WO2018235783A1 - 非水系インク組成物 - Google Patents
非水系インク組成物 Download PDFInfo
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- WO2018235783A1 WO2018235783A1 PCT/JP2018/023165 JP2018023165W WO2018235783A1 WO 2018235783 A1 WO2018235783 A1 WO 2018235783A1 JP 2018023165 W JP2018023165 W JP 2018023165W WO 2018235783 A1 WO2018235783 A1 WO 2018235783A1
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- Prior art keywords
- ink composition
- aqueous ink
- metal oxide
- oxide nanoparticles
- primary particle
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
Definitions
- the present invention provides (a) polythiophene, (b) a first metal oxide nanoparticle having an average primary particle diameter d 1 and a second metal oxide having an average primary particle diameter d 2 (d 1 ⁇ d 2 )
- Non-aqueous ink composition comprising metal oxide nanoparticles comprising at least nanoparticles and (c) a liquid carrier, and first metal oxide nanoparticles having an average primary particle diameter d 1 and an average primary particle diameter d 2
- the present invention relates to a pileup inhibitor comprising metal oxide nanoparticles comprising at least a second metal oxide nanoparticle having 1 ⁇ d 2 ) and a life extending agent for an organic EL device.
- OLEDs organic based organic light emitting diodes
- PLEDs polymer light emitting diodes
- PHOLEDs phosphorescent organic light emitting diodes
- OCVs organic photovoltaic devices
- HIL hole injection layer
- HTL hole transport layer
- the refractive index of most p-type doped polymers HIL is around 1.5, but the light emitting material is generally much larger (1.7 Or more) having a refractive index.
- HIL p-type doped polymers
- the light emitting material is generally much larger (1.7 Or more) having a refractive index.
- additive total internal reflection occurs at the EML / HIL (or HTL / HIL) and HIL / ITO interfaces, which reduces the light extraction efficiency.
- a method of forming a charge transporting thin film of an organic EL device such as HIL and HIL, using a conductive polymer as described above, it mainly comprises a liquid carrier in which the conductive polymer is dispersed or dissolved.
- the ink composition is applied on a substrate (in many cases exactly on a thin film electrode formed on a substrate) to form a coating, and the resulting coating is dried to remove the liquid carrier Therefore, a method of forming a charge transporting thin film is known. It is preferable that the ink composition is non-aqueous because the organic EL element deteriorates due to contact with moisture. Furthermore, non-aqueous ink compositions having various compositions have been proposed for the purpose of improving various properties of charge transport thin films and organic EL devices using the same.
- Patent Document 1 discloses a non-aqueous ink composition to which an amine compound is added. Not only does the presence of the amine compound in the non-aqueous ink composition result in a non-aqueous ink composition having good shelf life and stability, the thin film formed from the non-aqueous ink composition has excellent homogeneity OLED devices comprising and exhibiting HILs formed from the non-aqueous ink composition exhibit good performance.
- Patent Documents 2 and 3 disclose non-aqueous ink compositions to which metal and / or metalloid nanoparticles are added. These nanoparticles are useful for improving the characteristics of the organic EL element such as luminance, thermal stability, hole injection property, and reducing the variation in the characteristics of each product.
- an inkjet method droplet discharge method
- a non-aqueous ink composition is discharged as fine droplets from a nozzle and adhered to an object to be coated.
- inkjet method droplet discharge method
- a non-aqueous ink composition is discharged as fine droplets from a nozzle and adhered to an object to be coated.
- banks are formed on thin film electrodes (in many cases, patterned thin film electrodes) formed on a substrate
- the non-aqueous ink composition is applied by an ink jet method only to the film formation area to form a charge transport property.
- the method of forming a thin film is often employed.
- the charge transporting thin film formed as described above preferably has a uniform thickness over the entire thin film.
- the charge transport thin film may be in a non-uniform thickness state particularly when formed by the method using the bank as described above.
- 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.
- the side surface in contact is subjected to a treatment (for example, a predetermined plasma treatment) to exhibit liquid repellency to the non-aqueous ink composition, and the surface of the substrate (thin film electrode) to be a film formation region is not
- a treatment for example, another predetermined plasma treatment
- a substrate subjected to such processing is referred to as a "liquid-repellent bank-attached substrate".
- the pile up phenomenon may not be sufficiently suppressed.
- various additional components are often added to the non-aqueous ink composition for the purpose of improving various properties of the charge transporting thin film and the organic EL device using the same, but they are added.
- a pileup phenomenon may be induced.
- the present inventors have found that under certain conditions, the addition of metal oxide nanoparticles to the non-aqueous ink composition causes the occurrence of a pile-up phenomenon to be significant.
- the non-uniformity in thickness of the charge transport thin film caused by the pile-up phenomenon may cause electrical defects (generation of leak current, short circuit, etc.) through the portion where the thickness of the thin film is increasing, which is an organic matter. It leads to shortening of the life of the EL element.
- the non-uniformity of thickness in such a charge transporting thin film leads to the non-uniformity of thickness in the light emitting layer adjacent thereto, which may combine with the electrical defect to cause uneven light emission of the organic EL element There is.
- the ink composition in this case consists only of the liquid carrier and the conductive substance, and is not intended to suppress the pileup phenomenon in the ink composition to which the additional component is added as described above.
- the inventors of the present invention conducted intensive studies to develop means for suppressing the pile-up phenomenon in the non-aqueous ink composition to which the additional component as described above is added.
- the present inventors surprisingly found that, in a non-aqueous ink composition in which metal oxide nanoparticles are added to a combination of a specific polythiophene (conductive polymer) and a liquid carrier, the metal in the same composition. It has been found that there is a correlation between the dispersed state of the oxide nanoparticles and the occurrence of the pile-up phenomenon, and the more uniform the dispersed state, the more pronounced the occurrence of the pile-up phenomenon.
- the present inventors also show that the dispersion state of the metal oxide nanoparticles in the non-aqueous ink composition reflects the particle size distribution of the metal oxide nanoparticles, and the narrower the particle size distribution, the more the metal oxide nanoparticles are. It is considered that the dispersion state is appropriately controlled and the pile-up phenomenon can be suppressed by appropriately widening the particle size distribution of the metal oxide nanoparticles, since the dispersion state of the metal oxide particles is considered to be more uniform. I found it.
- the present inventors also use metal oxide nanoparticles containing at least two types of metal oxide nanoparticles having different primary particle sizes, as metal oxide nanoparticles having such a moderately wide particle size distribution. It has been found that the pileup phenomenon can be largely suppressed, and it becomes possible to easily obtain a charge transportable thin film having a uniform thickness.
- the present inventors further show that even when the above-mentioned metal oxide nanoparticles are not used, certain characteristics of the obtained organic EL device, for example, the current efficiency, tend to decrease even if the pile-up phenomenon is suppressed. On the other hand, it has been surprisingly found that the characteristics of the organic EL device are not excessively lowered when the metal oxide nanoparticles as described above are used. Based on the above new findings, the present invention has been completed.
- the main object of the present invention is to provide a non-aqueous ink composition which provides a charge transportable thin film having a uniform thickness without excessively degrading the properties of the organic EL device.
- Another object of the present invention is to provide a pileup inhibitor for non-water-based ink compositions and a life extender for organic EL elements without excessively degrading the properties of the organic EL elements.
- the present invention provides the following inventions.
- a non-aqueous ink composition comprising (A) 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 one or more, and R e is H, alkyl, fluoroalkyl or aryl).
- (B) At least the following (b-1) and (b-2): (B-1) First metal oxide nanoparticles having an average primary particle diameter d 1 (b-2) containing second metal oxide nanoparticles having an average primary particle diameter d 2 and having an average primary particle diameter d 1 and d 2 are metal oxide nanoparticles are in a relationship of d 1 ⁇ d 2; including and (c) a liquid carrier comprising one or more organic solvents, non-aqueous ink composition.
- the average primary particle diameter d 1 is smaller than 15 nm, the average primary particle diameter d 2 is 10nm or more, the composition of items 1, wherein.
- the average is less than the primary particle diameter d 1 is 3nm or more 15 nm, the average primary particle diameter d 2 is 10nm or more 30nm or less, item 1 or 2 composition.
- the amount of the metal oxide nanoparticles (b) is 1 wt% to 98 wt% based on the total weight of the metal oxide nanoparticles (b) and the polythiophene (a). 5.
- the non-aqueous ink composition according to any one of 5.
- the first metal oxide nanoparticles (b-1) and the second metal oxide nanoparticles (b-2) are each independently B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2 The GeO, As 2 O 4 , As 2 O 3 , As 2 O 5 , Sb 2 O 3 , TeO 2 , SnO 2 , SnO, or mixtures thereof as described in any one of the preceding paragraphs 1 to 7 Water-based ink composition.
- liquid carrier according to any one of the above items 1 to 9, which is a liquid carrier comprising one or more glycol solvents (A) and one or more organic solvents (B) excluding glycol solvents.
- A glycol solvents
- B organic solvents
- glycol solvent (A) is a glycol ether, a glycol monoether or a glycol.
- 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 of R a , R b , R c and R d is each independently H, halogen, alkyl, fluoroalkyl or aryl; and R e is H, alkyl, fluoroalkyl or aryl
- the non-aqueous ink composition according to any one of the preceding claims, wherein p is 1, 2, or 3; and R f is alkyl, fluoroalkyl or aryl.
- 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 Ink composition.
- 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 non-aqueous ink composition according to the above 16 or 17, which is (C 1 -C 8 ) alkyl, (C 1 -C 8 ) fluoroalkyl or phenyl.
- the polythiophene has the following formula: 13.
- 21 The non-aqueous ink composition according to item 20, wherein the polythiophene is sulfonated poly (3-MEET).
- the said polythiophene is more than 50% by weight, typically more than 80% by weight, more typically more than 90% by weight of recurring units according to formula (I), based on the total weight of the recurring units.
- non-aqueous ink composition according to any one of the preceding claims, further comprising a synthetic polymer containing one or more acidic groups.
- Said synthetic polymer 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, optionally at least one
- Said polymeric acid comprises recurring units according to formula (II) and recurring units according to formula (III): [In the formula, And each R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently H, halogen, fluoroalkyl or perfluoroalkyl; and X is — [OC (R h R i ) -C (R j R k )] q -O- [CR l R m ] z -SO 3 H, each R h , R i , R j , R k , R l and R
- non-aqueous ink composition according to the above 23, wherein the synthetic polymer is a polyether sulfone comprising one or more repeating units comprising at least one sulfonic acid (-SO 3 H) residue.
- non-aqueous ink composition according to any one of the preceding items 1 to 26, further comprising 27.1 or more types of amine compounds.
- 29 The non-aqueous ink composition according to the above-mentioned 28, wherein the amine compound other than the tertiary alkylamine compound is a primary alkylamine compound.
- non-aqueous ink composition according to the above-mentioned 30, wherein the primary alkylamine compound is 2-ethylhexylamine or n-butylamine.
- the non-aqueous ink composition is made of metal oxide nanoparticles and added to the non-aqueous ink composition
- the non-aqueous ink composition is applied to a liquid repellent bank substrate and dried to suppress a pile-up phenomenon when forming a charge transporting thin film Pile-up inhibitor, which At least the following (b-1) and (b-2):
- a pile-up inhibitor which is a metal oxide nanoparticle in which 1 and d 2 have a relationship of d 1 ⁇ d 2 .
- the average primary particle diameter d 1 and d 2 are, it satisfies the relationship represented by the formula d 2 / d 1> 1.5, pileup inhibitors of the preceding 32 description.
- the first metal oxide nanoparticles (b-1) and the second metal oxide nanoparticles (b-2) are each independently B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2
- a non-aqueous ink composition comprising (A) 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 one or more, and R e is H, alkyl, fluoroalkyl or aryl).
- (B) At least the following (b-1) and (b-2): (B-1) First metal oxide nanoparticles having an average primary particle diameter d 1 (b-2) containing second metal oxide nanoparticles having an average primary particle diameter d 2 and having an average primary particle diameter d Metal oxide nanoparticles wherein 1 and d 2 are in the relationship of d 1 ⁇ d 2 ; and (c) a liquid carrier comprising one or more organic solvents (d) a synthetic polymer comprising one or more acidic groups (e) Non-aqueous ink composition comprising one or more amine compounds.
- a life extending agent for an organic EL element comprising metal oxide nanoparticles, wherein At least the following (b-1) and (b-2): (B-1) First metal oxide nanoparticles having an average primary particle diameter d 1 (b-2) containing second metal oxide nanoparticles having an average primary particle diameter d 2 and having an average primary particle diameter d
- the life extending agent is a metal oxide nanoparticle in which 1 and d 2 have a relationship of d 1 ⁇ d 2 .
- the non-aqueous ink composition of the present invention is applied to a liquid repellent bank substrate and dried to suppress a pile-up phenomenon when forming a charge transporting thin film, so that the charge transporting property with uniform thickness can be obtained. Thin films are easily obtained. Furthermore, the non-aqueous ink composition of the present invention does not excessively deteriorate the characteristics of the organic EL element.
- FIG. 6 is a graph comparing the cross-sectional shapes of the charge transporting thin films obtained in Examples 2 to 5 and Comparative Examples 2 to 3.
- FIG. 6 is a graph comparing the cross-sectional shapes of the charge transporting thin films obtained in Examples 2 to 5 and Comparative Examples 2 to 3.
- 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 ) Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, triacontyl and 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
- 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-benzene, 1,3-benzene, 1,4-benzene and 2,6-naphthalene 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 is a monovalent unsaturated hydrocarbon group containing one or more 6-membered carbocycles, wherein the unsaturation is three conjugated doublets. It means a group that can be represented by a bond.
- Aryl groups include monocyclic aryl and polycyclic aryl.
- Polycyclic aryl is a monovalent unsaturated hydrocarbon group containing two or more 6-membered carbocycles, which is a group which can be represented by three conjugated double bonds. And groups in which adjacent rings are 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).
- 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 useful compounds in the electronic device, typically in the layer (HTL), in the hole injection layer (HIL) and in the electron blocking layer (EBL) of an organic electronic device such as an organic light emitting device etc. including.
- 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 changes the properties of the 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 as dopants in the present invention.
- 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.
- the present invention relates to a non-aqueous ink composition, and (A) 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 one or more, and R e is H, alkyl, fluoroalkyl or aryl).
- (B) At least the following (b-1) and (b-2): (B-1) First metal oxide nanoparticles having an average primary particle diameter d 1 (b-2) containing second metal oxide nanoparticles having an average primary particle diameter d 2 and having an average primary particle diameter d
- the present invention relates to a non-aqueous ink composition comprising a metal oxide nanoparticle in which 1 and d 2 are in the relationship of d 1 ⁇ d 2 ; and (c) a liquid carrier comprising one or more organic solvents.
- the ink composition of the present invention is non-aqueous.
- non-aqueous means that the total amount of water in the non-aqueous ink composition of the present invention is 0 to 2 wt% with respect to the total amount of the non-aqueous ink composition. Do. Typically, the total amount of water in the non-aqueous ink composition is 0 to 1 wt%, more typically 0 to 0.5 wt%, relative to the total amount of the non-aqueous ink composition. In one embodiment, the non-aqueous ink composition of the present invention is substantially free of water.
- Polythiophenes suitable for use in the present disclosure have 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 optionally halogen Embedded image is a hydrocarbylene group that is being formed, p is one or more, and R e is H, alkyl, fluoroalkyl or aryl).
- 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
- R a , R b , R c and R d are each independently H, halogen, alkyl, fluoroalkyl or aryl
- R e is H, alkyl, fluoroalkyl 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 repeat unit is derived from a 3-substituted thiophene.
- the polythiophenes may be regiorandom or regioregular compounds. Because of its asymmetric structure, the 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 characterization, including regioregular polythiophenes with pendant groups, are provided, for example, in US Pat. Nos. 6,602,974 to McCullough et al. And US Pat. No. 6,166,172 to McCullough et al.
- 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 . 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.
- 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.
- the polythiophene has the following formula:
- a repeating unit selected from the group consisting of a group represented by and a combination thereof.
- the repeating unit represented by is of the following formula:
- 3-MEET (2- (2-Methoxyethoxy) ethoxy) thiophene
- 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 the monomer represented by the structure shown in
- the repeating unit represented by is of the following formula:
- 3,4-Bis ((1-propoxypropan-2-yl) oxy) thiophene (referred to herein as 3,4-di PPT] It derives from the monomer represented by the structure shown by
- 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 according to 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 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.
- the sulfonated thiophene polymers and / or copolymers can be prepared using any method known to those skilled in the art.
- polythiophene can be sulfonated by reacting polythiophene 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.
- 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).
- 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 conjugated polymers and sulfonated 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.
- the polythiophene is sulfonated.
- 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 a (AB) n -multiblock copolymer.
- Polythiophenes have repeating units derived from other types of monomers such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes such as phenylenes, phenylene vinylenes, fluorenes, etc. May be included.
- the polythiophene comprises more than 50% by weight, typically more than 80% by weight, more typically more than 90% by weight of recurring units according to formula (I), based on the total weight of the recurring units. More, still more typically more than 95% by weight.
- 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 according to 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 is used after treatment with a reducing agent.
- a conjugated polymer such as polythiophene
- the chemical structure of a part of the repeating units constituting them may be an oxidized 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 conjugated polymers such as polythiophene.
- polaron structure or “bipolaron structure” which is generated by the above-mentioned doping reaction and imparts charge transportability to conjugated polymers such as 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.
- conjugated polymer before the occurrence of this doping reaction contains a quinoid structure is equivalent to the doping reaction in the production process of the conjugated polymer (particularly, in the sulfonation step in the case of sulfonation of the conjugated polymer) It is thought that it was caused by the unintended oxidation reaction.
- the dispersibility in organic solvents may vary from product to product, and one of the causes is the amount of quinoid structure introduced into polythiophene by the above-mentioned unintended oxidation reaction. It is thought that it fluctuates according to the difference in the production conditions of polythiophene of 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 non-aqueous ink composition which gives an excellent charge transporting thin film.
- the reducing agent used for this reduction treatment reduces the quinoid structure of polythiophene represented by the formula (I ′) to a non-oxidized structure, ie, a benzenoid of polythiophene represented by the formula (I)
- a non-oxidized structure ie, a benzenoid of polythiophene represented by the 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 the corresponding ammonium salt, for example, a trialkyl ammonium salt (sulfonated polythiophene amine adduct) and then subjected to a reduction treatment.
- polythiophene which was not dissolved in the reaction system at the start of the treatment may be dissolved at the completion of the treatment.
- polythiophene may be recovered by adding polythiophene and an incompatible organic solvent (acetone, isopropyl alcohol, etc.) to the reaction system to form a precipitate of polythiophene and filtering it. it can.
- an incompatible organic solvent acetone, isopropyl alcohol, etc.
- the non-aqueous ink composition of the present disclosure may optionally further include other hole carrier compounds.
- 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 4,4 ′, 4 ′ ′-tris (N, N-phenyl-3-methylphenylamino) triphenylamine (also called m-MTDATA, CAS # 124729-98-2); 'N, N'-diphen
- 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 polythiophenes comprising repeat units according to formula (I) may be doped or not.
- the polythiophene comprising a repeat unit according to formula (I) is doped with a dopant.
- Dopants are known in the art. See, for example, U.S. Patent Nos. 7,070,867; U.S. Publication 2005/0123793; and U.S. Publication 2004/0113127.
- the dopant may be an ionic compound.
- the dopant can include a cation and an anion.
- One or more dopants may be used to dope the polythiophene containing 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 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 the group —SO 3 M where M 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 group, where M 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 Include, but are 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 And borates such as, for example, tetrafluoroborate, tetraarylborate, and trifluoroborate, and the like.
- tetraaryl borates include, but are not limited to, halogenated tetraaryl borates such as tetrakis pentafluorophenyl borate (TPFB).
- 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.
- polythiophenes may be doped with a dopant.
- 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 the polythiophene.
- 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.
- 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).
- 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 may be one or more of the solvents described herein.
- 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 (e.g., by rotary evaporation of the solvent, etc.) by methods known to those skilled in the art to obtain a dry or substantially dry material (such as a powder).
- 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 non-aqueous ink composition of the present invention contains metal oxide nanoparticles.
- the metal oxide nanoparticles (b) used in the present invention are at least the following (b-1) and (b-2): (B-1) First metal oxide nanoparticles having an average primary particle diameter d 1 (hereinafter sometimes referred to as “component (b-1)”) (B-2) Second metal oxide nanoparticles having an average primary particle diameter d 2 (hereinafter sometimes referred to as “component (b-2)”) And the average primary particle diameters d 1 and d 2 have a relationship of d 1 ⁇ d 2 .
- metal refers to an element having properties of an intermediate or mixture of chemical and / or physical properties of metal and nonmetal.
- 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 a combination of two or more of metals such as tungsten) and the above-described semimetals.
- nanoparticles refers to nanoscale particles, wherein the average primary particle size (average primary particle size) is typically 500 nm or less. Say The average diameter of the primary particles can be converted from the specific surface area according to the BET method.
- the particles When converted from the specific surface area by the BET method, the particles can be regarded as true spheres, and the average particle diameter can be calculated by the following equation.
- d 6000 / (S ⁇ ⁇ )
- d Average particle size (nm)
- S specific surface area (m 2 / g)
- ⁇ True specific gravity (g / cm 3 )
- the BET method is a method utilizing adsorption of gas molecules on the particle surface, and it is premised that gas molecules are adsorbed on the entire particle surface. Therefore, application of the BET method is difficult when there is a region where gas molecules can not be adsorbed on the particle surface.
- the case where nanoparticles having significant aggregation are used can be mentioned, and such a state often occurs when the particle size is small (for example, 7 nm or less).
- the average diameter of the primary particles may be measured by a method other than the BET method.
- a titration method with sodium hydroxide can be mentioned (see, for example, George W. Sears Jr., Anal. Chem. 28 (12) p1981-3 (1956) and the like).
- the average particle diameter of primary particles of metal oxide nanoparticles represents a numerical value measured by a method of converting from the specific surface area according to the BET method.
- the average particle size of the primary particles of the metal oxide nanoparticles described herein is 500 nm or less; 250 nm or less; 100 nm or less; or 50 nm or less; or 25 nm or less.
- the metal oxide nanoparticles have a number average primary particle size of about 1 nm to about 100 nm, more typically about 2 nm to about 30 nm.
- the former average primary particle diameter d 1 and the latter average primary particle diameter d 2 are in a relationship of d 1 ⁇ d 2.
- a substrate with a liquid repellent bank can be used as the substrate and still be obtained by a pile-up phenomenon.
- the charge transporting thin film may be in a non-uniform thickness state.
- the present inventors have confirmed that such a pile-up phenomenon is particularly likely to occur in a non-aqueous ink composition to which metal oxide nanoparticles are added. Although the cause is not clarified, the metal oxide nanoparticles dispersed in the non-water-based ink composition are dried as a result of any interaction with other components in the composition, the substrate surface or the bank side. It is thought that a pile-up phenomenon occurs because it moves to the side of the bank during the process and further crawls along the bank.
- the dispersion state of the metal oxide nanoparticles in the non-aqueous ink composition is The more uniform, the more likely the occurrence of pile-up phenomenon will be, that is, there is a correlation between the dispersion state of metal oxide nanoparticles in the non-aqueous ink composition and the occurrence of pile-up phenomenon. Admitted. This suggests that the pileup phenomenon can be suppressed by appropriately controlling the dispersion state.
- the dispersed state of the metal oxide nanoparticles in the non-aqueous ink composition reflects the particle size distribution of the metal oxide nanoparticles.
- the narrower the particle size distribution the more uniformly the dispersed state of the metal oxide nanoparticles. It is considered to be. From this, when the particle size distribution of the metal oxide nanoparticles is excessively narrow, a pileup phenomenon easily occurs, and by appropriately widening the particle size distribution, the dispersed state is appropriately controlled to suppress the pileup phenomenon. It was estimated that it would be possible.
- the metal oxide nanoparticles unexpectedly have a particle diameter of about 4 nm to 80 nm, more preferably about It has been found that having a particle size distribution that includes particles of 5 nm to 40 nm, more preferably about 10 to 20 nm, is effective in suppressing the pile up phenomenon.
- Such an appropriately wide particle size distribution of metal oxide nanoparticles can be obtained by combining two or more kinds of metal oxide nanoparticles having different average primary particle sizes.
- the components (b-1) and (b-2) behave differently depending on the difference in average primary particle size. It is possible that the components (b-1) and (b-2) do not exhibit their interaction (eg, aggregation) which does not occur unless they are used in combination.
- the charge transportable thin film is formed using the non-aqueous ink composition of the present invention including the metal oxide nanoparticles as described above, in particular, the non-aqueous ink composition to which an amine compound is added, to form an organic EL
- the characteristic deterioration of the obtained organic EL device is not so remarkable and particularly the deterioration of the current efficiency is suppressed when used for the preparation of the device, as compared with the case where the conventional metal oxide nanoparticles are used. That is confirmed by the present inventors.
- the amine compound when the amine compound is added to the non-aqueous ink composition containing the metal oxide nanoparticles as described above, the amine compound remains in the obtained charge transport thin film. It has been confirmed by the present inventors that the amount is smaller than when conventional metal oxide nanoparticles are used, which contributes to the suppression of deterioration of characteristics (for example, current efficiency) in the organic EL device. It is estimated that And this may be caused by the interaction between the components (b-1) and (b-2) which does not occur when they are not used together.
- the non-aqueous ink composition of the present invention is used in which metal oxide nanoparticles containing two or more kinds of metal oxide nanoparticles having different average primary particle sizes are added to a specific polythiophene and liquid carrier combination.
- pile-up can be suppressed while avoiding excessive deterioration of the characteristics of the organic EL element.
- the metal oxide nanoparticles (b) as described above can be used as a pile-up inhibitor, and when this is added to a non-aqueous ink composition, the non-aqueous ink composition can be used as a liquid repellent bank substrate The pileup phenomenon at the time of forming a charge transportable thin film is suppressed by applying and drying it.
- the life of the organic EL device As described above, if the thickness of the charge transport thin film becomes uneven due to the pile-up phenomenon, there is a possibility that the life of the organic EL device may be shortened. However, the life of the organic EL device is extended by suppressing the pile-up phenomenon. be able to.
- the metal oxide nanoparticles (b) may optionally further include other metal oxide nanoparticles in addition to the component (b-1) and the component (b-2). Also, the metal oxide nanoparticles may be composed of the same chemical species or may be composed of different chemical species. In the present invention, it is preferable to combine two types of metal oxide nanoparticles having different average primary particle sizes from each other, and to combine two types of metal oxide nanoparticles consisting of the same chemical species and having only different average primary particle sizes. Is more preferred.
- Average primary particle diameter d1 of the first metal oxide nanoparticles (b-1) and the second metal oxide nanoparticles (b-2) at least included in the metal oxide nanoparticles (b) mean relates primary particle diameter d 2 (d 1 ⁇ d 2) of, d 1 is smaller than 15 nm, preferably has an average primary particle diameter d 2 is 10nm or more and less than 15 nm d 1 is 3nm or more, the average primary more preferably the particle size d 2 is 10nm or more 30 (or 50) nm or less.
- the component (b-1) and the component (b-2) contained at least in the metal oxide nanoparticles (b) have an average primary particle diameter d 2 of the latter with respect to the average primary particle diameter d 1 of the former.
- the ratio of d 1 ⁇ d 2 ), that is, d 2 / d 1 be in a relationship represented by a specific formula.
- d 1 and d 2 satisfy the relation represented by the formula d 2 / d 1 > 1.5, and it is more preferable that the relation represented by the formula d 2 / d 1 > 2.0 is satisfied. preferable.
- this ratio d 2 / d 1 d 1 and d 2 preferably satisfy the relationship represented by the formula d 2 / d 1 ⁇ 1000, and more preferably, the formula The relationship expressed by d 2 / d 1 ⁇ 100 is satisfied.
- a weight ratio of the first metal oxide nanoparticles (b-1) to the second metal oxide nanoparticles (b-2) (b-1) / (b ⁇ 2) is preferably in the range of 0.001 to 1000, and more preferably in the range of 0.01 to 100.
- Metal oxide nanoparticles suitable for use in the present invention include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), Nanoparticles of oxides such as titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta) and W (tungsten), or mixed oxides containing these It can be mentioned.
- 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 component (b-1) and the component (b-2) are each independently B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2 , GeO, As 2 O 4 , As 2 O 3 , As 2 O 5 , SnO 2 , SnO, Sb 2 O 3 , TeO 2 , or a mixture of these.
- both the component (b-1) and the component (b-2) contain SiO 2 .
- 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 sold by Nissan Chemical Industries, Ltd. (eg methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethyl acetamide, ethylene glycol, 2-propanol, methanol , 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 metal oxide nanoparticles used in the non-aqueous ink composition described herein is as a percentage by weight of the combined weight of metal oxide nanoparticles and the doped or non-doped polythiophene. , Can be adjusted and measured.
- the amount of metal oxide nanoparticles is 1 wt% to 98 wt%, typically the combined weight of the metal oxide nanoparticles and the doped or non-doped polythiophene. About 2 wt% to about 95 wt%, more typically about 5 wt% to about 90 wt%, still more typically about 10 wt% to about 90 wt%.
- the amount of metal oxide nanoparticles is typically about 20% by weight to about 98%, typically the combined weight of the metal oxide nanoparticles and the doped or non-doped polythiophene. Is about 25% to about 95% by weight.
- the liquid carrier used in the non-aqueous ink composition of the present invention contains one or more organic solvents.
- the liquid carrier consists essentially of or consists of one or more organic solvents.
- the liquid carrier may be an organic solvent or 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 suitable for use in liquid carriers include aliphatic and aromatic ketones, dimethylsulfoxide (DMSO) and 2,3,4,5-tetrahydrothiophene-1,1-dioxide (tetramethylene sulfone; sulfolane) Organic sulfur solvents; tetrahydrofuran (THF), tetrahydropyran (THP), tetramethylurea (TMU), N, N'-dimethylpropyleneurea, alkylated benzenes (such as xylene and its isomers), halogenated benzenes, N-methyl pyrrolidinone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dichloromethane, acetonitrile, dioxanes, ethyl acetate, ethyl benzoate, methyl benzoate, dimethyl carbonate, ethylene carbonate, propylene carbonate, 3-methoxypropane Pi
- 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.
- organic solvents which fully or partially solubilize the polythiophene or swell the polythiophene will also be considered. Such other solvents may be included in the liquid carrier in various amounts to adjust ink properties such as wettability, viscosity, morphology control.
- the liquid carrier may further comprise one or more organic solvents that act as non-solvents for the polythiophene.
- 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 etc .; diethylene glycol diethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; propylene glycol diethers 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 analogues of ethylene glycol and propylene glycol ether as referred to herein (ie, tri- and tetra-analogs such as triethylene glycol dimethyl ether, triethylene) And glycol diethers
- solvents such as ethylene glycol monoether acetate and propylene glycol monoether acetate (glycol ester ethers) can be considered, wherein 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 the higher 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 and the like can be considered, and also include higher glycol ether analogues (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) may also be considered for use in liquid carriers.
- 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), di-ethylene 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 Pill ether (propyl carbitol), diethylene glycol monohexyl ether
- the organic solvents disclosed herein can, for example, improve ink properties such as substrate wettability, ease of solvent removal, viscosity, surface tension and ejection. It can be used in various proportions in the liquid carrier.
- non-protonic non-polar solvents can provide the added benefit of extending the lifetime of devices (eg, such as PHOLEDs) comprising emitter technology that is sensitive to protons.
- the liquid carrier comprises dimethyl sulfoxide, ethylene glycol (glycols), tetramethyl urea 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 solvent The above glycol diethers, glycol ester ethers, glycol diesters, glycol monoethers, glycols and the like are collectively referred to as "glycol solvent”. That is, the “glycol solvent” in the present invention has the formula R 1 —O— (R—O) n —R 2 (wherein each R independently represents a linear C 2 -C 4. And R 1 and R 2 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 An unsubstituted aliphatic acyl group, n is an integer of 1 to 6, and the organic solvent does not have one or more aromatic structures.
- R is a C 2 or C 3 unsubstituted alkylene group.
- n is particularly preferably an integer of 1 to 4.
- 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.
- This glycol solvent includes, for example, the following solvents.
- glycol monoethers which are monoalkyl ethers of the glycols ⁇ glycol diethers which is a dialkyl ether of the glycols Ethers, glycol monoesters which are aliphatic carboxylic acid monoesters of the glycols, glycol diesters which are aliphatic carboxylic acid diesters of the glycols, glycol which is an aliphatic carboxylic acid monoester of the glycol monoethers Ester Ethers
- a liquid carrier containing a glycol solvent it is preferable to use.
- the former may be shown as (A) and the latter as (B), for the sake of convenience, comparing the glycol-based solvent and the organic solvent not corresponding thereto.
- the liquid carrier is a liquid carrier consisting of one or more glycol solvents (A).
- the liquid carrier is a liquid carrier comprising one or more glycol solvents (A), glycol diethers, glycol monoethers or glycols are preferably mentioned as the glycol solvents (A), May be mixed.
- examples include but are not limited to mixing three types of glycol monoethers, glycol diethers and glycols. Specific examples thereof include specific examples of the above-mentioned glycol monoethers, glycol diethers and glycols, preferably, diethylene glycol monobutyl ether as glycol monoethers, triethylene glycol dimethyl ether as glycol diethers And triethylene glycol butyl methyl ether, glycols such as ethylene glycol and diethylene glycol.
- the liquid carrier is a liquid carrier comprising one or more glycol solvents (A)
- glycols are preferably 30% or more of the liquid carrier, and more preferably 40% or more from the viewpoint of the solubility of polythiophene And 50% or more is more preferable.
- the liquid carrier is a liquid carrier comprising one or more glycol solvents (A) and one or more organic solvents (B) excluding glycol solvents.
- the glycol solvent (A) preferably those mentioned above are mentioned, but more preferably glycol diethers and glycols are mentioned, and these may be mixed. Examples include, but are not limited to, mixing two types of glycol diethers and glycols. Specific examples thereof include the specific examples of the above-mentioned glycol diethers and glycols, preferably triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether as glycol diethers, ethylene glycol as glycols, Diethylene glycol is mentioned.
- Preferred examples of the organic solvent (B) include nitriles, alcohols, aromatic ethers, and aromatic hydrocarbons.
- 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.
- alcohols are more preferable, and among the alcohols, 2- (benzyloxy) ethanol is more preferable.
- the organic solvent (B) By adding the organic solvent (B) to the glycol solvent (A), the aggregation of the metal oxide nanoparticles is appropriately controlled while maintaining the solubility of the ink solid content during film formation by ink jet coating, and flatter 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): wt B (weight)
- the formula (1) preferably satisfies the formula (1-1), more preferably the formula (1-2), and most preferably the formula (1-3).
- wtA indicates the total content (weight) of glycol solvents (A), and the organic solvent (B) is two or more
- wtB shows the total content (weight) of an organic solvent (B).
- the amount of liquid carrier in the non-aqueous ink composition of the present invention is about 50% by weight to about 99% by weight, typically about 75% by weight to about 98% by weight, based on the total weight of the ink composition. Typically from about 90% to about 95% by weight.
- the non-aqueous ink composition of the present invention can be prepared by mixing each component such as polythiophene in the form of a solution or dispersion (stock solution) in an organic solvent. The organic solvent added to the non-aqueous ink composition as a result of this operation is considered to be part of the liquid carrier.
- the non-aqueous ink composition of the present invention further comprises one or more amine compounds.
- Amine compounds suitable for use in the non-aqueous ink composition of the present invention include, but are not limited to, ethanolamines and alkylamines.
- Suitable ethanolamines 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].
- Alkyl amines include primary, secondary and tertiary alkyl amines.
- primary alkylamines 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 ], n-hexylamine [C 6 H 13 NH 2 ], 2-ethylhexylamine [C 8 H 17 NH 2 ], n-decylamine [C 10 H 21 NH 2 ], and ethylenediamine [H 2 NCH 2 CH 2 NH 2 ].
- Secondary alkylamines are, for example, diethylamine [(C 2 H 5 ) 2 NH], di (n-propylamine) [(nC 3 H 9 ) 2 NH], di (isopropylamine) [(i -C 3 H 9 ) 2 NH], and dimethylethylenediamine [CH 3 NHCH 2 CH 2 NHCH 3 ].
- Tertiary alkyl amines are, 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 one embodiment, the amine compound is triethylamine.
- the amine compound is a mixture of a tertiary alkylamine compound and an amine compound other than a tertiary alkylamine compound.
- the amine compound other than the tertiary alkylamine compound is a primary alkylamine compound.
- the primary alkylamine compound is preferably 2-ethylhexylamine or n-butylamine.
- the amount of amine compound can be adjusted and measured as a weight percentage to the total amount of the non-aqueous ink composition.
- the amount of amine compound 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 non-aqueous ink composition. Or at least 2.00% by weight.
- the amount of amine compound is about 0.01 to about 2.00 wt%, typically about 0.05 wt% to about 1.50 wt%, based on the total weight of the non-aqueous ink composition. %, More typically from about 0.1% to about 1.0% by weight.
- At least a portion of the amine compound may be present in the form of an ammonium salt with a sulfonated conjugated polymer, such as a trialkylammonium salt (sulfonated polythiophene amine adduct).
- a sulfonated conjugated polymer such as a trialkylammonium salt (sulfonated polythiophene amine adduct).
- this amine compound is usually added when preparing the final non-aqueous ink composition, it may be previously added before that time.
- an amine compound is added to a sulfonated conjugated polymer to convert it into the corresponding ammonium salt, for example, a trialkylammonium salt (sulfonated polythiophene amine adduct), and then subjected to a reduction treatment.
- an amine compound eg triethylamine
- an ammonium salt eg triethylammonium salt
- a solution obtained by adding water and triethylamine to a reduction treated sulfonated polythiophene to dissolve it and stirring it under heating (for example, 60 ° C.) Isopropyl alcohol and acetone may be added thereto to precipitate a sulfonated conjugated polymer triethylammonium salt, which may be filtered and recovered.
- the non-aqueous ink composition of the present invention may optionally further comprise one or more matrix compounds known to be useful in the hole injection layer (HIL) or the hole transport layer (HTL).
- HIL hole injection layer
- HTL hole transport layer
- the optional matrix compound 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 different from polythiophene. See, eg, US Patent Publication No. 2006/0175582 published Aug. 10, 2006.
- Synthetic polymers can, for example, comprise a carbon backbone.
- 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 is at least one alkyl or alkoxy group, optionally substituted by at least one fluorine atom and at least one sulfonic acid (—SO 3 H) residue, optionally A polymeric acid comprising one or more repeating units, including 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):
- 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 h R i ) -C (R j R k )] q -O- [CR l R m ] z -SO 3 H, and each R h , R i , R j , R k , R 1 and R m are independently H, halogen, fluoroalkyl or perfluoroalkyl; q 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 h , R i , R j , R k , R l and R m is independently F, (C 1 -C 8 ) fluoroalkyl, or (C 1 -C 8 ) perfluoro It is an alkyl.
- each R 1 and R m is F; q is 0; and z is 2.
- each R 5 , R 7 , and R 8 is F and R 6 is Cl; and each R 1 and R m is F; q is 0 And z is 2.
- each R 5 , R 6 , R 7 , and R 8 is F; and each R 1 and R m is F; q is 0; and z is 2
- the ratio of the number of repeating units according to Formula (II) (“n”) to the number of repeating units according to Formula (III) (“m”) is not particularly limited.
- the n: m ratio is typically 9: 1 to 1: 9, more typically 8: 2 to 2: 8. In one embodiment, the n: m ratio is 9: 1. In one embodiment, the n: m ratio is 8: 2.
- polymeric acids suitable for use in the present invention 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):
- Z 1 represents-[OC (R h R i ) -C (R j R k )] q -O- [CR l R m ] z -SO 2 F, and R h and R i , R j , R k , R 1 and R m , q and z are as defined in the present specification] and copolymerized by a known polymerization method, followed by hydrolysis of the sulfonyl fluoride group to give sulfone It can be produced by conversion to an acid group.
- TFE tetrafluoroethylene
- CTFE chlorotrifluoroethylene
- 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 Asahi It is marketed by Glass Co. under the trade name FLEMION®.
- the synthetic polymer 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):
- 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):
- 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):
- 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):
- the polyether sulfone is a compound of formula (XI):
- Polyethersulfone containing one or more repeating units comprising at least one sulfonic acid (-SO 3 H) residue are commercially available, for example, sulfonated polyether sulfone, Konishi Chemical Ind. Co., It is marketed as S-PES by Ltd.
- the optional matrix compound may be a leveling agent.
- the matrix compound or leveling agent may be, for example, an organic polymer (eg, poly (styrene) or poly (styrene) derivative; poly (vinyl acetate) or a derivative thereof; poly (ethylene glycol) or a derivative thereof; poly (ethylene-co-) Poly (pyrrolidone) or a derivative thereof (eg, poly (1-vinylpyrrolidone-co-vinyl acetate)); poly (vinylpyridine) or a derivative thereof; poly (methyl methacrylate) or a derivative thereof; poly (acrylic) (Butyl acid); poly (aryl ether ketone); poly (aryl sulfone); poly (ester) or derivatives thereof;
- organic polymer eg, poly (styrene) or poly (styrene) derivative
- poly (vinyl acetate) or a derivative thereof poly (ethylene glycol) or a derivative thereof
- the matrix compound is a poly (styrene) or poly (styrene) derivative.
- the matrix compound is poly (4-hydroxystyrene).
- the optional matrix compound or leveling agent may, for example, consist of at least one semiconductor matrix component.
- This semiconductor matrix component is different from the polythiophenes described herein.
- the semiconducting matrix 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 component may be neutral or doped and typically is an organic solvent (eg, toluene, chloroform, acetonitrile, cyclohexanone, anisole, chlorobenzene, o-dichlorobenzene, ethyl benzoate) And mixtures thereof and the like) and / or the like.
- the amount of optional matrix compound can be adjusted and measured as a weight percentage relative to the amount of doped or non-doped polythiophene.
- the amount of optional matrix compound is 0 to about 99.5 wt%, typically about 10 wt% to about 98 wt%, relative to the amount of doped or non-doped polythiophene. More typically from about 20% to about 95%, even more typically from about 25% to about 45% by weight. In embodiments where it is 0% by weight, the non-aqueous ink composition is free of matrix compound.
- the polythiophene comprising a repeat unit according to formula (I) is doped with a dopant.
- Dopants are known in the art. See, for example, U.S. Patent Nos. 7,070,867; U.S. Publication 2005/0123793; and U.S. Publication 2004/0113127.
- the dopant may be an ionic compound.
- the dopant can include a cation and an anion.
- One or more dopants may be used to dope the polythiophene containing 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 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 the group —SO 3 M where M 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 group, where M 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 Include, but are 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 And borates such as, for example, tetrafluoroborate, tetraarylborate, and trifluoroborate, and the like.
- tetraaryl borates include, but are not limited to, halogenated tetraaryl borates such as tetrakis pentafluorophenyl borate (TPFB).
- 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 sulfonic acid, a salt thereof (-SO 3 M (wherein, M is an alkali metal ion (e.g., Na +, Li +, K +, Rb +, Cs + , etc.), Ammonium (NH 4 + ), mono-, di-, and trialkyl ammonium such as triethyl ammonium etc.
- M is an alkali metal ion (e.g., Na +, Li +, K +, Rb +, Cs + , etc.)
- Ammonium NH 4 +
- mono-, di-, and trialkyl ammonium such as triethyl ammonium etc.
- 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 aryl sulfonic acid compounds, heteropoly acid compounds, ionic compounds comprising elements belonging to Groups 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 represents O, S or NH
- A represents a naphthalene ring or an anthracene ring which may have a substituent other than X and n (SO 3 H) groups
- B 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, which is substituted or unsubstituted.
- W 1 may be a single bond
- R 46 to R 59 each independently represent a hydrogen atom or a halogen atom
- n represents the number of sulfonic acid groups bonded to A.
- q represents the number of combinations of B and X, and is an integer satisfying 1 ⁇ q. ]
- 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 As the arylsulfonic acid compound according to the present invention, one 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, but O is particularly preferable because of easy synthesis.
- aryl group in the formulas (6) and (7) examples 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 (8) 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 (9). 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 alkynyl group or a nitro group, and more preferably a trifluoromethyl group, a perfluoropropenyl group or a nitro group.
- anion represented by the following formula (5a) or Z 1, also ionic compound consisting of the counter cation can be suitably used as a dopant.
- E represents an element belonging to Group 13 or 15 of the long period periodic table
- Ar 1 to Ar 4 each independently represent an aromatic hydrocarbon group which may have a substituent or a substituent Represents an aromatic heterocyclic group which may have a group
- E is preferably boron, gallium, phosphorus or antimony among the elements belonging to group 13 or 15 of the long period periodic table, and more preferably boron.
- examples of the aromatic hydrocarbon group and the aromatic heterocyclic group include monovalent groups derived from a 5- or 6-membered single ring or a 2 to 4 condensed ring.
- 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 1 to Ar 4 has one or more fluorine atoms or chlorine atoms as a substituent.
- a perfluoroaryl group in which all hydrogen atoms of Ar 1 to Ar 4 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.
- E2 is preferably a phosphorus atom, an arsenic atom or an antimony atom, and is preferably a phosphorus atom in terms of stability of the compound, easiness of synthesis and purification, and toxicity.
- X is preferably a fluorine atom or a chlorine atom from the viewpoint of the stability of the compound and easiness of synthesis and purification, and most preferably a fluorine atom.
- Patent Document 5 An ionic compound (see Patent No. 5381931 (Patent Document 5)) which is a combination of an anion and a cation represented by the following can be suitably used.
- 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 Phosphotungstic acid hydrate or 12-Tungstophosphoric acid n-hydrate, chemical formula: H 3 (PW 12 O 40 ) ⁇ nH 2 O), phosphomolybdic acid hydrate (Phosphohomolybdic acid hydrate), or 12-Molybdo (VI ) Phosphoric acid n-hydrate, chemical formula: H3 (PMo 12 O 40 ), n H 2 O (n ⁇ 30), Kanto Chemical Co., Ltd., Wako Pure Chemical Co., Ltd., Sigma Aldrich Japan Co., Ltd., Japan Inorganic They are available from manufacturers such as Chemical Industry Co., Ltd., Nippon Shin Metal Co., Ltd., and the like.
- a sulfonic acid ester compound represented by the following formula (1), which is its precursor, can also be used as a dopant.
- R 1 to R 4 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R 5 is optionally substituted carbon It represents a monovalent hydrocarbon group of several 2 to 20.
- the linear or branched alkyl group is not particularly limited, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an tert-butyl group, an n-hexyl group, etc. Can be mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable.
- Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms include alkyl groups such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, phenyl group, naphthyl group, phenanthryl group And aryl groups such as groups.
- R 1 or R 3 is a linear alkyl group having 1 to 3 carbon atoms, and the rest is a hydrogen atom. Furthermore, it is preferable that R 1 is a linear alkyl group having 1 to 3 carbon atoms, and R 2 to R 4 are hydrogen atoms.
- the linear alkyl group having 1 to 3 carbon atoms is preferably a methyl group.
- R 5 preferably a linear alkyl group or a phenyl group having 2 to 4 carbon atoms.
- a 1 represents —O— or —S—, preferably —O—.
- a 2 represents a (n + 1) -valent group derived from naphthalene or anthracene, but a group derived from naphthalene is preferred.
- a 3 represents an m-valent group derived from perfluoro biphenyl.
- n represents an integer satisfying 1 ⁇ n ⁇ 4, preferably 2.
- 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 may be one or more of the solvents described herein.
- 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 total solid content (% TS) in the non-aqueous ink composition of the present invention is about 0.1 wt% to about 50 wt%, typically about 0.3%, based on the total amount of the non-aqueous ink composition. % By weight to about 40% by weight, more typically from about 0.5% by weight to about 15% by weight, still more typically from about 1% by weight to about 5% by weight.
- the non-aqueous ink compositions described herein can be prepared by any suitable method known to those skilled in the art.
- the first aqueous mixture comprises an aqueous dispersion of polythiophene as described herein, optionally an aqueous dispersion of a polymeric acid, optionally another matrix compound, and optionally Prepared by mixing with an additional solvent.
- 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 and filtered under pressure to form a non-aqueous mixture.
- An amine compound may optionally be added to such non-aqueous mixtures.
- the non-aqueous mixture is then mixed with the non-aqueous dispersion of metal oxide nanoparticles to form the final non-aqueous ink composition.
- the non-aqueous 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 the polymeric acids described herein can be prepared by isolating the polymeric acids from the aqueous dispersion in the dry state, typically by evaporation. The dried polymeric acid is then combined with one or more organic solvents.
- Stock solutions of other optional matrix materials can be prepared as well.
- the stock solution of metal oxide nanoparticles may be a commercially available dispersion, which may be one or more organic solvents, which may be the same as 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 non-aqueous ink composition of the present invention.
- the non-aqueous ink composition described herein isolates the individual components in the dry state as described herein, but instead of preparing the stock solution, the dry component And then dissolved in one or more organic solvents to provide a non-aqueous ink composition.
- the non-aqueous ink composition of the present invention can be cast and annealed as a thin film on a substrate.
- the present invention is also a method of forming a hole transport thin film, 1) coating a substrate with the non-aqueous ink composition disclosed herein; and 2) forming a hole transport film by annealing the coating on the substrate.
- the coating of the non-aqueous ink composition on the substrate is, for example, spin casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, doctor blade method, and for example, preparation of organic electronic devices Can be carried out by methods known in the art, including any other method known in the art for Preferably, the substrate is coated with the non-aqueous ink composition by inkjet printing.
- 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.
- the term "annealing” refers to any of the general processes for forming a cured layer, typically a thin film, on a substrate coated with the non-aqueous ink composition of the present invention. It means that.
- General annealing processes are known to those skilled in the art.
- the solvent is removed from the substrate coated with the non-aqueous 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 may be carried out by heating the non-water based ink composition coated substrate using any method known to those skilled in the art, for example by heating in an oven or on a hot plate.
- Can. 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 invention relates to a hole transporting thin film formed by the method described herein.
- the thin film produced by the method of the present invention has 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%.
- the thin film produced by the method of the present invention 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 invention exhibits a transmission of at least about 90%, and is about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, more typically about 50 nm. It has a thickness of ⁇ 120 nm. In one embodiment, the thin film produced by the method of the present invention exhibits a transmission (% 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 invention can be produced on a substrate 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.
- the invention 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 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.
- 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; ambipolar light emitting FETs, wherein HILs are used to modulate 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.
- Photovoltaic devices can be prepared with a photoactive layer comprising, for example, a fullerene derivative mixed with a conducting polymer, as described, for example, in US Pat. Nos. 5,454,880; 6,812,399; and 6,933,436.
- 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.
- Electrode compounds and substrates, as well as 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 invention 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; a non-aqueous ink composition as described herein Forming a hole injection layer or a hole transport layer by laminating a non-aqueous ink composition on a transparent conductor; on a hole injection layer or a hole transport layer (HTL) Laminating the active layer; and laminating the cathode on the active layer.
- a transparent conductor such as indium tin oxide
- a non-aqueous ink composition 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.
- a method of manufacturing the device comprises: a non-aqueous 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 release device Application as part of a HIL or HTL layer in an electrochromic device, 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 non-aqueous ink compositions to form HIL or HTL layers can be performed by methods known in the art (eg, spin casting, spin coating, dip casting, dip coating, slot die coating, ink jet printing, gravure coating, etc.) , Doctor blade method, and any other method known in the art, for example, for the preparation of organic electronic devices. It is preferable to laminate the non-aqueous ink composition by inkjet printing.
- 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.
- 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.
- non-aqueous ink composition, pile-up inhibitor and lifetime extender for organic EL devices of the present invention are further illustrated by the following non-limiting examples.
- 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 ⁇ , ⁇ '-azobisisobutyronitrile
- QD1 ⁇ , ⁇ , ⁇ '-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-d
- Production Example 2 In 100 mL of 28% aqueous ammonia (manufactured by Junsei Chemical Co., Ltd.), 2.00 g of the S-poly (3-MEET) amine adduct obtained in Production Example 1 is dissolved, and the obtained solution is stirred overnight at room temperature. did. The resulting reaction mixture was subjected to reprecipitation treatment with 1500 mL of acetone, and the precipitate was collected by filtration. The obtained precipitate was redissolved 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.
- 28% aqueous ammonia manufactured by Junsei Chemical Co., Ltd.
- the resulting reaction mixture was cooled and then subjected to reprecipitation treatment 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 a charge transporting substance S-poly (3-MEET) -A which was treated with aqueous ammonia.
- S-poly (3-MEET) -A obtained in Production Example 2 is 1.13 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 1.95 g (manufactured by Co., Ltd.), 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 butylamine (Tokyo Chemical Co., Ltd.) It was made to melt
- the preparation of the solution was carried out by stirring for 1 hour at 80 ° C. 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, 0.75 g of EG-ST and 0.15 g of EG silica sol (2) were added, and the resulting mixture was stirred at 400 rpm and 80 ° C. for 10 minutes using a hot stirrer, and the obtained dispersion was subjected to pore size The mixture was filtered through a 0.2 ⁇ m PP syringe filter to obtain a 2 wt% charge transporting varnish.
- Example 2 First, the solvent of the D66-20BS aqueous solution was distilled off with an evaporator, and the obtained residue was dried under reduced pressure at 80 ° C. in a vacuum dryer for 1 hour to obtain a powder of D66-20BS. The obtained powder was used to prepare an ethylene glycol solution containing 10 wt% of D66-20BS. The preparation of the solution was carried out by stirring at 400 rpm and 90 ° C. for 1 hour using a hot stirrer.
- S-poly (3-MEET) -A obtained in Production Example 2 is 1.13 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 0.98 g, Triethylene glycol butyl methyl ether (Tokyo Chemical Industry Co., Ltd.) 2.93 g, Diethylene glycol monobutyl ether (Kanto Chemical Co., Ltd.) 3.91 g, and 2-ethylhexyl amine (Tokyo Kasei) It was made to melt
- Example 3 First, the solvent of the D66-20BS aqueous solution was distilled off with an evaporator, and the obtained residue was dried under reduced pressure at 80 ° C. in a vacuum dryer for 1 hour to obtain a powder of D66-20BS. The obtained powder was used to prepare a 10 wt% ethylene glycol solution of D66-20BS. The preparation of the solution was carried out by stirring at 400 rpm and 90 ° C. for 1 hour using a hot stirrer.
- S-poly (3-MEET) -A obtained in Production Example 2 is 1.20 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 0.98 g, Triethylene glycol butyl methyl ether (Tokyo Chemical Industry Co., Ltd.) 2.93 g, Diethylene glycol monobutyl ether (Kanto Chemical Co., Ltd.) 3.91 g, and 2-ethylhexyl amine (Tokyo Kasei) It was made to melt
- Example 4 First, the solvent of the D66-20BS aqueous solution was distilled off with an evaporator, and the obtained residue was dried under reduced pressure at 80 ° C. in a vacuum dryer for 1 hour to obtain a powder of D66-20BS. The obtained powder was used to prepare a 10 wt% ethylene glycol solution of D66-20BS. The preparation of the solution was carried out by stirring at 400 rpm and 90 ° C. for 1 hour using a hot stirrer.
- S-poly (3-MEET) -A obtained in Production Example 2 is 1.20 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 0.98 g, Triethylene glycol butyl methyl ether (Tokyo Chemical Industry Co., Ltd.) 2.93 g, Diethylene glycol monobutyl ether (Kanto Chemical Co., Ltd.) 3.91 g, and 2-ethylhexyl amine (Tokyo Kasei) It was made to melt
- Example 5 First, the solvent of the D66-20BS aqueous solution was distilled off with an evaporator, and the obtained residue was dried under reduced pressure at 80 ° C. in a vacuum dryer for 1 hour to obtain a powder of D66-20BS. The obtained powder was used to prepare a 10 wt% ethylene glycol solution of D66-20BS. The preparation of the solution was carried out by stirring at 400 rpm and 90 ° C. for 1 hour using a hot stirrer.
- S-poly (3-MEET) -A obtained in Production Example 2 is 0.41 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 0.98 g, Triethylene glycol butyl methyl ether (Tokyo Chemical Industry Co., Ltd.) 2.93 g, Diethylene glycol monobutyl ether (Kanto Chemical Co., Ltd.) 3.91 g, and 2-ethylhexyl amine (Tokyo Kasei) It was made to melt
- Comparative Example 1 First, the solvent of the D66-20BS aqueous solution was distilled off with an evaporator, and the obtained residue was dried under reduced pressure at 80 ° C. in a vacuum dryer for 1 hour to obtain a powder of D66-20BS. The obtained powder was used to prepare a 10 wt% ethylene glycol solution of D66-20BS. The preparation of the solution was carried out by stirring at 400 rpm and 90 ° C. for 1 hour using a hot stirrer.
- S-poly (3-MEET) -A obtained in Production Example 2 is 1.20 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 1.95 g (manufactured by Co., Ltd.), 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 butylamine (Tokyo Chemical Co., Ltd.) It was made to melt
- the preparation of the solution was carried out by stirring for 1 hour at 80 ° C. 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 EG-ST was added, and the resulting mixture was stirred at 80 ° C. for 10 minutes at 400 rpm using a hot stirrer, and the resulting dispersion was filtered through a PP syringe filter with a pore size of 0.2 ⁇ m. Thus, a 2 wt% charge transporting varnish was obtained.
- S-poly (3-MEET) -A obtained in Production Example 2 is 1.20 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 0.98 g, Triethylene glycol butyl methyl ether (Tokyo Chemical Industry Co., Ltd.) 2.93 g, Diethylene glycol monobutyl ether (Kanto Chemical Co., Ltd.) 3.91 g, and 2-ethylhexyl amine (Tokyo Kasei) It was made to melt
- S-poly (3-MEET) -A obtained in Production Example 2 is 0.40 g of ethylene glycol (manufactured by Kanto Chemical Co., Ltd.), diethylene glycol (Kanto Chemical 0.98 g, Triethylene glycol butyl methyl ether (Tokyo Chemical Industry Co., Ltd.) 2.93 g, Diethylene glycol monobutyl ether (Kanto Chemical Co., Ltd.) 3.91 g, and 2-ethylhexyl amine (Tokyo Kasei) It was made to melt
- Synthesis Example 1 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, 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% by mass) was obtained (P1). Mn of the obtained acrylic polymer P1 was 3,700, and Mw was 6,100.
- Synthesis Example 2 Acrylic by dissolving HPA-QD 2.50 g, PFHMA 7.84 g, MAA 0.70 g, CHMI 1.46 g, 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% by mass) was obtained (P2). Mn of the obtained acrylic polymer P2 was 4,300, and Mw was 6,300.
- a positive photosensitive resin composition was prepared by preparing a homogeneous solution.
- 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.
- compositions of the non-aqueous ink compositions used in Examples 1 to 5 and Comparative Examples 1 to 3 and changes in thickness of the obtained charge transporting thin film are shown in Table 2 below.
- Example 1 shows that the cross-sectional shape of the charge transportable thin film obtained in the Example is a comparison.
- the film creeping up (increase in film thickness) in the vicinity of the bank is clearly less. That is, in the embodiment, pileup is suppressed as compared with the comparative example.
- Example 5 corresponding to that in which 1.64 g of EG silica sol (2) in Comparative Example 3 is replaced with a combination of 0.01 g of EG-ST and 1.62 g of EG silica sol (2) Remarkable pile-up suppression was found for 3.
- Example 1 Preparation of Organic EL Element and Characteristic Evaluation
- the varnishes obtained in Example 1 and Comparative Example 1 were each applied to a banked ITO substrate using a spin coater and then dried at 120 ° C. for 1 minute in the atmosphere. .
- the dried substrate was inserted into a glove box and baked at 230 ° C. for 15 minutes in the atmosphere to form a 30 nm thin film on the substrate.
- a banked ITO substrate a polyimide film having a thickness of 1.1 ⁇ m is formed on the electrode surface of a 25 mm ⁇ 25 mm ⁇ 0.7 t glass substrate having an indium tin oxide (ITO) thin film electrode having a patterned thickness of 150 nm formed on the surface.
- ITO indium tin oxide
- ⁇ -NPD N, N'-di (1-naphthyl) -N, N 'using a vapor deposition apparatus (vacuum degree 1.0 ⁇ 10 -5 Pa) -Diphenylbenzidine
- the sealing substrate is an adhesive ((more manufactured by MORESCO, Mores moisture cut WB90US (P)
- a water-capturing agent (Dinic Co., Ltd. HD-07101010W-40) was placed in the sealing substrate together with the organic EL element. After irradiation (wavelength: 365 nm, irradiation dose: 6,000 mJ / cm 2 ), annealing was performed at 80 ° C. for 1 hour to cure the adhesive.
- the organic EL element produced using the non-aqueous ink composition of the present invention excessive deterioration of the characteristics is not recognized, and in particular, the deterioration of the current efficiency is suppressed. Furthermore, in this organic EL element, the half life of luminance, that is, the element life is extended, and the suppression of pile-up is reflected. That is, by using the non-aqueous ink composition of the present invention, it is possible to suppress pile-up while avoiding an excessive decrease in the characteristics of the organic EL element, thereby prolonging the life of the organic EL element.
Abstract
Description
以上の新たな知見に基づき、本発明を完成するに至った。
本発明の他の目的は、有機EL素子の特性を過度に低下させることのない、非水系インク組成物用のパイルアップ抑制剤及び有機EL素子用の寿命延長剤を提供することにある。
本発明の上記及びその他の諸目的、諸特徴ならびに諸利益は、添付の図面を参照しながら行なう以下の詳細な説明及び請求の範囲の記載から明らかになる。
(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)少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子;及び
(c)1種以上の有機溶媒を含む液体担体
を含む、非水系インク組成物。
[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、前項24記載の非水系インク組成物。
該金属酸化物ナノ粒子が、少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子である、パイルアップ抑制剤。
(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)少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子;及び
(c)1種以上の有機溶媒を含む液体担体
(d)1種以上の酸性基を含む合成ポリマー
(e)1種以上のアミン化合物
を含む、非水系インク組成物。
該金属酸化物ナノ粒子が、少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子である、寿命延長剤。
(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)少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子;及び
(c)1種以上の有機溶媒を含む液体担体
を含む、非水系インク組成物に関する。
[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。
ポリチオフェン等の共役ポリマーでは、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。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非水系インク組成物を、安定的に製造することが可能になる。
ポリチオフェンがスルホン化されている場合、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。
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子(以降、「成分(b-1)」と称する場合がある)
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子(以降、「成分(b-2)」と称する場合がある)
を含み、平均一次粒子径d1とd2はd1<d2の関係にある。
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)などの金属並びに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。
d=6000/(S×ρ)
d:平均粒子径(nm)
S:比表面積(m2/g)
ρ:真比重(g/cm3)
本明細書において、特に断りがない場合は、金属酸化物ナノ粒子の一次粒子の平均粒径は、BET法による比表面積から換算する方法で測定した数値を表す。
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。
具体例としては、上述のグリコールモノエーテル類、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、グリコールモノエーテル類として、ジエチレングリコールモノブチルエーテル、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。
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。
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)
0.10≦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。)
なお後述するように、本発明の非水系インク組成物は、ポリチオフェン等の各成分を、有機溶媒中の溶液又は分散液(ストック溶液)の形態で混合することにより調製することができる。この操作の結果非水系インク組成物に添加された有機溶媒は、液体担体の一部と見なされる。
本発明の非水系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。
[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。
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。
1)基板を本明細書に開示の非水系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。
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
[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と混合し、得られた混合物を回転蒸発により蒸発乾固した。次いで得られた残留物を、真空オーブンを用いて50℃で一晩更に乾燥して、S-ポリ(3-MEET)アミン付加物を、黒色粉末の生成物3.8gとして得た。
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、得られた溶液を室温にて終夜撹拌した。得られた反応混合物を、アセトン1500mLによる再沈殿処理に付し、析出物をろ過にて回収した。得られた析出物を、水20mL及びトリエチルアミン(東京化成工業(株)製)7.59gに再度溶解させ、60℃で1時間撹拌した。得られた反応混合物を冷却後、イソプロピルアルコール1000mLとアセトン500mLの混合溶媒による再沈殿処理に付し、析出物をろ過にて回収した。得られた析出物を、0mmHg、50℃にて1時間真空乾燥し、アンモニア水で処理した電荷輸送性物質であるS-ポリ(3-MEET)-A 1.30gを得た。
[実施例1]
初めに、D66-20BS水溶液の溶媒をエバポ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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)1.13g、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る、80℃での1時間の撹拌により行った。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、EG-STを0.75g、EGシリカゾル(2)を0.15g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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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が10wt%の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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)1.13g、ジエチレングリコール(関東化学(株)製)0.98g、トリエチレングリコールブチルメチルエーテル(東京化成工業(株)製)2.93g、ジエチレングリコールモノブチルエーテル(関東化学(株)製)3.91g及び2-エチルヘキシルアミン(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る、80℃での1時間の撹拌により行った。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、EG-STを0.75g、EGシリカゾル(2)を0.15g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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)0.98g、トリエチレングリコールブチルメチルエーテル(東京化成工業(株)製)2.93g、ジエチレングリコールモノブチルエーテル(関東化学(株)製)3.91g及び2-エチルヘキシルアミン(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る、80℃での1時間の撹拌により行った。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、EG-STを0.82g、EGシリカゾル(2)を0.02g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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)0.98g、トリエチレングリコールブチルメチルエーテル(東京化成工業(株)製)2.93g、ジエチレングリコールモノブチルエーテル(関東化学(株)製)3.91g及び2-エチルヘキシルアミン(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る、80℃での1時間の撹拌により行った。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、EG-STを0.75g、EGシリカゾル(1)を0.08g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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)0.41g、ジエチレングリコール(関東化学(株)製)0.98g、トリエチレングリコールブチルメチルエーテル(東京化成工業(株)製)2.93g、ジエチレングリコールモノブチルエーテル(関東化学(株)製)3.91g及び2-エチルヘキシルアミン(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る、80℃での1時間の撹拌により行った。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、EG-STを0.01g、EGシリカゾル(2)を1.62g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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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る、80℃での1時間の撹拌により行った。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、EG-ST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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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℃、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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)0.98g、トリエチレングリコールブチルメチルエーテル(東京化成工業(株)製)2.93g、ジエチレングリコールモノブチルエーテル(関東化学(株)製)3.91g及び2-エチルヘキシルアミン(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る、80℃での1時間の撹拌により行った。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、EG-ST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%の電荷輸送性ワニスを得た。
初めに、D66-20BS水溶液の溶媒をエバポ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る、400rpm、90℃での1時間の撹拌により行った。
次に、別の容器を用意し、製造例2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)0.40g、ジエチレングリコール(関東化学(株)製)0.98g、トリエチレングリコールブチルメチルエーテル(東京化成工業(株)製)2.93g、ジエチレングリコールモノブチルエーテル(関東化学(株)製)3.91g及び2-エチルヘキシルアミン(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る、80℃での1時間の撹拌により行った。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、EGシリカゾル(2)を1.64g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%の電荷輸送性ワニスを得た。
[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、島津製作所(株)製GPC装置(LC-20AD)、昭和電工製ShodexカラムKF-804Lおよび803Lを用い、溶出溶媒テトラヒドロフランを流量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。
MMA 10.0g、HEMA 12.5g、CHMI 20.0g、HPMA 2.50g、MAA 5.00g、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40質量%)を得た(P1)。得られたアクリル重合体P1のMnは3,700、Mwは6,100であった。
<合成例2>
HPMA-QD 2.50g、PFHMA 7.84g、MAA 0.70g、CHMI 1.46g、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20質量%)を得た(P2)。得られたアクリル重合体P2のMnは4,300、Mwは6,300であった。
(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[3]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1.0%TMAH水溶液に120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。
前記工程[4]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、比較例1~3で得られた電荷輸送性ワニスを吐出し、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、電荷輸送性薄膜を形成した。
実施例1~5及び比較例1~3で得られた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、開口部のそれぞれ図1(実施例1及び比較例1)及び図2(実施例2~5及び比較例2~3)に示す。
以上の結果から、本発明の非水系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。そしてこのことにより、本発明の非水系インク組成物を用いて得られる有機EL素子において、電気的欠陥に伴う寿命短縮や、発光層の不均一な厚みに伴う発光ムラが、他の特性を過度に低下させることなく、大幅に改善されることが期待される。
実施例1及び比較例1で得られたワニスを、各々スピンコーターを用いてバンク付ITO基板に塗布した後、大気下、120℃で1分間乾燥した。次に、乾燥させた基板をグローブボックス内に挿入し、大気下、230℃で15分間焼成し、基板上に30nmの薄膜を形成した。バンク付ITO基板としては、パターニングされた膜厚150nmの酸化インジウム錫(ITO)薄膜電極が表面に形成された25mm×25mm×0.7tのガラス基板の電極面に、膜厚1.1μmのポリイミド樹脂膜を形成し、この膜をパターニング(2×2mm角の正方形が多数描かれたパターン)してバンクを形成することにより作成したバンク付ITO基板を用い、その使用前に、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、薄膜を形成したバンク付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40nm、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。
Claims (40)
- 非水系インク組成物であって、
(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)少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子;及び
(c)1種以上の有機溶媒を含む液体担体
を含む、非水系インク組成物。 - 前記平均一次粒子径d1が15nmより小さく、前記平均一次粒子径d2が10nm以上である、請求項1記載の組成物。
- 前記平均一次粒子径d1が3nm以上15nm未満であり、前記平均一次粒子径d2が10nm以上30nm以下である、請求項1または2記載の組成物。
- 前記平均一次粒子径d1及びd2が、式d2/d1>1.5で表される関係を満足する、請求項1~3のいずれか一項記載の非水系インク組成物。
- 前記平均一次粒子径d1及びd2が、式d2/d1>2.0で表される関係を満足する、請求項1~4のいずれか一項記載の非水系インク組成物。
- 前記金属酸化物ナノ粒子(b)の量が、金属酸化物ナノ粒子(b)と、前記ポリチオフェン(a)とを合わせた重量に対して、1重量%~98重量%である、請求項1~5のいずれか一項記載の非水系インク組成物。
- 前記金属酸化物ナノ粒子(b)において、前記第一の金属酸化物ナノ粒子(b-1)と前記第二の金属酸化物ナノ粒子(b-2)の重量比(b-1)/(b-2)が、0.001~1000の範囲である、請求項1~6のいずれか一項記載の非水系インク組成物。
- 前記第一の金属酸化物ナノ粒子(b-1)及び第二の金属酸化物ナノ粒子(b-2)が、各々独立に、B2O3、B2O、SiO2、SiO、GeO2、GeO、As2O4、As2O3、As2O5、Sb2O3、TeO2、SnO2、SnO、又はこれらの混合物を含む、請求項1~7のいずれか一項記載の非水系インク組成物。
- 前記第一の金属酸化物ナノ粒子(b-1)及び第二の金属酸化物ナノ粒子(b-2)の両者が、SiO2を含む、請求項8記載の非水系インク組成物。
- 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1~9のいずれか一項記載の非水系インク組成物。
- 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10記載の非水系インク組成物。
- 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10または11記載の非水系インク組成物。
- 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1~12のいずれか一項記載の非水系インク組成物。
- R1が、Hであり、そしてR2が、H以外である、請求項13記載の非水系インク組成物。
- R1及びR2が、両方ともH以外である、請求項13記載の非水系インク組成物。
- 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、請求項15記載の非水系インク組成物。
- R1及びR2が、両方とも-O[C(RaRb)-C(RcRd)-O]p-Reである、請求項15記載の非水系インク組成物。
- 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16または17記載の非水系インク組成物。
- 前記ポリチオフェンが、スルホン化されている、請求項1~12のいずれか一項記載の非水系インク組成物。
- 前記ポリチオフェンが、スルホン化ポリ(3-MEET)である、請求項20記載の非水系インク組成物。
- 前記ポリチオフェンが、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1~21のいずれか一項記載の非水系インク組成物。
- 1種以上の酸性基を含む合成ポリマーを更に含む、請求項1~22のいずれか一項記載の非水系インク組成物。
- 前記合成ポリマーが、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、請求項23記載の非水系インク組成物。
- 前記合成ポリマーが、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、請求項23記載の非水系インク組成物。
- 1種以上のアミン化合物を更に含む、請求項1~26のいずれか一項記載の非水系インク組成物。
- 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、請求項27記載の非水系インク組成物。
- 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28記載の非水系インク組成物。
- 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、n-ヘキシルアミン、2-エチルヘキシルアミン、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29記載の非水系インク組成物。
- 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30記載の非水系インク組成物。
- 金属酸化物ナノ粒子からなり、非水系インク組成物に添加されると、該非水系インク組成物を撥液バンク基板に塗布して乾燥させ、電荷輸送性薄膜を形成する際のパイルアップ現象が抑制されるパイルアップ抑制剤であって、
該金属酸化物ナノ粒子が、少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子である、パイルアップ抑制剤。 - 前記平均一次粒子径d1及びd2が、式d2/d1>1.5で表される関係を満足する、請求項32記載のパイルアップ抑制剤。
- 前記平均一次粒子径d1及びd2が、式d2/d1>2.0で表される関係を満足する、請求項32または33記載のパイルアップ抑制剤。
- 前記第一の金属酸化物ナノ粒子(b-1)及び第二の金属酸化物ナノ粒子(b-2)が、各々独立に、B2O3、B2O、SiO2、SiO、GeO2、GeO、As2O4、As2O3、As2O5、Sb2O3、TeO2、SnO2、SnO、又はこれらの混合物を含む、請求項32~34のいずれか一項記載のパイルアップ抑制剤。
- 前記第一の金属酸化物ナノ粒子(b-1)及び第二の金属酸化物ナノ粒子(b-2)の両者が、SiO2を含む、請求項35記載のパイルアップ抑制剤。
- 非水系インク組成物であって、
(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)少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子;及び
(c)1種以上の有機溶媒を含む液体担体
(d)1種以上の酸性基を含む合成ポリマー
(e)1種以上のアミン化合物
を含む、非水系インク組成物。 - 金属酸化物ナノ粒子からなる有機EL素子用の寿命延長剤であって、
該金属酸化物ナノ粒子が、少なくとも下記(b-1)及び(b-2):
(b-1)平均一次粒子径d1を有する第一の金属酸化物ナノ粒子
(b-2)平均一次粒子径d2を有する第二の金属酸化物ナノ粒子
を含み、平均一次粒子径d1とd2がd1<d2の関係にある金属酸化物ナノ粒子である、寿命延長剤。 - 前記平均一次粒子径d1及びd2が、式d2/d1>1.5で表される関係を満足する、請求項38記載の寿命延長剤。
- 前記平均一次粒子径d1及びd2が、式d2/d1>2.0で表される関係を満足する、請求項38または39記載の寿命延長剤。
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US20200216696A1 (en) | 2020-07-09 |
CN110770307A (zh) | 2020-02-07 |
JP7306497B2 (ja) | 2023-07-11 |
TW201906946A (zh) | 2019-02-16 |
JPWO2018235783A1 (ja) | 2020-04-16 |
JP7099458B2 (ja) | 2022-07-12 |
KR20200020807A (ko) | 2020-02-26 |
TWI814728B (zh) | 2023-09-11 |
JP2022062075A (ja) | 2022-04-19 |
EP3643756A4 (en) | 2021-01-27 |
TW202348747A (zh) | 2023-12-16 |
EP3643756A1 (en) | 2020-04-29 |
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