WO2018135582A1 - インク組成物 - Google Patents
インク組成物 Download PDFInfo
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- WO2018135582A1 WO2018135582A1 PCT/JP2018/001382 JP2018001382W WO2018135582A1 WO 2018135582 A1 WO2018135582 A1 WO 2018135582A1 JP 2018001382 W JP2018001382 W JP 2018001382W WO 2018135582 A1 WO2018135582 A1 WO 2018135582A1
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- ink composition
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- VTYKNLXJSOTQMA-UHFFFAOYSA-N CCCCOCCOCCOc1c(C(C)(C)CC)[o]c(C(C)(C)C=C)c1OCCOCCOCCCC Chemical compound CCCCOCCOCCOc1c(C(C)(C)CC)[o]c(C(C)(C)C=C)c1OCCOCCOCCCC VTYKNLXJSOTQMA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/10—Metal compounds
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/361—Temperature
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- an OLED device produced using an ink composition containing a polythiophene compound, a dopant, and metal oxide nanoparticles has high transparency. Completed.
- the dopant substance includes at least one selected from the group consisting of an aryl sulfonic acid compound, a heteropoly acid compound, and an ionic compound containing an element belonging to Group 13 or 15 of the long-period periodic table.
- the ink composition as described.
- Polythiophene has the following formula: 13.
- 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 , TeO 2 , SnO. 2, SnO or a mixture thereof, the ink composition according to one of the preceding 1 to 15.
- An ink composition comprising: (A) polythiophene having the 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 .
- the dopant substance includes at least one selected from the group consisting of an aryl sulfonic acid compound, a heteropoly acid compound, and an ionic compound containing an element belonging to Group 13 or 15 of the long-period periodic table.
- Non-aqueous ink composition includes at least one selected from the group consisting of an aryl sulfonic acid compound, a heteropoly acid compound, and an ionic compound containing an element belonging to Group 13 or 15 of the long-period periodic table.
- 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 f ;
- Each 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.
- the non-aqueous ink composition according to any one of Items 101 to 105, wherein p is 1, 2, or 3; and R f is alkyl, fluoroalkyl, or aryl.
- Each R a , R b , R c , and R d is each independently H, (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl, or phenyl; and R e is 111.
- the non-aqueous ink composition according to any one of the items 105 to 110, which is selected from the group consisting of: (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl, or phenyl.
- Polythiophene has the following formula: 112.
- the polythiophene has a repeating unit according to formula (I) of more than 50%, typically more than 80%, more typically more than 90%, still more typically based on the total weight of the repeating units.
- the non-aqueous ink composition according to any one of items 101 to 114, which is contained in an amount of more than 95% by weight.
- liquid carrier according to any one of the above items 101 to 122, wherein the liquid carrier is a liquid carrier comprising one or more glycol solvents (A) and one or more organic solvents (B) excluding the glycol solvents.
- Non-aqueous ink composition is a liquid carrier comprising one or more glycol solvents (A) and one or more organic solvents (B) excluding the glycol solvents.
- the term “a”, “an”, or “the” means “one (one) or more” or “at least one (one)” unless otherwise specified. To do.
- alkyl refers to a monovalent straight or branched saturated hydrocarbon group, more typically a monovalent straight or branched saturated (C 1 -C 40).
- hydrocarbon radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, triacontyl and tetracontyl To do.
- 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 this disclosure.
- the term “undoped” with respect to a hole carrier compound, eg, a polythiophene polymer means that the hole carrier compound has not undergone the doping reaction described herein.
- the ink composition of the present disclosure may be non-aqueous or may contain water, but is preferably non-aqueous in terms 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 0-2% by weight relative 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 certain embodiments, the non-aqueous ink composition of the present disclosure is substantially free of water.
- the polythiophene includes a repeating unit represented by the formula (I).
- Polythiophene may be used alone or in combination of two or more.
- 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 are each independently H, fluoroalkyl, —O [C (R a R b ) —C (R c R d ) —O] p —R e , —OR f. Or R 1 and R 2 taken together form —O— (CH 2 ) q —O—, where (CH 2 ) q is optionally substituted with Y.
- Each 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; Yes; p is 1, 2, or 3; R f is alkyl, fluoroalkyl, or aryl; q is 1, 2, or 3; and Y is 1 to 10 carbons A linear or branched alkoxyalkyl group, the alkoxy Alkyl group, any position may be substituted with a sulfonic acid group.
- R 1 is H and R 2 is other than H.
- the repeating unit is derived from a 3-substituted thiophene.
- the degree of regioregularity can be, for example, about 0-100%, or about 25-99.9%, or about 50-98%.
- the regioregularity can be determined by standard methods known to those skilled in the art, such as using NMR spectroscopy.
- 3-Substituted thiophene monomers are commercially available or can be prepared by methods known to those skilled in the art. Synthesis methods, doping methods, and polymer characterization involving regioregular polythiophenes with pendant groups are provided, for example, in McCullough et al. US Pat. No. 6,602,974 and McCullough et al. US Pat. No. 6,166,172.
- 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 certain embodiments, 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.
- q is 2.
- —O— (CH 2 ) q —O— is substituted at one or more positions with Y. In certain embodiments, —O— (CH 2 ) q —O— is substituted at one position with Y.
- q is 2 and Y is a 3-sulfobutoxymethyl group.
- Y is a 3-sulfobutoxymethyl group.
- the —O— (CH 2 ) 2 —O— group is preferably substituted at one position with a 3-sulfobutoxymethyl group.
- the polythiophene has the formula:
- M is a repeating unit selected from the group consisting of H, alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium, and combinations thereof.
- 3-MEET (2- (2-methoxyethoxy) ethoxy) thiophene
- 3-MEET (2- (2-methoxyethoxy) ethoxy) thiophene
- M is H, alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium
- Sulfonated 3- (2- (2-methoxyethoxy) ethoxy) thiophene [referred to herein as sulfonated 3-MEET] Derived from a monomer represented by the structure represented by:
- 3,4-bis (2- (2-butoxyethoxy) ethoxy) thiophene (referred to herein as 3,4-diBEET] Derived from a monomer represented by the structure represented by:
- 3,4-bis ((1-propoxypropan-2-yl) oxy) thiophene (referred to herein as 3,4-diPPT] Derived from a monomer represented by the structure represented by the formula:
- the repeating unit represented by the following formula: Derived from a monomer represented by the structure represented by 3,4-ethylenedioxythiophene and having the following formula:
- 3,4-disubstituted thiophene monomers are commercially available or can be prepared by methods known to those skilled in the art.
- a 3,4-disubstituted thiophene monomer can be 3,4-dibromothiophene having the formula: HO— [Z—O] p —R e or HOR f wherein Z, R e , R f and p are And is synonymous with those in the present specification] by reacting with a metal salt, typically a sodium salt, of a compound given by reacting with a metal salt, typically a sodium salt, of a compound given by
- Polymerization of the 3,4-disubstituted thiophene monomer involves first brominating the 2- and 5-positions of the 3,4-disubstituted thiophene monomer to yield the corresponding 2,5-dibromo derivative of the 3,4-disubstituted thiophene monomer. Implemented 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 a method is described, for example, in US Pat. No. 8,865,025, which is incorporated herein by reference in its entirety.
- Another known method for polymerizing thiophene monomers uses a metal-free organic oxidant such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as the oxidant, or for example, by oxidative polymerization using transition metal halides such as iron (III) chloride, molybdenum (V) chloride, and ruthenium (III) chloride.
- 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.
- a polythiophene having a repeating unit according to formula (I) of the present disclosure can be further modified following its formation by polymerization.
- a polythiophene having one or more repeating units derived from a 3-substituted thiophene monomer has one or more hydrogens that can be replaced by substituents such as sulfonic acid groups (—SO 3 H) by sulfonation. You may have the site
- the term “sulfonated” in reference to a polythiophene polymer means that the polythiophene contains one or more sulfonic acid groups (—SO 3 H).
- the polythiophene is also referred to as “sulfonated polythiophene”.
- the sulfur atom of the —SO 3 H group is directly bonded to the basic skeleton of the polythiophene polymer and not to the side group.
- a side group is a monovalent group that does not reduce the length of the polymer chain when theoretically or actually removed from the polymer.
- the sulfonated polythiophene polymer and / or copolymer can be prepared using any method known to those skilled in the art.
- polythiophene can be sulfonated by reacting polythiophene with a sulfonated reagent such as fuming sulfuric acid, acetyl sulfate, pyridine SO 3 and the like.
- the monomer can be sulfonated using a sulfonate reagent and then polymerized by known methods and / or methods described herein.
- the sulfonic acid groups are based on basic compounds such as alkali metal hydroxides, ammonia and alkylamines such as mono-, di- and trialkylamines such as triethylamine. In the presence, it can lead to the formation of the corresponding salt or adduct.
- the term “sulfonated” in reference to polythiophene polymers means that the polythiophene has one or more —SO 3 M groups (where M is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + etc.), ammonium (NH 4 + ), mono-, di-, and trialkylammonium (which may be triethylammonium etc.)).
- M is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + etc.), ammonium (NH 4 + ), mono-, di-, and trialkylammonium (which may be triethylammonium etc.)).
- Sulfonated conjugated polymers and sulfonated conjugated polymers are described in Seshadri et al. US Pat. No. 8,017,241, which is incorporated herein by reference in its entirety. Sulfonated polythiophenes are also described in WO 2008/073149 and WO 2016/171935, which are incorporated herein by reference in their entirety.
- the polythiophene is sulfonated.
- the sulfonated polythiophene has the formula (I): [Wherein R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or —O— [Z—O] p —R e (wherein Z is an optionally halogenated hydrocarbylene group; p is 1 or more, and R e is H, alkyl, fluoroalkyl, or aryl).
- each R 1 and R 2 is —SO 3 M (M is H, an alkali metal ion, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium).
- M is H, an alkali metal ion, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium.
- each R 1 and R 2 is independently H, fluoroalkyl, —O [C (R a R b ) —C (R c R d ) —O] p —R e , — be oR f; wherein each of R a, R b, R c , and R d each independently, H, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl Or is aryl; p is 1, 2, or 3; and R f is alkyl, fluoroalkyl, or aryl
- R 1 is —SO 3 M and R 2 is other than —SO 3 M. 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 . 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 . In certain embodiments, 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 polythiophene has the formula (I):
- R 1 and R 2 are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or —O— [Z—O] p —R e (wherein Z is an optionally halogenated hydrocarbylene group; p is 1 or more, and R e is H, alkyl, fluoroalkyl, or aryl)] Obtained by sulfonation of polythiophene containing repeating units according to
- 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 f.
- each R a , R b , R c , and R d is each independently H, alkyl, fluoroalkyl, or aryl
- R e is H, alkyl, fluoroalkyl, or Is aryl
- p is 1, 2, or 3
- R f is alkyl, fluoroalkyl, or aryl.
- R 1 is H and R 2 is other than H.
- the repeating unit is derived from a 3-substituted thiophene.
- Sulfonated polythiophene is obtained from polythiophene which can be a regiorandom or regioregular compound. Due to its asymmetric structure, the polymerization of 3-substituted thiophene produces a mixture of polythiophene structures containing three possible regiochemical bonds between repeating units. The three orientations available when two thiophene rings are combined are the 2,2 ', 2,5', and 5,5 'couplings. 2,2 '(ie, head-to-head) coupling and 5,5' (ie, tail-to-tail) coupling are referred to as regiorandom coupling.
- 2,5 '(ie head-to-tail) coupling is referred to as regioregular coupling.
- the degree of regioregularity can be, for example, about 0-100%, or about 25-99.9%, or about 50-98%.
- the regioregularity can be determined by standard methods known to those skilled in the art, such as using NMR spectroscopy.
- 3-Substituted thiophene monomers are commercially available or can be prepared by methods known to those skilled in the art. Synthesis methods, doping methods, and polymer characterization involving regioregular polythiophenes with pendant groups are provided, for example, in McCullough et al. US Pat. No. 6,602,974 and McCullough et al. US Pat. No. 6,166,172. Sulfonated conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in US Pat. No. 8,017,241 to Seshadri et al.
- 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 each 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 e is H, methyl, propyl, or butyl.
- R f is CH 2 CF 3 .
- the sulfonated polythiophene has the formula:
- 3-MEET (2- (2-methoxyethoxy) ethoxy) thiophene
- the polythiophene is sulfonated poly (3-MEET).
- the polythiophene polymers used in the present disclosure may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers).
- block copolymers include, for example, AB diblock copolymers, ABAA triblock copolymers, and-(AB) n -multiblock copolymers.
- Polythiophenes contain repeat units derived from other types of monomers such as thienothiophene, selenophene, pyrrole, furan, tellurophene, aniline, arylamines, and arylenes such as phenylene, phenylene vinylene, and fluorene. May be included.
- the polythiophene contains more than 50%, typically more than 80%, more typically more than 90% by weight of repeating units according to formula (I), based on the total weight of the repeating units. Greater, still typically in an amount greater than 95% by weight.
- the polymer formed may contain repeating units derived from impurities.
- the term “homopolymer” is intended to mean a polymer comprising repeating units derived from one type of monomer, but containing repeating units derived from impurities. Also good.
- the polythiophene is a homopolymer where essentially all repeat units are repeat units according to formula (I).
- Polythiophene polymers 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 of about 5,000 to 100,000 g / mol, and still more typically between about 10,000 to about 50,000 g / mol. The number average molecular weight can be determined by methods known to those skilled in the art, such as gel permeation chromatography.
- the polythiophene may be used after being treated with a reducing agent.
- the chemical structure may be an oxidized structure called “quinoid structure”.
- quinoid structure is used for the term “benzenoid structure”.
- a double bond in the aromatic ring is moved out of the ring (its As a result, the aromatic ring disappears), which means a structure in which two exocyclic double bonds conjugated with other double bonds remaining in the ring are formed.
- This quinoid structure is a part of structures called “polaron structure” and “bipolaron structure” which are generated by the above-described doping reaction and impart charge transportability to polythiophene. These structures are known.
- polaron structure and / or a “bipolaron structure”.
- a charge transporting thin film formed from a charge transporting varnish is baked. Sometimes this is achieved by intentionally initiating the doping reaction.
- the polythiophene prior to causing the doping reaction contains a quinoid structure because the polythiophene is equivalent to the doping reaction in the production process (especially in the case of the sulfonated polythiophene, the sulfonation step therein). This is probably because an unintended oxidation reaction occurred.
- the reducing agent used for the reduction treatment reduces the quinoid structure to convert it into a non-oxidized structure, that is, the benzenoid structure (for example, in the polythiophene represented by the formula (I), the formula (I).
- the quinoid structure represented by ') is not particularly limited as long as it can convert the quinoid structure represented by the formula (I) into a structure represented by the above formula (I), and for example, aqueous ammonia, hydrazine, or the like is preferably used.
- the amount of the reducing agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of polythiophene to be treated.
- this treatment can be performed by simply contacting polythiophene with a reducing agent in the presence or absence of a suitable solvent.
- a suitable solvent usually, the dispersibility of polythiophene in an organic solvent is sufficiently improved by reduction treatment under relatively mild conditions such as stirring polythiophene in 28% ammonia water (for example, overnight at room temperature).
- the sulfonated polythiophene may be subjected to a reduction treatment after being converted into a corresponding ammonium salt, for example, a trialkylammonium salt (sulfonated polythiopheneamine adduct).
- the polythiophene that 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 in the case of sulfonated polythiophene, acetone, isopropyl alcohol, etc. is added to the reaction system to cause precipitation of polythiophene, followed by filtration, etc. Polythiophene can be recovered.
- the ink composition of the present disclosure may further contain other hole carrier compounds as the case may be.
- 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 (3-methyldiphenylamino) 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 '
- An 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] (commonly referred to as poly-TPD).
- poly-TPD poly [(9,9-dihe
- optional hole carrier compounds include, for example, US Patent Publication No. 2010/0292399 published November 18, 2010; 2010/010900 published May 6, 2010; and May 6, 2010. It is described in 2010/0108954 published in Japan.
- the optional hole carrier compounds described herein are known in the art and are commercially available.
- the polythiophene comprising repeat units according to formula (I) is doped with a dopant.
- Dopants are known in the art. See, for example, US Patent No. 7,070,867; US Publication No. 2005/0123793; and US Publication No. 2004/0113127.
- the dopant may be an ionic compound.
- the dopant can include cations and anions.
- One or more dopants may be used to dope the polythiophene comprising repeat units according to formula (I).
- 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 compound 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 group, where M is H + or an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + Etc.); or ammonium (which may be NH 4 + ).
- carboxylate refers to a —CO 2 M group, where M is H + or an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs + Or the like); or ammonium (which may be NH 4 + ).
- alkali metal ion eg, Na + , Li + , K + , Rb + , Cs + Or the like
- ammonium which may be NH 4 +
- sulfonate and carboxylate dopants are benzoate compounds, heptafluorobutyrate, methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, pentafluoropropionate, and polymer sulfonates, perfluorosulfonate-containing ionomers Including, but not limited to.
- the dopant does not include sulfonate or carboxylate.
- the dopant is a sulfonylimide (eg, bis (trifluoromethanesulfonyl) imide); an antimonate (eg, hexafluoroantimonate); an arsenate (eg, hexafluoroarsenate); a phosphorus compound (Eg, hexafluorophosphate, etc.); and borates (eg, tetrafluoroborate, tetraarylborate, trifluoroborate, etc.).
- sulfonylimide eg, bis (trifluoromethanesulfonyl) imide
- an antimonate eg, hexafluoroantimonate
- an arsenate eg, hexafluoroarsenate
- a phosphorus compound eg, hexafluorophosphate, etc.
- borates eg, tetrafluoroborate, tetraaryl
- tetraaryl borates include, but are not limited to, halogenated tetraaryl borates such as tetrakispentafluorophenyl borate (TPFB).
- TPFB tetrakispentafluorophenyl borate
- trifluoroborates are (2-nitrophenyl) trifluoroborate, benzofurazan-5-trifluoroborate, pyrimidine-5-trifluoroborate, pyridine-3-trifluoroborate, and 2,5-dimethylthiophene- Including but not limited to 3-trifluoroborate.
- the dopant may be, for example, a material from which doped polythiophene is generated by undergoing, for example, one or more electron transfer reactions with a conjugated polymer.
- the dopant can be selected to provide a suitable charge balancing counteranion.
- the reaction can occur by mixing polythiophene and a dopant, as is known in the art.
- the dopant can undergo spontaneous electron transfer from the polymer to a cation-anion dopant (such as a metal salt), leaving the conjugated polymer with its free metal in 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, upon reaction, form a doped polymer.
- the doping reaction may be a charge transfer reaction in which charge carriers are generated, and this reaction may be reversible or irreversible.
- silver ions can undergo electron transfer to and from silver metal and doped polymers.
- the composition may be distinctly different from the original combination of ingredients (ie, polythiophene and / or dopant may or may not be present in the final composition in the same form as before mixing). Also good).
- a dopant an inorganic acid, an organic acid, an organic or inorganic oxidizing agent, or the like is used.
- the organic acid a polymer organic acid and / or a low molecular organic acid (non-polymer organic acid) is used.
- the organic acid is a sulfonic acid and its salt (—SO 3 M, where M is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs +, etc.), Ammonium (NH 4 + ), mono-, di-, and trialkylammonium (such as triethylammonium) may be used, and among these sulfonic acids, arylsulfonic acids are preferred.
- M is an alkali metal ion (eg, Na + , Li + , K + , Rb + , Cs +, etc.)
- Ammonium NH 4 +
- mono-, di-, and trialkylammonium such as triethylammonium
- dopants include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid; aluminum (III) (AlCl 3 ), titanium (IV) tetrachloride (TiCl 4 ), three 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); polymer organics such as polystyrene sulfonic acid Acids: benzene sulfonic acid, tosylic acid, camphor sul
- the dopant includes at least one selected from the group consisting of an aryl sulfonic acid compound, a heteropoly acid compound, and an ionic compound containing an element belonging to Group 13 or 15 of the long-period periodic table.
- Particularly preferred dopants include polymer organic acids such as polystyrene sulfonic acid, 5-sulfosalicylic acid, dodecylbenzene sulfonic acid, 1,4-benzodioxane disulfonic acid derivatives described in International Publication No.
- JP2005 And low molecular organic acids such as dinonylnaphthalenesulfonic acid derivatives described in JP-A-108828.
- the sulfonic acid derivative shown by following formula (2) can also be used suitably.
- X represents O, S or NH
- A represents a naphthalene ring or anthracene ring which may have a substituent other than X and n (SO 3 H) groups
- B represents 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) group, S (O 2 ) group, or N, Si, P and P (O) groups
- W 1 may be a single bond
- R 46 to R 59 each independently represents a hydrogen atom or a halogen atom
- n represents the number of sulfonic acid groups bonded to A. Represents an integer satisfying 1 ⁇ n ⁇ 4, and q represents the number of bonds between B and X, and is an integer satisfying 1 ⁇ q. ]
- R 46 to R 59 in 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 R 46 to R 53 are all fluorine atoms.
- arylsulfonic acid compound As the arylsulfonic acid compound according to the present invention, those represented by the following formula (6) can also be used. (Wherein X represents O, S or NH, Ar 5 represents an aryl group, n represents the number of sulfone groups and is an integer satisfying 1 to 4)
- X represents O, S or NH, and O is particularly preferable because of easy synthesis.
- n-heptyl group n-octyl group, n-nonyl group, 2-ethylhexyl group, n-decyl group, cyclopentyl group, cyclohexyl group and the like.
- E2 is preferably a phosphorus atom, an arsenic atom, or an antimony atom, and a phosphorus atom is preferable from the viewpoint of stability of the compound, ease of synthesis and purification, and toxicity.
- X is preferably a fluorine atom or a chlorine atom, and most preferably a fluorine atom, from the viewpoint of stability of the compound, ease of synthesis and purification.
- heteropolyacid compound examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, phosphotungstomolybdic acid, silicotungstic acid, and the like, but considering the characteristics of the organic EL device including the thin film obtained, Phosphomolybdic acid, phosphotungstic acid and silicotungstic acid are preferred, and phosphotungstic acid is more preferred.
- These heteropolyacid compounds may be synthesized and used by a known synthesis method, but are also commercially available.
- 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)) is Kanto Chemical Co., Inc., Wako Pure Chemical Industries, Ltd., Sigma Aldrich Japan Co., Ltd., Japan It is available from manufacturers such as Inorganic Chemical Industry Co., Ltd. and Nippon Shin Metal Co., Ltd.
- the material can be purified to remove halogens and metals.
- Halogen includes, for example, chloride, bromide and iodide.
- Metals include, for example, dopant cations (including reduced forms of dopant cations), or metals left from catalyst or initiator residues.
- 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 particularly at a concentration exceeding 50 ppm.
- the doped polymer composition is formed by mixing the polythiophene and the dopant. Mixing can be accomplished using any method known to those 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 may be one or more of the solvents described herein. The reaction can occur by mixing polythiophene and a dopant, as is known in the art.
- the resulting doped polythiophene composition comprises from about 40 wt% to 75 wt% polymer and from about 25 wt% to 55 wt% dopant, based on the composition.
- the projected image of the nanoparticles is processed using image processing software, and then the area equivalent diameter (this is defined as the diameter of a circle having the same area as the nanoparticles) is obtained.
- the particle diameter can be measured by the method.
- image processing software provided by the manufacturer and distributor of TEM provided with a TEM (for example, transmission electron microscope HT7700 (available from Hitachi High-Technologies Corporation)) Process.
- the average particle diameter can be obtained as the number average of equivalent circle diameters.
- Non-limiting specific examples of suitable metal oxide nanoparticles 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 Nanoparticles including, but not limited to, Sb 2 O 3 , Sb 2 O 5 , TeO 2 , SnO 2 , ZrO 2 , Al 2 O 3 , ZnO and mixtures thereof.
- TFE tetrafluoroethylene
- CFE chlorotrifluoroethylene
- F 2 C ⁇ CF—O—CF 2 —CF 2 — SO 2 F
- F 2 C ⁇ CF—O—CF 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.
- the polyethersulfone has the formula (IV):
- R 21 to R 25 , R 27 , and R 28 are each H and R 26 is SO 3 H.
- the polyethersulfone has the formula (XI):
- the matrix compound is a poly (styrene) or poly (styrene) derivative.
- the matrix compound is poly (4-hydroxystyrene).
- the amount of optional matrix compound can be adjusted and measured as a weight percentage with respect to the amount of doped or undoped polythiophene.
- the amount of optional matrix compound is from 0 to about 99.5%, typically from about 10% to about 98% by weight, based on the amount of doped or undoped polythiophene. More typically from about 20% to about 95%, still more typically from about 25% to about 45%. In an embodiment that is 0% by weight, the ink composition is free of matrix compounds.
- the ink composition of the present disclosure optionally includes one or more amine compounds.
- Amine compounds suitable for use in the ink compositions of the present disclosure include, but are not limited to, ethanolamines and alkylamines.
- Alkylamines include primary, secondary, and tertiary alkylamines.
- primary alkylamines include, 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 ].
- Tertiary alkylamines include, for example, 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 ].
- the amine compound is a tertiary alkyl amine. In certain embodiments, the amine compound is triethylamine.
- the amine compound is a mixture of a tertiary alkylamine compound and an amine compound other than the tertiary alkylamine compound.
- the amine compound other than the tertiary alkyl amine compound is a primary alkyl amine compound.
- the primary alkylamine compound is preferably 2-ethylhexylamine or n-butylamine, more preferably 2-ethylhexylamine.
- the amount of the amine compound can be adjusted and measured as a weight percentage with respect to the total amount of the ink composition.
- the amount of amine compound is at least 0.01 wt%, at least 0.10 wt%, at least 1.00 wt%, at least 1.50 wt%, or at least relative to the total amount of the ink composition. 2.00% by weight.
- the amount of amine compound is about 0.01 to about 2.00% by weight, typically about 0.05% to about 1.50% by weight, based on the total amount of the ink composition. More typically from about 0.1% to about 1.0% by weight.
- Suitable organic solvents for use in the liquid carrier are aliphatic and aromatic ketones, such as dimethyl sulfoxide (DMSO) and 2,3,4,5-tetrahydrothiophene-1,1-dioxide (tetramethylene sulfone; sulfolane).
- DMSO dimethyl sulfoxide
- tetramethylene sulfone 2,3,4,5-tetrahydrothiophene-1,1-dioxide
- Aliphatic and aromatic ketones include acetone, acetonyl acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl isobutenyl ketone, 2-hexanone, 2-pentanone, acetophenone, ethyl phenyl ketone, cyclohexanone, and cyclopentanone.
- MEK methyl ethyl ketone
- ketones having a proton on the carbon located alpha to the ketone such as cyclohexanone, methyl ethyl ketone, and acetone, are avoided.
- organic solvents that fully or partially solubilize the polythiophene or swell the polythiophene polymer would also be considered. Such other solvents may be included in the liquid carrier in various amounts to adjust ink properties such as wettability, viscosity, and morphology control.
- the liquid carrier may further comprise one or more organic solvents that act as non-solvents for the polythiophene polymer.
- organic solvents suitable for use according to the present disclosure include ethers such as anisole, ethoxybenzene, dimethoxybenzene and glycol diethers (glycol diethers) such as ethylene glycol diether (1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-dibutoxyethane); diethylene glycol diether (such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether); propylene glycol diether (such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether) ); Dipropylene glycol diether (dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether) And higher order analogs of ethylene glycol and propylene glycol ether referred to herein (ie, tri- and tetra-analogs such as triethylene glycol dimethyl ether, triethylene, etc.).
- Still other solvents such as ethylene glycol monoether acetate and propylene glycol monoether acetate (glycol ester ethers) can be considered, where the ether is, for example, methyl, ethyl, n-propyl, iso- It can be selected from propyl, n-butyl, sec-butyl, tert-butyl and cyclohexyl. Also included are higher order glycol ether analogs such as di-, tri- and tetra- 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.
- glycol diacetate glycol diesters
- higher order glycol ether analogs such as di-, tri- and tetra-. Examples include, but are not limited to, ethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate.
- Alcohols such as, for example, methanol, ethanol, trifluoroethanol, n-propanol, isopropanol, n-butanol, t-butanol and alkylene glycol monoethers (glycol monoethers) can also be considered for use in the liquid carrier.
- 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), diethylene glycol Propylene glycol n-butyl ether (Dowanol DPnB), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol DPM), diisobutyl carbinol, 2-ethylhexyl alcohol, methyl isobutyl carbinol , Propylene glycol monopropyl ether (Dowanol PnP), diethylene glycol monopro Pyrether (propyl carbitol), diethylene glycol monohexyl ,
- the organic solvents disclosed herein can be used to improve ink properties such as, for example, substrate wettability, ease of solvent removal, viscosity, surface tension and emissivity. It can be used in various proportions in the liquid carrier.
- the use of an aprotic non-polar solvent can provide an additional benefit of extending the lifetime of devices with emitter technology that are sensitive to protons (eg, PHOLEDs, etc.).
- the liquid carrier comprises dimethyl sulfoxide, ethylene glycol (glycols), tetramethylurea or mixtures thereof.
- suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, dipropylene glycol, polypropylene glycol, propylene glycol, triethylene glycol, and the like.
- glycol solvents The above-mentioned glycol diethers, glycol ester ethers, glycol diesters, glycol monoethers and glycols are collectively referred to as “glycol solvents”. That is, the “glycol solvent” referred to in the present invention is a compound of the formula R 1 —O— (RO) n —R 2 (wherein each R is independently a linear C 2 -C 4).
- R 1 and R 2 are each independently a hydrogen atom, a linear, branched or cyclic C 1 -C 8 unsubstituted alkyl group or a linear or branched C 1 -C 8
- An organic solvent having no one or more aromatic structures represented by the following formula: n is an unsubstituted aliphatic acyl group, and n is an integer of 1 to 6.
- R is particularly preferably a C 2 or C 3 unsubstituted alkylene group.
- the n is particularly preferably an integer of 1 to 4.
- the alkyl group is preferably a linear, branched or cyclic C 1 -C 6 unsubstituted alkyl group, more preferably a linear C 1 -C 4 unsubstituted alkyl group, and a methyl group and an n-butyl group. Particularly preferred.
- the acyl group a linear or branched C 2 -C 6 unsubstituted aliphatic acyl group is preferable, a linear C 2 -C 4 unsubstituted acyl group is more preferable, and an acetyl group and a propionyl group are particularly preferable.
- the glycol solvent include the following solvents.
- Glycols that are ethylene glycol, propylene glycol, or oligomers thereof (dimer to tetramer, such as diethylene glycol)
- Glycol monoethers that are monoalkyl ethers of the glycols
- Glycol diesters that are dialkyl ethers of the glycols Ethers
- glycol monoesters that are aliphatic carboxylic acid monoesters of the glycols
- glycol diesters that are aliphatic carboxylic acid diesters of the glycols
- glycols that are aliphatic carboxylic acid monoesters of the glycol monoethers Ester ethers
- the glycol solvent may be compared with an organic solvent not corresponding thereto, and the former may be indicated by (A) and the latter by (B).
- the liquid carrier is a liquid carrier consisting of one or more glycol-based solvents (A).
- the liquid carrier is a liquid carrier comprising one or more glycol solvents (A) and one or more organic solvents (B) excluding the glycol solvents.
- the glycol solvent (A) is preferably glycol diethers, glycol monoethers or glycols, and these may be mixed. Examples include, but are not limited to, mixing glycol diethers and glycols. Specific examples include specific examples of the above-mentioned glycol diethers and glycols.
- the glycol diethers are triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, the glycols are ethylene glycol, Examples include diethylene glycol.
- Preferred examples of the organic solvent (B) include nitriles, alcohols, aromatic ethers, and aromatic hydrocarbons.
- Examples include, but are not limited to, nitriles such as methoxypropionitrile, ethoxypropionitrile, alcohols as benzyl alcohol, 2- (benzyloxy) ethanol, aromatic ethers as methylanisole, dimethylanisole, ethylanisole , Butylphenyl ether, butylanisole, pentylanisole, hexylanisole, heptylanisole, octylanisole, phenoxytoluene, aromatic hydrocarbons such as pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, cyclohexylbenzene or tetralin Can be mentioned.
- nitriles such as methoxypropionitrile, ethoxypropionitrile
- alcohols as benzyl alcohol, 2- (benzyloxy) ethanol
- aromatic ethers as
- alcohols are more preferable, and 2- (benzyloxy) ethanol is more preferable among alcohols.
- organic solvent (B) By adding the organic solvent (B) to the glycol solvent (A), the agglomeration of the metal oxide nanoparticles is appropriately controlled while maintaining the solubility of the ink solids during the film formation by ink jet coating, and more flat A simple film can be formed.
- the organic solvent (B) When the organic solvent (B) is added to the glycol solvent (A), the content of the glycol solvent (A): wtA (weight) and the content (weight) of the organic solvent (B): wtB (weight) ) Preferably satisfies formula (1-1), more preferably satisfies formula (1-2), and most preferably satisfies formula (1-3).
- composition of the present invention contains two or more glycol solvents (A), wtA indicates the total content (weight) of the glycol solvent (A), and two or more organic solvents (B). When contained, wtB represents the total content (weight) of the organic solvent (B).)
- the amount of liquid carrier in the ink composition of the present disclosure is from about 50% to about 99%, typically from about 75% to about 98%, more typically from the total amount of the ink composition. Is about 90% to about 95% by weight.
- the total solids (% TS) in the ink composition of the present disclosure is from about 0.1 wt% to about 50 wt%, typically from about 0.3 wt% to about 40% by weight, more typically from about 0.5% to about 15% by weight, and still more typically from about 1% to about 5% by weight.
- the ink composition described herein can be prepared by any appropriate method known to those skilled in the art.
- the initial aqueous mixture can be prepared by mixing an aqueous dispersion of the polythiophene described herein with an aqueous dispersion of a polymer acid, optionally another matrix compound, and optionally an additional solvent. Prepared by mixing with. 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 dimethyl sulfoxide and filtered under pressure to form a mixture. In some cases, an amine compound may be added to such a mixture. This mixture is then mixed with a dispersion of metal oxide nanoparticles to produce the final ink composition.
- the ink compositions described herein can be prepared from stock solutions.
- the polythiophene stock solutions described herein can be prepared by isolating polythiophene from an aqueous dispersion in a dry state, typically by evaporation. The dried polythiophene is then combined with one or more organic solvents and optionally an amine compound.
- the polymer acid stock solutions described herein can be prepared by isolating the polymer acid from the aqueous dispersion in a dry state, typically by evaporation. The dried polymer acid is then combined with one or more organic solvents.
- Stock solutions of other optional matrix materials can be prepared similarly.
- the metal oxide nanoparticle stock solution may be, for example, a commercially available dispersion that is one or more organic solvents, and may be the same as or different from the solvent (s) contained in the commercially available dispersion. It can be prepared by diluting with a good organic solvent. The desired amount of each stock solution is then combined to form the ink composition of the present disclosure.
- the ink composition described herein isolates the individual components in the dry state as described herein, but instead of preparing a stock solution, the dry components are combined. Can then be prepared by providing an NQ ink composition by dissolving in one or more organic solvents.
- the ink composition of the present disclosure can be cast and annealed as a thin film on a substrate.
- the present disclosure is also a method of forming a hole-transporting thin film, It relates to a method comprising: 1) coating a substrate with an 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, rotary casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, doctor blade method, and for example, for making organic electronic devices Can be performed by methods known in the art, including any other methods known in the art.
- the substrate may be flexible, rigid, organic or inorganic.
- Suitable substrate compounds include, for example, glass (including, for example, display glass), ceramic, metal, and plastic thin films.
- annealing refers to any general process for forming a cured layer, typically a thin film, on a substrate coated with an 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. Solvent removal may be accomplished, for example, by applying a substrate coated to a pressure below atmospheric pressure and / or heating the coating laminated to the substrate to a temperature (annealing temperature), and this temperature for a period of time (annealing time). And then the resulting layer, typically a thin film, can be achieved by slowly cooling to room temperature.
- the annealing step can be performed by heating the substrate coated with the ink composition using any method known to those skilled in the art, for example, in an oven or on a hot plate.
- Annealing can be performed in an inert environment, such as a nitrogen atmosphere or a rare gas (eg, argon gas) atmosphere.
- 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., and still more typically about 230 to About 300 ° C.
- the 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., and still more typically about 250 to About 300 ° C. and the annealing time is about 3 to about 40 minutes, typically about 15 to about 30 minutes.
- This disclosure relates to a hole-transporting thin film formed by the method described herein.
- a thin film produced by the disclosed method has a transmission (typically with a substrate) of at least about 85%, typically at least 90%, of light having a wavelength of about 380-800 nm. Can show. In certain embodiments, the transmittance is at least about 90%.
- the thin film produced by the method of the present disclosure 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 thin film produced by the method of the present disclosure exhibits a transmittance of at least about 90% and is from about 5 nm to about 500 nm, typically from about 5 nm to about 150 nm, more typically about 50 nm. It has a thickness of ⁇ 120 nm. In certain embodiments, the thin film produced by the method of the present disclosure exhibits a transmittance (% T) of at least about 90% and has a thickness of about 50 nm to 120 nm.
- the thin film produced by the method of the present disclosure can be produced on a substrate that optionally contains electrodes or additional layers that are 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 that are coated or deposited during device fabrication. Solvent.
- the thin film is, for example, resistant to toluene, which can then be a solvent in the ink for layers that are coated or deposited during device fabrication.
- the present disclosure also relates to a 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 and the solvent removed by standard methods.
- Thin films prepared by the methods described herein can be HIL and / or HTL layers in the device.
- OLEDs Organic light emitting diodes
- Conductive 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, multilayering, mixing, and compound synthesis and formulation are described in Kraft et al., “Electroluminescent Conjugated Polymers-Seeing Polymers in a New Light,” Angew. Chem. Int. Ed., 1998, 37, 402-428, the entirety of which is incorporated herein by reference.
- Luminescent materials known in the art and containing commercially available polymers and organic molecules can be used.
- organic electroluminescent compounds include: (I) poly (p-phenylene vinylene) and its derivatives substituted at various positions on the phenylene residue; (Ii) poly (p-phenylene vinylene) and its derivatives substituted at various positions on the vinylene residue; (Iii) poly (p-phenylene vinylene) and its derivatives substituted at various positions on the phenylene residue and also substituted at various positions on the vinylene residue; (Iv) poly (arylene vinylene), where the arylene may be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole and the like; poly (arylene vinylene); (V) a derivative of poly (arylene vinylene), wherein the arylene may be the same as in (iv) above and further has substituents at various positions on the arylene; (Vi) a derivative of poly (arylene vinylene), wherein the arylene may be
- 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)); (X) poly (arylene), where the arylene may be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole, etc .; poly (arylene); and various positions on the arylene residue Derivatives thereof substituted by: (Xi) a copolymer of an oligoarylene and a non-conjugated oligomer such as the compound in (x); (Xii) polyquinoline and its derivatives; (Xiii) a copolymer of
- Preferred organic light-emitting polymers include SUMATION's Light Emitting Polymers ("LEP”) or their families, copolymers, derivatives, or mixtures thereof that emit green, red, blue, or white light; Is available from Summation KK.
- LEP Light Emitting Polymers
- Other polymers include polyspirofluorene-like polymers available from Covion Organic Semiconductors GmbH, Frankfurt, Germany (now owned by Merck®).
- 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).
- the device can be manufactured using a multilayer structure that can be prepared by, for example, a dissolution method or a vacuum method, and further a printing method and a pattern formation method.
- a hole injection layer HIL
- HILs in the device include: 1) Hole injection in OLEDs including PLEDs and SMOLEDs; for example, HILs in PLEDs can use all classes of conjugated polymer emitters where the conjugation involves 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 HIL layers; Or SMOLED being processed from an aerosol spray or by any other processing method.
- HILs in dendrimer or oligomeric organic semiconductor based OLEDs include: HILs in dendrimer or oligomeric organic semiconductor based OLEDs; Bipolar light emitting FETs, where the HIL is used to regulate charge injection or as an electrode ; 2) hole extraction layer in OPV; 3) channel material in the transistor; 4) Channel material in a circuit containing a combination of transistors, such as logic gates; 5) electrode material in the transistor; 6) Gate layer in the capacitor; 7) A chemical sensor, wherein the adjustment of the doping level is achieved by the relationship between the species to be sensed and the conductive polymer; 8) Electrode or electrolyte material in the battery.
- Photovoltaic devices can be prepared, for example, with a photoactive layer comprising a fullerene derivative mixed with a conductive polymer, as described in US Pat. Nos. 5,454,880; 6,812,399; and 6,933,436.
- the photoactive layer can include a mixture of conductive polymers, a mixture of conductive polymers and semiconductor nanoparticles, and small bilayers such as phthalocyanines, fullerenes, and porphyrins.
- General electrode compounds and substrates, and encapsulated 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.
- an interface modification layer such as an intermediate layer and an optical spacer layer can be used.
- An electron transport layer can be used.
- the present disclosure also relates to a method for manufacturing the device described herein.
- a method of manufacturing a device includes: providing a substrate; for example, laminating a transparent conductor such as indium tin oxide on the substrate; and an ink composition as described herein. Providing; forming the hole injection layer or hole transport layer by laminating the ink composition on the transparent conductor; laminating the active layer on the hole injection layer or hole transport layer (HTL) And laminating a cathode on the active layer.
- a transparent conductor such as indium tin oxide
- HTL hole transport layer
- the substrate may be flexible, rigid, organic, or inorganic.
- Suitable substrate compounds include, for example, glass, ceramic, metal, and plastic thin films.
- a method of manufacturing a device comprises combining the ink composition described herein with an OLED, a photovoltaic device, an ESD, a SMOLED, a PLED, a sensor, a supercapacitor, a cation converter, a drug release device, an electro Application as part of a HIL or HTL layer in a chromic element, transistor, field effect transistor, electrode modifier, electrode modifier for organic field transistor, actuator, or transparent electrode.
- Lamination of the ink composition to form the HIL or HTL layer is performed by methods known in the art (for example, rotary casting, spin coating, dip casting, dip coating, slot die coating, inkjet printing, gravure coating, doctor Blade methods, and any other methods known in the art for the fabrication of organic electronic devices, for example).
- 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. Annealed.
- HIL or HTL can exhibit a transmittance (typically with a substrate) of light having a wavelength of about 380-800 nm of at least about 85%, typically at least about 90%. Can be prepared. In certain embodiments, the transmittance 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, more typically about 50 nm to 120 nm.
- the HIL layer exhibits a transmittance 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, more typically about 50 nm to 120 nm. . In certain embodiments, the HIL layer exhibits a transmission (% T) of at least about 90% and has a thickness of about 50 nm to 120 nm.
- Example 1 2.00 g of the S-poly (3-MEET) amine adduct obtained in Production Example 1 was dissolved in 100 mL of 28% aqueous ammonia (manufactured by Junsei Chemical Co., Ltd.) and stirred at room temperature overnight. The reaction solution was reprecipitated with 1500 mL of acetone, and the precipitate was collected by filtration. The obtained precipitate was dissolved again 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.
- Example 2-2 Synthesis of dopant B A sulfonic acid compound (dopant B) represented by the following formula was synthesized according to the method described in International Publication No. 2015-111654.
- Example 2-1 The solution was prepared using a hot stirrer and stirred at 350 rpm, 80 ° C. for 1 hour. Next, 0.015 g of the dopant A obtained in Example 2-1 was added as a dopant, and the mixture was stirred using a hot stirrer at 350 rpm, 80 ° C. for 1 hour. Finally, 1.24 g of EG-ST was added and stirred at 350 rpm, 30 ° 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 ⁇ m to transport 3 wt% of charge. Sex varnish A was obtained.
- Example 3-2 A charge transporting varnish B was obtained in the same manner as in Example 3-1, except that the dopant B obtained in Example 2-2 was used instead of the dopant A as the dopant.
- Example 3-3 A charge transporting varnish C was obtained in the same manner as in Example 3-1, except that phosphotungstic acid (manufactured by Kanto Chemical Co., Inc.) was used instead of dopant A as the dopant.
- phosphotungstic acid manufactured by Kanto Chemical Co., Inc.
- Example 3-4 0.032 g of the S-poly (3-MEET) amine adduct obtained in Production Example 1 was 0.73 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), 1.93 g of diethylene glycol (manufactured by Kanto Chemical Co., Ltd.), BA ( Dissolved in 0.047 g of Tokyo Chemical Industry Co., Ltd., 4.83 g of triethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.), and 0.97 g of 2- (benzyloxy) ethanol (manufactured by Kanto Chemical Co., Inc.) I let you. The solution was prepared using a hot stirrer and stirred at 350 rpm at 80 ° C.
- the solution was prepared using a hot stirrer and stirred at 350 rpm, 80 ° C. for 1 hour.
- 0.069 g of the dopant A obtained in Example 2-1 was added as a dopant, and the mixture was stirred at 350 rpm, 80 ° C. for 1 hour using a hot stirrer, and the resulting solution was added to a PP syringe filter having a pore diameter of 0.2 ⁇ m.
- 3 wt% charge transporting varnish D was obtained.
- Example 5-1 Preparation and characteristic evaluation of organic EL device
- the varnish A obtained in Example 3-1 was applied to an ITO substrate using a spin coater, then dried in air at 120 ° C. for 1 minute, and baked at 230 ° C. for 15 minutes. A thin film of 50 nm was formed.
- As the 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 an O 2 plasma cleaning apparatus (150 W, 30 seconds) before use. To remove impurities on the surface.
- ITO indium tin oxide
- ⁇ -NPD N, N′-di (1-naphthyl) -N, N′-diphenyl
- a vapor deposition apparatus vacuum degree 1.0 ⁇ 10 ⁇ 5 Pa
- Benzidine was deposited to a thickness of 30 nm at 0.2 nm / second.
- an electron block material HTEB-01 manufactured by Kanto Chemical Co., Inc. was formed to a thickness of 10 nm.
- a light emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and a light emitting layer dopant material Ir (PPy) 3 were co-evaporated.
- the deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and the layers were laminated to 40 nm.
- thin films of Alq 3 , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL element.
- the deposition rate was 0.2 nm / second for Alq 3 and aluminum, and 0.02 nm / second for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
- the characteristic was evaluated in order to prevent the characteristic deterioration by the influence of oxygen in the air, water, etc., after sealing the organic EL element with the sealing substrate, the characteristic was evaluated. Sealing was performed according to the following procedure.
- the organic EL element is placed between the sealing substrates, and the sealing substrate is bonded to an adhesive (MORESCO, Ltd., Mores Moisture Cut WB90US (P)
- an adhesive MORESCO, Ltd., Mores Moisture Cut WB90US (P)
- a water-absorbing agent manufactured by Dynic Co., Ltd., HD-0771010W-40
- UV light was applied to the bonded sealing substrate.
- the adhesive was cured by annealing at 80 ° C. for 1 hour.
- Example 5-2 An organic EL device was produced in the same manner as in Example 5-1, except that the charge transport varnish B was used instead of the charge transport varnish A.
- Example 5-3 An organic EL device was produced in the same manner as in Example 5-1, except that the charge transport varnish C was used instead of the charge transport varnish A.
- Example 5-4 The same method as in Example 5-1, except that the charge transporting varnish D was used in place of the charge transporting varnish A, the film was dried at 60 ° C. for 5 minutes in the atmosphere, and was baked at 230 ° C. for 15 minutes. Thus, an organic EL element was produced.
- the EL device including the charge transporting thin film of the present invention exhibited excellent current efficiency and external quantum efficiency. These results are considered to reflect the high transparency exhibited by the charge transporting thin film of the present invention, that is, the low absorbance with respect to visible light, by containing the metal oxide nanoparticles.
Abstract
Description
本開示は、ポリチオフェン化合物、ドーパント及び金属酸化物ナノ粒子を含む、インク組成物に関する。また、本開示は、有機電子デバイスにおける、このようなインク組成物の使用に関する。
該非水系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、該非水系インク組成物から形成される薄膜は、優れた均質性を示し、そして該非水系インク組成物から形成されるHILを含むOLEDデバイスは、良好な性能を示す。
しかし、OLEDデバイスの性能において、更なる高い透明度又は可視スペクトルでの低い吸光度を保持することが望まれている。
また、本発明の目的は、本明細書に記載の組成物を含むデバイスにおけるHILの電気的特性、熱安定性及び寿命を延ばせなくしていた(to unable increased lifetime)動作安定性を提供することである。
(a)ポリチオフェン化合物
(b)1種以上の金属酸化物ナノ粒子;
(c)1種以上のドーパント;及び
(d)1種以上の有機溶媒を含む液体担体
を含む組成物。
[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)]
〔式中、Xは、O、SまたはNHを表し、Aは、Xおよびn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またはアントラセン環を表し、Bは、非置換もしくは置換の炭化水素基、1,3,5-トリアジン基、または非置換もしくは置換の下記式(3)もしくは(4):
で示される基(式中、W1は、単結合、O、S、S(O)基、S(O2)基、または非置換もしくは置換基が結合したN、Si、P、P(O)基を示し、W2は、O、S、S(O)基、S(O2)基、または非置換もしくは置換基が結合したN、Si、P、P(O)基を示し、R46~R59はそれぞれ独立して水素原子またはハロゲン原子を表す)を表し、nは、Aに結合するスルホン酸基数を表し、1≦n≦4を満たす整数であり、qは、BとXとの結合数を示し、1≦qを満たす整数である。〕
(式中、Xは、O、SまたはNHを表し、Ar5は、アリール基を表し、nは、スルホン基数を表し、1~4を満たす整数である。)
0.05≦wtB/(wtA+wtB)≦0.50 (1-1)
(a)ポリチオフェンであって、式(I):
[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)1種以上の金属酸化物ナノ粒子;
(c)1種以上のドーパント
(d)1種以上の有機溶媒を含む液体担体;及び
(e)1種以上のアミン化合物
を含む組成物。
(a)式(I):
[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、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]
に従う繰り返し単位を含むポリチオフェン;
(b)1種以上の金属酸化物ナノ粒子;
(c)1種以上のドーパント;及び
(d)1種以上の有機溶媒を含む液体担体
を含む組成物。
〔式中、Xは、O、SまたはNHを表し、Aは、Xおよびn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またはアントラセン環を表し、Bは、非置換もしくは置換の炭化水素基、1,3,5-トリアジン基、または非置換もしくは置換の下記式(3)もしくは(4):
で示される基(式中、W1は、単結合、O、S、S(O)基、S(O2)基、または非置換もしくは置換基が結合したN、Si、P、P(O)基を示し、W2は、O、S、S(O)基、S(O2)基、または非置換もしくは置換基が結合したN、Si、P、P(O)基を示し、R46~R59はそれぞれ独立して水素原子またはハロゲン原子を表す)を表し、nは、Aに結合するスルホン酸基数を表し、1≦n≦4を満たす整数であり、qは、BとXとの結合数を示し、1≦qを満たす整数である。〕
(式中、Xは、O、SまたはNHを表し、Ar5は、アリール基を表し、nは、スルホン基数を表し、1~4を満たす整数である。)
0.05≦wtB/(wtA+wtB)≦0.50 (1-1)
また、本明細書に記載の組成物を含むデバイスにおけるHILの電気的特性、熱安定性及び寿命を延ばせなくしていた(to unable increased lifetime)動作安定性を提供できる。
[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]
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。
で示される基(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。
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:
で示される繰り返し単位は、下記式:
(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:
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、下記式:
で示される繰り返し単位は、下記式:
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、そして下記式:
で示される繰り返し単位は、下記式:
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。
典型的には、-SO3H基の硫黄原子は、ポリチオフェンポリマー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、ポリチオフェンは、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などのような、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、トリエチルアミンなど)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、ポリチオフェンポリマーに関連する「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+など)、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など)であってよい)を含んでもよいという意味を含む。
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号および国際公開第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。
ある実施態様において、スルホン化ポリチオフェンが、式(I):
[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、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、アルカリ金属イオン、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。]
に従う繰り返し単位を含むbポリチオフェンである。
ある実施態様において、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、-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、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。
ある実施態様において、R1が、-SO3Mであり、そしてR2が、-SO3M以外である。
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。
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。
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。
[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、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]
に従う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。
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。
[式中、R1及びR2は、式(I)において定義された通りである。]
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。
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。
ドーパントとしては、無機酸、有機酸、有機また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(-SO3M(ここで、Mは、アルカリ金属イオン(例えば、Na+、Li+、K+、Rb+、Cs+など)、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など))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。
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。
〔式中、Xは、O、SまたはNHを表し、Aは、Xおよびn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またはアントラセン環を表し、Bは、非置換もしくは置換の炭化水素基、1,3,5-トリアジン基、または非置換もしくは置換の下記式(3)もしくは(4):
で示される基(式中、W1およびW2は、それぞれ独立して、O、S、S(O)基、S(O2)基、または非置換も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またはハロゲン原子を表す。)を表し、nは、Aに結合するスルホン酸基数を表し、1≦n≦4を満たす整数であり、qは、BとXとの結合数を示し、1≦qを満たす整数である。〕
(式中、Xは、O、SまたはNHを表し、Ar5は、アリール基を表し、nは、スルホン基数を表し、1~4を満たす整数である。)
nは、ナフタレン環に結合するスルホン基数を表し、1~4を満たす整数であるが、当該化合物に高電子受容性および高溶解性を付与することを考慮すると、n=1または2が好ましい。中でも、下記式(7)で示される化合物が、好適である。
(式中、Ar5は、アリール基を表す。)
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(8)で示されるアリール基が好適に用いられる。
(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。)
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(9)で示されるアリール基を用いることが好ましい。
(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。)
(式中、Eは長周期型周期表の第13族または15族に属する元素を表し、Ar1~Ar4は、各々独立に、置換基を有しても良い芳香族炭化水素基又は置換基を有しても良い芳香族複素環基を表わす。)
更に、Ar1~Ar4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、Ar1~Ar4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。
(式中、E2は、長周期型周期表の第15族に属する元素を表わし、Xは、フッ素原子、塩素原子、臭素原子などのハロゲン原子を表す。)
Xは化合物の安定性、合成及び精製のし易さの点からフッ素原子、塩素原子であることが好ましく、フッ素原子であることが最も好ましい。
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、または12-Tungstophosphoric acid n-hydrate,化学式:H3(PW12O40)・nH2O)や、リンモリブデン酸(Phosphomolybdic acid hydrate、または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。
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)などの金属および上述した半金属のうち1種または2種以上の組み合わせの酸化物のことをいう。
[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(RhRi)-C(RjRk)]q-O-[CRlRm]z-SO3Hであって、各々のRh、Ri、Rj、Rk、Rl及びRm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;qは、0~10であり;そしてzは、1~5である]を含む。
[式中、Z1は、-[OC(RhRi)-C(RjRk)]q-O-[CRlRm]z-SO2Fであって、Rh、Ri、Rj、Rk、Rl及びRm、q、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。
[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。
本開示のインク組成物における使用に適したアミン化合物は、エタノールアミン類及びアルキルアミン類を含むが、これらに限定されない。
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およ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およ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。
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タート、2-エトキシエチルアセタート、2-ブトキシエチルアセタート、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。
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タートを含む。
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。
・エチレングリコール、プロピレングリコール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
インクジェット法による塗布性を考慮すると、グリコール系溶媒を含む液体担体を使用することが好ましい。
以降の記載において、便宜上、前記グリコール系溶媒とこれに該当しない有機溶媒を対比して、前者を(A)、後者を(B)で示すことがある。
ある実施態様において、液体担体は、1種以上のグリコール系溶媒(A)からなる液体担体である。
ある実施態様において、液体担体は、1種以上のグリコール系溶媒(A)と、グリコール系溶媒を除く1種以上の有機溶媒(B)とを含む液体担体である。
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、上述のグリコールジエーテル類およ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。
前記有機溶媒(B)として、好ましくは、ニトリル類、アルコール類、芳香族エーテル類、芳香族炭化水素類が挙げられる。
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また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。
グリコール系溶媒(A)に有機溶媒(B)を添加することにより、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ったまま金属酸化物ナノ粒子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。
0.05≦wtB/(wtA+wtB)≦0.50 (1-1)
0.10≦wtB/(wtA+wtB)≦0.40 (1-2)
0.15≦wtB/(wtA+wtB)≦0.30 (1-3)
(本発明の組成物にグリコール系溶媒(A)が2種以上含有されている場合、wtAはグリコール系溶媒(A)の合計含有量(重量)を示し、有機溶媒(B)が2種以上含有されている場合、wtBは有機溶媒(B)の合計含有量(重量)を示す。)
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。
(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、オキサジアゾールなど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)など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、オキサジアゾールなど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。
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。さらに、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。
[製造例1]
S-ポリ(3-MEET)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 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、真空オーブンで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。
製造例1で得られたS-ポリ(3-MEET)アミン付加物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。
[実施例3-1]
初めに、実施例1にて得た電荷輸送性物質であるS-ポリ(3-MEET)-A 0.030gを、エチレングリコール(関東化学(株)製)0.46g、ジエチレングリコール(関東化学(株)製)1.45g、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)4.83g、2-(ベンジルオキシ)エタノール(関東化学(株)製)1.93g及び2-エチルヘキシルアミン(東京化成工業(株)製)0.049gに溶解させた。溶液の調製はホットスターラーを用い、350rpm、80℃、1時間撹拌させた。次いで、ドーパントとして実施例2-1にて得たドーパントAを0.015g加え、ホットスターラーを用い、350rpm、80℃、1時間撹拌させた。最後に、EG-STを1.24g加え、ホットスターラーを用い、350rpm、30℃、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3wt%の電荷輸送性ワニスAを得た。
ドーパントとして、ドーパントAのかわりに実施例2-2にて得たドーパントBを用いた以外は、実施例3-1と同様の方法で電荷輸送性ワニスBを得た。
ドーパントとして、ドーパントAのかわりにリンタングステン酸(関東化学(株)製)を用いた以外は、実施例3-1と同様の方法で電荷輸送性ワニスCを得た。
製造例1で得たS-ポリ(3-MEET)アミン付加物0.032gをエチレングリコール(関東化学(株)製)0.73g、ジエチレングリコール(関東化学(株)製)1.93g、BA(東京化成(株)製)0.047g、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)4.83g、および、2-(ベンジルオキシ)エタノール(関東化学(株)製)0.97gに溶解させた。溶液の調製はホットスターラーを用い、350rpm、80℃、2時間撹拌させた。室温に戻した後、最後に、ドーパントとして、あらかじめ調製した、実施例2-1にて得たドーパントAの10%EG溶液0.32g、およびEG-ST 1.16gを加え、ホットスターラーを用い、350rpm、30℃、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3wt%の電荷輸送性ワニスDを得た。
実施例1にて得た電荷輸送性物質であるS-ポリ(3-MEET)-A 0.135gを、エチレングリコール(関東化学(株)製)1.50g、ジエチレングリコール(関東化学(株)製)1.50g、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)5.00g、2-(ベンジルオキシ)エタノール(関東化学(株)製)2.00g及び2-エチルヘキシルアミン(東京化成工業(株)製)0.216gに溶解させた。溶液の調製はホットスターラーを用い、350rpm、80℃、1時間撹拌させた。次いで、ドーパントとして実施例2-1にて得たドーパントAを0.069g加え、ホットスターラーを用い、350rpm、80℃、1時間撹拌させ、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3wt%の電荷輸送性ワニスDを得た。
石英基板に実施例3-1および比較例3-1で得られた各電荷輸送性ワニスAおよびDをスピンコートにより成膜し、大気中、ホットプレートにて120℃で1分間乾燥し、230℃で15分間の加熱焼成を行い、薄膜AおよびDを作製した。作製した薄膜の膜厚:100nmにおける可視域(波長:400nm~800nm)の平均透過率は、薄膜Aが99.0%、薄膜Dが54.7%であった。この結果、薄膜Aは金属酸化物ナノ粒子を含有することにより、含有していない薄膜Dに比べ、非常に高透明であることが分かる。
[実施例5-1]
実施例3-1で得られたワニスAを、スピンコーターを用いてITO基板に塗布した後、大気下、120℃で1分間乾燥し、230℃で15分間の加熱焼成を行い、ITO基板上に50nmの薄膜を形成した。ITO基板としては、インジウム錫酸化物(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。
次いで、薄膜を形成した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、関東化学社製の電子ブロック材料HTEB-01を10nm成膜した。次いで、新日鉄住金化学社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、Alq3、フッ化リチウムおよび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およ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および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。
電荷輸送性ワニスAのかわりに電荷輸送性ワニスBを用いた以外は、実施例5-1と同様の方法で有機EL素子を作製した。
電荷輸送性ワニスAのかわりに電荷輸送性ワニスCを用いた以外は、実施例5-1と同様の方法で有機EL素子を作製した。
電荷輸送性ワニスAのかわりに電荷輸送性ワニスDを用い、大気下、60℃で5分間乾燥し、230℃で15分間の加熱焼成を行った以外は、実施例5-1と同様の方法で有機EL素子を作製した。
Claims (27)
- インク組成物であって、
(a)ポリチオフェン化合物
(b)1種以上の金属酸化物ナノ粒子;
(c)1種以上のドーパント;及び
(d)1種以上の有機溶媒を含む液体担体
を含む組成物。 - 前記ポリチオフェン化合物(a)が下記式(I)で表される繰り返し単位を含む、請求項1記載の組成物。
[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)] - 前記ドーパント物質が、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族または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、請求項1または2記載のインク組成物。
- 前記ドーパント物質が、式(2)で表されるアリールスルホン酸化合物である、請求項1~3のいずれか一項記載のインク組成物。
〔式中、Xは、O、SまたはNHを表し、Aは、Xおよびn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またはアントラセン環を表し、Bは、非置換もしくは置換の炭化水素基、1,3,5-トリアジン基、または非置換もしくは置換の下記式(3)もしくは(4):
で示される基(式中、W1は、単結合、O、S、S(O)基、S(O2)基、または非置換もしくは置換基が結合したN、Si、P、P(O)基を示し、W2は、O、S、S(O)基、S(O2)基、または非置換もしくは置換基が結合したN、Si、P、P(O)基を示し、R46~R59はそれぞれ独立して水素原子またはハロゲン原子を表す)を表し、nは、Aに結合するスルホン酸基数を表し、1≦n≦4を満たす整数であり、qは、BとXとの結合数を示し、1≦qを満たす整数である。〕 - 前記ドーパント物質が、ヘテロポリ酸化合物である、請求項1~3のいずれか一項記載のインク組成物。
- 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、-ORfであり;ここで、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;そしてRfが、アルキル、フルオロアルキル、又はアリールである、請求項2~6のいずれか一項記載のインク組成物。
- R1が、Hであり、そしてR2が、H以外である、請求項2~7のいずれか一項記載のインク組成物。
- R1及びR2が、両方ともH以外である、請求項2~7のいずれか一項記載のインク組成物。
- 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が、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。
- 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。
- 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。
- ポリチオフェンが、スルホン化ポリ(3-MEET)である、請求項2~13のいずれか一項記載のインク組成物。
- ポリチオフェンが、式(I)に従う繰り返し単位を、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、請求項2~14のいずれか一項記載のインク組成物。
- 金属酸化物ナノ粒子が、B2O3、B2O、SiO2、SiO、GeO2、GeO、As2O4、As2O3、As2O5、Sb2O3、TeO2、SnO2、SnO又はそれらの混合物を含む、請求項1~15のいずれか一項記載のインク組成物。
- 金属酸化物ナノ粒子がSiO2を含む、請求項16記載のインク組成物。
- 1種以上のアミン化合物を更に含む、請求項1~17のいずれか一項記載のインク組成物。
- アミン化合物が、第三級アルキルアミン化合物と、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アミン化合物である、請求項18記載のインク組成物。
- 第三級アルキルアミン化合物以外のアミン化合物が、第一級アルキルアミン化合物である、請求項19記載のインク組成物。
- 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20記載のインク組成物。
- 第一級アルキルアミン化合物が、2-エチルヘキシルアミンまたはn-ブチルアミンである、請求項21記載のインク組成物。
- 前記液体担体が、1種以上のグリコール系溶媒(A)と、グリコール系溶媒を除く1種以上の有機溶媒(B)とを含む液体担体である、請求項1~22のいずれか一項記載のインク組成物。
- 前記グリコール系溶媒(A)が、グリコールエーテル類、グリコールモノエーテル類またはグリコール類である、請求項23記載のインク組成物。
- 前記有機溶媒(B)が、ニトリル類、アルコール類、芳香族エーテル類または芳香族炭化水素類である、請求項23または24記載のインク組成物。
- 前記グリコール系溶媒(A)の含有量:wtA(重量)と、前記有機溶媒(B)の含有量(重量):wtB(重量)とが、式(1-1)を満たす、請求項23~25のいずれか一項記載のインク組成物。
0.05≦wtB/(wtA+wtB)≦0.50 (1-1) - インク組成物であって、
(a)ポリチオフェンであって、式(I):
[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)1種以上の金属酸化物ナノ粒子;
(c)1種以上のドーパント
(d)1種以上の有機溶媒を含む液体担体;及び
(e)1種以上のアミン化合物
を含む組成物。
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KR1020197023728A KR102564836B1 (ko) | 2017-01-18 | 2018-01-18 | 잉크 조성물 |
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KR20190104212A (ko) | 2019-09-06 |
JP7077944B2 (ja) | 2022-05-31 |
KR102564836B1 (ko) | 2023-08-09 |
US20190330485A1 (en) | 2019-10-31 |
EP3573117A4 (en) | 2020-10-28 |
TW201839074A (zh) | 2018-11-01 |
CN110268540A (zh) | 2019-09-20 |
TWI771360B (zh) | 2022-07-21 |
JP2023108059A (ja) | 2023-08-03 |
CN110268540B (zh) | 2022-07-01 |
JP2022022288A (ja) | 2022-02-03 |
EP3573117A1 (en) | 2019-11-27 |
JPWO2018135582A1 (ja) | 2019-11-07 |
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