JP2019087532A - Conductor, conductive coating, and method for producing conductor - Google Patents

Abstract

To provide a conductor produced with carbon nanotubes, a conductive coating, and a method for producing the conductor, wherein, the conductor has both of high conductivity and excellent flexibility, and such a conductor can be obtained by the conductive coating and the method for producing the conductor.SOLUTION: A conductor C contains at least metal-containing bodies 1 and carbon nanotubes 21. Each metal-containing body 1 is surrounded and covered by the carbon nanotubes 21 so that the metal-containing bodies 1 are bonded together.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductor using carbon nanotubes, a conductive paint, and a method of manufacturing the conductor.

  In recent years, the demand for flexible conductors has increased due to the expanded use of wearable devices.

  As such a conductor, one obtained by impregnating, applying or printing a conductive paint on a flexible substrate (for example, yarn, cloth, paper, non-woven fabric, film) is known. (For example, refer patent documents 1-3 grade).

  However, conventional conductors can not be said to have both high conductivity and good flexibility.

  For example, the conductive portion described in Patent Document 1 is mainly carbon nanotubes in terms of unit area and unit mass, and the metal material is sub, so that the electrical resistance of the conductive yarn is 3 Ω at the lowest. It is / cm. Furthermore, detailed data on flexibility has not been published, and it can not be said that it has both high conductivity and good flexibility.

The volume resistivity of the flexible conductive material containing carbon nanotubes described in Patent Document 2 is as low as 7 × 10 ⁻² Ω · cm, and is too conductive for use in conductive parts such as wearable devices. Too low.

In addition, the stretchable conductor coated product containing carbon nanotubes described in Patent Document 3 has 1.1 Ω / □ as having the lowest surface resistivity, and has a thickness of 3 μm. It becomes 3 × 10 ^-4 Ω · cm. On the other hand, the rate of change of surface resistivity is based on less than 200% as one standard, and the specific numerical value is unknown, but the value is high from the standard value of 200%, and flexibility is good. I can not think at all.

Patent No. 6007350 JP, 2013-35974, A JP, 2016-35883, A

  An object of the present invention is to provide a conductor having both high conductivity and good flexibility, and a method for producing a conductive paint and conductor that can obtain such a conductor.

The conductor according to the present invention for solving the above object is
It is characterized in that it comprises at least a metal-containing body and a carbon nanotube, and the metal-containing bodies are bound together by covering the periphery of the metal-containing body with the carbon nanotube.

  In terms of unit area and unit mass, the conductor of the present invention is mainly a metal-containing body, and carbon nanotubes are sub. According to the first conductor of the present invention, high conductivity is ensured by the metal-containing body, and the carbon nanotube functions to bind the metal-containing body while exhibiting good flexibility. Thus, the conductor of the present invention combines both high conductivity and good flexibility.

Also,
It is more preferable that the metal-containing body is a metal-containing particle, and the adjacent metal-containing particles are arranged, on average, at a distance equal to or less than the diameter of the metal-containing particle.

  That is, it is preferable that the thickness of the binding layer of the carbon nanotube is equal to or less than the diameter of the metal-containing particle. In other words, when the adjacent metal-containing particles are separated by a distance exceeding the diameter, the metal-containing particles tend to be scattered in the conductive portion including a large number of carbon nanotubes. Although carbon nanotubes have good conductivity, metal-containing particles have higher conductivity than metal-containing particles. In the conductor of the present invention, carbon nanotubes are present between adjacent metal-containing particles, but when the adjacent metal-containing particles are separated by a distance exceeding the diameter, carbon nanotube binding layer is used. The height of the electrical resistance acts to increase the electrical resistance of the conductor as a whole, resulting in inferior conductivity.

Also,
The metal-containing body is also preferably a metal-coated body in which the surface of a nonmetal base material is coated with a metal, and the base material is more preferably made of an acrylic resin.

  The metal coating makes the entire conductor light.

Also,
It is also preferable that the metal contains at least one of silver and copper.

  Here, the metal may be silver 100%, copper 100%, an alloy containing silver, or an alloy containing copper. It may be an alloy containing both silver and copper.

  This aspect further improves the conductivity.

Also,
It is also preferable that the mass ratio of the carbon nanotube to 100 parts by mass of the metal coating is 0.1 or more and 20 or less.

Also,
The metal-containing body is a metal-coated particle obtained by coating the surface of a nonmetal matrix particle with metal,
It is also preferable that the metal-coated particles have a true density of 2.0 g / cm ³ or more and 4.5 g / cm ³ or less and an average particle diameter of the metal-coated particles of 2 μm or more and 20 μm or less.

  With this configuration, more metal coated particles can be included in the same mass, and the conductivity is improved.

Also,
It is also preferable that the average diameter of the carbon nanotubes is 20 nm or less.

  The smaller diameter carbon nanotubes have lower electrical resistance and superior flexibility than larger diameter carbon nanotubes, so if the average diameter is 20 nm or less, the conductivity and flexibility of the resulting conductor will be greater. It will be excellent.

The first conductive paint of the present invention which solves the above object is
A conductive paint containing at least 2% by mass to 80% by mass of a metal-coated body in which the surface of a nonmetallic matrix is coated with a metal, and 0.002% to 10% by mass of carbon nanotubes,
The metal coating contains at least one of silver and copper,
The carbon nanotubes have an average diameter of 20 nm or less,
A conductive paint, wherein a mass ratio of the carbon nanotube to 100 parts by mass of the metal coating is 0.1 or more and 20 or less.

  According to the first conductive paint of the present invention, high conductivity is ensured by the metal coating, and the carbon nanotube functions to bind the metal coating while exhibiting good flexibility, which is high. It combines both conductivity and good flexibility.

The second conductive paint of the present invention which solves the above object is
A conductive paint containing at least 2% by mass to 80% by mass of metal-coated particles in which the surface of a nonmetallic matrix particle is coated with metal, and 0.002% to 10% by mass of carbon nanotubes,
The metal-coated particles have a true density of 2.0 g / cm ³ or more and 4.5 g / cm ³ or less and an average particle diameter of 2 μm or more and 20 μm or less.

  According to the second conductive paint of the present invention, high conductivity is ensured by the metal-coated particles, and the carbon nanotube functions to bind the metal-coated particles while exhibiting good flexibility, which is high. It combines both conductivity and good flexibility.

A first method of manufacturing a conductor according to the present invention, which solves the above object,
A conductor is obtained by impregnating or applying the first or second conductive paint of the present invention to a thread-like substrate or a sheet-like substrate and then drying.

  According to the first method for manufacturing a conductor of the present invention, a linear or sheet-like electric wire can be obtained.

In the conductor of the present invention,
The metal-containing body is a plain metal particle having an average particle diameter of 5 nm or more and 100 nm or less,
The mass ratio of the carbon nanotube to 100 parts by mass of the non-base metal particle may be 20 or more and 300 or less.

A second method for producing a conductor according to the present invention, which solves the above object,
A first step of impregnating or coating a filamentous substrate or a sheet-like substrate with a first conductive paint containing 10% by mass to 80% by mass of at least a plain metal particle having an average particle diameter of 5 nm to 100 nm and drying;
A filamentous conductor or sheet-like conductor obtained by carrying out the first step is impregnated or coated with a second conductive paint containing at least 1% by mass and 9.5% by mass or less of carbon nanotubes, and then dried. And a second step of
The second step is a step of impregnating or applying the second conductive paint so that the mass ratio of the carbon nanotube is 20 or more and 300 or less with respect to 100 parts by mass of the pure metal particle after drying. I assume.

  According to the second manufacturing method of the conductor of the present invention, the layer of the second conductive paint is formed on the outside of the layer of the first conductive paint. The conductivity of the finished conductor is ensured by the layer of the first conductive paint, and the flexibility is determined by both the layer of the first conductive paint and the layer of the second conductive paint. That is, the carbon nanotube of the second conductive paint supplied in the second step is provided between adjacent non-base metal particles supplied to the thread-like substrate or the sheet-like substrate in the first step. In addition, the outside of the plain metal particle is covered by the carbon nanotube. According to the second method for manufacturing a conductor of the present invention, a conductor having both high conductivity and good flexibility can be manufactured.

  According to the present invention, it is possible to provide a conductor having both high conductivity and good flexibility, and a method for producing a conductive paint and a conductor from which such a conductor can be obtained.

It is the secondary electron image which expanded the conductor of one Embodiment of the conductor of this invention to 1000 times using the accelerating voltage of 5 kV with a field emission scanning electron microscope (FE-SEM). It is a secondary electron image which expanded the conductor of this embodiment shown in FIG. 1 to 3000 times using the accelerating voltage of 5 kV with the field emission scanning electron microscope. It is a secondary electron image which expanded the conductor of this embodiment shown in FIG. 1 to 10000 times using the accelerating voltage of 5 kV with the field emission scanning electron microscope. It is a graph which shows the mass ratio of carbon nanotube to 100 mass parts of metal covering particles, and conductivity when making a threadlike conductor into a sample, and conductivity.

  Hereinafter, the present invention will be described in detail.

  The present invention is a conductor and a conductive paint containing metal-containing particles and carbon nanotubes, wherein metal-containing particles are bonded together by carbon nanotubes in a well-dispersed state, so that they are flexible and strong between metal-containing particles. Physical and electrical connections are formed, enabling both high conductivity and good flexibility.

  FIG. 1 is a secondary electron image of a conductor according to an embodiment of the conductor of the present invention magnified by 1000 times using a field emission scanning electron microscope (FE-SEM) using an acceleration voltage of 5 kV.

  A conductor C shown in FIG. 1 is one in which carbon nanotubes cover the periphery of metal-coated particles in which an acrylic matrix particle is coated with silver. The layer which looks white around the particles is the silver metal-coated layer 11, and carbon nanotubes 21 intervene between the adjacent metal-coated particles 1 to bond the metal-coated particles 1 with each other.

  FIG. 2 is a secondary electron image in which the conductor of the present embodiment shown in FIG. 1 is magnified by 3000 times using a field emission scanning electron microscope using an acceleration voltage of 5 kV.

  As shown in FIG. 2, the periphery of the metal-coated particle 1 is covered by the binding layer 2 of the carbon tube.

  FIG. 3 is a secondary electron image in which the conductor of the present embodiment shown in FIG. 1 is magnified by 10000 with an accelerating voltage of 5 kV in a field emission scanning electron microscope.

  The carbon nanotubes 21 are wrapped in a binder resin, but from FIG. 3, in the binding layer 2, the carbon nanotubes 21 wrapped in the binder are entangled or mixed and bound I understand.

The type of metal-containing particles in the present embodiment is not particularly limited, and any metal-containing particles may be used, but metal-coated particles or base-free metal particles in which base material particles are coated with metal are used. Is preferred. The shape of the particles is not particularly limited, and spherical, spheroidal, square, round, needle-like, rod-like, cylindrical, indeterminate or the like may be used. That is, what has so far been referred to as metal-containing particles can be read as a metal-containing body (the same applies to the following), and what is called matrix particles can be read as a matrix (also in the following) As well). The particle diameter is not particularly limited, but in the case of using metal-coated particles, the average particle diameter is preferably 2 μm to 20 μm, and in the case of using plain metal particles, the average particle diameter is 5 nm to 100 nm preferable. In the case of metal-coated particles, weight reduction can be achieved by making the base material particles nonmetallic, and conductive paths can be easily formed by using particles with a larger particle size than plain metal particles, and the obtained conductivity can be obtained. The conductivity of the body is increased. However, when the average particle size becomes too large, the number of metal coated particles per unit area and unit mass decreases, the number of conductive paths also decreases, and the value of conductor resistance increases, and metal coated particles It is easy to fall off and lose flexibility. The true density is not particularly limited, but in the case of using metal-coated particles, it is preferably 2.0 g / cm ³ or more and 4.5 g / cm ³ or less. The size of the matrix particles and the thickness of the metal coating layer are determined so as to fall within the true density range. If the size of the matrix particles is the same, if the true density of the metal coated particles is low, the thickness of the metal coating layer is small and the conductivity is lowered, but the weight is reduced. Conversely, if the true density of the metal coated particles is high, metal Although the thickness of the covering layer is thick and the conductivity becomes high, it becomes heavy.

  The true density in the present embodiment is a density in which only the volume occupied by the substance itself is the volume for density calculation, and can be measured by a liquid phase replacement method, a gas phase replacement method, or the like. Measurement can be performed using BELPycno manufactured by Microtrack Bell Co., Ltd., MAT-7000 manufactured by Seishin Enterprise Co., Ltd., VM-100 manufactured by Seishin Enterprise Co., Ltd., and the like.

  In addition, there is no particular limitation on the metal species constituting the metal-containing particles, and silver, copper, gold, aluminum, magnesium, tungsten, cobalt, zinc, nickel, iron, platinum, tin, chromium, lead, titanium, manganese, mercury Any of them can be used, and they can be used alone, in combination or as an alloy, but from the viewpoint of conductivity, it is preferable to use silver or copper alone, as a combination or as an alloy.

  In the present embodiment, the type of carbon nanotube is not particularly limited, either single-walled carbon nanotube or multi-walled carbon nanotube can be used. Methods of producing carbon nanotubes include catalytic chemical vapor deposition (CCVD), laser evaporation, arc discharge, and the like. In the present embodiment, carbon nanotubes produced by any of the methods can be used. In terms of cost, it is preferable to use multi-walled carbon nanotubes. However, as will be described later, when single-walled carbon nanotubes are used, good conductivity can be obtained with a mass amount smaller than that when multi-walled carbon nanotubes are used, so even when single-walled carbon nanotubes are used In general, it can not be said that single-walled carbon nanotubes are inferior in cost to multi-walled carbon nanotubes since they can be reduced. Although the diameter of the carbon nanotube is not particularly limited, the carbon nanotube having an average diameter of 20 nm or less is used because the carbon nanotube having a smaller diameter has lower electric resistance and superior flexibility than a carbon nanotube having a larger diameter. This makes the conductivity and flexibility of the resulting conductor better. More specifically, it is preferable that the average diameter is 5 nm or more and 20 nm or less when using multi-walled carbon nanotubes, and the average diameter is less than 5 nm when using single-walled carbon nanotubes. The length of the carbon nanotube is not particularly limited, but it is preferable that the length be 0.5 μm or more because the physical and electrical connection between metal-containing particles may be insufficient if the length is short.

  In the present embodiment, the mass ratio of the metal-containing particles to the carbon nanotubes is not particularly limited, but in consideration of securing the physical and electrical connection between the metal-containing particles, the carbon nanotubes per 100 parts by mass of the metal-containing particles The mass ratio is preferably 0.1 or more and 300 or less. When metal-coated particles are used, the mass ratio of carbon nanotubes to 100 parts by mass of metal-coated particles is preferably 0.1 or more and 20 or less, and when non-base metal particles are used, 100 parts by mass of non-base metal particles The mass ratio of carbon nanotubes is preferably 20 or more and 300 or less. If the mass ratio of carbon nanotubes is too low, the physical function of binding metal-containing particles is reduced. In addition, the function of electrically connecting the metal-containing particles is also degraded. Although carbon nanotubes have good conductivity, metal-containing particles have higher conductivity than metal-containing particles. As shown in FIG. 2 etc., carbon nanotubes 21 are present between adjacent metal-containing particles, but if the mass ratio of carbon nanotubes is too high, the adjacent metal-containing particles will be separated too much. That is, the binding layer 2 of the carbon nanotube becomes thick, the height of the electrical resistance in the binding layer 2 acts, the electrical resistance as the whole conductor increases, and the conductivity becomes inferior. The conductor shown in FIGS. 1 to 3 uses multi-walled carbon nanotubes, but even if single-walled carbon nanotubes are used, the single-walled carbon nanotubes cover the periphery of the metal-containing particles. There is. Here, that the carbon nanotube covers the periphery of the metal-containing particle is not limited to covering the carbon nanotube without a gap, but a gap may exist, and it is preferable that the carbon nanotube exists uniformly. In addition, single-walled carbon nanotubes have a smaller average diameter than multi-walled carbon nanotubes, so they have low electrical resistance and excellent flexibility. That is, as described above, the carbon nanotube with a smaller diameter has a lower electrical resistance and is more flexible than a carbon nanotube with a larger diameter. For this reason, if single-walled carbon nanotubes are used, good conductivity can be obtained with a mass-wise smaller amount than when multi-walled carbon nanotubes are used, and the mass ratio of single-walled carbon nanotubes to 100 parts by mass of metal-coated particles Should be 0.1 or more. When plain metal particles are used, as described later, the method of producing a conductor is divided into two steps, and a layer containing carbon nanotubes is formed outside the layer containing metal-containing particles. The mass ratio of nanotubes is increased.

  The metal-coated particles in the present embodiment are particles in which the surface of a matrix particle is coated with a metal, and by selecting a material having a low true density as the matrix particle, the metal density is reduced with a true density lower than pure metal particles. Conductivity can be obtained. If the particle diameter and the conductivity are the same, the lower the true density, the larger the number of particles in the same added mass, and the more easily a conductive path is formed, the conductivity of the obtained conductor becomes high. In addition, since the amount of addition for obtaining conductivity similar to that of a conductor using a conventional conductive material may be small, the weight of the conductor can be reduced, which is advantageous in application to wearable devices. The material of the matrix particles is not particularly limited, but in view of the above, a material having a low true density is preferable. Silica or aluminum is preferred, and acrylic, phenolic or styrenic resins are particularly preferred.

  The plain metal particles in the present embodiment refer to metal particles that have not been plated.

  The conductive paint in this embodiment will be described. When metal coated particles are used, they contain at least 2 wt% to 80 wt% of metal coated particles and 0.002 wt% to 10 wt% of carbon nanotubes, and the mass ratio of carbon nanotubes to 100 wt parts of metal coated particles It is preferable to use a conductive paint in which is 0.1 or more and 20 or less. The concentration of the metal-coated particles and carbon nanotubes in the conductive paint is appropriate in consideration of the handling property of the conductive paint after the mass ratio of carbon nanotubes to 100 parts by mass of the metal-coated particles satisfies 0.1 to 20. Within the above viscosity range, it is preferable that the concentration be as high as possible within the above mass% range. When using plain metal particles, it is preferable to use a conductive paint containing at least 10 wt% to 80 wt% of plain metal particles and a conductive paint containing at least 1 wt% to 9.5 mass% of carbon nanotubes.

  The metal-coated particles, the plain metal particles and the carbon nanotubes in the conductive paint in the present embodiment are preferably in a well-dispersed state. Anionic surfactant comprising methyl naphthalene sulfonic acid formalin condensate salt, naphthalene sulfonic acid formalin condensate salt, and alkylene maleic acid copolymer salt as a dispersant, if necessary, water soluble xylan, xanthan gums, guar gums, Gellan gums, polysaccharides such as carboxymethyl cellulose, polyoxyalkylene (POA) octyl phenyl ether, POA nonyl phenyl ether, POA dibutyl phenyl ether, POA styryl phenyl ether, POA benzyl phenyl ether, POA bisphenol A ether, POA cumyl phenyl ether One or more nonionic surfactants such as can be used.

  The conductive resin in the present embodiment contains a binder resin. As the binder resin, acrylic resin, acrylonitrile butadiene copolymer resin, styrene butadiene copolymer resin, polyurethane resin, polyester resin, polyvinyl chloride resin, ethylene vinyl acetate copolymer resin, polyvinyl alcohol, methyl cellulose, Methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, modified starch, polyvinyl pyrrolidone and the like can be mentioned.

  Further, in the present embodiment, after the conductive paint is impregnated or applied to a thread-like substrate or a sheet-like substrate, a conductor is obtained by drying. The conductor thus obtained can be used as a linear or sheet-like electric wire.

  The thread-like base material in the present embodiment is not particularly limited as long as it can support a paint component when it is impregnated or applied with a conductive paint. Materials include synthetic fibers such as polyester, nylon and acrylic, regenerated fibers such as rayon, cupra, lyocell and acetate, and natural fibers such as cotton and silk, but any of them can be used, but lightness and flexibility (flexibility (flexibility) In terms of strength, etc., it is preferable to use one or more synthetic fibers.

  The sheet-like substrate in the present embodiment is not particularly limited as long as it can carry a coating component when it is impregnated or coated with a conductive coating. Specifically, uniaxially stretched sheet made of polyethylene, polypropylene, polybutene, polyethylene terephthalate, polyamide, polyvinyl chloride, polyvinylidene chloride, polymethylpentene or the like, synthetic resin sheet such as biaxially stretched sheet, cellulose fiber, synthetic resin fiber or Nonwoven fabric made of rayon fibers etc. by a dry method, wet method, spun bond method, melt blow method, thermal bond method, chemical bond method, needle punch method, spun lace method, stitch bond method or steam jet method Or papers such as high quality paper, art paper, coated paper, cast coated paper, kraft paper or impregnated paper, synthetic fibers such as polyester, nylon and acrylic, recycled fibers such as rayon, cupra, lyocell and acetate, cotton, silk etc Made from natural fibers of Mention may be made of the obtained cloth obtained by weaving the yarn.

  The manufacturing method of the conductor and conductive paint of this embodiment will be described.

  Since carbon nanotubes have the property of being easily aggregated, it is preferable to disperse the carbon nanotubes in advance using water as a solvent. Dispersion can be carried out using an ultrasonic homogenizer, homogenizer, high pressure homogenizer, ball mill, bead mill, colloid mill, high pressure jet disperser, roll mill or the like. Dispersion can also be carried out by adding a dispersant as required.

  When metal-coated particles are used, a conductive paint containing metal-coated particles and carbon nanotubes can be produced by adding the metal-coated particles to a carbon nanotube dispersion and stirring. A dispersing agent and a binder resin can also be added as needed. The conductive paint thus obtained can be impregnated or applied to a thread-like substrate or a sheet-like substrate and then dried to produce a thread-like or sheet-like conductor containing metal-coated particles and carbon nanotubes.

  When using plain metal particles, a plain metal particle is dispersed in a solvent to produce a conductive paint (corresponding to a first conductive paint) containing plain metal particles. As an example, a conductive paint containing 10% by mass to 80% by mass of plain metal particles having an average particle diameter of 5 nm to 100 nm is produced. The conductive paint is impregnated or applied to a thread-like substrate or a sheet-like substrate and then dried (corresponding to the first step) to obtain a thread- or sheet-like conductor containing a base-free metal. In addition, a carbon nanotube dispersion liquid (corresponding to the second conductive paint) containing 1% by mass or more and 9.5% by mass or less of carbon nanotubes is also prepared, and carbon nanotubes are used as the threadlike or sheet-like conductor containing the above-mentioned free metal. By impregnating or applying the dispersion and then drying (corresponding to the second step), a filamentous or sheet-like conductor containing a non-base metal and a carbon nanotube can be produced. According to the method for producing a conductor of the present embodiment, the first layer containing plain metal particles is formed into a thread-like or sheet-like conductor, and the second layer containing carbon nanotubes is formed outside the first layer. It will be done. The conductivity of the finished conductor is ensured in the first layer and the flexibility is determined by both the first and the second layer. That is, the carbon nanotube intervenes between the plain metal particles attached to the thread-like or sheet-like conductor, and the outside of the plain metal particle is covered with the carbon nanotube. For this reason, it is possible to make the second layer thicker, and increase the relative mass ratio of carbon nanotubes to metal-containing particles (base-free metal particles) as compared to the case where metal-coated particles are used as the metal-containing particles. It is possible.

  In the present embodiment, the method for impregnating or applying the conductive paint to the thread-like substrate is not particularly limited, but as an example, a large diameter roller in which the lower portion of the roll is immersed in the conductive paint and a small diameter rotation by rotation of the large diameter roller Using a yarn processing device having a roller, the large diameter roller is rotated, and a thread-like base material is passed between the large diameter roller and the small diameter roller while finely vibrating the small diameter roller using a vibrator. Excess conductive paint of the conductive paint carried on the thread-like substrate is shaken off by micro-vibration while the thread-like substrate passes between the large diameter roller and the small diameter roller. Thereafter, the thread-like substrate carrying an appropriate amount of conductive paint is dried. In addition, by repeating such steps a plurality of times as long as the flexibility and texture of the yarn are not lost, more conductive paint is supported on the thread-like base material, and the conductivity of the obtained thread-like conductor is obtained. Can be further enhanced. That is, the metal-containing particle layer in which the metal-containing particles are bound by the binding layer of the carbon nanotube covering the periphery of the metal-containing particles is formed by being superimposed on many layers, and the conductivity can be further enhanced.

  In the present embodiment, the method of impregnating the sheet-like substrate with the conductive paint is not particularly limited, but after the sheet-like substrate is dipped in an impregnating pan filled with the conductive paint, it is passed through nip rollers to It is preferred that the conductive paint be dropped and then dried. In addition, by repeating such steps a plurality of times within a range that does not impair the flexibility and texture of the sheet, more conductive paint is supported on the sheet-like base material, and the resulting sheet-like conductor can be obtained. The conductivity can be further enhanced.

  In the present embodiment, the method for applying the conductive paint to the sheet-like substrate is not particularly limited, but the conductive paint may be a wire bar coater, a knife coater, an air knife coater, a blade coater, a reverse roll coater, a die coater, a gravure coater, After applying to a sheet-like base material using a comma coater etc., the method to dry is preferable. In addition, by repeating such steps a plurality of times within a range that does not impair the flexibility and texture of the sheet, more conductive paint is supported on the sheet-like base material, and the resulting sheet-like conductor can be obtained. The conductivity can be further enhanced.

  FIG. 4 is a graph showing the relationship between the mass ratio of carbon nanotubes to 100 parts by mass of metal-coated particles and the conductivity when a thread-like conductor is used as a sample.

  The thread-like conductor used as a sample is a metal-coated particle in which an acrylic matrix particle is coated with silver and in which a carbon nanotube covers the periphery. Carbon nanotubes are multi-walled carbon nanotubes. The horizontal axis of the graph shown in FIG. 4 represents the mass ratio of carbon nanotubes to 100 parts by mass of silver-coated acrylic particles (hereinafter referred to as the CNT mass ratio), and the vertical axis represents conductivity. The conductivity is an index obtained from the resistance value (thread resistance value (Ω / cm)) of the thread-like conductor, and the lower the thread resistance value, the higher the conductivity.

  From the graph shown in FIG. 4, it can be seen that when multi-walled carbon nanotubes are used, the filamentary conductor having a CNT mass ratio of less than 5 has the best conductivity. When observing each sample using a field emission scanning electron microscope, in a filament conductor with a CNT mass ratio of less than 5, adjacent silver-coated acrylic particles are arranged, on average, at a distance equal to or less than the radius of the silver-coated acrylic particles. It was The observation result of the thread-like conductor having a CNT mass ratio of less than 5 was similar to the secondary electron image shown in FIGS. 1 to 3. Further, in the filamentary conductor having a CNT mass ratio of 9 or more, adjacent silver-coated acrylic particles are arranged, on average, at a distance longer than the radius of the silver-coated acrylic particles and less than the diameter. Furthermore, in the thread-like conductor having a CNT mass ratio of about 14, adjacent silver-coated acrylic particles are arranged, on average, at a distance of about the diameter of the silver-coated acrylic particles. From these facts, it can be understood that when the silver-coated acrylic particles are separated, the conductivity tends to decrease.

  On the other hand, in a filamentary conductor having a CNT mass ratio of about 2.5, the conductivity is lower than that of a filamentary conductor having a CNT mass ratio of less than 5, but this is because the CNT mass ratio is low. It is considered that the function of electrically connecting the silver-coated acrylic particles with each other is lowered and the conductivity is also lowered.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. Moreover, "part" and "%" show a mass part and mass% unless otherwise indicated in an Example and a comparative example. Furthermore, as a standard for dispersion treatment of carbon nanotubes in Examples and Comparative Examples, the particle diameter of carbon nanotubes is 0 in median diameter measured using a laser diffraction / scattering type particle size distribution measuring apparatus (MT-3300EX; manufactured by Nikkiso Co., Ltd.) And 10 to 80 μm.

(Preparation of Carbon Nanotube Dispersion 1)
100 parts of carbon nanotubes (trade name NC7000, manufactured by Nanocyl, average diameter 9.5 nm, length 1.5 μm) and 50 parts by solid content of carboxymethylcellulose as a dispersant were prepared. Next, carboxymethylcellulose was added to 850 parts of distilled water as a solvent, and stirred with a stirrer for 1 to 2 minutes. Furthermore, carbon nanotubes were added to this aqueous solution, and dispersion treatment was performed with an ultrasonic homogenizer (US-600fcat manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain a carbon nanotube dispersion 1.

(Preparation of Carbon Nanotube Dispersion 2)
200 parts of a carbon nanotube (trade name: CNTs 20, manufactured by SUSN, average diameter: 20 nm, length: 5 to 12 μm) was prepared, and 100 parts of solid content of carboxymethylcellulose as a dispersant was prepared. Next, carboxymethylcellulose was added to 700 parts of distilled water as a solvent, and stirred with a stirrer for 1 to 2 minutes. Furthermore, carbon nanotubes were added to this aqueous solution, and dispersion treatment was performed using an ultrasonic homogenizer (US-600fcat manufactured by Nippon Seiki Seisakusho Co., Ltd.), to obtain a carbon nanotube dispersion liquid 2.

(Preparation of Carbon Nanotube Dispersion 3)
100 parts of carbon nanotubes having an average diameter of 21 nm and a length of 5 to 12 μm, and 50 parts by solid content of carboxymethylcellulose as a dispersant were prepared. Next, carboxymethylcellulose was added to 850 parts of distilled water as a solvent, and stirred with a stirrer for 1 to 2 minutes. Furthermore, carbon nanotubes were added to this aqueous solution, and dispersion treatment was performed with an ultrasonic homogenizer (US-600fcat manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain carbon nanotube dispersion liquid 3.

(Preparation of Carbon Nanotube Dispersion 4)
Two parts of a carbon nanotube (trade name: TUBALL, manufactured by OCSiAl, average diameter: 1.6 nm, length: 5 μm) were prepared, and 4 parts in solid content of carboxymethylcellulose as a dispersant were prepared. Next, carboxymethylcellulose was added to 994 parts of distilled water as a solvent, and stirred with a stirrer for 1 to 2 minutes. Furthermore, carbon nanotubes were added to this aqueous solution, and dispersion treatment was performed with an ultrasonic homogenizer (US-600fcat manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain carbon nanotube dispersion liquid 4. The carbon nanotubes used for the carbon nanotube dispersions 1 to 3 are multi-walled carbon nanotubes, but the carbon nanotubes used for the carbon nanotube dispersion 4 are single-walled carbon nanotubes. The single-walled carbon nanotubes used here have an average diameter of 1 nm and a length of around 1 μm.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 1)
100 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 100 Parts and distilled water 50 parts were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 1.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 2)
100 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 4.1 g / cm ³ , average particle diameter 2 μm) 100 Parts and distilled water 50 parts were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 2.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 3)
100 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.0 g / cm ³ , average particle diameter 20 μm) 100 Parts and distilled water 50 parts were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 3.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 4)
50 parts of carbon nanotube dispersion 2 is put into a beaker and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) The mixture was added with 100 parts of distilled water and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 4.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 5)
10 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) Parts and 140 parts of distilled water were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 5.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 6)
100 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 50 Part and 17 parts of distilled water were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 6.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 7)
100 parts of carbon nanotube dispersion 1 is put into a beaker and stirred, and 100 parts of metal-coated particles (copper-coated acrylic particles, true density 2.2 g / cm ³ , average particle diameter 10 μm) and 50 parts of distilled water are added thereto The mixture was stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 7.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 8)
100 parts of carbon nanotube dispersion 1 is put into a beaker and stirred, and 100 parts of metal-coated particles (silver-coated aluminum particles, true density 4.5 g / cm ³ , average particle diameter 6 μm) and 50 parts of distilled water are added thereto The mixture was stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 8.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 9)
60 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 15 parts of a binder resin solution (Evaphanol HA-107C, manufactured by Nichika Chemical Co., Ltd., binder concentration 40%) and 25 parts of distilled water are added and stirred for 15 minutes to prepare a metal-coated particle / carbon nanotube mixed dispersion 9 I got

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 10)
100 parts of carbon nanotube dispersion liquid 3 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 100 Parts and distilled water 50 parts were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 10.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 11)
100 parts of carbon nanotube dispersion 1 is put into a beaker and stirred, and 100 parts of metal-coated particles (aluminum coated acrylic particles, true density 2.2 g / cm ³ , average particle diameter 10 μm) and 50 parts of distilled water are added thereto The mixture was stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 11.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 12)
100 parts of carbon nanotube dispersion 1 is put into a beaker and stirred, and 100 parts of metal coated particles (silver coated acrylic particles, true density 1.9 g / cm ³ , average particle diameter 21 μm) and 50 parts of distilled water are added thereto. The mixture was stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 12.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 13)
100 parts of carbon nanotube dispersion 1 is put into a beaker and stirred, and 100 parts of metal-coated particles (silver-coated acrylic particles, true density 4.6 g / cm ³ , average particle diameter 1 μm) and 50 parts of distilled water are added thereto. The mixture was stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 13.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 14)
9 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) Parts and 141 parts of distilled water were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 14.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 15)
The carbon nanotube dispersion liquid 1 is placed in a beaker of 158 parts and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 75 The mixture was added with 17 parts of distilled water and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 15.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 16)
0.5 part of a carbon nanotube dispersion 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 5 parts and 245.5 parts of distilled water were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 16.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 17)
0.25 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 2.5 parts and 247.25 parts of distilled water were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 17.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 18)
50 parts of carbon nanotube dispersion 1 are put into a beaker and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 200 The mixture was partially added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion 18.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 19)
125 parts of carbon nanotube dispersion liquid 2 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 125 The mixture was partially added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 19.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 20)
47.5 parts of carbon nanotube dispersion liquid 1 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 202.5 parts of the mixture and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 20.

(Preparation of metal-coated particle / carbon nanotube mixed dispersion 21)
137.5 parts of carbon nanotube dispersion liquid 2 is put into a beaker and stirred, and metal coated particles (silver coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , average particle diameter 10 μm) 112.5 parts of this and added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 21.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 22)
A carbon nanotube dispersion 4 using single-walled carbon nanotubes is put in a beaker of 50 parts and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm ³ , 100 parts of an average particle diameter of 10 μm and 100 parts of distilled water were added and stirred for 15 minutes to obtain a metal-coated particle / carbon nanotube mixed dispersion liquid 22.

(Preparation of metal coated particle / carbon nanotube mixed dispersion 23)
A carbon nanotube dispersion liquid 4 using single-walled carbon nanotubes is put in a beaker 2.5 parts and stirred, and metal-coated particles (silver-coated acrylic particles, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., true density 2.2 g / cm) ^3, average particle size 10 [mu] m) stirring to the distilled water was added 242.5 parts of 5 parts for 15 minutes to obtain a metal-coated particles / carbon nanotubes mixed dispersion 23.

Example 1
A polyester-based multifilament (150d-48f-1) was prepared as a filamentous substrate. This was immersed in the metal-coated particle / carbon nanotube mixed dispersion liquid 1 and dried at 120 ° C. for 1 minute to obtain a thread-like conductor. In Examples 1 to 17, metal-coated particles are used.

(Example 2)
A polyester film (E5101, manufactured by Toyobo Co., Ltd., 75 μm in thickness) was prepared as a sheet-like substrate. The metal-coated particle / carbon nanotube mixed dispersion 1 was bar-coated on the corona-treated surface of this polyester film, and dried at 120 ° C. for 2 minutes to obtain a sheet-like conductor.

(Example 3)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 2. In Example 3, the true density of the metal-coated particles is higher, and the particle size of the metal-coated particles is smaller.

(Example 4)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 2. Also in this Example 4, the true density of the metal-coated particles is higher, and the particle diameter of the metal-coated particles is smaller.

(Example 5)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 3. In Example 5, the true density of the metal-coated particles is lower, and the particle size of the metal-coated particles is larger.

(Example 6)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 3. Also in this Example 6, the true density of the metal-coated particles is lower, and the particle diameter of the metal-coated particles is larger.

(Example 7)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 4. In Example 7, the diameter of the carbon nanotube is larger.

(Example 8)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 4. Also in this Example 8, the diameter of the carbon nanotube is larger.

(Example 9)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 5. In this example 9, the mass ratio of CNT to metal-coated particles is lower.

(Example 10)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 5. Also in this Example 10, the mass ratio of CNT to metal-coated particles is lower.

(Example 11)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 6. In Example 11, the mass ratio of CNT to metal-coated particles is high.

(Example 12)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 6. Also in this Example 12, the mass ratio of CNT to metal-coated particles is high.

(Example 13)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 7. Although silver coated metal coated particles have been used up to now, in this Example 13, copper coated metal coated particles are used.

(Example 14)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 7. Also in this Example 14, copper-coated metal-coated particles are used.

(Example 15)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 8. Until now, acrylic matrix particles have been used as matrix particles of metal-coated particles, but in this Example 15, aluminum matrix particles are used.

(Example 16)
A sheet-like conductor was obtained in the same manner as in Example 2 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 8. In Example 16 also, aluminum base particles are used.

(Example 17)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 9. In Example 17, a binder resin solution is used.

(Example 18)
A polyester-based multifilament (150d-48f-1) was prepared as a filamentous substrate. This is immersed in a solid metal particle dispersion (51% by mass silver nanoparticle water dispersion, manufactured by Mitsubishi Paper Mills Ltd., average particle diameter 20 nm) corresponding to one example of the first conductive paint, and 1 at 120 ° C. Let dry for a minute. The obtained non-base metal particle-supporting filamentous base is immersed in a dispersion obtained by diluting the carbon nanotube dispersion 1, which corresponds to one example of the second conductive paint, with distilled water twice, and dried at 120 ° C. for 1 minute. A thread-like conductor containing 150 parts of carbon nanotubes with respect to 100 parts of plain metal particles was obtained. In Examples 18 to 22, pure metal particles are used.

(Example 19)
A thread-like conductive material containing 150 parts of carbon nanotubes per 100 parts of non-base metal particles in the same manner as in Example 18 except that a dispersion having an average particle size of 5 nm of silver nanoparticles in the base metal particle dispersion was used I got a body. In Example 19, a plain metal particle having a smaller particle size is used.

Example 20
A thread-like conductive material containing 150 parts of carbon nanotubes per 100 parts of non-base metal particles in the same manner as in Example 18 except that a dispersion in which the average particle diameter of silver nanoparticles in the base metal particle dispersion is 100 nm is used I got a body. In Example 20, plain metal particles having a relatively large particle size are used.

(Example 21)
A filamentous conductor containing 20 parts of carbon nanotubes with respect to 100 parts of non-base metal particles was obtained in the same manner as in Example 18 except that the dilution ratio of carbon nanotube dispersion liquid 1 was changed to 10 times. In Example 21, the mass ratio of CNT to plain metal particles is lower. In addition, the concentration of carbon nanotubes in the carbon nanotube dispersion corresponding to the second conductive paint is also lower.

(Example 22)
A filamentous conductor containing 300 parts of carbon nanotubes with respect to 100 parts of plain metal particles was obtained in the same manner as in Example 18 except that the dilution ratio of the carbon nanotube dispersion 1 was changed to 1.05. In Example 22, the mass ratio of CNT to plain metal particles is high. In addition, the concentration of carbon nanotubes in the carbon nanotube dispersion corresponding to the second conductive paint is also high.

(Example 23)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 10. In Examples 23 to 34, metal-coated particles are used, and in Example 23, carbon nanotubes with a large diameter are used.

(Example 24)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 11. In this example 24, metal coated particles coated with aluminum are used.

(Example 25)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 12. In Example 25, metal-coated particles having a low true density and a large particle size are used.

(Example 26)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 13. In this Example 26, metal-coated particles having a high true density and a small particle size are used.

(Example 27)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 14. In this example 27, the mass ratio of CNT to metal-coated particles is low.

(Example 28)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 15. In this Example 28, the mass ratio of CNT to metal-coated particles is high.

(Example 29)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 16 and the operations of immersion and drying were repeated 20 times. In Example 29, the concentration of metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is lower, and the concentration of carbon nanotubes is also lower.

(Example 30)
A thread-like conductor was obtained in the same manner as Example 1, except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 17 and the dipping and drying operations were repeated 40 times. In this Example 30, the concentration of metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is low, and the concentration of carbon nanotubes is also low.

(Example 31)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 18. In Example 31, the concentration of the metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is high.

(Example 32)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 19. In Example 32, the concentration of carbon nanotubes in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is high.

(Example 33)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 20. In this Example 33, the concentration of the metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is high.

(Example 34)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 21. In Example 34, the concentration of carbon nanotubes in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is high.

(Example 35)
A thread-like conductive material containing 150 parts of carbon nanotubes per 100 parts of non-base metal particles in the same manner as in Example 18 except that a dispersion wherein the average particle diameter of silver nanoparticles in the base metal particle dispersion is 4 nm was used I got a body. Also in this Example 35 to Example 42, a plain metal particle is used. In Example 35, plain metal particles having a small particle size are used.

(Example 36)
A thread-like conductive material containing 150 parts of carbon nanotubes per 100 parts of non-base metal particles in the same manner as in Example 18 except that a dispersion in which the average particle diameter of silver nanoparticles in the base metal particle dispersion is 101 nm was used I got a body. In Example 36, plain metal particles having a large particle size are used.

(Example 37)
A thread-like conductor containing 19 parts of carbon nanotubes to 100 parts of non-base metal particles was obtained in the same manner as in Example 18 except that the dilution ratio of carbon nanotube dispersion liquid 1 was changed to 11 times. In Example 37, the mass ratio of CNT to plain metal particles is low. In addition, the concentration of carbon nanotubes in the carbon nanotube dispersion corresponding to the second conductive paint is also low.

(Example 38)
In the same manner as in Example 18 except that the carbon nanotube dispersion 1 was used as a stock solution, a filamentous conductor containing 301 parts of carbon nanotubes to 100 parts of non-base metal particles was obtained. In Example 38, the mass ratio of CNT to plain metal particles is high. In addition, the concentration of carbon nanotubes in the carbon nanotube dispersion corresponding to the second conductive paint is also high.

(Example 39)
Filament containing 100 parts of carbon nanotubes per 100 parts of non-base metal particles in the same manner as in Example 18 except that the solvent of the non-base metal particle dispersion is partially evaporated to make the non-base metal particle concentration 80% by mass. I got a conductor. In Example 39, the concentration of the non-base metal particles in the conductive paint containing non-base metal particles corresponding to the first conductive paint is high.

(Example 40)
A carbon nanotube was prepared per 100 parts of pure metal particles in the same manner as in Example 18 except that the pure metal particle dispersion was diluted 5.1 times with distilled water to make the pure metal particle concentration 10% by mass. A filamentous conductor containing 200 parts was obtained. In Example 40, the concentration of the non-base metal particles in the conductive paint containing non-base metal particles corresponding to the first conductive paint is lower.

(Example 41)
A filament containing 95 parts of carbon nanotubes per 100 parts of non-base metal particles in the same manner as in Example 18 except that the solvent of the non-base metal particle dispersion is partially evaporated to make the base metal particle concentration 81% by mass. I got a conductor. In Example 41, the concentration of the non-base metal particles in the conductive paint containing non-base metal particles corresponding to the first conductive paint is high.

(Example 42)
A carbon nanotube was prepared to 100 parts of pure metal particles in the same manner as in Example 18 except that the pure metal particle dispersion was diluted 5.7 times with distilled water to make the pure metal particle concentration 9 mass%. A filamentous conductor containing 205 parts was obtained. In this example 42, the concentration of the non-base metal particles in the conductive paint containing non-base metal particles corresponding to the first conductive paint is low.

  Examples 1 to 42 described above are examples using multi-walled carbon nanotubes, while Examples 43 and 44 described below are examples using single-walled carbon nanotubes.

(Example 43)
A thread-like conductor was obtained in the same manner as in Example 1 except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 22. That is, this Example 43 is an example in which Example 9 using multi-walled carbon nanotubes is replaced with single-walled carbon nanotubes, and in Example 43, the average diameter of carbon nanotubes is short, and the mass ratio of CNT to metal-coated particles is Is lower.

(Example 44)
A thread-like conductor was obtained in the same manner as Example 1, except that the metal-coated particle / carbon nanotube mixed dispersion 1 was replaced with the metal-coated particle / carbon nanotube mixed dispersion 23 and the operations of immersion and drying were repeated 20 times. That is, this Example 44 is an example in which Example 29 using multi-walled carbon nanotubes is replaced with single-walled carbon nanotubes, and in Example 44 as well as Example 43, the average diameter of carbon nanotubes is short and metal The weight ratio of CNT to coated particles is lower. In Example 44, the concentration of metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is lower, and the concentration of carbon nanotubes is also lower.

(Comparative example 1)
A metal-coated particle dispersion was obtained by adding 40 parts of metal-coated particles (silver-coated acrylic particles, true density: 2.2 g / cm ³ , average particle diameter: 10 μm) to 60 parts of distilled water and stirring for 15 minutes. A polyester-based multifilament (150d-48f-1) was prepared as a thread-like base material, and this was dipped in a metal-coated particle dispersion and dried at 120 ° C for 1 minute to obtain a thread-like conductor. That is, Comparative Example 1 does not contain any carbon nanotube.

(Comparative example 2)
By partially evaporating the solvent of carbon nanotube dispersion liquid 1, the carbon nanotube concentration in the dispersion liquid was made 15 mass%. Two parts of metal-coated particles (silver-coated acrylic particles, true density 2.2 g / cm ³ , average particle size 10 μm) are added to 98 parts of the carbon nanotube dispersion, and the mixture is mixed with metal-coated particles / carbon nanotubes by stirring for 15 minutes. Dispersion 22 was obtained. A polyester-based multifilament (150d-48f-1) was prepared as a thread-like base material, and this was immersed in the metal-coated particle / carbon nanotube mixed dispersion 22 and dried at 120 ° C for 1 minute to obtain a thread-like conductor.

(Evaluation method)
(1) Each measurement is performed by applying a voltage of 1000 V to 10 thread-like conductor samples each having a length of 10 cm in a constant temperature and humidity environment at a wire resistance of 20 ° C. and 30% RH of the thread-like conductor The wire resistance value (Ω / cm) of each thread-like conductor was calculated by finding the average value of the resistance values of the thread-like conductor.
(2) Volume resistivity of sheet-like conductor Loresta AX MCP-T370 manufactured by Mitsubishi Chemical Analytech Co., Ltd. The surface resistivity of the sheet-like conductor is measured in accordance with JIS K 7194-1994 using a simple low resistance meter It was measured. The measurement was performed at 9 points per test piece, and the arithmetic average value was taken as the surface resistivity of the test piece. The volume resistivity of the sheet-like conductor was calculated by multiplying the value of the obtained surface resistivity by the thickness (cm) of the conductive part of the sheet-like conductor.
(3) Rate of increase in resistance after bending After bending the filamentous conductor or sheet-like conductor to a curvature radius of 1 cm, measure and calculate the wire resistance value for the filamentous conductor and the volume resistivity for the sheet-like conductor “100 × value after bending / value before bending−100” was taken as the rate of increase in resistance. The smaller this value is, the more excellent the flexibility (flexibility) can be said to be a conductor.
(4) Mass of conductive part in thread-like conductor The mass of thread-like conductor 1 m was measured by an electronic balance, and the obtained value was multiplied by 10000 to calculate the mass per 10000 m of thread-like conductor. A value obtained by subtracting a mass (167 g / 10000 m) per 10000 m of the thread-like base material from this value was taken as the mass of the conductive portion in the thread-like conductor. The smaller the value, the lighter the thread-like conductor.
(5) Mass of conductive portion in sheet-like conductor The mass (including base material) of the sheet-like conductor of 0.2 m square is measured by an electronic balance, and the obtained value is multiplied by 25 to obtain a sheet-like conductor. The mass per 1 m ² (including the base material) was calculated. A value obtained by subtracting the mass (105 g / m ² ) per 1 m ^{2 of the} sheet-like base material from this value was taken as the mass of the conductive portion in the sheet-like conductor. The smaller the value, the lighter the sheet-like conductor.
(6) Relative Resistivity The relative resistivity (X × Y) was determined by multiplying the value (X) of the conductor resistance and the value (Y) of the mass of the conductive part. The lower the relative resistivity, the higher the conductivity.

  The evaluation results obtained in each Example and Comparative Example 1 are shown in Table 1 together with the conditions in each Example and Comparative Example 1.

  In Comparative Example 1, the resistance after bending exceeded 10 7 Ω and was unmeasurable. This is considered to be broken, and it is considered that the flexibility was significantly reduced because the carbon nanotube was not added, and the wire was broken. Also, it can be seen that the conductor resistance is high even before the disconnection. This is because the metal-containing particles (silver-coated acrylic particles in Comparative Example 1) are not electrically connected because carbon nanotubes are not added, and the conductive path tends to be interrupted, and the conductivity of the obtained conductor is obtained. Is considered to have deteriorated.

  In Comparative Example 2, the ratio occupied by the metal-containing particles (silver-coated acrylic particles in Comparative Example 2) and the ratio occupied by the carbon nanotubes in the conductor are higher in the carbon nanotube, and as the state of the conductor, In terms of unit mass, carbon nanotubes are the main and metal-containing particles are the sub. When observation was carried out using a field emission scanning electron microscope, the metal-containing particles were not dotted in the CNT layer containing a large number of carbon nanotubes, not in a state where the carbon nanotubes covered the periphery of the metal-containing particles. . Although carbon nanotubes have good conductivity, metal-containing particles have higher conductivity than metal-containing particles. Therefore, it is considered that the relative electric resistance in the CNT layer acts to increase the electric resistance of the whole conductor and to deteriorate the conductivity.

  On the other hand, in each Example, as a result of observation with a field emission scanning electron microscope, it was confirmed that the metal-containing particles were covered with carbon nanotubes. From Table 1, it can be seen that each Example is superior in conductivity and flexibility to each Comparative Example.

  In particular, in Example 17 in which metal-coated particles are used, although the mass of the conductive portion is heavy, the value of the conductor resistance is the lowest, and the relative resistivity is also the lowest due to the low value of the conductor resistance. ing. As a factor of the lowest value of the conductor resistance in Example 17, the addition of a binder resin is considered. The binder resin has an effect of adhering metal-containing particles (silver-coated acrylic particles in Example 17), and the density of the metal-containing particles in the conductor is increased to facilitate formation of a conductive path, resulting in conductivity of the obtained conductor. I guess that sex has become high.

  Moreover, in Example 18 using plain metal particles, the relative resistivity is lower than the other examples using plain metal particles, and the increase in resistance after bending is appropriately suppressed, and plain metal particles are used. Among the examples, the balance between conductivity and flexibility is the best example. This is considered to be due to the fact that the mass ratio of the pure metal particle and the mass ratio of the carbon nanotube are well balanced.

  Here, Example 1 corresponds to an example of the thread-like conductor under the average conditions of the present invention using metal-coated particles, and Example 2 corresponds to the average conditions of the present invention using metal-coated particles. Corresponds to an embodiment of the sheet-like conductor in

Both Example 3 and Example 26 have a higher true density of metal-coated particles and a smaller average particle size than Example 1. From this, it is understood that the base material particles are extremely small and the thickness of the silver coating layer is large. In addition, since the metal-coated particles are small and the true density is high, the number of metal-coated particles decreases if the added mass is the same, and the conductive path can not be formed well. As a result, the conductor resistance is higher than Example 1. The value of is considered to be high. Furthermore, as the metal-coated particles become smaller, the contact resistance between the metal-coated particles can not be ignored, and the value of the conductor resistance tends to be high. In particular, when the true density exceeds 4.5 g / cm ³ as in Example 26, the value of the conductor resistance becomes a double value of Example 1. However, even in Example 26, the CNT mass ratio to the metal-coated particles is 10, the concentration of carbon nanotubes in the conductive paint is 4 mass%, and the conductor resistance value is 24 when the CNT mass ratio is 24. The conductivity is lower than in Example 34 where the concentration of carbon nanotubes in the conductive paint is 11% by mass.

Further, in both of Example 5 and Example 25, the average particle size of the metal-coated particles is larger than that of Example 1, and the true density is low. From this, it is understood that the base material particles are large and the thickness of the silver coating layer is thin. In Example 5 and Example 25, since the average particle diameter is large, the number of metal-coated particles per unit area and unit mass decreases, the number of conductive paths also decreases, and the value of conductor resistance increases. There is. Further, in relation to the true density, in Examples 5 and 25, the mass of the conductive portion is smaller than in Example 1. However, the relative resistivity is worse due to the increase in the value of the conductor resistance. In particular, when the true density is less than 2.0 g / cm ³ as in Example 25, the value of the conductor resistance becomes more noticeable than the weight becomes smaller. However, even in Example 25, the CNT mass ratio to metal-coated particles is 10, the concentration of carbon nanotubes in the conductive paint is 4 mass%, and the conductor resistance value is 24 The conductivity is lower than in Example 34 where the concentration of carbon nanotubes in the conductive paint is 11% by mass.

  It is understood that in Example 7 and Example 23, the average diameter of the carbon nanotube is larger than in Example 1, and the value of the conductor resistance is higher. It can also be seen that the rise in resistance after bending is also slightly higher. In particular, when the average diameter of the carbon nanotubes exceeds 20 nm as in Example 23, it can be seen that the value of the conductor resistance becomes high. It is considered that this is because, in the case of a carbon nanotube with a large diameter, the number is reduced if the mass is the same, and it becomes difficult to connect conductive paths.

  It is understood that Example 9 and Example 27 both have a lower mass ratio of CNT to metal-coated particles, a larger increase in resistance after bending, and a higher value of conductor resistance than Example 1. . In particular, in the case of using multi-walled carbon nanotubes, when the mass ratio of CNT to metal-coated particles is less than 1 as in Example 27, the value of conductor resistance is 1, the mass ratio of CNT is 1 in Example 9 It turns out that 0.4 ohms / cm is rising compared with that. It is considered that this is because the multi-walled carbon nanotubes run short, the function of electrically connecting the silver-coated acrylic particles with the multi-walled carbon nanotubes is reduced, and the conductivity is also reduced.

  On the other hand, in Example 43 in which multi-walled carbon nanotubes are used instead of single-walled carbon nanotubes, the value of the conductor resistance is equal to that of Example 9 even if the mass ratio of CNT to metal-coated particles is 0.1. It is better than 1.4 Ω / cm. It is considered that this is because the single-walled carbon nanotubes have a narrow average diameter, and even if the CNT mass ratio is 0.1, the number of carbon nanotubes is sufficient and the carbon nanotubes do not run short.

  It can be seen that Example 11 and Example 28 both have a higher CNT mass ratio to metal-coated particles and a considerably higher value of conductor resistance than Example 1. In particular, it can be seen that when the mass ratio of CNT to metal-coated particles exceeds 20 as in Example 28, the value of conductor resistance exceeds 2.5 Ω / cm. This is considered to be due to the decrease in conductivity due to the relative decrease in silver-coated acrylic particles.

  In both Example 13 and Example 24, the metal type of the metal coating layer is not silver, Example 13 is copper, and Example 24 is aluminum. The copper metallized layer of Example 13 has the same conductor resistance as the silver metallized layer of Example 1, and the increase in resistance after bending is the same. On the other hand, it can be seen that the metallized layer of aluminum of Example 24 has a considerably higher value of the conductor resistance than the metallized layer of silver of Example 1.

  Example 15 shows that the base material particle of a metal-coating layer is aluminum, and the base material particle has the value of conductor resistance considerably higher than Example 1 of an acrylic resin. In addition, the mass of the conductive portion is heavier than that of the first embodiment, and the relative resistivity is largely inferior. If the matrix particles are aluminum, the true density of the metal-coated particles is high, and if they have the same added mass, the number of metal-coated particles is smaller than in the case where the matrix particles are acrylic resin, and conductive paths are less likely to be formed. It is considered that the value of the conductor resistance is considerably high.

  Both Example 29 and Example 30 have a lower concentration of metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) and a lower concentration of carbon nanotubes than Example 1. In Example 29 and Example 30, compared with Example 1, while the value of conductor resistance is considerably high, it turns out that the rise in resistance after bending is also quite large. In particular, in Example 30, the increase in resistance after bending is the largest in the examples. It is considered that both the conductivity and the flexibility have been deteriorated because both the metal-coated particles and the carbon nanotubes are insufficient.

  Although Example 29 and Example 30 are examples using multi-walled carbon nanotubes, Example 44 in which Example 29 is replaced with single-walled carbon nanotubes is a metal-coated particle / carbon nanotube mixed dispersion (conductive The concentration of metal coated particles in the paint is the same as in Example 29, while the concentration of carbon nanotubes is one order of magnitude lower. However, the value of the conductor resistance is lower and superior in Example 44 than in Example 29. It is considered that this is because the number of carbon nanotubes is not reduced as the average diameter of the single-walled carbon nanotubes is reduced and the concentration of the carbon nanotubes in the conductive paint is reduced by one digit.

  In both Example 31 and Example 33, the concentration of the metal-coated particles in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is higher than in Example 1, and the conductor resistance is higher than in Example 1. It can be seen that the resistance increase after bending is large as well as the value of. In particular, in Example 33, the value of the conductor resistance is twice that of Example 1. This is considered to be due to a relative shortage of carbon nanotubes, a decrease in the function of electrically connecting silver-coated acrylic particles by the carbon nanotubes, and a decrease in conductivity.

  In both Example 32 and Example 34, the concentration of carbon nanotubes in the metal-coated particle / carbon nanotube mixed dispersion (conductive paint) is higher than in Example 1, and the conductor resistance is higher than in Example 1. The value is high. In particular, in Example 34, the value of the conductor resistance reaches 2.9 Ω / cm. This is because the silver-coated acrylic particles are relatively reduced, the conductivity is lowered, and the interval between the adjacent silver-coated acrylic particles is too wide, and the carbon-coated acrylic particles have more resistance than carbon. It is considered that the resistance value of the nanotube has become dominant.

  Example 19 and Example 35 are both examples using plain metal particles, and the mean particle size of plain metal particles is smaller and the value of conductor resistance is higher than Example 18 which similarly uses plain metal particles. It turns out that it has become. As in the metal-coated particles, as the average particle diameter decreases, the contact resistance between the non-base metal particles can not be ignored, the value of the conductor resistance tends to be high, and the average particle diameter of the non-base metal particles If it is less than 5 nm as in Example 35, it is understood that the value of the conductor resistance exceeds 2.5 Ω / cm.

  Example 20 and Example 36 are also examples using plain metal particles, and it can be seen that the mean particle size of plain metal particles is larger than that of Example 18 and the value of conductor resistance is considerably high. In particular, it can be seen that when the average particle size of the non-base metal particles exceeds 100 nm as in Example 36, the value of the conductor resistance is 2.9 Ω / cm. The larger the average particle diameter of the plain metal particles, the smaller the number of plain metal particles per unit area and unit mass. For this reason, it is considered that the number of conductive paths also decreases and the value of the conductor resistance increases.

  Example 21 and Example 37 are also examples using plain metal particles, and the CNT mass ratio to plain metal particles is lower than that of Example 18. In addition, the concentration of carbon nanotubes in the carbon nanotube dispersion liquid corresponding to the second conductive paint is also low. Also in Example 21 and Example 37, it can be seen that the rise in resistance after bending is considerably large, and the value of conductor resistance is also high. In particular, in Example 37, it can be seen that the value of the conductor resistance is increased by 0.5 Ω / cm as compared with Example 21. It is considered that this is because the carbon nanotube is insufficient, the function of electrically connecting the silver-coated acrylic particles with the carbon nanotube is lowered, and the conductivity is also lowered.

  Example 22 and Example 38 are also examples using plain metal particles, and the weight ratio of CNT to plain metal particles is higher than that of Example 18. In addition, the concentration of carbon nanotubes in the carbon nanotube dispersion liquid corresponding to the second conductive paint is also high. Also in Example 22 and Example 38, it can be seen that the value of the conductor resistance is considerably high. In particular, in Example 38, the value of the conductor resistance reaches 2.9 Ω / cm. However, the rise in resistance after bending is most suppressed in the examples. This is similar to the example of the metal-coated particles of Example 32 and Example 34, that the conductivity is lowered due to the relative reduction of the non-base metal particles, and the distance between the adjacent non-base metal particles. It is considered that this is because the resistance value of carbon nanotubes has become more dominant than the resistance value of plain metal particles, because

  Example 39 and Example 41 are also examples using plain metal particles, and the concentration of plain metal particles in the pure metal particle dispersion corresponding to the first conductive paint is higher than that of Example 18, and the resistance increase after bending Is high. Moreover, although the value of conductor resistance is low, the mass of the conductive part is heavy, and as a result, the relative resistivity is inferior. In particular, in Example 41, the relative resistivity exceeds 2400. This is considered to be due to the relative reduction of carbon nanotubes whose true density is lower than that of plain metal particles.

  Example 42 and Example 40 are also examples using plain metal particles, and the concentration of plain metal particles in the pure metal particle dispersion corresponding to the first conductive paint is lower than that of Example 18, and the value of conductor resistance Is high. In particular, in the example 42, the value of the conductor resistance exceeds 2.5. This is considered to be due to the decrease in the conductivity due to the relative decrease in the number of the nonmetallic particles.

  From Example 9 and Example 43 depending on whether the carbon nanotube used is a multilayer or a single layer, in the case of a single-walled carbon nanotube, a multi-walled carbon nanotube is used even if the mass ratio of CNT to metal-coated particles is 0.1. It can be seen that high conductivity and good flexibility equal to or higher than Example 9 (CNT mass ratio 1) used can be obtained.

  Further, from Example 29 and Example 44 depending on whether the carbon nanotube used is a multilayer or a single layer, if it is a single-walled carbon nanotube, the concentration of the carbon nanotube in the conductive paint is 0.002 mass%, and the metal Even when the mass ratio of CNT to coated particles is 0.1, Example 44 using a multi-walled carbon nanotube (the concentration of carbon nanotube in the conductive paint is 0.02 mass%, and the mass ratio of CNT is equal to 1) It can be seen that the above high conductivity and good flexibility can be obtained.

  The conductor and conductive paint of the present invention are flexible and excellent in conductivity, and thus can be used for a conductive portion of a wearable device or the like.

C Conductor 1 Metal-coated particle 11 Metal-coated layer 2 Binding layer 21 Carbon nanotube

Claims (13)

  A conductor comprising at least a metal-containing body and a carbon nanotube, wherein the metal-containing bodies are bonded together by covering the periphery of the metal-containing body with the carbon nanotube.   The conductor according to claim 1, wherein the metal-containing body is a metal-containing particle, and the adjacent metal-containing particles are arranged at a distance equal to or less than the diameter of the metal-containing particle on average.   The conductor according to claim 1, wherein the metal-containing body is a metal-coated body in which a surface of a nonmetal base material is coated with a metal.   The conductor according to claim 3, wherein the base material is made of an acrylic resin.   The conductor according to claim 3 or 4, wherein the metal contains at least one of silver and copper.   The conductor according to any one of claims 3 to 5, wherein a mass ratio of the carbon nanotube to 100 parts by mass of the metal coating is 0.1 or more and 20 or less. The metal-containing body is a metal-coated particle obtained by coating the surface of a nonmetal matrix particle with metal,
The conductor according to claim 1, wherein the true density of the metal-coated particles is 2.0 g / cm ³ or more and 4.5 g / cm ³ or less, and the average particle diameter of the metal-coated particles is 2 μm or more and 20 μm or less. .   The conductor according to any one of claims 1 to 5, wherein an average diameter of the carbon nanotube is 20 nm or less. A conductive paint containing at least 2% by mass to 80% by mass of a metal-coated body in which the surface of a nonmetallic matrix is coated with a metal, and 0.002% to 10% by mass of carbon nanotubes,
The metal coating contains at least one of silver and copper,
The carbon nanotubes have an average diameter of 20 nm or less,
A conductive paint, wherein a mass ratio of the carbon nanotube to 100 parts by mass of the metal coating is 0.1 or more and 20 or less. A conductive paint containing at least 2% by mass to 80% by mass of metal-coated particles in which the surface of a nonmetallic matrix particle is coated with metal, and 0.002% to 10% by mass of carbon nanotubes,
The conductive paint, wherein the metal-coated particles have a true density of 2.0 g / cm ³ or more and 4.5 g / cm ³ or less and an average particle diameter of 2 μm or more and 20 μm or less.   A method for producing a conductor, comprising: impregnating or applying the conductive paint according to claim 9 or 10 to a thread-like substrate or a sheet-like substrate, and drying the conductive paint. The metal-containing body is a plain metal particle having an average particle diameter of 5 nm or more and 100 nm or less,
The conductor according to claim 1 or 2, wherein a mass ratio of the carbon nanotube to 100 parts by mass of the plain metal particle is 20 or more and 300 or less. A first step of impregnating or coating a filamentous substrate or a sheet-like substrate with a first conductive paint containing 10% by mass to 80% by mass of at least a plain metal particle having an average particle diameter of 5 nm to 100 nm and drying;
A filamentous conductor or sheet-like conductor obtained by carrying out the first step is impregnated or coated with a second conductive paint containing at least 1% by mass and 9.5% by mass or less of carbon nanotubes, and then dried. And a second step of
The second step is a step of impregnating or applying the second conductive paint so that the mass ratio of the carbon nanotube is 20 or more and 300 or less with respect to 100 parts by mass of the pure metal particle after drying. And a method of manufacturing a conductor.