JP6960310B2 - Rough surface conductors and biological sensing devices - Google Patents

Description

The present invention relates to rough surface conductors and biological sensing devices.

Conventionally, as a flexible electrode used for wearable applications such as clothing, a fiber electrode having a conductive member obtained by impregnating a base fiber with a conductive composition containing a conductive polymer such as PEDOT / PSS has been developed. (For example, Patent Document 1). However, the conventional conductive member has a problem that the stretchability is low, and the conductivity is significantly lowered by stretching at a high magnification or repeating stretching a plurality of times.

International Publication No. 2013/073763

An object of the present invention is to provide a rough surface conductor having excellent stretchability and conductivity after stretching, and a biological sensing device including the rough surface conductor.

As a result of diligent studies to solve the above problems, the present inventor contains the conductive polymer (a) and the thermoplastic resin (b) on the rough surface resin base material (I) having a specific Ra. A rough surface conductor having a conductive coating layer (II), wherein the conductive coating layer (II) has a specific Ra, and the surface resistivity after being stretched twice is 1,000,000. The present invention has been completed by finding that a rough surface conductor having a thickness of 000 Ω / □ or less is excellent in stretchability and conductivity after stretching.

That is, the rough surface conductor of the present invention is a conductive coating containing a conductive polymer (a) and a thermoplastic resin (b) on a rough surface resin base material (I) having Ra of 0.1 μm or more. A rough surface conductor having a layer (II), the Ra of the conductive coating layer (II) is 0.1 μm or more, and the surface resistance after the double stretching treatment is 1,000,000,000 Ω. It is characterized by being less than or equal to / □.

The rough surface conductor of the present invention preferably contains at least one rough surface resin base material (I) selected from the group consisting of polyester, polyurethane, polyethylene, polypropylene, rayon, nylon and polystyrene.

In the rough surface conductor of the present invention, it is preferable that the rough surface resin base material (I) is a fiber aggregate.

The rough surface conductor of the present invention is preferably a fiber aggregate in which the rough surface resin base material (I) has a primer layer on the fibers.

The rough surface conductor of the present invention preferably further contains a polyether (c) in which the conductive coating layer (II) has two or more hydroxyl groups in the molecule, and the polyether (c) is a silicone-modified polyether (c1). ) Is preferable.

The biological sensing device of the present invention is characterized by comprising the rough surface conductor of the present invention.

The rough surface conductor of the present invention has a conductive coating layer (II) containing a conductive polymer (a) and a thermoplastic resin (b) on a rough surface resin base material (I) having a specific Ra. Since the conductive coating layer (II) has a specific Ra and the surface resistivity after the double stretching treatment is 1,000,000,000 Ω / □ or less. It has excellent stretchability and conductivity after stretching.

<< Rough surface conductor >>
The rough surface conductor of the present invention is
A rough surface conductor having a conductive coating layer (II) containing a conductive polymer (a) and a thermoplastic resin (b) on a rough surface resin base material (I) having Ra of 0.1 μm or more. There,
Ra of the conductive coating layer (II) is 0.1 μm or more, and
The surface resistivity after the double stretching treatment is 1,000,000,000,000 Ω / □ or less.

<Rough surface resin base material (I)>
The material of the rough surface resin base material (I) is not particularly limited, and examples thereof include polyester, polyurethane, polyethylene, polypropylene, rayon, nylon, polystyrene, and acrylic resin. Among these, from the viewpoint of elasticity and mechanical strength, it is preferable to contain at least one selected from the group consisting of polyester, polyurethane, polyethylene, polypropylene, rayon, nylon and polystyrene.

The Ra (arithmetic mean roughness) of the rough surface resin base material (I) is not particularly limited as long as it is 0.1 μm or more, but is preferably 0.2 μm or more, and more preferably 0.5 μm or more. .. If Ra is less than 0.1 μm, it may be difficult to adjust Ra of the conductive coating layer (II) to 0.1 μm or more. Even if Ra of the rough surface resin base material (I) is less than 0.1 μm, fine particles can be added to the conductive coating layer (II) to adjust Ra to 0.1 μm or more. In that case, Stretchability may decrease. The upper limit of Ra is not particularly limited, but is, for example, 5.0 μm. In this specification, Ra means an arithmetic mean roughness measured in accordance with JIS B0601.

The Rz (maximum height) of the rough surface resin base material (I) is not particularly limited, but is preferably 0.5 μm or more, and more preferably 1.0 μm or more. If Rz is less than 0.5 μm, it may be difficult to adjust Ra of the conductive coating layer (II) to 0.1 μm or more. The upper limit of Rz is not particularly limited, but is, for example, 20.0 μm. In addition, in this specification, Rz means ten-point average roughness measured in accordance with JIS B0601.

The shape of the rough surface resin base material (I) is not particularly limited, and examples thereof include a fiber aggregate, a sheet, and a film. Here, the sheet means a sheet having a thickness of 0.2 to 500 mm, and the film means a film having a thickness of 1 to 200 μm. Among these, a fiber aggregate is preferable from the viewpoint of breathability.

When the shape of the rough surface resin base material (I) is a fiber aggregate, from the viewpoint of preventing the composition for forming the conductive coating layer from seeping into the fiber aggregate and reducing the in-plane variation of the surface resistivity, from the viewpoint of reducing the in-plane variation of the surface resistivity. It is preferably a fiber aggregate having a primer layer on the fiber.

<Conductive coating layer (II)>
The conductive coating layer (II) is formed by forming a conductive coating layer containing a conductive polymer (a) and a thermoplastic resin (b) on a rough surface resin base material (I) having Ra of 0.1 μm or more. It is formed by applying a composition for use. Therefore, first, the composition of the composition for forming the conductive coating layer will be described.

The conductive polymer (a) is a compound for imparting conductivity to the composition for forming a conductive coating layer. The conductive polymer (a) is not particularly limited, and conventionally known conductive polymers can be used. Specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and the like. Derivatives of. These may be used alone or in combination of two or more. Among them, a conductive polymer containing at least one thiophene ring in the molecule is preferable because a molecule having high conductivity is easily formed by containing the thiophene ring in the molecule. The conductive polymer (a) may form a complex with a dopant such as a poly anion.

Among the conductive polymers containing at least one thiophene ring in the molecule, poly (3,4-disubstituted thiophene) is more preferable in that it is extremely excellent in conductivity and chemical stability. When the conductive polymer is poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a poly anion (dopment), the temperature is low and the time is short. It is possible to form a rough surface conductor, and the productivity is also excellent. The polyanion is a dopant of a conductive polymer, and its contents will be described later.

As the poly (3,4-disubstituted thiophene), poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable. The poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) has the following formula (I):

A cationic form of polythiophene consisting of the repeating structural units represented by is preferred.
Here, R ¹ and R ² independently represent a hydrogen atom or an alkyl group of _{C 1-4} , or an alkylene group _{of C 1-4} ^{when R 1} and R ² are bonded. Represents. The alkyl group of C _1-4 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. ..
When R ¹ and R ² are bonded, _{the alkylene group of C 1-4} is not particularly limited, but for example, a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1, 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. Can be mentioned. Among these, a methylene group, a 1,2-ethylene group and a 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable. Alkyl C _1-4, and _an alkylene group of _{C 1-4,} a portion of the hydrogen may be substituted. As the _{polythiophene having an alkylene group of C 1-4} , poly (3,4-ethylenedioxythiophene) is particularly preferable.

The weight average molecular weight of the conductive polymer (a) is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 1,500 to 20,000. If the weight average molecular weight is less than 500, the viscosity required for the composition for forming the conductive coating layer cannot be secured, and the conductivity of the conductive coating layer (II) may be lowered. be.

The dopant is not particularly limited, but a poly anion is preferable. The polyanion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water. The polyanion is not particularly limited, but is, for example, carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinylsulfonic acid, polyisoprene, etc.). Sulfonic acid, etc.) and the like. These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers, such as acrylates, styrene, vinyl naphthalene and other aromatic vinyl compounds. It may be. Of these, polystyrene sulfonic acid is particularly preferable.

The polystyrene sulfonic acid preferably has a weight average molecular weight of 20000 to 500,000, and more preferably 40,000 to 200,000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive polymer in water may decrease. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

The composite of the conductive polymer (a) and the poly anion is preferably a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid because it is particularly excellent in conductivity. ..

The conductivity of the conductive polymer (a) is not particularly limited, but is preferably 0.01 S / cm or more, preferably 1 S / cm, from the viewpoint of imparting sufficient conductivity to the conductive coating layer (II). It is more preferably cm or more.

The thermoplastic resin (b) is not particularly limited, and examples thereof include polyester resins, polyurethanes, (meth) acrylic resins, polyolefin resins, and carboxyl group-containing resins. These may be used alone or in combination of two or more.

The polyester resin is not particularly limited as long as it is a polymer compound obtained by polycondensing a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups. Examples thereof include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. These may be used alone or in combination of two or more.

The polyurethane is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group, and for example, ester-ether-based polyurethane, ether-based polyurethane, and polyester-based polyurethane. , Carbonate-based polyurethane, acrylic-based polyurethane and the like. These may be used alone or in combination of two or more.

The (meth) acrylic resin may be polymerized with the copolymerizable monomer as long as it contains the (meth) acrylic monomer as the main constituent monomer (for example, 50 mol% or more). In this case, the (meth) acrylic resin may be polymerized with the copolymerizable monomer. At least one of the (meth) acrylic monomer and the copolymerizable monomer may have an acid group. Examples of the (meth) acrylic resin include (meth) acrylic monomers having an acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.] or a copolymer thereof. Polymers, (meth) acrylic monomers that may have an acid group, and other polymerizable monomers that have an acid group [other polymerizable carboxylic acids, polymerizable polyvalent carboxylic acids or anhydrides , Vinyl aromatic sulfonic acid, etc.] and / or with the above-mentioned copolymerizable monomer [for example, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.] Copolymer, other polymer monomer having an acid group and (meth) acrylic copolymer [for example, (meth) acrylic acid alkyl ester, hydroxyalkyl (meth) acrylate, glycidyl (meth) acrylate , (Meta) acrylonitrile, etc.], rosin-modified urethane acrylate, specially modified acrylic resin, urethane acrylate, epoxy acrylate, urethane acrylate emulsion and the like. Among these (meth) acrylic resins, (meth) acrylic acid- (meth) acrylic acid ester polymer (acrylic acid-methyl methacrylate copolymer, etc.), (meth) acrylic acid- (meth) acrylic acid An ester-styrene copolymer (acrylic acid-methyl methacrylate-styrene copolymer, etc.) and the like are preferable.

The polyolefin-based resin is not particularly limited, and examples thereof include chlorinated polypropylene, non-chlorinated polypropylene, chlorinated polyethylene, and non-chlorinated polyethylene. These may be used alone or in combination of two or more.

The carboxyl group-containing resin is not particularly limited, but for example, an acid anhydride of a copolymer of a vinyl monomer such as styrene, ethylene, or methyl vinyl ether and maleic anhydride is ring-opened, half-esterified, or half. Examples thereof include amidated resins. These may be used alone or in combination of two or more.

The content of the thermoplastic resin (b) in the composition for forming the conductive coating layer is not particularly limited, but is 30 to 10,000 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer (a). Is preferable, and 50 to 5000 parts by weight is more preferable. If the content of the thermoplastic resin (b) is less than 30 parts by weight, the stretchability may decrease, and if it exceeds 10,000 parts by weight, the conductive polymer (a) in the composition for forming a conductive coating layer Since the ratio decreases, it may not be possible to secure sufficient conductivity.

The composition for forming the conductive coating layer may optionally contain other components in addition to the conductive polymer (a) and the thermoplastic resin (b). Examples of other components include a polyether (c) having two or more hydroxyl groups in the molecule, a solvent, an antioxidant, a preservative, a slip agent, a release agent, a defoaming agent, a leveling agent and the like.

In the rough surface conductor of the present invention, the composition for forming a conductive coating layer further contains a polyether (c) having two or more hydroxyl groups in the molecule as a stretchability imparting agent after stretchability and stretching. It is preferable because the conductivity can be further improved. The reason why the stretchability and the conductivity after stretching are improved by containing the polyether (c) is that the polyether (c) interposed between the molecules of the conductive polymer (a) is the conductive polymer (a). ) Is presumed to form a hydrogen bond.

In the polyether (c), the number of hydroxyl groups per molecule is not particularly limited as long as it is 2 or more, but it is preferably 3 or more, and more preferably 4 or more. If the number of hydroxyl groups per molecule is less than 2, the stretchability of the composition for forming a conductive coating layer may decrease.

Specific examples of the polyether (c) are not particularly limited, and examples thereof include silicone-modified polyether (c1), polyglycerin, pullulan, polyether polyols, and derivatives thereof. These may be used alone or in combination of two or more. Among these, silicone-modified polyether (c1) is preferable from the viewpoint of having leveling property.

The silicone-modified polyether (c1) is not particularly limited, and is, for example, a type having polyethers at both ends of the silicone main chain, a type in which a plurality of polyether side chains are bonded to the silicone main chain, and a polyether main chain. Examples thereof include a type in which a silicone side chain is bonded to the chain. These may be used alone or in combination of two or more.

The melting point of the polyether (c) (glass transition temperature in the absence of a melting point) is not particularly limited as long as it is 130 ° C. or lower, but is preferably 100 ° C. or lower, and more preferably 10 ° C. or lower. If the melting point (glass transition temperature in the absence of a melting point) exceeds 130 ° C., the stretchability of the composition for forming a conductive coating layer may decrease.

The boiling point of the polyether (c) (decomposition temperature when the boiling point does not exist) is not particularly limited, but is preferably 300 ° C. or higher, and more preferably 350 ° C. or higher. If the boiling point (decomposition temperature if there is no boiling point) is less than 300 ° C., the polyether (c) will volatilize or decompose during the heat treatment in the processing process, and the stretchability of the composition for forming the conductive coating layer will increase. May decrease.

The content of the polyether (c) in the composition for forming the conductive coating layer is not particularly limited, but may be 10 to 2000 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer (a). It is preferably 30 to 1000 parts by weight, more preferably 30 to 1000 parts by weight. If the content of the polyether (c) is less than 10 parts by weight, the stretchability of the composition for forming a conductive coating layer may decrease, and if it exceeds 2000 parts by weight, the composition for forming a conductive coating layer. Since the proportion of the conductive polymer (a) in the medium is reduced, it may not be possible to secure sufficient conductivity.

The solvent is not particularly limited, and is, for example, water; alcohols such as methanol, ethanol, 2-propanol, 1-propanol and glycerin; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; ethylene. Glycol ethers such as glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycol, dipropylene Propylene glycols such as glycol and tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, di Propylene glycol ethers such as propylene glycol diethyl ether; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydrofuran; acetone; Examples thereof include acetonitrile. These solvents may be used alone or in combination of two or more.

The solvent is preferably water or a mixture of water and an organic solvent. When the composition for forming a conductive coating layer contains water as a solvent, the content of water is not particularly limited, but is 20 to 10000 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer (a). Is preferable, and 200 to 500,000 parts by weight is more preferable. If the water content is less than 20 parts by weight, the viscosity may increase and handling may become difficult. If the water content exceeds 1,000,000 parts by weight, the concentration of the composition for forming the conductive coating layer becomes too low and the liquid is used. The amount may increase.

When the solvent contains a mixture of water and an organic solvent, the organic solvent is at least one selected from the group consisting of methanol, ethanol, 2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. Is preferable. The content of the organic solvent is not particularly limited, and is preferably 20 to 700,000 parts by weight, more preferably 200 to 350,000 parts by weight, based on 100 parts by weight of the solid content of the conductive polymer (a). The ratio of water to the organic solvent (water: organic solvent) is preferably 100: 0 to 5:95, more preferably 100: 0 to 30:70 in terms of weight ratio.

It is preferable that the solvent does not remain in the conductive coating layer (II) formed by using the composition for forming the conductive coating layer. In the present specification, a composition that completely dissolves all the components of the composition for forming a conductive coating layer (that is, a “solvent”) and a substance that disperses an insoluble component (that is, a “dispersion medium”) are used. Are described as "solvent" without any particular distinction.

The solid content of the composition for forming the conductive coating layer is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. If the solid content of the composition for forming a conductive coating layer is less than 0.1% by weight, sufficient conductivity may not be exhibited, and if it exceeds 10% by weight, the composition for forming a conductive coating layer is stored. It may be less stable.

The rough surface conductor of the present invention is produced by forming the conductive coating layer (II) by applying the above-mentioned composition for forming a conductive coating layer on the rough surface resin base material (I). When the composition for forming a conductive coating layer is applied on the rough surface resin base material (I), the ratio (weight ratio) between the rough surface resin base material (I) and the composition for forming a conductive coating layer is usually , 200: 1 to 5: 1. On the other hand, when the rough surface resin base material (I) is impregnated in the composition for forming the conductive coating layer, the ratio (weight ratio) between the rough surface resin base material (I) and the composition for forming the conductive coating layer is Usually, it is 1: 1 to 1:10.

The conductive coating layer (II) can be formed by applying the above-mentioned composition for forming a conductive coating layer on the rough surface resin base material (I) and then performing a drying treatment. The treatment temperature of the drying treatment is not particularly limited, but is preferably 30 to 150 ° C, more preferably 50 to 130 ° C. If the treatment temperature is less than 30 ° C., it may take a long time to dry, and if it exceeds 150 ° C., the rough surface resin base material (I) may be deformed. The treatment time is not particularly limited, but is preferably 0.5 to 60 minutes, more preferably 1 to 30 minutes. If the treatment time is less than 0.5 minutes, the solvent may remain, and if it exceeds 60 minutes, the rough surface resin base material (I) may be deformed.

The Ra (arithmetic mean roughness) of the conductive coating layer (II) is not particularly limited as long as it is 0.1 μm or more, but is preferably 0.2 μm or more, and more preferably 0.5 μm or more. If Ra is less than 0.1 μm, the surface area becomes small, the sensitivity of biosensing may decrease, and blocking may occur when the rough surface conductors are stacked and stored. The upper limit of Ra is not particularly limited, but is, for example, 5.0 μm.

The surface resistivity after being stretched twice as much as the rough surface conductor of the present invention is not particularly limited as long as it is 1,000,000 Ω / □ or less, but it should be 10,000,000 Ω / □ or less. Is preferable, and more preferably 5,000,000 Ω / □ or less. If the surface resistance after the double stretching treatment exceeds 1,000,000,000,000 Ω / □, sensing of biological information may become impossible. In the present specification, "double stretching" means stretching until the length is doubled.

The use of the rough surface conductor of the present invention is not particularly limited, but it can be suitably used, for example, as a biological sensing device, a packaging material produced through a stretch molding process, and a raw material thereof.

<< Biological sensing device >>
The biological sensing device of the present invention is characterized by comprising the rough surface conductor of the present invention. The biological sensing device is not particularly limited, but is, for example, a body surface-mounted bioelectrode for recording bioelectric signals such as electroencephalogram, event-related potential, evoked potential, electromyogram, and electrocardiogram, and electrical stimulation to the living body. Examples thereof include an implantable bioelectrode used for a heart pacemaker and a cochlear implant.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. Hereinafter, "parts" or "%" means "parts by weight" or "% by weight", respectively, unless otherwise specified.

(Material used)
1. 1. Rough surface resin base material (I)
・ Polyester microfiber (made by Teijin Frontier Co., Ltd., flexing)
-Polyurethane film (manufactured by DIC Bayer Polymer, T-9280)
Polystyrene film (obtained by the method described in Example 4 of JP2012-200906A)
-Polyester film (non-rough surface) (manufactured by Kasai Sangyo Co., Ltd., A-PET)

2. Primer / Acrylic water-based ink (manufactured by Mino Group Co., Ltd., binder BM, solid content 48% by weight)

3. 3. Conductive polymer (a)
-PEDOT: PSS (manufactured by Heraeus, Clevios P, solid content 1.3% by weight)
-PEDOT: PSS neutralized product (Clevios P neutralized with an aqueous solution of tetramethylammonium, solid content 1.4% by weight)
-Highly conductive PEDOT: PSS (manufactured by Heraeus, Clevios PH1000, solid content 1.2% by weight)
-Polyaniline (manufactured by ORMECON, D 1033, solid content 1.9% by weight)

4. Thermoplastic resin (b)
-Polyester (manufactured by Takamatsu Oil & Fat Co., Ltd., pesresin S-250, solid content 30% by weight)
-Polyurethane (manufactured by ADEKA Co., Ltd., Adecabon Tita HUX-350, solid content 30% by weight)

5. Polyester (c)
-Silicone-modified polyether (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-4272, number of hydroxyl groups per molecule: 2, solid content 100% by weight)
-Silicone-modified polyether (manufactured by Shin-Etsu Chemical Co., Ltd., KF-6015, number of hydroxyl groups per molecule: 0, solid content 100% by weight)
-Polyether polyol (manufactured by ADEKA Corporation, ADEKA polyether EDP-450, number of hydroxyl groups per molecule: 4, solid content 100% by weight)

6. Thermosetting resin
・ Melamine (manufactured by Nippon Carbide Co., Ltd., Nicarac MX-43, solid content 100% by weight)

7. Filler silica (manufactured by Nippon Catalyst Co., Ltd., Seahoster (registered trademark) KE-W30, solid content 20% by weight)

(Examples 1 to 4, Comparative Examples 1 and 2)
As the rough surface resin base material (I), a base material of the type and shape shown in Table 1 was used. In Example 1 only, 2 parts by weight of a robust enhancer F manufactured by Mino Group Co., Ltd. was added to 100 parts by weight of acrylic water-based ink, and the stirred product was screen-printed on a substrate with a # 100 mesh and then screen-printed at 150 ° C. A primer layer formed on the substrate by drying with a blower dryer for 3 minutes was used as the rough surface resin substrate (I). Ra of the rough surface resin base material (I) was measured by the following method.
The conductive coating layer is obtained by mixing each component at the weight ratio (solid content ratio) shown in Table 1, diluting with ethanol so that the solid content ratio becomes 1% by weight, and then adding 3% by weight of ethylene glycol. A composition for formation was obtained. The obtained composition for forming a conductive coating layer is applied onto a rough surface resin base material (I) using a wire bar with a wet film thickness of 7 μm, and dried in a blower dryer at 100 ° C. for 3 minutes. , A conductive coating layer (II) was formed to obtain a rough surface conductor. Ra of the obtained conductive coating layer (II) was measured by the following method. Further, the surface resistivity and the surface resistivity after double stretching of the obtained rough surface conductor were measured by the following methods. The above results are shown in Table 1.

(Evaluation method)
1. 1. Ra
The measurement was performed in DFM mode and a scanning speed of 0.5 Hz using an atomic force microscope device Nanocut manufactured by SII Nanotechnology.

2. Surface resistivity The following methods were selected and evaluated according to the surface resistivity of the conductive coating layer (II) and the measurable range of the apparatus.
When the surface resistivity is less than 1.0E + 06 (Ω / □): Measured at an applied voltage of 10V using an ESP probe of Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.
When the surface resistivity is 1.0E + 06 (Ω / □) to 1.0E + 08 (Ω / □): Measured at an applied voltage of 10V using a UA probe of Hiresta UP (MCP-HT450 type) manufactured by Mitsubishi Chemical Corporation. bottom.
When the surface resistivity is 1.0E + 08 (Ω / □) or more: Measured at an applied voltage of 250V using a UA probe of Hiresta UP (MCP-HT450 type) manufactured by Mitsubishi Chemical Corporation.

3.2 Surface resistivity after 2-fold stretching The rough surface conductors obtained in each Example and Comparative Example were cut to a size of 10 cm × 10 cm, one side was fixed to the stage, and the other side was pulled to 10 cm. The rough surface conductor was stretched twice by fixing the whole to the stage in a state of being stretched to × 20 cm. Only in Comparative Example 1, stretching was performed while heating at 110 ° C. After that, the above 2. The surface resistivity was measured by the method described in 1.

Claims (6)

A rough surface conductor having a conductive coating layer (II) containing a conductive polymer (a) and a thermoplastic resin (b) on a rough surface resin base material (I) having Ra of 0.1 μm or more. There,
Ra of the conductive coating layer (II) is 0.1 μm or more, and
The surface resistivity after stretching doubled 1,000,000,000Ω / □ Ri der below,
A rough surface conductor comprising a rough surface resin base material (I) at least selected from the group consisting of polyester, polyurethane, polyethylene, polypropylene, rayon, nylon and polystyrene. The rough surface conductor according to claim 1 , wherein the rough surface resin base material (I) is a fiber aggregate. The rough surface conductor according to claim 1 or 2 , wherein the rough surface resin base material (I) is a fiber aggregate having a primer layer on the fibers. The rough surface conductor according to any one of claims 1 to 3 , wherein the conductive coating layer (II) further contains a polyether (c) having two or more hydroxyl groups in the molecule. The rough surface conductor according to claim 4 , wherein the polyether (c) is a silicone-modified polyether (c1). A biological sensing device comprising the rough surface conductor according to any one of claims 1 to 5.