WO2021106188A1

WO2021106188A1 - Conductive leather, conductive fiber, and method for producing conductive leather or conductive fiber

Info

Publication number: WO2021106188A1
Application number: PCT/JP2019/046763
Authority: WO
Inventors: 誠之島田
Original assignee: 株式会社ジャパンナノコート
Priority date: 2019-11-29
Filing date: 2019-11-29
Publication date: 2021-06-03
Also published as: JPWO2021106188A1

Abstract

The purpose of the present invention is to provide a leather or fiber, which is imparted with electrical conductivity without a change of the texture of a base material, while having excellent friction resistance.　A conductive leather or conductive fiber, which is characterized by sequentially comprising in the following order from the surface: (A) a first layer that contains single-walled carbon nanotubes, graphene nanoparticles and single nanoparticles of silica in such a manner that from 40 to 60 parts by mass of single nanoparticles of silica having a size of 5 nm or less as measured by a transmission electron microscope and from 60 to 40 parts by mass of single nanoparticles of tin oxide having a size of 2 nm or less as measured by a transmission electron microscope are contained with respect to a total of 100 parts by mass of the single nanoparticles of silica and the single nanoparticles of tin oxide; and (B) a second layer that contains a water repellent agent and a conductive material.

Description

Conductive leather or conductive fibers, and methods for producing conductive leather or conductive fibers

The present invention relates to conductive leather or conductive fibers, and a method for producing conductive leather or conductive fibers.

Currently, with the spread of smartphones and the like, touch panel operations are being performed on a daily basis. Since this touch panel is used, products that can be used while wearing winter clothes gloves and the like are on sale.

However, conductive threads are generally used in these products. For example, when metallic conductive threads are used, the appearance of the products is different because the color of the products differs only in the part where the conductive threads are used. In addition to damaging, it may cause an allergic reaction depending on the type of metal. Further, since the conductive yarn is generally not relatively strong against friction, the conductivity often decreases due to friction.

Processing to impart conductivity is used for synthetic fibers and the like. On the other hand, it seems that there are few products that use conductive processing for natural fibers and natural leather. In particular, since many natural leather products are high-class products, products that do not change the texture such as color are required from the viewpoint of design. In addition, among the characteristics required for products such as gloves for smartphones, there is a desire to make the surface of the product water-repellent, but the surface treatment agent that imparts water repellency is due to the surface of the product becoming insulating. , Products used on the entire surface of the product are not widespread because they hinder the continuity of the product surface. As a result, in the case of gloves for smartphones, it is usual to make only a part of the fingertips conductive (for example, Patent Document 1).

JP-A-2017-160582

An object of the present invention is to provide leather or fiber which is imparted with conductivity without changing the texture of the base and has excellent abrasion resistance.

The present invention relates to conductive leather or conductive fibers that solve the above problems by having the following configurations, and a method for producing conductive leather or conductive fibers.
[1] (A) Containing single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, and tin oxide single nanoparticles.
For a total of 100 parts by mass of the single nanoparticles of silica and the single nanoparticles of tin oxide, single nanoparticles of silica of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured tin oxide particles of 2 nm or less: the first layer containing 60 to 40 parts by mass, and
(B) A second layer containing a water repellent and a conductive material,
Conductive leather or textiles, characterized in that they are provided in this order from the surface.
[2] The conductive leather or conductive fiber according to the above [1], wherein the sheet resistance on the surface is 9.9 × 10 ^{6 Ω / □ or less.}
[3] A process for the surface of leather or fiber.
(A) Containing single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, tin oxide single nanoparticles, and water.
For a total of 100 parts by mass of silica single nanoparticles and tin oxide single nanoparticles, silica single nanoparticles of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured single nanoparticles of tin oxide of 2 nm or less: A step of applying a dispersion liquid for forming a first layer containing 60 to 40 parts by mass on the surface or immersing the surface to form the first layer.
(B) Conductivity including a step of applying a second layer forming aqueous solution containing a water repellent, a conductive material, and water to the surface or immersing the surface to form the second layer in this order. A method for producing leather or conductive fibers.
[4] The method for producing conductive leather or conductive fibers according to the above [3], wherein in the step (A), a dispersion liquid for forming a transparent conductive thin film is applied to a surface or the surface is immersed and then rolled.

According to the present invention [1], it is possible to provide leather or fiber which is imparted with conductivity without changing the texture of the base and has excellent abrasion resistance.

According to the present invention [3], it is possible to easily produce leather or fiber which is imparted with conductivity and has excellent abrasion resistance without changing the texture of the base.

[Conductive leather or conductive fiber]
The conductive leather or conductive fiber of the present invention (hereinafter referred to as conductive leather, etc.) includes (A) single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, and tin oxide single nanoparticles. Including
For a total of 100 parts by mass of silica single nanoparticles and tin oxide single nanoparticles, silica single nanoparticles of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured single nanoparticles of tin oxide of 2 nm or less: the first layer containing 60-40 parts by mass, and
(B) A second layer containing a water repellent and a transparent conductive material,
Is provided in this order from the surface. Both the first layer and the second layer can be formed by a dispersion liquid described later.

According to this configuration, the present invention can provide leather or fiber which is imparted with conductivity without changing the texture of the base and has excellent abrasion resistance.

The present invention forms a transparent conductive film on leather or fiber (hereinafter referred to as leather or the like). The transparent conductive film, using a single-wall carbon nanotubes and graphene, without lowering the transparency, the first layer of the surface resistance value in the following human hand equivalent 10 ⁶ Ω / □ base, a first layer thereon and water repellent for not drop conductivity of, by forming a second layer containing tin oxide as a conductive material, the sheet resistance without reducing the 10 ⁷ Ω / □ base, water repellent It becomes possible to form a transparent conductive film which is a coat. The present invention can realize water-repellent conductivity without changing the texture of leather or the like by this transparent conductive film, and unlike synthetic fibers or synthetic leather in which a conductive agent or the like is kneaded, natural fibers or natural materials can be realized. It can contribute to the multifunctionalization of leather.

The leather is not particularly limited, but examples thereof include natural leather and artificial leather. An example of the thickness of leather is 0.5 to 2 mm, and in particular, leather for gloves is about 0.5 mm.

The fibers are not particularly limited, and examples thereof include natural fibers (cotton, linen, silk, etc.), synthetic fibers, and the like.

The single-wall carbon nanotubes are not particularly limited, but the single-wall carbon nanotubes preferably have a fiber diameter of 0.5 nm or less, an aspect ratio of 5 or more, and a length of 10 nm or less. Among the single-walled carbon nanotubes, single-walled carbon nanotubes are more preferable. The single-walled carbon nanotubes having a fiber diameter and an aspect ratio can be uniformly dispersed in a solvent and can form sufficient contact points with each other.

The fiber diameter of the single-wall carbon nanotube is the mass average particle diameter obtained by observing a transmission electron micrograph (magnification of 100,000 times) (n = 50). The aspect ratio of the single-wall carbon nanotubes is obtained by observing a transmission electron micrograph (magnification of 100,000 times) and calculating (length / fiber diameter) (n = 50).

Further, it is preferable that the single-wall carbon nanotubes can be dispersed in a solvent without using a dispersant. Examples of the treatment for making the single-walled carbon nanotubes dispersible in a solvent include treatment with a strong acid such as sulfuric acid. In addition, a single-wall carbon nanotube dispersion liquid that does not use a dispersant is also commercially available.

Examples of graphene nanoparticles include graphene nanoparticles having an average thickness (c-axis direction) of 50 nm or less and a radial (a-axis direction) diameter of 2 μm or less dispersed in water. The powder having an average thickness of graphene nanoparticles of 5 nm or less imparts antistatic property and abrasion resistance to the thin film formed from the coating agent. An example of graphene length is 5 nm to 3 μm. The average thickness of graphene is preferably 1 to 5 nm from the viewpoint of flame retardancy and film formation having a uniform thickness. Here, the average thickness and length of graphene are mass average particle diameters obtained by observing a transmission electron micrograph (magnification of 100,000 times) (n = 50).

Single nanoparticles refer to particles having a particle size (n = 50) measured with a transmission electron microscope of less than 10 nm. With respect to 100 parts by mass of the single nanoparticles, the single nanoparticles of silica having a size of 5 nm or less are preferably 40 to 60 parts by mass, and the single nanoparticles of silica having a size of 2 nm or less are preferably 30 to 40 parts by mass. Here, when silica nanoparticles having a diameter of 10 nm or more are used, the increase in the transmittance of the substrate with the transparent conductive thin film becomes low, and the wear resistance of the transparent conductive thin film becomes low. In addition, the conductivity tends to decrease. If the amount of silica single nanoparticles of 2 nm or less exceeds 40 parts by mass, the dispersion liquid for forming a transparent conductive thin film tends to gel. The silica single nanoparticles of 2 nm or less are preferably 0.5 nm or more from the viewpoint of handleability and availability.

It is preferable that the silica single nanoparticles of 2 nm or less contain amorphous silica. It is confirmed by X-ray diffraction that it is amorphous.

With respect to 100 parts by mass of single nanoparticles, single nanoparticles of tin oxide of 2 nm or less are 60 to 40 parts by mass, and 50 parts by mass or more, from the viewpoint of conductivity, transmittance, and abrasion resistance of the first layer. Is preferable. Tin oxide powder having an average particle size of primary particles of 10 nm or more is less likely to cause secondary agglomeration by itself, but is not preferable because secondary agglomeration is likely to occur when mixed with other materials.

The thickness of the first layer is preferably 50 to 300 nm from the viewpoint of conductivity, transparency and abrasion resistance, and 50 to 80 nm from the viewpoint of the influence of color on leather and the like. , More preferred. The thickness of the first layer, when less than 50 nm, the sheet resistance of the surface of the leather or the like, tends to be higher than 10 ⁶ Ω / □ base, the touch panel becomes unresponsive. If it is thicker than 300 nm, cracks will occur during film formation and it will be easy to peel off. In the applications of the touch panel, the sheet resistance of the surface of the leather or the like, at a 10 ⁷ Ω / □ stand, it becomes difficult to use, the sheet resistance of the surface, if it is 9.9 × 10 ⁶ Ω / □ or less ,preferable.

The second layer contains a water repellent agent for not reducing the conductivity of the first layer and a conductive material having a transparent antistatic property.

Examples of the water repellent include a fluororesin, a silicone resin, and the like, which may be used alone or in combination of two or more. As a fluororesin, AGC's Asahi Guard series AG-E600, and as a silicone resin, Shin-Etsu Silicone's water-based emulsion POLON-SR CONIC, etc. can be used in combination with antistatic agents such as ionic surfactants. Preferable as an agent.

Examples of the conductive material include tin oxide powder and an ionic surfactant, and it is preferable to use tin oxide alone or a combination of tin oxide powder and an ionic surfactant. The tin oxide powder is as described above, and examples of the ionic surfactant include a quaternary ammonium salt. As the ionic surfactant, an amphoteric surfactant having both cation and anion polarities is preferable.

Examples of the quaternary ammonium salt include alkyltrimethylammonium salts and dialkyldimethylammonium salts, and examples of commercially available products include the 1SX series manufactured by Taisei Fine Chemicals Co., Ltd.

As the dispersion liquid for forming the second layer for forming the second layer, a dispersion liquid manufactured by Japan Nanocoat (product name: AS-WR) is easily used because each component is mixed in advance.

The thickness of the second layer is preferably 20 to 100 nm from the viewpoint of water repellency and conductivity. If it is less than 20 nm, the water repellency tends to be insufficient, and if it is thicker than 100 nm, the conductivity tends to decrease.

The effect of the present invention can be exhibited as long as the second layer is 1 × 10 ¹⁰ Ω / □ or less and the transparency is not deteriorated (change in color tone is not visually observed).

[Manufacturing method of conductive leather or conductive fiber]
The method for producing conductive leather or conductive fiber of the present invention is:
A process on the surface of leather or fibers
(A) Containing single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, tin oxide single nanoparticles, and water.
For a total of 100 parts by mass of silica single nanoparticles and tin oxide single nanoparticles, silica single nanoparticles of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured single nanoparticles of tin oxide of 2 nm or less: A step of applying a dispersion liquid for forming a first layer containing 60 to 40 parts by mass on the surface or immersing the surface to form the first layer.
(B) A step of applying a second layer forming aqueous solution containing a water repellent, a conductive material, and water to the surface or immersing the surface to form the second layer is included in this order.

[Step (A)]
The step (A) includes single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, tin oxide single nanoparticles, and water.
For a total of 100 parts by mass of single nanoparticles of silica and single nanoparticles of tin oxide, single nanoparticles of silica of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. A first layer forming dispersion containing 60 to 40 parts by mass of the measured single nanoparticles of tin oxide of 2 nm or less is applied to or immersed in the surface to form the first layer.

The dispersion liquid for forming the first layer contains (A) single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, tin oxide single nanoparticles, and water.
For a total of 100 parts by mass of single nanoparticles of silica and single nanoparticles of tin oxide, single nanoparticles of silica of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured single nanoparticles of tin oxide of 2 nm or less: Contains 60 to 40 parts by mass.

The single-wall carbon nanotubes, graphene nanoparticles, and silica single nanoparticles are as described above.

The amount of single-wall carbon nanotubes is preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the dispersion liquid for forming the first layer. More preferably, 0.03 to 0.06 parts by mass. If it is 0.2 parts by mass or more, thickening and aggregation are likely to occur, and the transmittance is lowered.

The graphene nanoparticles are preferably 0.001 to 0.1 parts by mass, more preferably 0.005 to 0.01% by mass, based on 100 parts by mass of the dispersion liquid for forming the first layer.

The single nanoparticles are preferably 18 to 99.5 parts by mass with respect to 100 parts by mass in total of the single nanoparticles, single-wall carbon nanotubes and graphene nanoparticles. If the number of single nanoparticles is less than 18 parts by mass, the adhesion of the transparent conductive thin film tends to decrease, and if it exceeds 99.5 parts by mass, the conductivity and heat dissipation of the transparent conductive thin film tend to decrease. Further, the silica single nanoparticles are 40 to 60 parts by mass with respect to 100 parts by mass in total of the silica single nanoparticles, single-wall carbon nanotubes, graphene nanoparticles and tin oxide single nanoparticles. It is more preferable because the layer becomes highly conductive and highly transparent.

The amount of water is preferably 99.0 to 99.5 parts by mass with respect to 100 parts by mass of the dispersion liquid for forming the first layer. Although an organic solvent other than water can be used as the solvent, water is used from the viewpoint of suppressing environmental pollution due to solvent volatilization.

The dispersion liquid for forming the first layer can be obtained, for example, by stirring, melting, mixing, and dispersing various nanopowder, solvent, and other additives at the same time or separately, with heat treatment if necessary. it can. The apparatus for mixing, stirring, dispersing, etc., is not particularly limited, but a Raikai machine, a ball mill, a planetary mixer, a bead mill, or the like can be used. Moreover, you may use these devices in combination as appropriate. A dispersion liquid for forming a second layer, which will be described later, can also be obtained in the same manner.

Additives and the like can be further added to the dispersion liquid for forming the first layer as long as the object of the present invention is not impaired.

As a commercially available product of the dispersion liquid for forming the first layer, AS-SCNT manufactured by Japan Nanocoat can be mentioned.

The method of applying the dispersion liquid for forming the first layer to the surface of leather or the like or immersing the surface is not particularly limited, and examples thereof include brush coating, spray coating, and dipping.

As described above, the thickness of the first layer is preferably 50 to 300 nm. In the case of leather (thickness 0.5 to 2 mm, particularly 0.5 mm for gloves), the pickup rate (mass of the first layer with respect to 100% by mass of leather) is preferably 60%. In the case of cloth, the pick-up rate is preferably 200 to 300% after coating and dipping, 60 to 120% after rolling, and more preferably 100%.

In step (A), when the dispersion liquid for forming a transparent conductive thin film is applied to the surface or immersed in the surface and then rolled, the single-wall carbon nanotubes and graphene are likely to be oriented horizontally with respect to the surface of leather or the like. Therefore, it is preferable from the viewpoint of improving conductivity and transparency.

[Step (B)]
In the step (B), an aqueous solution for forming a second layer containing a water repellent, a conductive material, and water is applied to or immersed in the surface to form the second layer.

The aqueous solution for forming the second layer contains a water repellent, a conductive material, and water.

The water repellent and conductive material are as described above. Although an organic solvent other than water can be used as the solvent, water is used from the viewpoint of suppressing environmental pollution due to solvent volatilization.

The water repellent is preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the dispersion liquid for forming the second layer.

The transparent conductive material is preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the dispersion liquid for forming the second layer.

The amount of water is preferably 99.4 to 99.94 parts by mass with respect to 100 parts by mass of the dispersion liquid for forming the second layer.

Additives and the like can be further added to the dispersion liquid for forming the second layer as long as the object of the present invention is not impaired.

As a commercially available product of the dispersion liquid for forming the second layer, a dispersion liquid manufactured by Japan Nanocoat (product name: AS-WR) can be mentioned. It is preferable to dilute this dispersion liquid manufactured by Japan Nanocoat (product name: AS-WR) about 20 times and use it from the viewpoint of thickness control and the like.

The method of applying the second layer forming dispersion liquid to the surface of leather or the like or immersing the surface is not particularly limited, and the method of applying the first layer forming dispersion liquid to the surface of leather or the like or immersing the surface is used. , The same is true.

As described above, the thickness of the second layer is preferably 20 to 100 nm. In the case of leather (thickness 0.5 to 2 mm, particularly 0.5 mm for gloves), the pickup rate (mass of the first layer with respect to 100% by mass of leather) is preferably 60%. In the case of cloth, the pick-up rate is preferably 200 to 300% after coating and dipping, 60 to 120% after rolling, and more preferably 100%.

The present invention will be described with reference to Examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.

As the dispersion liquid for forming the first layer of Example 1, a water-based antistatic coating agent (product name: AS-SCNT) manufactured by Japan Nanocoat was used. This AS-SCNT consists of silica nanoparticles: 0.21%, tin oxide nanoparticles: 0.24%, single carbon nanotubes: 0.04%, graphene: 0.01%, and the balance: water. In Comparative Example 4, silica nanoparticles having an average particle size of 6 nm (manufactured by Fuso Chemical Manufacturing Co., Ltd., product name: PL-06L) were used. In Comparative Example 5, a mixture of 20 parts by mass of silica nanoparticles having an average particle size of 15 nm (manufactured by Fuso Chemical Co., Ltd., product name: PL-1) and 80 parts by mass of water was used.

The dispersion liquid for forming the second layer is 20 of Japan Nanocoat dispersion liquid (product name: AS-WR, fluororesin: 5% by mass, silicone resin: 5% by mass, tin oxide 0.1% by mass, balance: water). A double diluted solution was used.

The surface resistance value was measured by Hozan Co., Ltd. (model number: F-109). The transparency was measured by measuring the transparency of the transparent conductive thin film formed on the glass base material (float glass) using a glass transmittance measuring device (model number: MJ-TM110) manufactured by Sato Shoji Co., Ltd. As for the transmittance, those having a decrease rate of less than 1% from the float glass transmittance were accepted. For the wear resistance test, use (Imoto Seisakusho's rubbing tester tester), and apply a cotton cloth on the coated surface under the condition of 1 kg load, and after 20000 rotations, the surface resistance value does not drop to the 7th power of 10. , Passed.

[Example 1]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. % Liquid (silica solid content: 1.4%, tin oxide solid content: 1.6%) 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (product name: graphene 0.1% aqueous dispersion) was added, and the balance was 55 parts by mass of water for forming the first layer of Example 1. An aqueous solution was prepared.

20 ° C. for a glass substrate (float glass, transmittance: 91.6%, refractive index: 1.51, surface resistance value: 10 ^{13 Ω) having a width of 50 mm, a length of 100 mm, and a thickness of 3 mm.} The first layer forming aqueous solution of Example 1 at ~ 25 ° C. ^{was placed in a 300 cm 3} beaker, the glass base material was immersed for 20 seconds, and then the glass base material was erected vertically and the first layer forming aqueous solution was poured. The coating was applied under the conditions of atmospheric temperature: 20 to 25 ° C. and humidity: 50 to 55%. The coated glass substrate was dried at a temperature of 20 ° C. for 10 minutes to obtain a glass substrate with a first layer having a center thickness of about 60 nm.

The first layer-attached glass substrate thus obtained, the transmittance: 91.5%, surface resistivity: was 3.21 × 10 ⁶ Ω.

Next, on the first layer, AS-WR as a dispersion liquid for forming the second layer diluted 20-fold with water was applied by dipping, and the transmittance was 91.0% and the surface resistance value was 5.46. A substrate of × 10 ⁶ Ω was obtained. Transmittance after the abrasion test is 91.0% the surface resistance value was 7.32 × 10 ⁶ Ω.

Natural leather (thickness: 0.5 mm) was treated in the same process. Color of the treated leather is not changed, the surface resistivity is 3.64 × 10 ⁶ Ω, the surface resistivity value after the abrasion test, a large decrease and 5.21 × 10 ⁶ Ω was observed .. At this time, the pickup rate of the first layer was 160%, and the pickup rate of the second layer was 160%.

[Example 2]
Solid content prepared by mixing Japan Nanocoat silica binder (product name: B-30 (solid content 3%)), Japan Nanocoat tin oxide dispersion (product name: tin oxide 4% dispersion), and water. 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat in 15 parts by mass of 3% liquid (silica solid content 1.2%, tin oxide solid content 1.8%) Was added, 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (product name: graphene 0.1% aqueous dispersion) was added, and the balance was 55 parts by mass of water, which is the first layer forming aqueous solution of Example 2. Was produced.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 91.0%, surface resistivity: 8,35 was × 10 ⁵ Ω.

Next, on the first layer, AS-WR diluted 20-fold with water was applied by dipping.
Transmittance: 90.5%, surface resistivity: to obtain a substrate of 3.34 × 10 ⁶ Ω. Transmittance after the abrasion test is 90.5% the surface resistance value was 5.77 × 10 ⁶ Ω.

[Example 3]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat is added to 15 parts by mass of the% liquid (silica solid content 1.8%, tin oxide solid content 1.2%). In addition, 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (product name: graphene 0.1% aqueous dispersion) was added to prepare an aqueous solution for forming the first layer of Example 3 in which the balance was 55 parts by mass of water. did.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 91.5%, surface resistivity: 6.46 was × 10 ⁶ Ω.
Next, AS-WR diluted 20-fold with water was applied by dipping on the first layer.
Transmittance 90.9%, it was prepared equipment surface resistance value 6.77 × 10 ⁶ Ω. Transmittance after the abrasion test was 90.8%, and a surface resistance value 8.77 × 10 ⁶ Ω.

[Comparative Example 1]
Japan Nanocoat silica binder product name: B-30 (solid content 3%) 15 parts by mass, Japan Nanocoat CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) 20 parts by mass added, Japan 10 parts by mass of a 0.1% aqueous dispersion of a graphene solution made by Nanocoat (trade name: 0.1% aqueous dispersion of graphene) was added to prepare an aqueous solution for forming the first layer of Comparative Example 1 in which the balance was 55 parts by mass of water.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 91.2%, surface resistivity: 6.37 a × 10 ⁷ Omega, conductivity was low.

[Comparative Example 2]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat was added to 15 parts by mass of% liquid (silica solid content 2%, tin oxide solid content 1%), and Japan Nanocoat 10 parts by mass of a 0.1% aqueous dispersion of graphene (trade name: 0.1% aqueous dispersion of graphene) was added to prepare an aqueous solution for forming the first layer of Comparative Example 2 in which the balance was 55 parts by mass of water.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 91.5%, surface resistivity: 8.76 was × 10 ⁶ Ω.

Next, on the first layer, AS-WR diluted 20-fold with water was applied by dipping.
Transmittance: 91.2%, surface resistivity: to obtain a substrate of 3.21 × 10 ⁷ Ω. The conductivity after the formation of the second layer was low.

[Comparative Example 3]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat was added to 15 parts by mass of the% liquid (silica solid content: 1%, tin oxide solid content: 2%). 10 parts by mass of a 0.1% aqueous dispersion of graphene solution manufactured by Japan Nanocoat (trade name: 0.1% aqueous dispersion of graphene) was added to prepare an aqueous solution for forming the first layer of Comparative Example 3 in which the balance was 55 parts by mass of water.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 90.3%, surface resistivity: was 7.86 × 10 ⁵ Ω.

Next, on the first layer, AS-WR diluted 20-fold with water was applied by dipping.
Transmittance: 90.1%, surface resistivity: to obtain a substrate of 1.56 × 10 ⁶ Ω. In this comparative example, the transmittance was low. Further, transmittance after the abrasion resistance test: 90.3%, surface resistivity: 3.36 next × 10 ⁷ Omega, wear resistance was also low.

[Comparative Example 4]
Product name of silica binder manufactured by Fuso Chemical Co., Ltd .: PL-06L (solid content 6%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide 4% dispersion liquid), and water are mixed to prepare a solid content 3 % Liquid (silica solid content: 1.8%, tin oxide solid content: 1.2%) 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (product name: graphene 0.1% aqueous dispersion) was added, and the balance was 55 parts by mass of water, which is the first layer forming aqueous solution of Comparative Example 4. Was produced.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 89.5%, surface resistivity: 7.46 a × 10 ⁷ Omega, transmittance and conductivity were low ..

[Comparative Example 5]
Product name of Fuso Chemical's silica binder: PL-1 (solid content 12%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide 4% dispersion liquid), and water were mixed to prepare a solid content 3 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat is added to 15 parts by mass of the% liquid (silica solid content 1.8%, tin oxide solid content 1.2%). In addition, 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (product name: graphene 0.1% aqueous dispersion) was added to prepare an aqueous solution for forming the first layer of Comparative Example 4 in which the balance was 55 parts by mass of water. did.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 90.7%, surface resistivity: 7.76 was × 10 ⁶ Ω.

Next, on the first layer, AS-WR diluted 20-fold with water was applied by dipping.
Transmittance 90.3% to obtain a base material of the surface resistance value 1.31 × 10 ⁷ Ω. The conductivity and transmittance after the formation of the second layer were low.

[Comparative Example 6]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), 10 nm tin oxide dispersion liquid (solid content 4%) in which 10 nm tin oxide powder is dispersed with water, and water are mixed and prepared. 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat was added to 15 parts by mass of the solid content 3% liquid (silica solid content 1%, tin oxide solid content 2%). In addition, 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (product name: graphene 0.1% aqueous dispersion) was added to prepare an aqueous solution for forming the first layer of Comparative Example 6 in which the balance was 55 parts by mass of water. did.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 89.3%, surface resistivity: a 1.86 × 10 ⁷ Ω, the transmittance and conductivity were low ..

[Comparative Example 7]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. 20 parts by mass of CNF 0.2% aqueous dispersion (product name: SCNT 0.2% aqueous dispersion) manufactured by Japan Nanocoat is added to 15 parts by mass of the% liquid (silica solid content 1.4%, tin oxide solid content 1.6%). In addition, an aqueous solution for forming the first layer of Comparative Example 6 in which the balance was 65 parts by mass of water was prepared.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 90.3%, surface resistivity: a 1.36 × 10 ⁷ Ω, the transmittance and conductivity were low ..

[Comparative Example 8]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. % Liquid (silica solid content 1.4%, tin oxide solid content 1.6%) 15 parts by mass, Japan Nanocoat graphene liquid 0.1% aqueous dispersion (product name graphene 0.1% aqueous dispersion) 10 mass Parts were added to prepare an aqueous solution for forming the first layer of Comparative Example 7 in which the balance was 75 parts by mass of water.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the transmittance: 91.5%, surface resistivity: A 3.21 × 10 ⁸ Ω, conductivity was low.

[Comparative Example 9]
Product name of silica binder manufactured by Japan Nanocoat: B-30 (solid content 3%), tin oxide dispersion liquid manufactured by Japan Nanocoat (product name: tin oxide dispersion liquid), and water are mixed to prepare solid content 3. % Liquid (silica solid content 1.4%, tin oxide solid content 1.6%) 15 parts by mass, Japan Nanocoat Multi CNF (multi-wall carbon nanofiber) 3% aqueous dispersion (Product name: CNT 3% aqueous dispersion) ) 10 parts by mass was added, and 10 parts by mass of Japan Nanocoat's graphene solution 0.1% aqueous dispersion (trade name: Graphene 0.1% aqueous dispersion) was added, and the balance was 65 parts by mass of water, the first layer of Comparative Example 9. An aqueous solution for formation was prepared. Met.

The first layer-attached glass substrate was obtained in the same manner as in Example 1, the center thickness of about 100 nm, the transmittance: 79.3%, surface resistivity: a 2.86 × 10 ⁵ Ω, the transmittance It was low.

Next, on the first layer, the AS-WR and dip coating a material obtained by diluting 20-fold with water, permeability: to give a 1.56 × 10 ⁹ Ω substrates 78.1% surface resistivity It was. Not only the transmittance is low, but also the surface resistance value is remarkably increased by applying the same water-repellent coating as in Example 1, so that the conductivity of the substrate is conductive even if the thickness is thin. It was found that excellent single nanocarbon nanotubes are excellent.

Claims

(A) Containing single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, and tin oxide single nanoparticles.
For a total of 100 parts by mass of silica single nanoparticles and tin oxide single nanoparticles, silica single nanoparticles of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured single nanoparticles of tin oxide of 2 nm or less: the first layer containing 60-40 parts by mass, and
(B) A second layer containing a water repellent and a conductive material,
Conductive leather or textiles, characterized in that they are provided in this order from the surface.
The conductive leather or textile according to claim 1, wherein the sheet resistance of the surface is 9.9 × 10 6 Ω / □ or less.
A process on the surface of leather or fibers
(A) Containing single-wall carbon nanotubes, graphene nanoparticles, silica single nanoparticles, tin oxide single nanoparticles, and water.
For a total of 100 parts by mass of silica single nanoparticles and tin oxide single nanoparticles, silica single nanoparticles of 5 nm or less measured with a transmission electron microscope: 40 to 60 parts by mass, and with a transmission electron microscope. Measured single nanoparticles of tin oxide of 2 nm or less: A step of applying a dispersion liquid for forming a first layer containing 60 to 40 parts by mass on the surface or immersing the surface to form the first layer.
(B) Conductivity including a step of applying a second layer forming aqueous solution containing a water repellent, a conductive material, and water to the surface or immersing the surface to form the second layer in this order. A method for producing leather or conductive fibers.
The method for producing conductive leather or conductive fiber according to claim 3, wherein in the step (A), a dispersion liquid for forming a transparent conductive thin film is applied to a surface or immersed in the surface and then rolled.