JP4735540B2 - Method for producing carbon nanotube-containing body - Google Patents

Description

  The present invention relates to a method for producing a carbon nanotube-containing body.

C ₆₀ or carbon nanotubes become late 20th century adds to the carbon material so far, the IV _b group element "carbon" is adapted to constitute the most diverse group of substances in the periodic table. As a material that leads nanotechnology, which is regarded as the fundamental technology of the 21st century, there is great expectations for carbon tubes, or “carbon nanotubes”. The diversity of structures and functions of carbon materials depends on the bonding method of carbon atoms by sp, sp ² , sp ³ , which is the outstanding individuality of carbon, and the same group IV _b element silicon and germanium This is a very different point, and this diversity of bonds is the source of the diversity of rare carbon species.

Despite the fact that carbon nanotubes are composed of a single carbon atom, the electronic properties of semiconductors, metals, and electronic structures vary greatly depending on the structure. This is because carbon hexagonal network planes form nano-sized cylinders, resulting in carbon bonding. This is because the diversity of the above was reflected additively. In other words, the carbon nanotubes themselves are rich and diverse substances, and are expected to be applied in a wide range. Even with the same sp ² carbon, fullerenes such as graphite, carbon nanotubes, C _60, etc. have different geometrical structures (the bond spreading dimension changes from 2 dimensions, pseudo 1 dimensions, and pseudo 0 dimensions). The boundary conditions for the wave function of the electrons change, and the density of states of the electron changes with the band structure as a solid, the band structure with Van Hove divergence, and the discrete electron level as a molecule, and exhibits completely different physical properties.

An example of a thin film containing the carbon nanotube is disclosed in Patent Document 1. The thin film described in Patent Document 1 is an aromatic polyamide film containing carbon nanotubes, and the rigidity and the like are improved by containing the carbon nanotubes.
JP 2003-138040 A

  As described above, carbon nanotubes have excellent properties such as changing their electronic properties depending on the structure, and improving the rigidity of the film by being contained in the film. Although there are great expectations, there are still many unknown parts.

  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.

In order to solve the above problems, the method for producing a carbon nanotube-containing body of the present invention is as follows.
Comprising a coating step of coating a dispersion containing carbon nanotubes and a binder on a predetermined transported support;
Using the dispersion liquid as a first coating liquid, the first coating liquid is applied onto the support while applying a shear stress to the first coating liquid in the transport direction of the support. And after the coating film is gelled in the gelation process, the coating film is dried in the drying process to obtain a dry film containing carbon nanotubes that are dispersed independently of each other and oriented in the support transport direction . .

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
With respect to the first coating liquid, a shear stress is applied in the conveying direction of the support by a bar-type coating method.
It is characterized by applying .

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
With respect to the first coating liquid, a shearing stress is applied in the support transport direction by a stripe coating method.
It is characterized by applying .

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The coating process is repeated a plurality of times.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
After the coating step, 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.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The coating process in the second coating process is performed by any one of an applicator method, an extrusion method, a slide bead method, a curtain method, a gravure method, a spray method, an air doctor method, a dip method, and a blade method. It is said.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The second application step is repeated a plurality of times.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The carbon nanotube is a single-walled carbon nanotube.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The binder is water-soluble.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The binder has no optical anisotropy.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The binder is gelatin.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The first coating liquid contains a hardener.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
It has the orientation process of orientating the carbon nanotube in the 1st coating liquid already applied after the application process.

One aspect of the present invention is:
In the method for producing a carbon nanotube-containing body as described above,
The alignment step uses an electric field.

In the present invention , carbon nanotubes are used to form a coating film by applying the first coating liquid on the support while applying a shear stress to the first coating liquid in the transport direction of the support. The first coating liquid can be applied on the support while being stretched in the conveying direction of the support on which the shear stress acts. Therefore, in the carbon nanotube-containing film composed of the first coating solution, the carbon nanotubes are oriented in the support transport direction in accordance with the shear stress, so that the carbon nanotube-containing film exhibits an optically excellent function. be able to.

Further, in the present invention, the orientation of the carbon nanotubes of the carbon nanotube-containing film so as not to turbulent can be gelled and dried.

  In one embodiment of the present invention, 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.

  In one embodiment of the present invention, the surface of the carbon nanotube-containing film can be smoothed, and an optical function without unevenness can be provided on the surface.

  In one embodiment of the present invention, light having a specific wavelength can be absorbed and light having a specific wavelength can be emitted.

  In one aspect of the present invention, when the first and second coating liquids are aqueous solutions, the solubility with the first and second coating liquids can be increased.

  In one aspect of the present invention, aggregation of carbon nanotubes can be suppressed and stably dispersed in the first coating solution.

  In one aspect of the present invention, it is possible to prevent moisture from entering the carbon nanotube-containing film and destroying the carbon nanotube-containing film, thereby reliably preventing the orientation of the carbon nanotube from being disturbed. it can.

1 is a perspective view showing a schematic configuration of a carbon nanotube-containing film 1. FIG. 1 is a side view showing a schematic configuration of a film forming apparatus 10. 2 is a cross-sectional view showing a schematic configuration of a wire bar 14. FIG. 5 is a drawing showing a polarized light absorption spectrum of Sample A. 5 is a drawing showing a fluorescence spectrum of Sample A. It is drawing which shows the modification of FIG. 2 is a side view showing a schematic configuration of a coating apparatus 30. FIG. 3 is a side view showing a schematic configuration of an electric field orientation device 40. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Carbon nanotube containing body 2 Substrate 3 Carbon nanotube 4 Carbon nanotube containing film 5 Overcoat film

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples.

  FIG. 1 is a perspective view showing a schematic configuration of a carbon nanotube-containing body 1.

  As shown in FIG. 1, the carbon nanotube-containing body 1 includes a support 2, and a carbon nanotube-containing film 4 containing a large number of carbon nanotubes 3, 3. An overcoat film 5 for covering the film is formed. However, in FIG. 1, in order to easily understand the film configuration of the carbon nanotube-containing film 4 and the overcoat film 5, 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. Examples of plastic film materials include polyolefins such as polyethylene and polypropylene, vinyl polymers such as polyvinyl acetate, polyvinyl chloride and polystyrene, polyamides such as 6,6-nylon and 6-nylon, and polyethylene terephthalate (hereinafter referred to as “PET”). ), Polyesters such as polyethylene-2,6-naphthalene dicarboxylate (hereinafter referred to as “PEN”), polycarbonate, cellulose triacetate (hereinafter referred to as “TAC”), cellulose esters such as cellulose diacetate, and the like. It is done.

  Among the plastic film materials, it is preferable to apply PET, PEN and TAC used as photographic polyester.

  The support 2 may be subjected to various surface treatments as described in JP-A-9-108613.

  Further, the support 2 can be applied with any of insulating, conductive, and semiconducting properties, such as single crystal silicon, quartz, glass, quartz glass, ceramics, metal, and silicon. Can be used. When the support 2 is made of glass, it is desirable to use a transparent glass such as soda lime glass, low soda glass, lead alkali silicate glass, borosilicate glass, etc., particularly high strain point low soda glass and low soda glass. It is preferable to constitute the support 2. When the support 2 is made of ceramic, alumina, zirconia, titania, silicon nitride, silicon carbide, or the like can be used.

  Further, a metal plate such as aluminum, stainless steel, copper, silver, titanium, nickel, cobalt, manganese, iron, gold, or platinum may be applied as the support 2, and a plastic or ceramic thin film is formed on the metal plate. You may apply what formed.

  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,...” Means that the fiber diameter (D) is about 1 to 1,000 nm and the length (L) is about 0.1 to 1,000 μm, and the L / D is 100 This is an aggregate of carbon having a large aspect ratio of about 10,000 and exhibiting a tube shape. The carbon nanotubes 3, 3,... Can be manufactured by an arc discharge method, a laser vapor deposition method, a catalytic chemical vapor deposition method, and the like. The manufacturing method is disclosed.

  There are two types of ordinary carbon nanotubes: “single-walled carbon nanotubes” and “multi-walled carbon nanotubes”. A single-walled carbon nanotube is a tube of monoatomic layer thickness in which one graphene (a carbon hexagonal network surface of a monoatomic layer) is closed in a cylindrical shape. As the carbon nanotubes 3, 3,..., As long as they are so-called carbon nanotubes, any of single-walled and multi-walled types can be applied.

  Carbon nanotubes 3, 3,... For practical use include single-walled carbon nanotubes (available from Carbon Nanotechnologies) produced by HiPco (High Pressure CO) method, ACCVD (Alcohol Catalytic Chemical Vapor) Single-walled carbon nanotubes produced by the Deposition method can be suitably used, and Hyperion Graphite fibril (registered trademark), Showa Denko, ASISH Pyrograf III (registered trademark), and the like can also be used. Of course, the carbon nanotube 3 is not limited to these.

Carbon nanotubes 3,3, ... may be of other things, such as not limited to a carbon product, for example, BN (boron nitride) nanotube a part of the carbon was replaced with boron and nitrogen.

  As described above, the carbon nanotubes 3, 3,... Are oriented in the carbon nanotube-containing film 4, but “each carbon nanotube 3 is oriented” means that the polarization absorption spectrum of the carbon nanotube-containing film 4 is When measured under the same conditions, it means that a difference in absorption occurs depending on the angle of incident polarized light. That is, the polarization absorption spectrum of the non-oriented carbon nanotube-containing film has a constant absorption peak intensity at a specific wavelength regardless of the polarization incident angle, whereas the polarization absorption spectrum of the aligned carbon nanotube-containing film 4 has its absorption peak. There is a polarization incident angle at which no absorption peak exists at a specific wavelength corresponding to (or there exists an absorption peak weaker than the absorption peak).

  Further, “the carbon nanotubes 3 are dispersed independently of 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 obtained by dispersing, stirring, and mixing a large number of the above-described carbon nanotubes 3, 3,..., A surfactant, a solvent, and a transparent binder, and then applying the dispersion onto the support 2. Yes, an additive such as a hardening agent may be added to the coating solution.

Hereinafter, applicable surfactants, solvents, transparent binders, and hardeners will be described in detail.
(Surfactant)
As the surfactant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. Preferably, for example, alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenes are used. Anionic surfactants such as sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines, saponins, alkylene oxide derivatives, sugars Nonionic surfactants such as alkyl esters are preferably used.

A fluorine-containing surfactant can also be preferably used as the surfactant. Examples thereof include fluorine-containing alkyl anionic surfactants, fluorine-containing alkyl cationic surfactants, fluorine-substituted alkylene oxide surfactants, perfluorocycloalkane surfactants, and the like.
(solvent)
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, and halogens such as methylene chloride, carbon tetrachloride, and trichloroethane. Hydrocarbons, alcohols such as methanol, ethanol and 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 It is possible to use fatty alcohol derivatives, fatty acids such as acetic acid, phenols, and other compounds containing nitrogen and sulfur. These solvents may be used alone or in combination of two or more.

Moreover, an ionic liquid can also be used as a solvent. As is well known, 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). Salt. As the solvent, various conventionally known ionic liquids can be used, and those which exhibit a liquid at room temperature (room temperature) or as close to room temperature as possible and are stable are preferable.
(Transparent binder)
A transparent binder having water solubility and / or optical anisotropy is preferably applied. Specifically, gelatin can be suitably used as the transparent binder. Such gelatins are generally produced from beef bone, cow skin, pig skin, etc., and there are alkali-treated gelatin accompanied by treatment with lime and acid-treated gelatin accompanied by treatment with hydrochloric acid, etc. in the production process from collagen. Any gelatin may be used as a component of the coating solution.

  For details on the production method and properties of these gelatins, see, for example, Arthur Veis, “The Macromolecular Chemistry of Gelatin”, pages 187-217, (1964), (Academic Press), THJames, “The Theory of the photographic. Process ", 4th. ed. , 55, (1977), (Macmillan), “Niwato Gelatin”, published by Nihonkawa Gelatin Industry Association, (1987), “Basics of Photographic Engineering, Silver Salt Photography”, 119-124, (Corona) It is described in.

  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, and particularly preferably 3000 ppm or less.

  As gelatin, alkali-treated gelatin having a molecular weight of about 100,000, acid-treated gelatin, oxidized gelatin, Bull. Soc. Sci. Photo. Japan. 16. Enzyme-treated gelatin as described in 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-9-251193, and the like.

  The gelatin preferably has a methionine content of less than 30 μmol / g, more preferably less than 20 μmol / g, and even more preferably 0.1 to 10 μmol / g. In order to reduce the methionine content in gelatin to less than 30 μmol / g, oxidation treatment of alkali-treated gelatin with an oxidizing agent is effective. Examples of the oxidizing agent that can be used for the oxidation treatment of gelatin include hydrogen peroxide, ozone, peroxy acid, halogen, thiosulfonic acid compounds, quinones, and organic peracids. Hydrogen peroxide is used. Is most preferred. There are many literatures on methods for measuring the methionine content of gelatin. For example, Journal of Photographic Science 28, 111, 40, 149, 41, 172, 42, 117, Journal of Imaging Science, 33, 10; Journal of・ Reference is made to Imaging Science and Technology vol.39, p.367. By referring to these documents, the methionine content of gelatin can be measured by amino acid analysis, HPLC (High Performance Liquid Chromatograpy) method, gas chromatography method, silver ion titration method and the like.

In addition to gelatin, the transparent binder includes, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate; sodium alginate Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinyl imidazole, polyvinylpyrazole etc. Alternatively, a semi-synthetic hydrophilic polymer material can be applied.
(Hardener)
The hardening agent is one in which a transparent binder is hardened mainly with the gelatin, and the hygroscopicity, film strength, etc. of the coating film can be adjusted by the amount thereof. Examples of the hardener include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucohalogenoic acids (mucochloric acid, mucophenoxycyclolic acid, etc.), epoxy compounds, active halogen compounds (2,4-dichloro-6-hydroxy). -S-triazine, etc.), active vinyl derivatives (1,3,5-triacryloylhexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β- (vinylsulfonyl (propionamide)) Etc.) Organic hardeners such as ethyleneimines, carbodiimides, methanesulfonates, isoxazoles, inorganic hardeners such as chromium alum, U.S. Pat. Nos. 3,057,723, 3,396 Polymer hardeners described in No. 029, No. 4, 161, 407, etc. Can be used. It may also be used These hardeners can be used alone, it may be used in combination of two or more.

  Specific examples of the hardener are shown in the following chemical formulas (H-1) to (H-16). However, regarding the chemical formulas (H-10) to (H-16), a mixture of two compounds is shown. Among these compounds represented by chemical formulas (H-1) to (H-16), compounds (mixtures) represented by chemical formulas (H-3) to (H-7) and (H-10) to (H-16) It is preferable to apply as an agent.

  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 solution is formed by removing the carbon nanotubes 3, 3,... From the coating solution constituting the carbon nanotube-containing film 4. Is good.

  The overcoat film 5 is preferably made of gelatin, but may be made of resin. When the overcoat film 5 is made of a resin, a curable resin can be used. The overcoat film 5 made of a curable resin may have various functions other than the overcoat. The overcoat film 5 made of a curable resin may be a film formed by polymerizing a component containing at least one monomer having an ethylenically unsaturated bond. As a film formed by polymerizing a component containing a monomer having an ethylenically unsaturated bond, a film formed by curing an actinic radiation curable resin or a thermosetting resin is preferably used, but an active film is particularly preferably used. It is a line 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 radiation curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may also be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. Can do.

  Specific examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like.

  In general, UV-curable acrylic urethane resins include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. And acrylate-based monomers such as 2-hydroxypropyl acrylate, which are easily formed by reaction with acrylate monomers having hydroxyl groups, such as those described in JP-A-59-151110. Can be used.

  Examples of UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as disclosed in JP-A-59-151112. Those described can be used.

  Examples of the ultraviolet curable epoxy acrylate resin include epoxy acrylate as an oligomer, and a reactive diluent and a photoreaction initiator added thereto to react with each other. JP-A-1-105738 discloses Those described can be used.

  Specific examples of these photoinitiators include benzoin and derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  The photoinitiator can also be used as a photosensitizer. Further, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

These actinic radiation curable resin films can be applied by a known method. As 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. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, etc. can be used. As the resin constituting the overcoat film 5, for example, vinyl chloride / vinyl acetate Copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl alcohol Copolymers, vinyl homopolymers or copolymers such as chlorinated polyvinyl chloride, ethylene / vinyl chloride copolymers, ethylene / vinyl acetate copolymers, cellulose nitrate, cellulose acetate propionate, cellulose diacetate Cellulose ester resins such as cellulose triacetate, cellulose acetate phthalate, cellulose acetate butyrate resin, copolymers of maleic acid and / or acrylic acid, acrylic acid ester copolymers, acrylonitrile / styrene copolymers, chlorinated polyethylene, acrylonitrile / chlorinated polyethylene / Styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene / Rubber resins such as butadiene resin and butadiene / acrylonitrile resin; Recone resin, fluorine resin, polymethyl methacrylate, can be mentioned copolymers of polymethyl methacrylate and polymethyl acrylate, but is not limited thereto. In particular, as the resin constituting the overcoat film 5, it is preferable to use a cellulose resin such as cellulose diacetate or cellulose acetate propionate.

  The overcoat film 5 may be composed of one layer as in the carbon nanotube-containing film 4 or may be composed of two or more layers.

  Subsequently, a film forming apparatus 10 for forming the carbon nanotube-containing film 4 on the substrate 2 will be described.

  FIG. 2 is a side view showing a schematic configuration of the film forming apparatus 10.

  As shown in FIG. 2, the film forming apparatus 10 has an original winding roller 11 around which a long support 2 is wound. Below the original winding roller 11, a transport roller 12 that transports the support 2 while supporting it is disposed. The conveyance roller 12 rotates in the counterclockwise direction in FIG. 2 and conveys the support 2 in the rotation 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.

  A wire bar 14 for scraping off the coating liquid applied to the support 2 is disposed obliquely above and to the right of the conveying roller 12. FIG. 3 is a cross-sectional view showing a schematic configuration of the wire bar 14. As shown in FIG. 3, 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. As shown in FIG. 1, the wire bar 14 rotates in a clockwise direction in FIG. 2 at a slightly lower speed than the conveyance 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 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. In the film forming apparatus 10, by keeping the distance between the wire bar 14 and the support 2 constant, the coating liquid applied to the support 2 can be scraped uniformly.

  Instead of the wire bar 14, a wireless bar in which grooves corresponding to the rod 14a are formed at regular intervals may be applied.

  A receiver 16 that receives the coating liquid scraped 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 conveying 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. In the film forming apparatus 20, when the pump 19 is operated, 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 and the receiver. It is the structure which circulates between 16.

  Two second transport rollers 21 and 22 that transport while supporting the support 2 are disposed above the wire bar 14. An AC power supply 23 is connected to each of the second transport rollers 21 and 22, and an electric field is formed between each of the second transport rollers 21 and 22.

  On the left side of the second conveying roller 22, a cooling chamber 24 that cools and gelates the coating solution film applied to the support 2, and a drying chamber 25 that dries the coating solution film applied to the support 2. And a take-up roller 26 that winds up the support 2 is disposed. 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 a counterclockwise direction in FIG. 2 and winds up the support 2 that has passed through the cooling chamber 24 and the drying chamber 25.

  Then, the manufacturing method of the carbon nanotube containing body 1 is demonstrated.

  First, a first film forming method for forming the carbon nanotube-containing film 4 on the support 2 will be described.

  First, an additive such as the above-described carbon nanotubes 3, 3,..., A surfactant is added to a solvent to prepare a carbon nanotube-containing liquid (preparation step). For example, when single-walled carbon nanotubes generated by the HiPco method are used as the carbon nanotubes 3, 3,..., SDS (Sodium Dodecyl Sulfate) as the surfactant, and heavy water as the solvent, a large number of carbon nanotubes 3, 3 are used. ,... And a surfactant are added to a solvent to prepare a carbon nanotube-containing liquid.

  Once the carbon nanotube-containing liquid is prepared, the carbon nanotube-containing liquid is sequentially subjected to dispersion treatment and ultracentrifugation treatment (dispersion process, separation process), and the supernatant is recovered from the carbon nanotube-containing liquid after ultracentrifugation (extraction process) ), A carbon nanotube dispersion liquid in which each carbon nanotube 3 is dispersed in a solvent is obtained.

  Dispersion processing in the dispersion process includes well-known stirring processing and ultrasonic processing, and as a disperser used for the processing in the dispersion step, a high-speed stirring type disperser having a large shearing force, high-intensity ultrasonic energy There are dispersers that give Specifically, 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. A preferred high-speed agitating type disperser for use in the dispersion step is a dissolver, polytron, homomixer, homoblender, kedy mill, jet agitator, etc. Preferably, it is a disperser of the type of 2,000 to 4,000 rpm. The high-speed agitation type disperser is also called a dissolver or a high-speed impeller disperser. As described in JP-A-55-129136, serrated blades are alternately arranged in the vertical direction on a high-speed rotating shaft. A device equipped with a bent impeller is also a preferred example of a high-speed stirring type disperser.

  After the dispersion, separation, and extraction steps, the carbon nanotube dispersion and the transparent binder are mixed and each carbon nanotube 3 is stirred in the transparent binder (stirring step).

  In the stirring step, for example, when gelatin is applied as a transparent binder, gelatin (or gelatin solution) is added to the carbon nanotube dispersion. Gelatin dissolution is allowed to stand for a certain period of time at room temperature to swell and then heated, or heated to dissolve immediately after addition. Moreover, you may perform the dispersion | distribution process of the said dispersion | distribution process again as needed.

  As described above, the transparent binder is dissolved in the carbon nanotube dispersion liquid to obtain a carbon nanotube dispersion coating liquid as a first coating liquid that is used for processing in the coating process described later.

  Note that the carbon nanotube dispersion coating liquid forms the carbon nanotube dispersion film 4 in the subsequent treatment, but the carbon nanotube dispersion coating liquid contains the carbon nanotube dispersion coating liquid before coating for the purpose of curing the carbon nanotube dispersion film 4. A hardener may be added.

  After the stirring step, a carbon nanotube dispersion coating solution is applied on the support 2 by a wire bar method (application step), and a carbon nanotube-containing film 4 composed of the carbon nanotube dispersion coating solution is formed on the support 2.

  In the following steps, processing in each step will be described with reference to the film forming apparatus 10 shown in FIG.

  In a state where the support 2 is wound between the original winding roller 11 and the winding roller 26 (as shown in FIG. 2) and the carbon nanotube dispersion coating liquid is stored in the coating device 13, the transport roller 12, The second conveying rollers 21 and 22 and the take-up roller 26 rotate, and the support 2 is conveyed from the original winding roller 11 to the conveying roller 12 and passes through the conveying roller 12 while being supported by the conveying roller 12. At this time, the coating device 13 applies an excessive amount of the carbon nanotube dispersion coating solution toward the support 2.

  When the support 12 passes through the transport roller 12, the support 12 passes near 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, and the carbon nanotube dispersion film 4 having a uniform film thickness is formed on the support 12.

  Here, the carbon nanotube dispersion coating solution applied on the support 2 is accompanied by the conveyance of the support 2, but is largely extended in the conveyance direction of the support 2 due to the action in the conveyance direction and the presence of the wire bar 14. It is conveyed while being pushed. At this time, a shear stress is applied to the carbon nanotube dispersion coating liquid, and the carbon nanotube dispersion coating liquid is applied onto the support 2 while receiving the shear stress. As a result, the carbon nanotubes 3 in the carbon nanotube dispersion coating solution are arranged in a certain direction along the transport direction of the support 2 while being dispersed independently of each other in the carbon nanotube dispersion coating solution (in an isolated state). To be oriented. The most preferable orientation state of each carbon nanotube 3 is uniaxial orientation.

  In the coating process, it is preferable that the conveyance speed (stretching speed) of the support 2 with respect to the wire bar 14 is as large as possible. The speed is preferably 5 times or more, more preferably 10 times, and even more preferably 50 times or more. Is good. Further, in the coating process, since the shear stress is applied not only in the transport direction of the support 2 but also in the direction orthogonal to the transport direction of the support 2, each carbon nanotube 3 is transported in the transport direction of the support 2. And it will be oriented in the film plane.

  The excess carbon nanotube dispersion coating liquid scraped off by the wire bar 14 with the carbon nanotube dispersion coating liquid coated on the support 2 falls on the receiver 16, and then the tube 17, the tank 18, the pump 19, and It is supplied to the coating device 13 through the tube 20 and applied again to the support 2 as a coating liquid for coating.

  After the coating step, 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. At this time, an electric field is formed between the two second transport rollers 21 and 22 by the AC power source 23 so that the electric field is applied to the carbon nanotube-containing film 4 disposed between the second transport rollers 21 and 22. (Electric field orientation process).

  In the electric field alignment step, the carbon nanotubes 3 in the carbon nanotube-containing film 4 are linearly aligned by pulling the ends together by electrostatic alignment so that the orientation in a certain direction in the coating step is more reliable. can do. That is, when a voltage is applied to the carbon nanotubes 3, 3,..., One end is on the side of one electrode (second transport roller 21 or second transport roller 22), and the other end is on the other electrode (second transport). The electrostatic charges are oriented toward the transport roller 22 or the second transport roller 21), and the positive charge and the negative charge are attracted and aligned in a straight line at both ends of the carbon nanotubes 3, 3,. be able to.

  Therefore, as shown in FIG. 2, the AC power supply 3 is applied as a voltage source, and the voltage applied between the second transport rollers 21 and 22 is set to the AC voltage, so that the second transport roller 21 before the electric charge moves. It is thought that the positive and negative electrodes can be reversed by the second transport roller 22 and the aligned carbon nanotubes 3 can be prevented from separating.

  Therefore, in the film forming apparatus 10, an AC voltage is applied between the second transport rollers 21 and 22 from the AC power source 23, and a direct current voltage is applied as a voltage applied between the transport rollers 21 and 22. Each carbon nanotube 3 can be more reliably oriented.

  The applied voltage applied between the transport rollers 21 and 22 is preferably set to 1 to 15 kV / cm, but is not limited to this range. If the applied voltage is less than 1 kV / cm, the carbon nanotubes 3 may not be sufficiently oriented. If the applied voltage is greater than 15 kV / cm, the dielectric liquid is disturbed and the orientation of the carbon nanotubes 3 is inhibited. Therefore, it is preferable to set the applied voltage at 1 to 15 kV / cm. The applied voltage can be appropriately adjusted according to the fluidity, viscosity, film thickness, and density of the carbon nanotubes 3, 3,.

  In addition, it is good also considering the voltage applied between each conveyance roller 21 and 22 as a direct current voltage instead of the alternating current power supply 23 with a direct current power supply. The applied voltage of the DC power source 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 increased as compared with the case of AC voltage. be able to.

  After the electric field orientation step, 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 held 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).

  In the gelation step, it is preferable to quickly gel the carbon nanotube-containing film 4 on the support 2. When the time for which the carbon nanotube-containing film 4 is held in a liquid state is long, not only the orientation of each carbon nanotube 3 is disturbed but also the uniformity as a coating film cannot be maintained due to fluid phenomena such as liquid dripping and leveling. Therefore, immediately after applying the carbon nanotube dispersion coating liquid, it is necessary to quickly reduce or eliminate the fluidity of the carbon nanotube-containing film 4. 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 kept in a low temperature atmosphere of 20 ° C. or less, preferably 15 ° C. or less, more preferably 10 ° C. or less.

  In the gelation process, 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 gelation process, the thickness of the support 2, etc., but immediately before being brought into the cooling chamber 24. If the temperature of the carbon nanotube-containing film 4 is a normal coating solution temperature (35 to 50 ° C.), the time during which the carbon nanotube-containing film 4 stays inside the cooling chamber 24 (the carbon nanotube-containing film 4 is inside the cooling chamber 24). The time taken to pass through is usually set in the range of 1 to 100 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 gelation process by any method that can quickly cure the carbon nanotube-containing film 4 immediately after the application of the carbon nanotube dispersion coating solution. For example, a method of curing using various curable resins such as a well-known UV (Ultra Violet) curable resin and a thermosetting resin can also be applied. Further, the treatment by the gelation step may be performed to improve the viscosity of the carbon nanotube-containing film 4 and to suppress the flow of the carbon nanotube-containing film 4 to the necessary minimum even if the carbon nanotube-containing film 4 is not sufficiently gelled.

  After the gelation step, the support 2 carried out from the cooling chamber 24 is carried into the drying chamber 25. The drying chamber 25 is a chamber in which air at a constant temperature is circulated in the chamber, 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 from 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, it is preferable to dry the carbon nanotube-containing film 4 at a low temperature so that the gelatin remains in a gelled state at a low temperature. Moreover, when only the fluidity | liquidity of the carbon nanotube containing film | membrane 4 is made small by the gelatinization process, it is preferable to dry the carbon nanotube containing film | membrane 4 under low temperature so that the fluidity | liquidity may not improve.

  In the drying step, it is preferable to dry the carbon nanotube-containing film 4 by blowing air at 20 to 70 ° C. on the carbon nanotube-containing film 4. In this case, when 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 once formed is destroyed, and the fluidity of the carbon nanotube-containing film 4 is increased. Since the orientation of the carbon nanotubes 3 is disturbed and the carbon nanotube-containing film 4 is not uniform as a coating film, the temperature of the drying air in the drying chamber 25 is preferably set to 50 ° C. or lower. In addition, the humidity of the wind in the drying process is usually preferably set in a range of 10 to 50%, and after the carbon nanotube-containing film 4 is completely dried, the relative humidity is 30 to 70% for a certain time (for example, 20 to 20%). It is preferable to adjust the humidity for 180 seconds.

  After the drying process, the support 2 carried out from the drying chamber 25 is wound around the winding roller 26. The carbon nanotube-containing film 4 can be formed on the support 2 by the first film forming method described above.

  In the first film forming method, the coating process using the bar method using the wire bar 14 is performed in the coating process. Instead, a coating process using a known stripe coating system may be performed. . Further, although the electric field alignment step is provided in the first film forming method, the electric field alignment step is not necessary. The coating step, the gelation step, and the drying step may be repeated a plurality of times to form a plurality of carbon nanotube-containing films 4 on the support 2.

  Next, a second film forming method for forming an overcoat film on the carbon nanotube-containing film 4 will be described.

  In the first film formation method, the carbon nanotubes 3, 3,... Are omitted, and the other steps are the same as the preparation process, the dispersion process, the separation process, the extraction process, and the stirring process of the first film formation method. An overcoat coating solution as a second coating solution is obtained.

  When the overcoat coating solution is obtained, the overcoat coating solution is applied on the carbon nanotube-containing film 4 according to a known coating process (second coating step), and the overcoat film 5 is formed on the carbon nanotube-containing film 4. . In this application process, 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 tension A coating process such as a method can be applied.

  When the overcoat film 5 is formed, the chamber corresponding to the cooling chamber 24 in FIG. 2 is passed through the overcoat film 5 in the same manner as in the gelation step and the drying step of the first film formation method (first step). 2), and then, a chamber corresponding to the drying chamber 25 of FIG. 2 is passed (second drying step). The overcoat film 5 can be formed on the carbon nanotube-containing film 4 by the second film forming method described above.

  In the second film forming method, the second coating step, the second gelation step, and the second drying step are repeated a plurality of times to form a plurality of overcoat films 5 on the carbon nanotube-containing film 4. A film may be formed.

  Moreover, although the example which applied the thing which was elongate and exhibited the film form as the support body 2 was shown above, as shown in FIG. Good. The support 2 in this case may be made of the same material as described above.

  When a substrate is applied as the support 2, the coating apparatus 30 and the electric field orientation apparatus 40 shown in FIGS.

  As shown in FIG. 7, the coating apparatus 30 includes a tank 31 that stores a carbon nanotube dispersion coating solution, and a coating roller 32 is disposed in the tank 31. The application roller 32 rotates in the counterclockwise direction in FIG. 7 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 34. The wire bar 33 is the same as the wire bar 14 of FIG. 2, and the holder 34 is the same as the holder 15 of FIG.

  In the coating process using the coating device 30, the support 2 is transported in a state where the coating roller 32 and the wire bar 33 are rotated and supported by them, and the coating roller 32 is supported by the support 2 during the transportation. The carbon nanotube-dispersed coating solution is transferred and applied to the substrate, and the excess carbon nanotube-dispersed coating solution coated with the wire bar 33 is scraped off to form the carbon nanotube-containing film 4 on the support 2.

  Moreover, as shown to Fig.8 (a), the electric field orientation apparatus 40 has the four conveyance rollers 41-44 conveyed while supporting the support body 2. As shown in FIG. 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 of FIG. 2 and may be replaced with a DC power supply.

  As shown in FIG. 8B, conductive endless belts 46 and 47 may be wound between the conveying rollers 41 and 42 and between the conveying rollers 43 and 44, respectively.

  And in the electric field orientation process which applied the electric field orientation apparatus 40, the support body 2 passes between each conveyance rollers 42 and 43, being supported by the four conveyance rollers 41-44, and the carbon nanotube dispersion film 4 is passed through the passage. An electric field is applied, and each carbon nanotube 3 is oriented.

(1) Preparation of Sample A (1.1) Preparation of Carbon Nanotube Dispersion Coating Solution 10 g of SDS (Sodium Dodecyl Sulfate) was dissolved in 1000 cc of pure water to prepare a 1% SDS aqueous solution. When the SDS aqueous solution is prepared, 1.5 g of a well-known single-walled carbon nanotube produced by the HiPco method is added to the SDS aqueous solution, and the room temperature is measured using a jet stream inductor mixer TDS manufactured by Mitamura Riken Kogyo Co., Ltd. With suction and dispersion. After aspiration and dispersion, the dispersion was divided into 500 cc × 2, and each dispersion was centrifuged at 15,000 rpm for 8 hours using a centrifuge (Jouan KR25i). After centrifugation, the supernatant was collected from each dispersion after the centrifugation to obtain 800 cc of carbon nanotube dispersion.

Once the carbon nanotube dispersion liquid is obtained, 80 g of commercially available gelatin for biochemicals (WAKO, 074-02761) is added to the carbon nanotube dispersion liquid, and the gelatin is allowed to swell for 15 minutes at room temperature to disperse the carbon nanotubes. The mixture of the solution and gelatin was heated to 50 ° C. in a thermostatic bath to dissolve gelatin in the carbon nanotube dispersion. Thereafter, the mixed liquid of the carbon nanotube dispersion liquid after heating and gelatin was subjected to two-stage pressure filtration with TCP10 manufactured by Toyo Filter Paper Co., Ltd. to obtain 800 cc of a carbon nanotube dispersion coating liquid for coating. Hereinafter, the carbon nanotube dispersion coating solution is referred to as “coating solution A”.
(1.2) Preparation of overcoat coating solution 10 g of SDS was dissolved in 1000 cc of pure water to prepare a 1% SDS aqueous solution. When the SDS aqueous solution is prepared, 80 g of commercially available gelatin for biochemistry (WAKO, 074-02761) is added to the SDS aqueous solution, and the gelatin is allowed to swell for 15 minutes at room temperature to mix the aqueous SDS solution and gelatin. The solution was stirred while being heated to 50 ° C. in a thermostatic bath to dissolve gelatin in the aqueous SDS solution. Thereafter, the mixed solution of the heated SDS aqueous solution and gelatin was subjected to two-stage pressure filtration with TCP10 manufactured by Toyo Filter Paper Co., Ltd. to obtain about 800 cc of an overcoat coating solution for coating. Hereinafter, the overcoat coating solution was referred to as “coating solution B”.
(1.3) Film formation of carbon nanotube-containing film A vinylsulfone type hardener (compound of chemical formula (H-6) in the above embodiment) is added to 50 cc of the coating liquid A, and the coating liquid is then added within 3 minutes. While maintaining A at 50 ° C., an excessive amount of coating solution A is applied to the extrusion type coating on a commercially available quartz glass substrate (100 mm × 100 mm × 0.5 mm, manufactured by Techno Quartz) assuming the support 2 in the above embodiment. And applied. After coating the coating liquid A, an excessive amount of the coating liquid A is scraped off with a wire bar in which a stainless steel wire having a diameter of 0.2 mm is wound around an 8 mm stainless steel rod, and a carbon nanotube-containing film composed of the coating liquid A is formed. A film was formed on a quartz glass substrate. However, the coating treatment here was carried out at a coating speed of 2 m / sec and keeping the quartz glass substrate 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, a 25 ° C wind (relative humidity 15%) is applied to the carbon nanotube-containing film for 60 seconds, a 45 ° C wind (relative humidity 25%) is applied for 60 seconds, and a 50 ° C wind (relative humidity 25%) is applied. The carbon nanotube-containing film was sequentially applied for 60 seconds to dry, and the quartz glass substrate on which the dried carbon nanotube-containing film was formed was left for 1 hour in an atmosphere at a temperature of 30 ° C. and a relative humidity of 60%. The above coating, cooling, and drying steps were repeated four times to form a four-layer carbon nanotube-containing film on a quartz glass substrate.
(1.4) Formation of Overcoat Film A vinyl sulfone type hardener (compound of chemical formula (H-6) in the above embodiment) is added to the coating liquid B, and the coating liquid B is added within 3 minutes thereafter. The coating liquid B is applied onto the carbon nanotube-containing film using an applicator coating apparatus for a coating thickness of 80 μm while maintaining the temperature at 40 ° C., and an overcoat film composed of the coating liquid B is formed on the carbon nanotube-containing film. Filmed.

Thereafter, the quartz glass substrate on which the overcoat film was formed was cooled at 0 ° C. for 20 seconds. After 20 seconds, 25 ° C wind (relative humidity 15%) is applied to the overcoat film for 60 seconds, 45 ° C wind (relative humidity 25%) is applied for 60 seconds, and 50 ° C wind (relative humidity is 25%). The overcoat film was sequentially applied for 60 seconds to dry, and "Sample A" for measurement was obtained.
(2) Measurement of polarized light absorption spectrum of sample A Using a UV-3150 spectroscope manufactured by Shimadzu Corporation, a polarized light absorption spectrum of sample A was measured with a polarizer interposed between the light source and sample A. However, the measurement of the polarized light absorption spectrum is performed when linearly polarized in the direction along the alignment direction (direction corresponding to the moving direction of the wire bar) of each carbon nanotube of sample A and in the direction orthogonal to the alignment direction. This was done in two cases: polarized light.

  The measurement result of the polarization absorption spectrum of Sample A is shown in FIG. In FIG. 4, the upper solid line shows a polarization absorption spectrum when linearly polarized in the direction along the alignment direction of each carbon nanotube of sample A, and the lower solid line is orthogonal to the alignment direction of each carbon nanotube of sample A. The polarization absorption spectrum when linearly polarized in the direction to be shown is shown.

In the two polarization absorption spectra shown in FIG. 4, each peak around wavelengths 500 to 900 nm and 1000 to 1500 nm corresponds to each carbon nanotube in the carbon nanotube-containing film. A remarkable difference in absorption at the same wavelength is observed between each peak of the polarized absorption spectrum at the bottom, and it can be seen that the carbon nanotubes are certainly oriented in one direction along the moving direction of the wire bar.
(3) Measurement of fluorescence spectrum of sample A The fluorescence spectrum of sample A was measured using a Joby Yvon spectroscope manufactured by HORIBA, Ltd. with slit plates having a slit width of 13 nm on the light incident side and the light exit side, respectively. However, the measurement of the fluorescence spectrum was performed in two cases: the case where the sample A was irradiated with light having a wavelength of 650 nm as the excitation light, and the case where the sample A was irradiated with light having a wavelength of 720 nm as the excitation light.

  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 the sample A is irradiated with 650 nm excitation light, and the lower solid line shows the fluorescence spectrum when the sample A is irradiated with 720 nm excitation light.

  In the fluorescence spectrum shown in the upper part of FIG. 5, the peak near the emission wavelength of 1050 nm corresponds to the carbon nanotube with the chiral vector of (7,5), and the peak near the emission wavelength of 1150 nm corresponds to the carbon nanotube with the chiral vector of (7,6). When the carbon nanotube-containing film assumed in Sample A is irradiated with visible light having a wavelength of 650 nm as the excitation light due to the presence of the respective peaks near the emission wavelengths of 1050 nm and 1150 nm, the near-infrared wavelengths of 1050 nm and 1150 nm are used. It can be seen that light is emitted.

  In the fluorescence spectrum shown in the lower part of FIG. 5, the peak near the emission wavelength of 1120 nm is a carbon nanotube with a chiral vector of (9, 4), and the peak near the emission wavelength of 1200 nm is a carbon nanotube with a chiral vector of (8, 6). Corresponding, when the carbon nanotube-containing film assumed in the sample A is irradiated with visible light having a wavelength of 720 nm as excitation light due to the presence of the respective peaks near the emission wavelengths of 1120 nm and 1200 nm, the wavelengths near 1120 nm and 1200 nm are observed. It turns out that infrared rays are emitted. From this, it can be seen that the carbon nanotubes in the contained film are dispersed independently (in an isolated state).

(1) Preparation of Sample B (1.1) Preparation of Carbon Nanotube Dispersion Coating Solution and Overcoat Coating Solution In the same manner as in Example 1 (1.1) and (1.2) above, the carbon nanotube dispersion coating solution and overcoat Coat coating solutions were prepared, and these were designated as “coating solution A” and “coating solution B” in the same manner as described above.
(1.2) Film formation of carbon nanotube-containing film A vinylsulfone type hardener (compound of chemical formula (H-6) in the above embodiment) is added to 50 cc of the coating liquid A, and the coating liquid is then added within 3 minutes. A was extruded and applied onto a commercially available quartz glass substrate (100 mm × 300 mm × 0.5 m, manufactured by Techno Quartz) maintained at 40 ° C., and a carbon nanotube-containing film was formed on the quartz glass substrate. The quartz glass substrate used here assumes the support 2 in the above embodiment.

  The coating process here was performed at a coating speed of 1 m / sec, and the final coating film thickness was 60 μm.

  After the carbon nanotube-containing film is formed, the quartz glass substrate is passed between two conveying rollers (φ20) to which a DC voltage is applied while keeping the quartz glass substrate at 40 ° C., and an electric field is applied to the carbon nanotube-containing film (each carbon nanotube inside). Each carbon nanotube was oriented in a certain direction. However, the interval between the conveyance rollers was 30 mm, the conveyance speed of the quartz glass substrate was 1 m / sec, and the voltage applied between the conveyance rollers was 6 kV / cm.

Thereafter, the quartz glass substrate on which the carbon nanotube-containing film that had been subjected to orientation treatment by an electric field was formed was cooled at 0 ° C. for 20 seconds. After 20 seconds, a 25 ° C wind (relative humidity 15%) is applied to the carbon nanotube-containing film for 60 seconds, a 45 ° C wind (relative humidity 25%) is applied for 60 seconds, and a 50 ° C wind (relative humidity 25%) is applied. The carbon nanotube-containing film was sequentially applied for 60 seconds to dry, and the quartz glass substrate on which the dried carbon nanotube-containing film was formed was left in an atmosphere of a temperature of 0 ° C. and a relative humidity of 60% for 1 hour. The above coating, cooling, and drying steps were repeated four times to form a four-layer carbon nanotube-containing film on a quartz glass substrate.
(1.3) Formation of Overcoat Film A vinyl sulfone type hardener (compound of chemical formula (H-6) in the above embodiment) is added to the coating liquid B, and the coating liquid B is added within 3 minutes thereafter. The coating liquid B is applied onto the carbon nanotube-containing film using an applicator coating apparatus for a coating thickness of 80 μm while maintaining the temperature at 40 ° C., and an overcoat film composed of the coating liquid B is formed on the carbon nanotube-containing film. Filmed.

Thereafter, the quartz glass substrate on which the overcoat film was formed was cooled at 0 ° C. for 20 seconds. After 20 seconds, 25 ° C wind (relative humidity 15%) is applied to the overcoat film for 60 seconds, 45 ° C wind (relative humidity 25%) is applied for 60 seconds, and 50 ° C wind (relative humidity is 25%). The overcoat film was sequentially applied for 60 seconds and dried to obtain “Sample B” for measurement.
(2) Measurement of polarization absorption spectrum and fluorescence spectrum of sample B The polarization absorption spectrum and fluorescence spectrum of sample B were measured in the same manner as the items (2) and (3) of the first example. Although the measurement result is not shown in the figure, in the polarization absorption spectrum, the difference in absorption more than that shown in FIG. 4 is recognized in each peak of the two polarization absorption spectra, and the emission intensity of each peak in the fluorescence spectrum is more than that shown in FIG. It was big. For these reasons, if 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.

  As described above, 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.

Claims (14)

Comprising a coating step of coating a dispersion containing carbon nanotubes and a binder on a predetermined transported support;
Wherein the coating step, as the dispersion of the first coating solution to the first coating solution, while applying a shear stress to the conveying direction of the support, said first coating solution onto said support Coating is performed to form a coating film. After the coating film is gelled in the gelation process, the coating film is dried in the drying process to obtain a dry film containing carbon nanotubes that are dispersed independently of each other and oriented in the support transport direction. A method for producing a carbon nanotube-containing body, comprising: In the manufacturing method of the carbon nanotube containing body of Claim 1,
A method for producing a carbon nanotube-containing body, wherein a shear stress is applied to the first coating liquid in a transport direction of the support by a bar-type coating method. In the manufacturing method of the carbon nanotube containing body of Claim 1,
A method for producing a carbon nanotube-containing body, wherein a shear stress is applied to the first coating liquid in a transport direction of the support by a stripe coating method. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The method for producing a carbon nanotube-containing body, wherein the coating step is repeated a plurality of times. In the manufacturing method of the carbon nanotube containing body of Claim 1,
After the coating step, 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. A method for producing a carbon nanotube-containing body as a feature. In the manufacturing method of the carbon nanotube containing body according to claim 5 ,
The coating process in the second coating process is performed by any one of an applicator method, an extrusion method, a slide bead method, a curtain method, a gravure method, a spray method, an air doctor method, a dip method, and a blade method. A method for producing a carbon nanotube-containing body. In the manufacturing method of the carbon nanotube containing body according to claim 5 ,
The method for producing a carbon nanotube-containing body, wherein the second coating step is repeated a plurality of times. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The method for producing a carbon nanotube-containing body, wherein the carbon nanotube is a single-walled carbon nanotube. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The method for producing a carbon nanotube-containing body, wherein the binder is water-soluble. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The method for producing a carbon nanotube-containing body, wherein the binder does not have optical anisotropy. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The method for producing a carbon nanotube-containing body, wherein the binder is gelatin. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The method for producing a carbon nanotube-containing body, wherein the first coating liquid contains a hardener. In the manufacturing method of the carbon nanotube containing body of Claim 1,
The manufacturing method of the carbon nanotube containing body characterized by having the orientation process of orientating the carbon nanotube in the said 1st coating liquid already apply | coated after the said application | coating process. In the manufacturing method of the carbon nanotube containing body according to claim 13 ,
The method for producing a carbon nanotube-containing body, wherein an electric field is used in the alignment step.

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