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WO2009101985A1 - Papier conducteur et son procédé de fabrication, composition de cellulose conductrice et son procédé de fabrication, articles et dispositifs électroniques - Google Patents

Papier conducteur et son procédé de fabrication, composition de cellulose conductrice et son procédé de fabrication, articles et dispositifs électroniques Download PDF

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Publication number
WO2009101985A1
WO2009101985A1 PCT/JP2009/052322 JP2009052322W WO2009101985A1 WO 2009101985 A1 WO2009101985 A1 WO 2009101985A1 JP 2009052322 W JP2009052322 W JP 2009052322W WO 2009101985 A1 WO2009101985 A1 WO 2009101985A1
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Prior art keywords
conductive
cellulose
paper
ionic liquid
conductive paper
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Japanese (ja)
Inventor
Takao Someya
Tsuyoshi Sekitani
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University of Tokyo NUC
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University of Tokyo NUC
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Priority to JP2009553445A priority Critical patent/JP5660595B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material

Definitions

  • the present invention relates to a conductive paper and a manufacturing method thereof, a conductive cellulose composition and a manufacturing method thereof, an article, and an electronic device.
  • Patent Document 1 proposes that a paper sheet made of paper containing a conductive polymer is made to obtain a conductive polymer composite paper. JP 2000-160500 A
  • this paper exhibits only a conductivity of about 1 S / cm at most, and the conductivity is too insufficient to be used for electrical and electronic applications.
  • the present invention has been made in view of the above circumstances, and provides a conductive paper having excellent conductivity that can be sufficiently applied to an electronic device, a conductive cellulose composition, and a method for producing the same. With the goal.
  • the conductive paper of the present invention is characterized in that cellulose and a conductive substance are mixed.
  • This conductive paper has a structure in which cellulose and a conductive substance are entangled with each other and uniformly dispersed.
  • conductive cellulose which is a mixture of cellulose and a conductive substance, is intertwined to form a solid, so that a network of conductive substances is formed inside, and good conductivity is achieved.
  • the degree of mixing of the cellulose and the conductive material may be such that the phase separation does not occur when these admixtures are dispersed in the dispersion medium.
  • a better conductive property can be obtained and a conductive paper excellent in recyclability can be obtained.
  • the conductive paper may contain an ionic liquid.
  • the conductive paper of the present invention uses an ionic liquid in its production process. When the ionic liquid is contained, better conductivity can be obtained. Further, since it is a liquid component, curing due to the addition of a conductive material that is often hard such as carbon nanotubes or a conductive polymer can be suppressed, and a conductive paper that is soft and excellent in texture can be obtained. That is, the ionic liquid also acts as a plasticizer for conductive paper.
  • the conductive paper can be regenerated by dissolving it in a liquid. That is, the conductive paper of the present invention can be recycled very easily as with normal paper.
  • the conductive paper preferably has a conductivity of 1 S / cm or more. Although there is no restriction
  • the conductive substance is preferably a carbon nanotube, and the length of the carbon nanotube is more preferably 1 ⁇ m or more and 10 cm or less.
  • the conductive substance is preferably a conductive polymer.
  • the conductive paper may be configured such that the ionic liquid is hydrophilic. According to this configuration, hydrophilic conductive paper can be obtained. Further, if the ionic liquid is configured to be hydrophobic, hydrophobic conductive paper can be obtained.
  • conductive materials are mixed in the conductive paper. According to this configuration, the electrical conductivity can be further improved and the mechanical characteristics can be improved.
  • a metal and a conductive polymer can be used, for example.
  • the conductive cellulose composition of the present invention is characterized in that cellulose and a conductive substance are mixed. According to this configuration, it is possible to provide a conductive cellulose composition suitable as a constituent material of conductive paper or as a liquid material having conductivity. By mixing the cellulose and the conductive material, the conductive cellulose, which is a mixture of these, becomes a dispersion liquid that is uniformly dispersed in the dispersion medium and does not phase-separate.
  • the conductive cellulose composition may contain an ionic liquid.
  • the ionic liquid When the ionic liquid is included, the ionic liquid exhibits affinity for both the conductive material and cellulose, and thus the conductive cellulose composition in which the conductive material and cellulose are more uniformly dispersed is obtained. Since an ionic liquid is used in the process for producing a conductive cellulose composition, the conductive cellulose composition usually contains an ionic liquid.
  • the conductive cellulose composition may contain other conductive substances. According to this configuration, functionality can be further imparted to the conductive cellulose composition by another conductive substance.
  • the conductive cellulose composition is preferably pasty, gelled, or liquid. By setting it as such a liquid composition, it becomes an electroconductive cellulose composition which can be used as an ink (liquid material) of all the printing machines including screen printing, inkjet printing, a dispenser etc., and can be printed on a predetermined pattern.
  • the article of the present invention comprises the conductive paper of the present invention or the conductive cellulose composition of the present invention.
  • the electronic device of the present invention includes the conductive paper of the present invention or the conductive cellulose composition of the present invention.
  • the conductive paper manufacturing method of the present invention includes a step 1 for preparing a mixture of an ionic liquid and a conductive substance, a step 2 for preparing a dispersion by dispersing cellulose in the mixture, and a step for drying the dispersion. 3.
  • this manufacturing method it is possible to obtain a mixture in which the conductive substance and the ionic liquid are uniformly dispersed by the action of the ionic liquid, and when cellulose is added to the mixture, the cellulose and A dispersion in which the conductive substance and the ionic liquid are uniformly dispersed can be obtained. Thereby, the dispersion liquid containing the electroconductive cellulose with which the cellulose and the electroconductive substance were mixed can be obtained. And the electrically conductive paper which has electroconductive cellulose can be manufactured by drying a dispersion liquid.
  • the method for producing conductive paper may further include a step 4 of removing the ionic liquid from the dried product of the dispersion.
  • the ionic liquid can be removed from the conductive paper and recovered. And since the collect
  • the ionic liquid when the ionic liquid is hydrophilic, it is preferable to add water as a dispersion medium in the step of preparing the dispersion. According to this manufacturing method, it is possible to manufacture hydrophilic conductive paper having conductive cellulose in which a conductive substance and cellulose are uniformly dispersed.
  • the ionic liquid when the ionic liquid is hydrophobic, it is preferable to add a dispersion medium other than water in the step of preparing the dispersion.
  • a dispersion medium other than water for example, a hydrophilic organic solvent such as ethanol or methanol can be used, and may be appropriately changed according to the type of cellulose.
  • the method for producing a conductive cellulose composition of the present invention includes a step 1 for preparing a mixture of an ionic liquid and a conductive substance, and a step 2 for preparing a dispersion by dispersing cellulose in the mixture.
  • a conductive cellulose composition as a dispersion in which conductive cellulose in which a conductive substance and cellulose are mixed is dispersed.
  • the electrically conductive paper which can acquire high electrical conductivity, big mechanical flexibility, and durability can be provided by mixing cellulose and an electroconductive substance.
  • the conductive paper of the present invention can be easily recycled.
  • goods and electronic device using the high electrical conductivity of conductive paper can be provided. According to the production method of the present invention, a conductive paper and a conductive cellulose composition having high conductivity can be easily produced.
  • the figure which shows a conductive cellulose composition The flowchart which shows the manufacturing method of conductive paper.
  • the graph which shows the change of the resistance value with respect to a bending radius.
  • the graph which shows the electrical property of conductive paper A graph showing a change in conductivity when conductive paper is recycled.
  • the conductive cellulose composition of the present invention has a conductive cellulose in which cellulose and a conductive substance are mixed, and in some cases includes an ionic liquid occluded in the conductive cellulose.
  • the conductive cellulose composition of the present invention can be used in various forms such as liquid, gel, solid, paper, etc., depending on the presence or absence of an ionic liquid, the presence or absence of a dispersion medium such as water or an organic solvent, and characteristics. Can take form.
  • Fig.1 (a) is a schematic diagram which shows the electroconductive cellulose composition which concerns on this invention
  • FIG.1 (b) is a schematic diagram which expands and shows the fiber shown to Fig.1 (a).
  • the conductive cellulose composition according to the present invention includes a large number of conductive celluloses 10.
  • each conductive cellulose 10 has a structure in which a large number of carbon nanotubes 12 that are conductive materials are entangled around a cellulose fiber 11.
  • the cellulose fibers 11 and the carbon nanotubes 12 are mixed to such an extent that the fibers are intertwined in a complicated manner and the cellulose fibers 11 and the carbon nanotubes 12 are not phase-separated even when the conductive cellulose 10 is dispersed in a dispersion medium such as water or an organic solvent. Matching. In the present invention, such a state is defined as a state in which cellulose and a conductive substance are “mixed”. In addition, it is impossible to separate the cellulose fibers 11 and the carbon nanotubes 12 that are mixed without damaging them, and it can be said that they are in a state of being mixed so as not to be separated.
  • the conductive cellulose 10 shown in FIG. 1 is an example of the conductive cellulose composition according to the present invention, and details will be described later, but the conductive material is not limited to the carbon nanotubes 12. For example, a metal nanotube or a conductive polymer can be used.
  • a representative form of the conductive cellulose composition of the present invention is conductive paper obtained by forming a dispersion of conductive cellulose 10 into a sheet and drying it.
  • the conductive paper according to the present invention possesses the function as paper without impairing the characteristics and form of the base material cellulose, and at the same time has high conductivity imparted from a conductive substance.
  • Such a conductive paper is an innovative new material that can be realized for the first time by the present invention, and can be suitably used for a wiring pattern of an electronic circuit because of its excellent conductivity.
  • a conductive paper since it is composed of the conductive cellulose 10 in which cellulose (cellulose fibers 11) and a conductive substance (carbon nanotubes 12) are mixed, a complicated network of conductive substances is formed in the conductive paper. Therefore, it is possible to obtain a high conductivity that could not be obtained at all with a conductive paper obtained by impregnating paper with a conventionally known conductive material.
  • a conductivity of 1 S / cm or more is preferable because it can be used as wiring for an electronic circuit.
  • the conductive paper of the present invention since the conductive paper of the present invention has a network of conductive materials inside as described above, it does not lose its conductivity even if it is folded or stretched. Therefore, it is a conductive paper having excellent flexibility and workability that cannot be obtained by a conductive paper in which a conductive material layer is formed on a conventional paper. Furthermore, the conductive paper of the present invention can be easily redispersed in water or a solvent, just as ordinary paper can be easily recycled simply by dissolving it in water. Therefore, it can be easily recycled without giving high energy such as heat.
  • the conductivity, bending resistance, and recyclability of the conductive paper according to the present invention are described in detail in the following examples.
  • the conductive paper of the present invention is not limited to paper or thin film, and the conductive cellulose composition is made into a solid material (three-dimensional structure such as rod, box, frame, and cylinder) using a mold or the like. Includes processed products. Furthermore, machining may be added to solid conductive paper. For example, the sheet-like conductive paper may be thinned by stretching by press working or the like. Conductive paper formed as such a solid substance or processed conductive paper can also be suitably used as a conductive member of an article or a constituent member of an electronic circuit.
  • the conductive paper of the present invention usually contains the ionic liquid used in the manufacturing process together with the conductive cellulose 10.
  • the ionic liquid is also called a room temperature molten salt or simply a molten salt, and is a salt that exhibits a molten state in a wide temperature range including normal temperature.
  • the details of the ionic liquid will be described in the description of the production method at a later stage, and this ionic liquid also has the effect of increasing the conductivity in the conductive paper of the present invention.
  • the ionic liquid is a liquid at room temperature, the conductive paper containing the ionic liquid exhibits a moist and smooth texture and is closer to paper.
  • the ionic liquid can also be removed from the conductive paper or the conductive cellulose composition by using a Soxhlet method or the like.
  • the conductivity of the conductive paper (conductive cellulose composition) from which the ionic liquid has been removed is lower than that of the conductive paper containing the ionic liquid, but the removed ionic liquid can be recovered and the conductive cellulose composition can be produced. Can be reused.
  • a dispersion of conductive cellulose 10 is a dispersion of conductive cellulose 10.
  • a dispersion can take various forms such as a liquid, a gel, and a paste depending on the properties of the ionic liquid and the dispersion medium.
  • Such a fluid dispersion can be processed into conductive paper by solidifying it by heat, drying, or the like, and is suitable for producing a molded conductive paper.
  • the prepared conductive cellulose dispersion is used as ink (liquid material) for any printing press including screen printing, ink jet printing, dispenser, etc., and printed in a predetermined pattern, and then dried to produce conductive paper. It is possible to easily form patterns and wirings made of Thus, an article provided with a pattern or wiring made of conductive cellulose, or an electronic circuit provided with a conductive cellulose composition can be produced.
  • a conductive material that is the same as or different from the conductive material constituting the conductive cellulose can be added to the conductive paper or the conductive cellulose dispersion.
  • a fibrous conductor such as carbon nanotube or silver nanotube
  • higher conductivity and strength as paper can be obtained.
  • the conductive material constituting the conductive cellulose 10 is not limited to the carbon nanotubes 12 including single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT), but also metal nanotubes (metal nanofibers) including silver.
  • Any conductive material can be used as long as it is a conductive material such as a conductive polymer.
  • the conductive material needs to be in a form that can be mixed with cellulose. Therefore, the type of the conductive material is not limited, but a conductive material manufactured or processed to a size equal to or smaller than that of cellulose fibers is used.
  • a conductive paper or a conductive cellulose composition having high conductivity and being supple like paper it is important to use a conductive material having high conductivity.
  • the carbon nanotubes are long, have high purity, and have a high specific surface area. Therefore, in general, single-walled carbon nanotubes having a high specific surface area and a long length are more preferable than multi-walled carbon nanotubes having a low specific surface area and a short length.
  • the carbon nanotube is desirably as long as possible. This is because, when the carbon nanotube network (knitted structure) in the conductive cellulose composition is composed of long carbon nanotubes, more paths for conducting electricity can be formed, and even when bent, the network is more difficult to break. Because.
  • the length of the conductive material for obtaining high conductivity and flexibility in the conductive cellulose composition there is no upper limit to the length of the conductive material for obtaining high conductivity and flexibility in the conductive cellulose composition, but in general, longer materials have lower dispersibility and the production of the conductive cellulose composition can be reduced. It becomes difficult.
  • carbon nanotubes when carbon nanotubes are used, carbon nanotubes having a length of 1 ⁇ m or more and 10 cm or less have good dispersibility, are easily obtained with high purity, and are preferable for obtaining high conductivity and flexibility. When the length is 1 ⁇ m or less, the conductivity is extremely lowered, which is not preferable. Conversely, carbon nanotubes having a length of 10 cm or more have poor dispersibility and are easily cut during the dispersion process.
  • the carbon nanotube is a very long and narrow nanomaterial having a nanoscale diameter and a long length, it is very difficult to measure the length of each one.
  • the following method can be used when measuring the length of the carbon nanotube.
  • a liquid sample is prepared by thinly diluting a mixture of carbon nanotubes and ionic liquid, or a dispersion in which cellulose is dispersed in such a mixture with an organic solvent or the like.
  • the liquid sample dropped onto the substrate and then dried is observed with a scanning atomic force microscope or the like.
  • the length of the bundle (bundle of carbon nanotubes) is measured instead of the length of each carbon nanotube.
  • the length of the carbon nanotube bundle measured by the scanning atomic force microscope and the length of the carbon nanotube constituting the bundle, and the bundle constituted by the long carbon nanotube becomes long. Thereby, the length of the carbon nanotube can be evaluated.
  • a conductive cellulose composition there is no limitation on the characteristics and length of the carbon nanotube, and a conductive cellulose composition can be produced.
  • a carbon nanotube produced by a super-growth method is used as a long carbon nanotube that can obtain higher conductivity and flexibility.
  • a method for producing carbon nanotubes by the super-growth method is described, for example, in International Publication No. 06/011655.
  • the super-growth method is a technique for synthesizing carbon nanotubes by a moisture-added CVD method, and long and high-purity single-walled carbon nanotubes can be obtained.
  • a carbon nanotube alignment aggregate vertically aligned on a growth substrate can be grown, and this carbon nanotube alignment aggregate can be peeled off from the growth substrate and used.
  • the height of the aligned carbon nanotube assembly can be defined as the length of the carbon nanotube.
  • the carbon nanotubes be as pure as possible.
  • Purity is carbon purity and shows what percentage of the weight of a carbon nanotube is comprised with carbon. Although there is no upper limit to the purity for obtaining high conductivity and high elongation, it is difficult to obtain 99.9999% or more of carbon nanotubes for the convenience of production.
  • impurities such as metals are included and the carbon purity is less than 90%, the metal impurities are aggregated during the manufacturing process, and the carbon nanotubes are not easily entangled with the fibers of cellulose, resulting in insufficient mixing. It becomes difficult to obtain high bending resistance. From these points, the purity of the carbon nanotube is preferably 90% or more.
  • the purity of carbon nanotubes is obtained from the results of elemental analysis using fluorescent X-rays.
  • Super-growth (SG) single-walled carbon nanotubes (SWNT) used in specific examples to be described later were subjected to elemental analysis by fluorescent X-rays. As a result, carbon was 99.98%, iron was 0.013%, and other elements were measured. Was not.
  • the carbon nanotube has as high a specific surface area as possible. This is because carbon nanotubes having a high specific surface area have many surfaces, and therefore, the number of interfaces with the ionic liquid used in the production process of the conductive cellulose composition increases, and the carbon nanotubes easily interact with each other. Carbon nanotubes with a high specific surface area contain a small amount of carbon impurities other than carbon nanotubes and impurities such as metals other than carbon, and are suitable for the reasons described above.
  • Single-walled carbon nanotubes having a specific surface area of less than 600 m 2 / g contain impurities such as metals or carbon impurities of several tens of percent (about 40%) by weight, and may exhibit the original functions of single-walled carbon nanotubes. It cannot be done and is inappropriate.
  • the unopened one is about 1300 m 2 / g, and the opened one is about 2600 m 2 / g. is there.
  • the specific surface area of the single-walled carbon nanotube can be obtained by measuring an adsorption / desorption isotherm of liquid nitrogen at 77K.
  • 30 mg of the aligned single-walled CNT aggregate can be obtained from an adsorption / desorption isotherm curve measured using BELSORP-MINI (manufactured by Nippon Bell Co., Ltd.) (adsorption equilibrium time was 600 seconds).
  • examples of the conductive polymer include a polyaniline polymer, a polypyrrole polymer, and a polythiophene polymer.
  • examples of particularly highly conductive polymers include polyparaphenylene, polyaniline, polythiophene, polyparaphenylene vinylene, polypyrrole, polyacetylene, polyphenylene vinylene, and polyethylenedioxythiophene (hereinafter simply referred to as PEDOT).
  • PEDOT polyethylenedioxythiophene
  • a typical example is PEDOT, and its aqueous dispersion is commercially available from TA Chemical Company under the trade name “Baytron PH500”.
  • the size of the conductive polymer is smaller than that of the cellulose fiber 11 and the carbon nanotube 12, and therefore the cellulose fiber 11 as shown in FIG.
  • the conductive polymer is adsorbed so as to cover the surface of the cellulose fiber 11 and become the conductive cellulose 10.
  • the conductive cellulose 10 in which the conductive polymer is adsorbed on the cellulose fiber 11 is dispersed in the dispersion medium, the cellulose fiber 11 and the conductive polymer are not phase-separated. It is defined as a state in which cellulose and a conductive polymer are mixed. The conductive polymer thus adsorbed cannot be separated without damaging the cellulose and the conductive polymer.
  • the cellulose used in the present invention is not particularly limited, and may be any cellulose material (aggregate is pulp) used for ordinary papermaking. Commonly known pulp is formed from cellulose fibers. For example, any fibrous pulp such as wood pulp, waste paper pulp, non-wood pulp, more specifically softwood sulfite pulp, softwood bleached kraft pulp, hardwood sulfite pulp, hardwood bleached kraft pulp, and linter pulp may be used. As the cellulose, any cellulose such as natural cellulose, regenerated cellulose, cotton cellulose, linter, rayon, and amorphous cellulose can be used. Furthermore, the pulp is not limited to cellulose and cellulose, and any fiber that generates hydrogen bonds can be used as a raw material. Therefore, pulp extracted from raw materials such as grass, straw, and bamboo may be used.
  • microfibril cellulose that has been defibrated in advance into fine cellulose fibers in order to obtain paper having excellent conductivity.
  • microfibril cellulose is not particularly limited, and may be any commercially available one.
  • a typical example of commercially available microfibril cellulose is Celish manufactured by Daicel Chemical Industries.
  • Carbon nanotubes are used as the conductive substance
  • the conductive cellulose composition of the present invention higher conductivity is obtained as the carbon nanotubes are uniformly dispersed in the composition. That is, in order to realize the conductive cellulose composition of the present invention having both high conductivity and flexibility, a carbon nanotube having a long length, high purity, and high specific surface area can be obtained without degrading its function. It is important to uniformly disperse the water.
  • carbon nanotubes are materials with very low solubility, have low affinity with cellulose, and do not disperse in cellulose. Therefore, it has been extremely difficult to realize a conductive cellulose composition and conductive paper in which carbon nanotubes are uniformly dispersed and have both high conductivity and flexibility.
  • the present inventor has made sincerity and found that it is preferable to use an ionic liquid in order to increase the dispersibility of the conductive material and cellulose including carbon nanotubes.
  • an ionic liquid in order to increase the dispersibility of the conductive material and cellulose including carbon nanotubes.
  • carbon nanotubes and ionic liquid have a high affinity, and the carbon nanotubes are gelled by being dispersed in the ionic liquid.
  • van der is that the ionic liquid is adsorbed on each carbon nanotube and bonds the carbon nanotubes together. It is thought that the virus power is weakened.
  • the carbon nanotubes that are usually easily bundled are dispersed in the ionic liquid to form a gel composition.
  • the ionic liquid is considered to function as a dispersant for carbon nanotubes.
  • the inventor has found that when cellulose and a conductive substance that are miscible with the ionic liquid are used, a dispersion in which cellulose is uniformly dispersed in the gel composition can be obtained.
  • the conductive cellulose composition having high electrical conductivity and the flexibility of paper and a method for producing conductive paper have been realized.
  • the detailed mechanism by which the conductive cellulose composition is formed by mixing is unknown at this time.
  • the ionic liquid adsorbed on the conductive material has affinity with cellulose and mixes the conductive material into the cellulose. It is considered that a conductive substance such as a carbon nanotube that can be dissolved and normally difficult to disperse in cellulose is uniformly dispersed in cellulose.
  • the mixing in the dispersion means that the ionic liquid, cellulose, pulp as a base material, and, if necessary, a dispersion containing water or an organic solvent are mixed to such an extent that they do not undergo phase separation.
  • the degree of blending There is no upper limit to the degree of blending, and the conductive cellulose composition, the ionic liquid, and water and organic solvents, if necessary, are finally mixed together.
  • the conductive cellulose composition has high conductivity and flexibility. In general, it is suitable if the dispersion containing an ionic liquid and cellulose or cellulose pulp, and water or an organic solvent as required, does not undergo phase separation for several hours, more preferably for several days. .
  • the ionic liquid and cellulose or cellulose pulp and, if necessary, water or an organic solvent are compatible with each other in order to achieve better dispersibility.
  • the term “compatible” refers to the property that two or more substances have an affinity for each other and form a solution or a mixture.
  • the method for producing a conductive cellulose composition of the present invention is based on the above findings, Step 1 of preparing a mixture of an ionic liquid and a conductive material, and dispersing the cellulose in the mixture Step 2 of preparing
  • the method for producing a conductive paper according to the present invention is based on the above knowledge. Step 1 of preparing a mixture of an ionic liquid and a conductive substance, and preparing a dispersion by dispersing cellulose in the mixture And a step 3 of drying the dispersion.
  • FIG. 2 is a flowchart showing a method for producing conductive paper according to an embodiment of the present invention.
  • the method for producing conductive paper of the present invention comprises a mixture preparation step S1 for preparing a mixture of a conductive substance and an ionic liquid, and a dispersion is prepared by dispersing cellulose in the obtained mixture. It includes a step of producing a conductive cellulose composition by the dispersion liquid preparation step S2, and further includes a drying step S3 of drying the obtained conductive cellulose composition to produce conductive paper.
  • the ionic liquid recovery step S4 for recovering the ionic liquid from the conductive paper is a step performed as necessary.
  • any conductive material that is miscible with cellulose can be used as described above. That is, carbon nanotubes, metal nanotubes, highly conductive polymers, and the like can be used.
  • the ionic liquid is also called a room temperature molten salt or simply a molten salt, and is a salt that exhibits a molten state in a wide temperature range including normal temperature.
  • conventionally known various ionic liquids can be used, and examples thereof include those described in Japanese Patent No. 3676337 and Japanese Patent No. 3880580.
  • both hydrophilic and hydrophobic ionic liquids can be used as the ionic liquid.
  • the hydrophilic ionic liquid include N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF 4 ).
  • DEMEBF 4 N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate
  • hydrophobic ionic liquid examples include N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide (DEMETFSI), 1-ethyl-3-methylimidazolium tetra Fluoroborate (EMIBF 4 ), 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF 6 ), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMITFSI), 1-butyl-3 - methylimidazolium tetrafluoroborate (BMIBF 4), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF 6), 1- butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ( MITFSI) can be mentioned.
  • DEMETFSI 1-ethyl-3
  • cellulose may be directly dispersed in the mixture obtained in the mixture preparation step S1, and a dispersion medium such as water or an organic solvent can be used as necessary.
  • a dispersion medium such as water or an organic solvent
  • a hydrophilic ionic liquid water can be used as a suitable dispersion medium.
  • a hydrophobic ionic liquid it is preferable to use a hydrophilic organic solvent.
  • useful hydrophilic organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, formic acid, acetic acid, acetone, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, and N, N-dimethylformamide.
  • a typical example is ethanol.
  • the organic solvent is not limited to the above, and a solvent that disperses and dissolves cellulose to be used can be appropriately selected and used. Specifically, toluene, xylene, carbon tetrachloride, or the like can be used.
  • the dispersion medium such as water and organic solvent mentioned above can be used not only in the dispersion preparation step S2 but also in the mixture preparation step S1 as necessary.
  • PEDOT which is a conductive polymer
  • dimethyl sulfoxide which is an organic solvent
  • the effect of remarkably improving the conductivity of PEDOT can be obtained.
  • the conductive cellulose composition of the present invention can be produced either in an organic solvent or in water.
  • the hydrophilicity and hydrophobicity of the conductive cellulose composition and the conductive paper are controlled by the combination of the ionic liquid used in the mixture preparation step S1 and the dispersion medium used in the dispersion preparation step S2 after adding cellulose. can do.
  • cellulose miscible with water and an ionic liquid miscible with water are used. That is, in the mixture preparation step S1, for example, DEMEBF 4 is used as an ionic liquid, and in the dispersion preparation step S2, a dispersion liquid containing a conductive substance, an ionic liquid, and cellulose mixed with water is used using water as a dispersion medium.
  • a dispersion liquid containing a conductive substance, an ionic liquid, and cellulose mixed with water is used using water as a dispersion medium.
  • a hydrophobic conductive cellulose composition and conductive paper when producing a hydrophobic conductive cellulose composition and conductive paper, a hydrophobic ionic liquid, an organic solvent mixed therewith, and a conductive material mixed with the organic solvent are used. That is, in the mixture preparation step S1, for example, DEMETFSI or BMIBF 4 is used, and in the dispersion preparation step S2, for example, ethanol is used as a dispersion medium to prepare a dispersion containing a conductive substance, an ionic liquid, and cellulose. In addition, a miscible combination is selected for the dispersion medium and cellulose. For example, microfibril cellulose can be dissolved in a polar solvent such as ethanol or methanol (the hydrophilic organic solvent described above), so that these combinations can be suitably used for the production of hydrophobic conductive paper.
  • a polar solvent such as ethanol or methanol (the hydrophilic organic solvent described above
  • the mixture preparation step S1 the above-described conductive substance and ionic liquid are prepared and mixed uniformly. Thereby, the mixture (gel composition) of an electroconductive substance and an ionic liquid is prepared.
  • a jet mill, a ball mill, an ultrasonic disperser, a mortar, an automatic mortar or the like can be used for mixing and dispersing each component.
  • conductive devices such as carbon nanotubes and conductive polymers are more uniformly dispersed in the gel composition, and from the viewpoint of avoiding cutting of the carbon nanotubes and lowering of the conductive polymer due to the mixing process. Selected. From the viewpoint of preventing the carbon nanotube from being cut, it is preferable to use a jet mill.
  • the method for producing a gel composition in which carbon nanotubes and an ionic liquid are mixed is not limited to this method, and is disclosed in Japanese Patent Nos. 3676337, 3880560, 3924273, and 2004-254881. Known methods described in Japanese Patent Laid-Open No. 2005-176428 and the like can also be used. Further, the present invention is not limited to the mixing / dispersing method using the apparatus described above or the method described in the above document, and any method can be used as long as it can uniformly mix and disperse the conductive substance and the ionic liquid. This method can be adopted.
  • the gel composition containing the conductive material and the ionic liquid obtained in the mixture preparation step S1 and cellulose are mixed and dispersed by adding water or an organic solvent as necessary. Let As a result, the conductive cellulose composition of the present invention in the form of a liquid, paste or gel dispersion is obtained.
  • the viscosity of the resulting dispersion can be adjusted by adding or removing water or an organic solvent. That is, the viscosity of the dispersion can be reduced by adding water or an organic solvent as appropriate to the gel composition or the dispersion before, during, or after the dispersion preparation step S2. Alternatively, before or during the dispersion preparation step S2, water or an organic solvent contained in the gel composition or the dispersion can be partially removed by evaporation or the like to increase the viscosity of the dispersion. .
  • a jet mill, a ball mill, an ultrasonic disperser, a mortar, an automatic mortar, or the like can also be used for mixing and dispersion in the dispersion preparation step S2, and among these, a jet mill that can prevent cutting of carbon nanotubes should be used.
  • a jet mill that can prevent cutting of carbon nanotubes should be used.
  • the present invention is not limited to the mixing / dispersing method using these apparatuses, and any method can be adopted as long as the conductive substance, the ionic liquid, and cellulose can be uniformly mixed and dispersed. it can.
  • a part of or all of the water and the organic solvent contained in the dispersion (conductive cellulose composition) obtained in the dispersion preparation step S2 is dried, heated, evacuated, and the like. Use to remove and solidify the conductive cellulose composition. Thereby, the conductive paper of the present invention is obtained.
  • the conductive paper of a desired shape in drying process S3 you may shape
  • a known method for molding a fluid paste or liquid composition can be used, and examples thereof include coating, printing, extrusion, casting, and injection.
  • the forming process of the conductive cellulose composition is not limited to being performed in a dispersion state. That is, after the conductive cellulose composition is solidified in the drying step S3, the obtained conductive paper may be machined into a desired shape. For example, the thickness of the conductive paper can be reduced by pressing or the like.
  • the conductive paper obtained in the drying step S3 can be used for the ionic liquid recovery step S4.
  • This ionic liquid recovery step S4 is a step that is performed as necessary, and removes the ionic liquid from the conductive paper using a Soxhlet method or the like.
  • the conductive paper which consists of an electroconductive substance and a cellulose is obtained.
  • the conductivity of the conductive paper from which the ionic liquid has been removed is lower than that of the conductive paper containing the ionic liquid.
  • the ionic liquid removed from the conductive paper can be recovered and reused in the mixture preparation step S1, as shown in FIG. Thereby, manufacturing cost can be reduced significantly.
  • the dried conductive paper is used for the ionic liquid recovery step S4, but the dispersion (conductive cellulose composition) obtained in the dispersion preparation step S2 is used for the ionic liquid recovery step S4. May be. Also in this case, the ionic liquid can be recovered from the conductive cellulose composition and reused.
  • the manufacturing process demonstrated above is an example of the manufacturing process for obtaining the electroconductive cellulose composition and conductive paper which concern on this invention, and is not limited to the said example. That is, some steps may be omitted or the order may be changed as necessary. Moreover, you may add another electroconductive substance, another cellulose, another solvent, and another ionic liquid in a suitable process as needed.
  • the conductive substance and the ionic liquid are uniformly obtained by using the ionic liquid in the mixture preparation step S1.
  • a mixed mixture (gel composition) can be obtained.
  • the bundles can be dispersed while being separated into individual carbon nanotubes by the action of the ionic liquid.
  • the conductive polymer can be uniformly dispersed in the ionic liquid having an affinity for the conductive polymer.
  • cellulose and an electroconductive substance are ionized by disperse
  • the ionic liquid recovery step S4 the ionic liquid can be recovered from the produced conductive paper or dispersion (conductive cellulose composition). And since the collect
  • the conductive paper of the present invention can be easily recycled.
  • the conductive paper produced through the drying step S3 or the ionic liquid recovery step S4 is dissolved in a liquid in the dissolving step S5, thereby dispersing the conductive cellulose uniformly dispersed (conductive cellulose composition). Thing).
  • dissolving conductive paper can be reproduce
  • the dissolution step S5 is a step in which used conductive paper is immersed in a dispersion medium such as water or an organic solvent and stirred.
  • the dispersion medium used in the dissolving step S5 is appropriately selected according to the hydrophilicity and hydrophobicity of the conductive paper to be dissolved. That is, water is used as a dispersion medium when dissolving hydrophilic conductive paper, and an organic solvent (dispersion medium other than water) is used as a dispersion medium when dissolving hydrophobic conductive paper.
  • the dispersion medium it is preferable to use the same dispersion medium as used in the dispersion liquid preparation step S2 when the conductive paper to be subjected to the dissolution step S5 is manufactured. In addition, you may add an ionic liquid to a dispersion medium as needed.
  • the conductive paper of the present invention can be recycled by a very simple process of dissolving in a dispersion medium.
  • metal is used for the conductive member, and recycling requires high energy such as heating, but by using the conductive paper of the present invention, high energy such as heat is not given.
  • An electronic device that can be easily recycled can be formed.
  • FIG. 3 is a diagram illustrating an example of a process for producing conductive paper using carbon nanotubes as a conductive substance.
  • Step1, Step2, and Step3 correspond to the mixture preparation step S1, the dispersion preparation step S2, and the drying step S3, respectively, in the conductive paper manufacturing method of the present invention.
  • single-walled carbon nanotubes (purity> 99.98%, length less than 1 mm, diameter 3 nm) produced by the super-growth (SG) method were used as the carbon nanotubes that are conductive materials.
  • Such carbon nanotubes are obtained, for example, by peeling an aligned aggregate of carbon nanotubes grown from a substrate by using the method described in WO2006 / 011655 from the growth substrate.
  • N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF 4 ) was used as the ionic liquid.
  • Step 1 mixture preparation step S1
  • 50 mg of the above single-walled carbon nanotubes were added to N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, which is a hydrophilic ionic liquid.
  • DEMEBF 4 N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate
  • Step 2 (dispersion liquid preparation step S2), 150 mg of the carbon nanotube dispersion gel obtained in Step 1 is mixed with 10 ml of deionized water as a dispersion medium, microfibril cellulose (Celish manufactured by Daicel Chemical Industries, 10% cellulose) 200 mg of an aqueous liquid containing the solution was sequentially added. The resulting mixture was then stirred with a stirrer at 25 ° C. for 1 hour, and then sonicated with SMT UH-50 at 30 ° C. for 10 minutes. As a result, a conductive cellulose composition (nanotube-dispersed aqueous solution) in which single-walled carbon nanotubes, an ionic liquid, and microfibril cellulose were uniformly dispersed was obtained.
  • a conductive cellulose composition nanotube-dispersed aqueous solution in which single-walled carbon nanotubes, an ionic liquid, and microfibril cellulose were uniformly dispersed was obtained.
  • Step 3 drying step S3
  • the nanotube-dispersed aqueous solution obtained in Step 2 was drop-cast on a polytetrafluoroethylene (PTFE) plate and air-dried over 24 hours.
  • PTFE polytetrafluoroethylene
  • FIG. 4 is a diagram illustrating an example of a process for producing conductive paper using PEDOT as a conductive substance.
  • Step1, Step2, and Step3 correspond to the mixture preparation step S1, the dispersion preparation step S2, and the drying step S3, respectively, in the conductive paper manufacturing method of the present invention.
  • PEDOT a highly conductive polymer obtained by polymerizing 3,4-ethylenedioxythiophene in a high molecular weight polystyrenesulfonic acid aqueous solution (manufactured by TA Chemical Co., Ltd.). Baytron PH500, PEDOT content 1 wt%) was used.
  • the ionic liquid N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF 4 ) was used.
  • DEMEBF 4 dimethyl sulfoxide
  • DMSO dimethyl sulfoxide
  • Step 1 mixture preparation step S1
  • 4 g of PEDOT 1% aqueous solution 40 mg of PEDOT
  • 50 mg of hydrophilic ionic liquid DEMEBF 4
  • DMSO dimethyl sulfoxide
  • Step 2 (dispersion preparation step S2), 10 ml of deionized water as a dispersion medium and 100 mg of microfibril cellulose were sequentially added to the PEDOT-PSS gel obtained in Step 1. The resulting mixture was then stirred at 25 ° C. for 1 hour. As a result, a conductive cellulose composition (PEDOT-PSS gel-dispersed aqueous solution) in which PEDOT, an ionic liquid, and microfibril cellulose were uniformly dispersed was obtained.
  • PEDOT-PSS gel-dispersed aqueous solution in which PEDOT, an ionic liquid, and microfibril cellulose were uniformly dispersed was obtained.
  • Step 3 drying step S3
  • the PEDOT-PSS gel-dispersed aqueous solution was poured onto a PTFE plate by drop casting and air-dried over 24 hours.
  • conductive paper PEDOT-PSS conductive paper
  • PEDOT-PSS highly conductive polymer
  • FIG. 5 is a graph showing the relationship between cellulose content and electrical conductivity.
  • FIG. 6 is a planar SEM photograph of carbon nanotube conductive paper and PEDOT-PSS conductive paper.
  • the maximum conductivity (72 S / cm) was obtained when the cellulose content was 12 wt% and the mixing ratio of SWNT and DENEBF 4 was 1: 2. To the best of the inventors' knowledge, this is the highest reported soft material (paper or polymer), and previously reported non-insulating paper (eg Yoon SH, Jin HJ, Kook MC, Pyun YR (2006) Electrically conductive bacterial cellulose by incorporation of carbon nanotubes, Biomacromolecules 7: 1280-1284), which is about three orders of magnitude larger than the conductivity (about 0.1 S / cm).
  • single-walled carbon nanotubes have strong covalent bonds and tend to form bundles, they tend to aggregate when mixed with polymers and other materials.
  • the ionic liquid used in the present invention can prevent entanglement of single-walled carbon nanotubes.
  • the content of the single-walled carbon nanotubes can be as large as 30 wt% without adversely affecting the softness of the paper, and the high-aspect ratio super-growth carbon nanotubes can be uniformly dispersed in the microfibril cellulose. I was able to. As a result, a large electrical conductivity was realized as described above.
  • PEDOT-PSS conductive paper As shown in FIG. 6, the surface became rough as the cellulose content increased.
  • a thick and porous PEDOT-PSS conductive paper was obtained.
  • a brittle PEDOT-PSS conductive paper was obtained.
  • the maximum conductivity (75 S / cm) was obtained when the cellulose content was 10 wt% and the mixing ratio of PEDOT and DENEBF 4 was 4: 5.
  • PEDOT-PSS conductive paper not only had high electrical conductivity, but also excellent flexibility and softness.
  • FIG. 7 is a graph showing a change in resistance value with respect to a bending radius when the carbon nanotube conductive paper and the PEDOT-PSS conductive paper produced in this example are bent. The measurement was performed by bending the conductive paper using a stress device equipped with an accurate mechanical stage and measuring the resistance value after bending.
  • the resistance value when bent is almost constant, and the fluctuation range of the resistance value is completely bent (the bending radius is 100 ⁇ m). Is less than negligible. From this, it was confirmed that the conductive paper of the present invention has great mechanical flexibility and is excellent in durability under bending stress.
  • a stress acts on the interface between the metal thin film and the paper / plastic, and the metal thin film is easily broken.
  • the conductive cellulose is entangled with each other to form the conductive paper, so that both high electrical conductivity and high mechanical flexibility / durability can be realized at the same time.
  • the PEDOT-PSS conductive paper of this embodiment can be bent completely and has properties that are significantly different from those of conventional PEDOT films. This is considered to be because the mixture of the ionic liquid and PEDOT formed a gel and could be uniformly dispersed in the microfibril cellulose.
  • FIG. 8 is a graph showing the results of measuring the transmission characteristics of the carbon nanotube conductive paper and PEDOT-PSS conductive paper prepared in this example. Measurement results for copper wiring are also shown for comparison. The measurement was performed using a network analyzer (Agilent 4395A). The length, width, and thickness of the carbon nanotube conductive paper and PEDOT-PSS conductive paper used for the measurement were 30 mm, 5 mm, and 70 ⁇ m, respectively.
  • the transmission loss of the carbon nanotube conductive paper and the PEDOT-PSS conductive paper was within ⁇ 2 dB up to 100 MHz. Even when compared with the transmission loss of the copper wiring, the difference was less than 37%.
  • Another important advantage of the conductive paper of the present invention is that the current flowing through the paper is dependent on electrons rather than ions. As a result, excellent electrical characteristics can be realized in the MHz region as shown.
  • FIG. 9 is a graph showing electrical characteristics of the carbon nanotube conductive paper and the PEDOT-PSS conductive paper.
  • FIG. 9A is a graph showing transmission characteristics
  • FIG. 9B is a graph showing the relationship between temperature and conductivity.
  • the maximum power that can be transmitted through the carbon nanotube conductive paper was 35 W
  • the maximum power that could be transmitted through the PEDOT-PSS conductive paper was 38 W.
  • Transmission characteristics were measured using a 13.56 MHz power generator (ULGN RGN-1302) and a spectrum analyzer (Agilent 4395A) for measuring the transmitted power.
  • FIG. 9B although there are variations, both the carbon nanotube conductive paper and the PEDOT-PSS conductive paper retain excellent conductivity even after being heated to 300 ° C. Also confirmed to be excellent.
  • Both the carbon nanotube conductive paper and the PEDOT-PSS conductive paper can be recycled using water.
  • these conductive papers are immersed in water, hydrogen bonds between the conductive celluloses are weakened by water.
  • the conductive cellulose forming the paper rapidly dissolves in water and returns to the dispersion in which the conductive cellulose is dispersed. Thereafter, by drying the obtained dispersion, conductive paper can be formed without additional steps such as purification. Such regeneration of the conductive paper can be performed in exactly the same manner for a circuit pattern formed by printing.
  • FIG. 10 is a graph showing the change in conductivity when the carbon nanotube conductive paper and PEDOT-PSS conductive paper produced in this example are recycled.
  • FIG. 11 is a planar SEM photograph of carbon nanotube conductive paper and PEDOT-PSS conductive paper after recycling.
  • carbon nanotube conductive paper and PEDOT-PSS conductive paper are stirred in water at 30 ° C. for 1 hour to dissolve these conductive papers to obtain a carbon nanotube dispersed aqueous solution and a PEDOT-PSS dispersed gel aqueous solution.
  • the obtained dispersion is again poured onto the PTFE plate by drop casting, air-dried for 24 hours, and regenerated as carbon nanotube conductive paper and PEDOT-PSS conductive paper, respectively.
  • the above process was set as one cycle, and 10 times of recycling was performed as shown in FIG. 10, and the conductivity was measured every time it was recycled.
  • the conductive paper becomes hydrophilic when made using a hydrophilic ionic liquid, and becomes hydrophobic when a hydrophobic ionic liquid is used instead of the hydrophilic ionic liquid.
  • hydrophobic conductive paper in the previous manufacturing process of carbon nanotube conductive paper, DEMETFSI was used as the hydrophobic ionic liquid, and ethanol was used to disperse the carbon nanotube dispersion gel.
  • a carbon nanotube conductive paper was prepared. The ratio of the content of the single-walled carbon nanotube and the ionic liquid (DEMETFSI) in the hydrophobic carbon nanotube conductive paper was 1: 1.
  • a hydrophobic PEDOT-PSS conductive paper was prepared using DEMETFSI as a hydrophobic ionic liquid and ethanol as a dispersion medium in the previous manufacturing process of PEDOT-PSS conductive paper.
  • FIG. 12 (a) is a graph comparing the change in conductivity with respect to the cellulose content for hydrophilic carbon nanotube conductive paper and hydrophobic carbon nanotube conductive paper.
  • FIG. 12 (b) is a graph comparing the change in conductivity with respect to the cellulose content for hydrophilic PEDOT-PSS conductive paper and hydrophobic PEDOT-PSS conductive paper.
  • FIG. 13 is a graph showing changes in resistance values when the hydrophilic and hydrophobic carbon nanotube conductive paper and the hydrophilic and hydrophobic carbon nanotube conductive paper are immersed in water, respectively.
  • the resistance value of the hydrophobic carbon nanotube conductive paper did not change even when immersed in water.
  • the resistance value of the hydrophilic carbon nanotube conductive paper starts to increase immediately after immersion. This is because the hydrophilic carbon nanotube conductive paper begins to dissolve in water within a few seconds.
  • FIG. 14 shows a carbon nanotube conductive paper (indicated as “SG” in the figure) using a single-walled carbon nanotube produced by a super-growth method as a conductive substance, and a single-walled carbon nanotube produced by a commercially available HiPco method. It is a figure which shows the comparison with the used carbon nanotube conductive paper (it shows as "HiPco” in a figure).
  • the carbon nanotube conductive paper (SG) using single-walled carbon nanotubes by the super-growth method has a much larger conductive property than the carbon nanotube conductive paper (HiPco) using single-walled carbon nanotubes by the HiPco method. Showed the rate.
  • the carbon nanotube conductive paper using single-walled carbon nanotubes by a commercially available HiPco method as the conductive material has a conductivity of 5.7 S / cm, which is sufficiently higher than that of conventionally known conductive paper.
  • the conductive paper using the single-walled carbon nanotubes by the super-growth method further obtained a conductivity of 10 times or more. It can be seen that a large aspect ratio of single-walled carbon nanotubes by the super-growth method is important in obtaining a large electrical conductivity.
  • the surface of the conductive paper using single-walled carbon nanotubes by the super-growth method was much smoother than the surface of the conductive paper using single-walled carbon nanotubes by the HiPco method. This means that single-walled carbon nanotubes obtained by the super-growth method can be uniformly dispersed in cellulose.
  • FIG. 15A is a photograph of a touch sensor made of only paper including 8 ⁇ 8 conductive paper capacitors connected in the vertical and horizontal directions by paper wiring.
  • FIG. 15B is a circuit diagram of the touch sensor.
  • FIG. 16A is a schematic diagram of 2 ⁇ 2 cells of the touch sensor shown in FIG.
  • FIG. 16B is an explanatory diagram showing the change in the capacity of the cell of the touch sensor as a function of time.
  • the touch sensor 100 includes a conductive paper wiring 102 extending vertically and horizontally, and a conductive paper capacitor 101 (size: 5 ⁇ 5 mm) formed corresponding to the intersection of the conductive paper wiring 102. 2 ).
  • a plurality of conductive paper capacitors 101 arranged in a matrix form individual cells of the touch sensor 100.
  • the touch sensor 100 has a configuration in which conductive paper patterns 105 are formed on both surfaces of an insulating paper 103 having a thickness of 15 ⁇ m.
  • the conductive paper pattern 105 formed on the upper surface of the insulating paper 103 has a rectangular electrode 101a and a conductive paper wiring (bit line) 102a.
  • the conductive paper pattern 105 formed on the lower surface of the insulating paper 103 has a rectangular electrode 101b and a conductive paper wiring 102b (word line).
  • the electrode 101a and the electrode 101b arranged to face each other and the insulating paper 103 sandwiched therebetween constitute the conductive paper capacitor 101.
  • FIG. 16 (b) Changes from 45 pF to 150 pF, for example. Thereby, the position touched by the finger on the touch sensor 100 can be detected.
  • the response time of the touch sensor 100 is less than 100 milliseconds, and this high sensitivity and high-speed response can be realized by fully utilizing the large conductivity of the conductive paper of the present invention.
  • a conductive paper and a conductive cellulose composition having sufficient conductivity and elasticity can be provided.
  • These conductive paper and conductive cellulose composition can be suitably used for conductive members of various articles, and can be particularly suitably used for electronic devices.
  • the conductive paper of the present invention can be easily recycled in the same way as ordinary paper, and has extremely great advantages not only from the viewpoint of resource saving and environmental protection, but also from the viewpoint of the efficiency of creating electrical and electronic circuits. It is what brings.

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Abstract

L'invention porte sur un papier conducteur et sur une composition de cellulose conductrice, qui sont caractérisés par le fait qu'ils sont un mélange de cellulose et de matériau conducteur. Ce papier conducteur et la composition de cellulose conductrice ont une conductivité élevée, sont particulièrement appropriés pour être utilisés dans des dispositifs électroniques et peuvent être dissous dans des liquides et facilement recyclés de la même manière que du papier ordinaire.
PCT/JP2009/052322 2008-02-11 2009-02-12 Papier conducteur et son procédé de fabrication, composition de cellulose conductrice et son procédé de fabrication, articles et dispositifs électroniques Ceased WO2009101985A1 (fr)

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011118407A1 (fr) 2010-03-25 2011-09-29 凸版印刷株式会社 Film conducteur et procédé de fabrication associé
JP2011241499A (ja) * 2010-05-18 2011-12-01 Yokohama National Univ カーボンナノチューブを含む物品
WO2012023989A2 (fr) 2010-08-20 2012-02-23 Rhodia Operations Compositions de polymère, films en polymère, gels en polymère, mousses en polymère et dispositifs électroniques contenant de tels films, gels, et mousses
CN102677546A (zh) * 2012-05-02 2012-09-19 清华大学 一种离子液体包裹的薄壁碳纳米管的纸及其制备方法
JP2012236983A (ja) * 2011-04-28 2012-12-06 Nagoya Univ 導電性組成物
JP2013216766A (ja) * 2012-04-06 2013-10-24 Nagoya Univ 導電性組成物
WO2014030556A1 (fr) * 2012-08-23 2014-02-27 独立行政法人科学技術振興機構 Nanomatière de carbone, composition, matière conductrice et son procédé de fabrication
JP2014189932A (ja) * 2013-03-28 2014-10-06 Nippon Zeon Co Ltd 不織布
JP2015019806A (ja) * 2013-07-18 2015-02-02 独立行政法人科学技術振興機構 生体適合性電極構造体及びその製造方法、並びに、デバイス及びその製造方法
JPWO2014054586A1 (ja) * 2012-10-02 2016-08-25 国立研究開発法人科学技術振興機構 信号検出装置および信号検出方法
EP2949624A4 (fr) * 2013-01-24 2017-01-04 Zeon Corporation Dispersion de nanotubes de carbone, procédé de fabrication de cette dispersion, composition de nanotubes de carbone, et procédé de fabrication de cette composition
JP2017502495A (ja) * 2013-11-05 2017-01-19 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア グラフェン酸化物とカーボンナノチューブのインク及び、これを生成する方法
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JP2020023692A (ja) * 2018-08-01 2020-02-13 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ 導電性高分子複合材料およびコンデンサ
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CN115182192A (zh) * 2022-07-14 2022-10-14 陕西科技大学 一种银基导电纸及其制备方法、应用
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WO2025176312A1 (fr) * 2024-02-23 2025-08-28 Ntt Research, Inc. Feuille conductrice pour une électrode d'un biocapteur et/ou d'un capteur d'alcool

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102292189B1 (ko) * 2019-10-23 2021-08-24 고려대학교 산학협력단 유기 이온 전도성 폴리머 겔 탄성체 및 이의 제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003323897A (ja) * 2002-05-01 2003-11-14 Mitsubishi Rayon Co Ltd 炭素繊維紙、それを用いた燃料電池用多孔質炭素電極とその基材、および膜・電極接合体
JP3676337B2 (ja) * 2002-10-23 2005-07-27 独立行政法人科学技術振興機構 カーボンナノチューブとイオン性液体とから成るゲル状組成物とその製造方法
JP2005260214A (ja) * 2004-02-12 2005-09-22 Toray Ind Inc 電磁波シールド材、立体構造体、電磁波シールド性内装材、および画像表示装置
JP2007329107A (ja) * 2006-06-09 2007-12-20 Arisawa Mfg Co Ltd リチウムイオン二次電池

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0219599A (ja) * 1988-07-05 1990-01-23 Tokai Carbon Co Ltd 導電紙の製造方法
JP2821762B2 (ja) * 1989-03-27 1998-11-05 白水化学工業株式会社 粉末状導電性付与剤及びそれを用いた帯電防止体
JPH05262509A (ja) * 1991-06-13 1993-10-12 Japan Synthetic Rubber Co Ltd カーボンブラック水性分散体およびカーボンブラック含有紙
US6808557B2 (en) * 2001-10-03 2004-10-26 The University Of Alabama Cellulose matrix encapsulation and method
JP4691703B2 (ja) * 2005-03-31 2011-06-01 独立行政法人産業技術総合研究所 アクチュエータ素子およびその製造方法
JP4873453B2 (ja) * 2005-03-31 2012-02-08 独立行政法人産業技術総合研究所 導電性薄膜、アクチュエータ素子及びその製造方法
EP2204493A4 (fr) * 2007-10-23 2010-11-10 Tokushu Paper Mfg Co Ltd Article en forme de feuille et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003323897A (ja) * 2002-05-01 2003-11-14 Mitsubishi Rayon Co Ltd 炭素繊維紙、それを用いた燃料電池用多孔質炭素電極とその基材、および膜・電極接合体
JP3676337B2 (ja) * 2002-10-23 2005-07-27 独立行政法人科学技術振興機構 カーボンナノチューブとイオン性液体とから成るゲル状組成物とその製造方法
JP2005260214A (ja) * 2004-02-12 2005-09-22 Toray Ind Inc 電磁波シールド材、立体構造体、電磁波シールド性内装材、および画像表示装置
JP2007329107A (ja) * 2006-06-09 2007-12-20 Arisawa Mfg Co Ltd リチウムイオン二次電池

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