JP2019179686A - Conductive sheet with electrode and conductive sheet - Google Patents

Abstract

To provide a conductive sheet with an electrode, having a temporal high stability of an electric resistance with thin a conductive striped body to be used.SOLUTION: A conductive sheet with an electrode and a conductive sheet used for them, comprises: a pseudo sheet structure body in which a plurality of conductive striped bodies extended to one direction of which a diameter D is 100 μm or less is arranged with an interval while holding a constant distance of the adjacent conductive striped bodied; an adhesive agent layer provided on one surface side of the pseudo sheet structure body, and in which the pseud sheet structure body is embedded; a pair of band electrodes provided in a longitudinal direction both end part of the plurality of conductive striped bodies so as to be electrically connected; and a band-shaped auxiliary electrode which is a pair of the band auxiliary electrode that is provided at a position interposed between the longitudinal direction both end part of the plurality of conductive striped bodies and the prat of band electrode, and is electrically connected, and of which a thickness tis 150 μm or less. The relationship between a width We of the band electrode and a width Ws of the band-shaped auxiliary electrode satisfies the following equation: Ws/We≤1.5, and the relationship between the diameter D of the plurality of conductive striped bodies and the thickness tof the adhesive agent layer satisfies the following equation: t≥1.2×D.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive sheet with electrodes and a conductive sheet.

Various conductive sheets are used as heat-generating sheets such as ice-snow melting heat-generating sheets and heating heat-generating sheets.
For example, Patent Document 1 states that “a plurality of linear bodies having a volume resistivity R of 1.0 × 10 ⁻⁷ Ωcm to 1.0 × 10 ⁻¹ Ωcm and extending in one direction are parallel to each other. A pseudo-sheet structure that is arranged at intervals, wherein the relationship between the diameter D of the linear body and the interval L between the adjacent linear bodies satisfies the formula: L / D ≧ 3, and the linear body The relationship between the distance L between the adjacent linear bodies and the volume resistivity R of the linear bodies is expressed by the formula: (D2 / R) × (1 / L) ≧ 0.003 (in the formula D and L are in cm.) ”.

Japanese Patent No. 6178948

  By the way, a conductive sheet having a pseudo sheet structure in which a plurality of conductive linear bodies are arranged and an adhesive layer is used as a conductive sheet with an electrode electrically connected to a pair of strip electrodes. The pair of strip electrodes are disposed so as to be electrically connected (conductive) to both longitudinal ends of the plurality of conductive linear members in the pseudo sheet structure.

However, in the conductive sheet, the pseudo sheet structure (that is, the plurality of conductive linear bodies) is embedded in the adhesive layer. In this state, if the diameter D of the conductive linear body is as thin as 100 μm or less, the contact area between the conductive linear body and the strip electrode becomes excessively small, resulting in poor connection. Therefore, it is difficult for the conductive sheet with electrodes to maintain a stable electrical connection state (conduction) between the conductive linear body and the strip electrode over time. As a result, the temporal stability of the electrical resistance is lowered.
On the other hand, in order to increase the contact area between the conductive linear body and the strip electrode and to maintain a stable connection state over time between the conductive linear body and the strip electrode, the diameter D of the conductive linear body is increased. Then, when used for the application described in Patent Document 1, it becomes difficult to maintain the transparency of the conductive sheet, the overall thickness of the conductive sheet increases, or the flexibility of the conductive sheet is low. There is a possibility that the advantages as a sheet cannot be obtained sufficiently.

  Then, the subject of this invention is providing the electroconductive sheet with an electrode with the electroconductive sheet | seat with which the electroconductive linear body to be used is thin, and electrical resistance is high with time, and the electroconductive sheet with an electrode concerned. That is.

  The above problem is solved by the following means.

<1>
A plurality of conductive linear bodies extending in one direction having a diameter D of 100 μm or less, and a pseudo sheet structure in which a distance between adjacent conductive linear bodies is arranged at a constant interval;
An adhesive layer provided on one side of the pseudo-sheet structure and embedded with the pseudo-sheet structure; and
A pair of strip electrodes provided to be electrically connected to both longitudinal ends of the plurality of conductive linear bodies;
A pair of band-like auxiliary electrodes provided at positions interposed between both ends in the longitudinal direction of the plurality of conductive linear bodies and the pair of band-like electrodes, and electrically connecting each other, and having a thickness t _s A belt-like auxiliary electrode having a thickness of 150 μm or less,
Have
The relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula; Ws / We ≦ 1.5,
Wherein the plurality of relationships of electrically diameter D of the conductive wire-like body with the thickness t _a of the adhesive layer, wherein: t _a ≧ 1.2 × electrodes with the conductive sheet satisfies the relationship D.
<2>
The conductive sheet with an electrode according to <1>, wherein the relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula: Ws / We ≦ 1.0.
<3>
The conductive sheet with an electrode according to <1>, wherein the relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula: Ws / We ≦ 0.7.
<4>
The conductive sheet with electrode according to any one of <1> to <3>, wherein an interval L between the plurality of conductive linear bodies is 3 mm or less.
<5>
<1>-<4> The electrode-attached conductivity according to any one of <1> to <4>, further comprising a base material provided on the surface of the adhesive layer opposite to the side on which the pseudo sheet structure is embedded. Sheet.
<6>
A plurality of conductive linear bodies extending in one direction with a diameter D of 100 μm or less are pseudo-sheet structures in which the distance between adjacent conductive linear bodies is kept constant, and the plurality of the conductive linear bodies are arranged. A pseudo sheet structure in which a pair of strip electrodes are electrically connected to both ends in the longitudinal direction of the conductive linear body;
An adhesive layer provided on one side of the pseudo-sheet structure and embedded with the pseudo-sheet structure; and
When the pair of strip-like electrodes are electrically connected to both ends in the longitudinal direction of the plurality of conductive linear bodies, the longitudinal ends of the plurality of conductive linear bodies and the pair of strip-like electrodes provided in a position interposed between a pair of strip-shaped auxiliary electrode a pair of strip-shaped auxiliary electrode, the thickness t _s following 150μm electrically connected to each other,
Have
The relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula; Ws / We ≦ 1.5,
The conductive sheet in which the adhesive layer is a pressure-sensitive adhesive layer, and the adhesive strength of the conductive sheet in a state where the pseudo sheet structure is embedded in the pressure-sensitive adhesive layer is 1 N / 25 mm or more.

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive sheet with an electrode with which the electroconductive linear body to be used is thin and whose electrical resistance is high with time, and the electroconductive sheet utilized for the said electroconductive sheet with an electrode can be provided.

It is a schematic plan view which shows the electroconductive sheet with an electrode which concerns on this embodiment. It is a schematic perspective view which shows the electroconductive sheet which concerns on this embodiment. It is a schematic perspective view which shows the electrode sheet which concerns on this embodiment. It is a schematic sectional drawing which shows the electroconductive sheet with an electrode which concerns on this embodiment. It is a partial expanded sectional view which shows the circumference | surroundings of the strip | belt-shaped auxiliary electrode of the electroconductive sheet with an electrode which concerns on this embodiment. It is a schematic plan view which shows the 1st modification of the electroconductive sheet which concerns on this embodiment. It is a schematic plan view which shows the 2nd modification of the electroconductive sheet which concerns on this embodiment.

Hereinafter, an embodiment which is an example of the present invention will be described in detail.
In the present specification, members having substantially the same function are given the same reference numerals throughout the drawings, and redundant description may be omitted.
A numerical range using “to” means a numerical range in which the numerical values shown before and after “to” are included as a minimum value and a maximum value, respectively.

<Conductive sheet>
The conductive sheet according to this embodiment is
A plurality of conductive linear bodies extending in one direction and having a diameter of D100 μm or less, arranged at intervals, keeping the distance between adjacent conductive linear bodies constant;
An adhesive layer provided on one side of the pseudo-sheet structure and embedded with the pseudo-sheet structure;
A pair of strip electrodes that are electrically connected to both longitudinal ends of the plurality of conductive linear bodies;
Provided at a position interposed between the longitudinal ends and a pair of strip electrodes of the plurality of conductive linear member, a pair of strip-shaped auxiliary electrode electrically connected to each other, the thickness t _s is 150μm A pair of belt-like auxiliary electrodes:
Have
In the conductive sheet with electrode according to the present embodiment, the relationship between the width We of the strip electrode and the width Ws of the strip auxiliary electrode satisfies the relationship of the formula; Ws / We ≦ 1.5, and a plurality of conductive properties. relation between the thickness t _a of the diameter D of the linear body wherein the adhesive layer is of the formula: satisfies the relation of t _a ≧ 1.2 × D.

The conductive sheet with an electrode according to the present embodiment is obtained by interposing a strip-shaped auxiliary electrode satisfying the relationship of formula: Ws / We ≦ 1.5 between the conductive linear body and the strip-shaped electrode. Even if the diameter of the strip is small, the contact area between the conductive linear strip and the strip electrode increases. Therefore, even if the relationship of the formula: t _a ≧ 1.2 × D is satisfied and the pseudo sheet structure is embedded in the adhesive layer, stable contact between the conductive linear body and the strip electrode can be ensured. That is, a stable electrical connection state (conduction) between the conductive linear body and the strip electrode is maintained over time.
Therefore, the conductive sheet with an electrode according to the present embodiment has a low electrical resistance and a high temporal stability of the electrical resistance.

  Further, even when the adherend of the conductive sheet with electrodes has a three-dimensional shape, the strip electrode and the strip auxiliary electrode can be installed in advance at a predetermined location. It can be only a part (pseudo sheet structure etc.) other than. Therefore, since it is not necessary to extend the strip electrode and the strip auxiliary electrode itself, a stable electrical connection state (conduction) between the conductive linear body and the strip electrode is maintained over time.

  Hereinafter, an example of the configuration of the conductive sheet according to the present embodiment will be described with reference to the drawings.

  The electroconductive sheet 100 with an electrode which concerns on this embodiment has the electroconductive sheet 10 and the electrode sheet 50, for example, as shown in FIGS.

  The conductive sheet 10 includes, for example, a pseudo sheet structure 20 in which a plurality of conductive linear bodies 22 are arranged, and an adhesive that is provided on one surface side of the pseudo sheet structure and in which the pseudo sheet structure is embedded. The base material 30 provided on the surface of the adhesive layer 32 opposite to the side where the agent layer 32 and the pseudo sheet structure 20 are embedded, and the longitudinal ends of the plurality of conductive linear bodies And a pair of band-like auxiliary electrodes 34 provided on the substrate.

  The electrode sheet 50 includes, for example, a pair of strip electrodes 52 and an electrode support substrate 54 that supports the pair of strip electrodes 52.

  The conductive sheet with electrode 100 is electrically connected to the conductive sheet 10 while the longitudinal ends of the plurality of conductive linear members and the pair of strip electrodes 52 are electrically connected with the strip auxiliary electrode 34 interposed therebetween. The electrode sheet 50 is bonded together.

In the conductive sheet with electrode 100, the relationship between the width We of the strip electrode 52 and the width Ws of the strip auxiliary electrode 34 satisfies the relationship of the formula: Ws / We ≦ 1.5. By satisfying the relationship of the formula: Ws / We ≦ 1.5, a stable electrical connection state (conduction) between the conductive linear body 22 and the strip electrode 52 is maintained over time. However, if the width of the band-like auxiliary electrode 34 is excessively larger than the width of the band-like electrode 52, the area of the portion where the pseudo sheet structure functions as the sheet-like conductive material is reduced by the increase in the width of the band-like electrode 52. Therefore, for example, the formula: 0.25 ≦ Ws / We.
On the other hand, the relationship between the width We of the belt-like electrode 52 and the width Ws of the belt-like auxiliary electrode 34 preferably satisfies the relationship of the formula: Ws / We ≦ 1.0, and the relationship of the formula: Ws / We ≦ 0.7 is satisfied. It is more preferable to satisfy. When these relationships are satisfied, the adhesive layer adheres to the surplus portion of the surface of the strip electrode 52 that does not overlap with the strip auxiliary electrode 34. Therefore, the contact between the strip electrode 52 and the strip auxiliary electrode 34 can be further stabilized.

  In addition, in the electroconductive sheet 100 with an electrode, the base material 30 and the electrode support substrate 54 are base materials provided arbitrarily.

(Pseudo sheet structure)
The pseudo sheet structure 20 is composed of a structure in which a plurality of conductive linear bodies 22 extending in one direction are arranged with a distance from each other while keeping the distance between adjacent conductive linear bodies 22 constant. . Specifically, the pseudo sheet structure 20 includes, for example, linearly extending conductive linear bodies 22 that are parallel to each other in a direction perpendicular to the length direction (or extending direction) of the conductive linear bodies 22. It is composed of a plurality of structures arranged at regular intervals. That is, the pseudo sheet structure 20 is configured by, for example, a structure in which the conductive linear bodies 22 are arranged in a stripe shape. The intervals between the plurality of conductive linear bodies 22 are preferably equal intervals, but may be unequal intervals.

  The pseudo sheet structure 20 is embedded and disposed in the adhesive layer 32.

In the pseudo sheet structure 20, the relationship between the thickness t _a of a plurality of diameter D and the adhesive layer 32 of the conductive wire-like body 22 has the formula: satisfies the relation of t _a ≧ 1.2 × D.
Wherein: t is satisfied the relationship _a ≧ 1.2 × D, when obtaining the conductive sheet 10 prefabricated, electrodes with the conductive sheet 100 bonded to the conductive sheet 10 to the electrode sheet 50 as described later In addition, it is possible to avoid the conductive linear body 22 from excessively protruding from the surface of the adhesive layer 32. As a result, the adhesiveness of the conductive sheet 10 to the pair of strip electrodes 52 and the electrode support substrate 54 is improved. For example, if the adhesive layer 32 is a pressure-sensitive adhesive layer, the adhesive strength of the conductive sheet 10 is increased. Also, in terms of non-adhesion of the conductive sheet 10, the formula: t _a By satisfying the relation of ≧ 1.2 × D, unevenness due to the conductive linear body 22 of the electrode with the conductive sheet 100 It becomes easy to prevent appearing on the surface, or after the production of the conductive sheet with electrode 100, due to the presence of the conductive linear body 22, between the adhesive layer 32 and the electrode support substrate 54 or with the adhesive layer 32. The effect that it becomes easy to prevent that the adhesiveness between the strip | belt-shaped electrodes 52 falls is acquired. On the other hand, in this manner, when the thickness t _a of adhesive layer 32 is thick relative to the diameter D of the conductive wire-like body 22, the conductive wire-like body 22 (i.e. pseudo-sheet structure 20) adhesive It is easy to be completely buried in the layer 32, and the contact between the conductive linear body 22 and the pair of strip electrodes 52 tends to be unstable. However, by interposing the strip-shaped auxiliary electrode 34, even if the pseudo sheet structure is embedded in the adhesive layer, a stable contact state between the conductive linear body and the strip-shaped electrode can be secured. The thickness t _a of adhesive layer 32, if the adhesive layer 32 is formed from a plurality of layers is the total thickness of these layers.
In view of suppressing excessive thickening of the electrode with the conductive sheet 100, the thickness t _a of adhesive layer 32 is, for example, 5 × D ≧ t _a. In addition, when manufacturing the conductive sheet with electrode 100, pressure was applied to the adhesive layer 32 when the pseudo-sheet structure 20 was bonded to the belt-like auxiliary electrode 34 while being embedded in the adhesive layer 32, or after bonding. Sai etc., as strip auxiliary electrode 34 and the conductive linear member 22 is easily contacted, preferably satisfies 3 × D ≧ t _a, further preferably satisfies 2 × D ≧ t _a.

Here, the diameter D of the conductive linear body 22 is 100 μm or less. The diameter D of the conductive linear body 22 is preferably 5 μm to 75 μm, more preferably 8 μm to 60 μm, and still more preferably 12 μm to 40 μm. When the diameter D of the conductive linear body 22 is in the above range, an increase in sheet resistance of the pseudo sheet structure 20 can be suppressed. Moreover, even if the conductive linear body 22 is embedded in the adhesive layer 32 without excessively increasing the thickness of the base material 30, the conductive sheet 100 with an electrode is present at the portion where the conductive linear body 22 exists. It is possible to avoid the surface of the swell.
In particular, when the diameter D of the conductive linear body 22 is 8 μm or more, the sheet resistance of the pseudo sheet structure 20 is likely to be reduced.

  The diameter D of the conductive linear body 22 is determined by observing the conductive linear body 22 of the pseudo sheet structure 20 using a digital microscope, and the diameter of the conductive linear body 22 at five randomly selected locations. And measure the average value.

  On the other hand, the distance L between the conductive linear bodies 22 is preferably 3 mm or less. When the distance L between the conductive linear bodies 22 is 3 mm or less, the electrical resistance of the pseudo sheet structure 20 can be kept low. When the distance L between the conductive linear bodies 22 is small, the adhesiveness between the adhesive layer 32 and the electrode sheet 50 tends to decrease. However, if the formula: ta ≧ 1.2 × D is satisfied, the adhesiveness between the adhesive layer 32 and the electrode sheet 50 can be maintained even when the distance L between the conductive linear bodies 22 is small.

  In addition, when the distance L between the conductive linear bodies 22 is 3 mm or less, the electric resistance of the pseudo sheet structure 20 increases, or when the electrode-attached conductive sheet 100 is used as a heat generating sheet, there is a region that does not generate heat. It is possible to suppress a decrease in the function of the conductive sheet 100 with a conductive electrode, such as an increase in temperature distribution and uneven distribution (temperature rise unevenness). From these viewpoints, the distance L between the conductive linear bodies 22 is preferably 0.1 mm to 2 mm, and more preferably 0.3 mm to 1.5 mm.

The distance L between the conductive linear bodies 22 is measured by observing the conductive linear bodies 22 of the pseudo-sheet structure 20 using a digital microscope and measuring the distance between two adjacent conductive linear bodies 22.
The interval L between two adjacent conductive linear bodies 22 is a length along the direction in which the conductive linear bodies 22 are arranged, and the two conductive linear bodies 22 are opposed to each other. It is the length between the parts to perform (refer FIG. 4). The interval L is an average value of intervals between all adjacent conductive linear bodies 22 when the arrangement of the conductive linear bodies 22 is unequal, but the value of the interval L can be easily controlled. From the viewpoint of ensuring functional uniformity such as light transmittance and heat generation, the conductive linear bodies 22 are preferably arranged in the pseudo sheet structure 20 at substantially equal intervals.

The volume resistivity R of the conductive linear body 22 is preferably 1.0 × 10 ⁻⁹ Ω · m to 1.0 × 10 ⁻³ Ω · m, and 1.0 × 10 ⁻⁸ Ω · m to 1. 0 × 10 ⁻⁴ Ω · m is more preferable. When the volume resistivity R of the conductive linear body 22 is in the above range, the sheet resistance of the pseudo sheet structure 20 is likely to be reduced.

  The measurement of the volume resistivity R of the conductive linear body 22 is as follows. First, the diameter D of the conductive linear body 22 is obtained according to the method described above. Next, a silver paste is applied to both ends of the conductive linear body 22 and the resistance of a portion having a length of 40 mm is measured to determine the resistance value of the conductive linear body 22. For example, in the case where a columnar body having a diameter D is used as the conductive linear body 22, the cross-sectional area of the conductive linear body 22 is calculated, and the volume is calculated by multiplying this by the measured length. To do. The obtained resistance value is divided by this volume to calculate the volume resistivity R of the conductive linear body 22.

  The conductive linear body 22 is not particularly limited as long as it has conductivity, and examples thereof include a linear body including a metal wire and a linear body including a conductive thread. The conductive linear body 22 may be a linear body including a metal wire and a conductive thread (such as a linear body in which a metal wire and a conductive thread are twisted).

  Since the linear body including the metal wire and the linear body including the conductive yarn both have high conductivity and high electrical conductivity, when applied as the conductive linear body 22, the surface of the pseudo sheet structure 20 It is easy to reduce the resistance. In addition, when the conductive sheet with electrode 100 is used as a heating element, rapid heat generation is easily realized. Furthermore, it is easy to obtain a linear body having a small diameter.

  Metal wires include copper, aluminum, tungsten, iron, molybdenum, nickel, titanium, silver, gold and other metals, or alloys containing two or more metals (for example, steels such as stainless steel and carbon steel, brass, phosphorus Bronze, zirconium copper alloy, beryllium copper, iron nickel, nichrome, nickel titanium, cantal, hastelloy, rhenium tungsten, etc.). In addition, the metal wire may be plated with tin, zinc, silver, nickel, chromium, nickel-chromium alloy, solder, or the like, or may be one whose surface is coated with a carbon material or polymer described later. .

  An example of the metal wire is a metal wire coated with a carbon material. When the metal wire is covered with the carbon material, the adhesion between the surface of the metal wire and the adhesive layer 32 is lowered. Therefore, when a linear body including a metal wire coated with a carbon material is applied as the conductive linear body 22, the corrugated conductive wire follows the elongation of the conductive sheet with electrode 100 by three-dimensional molding. Even when the linear body 22 is linearized and stretched, the conductive linear body 22 can be easily peeled off from the adhesive layer 32, and the conductive linear body 22 can be easily stretched. Further, when the metal wire is coated with a carbon material, metal corrosion is also suppressed.

  Examples of the carbon material covering the metal wire include amorphous carbon such as carbon black, activated carbon, hard carbon, soft carbon, mesoporous carbon, and carbon fiber; graphite; fullerene; graphene; carbon nanotube.

On the other hand, the linear body including the conductive yarn may be a linear body composed of one conductive thread, or may be a linear body obtained by twisting a plurality of conductive threads.
Conductive yarns include yarns containing conductive fibers (metal fibers, carbon fibers, ionic conductive polymer fibers, etc.), yarns plated or vapor-deposited with metal (copper, silver, nickel, etc.) on the surface, metal oxides, etc. Examples thereof include impregnated yarn.

As the linear body including the conductive yarn, a linear body including a yarn using carbon nanotubes (hereinafter also referred to as “carbon nanotube linear body”) is particularly preferable.
The carbon nanotube linear body is, for example, a carbon nanotube forest (a growth body in which a plurality of carbon nanotubes are grown on a substrate so as to be oriented in a direction perpendicular to the substrate, and is called an “array”. The carbon nanotubes are drawn out in the form of a sheet from the end of the carbon nanotube sheet, the bundled carbon nanotube sheets are bundled, and then the bundle of carbon nanotubes is twisted. In such a production method, a ribbon-like carbon nanotube linear body is obtained when twisting is not applied during twisting, and a thread-like linear body is obtained when twisting is applied. The ribbon-like carbon nanotube linear body is a linear body having no structure in which the carbon nanotubes are twisted. In addition, a carbon nanotube linear body can be obtained by spinning from a carbon nanotube dispersion. The production of the carbon nanotube linear body by spinning can be performed by, for example, a method disclosed in US Publication No. 2013/0251619 (Japanese Unexamined Patent Publication No. 2011-253140). From the viewpoint of obtaining a uniform diameter of the carbon nanotube linear body, it is desirable to use a filamentous carbon nanotube linear body. From the viewpoint of obtaining a highly pure carbon nanotube linear body, the carbon nanotube sheet is twisted. It is preferable to obtain a filamentous carbon nanotube linear body. The carbon nanotube linear body may be a linear body in which two or more carbon nanotube linear bodies are knitted together.

  The carbon nanotube linear body may be a linear body including carbon nanotubes and a metal (hereinafter also referred to as “composite linear body”). The composite linear body easily improves the conductivity of the linear body while maintaining the above-described characteristics of the carbon nanotube linear body. That is, it becomes easy to reduce the resistance of the pseudo sheet structure 20.

As the composite linear body, for example, (1) a carbon nanotube linear body in which carbon nanotubes are drawn out from the end of a carbon nanotube forest into a sheet shape, the carbon nanotube sheets pulled out are bundled, and then a bundle of carbon nanotubes is twisted In the process of obtaining a composite linear body in which a single metal or a metal alloy is supported by vapor deposition, ion plating, sputtering, wet plating, etc. on the surface of a carbon nanotube forest, sheet or bundle, or a twisted linear body (2) A single linear body or a metal alloy linear body or a composite linear body and a composite linear body obtained by twisting a bundle of carbon nanotubes, and (3) a single metal linear body or metal alloy Composite linear bodies knitted from linear bodies or composite linear bodies and carbon nanotube linear bodies or composite linear bodies, etc. It is. In the composite linear body of (2), when twisting a bundle of carbon nanotubes, a metal may be supported on the carbon nanotubes as in the composite linear body of (1). Further, the composite linear body of (3) is a composite linear body when two linear bodies are knitted, but at least one linear body of metal or a linear body of metal alloy or composite If a linear body is included, three or more carbon nanotube linear bodies, a single metal linear body, a metal alloy linear body, or a composite linear body may be knitted.
Examples of the metal of the composite linear body include, for example, simple metals such as gold, silver, copper, iron, aluminum, nickel, chromium, tin, and zinc, and alloys containing at least one of these simple metals (copper-nickel-phosphorus alloy, Copper-iron-phosphorus-zinc alloy, etc.).

(Adhesive layer)
The adhesive layer 32 is a layer containing an adhesive. In the adhesive layer 32, the pseudo sheet structure 20 (that is, the conductive linear body 22) is embedded in the adhesive layer. The adhesive layer 32 adheres to the electrode sheet 50 via the pseudo sheet structure 20.

  The adhesive layer 32 may be curable. By hardening the adhesive layer, the adhesive layer 32 is given sufficient hardness to protect the pseudo sheet structure 20. Moreover, the impact resistance of the cured adhesive layer 32 is improved, and deformation of the cured adhesive layer 32 due to impact can be suppressed.

The adhesive layer 32 is preferably energy ray curable such as ultraviolet rays, visible energy rays, infrared rays, and electron beams in that it can be easily cured in a short time. The “energy ray curing” includes thermal curing by heating using energy rays.
The curing conditions with energy rays vary depending on the energy rays to be used. For example, when curing by ultraviolet irradiation, the irradiation amount of ultraviolet rays is 10 mJ / cm ^{2 to} 3,000 mJ / cm ² , and the irradiation time is 1 second to 180 seconds. It is preferable that

  Examples of the adhesive of the adhesive layer 32 include a so-called heat seal type adhesive that is bonded by heat, an adhesive that is moistened to express stickiness, and the like. A pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive (pressure-sensitive adhesive) is preferred. The pressure-sensitive adhesive of the pressure-sensitive adhesive layer is not particularly limited. For example, examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and polyvinyl ether-based pressure-sensitive adhesives. Among these, the adhesive is preferably at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, and a rubber adhesive, and more preferably an acrylic adhesive.

  Examples of the acrylic pressure-sensitive adhesive include a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear alkyl group or a branched alkyl group (that is, a polymer obtained by polymerizing at least an alkyl (meth) acrylate) ), An acrylic polymer containing a structural unit derived from a (meth) acrylate having a cyclic structure (that is, a polymer obtained by polymerizing at least a (meth) acrylate having a cyclic structure) and the like. Here, “(meth) acrylate” is used as a term indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms.

  When the acrylic polymer is a copolymer, the form of copolymerization is not particularly limited. As an acrylic copolymer, any of a block copolymer, a random copolymer, or a graft copolymer may be sufficient.

Among these, the acrylic pressure-sensitive adhesive is derived from an alkyl (meth) acrylate (a1 ′) having a chain alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “monomer component (a1 ′)”). The acrylic copolymer containing the structural unit (a2) derived from the structural unit (a1) and the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer component (a2 ′)”) is preferable.
The acrylic copolymer further includes a structural unit (a3) derived from the monomer component (a3 ′) other than the monomer component (a1 ′) and the monomer component (a2 ′). You may go out.

  The number of carbon atoms of the chain alkyl group contained in the monomer component (a1 ′) is preferably 1 to 12, more preferably 4 to 8, and still more preferably 4 to 6, from the viewpoint of improving the adhesive property. Examples of the monomer component (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) ) Acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and the like. Among these monomer components (a1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.

  The content of the structural unit (a1) is preferably 50% by mass to 99.5% by mass, more preferably 55% by mass to 99% by mass with respect to all the structural units (100% by mass) of the acrylic copolymer. %, More preferably 60% by mass to 97% by mass, and still more preferably 65% by mass to 95% by mass.

Examples of the monomer component (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. Can be mentioned. Among these monomer components (a2 ′), a hydroxy group-containing monomer and a carboxy group-containing monomer are preferable.
Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate etc. are mentioned, 2-hydroxyethyl (meth) acrylate is preferable.
Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, and (meth) acrylic acid is preferable.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate.
Examples of the amino group-containing monomer include diaminoethyl (meth) acrylate.
Examples of the cyano group-containing monomer include acrylonitrile.

  The content of the structural unit (a2) is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to the total structural unit (100% by mass) of the acrylic copolymer. It is 40 mass%, More preferably, it is 1.0 mass%-30 mass%, More preferably, it is 1.5 mass%-20 mass%.

  Examples of the monomer component (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclohexane. Examples thereof include (meth) acrylates having a cyclic structure such as pentenyloxyethyl (meth) acrylate, imide (meth) acrylate, and acryloylmorpholine; vinyl acetate; styrene.

  The content of the structural unit (a3) is preferably 0% by mass to 40% by mass, more preferably 0% by mass to 30% by mass, with respect to all the structural units (100% by mass) of the acrylic copolymer. More preferably, it is 0 mass%-25 mass%, More preferably, it is 0 mass%-20 mass%.

  In addition, the above-mentioned monomer component (a1 ′) may be used alone or in combination of two or more, and the above-mentioned monomer component (a2 ′) is used alone or in combination of two or more. The monomer component (a3 ′) described above may be used alone or in combination of two or more.

  The acrylic copolymer may be crosslinked with a crosslinking agent. Examples of the crosslinking agent include known epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and the like. When the acrylic copolymer is cross-linked, the functional group derived from the monomer component (a2 ′) can be used as a cross-linking point that reacts with the cross-linking agent.

The pressure-sensitive adhesive layer may contain an energy ray-curable component in addition to the pressure-sensitive adhesive.
As the energy ray-curable component, for example, when the energy ray is ultraviolet ray, for example, trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 1, 4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dicyclopentadiene dimethoxydi (meth) acrylate, poly Compounds such as ethylene glycol di (meth) acrylate, oligoester (meth) acrylate, urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate, polyether (meth) acrylate, etc., which are UV-polymerizable in one molecule Examples include compounds having two or more functional groups.
The energy ray curable components may be used alone or in admixture of two or more.

  When an acrylic pressure-sensitive adhesive is applied as the pressure-sensitive adhesive, a functional group that reacts with a functional group derived from the monomer component (a2 ′) in the acrylic copolymer as an energy ray-curable component, and an energy ray A compound having a polymerizable functional group in one molecule may be used. Due to the reaction between the functional group of the compound and the functional group derived from the monomer component (a2 ′) in the acrylic copolymer, the side chain of the acrylic copolymer can be polymerized by irradiation with energy rays. Even if the pressure-sensitive adhesive is other than an acrylic pressure-sensitive adhesive, a component having a side chain that is energy ray polymerizable may be used as a copolymer component other than the copolymer that becomes the pressure-sensitive adhesive.

  When the pressure-sensitive adhesive layer is energy ray curable, the pressure-sensitive adhesive layer preferably contains a photopolymerization initiator. The speed at which the pressure-sensitive adhesive layer is cured by irradiation with energy rays can be increased by the photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4-diethylthioxanthone. 1-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, 2-chloroanthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzothiazole-N, N-diethyldithiocarbamate, oligo {2-hydroxy-2-methyl-1- [4 (1-propenyl) phenyl] propanone}, and the like.

  The adhesive layer 32 may contain an inorganic filler. By containing an inorganic filler, the hardness of the adhesive layer 32 after curing can be further improved. Further, the thermal conductivity of the adhesive layer 32 is improved. Furthermore, when the adherend is mainly composed of glass, the linear expansion coefficient of the conductive sheet 100 with an electrode and the adherend can be made closer, whereby the conductive sheet 100 with an electrode is attached to the adherend. And the reliability of the device obtained by curing as necessary is improved.

  Examples of the inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing them; single crystal fibers; glass fibers and the like. Among these, as an inorganic filler, a silica filler and an alumina filler are preferable. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

The inorganic filler is preferably surface-modified (coupled) with a compound having a curable functional group.
Examples of the curable functional group include a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an epoxy group, an ether group, an ester group, and a group having an ethylenically unsaturated bond. Examples of the compound having a curable functional group include a silane coupling agent.

Inorganic fillers are energy ray-curable functional groups such as groups having an ethylenically unsaturated bond, since the fracture resistance of the adhesive layer 32 after curing (strength of the adhesive layer 32 after curing) is easily maintained. It is more preferable that the surface is modified with a compound having Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) acryloyl group, and a maleimide group, and a (meth) acryloyl group is preferable from the viewpoint of high reactivity and versatility.
When the inorganic filler is surface-modified with a compound having an energy ray-curable functional group, for example, the cured adhesive layer 32 becomes tough.
In addition, when the adhesive layer 32 contains the inorganic filler by which the surface modification was carried out, it is preferable that the adhesive layer 32 contains the energy-ray-curable component separately.

The average particle size of the inorganic filler is preferably 1 μm or less, and more preferably 0.5 μm or less. If the average particle diameter of the inorganic filler is in such a range, the light transmittance of the adhesive layer 32 is easily improved, and the haze of the conductive sheet with electrode 100 (that is, the adhesive layer 32) is reduced. It can be made easier. Although the minimum of the average particle diameter of an inorganic filler is not specifically limited, It is preferable that it is 5 nm or more.
The average particle diameter of the inorganic filler is determined by observing 20 inorganic fillers with a digital microscope, measuring the average diameter of the maximum diameter and the minimum diameter of the inorganic filler as a diameter, and taking the average value.

  The content of the inorganic filler is preferably 0% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, and more preferably 10% by mass to 80% by mass with respect to the entire adhesive layer 32. % Is more preferable.

  The pencil hardness of the cured adhesive layer 32 is preferably HB or higher, more preferably F or higher, and even more preferably H or higher. Thereby, the function in which the adhesive layer 32 after hardening further protects the pseudo sheet structure 20 is further improved, and the pseudo sheet structure 20 can be more sufficiently protected. In addition, pencil hardness is the value measured according to JISK5600-5-4.

  The adhesive layer 32 may contain other components. As other components, for example, colorants, organic solvents, flame retardants, tackifiers, ultraviolet absorbers, antioxidants, antiseptics, antifungal agents, plasticizers, antifoaming agents, wettability adjusting agents, etc. These additives may be mentioned.

  The thickness of the adhesive layer 32 is, for example, preferably 3 μm to 150 μm, and more preferably 5 μm to 100 μm from the viewpoint of adhesiveness.

(Base material)
The base material 30 has a function of supporting the adhesive layer. The base material 30 is a member that also functions as a resin protective layer, for example. In addition, the base material 30 may be a sheet shape, a long shape, or any other shape.

Examples of the base material 30 include a layer containing a thermoplastic resin.
Examples of the thermoplastic resin include polyolefin resin, polyester resin, polyacryl resin, polystyrene resin, polyimide resin, polyimide amide resin, polyamide resin, polyurethane resin, polycarbonate resin, polyarylate resin, melamine resin, epoxy resin, urethane resin, A layer containing a well-known resin such as a silicone resin or a fluororesin, or a mixed resin containing two or more of these may be used, and a resin film containing these resins is preferably used.

The base material 30 may be a layer containing a thermosetting resin.
Examples of the thermosetting resin include layers of well-known compositions such as an epoxy resin composition, a resin composition that cures by a urethane reaction, and a resin composition that cures by a radical polymerization reaction. When forming the base material 30 by application of such a curable resin composition, it is easy to obtain the base material 30 containing the heat conductive inorganic filler mentioned later.

Epoxy resin compositions include polyfunctional epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, amine compounds, phenolic curing agents, etc. And a combination of these curing agents.
As a resin composition hardened | cured by urethane reaction, the resin composition containing a (meth) acryl polyol and a polyisocyanate compound is mentioned, for example.
Examples of the resin composition cured by radical polymerization reaction include resin compositions capable of radical polymerization reaction such as (meth) acryloyl groups and unsaturated polyesters. For example, (meth) acryl having a radical polymerizable group in the side chain. Resin (a polymer of a vinyl monomer having a reactive group (hydroxy (meth) acrylate, glycidyl (meth) acrylate, etc.)) having a group capable of reacting with the reactive group of the copolymer and radically polymerizable Group-containing monomers ((meth) acrylic acid, isocyanate group-containing (meth) acrylate etc.) reacted (meth) acrylic resin, etc.), (meth) acrylic acid etc. were reacted at the end of the epoxy resin Unsaturated polyester obtained by condensing epoxy acrylate having (meth) acrylic group and carboxylic acid (such as fumaric acid) having unsaturated group with diol And the like.

  The base material 30 may contain a heat conductive inorganic filler. When the base material 30 includes a heat conductive inorganic filler, when the electrode-equipped conductive sheet 100 is applied as a heat generating sheet, surface temperature unevenness (non-uniform temperature increase) is more effectively prevented. it can.

The thermal conductive inorganic filler is not particularly limited as long as the thermal conductivity is an inorganic filler having a thermal conductivity of 10 W / mK or more, and metal particles, metal oxide particles, metal hydroxide particles, metal nitride-based particles. Etc. Specific examples of the thermally conductive inorganic filler include silver particles, copper particles, aluminum particles, nickel particles, zinc oxide particles, aluminum oxide particles, aluminum nitride particles, silicon oxide particles, magnesium oxide particles, aluminum nitride particles, Well-known inorganic particles such as titanium particles, boron nitride particles, silicon nitride particles, silicon carbide particles, diamond particles, graphite particles, carbon nanotube particles, metal silicon particles, carbon fiber particles, fullerene particles, and glass particles can be used.
A heat conductive inorganic filler may be used individually by 1 type, and may be used together 2 or more types.

  The content of the thermally conductive inorganic filler is preferably 1% by mass to 90% by mass, more preferably 2% by mass to 70% by mass with respect to the entire resin protective layer, and 5% by mass to More preferably, it is 50 mass%.

The base material 30 may contain a colorant. When the base material 30 includes a colorant and the base material 30 is a colored layer, the concealability of the conductive linear body 22 is increased.
There is no restriction | limiting in particular as a coloring agent, According to the objective, well-known coloring agents, such as an inorganic pigment, an organic pigment, dye, can be applied.

  The base material 30 may contain other additives. Examples of other additives include a curing agent, an anti-aging agent, a light stabilizer, a flame retardant, a conductive agent, an antistatic agent, and a plasticizer.

  An image (for example, an image such as a figure, a character, a pattern, or a pattern) may be formed on the surface of the base material 30 on the pseudo sheet structure 20 side using an image forming material (ink, toner, etc.). As an image forming method, a known printing method such as gravure printing, offset printing, screen printing, inkjet printing, thermal transfer printing, or the like is applied. In this case, the base material 30 functions as a decoration layer and has a function of protecting decoration by an image. In this case, the electrode-attached conductive sheet 100 can be applied as a three-dimensional decorative sheet.

  The thickness of the base material 30 is, for example, preferably 4 μm to 2500 μm, more preferably 10 m to 2300 μm, and still more preferably 15 μm to 2000 μm.

(Strip auxiliary electrode)
The strip-shaped auxiliary electrode 34 is a layer containing a conductive material. The belt-like auxiliary electrode 34 may be an electrode in which a solid conductive foil or plate is interposed between the conductive wire 22 and the belt electrode 52 in advance. From the viewpoint of securing a stable electrical connection state with the electrode 52 over time, an electrode obtained by solidifying a liquid conductive material (that is, an electrode made of a solidified liquid conductive material) is preferable.

  The band-like auxiliary electrode 34 obtained by solidifying the liquid conductive material can be provided in contact with the surface shape of the conductive linear body appearing on the adhesive layer 32. In the surface layer region of the adhesive layer 32, a part of the belt-like auxiliary electrode 34 is located at the boundary between the adhesive layer 32 and the pseudo sheet structure (that is, the conductive linear body) embedded in the adhesive layer 32. It can be interposed between the conductive linear body 22 and the strip electrode 52 in a state of entering (see FIG. 5). Therefore, even if the pseudo sheet structure 20 is embedded in the adhesive layer 32, a stable contact state between the conductive linear body 22 and the strip electrode 52 can be more effectively secured.

A typical example of the liquid conductive material is a conductive paste. As the conductive paste, for example, a paste in which metal particles or carbon particles are dispersed in a binder resin and / or an organic solvent can be applied. Examples of the metal particles include metal particles such as gold, silver, copper, and nickel. Examples of the binder resin include known resins such as a polyester resin, a polyurethane resin, an epoxy resin, and a phenol resin.
In addition to the conductive paste, for example, solder, conductive ink, or the like may be applied as the liquid conductive material.

The thickness _{t s} of the strip auxiliary electrode 34 is 150μm or less. And the thickness t _s of the strip auxiliary electrode 34 and 150μm or less, between the adhesive layer 32 and the band-shaped electrodes 52, or excessive clearance is suppressed from occurring between the adhesive layer 32 and the electrode supporting substrate 54 The contact between the strip electrode 52 and the strip auxiliary electrode 34 is prevented from becoming unstable. As a result, a stable contact state between the conductive linear body 22 and the strip electrode 52 can be ensured.
The thickness _{t s} of the strip auxiliary electrode 34 is preferably 5Myuemu～120myuemu, more preferably 10 m - 100 m.

(Strip electrode)
The strip electrode 52 is disposed so as to be electrically connected to both ends in the longitudinal direction of the conductive linear body via the strip auxiliary electrode 34.
A conductive foil or plate is applied to the strip electrode 52. Specifically, for example, a metal foil or plate such as gold, silver, copper, nickel, iron, aluminum, tungsten, molybdenum, and titanium is applied. In addition, the strip electrode 52 is made of the above metals and other metals, stainless steel containing non-metallic elements, carbon steel, brass, phosphor bronze, zirconium copper alloy, beryllium copper, iron nickel, nichrome, nickel titanium, cantal, hastelloy, A foil or a plate of an alloy such as rhenium tungsten may be applied, and a band containing a carbon material such as carbon nanotube, carbon nanofiber, or graphene may be used.
The thickness of the strip electrode 52 is preferably 5 μm to 120 μm, more preferably 10 μm to 100 μm.

(Electrode support substrate 54)
The electrode support substrate 54 is a member that supports the pair of strip electrodes 52.
As a structure of the electrode support substrate 54, the same structure as the base material 30 can be illustrated, and description of such an aspect is omitted. Further, an inflexible material such as a glass plate may be used as the electrode support substrate. The conductive sheet with electrode 100 may not have the electrode support substrate 54 by having an alternative means that can support the belt-like electrode 52, for example, a clamp or the like. Even when the electrode conductive sheet 100 has the electrode support substrate 54, the electrode support substrate 54 may not be continuous from the strip electrode 52 at one end to the strip electrode 52 at the other end.

(Sheet resistance)
In the conductive sheet 100 with electrodes, the sheet resistance (Ω / □ = Ω / sq.) Of the sheet (the pseudo sheet structure 20) is preferably 800Ω / □ or less, more preferably 0.01Ω / □ to 500Ω / □. Preferably, 0.05Ω / □ to 300Ω / □ is more preferable. From the viewpoint of reducing the applied voltage, a conductive sheet 100 with an electrode having a low surface resistance is required. If the sheet resistance is 800 Ω / □ or less, the applied voltage can be easily reduced.

  The sheet resistance is measured by the following method. First, in order to improve electrical connection, a silver paste is applied to both ends of the pseudo sheet structure 20. Then, after pasting the conductive sheet with electrode 100 on the glass substrate with the copper tape pasted on both ends so that the silver paste and the copper tape are in contact with each other, the resistance is measured using an electric tester to calculate the sheet resistance. To do.

(Sheet manufacturing method)
The manufacturing method of the electroconductive sheet 100 with an electrode is not specifically limited. The conductive sheet 100 with an electrode is manufactured through the following steps, for example.
First, the composition for forming the adhesive layer 32 is applied on the base material 30 to form a coating film. Next, the coating film is dried to produce the adhesive layer 32. Next, on the laminated body (the adhesive layer 32) of the base material 30 and the adhesive layer 32, the conductive linear bodies 22 are arranged while being arranged to form the pseudo sheet structure 20. For example, the conductive linear body 22 is spirally formed on the surface of the adhesive layer 32 while rotating the drum member in a state where the laminate of the base material 30 and the adhesive layer 32 is disposed on the outer peripheral surface of the drum member. Wrap around.
Thereafter, the bundle of conductive linear bodies 22 wound in a spiral shape is cut along the axial direction of the drum member. As a result, the pseudo sheet structure 20 is formed, and the conductive sheet 10 disposed on the surface of the adhesive layer 32 is obtained. And the laminated body of the base material 30, the adhesive bond layer 32, and the pseudo sheet | seat structure 20 is taken out from a drum member.

Next, on the surface of the pseudo sheet structure 20 of the conductive sheet 10 provided with the pseudo sheet structure 20, a conductive material such as a silver paste is linearly provided near both longitudinal ends of the conductive linear body 22 such as a wire. The belt-like auxiliary electrode 34 is formed by means such as coating in the shape of a coating and heating only the vicinity of the coating portion.
Thereafter, the conductive sheet 10 provided with the pseudo-sheet structure 20 and the band-shaped auxiliary electrode 34 is bonded to the electrode sheet 50 formed by bonding a pair of copper tapes or the like to the electrode support substrate 54 as a pair of band-shaped electrodes 52, for example. . This bonding may be performed so that both ends in the longitudinal direction of the conductive linear body 22 such as a wire and the strip electrode 52 are electrically connected via the strip auxiliary electrode 34.

  The electrode sheet 50 may be bonded to the surface of the pseudo-sheet structure 20 that is a laminated body in a state of being disposed on the drum member. According to this method, for example, while rotating the drum member, the conductive portions adjacent to each other in the pseudo sheet structure 20 are moved by moving the feeding portion of the conductive linear body 22 along the direction parallel to the axis of the drum member. It becomes easy to adjust the space | interval L of the property linear body 22. FIG.

  In addition, it was obtained after forming the pseudo-sheet structure 20 by arranging the conductive linear bodies 22 without arranging the laminate of the base material 30 and the adhesive layer 32 on the outer peripheral surface of the drum member. One surface of the pseudo sheet structure 20 is bonded to the laminate (the adhesive layer 32) of the base material 30 and the adhesive layer 32. Thereafter, the other surface of the pseudo sheet structure 20 and the electrode sheet 50 may be bonded together to produce the conductive sheet 100 with an electrode.

  A part or all of the adhesive layer 32 may be provided in advance on the electrode sheet 50 before the pseudo sheet structure 20 is laminated. In this case, the thickness of the adhesive layer 32 provided on the electrode sheet 50 is preferably 1 to 70 μm so that the belt-like auxiliary electrode 34 can easily come into contact with the belt-like electrode 52.

  As one embodiment of the present invention, the conductivity of the conductive sheet 10 used in such a production method is a pressure-sensitive adhesive layer, and the conductivity in a state where the pseudo sheet structure is embedded in the adhesive layer. The adhesive strength of the sheet 10 is 1 N / 25 mm or more. When the adhesive strength of the conductive sheet 10 is 1 N / 25 mm or more, the adhesion of the conductive sheet 10 to the electrode sheet 50 can be strengthened. The adhesive strength of the conductive sheet 10 is preferably 5 N / 25 mm or more, and more preferably 10 N / 5 mm or more.

Here, the adhesive strength of the conductive sheet 10 is a value measured as follows.
A test piece (25 mm in width) having an adhesive layer 32 in a state where the pseudo sheet structure is embedded in the adhesive layer is prepared. A soda lime glass plate washed with toluene and stored in an environment of 23 ° C. and 50% relative humidity for 24 hours is prepared as an adherend. The surface of the adhesive layer 32 of the test piece on the side where the pseudo sheet structure is embedded is made to face, and a sample is attached to the surface of the adherend. In that state, a 180 ° peel test specified in JIS-Z0237 (2000) is carried out after 30 minutes have elapsed with the load applied. Specifically, using a tensile tester, the surface layer is pulled in the direction of 180 ° at a speed of 300 mm / min, and the force required for the surface layer to peel from the adherend is defined as the adhesive strength of the conductive sheet 10. taking measurement. The conditions for applying the load are also as described in the above JIS.
However, when the conductive sheet 10 does not have the substrate 30, a polyethylene terephthalate film having a thickness of 50 μm is formed on the surface of the conductive sheet 10 opposite to the side where the pseudo sheet structure 22 is embedded. The adhesive force measured by bonding as a backing substrate is taken as the adhesive force of the conductive sheet 10.

(Use of sheet)
The conductive sheet with electrode 100 is, for example, the surface of a surface heat-generating article such as a surface conductive article such as a curved touch panel, a heat-generating article for melting ice and snow (such as a traffic light lighting part), and a heat-generating article for heating (such as an interior product that generates heat from an automobile). It can be used as a conductor.
The electrode-equipped conductive sheet 100 is formed on the surface of a molded product used for an electrical casing, a vehicle interior part, a building material interior material, etc., using a three-dimensional molding method such as TOM molding, film insert molding, vacuum molding, It can also be used as a sheet for covering a molded product.

(Modification)
The electrode-attached conductive sheet 100 according to the present embodiment is not limited to the above form, and may be modified or improved. Hereinafter, the modification of the electroconductive sheet 100 with an electrode which concerns on this embodiment is demonstrated. In the following description, if it is the same as the member demonstrated with the electroconductive sheet 100 with an electrode which concerns on this embodiment, the same code | symbol is attached | subjected in a figure and the description is abbreviate | omitted or simplified.

-First modification-
The conductive sheet with electrode 100 according to the present embodiment is not limited to the above layer configuration, for example, and may have another layer configuration.
For example, as shown in FIG. 6, the conductive sheet with electrode 100 is based on the layer configuration illustrated in FIG. 4, 1) a resin layer 36 (between the base material 30 and the adhesive layer 32 ( (Hereinafter also referred to as “intermediate resin layer 36”) 2) Resin layer 38 (hereinafter also referred to as “lower resin layer 38”) provided on the surface of the pseudo sheet structure 20 opposite to the side having the adhesive layer 32. The electrode-attached conductive sheet 101 having at least one layer.

  FIG. 6 shows a conductive sheet 101 with an electrode that further includes an intermediate resin layer 36 and a lower resin layer 38 in the conductive sheet 100 with an electrode.

The intermediate resin layer 36 will be described.
The intermediate resin layer 36 is a layer provided as a functional layer such as a heat conductive layer, a colored layer, a decoration layer, a primer layer, or a component migration prevention layer. The intermediate resin layer 36 may be provided with a plurality of layers having different functions. The intermediate resin layer 36 is a single layer and may have a plurality of functions.

For example, when the intermediate resin layer 36 is a heat conductive layer, the intermediate resin layer 36 is composed of, for example, a layer containing a heat conductive inorganic filler and a thermoplastic resin. When the intermediate resin layer 36 is a heat conductive layer, when the electrode-attached conductive sheet 101 is applied as a heat generating sheet, it is possible to more effectively prevent the occurrence of surface temperature rise unevenness.
Moreover, when the intermediate resin layer 36 is a colored layer, the intermediate resin layer 36 is comprised by the layer containing a coloring agent and a thermoplastic resin, for example. When the intermediate resin layer 36 is a colored layer, the concealability of the conductive linear body 22 is enhanced. In this case, a layer having optical transparency may be applied as the substrate 30.
When the intermediate resin layer 36 is a decorative layer, a resin layer (for example, a heat layer) on which an image (for example, an image such as a figure, a character, a pattern, or a pattern) is formed on the surface with an image forming material (ink, toner, or the like) A layer containing a plastic resin). As an image forming method, a known printing method such as gravure printing, offset printing, screen printing, inkjet printing, thermal transfer printing, or the like is applied. When the intermediate resin layer is a decorative layer, the electrode-attached conductive sheet 101 can be applied as a decorative sheet. In this case, a layer having light permeability is applied to the base material 30.

  In addition, the said each component which comprises the intermediate | middle resin layer 36, and another component are illustrated the same component as the base material 30.

  The thickness of the intermediate resin layer 36 is, for example, preferably 5 to 1300 μm, more preferably 10 to 1000 μm, and still more preferably 15 to 900 μm, from the viewpoint of securing each function of the base material 30.

Here, the layer including the colored layer (colored layer) is not limited to the intermediate resin layer 36, and is formed on at least one layer constituting a layer provided on the surface of the pseudo sheet structure 20 on the side having the base material 30. Can be applied.
Further, the layer containing the heat conductive inorganic filler (heat conductive layer) is not limited to the intermediate resin layer 36, and at least constitutes a layer provided on the surface of the pseudo sheet structure 20 on the side having the base material 30. It can be applied to any one layer.
Further, the decorative layer is not limited to the intermediate resin layer 36, and can be applied to at least any one of the layers provided on the surface of the pseudo sheet structure 20 on the side having the base material 30.

The lower resin layer 38 will be described.
When the lower resin layer 38 uses the conductive sheet 101 with an electrode as a three-dimensional molding sheet, when the three-dimensional molding is applied to the surface of the molded product, the conductive sheet 101 with an electrode is applied to the surface of the molded product. It is a resin layer for heat welding. In particular, the electrode-attached conductive sheet 101 having the lower resin layer 38 is suitable for the film insert method among the three-dimensional molding methods.

  As the lower resin layer 38, for example, a layer containing a thermoplastic resin is applied. And as for each said component which comprises the lower resin layer 38, and another component, the same component as the base material 30 is illustrated. In particular, the lower resin layer 38 is preferably a layer made of polyolefin such as polypropylene, a layer made of acrylonitrile-butadiene-styrene copolymer, or the like, from the viewpoint of improving the heat-fusibility to a molded product.

  The thickness of the lower resin layer 38 is, for example, preferably from 5 to 1300 μm, more preferably from 10 to 1000 μm, and still more preferably from 15 to 900 μm, from the viewpoint of improving the heat-fusibility to the molded product.

  In addition, the conductive sheet 100 with an electrode according to the present embodiment includes, for example, an aspect in which another adhesive layer is provided on the surface of the pseudo sheet structure 20 on the side opposite to the side having the adhesive layer 32. It may be. In addition, the conductive sheet with electrode 100 may have a configuration that does not include any of the intermediate resin layer 36, the lower resin layer 38, and the base material 30. In this case, the adhesive layer 32 is cured to form a surface film. Preferably it can be formed.

-Second modification-
For example, as shown in FIG. 7, the conductive sheet with electrode 100 according to the present embodiment is a conductive sheet with electrode in which the conductive linear body 22 of the pseudo-sheet structure 20 is bent or bent periodically or irregularly. 102. Specifically, the conductive linear body 22 may have a wave shape such as a sine wave, a rectangular wave, a triangular wave, and a sawtooth wave. In other words, the pseudo sheet structure 20 has, for example, a structure in which a plurality of wavy conductive linear bodies 22 extending in one direction are arranged at equal intervals in a direction orthogonal to the extending direction of the conductive linear bodies 22. Also good.

  7 shows a pseudo sheet structure 20 in which a plurality of wavy conductive linear bodies 22 extending in one direction are arranged at equal intervals in a direction orthogonal to the extending direction of the conductive linear bodies 22. A conductive sheet 102 with electrodes is shown.

  By applying a corrugated linear body as the conductive linear body 22, when the conductive sheet 102 with an electrode is three-dimensionally formed and coated on the surface of the molded product, the conductive sheet 102 with an electrode can be extended. Following this, in the direction in which the conductive linear body 22 extends, the wavy conductive linear body 22 can be straightened and easily extended. Therefore, in the direction in which the conductive linear body 22 extends, the conductive sheet with electrode 102 can be easily extended without being limited to the conductive linear body 22.

  On the other hand, since the conductive linear bodies 22 are not connected to each other in the arrangement direction of the conductive linear bodies 22, the conductive sheet with electrode 102 is easily stretched without being limited to the conductive linear bodies 22. can do.

  That is, when the conductive sheet 102 with an electrode is three-dimensionally formed and coated on the surface of the molded product by applying a corrugated linear body as the conductive linear body 22, Extension failure or damage to the conductive linear body 22 is suppressed.

Here, from the viewpoint of suppressing the expansion failure of the conductive sheet with electrode 102 or the breakage of the conductive linear body 22, the wavelength λ (waveform pitch: see FIG. 7) of the corrugated conductive linear body 22 is 0.3 mm to 100 mm is preferable, and 0.5 mm to 80 mm is more preferable.
From the same viewpoint, the amplitude A (see FIG. 7) of the wave-shaped conductive linear body 22 is preferably 0.3 mm to 200 mm, and more preferably 0.5 mm to 160 mm. The amplitude A means the total amplitude (peak to peak).

Here, the 1st-2nd modification is an example, and the electroconductive sheet 100 with an electrode which concerns on this embodiment can be set as a various structure according to the objective.
For example, although not illustrated, the conductive sheet with electrode 100 according to the present embodiment may be a sheet in which a plurality of pseudo sheet structures 20 are arranged in the sheet surface direction (direction along the sheet surface). The plurality of pseudo sheet structures may be arranged in parallel in the direction in which the conductive linear bodies 22 extend, or may be arranged so as to intersect each other.
In the case of this layer configuration, for example, the strip electrode 52 is electrically connected to the “both longitudinal ends of the plurality of conductive linear bodies” in each pseudo sheet structure 20 via the strip auxiliary electrode 34. To do. In addition, after “a plurality of conductive linear bodies” in each pseudo-sheet structure 20 are electrically connected to each other, the conductive linear bodies that have been electrically connected are taken as one linear body, and strip-like auxiliary electrodes are formed at both ends in the longitudinal direction. A configuration may be adopted in which the strip electrode 52 is electrically connected via 34.

Although not shown, the conductive sheet with electrode 100 according to the present embodiment may have a release layer for the purpose of surface protection.
The release layer is not particularly limited. For example, from the viewpoint of ease of handling, the release layer preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate. Moreover, the release layer may be provided with a release agent layer only on one side of the release substrate, or may be provided with a release agent layer on both sides of the release substrate.
Examples of the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin (polyethylene, etc.) on a paper substrate, a plastic film, and the like. Examples of the paper substrate include glassine paper, coated paper, cast coated paper, and the like. Examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene and polyethylene. Examples of the release agent include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, silicone resins, and the like.

The thickness of the release layer is not particularly limited. Usually, the thickness of the release layer is preferably 20 μm to 200 μm, and more preferably 25 μm to 150 μm.
The thickness of the release agent layer of the release layer is not particularly limited. When a release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 μm to 2.0 μm, and more preferably 0.03 μm to 1.0 μm.
When using a plastic film as a peeling substrate, the thickness of the plastic film is preferably 3 μm to 150 μm, and more preferably 5 μm to 100 μm.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.

[Example 1]
A pressure-sensitive adhesive sheet (Lintec Co., Ltd., PET50 (A) PL Thin 8LK) having an acrylic pressure-sensitive adhesive layer having a thickness of 22 μm as an adhesive layer on a 100 μm-thick polypropylene film (Toyobo Co., Ltd. PET100 A4300) as a base material , Size: 120 mm × 120 mm). A tungsten wire (diameter: 14 μm, (manufacturer name: manufactured by Tokusai Corporation, (product name: TGW-B)) coated with carbon was prepared as a conductive linear body.

  Next, wrap the adhesive sheet around a drum member whose outer peripheral surface is made of rubber and wind the adhesive layer so that the surface of the adhesive layer faces outwards without wrinkles, and fix both ends of the adhesive sheet in the circumferential direction with double-sided tape. did. The wire wound around the bobbin is attached to the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet located near the end of the drum member, and then wound up with the drum member while feeding the wire. The wire was moved in parallel, and the wire was wound around the drum member while drawing a spiral at equal intervals. In this way, a plurality of wires were provided on the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet while keeping the distance between adjacent wires constant, thereby forming a pseudo sheet structure made of wires. The wires were provided at regular intervals, and the intervals were 0.5 mm.

Next, on the surface of the pseudo sheet structure of the pressure-sensitive adhesive sheet (conductive sheet) provided with the pseudo sheet structure, a silver paste (Dotite D-500, manufactured by Fujikura Kasei Co., Ltd.) is placed around 10 mm from both ends in the longitudinal direction of the wire. The coating was applied in a straight line, and only the vicinity of the coating part was heated. Thereby, a strip-like auxiliary electrode made of silver paste was formed. The band-shaped auxiliary electrode was 0.05 mm thick and 3 mm wide.
Thereafter, an adhesive sheet (conductive sheet) provided with a pseudo-sheet structure and a strip-like auxiliary electrode was bonded to a glass substrate on which a pair of 6 mm-wide copper tape was stuck as a pair of strip-like electrodes. This bonding was performed so that both ends in the longitudinal direction of the wire and the pair of copper tapes were electrically connected via a band-shaped auxiliary electrode made of silver paste.
Note that the surplus portions of the strip electrode where the strip electrode and the strip auxiliary electrode do not overlap in the width direction were connected such that the width of the surplus portion was the same on both sides in the width direction of the strip electrode. In an experimental example other than this example, when there is a surplus portion in the strip-shaped auxiliary electrode, the surplus portion of the strip-shaped auxiliary electrode is similarly set to have the same width on both sides in the width direction of the strip-shaped auxiliary electrode. Connected.

  Through the above steps, a conductive sheet with an electrode was obtained.

[Example 2]
A conductive sheet with an electrode was obtained in the same manner as in Example 1 except that the thickness of the strip-like auxiliary electrode made of silver paste was changed to 0.13 mm.

[Example 3]
A conductive sheet with an electrode was obtained in the same manner as in Example 1 except that a belt-like auxiliary electrode was formed using a carbon paste (ELECTRIC PAINT manufactured by Bare Conductive) instead of the silver paste.

[Example 4]
A conductive sheet with an electrode was obtained in the same manner as in Example 1 except that the width of the belt-like auxiliary electrode made of silver paste was changed to 7 mm.

[Comparative Example 1]
A conductive sheet with an electrode was obtained in the same manner as in Example 1 except that the band-shaped auxiliary electrode was not formed with silver paste.

[Comparative Example 2]
A conductive sheet with an electrode was obtained in the same manner as in Example 1 except that the thickness of the belt-like auxiliary electrode made of silver paste was changed to 0.25 mm.
In addition, about this example, only the measurement of the initial resistance value, the contact quality of the electrode, and the measurement of the adhesive strength of the conductive sheet were performed.

[Comparative Example 3]
A conductive sheet with an electrode was obtained in the same manner as in Example 1 except that the width of the band-like auxiliary electrode made of silver paste was changed to 12 mm.
In addition, about this example, only the measurement of the initial resistance value, the contact quality of the electrode, and the measurement of the adhesive strength of the conductive sheet were performed.

[Comparative Example 4]
Except that the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was changed to 12 μm, a conductive sheet with an electrode was produced in the same manner as in Example 1. As a result, the electrode sheet was not attached to the pressure-sensitive adhesive sheet. Except for the measurement of force, none of the evaluations and tests described below was performed.

[Comparative Example 5]
An electroconductive sheet with an electrode was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was changed to 12 μm and the wire interval L was changed to 5 mm.

[Change in electrical resistance over time]
The value of the sheet resistance of the conductive sheet with electrode obtained in each example was measured with an electric tester.
Next, the conductive sheet with electrodes was stored in an environment of 23 ° C. and 50% relative humidity for 7 days from the first measurement, and then the same measurement was performed again.
Then, the change “resistance value after 7 days / initial resistance value × 100” was confirmed.

[Judgment of electrode contact quality]
The coefficient of variation (relative standard deviation) was determined for the variation when the sheet resistance value of the conductive sheet with electrode obtained in each example was measured five times. When the coefficient of variation (relative standard deviation) exceeded 30%, it was determined that the electrode contact was poor, and when it was 30% or less, it was determined that the electrode contact was good and OK.

[Adhesive strength of conductive sheet]
According to the method described above, the adhesive force of the conductive sheet in a state where the pseudo sheet structure is embedded in the adhesive layer was measured.

  From the above results, the electrode-attached conductive sheet of this example is good in both the change in electrical resistance with time, the contact quality of the electrode, and the evaluation of the resistance value on the first day, the electrical resistance is low, and the electrical resistance over time. It can be seen that the stability is high.

DESCRIPTION OF SYMBOLS 10 Conductive sheet 20 Pseudo sheet structure 22 Conductive linear body 30 Base material 32 Adhesive layer 34 Band-like auxiliary electrode 36 Intermediate resin layer 36 Resin layer 38 Resin layer 50 Electrode sheet 52 Band-like electrode 54 Electrode support substrate 100 Conductive with electrode Conductive sheet 101 conductive sheet with electrode 102 conductive sheet with electrode

Claims (6)

A plurality of conductive linear bodies extending in one direction having a diameter D of 100 μm or less, and a pseudo sheet structure in which a distance between adjacent conductive linear bodies is arranged at a constant interval;
An adhesive layer provided on one side of the pseudo-sheet structure and embedded with the pseudo-sheet structure; and
A pair of strip electrodes provided to be electrically connected to both longitudinal ends of the plurality of conductive linear bodies;
A pair of band-like auxiliary electrodes provided at positions interposed between both ends in the longitudinal direction of the plurality of conductive linear bodies and the pair of band-like electrodes, and electrically connecting each other, and having a thickness t _s A belt-like auxiliary electrode having a thickness of 150 μm or less,
Have
The relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula; Ws / We ≦ 1.5,
Wherein the plurality of relationships of electrically diameter D of the conductive wire-like body with the thickness t _a of the adhesive layer, wherein: t _a ≧ 1.2 × electrodes with the conductive sheet satisfies the relationship D.   The conductive sheet with an electrode according to claim 1, wherein a relationship between a width We of the belt-like electrode and a width Ws of the belt-like auxiliary electrode satisfies a relationship of formula; Ws / We ≦ 1.0.   The conductive sheet with an electrode according to claim 1, wherein the relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula: Ws / We ≦ 0.7.   4. The conductive sheet with electrode according to claim 1, wherein an interval L between the plurality of conductive linear bodies is 3 mm or less. 5.   The electroconductive with electrode according to any one of claims 1 to 4, further comprising a base material provided on the surface of the adhesive layer opposite to the side on which the pseudo sheet structure is embedded. Sheet. A plurality of conductive linear bodies extending in one direction with a diameter D of 100 μm or less are pseudo-sheet structures in which the distance between adjacent conductive linear bodies is kept constant, and the plurality of the conductive linear bodies are arranged. A pseudo sheet structure in which a pair of strip electrodes are electrically connected to both ends in the longitudinal direction of the conductive linear body;
An adhesive layer provided on one side of the pseudo-sheet structure and embedded with the pseudo-sheet structure; and
When the pair of strip-like electrodes are electrically connected to both ends in the longitudinal direction of the plurality of conductive linear bodies, the longitudinal ends of the plurality of conductive linear bodies and the pair of strip-like electrodes provided in a position interposed between a pair of strip-shaped auxiliary electrode a pair of strip-shaped auxiliary electrode, the thickness t _s following 150μm electrically connected to each other,
Have
The relationship between the width We of the belt-like electrode and the width Ws of the belt-like auxiliary electrode satisfies the relationship of the formula; Ws / We ≦ 1.5,
The conductive sheet in which the adhesive layer is a pressure-sensitive adhesive layer, and the adhesive strength of the conductive sheet in a state where the pseudo sheet structure is embedded in the pressure-sensitive adhesive layer is 1 N / 25 mm or more.