホスト材料ＮＳ６０と発光層ドーパント材料Ｉｒ（ＰＰｙ）3を共蒸着した。共蒸着はＩｒ（ＰＰｙ）3の濃度が６％になるように蒸着レートをコントロールし、４０ｎｍ積層させた。次いで、電子輸送層としてＡｌｑ3、電子注入層としてフッ化リチウム及び陰極層としてアルミニウムの薄膜を順次積層して有機ＥＬ素子を得た。この際、蒸着レートは、Ａｌｑ3及びアルミニウムについては０．２ｎｍ／秒、フッ化リチウムについては０．０２ｎｍ／秒の条件でそれぞれ行い、膜厚は、それぞれ２０ｎｍ、０．５ｎｍ及び８０ｎｍとした。
　なお、空気中の酸素、水等の影響による特性劣化を防止するため、有機ＥＬ素子は封止基板により封止した後、その特性を評価した。封止は、以下の手順で行った。酸素濃度２ｐｐｍ以下、露点－７６℃以下の窒素雰囲気中で、有機ＥＬ素子を封止基板の間に収め、封止基板を接着剤（（株）ＭＯＲＥＳＣＯ製、モレスコモイスチャーカット　ＷＢ９０ＵＳ（Ｐ））により貼り合わせた。この際、捕水剤（ダイニック（株）製，ＨＤ－０７１０１０Ｗ－４０）を有機ＥＬ素子と共に封止基板内に収めた。貼り合わせた封止基板に対し、ＵＶ光を照射（波長：３６５ｎｍ、照射量：６，０００ｍＪ／ｃｍ2）した後、８０℃で１時間、アニーリング処理して接着剤を硬化させた。 Next, for the ITO substrate on which the hole injection layer is formed, α-NPD (N, N′-di (1-) is used as a hole transport layer using a vapor deposition apparatus (vacuum degree 1.0 × 10 −5 Pa). Naphthyl) -N, N'-diphenylbenzidine) was deposited to a thickness of 30 nm at 0.2 nm / sec. Next, 10 nm of electron block material HTEB-01 manufactured by Kanto Chemical Co., Ltd. was formed as a hole transport layer. Next, a light emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and a light emitting layer dopant material Ir (PPy) 3 were co-deposited as a light emitting layer. In the co-evaporation, the deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and 40 nm was laminated. Then, thin films of Alq 3 as an electron transport layer, lithium fluoride as an electron injection layer, and aluminum as a cathode layer were sequentially laminated to obtain an organic EL element. At this time, the deposition rate was 0.2 nm / sec for Alq 3 and aluminum and 0.02 nm / sec for lithium fluoride, and the film thickness was 20 nm, 0.5 nm and 80 nm, respectively.
In addition, in order to prevent the characteristic degradation by the influence of oxygen in the air, water, etc., after sealing the organic EL element with a sealing substrate, the characteristic was evaluated. Sealing was performed in the following procedure. The organic EL element is housed between the sealing substrate in a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76 ° C. or less, and the sealing substrate is an adhesive (Moresco Co., Ltd., Mores moisture cut WB90US (P)) Bonded together. At this time, a water-capturing agent (manufactured by Dynik Co., Ltd., HD-071010W-40) was placed in the sealing substrate together with the organic EL element. The sealing substrate thus bonded was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
　実施例２－１～２－４の素子について、輝度１００００ｃｄ／ｍ2で駆動した場合における駆動電圧、電流密度及び発光効率（電流効率及び外部量子効率）、並びに輝度の半減期（初期輝度１００００ｃｄ／ｍ2が半分に達するのに要する時間）を測定した。結果を表１に示す。 The driving voltage, current density, and luminous efficiency (current efficiency and external quantum efficiency) when driven at a luminance of 10000 cd / m 2 and the half life of the luminance (initial luminance 10000 cd / m) of the devices of Examples 2-1 to 2-4. The time taken for the m 2 to reach half was measured. The results are shown in Table 1.
　なお、輝度、駆動電圧、電流密度、電流効率及び外部量子効率は、（株）イーエッチシー製　多チャンネルＩＶＬ測定装置により測定した。輝度半減期は、（株）イーエッチシー製　有機ＥＬ輝度寿命評価システムＰＥＬ－１０５Ｓにより測定した。 The luminance, driving voltage, current density, current efficiency, and external quantum efficiency were measured with a multi-channel IVL measuring device manufactured by E-Hetchsee. The luminance half life was measured by an organic EL luminance life evaluation system PEL-105S manufactured by E-HC.
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000076
　実施例２－１～２－４に示すように、（Ａ）式（Ｉ）で表される繰り返し単位を含むポリチオフェン、（Ｂ）式（ａ１）又は（ａ２）で表されるアニオンと対カチオンとからなるオニウムボレート塩、及び有機溶媒を含む液体担体を含むインク組成物は、ウェットプロセスに適用可能であり、該組成物から形成される正孔注入層は良好に有機ＥＬ素子として駆動した。 As shown in Examples 2-1 to 2-4, (A) a polythiophene containing a repeating unit represented by the formula (I), (B) an anion represented by the formula (a1) or (a2) and a counter cation An ink composition comprising a liquid carrier containing an onium borate salt comprising the compound and an organic solvent is applicable to a wet process, and a hole injection layer formed from the composition is well driven as an organic EL element.
　実施例２－１と２－２の比較より、インク組成物が更に（Ｆ）マトリックス化合物を含有すると、作製された有機ＥＬ素子の電流効率、外部量子効率及び輝度半減期が向上し、好ましい。実施例２－１と２－３の比較より、インク組成物が更に（Ｅ）金属酸化物ナノ粒子を含有すると、作製された有機ＥＬ素子の電流効率、外部量子効率及び輝度半減期が向上し、好ましい。 From the comparison of Examples 2-1 and 2-2, when the ink composition further contains (F) a matrix compound, the current efficiency, the external quantum efficiency and the luminance half life of the produced organic EL device are improved, which is preferable. From the comparison of Examples 2-1 and 2-3, when the ink composition further contains (E) metal oxide nanoparticles, the current efficiency, the external quantum efficiency and the luminance half life of the manufactured organic EL device are improved. ,preferable.
［５］ポジ型感光性樹脂組成物の調製
　以下の合成例で用いる略号の意味は、次の通りである。
ＭＭＡ：メチルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＨＰＭＡ：４－ヒドロキシフェニルメタクリレート
ＨＰＭＡ－ＱＤ：４－ヒドロキシフェニルメタクリレート１ｍｏｌと、１，２－ナフトキノン－２－ジアジド－５－スルホニルクロリド１．１ｍｏｌの縮合反応によって合成される化合物
ＣＨＭＩ：Ｎ－シクロヘキシルマレイミド
ＰＦＨＭＡ：２－（パーフルオロヘキシル）エチルメタクリレート
ＭＡＡ：メタクリル酸
ＡＩＢＮ：α、α’－アゾビスイソブチロニトリル
ＱＤ１：α、α、α’－トリス（４－ヒドロキシフェニル）－１－エチル－４－イソプロピルベンゼン１ｍｏｌと、１，２－ナフトキノン－２－ジアジド－５－スルホニルクロリド１．５ｍｏｌの縮合反応によって合成される化合物
ＧＴ－４０１：ブタンテトラカルボン酸テトラ（３，４－エポキシシクロヘキシルメチル）修飾ε－カプロラクトン（商品名：エポリードＧＴ－４０１（株式会社ダイセル製））
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＣＨＮ：シクロヘキサノン [5] Preparation of Positive-Type Photosensitive Resin Composition The meanings of the abbreviations used in the following synthesis examples are as follows.
MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate HPMA-QD: condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Compound CHMI synthesized by: N-cyclohexylmaleimide PFHMA: 2- (perfluorohexyl) ethyl methacrylate MAA: methacrylic acid AIBN: α, α'-azobisisobutyronitrile QD1: α, α, α'-tris ( Compound GT-401 synthesized by condensation reaction of 1 mol of 4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene with 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride: Tan tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε- caprolactone (trade name: Epolead GT-401 (manufactured by KK Daicel))
PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate CHN: cyclohexanone
［数平均分子量及び重量平均分子量の測定］
　以下の合成例に従い得られた共重合体の数平均分子量及び重量平均分子量を、東ソー（株）製ＧＰＣ装置（ＳｈｏｄｅｘカラムＫＤ８００及びＴＯＳＯＨカラムＴＳＫ－ＧＥＬ）を用い、溶出溶媒Ｎ，Ｎ’－ジメチルホルムアミド（添加剤として、臭化リチウム－水和物（ＬｉＢｒ・Ｈ２Ｏ）を１０ｍｍｏｌ／Ｌ（リットル）混合）を流量１ｍｌ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表される。 [Measurement of Number Average Molecular Weight and Weight Average Molecular Weight]
The number average molecular weight and weight average molecular weight of the copolymer obtained according to the following synthesis example were determined using a GPC apparatus (Shodex column KD 800 and TOSOH column TSK-GEL) manufactured by Tosoh Corp. Elution condition by flowing formamide (10 mmol / L (liter) mixture of lithium bromide-hydrate (LiBr · H 2 O) as an additive) at a flow rate of 1 ml / min into the column (column temperature 40 ° C.) It measured by. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
＜合成例４＞
　ＭＭＡ １０．０ｇ、ＨＥＭＡ １２．５ｇ、ＣＨＭＩ ２０．０ｇ、ＨＰＭＡ ２．５０ｇ、ＭＡＡ ５．００ｇ及びＡＩＢＮ ３．２０ｇをＰＧＭＥ ７９．８ｇに溶解し、６０℃乃至１００℃にて２０時間反応させることにより、アクリル重合体溶液（固形分濃度４０ｗｔ％）を得た（Ｐ３）。得られたアクリル重合体Ｐ３のＭｎは３，７００、Ｍｗは６，１００であった。 Synthesis Example 4
Dissolve 10.0 g of MMA, 12.5 g of HEMA, 20.0 g of CHMI, 2.50 g of HPMA, 5.00 g of MAA and 3.20 g of AIBN in 79.8 g of PGME and react at 60 ° C. to 100 ° C. for 20 hours Thus, an acrylic polymer solution (solid content concentration 40 wt%) was obtained (P3). Mn of the obtained acrylic polymer P3 was 3,700, and Mw was 6,100.
＜合成例５＞
　ＨＰＭＡ－ＱＤ ２．５０ｇ、ＰＦＨＭＡ ７．８４ｇ、ＭＡＡ ０．７０ｇ、ＣＨＭＩ １．４６ｇ及びＡＩＢＮ ０．３３ｇをＣＨＮ ５１．３ｇに溶解し、１１０℃にて２０時間撹拌して反応させることにより、アクリル重合体溶液（固形分濃度２０ｗｔ％）を得た（Ｐ４）。得られたアクリル重合体Ｐ４のＭｎは４，３００、Ｍｗは６，３００であった。 Synthesis Example 5
Acrylic by dissolving HPA-QD 2.50 g, PFHMA 7.84 g, MAA 0.70 g, CHMI 1.46 g and AIBN 0.33 g in 51.3 g of CHN and agitating at 110 ° C. for 20 hours A polymer solution (solid content concentration 20 wt%) was obtained (P4). Mn of the obtained acrylic polymer P4 was 4,300, and Mw was 6,300.
　合成例４で得られたＰ３ ５．０４ｇ、合成例５で得られたＰ４ ０．０５ｇ、ＱＤ１ ０．４０ｇ、ＧＴ－４０１ ０．０９ｇ及びＰＧＭＥＡ ６．４２ｇを混合し、室温で３時間撹拌して均一な溶液とすることにより、ポジ型感光性樹脂組成物を調製した。 5.04 g of P3 obtained in Synthesis Example 4, 0.05 g of P4 obtained in Synthesis Example 5, 0.40 g of QD1, 0.09 g of GT-401 and 6.42 g of PGMEA are mixed and stirred at room temperature for 3 hours. A positive photosensitive resin composition was prepared by preparing a homogeneous solution.
［６］バンク付基板の作製
　（株）テクノビジョン製ＵＶ－３１２を用いて１０分間オゾン洗浄したＩＴＯ－ガラス基板上に、スピンコーターを用いて、前記工程［５］にて得られたポジ型感光性樹脂組成物を塗布した後、基板をホットプレート上でのプリベーク（温度１００℃で１２０秒間加熱）に付して、膜厚１．２μｍの薄膜を形成した。この薄膜に、長辺２００μｍ、短辺１００μｍの長方形が多数描かれたパターンのマスクを介して、キヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより、紫外線（３６５ｎｍにおける光強度：５．５ｍＷ／ｃｍ２）を一定時間照射した。その後、薄膜を２．３８％ＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液に２０秒間浸漬して現像を行った後、超純水による薄膜の流水洗浄を２０秒間行った。次いで、この長方形パターンが形成された薄膜をポストベーク（温度２３０℃で３０分間加熱）に付して硬化させ、バンク付基板を作製した。 [6] Preparation of Banked Substrate The positive type obtained in the above step [5] using a spin coater on an ITO-glass substrate that has been ozone-cleaned for 10 minutes using UV-312 manufactured by Technovision, Inc. After the photosensitive resin composition was applied, the substrate was subjected to prebaking (heating at a temperature of 100 ° C. for 120 seconds) on a hot plate to form a thin film having a thickness of 1.2 μm. Ultraviolet light (light intensity at 365 nm: 5.5 mW / cm) was obtained by using a UV-ray irradiator PLA-600FA manufactured by Canon Inc. through a mask of a pattern in which a large number of rectangles with long sides of 200 μm and short sides of 100 μm were drawn on this thin film. 2 ) was irradiated for a fixed time. Thereafter, the thin film was developed by immersing the thin film in a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) for 20 seconds, and then the thin film was washed with running ultrapure water for 20 seconds. Then, the thin film on which the rectangular pattern was formed was subjected to post-baking (heating at a temperature of 230 ° C. for 30 minutes) to be cured, thereby producing a banked substrate.
［７］電荷輸送性薄膜の断面形状の評価
［実施例３］及び［比較例２］
　前記工程［６］にて得られたバンク付基板上の長方形の開口部（膜形成領域）に、クラスターテクノロジー（株）製　Ｉｎｋｊｅｔ　Ｄｅｓｉｇｎｅｒを用いて、実施例１－５及び比較例１で得られたインク組成物をそれぞれ吐出し、得られた塗膜を、１０Ｐａ以下の減圧度（真空度）で１５分減圧乾燥し、その後ホットプレートにて２３０℃で３０分乾燥させて、実施例３及び比較例２の電荷輸送性薄膜を形成した。
　実施例３及び比較例２の電荷輸送性薄膜の断面の形状を、微細形状測定機ＥＴ４０００Ａ（（株）小坂研究所製）にて測定した。得られた結果を、図１に示す。 [7] Evaluation of cross-sectional shape of charge transporting thin film [Example 3] and [Comparative Example 2]
It is obtained in Example 1-5 and Comparative Example 1 using Inkjet Designer manufactured by Cluster Technology Inc. in the rectangular opening (film formation region) on the banked substrate obtained in the step [6]. The resulting ink composition is discharged, and the resulting coated film is dried under reduced pressure at a reduced pressure (vacuum degree) of 10 Pa or less for 15 minutes, and then dried on a hot plate at 230 ° C. for 30 minutes. The charge transporting thin film of Comparative Example 2 was formed.
The shape of the cross section of the charge transporting thin film of Example 3 and Comparative Example 2 was measured with a fine shape measuring machine ET4000A (manufactured by Kosaka Laboratory). The obtained result is shown in FIG.
　実施例３と比較例２を比較すると、実施例３の電荷輸送性薄膜の断面の形状は、比較例２の薄膜の断面のそれと比較して、バンク近傍での膜の這い上がり（膜厚の増加）が明らかに少ない。
　以上の結果から、（Ａ）式（Ｉ）で表される繰り返し単位を含むポリチオフェン、（Ｂ）式（ａ１）、（ａ２）又は（ａ５）で表されるアニオンと対カチオンとからなるオニウムボレート塩、（Ｃ）有機溶媒を含む液体担体、及び（Ｆ）マトリックス化合物を含むインク組成物を用いることにより、電荷輸送性薄膜形成時のパイルアップの抑制が可能となることが確認された。このことより、本発明のインク組成物を用いて得られる有機ＥＬ素子において、パイルアップに伴う開口部の減少や、発光層の不均一な厚みに伴う発光ムラ等がなく、素子特性が大幅に改善されることが期待される。 Comparison of Example 3 and Comparative Example 2 shows that the cross-sectional shape of the charge transportable thin film of Example 3 is higher than that of the cross section of the thin film of Comparative Example 2 in that the film creeps up near the bank (film thickness Clearly less).
From the above results, (A) a polythiophene containing a repeating unit represented by formula (I), (B) an onium borate comprising an anion represented by formula (a1), (a2) or (a5) and a counter cation It was confirmed that pileup at the time of charge transport thin film formation can be suppressed by using the ink composition containing a salt, (C) a liquid carrier containing an organic solvent, and (F) a matrix compound. From this, in the organic EL device obtained by using the ink composition of the present invention, there is no decrease in the opening due to pileup, no light emission unevenness due to the uneven thickness of the light emitting layer, and the like. It is expected to be improved.
　本発明のインク組成物は、有機エレクトロルミネッセンス素子の電荷輸送性薄膜用材料として使用することができる。 The ink composition of the present invention can be used as a charge transporting thin film material of an organic electroluminescent device.

Claims (27)

  1. 　インク組成物であって、
    　（Ａ）式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
    ［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、－ＳＯ３Ｍ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－Ｚ－Ｏ－を形成する
    （式中、
    　Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、
    　Ｚは、場合によりハロゲン又はＹで置換されているヒドロカルビレン基（ここで、Ｙは、炭素数１～１０の直鎖又は分岐鎖のアルキル基又はアルコキシアルキル基であり、該アルキル基又はアルコキシアルキル基は、任意の位置がスルホン酸基で置換されていてもよい）であり、
    　ｐは、１以上の整数であり、そして
    　Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）］
    で表される繰り返し単位を含むポリチオフェン；
    　（Ｂ）オニウムボレート塩であって、式（ａ１）：
    Figure JPOXMLDOC01-appb-C000002
    で表されるアニオン、及び式（ａ２）：
    Figure JPOXMLDOC01-appb-C000003
    で表される１価又は２価のアニオン
    ［式中、
    　Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、
    　Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基であり、
    　Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－である］
    からなる群より選択される少なくとも１種のアニオンと対カチオンとからなるオニウムボレート塩（ただし、電気的中性な塩である）；及び
    　（Ｃ）有機溶媒を含む液体担体
    を含む組成物。     An ink composition,
    (A) Formula (I):
    Figure JPOXMLDOC01-appb-C000001
    [Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or R 1 and R 2 together form —OZ—O— (wherein:
    M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium,
    Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl group or alkoxy The alkyl group is optionally substituted with a sulfonic acid group),
    p is an integer of 1 or more, and R e is H, alkyl, fluoroalkyl or aryl)]
    A polythiophene containing a repeating unit represented by
    (B) an onium borate salt, which is represented by the formula (a1):
    Figure JPOXMLDOC01-appb-C000002
    And the anion represented by and the formula (a2):
    Figure JPOXMLDOC01-appb-C000003
    A monovalent or divalent anion represented by
    Ar independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent,
    R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a fluoroaralkyl group having 7 to 10 carbon atoms And
    L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -]
    A composition comprising a liquid carrier comprising an onium borate salt (but an electrically neutral salt) consisting of at least one anion selected from the group consisting of and a counter cation; and (C) an organic solvent.
  2. 　Ａｒが、１又は２以上の電子吸引性置換基を有するアリール基である、請求項１記載のインク組成物。 The ink composition according to claim 1, wherein Ar is an aryl group having one or more electron withdrawing substituents.
  3. 　電子吸引性置換基が、ハロゲン原子である、請求項２記載のインク組成物。 The ink composition according to claim 2, wherein the electron withdrawing substituent is a halogen atom.
  4. 　前記アニオンが、式（ａ３）で表される、請求項１～３のいずれか一項記載のインク組成物。
    Figure JPOXMLDOC01-appb-C000004
         The ink composition according to any one of claims 1 to 3, wherein the anion is represented by formula (a3).
    Figure JPOXMLDOC01-appb-C000004
  5. 　対カチオンが、式（ｃ１）～（ｃ５）：
    Figure JPOXMLDOC01-appb-C000005
    からなる群より選択される、請求項１～４のいずれか一項記載のインク組成物。     The counter cation is represented by formulas (c1) to (c5):
    Figure JPOXMLDOC01-appb-C000005
    The ink composition according to any one of claims 1 to 4, which is selected from the group consisting of
  6. 　（Ｂ）成分が下記式で表される、請求項１～５のいずれか一項記載のインク組成物。
    Figure JPOXMLDOC01-appb-C000006
         The ink composition according to any one of claims 1 to 5, wherein the component (B) is represented by the following formula.
    Figure JPOXMLDOC01-appb-C000006
  7. 　Ｒ１及びＲ２が、それぞれ独立に、Ｈ、フルオロアルキル、－ＳＯ３Ｍ、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－（ＣＨ２）ｑ－Ｏ－（ここで、（ＣＨ２）ｑは、場合によりＹで置換されている）を形成し；ここで、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄが、それぞれ独立に、Ｈ、ハロゲン、アルキル、フルオロアルキル、又はアリールであり；Ｒｅが、Ｈ、アルキル、フルオロアルキル、又はアリールであり；ｐが、１、２、又は３であり；Ｒｆが、アルキル、フルオロアルキル、又はアリールであり；ｑが、１、２、又は３であり；そしてＹが、炭素数１～１０の直鎖又は分岐鎖のアルコキシアルキル基であり、該アルコキシアルキル基は任意の位置がスルホン酸基で置換されていてもよい、請求項１～６のいずれか一項記載のインク組成物。 R 1 and R 2 are each independently H, fluoroalkyl, -SO 3 M, -O [C (R a R b ) -C (R c R d ) -O] p -R e , or -OR f or R 1 and R 2 taken together are —O— (CH 2 ) q —O— (wherein (CH 2 ) q is optionally substituted by Y) Wherein M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium or trialkylammonium, and each of R a , R b , R c and R d is independently H, halogen, alkyl, fluoroalkyl or aryl; R e is H, alkyl, fluoroalkyl or aryl; p is 1, 2 or 3; R f is alkyl, fluoroalkyl Or Q is 1, 2, or 3; and Y is a linear or branched alkoxyalkyl group having 1 to 10 carbon atoms, and the alkoxyalkyl group is a sulfonic acid group at any position. The ink composition according to any one of claims 1 to 6, which may be substituted by
  8. 　Ｒ１が、Ｈであり、そしてＲ２が、Ｈ以外である、請求項１～７のいずれか一項記載のインク組成物。 The ink composition according to any one of the preceding claims, wherein R 1 is H and R 2 is other than H.
  9. 　Ｒ１及びＲ２が、両方ともＨ以外である、請求項１～７のいずれか一項記載のインク組成物。 The ink composition according to any one of claims 1 to 7, wherein R 1 and R 2 are both other than H.
  10. 　Ｒ１及びＲ２が、それぞれ独立に、－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅ、又は－ＯＲｆであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－（ＣＨ２）ｑ－Ｏ－を形成する、請求項９記載のインク組成物。 R 1 and R 2 are each independently —O [C (R a R b ) —C (R c R d ) —O] p —R e or —OR f , or R 1 and R 2 R 2 together -O- (CH 2) forming a q -O-, 9. the ink composition.
  11. 　Ｒ１及びＲ２が、両方とも－Ｏ［Ｃ（ＲａＲｂ）－Ｃ（ＲｃＲｄ）－Ｏ］ｐ－Ｒｅである、請求項９記載のインク組成物。 The ink composition according to claim 9, wherein R 1 and R 2 are both -O [C (R a R b ) -C (R c R d ) -O] p -R e .
  12. 　各々のＲａ、Ｒｂ、Ｒｃ、及びＲｄが、それぞれ独立に、Ｈ、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルであり；そしてＲｅが、（Ｃ１－Ｃ８）アルキル、（Ｃ１－Ｃ８）フルオロアルキル、又はフェニルである、請求項７～１１のいずれか一項記載のインク組成物。 And each R a , R b , R c and R d is independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl; and R e is The ink composition according to any one of claims 7 to 11, which is (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl, or phenyl.
  13. 　（Ａ）成分が、下記式：
    Figure JPOXMLDOC01-appb-C000007
    で表される基（式中、Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムである）、及びこれらの組合せからなる群より選択される繰り返し単位を含む、請求項１～１２のいずれか一項記載のインク組成物。     The component (A) has the following formula:
    Figure JPOXMLDOC01-appb-C000007
    A repeating unit selected from the group consisting of a group represented by: wherein M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium, and combinations thereof, The ink composition according to any one of claims 1 to 12.
  14. 　（Ａ）成分が、スルホン化ポリ（３－ＭＥＥＴ）である、請求項１～１３のいずれか一項記載のインク組成物。 The ink composition according to any one of claims 1 to 13, wherein the component (A) is sulfonated poly (3-MEET).
  15. 　（Ａ）成分が、式（Ｉ）で表される繰り返し単位を、繰り返し単位の総重量に基づいて５０重量％より多い量で含む、請求項１～１４のいずれか一項記載のインク組成物。 The ink composition according to any one of claims 1 to 14, wherein the component (A) contains the repeating unit represented by the formula (I) in an amount of more than 50% by weight based on the total weight of the repeating unit. .
  16. 　（Ｃ）成分が、グリコールモノエーテル類、グリコールジエーテル類及びグリコール類からなる群より選択される少なくとも１種を含む、請求項１～１５のいずれか一項記載のインク組成物。 The ink composition according to any one of claims 1 to 15, wherein the component (C) comprises at least one selected from the group consisting of glycol monoethers, glycol diethers and glycols.
  17. 　更に、（Ｄ）アミン化合物を含む、請求項１～１６のいずれか一項記載のインク組成物。 The ink composition according to any one of claims 1 to 16, further comprising (D) an amine compound.
  18. 　（Ｄ）成分が、（Ｄ１）第三級アルキルアミン化合物と、（Ｄ２）第三級アルキルアミン化合物以外のアミン化合物とを含む、請求項１７記載のインク組成物。 The ink composition according to claim 17, wherein the component (D) comprises (D1) a tertiary alkylamine compound and (D2) an amine compound other than the tertiary alkylamine compound.
  19. 　（Ｄ２）成分が、第一級アルキルアミン化合物である、請求項１８記載のインク組成物。 The ink composition according to claim 18, wherein the component (D2) is a primary alkylamine compound.
  20. 　第一級アルキルアミン化合物が、エチルアミン、ｎ－ブチルアミン、ｔ－ブチルアミン、２－エチルヘキシルアミン、ｎ－ヘキシルアミン、ｎ－デシルアミン及びエチレンジアミンからなる群より選択される少なくとも１種である、請求項１９記載のインク組成物。 20. The method according to claim 19, wherein the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine and ethylenediamine. Ink composition.
  21. 　第一級アルキルアミン化合物が、ｎ－ブチルアミンである、請求項１９又は２０記載のインク組成物。 The ink composition according to claim 19 or 20, wherein the primary alkylamine compound is n-butylamine.
  22. 　更に、（Ｅ）金属酸化物ナノ粒子を含む、請求項１～２１のいずれか一項記載に記載のインク組成物。 The ink composition according to any one of claims 1 to 21, further comprising (E) metal oxide nanoparticles.
  23. 　更に、（Ｆ）マトリックス化合物を含む、請求項１～２２記載のインク組成物。 The ink composition according to any one of claims 1 to 22, further comprising (F) a matrix compound.
  24. 　請求項１～２３のいずれか一項記載のインク組成物から形成された電荷輸送性薄膜。 A charge transporting thin film formed from the ink composition according to any one of claims 1 to 23.
  25. 　請求項２４記載の電荷輸送性薄膜を有する有機エレクトロルミネッセンス素子。 An organic electroluminescent device comprising the charge transporting thin film according to claim 24.
  26. 　請求項１～２３のいずれか一項記載のインク組成物を基材上に塗布し、溶媒を蒸発させることを特徴とする電荷輸送性薄膜の製造方法。 A method of producing a charge transporting thin film, comprising: applying the ink composition according to any one of claims 1 to 23 on a substrate and evaporating a solvent.
  27. 　インク組成物であって、
    　（Ａ）式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000008
    ［式中、Ｒ１及びＲ２は、それぞれ独立に、Ｈ、アルキル、フルオロアルキル、アルコキシ、フルオロアルコキシ、アリールオキシ、－ＳＯ３Ｍ、又は－Ｏ－［Ｚ－Ｏ］ｐ－Ｒｅであるか、あるいは、Ｒ１及びＲ２は、一緒になって－Ｏ－Ｚ－Ｏ－を形成する
    （式中、
    　Ｍは、Ｈ、アルカリ金属、アンモニウム、モノアルキルアンモニウム、ジアルキルアンモニウム、又はトリアルキルアンモニウムであり、
    　Ｚは、場合によりハロゲン又はＹで置換されているヒドロカルビレン基（ここで、Ｙは、炭素数１～１０の直鎖又は分岐鎖のアルキル基又はアルコキシアルキル基であり、該アルキル基又はアルコキシアルキル基は、任意の位置がスルホン酸基で置換されていてもよい）であり、
    　ｐは、１以上の整数であり、そして
    　Ｒｅは、Ｈ、アルキル、フルオロアルキル、又はアリールである）］
    で表される繰り返し単位を含むポリチオフェン；
    　（Ｂ）オニウムボレート塩であって、式（ａ１）：
    Figure JPOXMLDOC01-appb-C000009
    で表されるアニオン、式（ａ２）：
    Figure JPOXMLDOC01-appb-C000010
    で表される１価又は２価のアニオン、及び（ａ５）
    Figure JPOXMLDOC01-appb-C000011
    で表されるアニオン
    ［式中、
    　Ａｒは、それぞれ独立して、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、
    　Ｒは、炭素数１～１０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数１～１０のフルオロアルキル基、炭素数７～１０のアラルキル基又は炭素数７～１０のフルオロアラルキル基であり、
    　Ｌは、アルキレン基、－ＮＨ－、酸素原子、硫黄原子又は－ＣＮ+－であり、
    　Ｅは長周期型周期表の第１３族又は第１５族に属する元素を表す］
    からなる群より選択される少なくとも１種のアニオンと対カチオンとからなるオニウムボレート塩（ただし、電気的中性な塩である）；
    　（Ｃ）有機溶媒を含む液体担体；及び
    　（Ｆ）マトリックス化合物
    を含む組成物。     An ink composition,
    (A) Formula (I):
    Figure JPOXMLDOC01-appb-C000008
    [Wherein, R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO 3 M, or —O— [Z—O] p —R e Or R 1 and R 2 together form —OZ—O— (wherein:
    M is H, an alkali metal, ammonium, monoalkyl ammonium, dialkyl ammonium or trialkyl ammonium,
    Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group, said alkyl group or alkoxy The alkyl group is optionally substituted with a sulfonic acid group),
    p is an integer of 1 or more, and R e is H, alkyl, fluoroalkyl or aryl)]
    A polythiophene containing a repeating unit represented by
    (B) an onium borate salt, which is represented by the formula (a1):
    Figure JPOXMLDOC01-appb-C000009
    Anion represented by the formula (a2):
    Figure JPOXMLDOC01-appb-C000010
    And a monovalent or divalent anion represented by and (a5)
    Figure JPOXMLDOC01-appb-C000011
    An anion represented by
    Ar independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent,
    R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a fluoroaralkyl group having 7 to 10 carbon atoms And
    L is an alkylene group, -NH-, an oxygen atom, a sulfur atom or -CN + -,
    E represents an element belonging to Group 13 or Group 15 of the long period periodic table]
    An onium borate salt consisting of at least one anion selected from the group consisting of: and a counter cation (however, an electrically neutral salt);
    A composition comprising (C) a liquid carrier comprising an organic solvent; and (F) a matrix compound.
PCT/JP2018/032787 2017-09-06 2018-09-04 Ink composition WO2019049867A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020158410A1 (en) * 2019-01-31 2020-08-06 日産化学株式会社 Charge-transporting varnish
JPWO2020203407A1 (en) * 2019-03-29 2020-10-08
WO2023003038A1 (en) * 2021-07-21 2023-01-26 昭和電工マテリアルズ株式会社 Organic electronics material and organic electronics element
WO2023140300A1 (en) * 2022-01-19 2023-07-27 三菱マテリアル株式会社 Metallic ink, method for producing metallic ink, method for producing metallic layer, and metallic layer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7120242B2 (en) 2017-09-06 2022-08-17 日産化学株式会社 ink composition

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005314682A (en) * 2004-03-31 2005-11-10 Sumitomo Chemical Co Ltd Polymer composition
JP2010171373A (en) * 2008-12-25 2010-08-05 Sumitomo Chemical Co Ltd Organic electroluminescent element
JP2011516695A (en) * 2008-04-11 2011-05-26 プレックストロニクス インコーポレーティッド Doped conjugated polymers, devices, and methods of making devices
JP2012507151A (en) * 2008-10-27 2012-03-22 プレックストロニクス インコーポレーティッド Charge injection layer and transport layer
WO2012133315A1 (en) * 2011-03-28 2012-10-04 富士フイルム株式会社 Electrically conductive composition, electrically conductive film using said composition and production method therefor
WO2016100313A1 (en) * 2014-12-15 2016-06-23 Solvay Usa, Inc. Compositions containing hole carrier materials and fluoropolymers, and uses thereof
WO2016100321A1 (en) * 2014-12-15 2016-06-23 Solvay Usa, Inc. Compositions containing hole carrier materials and poly(aryl ether sulfone)s, and uses thereof
WO2017115467A1 (en) * 2015-12-28 2017-07-06 Nissan Chemical Industries, Ltd. Nanoparticle-conducting polymer composite for use in organic electronics
WO2017150412A1 (en) * 2016-03-03 2017-09-08 日産化学工業株式会社 Charge-transporting varnish
WO2018135581A1 (en) * 2017-01-18 2018-07-26 日産化学工業株式会社 Ink composition containing sulfonated conjugated polymer
WO2018135582A1 (en) * 2017-01-18 2018-07-26 日産化学工業株式会社 Ink composition
WO2018147204A1 (en) * 2017-02-07 2018-08-16 日産化学工業株式会社 Charge transporting varnish

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201209431D0 (en) * 2012-05-28 2012-07-11 Cambridge Display Tech Ltd Organic light-emitting device
JP7120242B2 (en) 2017-09-06 2022-08-17 日産化学株式会社 ink composition

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005314682A (en) * 2004-03-31 2005-11-10 Sumitomo Chemical Co Ltd Polymer composition
JP2011516695A (en) * 2008-04-11 2011-05-26 プレックストロニクス インコーポレーティッド Doped conjugated polymers, devices, and methods of making devices
JP2012507151A (en) * 2008-10-27 2012-03-22 プレックストロニクス インコーポレーティッド Charge injection layer and transport layer
JP2010171373A (en) * 2008-12-25 2010-08-05 Sumitomo Chemical Co Ltd Organic electroluminescent element
WO2012133315A1 (en) * 2011-03-28 2012-10-04 富士フイルム株式会社 Electrically conductive composition, electrically conductive film using said composition and production method therefor
WO2016100313A1 (en) * 2014-12-15 2016-06-23 Solvay Usa, Inc. Compositions containing hole carrier materials and fluoropolymers, and uses thereof
WO2016100321A1 (en) * 2014-12-15 2016-06-23 Solvay Usa, Inc. Compositions containing hole carrier materials and poly(aryl ether sulfone)s, and uses thereof
WO2017115467A1 (en) * 2015-12-28 2017-07-06 Nissan Chemical Industries, Ltd. Nanoparticle-conducting polymer composite for use in organic electronics
WO2017150412A1 (en) * 2016-03-03 2017-09-08 日産化学工業株式会社 Charge-transporting varnish
WO2018135581A1 (en) * 2017-01-18 2018-07-26 日産化学工業株式会社 Ink composition containing sulfonated conjugated polymer
WO2018135582A1 (en) * 2017-01-18 2018-07-26 日産化学工業株式会社 Ink composition
WO2018147204A1 (en) * 2017-02-07 2018-08-16 日産化学工業株式会社 Charge transporting varnish

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020158410A1 (en) * 2019-01-31 2020-08-06 日産化学株式会社 Charge-transporting varnish
JPWO2020203407A1 (en) * 2019-03-29 2020-10-08
WO2020203407A1 (en) * 2019-03-29 2020-10-08 日産化学株式会社 Charge-transporting varnish
CN113646376A (en) * 2019-03-29 2021-11-12 日产化学株式会社 Charge-transporting varnish
CN113646376B (en) * 2019-03-29 2023-09-26 日产化学株式会社 Charge-transporting varnish
WO2023003038A1 (en) * 2021-07-21 2023-01-26 昭和電工マテリアルズ株式会社 Organic electronics material and organic electronics element
WO2023140300A1 (en) * 2022-01-19 2023-07-27 三菱マテリアル株式会社 Metallic ink, method for producing metallic ink, method for producing metallic layer, and metallic layer
JP7464202B2 (en) 2022-01-19 2024-04-09 三菱マテリアル株式会社 Metallic ink, method for producing metallic ink, method for producing metallic layer, and metallic layer

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