WO2009102077A1 - Composition de caoutchouc à nanotube de carbone, câblage, pâte électroconductrice, circuit électronique et procédé de fabrication de la composition de caoutchouc à nanotube de carbone - Google Patents

Composition de caoutchouc à nanotube de carbone, câblage, pâte électroconductrice, circuit électronique et procédé de fabrication de la composition de caoutchouc à nanotube de carbone Download PDF

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Publication number
WO2009102077A1
WO2009102077A1 PCT/JP2009/052825 JP2009052825W WO2009102077A1 WO 2009102077 A1 WO2009102077 A1 WO 2009102077A1 JP 2009052825 W JP2009052825 W JP 2009052825W WO 2009102077 A1 WO2009102077 A1 WO 2009102077A1
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WIPO (PCT)
Prior art keywords
carbon nanotube
rubber
wiring
ionic liquid
rubber composition
Prior art date
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PCT/JP2009/052825
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English (en)
Japanese (ja)
Inventor
Takao Someya
Tsuyoshi Sekitani
Kenji Hata
Original Assignee
The University Of Tokyo
National Institute Of Advanced Industrial Science And Technology
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Publication date
Application filed by The University Of Tokyo, National Institute Of Advanced Industrial Science And Technology filed Critical The University Of Tokyo
Priority to JP2009553493A priority Critical patent/JPWO2009102077A1/ja
Priority to PCT/JP2009/052825 priority patent/WO2009102077A1/fr
Publication of WO2009102077A1 publication Critical patent/WO2009102077A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0277—Bendability or stretchability details
    • H05K1/0283—Stretchable printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0133—Elastomeric or compliant polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/026—Nanotubes or nanowires
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
    • H05K2203/0271—Mechanical force other than pressure, e.g. shearing or pulling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a carbon nanotube rubber composition, a carbon nanotube rubber, a carbon nanotube rubber paste, a wiring, a conductive belt, an electronic circuit and a method for producing the same.
  • the present invention provides a carbon nanotube rubber composition that provides a truly rubbery elastic conductor, carbon nanotube rubber, carbon nanotube rubber paste, wiring, conductive paste, a method for producing the same, and an electron using the same. It relates to the circuit.
  • Organic transistors can be fabricated on plastic films in a low temperature process, unlike conventional inorganic materials such as silicon, making it possible to make electronic devices that are both light and bendable. In addition, since it can be manufactured using printing technology, the manufacturing cost for making large-area products is also much lower than silicon. Applications of organic transistors to drive circuits for wireless tags and electronic paper are expected using this feature.
  • the present inventors worked on researches to apply organic transistors to large-area sensors and large-area sensors, electronic artificial skin for robots, sheet-type scanners, ultra-thin Braille displays, wireless power transmission sheets, We have shown the possibility of applying organic transistors to large area electronics, such as realizing communication sheets. In particular, machined polymer films printed with organic transistors.
  • JP-A-2001-185 there is disclosed a gel-like composition comprising carbon nanotubes and an ionic liquid.
  • a gel-like composition obtained by adding a polymer component to a gel and an ionic liquid has been proposed, and it has also been proposed to form an electronic circuit using such a gel-like composition.
  • materials obtained from these gel compositions have not been able to provide sufficient conductivity to the extent that they can be used as constituent materials of electronic circuits. Disclosure of the invention
  • the present invention solves the problems of the prior art as described above, has sufficient conductivity for use as a component material of an electronic circuit, and elasticity equal to that of a normal rubber material, and realizes flexible electronics.
  • Carbon nanotube rubber composition capable of providing stretchable electronic devices, carbon nanotube rubber, carbon nanotube rubber paste, wiring, conductive paste, and articles comprising them, and electronic circuit And to provide a method for manufacturing the same.
  • the present invention provides means for solving the above problems, and comprises the following.
  • a carbon nanotube rubber composition comprising carbon nanotubes, rubber and an ionic liquid
  • a carbon nanotube rubber composition characterized in that the rubber is miscible with an ionic liquid.
  • An article comprising the carbon nanotube rubber composition according to any one of 1 to 10 above.
  • the force-on-nanotube contained in the carbon nanotube rubber is a single-walled carbon nanotube.
  • An electronic circuit comprising: a substrate; an electronic component provided on the substrate; and stretchable wiring electrically connected to the electronic component.
  • the stretchable wiring comprises a wiring containing a carbon nanotube and a rubber-containing carbon nanotube rubber composition.
  • the carbon nanotube contained in the carbon nanotube rubber composition is a single-walled carbon nanotube,
  • the electronic circuit according to any one of the items 3 to 4 above.
  • Step 1 A step of preparing a carbon nanotube ionic liquid gel in which carbon nanotubes, an ionic liquid, and, if necessary, an organic solvent are dispersed.
  • Step 2 Preparation of carbon nanotube paste in which carbon nanotube ionic liquid gel, rubber polymer and optionally organic solvent are dispersed
  • Process 3 Process of removing organic solvent from carbon nanotube paste and manufacturing carbon nanotube rubber
  • a method of producing a carbon nanotube rubber composition comprising the following steps:
  • Step 1 Preparation of a carbon nanotube ionic liquid gel in which carbon nanotubes, an ionic liquid, and, if necessary, an organic solvent are dispersed
  • Step 2 Preparation of carbon nanotube nanotube paste in which carbon nanotube ionic liquid gel, rubber polymer and, if necessary, organic solvent are dispersed
  • Step 3 A step of removing the organic solvent from carbon nanotube paste to produce carbon nanotube rubber
  • Step 4 Removal of ionic liquid from carbon nanotube rubber
  • a method of producing a stretchable wiring comprising the following steps: Step 1: A step of preparing a carbon nanotube, an ionic liquid, and, if necessary, a carbon nanotube ionic liquid gel in which an organic solvent is dispersed. Step 2: Preparation of carbon nanotube paste in which carbon nanotube ionic liquid gel, rubber polymer and, if necessary, organic solvent are dispersed
  • Step 3 Remove organic solvent from carbon nanotube paste and manufacture stretchable wire containing carbon nanotube rubber
  • a method of manufacturing a carbon nanotube rubber wiring comprising the steps of:
  • Step 1 A step of preparing a carbon nanotube ionic liquid gel in which carbon nanotubes, an ionic liquid, and, if necessary, an organic solvent are dispersed.
  • Step 2 Preparation of carbon nanotube paste in which carbon nanotube ionic liquid gel, rubber polymer and, if necessary, organic solvent are dispersed
  • Process 3 A process of removing the organic solvent from carbon nanotube paste to produce carbon nanotube rubber
  • Process 4 A process of removing an ionic liquid from carbon nanotube rubber to produce a stretchable wiring
  • a method for producing a conductive paste comprising the following steps.
  • Step 1 Preparation of carbon nanotube ionic liquid gel in which carbon nanotubes, ionic liquid and, if necessary, organic solvent are dispersed
  • Step 2 Process for producing conductive paste including carbon nanotube paste in which carbon nanotube ionic liquid gel, rubber polymer and, if necessary, organic solvent are dispersed
  • the carbon nanotube rubber composition of the present invention carbon nanotube rubber, carbon nanotube rubber paste, wiring, conductive base
  • One of the strips has sufficient conductivity and extensibility when used as a constituent material of an electronic circuit, thereby providing an extensible electronic device.
  • FIG. 1 is an image of the carbon nanotube rubber of the present invention molded into a film shape obtained in one example of the present invention and photographed with a digital camera.
  • FIG. 2 is a digital camera photographed image of a reticulated carbon nanotube rubber obtained by machining holes in the plate-like carbon nanotube rubber obtained in one embodiment of the present invention.
  • FIG. 3 is a digital camera image of the carbon nanotube rubber paste obtained in one embodiment of the present invention.
  • FIG. 4 is a digital camera image of an article obtained by coating the carbon nanotube rubber obtained in one example of the present invention with a silicone rubber (P D M S) based on dimethylsiloxane.
  • FIG. 5 is a digital camera photographed image of an electronic circuit in which a carbon nanotube rubber is incorporated as a wire, obtained in one embodiment of the present invention.
  • FIG. 6 is a digital camera photographed image in a state where the active matrix constituting the circuit of FIG. 5 is expanded.
  • FIG. 7 is a schematic view showing an example of the method for producing a carbon nanotube rubber composition of the present invention.
  • FIG. 8 is a digital camera photographed image of carbon nanotube rubber obtained in one example.
  • FIG. 9 is a digital camera image of a wire made of patterned carbon nanotube rubber obtained in one embodiment.
  • FIG. 10 is a digital camera photographed image in a state in which the wiring made of carbon nanotube rubber in FIG. 9 is bent.
  • FIG. 11 is a scanning electron micrograph image of a portion of the patterned carbon nanotube rubber of FIG.
  • FIG. 12 is a graph showing the relationship between the carbon nanotube content and the conductivity and elongation rate in the carbon nanotube rubber composition obtained in one example of the present invention.
  • FIG. 13 is a photographic image showing the miscibility between various ionic liquids and rubber necessary for producing the carbon nanotube rubber composition of the present invention.
  • Figures 14 to 17 show the carbon nanotube rubber composition, carbon nanotube rubber, carbon nanotube rubber paste, stretchable carbon nanotube, ionic liquid, obtained in one embodiment of the present invention, respectively.
  • Fig.14 is a graph showing changes in conductivity and elongation when the composition ratio of rubber is changed.
  • Fig.14, Fig.15, Fig.16 show the strain and stress characteristics at that time,
  • Fig.17 shows the electric characteristics Indicates
  • FIG. 18 is a graph showing the relationship between the elongation and the conductivity in the carbon nanotube rubber composition obtained in one example of the present invention.
  • FIG. 19 is a graph showing the relationship between the content of carbon nanotubes, ionic liquid and rubber in the carbon nanotube-based rubber composition obtained in one example of the present invention and the conductivity.
  • FIG. 20 is a graph showing the relationship between the content of carbon nanotubes, ionic liquid and rubber in the carbon nanotube rubber composition obtained in one example of the present invention and the conductivity.
  • FIG. 21 is a graph showing the relationship between the rubber content in the carbon nanotube-rubber dispersed gel and the conductivity in the carbon nanotube rubber composition obtained in one example of the present invention.
  • FIG. 22 is a graph showing the relationship between the rubber content in the carbon nanotube / rubber dispersion gel and the critical elongation in the carbon nanotube rubber composition obtained in one example of the present invention.
  • Figures 23 and 24 show stretchability obtained by electrically connecting the stretchable wiring according to the present invention and a known electronic component using a stretchable wiring or a conductive paste according to an embodiment of the present invention. It is a figure explaining the manufacturing process of the electronic circuit which has.
  • FIG. 25 is a schematic view showing one constitutional unit of the extendable active matrix constituting the circuit of FIG.
  • Figures 26 to 29 show, for the expandable matrix that constitutes the circuit of Figure 5, 0 to 100% of this active matrix sheet in the axial or biaxial directions. After stretching with various tensile stresses, the elongation strain is released, and the transfer curve obtained when the channel current (I D s) in the transistor placed on the sheet at that time is measured. And the relationship between the tensile stress at that time and the channel current (I D s ), where FIGS. 26 and 28 are graphs of the transfer curves, and FIGS. It is a graph which shows the relation between stress and channel current ( IDS ).
  • FIG. 30 is a graph showing the relationship between the elongation and the conductivity in the carbon nanotube rubber composition obtained in one example of the present invention and in the carbon nanotube rubber composition obtained in the comparative example. is there.
  • the carbon nanotube rubber composition of the present invention is a material containing carbon nanotubes, rubber, and, if necessary, an ionic liquid, and is in the form of liquid, gel, solid, rubber or paste. It may be in a form. Furthermore, it may contain an organic solvent, if necessary.
  • the carbon nanotube rubber composition of the present invention preferably has a conductivity of 1 S / cm or more and an extensibility of 10% or more. In the present specification, extension and extension are used in the same sense.
  • carbon having both extensibility and conductivity as in the present invention is obtained. It is not possible to make nanotube compositions. That is, a carbon nanotube composition having both extensibility and conductivity is an innovative new material that can only be realized by the present invention.
  • a carbon nanotube rubber composition a carbon nanotube rubber and a carbon nanotube rubber paste, which will be described in detail below, can be exemplified.
  • the carbon nanotube rubber of the present invention is a rubber-like elastic body and a carbon nanotube rubber composition which also has high conductivity imparted from carbon nanotubes.
  • the carbon nanotube rubber of the present invention preferably has a conductivity of 1 S / cm or more and an extensibility of 10% or more. Even if carpone nanotubes and rubber are dispersed using known methods, or rubber is impregnated into carbon nanotubes using known methods, the extensibility and conductivity as in the present invention can be achieved as in the present invention. It is impossible to produce carbon nanotube rubber that has both.
  • carpone nanotube rubber having both extensibility and conductivity is an innovative new material that can be realized for the first time by the present invention, and it can be used for various flexible and stretchable articles that require extensibility and conductivity. It can be used.
  • carbon nanotube rubber has stretchability. Such stretchable wiring is suitable for producing stretchable electronic circuits.
  • the conductivity of the rubber nanotube tube rubber according to the present invention is high, but it is not possible to obtain conductivity higher than the conductivity of the rubber ribbon tube itself.
  • conductivity is lSzcm or more, it can be used as a circuit wiring, which is preferable. If the conductivity is 1 O S / cm or more, it is suitable for use as a wiring of a large area device. further. Conductivity is
  • the upper limit of the elongation of rubber is 400% and the upper limit of the elongation of carbon nanotube rubber.
  • the elongation rate is 10% or more, it is preferable to use carbon nano tube rubber as wiring of a stretchable circuit. If the elongation rate is 25% or more, the carbon nanotube rubber can be bent, which is suitable for use as a bendable flexible member. Further, if the elongation rate is 50% or more, carbon nanotube rubber can be disposed on a free-form surface, and can be suitably used for three-dimensional devices of various shapes and shapes.
  • the shape of carbon nanotube rubber in the present invention is Depending on the application, an appropriate form can be considered. For example, in addition to a flat surface, a film, a rod, a solid, etc. may be used, and the thickness does not matter.
  • the ionic liquid is removed from the tube rubber composition by Soxhlet method etc., carbon nanotube, carbon nanotube rubber consisting of rubber, carbon nanotube rubber paste, carbon nanotube rubber composition are also manufactured by the method of the present invention. it can. Although the conductivity of the carbon nanotube rubber from which the ionic liquid has been removed is lowered as compared with the case where it contains an ionic liquid, the recovered ionic liquid can be reused, and the manufacturing cost can be significantly reduced. . If a method capable of recovering ionic liquid such as the Soxhlet method is used, the fluid can be recovered with as much as 99% ion. Therefore, using this method, it is possible to know whether or not the carbon nanotube rubber, carbon nanotube rubber paste, carbon nanotube rubber composition contains an ionic liquid, and if it contains, its mass%.
  • carbon nanotube rubber paste in the present invention refers to a liquid, gel-like, fluid nanotube rubber composition.
  • the carbon nanotube rubber paste of the present invention preferably has a conductivity of 1 Szcm or more and an extensibility of 10% or more. Even if carbon nanotubes and rubber are simply dispersed using a known method, or rubber is impregnated onto carbon nanotubes using a known method, carbon having both extensibility and conductivity as in the present invention It is not possible to produce nanotube rubber paste. By removing at least a part of the organic solvent from the carbon nanotube tube rubber paste by heat drying or the like, and solidifying the carbon nanotube rubber paste, the carbon nanotube rubber paste from the conductive carbon nanotube rubber is obtained. Can be manufactured. If necessary, a crosslinking agent or a crosslinking initiator may be added to the carpone nanotube rubber base. The crosslinking agent and crosslinking initiator can control the viscosity and extensibility of the rubber tube.
  • Carbon nanotube rubber paste can be easily molded and processed
  • a processed carbon nanotube rubber paste is suitable for producing a conductive carbon nanotube rubber of a desired shape.
  • the prepared carbon nanotube rubber paste can be cast on a predetermined substrate, dried to form a film, and then machined to form a predetermined conductive carbon nanotube rubber.
  • the prepared carbon nanotube rubber paste is used as an ink for all printing presses including screen printing, ink jet printing, dispensers, etc., and then printed in a predetermined pattern and then dried. It is possible to form a pattern consisting of a carbon nanotube rubber.
  • a pattern made of a carbon nanotube rubber can be used as a wire having stretchability. Furthermore, it enables the manufacture of elastic articles and electronic circuits provided with elastic wiring.
  • Carbon nanotube rubber composition, carbon nanotube rubber foam, carbon nanotube rubber, etc. may be disposed on an elastic material such as rubber, or an elastic material such as rubber, carbon nanotube rubber composition, carbon nanotube rubber paste, etc.
  • the carbon nanotube rubber may be covered.
  • the conductive carbon nanotube rubber composition, carbon nanotube rubber paste, carbon nanotube rubber can be isolated from the surroundings, or the elastic function of the rubber can be added.
  • the wiring of the present invention refers to a wiring which has both a carbon nanotube and rubber, and thus has both extensibility and conductivity.
  • a wire having a stretchability of 10% or more is called a stretchable wire.
  • a wire having both extensibility and conductivity preferably has a conductivity of lSZ cm or more and 10% or more.
  • carbon nanotubes and rubber using known methods Even if it is dispersed or rubber is impregnated into a carbon nanotube using a known method, it is not possible to produce a wire having both extensibility and conductivity as in the present invention.
  • a wire having a conductivity of more than 1 S / cm and an extensibility of 10% or more is a revolutionary electronic component realized for the first time by the present invention.
  • the wiring of the present invention can be manufactured from a carbon nanotube rubber composition, a carbon nano tube rubber paste, and a carbon nanotube rubber.
  • the wiring may contain an ionic liquid as needed.
  • the conductivity of the wire is increased and the stretchability is improved by the ionic liquid.
  • at least a portion of the wire is disposed on an elastic material such as rubber, or at least a portion of the wire is rubber or the like. It may be coated with an elastic material. This is suitable to insulate at least a part of the wiring and to add a rubber elastic function to the wiring.
  • the conductivity of carbon nanotubes is the upper limit of the conductivity of wiring. If the conductivity of the wiring is 1 S Z cm or more, it can be used as a circuit wiring. If the conductivity is 10 S z cm or more, it is suitable for use as a wiring of a large area device. Further, if the conductivity is 20 Szcm or more, the current which can flow in the wiring is increased, which is preferable because various devices can be driven.
  • the upper limit 4000% of the elongation rate of the rubber is the upper limit of the elongation rate of the wiring.
  • the wire can be used as a wire of a stretchable circuit, which is preferable. If the expansion rate is 25% or more, you can bend the wiring. Suitable for use as flexible flexible wiring. Also, if the extension ratio is 50% or more, the wiring can be disposed on a free-form surface, which is suitable for manufacturing three-dimensional wiring of various shapes and forms.
  • the conductive paste of the present invention includes a carbon nanotube rubber paste containing carbon nanotubes and rubber, and therefore refers to a conductive paste having both extensibility and conductivity.
  • the conductive base of the present invention preferably has a conductivity of lS / cm or more and a extensibility of 10% or more. Even if the carbon nanotube and the rubber are simply dispersed using a known method, or if the rubber is impregnated into the carbon nanotube using a known method, both extensibility and conductivity are achieved as in the present invention. It is not possible to produce conductive paces.
  • the conductive paste which has both conductivity and extensibility, has a conductivity of more than 1 S / cm and a stretchability of 10% or more, is the innovative electronic component material realized for the first time by the present invention.
  • the conductive paste of the present invention can be produced from a carbon nanotube rubber composition and carbon nanotube rubber paste.
  • the conductive base may contain an ionic liquid as needed. The ionic liquid increases the conductivity of the conductive paste and improves the stretchability.
  • the conductive paste may be disposed on an elastic material such as rubber, or at least a portion of the conductive paste may be coated with an elastic material such as rubber. This is suitable to insulate at least a part of the conductive paste and to add the elastic function of the rubber to the wiring.
  • the conductivity of the conductive paste is more preferable, but it is not possible to obtain conductivity exceeding that of the carbon nanotube itself. Therefore, the conductivity of the carbon nanotube 1 0 0 OSZ cm is the conductivity It is the upper limit of the conductivity of the pacemaker. If the conductivity of the conductive paste is 1 SZ cm or more, it can be used to electrically connect the conductive terminal and the wiring. A conductivity of 10 Sz cm or more is suitable for electrically connecting the conductive terminals of the large area device and the wiring. Furthermore, if the conductivity is 2 OS / cm or more, the current that can flow to the electrical connection between the conductive terminal and the wiring increases, which is preferable because it can drive various devices.
  • the upper limit of the elongation of rubber is 400% and the upper limit of the elongation of conductive paste. If the elongation rate is 10% or more, the conductive paste can be used to electrically connect the conductive terminal of the stretch circuit and the wiring, which is preferable. If the elongation rate is 25% or more, the wiring can be bent, which is suitable for use as a bendable flexible wiring. Also, if the elongation rate is 50% or more, the wiring can be disposed on a free-form surface, which is suitable for manufacturing three-dimensional wiring of various shapes and shapes.
  • Stretchable wiring according to the present invention conductivity A pace can be combined with a known existing substrate and a known existing electronic component to produce an electronic circuit having stretchability.
  • an electronic circuit having a stretchability of preferably 10% or more is referred to as a stretchable electronic circuit.
  • stretchability obtained by electrically connecting a known existing electronic component provided on a known existing substrate to a stretchable wiring using a conductive paste or stretchable wiring.
  • a circuit can be illustrated.
  • the substrate be harder than the stretchable wiring.
  • “hard” means that Young's elastic modulus is large.
  • known existing substrates known already The existing electronic components are hard and have no stretchability.
  • existing electronic components have the problem that their electrical characteristics change when they are distorted.
  • the electronic circuit configuration when the electronic circuit is distorted, the softer stretchable wiring is distorted and the hard substrate is not distorted. As a result, the electrical characteristics of the electronic component on the substrate do not change. Furthermore, the electronic component can be electrically connected to the stretchable wiring by connecting the electronic component on the board and the stretchable wiring using the conductive paste having stretchability and the stretchable wiring.
  • the conductive paste stretches and stretches the elastic wiring to absorb the strain, so that the electronic component is not distorted and the electrical characteristics of the electronic component do not change.
  • the electronic circuit having such a configuration is characterized in that the entire circuit is stretchable, and the change in the electrical characteristics of the circuit is small even if it is stretched. Such a stretchable electronic circuit is realized for the first time by the present invention.
  • a substrate useful for electronic circuits there is no particular limitation on a substrate useful for electronic circuits, and any known substrate that can be provided with electronic components and harder than stretchable wiring can be used, regardless of the shape, material, and thickness.
  • Examples include flat, curved, and flexible substrates made of various metals, ceramics, silicon, resins, and the like.
  • the electronic component of the present invention is not particularly limited, and any known electronic component which can be electrically connected by a conductive paste or stretchable wiring can be used. It can be exemplified by CMOS circuits, transistors, integrated circuits, organic transistors, light emitting elements, actuators, memories, sensors, coils, capacitors, resistors, and combinations thereof.
  • Fig. 1 shows an image of a carbon nanotube rubber of the present invention molded and processed into a film shape with a digital camera.
  • Fig. 2 shows a mesh-like carbon nanotube rubber machined with holes in a plate-like carbon nanotube rubber
  • Fig. 3 shows an image of a conductive carbon nanotube rubber paste taken with a digital camera.
  • Fig. 4 is an image of a carbon nanotube rubber coated with dimethyl siloxane based silicone rubber (PDMS) taken with a digital force camera.
  • Fig. 5 is an organic image provided on a polyimide substrate.
  • Fig. 6 is an image of the stretched elastic circuit shown in Fig. 5 taken with a digital camera.
  • any of single-walled carbon nanotube (SWNT) and multi-walled carbon nanotube (MWNT) can be appropriately selected. It can be used.
  • the carbon nano tube is long, the purity is high, and the specific surface area is high. Therefore, single-walled carbon nanotubes having a high specific surface area and a long length are more preferable than multi-walled carbon nanotubes generally having a low specific surface area and a short length.
  • carbon nanotubes be as long as possible. This is because, in the case where the carbon nanotube network (knit structure) in the carbon nanotube polymer composition is composed of long carbon nanotubes, more electrical paths can be formed and the network can extend even if it extends. Is more difficult to be destroyed. There is no upper limit on the length of carbon nanotube to obtain high conductivity and high elongation rate, but it is generally long Carbon nanotubes have lower dispersibility, which makes it difficult to produce a carbon nanotube rubber composition.
  • carbon nanotubes having a length of 1 or more and 10 cm or less have good dispersibility, are easily obtained in high purity, and are preferable in obtaining high conductivity and high elongation.
  • Carbon nanotubes with a length of 1 m or less make it difficult to form a network to achieve high conductivity and high elongation.
  • Carbon nanotubes having a length of 10 cm or more have poor dispersibility, and are easily cut during dispersion processing.
  • a solution of carpone nanotubes containing a solvent, rubber or polymer of rubber is diluted thinly with an organic solvent etc. and dropped onto a substrate, and then scanned with a scanning atomic force microscope.
  • the length of one carbon nanotube instead, it can be evaluated by measuring the length of the bundle.
  • a carbon nanotube bundle having a length of 1 m or more and 10 cm or less is preferable for obtaining high conductivity and high elongation rate.
  • carbon nanotubes are vertically aligned from a substrate by using the method described in Japanese Patent Application No. 2 0 6 5 2 5 8 9 4 4 (corresponding to WO 2 0 6 0 6 0 1 5 5 5 5 5 6 5 6 5 6 5 6 9 8
  • the height of the aligned carbon nanotube aligned aggregate can be the length of the carbon nanotube. That is, a carbon nanotube oriented aggregate having a height of 1 m or more and 10 cm or less is preferable in order to obtain high conductivity and high elongation. In order to obtain high conductivity and high elongation, it is desirable that carbon nanotubes be as pure as possible.
  • the term "purity" as used herein is carbon purity, and indicates what percentage of the mass of carbon nanotubes consists of carbon. There is no upper limit to the purity to obtain high conductivity and high elongation rate, but it is difficult to obtain carbon nanotubes of 99.9999% or more due to manufacturing convenience. If the carbon purity is less than 90%, including impurities such as metals, the metal impurities will agglomerate during the manufacturing process and the carbon nanotube rubber composition becomes brittle, making it difficult to obtain high conductivity and high elongation. It becomes. From these points, it is preferable that the purity of carbon nanotube is 90% or more.
  • the purity of carbon nanotubes can be obtained by elemental analysis using fluorescent X-rays. Elemental analysis of the single-walled carbon nanotube used in Example 1 later described by fluorescence X-ray analysis revealed that it was 9 9. 9 8% in carbon, 0. 0 13% in iron, and other elements were not measured. .
  • carbon nanotubes have as high specific surface area as possible. This is because carbon nanotubes having a high specific surface area have many surfaces, so the interface between the ionic liquid and the rubber is large and they are likely to interact.
  • carbon nanotubes with high specific surface area contain less carbon impurities other than carbon nanotubes and impurities other than carbon such as metals, and are preferable for the reasons described above.
  • Single-walled carbon nanotubes whose specific surface area is less than 600 m 2 / g contain several tens percent (about 40%) of impurities such as metals or carbon impurities, Can not express the function of
  • the specific surface area of single-walled carbon nanotubes can be determined by measuring the adsorption / desorption isotherm at 77 K of liquid nitrogen. As an example, it can be determined from adsorption / desorption isothermal curves measured using BELS ORP-MINI (made by Nippon Bell Co., Ltd.) for 30 mg of single-walled CNT aggregate (adsorption equilibrium time was set to 600 seconds) ). When the specific surface area was measured by the method of Brunauer, EmmeU, Teller from the adsorption-desorption isotherm of the single-walled carbon nanotube used in the present invention, it was 110 m 2 Z g.
  • the specific surface area of single-walled single-walled nanotubes in the range of 1000 Om 2 / g to 230 m 2 Zg can be obtained by changing the opening treatment temperature from 350 ° C. to 600 ° C.
  • Such single-walled carbon nanotubes are suitable for realizing the carbon nanotube rubber composition of the present invention having both high conductivity and high elongation rate.
  • the ionic liquid useful for the carbon nanotube rubber composition, carbon nanotube rubber, carbon nanotube paste, wiring and conductive belt of the present invention is not particularly limited, but carbon nanotube may be used. It is preferable to have high affinity to the gel and to become gel-like after dispersion treatment, for example, 1-ethyl 3-methylimidazolium tetrafluoroporate (EM IBF 4 ), 1-ethyl-3-methylimidazole Xaflurophosphate (EM IPF 6 ), 1-ethyl 3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EM ITFSI), 1-butyl-3-methylimidazole tetrafluorinated ⁇ (BM IBF 4 ), 1-butyl 3-methylimidazolium hexafluorophosphate (BIPF 6 ), 1 1-ptyru 3-methyl-i Named midazolium bis (trifluoromethylsulfonyl) imide (BM ITFSI) Can
  • a carbon nanotube composition having both extensibility and conductivity can be manufactured.
  • the carbon nanotube rubber composition of the present invention is not particularly limited as a rubber useful for carbon nanotube rubber, carbon nanotube paste wiring, conductive base, and in a broad sense, it may be any elastomer.
  • an elastic material having an organic polymer such as natural rubber or synthetic rubber as a main component, that is, elastic rubber is preferable.
  • fluorine rubber for example, Daikin Industries, Ltd., D ai e 1-G 8 0 1 D a i e
  • any solvent capable of dissolving such rubber can be used, and it can be appropriately selected and used depending on the rubber to be used.
  • 4-methyl-2-pentanone is particularly preferable because toluen xylene, asphalt, carbon tetrachloride and the like can be used, and many rubbers including fluororubber and silicone rubber are soluble.
  • carbon nanotube rubber composition carbon nanotube In rubber, carbon nanotube paste, wiring, and conductive paste
  • the more uniformly carbon nanotubes are dispersed in the composition the higher the conductivity and the stretch elasticity. That is, in order to realize the article of the present invention having both high conductivity and high elongation rate, carbon nanotubes which are long, high in purity and high in specific surface area can be incorporated into rubber without impairing their functions. It is important to have uniform dispersion.
  • carbon nanotubes are materials with very low solubility, low affinity with rubber materials, and do not disperse in rubber.
  • the inventor of the present invention has made extensive efforts and found that it is preferable to use an ionic liquid in order to enhance the dispersibility of carbon nanotubes and rubber.
  • an ionic liquid As described in Japanese Patent Application Laid-Open No. 200-15764, the force-carbon nanotube and the ionic liquid have a high affinity, and the force-containing tube is dispersed in the ionic liquid. It becomes gel-like by doing.
  • this carbon nanotube ionic liquid gel is formed is unknown at present, the ionic liquid is adsorbed to each carbon nanotube and the van der Waals force that bonds the carbon nanotubes is I think that it is weakening. As a result, the carbon nanotubes, which are usually easily bundled, disperse in the ionic liquid to form a gel-like composition. So to speak, it is believed that ionic liquids function as dispersants for carbon nanotube.
  • the inventor has found that, by using a polymer miscible with the ionic liquid, the rubber can be uniformly dispersed in the carbon nanotube ionic liquid gel, and the high conductivity of the present invention, high We have realized a carbon nanotube rubber composition that also has an elongation rate.
  • carbon nanotube rubber composition is formed by mixing
  • the ionic liquid adsorbed to the carbon nanotube has an affinity to the rubber and mixes it, which makes it possible to dissolve the carbon nanotube in the rubber, usually in the rubber Carbon nanotubes that are difficult to disperse are considered to be uniformly dispersed in rubber.
  • miscibility refers to the property that the ionic liquid, the rubber or rubber polymer, and, if necessary, the dispersion solution containing the organic solvent are mixed to such an extent that they do not phase separate.
  • miscibility there is no upper limit to the preferred degree of miscibility, and substantially, the above-mentioned carbon nanotube, rubber and ionic liquid, and, if necessary, organic solvent are mixed, carbon nanotube is uniformly dispersed in the rubber, and the final It is sufficient that carbon nanotube rubber compositions having both extremely high conductivity and high elongation rate can be produced, and the number of dispersions containing an ionic liquid, a polymer of rubber or rubber, and, optionally, an organic solvent may be sufficient. It is suitable that the time does not cause phase separation more preferably for several days.
  • compatibility means the property that two or more kinds of substances have an affinity to each other to form a solution or a mixture.
  • carbon nanotubes are uniformly dispersed in the rubber. That is, the carbon nanotube rubber composition of the present invention in which carbon nanotubes, ionic liquid and rubber are uniformly dispersed and mixed, carbon nanotube rubber, carbon nanotube paste, wiring and conductive paste are produced. Jet mill and pole mill for mixing and dispersing each component An ultrasonic dispersing machine or the like can be used, and from the viewpoint of dispersing carbon nanotubes more uniformly in the composition, it is preferable to use a jet mill.
  • step S 1 carbon nanotubes, an ionic liquid, and an organic solvent are mixed and dispersed using a stirrer, jet mill or the like to obtain a carbon nanotube ionic liquid gel (step S 1).
  • the method of producing the carbon nanotube ionic liquid gel is not limited to the present method, and the patent 367 367, the patent 3 8 8 5 6 0, the patent 3 9 2 4 2 7 A known method for producing a carbon nanotube ionic liquid gel as described in JP-A-3, JP-A-2005-25054, JP-A-2008-17664-28, etc. The following method can be used.
  • step S 2 the obtained carbon nanotube ionic liquid gel, rubber, and, if necessary, an organic solvent are mixed and dispersed to obtain a carbon nanotube tube rubber paste of the present invention.
  • An organic solvent is added as appropriate before, during, or after the dispersion process, or the organic solvent is partially removed by evaporation, etc. before, during, or after the dispersion process to obtain a carbon nanotube rubber paste.
  • the viscosity of can be adjusted.
  • An example of the conductive paste of the present invention is one containing a carbon nanotube rubber paste having an appropriate viscosity, conductivity and elongation.
  • a carbon nanotube rubber paste may be molded as required to obtain a carbon nanotube rubber of a desired shape.
  • a known method of molding and processing a flowable paced rod-shaped article can be used, and examples thereof include coating, printing, extrusion, casting, and injection.
  • the carbon nanotube rubber paste is dried, heated, evacuated or the like to remove all or part of the organic solvent, and solidified to obtain the conductive carbon nanotube rubber of the present invention ( Process S 4). After solidification, the obtained carbon nanotube rubber can be machined to form a conductive carbon nanotube rubber having a predetermined shape.
  • the carbon nanotube rubber composition containing carbon nanotubes, ionic liquid, rubber, carbon nanotube rubber paste, carbon nanotube rubber, the ionic liquid is removed using the Soxhlet method etc.
  • carbon nanotube rubber comprising carbon nanotubes and rubber may be manufactured (step S 5). The conductivity of the carbon nanotube rubber from which the ionic liquid has been removed is reduced compared to the case where the ionic liquid is contained, but the recovered ionic liquid can be reused, and the production cost can be significantly reduced. Ru.
  • An example of the conductive paste of the present invention is one containing a carbon nanotube rubber paste having appropriate conductivity and extensibility.
  • the preparation procedure for obtaining the carbon nanotube rubber composition, the carbon nanotube rubber tube, and the carbon nanotube rubber according to the present invention is not limited to the above-mentioned example, and may be appropriately selected as needed. , Some steps may be omitted, or the order may be changed. For example, the forming process of step S3 may be omitted, and the forming process may be performed after step S4. If necessary, a crosslinking agent, a crosslinking initiator, etc. may be added as appropriate in an appropriate step.
  • step S1 and step S2 for producing the carbon nanotube rubber composition is not limited to the above, and a method capable of uniformly dispersing carbon nanotubes, ionic liquid and rubber. If it is, well-known carbon nanotube dispersion method can be used suitably.
  • a powdery single-walled carbon nanotube (hereinafter SWN T) in which the oriented aggregate was peeled from the growth substrate was used.
  • the carbon nanotube has a density of 0.03 g / cm 3 , a BET specific surface area of 120 m 2 / g, an outer diameter of 2.5 nm, a half width of 2 nm, and a carbon purity of 99.9% Hermann's orientation coefficient of 0.8, length of 3 0 0 0 m or more and 8 0 0 or less.
  • this carbon nanotube ionic liquid gel is treated with an organic solvent 4 -Methyl mono-pentanone (typical amount 80 m)) miscible with ionic liquid, compatible fluoro rubber (D ai-kin Industries D aie 1-G 9 12) (typical amount 5 0-1 50 O mg) is added, and the mixture is stirred at room temperature for 16 hours under the condition of about 300 rpm using a stirrer to obtain a carbon nanotube rubber paste as shown in FIG. (Step S 2).
  • organic solvent 4 -Methyl mono-pentanone typically amount 80 m
  • compatible fluoro rubber typically 5 0-1 50 O mg
  • the carbon nanotube-rubber dispersion gel is dried at room temperature for 12 hours to obtain a carbon nanotube rubber shown in FIG. 8 (step S 4).
  • the composition of this carbon nanotube rubber was 1 wt% of S WN T 2, 3 wt% of B M IT F S I 4, and 6 wt% of G 9 1 2 36 5.
  • the conductivity showed 7 3 S Z cm.
  • the carbon nanotube rubber foam obtained in step S2 is dried at room temperature for 6 hours, and part of 4-methyl-2-pentaninone is evaporated to adjust the viscosity, and then the silicone elastomer is removed.
  • the desired pattern was printed on one substrate (PDM S, 3 1 &]: & (1 84, 00-(0) "] 1 11 stock company) (step S3). It is preferable to adjust the viscosity to about 1 Pas in the case of using the frame printing, the die-off printing, etc., and to set the viscosity to about 10 m Pas in the case of the dispenser or the ink jet printing.
  • the carbon nanotube rubber paste printed on the PDMS substrate is further dried to form a wiring composed of carbon nanotube rubber on the PDM S substrate patterned to a line width of 100 m shown in FIG. Obtained (step S 4).
  • Fig. 10 is a view showing a bent Pon Nano tube rubber wire on such a PDM substrate. It is understood that the wiring made of carbon nanotube rubber has extensibility, without the wiring being broken. Such a carbon nanotube rubber is an example of the stretchable wiring of the present invention.
  • Figure 1 1 shows the patterned force on Figure 9 It is the image of the scanning electron microscope which expanded a part of blobs.
  • FIGS. 12A and 12B The relationship between the SWNT content and the conductivity and elongation at this time is shown in FIGS. 12A and 12B. As can be seen from Fig. 12 A, conductivity and elongation are in a contradictory relationship with SWNT content.
  • the wire made of carbon nanotube rubber obtained as described above was confirmed to exhibit conductivity of 1 S / cm to 10 2 SZ cm and elongation rate of 2 9 to 1 2 9%.
  • the results show that by controlling the content of carbon nanotube, it is possible to control continuously the conductivity and elongation rate of carbon nanotube composition, carbon nanotube rubber and wiring. Moreover, in the manufacturing method of the present embodiment, the range of the content of carbon nanotube from 1.4 mass% to 15.58 mass% is suitable for achieving high conductivity and high elongation rate. It is shown that.
  • the wiring made of this carbon nanotube rubber does not change its conductivity even when it is expanded and contracted, and is suitable as an elastic wiring. I understand that there is.
  • silicone rubber (Sy 1 gard 84 or SH 9 5 5 made by Dow Corning Co., Ltd.) is used in place of fluorine rubber (D aiel — G 9 1 2) to further enhance the expansion ratio.
  • fluorine rubber D aiel — G 9 1 2
  • the miscibility between the ionic liquid and the rubber necessary for producing the carbon nanotube rubber composition of the present invention was investigated.
  • As the ionic liquid BMITFSI and EMIBF 4 BMIBF 4 were used, and as the rubber, G801, G921 and Kyner were used.
  • Each rubber polymer (300 mg) and each ionic liquid (300 mg) are mixed with 1 ml of 2 ml of 2-methyl 2-pentanone, and the resulting solution is stirred using a stirrer at room temperature for 12 hours. did. Thereafter, the dispersion was allowed to stand for 3 days and then observed. As shown in Fig. 13, phase separation of the ionic liquid and the rubber polymer was observed in 5 of the 9 combinations.
  • the conductivity and elongation were evaluated by changing the composition ratio of carbon nanotube rubber composition, carbon nanotube rubber, carbon nanotube rubber paste, stretchable wires SWNT, BMITFSI, and G9122 according to the above manufacturing method.
  • the content ratio of SWTN to BMITFSI is fixed at 1: 2, the amount of 09 12 is set to 100 1118, and SWNT is varied in the range of 1.4 mass% to 18.58 mass%.
  • Fig. 14 shows the strain-stress characteristics and Fig. 17 shows the electrical characteristics.
  • the strain and stress characteristics when the ionic liquid is removed and the SWTN is changed in the range of 1.5 mass% to 23 mass% are shown in FIG. 15, and the electrical characteristics are shown in FIG.
  • the figure shows the strain-one stress characteristics when the amounts of SWTN and G912 are 3 O mg and 50 O mg, respectively, and the BM ITFSI content is changed in the range of 0 to 32 mass%. Shown in 1 6
  • Fig. 14 and Fig. 15 show that the elongation rate according to the manufacturing method of this example is in the range of 1.4 mass% to 23 mass% of SWTN, regardless of including ionic liquid. It has been shown that it is possible to produce good carbon nanotube rubber composition, carbon nanotube rubber, carbon nanotube rubber paste, and stretchable wiring in excess of 10%.
  • the carbon nanotube has a density of 0.53 g / cm 3 , a BET surface area of 1 200 m 2 Z g, an average outer diameter of 2.5 nm, a half width of 2 nm, and a carbon purity of 9 9. 9% Hermann's orientation coefficient is 0.8, and the length is 3 0 0 to 8 0 0 m.
  • SWNT 50 mg
  • BITFSI ionic liquid
  • This gel 10 O mg, in turn, 8 ml of 2-methyl-2-pentanone and vinylidene fluoride-one hexafluoropropyrene copolymer 1 (Daikin Industries, D aie 1-G 800, less than 2-methyl-2-pentanone, The mixture was stirred at 25 ° C. for 1 hour and sonicated at 30 ° C. for 1 hour (SMT). UH _ 5 0). Stirring again at 80 ° C. for 1 hour gave an expanded carbon nanotube rubber paste (step S 2).
  • Step S 3 Pour this carbon nanotube rubber paste onto a glass plate by drop casting (Step S 3), let it air dry for 24 hours, and remove the organic solvent, as shown in Figure 1, a film The carbon nanotube rubber was obtained (Step S 4).
  • step S 5 When the ionic liquid was recovered using the Soxhlet method, it was possible to recover the liquid with 99% of the ions used (step S 5).
  • the conductivity of the produced carbon nanotube rubber containing no ionic liquid was 10 S Z cm, and the elongation was 10% or more.
  • This film-like carbon nanotube rubber has flexibility and extensibility, but the shrinkage is not so great.
  • a film-like carbon nanotube rubber is machined using a numerical control (NC) punching system to form a net-like structure as shown in FIG. It was covered with a base silicone rubber (PDM S, Dow Corning S y 1 gard 1 84 or SH 9 5 5).
  • NC numerical control
  • PDM S Dow Corning S y 1 gard 1 84 or SH 9 5 5
  • the resultant P-DM S-coated film-like carbon nanotube rubber is shown in FIG.
  • a film-like carbon nanotube rubber coated with PDM S is useful as a stretchable wire because it has both extensibility and conductivity.
  • a film-like carbon nanotube rubber coated with P DM S, which has been formed into a suitable network, linear, wire or the like, is an example of the stretchable wiring of the present invention.
  • Film-like carbon nanotube rubber and PD obtained from the above The carbon nanotube rubber in the form of an MS-coated film was stretched, and its electrical and mechanical properties were examined.
  • Figure 18 shows the conductivity when stretched.
  • commercial conductive rubber containing carbon particles (Kinugawa Rubber Industry) is also shown.
  • the elongation rate of commercially available conductive rubber exceeded 150%, the conductivity was as low as 0.1 S / cm (curve 3). This conductivity is insufficient for use as wiring of electronic circuits.
  • the film-like carbon nanotube rubber exhibited a very high conductivity of 5 7 SZ cm, and when the elongation rate was 38% or less, no significant change was observed in the conductivity and mechanical deterioration ( Curve 1).
  • the carbon nanotube rubber coated with PDM S showed a large conductivity of 5 7 S / cm, and even if it was stretched to 134%, the conductivity decreased only gradually (curve 2) The conductivity was 6 SZ cm even under the elongation of 134% ⁇
  • the above results show that the carbon nanotube rubber made of the carbon nanotube rubber and the PDM S coated film-like carbon nanotube rubber manufactured according to the present example elongates. It shows that it has both conductivity and conductivity.
  • the miscibility of the carbon nanotube rubber composition of this example, the carbon nanotube rubber, the carbon nanotube rubber belt, and the ionic liquid necessary for producing a stretchable wiring was examined.
  • the composition ratios of the rubber polymer were 0.78: 0.22 (G801) and 0.88: 0.12 (AKYMA manufactured by KYNAR-FLEX, hereinafter referred to simply as KYNAR).
  • BMIPF 6 and BMIBF 4 were used for vinylidene fluoride-hexafluoro-propylene copolymer and ionic liquids.
  • the film-like carbon nanotube rubber obtained is very smooth when using G801 and BM ITFSI, which are combinations of mutually compatible rubber polymer and ionic liquid. It was flat, uniform, and, as mentioned above, had both extensibility and conductivity.
  • the amounts of SWNT and G801 were 50 mg and 100 mg, respectively, and the content of BMITFSI was changed in the range of 12 to 47% by weight.
  • the content of BM ITFSI was more than 40% by weight, film-like carbon nanotube rubber could not be produced.
  • carbon nanotube rubber became brittle and the conductivity was small.
  • FIG. 19 when the content of BMITFSI was 10% by mass or more and 40% by mass or less, a carbon nanotube rubber having both extensibility and conductivity could be produced.
  • the film-like carbon nanotube rubber produced in this manner exhibited a very smooth surface and excellent mechanical properties in addition to excellent electrical properties, and could be suitably used for stretchable wiring.
  • the maximum conductivity of 57 S / cm was obtained when the contents of SWNT and BMITFSI were both 20% by mass. Such a high conductivity was realized because a good carbon nanotube rubber could be produced without the sacrifice of flexibility or flexibility, even if the content of SWN T was 20% by mass. . This is because the ionic liquid and the rubber are miscible and compatible, and the carbon nanotubes were uniformly dispersed in the rubber. That is, carbon nanotube rubber in which carbon nanotubes, ionic liquid and rubber are uniformly dispersed and mixed can be produced.
  • the ionic liquid is preferable for good carbon nanotube rubber production and has a remarkable effect of improving the extensibility and the conductivity. Furthermore, a carbon nanotube rubber composition having both extensibility and conductivity, carbon nanotube rubber, carbon nanotube rubber paste, and an elastic liquid, the content of the ionic liquid is 10% by mass or more. It is indicated that mass% or less is preferable.
  • the content ratio of SWNT and BM ITFSI was fixed at 1: 1, the amount of G801 was 10 O mg, and SWNT was varied in the range of 1 wt% to 45 wt%.
  • the content of SWN T was less than 10% by mass, film-like carbon nanotube rubber could not be produced.
  • the content of SWNT content was 30% by mass or more, the carbon nanotube rubber became brittle and the conductivity was small.
  • FIG. 20 when the content of SWTN was 10% by mass or more and 30% by mass or less, a carbon nanotube rubber having both extensibility and conductivity could be produced.
  • the film-like carbon nanotube rubber produced in this manner exhibited a very smooth surface and excellent mechanical properties in addition to excellent electrical properties, and could be suitably used for stretchable wiring.
  • the content of S WNT is 16 mass At%, the conductivity increased to 5 3 S cm.
  • the results show that in this example, the carbon nanotube rubber composition having both extensibility and conductivity, carbon nanotube rubber, carbon nanotube rubber paste, and SWNT content of 10% by mass for elastic wiring. It has shown that 30 mass% or less is preferable.
  • the amount of G801 is set to 10 Omg
  • the content ratio of SWNT and BMITFSI is changed from 1: 2 to 2: 1, and SWTN and B M
  • the content of 1 T F S I was changed to 3 0 O mg.
  • the conductivity is shown in Fig. 2 1 and the limit elongation rate (extension rate at which the object breaks) in Fig. 2 2 when the content ratio of SWNT and BM ITFSI is in the range of 1: 2 to 1: 2
  • the carbon nanotube rubber composition having both extensibility and conductivity, carbon nanotube rubber, carbon nanotube rubber paste, and a SWNT / BMITFSI content ratio of 1: 1 for stretch wiring. It is shown that 2 to 2: 1 is preferable.
  • Conductivity based on SWTN is obtained by crosslinking the polymer matrix consisting of G801 using the carbon nanotube rubber paste containing G801 obtained in step S2 of Example 2.
  • Produced a sex paste That is, a peroxide crosslinking initiator (NO.F. Perhexane-having the following structure) was used in a carbon nanotube rubber paste containing G 801.
  • an array of 19.times.3 7 organic transistors was formed on a polyimide substrate, with a channel of pendentene and a gate insulator of polyimide.
  • the polyimide substrate is harder than stretchable wiring.
  • the organic transistor was manufactured using a known ink jet printing, screen printing, and a vacuum evaporation apparatus of Penthene (Step 4-A).
  • Step 4-A an mechanical punching device
  • the organic transistor section except that the polyimide substrates were partially removed so that the organic transistors could be connected to each other at the four corners through the polyimide substrate
  • the organic transistor array to which the four corners are connected is a 500 m thick silicone rubber based on dimethylsiloxane (PDM S, Dow Corning S y l g a r d l 4 or
  • Step 4-C Paste to 5 H 9 5 5 5 5)
  • Step 4-D the connections connecting the organic transistors were removed using a mechanical punching device (MP-8200 Z, UHT Co., Ltd.), and each organic transistor was separated (step 4-D).
  • the substrate containing this discrete organic transistor array was uniformly covered with a 5 parylene seal layer.
  • a mechanical punching device holes of 1 mm in diameter for via wiring were made in the source, drain and gate electrodes, and the holes were filled with Ag paste to form conductive terminals (step 4-E).
  • a stretchable wiring comprising PDM S coated carbon nanotube rubber according to Example 2 of the present invention for the conductive terminals of the gate electrode, the source electrode and the drain electrode. They were electrically connected as word lines (gate electrodes) and bit lines (source electrodes) (step 4 F, step 4 1 G).
  • the properties of the organic transistor did not change even after electrically connecting the produced stretchable wiring with a conductive paste.
  • Fig. 5 shows a photograph of an electronic circuit containing conductive pastes that are connected in series
  • Fig. 25 shows a schematic diagram of one configuration unit of this electronic circuit.
  • the electronic circuit having the organic transistor array obtained as described above, as shown in FIG. 6, the electronic circuit is stretched while the tensile stress is increased, and the transistor provided in the stretched electronic circuit is obtained. I investigated the nature of That is, the electronic circuit is uniaxially or biaxially
  • the electrical characteristics of the electronic circuit were measured by stretching at various expansion rates from 0 to 100%. We also released the strain and measured the electrical characteristics of the transistor in the electronic circuit.
  • FIGS 2 6 and 2 8 electrical characteristics obtained, also showing the relationship between the elongation and the channel current (I D s) in FIGS 2 7 and 2 9.
  • the value of I D s are those standardized by the I D s, measured in the initial state before the experiment.
  • FIGS. 26 to 29 when the elongation is 70% or more, irreversible deterioration occurs, but when the elongation of the electronic circuit is less than 70%, the change in the electrical characteristics is negligible.
  • the stretchable electronic circuit can be easily manufactured using the stretchable wiring according to the present invention and the conductive paste.
  • Such an expansion material and an electronic circuit provided with the same can be suitably used for various types of electronic devices.
  • Fig. 30 shows the change in conductivity when the elongation rate is changed Film-like according to Example 2 While carbon nanotube rubber shows high conductivity regardless of elongation rate, film-like carbon nanotube rubber consisting of single-walled carbon nanotube with short length, low specific surface area and low carbon purity is conductive Conductivity is lowered as the elongation is low. The This indicates that long, high specific surface area, high purity single-walled carbon nanotubes are suitable for realizing the carbon nanotube rubber composition of the present invention having both conductivity and high elongation rate. ing.
  • the inventors of the present invention have achieved the highest conductivity (10 2 S / cm) as a chemically stable elastomer (rubber-like elastic body) using a carbon nanotube.
  • a new stretchable conductor with Furthermore, by using this new material as the wiring of the organic transistor integrated circuit, a self-expanding integrated circuit sheet like rubber is realized.
  • Stretchable integrated circuit sheets can be used in many new applications, such as elastic electronic artificial skin that can be attached to moving parts of machines such as the joints of a rodot. .
  • the present invention is extremely useful in industry because it can provide a carbon nanotube rubber composition having sufficient conductivity and elasticity when used as a constituent material of an electronic circuit.

Abstract

L'invention concerne une composition de caoutchouc à nanotube de carbone qui comprend un nanotube de carbone, un liquide ionique et un caoutchouc miscible avec le liquide ionique. La composition est fabriquée en préparant un gel à nanotube de carbone dispersé contenant un nanotube de carbone, un liquide ionique et éventuellement un solvant organique dispersé dans le gel, en préparant un gel à nanotube de carbone/caoutchouc dispersé contenant le gel à nanotube de carbone dispersé, un caoutchouc et éventuellement un solvant organique dispersé dans le gel, et en séchant le gel à nanotube de carbone/caoutchouc dispersé. La composition permet d'obtenir un caoutchouc à nanotube de carbone, une pâte en caoutchouc à nanotube de carbone, un câblage, une pâte électroconductrice et un circuit électronique.
PCT/JP2009/052825 2008-02-11 2009-02-12 Composition de caoutchouc à nanotube de carbone, câblage, pâte électroconductrice, circuit électronique et procédé de fabrication de la composition de caoutchouc à nanotube de carbone WO2009102077A1 (fr)

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PCT/JP2009/052825 WO2009102077A1 (fr) 2008-02-11 2009-02-12 Composition de caoutchouc à nanotube de carbone, câblage, pâte électroconductrice, circuit électronique et procédé de fabrication de la composition de caoutchouc à nanotube de carbone

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