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WO2006008978A1 - Méthode pour produire un corps contenant des nanotubes de carbone - Google Patents

Méthode pour produire un corps contenant des nanotubes de carbone Download PDF

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Publication number
WO2006008978A1
WO2006008978A1 PCT/JP2005/012586 JP2005012586W WO2006008978A1 WO 2006008978 A1 WO2006008978 A1 WO 2006008978A1 JP 2005012586 W JP2005012586 W JP 2005012586W WO 2006008978 A1 WO2006008978 A1 WO 2006008978A1
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WO
WIPO (PCT)
Prior art keywords
carbon nanotube
coating
producing
containing body
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/012586
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English (en)
Japanese (ja)
Inventor
Yoshikazu Kondo
Atsushi Saito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2006528975A priority Critical patent/JP4735540B2/ja
Publication of WO2006008978A1 publication Critical patent/WO2006008978A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to a method for producing a carbon nanotube-containing body.
  • Group IV element “Carbon” constitutes the most diverse group of substances in the periodic table b
  • carbon tubes or “carbon nanotubes,” are now highly anticipated as materials that lead nanotechnology, which is regarded as a fundamental technology in the 21st century.
  • the diversity of structures and functions of carbon materials depends on the carbon atoms adopting the sp, sp 2 , sp 3 bonding method, which is an excellent individuality of carbon, and the same group IV elements such as key elements and germanium.
  • the diversity of this bond is the root of the diversity of rare carbon species.
  • carbon nanotubes are composed of a single carbon atom !, semiconductors, metals, and electronic properties vary greatly depending on the structure. This is because the diversity of carbon bonds was reflected additively. In other words, carbon nanotubes themselves are rich and diverse materials, and are expected to be applied in a wide range. Even with the same sp 2 carbon, fullerenes such as graphite, carbon nanotube, and C have different geometrical structures (bonding
  • the boundary condition for the electron wave function changes due to the change of the dimension of spread to 2D, quasi-1D, and quasi0D), and the state density function of the electron has a band structure as a solid and Van Hove divergence.
  • Patent Document 1 An example of a thin film containing the carbon nanotube is disclosed in Patent Document 1.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2003-138040
  • carbon nanotubes have excellent characteristics when the electronic properties change depending on the structure or when the rigidity of the film is improved by being contained in the film. Although there are great expectations for availability, there are still many unknowns.
  • An object of the present invention is to provide a method for producing a carbon nanotube-containing body containing a carbon nanotube and exhibiting an optically excellent function.
  • the method for producing a carbon nanotube-containing body of the present invention comprises a coating step of applying a dispersion containing carbon nanotubes and a binder onto a predetermined support,
  • the dispersion liquid is used as a first coating liquid, and the first coating liquid is coated on the support while applying a shear stress to the first coating liquid.
  • One aspect of the present invention is:
  • the first coating liquid is coated on the support so that the carbon nanotubes are oriented in a certain direction.
  • One aspect of the present invention is:
  • the coating process in the coating process is performed by a bar method.
  • the coating process in the coating process is performed by a stripe coating method.
  • the coating process is repeated a plurality of times.
  • One aspect of the present invention is:
  • a second coating step of coating the second coating solution on the coated first coating solution using a binder-containing solution containing a binder as the second coating solution is provided. It is a feature.
  • the applicator method, extrusion method, slide bead method, curtain method, gravure method, spray method, air doctor method, date method, and blade method are all applied in the second application process. It is characterized by being! /
  • the second application step is repeated a plurality of times.
  • the carbon nanotube is a single-walled carbon nanotube.
  • the noinda is water-soluble.
  • the binder is characterized by having no optical anisotropy.
  • the noinda is gelatin.
  • the first coating liquid contains a hardening agent.
  • the alignment step uses an electric field.
  • the first coating solution in order to apply the first coating solution onto the support while applying a shear stress to the first coating solution, the first coating solution is stretched in the direction in which the shear stress acts. Can be coated on a support. Therefore, in the carbon nanotube-containing film composed of the first coating solution, the carbon nanotubes can be oriented in a desired direction according to the shear stress, and the carbon nanotube-containing film can exhibit an optically excellent function. it can.
  • carbon nanotubes can be oriented in the same fixed direction in the carbon nanotube-containing film.
  • the carbon nanotube-containing film can be gel-dried without disturbing the orientation of the carbon nanotubes.
  • a carbon nanotube-containing film over a plurality of layers can be formed on a support, and a carbon nanotube-containing film containing a large amount of carbon nanotubes can be provided.
  • the surface of the carbon nanotube-containing film can be smoothed.
  • light having a specific wavelength can be absorbed to emit light having a specific wavelength.
  • the solubility with the first and second coating liquids can be increased.
  • the carbon nanotubes can be prevented from agglomerating in the first coating solution and can be stably dispersed.
  • FIG. 1 is a perspective view showing a schematic configuration of a carbon nanotube-containing film 1.
  • FIG. 2 is a side view showing a schematic configuration of a film forming apparatus 10.
  • FIG. 3 is a cross-sectional view showing a schematic configuration of the wire bar 14.
  • FIG. 4 is a drawing showing the polarization absorption spectrum of Sample A.
  • FIG. 5 is a drawing showing the fluorescence spectrum of Sample A.
  • FIG. 6 is a drawing showing a modification of FIG. 1.
  • FIG. 7 is a side view showing a schematic configuration of a coating apparatus 30.
  • FIG. 8 is a side view showing a schematic configuration of the electric field orientation device 40.
  • FIG. 1 is a perspective view showing a schematic configuration of the carbon nanotube-containing body 1.
  • the carbon nanotube-containing body 1 includes a support 2, and the carbon nanotube-containing film 4 containing a large number of carbon nanotubes 3, 3,.
  • An overcoat film 5 that covers the containing film 4 is formed.
  • a part of the support 2 is cut and illustrated. In addition, it has a film shape.
  • the support 2 is made of a plastic film.
  • plastic film materials include polyethylene, polypropylene and other polyolefins, polyacetate butyl, polychlorinated butyl, polystyrene and other butyl polymers, 6, 6-nylon, 6-nylon and other polyamides, polyethylene terephthalate (hereinafter referred to as “polyethylene terephthalate”).
  • Cell ports such as polyethylene, 2,6-naphthalenedicarboxylate (hereinafter “PEN”), polyester, polycarbonate, cellulose triacetate (hereinafter “TAC”), cellulose diacetate, etc. And so on.
  • PE used as photographic polyester
  • T PEN, and TAC are preferably applied.
  • the support 2 may be subjected to various surface treatments as described in JP-A-9-108613.
  • the support 2 can be applied even if it has insulating, conductive, and semiconducting properties such as! / And misalignment, for example, single crystal silicon, quartz, glass, quartz glass, ceramics, gold Materials such as genus and silicon can be used.
  • the support 2 is composed of glass, it is desirable to use transparent glass such as soda lime glass, low soda glass, lead alkali silicate glass, borosilicate glass, etc. Especially high strain point low soda glass, low soda glass.
  • the support 2 is constituted by the following.
  • the support 2 is made of ceramic, alumina, zirconium, titanium dioxide, silicon nitride, silicon carbide, or the like can be used.
  • the carbon nanotube-containing film 4 is a film in which the carbon nanotubes 3 are dispersed (isolated) independently of each other, and the carbon nanotubes 3 are oriented in a certain direction in the carbon nanotube-containing film 4.
  • Carbon nanotubes 3, 3, are those having a fiber diameter (D) of about 1-1 nm and a length (L) of about 0.1-1,000 / zm.
  • LZD is an aggregate of carbon having a large aspect ratio of about 100 to 10,000 and having a tubular shape.
  • the carbon nanotubes 3, 3, ... can be manufactured by methods such as arc discharge, laser deposition, and catalytic chemical vapor deposition. The manufacturing method is disclosed in
  • a single-walled carbon nanotube is a tube of monoatomic layer thickness in which a single darafen (monoatomic carbon hexagonal network surface) is closed in a cylindrical shape.
  • a single darafen monoatomic carbon hexagonal network surface
  • So-called carbon nanotubes can be applied to single-walled, multi-walled, and misaligned types.
  • Carbon nanotubes 3, 3, ... for practical use include single-walled carbon nanotubes (available from Carbon Nanotechnologies) produced by the HiPco (High Pressure CO) method, ACCVD ( Single-walled carbon nanotubes produced by the Alcohol Catalytic Chemical Vapor Deposition) method can be suitably used. Furthermore, Hyperion's Graphite fibril (registered trademark), Showa Denko, ASISH Pyrograf III (registered trademark), etc. Can also be used. Of course, the carbon nanotube 3 is not limited to these.
  • the carbon nanotubes 3, 3,... are not limited to carbon products, and may be other things such as BN (boron nitride) nanotubes in which part or all of the carbon is replaced with boron and nitrogen. .
  • each carbon nanotube 3 is oriented means that the carbon nanotube-containing film 4
  • the polarization absorption spectrum is measured under the same conditions, it means that there is a difference in absorption depending on the angle of the incident polarized light. That is, the carbon nanotubes that are not oriented
  • the polarization absorption spectrum of the Ub-containing film has a constant absorption peak intensity at a specific wavelength regardless of the polarization incident angle
  • the polarized absorption spectrum of the aligned carbon nanotube-containing film 4 has a specific wavelength corresponding to the absorption peak. There is a polarization incident angle in which no absorption peak exists (or an absorption peak weaker than the absorption peak exists).
  • the carbon nanotubes 3 are dispersed independently from each other” means that the carbon nanotube-containing film 4 emits light when irradiated with light of a specific wavelength.
  • the carbon nanotube-containing film 4 is prepared by dispersing and stirring a large number of the above-mentioned carbon nanotubes 3, 3,..., A surfactant, a solvent and a transparent binder, and the dispersion liquid is formed on the support 2. A hardener and some additives may be added to the coating solution.
  • any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.
  • alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalenes are used.
  • non-ionic surfactants such as oxide derivatives and alkyl esters of sugars.
  • a fluorine-containing surfactant can also be preferably used.
  • examples include fluorine-containing alkyl-based surfactants, fluorine-containing alkyl cationic surfactants, fluorine-substituted alkylene oxide surfactants, perfluorocyclohexane surfactants, etc. Is mentioned.
  • Solvents include, for example, water such as heavy water, aliphatic hydrocarbons such as heptane, petroleum benzine, and cyclohexane, aromatic hydrocarbons such as benzene, xylene, and ethylbenzene, methylene chloride, carbon tetrachloride, and trichloro.
  • Halogenated hydrocarbons such as ethane, methanol Alcohols such as ethanol, n -propanol, ethers such as ethyl ether and tetrahydrofuran, ketones such as methyl ethyl ketone and cyclohexanone, esters such as methyl formate and acetic acid —n-propyl, and ethylene glycol monoethyl ether.
  • Divalent alcohol derivatives, fatty acids such as acetic acid, phenol, and other compounds containing nitrogen and sulfur can be used. These solvents may be used alone or in combination of two or more.
  • An ionic liquid can also be used as a solvent.
  • an ionic liquid is also called a room temperature molten salt or simply a molten salt, and exhibits a molten state in a wide temperature range including room temperature (room temperature). It is salt.
  • the solvent various ionic liquids known in the art can be used, but those which are stable at room temperature (room temperature) or as close to room temperature as possible and exhibiting a liquid are preferable.
  • gelatin can be suitably used as the transparent binder.
  • Such gelatin is generally produced from cow bone, cow skin, pork skin, etc. as raw materials, and in the production process from collagen, it is treated with alkali-treated gelatin accompanied by treatment with lime or acid treatment with hydrochloric acid or the like. There is gelatin, and any gelatin can be applied as a component of the coating solution.
  • Gelatin preferably has a jelly strength (by PAGI method) of 250 g or more.
  • Gelatin preferably has a calcium content (according to the PAGI method) of 4000 ppm or less, particularly preferably 3000 ppm or less.
  • Gelatin is usually alkali-treated gelatin or acid-treated gelatin having a molecular weight of about 100,000. Oxidized gelatin, enzyme-treated gelatin as described in Bull. So Sci. Photo. Japan. No. 16. P30 (1966) can be preferably used, and chemically modified gelatin is also preferably used. Examples of the chemically modified gelatin include gelatin substituted with an amino group described in JP-A-5-72658, JP-A-9 197595, JP-A-9251193, and the like.
  • the gelatin preferably has a methionine content of less than 30 ⁇ mol Zg, more preferably less than 20 ⁇ mol Zg, and even more preferably 0.1 to 10 mol Zg.
  • oxidation treatment of alkali-treated gelatin with an oxidizing agent is effective.
  • the oxidizing agent that can be used in the acid treatment of gelatin include hydrogen peroxide, ozone, peroxy acid, halogen, thiosulfonic acid compound, quinones, and organic peracids. It is most preferable to use hydrogen.
  • the transparent binder in addition to the above gelatin, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc.
  • a variety of synthetic or semi-synthetic hydrophilic polymer materials such as mono- or copolymers of can be applied.
  • Hardeners harden the transparent binder centering on the gelatin, hygroscopicity of the coating film, The film strength and the like can be adjusted by the amount.
  • hardeners include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucoha genoic acid.
  • the carbon nanotube-containing film 4 may be composed of one layer, or may be composed of two or more layers.
  • the overcoat film 5 is formed for the purpose of smoothing the surface of the carbon nanotube-containing film 4, and is formed on the carbon nanotube-containing film 4.
  • the overcoat film 5 is preferably formed by a well-known coating method, and the coating liquid is the same as the coating liquid power constituting the carbon nanotube-containing film 4 except for the carbon nanotubes 3, 3,. So it is better to configure.
  • the overcoat film 5 is preferably made of gelatin, but may be made of greaves.
  • a curable resin can be used.
  • the overcoat film 5 made of curable resin may have various functions other than the overcoat.
  • the overcoat film 5 made of curable resin may be a film formed by polymerizing a component containing at least one monomer having an ethylenically unsaturated bond.
  • a film formed by polymerizing a component containing a monomer having an ethylenically unsaturated bond a film formed by curing actinic ray-cured resin or heat-cured resin is preferably used, but particularly preferably used. Is an actinic radiation curable resin film.
  • Actinic radiation curable resin film refers to a film containing, as a main component, a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
  • Typical examples of the actinic ray curable resin include an ultraviolet curable resin and an electron beam curable resin.
  • the active ray curable resin is a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams. A little.
  • Examples of the ultraviolet curable resin include, for example, an ultraviolet curable acrylic urethane resin, an ultraviolet ray curable polyester acrylate resin, and an ultraviolet curable epoxy acrylate resin.
  • UV curable polyol acrylate resin or UV curable epoxy resin UV curable polyol acrylate resin or UV curable epoxy resin.
  • Specific examples include, for example, trimethylolpropane tritalylate, ditrimethylol propane pantetratalylate, pentaerythritol tritalylate, pentaerythritol tetratalate, dipentaerythritol hexaatalylate, alkyl-modified dipentaerylate.
  • Examples include sitolitol pentaacrylate.
  • the ultraviolet curable acrylic urethane resin generally 2-hydroxyethyl talylate
  • 2-hydroxyethyl is further added to a product obtained by reacting a polyester polyol with a isocyanate monomer or a prepolymer.
  • Metatalylate hereinafter referred to as only including talate is included in acrylate
  • 2-hydroxypropyl acrylate, etc. which are easily formed by reacting an acrylate monomer having a hydroxyl group.
  • JP-A-59-151110 can be used.
  • Examples of UV-curable polyester acrylate-based resins generally include those that are easily formed by reacting 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers to polyester polyol. And those described in JP-A-59-151112 can be used.
  • Examples of the ultraviolet curable epoxy acrylate resin include those produced by reacting an epoxy acrylate with an oligomer and adding a reactive diluent and a photoinitiator. And those described in JP-A-1-105738 can be used.
  • photoinitiators include benzoin and derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, a amioxime ester, thixanthone, and the like. . Use with photosensitizers.
  • the above photoinitiator can also be used as a photosensitizer.
  • epoxy acrylate When the photoinitiator is used, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
  • Examples of the resin monomer include, for example, a monomer having an unsaturated double bond such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, styrene, and the like.
  • a monomer having an unsaturated double bond such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, styrene, and the like.
  • the following general monomers can be mentioned.
  • ethylene glycol ditalylate propylene glycol ditalylate, dibutenebenzene, 1,4-cyclohexane diatalylate, 1,4-cyclohexyldimethyl asialate
  • examples thereof include the above-mentioned rates, the above-mentioned trimethylol-type pantriatalylate, and pentaerythritol tetraacrylic ester.
  • actinic radiation curable resin films can be applied by a known method.
  • a light source for curing the ultraviolet curable resin by a photocuring reaction any light source that generates ultraviolet light can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, etc. can be used.
  • the resin constituting the overcoat film 5 for example, butyl chloride / Z-acetate copolymer, vinyl chloride / vinyl acetate, vinyl acetate / butyl alcohol copolymer, partially hydrolyzed Salt-Buhl Z vinyl acetate copolymer, Vinyl chloride Z chloride vinylidene copolymer, Bulle Z acrylonitrile copolymer, Ethylene z butyl alcohol copolymer, Chlorinated polychloride butyl, Ethylene z butyl chloride copolymer, Ethylene Z butyl acetate copolymer Cellulose homopolymer or copolymer, Cellulose nitrite, Cenorelose acetate propionate, Cenorelose diacetate, Cenorel lip triacetate, Cenorelose acetate phthalate, Cenorelose acetate butyrate Copolymers of rain acid and z or acrylic acid, acrylic acid ester
  • the overcoat film 5 may be composed of one layer as in the case of the carbon nanotube-containing film 4, or may be composed of two or more layers.
  • FIG. 2 is a side view showing a schematic configuration of the film forming apparatus 10.
  • the film forming apparatus 10 includes an original winding roller 11 around which a long support 2 is wound. Below the original winding roller 11, a conveying roller 12 that conveys the support 2 while supporting it is disposed. The transport roller 12 rotates in the counterclockwise direction in FIG. 2 and transports the support 2 in the rotational direction!
  • a coating device 13 for coating the coating liquid on the support 2 is disposed below the transport roller 12.
  • the coating device 13 is disposed below the conveying roller 12 so as to face the conveying roller 12.
  • the coating device 13 has a configuration capable of storing a certain amount of coating liquid, and applies the stored coating liquid toward the support 2 supported by the transport roller 12.
  • FIG. 3 is a cross-sectional view showing a schematic configuration of the wire bar 14.
  • the wire bar 14 has a long and cylindrical rod 14a, and has a configuration in which a wire 14b such as a stainless wire or a piano wire is wound around the rod 14a.
  • the wire bar 14 rotates in a clockwise direction in Fig. 2 at a speed slightly slower than the conveying speed of the support 2 and rotates so as to synchronize with the support 2 passing near the wire bar 14. However, the coating liquid on the support 2 is being scraped off.
  • the wire bar 14 is held at a predetermined position by the holder 15, and the distance between the wire bar 14 and the support 2 is kept constant.
  • the coating solution applied to the support 2 can be uniformly sprinkled off.
  • a receiver 16 that receives the coating liquid sprinkled off by the wire bar 14 is disposed in the vicinity of the wire bar 14 and downstream of the wire bar 14 in the transport direction of the support 2.
  • a tank 18 is connected to the receiver 16 via a tube 17. The tank 18 temporarily stores the coating liquid received by the receiver 16, and the coating liquid received by the receiver 16 is temporarily stored in the tank 18 through the tube 17.
  • the tank 18 and the coating device 13 are connected to each other by a tube 20 via a pump 19.
  • the coating liquid stored in the tank 18 is supplied to the coating apparatus 13 through the pump 19 and the tube 20, and the coating liquid is sequentially applied to the coating apparatus 13.
  • the receiver 16 are configured to circulate.
  • a cooling chamber 24 for cooling the coating liquid film applied to the support 2 and the coating liquid film applied to the support 2 are dried.
  • a drying chamber 25 and a take-up roller 26 that winds up the support 2 are provided.
  • the cooling chamber 24 is maintained in a low temperature atmosphere below a certain temperature, and has a configuration in which the film on the support 2 passing through the cooling chamber 24 is cooled and gelled.
  • the drying chamber 25 is a chamber in which air at a constant temperature is circulated in the room, and has a configuration in which air is blown onto the film on the support 2 to dry the film.
  • the feeding roller 26 rotates in the counterclockwise direction in FIG. 2, and takes up the support 2 that has passed through the cooling chamber 24 and the drying chamber 25.
  • an additive such as the above-mentioned carbon nanotubes 3, 3,..., A surfactant is added to a solvent to prepare a carbon nanotube-containing liquid (preparation step).
  • a surfactant is added to a solvent to prepare a carbon nanotube-containing liquid (preparation step).
  • SDS Sodium Dodecyl Sulfate
  • heavy water as a solvent
  • a large number of carbon nanotubes 3 , 3, ... and a surfactant are added to a solvent to prepare a carbon nanotube-containing solution.
  • the carbon nanotube-containing liquid is sequentially subjected to a dispersion process and an ultracentrifugation process (dispersion process, separation process), and the supernatant is removed from the carbon nanotube-containing liquid after ultracentrifugation. Collecting (extraction step), a carbon nanotube dispersion liquid in which each carbon nanotube 3 is dispersed in a solvent is obtained.
  • Dispersion processing in the dispersion step includes well-known stirring processing, ultrasonic processing, and the like.
  • Dispersers used for the processing in the dispersion step include high-speed stirring type dispersing devices having a large shear force, There are dispersers that give strong ultrasonic energy.
  • the disperser is a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic distortion ultrasonic generator, an emulsifying device having a Paulman whistle, or the like.
  • High-speed agitating type dispersers that are preferred for use in the dispersion process include high-speed rotation in the liquid (500 to 15), such as dissolvers, polytrons, homomixers, homoplenders, kedy mills, and jet agitators. , OOOrpm, preferably 2,000 to 4, OOOrpm).
  • the high-speed agitation type disperser is also called a dissolver or a high-speed impeller disperser.
  • saw-tooth blades are alternately arranged on a high-speed rotating shaft.
  • a device equipped with an impeller that is bent in the vertical direction is also a preferred example of a high-speed stirring type disperser.
  • the carbon nanotube dispersion and the transparent binder are mixed, and each carbon nanotube 3 is stirred in the transparent binder (stirring step).
  • gelatin for example, when gelatin is applied as a transparent binder, gelatin (or gelatin solution) is added to the strong bon nanotube dispersion.
  • Gelatin dissolution Leave the solution at room temperature for a period of time to swell and then warm, or dissolve it immediately after the addition. If necessary, the dispersion process of the dispersion process may be performed again.
  • the transparent binder is dissolved in the carbon nanotube dispersion liquid to obtain the carbon nanotube dispersion coating liquid as the first coating liquid that is used for the processing in the coating process described later.
  • the carbon nanotube dispersion coating liquid constitutes the carbon nanotube dispersion film 4 in the subsequent processing, and the carbon nanotube dispersion coating liquid is said to cure the carbon nanotube dispersion film 4.
  • the above hardener may be added before coating.
  • a carbon nanotube dispersion coating solution is applied onto the support 2 by a wire bar method (application step), and the carbon nanotube-containing film 4 composed of the carbon nanotube dispersion coating solution is applied onto the support 2 Form a film.
  • the support 12 passes through the transport roller 12, the support 12 passes in the vicinity of the wire bar 14. At this time, the carbon nanotube dispersion coating solution applied on the support 12 is scraped off by the wire bar 14 to form a carbon nanotube dispersion film 4 having a uniform film thickness on the support 12. .
  • the carbon nanotube dispersion coating solution applied on the support 2 is accompanied by the transport of the support 2, and the transport direction of the support 2 depends on the action in the transport direction and the presence of the wire bar 14. It is conveyed while being greatly stretched. At this time, a shear stress is applied to the carbon nanotube dispersion coating liquid, and the carbon nanotube dispersion coating liquid is subjected to the shear stress. It is applied onto the support 2 while receiving.
  • the carbon nanotubes 3 in the carbon nanotube dispersion coating solution are arrayed in a certain direction along the transport direction of the support 2 while being dispersed (isolated) independently of each other in the carbon nanotube dispersion coating solution. To be oriented. The most preferred orientation state of each carbon nanotube 3 is uniaxial orientation.
  • each carbon nanotube 3 transports the support 2. It will be in the direction and in the film plane.
  • the support 2 that has passed in the vicinity of the wire bar 14 passes between the second transport rollers 21 and 22 while being supported by the two second transport rollers 21 and 22.
  • an electric field is formed between the two second conveying rollers 21 and 22 by the AC power source 23, and an electric field is applied to the carbon nanotube-containing film 4 disposed between the second conveying ports 21 and 22. (Electric field alignment process).
  • the carbon nanotubes 3 in the carbon nanotube-containing film 4 are aligned with each other in a linear manner by pulling the ends together by electrostatic alignment to further improve the orientation in a certain direction in the coating step. It can be certain. That is, when a voltage is applied to the carbon nanotubes 3, 3,..., One end thereof is on one electrode (second transport roller 21 or second transport roller 22) side, and the other end is on the other electrode ( The positive and negative charges attract each other at the opposite ends of the carbon nanotubes 3, 3,... That are electrostatically oriented so that they are directed toward the second transport roller 22 or the second transport roller 21). Can be oriented upwards. Therefore, as shown in FIG.
  • the AC power supply 3 is applied as a voltage source and the voltage applied between the second transport rollers 21 and 22 is changed to the AC voltage, so that the second charge is transferred before the electric charge moves. It is considered that the positive and negative electrodes can be reversed by the transport roller 21 and the second transport roller 22 to prevent the aligned carbon nanotubes 3 from being separated.
  • the applied voltage applied between the conveying rollers 21 and 22 is preferably set to 1 to 15 kVZcm, but is not limited to this range. If the applied voltage is smaller than lkVZcm, the carbon nanotubes 3 may not be sufficiently oriented. If the applied voltage is greater than 15 kVZcm, the dielectric liquid may be disturbed and the orientation of the carbon nanotubes 3 may be disturbed. Therefore, it is preferable to set the applied voltage at 1 to 15 kVZcm.
  • the applied voltage can be appropriately adjusted according to the fluidity, viscosity, film thickness, and density of the carbon nanotubes 3, 3,.
  • the AC power supply 23 may be replaced with a DC power supply, and the voltage applied between the transport rollers 21 and 22 may be a DC voltage.
  • the applied voltage of the DC power supply may be set within the same range as described above, or may be changed as appropriate. Even in this case, for example, by actively imparting conductivity to the surface of each carbon nanotube, changing the dielectric liquid, or using a surfactant, the orientation of each carbon nanotube 3 is changed to an AC voltage. It can be increased.
  • the support 2 that has passed between the transport rollers 21 and 22 is carried into the cooling chamber 24.
  • the cooling chamber 24 is maintained in a low temperature atmosphere below a certain temperature, and the carbon nanotube-containing film 4 on the support 2 gels while being cooled while passing through the cooling chamber 24 (gelation step).
  • the gelling process it is preferable to quickly gel the carbon nanotube-containing film 4 on the support 2 U, U. If the carbon nanotube-containing film 4 is kept in a liquid state for a long time, the orientation of each carbon nanotube 3 is disturbed due to fluid phenomena such as liquid dripping and leveling, and the uniformity as a coating film is maintained. become unable. Therefore, immediately after the carbon nanotube dispersion coating solution is applied, the flow of the carbon nanotube-containing film 4 It is necessary to quickly reduce or eliminate sex. When gelatin is used as the transparent binder constituting the carbon nanotube-containing film 4, it can be easily gelled by cooling the carbon nanotube-containing film 4 and lowering the film temperature.
  • the inside of the cooling chamber 24 is preferably maintained in a low temperature atmosphere of 20 ° C or lower, preferably 15 ° C or lower, more preferably 10 ° C or lower.
  • the temperature varies depending on the temperature of the carbon nanotube-containing film 4, the wet film thickness of the carbon nanotube-containing film 4 before the gelling process, the thickness of the support 2, and the like. If the temperature of the carbon nanotube-containing film 4 immediately before being carried in is a normal coating solution temperature (35 to 50 ° C), the time for the carbon nanotube-containing film 4 to stay inside the cooling chamber 24 (the carbon nanotube-containing film) The time required for 4 to pass through the inside of the cooling chamber 24) is usually set in the range of 1 to: LOO seconds, preferably 5 to 50 seconds. Thereby, the fluidity of the coating film of the carbon nanotube-containing film 4 can be quickly reduced, the orientation of each carbon nanotube 3 is not disturbed, and the carbon nanotube-containing film 4 can be made uniform as a coating film.
  • the carbon nanotube-containing film 4 can be cured by the gelling process as long as the method can quickly cure the carbon nanotube-containing film 4 immediately after the application of the carbon nanotube dispersion coating solution.
  • a method of curing using various curable resins such as well-known UV (Ultra Violet) curable resins and thermosetting resins can also be applied.
  • the treatment by the gelation process does not sufficiently gel the carbon nanotube-containing film 4 to improve its viscosity and suppress the flow of the carbon nanotube-containing film 4 to the necessary minimum. As a thing.
  • the drying chamber 25 is a chamber in which air at a constant temperature is circulated in the room, and the carbon nanotube-containing film 4 on the support 2 is dried while receiving the circulating air while passing through the drying chamber 25. (Drying process).
  • the drying step is a step of removing the solvent of the carbon nanotube-containing film 4 and it is necessary to dry the carbon nanotube-containing film 4 so as not to disturb the alignment of the aligned carbon nanotubes 3. Therefore, when gelatin is used as the transparent binder, The carbon nanotube-containing film 4 is preferably dried at a low temperature so that the gelatin remains in a gelled state at a low temperature. In addition, when the fluidity of the carbon nanotube-containing film 4 is only reduced in the gelation step, it is preferable to dry the carbon nanotube-containing film 4 at a low temperature so that the fluidity is not improved.
  • the drying step it is preferable to dry the carbon nanotube-containing film 4 by blowing air of 20 to 70 ° C to the carbon nanotube-containing film 4.
  • the cooled region of the carbon nanotube-containing film 4 is immediately dried at a high temperature, the three-dimensional structure of the carbon nanotube-containing film 4 that has been formed is destroyed, and the carbon nanotube-containing film 4 of the carbon nanotube-containing film 4 is destroyed.
  • the flow of the carbon nanotubes 3 is disturbed, and the carbon nanotube-containing film 4 is not uniform as a coating film, so the temperature of the drying air in the drying chamber 25 is set to 50 ° C or lower. Is preferred.
  • the humidity of the wind in the drying process should normally be set in the range of 10-50%.
  • the relative humidity of 30-70% for a certain period of time for example, It is preferable to adjust the humidity for 20 to 180 seconds.
  • the support 2 carried out of the drying chamber 25 is wound around the scooping roller 26.
  • the carbon nanotube-containing film 4 can be formed on the support 2 by the first film formation method described above.
  • the force of applying the bar method using the wire bar 14 in the coating process is replaced by a coating process using a known stripe coating method. May be.
  • the electric field alignment step is provided in the first film forming method, the electric field alignment step is not necessary.
  • a plurality of carbon nanotube-containing films 4 may be formed on the support 2 by repeating the coating step, the gelation step, and the drying step a plurality of times.
  • the carbon nanotubes 3, 3, ... are omitted, and the other steps are the same as those in the preparation step, dispersion step, separation step, extraction step, and stirring step of the first film formation method.
  • an overcoat coating solution as a second coating solution is obtained.
  • the overcoat coating solution is applied onto the carbon nanotube-containing film 4 according to a known coating process (second coating step), and the overcoat film 5 is applied to the carbon nanotube-containing film 4 Form on top.
  • applicator method for example, applicator method, extrusion method, slide bead method, curtain method, gravure method, spray method, air doctor method, dip method, blade method, bar coating method, slot method, slide method, web
  • a coating method such as a tension method can be applied.
  • a chamber corresponding to the cooling chamber 24 in FIG. 2 is formed on the overcoat film 5 in the same manner as the gelling process and the drying process of the first film forming method. Pass through (second gelation step), and then pass through a chamber corresponding to the drying chamber 25 in FIG. 2 (second drying step).
  • the overcoat film 5 can be formed on the carbon nanotube-containing film 4 by the second film formation method described above.
  • the second coating step, the second gelling step, and the second drying step are repeated a plurality of times so that a plurality of layers are overlaid on the carbon nanotube-containing film 4. Even if coat film 5 is formed.
  • the support 2 In the above, an example in which a long and film-like one is applied as the support 2 has been described. However, as shown in FIG. 6, a substrate having a rectangular shape is applied as the support 2. May be. In this case, the support 2 should be made of the same material as above.
  • the coating apparatus 30 and the electric field alignment apparatus 40 shown in FIGS. 7 and 8 are applied to the first film forming method in the application process and the electric field alignment process.
  • the coating apparatus 30 has a tank 31 for storing the carbon nanotube dispersion coating liquid, and a coating roller 32 is disposed in the tank 31.
  • the application roller 32 rotates in the counterclockwise direction in FIG. 7 so as to transfer and apply the carbon nanotube dispersion coating liquid to the support 2 while supporting the support 2.
  • a wire bar 33 is disposed on the left side of the application roller 32, and the wire bar 33 is held at a predetermined position by a holder.
  • the wire bar 33 is the same as the wire bar 14 shown in FIG. 2, and the holder 34 is the same as the holder 15 shown in FIG. [0127]
  • the support 2 is transported in a state where the coating roller 32 and the wire bar 33 are rotated and supported by them. 32 transfers the carbon nanotube dispersion coating solution onto the support 2, and the wire bar 33 sprinkles off the coated carbon nanotube dispersion coating solution to form a carbon nanotube-containing film 4 on the support 2. .
  • the electric field orientation device 40 has four transport rollers 41 to 44 that transport while supporting the support 2.
  • An AC power supply 45 is disposed on each of the transport rollers 42 and 43, and an electric field is formed between the transport rollers 42 and 43.
  • the AC power supply 45 is the same as the AC power supply 23 in FIG. 2, and a DC power supply may be substituted.
  • conductive endless belts 46, 47 may be wound between the transport rollers 41, 42 and between the transport rollers 43, 44, respectively. ,.
  • the support 2 passes between the transport rollers 42 and 43 while being supported by the four transport rollers 41 to 44.
  • An electric field is applied to the nanotube dispersion film 4, and the carbon nanotubes 3 are oriented.
  • the carbon nanotube dispersion coating solution is referred to as “coating solution A”.
  • the coating treatment here was performed at a coating speed of 2 mZsec, and the quartz glass substrate was kept at 20 ° C. Thereafter, the quartz glass substrate on which the carbon nanotube-containing film was formed was cooled at 0 ° C. for 20 seconds. . After 20 seconds, wind at 25 ° C (relative humidity 15%) for 60 seconds, 45 ° C wind (relative humidity 25%) for 60 seconds, 50 ° C wind (relative humidity) 25%) for 60 seconds in order to dry the carbon nanotube-containing film, and the strength after drying.
  • the quartz glass substrate on which the single-bonn nanotube-containing film was formed was placed in an atmosphere at a temperature of 30 ° C and a relative humidity of 60%. Left for 1 hour. Repeat the above coating, cooling, and drying processes four times, A carbon nanotube-containing film was formed on a quartz glass substrate.
  • the quartz glass substrate on which the overcoat film was formed was cooled at 0 ° C for 20 seconds.
  • the polarization absorption spectrum of sample A was measured with a polarizer interposed between the light source and sample A.
  • the measurement of the polarization absorption spectrum is performed in the case of linearly polarized in the direction along the alignment direction of each carbon nanotube of sample A (direction corresponding to the moving direction of the wire bar) and in the direction orthogonal to the alignment direction. This was done in two cases, with linear polarization.
  • Figure 4 shows the measurement results of the polarization absorption spectrum of Sample A.
  • the solid line at the top shows the polarization absorption spectrum when linearly polarized in the direction along the alignment direction of each carbon nanotube of sample A
  • the solid line at the bottom shows the alignment direction of each carbon nanotube in sample A.
  • the polarization absorption spectrum when linearly polarized in the orthogonal direction is shown.
  • Fig. 4 Two polarized absorption absorption spectra shown here] The peaks around the wavelengths of 500 to 900 nm and 1000 to 150 Onm correspond to the carbon nanotubes in the carbon nanotube-containing film. Since there is a significant difference in absorption at the same wavelength between each peak in the upper polarized absorption spectrum and each peak in the lower polarized absorption spectrum, each carbon nanotube surely moves in the direction of movement of the wire bar. The orientation is in one direction along the axis.
  • FIG. 5 The measurement result of the fluorescence spectrum of Sample A is shown in FIG. In Fig. 5, the upper solid line shows the fluorescence spectrum when sample A is irradiated with 650 nm excitation light, and the lower solid line shows the fluorescence spectrum when sample A is irradiated with 720 nm excitation light.
  • the peak near the emission wavelength of 1050 nm is the carbon nanotube with the force vector (7, 5), and the peak near the emission wavelength of 1150 nm is the chiral vector force S (7, 6).
  • the carbon nanotubes from the presence of each peak at the emission wavelength of 1050 nm, near 1150 nm, when the bonbon nanotube-containing film assumed in sample A is irradiated with visible light having a wavelength of 650 nm as excitation light, It can be seen that near infrared rays having wavelengths of 1050 nm and 1150 nm are emitted.
  • the peak near the emission wavelength of 1120 nm is the carbon nanotube with the chiral vector (9, 4), and the peak near the emission wavelength of 1200 nm is the chiral vector (8, 6). Because of the presence of each peak at emission wavelengths near 1120 nm and 1200 nm, the carbon nanotube-containing film assumed in Sample A is irradiated with visible light having a wavelength of 720 nm as excitation light. It can be seen that near infrared light of 1120nm and 1200nm is emitted. This indicates that the carbon nanotubes in the contained film are dispersed independently (in an isolated state).
  • a Bulsulfone type hardener (compound of the chemical formula (H-6) in the above embodiment) is added to coating solution A50cc, and within 3 minutes, the coating solution A is kept on the market at 40 ° C. Extrusion was performed on a Sekiei glass substrate (100 mm X 300 mm X 0.5 m, manufactured by TechnoQuartz), and a carbon nanotube-containing film was formed on the Sekiei glass substrate.
  • the quartz glass substrate used here assumes the support 2 in the above embodiment.
  • the coating treatment here was performed at a coating speed of lmZsec, and the final coating thickness was 60 m.
  • the quartz glass substrate was passed between two conveying rollers ( ⁇ 20) to which a direct voltage was applied while keeping the quartz glass substrate at 40 ° C, and the carbon nanotube-containing film (in each An electric field was applied to the carbon nanotubes to orient each carbon nanotube in a certain direction.
  • the spacing between the transport rollers was 30 mm
  • the transport speed of the quartz glass substrate was lmZsec
  • the voltage applied between the transport rollers was 6 kVZcm.
  • the quartz glass substrate on which the carbon nanotube-containing film that had been subjected to the alignment treatment by the electric field was formed was cooled at 0 ° C for 20 seconds. After 20 seconds, wind at 25 ° C (15% relative humidity) for 60 seconds, 45 ° C (25% relative humidity) for 60 seconds, and 50 ° C wind (relative humidity) for the film containing carbon nanotubes.
  • the glass nanotube-containing film is dried for 60 seconds in succession (humidity 25%), and the quartz glass substrate on which the dried carbon nanotube-containing film has been formed is placed in an atmosphere at a temperature of 0 ° C and a relative humidity of 60% for 1 hour. I left it alone.
  • the above coating / cooling-drying process was repeated four times to form a four-layer carbon nanotube-containing film on the quartz glass substrate.
  • the quartz glass substrate on which the overcoat film was formed was cooled at 0 ° C for 20 seconds. After 20 seconds, wind at 25 ° C (relative humidity 15%) for 60 seconds, wind at 45 ° C (25% relative humidity) for 60 seconds, and wind at 50 ° C (relative humidity 25 %) Were sequentially applied for 60 seconds to dry the overcoat film, and “Sample B” for measurement was obtained.
  • each peak of the two polarization absorption spectra shows an absorption difference larger than that shown in FIG. 4, and the emission intensity of each peak in the fluorescence spectrum is also shown in FIG. It was bigger than shown.
  • an electric field alignment step is provided in the film formation process of the carbon nanotube-containing film, each carbon nanotube can be reliably aligned, and the optical function of emitting high-intensity near-infrared light is fully exhibited. I was able to.
  • the method for producing a carbon nanotube-containing body according to the present invention can provide a method for producing a carbon nanotube-containing body that exhibits an optically excellent function.

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Abstract

Méthode pour produire un corps contenant des nanotubes de carbone comprenant une étape de recouvrement impliquant d'appliquer un liquide de dispersion, contenant des nanotubes de carbone, et un liant sur un corps de support prédéterminé. La méthode pour produire un corps contenant des nanotubes de carbone est caractérisée en ce que, lors de l'étape de recouvrement, le liquide de dispersion est appliqué sur le corps de support, en tant que premier liquide de recouvrement, tout en étant appliqué avec une contrainte de cisaillement.
PCT/JP2005/012586 2004-07-16 2005-07-07 Méthode pour produire un corps contenant des nanotubes de carbone Ceased WO2006008978A1 (fr)

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JP2008159812A (ja) * 2006-12-22 2008-07-10 Sharp Corp 半導体層形成装置および半導体層形成方法
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WO2013035507A1 (fr) * 2011-09-07 2013-03-14 富士フイルム株式会社 Procédé pour fabriquer un matériau de revêtement contenant une charge en forme de ruban
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WO2008074087A1 (fr) * 2006-12-21 2008-06-26 The University Of Western Australia Procédé pour l'enrobage de nanoparticules
JP2008159812A (ja) * 2006-12-22 2008-07-10 Sharp Corp 半導体層形成装置および半導体層形成方法
JP2008201635A (ja) * 2007-02-21 2008-09-04 Hokkaido Univ 微小カーボン単分子膜の形成方法及び表面コーティング方法並びにコーティング体
JP2008273806A (ja) * 2007-05-07 2008-11-13 Hokkaido Univ 微細炭素繊維分散皮膜およびその製造方法
WO2008139962A1 (fr) * 2007-05-07 2008-11-20 Hokkaido University Film fin de dispersion à fibre de carbone fine et procédé de production associé
JP2010538861A (ja) * 2007-08-16 2010-12-16 エアバス オペレーションズ リミティド 複合材料から部品を製造する方法および装置
JP2009067932A (ja) * 2007-09-14 2009-04-02 Toyo Ink Mfg Co Ltd カーボンナノチューブを含むコーティング用組成物
JP2010132812A (ja) * 2008-12-05 2010-06-17 Nec Corp カーボンナノチューブインク組成物及びカーボンナノチューブインク組成物の噴霧方法
JP2013514193A (ja) * 2009-12-17 2013-04-25 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング ナノ粒子の堆積
JP2013527806A (ja) * 2010-03-30 2013-07-04 ナンテロ，インク． ネットワーク、ファブリック及びフィルム内にナノスケール要素を配列させるための方法
JP2013523591A (ja) * 2010-04-06 2013-06-17 ウィリアム・マーシュ・ライス・ユニバーシティ 高導電性のカーボンナノチューブ−ポリマー複合材の製造
WO2013035507A1 (fr) * 2011-09-07 2013-03-14 富士フイルム株式会社 Procédé pour fabriquer un matériau de revêtement contenant une charge en forme de ruban
CN103781559A (zh) * 2011-09-07 2014-05-07 富士胶片株式会社 用于制造含有线状填充物的涂布材料的方法
JP2013056291A (ja) * 2011-09-07 2013-03-28 Fujifilm Corp 紐状フィラー含有塗布物の製造方法
JP2015051951A (ja) * 2013-09-06 2015-03-19 国立大学法人 千葉大学 可溶化剤及びこれを用いたカーボンナノ材料層の形成方法
US11021368B2 (en) 2014-07-30 2021-06-01 General Nano Llc Carbon nanotube sheet structure and method for its making
WO2016182018A1 (fr) * 2015-05-13 2016-11-17 昭和電工株式会社 Procédé de fabrication de feuille composite de nanotubes de carbone
JPWO2016182018A1 (ja) * 2015-05-13 2018-03-01 昭和電工株式会社 カーボンナノチューブ複合シートの製造方法
US10758936B2 (en) 2015-12-08 2020-09-01 The Boeing Company Carbon nanomaterial composite sheet and method for making the same
CN109563285A (zh) * 2016-08-04 2019-04-02 通用纳米有限责任公司 碳纳米管膜结构及其制备方法
EP3494167A4 (fr) * 2016-08-04 2020-04-08 General Nano LLC Structure formée d'un film de nanotubes de carbone et son procédé de fabrication
CN111542140A (zh) * 2020-06-08 2020-08-14 大连工业大学 一种基于碳纳米管膜的便携式电热元件的制备方法

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