JP2016168809A - Conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive laminate in which a surface resistance value after molding is suppressed.SOLUTION: A conductive laminate has a conductive layer 3 containing a carbon nanotube on at least one surface of a laminated film 1. The laminated film 1 is a conductive laminate satisfying (i) to (iii): (i) the conductive laminate has a structure in which 30 or more layers of layers (A layers) containing resins A and layers (B layers) containing resins B are alternately laminated; (ii) the conductive laminate has absolute reflectance at any wavelength in a wavelength band of 400-700 nm of 30% or more; and (iii) the resin A is polyethylene terephthalate and/or polyethylene naphthalate, and resin B is polyester containing spiroglycol.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive laminate. More specifically, the present invention relates to a conductive laminate having good moldability.

  Conventionally, conductive laminates have been used for various products such as touch panel applications such as resistive film type and capacitance type, electronic paper applications, and digital signage applications. Indium tin oxide (hereinafter referred to as ITO), silver nanowires (hereinafter referred to as AgNW), carbon nanotubes (hereinafter referred to as CNT), conductive polymers, and the like are used as a conductive material for developing conductivity. In the above applications, it is mostly used on a flat or flexible substrate, and the necessity of molding the conductive laminate has not been so much required. So far, studies have been made on CNT suitable for a flexible substrate requiring flexibility, and Patent Document 1 proposes a conductive laminate using a CNT having excellent bending resistance as a conductive film.

  However, from the viewpoint of operability and design, a three-dimensional touch panel instead of a flat surface will be required in the future. ITO and AgNW that have been studied so far have no flexibility, and after the molding process, the surface resistance value increases significantly due to the occurrence of cracks in the ITO layer and the AgNW itself breaking, etc. As a result, it becomes impossible to take conduction, and as a conductive laminate It is expected that this function cannot be maintained. Therefore, in order to suppress the surface resistance value change R after molding, studies have been made with CNT and a conductive polymer which are originally more flexible and advantageous for molding.

  Patent Document 2 proposes a moldable molding conductive film with improved dispersibility of CNTs as an antistatic treatment application to prevent static electricity generated in a molded synthetic resin molded product and prevent the adhesion of dust. Has been made.

JP 2012-66580 A JP 2006-35772 A

  However, in Patent Document 1, the bending resistance is excellent. However, when molding is performed, conductivity is not exhibited after molding due to CNT tearing or cracks in the transparent protective film. In Patent Document 2, a conductive film for molding using CNT is proposed, and the surface resistance value below a certain level is maintained even after molding, but the rate of change of the surface resistance value is large, and it is used as a touch panel application. It is difficult to do.

  Therefore, in view of the above problems, an object of the present invention is to provide a conductive laminate in which the surface resistance value after molding is suppressed.

In order to solve the problems, the present invention comprises the following methods.
(1) A conductive laminate having a conductive layer containing carbon nanotubes on at least one surface of the laminate film, wherein the laminate film satisfies the following (i) to (iii).
(I) having a structure in which a layer containing resin A (A layer) and a layer containing resin B (B layer) are alternately laminated by 30 layers or more (ii) absolute at any wavelength in the wavelength band of 400 to 700 nm Reflectivity of 30% or more (iii) Resin A is polyethylene terephthalate and / or polyethylene naphthalate, and resin B is polyester comprising spiroglycol (2) Surface resistance when the conductive laminate is stretched twice Value change is 1 to 5 times.
(3) The surface resistance when the conductive laminate is stretched twice is 10Ω / □ or more and 2,000Ω / □ or less.
(4) The haze when the conductive laminate is stretched twice is 0% or more and 5% or less.

  The present invention also provides a molded body using the above-described conductive laminate and a capacitive touch sensor using the molded body.

  ADVANTAGE OF THE INVENTION According to this invention, the electrically conductive laminated body by which the surface resistance value after shaping | molding was suppressed, having the outstanding moldability can be provided. By suppressing the change in the surface resistance value after molding, since the variation in the surface resistance value is small in a curved touch panel display, good operability can be obtained. For example, if the variation in the surface resistance value is large, it is difficult to recognize the accurate position information of the position touched by the touch panel, but if the variation in the surface resistance value is small, the accurate position information of the position touched by the touch panel is recognized and the operability Can be used as a good touch panel. Moreover, since the process of bonding with a conductive laminated body can be excluded by having decorating property, productivity improves.

It is a cross-sectional schematic diagram of the electrically conductive laminated body of this invention.

  In the present invention, as shown in FIG. 1, the absolute reflectance at any wavelength in the wavelength band of 400 to 700 nm is 30% or more, and a layer mainly composed of resin A (A layer) and resin B as main components. The present invention relates to a conductive laminate having a conductive layer containing carbon nanotubes on at least one side of a laminated film having a structure in which 30 or more layers (B layers) are alternately laminated.

  In particular, it is possible to obtain a conductive laminate having both good appearance, operability, and display quality by controlling the resistance value after molding while having a decorative property.

[Conductive laminate]
The conductive laminate used in the present invention includes at least a biaxially oriented polyester film for molding and a conductive layer containing CNTs.

The conductive laminate of the present invention preferably has a surface resistance value change of 1 to 5 times when the conductive laminate is stretched 2 times, more preferably 1 to 3 times, and more preferably 1 time. It is more preferably 2 times or less and particularly preferably 1 time or more and 1.5 times or less. When the conductive laminate is stretched 2 times, the surface resistance value change is from 1 to 5 times, so that there is little variation in conductivity when used as a touch panel or the like, which is preferable because it can be suitably used as a product. . Here, the surface resistance value change will be described in detail in the section of Examples, but from the surface resistance value R ₀ of the conductive laminate before stretching and the surface resistance value R ₁ of the conductive laminate after stretching, This is the value R calculated by equation (1).
_{R = R 1 / R 0 (} 1).

  Here, the surface resistance value of the conductive laminate is appropriately determined depending on the stretching ratio of the molded body, but the surface resistance value when the conductive laminate is stretched twice is preferably 10Ω / □ or more and 2,000Ω / □ or less. Moreover, although it determines suitably according to the device to be used, For example, in the case of a touch switch, Preferably it is 100-2,000 ohm / square, More preferably, it is 100-1,000 ohm / square, More preferably, it is 100-500 ohm / square. is there. For example, in the case of a touch panel, it is preferably 10 to 1,000 Ω / □, more preferably 50 to 500 Ω / □, and still more preferably 100 to 300 Ω / □. Within these ranges, the IC controller can be easily designed and good operability can be obtained.

  Further, as shown in FIG. 1, an undercoat layer or an overcoat layer on the conductive layer is formed between the biaxially oriented polyester film for molding and the conductive layer as necessary for improving interlayer adhesion and reliability. A functional layer may be provided.

[Laminated film]
The resin used for the laminated film in the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, or may be a copolymer or a blend of two or more. More preferably, it is a thermoplastic resin because of good moldability. In each resin, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate.・ Polybutyl succinate ・ Polyester resin such as polyethylene-2,6-naphthalate, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin・ Fluorine resin such as ethylene tetrafluoride-6-propylene copolymer / vinylidene fluoride resin, acrylic resin, methacrylic resin, polyacetal resin, It can be used polyglycolic acid resin, polylactic acid resin, and the like. Among these, polyester is particularly preferable from the viewpoint of strength, heat resistance, and transparency.

  The polyester referred to in the present invention refers to a homopolyester or a copolyester that is a polycondensate of a dicarboxylic acid component skeleton and a diol component skeleton. Here, typical examples of the homopolyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate. In particular, polyethylene terephthalate is preferable because it is inexpensive and can be used in a wide variety of applications.

  The copolyester in the present invention is defined as a polycondensate comprising at least three or more components selected from the following components having a dicarboxylic acid skeleton and components having a diol skeleton. Components having a dicarboxylic acid skeleton include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid. 4,4′-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid and ester derivatives thereof. Examples of the component having a glycol skeleton include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, and 2,2-bis. (4′-β-hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol and the like can be mentioned.

  Further, regarding the A layer and the B layer referred to in the present invention, the in-plane average refractive index of the A layer is relatively higher than the in-plane average refractive index of the B layer. The difference between the in-plane average refractive index of the A layer and the in-plane average refractive index of the B layer is preferably 0.03 or more. More preferably, it is 0.05 or more, More preferably, it is 0.1 or more. When the refractive index difference is smaller than 0.03, a sufficient reflectance cannot be obtained, which is not preferable. Further, when the difference between the in-plane average refractive index and the thickness direction refractive index of the A layer is 0.03 or more, and the difference between the in-plane average refractive index and the thickness direction refractive index of the B layer is 0.03 or less, the incident angle Since the reflectance of the reflection peak is unlikely to decrease even when the value of the value increases, it is more preferable.

  As a preferable combination of the resin A and the resin B in the present invention, it is first preferable that the absolute value of the difference in SP value between the resin A and the resin B is 1.0 or less. When the absolute value of the difference in SP value is 1.0 or less, delamination hardly occurs. More preferably, it has a layer made of the resin A and a layer made of the resin B containing the same basic skeleton as the resin A. Here, the basic skeleton is a repeating unit constituting the resin. For example, when one resin is polyethylene terephthalate, ethylene terephthalate is the basic skeleton. As another example, when one resin is polyethylene, ethylene is a basic skeleton. When the resin A and the resin B are resins containing the same basic skeleton, peeling between layers is less likely to occur.

  As a preferable combination of the resin A and the resin B, the glass transition temperature difference between the resin A and the resin B is preferably 20 ° C. or less. When the glass transition temperature difference is larger than 20 ° C., the thickness uniformity at the time of forming the laminated film becomes poor, resulting in poor appearance such as uneven color. Also, when a laminated film is formed, problems such as overstretching tend to occur.

  Moreover, in the laminated film constituting the conductive laminate of the present invention, it is preferable that the resin A is polyethylene terephthalate and / or polyethylene naphthalate, and the resin B is a polyester containing spiroglycol. The polyester comprising spiroglycol refers to a copolyester copolymerized with spiroglycol, a homopolyester, or a polyester blended with them. Polyesters containing spiroglycol are preferred because they have a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, so that they are not easily stretched at the time of molding and are also difficult to delaminate. More preferably, the resin A is polyethylene terephthalate and / or polyethylene naphthalate, and the resin B is preferably a polyester comprising spiroglycol and cyclohexanedicarboxylic acid. The polyester in which the resin B contains spiroglycol and cyclohexanedicarboxylic acid is a polyester copolymerized with spiroglycol and cyclohexanedicarboxylic acid (or an ester derivative of cyclohexanedicarboxylic acid), a homopolyester, or a polyester blended with the polyester. Say. If the resin B is a polyester comprising spiroglycol and cyclohexanedicarboxylic acid, the difference in the in-plane refractive index from polyethylene terephthalate or polyethylene naphthalate is increased, so that high reflectance is easily obtained. Further, since the glass transition temperature difference between polyethylene terephthalate and polyethylene naphthalate is small, it is difficult to be over-stretched during molding, and is also difficult to delaminate.

  Having a structure in which layers containing the resin A of the present invention (A layer) and layers containing the resin B (B layer) are alternately laminated means having a structure in which the A layers and B layers are alternately laminated in the thickness direction. Is defined to exist. That is, it is preferable that the order of arrangement in the thickness direction of the A layer and the B layer in the film of the present invention is not in a random state, and the order of arrangement of the third layer or more other than the A layer and the B layer is as follows. It is not particularly limited. Moreover, when it has a C layer which consists of A layer, B layer, and resin C, it is more preferable to laminate | stack by regular permutation, such as A (BCA) n, A (BCBA) n, A (BABCBA) n. . Here, n is the number of repeating units. For example, in the case of A (BCA) n where n = 3, this indicates that the layers are stacked in a permutation of ABCABCABCA in the thickness direction.

  Further, in the present invention, it is preferable to include 30 layers or more alternately each including a layer containing resin A (A layer) and a layer containing resin B (B layer). More preferably, it is 200 layers or more. Further, the total number of layers of the A layer and the B layer is preferably 600 layers or more. If the structure in which 30 layers or more of the A layer and the B layer are laminated is not included, sufficient reflectance cannot be obtained and an appearance with low luminance may be obtained. Moreover, when 200 layers or more of layers containing resin A (A layer) and layers containing resin B (B layer) are alternately included, the reflectance in the wavelength band of 400 nm to 1,000 nm is set to 40% or more. It is preferable because it becomes easy. Further, when the total number of laminated layers of the A layer and the B layer is 600 or more, it becomes easy to set the reflectance in the wavelength band of 400 nm to 1,000 nm to 60% or more, and the metallic appearance with very high brightness. Since it becomes easy to have, it is preferable. In addition, the upper limit value of the number of layers is not particularly limited, but considering the decrease in wavelength selectivity accompanying the decrease in stacking accuracy due to the increase in the size of the device and the increase in the number of layers, 1,500 layers or less It is preferable that

  The laminated film constituting the conductive laminate of the present invention preferably has an absolute reflectance of 30% or more at any wavelength in the wavelength band of 400 to 700 nm. It is preferable that the absolute reflectance at any wavelength in the wavelength band of 400 nm to 700 nm is 30% or more because it is possible to obtain a high-quality dichroic or metallic film with high brightness. Here, the absolute reflectance at any wavelength in the wavelength band of 400 nm to 700 nm is 30% or more, as will be described in detail in the section of the examples. However, the absolute reflectance in the range of 400 nm to 1,200 nm with a wavelength of 1 nm is used. When the reflectance is measured, it means that there is at least one wavelength at which the absolute reflectance is 30% or more.

  More preferably, the absolute reflectance in the wavelength band of 400 nm to 1,000 nm is 30% or more. In this case, the metallic tone is maintained even after molding, and the color hardly changes depending on the viewing angle. This is because the absolute reflectance is also 30% or higher on the higher wavelength side (700 nm or more) than visible light. Even if the film thickness is reduced by stretching or the reflection band is shifted to the lower wavelength side depending on the viewing angle. This is because the absolute reflectance in the visible light region can be maintained at 30% or more. More preferably, the absolute reflectance in the wavelength band of 400 nm to 1,000 nm is 40% or more. More preferably, the absolute reflectance in the wavelength band of 400 nm to 1,000 nm is 80% or more. The higher the absolute reflectance, the higher the brightness of the metallic tone. Moreover, it is more preferable that the absolute reflectance in the wavelength band of 400 nm to 1,200 nm is 30% or more. In this case, even if the molding is performed at a higher drawing ratio, coloring or the like hardly occurs and the metallic tone can be maintained.

  The laminated film constituting the conductive laminate of the present invention preferably has a tensile stress of 3 MPa or more and 90 MPa or less at 100% elongation in the film longitudinal direction and width direction in a tensile test at 150 ° C. In such a case, the moldability is excellent, and in any shape such as vacuum forming, vacuum pressure forming, plug assist vacuum pressure forming, in-mold forming, insert forming, cold forming, press forming, etc., it is formed into an arbitrary shape. Easy to do. More preferably, in a tensile test at 150 ° C., the tensile stress at 100% elongation in the film longitudinal direction and the width direction is 3 MPa or more and 50 MPa or less. In such a case, molding can be performed even with a higher drawing ratio. In the tensile test at 150 ° C., in order for the tensile stress at 100% elongation in the film longitudinal direction and the width direction to be 3 MPa or more and 90 MPa or less, the resin A is a crystalline resin and the resin B is cyclohexanedimethanol, spiro. It is preferably an amorphous resin having a bulky group such as glycol or neopentyl glycol. In such a case, since the resin B is hardly oriented and crystallized even after biaxial stretching, the tensile stress is low. It is also preferred that the time required for forming a laminate comprising the A layer and the B layer at the melting point of each resin to cool and solidify is 3 minutes or more. This is presumed that the tensile stress was lowered because the mixed layer formed at the interface between the A layer and the B layer was thick. Furthermore, it is preferable that the layer thickness is 20 nm or less. When the layer thickness is 20 nm or less, the orientation is difficult to proceed even if stretched, and the tensile stress is also reduced.

  In the laminated film constituting the conductive laminate of the present invention, the number of layers having a layer pair thickness of 10 nm to 220 nm is preferably larger than the number of layers having a layer pair thickness of 220 nm to 320 nm. By doing in this way, it becomes possible to make the metallic tone almost uncolored. Here, the layer pair thickness is a thickness obtained by adding the respective layer thicknesses of a layer made of the resin A (A layer) and a layer made of the resin B (B layer). The layer pair thickness should be the sum of the layer thicknesses of the mth A layer counted from one surface for only the A layer and the mth B layer counted from the same surface for only the B layer. Here, m represents an integer. For example, when A1 layer / B1 layer / A2 layer / B2 layer / A3 layer / B3 layer ... are arranged in order from one surface to the opposite surface, the A1 layer and the B1 layer are the first layer. The A2 layer and the B2 layer are the second layer pair, and the A3 layer and the B3 layer are the third layer pair. If the number of layers having a thickness of 10 nm to 220 nm is the same as or less than the number of layers having a thickness of 220 nm to 320 nm, the reflectance decreases as the wavelength decreases in the reflection band of the wavelength band of 400 nm to 1,100 nm. The yellowish appearance is not preferable. This occurs because the density of the layer pair that causes reflection on the low wavelength side is reduced. Therefore, as an order of the layer pair thickness of the layers constituting the laminated film, the layer pair thickness does not increase or decrease monotonically in a monotonic sequence, but the layer pair thickness in a geometric sequence while satisfying the above conditions. It is preferable to increase or decrease. More preferably, the number of layers having a layer pair thickness of 120 nm to 220 nm is 1.05 to 2.5 times the number of layers having a layer pair thickness of 220 nm to 320 nm. In this case, it is possible to obtain a metallic tone without any coloration.

  The dynamic friction coefficient of the laminated film of the present invention is preferably 0.5 or less. When the dynamic friction coefficient of the laminated film is 0.5 or less, since the sliding with the mold used for molding is improved, the moldability is further improved.

  In the laminated film of the present invention, it is preferable that the relative reflectance in the wavelength band of 400 nm to 700 nm in the stretched portion of 1.2 to 2 times is 30% or more. When the relative reflectance in the wavelength band of 400 nm to 700 nm in the stretched portion of 1.2 times or more and 2 times or less is 30% or more, the metallic tone can be maintained without being colored even after molding.

  The laminated film of the present invention preferably has a layer containing polyethylene terephthalate and / or polyethylene naphthalate of 3 μm or more on at least one side. More preferably, it has a layer containing polyethylene terephthalate or polyethylene naphthalate of 5 μm or more. Further, it is more preferable to have a layer mainly composed of polyethylene terephthalate or polyethylene naphthalate of 3 μm or more on both sides. When there is no layer containing polyethylene terephthalate or polyethylene naphthalate having a size of 3 μm or more, it is not preferable because scratches are very visible when the surface is scratched.

  In the laminated film of the present invention, an easy-adhesion layer, an easy-slip layer, a hard coat layer, an antistatic layer, an anti-abrasion layer, an antireflection layer, a color correction layer, an ultraviolet absorption layer, a printing layer, a metal layer are provided on the surface. Functional layers such as a transparent conductive layer, a gas barrier layer, a hologram layer, a release layer, an adhesive layer, an emboss layer, and an adhesive layer may be formed.

[Conductive layer]
The “conductive layer” in the present invention refers to a layer obtained by combining a carbon nanotube-containing layer and an overcoat layer, which will be described later. In the present invention, the thickness of the conductive layer is preferably 20 nm or more and 500 nm or less. From the viewpoint of conductivity and weather resistance, 50 nm to 400 nm is more preferable, 60 nm to 300 nm is more preferable, and 70 nm to 200 nm is particularly preferable.

  In the present invention, for example, the conductive layer is produced by forming a layer containing carbon nanotubes on a biaxially oriented polyester film for molding and then laminating and forming an overcoat layer. In the present invention, since the overcoat layer penetrates into the layer containing carbon nanotubes and forms a layer in a mixed state, there may be no clear interface between the layer containing carbon nanotubes and the overcoat layer.

[Undercoat layer]
In the present invention, an undercoat layer may be disposed on the biaxially oriented polyester film for molding. The surface of the undercoat layer is preferably highly hydrophilic. Specifically, the hydrophilicity preferably has a water contact angle in the range of 5 to 40 °. The undercoat layer is preferably composed mainly of an inorganic oxide such as titania, alumina or silica, or composed mainly of an acrylic resin having a hydrophilic group (—OH) group, and above all, silica is the main component. Those are preferred. In the present invention, the main component means a component contained in 50% by mass or more in all components, more preferably 60% by mass or more, and further preferably 80% by mass or more (hereinafter referred to as others). The same applies to the other components).

  These substances are preferable because they have a hydrophilic group (—OH) group on the surface and high hydrophilicity can be obtained. Since the material of the undercoat layer is hydrophilic, the dispersant, which is an insulator contained in the carbon nanotube-containing layer, is preferentially adsorbed on the undercoat layer, and the conductivity of the layer containing the carbon nanotube is improved. Therefore, it is preferable.

  In the present invention, the method for providing the undercoat layer on the biaxially oriented polyester film for molding is not particularly limited. Known wet coating methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, slot die coating, roll coating, bar coating, screen printing, inkjet printing, pad printing, other types of printing methods Etc. are available. Further, a dry coating method may be used. As the dry coating method, physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used. Moreover, application | coating may be performed in multiple times and it may combine two different types of application | coating methods. Preferred coating methods are wet coating gravure coating, bar coating, and die coating.

  After the coating step, the solvent is removed from the undercoat coating solution containing the undercoat component applied in the drying step. Solvent removal methods include convection hot-air drying in which hot air is applied to the biaxially oriented polyester film for molding, and radiation from the infrared drying device that absorbs infrared rays into the molding biaxially oriented polyester film to convert it into heat and heat to dry. Drying, conductive heat drying by heating and drying by heat conduction from a wall surface heated by a heat medium, and the like can be applied. Of these, convection hot air drying is preferred because of its high drying rate.

  In the present invention, the thickness of the undercoat layer is not particularly limited. From the viewpoint that the dispersant, which is an insulator contained in the layer containing carbon nanotubes, preferentially adsorbs to the undercoat layer, it is preferably in the range of 1 to 1000 nm.

  In the present invention, the water contact angle of the undercoat layer is preferably 40 ° or less from the viewpoint of applicability of the carbon nanotube dispersion on the undercoat layer. When the water contact angle exceeds 40 °, the carbon nanotube dispersion may not be uniformly applied on the undercoat.

  The water contact angle of the undercoat layer can be measured using a commercially available contact angle measuring device. The water contact angle is measured in accordance with JIS R 3257 (1999) by dripping 1 to 4 μL of water onto the surface of the undercoat layer with a syringe in an atmosphere of room temperature of 25 ° C. and relative humidity of 50%. The angle formed between the tangent at the edge of the droplet and the surface of the undercoat layer is determined.

[Overcoat layer]
As the material for the overcoat layer used in the present invention, a resin having a value in which the water contact angle on the surface of the overcoat layer is close to the water contact angle of the conductive layer is preferably used. Specifically, the value close to the water contact angle of the conductive layer is preferably 60 ° or more and 80 ° or less. Since the water contact angle between the conductive layer and the overcoat layer is close, the carbon nanotube and the overcoat component can be mixed easily, and a uniform conductive layer can be formed. This is preferable because a conductive laminate excellent in resistance value stability when bonded can be obtained. In addition, the resin used for the overcoat layer can be selected according to the characteristics required for the transparent conductive laminate, and the surface hardness, an acrylic resin or a polyester resin capable of obtaining adhesion with the biaxially oriented polyester film for molding, A polyurethane resin or the like excellent in stretch followability can be suitably used. Further, these plural resins can be used in combination.

  The method for preparing the overcoat layer is to adjust the solids concentration so that the thickness after drying the paint containing the resin used for the overcoat layer is the desired thickness, reverse coat method, gravure coat method, rod coat method, bar coat It is preferably applied by a method, a die coating method, a spray coating method, a spin coating method or the like. The paint containing a resin can be used in a state where the resin is dissolved in a solvent or the resin is dispersed in a dispersion medium. As the solvent and dispersion medium used in the paint containing the resin used for the overcoat layer of the present invention, water, an organic solvent, and the like can be used. From the viewpoint of coating suitability, water, alcohol solvents such as isopropyl alcohol and ethanol Ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as cyclohexanone and methyl ethyl ketone, and hydrocarbon solvents such as xylene and toluene are preferably used. These solvents may be used alone or in combination of two or more.

  Various additives can be blended in the coating material containing the resin used for the overcoat layer, if necessary, as long as the effect of the overcoat layer is not impaired. For example, a catalyst, an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent, or the like can be used.

  Next, it is preferable to dry the coated film after application to remove the solvent and the dispersion medium. Here, there is no restriction | limiting in particular as a heat source used for drying, Arbitrary heat sources, such as a steam heater, an electric heater, and an infrared heater, can be used. The heating temperature is preferably 50 to 150 ° C. The heat treatment time is preferably several seconds to 1 hour. Furthermore, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Moreover, you may heat-process, adjusting humidity in the range of 20 to 90% RH by relative humidity during a drying process. You may perform the said heat processing in the state enclosed with air | atmosphere or inert gas.

  Next, the composition of the coating film can be modified by applying an active energy ray irradiation treatment such as ultraviolet irradiation to the coating film containing the resin after drying as necessary, and the overcoat layer in the present invention can be obtained. The ultraviolet treatment may be performed only once or repeated twice or more. From the viewpoint of controlling the composition of the overcoat layer, the oxygen concentration during the ultraviolet treatment is preferably 1.0% by volume or less when the total amount of gas in the system during overcoating is 100% by volume. 5 volume% or less is more preferable. The relative humidity may be arbitrary. In the ultraviolet treatment, it is more preferable to reduce the oxygen concentration using nitrogen gas.

  As the ultraviolet ray generation source, a known source such as a high pressure mercury lamp metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp or the like can be used.

Integrated light quantity of ultraviolet irradiation is preferably from ^{50~3,000mJ / cm 2, 100~1,000mJ / cm} 2 is more preferable. If the integrated light quantity is 50 mJ / cm ² or more, a desired overcoat layer can be obtained, which is preferable. Moreover, it is preferable if the integrated light quantity is 3,000 mJ / cm ² or less because damage to the biaxially oriented polyester film for polymer molding can be reduced.

[carbon nanotube]
The carbon nanotube used in the present invention is not particularly limited as long as it has a shape obtained by winding one surface of graphite into a cylindrical shape. Single-wall carbon in which one surface of graphite is wound in one layer. Both nanotubes and multi-walled carbon nanotubes wound in multiple layers can be applied. Among them, in particular, carbon nanotubes in which 50 single-walled carbon nanotubes in which one surface of graphite is wound in two layers are contained in 100 or more, This is preferable because the conductivity and the dispersibility of the carbon nanotubes in the coating dispersion are extremely high. More preferably, 75 or more of 100 are double-walled carbon nanotubes, and most preferably 80 or more of 100 are double-walled carbon nanotubes. In addition, the fact that 50 of the double-walled carbon nanotubes are contained in 100 may be expressed as 50% of the double-walled carbon nanotubes. In addition, the double-walled carbon nanotube is preferable because the original function such as conductivity is not impaired even if the surface is functionalized by acid treatment or the like.

  For example, the carbon nanotube is manufactured as follows. A powdery catalyst in which iron is supported on magnesia is present in the entire horizontal cross-sectional direction of the reactor in a vertical reactor, and methane is supplied in the vertical direction into the reactor. The carbon nanotubes containing single- to five-layer carbon nanotubes can be obtained by contacting the carbon nanotubes at 200 ° C. to produce carbon nanotubes and then oxidizing the carbon nanotubes. Carbon nanotubes can be manufactured and then subjected to an oxidation treatment to increase the ratio of single-layer to five-layer, particularly the ratio of two- to five-layer. The oxidation treatment is performed, for example, by a nitric acid treatment method. Nitric acid is preferred because it acts as a dopant for the carbon nanotubes. The dopant is a function of giving a surplus electron to the carbon nanotube or taking away the electron to form a hole, thereby generating a freely movable carrier, thereby improving the conductivity of the carbon nanotube. Is. The nitric acid treatment method is not particularly limited as long as the carbon nanotube of the present invention can be obtained, but is usually performed in an oil bath at 140 ° C. The nitric acid treatment time is not particularly limited, but is preferably in the range of 5 to 50 hours.

[Dispersant]
As the carbon nanotube dispersant, a surfactant, various polymer materials (water-soluble polymer material, etc.) and the like can be used, and an ionic polymer material having high dispersibility is preferable. Examples of the ionic polymer material include an anionic polymer material, a cationic polymer material, and an amphoteric polymer material. Any type can be used as long as it has a high carbon nanotube dispersibility and can maintain dispersibility, but an anionic polymer material is preferred because of its excellent dispersibility and dispersion retainability. Of these, carboxymethylcellulose and its salts (sodium salt, ammonium salt, etc.) and polystyrenesulfonic acid salt are preferable because they can efficiently disperse carbon nanotubes in the carbon nanotube dispersion.

  In the present invention, when carboxymethyl cellulose salt or polystyrene sulfonate is used, examples of the cationic substance constituting the salt include alkali metal cations such as lithium, sodium and potassium, and alkaline earth such as calcium, magnesium and barium. Metal cation, ammonium ion, or onium ion of organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, beef tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine, Alternatively, these polyethylene oxide adducts can be used, but are not limited thereto.

[solvent]
In the present invention, the solvent used in the carbon nanotube dispersion liquid is preferably water from the viewpoints that the dispersant can be easily dissolved and that the waste liquid can be easily treated.

[Carbon nanotube dispersion]
Although the preparation method of the carbon nanotube dispersion liquid used in this invention is not specifically limited, For example, it can carry out in the following procedures. Since the treatment time at the time of dispersion can be shortened, once a dispersion liquid containing carbon nanotubes in a concentration range of 0.003 to 0.15 mass% in the dispersion medium is prepared, dilution is performed to obtain a predetermined concentration. It is preferable to do. In the present invention, the mass ratio of the dispersant to the carbon nanotube (dispersant / carbon nanotube) is preferably 10 or less. Within such a preferable range, it is easy to uniformly disperse, but there is little influence of the decrease in conductivity. The mass ratio is more preferably 0.5 to 9, further preferably 1 to 6, and the mass ratio of 2 to 3 is particularly preferable because high transparent conductivity can be obtained.

  As a dispersing means at the time of preparation, a carbon nanotube and a dispersing agent are mixed and dispersed in a dispersion medium commonly used for coating production (for example, ball mill, bead mill, sand mill, roll mill, homogenizer, ultrasonic homogenizer, high pressure homogenizer, ultrasonic device, And mixing using an attritor, a resolver, a paint shaker, and the like. Moreover, you may disperse | distribute in steps, combining these some mixing dispersers. Among them, the method of preliminarily dispersing with a vibration ball mill and then dispersing using an ultrasonic device is preferable because the dispersibility of the carbon nanotubes in the obtained coating dispersion liquid is good.

[Haze]
In the conductive laminate of the present invention, the haze when the conductive laminate is stretched twice is preferably from 0% to 5%, more preferably from 0% to 3%, and even more preferably from 0% to 1%. . The haze here is a value measured based on JIS-K7361 (1997). When the haze is in this range, for example, when used for a touch panel or a touch switch, it can be used favorably without deteriorating the display quality, which is preferable.

[Molding process]
The conductive laminate of the present invention can be molded using various molding methods. It can be formed by a forming method such as vacuum forming, compressed air forming, compressed air vacuum forming combining vacuum forming and compressed air forming, press forming, plug forming, laminate forming, in-mold forming, and insert forming. In the present invention, the properties of the resin used for the biaxially oriented polyester film for molding of the conductive laminate, the properties of the resin used for the layer laminated on the biaxially oriented polyester film for molding, and the thickness, molding of each A molding method suitable for the shape to be made can be selected.

[Molded body]
The molded product as used in the present invention refers to a product obtained by molding the conductive laminate of the present invention by, for example, the method described in the above-mentioned section [Molding]. Moreover, the molded object of this invention can also be used by bonding with other resin materials.

[Usage]
The conductive laminate and molded body of the present invention can be preferably used for capacitive touch sensors such as touch switches and touch panels. It can also be used for planar heating elements, electromagnetic wave shields, antenna members, and the like. In particular, it can be preferably used for a capacitive touch sensor for home appliances or in-vehicle use that requires design.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.

[Evaluation method]
(1) Surface resistance value The conductive laminate was cut to a length L of 150 mm and a width of W 20 mm, and silver paste (made by Taiyo Ink Co., ECM-100) was applied to both ends on the conductive layer side of the conductive laminate to a width of 90 mm. After drying for 30 minutes at a temperature, the inter-terminal resistance value Rs was measured with a tester and converted to the surface resistance value R1 by the following formula (1).
R1 = Rs × L / W (1).

(2) Surface resistance value change R
The surface resistance value R _{0 on the} surface of the conductive layer of the conductive laminate before stretching and the surface resistance value R ₁ on the surface of the conductive layer of the conductive laminate after stretching are measured by the measurement method, and the surface is expressed by the following formula (1). Resistance value change R was calculated.
R = R ₁ / R ₀ (2).

(3) Film cross-sectional observation The layer constitution of the film was determined by electron microscope observation of a sample cut out of the cross section using a microtome. That is, using a transmission electron microscope HU-12 type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 40,000 times, and a cross-sectional photograph was taken. The embodiment of the present invention was not carried out because a sufficient contrast was obtained, but depending on the combination of resins used, the contrast may be increased by using a known dyeing technique using RuO ₄ or OsO ₄ .

(4) Absolute reflectance A spectrophotometer UV-3150 manufactured by Shimadzu Corporation is attached with an absolute reflectance measuring device ASR-3105 having an incident angle of 5 °, and 400 to 1,200 nm under the following conditions according to the attached instruction manual. The absolute reflectance up to was measured.
Scan speed: High-speed sampling pitch: 1 nm
Measurement mode: Single slit width: 30 nm
Light source switching wavelength: 360 nm
Detector switching wavelength: 805 nm
S / R switching: Standard detector lock: Automatic slit program: Standard.

(5) Glass transition temperature It measured and calculated according to JIS-K-7122 (1987) using differential calorimetry (DSC). First, at 1st Run, 20 ° C./min. From 25 ° C. to 290 ° C. The temperature was raised at 290 ° C., held at 290 ° C. for 5 minutes, and then rapidly cooled to 25 ° C. Moreover, in 2nd Run which continues, it is 20 degrees C / min. From 25 degreeC to 290 degreeC. The temperature was raised. As the glass transition temperature of the resin, the glass transition temperature at 2nd Run was used.
Equipment: “Robot DSC-RDC220” manufactured by Seiko Electronics Industry Co., Ltd.
Data analysis “disc session SSC / 5200”.

(6) Number of layers, layer pair thickness Using a scanner (CanonScanD123U manufactured by Canon, Inc.), a cross-sectional image of a film obtained with a transmission electron microscope is used to scan an image with an image size of 720 dpi. Saved as a map file (BMP). Next, image processing software Image-Pro Plus ver. 4 (Media Cybernetics) was used to open this BMP file and perform image analysis. The typical image processing conditions are described below. First, after processing a low-pass filter (size: 7 × 7, strength: 10, number of times: 10), position and luminance numerical data were obtained in the vertical thick profile mode. The position was previously scaled by spatial calibration. This position and luminance data were subjected to sampling step 6 (thinning 6) and three-point moving average processing on Microsoft Excel CEL2000. Further, the obtained luminance was differentiated by position, and the maximum value and the minimum value of the differential curve were calculated. Then, the distance between the positions where the adjacent maximum value-maximum value or the adjacent minimum value-minimum value is set as the layer pair thickness, and all the layer pair thicknesses were calculated.

[Production of laminated film]
1. Synthesis of polyester 1 67.6 parts by weight of dimethyl terephthalate, 17.4 parts by weight of dimethyl 1,4-cyclohexanedicarboxylate having a cis / trans ratio of 72/28, 54 parts by weight of ethylene glycol, and 20 parts of spiro glycol Part by mass, 0.04 part by mass of manganese acetate tetrahydrate and 0.02 part by mass of antimony trioxide were weighed and charged into a transesterification reactor. The contents were dissolved at 150 ° C. and stirred. Subsequently, methanol was distilled while slowly raising the temperature of the reaction contents to 235 ° C. while stirring. After distillation of a predetermined amount of methanol, an ethylene glycol solution containing 0.02 parts by mass of trimethyl phosphoric acid was added. After adding trimethyl phosphoric acid, the mixture was stirred for 10 minutes to complete the transesterification reaction. Thereafter, the transesterification reaction product was transferred to a polymerization apparatus.

  Next, the content of the polymerization apparatus was stirred and the pressure was reduced and the temperature was raised, and polymerization was carried out while distilling ethylene glycol. The reduced pressure was reduced from normal pressure to 133 Pa or less over 90 minutes, and the temperature was raised from 235 ° C. to 285 ° C. over 90 minutes. When the stirring torque of the polymerization apparatus reached a predetermined value, the inside of the polymerization apparatus was returned to normal pressure with nitrogen gas, the valve at the bottom of the polymerization apparatus was opened, and a gut-shaped polymer was discharged into the water tank. The polyester gut cooled in the water tank was cut with a cutter to obtain chips, and polyester 1 was obtained.

  The obtained polyester 1 had an intrinsic viscosity of 0.78. The dicarboxylic acid component of the polyester 1 was 80 mol% terephthalic acid and 20 mol% cyclohexanedicarboxylic acid. The diol component of polyester 1 was 85 mol% ethylene glycol and 15 mol% spiroglycol.

2. Synthesis of polyester 2 Similarly, polyester 2 (polyethylene terephthalate) was polymerized in the same manner as described above except that 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol were used. The obtained polyester 2 had an intrinsic viscosity of 0.65 and a Tg of 80 ° C.

3. Formation of laminated film Polyester 2 was used as resin A. As resin B, polyester 2 (polyethylene / spiroglycol / terephthalate / cyclohexanedicarboxylic acid) was used. These resins A and B were each dried and then fed to separate extruders.

  Resins A and B were each melted at 280 ° C. with an extruder, passed through a gear pump and a filter, and then merged in a 801-layer feed block. As the 801-layer feed block, an apparatus as shown in FIGS. 1 and 4 was used. The feed block was composed of three slit members having 267 slits. In the feed block, the merged resins A and B are changed so that the thickness of each layer gradually increases from the surface side toward the opposite surface side, and the thickness direction in which the resin A is 401 layers and the resin B is 400 layers. It was set as the structure laminated | stacked alternately. Here, the thickness of each layer pair was targeted at the line A in FIG. 5, the flow rate of each slit was calculated from this, and the shape of the fine slit provided in the flow path of each layer in the feed block was adjusted. Moreover, the slit shape was designed so that both surface layer parts might be resin A, and the layer thickness of the adjacent A layer and B layer might become substantially the same. In this design, a reflection band exists between 400 nm and 1,200 nm. The thus obtained laminate comprising 801 layers is supplied to a multi-manifold die, and further, a layer made of resin A supplied from another extruder is formed on the surface layer, and after forming into a sheet shape, Rapid solidification was effected on a casting drum maintained at a surface temperature of 25 ° C. by application of electricity. The flow path shape and the total discharge amount were set so that the time from when the resin A and the resin B merged to when rapidly solidified on the casting drum was about 8 minutes.

  The obtained cast film was heated with a roll group set at 75 ° C., and then stretched 3.0 times in the longitudinal direction while rapidly heating from both sides of the film with a radiation heater between 100 mm in the stretch section length. Cooled down. Subsequently, both sides of this uniaxially stretched film were subjected to corona discharge treatment in air, the wetting tension of the base film was set to 55 mN / m, and the treated surface (polyester resin having a glass transition temperature of 18 ° C.) / (Glass transition) Polyester resin having a temperature of 82 ° C.) / Laminate-forming film coating liquid composed of silica particles having an average particle diameter of 100 nm was applied to form a transparent, easy-sliding, and easy-adhesion layer.

  This uniaxially stretched film was guided to a tenter, preheated with hot air at 100 ° C., and stretched 3.3 times in the transverse direction at a temperature of 110 ° C. The stretched film is directly heat-treated in a tenter with hot air at 240 ° C., then subjected to a relaxation treatment of 8% in the width direction at the same temperature, and then gradually cooled to room temperature, wound up, and laminated film 1 was obtained. The film thickness was 100 μm.

[Preparation of CNT dispersion]
[CNT dispersion (1)]
The obtained wet CNT aggregate, 6% by mass sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen 5A (mass average molecular weight: 80,000)) aqueous solution, ion-exchanged water, zirconia beads (Toray Industries, Inc.) “Traceram” (registered trademark), bead size: 0.8 mm) was added to the container, and the pH was adjusted to 10 using a 28% by mass aqueous ammonia solution (Kishida Chemical Co., Ltd.) (Dispersant / CNT mass ratio = 2.5) This container was shaken for 2 hours using a vibration ball mill (manufactured by Irie Trading Co., Ltd., VS-1, frequency: 1,800 cpm (60 Hz)) to obtain a CNT paste. Was prepared.

  Next, this CNT paste was diluted with ion-exchanged water so that the concentration of CNTs was 0.15% by mass, and adjusted to pH 10 with a 28% by mass aqueous ammonia solution again with respect to 10 g of the diluted solution. The aqueous solution was subjected to dispersion treatment under ice-cooling for 1.5 minutes (0.6 kW · min / g) with an output of an ultrasonic homogenizer (manufactured by Ieda Trading Co., Ltd., VCX-130) at 20 W. At that time, the liquid temperature during dispersion was set to 10 ° C. or lower. The obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge (Tomy Seiko Co., Ltd., MX-300) to obtain a CNT dispersion. Thereafter, water was added to prepare a CNT dispersion by adjusting the final concentration so that the concentration of the CNT aggregate was 0.06% by mass.

[Corona treatment]
Using a corona surface modification evaluation device TEC-4AX manufactured by Kasuga Electric Co., Ltd., a biaxially oriented polyester film for molding was placed on a ground plate, corona treatment output 100W, discharge gap 1mm with ceramic electrode, electrode moving speed 6m Corona treatment was performed under the conditions of 5 treatments per minute / minute.

[Stretching method]
The conductive laminate is cut into a length of 150 mm and a width of 20 mm, and the conductive laminate is placed on a tensile tester (manufactured by Tensilon Yamato Kagaku Co., Ltd.) so that the test length is 30 mm. (2 times stretching), it was fixed for 10 seconds as it was, and then the sample was taken out. The sample obtained under the above conditions is hereinafter referred to as “a conductive laminate after stretching”.

Example 1
The easy adhesion layer surface of the laminated film was subjected to corona treatment by the above method, and the CNT dispersion (1) was applied to the corona treated surface using a wire bar and dried at 100 ° C. for 1 minute to obtain a conductive laminate 1. . Table 1 shows the measurement results of the surface resistance and haze of the obtained conductive laminate.

  Next, about the obtained conductive laminated body, it extended | stretched with the said extending | stretching method, and the conductive laminated body 1 after extending | stretching was obtained. Table 1 shows the surface resistance value and haze measurement result of the obtained conductive laminate 1 after stretching.

(Example 2)
The anchor coat surface of the laminated film 1 was subjected to corona treatment by the above method, and the CNT dispersion (1) was applied to the corona treated surface using a wire bar and dried at 100 ° C. for 1 minute to form a CNT layer. The coating liquid used as the overcoat layer was an acrylic resin (“Light Acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd.) diluted with ethyl acetate to a solid content of 1.0% by mass, and a photopolymerization initiator (“IRGACURE 184” manufactured by BASF). ) Was added to the resin solid content in an amount of 5% by mass. This coating solution is applied onto the CNT layer using a wire bar, dried at 125 ° C. for 1 minute, and accumulated light amount of 400 mJ under a nitrogen atmosphere using a UV irradiation device (“ECS-301” manufactured by Eye Graphics Co., Ltd.). The overcoat layer was cured by UV irradiation with a dose of / cm ² to obtain a conductive laminate 2 and a stretched conductive laminate 2.

(Example 3)
The anchor coat surface of the laminated film 1 was subjected to corona treatment by the above method. An aqueous dispersion of a hydrophilic acrylic-modified polyester resin (“Pesresin A647-GEX” manufactured by Takamatsu Yushi Co., Ltd.) was used as the coating liquid for the undercoat layer. The A647-GEX was adjusted with pure water to a solid content of 5% by mass to obtain a coating solution for preparing an undercoat layer. A coating solution for preparing an undercoat layer was applied to the corona-treated surface of the substrate with a wire bar and dried in a dryer at 125 ° C. for 1 minute to prepare an undercoat layer. Thereafter, the CNT dispersion (1) was applied onto the undercoat layer using a wire bar, and dried at 100 ° C. for 1 minute to form a CNT layer. The coating liquid used as the overcoat layer was an acrylic resin (“Light Acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd.) diluted with ethyl acetate to a solid content of 1.0% by mass, and a photopolymerization initiator (“IRGACURE 184” manufactured by BASF). ) Is added to the CNT layer with a wire bar, and dried at 80 ° C. for 1 minute with a UV irradiation device (“ECS-301” manufactured by Eye Graphics Co., Ltd.). Using this, UV irradiation was performed with an irradiation amount of 400 mJ / cm ^{2 in} a nitrogen atmosphere, the overcoat layer was cured, and the conductive laminate 3 was obtained. Next, about the obtained conductive laminated body, it extended | stretched with the said extending | stretching method, and the conductive laminated body 3 after extending | stretching was obtained.

1: Laminated film 2: Undercoat layer 3: Layer containing carbon nanotubes 4: Overcoat layer

Claims (6)

A conductive laminate having a conductive layer containing carbon nanotubes on at least one surface of the laminate film, wherein the laminate film satisfies the following (i) to (iii):
(I) having a structure in which a layer containing resin A (A layer) and a layer containing resin B (B layer) are alternately laminated by 30 layers or more (ii) absolute at any wavelength in the wavelength band of 400 to 700 nm Reflectivity of 30% or more (iii) Resin A is polyethylene terephthalate and / or polyethylene naphthalate, and resin B is a polyester comprising spiroglycol The conductive laminate according to claim 1, wherein a change in surface resistance when the conductive laminate is stretched twice is 1 to 5 times. The conductive laminate according to claim 1, wherein the conductive laminate has a surface resistance value of 10 Ω / □ or more and 2,000 Ω / □ or less when stretched twice. The haze when the conductive laminate is stretched twice is 0% or more and 5% or less. The molded object using the electrically conductive laminated body in any one of Claims 1-4. A capacitive touch sensor using the molded body according to claim 5.

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