WO2020149283A1 - Matériau de revêtement antistatique de nanobrosse en carbone - Google Patents

Matériau de revêtement antistatique de nanobrosse en carbone Download PDF

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Publication number
WO2020149283A1
WO2020149283A1 PCT/JP2020/000975 JP2020000975W WO2020149283A1 WO 2020149283 A1 WO2020149283 A1 WO 2020149283A1 JP 2020000975 W JP2020000975 W JP 2020000975W WO 2020149283 A1 WO2020149283 A1 WO 2020149283A1
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Prior art keywords
coating film
carbon nanohorn
mass
carbon
fibrous
Prior art date
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PCT/JP2020/000975
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English (en)
Japanese (ja)
Inventor
眞由美 小坂
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日本電気株式会社
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Priority to JP2020566419A priority Critical patent/JP7230928B2/ja
Publication of WO2020149283A1 publication Critical patent/WO2020149283A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to a coating film containing a fibrous carbon nanohorn aggregate and a method for producing an antistatic coating film.
  • Patent Document 1 discloses a coating composition containing carbon nanotubes.
  • An object of the present invention is to provide a coating film having high antistatic performance.
  • the coating film of the present invention is characterized in that single-layer carbon nanohorns are radially aggregated and include a conductive component including a fibrous carbon nanohorn aggregate that is connected in a fibrous form.
  • a coating film having high antistatic performance can be provided.
  • the coating film according to the present embodiment includes a fibrous carbon nanohorn aggregate.
  • the fibrous carbon nanohorn aggregate is also called a carbon nanobrush (CNB), and has a structure in which single-layer carbon nanohorns are radially aggregated and connected in a fibrous shape.
  • the fibrous carbon nanohorn aggregate can maintain a fibrous shape even if an operation such as centrifugation or ultrasonic dispersion is performed, unlike the one in which a plurality of single-walled carbon nanohorns appear simply as fibrous.
  • the single-layer carbon nanohorn is a carbon structure of a conical shape with a diameter of 1 nm to 5 nm and a length of 30 nm to 100 nm, in which the tip of a structure in which a graphene sheet is wound is sharpened in the shape of an angle (horn) with a tip angle of about 20°.
  • the carbon structure is a structure mainly containing carbon and may contain a light element or a catalytic metal.
  • the fibrous carbon nanohorn aggregate is a fibrous carbon structure, and generally has a diameter of 30 nm to 200 nm and a length of 1 ⁇ m to 100 ⁇ m, for example, 2 ⁇ m to 30 ⁇ m.
  • the aspect ratio (length/diameter) of the fibrous carbon nanohorn aggregate is generally 4 to 4000, for example, 5 to 3500.
  • projections of a single-layer carbon nanohorn having a diameter of 1 nm to 5 nm and a length of 30 nm to 100 nm are provided.
  • the single-walled carbon nanohorns having high conductivity are connected in a fibrous shape and are characterized by a structure having a long conductive path, so that the fibrous carbon nanohorn aggregate has high conductivity.
  • the fibrous carbon nanohorn aggregate has high dispersibility as well, and is highly effective in imparting conductivity.
  • Fibrous carbon nanohorn aggregates are generally formed by connecting seed, bud, dahlia, petal dahlia, and petal (graphene sheet structure) carbon nanohorn aggregates. That is, one or more of these carbon nanohorn aggregates are contained in the fibrous structure.
  • the seed mold has a shape with little or no angular protrusions on the surface of the aggregate
  • the bud type has a shape with some angular protrusions on the surface of the aggregate
  • the dahlia type has a surface of the aggregate.
  • the petal type has a shape in which a large number of angular protrusions are seen on the surface
  • the petal type has a petal-shaped protrusion on the surface of the aggregate.
  • the petal structure is a graphene sheet structure having a width of 50 nm to 200 nm and a thickness of 0.34 nm to 10 nm and 2 to 30 sheets.
  • the petal-dahlia type is an intermediate structure between the dahlia type and the petal type.
  • the shape and particle size of the generated carbon nanohorn aggregate vary depending on the type and flow rate of gas.
  • the fibrous carbon nanohorn aggregate is also described in detail in International Publication No. 2016/147909. 1 and 2 of WO 2016/147909 disclose transmission micrographs of a fibrous carbon nanohorn aggregate. In the fibrous carbon nanohorn aggregate shown in this transmission micrograph, the single-layer carbon nanohorn aggregates (carbon nanohorn aggregates) that are radially aggregated are connected in a fibrous form. The entire disclosure of WO 2016/147909 is incorporated herein by reference.
  • carbon containing a catalyst is used as a target (referred to as a catalyst-containing carbon target), and a nitrogen atmosphere, an inert atmosphere, hydrogen is generated while rotating the target in a container in which the catalyst-containing carbon target is placed.
  • the target is heated by laser ablation in a mixed atmosphere of carbon dioxide or carbon dioxide to evaporate the target.
  • a fibrous carbon nanohorn aggregate is obtained in the process of cooling the evaporated carbon and the catalyst.
  • an arc discharge method or a resistance heating method can be used.
  • the laser ablation method is more preferable from the viewpoint of continuous production at room temperature and atmospheric pressure.
  • the laser ablation method applied in the present invention irradiates the target with laser light in a pulsed or continuous manner, and when the irradiation intensity becomes equal to or higher than a threshold value, the target converts energy, and as a result, a plume is generated and a product is generated. Is deposited on a substrate provided on the downstream side of the target, or is generated in a space inside the apparatus, and is recovered in a recovery chamber.
  • CO 2 lasers CO 2 lasers, YAG lasers, excimer lasers, and the like can be used a semiconductor laser, high output easy CO 2 laser is most suitable.
  • the CO 2 laser can use an output of 1 kW/cm 2 to 1000 kW/cm 2 , and can perform continuous irradiation and pulse irradiation. Continuous irradiation is preferable for the production of fibrous carbon nanohorn aggregates.
  • Laser light is condensed by a ZnSe lens or the like and irradiated.
  • the target rotation speed can be set arbitrarily, but 0.1 rpm to 6 rpm is particularly preferable.
  • Graphitization can be suppressed at 0.1 rpm or more, and increase in amorphous carbon can be suppressed at 6 rpm or less.
  • the laser output is preferably 15 kW/cm 2 or more, and 30 kW/cm 2 to 300 kW/cm 2 is most effective.
  • the laser output is 15 kW/cm 2 or more, the target is appropriately evaporated and the fibrous carbon nanohorn aggregate is easily produced.
  • the laser output is 300 kW/cm 2 or less, the increase of amorphous carbon can be suppressed.
  • the pressure in the container (chamber) can be set to 13332.2 hPa (10000 Torr) or less, but as the pressure becomes closer to vacuum, carbon nanotubes are more likely to be formed and a fibrous carbon nanohorn aggregate cannot be obtained.
  • the pressure in the container (chamber) is preferably 666.61 hPa (500 Torr) to 1266.56 hPa (950 Torr), and more preferably around normal pressure (1013 hPa (1 atm ⁇ 760 Torr)) for mass synthesis and cost reduction. Also suitable for.
  • the irradiation area can be controlled by the laser output and the degree of focusing by the lens, and 0.005 cm 2 to 1 cm 2 can be used.
  • the catalyst can use Fe, Ni, Co alone or as a mixture.
  • concentration of the catalyst can be appropriately selected, but it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on carbon.
  • the content is 0.1% by mass or more, the formation of the fibrous carbon nanohorn aggregate is ensured.
  • it is 10 mass% or less, an increase in target cost can be suppressed.
  • the inside of the container can be used at any temperature, preferably 0° C. to 100° C., and more preferably used at room temperature is suitable for mass synthesis and cost reduction.
  • the atmosphere described above is created by introducing nitrogen gas, inert gas, hydrogen gas, CO 2 gas, etc. singly or in a mixture into the container. From the viewpoint of cost, nitrogen gas and Ar gas are preferable. These gases circulate in the reaction vessel, and the produced substances can be recovered by the flow of this gas.
  • the atmosphere gas flow rate may be any amount, but is preferably in the range of 0.5 L/min to 100 L/min. In the process of vaporizing the target, the gas flow rate is controlled to be constant.
  • the fibrous carbon nanohorn aggregate obtained as described above is usually obtained together with the spherical carbon nanohorn aggregate.
  • the mixture of the fibrous carbon nanohorn aggregates and the spherical carbon nanohorn aggregates is also simply referred to as carbon nanohorn aggregates.
  • the spherical carbon nanohorn aggregate is a spherical carbon structure in which single-layer carbon nanohorns are radially aggregated.
  • the spherical carbon nanohorn aggregate has a diameter of about 30 nm to 200 nm and a substantially uniform size.
  • a part of the carbon skeleton thereof may be substituted with a catalytic metal element, a nitrogen atom or the like.
  • the fibrous carbon nanohorn aggregate may be isolated and used.
  • the fibrous carbon nanohorn aggregate may be used together with other carbon materials such as spherical carbon nanohorn aggregates.
  • the fibrous carbon nanohorn aggregate and the spherical carbon nanohorn aggregate can be separated according to the difference in size.
  • impurities other than the carbon nanohorn aggregates they can be removed by a centrifugation method, a difference in sedimentation speed, separation by size, or the like.
  • the ratio of the fibrous carbon nanohorn aggregates to the spherical carbon nanohorn aggregates can be changed by changing the production conditions.
  • the carbon nanohorn aggregate When fine holes are made in the carbon nanohorn aggregate (opening), it can be done by oxidation treatment.
  • oxidation treatment By this oxidation treatment, surface functional groups containing oxygen are formed in the openings.
  • a gas phase process and a liquid phase process can be used for the oxidation treatment.
  • heat treatment is performed in an atmosphere gas containing oxygen such as air, oxygen, carbon dioxide, etc. Above all, air is suitable from the viewpoint of cost.
  • the temperature can be used in the range of 300°C to 650°C, and 400°C to 550°C is more suitable. If the temperature is 300° C. or higher, the carbon burns and the pores can be reliably formed. Further, at 650° C.
  • the liquid phase process it is performed in a liquid containing an oxidizing substance such as nitric acid, sulfuric acid, hydrogen peroxide.
  • an oxidizing substance such as nitric acid, sulfuric acid, hydrogen peroxide.
  • nitric acid it can be used in the temperature range of room temperature to 120°C. If it is 120°C or lower, it is not oxidized more than necessary.
  • hydrogen peroxide it can be used in the temperature range of room temperature to 100° C., more preferably 40° C. or higher. In the temperature range of 40° C. to 100° C., the oxidizing power acts efficiently and the pores can be formed efficiently. In addition, it is more effective to use light irradiation together in the liquid phase process.
  • the catalytic metal contained during the formation of the carbon nanohorn aggregate can be removed if necessary.
  • the catalytic metal dissolves in nitric acid, sulfuric acid and hydrochloric acid and can be removed. From the viewpoint of ease of use, hydrochloric acid is suitable.
  • the temperature at which the catalyst is dissolved can be appropriately selected, but in the case of sufficiently removing the catalyst, it is desirable to perform heating at 70°C or higher.
  • the removal of the catalyst and the formation of the openings can be performed simultaneously or successively.
  • the catalyst since the catalyst may be covered with the carbon coating when the carbon nanohorn aggregates are formed, it is desirable to perform a pretreatment to remove the carbon coating.
  • the pretreatment is preferably performed in air at about 250°C to 450°C. At 300° C. or higher, some openings may be formed as described above.
  • the carbon nanohorn aggregate is easier to remove the catalytic metal than the carbon nanotube. In the present embodiment, by using the carbon nanohorn aggregate from which the catalyst metal has been removed, it is possible to form a coating film that does not substantially contain the metal and does not elute the metal. This can prevent metal elution from the coating film.
  • the carbon nanohorn aggregate can be improved in crystallinity by heat treatment in a non-oxidizing atmosphere such as an inert gas, hydrogen, or vacuum.
  • the heat treatment temperature may be 800°C to 2000°C, preferably 1000°C to 1500°C.
  • a surface functional group containing oxygen is formed in the opening portion, but it can be removed by heat treatment.
  • the heat treatment temperature may be 150°C to 2000°C.
  • 150° C. to 600° C. is desirable for removing the surface functional groups such as carboxyl group and hydroxyl group.
  • the surface functional group can be removed by reducing under a gas or liquid atmosphere. Hydrogen can be used for the reduction in a gas atmosphere, and can be combined with the above-mentioned improvement of crystallinity. In a liquid atmosphere, hydrazine or the like can be used.
  • the coating material according to the present embodiment contains a conductive component containing a fibrous carbon nanohorn aggregate.
  • the conductive component other than the fibrous carbon nanohorn aggregate include spherical carbon nanohorn aggregates, carbon materials such as carbon nanotubes and graphite.
  • the conductive component is a component composed of a conductive material, and may include other various conductive materials.
  • the conductive component may include, for example, conductive metal particles, a conductive polymer, or the like in addition to the carbon material.
  • the electrically conductive material is a material having a volume resistivity (20° C.) of about 10 ⁇ 3 ⁇ cm or less.
  • the base material of the paint is not particularly limited, and may be a material such as a resin that can form a coating film on a base material, a polymerizable monomer, or the like that is generally used for paint.
  • the resin include alkyd resin, unsaturated polyester resin, melamine resin, phenol resin, epoxy resin, vinyl chloride resin, acrylic resin, acrylic urethane resin, urethane resin, silicone resin, acrylic silicone resin, and fluororesin. ..
  • polymerizable monomer examples include styrene, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, maleic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, o- and p-styrenesulfonate, divinylbenzene, and the like.
  • polymerizable monomer examples include styrene, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, maleic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, o- and p-styrenesulfonate, divinylbenzene, and the like.
  • examples thereof include ethylene diacrylate and N,N-methylenebisacrylamide.
  • the paint may contain water and/or organic solvents.
  • organic solvent include alcohols such as methanol, ethanol and isopropanol, glycols such as ethylene glycol, ketones and ethers.
  • the paint may include a curing agent suitable for the base material (particularly the polymerizable monomer). Further, the coating material may optionally contain conventionally known additives such as a leveling agent, a slip agent, a plasticizer, a thickener, a drying agent, an antifoaming agent, a pigment and a dye.
  • a leveling agent such as a leveling agent, a slip agent, a plasticizer, a thickener, a drying agent, an antifoaming agent, a pigment and a dye.
  • a coating film can be formed by applying a coating material to a substrate. If necessary, the coating film may be further dried to remove volatile components such as water and organic solvents. The coating film may be further cured if necessary.
  • the method of curing the coating film is appropriately determined according to the type of base material, particularly the polymerizable monomer. For example, heat curing or light curing can be adopted.
  • the thickness of the coating film is not particularly limited, but is, for example, in the range of 1 ⁇ m to 50 ⁇ m.
  • the amount of fibrous carbon nanohorn aggregates contained in the coating film is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and further preferably 0.003% by mass or more. When the amount of the fibrous carbon nanohorn aggregate is within this range, the conductivity of the coating film can be increased.
  • the amount of the fibrous carbon nanohorn aggregate contained in the coating film is preferably 1% by mass or less, more preferably 0.1% by mass or less, further preferably 0.01% by mass or less, and particularly preferably 0.005% by mass. It is the following. When the amount of the fibrous carbon nanohorn aggregates is within this range, the fibrous carbon nanohorn aggregates are less likely to affect the tint of the coating film and a transparent coating film can be formed.
  • the total amount of the conductive component or carbon material contained in the coating film is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and further preferably 0.01 mass% or more.
  • the total amount of conductive components or carbon materials contained in the coating film is preferably 1% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.08% by mass or less.
  • a release sheet may be attached to the surface of the formed coating film to further enhance the conductivity of the coating film.
  • the surface of the coating film can be fluffed by peeling the release sheet from the coating film. On the fluffy surface of the coating film, the tips of the fibrous carbon nanohorn aggregates are exposed, and the conductivity of the coating film is increased.
  • the release sheet is preferably an easily peelable adhesive sheet having an adhesive layer containing an adhesive component.
  • the pressure-sensitive adhesive component used in the pressure-sensitive adhesive layer of the easily peelable pressure-sensitive adhesive sheet include rubber-based resins, acrylic resins, silicone resins, urethane resins, vinyl ether resins and the like.
  • commercially available dicing tapes or masking tapes can be preferably used as the easily peelable pressure-sensitive adhesive sheet.
  • the adhesive surface of the easily peelable adhesive sheet has a part having a high adhesive force (adhesive part) and a part having a low adhesive force (non-adhesive part).
  • a release component such as a silicone release agent or a long-chain alkyl release agent can be used in the non-adhesive portion.
  • an adhesive component such as rubber resin, acrylic resin, silicone resin, urethane resin, vinyl ether resin can be used.
  • a release agent layer may be provided on the base material, and an adhesive layer may be provided on a part of the release agent layer to form an adhesive portion and a non-adhesive portion.
  • an adhesive layer may be provided on the base material, and a release agent layer may be provided on a part of the adhesive layer to form an adhesive portion and a non-adhesive portion.
  • the shape of the adhesive portion or the non-adhesive portion is not particularly limited, and examples thereof include a lattice shape, a dot shape, a perforated shape, and a striped shape.
  • the area ratio of the adhesive portion to the non-adhesive portion on the adhesive surface of the easily peelable adhesive sheet may be, for example, 1:10 to 10:1, preferably 1:3 to 3:1.
  • the peeling adhesive force between the coating film and the release sheet is within a predetermined range.
  • the peeling adhesive strength between the coating film and the release sheet is preferably 0.1 N/cm or more, more preferably 1 N/cm or more, still more preferably 2 N/cm or more.
  • the peeling adhesive strength between the coating film and the release sheet is preferably 10 N/cm or less, more preferably 8 N/cm or less, and further preferably 4 N/cm or less.
  • the peeling adhesive strength is measured by JIS Z 0237 (a test method of peeling a release liner at 180° to the adhesive surface of a tape or sheet). According to JIS Z 0237, the peeling adhesive strength is measured by a tensile tester, and the peeling speed of the tensile tester is 5.0 ⁇ 0.2 mm/s.
  • the coating film according to this embodiment has high conductivity even when the content of the conductive component is small as described above.
  • the surface resistivity of the coating film is generally 1 ⁇ 10 14 ⁇ / ⁇ or less, preferably 1 ⁇ 10 11 ⁇ / ⁇ or less, more preferably 1 ⁇ 10 10 ⁇ / ⁇ or less, and further preferably 1 ⁇ 10 10. 9 ⁇ / ⁇ or less.
  • the surface resistivity of the coating film is generally 1 ⁇ 10 5 ⁇ / ⁇ or more.
  • the surface resistivity can be measured according to JIS K6911.
  • the amount of the conductive material other than the carbon material in the conductive component is preferably 1% by mass or less, more preferably 0.
  • the coating film does not include a conductive material other than a carbon material (except a metal derived from a catalyst for producing a fibrous carbon nanohorn aggregate) other than the conductive component.
  • the amount of carbon material in the conductive component is preferably 50% by weight or more, more preferably 80% by weight or more, and may be 100% by weight.
  • a carbon material mixture containing a fibrous carbon nanohorn aggregate (hereinafter referred to as a CNB product) was produced by CO 2 laser ablating a carbon target containing iron in a chamber under a nitrogen atmosphere. Specifically, a carbon target containing 1% by weight of iron was rotated at 2 rpm and continuously irradiated with a CO 2 laser. The energy density of the CO 2 laser was 50 kW/cm 2 . The temperature in the chamber was room temperature, and the flow rate of nitrogen supplied to the chamber was adjusted to 10 L/min. The pressure in the chamber was controlled to 933.254 hPa to 1266.559 hPa (700 Torr to 950 Torr).
  • fibrous substances fibrous carbon nanohorn aggregates
  • spherical substances spherical carbon nanohorn aggregates
  • graphite were observed.
  • the fibrous carbon nanohorn aggregate had a diameter of about 30 nm to 100 nm and a length of several ⁇ m to several tens of ⁇ m.
  • Most of the spherical carbon nanohorn aggregates had a substantially uniform size in the diameter range of about 30 nm to 200 nm.
  • the graphite had a size of 1 ⁇ m to several tens of ⁇ m.
  • the CNB product was found to be 4% by mass of fibrous carbon nanohorn aggregates, 62% by mass of spherical carbon nanohorn aggregates, 21% by mass of graphite, 13% by mass of iron oxide. It was confirmed that it contains.
  • Example 1 0.05 part by mass of the CNB product was added to 100 parts by mass of a silicone resin emulsion (Asahi Kasei SILRES (registered trademark), containing 60% by mass of non-volatile components) and kneaded by a three-roll mill.
  • the paint diluted with water was applied to the substrate with a roller and cured at 200° C. for 1 hour.
  • the surface resistivity of this coating film was measured by a four-point probe method using a semiconductor parameter analyzer (trade name: Agilent 4155C, manufactured by Agilent Technologies) under the condition of 25° C. It was 2 ⁇ 10 10 ⁇ / ⁇ .
  • Example 2 A dicing tape (Hitachi Kasei HAE-1503L) was attached to the surface of the coating film obtained in Example 1 and peeled off.
  • the surface resistivity of the coating film was 3 ⁇ 10 8 ⁇ / ⁇ .
  • ⁇ Comparative example 2> A dicing tape was attached to the surface of the coating film obtained in Comparative Example 1 and peeled off.
  • the surface resistivity of the coating film was 2 ⁇ 10 12 ⁇ / ⁇ , and the effect of the surface treatment was small as compared with the coating film to which the CNB product was added. Since the fibrous carbon nanohorn aggregate has an uneven shape, there are many parts to be bonded to the dicing tape, and it is considered that the effect of the surface treatment is increased.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Le but de la présente invention est de fournir un film de revêtement qui a une performance antistatique élevée. Le film de revêtement de la présente invention est caractérisé en ce qu'il comprend un composant conducteur qui comprend un agrégat de nanocornet de carbone fibreux dans lequel des nanocornets de carbone monocouche sont agrégés de manière radiale et liés de manière fibreuse.
PCT/JP2020/000975 2019-01-16 2020-01-15 Matériau de revêtement antistatique de nanobrosse en carbone WO2020149283A1 (fr)

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JP2020566419A JP7230928B2 (ja) 2019-01-16 2020-01-15 カーボンナノブラシ帯電防止塗料

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JP2019005018 2019-01-16
JP2019-005018 2019-01-16

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008168591A (ja) * 2007-01-15 2008-07-24 Dainippon Printing Co Ltd 光学積層体、偏光板及び画像表示装置
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