WO2007024206A2 - Liant fluoropolymere pour revetements conducteurs transparents a base de nanotubes de carbone - Google Patents

Liant fluoropolymere pour revetements conducteurs transparents a base de nanotubes de carbone Download PDF

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Publication number
WO2007024206A2
WO2007024206A2 PCT/US2005/028479 US2005028479W WO2007024206A2 WO 2007024206 A2 WO2007024206 A2 WO 2007024206A2 US 2005028479 W US2005028479 W US 2005028479W WO 2007024206 A2 WO2007024206 A2 WO 2007024206A2
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coating
film
binder
cnt
wsh
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PCT/US2005/028479
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WO2007024206A3 (fr
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Jiazhong Luo
David J. Arthur
Paul J. Glatkowski
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Eikos, Inc.
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Priority claimed from US11/014,233 external-priority patent/US20050209392A1/en
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Publication of WO2007024206A2 publication Critical patent/WO2007024206A2/fr
Publication of WO2007024206A3 publication Critical patent/WO2007024206A3/fr

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    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic

Definitions

  • the present invention is directed to flexible, optically transparent and conductive coatings and films comprised of carbon nanotubes (CNT) and polymer binders on optically clear substrates such as PET and glass for display and electronic applications, and to the corresponding fabrication methods, coating layer structures and processes.
  • the invention is directed to fiuoropolymer binders applied to the CNT layer to provide protection and enhancement of properties such as increased electrical conductivity, increased optically transparency, moisture resistance, thermal resistance, abrasion resistance and interfacial adhesion.
  • Transparent and electrically conductive coatings and films are used for versatile applications particularly in flat panel displays, touch screen panel and other electronic applications.
  • These transparent conductors mainly include metal oxides particularly indium-tin oxide (ITO).
  • ITO indium-tin oxide
  • CVD chemical vapor deposition
  • sputtering and other approaches followed by annealing. This offers high electrical conductivity and optical transparency.
  • ITO-based coating and film have inferior abrasion resistance and flexibility.
  • Intrinsically conductive polymers such as polyaniline and polythiophene are also used to make flexible transparent conductive coating and films.
  • polyaniline and polythiophene are also used to make flexible transparent conductive coating and films.
  • Carbon nanotubes (CNT) of different forms have been discovered including single-wall, dual- wall and multiple- wall. These forms have been incorporated into a number of plastics and films.
  • SWNTs Single-wall carbon nanotubes
  • CVD chemical vapor deposition
  • HIPCO high pressure carbon monoxide
  • Dilute carbon nanotube dispersions in aqueous or solvent mixtures are referred to as CNT inks.
  • CNTs include single walled (SWNT), double walled (DWNT) and multi walled carbon nanotubes (MWNT). These forms of CNTs are synthesized by arc-discharge, laser ablation and chemical vapor deposition (CVD), to name a few. (See Carbon Nanotubes Science and Applications; edited by M. Meyyappan, CRC Press, 2004). Carbon nanotubes especially SWNT can also have high electrical and thermal conductivity in addition to good mechanical properties.
  • SWNT single walled
  • DWNT double walled
  • MWNT multi walled carbon nanotubes
  • Carbon nanotubes are generally mixed with polymers (or monomers followed by polymerization) to form nanocomposites.
  • U.S. Patent No. 6,265,466 relates to electromagnetic shielding composites comprising nanotubes and polymers.
  • Significant research efforts are focusing on preparation of nanocomposites using this approach.
  • the challenges for this approach include difficulty in uniform mixing due to bundles and
  • Transparent conductive coatings and films can be made by incorporating CNT into clear polymers at a desired thickness (See generally United States Patent Nos. 5,583,887 and 5,908, 585).
  • U.S. Patent Application Nos. 10/105,623 and 10/442,176 relate to transparent conductive coatings and films with or without certain patterning formed by using single-wall carbon nanotubes (SWNT) through a two step method (e.g. formation of CNT layer via wet process followed by polymer binder coating).
  • SWNT single-wall carbon nanotubes
  • This type of CNT network coating on the substrates is sensitive to environmental conditions including moisture and heat. Sheet resistance of a dried bare carbon nanotube coating on the substrates could decrease when first exposed to low moisture level, and then significantly increases at different moisture levels after reaching equilibrium. Sheet resistance also increased upon heating especially at high temperatures such as in the range of 125-400 0 C. The effects of both moisture and temperature are fully or partially reversible.
  • the resulting CNT network coating has very good flexibility.
  • these coated substrates often do not have extremely high adhesion and abrasion resistance.
  • Typical substrate types include glass, plastic, ceramic and similar materials.
  • ITO transparent conductive coatings and films made from ITO, conducting polymer, and nanocomposites containing nanotubes or other conductive particulates
  • these coating and films are formed as a solid layer to which additional layers of materials can be applied above or below to provided further function or protection from environmental influence.
  • ITO is coated on a flexible transparent polymeric film and over coated with an abrasion resistant polymer such as an acrylic to protect the surface during handling in the factory or by the end user.
  • the acrylic top coating also serves to electrically insulate the coated surface, making contact to the conductive ITO difficult or impossible. Since most commercially available transparent conductive coatings and films are solid materials, the addition of other layers typically interferes with this function of surface conductivity.
  • the polymer in the composite can be selected to provide additional functions such as abrasion, humidity, temperature, adhesion and maintain the conductive properties of the layer.
  • This approach is used commercially to form transparent conductive coatings with PEDOT and polymeric resins to form a solid layer.
  • the disadvantage to this approach is that in these composite coatings, conductivity is greatly reduced by the presence of polymeric resins which serve to dilute and interrupt the conductive pathways. Summary of the Invention
  • the present invention overcomes the problems and disadvantages associated with current strategies and designs and provides new tools and methods for providing carbon nanotube coated substrates.
  • One embodiment of the invention is directed to a conductive coating or film comprised of carbon nanotubes and a fluoromonomer or fluoropolymer binder.
  • Carbon nanotubes are preferably less than 3.5 nm in diameter, and more preferably single- walled carbon nanotubes.
  • Fluoromonomer and fluoropolymer binders that are useful in the invention include crystalline and semicrystalline fluoromonomers and fluoropolymers, amorphous fluoromonomers and fluoropolymers, fluoroplastics, fluoroelastomers, fluoroacrylates, fluorourethanes, terfluoromonomers and terfluoropolymers, perfluoro carbon-based monomers and polymers, fluoro-containing thermoplastics, thermosets and elastomers, blends of one or more different fluoromonomers and fluoropolymers, and combinations thereof.
  • Another embodiment of the invention is directed to conductive coatings films of the invention that are optically transparent.
  • these coatings or films have a transmittance value to light at 550 nm of greater than 65%, and more preferably greater than 90%.
  • these coatings or films have a transmittance value to light at 550 nm of greater than the corresponding transmittance value of the coating or film without
  • these coatings or films preferably have a transmittance value of up to
  • Another embodiment of the invention is directed to conductive coatings films of the invention that have a sheet resistance of from 10 "1 to 10 4 ⁇ /D, more preferably from
  • Another embodiment of the invention is directed to conductive coatings films of the invention that have a fluoropolymer binder containing an additive, preferably wherein the additive is selected from the group consisting of silanes, fluorosilanes, siloxanes, and metal alkoxides, and combinations thereof.
  • Another embodiment of the invention is directed to a method of forming a conductive coating or film comprising applying to a substrate a layer of carbon nanotubes and a layer of a fluoropolymer, preferably wherein the coating or film is optically transparent.
  • the coating or film has a transmittance value to light at
  • the transmittance value to light at 550 nm is greater than the corresponding transmittance value of the coating or film without said binder, preferably at least 5%, and more preferably at least 50% greater than the corresponding transmittance value of the coating or film without said binder.
  • Another embodiment of the invention is directed to a method of increasing the conductivity of a conductive film comprising applying a layer of carbon nanotubes to a surface to form a conductive film; applying another layer of material to said carbon nanotube layer that compresses said carbon nanotubes and increases sheet conductivity across a surface of said conductive film, preferably wherein the another layer contains a fluoropolymer or fluoromonomer binder.
  • Figure 1 Different coating layer structures by using carbon nanotubes and binders.
  • Figure 2. Moisture Resistance of CNT network coating on glass with or without
  • Figure 5 TEM image of nanotube coating showing open space between ropes of nanotubes.
  • Figure 6. SPM Image of single-walled nanotube coating with 500 ⁇ /D resistivity.
  • Figure 7. Profilometry of CNT coating thickness on glass substrate. Description of Invention
  • Suitable binder layers comprise chemicals that have a low index of refraction or low dielectric constant, and which may also be water resistant. Such chemicals include halogen containing polymers such as, but not limited to, chloromonomers and chloropolymers, and fluoromonomers and fluoropolymers. Of even greater surprise was., the discovery that such binders result in a CNT composite with increased conductivity and also correspondingly decreased resistivity.
  • the invention is directed to optically clear substrates such as, but not limited to, PET and glass, containing conductive coatings of carbon nanotubes. The invention is also directed to methods of forming substrates of
  • Substrates of the invention contain a layer of CNT, which are typically highly purified, applied to a substrate through, preferably, spraying or dip coating. This forms a nanometer level thick transparent conductive coating.
  • Preferred thicknesses range from 0.5 to 5,000 nm, from 1 to 3,000 nm, from 5 to 2,000 nm, and from 2 to 500 nm, from 2 to 300 nm, from 1 to 200 nm, and from 1 to 100 nm. More preferable thicknesses ranges can be from 1 to 2,000 nm, from 2 to 1,000 nm, from 2 to 500 nm, and from 2 to 100 nm.
  • a polymer also at nanometer thickness, is applied to this conductive coating.
  • the thickness of the polymer coating is often greater than the CNT coating, but not necessarily.
  • Polymer coatings can be the same or have a higher or lower thickness than the CNT coatings.
  • Polymer coatings are typically from 0.5 to 5,000 nm, from 1 to 4,000 nm, from 2 to 1,000 nm, from 1 to 500 nm and from 1 to 100 nm. These coatings are preferably applied by dip or spraying coating to provide protection to the conductive layer.
  • a variety of polymers including non-fluoropolymer and fluoropolymers are suitable for this function.
  • This invention also provides binders combined with CNT/substrate with significant improvement in transparency and either no change or an improvement in surface conductivity (with a corresponding decrease in Rs). These binders further improve properties including resistance to moisture, temperature, abrasion and bending.
  • the solvents used are also compatible with sensitive substrates such as polycarbonate and acrylic (e.g. PMMA).
  • One embodiment of the invention is directed to methods of forming CNT coating materials with binders, and in particular, fluoropolymer binders.
  • binders with CNTs is advantageous at least because:
  • CNTs such as SWCNT that applied to a substrate are fixed into position maintaining or improving most of or all of the electrical properties, optical transmission and reduction of haze of the applied film. Sheet resistance is at least maintained (i.e. does not change as compared to without binder). 2. CNT's when applied with a binder do not loose contact with each other over time (which varies greatly depending on the substrate and use of the materials). A loss of
  • the binder serves as a top coating, thereby protecting the material against environmental forces. Further, this top coating can be thin, unlike conventional overcoating which typically requires thicker coatings to achieve the same degree of protection.
  • CNT's can be applied in a fashion that allows the tubes to rope together, which is believed to be an important feature for maintaining conductivity.
  • the binder stabilizes the self-assembled network of CNTs preventing unraveling of the network.
  • a fluoropolymer containing binder which is a solution of one f ⁇ uoropolymer or a blend of fluoropolymers, which may be formulated with additives, is applied onto carbon nanotube-based transparent conductive coating on a clear substrate such as PET and glass. Both the binder and CNT coatings are at a nanometer level of thickness (for example but not limited to 10-200 nm) with interpenetration to each other.
  • the fluoropolymers or blend can be either semi-crystalline (with low level of crystallinity) or amorphous, preferably to be amorphous with low refraction of index.
  • This binder topcoat significantly improves optical transparency (and reduces haze), as compared to CNT coatings without binder (preferably by 5%, by 10%, by 15%, by 20%, by 25%, by 35%, by 40%, by 50%, and more preferably by up to 75% or more), and also CNT coatings with conventional binders, and also keeps or even increases conductivity of the CNT based coating.
  • the solvents used are also compatible with sensitive substrates such as polycarbonate and acrylic (e.g. PMMA). This binder coating and the resulting products are used for display and electronic applications.
  • This invention is also directed to approaches to protect CNT-based, and preferably SWNT-based, transparent conductive coatings by selectively utilizing polymer binders.
  • SWNT When SWNT is first applied onto a substrate, a conductive CNT network coating having an open structure (open volume approximately 40-60%) is formed.
  • polymer binder subsequently applied provides protection by infiltration into the CNT network. Without significant decrease in optical transparency and surface conductivity, the polymer binders provide the resulting products with good stability upon exposure to harsh environments such as moisture and high temperature. In addition, binders may also increase optical transmission, reduce haze, increase conductivity, and provide excellent flexibility, adhesion and abrasion resistances.
  • Such binders include, but are not limited to polyesters, polyurethanes, polyolefins, fluoroplastics and fluoroelastomers, thermoplastic elastomers, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), polyvinylalkyl vinyl ether, acrylates, epoxies, melamines, silicones, organosilicon polymers, fluorosili cones, and other similar copolymer or hybrid polymeric materials, and combinations thereof.
  • This invention also provides combinations of a CNT coating as primary conductor layer and a conductive polymer as the binder to have transparent and electrically conductive coating and film products.
  • the CNT and polymer binder coatings can be fabricated as layered structures.
  • Another embodiment of the invention is directed to flexible, transparent and conductive coatings and films comprising carbon nanotubes and polymer binders, and the corresponding fabrication methods, coating layer structures, processes and resulting articles.
  • Selective utilization of polymer binders and coating layer structures gives protection of the CNT coating by infiltration into the CNT network from environmental and mechanical conditions. Such conditions include, but are not limited to moisture, heat or cold (i.e. thermal), wear and abrasion.
  • Another embodiment of the invention is directed to single walled carbon nanotubes (SWNT) applied to transparent substrates to form one or multiple layers of coating at a nanometer level, with one or more polymer binders.
  • the one or more polymer binders are selectively utilized to protect the CNT conductive layers.
  • the polymers can be a thermoplastic or thermoset, or a combination thereof.
  • the polymers are preferably hydrophobic for superior moisture resistance.
  • High molecular weight thermoplastics and cross-linked thermosets for also preferred for increased abrasion resistance and heat stability, as compared to non-binder coatings.
  • These binders are also chemically compatible with the CNT's and also each other, for good adhesion
  • Polymers can be in a single layer as either a basecoat underneath the nanotube coating, or a topcoat above the nanotube coating, or a combination of both. Binders can be formed in two or more layers in the basecoat, the topcoat or both, forming a sandwich structure. This embeds the nanotube coating in the middle, which provides good interpenetration and interfacial bonding.
  • the CNT conductive coating layers and the binder layers number from single to multiple can be in any suitable combinations.
  • the definition of a layer for purposes of the invention, is not limited to the conventional meaning of a layer as a separate, independent material.
  • layers of polymer binder can also be considered to infiltrate into the CNT network coating.
  • the layer is considered a traditional layer in that it sits upon and flattens the CNTs. Without limiting the invention to a theory, it is believed that this flattening or compression of the CNT layer results in an increased electrically conductivity and/or decreased electrical resistance, as compared to coatings or films without binder (or at least maintaining the same resistance and/or conductivity). Preferred decreases in sheet resistances are from 5% to 80%, from 10% to 70%, from 15% to 50%, or more preferably from 10% to 50%. Also preferred is maintaining the same sheet resistance. It is believed that no such observation has previously been described for CNT materials.
  • Another embodiment of the invention is directed to layers of the invention that are further modified by surface modification either chemically or physically, such as by, although not limited to, deposition of inorganic polymeric materials such as, for example, silane and metal alkoxides, silicones, polysilanes, polysilazanes, polygermanes, polystannanes, polyphospahazenes.
  • inorganic polymeric materials such as, for example, silane and metal alkoxides, silicones, polysilanes, polysilazanes, polygermanes, polystannanes, polyphospahazenes.
  • silicones such as, for example, silane and metal alkoxides, silicones, polysilanes, polysilazanes, polygermanes, polystannanes, polyphospahazenes.
  • silicones such as, for example, silane and metal alkoxides, silicones, polysilanes, polysilazanes, polygermanes, polystannanes
  • Another embodiment of the invention is directed to conductive networks of CNT formed with binder materials.
  • This approach allows the formation of multilayer coating consisting of several binder materials that do not necessarily cover the conductive CNT layer.
  • the binder coating is added to the CNT network to partially (e.g. less than 90%,
  • ODMAVPCDOCSWSHU ⁇ U ⁇ V- J Q less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than
  • top coating/binder not only penetrates the CNT layer, but also passes through the CNT layer down to the supporting substrate where the binder adheres or reacts to bond the materials and layer together. This resulting composite structure is not possible by conventional means for forming transparent conductive coatings and films.
  • a binder to the CNT network layer can be done such that only a small fraction of the available free space between the CNT network is filled, thereby leaving room for additional resins, reactants, gases to interface/interact with the CNT network (see Figures 5 and 6).
  • This approach allows for the same CNT layer to be useful in a variety of applications by selecting binder materials which add additional functional characteristics.
  • the polymer binder is applied using dilute solutions (e.g. less than 5%, less than
  • a thin binder coating of the same materials provide protection to the transparent conductive layer comprising nanotubes.
  • the coating can be deposited using conventional coating process such as dip, flow, spin, gravure, roll, or spray, or any others known to those skilled in the art.
  • Another surprising and unexpected result of the invention is that such thin coatings are effective at providing environmental protection commonly requiring much thicker coatings.
  • the protection provided by the very thin coating on the nanotubes is at least partly attributed to nanoscopic scale of the composite which is formed.
  • a resistive touch screen employs ITO deposited on glass to form one electrode and also has a second electrode made from ITO deposited on PET polymer film placed on top of the ITO/glass layers.
  • ITO deposited on glass
  • PET polymer film placed on top of the ITO/glass layers.
  • a binder material is added that provides a more durable, long-lasting coating which is bonded to the polymer or glass substrate to prevent failure.
  • Conventional ITO cannot be modified in this way especially when dispersed in a binder material and coated. The resulting ITO composite would not have the same electrical and optical performance characteristics as that of the solid layer of ITO.
  • This present invention is also useful as a direct replacement in all applications where ITO is used as a transparent conductive coating or electrode in products, such as, but not limited to, touch screens; LCD, plasma and OLED displays; ESD coatings, EMI shielding coatings; windows and lenses; electrochromic, electroluminescent and field emission displays, heat reflective coatings, energy efficient windows, gas sensors, and photo voltaics.
  • products such as, but not limited to, touch screens; LCD, plasma and OLED displays; ESD coatings, EMI shielding coatings; windows and lenses; electrochromic, electroluminescent and field emission displays, heat reflective coatings, energy efficient windows, gas sensors, and photo voltaics.
  • Transparent and conductive coatings in this invention can be made at least using the following combinations of materials, coating layer structures, fabrication methods and processes. The selection and combinations of these parameters deliver the products that meet desired performance criteria after addition of topcoat including higher conductivity (e.g. decrease in sheet resistivity by 10-70%), optical transparency (e.g. greater than 60%T, greater than 70%T, greater than 80%T, and more preferably greater than 90%T), haze reduction (preferably more than 1%, more than 5%, more than 10%, more than 15%, more than 20%, and more preferably up to 50%), flexibility (e.g. withstanding cycle testing until cracking at about 27,000 cycles, and more preferably cycle testing until cracking at about 32,000 cycles or
  • abrasion resistance increase by up to 33,600% measured by change in Rs after abrasion for 60 cycles
  • adhesion e.g. up to 5,000% increase measured in change in Rs after peeling using scotch tape for 4 times
  • environmental such as moisture resistance (e.g. 40-100%, 50-100% and more preferably 60-100% measured increase change in Rs from dry to RH75% after stabilized for 24 hrs), temperature resistance (e.g. up to 90% change measured by change in Rs after 125 0 C /2hrs and then room temperature for 16 hours), and long-term durability.
  • Carbon nanotubes are applied onto transparent substrates to form one or multiple primary conductive layers.
  • Polymers can be used as binders (and potentially secondary conductors in case of conductive polymers) in a coating layer structure to deliver products having good mechanical, thermal and/or electrical properties, as desired.
  • Highly pure carbon nanotubes and bundles are preferred.
  • Single-wall or dual- wall carbon nanotubes are also preferred for high conductivity.
  • Perfect and pure single walled carbon nanotubes (SWNT) having high content of metallic nanotubes are more preferable.
  • Average outer diameter of the carbon nanotubes is generally 3.5 nm or less.
  • CNT's are generally made by the method of arc-discharge, chemical vapor deposition, or laser ablation followed by purification, although other productions methods are known and available. Purification methods include acid treatment followed by extraction, field flow fractionation (FFF), thermal oxidation, centrifugation, and any other standard or conventional methods.
  • FFF field flow fractionation
  • Purified carbon nanotubes are generally dispersed into the organic solvents such as mixture of water and alcohol, or another solvent.
  • the CNT's are applied onto the substrate, for example, by spraying coating, dipping coating, spinning coating, and other deposition methods in wet or dry states.
  • the coating thickness of the CNT network coating is preferably in the range of about 10 to 1,000 nm, depending on the sheet resistance value desired. Preferred ranges are 10 to 500 nm for sheet resistance range of lO ⁇ -lO 5 ⁇ /D.
  • Transparent substrates are primarily polymer films and glasses. These include, but are not limited to polyester, polycarbonate, polyolefins, polyurethanes, acrylates,
  • Thermoplastics such as polyethylene tetraphthalate (PET) and polyethylene naphthalate (PEN) are preferred for products used for display applications. Such products include Melinex (PET manufactured by Dupont-Teijin), Lumirror (PET manufactured by Toray) and Teonex (PEN manufactured by Dupont-Teijin).
  • the transmittance value of the films at wavelength of 550 run is in the range of 60-99% transmittance, preferably from 75-95% and more preferred, greater than 90% transmittance.
  • Glass substrates include regular and optical display grades of glass such as Corning 1737 and Corning Eagle 2000TM. Corresponding transmittance at 550 nm is generally higher than 90% (more preferably greater than or equal to 91 %).
  • the polymer binders include, but are not limited to, polymers that are thermoplastics or thermosets, or any combination of one or more types of either or both.
  • Polymer binders are applied by dip coating in the form of dilute solution, chemical deposition in the vapor state, sputtering in solid state, or by another conventional method. Dip coating is one of the preferred methods in which the polymer solution concentration is generally in the range of 0.01-5% (more preferably in the range of 0.1-1%) to achieve desired coating thickness.
  • the polymer is dissolved in organic solvents having low boiling point. Such solvents include, but are not limited to acetone, toluene, methyl ethyl ketone (MEK), water, other similar chemicals or mixtures, and any combination thereof. Solvents are dried off after coating.
  • Thermoplastic polymers include, but are not limited to polyesters, polyurethanes, polyolefins, chloro- or fluoroplastics and chloro- or fluoroelastomers, thermoplastic elastomers, similar chemicals and any combination thereof.
  • Fluorine-containing polymers include, but are not limited to polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), polyvinylalkyl vinyl ether, any copolymers or polymer mixtures.
  • Thermoplastics may be directly applied to form coating through drying process.
  • Thermosetting polymers of the invention include, but are not limited to cross- linked polyesters, polyurethanes, acrylates, epoxies, melamines, silicones, organosilicon
  • thermoplastic precursors can be applied onto the substrate followed by drying and cross-linking reaction (such as curing). Substrates can be cured through heating, moisture, visible light, UV or other irradiation, or with combined curing processes. Binders can also be applied and the materials partially or fully cured in the course of fabrication, and fully cured in the end of processes.
  • the partially cured or "B-staged" prepolymers provide advantages in processing because the CNT conductive layer can be pressed into the binders while maintaining high conductivity.
  • Polymer binders useful with UV or irradiation curing are acrylates polymerized through free-radical mechanism, epoxy cured through cationic polymerization, or similar materials using curing mechanism such as thio-vinly reaction chemistries. The materials without oxygen inhibition are preferred for easy processing in air.
  • polymers have the following options and/or combinations : hi one preferred embodiment, polymers have medium or high hydrophobilicity in chemical nature for high moisture resistance.
  • These regular and fluoro-containing thermoplastics, thermosets and elastomers are described herein.
  • regular polymer is polyester solution LCC-4 (available from Flexcon) dissolved in the mixture of acetone and toluene.
  • fluoropolymer is PVDF (Hylar SN manufactured by Solvay) dissolved in, for example, N,N-dimethylacetamide or acetone.
  • Fluoropolymers are formed in a solution of one polymer or a blend or formulation of several fluoropolymer components, which are amorphous or partially crystalline.
  • Amorphous fluoropolymers such as Teflon AF are preferred. These polymers have very good optical transparency with low refraction of index, in combination with excellent chemical resistance and thermal resistance.
  • Their solutions in fluorosolvents can be used for dip or spraying coating onto CNT based transparent conductive coating on substrates such as, for example, PET, PEN, polycarbonate, acrylic and glass.
  • Fluoropolymers include, but are not limited to amorphous perfluorocarbon-based polymers.
  • the amorphous fluoropolymers are known as fluorinated carbon-based
  • Grade 1600 and 2400 are commercially available and can be dissolved in fluorine containing solvents such as Fluorinert FC 75 and FC40;
  • CytopTM from Asahi Glass Company having refraction index of 1.34, which is amorphous fluoropolymers and also dissolvable in perfluorosolvent; and FluoroPel PFC series (from Cytonix) including PFC 501A 5 502A, 504A,
  • Refraction index of this type of amorphous fluoropolymer is 1.32. They are generally dissolved in fluorosolvents such as 3 M HFE 7100 and like chemicals.
  • fluorocarbon polymers are also useful with the invention. Many of these chemicals are fluorocarbon-based fluoroplastics and fluoroelastomers, which are generally copolymer or terpolymers of TFE and other monomers such as perfluoro vinyether. These polymers are commercially available from Dupout, Dupont
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • VDF vinylidiene fluoride
  • fluoropolymers include, but are not limited to fluoroplastics and fluoroelastomers such as, but not limited to: fluoroacrylate, fluorourethane, perfluoroether; and similar chemicals.
  • Blends of fluoropolymers are also useful with the present invention. These blends include, but are not limited to, blends of amorphous and semi-crystalline fluoropolymer (e.g. fluoroelastomers); blend of fluorocarbon polymers and any other fluoropolymers such as fluoroacrylates, fluorourethane and perfluoroether, and similar chemicals, blend of combination of fluoroacrylates, fluorourethane and perfluoroether, and other similar chemicals.
  • amorphous and semi-crystalline fluoropolymer e.g. fluoroelastomers
  • blend of fluorocarbon polymers and any other fluoropolymers such as fluoroacrylates, fluorourethane and perfluoroether, and similar chemicals
  • blend of combination of fluoroacrylates, fluorourethane and perfluoroether and other similar chemicals.
  • Suitable fluoropolymer or blends can be dissolved in regular organic solvents or fluorosolvent for solution dip coating or spray coating.
  • fluorosolvent is perfluoro(2-n-butyl tetrahydrofuran) available from 3M as Fluorinert FC-75. They may have low boiling points from 50-150 0 C.
  • the fluoropolymers can be formulated with addition of other ingredients such as fluorosilanes to improve adhesion. Other additives can be included for desired properties.
  • polymers are thermoplastics having high molecular weight or thermosets having cross-linking structures for high thermal and mechanical durability.
  • the thermosetting polymers are used to bond nanotubes together nanomechanically to improve conductivity stability under heating. Another advantage of this approach is to increase abrasion resistance.
  • thermoplastic polymer is the polyester solution LCC-4 (Flexcon) dissolved in the mixture of acetone and toluene.
  • the thermosetting polymers can be melamine/acrylic copolymers, UV curable epoxy or other systems.
  • polymers can be conductive polymers including
  • polymers can be chemically compatible with nanotube and the substrates to display good interfacial bonding and adhesion.
  • surface treatment with inorganic-organic hybrid compound forms interfacial bonding or binders.
  • interfacial bonding or binders include silanes, fluorosilane, metal alkoxides, and other related materials.
  • these polymers are selected from any preferred embodiment, or any combination of these preferred selections to achieve desired property combination.
  • the binder coating thickness is preferably in the range of 10 to 1,000 nm depending on sheet resistance value required.
  • a more preferred rage is 10 to 500 nm for sheet resistance range of 10 "1 to 10 6 ⁇ /D (also 10 1 to 10 3 ⁇ /D; 10° to 10 4 ⁇ /D; 10 "1 to 10 5 ⁇ /O).
  • This binder layer diffuses into the CNT network or mat and provide protection from mechanical damage and moisture infiltration while also exposed some CNT on the
  • Coating thickness can be controlled by the binder solution concentration and dip coating conditions such as speed and angles. Properties such as abrasion resistance and moisture resistance depending on coating thickness can be further optimized by these parameters.
  • fluoropolymers are used as binder coating for
  • Sensitive substrates have a limited selection of regular binders and solvents for coating. Since perfluorosolvents used in this invention may be inert to these sensitive substrates, the invention provides a new approach to coated CNT transparent conductive coating on the sensitive substrates.
  • amorphous fluoropolymer is used to coat CNT transparent conductive coating for its extremely good abrasion resistance, which is much better than that of other polymer binders.
  • fluoropolymer coated CNT coating is thermally treated because treatment can enhance properties such as interfacial adhesion and chemical resistance.
  • fluoropolymers can be formulated with fluorosilanes and other ingredient to further improve adhesion. Fluoropolymers coated
  • Fluorosilane can be mono- or bifunctional silanes, which has fluorocarbon or perfluoroether-type of structures.
  • fluoropolymers can be used as a single layer only, or as dual or multiple coatings in the same film.
  • Teflon AF can be coated to glass substrate first. After heat treatment and cooling down, CNT can be coated onto the surface followed by another layer of Teflon AF, to form a type of sandwich structure.
  • fluorosolvents and fluoropolymers used may contain or dissolve a high percentage of oxygen, which is a dopant for semiconductive carbon nanotube.
  • these chemicals can act as a solution to remove water trapped in the carbon nanotubes.
  • fluoropolymers can be applied onto the substrate first to form a passivation layer before CNT coating.
  • Fluoropolymers disclosed in this invention may also be used to form CNT based conductive layer or a pattern which is highly hydrophobic.
  • the preferred embodiments may also be performed with the use of monomers as the binder coating to form CNT conductive layers.
  • the selected polymer binder is applied onto the transparent substrates first, following by a layer of carbon nanotube network coating on the top.
  • the nanotube coating is pressed into thermoplastic or partially cured ("B- staged") polymer binder layer.
  • the "B-staged” polymer binders can be further cured to form cross-linked structure. Bare carbon nanotubes exposed to the outer surface ensure further electrical connection during service. High degree of penetration of CNT layer into the thermoplastic or "B-staged” thermoset binders is preferred.
  • Topcoat As shown in Figure l(B), the selected polymer binder is applied after the CNT conductive coating has been coated onto the substrate.
  • the thermoplastics can be directly applied while thermosetting polymers need to be cured afterwards.
  • This binder layer is expected to diffuse into the CNT network or mat and provide protection from mechanical damage and moisture infiltration while also exposed some CNT on the surface for conductivity.
  • topcoat is preferred due to its better protection than that with the basecoat only.
  • the topcoat is preferably water resistant to subsequent binding.
  • Additives may be included before deposition or the surface of the binder layer be subsequently treated by, for example, heat treatment, plasma treatment, corona treatment, or a combination thereof.
  • the same or different polymers are applied as combinations of basecoat and topcoat as shown in Figure l(C).
  • Thermoplastics and partially cured (“B-staged") thermosets are treated the same way as described herein. This "sandwich structure" is also preferred for better protection and higher adhesion.
  • the basecoat is a partially cured "B-staged” binder followed by formation of CNT network coating. After the CNT network is pressed into the "B-staged" thermoset binder, the binder will be fully cured.
  • the topcoat is formed through subsequent coating with a thermoplastic or thermoset binder. In this way the basecoat is protected from solvents during the late process. The resulting products have good mechanical properties and chemical resistance.
  • the combinations of basecoat, topcoat and surface treatment can vary in different layers ranging from single to multiple layers.
  • This invention also provides all the related fabrication methods and processes using the related materials and coating layer structures as described.
  • This invention also provides all the related methods and resulting products in any form such as coating, film, articles and part of devices.
  • the resulting products have excellent optical transparency and high electrical conductivity.
  • the conductivity can also be adjusted to in a broad range of sheet resistance. They also offer other advantages including neutral color tone, good adhesion, flexibility, abrasion resistance and environmental resistance (to heat and moisture). Therefore, these products can be used as transparent conductors in display applications.
  • Carbon nanotubes are coated onto the substrates by spraying purified SWNT inks dispersed in EPAZH 2 O (3:1).
  • the substrate is a glass slide (1x3" in size for testing), or PET film (typically Melinex ST505 in 6 x 8 cm size for testing).
  • the both ends of the sample are coated with gold by sputtering, or with silver paste as the testing electrodes.
  • Polymer binders are dissolved in the corresponding solvents to make dilute solutions.
  • the polymer binders are then applied onto the surface by dip coating manually or by automatically using machine.
  • the samples are dried and cured subsequently.
  • CNT layer is pressed into the binder layer under a mechanical press with very flat surface (about 4,500 psi of pressure for 5-10 minutes) before full curing.
  • MEK methyl ethyl ketone
  • PVDF Polyvinylidiene fluoride
  • NP resin nitrocellulose/acylic mixture
  • MEK methyl ethyl ketone
  • Teflon AF available from Dupont
  • Fluorinet FC 75 available from 3M
  • SIFEL 611 (a thermal curable fluoropolymer available from Shin-Etsu) dissolved in the solvent X-70580 (available from Shin-Etsu);
  • An experimental nanosilicate compound is curable under heating through condensation reaction (available from Dupont) diluted in mixture of D? A/water.
  • Sheet resistance (Rs in unit of ⁇ /D) is measured by the well-known two-probe
  • DMM method or four-point probe method Preferred ranges are from 10 "1 to 10 5 ⁇ /D,
  • Fluoropolymer added as a topcoat produced the surprising result of decreased resistance by a factor of between 10-20%, 10-30%, 10-40% and most preferably 10-50%.
  • Rs value is tested after exposure to different relative humidity (RH%) at the same ambient temperature for about 24 hours.
  • the relative humidity (RH) level in the desiccator with drierite is expected to be zero.
  • Different RH levels are controlled by different saturated solutions in a closed chamber (e.g., KOH, K 2 CO 3 , NaCl for RH 9, 43.1, 75.4%, respectively).
  • Each Rs value measured after equilibrium at each RH level is then compared to the value at RH 0% by calculating the change percentage, m most of the situations, the change in stabilized Rs value from the dry state to that at RH 75% is used. Minimum change is preferred.
  • Thermal resistance of the samples in air is evaluated by a quick screening method. This method involves treatment at 125 0 C for 2 hours in air following by cooling at the similar ambient conditions for at 16 hours. The change in Rs value compared to the initial Rs value in air is then calculated. Minimum change is preferred. Abrasion Resistance and Flexibility
  • the sample surface is abraded by using a weight wrapped with cotton cloth for 60 cycles. Before and after the abrasion test, Rs value is tested and compared. For the sample size in 6 x 8 cm, a weight of 204 g is used while a weight of 100 g is used for the sample in 1x3" in size. Minimum change means high abrasion resistance.
  • Example 3 #WE 1 : CNT/glass with PVDF as the binder (Topcoat)
  • the sample of. CNT/glass were made. It was then dip-coated with 1% of polyvinylidiene fluoride (PVDF) solution dissolved in N,N-dimethyl acetamide followed by drying, and then tested for moisture resistance in the same way as described. The sample was also coated with PVDF multiple times for better coating quality and higher thickness. The sample was tested each time after coating. The. results are shown in Figure 2, Figure 3 and Table 2.
  • PVDF polyvinylidiene fluoride
  • PVDF as a type of thermoplastic fluoropolymer improves moisture resistance significantly. With multiple-time coating, moisture resistance is further increased but this improvement tends to level off after 3x coating ( Figure 2 and Figure 3).
  • An identical sample of the working example #WE was evaluated for thermal resistance after triple coating with PVDF binder. As shown in Figure 4, Rs increased by
  • Example #WE 6-7 in the Table 4 illustrate using polyester and PVDF as top coat binder for the CNT based transparent conductive coating. After binder coating especially after coating for multiple times, all the performance parameters have been improved. Stability of sheet resistance value is further improved by preheating the sample.
  • Example #WE 8-13 in the Table 5 illustrate using more different polymers including both thermoplastics and thermoset as topcoat binders for the CNT based transparent conductive coating.
  • a sheet of PET (Melinex ST 505, 5 mil, available from Dupont Teijin) was spray-coated with CNT. Its sheet resistance was about 500 ⁇ /D while light transmittance was about 89-90% at the wavelength of 550 nm. Different binders were evaluated as topcoat.
  • polyester and PVDF also include Teflon AF (a thermoplastic fluoropolymer from Dupont) dissolved in Fluorinet FC75; SIFEL 611 (a thermal curable fluoropolymer available from Shin-Etsu) dissolved in the solvent X-70580 (available from Shin-Etsu), a nitrocellulose/acylic polymer mixture ("NP resin” in short), and UV curable epoxy UV 15 without oxygen inhibition issue in air (available from Masterbond). Based on the results, selective utilization of polymer binders can result in property improvement including environmental resistance and flexibility.
  • Teflon AF a thermoplastic fluoropolymer from Dupont
  • SIFEL 611 a thermal curable fluoropolymer available from Shin-Etsu
  • solvent X-70580 available from Shin-Etsu
  • NP resin nitrocellulose/acylic polymer mixture
  • UV curable epoxy UV 15 without oxygen inhibition issue in air available from Masterbond
  • Example #WE 14-21 in the Table 6 illustrate using polymer binders at different concentration for the CNT based transparent conductive coating.
  • a grade of CNT ink having higher quality (referred as "A-grade” ink) was used.
  • a sheet of PET (Melinex ST 505, 5 mil, available from Dupont Teijin) was spray-coated with CNT. Its sheet resistance was about 500 ⁇ /D while light transmittance was about 90-92% at the wavelength of 550 nm.
  • the binders were dip-coated onto the sample manually. The testing results demonstrate the feasibility to adjust the properties by adjusting the binder concentration, in addition to the type of binder selected. Particularly this adjustment needs to correspond to the CNT quality.
  • the polyester binder is one of the preferred binder. Its best concentration for this manual coating procedures, 0.13% of concentration is preferred for good balance in different properties.
  • Example #WE 22-25 in the Table 7 illustrate the feasibility of using coating binder conditions to adjust the properties.
  • a grade of CNT ink having higher quality (referred as "A-grade” ink) was sprayed onto PET (Melinex ST 505, 5 mil, available from Dupont Teijin). Its sheet resistance was about 500 ⁇ /D while light transmittance was about 90-92% at the wavelength of 550 nm.
  • the binders were dip-coated onto the sample thorough automatic dip-coating process.
  • the polyester solution at a certain concentration was filled into a tank to immerse the CNT/PET samples for a certain period of time. And then the solution was pumped out at a certain speed.
  • two set of processing conditions have been tried with slightly different concentrations.
  • polyester solution is filled into a closed tank to immerse CNT/PET samples hanged in the middle. After immersion for 5 minutes, a liquid level is dropped at a rate of 2.5 inches per minute. After all the solutions are pumped out, the film is then pulled out and dried with 100 0 C hot air in the entrance of the tank.
  • polyester solution is pumped into the tank to immerse the CNTYPET film hanged in the middle. After immersion for 20 minutes, the solution level is dropped at a rate of 0.5 inch per minute. After completely draining the solution, the film is then set in the closed tank for 30 minutes for drying at room temperature. The sample is finally dried at 85 0 C in the oven for 10 minutes.
  • Example 9 #WE 26-33: CNT/PET with different coating layer structures
  • Table 8 shows the examples (#WE 26-33) having different coating layer structure.
  • the topcoat and basecoat compositions are specified.
  • the polyester used is LCC-4 available from Flexcon.
  • the polymer mixture of thermal curable melamine/acrylic is LCC-5 available from Flexcon. All the concentration used is 1%.
  • thermoplastic polyester was used as the basecoat, CNT coating was pressed under heating and pressure conditions after spray coating, hi the case of curable materials as basecoat, the layer is partially cured first to form a "B-stage" perform and then the CNT layer is pressed after spraying coating.
  • these samples using carbon nanotubes and polymer binders have significant advantages in improved abrasion resistance and flexibility.
  • Conductive polymers such as polythiophenes and different surface treatments through chemical or physical means are applicable to this invention. Multiple layers of coating structures can be fabricated in different approaches.
  • a transparent and conductive coating or film comprised of carbon nanotubes and a polymer binder which together form a network, wherein the polymer binder protects the
  • Transparent and conductive coatings or films preferably comprise a transparent substrate which is polymer films including both thermoplastics and thermosets including polyesters, polycarbonates, polyolefms, fluoropolymers, or glass ranging from regular glass to optical display type of glass.
  • Carbon nanotubes are preferably single walled carbon nanotubes (SWNT) having a desired range of dimension.
  • SWNT single walled carbon nanotubes
  • Preferred binders are thermoplastics or thermosetting polymers, or any combination of both, including polyesters, polyurethanes, acrylates, epoxies, melamines, silicones, fluoroplastics, fluoroelastomers, and any other copolymer or hybrid polymers via heating, visible light, UV, irradiation or moisture curing or any dual curing mechanisms.
  • Thermosetting polymers can be partially cured (B-staged) and used as basecoat before nanotube coating during the fabrication and permit the CNT coating and polymer binder coating to have interpenetration into each other.
  • polymers are hydrophobic in chemical nature for high moisture resistance, including regular and fluoro-containing thermoplastics, thermosets and elastomers as described herein.
  • polymers are thermoplastic having high molecular weight or thermoset with cross-linking structures for high abrasion resistance and thermal resistance.
  • polymers can be any conductive polymers including polythiophenes, polyanilines and their derivatives with substitution groups for high surface conductivity.
  • polymers can be chemically compatible with nanotube and the substrates to display good interpenetration, interfacial bonding and adhesion.
  • surface treatment with inorganic-organic hybrid compound is necessary to form interfacial bonding or binders itself.
  • These include silanes, fluorosilane, metal alkoxides, and other related materials.
  • These polymers can be any selection or any combination of these preferred selections to achieve desired properties.
  • the coating layer structures (previously referred as "construction structures") using nanotube and polymer binders can be in different sequences.
  • One or multiple layers of polymers can be in a single layer only as either basecoat underneath the nanotube coating, or topcoat above the nanotube coating, or any combinations of both.
  • Polymer binders can be used as the basecoat only in between transparent substrates and carbon nanotube coating.
  • the nanotube coating can be pressed into flexible thermoplastic or partially cured (B-staged) polymer binder layer.
  • Polymer binders can be used as the topcoat only on the surface of carbon nanotube coating on the transparent substrates.
  • the same or different polymers can be applied as combinations of basecoat and topcoat to sandwich the carbon nanotube coating, in which thermoplastic or partially cured (B-staged) polymer binders can be used as the basecoat in the process.
  • Single or multiple layers of binders and conductive layers can be in any combination of these described herein.
  • a carbon nanotube coating is not limited to single layer.
  • Binder coating thickness can be adjusted by changing polymer binder concentration during the coating process for desired properties.
  • Binder coating thickness can be adjusted by changing coating speed during the coating process for desired properties. Binder coating thickness can be adjusted by changing immersion time, coating angles and other coating processing parameters during the coating process for desired properties.
  • Table 9 shows examples (#EX 1-12) having Teflon coating.
  • Purified carbon nanotube ink dispersed in 3/1 IP A/water is sprayed onto the clean substrates such as PET and glass.
  • T% represents the total transparency of the sample.
  • Transparency of the substrate is improved by greater than 60%, greater than 70%, greater than 80%, and more preferably, greater than 90% after addition of a fluoropolymer as a topcoat.
  • Transmittance value is at least 5% greater than the corresponding transmittance value of the coating or film without said binder.
  • This coating also provides high abrasion resistance and good adhesion for CNT on glass.
  • Adhesion is measured by Rs change % after peeling by scotch tape for 4 times.
  • Abrasion resistance is measured by Rs change % after abraded by 100 g weight wrapped with 8 layers of cheese cotton cloth.
  • Teflon AF coating CNT/glass showed Rs increase by 409% after the tape peel test for 4 cycles, a Rs increase by 33600% after the abrasion test for 60 cycles. This is in sharp contrast to the samples with Teflon AF coating.
  • Ex. 1 showed no change in Rs at all after the peel test, and only 20% of Rs increases after abrasion for 60 cycles.
  • fluorosolvent used for Teflon AF coating is compatible with sensitive substrates such as acrylic and polycarbonate. Therefore, this invention provides a broad range of application in display, electronic and ESD areas.

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Abstract

L'invention se rapporte à des revêtements et à des films transparents et conducteurs, flexibles, formés à partir de nanotubes de carbone (NTC) et en particulier à partir de nanotubes de carbone monofeuillet, et de liants polymères. Ces revêtements et ces films sont formés de préférence à partir de nanotubes de carbone appliqués sur des substrats transparents, formant une ou plusieurs couches conductrices d'une épaisseur d'ordre nanométrique. Des liants polymères sont appliqués sur un revêtement formée d'un réseau de NTC présentant une structure ouverte, de manière à former une protection par infiltration. Ce traitement permet d'améliorer les propriétés telles que la résistance à l'humidité, la résistance thermique, la résistance à l'abrasion et l'adhésion interfaciale. Ces polymères peuvent être des polymères thermoplastiques ou thermodurcissables, ou une combinaison des deux. Ils peuvent en outre être isolants ou intrinsèquement conducteurs, ou présenter une combinaison quelconque de ces deux propriétés. Ces polymères peuvent comprendre une ou plusieurs couches formant une couche de fond sous un revêtement de NTC, ou une couche de finition par-dessus un revêtement de NTC, ou une combinaison d'une couche de fond et d'une couche de finition formant une structure en sandwich. Un liant contenant un fluoropolymère, constitué d'une solution d'un seul fluoropolymère ou d'un mélange de fluoropolymères, contenant éventuellement des additifs, est appliqué sur un revêtement conducteur transparent de nanotubes de carbone d'épaisseur nanométrique, formé sur un substrat transparent tel qu'un substrat de PET et de verre. Les fluoropolymères où le mélange de ceux-ci peuvent être soit semi-cristallins (présentant un faible taux de cristallinité) soit amorphes, la préférence allant à des fluoropolymères amorphes avec un faible indice de réfraction. L'épaisseur de la couche de liant peut être régulée par modification de la concentration de liant, de la vitesse d'application et/ou d'autres conditions de traitement. Cette couche de liant permet d'améliorer notablement la transparence optique, et de conserver ou d'accroître la conductivité de la couche de NTC. Du fait de ces avantages, joints à d'autres qualités telles que la résistance à l'abrasion, la résistance thermique, et la résistance à l'humidité, ce revêtement de liant, et les produits résultants, conviennent pour des applications comprenant les afficheurs et l'électronique.
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EP1922737A2 (fr) * 2005-06-02 2008-05-21 Eastman Kodak Company Conducteur multicouches avec nanotubes en carbone
US7727578B2 (en) 2007-12-27 2010-06-01 Honeywell International Inc. Transparent conductors and methods for fabricating transparent conductors
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US8445788B1 (en) 2009-01-05 2013-05-21 The Boeing Company Carbon nanotube-enhanced, metallic wire
US7897876B2 (en) 2009-01-05 2011-03-01 The Boeing Company Carbon-nanotube/graphene-platelet-enhanced, high-conductivity wire
US7875802B2 (en) 2009-01-05 2011-01-25 The Boeing Company Thermoplastic-based, carbon nanotube-enhanced, high-conductivity layered wire
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WO2011060774A2 (fr) 2009-11-23 2011-05-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Élément électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère et son procédé de production
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US9329544B2 (en) 2010-01-25 2016-05-03 Xerox Corporation Polymer-based long life fusers and their methods of making
US9471019B2 (en) 2010-01-25 2016-10-18 Xerox Corporation Polymer-based long life fusers
CN104428928A (zh) * 2012-07-13 2015-03-18 古河电气工业株式会社 集电体、电极、二次电池以及电容器
WO2014023977A1 (fr) * 2012-08-08 2014-02-13 Innovative Carbon Limited Matériaux polymères conducteurs, préparation et utilisation de ceux-ci
GB2522319A (en) * 2013-11-20 2015-07-22 Preservation Paints Ltd Composition
TWI627777B (zh) * 2017-07-26 2018-06-21 財團法人工業技術研究院 光學補償結構

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