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WO2009125754A1 - Dispositif - Google Patents

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Publication number
WO2009125754A1
WO2009125754A1 PCT/JP2009/057092 JP2009057092W WO2009125754A1 WO 2009125754 A1 WO2009125754 A1 WO 2009125754A1 JP 2009057092 W JP2009057092 W JP 2009057092W WO 2009125754 A1 WO2009125754 A1 WO 2009125754A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive layer
liquid crystal
walled carbon
substrate
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/057092
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English (en)
Japanese (ja)
Inventor
北野　高広
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
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Kuraray Co Ltd
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Filing date
Publication date
Priority claimed from JP2008100373A external-priority patent/JP5319951B2/ja
Priority claimed from JP2008100372A external-priority patent/JP5388021B2/ja
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of WO2009125754A1 publication Critical patent/WO2009125754A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/12—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/36—Micro- or nanomaterials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a device having a conductive layer composed of entangled single-walled carbon nanotubes and fullerene (but not using a binder resin).
  • This device is, for example, a liquid crystal display device or a solar battery.
  • liquid crystal display devices are required to be thinner.
  • a liquid crystal display device using a resin film substrate instead of a glass substrate has been proposed.
  • a conductive layer for applying voltage to liquid crystal molecules is necessary.
  • a ceramic material typified by indium tin oxide (ITO) has been used.
  • a dye-sensitized solar characterized in that a nanocarbon film made of fibrous carbon having a diameter of nanometer size selected from the group of single wall carbon nanotubes, multiwall carbon nanotubes, and carbon nanofibers is used as an electrode.
  • a battery has been proposed (Japanese Patent Application Laid-Open No. 2004-111216).
  • a dye-sensitized solar cell electrode substrate having a transparent substrate and a transparent electrode formed on one side of the transparent substrate, the transparent electrode being formed on the transparent substrate,
  • a transparent first conductive layer made of a metal oxide such as ITO or ZnO
  • a second conductive layer made of a metal such as Pt, Au, or Ni formed on the first conductive layer
  • the second For a dye-sensitized solar cell, comprising a third conductive layer formed on a conductive layer, for example, one or two or more carbons selected from the group consisting of fullerenes, fullerene derivatives and carbon nanotubes
  • the p-type semiconductor material or the n-type semiconductor material is in a state where a plurality of carbon nanotubes are electrically connected to each other.
  • a solar cell characterized in that it is made of a structure film arranged in the form of JP-A-2006-237204. JP2004-202948 JP 2005-255985 JP2004-1111216 JP 2005-142088 A JP 2006-237204 A
  • the first problem to be solved by the present invention is to provide a device with high durability.
  • the second problem to be solved by the present invention is to provide a high-quality liquid crystal display device that is flexible, hardly damaged, durable, and hardly causes malfunction.
  • a third problem to be solved by the present invention is to provide a low-cost and highly durable solar cell device.
  • a device having a conductive layer comprising:
  • the conductive layer is Having entangled single-walled carbon nanotubes and fullerenes, This is solved by a device characterized by having no binder resin.
  • the single-walled carbon nanotubes contained in the conductive layer of the device are preferably single-walled carbon nanotubes obtained by an arc discharge method.
  • the single-walled carbon nanotubes contained in the conductive layer of the device are preferably acid-treated single-walled carbon nanotubes.
  • the fullerene contained in the conductive layer of the device is particularly preferably a fullerene hydroxide.
  • the amount of fullerene contained in the conductive layer of the device is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the single-walled carbon nanotube.
  • a protective layer is provided on the conductive layer of the device.
  • the conductive layer of the device is preferably provided on a resin substrate.
  • the second problem is A device for a liquid crystal display in which a liquid crystal layer is provided between a conductive layer and a conductive layer, This is solved by a device characterized in that at least one of the conductive layers is a conductive layer of the device.
  • the third problem is A solar cell device comprising an electrode substrate having a conductive layer, Solved by a device characterized in that the conductive layer is a conductive layer of the device.
  • the solar cell is preferably a solar cell using a redox reaction of a dye.
  • the device of this invention is excellent in electroconductivity. In addition, it has excellent durability.
  • the conductive layer is rich in flexibility.
  • the conductive layer can be bent following a substrate made of a resin film, for example. Therefore, this device is not easily damaged and is highly durable. Even in the case of a device that requires operability, it is difficult for malfunction to occur. In addition, the operability is excellent.
  • the conductive layer of the present invention when the conductive layer of the present invention is applied to a solar cell, this layer has excellent conductivity and durability. And since a conductive layer can be comprised simply, a high quality and highly durable solar cell can be obtained at low cost.
  • a substrate layer made of a transparent resin and a conductive layer laminated on the substrate layer are provided so that the conductive layer is disposed to face the substrate side conductive layer and the substrate side conductive
  • a sheet-like resin laminate for a touch panel which is in an energized state in contact with a layer
  • the conductive layer is made of a resin composition in which carbon nanowires are dispersed in a transparent matrix resin Sheet-like resin laminate "A state in which a sheet-like resin laminate for a touch panel comprising a base material layer made of a transparent resin and a conductive layer laminated on the base material layer faces the conductive layer on the substrate-side conductive layer
  • Patent Document 2 states that “in the carbon nanotube-containing coating film applied on the substrate, the carbon nanotube-containing coating film has a three-dimensional network structure, and the carbon nanotube-containing coating film is a carbon nanotube-containing coating film”.
  • a carbon nanotube-containing coating film characterized by being exposed on the surface is disclosed.
  • Patent Documents 1 and 2 do not disclose any liquid crystal cells. In addition, a description resemble of a liquid crystal cell is not recognized. That is, Patent Document 1 is only used for a touch panel. Patent Document 2 discloses ESD protection, EMI / RFI shielding, low visibility, polymer electronics (for example, transparent conductive layers of OLED displays, EL lamps, plastic chips, etc.) as applications of carbon nanotube-containing coating films. It has only been done.
  • the carbon nanotube is used for the electrode of a solar cell.
  • a solar cell with high durability cannot be obtained only by using carbon nanotubes. That is, with the thing of patent document 3, the feature which this invention show
  • Patent Document 4 describes the use of one or more carbons selected from the group consisting of fullerenes, fullerene derivatives and carbon nanotubes.
  • the conductive layer of the electrode substrate is made of, for example, a transparent first conductive layer made of a metal oxide such as ITO or ZnO, and formed on the first conductive layer, for example, Pt, Au, Ni.
  • a second conductive layer made of a metal such as a third conductive layer formed on the second conductive layer, for example, one or two or more carbons selected from the group consisting of fullerenes, fullerene derivatives, and carbon nanotubes And a three-layer laminated conductive layer. For this reason, the flexibility of the conductive layer is lacking.
  • the above-mentioned hard conductive layer cannot follow such a flexible substrate, and damage is likely to occur. That is, the durability is inferior. Furthermore, as a result of research by the present inventor, it was found that the latter is more durable when only the carbon nanotubes are used in the conductive layer and when the carbon nanotubes and fullerenes are used in combination. It is.
  • Patent Document 4 describes “a third conductive layer made of one or more carbons selected from the group consisting of fullerenes, fullerene derivatives and carbon nanotubes”, and details of the invention of the specification In the description column, for example, paragraph number [0044] describes that “fullerene, fullerene derivative or carbon nanotube is preferably used”, and “combination of carbon nanotube and fullerene” is not described at all. . Furthermore, even in the examples in which the best mode of the invention is described, there is no description about “combination of carbon nanotube and fullerene”. Moreover, in the thing of patent document 4, binder resin is used for the structure of a conductive layer, As a result, electroconductivity falls. Furthermore, since the conductive layer has a three-layer structure, the cost is high.
  • Patent Document 5 carbon nanotubes are used for solar cells, but carbon nanotubes are not used for the conductive layer of the electrode substrate.
  • the present invention is a device having a conductive layer.
  • This device is a liquid crystal display device or a solar cell device.
  • a liquid crystal display device in which a liquid crystal layer is provided between a conductive layer and a conductive layer.
  • the device of the solar cell which comprised the electrode substrate which has a conductive layer.
  • the conductive layer constituting the device. That is, the conductive layer (at least one conductive layer in the case of a device for a liquid crystal display) is configured by using both entangled single-walled carbon nanotubes and fullerenes. That is, the conductive layer has entangled single-walled carbon nanotubes and fullerenes. However, the conductive layer does not have a binder resin. As shown in FIG. 1, the conductive layer 12 is provided on a substrate (for example, a resin substrate) 11. The conductive layer 12 is configured without using a binder resin.
  • single-walled carbon nanotubes constituting the conductive layer 12 have a structure in which the single-walled carbon nanotubes are intertwined with each other. As a result, the single-walled carbon nanotubes are in direct contact with each other. Therefore, since there is no intervening insulator, the conductivity is good. In addition, since the single-walled carbon nanotubes are entangled with each other, the conductive layer 12 does not require a binder resin. If the surface of the conductive layer is observed with a scanning electron microscope, it can be confirmed / determined whether the single-walled carbon nanotubes are intertwined.
  • the single-walled carbon nanotube may be a single-walled carbon nanotube obtained by any manufacturing method.
  • single-walled carbon nanotubes obtained by production methods such as arc discharge, chemical vapor deposition, and laser evaporation can be used.
  • single-walled carbon nanotubes obtained by an arc discharge method are preferred from the viewpoint of crystallinity. And this thing is also easily available.
  • the single-walled carbon nanotube is preferably a single-walled carbon nanotube subjected to acid treatment.
  • the acid treatment is performed by immersing single-walled carbon nanotubes in an acidic liquid.
  • a technique called spraying may be employed instead of immersion.
  • Various kinds of acidic liquids are used.
  • an inorganic acid or an organic acid is used.
  • inorganic acids are preferred.
  • nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, or a mixture thereof can be used.
  • acid treatment using nitric acid or a mixed acid of nitric acid and sulfuric acid is preferable.
  • Preferable acid treatment conditions are conditions in which the reaction is carried out at a temperature of 80 ° C. to 100 ° C.
  • the single-walled carbon nanotube is preferably a single-walled carbon nanotube in which impurities are removed by filtration and purity is improved. This is because a decrease in conductivity and a decrease in light transmittance due to impurities are prevented.
  • Various methods are employed for filtration. For example, suction filtration, pressure filtration, cross flow filtration and the like are used. Among these, from the viewpoint of scale-up, it is preferable to employ cross flow filtration using a hollow fiber membrane.
  • the conductive layer 12 includes not only entangled single-walled carbon nanotubes but also fullerenes (in the present specification, “fullerene” includes “fullerene analogues”, the same shall apply hereinafter). This is because the heat resistance is improved by including fullerene. Moreover, it is because it was excellent also in electroconductivity.
  • the fullerene may be any fullerene.
  • C60, C70, C76, C78, C82, C84, C90, C96 etc. are mentioned.
  • a mixture of plural kinds of fullerenes may be used.
  • C60 is particularly preferable from the viewpoint of dispersion performance.
  • C60 is easy to obtain.
  • not only C60 but also a mixture of C60 and another kind of fullerene (for example, C70) may be used.
  • the metal atom may be included in the fullerene.
  • Examples of the fullerene analog include those containing a functional group (for example, a functional group such as OH group, epoxy group, ester group, amide group, sulfonyl group, ether group).
  • fullerene having an OH group (hydroxyl group) (fullerene hydroxide) is preferable. This is because the dispersibility during coating of the single-walled carbon nanotube dispersion was high. In addition, when there is little quantity of a hydroxyl group, the dispersibility improvement degree of a single-walled carbon nanotube will fall. On the other hand, if too much, synthesis is difficult. Accordingly, the amount of OH groups is preferably 5 to 30 per molecule of fullerene. In particular, 8 to 15 are preferable.
  • the amount of fullerene is preferably 10 to 1000 parts by mass (particularly 20 parts by mass or more and 100 parts by mass or less) with respect to 100 parts by mass of single-walled carbon nanotubes.
  • a protective layer 13 is provided on the conductive layer 12 in the device of the present invention.
  • the material used for the protective layer 13 for example, a thermoplastic resin such as a polyester resin, a cellulose resin, a polyvinyl alcohol resin, a vinyl resin, a cycloolefin resin, a polycarbonate resin, an acrylic resin, or an ABS resin is used.
  • well-known coating materials such as a photocurable resin and a thermosetting resin, may be used.
  • the material of the protective layer 13 is preferably the same (same system) material as the substrate 11 from the viewpoint of adhesion.
  • the protective layer 13 is also preferably a polyester resin.
  • the thickness of the protective layer 13 is preferably 1 nm to 1 ⁇ m. In particular, 10 nm or more is preferable. Moreover, 100 nm or less is preferable.
  • a liquid crystal cell is provided with a liquid crystal layer between a conductive layer and a conductive layer. More specifically, in the liquid crystal cell, a layer (liquid crystal layer) made of liquid crystal molecules is provided between the electrode substrate and the electrode substrate.
  • the electrode substrate is obtained by providing a conductive layer on a transparent substrate, for example.
  • at least one of the conductive layers is composed of the conductive layer of the present invention (binder resin is not included. Entangled single-walled carbon nanotubes and fullerenes are included).
  • both conductive layers are composed of the conductive layer of the present invention. However, only one of them has an effect.
  • the liquid crystal cell is used to form a liquid crystal display device.
  • the basic structure of a liquid crystal cell is one in which a conductive layer is provided on at least one substrate.
  • an alignment film is provided on the substrate. This alignment film is arranged in opposition to the inside.
  • liquid crystal molecules are sealed between the alignment films arranged opposite to each other.
  • the conductive layer in such a liquid crystal display element is generally configured in the form of a display pattern such as a stripe shape or a lattice shape on a substrate.
  • the alignment film is provided by coating (or vapor deposition) on the entire surface of the transparent electrode and the exposed substrate (other than the display pattern).
  • Each of the transparent electrode substrates including the two conductive layers is arranged with the alignment film inside.
  • a liquid crystal cell is formed by enclosing a liquid crystal material in the meantime. Accordingly, the encapsulated liquid crystal molecules are generally in contact only with the alignment film.
  • the alignment film is provided because it is necessary to align (that is, align) the liquid crystals in a certain direction. Thereby, the liquid crystal molecules are aligne
  • TN Transmission T Nematic
  • VA Vertical Alignment
  • IPS In-Plane Switching
  • OCB optically ⁇ compensated birefringence
  • liquid crystal molecules are used.
  • a rod-like molecular compound is preferably used.
  • liquid crystal compounds of TN, VA, IPS, and OCB examples include the liquid crystal compounds described in JP-A-11-302653, JP-A-9-249481, JP-A-2002-193853, and JP-A-2003-73670.
  • a color filter layer can be provided.
  • the electrode substrate is preferably a sheet or film.
  • the substrate preferably has a total light transmittance of 80% to 100%.
  • the material of the substrate A flexible transparent substrate is preferable.
  • thermoplastic resins for example, polyester resin, cellulose resin, polyvinyl alcohol resin, vinyl chloride resin, cycloolefin resin, polycarbonate resin, acrylic resin, ABS resin, etc.
  • a photocurable resin or a thermosetting resin is also used.
  • the thickness of the transparent substrate 11 depends on the application. When a sheet shape is required, it is about 500 ⁇ m to 10 mm. When a film shape is required, it is about 10 ⁇ m to 500 ⁇ m.
  • any of the two substrates may be a sheet or a film. One may be a sheet and the other may be a film.
  • the device of the present invention may be one in which only the conductive layer provided on one transparent substrate is composed of the single-walled carbon nanotubes of the present invention. That is, the conductive layer provided on the other electrode substrate may be made of, for example, ITO. Of course, it is preferable that both conductive layers are composed of single-walled carbon nanotubes.
  • the total light transmittance of the electrode substrate at the stage where the conductive layer is laminated on the substrate is preferably 60% to 100%.
  • the surface resistance value is 1 ⁇ / ⁇ to 1000 ⁇ / ⁇ . This is because if the total light transmittance is too low, the visibility is lowered.
  • a conductive layer using single-walled carbon nanotubes has a trade-off relationship between the total light transmittance and the surface resistance value. Accordingly, the surface resistance value is preferably low as long as the liquid crystal cell operates.
  • the total light transmittance is the total light transmittance including not only the conductive layer containing single-walled carbon nanotubes but also the base material.
  • the total light transmittance is 70% or more, and the surface resistance value is 10 ⁇ / ⁇ to 100 ⁇ / ⁇ .
  • the total light transmittance is 80% or more and the surface resistance is 10 ⁇ / ⁇ to 50 ⁇ / ⁇ .
  • the liquid crystal cell of the present invention can be produced by the following steps.
  • Step 1 Process for obtaining crude carbon nanotubes
  • Step 2 Acid treatment process for treating crude carbon nanotubes with acid
  • Step 3 Filtration process for filtering single-walled carbon nanotubes obtained in Step 2
  • Step 4 With single-walled carbon nanotubes Dispersion process step 5 in which the solvent is mixed and ultrasonic irradiation is performed: Single-walled carbon nanotube dispersion obtained in step 4 is applied onto the substrate.
  • Application step 6 On the electrode substrate obtained in step 5
  • Step 7 in which an alignment film is formed
  • Step Step in which the electrode substrate obtained in Step 6 is opposed to each other through a spacer and liquid crystal molecules are filled in the gaps. Steps 1 to 7 are performed in this order. Are preferred.
  • Step 1 There are no particular restrictions on the method of obtaining the crude carbon nanotube. Any manufacturing method such as an arc discharge method, a chemical vapor phase method, or a laser evaporation method can be used. From the viewpoint of crystallinity, the arc discharge method is preferably used. And this thing is also easy to obtain.
  • Any manufacturing method such as an arc discharge method, a chemical vapor phase method, or a laser evaporation method can be used. From the viewpoint of crystallinity, the arc discharge method is preferably used. And this thing is also easy to obtain.
  • Step 2 is a step in which single-walled carbon nanotubes are heated in an acidic liquid.
  • acidic liquids There are no particular restrictions on acidic liquids.
  • nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and a mixture thereof can be used.
  • Nitric acid or a mixed acid of nitric acid and sulfuric acid is preferably used.
  • the heating temperature is preferably 80 ° C. to 100 ° C.
  • the heating time is preferably 1 to 7 days.
  • Step 3 is a step in which the single-walled carbon nanotubes obtained in Step 2 are filtered. Thereby, impurities such as carbon particles are removed. That is, the carbon nanotube solution after acid treatment is dispersed (or precipitated) in the solution in a state where, for example, impurity particles having a diameter of about 20 nm and carbon nanotube bundles are separated. For this reason, the impurities are removed by filtration using a filter having a pore size larger than the impurities and smaller than the bundle of carbon nanotubes.
  • Various methods can be adopted as the filtration method. For example, suction filtration, pressure filtration, cross flow filtration and the like are used. Among these, from the viewpoint of scale-up, cross flow filtration using a hollow fiber membrane is preferable.
  • Step 4 is a step in which a single-walled carbon nanotube dispersion is produced.
  • fullerene is added.
  • the fullerene is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the single-walled carbon nanotube.
  • the fullerene concentration is preferably 1 to 100,000 ppm.
  • the fullerene is preferably a fullerene having a functional group.
  • fullerene having an OH group fulllerene hydroxide
  • Various methods can be adopted as the ultrasonic irradiation method.
  • a bus type ultrasonic irradiator or a chip type ultrasonic irradiator is used. From the viewpoint of processing in a shorter time, it is preferable to employ a chip-type ultrasonic irradiator.
  • a solvent having a boiling point of 200 ° C. or lower preferably lower limit is 25 ° C., further 30 ° C.
  • the low boiling point solvent is preferred because it is easy to dry after coating.
  • alcohol for example, alcohol such as methanol, ethanol, normal propanol, and isopropanol (particularly alcohol having 7 or less carbon atoms, particularly aliphatic alcohol)
  • a mixture thereof is preferable.
  • alcohol for example, alcohol such as methanol, ethanol, normal propanol, and isopropanol (particularly alcohol having 7 or less carbon atoms, particularly aliphatic alcohol)
  • a mixture thereof is preferable.
  • ketone compounds eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • ester compounds eg, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methoxyethyl acetate, etc.
  • ether compounds For example, diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, dioxane etc.), aromatic compounds (eg toluene, xylene etc.), aliphatic compounds (eg pentane, hexane etc.), halogenated hydrocarbons (eg For example, methylene chloride, chlorobenzene, chloroform, etc.), and mixtures thereof may be used.
  • ester compounds eg, methyl acetate, ethyl
  • Step 5 is a step in which the single-walled carbon nanotube dispersion obtained in step 4 is applied onto the substrate. That is, it is a step in which a conductive layer is formed on the substrate. Specifically, this is a step in which the dispersion is applied onto a transparent substrate by a desired application method (for example, spray coating, bar coating, roll coating, ink jet method, screen coating, die coating, etc.). If necessary, drying is performed after the coating step in order to remove the solvent contained in the coating film. A drying device (for example, a heating furnace, a far infrared furnace, a super far infrared furnace, or the like) is used for drying. Further, the substrate is cleaned as necessary.
  • a desired application method for example, spray coating, bar coating, roll coating, ink jet method, screen coating, die coating, etc.
  • Step 6 is a step in which an alignment film is formed on the electrode substrate obtained in step 5.
  • an alignment film necessary for aligning liquid crystal molecules is formed.
  • a polymer film such as polyimide is provided on a substrate such as glass.
  • a method (rubbing) called friction with a cloth or the like in one direction is used.
  • the liquid crystal molecules in contact with the substrate are arranged so that their long axes (directors) are parallel to the rubbing direction.
  • a technique such as a photo-alignment method that does not require rubbing may be used.
  • a photo-alignment group a compound having a group (hereinafter, abbreviated as a photo-alignment group) whose light absorption ability varies depending on the direction of the electric vector of polarized light.
  • a photo-alignment group arranges in a fixed direction, and liquid crystal alignment ability expresses.
  • the photoalignment group include a group causing a photoisomerization reaction such as azobenzene, a group causing a photodimerization reaction such as a cinnamoyl group, a coumarin group, and a chalcone group, a group causing a photocrosslinking reaction such as a benzophenone group, or the like.
  • a polyimide, a silane compound, etc. are known.
  • Step 7 In step 7, usually, first, a sealing material is applied to the peripheral edge of the surface of one of the substrates. At that time, a liquid crystal injection port is formed in a part of the sealing material. Next, a spacer is provided inside the sealing material. And the other board
  • a droplet assembly method in which liquid crystal is applied onto a substrate using a droplet discharge device such as an inkjet may be used. Specifically, first, a sealing material made of a thermosetting resin or the like is applied to the surface peripheral portion of one substrate. Next, a predetermined amount of liquid crystal is dropped inside the sealing material by a droplet discharge device. Finally, the other substrate is bonded through a sealing material, whereby a liquid crystal cell is obtained.
  • a liquid crystal display device is obtained by combining a liquid crystal cell obtained as described above with a polarizing filter, a retardation film, or the like.
  • Examples of solar cells that require a conductive layer include dye-sensitized solar cells, single crystal silicon solar cells, other crystal silicon solar cells, and solar cells using indirect transition semiconductors such as amorphous silicon solar cells. It is done. Further, CuInSe 2 (CIS), Cu (In, Ga) solar cell using a direct transition type semiconductor such as Se 2 (CIGS) can also be mentioned. However, a dye-sensitized solar cell (a solar cell using a redox reaction of a dye) is particularly preferable.
  • the layer configuration of transparent substrate / transparent electrode layer / photocatalyst layer / electrolyte layer / transparent electrode layer / substrate is exemplified.
  • a layer configuration of transparent substrate / transparent electrode / p-type semiconductor / n-type semiconductor is given as an example.
  • the layer configuration of substrate / electrode / light absorption layer / buffer layer / transparent electrode layer / antireflection layer is an example.
  • the present invention is suitably used for a dye-sensitized solar cell. Therefore, in the following, the dye-sensitized solar cell will be described in detail.
  • At least one of the two substrates has light transmittance. Specifically, the total light transmittance is 80% or more and 100% or less. And preferably, a sheet form or a film form is used.
  • the board material there are no special restrictions on the board material.
  • ceramic such as glass can be used.
  • thermoplastic resins such as polyester resin, cellulose resin, vinyl alcohol resin, vinyl chloride resin, cycloolefin resin, polycarbonate resin, acrylic resin, and ABS resin can be used.
  • a photocurable resin, a thermosetting resin, etc. are mentioned.
  • it is preferably made of resin.
  • the thickness of the substrate depends on the application. In the case of a sheet shape, for example, it is 500 ⁇ m to 10 mm. In the case of a film, it is, for example, 10 ⁇ m to 500 ⁇ m.
  • An oxide for example, anatase type titanium oxide, rutile type titanium oxide, zinc oxide, tin oxide, nibismuth trioxide, etc.
  • sol-like anatase-type titanium oxide TiO 2 is preferable. This is because when a sol-like anatase-type titanium oxide TiO 2 is used, an extremely smooth surface is formed when the contacting side is hydrophilic.
  • the film thickness of the photocatalyst layer is preferably 0.01 ⁇ m to 10 ⁇ m when anatase TiO 2 is used. This is because when the film thickness is less than 0.01 ⁇ m, problems such as coating defects such as pinholes are likely to occur. Conversely, if the film thickness exceeds 10 ⁇ m and becomes too thick, the light transmittance decreases.
  • the photocatalyst layer is formed by forming (or adsorbing) a dye layer made of a ruthenium complex on the surface of titanium oxide TiO 2 .
  • a dye may be any substance that has an improved absorption function in the wavelength range of sunlight. For example, chlorophyll and rhodamine are used.
  • a redox redox solution is used for the electrolyte layer.
  • a couple of anions that rapidly change between a plurality of different oxidation states by light irradiation and electron supply are used as the electrolyte.
  • the anion couple having such a property include halogen couples such as iodine (I ⁇ / I 3 ⁇ ), bromine (Br 2 ⁇ / Br ⁇ ), and chlorine (ClO ⁇ / Cl ⁇ ).
  • the degree of ionization is I>Br> Cl.
  • the electrolytic solution may be impregnated and used in a porous material typified by cloth, paper or the like.
  • the conductive layer in the solar cell preferably has a total light transmittance of 60% to 100%.
  • the surface resistance value is 10 ⁇ / ⁇ to 1000 ⁇ / ⁇ or less. This is because if the total light transmittance is too low, the power generation is reduced.
  • the surface resistivity is preferably higher as long as the solar cell operates.
  • the solar cell of the present invention can be produced by the following steps.
  • Step 11 Step for obtaining crude carbon nanotube
  • Step 12 Acid treatment step for acid treatment of crude carbon nanotube
  • Step 13 Filtration step for filtering the single-walled carbon nanotube obtained in Step 12
  • Step 14 Single-walled carbon nanotube and solvent Are dispersed and ultrasonic irradiation is performed.
  • Dispersion process step 15 Single-walled carbon nanotube dispersion obtained in step 14 is applied onto the substrate.
  • Application step 16 On the electrode substrate obtained in step 15. Step for Forming Photoelectric Conversion Layer
  • the above steps 11 to 16 are preferably performed in this order.
  • Step 11 is performed in the same manner as step 1.
  • Step 12 is performed in the same manner as step 2.
  • Step 13 is performed in the same manner as step 3.
  • Step 14 is performed in the same manner as step 4.
  • Step 15 is performed in the same manner as step 5.
  • Step 16 is a step in which a photoelectric conversion layer is formed on the electrode substrate obtained in Step 15.
  • a known method is used for each of the solar cell types, that is, a dye-sensitized solar cell, a silicon-based solar cell, and a CIGS-based solar cell.
  • the process heated in the process 16 1500 degrees C or less is preferable.
  • inert gas atmosphere such as nitrogen, neon, and argon.
  • Example 1 [Production of electrode substrate] Single-walled carbon nanotubes produced by the arc discharge method were treated with acid (treated with 63% nitric acid at 85 ° C. for 2 days (reaction)). Filtration was then performed. As a result, single-walled carbon nanotubes were purified and recovered. 10 mg of this single-walled carbon nanotube, 10 mg of hydroxyl group-containing fullerene (trade name Nanomuspectra D-100 Frontier Carbon), 1 mg of sodium hydroxide (Wako Pure Chemical Industries), 5 ml of water, 5 ml of 2-propanol, Were mixed.
  • the transparent conductive layer was immersed in a solution diluted with 2-propanol so that the solid content concentration of the acrylic resin (trade name Watersol S-707-IM) was 1% by mass. Then, a protective layer having a wet thickness of 10 nm was formed, and an electrode substrate was obtained. In addition, it was 31 ⁇ / ⁇ where the surface resistance after being left in an oven at 80 ° C. for 10 days was measured. That is, it can be seen that the resistance value hardly changes, and the durability is excellent.
  • An electrode substrate obtained by spray-coating the above single-walled carbon nanotube dispersion on a PET film (trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) was wound around a rod.
  • the surface resistance was measured by the two-terminal method while being pulled with a constant load.
  • the limit radius of curvature was 2 mm or less.
  • the critical curvature radius of the PET film with ITO in which the conductive layer was made of ITO was examined, it was 10 mm. This indicates that the conductive layer according to the present invention is rich in flexibility.
  • the electrode substrate was cut into 25 mm squares and arranged such that the conductive layers faced each other.
  • the two electrode substrates were fixed with a room temperature curing type epoxy resin (trade name: Quick5 manufactured by Konishi Co., Ltd.) through a 50 ⁇ m spacer. After the epoxy resin was cured, the spacer was removed. Liquid crystal molecules (4-cyano-4′-pentylbiphenyl, manufactured by Tokyo Chemical Industry Co., Ltd.) were injected. After the injection, the injection port was sealed with a room temperature curable epoxy resin. As a result, a liquid crystal cell was produced (see FIGS. 1, 2 and 3). Thereafter, polarizing plates were bonded to both surfaces of the liquid crystal cell (see FIG. 4).
  • the bonded polarizing plates are orthogonal to each other. Then, a polarizing plate was bonded, and a voltage (500 Hz, 10 v) was applied to the liquid crystal cell. The transmittance before and after this was measured with a spectrophotometer. The result is shown in FIG. From FIG. 5, it can be seen that the light transmittance is lower after the voltage application than before the voltage application, and operates as a liquid crystal cell.
  • Example 1 In Example 1, the same procedure was performed except that the hydroxyl group-containing fullerene was not used when preparing the single-walled carbon nanotube dispersion.
  • the liquid crystal cell of this comparative example was examined in the same manner as in Example 1. As a result, it was found to operate as a liquid crystal cell. However, the liquid crystal cell produced with the electrode after being held at 80 ° C. for 10 days did not operate. This indicates that the liquid crystal cell of this comparative example is inferior in durability and reliability as compared with the liquid crystal cell of the present invention in which the conductive layer has fullerene.
  • Example 2 In Example 1, the same procedure was performed except that 0.1 mg of polyvinylpyrrolidone was used as the binder resin when the single-walled carbon nanotube dispersion was prepared.
  • the liquid crystal cell of this comparative example was examined in the same manner as in Example 1. As a result, it was found to operate as a liquid crystal cell. However, operation required a voltage of 30V. This indicates that the liquid crystal cell of this comparative example is inferior to the liquid crystal cell of the present invention in which the conductive layer does not contain a binder resin.
  • mallow blue (Asahi Sangyo Co., Ltd.) was immersed in distilled water. And the mallow blue aqueous solution was produced. Then, the fired electrode was immersed in a mallow blue aqueous solution. As a result, mallow blue was adsorbed on the titanium oxide layer. Next, the electrode with a titanium oxide layer and the untreated electrode were stacked so that the electrodes face each other. Then, the two opposite sides were fixed with a room temperature curable epoxy resin (trade name: Quick5 manufactured by Konishi Co., Ltd.).
  • an iodide electrolyte solution (a mixture of 0.5 M potassium iodide solution and 0.05 M iodine solution) was injected between the electrodes.
  • an iodide electrolyte solution (a mixture of 0.5 M potassium iodide solution and 0.05 M iodine solution) was injected between the electrodes.
  • a dye-sensitized solar cell was produced (see FIGS. 7 and 8).
  • the solar cell obtained as described above was irradiated with UV by a UV irradiation device (trade name Toscure 401, manufactured by Harrison Toshiba Lighting). As a result, power with a voltage of 260 mV and a current of 2.1 ⁇ A was obtained.
  • Example 11 In Example 11, the same procedure was performed except that 0.1 mg of polyvinyl pyrrolidone was used as the binder resin when preparing the single-walled carbon nanotube dispersion. The durability of the electrode substrate of the solar cell thus obtained was examined. As a result, the resistance (30 ⁇ / ⁇ ) before being left in an 80 ° C. oven for 10 days was 32 ⁇ / ⁇ after being left in an 80 ° C. oven for 10 days. The power characteristics examined in the same manner as in Example 11 were a voltage of 200 mV and a current of 1.8 ⁇ A. This shows that the solar cell of this comparative example is inferior to the solar cell of Example 11.
  • Example 12 In Example 11, the same procedure was performed except that the hydroxyl group-containing fullerene was not used. The durability of the electrode substrate of the solar cell thus obtained was examined. As a result, the resistance (30 ⁇ / ⁇ ) before being left in an oven at 80 ° C. for 10 days increased to 300 ⁇ / ⁇ after being left in an oven at 80 ° C. for 10 days, which was inferior in durability.
  • the power characteristics examined in the same manner as in Example 11 were a voltage of 40 mV and a current of 0.3 ⁇ A. This shows that the solar cell of this comparative example is inferior to the solar cell of Example 11.

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Abstract

L'invention concerne un dispositif à durabilité élevée. Dans un dispositif qui comprend une couche conductrice, ladite couche conductrice comporte des nanotubes de carbone monocouche entrelacés et du fullerène, mais pas de résine de liaison.
PCT/JP2009/057092 2008-04-08 2009-04-07 Dispositif Ceased WO2009125754A1 (fr)

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JP2008-100373 2008-04-08
JP2008100373A JP5319951B2 (ja) 2008-04-08 2008-04-08 太陽電池
JP2008100372A JP5388021B2 (ja) 2008-04-08 2008-04-08 液晶セルおよび液晶ディスプレイ装置
JP2008-100372 2008-04-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024195473A1 (fr) * 2023-03-23 2024-09-26 ナガセケムテックス株式会社 Composition conductrice

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JP2004111216A (ja) * 2002-09-18 2004-04-08 Inst Of Research & Innovation 色素増感型太陽電池およびナノカーボン電極
JP2004230274A (ja) * 2003-01-30 2004-08-19 Sony Corp 水素吸蔵材料の製造方法及び水素吸蔵材料
JP2005142088A (ja) * 2003-11-07 2005-06-02 Dainippon Printing Co Ltd 色素増感型太陽電池用電極基板及び色素増感型太陽電池
WO2005110594A1 (fr) * 2004-05-13 2005-11-24 Hokkaido Technology Licensing Office Co., Ltd. Dispersion de fines particules de carbone
JP2006281189A (ja) * 2005-04-04 2006-10-19 Mikuni Denshi Kk インクジェット塗布溶液と乾燥方法
JP2007529884A (ja) * 2004-03-12 2007-10-25 エイコス・インコーポレーテッド カーボンナノチューブ剥離溶液および方法

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Publication number Priority date Publication date Assignee Title
JP2004111216A (ja) * 2002-09-18 2004-04-08 Inst Of Research & Innovation 色素増感型太陽電池およびナノカーボン電極
JP2004230274A (ja) * 2003-01-30 2004-08-19 Sony Corp 水素吸蔵材料の製造方法及び水素吸蔵材料
JP2005142088A (ja) * 2003-11-07 2005-06-02 Dainippon Printing Co Ltd 色素増感型太陽電池用電極基板及び色素増感型太陽電池
JP2007529884A (ja) * 2004-03-12 2007-10-25 エイコス・インコーポレーテッド カーボンナノチューブ剥離溶液および方法
WO2005110594A1 (fr) * 2004-05-13 2005-11-24 Hokkaido Technology Licensing Office Co., Ltd. Dispersion de fines particules de carbone
JP2006281189A (ja) * 2005-04-04 2006-10-19 Mikuni Denshi Kk インクジェット塗布溶液と乾燥方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024195473A1 (fr) * 2023-03-23 2024-09-26 ナガセケムテックス株式会社 Composition conductrice

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