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WO2019244479A1 - Composition contenant des nanotubes de carbone et procédé de production d'un produit thermodurci d'une composition contenant des nanotubes de carbone - Google Patents

Composition contenant des nanotubes de carbone et procédé de production d'un produit thermodurci d'une composition contenant des nanotubes de carbone Download PDF

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Publication number
WO2019244479A1
WO2019244479A1 PCT/JP2019/017549 JP2019017549W WO2019244479A1 WO 2019244479 A1 WO2019244479 A1 WO 2019244479A1 JP 2019017549 W JP2019017549 W JP 2019017549W WO 2019244479 A1 WO2019244479 A1 WO 2019244479A1
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Prior art keywords
carbon nanotube
containing composition
thermosetting
organic solvent
mass
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English (en)
Japanese (ja)
Inventor
稔 森田
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Priority to CN201980003598.0A priority Critical patent/CN110914370B/zh
Priority to JP2019551406A priority patent/JP7247098B2/ja
Priority to KR1020207001362A priority patent/KR102291539B1/ko
Publication of WO2019244479A1 publication Critical patent/WO2019244479A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention can be used as, for example, a continuity test conductive member that can be electrically connected to a test electrode of a circuit device to perform a continuity test on the test electrode, and that does not include a metal component as a conductive material.
  • the present invention relates to a composition which can be produced and a method for producing a thermosetting product thereof.
  • an electrical connector called a contact probe has been used to check the normal conduction of wiring of a semiconductor package or the like.
  • a contact probe is a precision mechanical part including a spring, a thin metal tube, and the like, and there is a limit to miniaturization. For this reason, with the narrower pitch of the wiring of the semiconductor package or the like, a conductive member for continuity inspection such as an anisotropic conductive sheet may be used instead of the contact probe as the electrical connector.
  • the conductive member for continuity inspection such as the anisotropic conductive sheet
  • a plurality of core sheets including a plurality of metal wires arranged in parallel on the same plane are formed in a sheet-like member and included in one core sheet.
  • a laminate is formed by laminating two or more core sheets in a state where the direction of the metal wire to be formed and the direction of the metal wire included in the other core sheet are substantially matched.
  • an anisotropic conductive sheet obtained by cutting from a direction substantially perpendicular to the width direction Patent Document 1.
  • the conductive member for continuity inspection of Patent Literature 1 in order to cope with a narrower pitch of wiring of a semiconductor package or the like, it is necessary to reduce the interval between metal wires arranged in parallel. However, if the distance between the metal wires is reduced, the metal wires may come into contact with each other. Therefore, the conductive member for continuity inspection of Patent Literature 1 still has a limit in responding to the narrow pitch of wiring of a semiconductor package or the like.
  • an insulating sheet body made of an elastic polymer material having a plurality of through-holes formed therein, and an insulating sheet body formed in the plurality of through-holes An anisotropic conductive sheet having a conductive path forming portion containing a conductive material in the conductive material has been proposed (Patent Document 2).
  • a conductive material contained in an elastic polymer substance conductive metal particles are used.
  • Patent Documents 1 and 2 a metal material is used for imparting conductivity to the conductive member for continuity inspection.
  • a metal material is used for the continuity inspection conductive member, there may be a problem that the electrode or circuit device to be inspected is contaminated with the metal material.
  • a conductive member for conduction inspection that does not use a metal component as a conductive material.
  • an object of the present invention is to provide a continuity test even when the wiring of a circuit device to be inspected has a narrow pitch and the wiring has been thinned. It is an object of the present invention to provide a composition and a method for producing a thermosetting product of the composition, which can be used as a conductive member for conduction inspection containing no metal component as a material.
  • composition containing carbon nanotubes is provided.
  • the gist of the configuration of the present invention is as follows.
  • [1] comprising (A) a carbon nanotube, (B) an organic solvent, and (C) a thermosetting resin, A carbon nanotube-containing composition wherein the difference between the absolute value of the boiling point (T1) of the organic solvent (B) and the thermosetting reaction start temperature (T2) of the thermosetting resin (C) is 70 ° C. or less.
  • T1 the absolute value of the boiling point
  • T2 the thermosetting reaction start temperature
  • the intensity ratio G / D between the G band and the D band of the Raman spectrum of the carbon nanotube (A) obtained by Raman spectroscopy is 1.0 or more, and the average length of the carbon nanotube (A) is 1
  • thermosetting resin (C) is an epoxy resin.
  • thermosetting resin (C) is an epoxy resin.
  • thermosetting product according to [5] having a volume resistivity of 0.1 ⁇ ⁇ cm or less.
  • thermosetting resin (B) the boiling point (T1) of the organic solvent and (C) the thermosetting resin Applying a carbon nanotube-containing composition having a difference of an absolute value from the thermosetting reaction initiation temperature (T2) of 70 ° C.
  • thermosetting product of a carbon nanotube-containing composition comprising: [8] The production method according to [7], wherein the thermosetting material forms a conductive sheet having a thickness of 1 ⁇ m or more and 500 ⁇ m or less.
  • thermosetting reaction start temperature (T2) means the temperature measured as follows. A thermosetting resin is charged into a sample container of a differential scanning calorimeter (DSC), and the temperature is raised from room temperature to 300 ° C. at a rate of 5 ° C./min in a nitrogen atmosphere as a closed container. Is shown to determine the reaction initiation temperature. As shown in FIG. 1, the rising temperature (DSC onset) of the exothermic curing peak is determined from the obtained DSC chart, and this is defined as the thermosetting reaction start temperature (T2).
  • DSC differential scanning calorimeter
  • Carbon nanotubes have the property of agglomerating, that is, properties such as conductivity are reduced when the dispersibility is reduced.
  • an organic solvent is blended as a dispersion medium of the carbon nanotube and the thermosetting resin, and the boiling point (T1) of the organic solvent and the thermosetting reaction start temperature of the thermosetting resin ( Since the difference in absolute value from T2) is suppressed to 70 ° C. or less, the volatilization of the organic solvent and the thermosetting of the thermosetting resin are synchronized in the thermosetting treatment of the composition.
  • thermosetting treatment As described above, even when the composition of the present invention is subjected to the thermosetting treatment, the dispersibility of the carbon nanotubes in the thermoset can be maintained in an excellent state. Therefore, by conducting the thermosetting treatment of the composition of the present invention in a predetermined form, the wiring of the circuit device to be inspected can be narrowed and the continuity test can be appropriately performed even if the wiring is thinned. A conductive member for continuity inspection excellent in conductivity can be obtained.
  • the carbon nanotube is used as the conductive material instead of the metal component, the electrode or the circuit device to be inspected is contaminated by the metal material during the continuity test. Can be prevented.
  • the intensity ratio G / D between the G band and the D band in the Raman spectrum of the carbon nanotube is 1.0 or more, and the average length of the carbon nanotube is 1.0 ⁇ m or more.
  • the carbon nanotubes are included in the composition in an amount of 0.1% by mass or more and 15% by mass or less in 100% by mass of the total solid components contained in the composition, so that a conductive material excellent in a thermosetting product is obtained. Good moldability can be obtained while imparting excellent properties and excellent dispersibility of carbon nanotubes.
  • FIG. 3 is an explanatory diagram of a method for measuring a thermosetting reaction start temperature.
  • the composition of the present invention comprises (A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin, wherein (B) the boiling point (T1) of the organic solvent and (C)
  • the carbon nanotube-containing composition has a difference in absolute value from the thermosetting reaction start temperature (T2) of the curable resin of 70 ° C. or less.
  • the carbon nanotube is not particularly limited, and a known carbon nanotube can be used. Specifically, for example, a single-walled carbon nanotube in which one surface of graphite is wound in one layer, a multi-walled carbon nanotube in which multiple layers are wound, and the like are exemplified.
  • the diameter (fiber diameter) and the average length of the carbon nanotube are not particularly limited, but from the viewpoint of conductivity, moldability, and the like, use of the carbon nanotube having a long average length is preferable. It is particularly preferable to use single-walled carbon nanotubes having a long average length. In addition, you may use combining a single-walled carbon nanotube and a multi-walled carbon nanotube as needed.
  • the lower limit of the average length of the single-walled carbon nanotube is preferably 1.0 ⁇ m, more preferably 5.0 ⁇ m, and particularly preferably 10 ⁇ m from the viewpoint of further improving conductivity.
  • the upper limit of the average length of the single-walled carbon nanotube is preferably 200 ⁇ m, more preferably 150 ⁇ m, and particularly preferably 100 ⁇ m, from the viewpoint of preventing deterioration of the surface appearance when formed into a molded product or a film.
  • the lower limit of the diameter of the single-walled carbon nanotube is preferably 0.5 nm, particularly preferably 1.0 nm, from the viewpoint of suppressing aggregation when dispersed in a thermosetting resin and an organic solvent.
  • the upper limit of the diameter of the single-walled carbon nanotube is preferably 15 nm, particularly preferably 10 nm, from the viewpoint of improving the mechanical properties by the nano effect.
  • the aspect ratio of the single-walled carbon nanotube is not particularly limited, and can be appropriately selected from the viewpoint of conductivity, dispersibility, and the like.
  • the lower limit of the aspect ratio of the single-walled carbon nanotube is high, because the conductivity is secured with a small number of electrical contacts and the number of electrical contacts with one carbon nanotube in another carbon nanotube increases. From the viewpoint that an electric network can be formed, 1000 is preferable, and 5000 is particularly preferable.
  • the upper limit of the aspect ratio of the single-walled carbon nanotube is preferably 200,000, particularly preferably 100,000, from the viewpoint of obtaining excellent dispersibility in an organic solvent and a thermosetting resin.
  • the intensity ratio G / D (hereinafter, sometimes referred to as “G / D band ratio”) between the G band and the D band of the Raman spectrum obtained by Raman spectroscopy of the single-walled carbon nanotube is not particularly limited.
  • the lower limit of the D band ratio is preferably 1.0, more preferably 4.0, and particularly preferably 6.0 from the viewpoint of further improving conductivity.
  • the upper limit of the G / D band ratio is preferably as high as possible.
  • the G band is a Raman shift seen near 1590 cm ⁇ 1 in the Raman spectrum and is derived from graphite.
  • the D band is a Raman shift seen in the vicinity of 1350 cm ⁇ 1 in the Raman spectrum, and is derived from defects of amorphous carbon and graphite. That is, the higher the G / D ratio, which is the ratio of the peak heights of the G band and the D band, to the carbon nanotube has higher linearity and crystallinity and higher quality.
  • the G / D band ratio is measured by Raman spectroscopy at least at three different locations, and the arithmetic mean value is defined as the G / D band ratio in the present specification.
  • the multi-walled carbon nanotube may be a double-walled carbon nanotube (DWNT) or a multi-walled carbon nanotube (MWNT) having three or more layers.
  • the lower limit of the average length of the multi-walled carbon nanotube is preferably 1.0 ⁇ m, more preferably 5.0 ⁇ m, and particularly preferably 10 ⁇ m from the viewpoint of further improving the conductivity.
  • the upper limit of the average length of the multi-walled carbon nanotube is preferably 200 ⁇ m, more preferably 150 ⁇ m, in the same manner as in the single-walled carbon nanotube, from the viewpoint of preventing deterioration of the surface appearance when formed into a film or a film. , 100 ⁇ m are particularly preferred.
  • the lower limit of the diameter of the multi-walled carbon nanotube is preferably 0.5 nm, as in the case of the single-walled carbon nanotube, from the viewpoint of suppressing aggregation when dispersed in a thermosetting resin and an organic solvent. Particularly preferably, it is 0 nm.
  • the upper limit of the diameter of the multi-walled carbon nanotube is preferably 15 nm, particularly preferably 10 nm, from the viewpoint of improving the mechanical properties by the nano effect, as in the case of the single-walled carbon nanotube.
  • the aspect ratio of the multi-walled carbon nanotube is not particularly limited, and can be appropriately selected from the viewpoint of conductivity, dispersibility, and the like.
  • the lower limit of the aspect ratio of the multi-walled carbon nanotube is the same as that of the above-mentioned single-walled carbon nanotube. From the viewpoint that the number of points increases and a high-dimensional electrical network can be formed, 1000 is preferable, and 5000 is particularly preferable.
  • the upper limit value of the aspect ratio of the multi-walled carbon nanotube is preferably 200,000, particularly preferably 100,000, from the viewpoint of obtaining excellent dispersibility in an organic solvent and a thermosetting resin, similarly to the single-walled carbon nanotube.
  • the G / D band ratio of the multi-walled carbon nanotube is not particularly limited, but the lower limit of the G / D band ratio is preferably 1.0, as in the case of the single-walled carbon nanotube, from the viewpoint of further improving conductivity. 0.0 is more preferable, and 6.0 is particularly preferable.
  • the upper limit of the G / D band ratio is preferably as high as possible, but is, for example, 100.
  • the content of the carbon nanotubes is not particularly limited, but the lower limit is the total solid component of the carbon nanotube-containing composition from the viewpoint of providing the thermosetting material with excellent electrical conductivity of 0.1 ⁇ cm or less in volume resistivity. 0.1% by mass is preferable in 100% by mass, 1.0% by mass is more preferable, 3.0% by mass is more preferable, and 5.0% by mass is particularly preferable.
  • the upper limit of the content of the carbon nanotubes is preferably 15% by mass in 100% by mass of the total solid components of the carbon nanotube-containing composition, from the viewpoint of obtaining excellent dispersibility of the carbon nanotubes in the thermosetting product.
  • all solid components means components obtained by removing volatile components such as an organic solvent from a carbon nanotube-containing composition.
  • the BET specific surface area of the carbon nanotube is not particularly limited, but is preferably 600 m 2 / g or more from the viewpoint of conductivity.
  • BET specific surface area means the nitrogen adsorption specific surface area measured using the BET method.
  • the organic solvent is blended as a dispersion medium of the carbon nanotube and a thermosetting resin described below.
  • the type of the organic solvent is set so that the difference between the absolute value of the boiling point (T1) of the organic solvent and the thermosetting reaction start temperature (T2) of the thermosetting resin described below is 70 ° C. or less. Selected. Therefore, the organic solvent is adjusted so that the boiling point (T1) of the organic solvent falls within the range of T2 ⁇ 70 ° C. ⁇ T1 ⁇ T2 + 70 ° C. according to the value of the thermosetting reaction initiation temperature (T2) of the thermosetting resin to be compounded. Is selected.
  • thermosetting treatment of the carbon nanotube-containing composition is The volatilization of the organic solvent and the thermosetting of the thermosetting resin are synchronized.
  • the state in which the carbon nanotubes are dispersed in the thermosetting product can be kept excellent. Therefore, by performing the thermosetting treatment of the carbon nanotube-containing composition of the present invention, it is possible to make the conductivity uniform throughout the thermosetting product, and to obtain excellent conductivity with a volume resistivity of 0.1 ⁇ cm or less. Accordingly, even if the wiring of the circuit device to be inspected is narrowed and the wiring is thin, a conductive member for continuity inspection can be obtained, which can appropriately perform the continuity inspection.
  • the boiling point (T1) of the organic solvent is also thermosetting of the thermosetting resin.
  • the reaction initiation temperature (T2) is also not particularly limited, but from the viewpoint of further improving the dispersibility of the carbon nanotubes in the thermosetting product, the boiling point (T1) of the organic solvent is set at the thermosetting reaction initiation temperature (T2) of the thermosetting resin. ) Is preferably higher.
  • the difference between the absolute value of the boiling point (T1) of the organic solvent and the thermosetting reaction start temperature (T2) of the thermosetting resin is not particularly limited as long as it is 70 ° C. or less, but is particularly preferably 65 ° C. or less.
  • the content of the organic solvent in the carbon nanotube-containing composition is not particularly limited, but is preferably contained in the carbon nanotube-containing composition in an amount of from 80% by mass to 98% by mass, and more preferably in a range of from 85% by mass to 95% by mass. Is particularly preferred.
  • thermosetting resin functions as a binder resin.
  • examples of the thermosetting resin include an epoxy resin, a phenol resin, an amino resin, an unsaturated polyester resin, a polyurethane resin, a silicone resin, and a thermosetting polyimide resin.
  • the thermosetting resins may be used alone or in combination of two or more. Among these thermosetting resins, epoxy resins and silicone resins are particularly preferred.
  • the epoxy resin examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol AF epoxy resin, and biphenyl epoxy.
  • the content of the thermosetting resin in the carbon nanotube-containing composition is not particularly limited, but the total content of the thermosetting resin and the carbon nanotubes is 2% by mass or more and 20% by mass or less in the carbon nanotube-containing composition. It is preferable to include a thermosetting resin so as to satisfy the condition described above, and it is particularly preferable to include the thermosetting resin so as to be 5% by mass or more and 15% by mass or less.
  • a curing agent epoxy resin curing agent
  • the epoxy resin curing agent include, for example, known curing agents such as amines, acid anhydrides, and polyhydric phenols, and exhibit curability at a predetermined temperature equal to or higher than room temperature, and exhibit rapid curability.
  • a latent curing agent that exerts its effect is preferred.
  • the latent curing agent dicyandiamide, imidazoles, hydrazides, boron trifluoride-amine complexes, amine imides, polyamine salts and modified products thereof, and microcapsules can also be used. These may be used alone or in combination of two or more.
  • the content of the epoxy resin curing agent is not particularly limited, and for example, is 0.5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the epoxy resin.
  • a curing agent silicone resin curing agent
  • the silicone resin curing agent include an alkoxysilane compound.
  • the alkoxysilane compound include silane compounds having an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group.
  • methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyl Examples include diethoxysilane, tetraethoxysilane, glycidyloxypropyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.
  • the content of the silicone resin curing agent is not particularly limited, and may be, for example, 1.0 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the silicone resin.
  • a crosslinking agent such as an isocyanate-based, epoxy-based, melamine-based, or peroxide-based, a silane coupling agent, and a surfactant.
  • Agents a conductive filler (filler), a flame retardant, an ion trapping agent, a thickener, an antioxidant, an antioxidant, and the like.
  • the method for preparing the carbon nanotube-containing composition of the present invention is not particularly limited.
  • carbon nanotubes are dispersed in an organic solvent to obtain organic solvent-dispersed carbon nanotubes.
  • the method of dispersing the carbon nanotubes in the organic solvent is not particularly limited. Examples of the method include dispersion.
  • a thermosetting resin and, if necessary, a curing agent are added to the obtained organic solvent-dispersed carbon nanotubes, and the mixture is stirred at room temperature using a stirrer for a predetermined time to obtain a carbon nanotube-containing composition.
  • the stirring device include a jet mill, a cutting mill, a disk mill, and a ball mill.
  • the method for producing a thermosetting product of the carbon nanotube-containing composition includes, for example, (A) a carbon nanotube, (B) an organic solvent, and (C) a thermosetting resin, and (B) a boiling point of the organic solvent. Applying a carbon nanotube-containing composition having a difference in absolute value between (T1) and the thermosetting reaction start temperature (T2) of the thermosetting resin (T2) of 70 ° C. or less to a film; A step of subjecting the nanotube-containing composition to a heat treatment to evaporate the (B) organic solvent and start the (C) thermosetting reaction of the thermosetting resin.
  • Step of coating on film By applying the carbon nanotube-containing composition prepared as described above on a film, a laminated structure of a coating film and a film of the carbon nanotube-containing composition can be obtained. At this time, when the carbon nanotube-containing composition is applied in the form of a sheet, a sheet-like laminated structure can be obtained.
  • the method for applying the carbon nanotube-containing composition is not particularly limited, and examples thereof include a comma coater method, a screen printing method, an inkjet method, a roll coater method, a bar coater method, a spray coater method, a curtain flow coater method, a squeegee method, and an applicator method.
  • the thickness of the coating film of the carbon nanotube-containing composition is not particularly limited, and may be, for example, in the range of 5 to 100 ⁇ m.
  • examples of the material of the film include polyimide, polyester (polyethylene, polypropylene, polyethylene terephthalate, etc.).
  • thermosetting resin is thermoset while the organic solvent is volatilized, and the coating film of the carbon nanotube-containing composition can be thermoset.
  • the temperature of the heat treatment can be appropriately selected according to the thermosetting start temperature of the thermosetting resin. For example, when an epoxy resin or a silicone resin is used as the thermosetting resin, 70 to 250 ° C.
  • the heat treatment time may be, for example, 1 to 60 minutes.
  • thermosetting product of the carbon nanotube-containing composition for example, a sheet-shaped thermosetting product
  • Example 1 ⁇ Preparation of carbon nanotube-containing composition> Bisphenol A type epoxy resin (trade name: YD-128, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., mass average molecular weight: 400, softening point: 25 ° C.
  • Bisphenol A type epoxy resin (trade name: YD-128, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., mass average molecular weight: 400, softening point: 25 ° C.
  • Example 2 In the preparation of the carbon nanotube-containing composition, a single-walled carbon nanotube dispersed in N-methyl-2-pyrrolidone (trade name: EC1.5P-NMP, manufactured by Meijo Nanocarbon Co., Ltd., solid content 0.2% by mass, average A sheet-shaped conductive member according to Example 2 was obtained in the same manner as in Example 1 except that 265 parts by mass of a length of 5 to 10 ⁇ m and a G / D band ratio of 50 or more were used.
  • N-methyl-2-pyrrolidone trade name: EC1.5P-NMP, manufactured by Meijo Nanocarbon Co., Ltd.
  • Example 3 In the preparation of the carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrrolidone (trade name: EC2.0P-NMP, manufactured by Meijo Nanocarbon Co., Ltd., solid content 0.2% by mass, average A sheet-shaped conductive member according to Example 3 was obtained in the same manner as in Example 1, except that 265 parts by mass of a length of 10 to 15 ⁇ m and a G / D band ratio of 50 or more were used.
  • N-methyl-2-pyrrolidone trade name: EC2.0P-NMP, manufactured by Meijo Nanocarbon Co., Ltd.
  • Example 4 In the preparation of the carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrrolidone (trade name: EC2.0P-NMP, manufactured by Meijo Nanocarbon Co., Ltd., solid content 0.2% by mass, average A sheet-like conductive member according to Example 4 was obtained in the same manner as in Example 1, except that 375 parts by mass (length: 10 to 15 ⁇ m, G / D band ratio: 50 or more) was used.
  • N-methyl-2-pyrrolidone trade name: EC2.0P-NMP, manufactured by Meijo Nanocarbon Co., Ltd.
  • Example 5 In the preparation of the carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrrolidone (trade name: EC2.0P-NMP, manufactured by Meijo Nanocarbon Co., Ltd., solid content 0.2% by mass, average A sheet-like conductive member according to Example 5 was obtained in the same manner as in Example 1, except that 555 parts by mass (length: 10 to 15 ⁇ m, G / D band ratio: 50 or more) was used.
  • N-methyl-2-pyrrolidone trade name: EC2.0P-NMP, manufactured by Meijo Nanocarbon Co., Ltd.
  • Example 6 In preparing the carbon nanotube-containing composition, a hardly crystallizable liquid epoxy resin (trade name: ZX-1059, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., viscosity 2250 mPa ⁇ s, softening point: 25 ° C.) instead of bisphenol A type epoxy resin
  • a sheet-like conductive member according to Example 6 was obtained in the same manner as in Example 2 except that 9 parts by mass of liquid and epoxy equivalent: 165) were used.
  • Example 7 In the preparation of the carbon nanotube-containing composition, a cycloaliphatic diglycidyl ether-based epoxy resin (trade name: ZX-1658GS, manufactured by Nippon Epoxy Manufacturing Co., Ltd., viscosity: 50 mPa ⁇ s, softening point) was used instead of the bisphenol A type epoxy resin. : 25 ° C or lower, liquid, epoxy equivalent: 133) in the same manner as in Example 2 except that 9 parts by mass were used to obtain a sheet-shaped conductive member according to Example 7.
  • a cycloaliphatic diglycidyl ether-based epoxy resin trade name: ZX-1658GS, manufactured by Nippon Epoxy Manufacturing Co., Ltd., viscosity: 50 mPa ⁇ s, softening point
  • Example 8 In the preparation of the carbon nanotube-containing composition, 7 parts by mass of a polydimethylsiloxane having a silanol group (trade name: XP1434, manufactured by JNC, viscosity: 50 mPa ⁇ s, liquid) instead of the bisphenol A type epoxy resin is a silicone resin.
  • Example 8 was repeated in the same manner as in Example 2 except that 3 parts by mass of alkoxyepoxysilane (trade name: S-510, manufactured by JNC, 3-glycidyloxypropyltrimethoxysilane) was used instead of diethylenetriamine.
  • the sheet-shaped conductive member was obtained.
  • Example 9 In the preparation of the carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrrolidone (trade name: ZEONANO (registered trademark) 03DS-NP-RD, manufactured by Zeon Corporation, solid content 0.3 mass%, average length of 100 ⁇ m or more, G / D band ratio of 5.0 or more) in the same manner as in Example 1 except that 500 parts by mass of the sheet-like conductive member according to Example 9 was used. Obtained.
  • N-methyl-2-pyrrolidone trade name: ZEONANO (registered trademark) 03DS-NP-RD, manufactured by Zeon Corporation, solid content 0.3 mass%, average length of 100 ⁇ m or more, G / D band ratio of 5.0 or more
  • Example 10 In the preparation of the carbon nanotube-containing composition, a polydimethylsiloxane having a silanol group (trade name: FM-9915, manufactured by JNC, viscosity 130 mPa ⁇ s, liquid), which is a silicone resin, was used instead of bisphenol A type epoxy resin.
  • Example 2 was repeated in the same manner as in Example 2 except that 3 parts by mass of alkoxyepoxysilane (trade name: S-510, manufactured by JNC, 3-glycidyloxypropyltrimethoxysilane) was used instead of diethylenetriamine. 10 was obtained.
  • Comparative Example 1 In the preparation of the carbon nanotube-containing composition, a single-walled carbon nanotube dispersed in methyl ethyl ketone (trade name: 03DS-MK-RD, manufactured by Zeon Corporation, solid content: 0.35% by mass, average length: 100 ⁇ m or more, G / A sheet-like conductive member according to Comparative Example 1 was obtained in the same manner as in Example 1 except that 151 parts by mass (D band ratio 5.0) was used.
  • methyl ethyl ketone trade name: 03DS-MK-RD, manufactured by Zeon Corporation, solid content: 0.35% by mass, average length: 100 ⁇ m or more
  • G / A sheet-like conductive member according to Comparative Example 1 was obtained in the same manner as in Example 1 except that 151 parts by mass (D band ratio 5.0) was used.
  • Comparative Example 2 In the preparation of the carbon nanotube-containing composition, a single-walled carbon nanotube dispersed in methyl ethyl ketone (trade name: EC1.5P-MEK, manufactured by Meijo Nanocarbon Co., Ltd., solid content 0.2% by mass, average length 5 to 10 ⁇ m, A sheet-like conductive member according to Comparative Example 2 was obtained in the same manner as in Example 1, except that 265 parts by mass of the G / D band ratio was used.
  • methyl ethyl ketone trade name: EC1.5P-MEK, manufactured by Meijo Nanocarbon Co., Ltd.
  • Organic solvent boiling point (T1) Regarding the organic solvent used for the organic solvent-dispersed carbon nanotubes used in each of the examples and comparative examples, a melting point measuring device (model number: M-560, manufactured by Shibata Scientific Co., Ltd.) was used at a heating rate of 5 ° C./min. The boiling point (T1) of the organic solvent was measured. The results are shown in Tables 1 and 2 below.
  • thermosetting reaction start temperature (T2) With respect to the thermosetting resin and the curing agent used in each of the examples and comparative examples, the amounts shown in Tables 1 and 2 were weighed into a 250 ml plastic container (trade name: Pac Ace P-250, manufactured by Teraoka Co., Ltd.) Stirring was performed for 10 minutes with a stirring and defoaming device (trade name: Mazerustar KK-250, manufactured by Kurashiki Spinning Co., Ltd.). According to the above-mentioned measurement method, these samples were measured by heating from a room temperature to 300 ° C. at a heating rate of 5 ° C./min with a differential scanning calorimeter (model number: DSC7000, manufactured by Hitachi High-Tech Science Corporation). From the exothermic peak, the thermosetting reaction start temperature (T2) was measured.
  • thermosetting coating film was peeled off from the conductive member according to each of the examples and comparative examples, the state of breakage of the thermosetting coating film was visually evaluated.
  • thermosetting coating film could be peeled without breaking, it was evaluated as ⁇ , and when the thermosetting coating film broke, it was evaluated as x.
  • the conductive member obtained in each of the examples and comparative examples was cut out with a punch having a diameter of 12.5 mm to obtain a disk-shaped test piece having a diameter of 12.5 mm and a thickness of 10 ⁇ m.
  • the volume resistivity of this test piece was measured by a four-terminal method using a high-precision, high-function, low-resistivity meter (model number: Loresta GX, manufactured by Mitsubishi Chemical Analytech Co., Ltd., measuring terminal: PSP probe MCP-TP06P RMH112). The results are shown in Tables 1 and 2.
  • Example 1 to 8 and 10 in which the carbon nanotubes are contained in an amount of 5% by mass or more and 10% by mass or less in 100% by mass of the total solid components of the carbon nanotube-containing composition, the carbon nanotubes are contained in the total solid components of the carbon nanotube-containing composition.
  • Example 9 in which 13% by mass was contained in 100% by mass, it was found that the film was excellent in film formability and could be easily formed into a sheet.
  • Examples 1 to 10 carbon nanotubes were used as the conductive material, and no metal component was blended. Therefore, even when used as a conductive member for continuity inspection, electrodes and circuit devices to be inspected were contaminated by the metal material. Can be prevented.
  • the carbon nanotube-containing composition of the present invention can obtain excellent conductivity throughout the conductive member that is a thermosetting product, it can be used as a conductive member for a continuity test containing no metal component as a conductive material. it can. Moreover, since the conductive member which is a thermosetting product of the carbon nanotube-containing composition can be formed into a sheet shape, a conductive sheet for conduction inspection can be formed. Further, the anisotropic conductive sheet is formed by filling the through-holes of the insulating sheet body provided with a plurality of through-holes penetrating in the thickness direction with the carbon nanotube-containing composition of the present invention and curing the same. You can also.

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Abstract

Le but de la présente invention consiste à fournir : une composition dans laquelle un test de continuité peut être réalisé même lorsqu'un câblage d'un dispositif de circuit à inspecter est étroitement ajusté, et un câblage est fin et aminci, et qui présente une excellente conductivité et peut être utilisé comme élément conducteur pour un test de conductivité qui ne contient pas d'élément métallique comme matériau conducteur ; et un procédé de production d'un produit thermodurci de ladite composition. Cette composition contenant des nanotubes de carbone comprend (A) un nanotube de carbone, (B) un solvant organique, et (C) une résine thermodurcissable, où une différence en valeur absolue entre le point d'ébullition (T1) de (B) le solvant organique et la température de départ de la réaction de thermodurcissage (T2) de (C) la résine thermodurcissable est de 70 °C ou moins.
PCT/JP2019/017549 2018-06-20 2019-04-25 Composition contenant des nanotubes de carbone et procédé de production d'un produit thermodurci d'une composition contenant des nanotubes de carbone Ceased WO2019244479A1 (fr)

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KR1020207001362A KR102291539B1 (ko) 2018-06-20 2019-04-25 탄소 나노 튜브 함유 조성물 및 탄소 나노 튜브 함유 조성물의 열경화물의 제조방법

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