TW202202096A - Conductive laminate sheet for attachment to clothing fabrics and method for producing same - Google Patents

Abstract

Provided is a stretchable conductive laminate sheet that is for attachment to clothing fabrics and that makes it possible to realize a clothing-type device for biological information measurement with excellent washing durability. The conductive laminate sheet for attachment to clothing fabrics includes: a stretchable conductive layer that contains a flexible resin and a conductive filler as at least the constituent components thereof; a stretchable adhesion promoting layer; a stretchable hot-melt adhesive layer; and a mold release film, in this order.

Description

Conductive laminated sheet for attaching clothing fabrics and method for producing the same

The present invention relates to a conductive laminate sheet for attaching clothing fabrics, which is stretchable and can be attached to other objects. , robots, etc., the softness of objects that change shape during use.

Clothes-type bioinformatics measuring devices for measuring bioinformatics such as electrocardiographic information are being developed. In such a clothing-type device, it is necessary to attach electrical wiring to the cloth constituting the clothing. In the case of electrical wiring, materials that can expand and contract according to the deformation of clothing must be used. Such deformable wiring harnesses, such as wiring harnesses using conductive yarns or metal foils patterned in a meandering shape, can be attached to fabrics by arranging conductors so that they have a deformable degree of freedom. The technology of deformation is known.

For example, Patent Document 1 discloses a knitted fabric using a conductive yarn that can be used as a wearable material such as a wearable computer for human body fitting. There are also attempts to use conductive ink on fabrics for wiring. For example, Patent Document 2 discloses an electronic cloth or an electronic cloth composed of the above-mentioned electronic cloth, which is characterized by having a light-emitting device, a sensor, etc. Electronic devices and electronic cloth or electronic clothing for wiring patterns, electronic circuits, etc. for functioning of the above-mentioned electronic devices, any or all of the electronic devices, wiring patterns, electronic circuits, etc. on the cloth surface are made of conductive ink, etc. It is formed by printing method.

A technique of using a stretchable conductive composition obtained from an elastomer and a conductive filler for wiring has been proposed. For example, Patent Document 3 discloses a method for producing a stretchable electrode sheet, which includes the following steps: A step of applying a hot-melt paste to a release sheet and drying to produce a stretchable conductor layer; a step of superimposing the first hot-melt sheet on the above-mentioned stretchable conductor layer to obtain a 3-layer sheet; A step of punching a part of the sheet; and a hot pressing step of superimposing the above-mentioned three-layer sheet after the above-mentioned die-cutting step on a cloth so that the above-mentioned first hot-melt sheet and the above-mentioned cloth are brought into contact. Another patent document 4 discloses a stretchable conductive film for textiles, which comprises a stretchable conductive layer with stretchability and a hot-melt adhesive layer formed on one surface of the stretchable conductive layer, And the said stretchable conductive layer is comprised by the conductive composition which contains the elastic body and the conductive filler filled in the said elastic body.

These techniques can be understood as techniques for electronically consuming clothing. In the case of clothing, however, there are a variety of different situations in conventional electronics and use cases. Particularly problematic is the operation of washing accessories on clothing. In general, electronic products are designed and manufactured without the assumption that they will be put into a washing machine. The conductive yarn is mainly produced by a method such as metal plating on the surface of the non-conductive yarn. Such a conductive yarn may peel off the plated metal due to strong friction during cleaning, thereby reducing the conductivity. The same is true for the case of using conductive ink, but problems such as ink peeling may occur due to friction during cleaning, repeated bending, and compression. The stretchable conductive layer obtained from the stretchable conductive composition is relatively resistant to repeated bending, compression, and friction. If it can be adhered to the cloth of clothes by appropriate means, it will be able to expect high cleaning. Durable. Hot-melt adhesive sheets are easy to handle because they are solvent-free, and can be used without problems even at the manufacturing sites of clothing retailers that are not equipped with ventilation equipment such as chemical factories, so they are widely used in clothing manufacturing sites. It is widely used for the bonding of linings and the bonding of clothing accessories. Therefore, it can be said that it is one of the ideal methods for adhering the stretchable conductive layer to clothing. [Prior Art Literature]

[Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2007-191811 [Patent Document 2] Japanese Patent Laid-Open No. 2005-146499 [Patent Document 3] Japanese Patent Laid-Open No. 2018-102965 [Patent Document 4] Japanese Patent Laid-Open No. 2017-101124

[The problem to be solved by the invention]

However, in the case of a hot-melt adhesive sheet preset for bonding to fabrics, there are cases where the adhesiveness to materials other than fabrics may not be ideal. Generally, a stretchable conductive composition has a conductive filler and a soft binder resin as the main components. Because the electrical conductivity is produced by the direct contact between the conductive fillers, the proportion of the binder resin is very small compared to the general paint, and the three-dimensional geometry is compared with the conductive filler and the conductive filler. The conductive fillers are blended with a smaller amount that is completely buried between them. As a result, there is a portion where the conductive filler is directly exposed on the surface of the conductive layer. This is of course an advantageous state when the conductive layer is used as an electrode. However, when considering the use of an adhesive for bonding with other materials, the adhesive is required to have adhesion to both the adhesive resin and the conductive filler. The conductive filler is metal powder in most cases, mainly silver powder. Hot-melt adhesive sheets for clothing applications are not necessarily designed in consideration of the adhesion to the surface of these metal powders. Often the lack of adhesion always emerges during cleaning. That is, the stretchable conductive layer adhered by the hot-melt adhesive sheet may peel off at the interface between the conductive layer and the hot-melt adhesive sheet during repeated cleaning. Because the mechanical strength of the conductive layer is not strong compared to the surrounding materials, the peeled part will fall off the clothing, which often causes fatal damage to the wiring function of the clothing.

That is, the technique of adhering a stretchable conductive layer to a cloth using a hot-melt adhesive sheet is an easy-to-use technique for providing electrical wiring to clothing, but has problems peculiar to clothing. There is still room for improvement in the durability of cleaning. The inventors of the present invention have made diligent studies in order to solve this problem, and as a result, have found that by providing an adhesion promoting layer interposed between the stretchable conductive layer and the hot-melt adhesive layer, the problem can be solved. Problem solved. [Means of Solving Problems]

That is, this invention consists of the following structures. [1] A conductive laminate sheet for attaching clothing fabrics, comprising, in the following order: A stretchable conductive layer (hereinafter, also simply referred to as "stretchable conductive layer", "stretchable conductive layer" or "conductive layer") comprising at least a flexible resin and a conductive filler as constituent components, A stretchable adhesion-promoting layer (hereinafter, also simply referred to as an "adhesion-promoting layer".), A stretchable hot-melt adhesive layer (hereinafter, also simply referred to as a "hot-melt adhesive layer".), and Release film. [2] A conductive laminate sheet for attaching clothing fabrics, which is a conductive laminate sheet for attaching clothing fabrics with a surface insulating layer, comprising in the following order: A stretchable surface insulating layer (hereinafter, also simply referred to as "surface insulating layer" or "surface insulating layer".), A stretchable conductive layer composed of at least a flexible resin and a conductive filler, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. [3] A conductive laminate sheet for attaching clothing fabrics, comprising in the following order: A stretchable first conductive layer (hereinafter, also simply referred to as "stretchable first conductive layer" or "first conductive layer") composed of at least a flexible resin and a carbon-based conductive filler, A stretchable second conductive layer (hereinafter, also simply referred to as "stretchable second conductive layer" or "second conductive layer") comprising at least a flexible resin and a metal-based conductive filler as constituent components, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. [4] A conductive laminate sheet for attaching clothing fabrics, comprising, in the following order: Retractable surface insulation, A stretchable first conductive layer composed of at least a flexible resin and a carbon-based conductive filler, A stretchable second conductive layer composed of at least a flexible resin and a metal-based conductive filler, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. [5] A method for manufacturing a conductive laminate for attaching clothing fabrics as claimed in claim 1 or 2, comprising at least the following steps: Forming a stretchable conductive layer on a temporary support, forming an adhesion promoting layer on the stretchable conductive layer, and A stretchable hot melt adhesive layer is formed over the adhesion promoting layer. [6] A method for manufacturing a conductive laminated sheet for attaching clothing fabrics as claimed in claim 3 or 4, comprising at least the following steps: A stretchable first conductive layer is formed on the temporary support, Furthermore, a stretchable second conductive layer is formed, forming an adhesion promoting layer over the stretchable second conductive layer, and A stretchable hot melt adhesive layer is formed on the adhesion promoting layer.

Further, the present invention preferably has the following constitution. [7] A conductive laminate sheet for attaching clothing fabrics, comprising in the following order: A stretchable conductive layer composed of at least a flexible resin and a conductive filler, Retractable bond-promoting layer, Retractable 1st Hot Melt Adhesive Layer, retractable insulation, a retractable second layer of hot melt adhesive, and Release film. [8] A conductive laminate sheet for attaching clothing fabrics, which is a conductive laminate sheet for attaching clothing fabrics with a surface insulating layer, comprising in the following order: Retractable surface insulation, A stretchable conductive layer composed of at least a flexible resin and a conductive filler, Retractable bond-promoting layer, Retractable 1st Hot Melt Adhesive Layer, retractable insulation, a retractable second layer of hot melt adhesive, and Release film. [9] A conductive laminate sheet for attaching clothing fabrics, comprising, in the following order: A stretchable first conductive layer composed of at least a flexible resin and a carbon-based conductive filler, A stretchable second conductive layer composed of at least a flexible resin and a metal-based conductive filler, Retractable bond-promoting layer, Retractable 1st Hot Melt Adhesive Layer, retractable insulation, a retractable second layer of hot melt adhesive, and Release film. [10] A conductive laminate sheet for attaching clothing fabrics, comprising in the following order: Retractable surface insulation, A stretchable first conductive layer composed of at least a flexible resin and a carbon-based conductive filler, A stretchable second conductive layer composed of at least a flexible resin and a metal-based conductive filler, Retractable bond-promoting layer, Retractable 1st Hot Melt Adhesive Layer, retractable insulation, a retractable second layer of hot melt adhesive, and Release film. [11] According to any one of [1]~[4], [7]~[10], the conductive laminate for attaching clothing fabrics, and [5] or [6] for attaching clothing fabrics A method of manufacturing a conductive laminate, wherein the adhesion promoting layer is an elastomer having a cross-linked structure. [12] According to any one of [1]~[4], [7]~[10], the conductive laminate for attaching clothing fabrics, and [5] or [6] for attaching clothing fabrics The manufacturing method of the electroconductive laminated sheet in which the said adhesion promotion layer is a urethane resin which has a crosslinked structure. [13] According to any one of [1]~[4], [7]~[10], the conductive laminate for attaching clothing fabrics, and [5] or [6] for attaching clothing fabrics The manufacturing method of the electroconductive laminated sheet whose said adhesion promotion layer is a thermoplastic resin whose glass transition temperature is 90 degreeC or more. [14] According to any one of [1]~[4], [7]~[10], the conductive laminate for attaching clothing fabrics, and [5] or [6] for attaching clothing fabrics The manufacturing method of the electroconductive laminated sheet whose said adhesion promotion layer is an acrylic resin. [Effect of invention]

By inserting the adhesion promoting layer between the stretchable conductive layer and the hot melt adhesive layer as in the present invention, the adhesion between the conductive layer and the hot melt adhesive layer is stabilized. It is considered that this is because the adhesion promoting layer has high adhesion to both the surface of the conductive filler (especially the metallic filler) of the conductive layer and the hot melt adhesive layer. First, the surface of the stretchable conductive layer is not a flat surface in the microscopic view. When magnified, the conductive fillers (especially the metallic fillers) are exposed as rock-like unevenness, and the soft resin fills the gaps, which can be said to be like a rock garden. When using a hot-melt adhesive to bond on a surface with such large irregularities, it is necessary to heat the hot-melt adhesive to sufficiently soften it. It is difficult to raise the temperature until sufficient softening is limited due to heat resistance and the like. Also, even if a hot melt adhesive with a low softening temperature is used, compared with the so-called solvent-based adhesive, which is in a liquid state from the beginning, the followability to the uneven surface is still not high, so It is difficult to fully engage the bonding surface. Further, when the softening temperature is unnecessarily lowered, a problem is likely to occur when a relatively high temperature is applied to operations such as ironing, a drying step after washing, and the like. As a result, when a hot melt adhesive is used, the actual bonded area is small relative to the apparent bonded area.

From a macroscopic point of view, the hot melt adhesive resin used for clothing is designed to have relatively soft mechanical properties in order to accommodate the deformation of the fabric to a certain extent. On the other hand, hot melt adhesives intended for apparel use are not necessarily designed to be conscious of their bonding to metal. When using this kind of hot-melt adhesive to bond with the conductive layer, the hot-melt adhesive will only have a strong bond with the resin part exposed on the surface of the conductive layer. Adhesion is weak. When the deformation stress is applied to the bonding interface, the bonding part with the conductive filler will peel off first, and then the stress will be concentrated on the bonding interface between the hot melt adhesive and the resin part.

When the contact surface between the hot melt adhesive and the conductive filler is peeled off, minute voids are formed there. In the atmosphere, this void will be filled with air which is a compressive fluid. However, a lotion solution, ie, an aqueous fluid containing a surfactant, can intrude into this void during cleaning. Because the water-based fluid system is incompressible, the liquid trapped in the tiny space at the interface will move to other places due to the pressure exerted by the expansion, bending, compression, torsion and other deformations associated with the cleaning operation, and the adjacent heat will be moved to other places. The adhesive surface of the melt adhesive and the resin part is pressed in the direction of peeling. Or, it moves in the free space inside the conductive layer, which is originally heterogeneous. The lotion solution has low surface tension and excellent wettability to the solid surface, so it is easy to penetrate into narrow gaps and small voids. As a result, in addition to peeling off the interface between the conductive layer and the hot melt adhesive layer, it also exhibits The conductive layer itself is weakened from the inside, and the conductive layer collapses due to the load applied by cleaning. As a result of these actions, when a conventional hot-melt adhesive is used to adhere the conductive layer to the cloth, the conductive layer is partially collapsed and peeled off after repeated cleaning.

Since the adhesion promoting layer of the present invention is preferably in a liquid state, it is in close contact with both the resin part and the conductive filler part on the surface of the conductive layer with severe unevenness, and exhibits high adhesion. And because the surface of the adhesion promoting layer is smooth, it also exhibits good adhesion with the hot melt adhesive layer. Therefore, it will not cause microscopic peeling caused by partial stress concentration as described above, and microscopic damage to the conductive layer caused by the intrusion of the lotion solution into the peeling interface. Bonded state.

The stretchable conductive layer of the present invention refers to a layer comprising at least a flexible resin and a conductive filler as constituents. It means that a layer composed of a material having stretchability and a specific resistance of 1×10 ¹ Ωcm or less is preferable. The stretchable conductive layer of the present invention has stretchability. The stretchability in the present invention means that the stretchability can be repeated by 10% or more while maintaining the conductivity. As far as the stretchable conductive layer of the present invention is concerned, when the conductive layer exists alone, it is ideal to have an elongation at break of more than 40%, and it is more ideal to have an elongation at break of more than 50%, and it has an elongation at break of more than 80%. more ideal. In addition, the tensile elastic modulus of the stretchable conductive layer of the present invention is preferably 0.5 to 300 MPa. A material capable of forming a stretchable conductive layer having such stretchability is called a stretchable conductor composition. The stretchable conductor composition is a composite comprising at least a flexible resin and a conductive filler.

As the flexible resin of the present invention, for example, thermoplastic resins, thermosetting resins, rubbers, etc. having an elastic modulus of preferably 0.1 to 1000 MPa are exemplified, and thermoplastic resins or rubbers are preferable in order to exhibit the stretchability of the film, It is more ideal for urethane resin or rubber. As the rubber, nitrile-containing rubber such as urethane rubber, acrylic rubber, polysiloxane rubber, butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, isoprene rubber, vulcanized rubber, styrene-butadiene rubber, etc. may be mentioned. Diene rubber, butyl rubber, chlorinated polyethylene rubber, ethylene propylene rubber, vinylidene fluoride copolymer, etc. Among them, nitrile group-containing rubber, chloroprene rubber, and chloroprene rubber are preferable, and nitrile group-containing rubber is particularly preferable. In the present invention, the preferred range of the elastic modulus is 0.1 to 600 MPa, more preferably 0.2 to 500 MPa, and still more preferably 0.5 to 300 MPa. The nitrile group-containing rubber is not particularly limited as long as it is a nitrile group-containing rubber or elastomer, but nitrile rubber and hydrogenated nitrile rubber are preferable. In the nitrile rubber-based copolymer of butadiene and acrylonitrile, when the amount of acrylonitrile bound is increased, the affinity with the metal increases, but on the contrary, the rubber elasticity which contributes to the stretchability decreases. Therefore, the amount of acrylonitrile bound in the acrylonitrile-butadiene copolymer rubber is preferably 18 to 65 mass %, and particularly preferably 40 to 60 mass %.

For the urethane resin, a polyurethane elastomer is preferable, and for the polyurethane elastomer, a polyurethane with a glass transition temperature (Tg) of -60°C or higher can be used Elastomers are more desirable, more desirably above -50°C, and the upper limit is desirably 10°C, more desirably 0°C. In the polyurethane elastomer of the present invention, a soft segment composed of a polyether-based, polyester-based, or polycarbonate-based polyol or the like and a hard segment composed of a diisocyanate or the like A polyurethane elastomer obtained by the reaction is preferable. Then, in terms of the soft segment components, polyester polyols are more desirable from the viewpoint of the degree of freedom in molecular design.

Examples of the polyether-based polyol of the present invention include polyethylene glycol, polypropylene glycol, polyglycerol, polypropylene erythritol, polytetramethylene glycol, polybutylene triol, and cyclic ethers to be used for their synthesis. Polyalkylene glycols such as copolymers obtained by copolymerizing monomeric materials, derivatives, modified products, and mixtures thereof obtained by introducing side chains or branched structures into them. Among these, polytetramethylene glycol is preferable. The reason for this is because its mechanical properties are excellent.

As the polyester polyol of the present invention, an aromatic polyester polyol, an aromatic/aliphatic copolymer polyester polyol, an aliphatic polyester polyol, and an alicyclic polyester polyol can be used. For the polyester polyol of the present invention, both saturated and unsaturated types may be used. Among them, aliphatic polyester polyols are preferred.

The conductive filler of the present invention is preferably composed of a material having a specific resistance of 1×10 ^-1 Ωcm or less. Moreover, it is preferable that the particle diameter is 100 micrometers or less. As a material whose specific resistance is 1×10 ⁻¹ Ωcm or less, for example, metals, alloys, carbon, doped semiconductors, conductive polymers, and the like can be exemplified. The conductive fillers that can be ideally used in the present invention are metals such as silver, gold, platinum, palladium, copper, nickel, aluminum, zinc, lead, tin, etc.; alloy particles such as brass, bronze, cupronickel, solder, etc.; mixed particles such as copper; and metal-plated polymer particles, metal-plated glass particles, metal-coated ceramic particles, etc. These are referred to as metal-based conductive fillers.

For the metal-based conductive filler of the present invention, it is preferable to use flaky silver particles or amorphous agglomerated silver powder. The particle size of the flaky powder is not particularly limited, and it is preferable that the average particle size (50% D) measured by the dynamic light scattering method is 0.5 to 20 μm. 3~12μm is more ideal. When the average particle diameter exceeds 15 μm, it becomes difficult to form fine wirings, and clogging may occur in the case of screen printing or the like. When the average particle diameter is less than 0.5 μm, there is a possibility that the particles cannot be brought into contact with each other at the time of low-level filling, thereby deteriorating the conductivity. The particle size of the amorphous aggregated powder is not particularly limited, and it is preferable that the average particle size (50% D) measured by the light scattering method is 1 to 20 μm. 3~12μm is more ideal. When the average particle diameter exceeds 20 μm, the dispersibility decreases and it becomes difficult to form a paste. When the average particle diameter is less than 1 μm, the effect of the agglomerated powder is lost, and there is a possibility that the good conductivity cannot be maintained at the time of low filling.

In the present invention, a carbon-based conductive filler can be used. For the carbon-based conductive filler of the present invention, graphite powder, activated carbon powder, flake graphite powder, acetylene black, ketjen black, fullerene, single-layer carbon nanotube, and multi-layer nanocarbon can be used. Tubes, carbon nanocones, etc. In the present invention, the carbon-based conductive fillers that can be preferably used are graphite powder, flake graphite powder, activated carbon powder, and ketjen black. In the present invention, it is also preferable to use a carbon-based conductive filler having at least a BET specific surface area of 1000 m ² /g or more.

The stretchable conductor composition constituting the stretchable conductive layer of the present invention is composed of at least the above-described conductive filler and flexible resin (hereinafter, also referred to as a binder). In the case of the metal-based conductive filler, the metal-based conductive filler can be blended in a ratio of 40 to 92% by mass relative to the total mass of the metal-based conductive filler and the binder. The metal-based conductive filler of the present invention is preferably contained in a ratio of 50 to 90 mass % relative to the total mass of the metal-based conductive filler and the binder, more preferably 58 to 89 mass %, and 66 to 88 mass %. The mass % is more ideal, and the content of 70~87 mass % is even more ideal. When the content of the metal-based conductive filler falls within this range, necessary conductivity and sufficient elongation of the conductive layer required to exhibit stretchability can be obtained.

When a carbon-based conductive filler is used as the conductive filler, the carbon-based conductive filler can be blended in a ratio of 18 to 65% by mass relative to the total mass of the carbon-based conductive filler and the binder. The carbon-based conductive filler of the present invention is preferably contained in a ratio of 22.5 mass % or more, more preferably 25 mass % or more, and 27.5 mass % or more, based on the total mass of the carbon-based conductive filler and the binder. Very desirable, and even more desirable to contain 30% by mass or more. The content of the carbon-based conductive filler is preferably 62.5 mass % or less, more preferably 60 mass % or less, based on the total mass of the carbon-based conductive filler and the binder. By making the content of the carbon-based conductive filler fall within a predetermined range, the conductivity necessary for the conductive layer and a sufficient elongation ratio of the conductive layer required to exhibit stretchability can be obtained.

In the present invention, non-conductive particles may be blended into the stretchable conductor composition. The non-conductive filler of the present invention is preferably a particle composed of an organic or inorganic insulating substance. The inorganic particles of the present invention are added for the purpose of improving the printing properties, the stretching properties, and the surface properties of the coating film, and silicon dioxide, titanium oxide, talc, aluminum oxide, and glass beads can be used as metal oxides. Phosphates, titanates, carbonates, sulfates of alkali metals or alkaline earth metals, such as barium sulfate, sodium phosphate, etc.; and their mixtures, as well as inorganic particles such as kaolin from natural products, composed of resin materials Microgels etc.

The stretchable conductor composition can be produced by blending a flexible resin, a conductive filler, and other necessary components, and performing melt-kneading with an extruder or the like. Moreover, after adding a solvent and kneading in a slurry state, it can also be obtained by apply|coating this to some kind of base material, and making it dry to remove a solvent. From the viewpoint of thinning in order to obtain a stretchable conductive layer, the latter method of kneading in a slurry state using a solvent is preferable. The paste-like mixture containing the conductive filler, the flexible resin, and the solvent can also be used in the printing step as ink or paste. In this case, additional materials such as a defoaming agent, a leveling material, and a thixotropy imparting material may be further added.

In one aspect of the present invention, for example, a stretchable conductive layer using a flexible resin and a carbon-based conductive filler is used as the stretchable first conductive layer, and a flexible resin and a metal-based conductive layer are used. The stretchable conductive layer of the conductive filler is a combination of the stretchable second conductive layer. In this case, the first conductive layer can be used as an electrode layer in contact with the living body. On the surface of the electrode that is in direct contact with the surface of the living body, there will be pollution caused by the environment, adhesion of body fluids such as sweat, saliva, and saliva from the living body, and the surface of the metal-based filler will be oxidized or vulcanized to increase the contact resistance value. Insulation may occur on the electrode surface depending on the situation. However, although carbon-based conductive fillers are inferior to metal fillers in terms of electrical conductivity, they are preferably used as conductive fillers for forming conductive layers of electrode surface layers because of their strong chemical resistance.

In the present invention, a stretchable surface insulating layer can be provided on the stretchable conductive layer. That is, in the conductive layer, where the function of contacting the electrode with the living body is not required and is only used for signal or power transmission, it is possible to consider the protection of the conductive layer, the prevention of noise mixing, and the safety of the living body. Insulate its surface in advance. For the stretchable surface insulating layer, a resin material equivalent to that of a flexible resin system using a conductive binder resin can be used. More desirably, it is preferable to use a conductive binder resin as a basic skeleton and to appropriately impart a cross-linked structure. That is, as far as the stretchable surface insulating layer is concerned, urethane rubber, acrylic rubber, polysiloxane rubber, butadiene rubber, nitrile rubber, hydrogenated nitrile rubber and other nitrile-containing rubber, isoprene rubber, etc. , vulcanized rubber, styrene butadiene rubber, butyl rubber, chlorinated polyethylene rubber, ethylene propylene rubber, vinylidene fluoride copolymer, etc. are ideal. Made of rubber material. In the case of urethane resins, those obtained by combining soft segments composed of polyether-based, polyester-based, or polycarbonate-based polyols and the like and hard segments composed of diisocyanates and the like can be used. Polyurethane elastomer. Here, a crosslinked structure can be easily formed by blending a trifunctional or higher polyol.

The present invention is provided with a stretchable hot melt adhesive layer. The conductive laminate sheet for attaching clothing fabrics of the present invention is bonded to a stretchable object such as a fabric by the hot-melt adhesive layer. As for the hot melt adhesive layer of the present invention, it is made of a thermoplastic resin that can be adhered to the fabric by heating in the range of 45°C to 250°C, or is made of a so-called reactive hot melt adhesive. An adhesive composed of a thermosetting resin in an uncured or semi-cured state is ideal. More specifically, polyester-based, polyurethane-based, ethylene vinyl acetate-based, polyamide-based, polyolefin-based, polyparaffin-based, epoxy-based, and acrylic-based hot melt adhesives can be used. resin. The hot-melt adhesive layer of the present invention is preferably adhered to the fabric by heating in the range of 60°C to 230°C, the range of 80°C to 210°C is more ideal, and the range of 90°C to 180°C is even more ideal. . The bonding temperature is appropriately selected according to the heat resistance of the fabric. Generally, the case of chemical fibers is in the lower temperature range below 150 °C, but for the fabrics made of cotton and heat-resistant fibers, it may be used above 150 °C, or even higher. Heating above 180°C for bonding. The thickness of the hot melt adhesive layer is preferably 5 to 200 μm, more preferably 12 to 150 μm, and even more preferably 20 to 120 μm. In the conductive laminated sheet for attaching clothing fabrics, the hot-melt adhesive layer may be one layer, or may be a plurality of layers of two or more layers.

In the present invention, a stretchable adhesion promoting layer is provided between the stretchable conductive layer and the stretchable hot-melt adhesive layer. The adhesion promotion layer, as mentioned above, is interposed between the hot melt adhesive and the stretchable conductive layer, which is not necessarily designed for adhesion with the stretchable conductor composition (stretchable conductive layer), so as to allow The adhesion between the two is greatly improved. The chemical composition of the resin used for the adhesion promoting layer is not particularly limited, and the elongation at break of the adhesion promoting layer itself is preferably 50% or more. It is desirable to have a cross-linked structure, and it is desirable to have a resin that does not have fluidity in the temperature range of 60°C or lower, more desirably 90°C or lower, and even more desirably 120°C or lower. It is ideal to have a cross-linked structure. As a compound which has a low glass transition temperature and has a crosslinked structure, the compound used for an adhesive composition, an adhesive agent, etc. can be illustrated, for example.

As for the stretchable resin composition that can be used in the adhesion promoting layer, it is desirable to introduce a cross-linked structure into urethane rubber, acrylic rubber, silicone rubber, butadiene rubber, nitrile rubber. Or hydrogenated nitrile rubber and other rubbers containing nitrile rubber, isoprene rubber, vulcanized rubber, styrene butadiene rubber, butyl rubber, chlorinated polyethylene rubber, ethylene propylene rubber, vinylidene fluoride copolymer, etc. Material. Mixtures of these elastomers with thermosetting resins such as epoxy resins can also be used.

Also, resins made of polyurethane resins and polyester resins with a glass transition temperature in the range of -70°C to 0°C can be used. In the case of the polyurethane resin, a polymer obtained by combining a soft segment composed of a polyether-based, polyester-based, or polycarbonate-based polyol or the like with a hard segment composed of a diisocyanate or the like can be used. Urethane elastomer. Here, a cross-linked structure can be easily formed by blending a trifunctional or higher polyol. Alternatively, post-crosslinking may be performed by additionally blending and reacting a polyisocyanate compound.

In addition, UV-curable or electron beam-curable acrylic resins can be used, or a silane-based coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, etc. can be blended into the resin after curing as necessary. A UV-curable (cross-linked) type of flexible resin formed from a blend of monofunctional and polyfunctional (meth)acrylates with low glass transition temperature. For the flexible resin used in the adhesion promoting layer of the present invention, in order to obtain strong adhesion with the conductive layer, it is applied in a liquid state to the conductive layer on the adhesion surface and then chemically reacted or dried. A cured resin is preferred.

As the release film used in the present invention, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), and PBT (polybutylene terephthalate) can be used. It is a film formed by using a polyester-based film as a base material, and at least one side is subjected to a mold release treatment. In addition, as the release film used in the present invention, a so-called release paper obtained by performing release treatment on one side or both sides of paper can be used. That is, although this invention calls it a release film for convenience, the material of a base material is not specifically limited. The mold release treatment of the present invention may, for example, be fluorine resin coating, silicone resin coating, or fluorine plasma treatment. Then, in the present invention, films or sheets made of untreated polyimide films, fluororesin films, polysiloxane sheets, polypropylene films, polyethylene films and other materials lacking adhesiveness can also be used. material. Of course, these difficult-to-bond films can also be surface treated. In addition, in the present invention, a metal foil of a metal called a hard-to-bond metal such as molybdenum, tungsten, chromium, stainless steel, and aluminum can be used as a mold release film. The surface metallized polymer film formed by forming these metals on the surface of polymer films such as PET, PEN, and polyimide by vacuum evaporation or sputtering can be used as a mold release film. use. The thickness of the mold release film of the present invention is preferably 15-190 μm, more preferably 24-130 μm, and more preferably 40-105 μm. If the thickness of the release film is not within the predetermined range, when only the laminated stretchable conductor sheet portion is cut, the cutting may be insufficient, or even the release film may be cut.

The release film of the present invention may preferably have transparency. The average transmittance of visible light of the mold release film of the present invention is preferably 30% or more, more preferably 50% or more, and even more preferably 70% or more. When the transparency of the mold release film is insufficient, it may be difficult to align the stretchable conductive sheet obtained by pre-cutting and removing unnecessary parts to fabric.

It is desirable for the release film of the present invention to have some degree of heat resistance. Heat resistance is judged by glass transition temperature or softening temperature. In the present invention, the glass transition temperature or softening temperature, whichever is higher, is preferably 50°C or higher, more preferably 65°C or higher, more preferably 85°C or higher, even more preferably 125°C or higher, and 175°C or higher The above is particularly ideal. The heat resistance of the mold release film is appropriately selected and used according to the temperature at the time of bonding the stretchable conductive sheet to the fabric using the hot-melt adhesive layer. In the present invention, the adhesive strength between the hot melt adhesive layer and the mold release film is preferably 0.03N/cm~4.0N/cm, and more preferably 0.1N/cm~2.0N/cm. If the adhesive strength is below this range, there is a possibility that the sheet is peeled off during handling, and handling becomes difficult.

In the present invention, a temporary support can be used in the process of manufacturing the conductive laminated sheet for attaching clothing fabrics. The temporary support of the present invention refers to a substrate when forming a stretchable conductive layer or the like, which is eventually removed. As for the temporary support, the same category as the release film system can be used. However, since strength is required to support the laminated sheet during the manufacturing process, thicker ones, such as PET film, PEN film, PP film, PI film, etc., with a thickness of about 100 μm can be used. In order to remove the temporary support in a subsequent step, those obtained after the release treatment of these polymer films can be preferably used. Moreover, you may carry the metal plate, metal foil, glass plate, etc. which were similarly performed after mold release processing as needed. In addition, in consideration of productivity, since it is preferable to wind up in a roll shape in the step, it is recommended to use a long release film.

In the present invention, a stretchable surface insulating layer can be formed as a layer protecting the surface of the above-mentioned conductive layer. The surface insulating layer may insulate the surface of the conductive layer. For the surface insulating layer, non-thermoplastic films can be used. Then, in the present invention, a non-thermoplastic film may be used on a part of the conductive laminated sheet for attaching fabrics for clothing. For the purpose of improving electrical insulation and mechanical strength on the surface side of clothing, etc., or for improving handleability, etc., a non-thermoplastic film can be inserted into the intermediate layer on the side of the hot-melt adhesive layer of the conductive layer. way to use. The non-thermoplastic film of the present invention is preferably composed of a stretchable resin composition like the conductive layer and the hot-melt adhesive layer, and urethane resin, elastomer having a cross-linked structure, polysiloxane can be used. Rubber sheets, etc. The term "non-thermoplastic" as used herein means that it will not liquefy under the use environment of ordinary clothing fabrics and the processing temperature used in the manufacture of clothing-type biological information measurement devices. As long as it is stretchable at room temperature, it can be used. Those with high melting points (classified as thermoplastic resins in the strict sense). The non-thermoplastic resin film is preferably attached to the laminated sheet by a hot melt adhesive.

The manufacturing process of the electroconductive laminated sheet for clothing fabric sticking of this invention is demonstrated using FIG. 7. FIG. In addition, the up-down relationship of each step diagram in FIG. 7 is opposite to the up-down relationship of step 1 to step 8 in FIG. 7 in actual operation in order to match the up-down relationship of the final step. Step 1: First, regarding the temporary support body 30, the use of a mold release PET film is used as an example here. Although a release film can also be used as a temporary support, the temporary support should not be regarded as the release film of the present invention. Step 2, Step 3: forming a stretchable first conductive layer 11 and a stretchable second conductive layer 12 on the mold release PET film in sequence. Each conductive layer can be formed by coating and drying those prepared in the form of a paste containing a solvent by a general method. The coating and drying may be performed sequentially for the first and second conductive layers, respectively, or may be formed by a so-called "wet-on-wet" method in which both pastes are double-coated and then dried at the same time. Here, the description is made for the case where the stretchable conductive layer is composed of two layers. Even when the conductive layer is a single layer, the conductive layer can be formed by applying and drying in the same manner. Step 4: In this way, an adhesion promoting layer 50 is further formed on the surface of the conductive layer formed on the release PET film. As for the formation means of the adhesion promotion layer, coating or lamination can be performed according to the material of the adhesion promotion layer to be used. As the coating means, depending on the material, a method of applying a liquid material and drying and solidifying it, a method of reacting and solidifying it by heating, ultraviolet irradiation, or the like, or a melt extrusion coating, etc. can also be used. method. As the coating method, methods such as spray coating, curtain coating, die coating, rod coating, screen printing, etc. can be used depending on the viscosity of the coating liquid.

Step 5: Adhering the first hot melt adhesive layer on the adhesion promoting layer. In this step, in order to prevent the hot-melt adhesive from adhering to the hot roll or hot plate of the laminator, the first release film can be superimposed on the hot-melt adhesive layer to promote adhesion. Use the opposite side of the layer. If the mold release PET film which is a temporary support is removed at this stage, it will become the electroconductive laminated sheet for clothing fabric attachment which has the stretchability which satisfies the requirements of this invention. Then, after removing the temporary support, the first conductive layer is coated with a stretchable insulating layer, whereby a conductive laminated sheet for attaching clothing fabrics having the stretchability satisfying the second requirement of the present invention can be obtained. In order to apply it to an actual garment-type biometric information measuring device, as an example in the subsequent steps, an operation of imparting a predetermined shape to the conductive laminate sheet and the surface insulating layer may be added.

Step 6: Cut the conductive laminate sheet obtained in the previous step into a predetermined shape. As the cutting means, known methods such as laser cutting, cutting with a Thomson blade, and press punching can be used. Since the conductive laminated sheet of the present invention has high flexibility (in vernacular, it is soft), if the size exceeds a certain level, handling may become difficult. Therefore, a so-called half-cut method can be used, and only a portion of the conductive laminate sheet can be cut while leaving the temporary support. Half-cutting can be a useful method especially when the intended pattern is a complex shape including thin lines. FIG. 7 exemplifies the case of half-cutting. In addition, the temporary support can be peeled off and removed at this stage without causing any trouble. When the predetermined shape is a relatively simple shape and a tough material is used for the first release film, the temporary support can be removed at a relatively early stage.

Step 7: Remove the unwanted parts created by cutting. Step 8: Peel off the first release film. Moreover, you may peel off the 1st release film immediately after step 5, or after the cutting of step 6. Step 9: Adhering the first non-thermoplastic film, the second hot-melt adhesive layer, and the second mold release film to the first hot-melt adhesive layer. In this step, after the first non-thermoplastic film is bonded, the second hot-melt adhesive layer and the second release film can be attached together. Alternatively, a sheet formed by laminating the first non-thermoplastic film, the second hot-melt adhesive layer, and the second release film can be integrated in advance and then bonded to the first hot-melt adhesive layer .

Step 10: The temporary support is peeled off here. Alternatively, as mentioned above, the temporary support can also be peeled off prior to this step. Step 11: Adhering the second non-thermoplastic film to all or a part of the conductive layer side. In this example, the second non-thermoplastic film is bonded using the third hot-melt adhesive, but when the non-thermoplastic film itself has the bonding function, the third hot-melt adhesive is not required. For example, it can be formed by coating or pressing a resin in a liquid or semi-cured state, and then curing it by heating or ultraviolet irradiation, or by coating it in a solution state and then drying and curing. wait to form. When the conductive layer of the present invention is used simply as a wiring, it is preferable to cover it with a second non-thermoplastic film equivalent to an insulating surface coating. The conductive layer of the present invention is not covered with the second non-thermoplastic film in the portion where the conductive layer of the present invention is used as a contact electrode to the surface of the living body or is used for electrical connection with other components such as connectors. Also, although omitted in this figure, a mold release film may be provided on the second non-thermoplastic film (the surface opposite to the bonding surface). In addition, the release film can not only cover the second non-thermoplastic film, but also cover the part not covered by the second non-thermoplastic film, that is, the electrode part that contacts the living body and the part that is electrically connected to other parts. , to include and overwrite all of them. This is to protect the electrode surface and the like when the conductive laminated sheet is bonded to the cloth using a punch or the like. The timing of peeling off the release film basically only needs to be peeled immediately before any processing is performed on the surface to which the release film is attached, but in the case of handling, or in the case of processing such as cutting. If necessary, it can be peeled off at any time as needed. After peeling off again, you may cover again with a release film, a protective film, or the like. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited only by the following examples, and it goes without saying that changes can be appropriately added within the scope that can meet the meanings described above and below, and no matter which of these All are included in the technical scope of the present invention. The conductive silver paste, the conductive carbon paste, and the resin for forming an adhesion promoting layer in the following examples were prepared as follows.

[Preparation of stretchable conductive silver paste (second stretchable conductor composition)] 20 parts by mass of nitrile rubber (NBR) [Nipol (registered trademark) "DN003", manufactured by ZEON Corporation) as a flexible resin (binder) was dissolved in 80 parts by mass of isophorone to prepare an NBR solution. To 100 parts by mass of the obtained NBR solution, 110 parts by mass of silver powder (aggregated silver powder "G-35" manufactured by DOWA ELECTRONICS, average particle size of 5.9 μm) was mixed, and kneaded with a three-roll mill to prepare a conductive silver paste ag. For the basic evaluation of the obtained conductive silver paste, it was confirmed that a stretchable conductive layer (stretchable silver paste) obtained by screen printing the paste so as to have a thickness of 25 μm and drying at 100° C. for 20 minutes The initial specific resistance of the conductor sheet) is 250 μΩ･cm, and it has stretchability to maintain conductivity even after repeating 20% stretching for 100 times, and is stretchable.

[Preparation of stretchable conductive carbon paste (first stretchable conductor composition)] 20 parts by mass of nitrile rubber [Nipol (registered trademark) "DN003" manufactured by ZEON Co., Ltd., Japan), Ketjen carbon black (registered trademark) EC300J manufactured by Lion Specialty Chemicals Co., Ltd., and After preliminarily stirring 50 parts by mass of ethylene glycol monoethyl ether acetate as the solvent, it was dispersed with a three-roll mill to obtain a conductive carbon paste CB. For the basic evaluation of the obtained conductive carbon paste, it was confirmed that a stretchable conductive layer (stretchable carbon layer) obtained by screen printing the paste so as to have a thickness of 25 μm and drying at 100° C. for 20 minutes The initial specific resistance of the conductor sheet) is 0.14 Ω･cm, and it has stretchability to maintain conductivity even after repeated 20% stretching for 100 times, and is stretchable.

[Stretchable Adhesion Promotion Layer Forming Resin AD1] 18 parts by mass of nitrile rubber (NBR) [Nipol (registered trademark) "DN003", manufactured by ZEON, Japan), 1.4 mass parts of bisphenol A epoxy resin (jER (registered trademark) 1001) manufactured by Mitsubishi Chemical Corporation parts were dissolved in 80 parts by mass of isophorone to obtain a mixed solution of NBR and epoxy resin. To the obtained mixed solution of NBR and epoxy resin, 0.6 part by mass of an epoxy resin hardener (YN100) manufactured by Mitsubishi Chemical Corporation was further added, and the mixture was stirred and mixed to obtain a coating liquid AD1 for forming an adhesion promoting layer.

[Stretchable Adhesion Promotion Layer Forming Resin AD2] To 96 parts by mass of the one-component UV curable elastic adhesive "SX-UV220" containing an acrylic copolymer manufactured by CEMEDINE Co., Ltd. as a main component, 3-methyl group manufactured by Shin-Etsu Chemical Co., Ltd. was added 2 parts by mass of acryloxypropyl methyldimethoxysilane "KBM-502", and 2 parts by mass of titanate-based coupling agent "Plenact (registered trademark) 238S" manufactured by Ajinomoto Fine-Techno Co., Ltd. , and stirred and mixed to obtain a UV-curable adhesive-promoting layer-forming coating solution AD2.

[Stretchable Adhesion Promotion Layer Forming Resin AD3] 20 parts by mass of polyester resin "VYLON (registered trademark) 550" (Tg=-15°C, hydroxyl value: 4 mg/KOH) manufactured by Toyobo Co., Ltd., polyester urethane manufactured by Toyobo Co., Ltd. 70 parts by mass of resin "VYLON UR8700" (Tg=-22°C, hydroxyl value: 4 mg/KOH) and 10 parts by mass of aromatic polyisocyanate hardener "Coronate (registered trademark) L" manufactured by Nippon Polyurethane Co., Ltd. were dissolved In 200 mass parts of mixed solvents (methyl ethyl ketone/toluene/cyclohexanone=1/1/1 mass ratio), the coating liquid AD3 for adhesion promotion layer formation was obtained.

(Example 1) A mold release PET film whose surface was treated with a polysiloxane-based mold release agent was used as a temporary support, and the procedure shown in FIG. 7 was followed to make the dry thickness 15 μm. The stretchable conductive carbon paste CB was coated on the mold release layer side of the mold release PET film, and dried to obtain a first conductive layer. Then, the stretchable conductive silver paste AG was applied on the first conductive layer with an applicator bar so that the dry thickness might be 35 μm, and dried to obtain a second conductive layer. Next, the resin AD1 for forming an adhesion promoting layer was applied on the second conductive layer with a spreader bar so that the dry film thickness would be 5 μm, and the adhesion promoting layer was formed by heating and drying at 100° C. for 30 minutes while reacting the epoxy compound to form the adhesion promoting layer. Floor. After that, the hot-melt sheet side of the hot-melt urethane sheet MOBILON (registered trademark) MOB100 (polyurethane hot-melt sheet/release paper) manufactured by Nisshinbo Co., Ltd. The direction in which the layers are in contact is covered on the adhesion promoting layer as the first hot-melt adhesive layer/first release film, and the pressure is 0.5 kg/cm ² , the temperature is 130° C., and the pressing time is 20 seconds using a hot press. The conditions were pressurized and heated to adhere, and then the temporary support was peeled off to obtain an electroconductive laminated sheet for attaching clothing fabrics (S1).

(Example 2) Up to the second conductive layer, the same operation as in S1 described above was performed. Then, the resin AD2 for forming an adhesion promoting layer was applied on the second conductive layer with a smear bar so that the cured film thickness might be 10 μm, and then ultraviolet rays were irradiated with a high-pressure mercury lamp so that the cumulative light intensity would be 1000 mJ/cm ² . , forming an adhesion promoting layer. Then, similarly to S1, the hot-melt adhesive sheet/release film is bonded to obtain a conductive laminated sheet for clothing fabric sticking (S2).

(Example 3) Up to the second conductive layer, the same operation as the above-mentioned S1 is performed. Then, the resin AD3 for forming an adhesion promoting layer was applied on the second conductive layer with an applicator bar so that the dry film thickness might be 3 μm, and the adhesion promoting layer was formed by drying at 100° C. for 30 minutes while performing a crosslinking reaction. Then, similarly to S1, the hot-melt-adhesive sheet/release film is adhered to obtain a conductive laminated sheet for attaching clothing fabrics (S3).

(Example 4) Up to the first conductive layer, the same operation as the above-mentioned S1 is performed. Then, the resin AD1 for forming an adhesion promoting layer was applied on the first conductive layer with an applicator bar so that the dry film thickness might be 12 μm, and the adhesion promoting layer was formed by drying at 100° C. for 30 minutes while performing a crosslinking reaction. Then, similarly to S1, the hot-melt adhesive sheet/release film is bonded to obtain a conductive laminated sheet for attaching clothing fabrics (S4).

(Comparative Example 1) Up to the second conductive layer, the same operation as the above-mentioned S1 is performed. Then, without performing the step of forming the adhesion promoting layer, the hot-melt adhesive sheet/release film was bonded together in the same manner as in S1 to obtain an electroconductive laminate for clothing fabric attachment (S0).

(Evaluation of Washing Durability) The obtained conductive laminated sheet for attaching clothing fabrics was cut out into a rectangle having a width of 10 mm and a length of 100 mm, and the release film was removed. The M size T-shirt made of polyester 70 and cotton 30 blended double warp knitted fabric is turned inside out, so that the hot melt adhesive layer of the conductive laminated sheet contacts the part of the chest (usually when wearing The inner side of the T-shirt, which is also the side that is in contact with the human body) is superimposed, and is attached by pressing and heating under the conditions of pressure 0.5kg/cm ² , temperature 130°C, and pressing time 20 seconds. This was used as a sample for cleaning durability evaluation. The initial resistance value of the conductive laminated sheet portion of the obtained sample for cleaning durability evaluation was measured in the longitudinal direction of the rectangle. The results are shown in Table 1. In addition, regarding the resistance value, when the resistance value was 100Ω or less, it was measured by Kelvin connection using a milliohmmeter 4338B manufactured by Agilent Technologies. When the resistance value exceeds 100Ω, use a digital tester to measure. Then, in accordance with the 5-fold accelerated test of the 103 method in JIS L 1096 fabrics and knitted fabrics test methods (after 5 cycles of continuous cleaning, dry once in the shade), the cleaning durability evaluation sample was used in a household washing machine ( ASW-50F5 (HS) manufactured by SANYO Co., Ltd. and the automatic control device for cleaning test (Tsujii Dyeing Machinery Co., Ltd., SAD-135 type) were cleaned for a total of 100 cycles in the presence of a cleaning net. The water flow was "strong", the liquor ratio was 1:30, the washing water temperature was 40°C, the washing time was 5 minutes, the rinsing water temperature was 25°C, and the rinsing time was 2 minutes. The lotion was an Attack powder type. In addition, one cycle (one time) of cleaning here refers to one cycle of stirring, dehydration, rinsing, dehydration, rinsing, and dehydration in the aqueous lotion solution in the washing tank. In order to meet the liquor ratio, use the sample T-shirt that meets the necessary amount. The resistance value was measured after every 5 cycles of washing and drying in the shade. The resistance values after 100 cycles of cleaning are shown in Table 1. In addition, when a disconnection occurred on the way and the resistance could not be measured, this fact was recorded. It was confirmed that the electroconductive laminated sheet of the Example did not peel off from the T-shirt even after the washing test, the resistance value could be measured, and the electroconductivity was maintained. In one of the comparative examples, a part of the conductive layer of the conductive laminate sheet fell off after 80 cycles of cleaning, and resistance measurement became impossible.

(Example 5) It carried out similarly to Example 1, and performed the operation before peeling of a temporary support body, and obtained the electroconductive laminated sheet S1 with a temporary support body. As shown in step 6 of FIG. 7 , half-cutting is performed from the release film side with a Thomson blade, and unnecessary parts are removed as shown in step 7 to obtain the predetermined electrode+wiring pattern shown in FIG. 8( a ). Again, as in step 8, the first release film is peeled off. The hot-melt urethane sheet MOBILON (registered trademark) MF-10F3 (non-thermoplastic polyurethane sheet/polyurethane hot-melt sheet/release paper) manufactured by Nisshinbo Co., Ltd. Cut into a predetermined base insulating layer pattern as shown in FIG. 8(b), and contact the conductive laminate sheet with a non-thermoplastic polyurethane sheet (equivalent to the first non-thermoplastic film). 1. The directions of the surfaces formed after the release film is peeled off are superimposed, and then pressurized and heated by hot pressing under the conditions of a pressure of 0.5 kg/cm ² , a temperature of 130° C., and a pressing time of 20 seconds (step 9). Then the temporary support is peeled off (step 10), and the hot melt adhesive layer side of MOBILON (registered trademark) MF-10F3 cut into a predetermined surface insulating layer pattern as shown in FIG. The first conductive layers are in contact with each other, and are pressed and bonded in the same way. After that, the release paper attached to MF-10F3 is peeled off (step 11) to obtain a conductive laminate having a base insulating layer and a surface insulating layer. Sheet S10 (FIG. 8(d)). Here, the conductive layer exposed from the large window portion of the surface insulating layer pattern is the electrode portion, and the conductive layer exposed from the small window portion is the connecting portion where the connector is mounted, and the part between the two is covered by the surface insulating layer. It is equivalent to the wiring part.

(Examples 6 to 8, Comparative Example 2) In the same manner as in Example 5, the conductive laminate sheets S2, S3, and S3 with temporary supports obtained in Examples 2 to 4 were subjected to the same additional processing and obtained respectively. Conductive laminated sheet S20, S30, S40. Also about the comparative example 1, additional processing was performed similarly, and the electroconductive laminated sheet S00 which is the comparative example 2 was obtained. Each obtained electroconductive laminated sheet was pressurized and heated under the conditions of a pressure of 0.5 kg/cm ² , a temperature of 130° C., and a press time of 40 seconds by hot pressing, and was adhered to the skin side of the lower part of the bra. Then, as shown in Fig. 8(e), a female snap of stainless steel as a connector is attached so that the convex portion faces the opposite side to the skin side. The snap button system is riveted through the conductive laminated sheet and the lower fabric of the brassiere to ensure the electrical connection with the conductive layer. By connecting the heart rate sensor "WHS-3" manufactured by UNION TOOL Co., Ltd. to the connector, it is used as a bra that can measure electrocardiogram, that is, a clothing-type biological information measuring device. Wear the obtained clothing-type biometric information measurement device on three healthy women aged 20, 30, and 40, and observe the first radio gymnastics and the second radio gymnastics while resting and vigorously performing the exercises. electrocardiogram at the time. Either can measure the electrocardiogram without problems. Then, a washing test of 100 cycles was carried out under the same conditions as in Example 1, and the clothes were put on and electrocardiogram measurement was carried out in the same manner. The results are shown in Table 2. When the conductive laminates of Examples 5 to 8 were used, the electrocardiogram measurement was performed in the same manner as at the beginning, and in Comparative Example 2, the wearer's electrocardiogram observation at rest was also possible, but noise occurred during exercise. Mixed into the waveform and cannot observe a clear and beautiful waveform. After the action test, the continuity between the button part and the electrode part of the conductive laminated sheet attached to the bra was tested. The results ensured the continuity of the embodiment and the comparative example. However, in the comparative example 2, the electrode Peeling of the conductive layer was observed in a part of the part.

[Table 1] Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Conductive Laminated Sheet S0 S1 S2 S3 S4 1st conductive layer CB(15μm) CB(15μm) CB(15μm) CB(15μm) CB(50μm) 2nd conductive layer AG(35μm) AG(35μm) AG(35μm) AG(35μm) without adhesion promoting layer without AD1(5μm) AD2(10μm) AD3(3μm) AD1(12μm) 1st hot melt adhesive layer MOB100 MOB100 MOB100 MOB100 MOB100 1st release film Initial resistance value [Ω] 85 83 85 82 31k Resistance value after cleaning test [Ω] Disconnected after 80 cycles of cleaning 370 250 2.8k 64k

[Table 2] Comparative Example 2 Example 5 Example 6 Example 7 Example 8 Conductive Laminated Sheet S00 S10 S20 S30 S40 1st conductive layer CB(15μm) CB(15μm) CB(15μm) CB(15μm) CB(50μm) 2nd conductive layer AG(35μm) AG(35μm) AG(35μm) AG(35μm) without adhesion promoting layer without AD1(5μm) AD2(10μm) AD3(3μm) AD1(12μm) 1st hot melt adhesive layer HM layer of MOB100 HM layer of MOB100 HM layer of MOB100 HM layer of MOB100 HM layer of MOB100 1st non-thermoplastic film MF-10F3 MF-10F3 MF-10F3 MF-10F3 MF-10F3 2nd hot melt adhesive layer 2nd non-thermoplastic film MF-10F3 MF-10F3 MF-10F3 MF-10F3 MF-10F3 3rd hot melt adhesive layer initial action test during rest good good good good good when exercising good good good good good Action test after cleaning test during rest good good good good good when exercising noise mixing good good good good [industrial applicability]

As described above, the stretchable conductive laminate sheet for attaching clothing fabrics of the present invention can be attached by providing an adhesion promoting layer between the stretchable conductive layer and the hot-melt adhesive layer. Electrodes and wirings for biological information measurement with excellent cleaning durability in clothing fabrics. The conductive laminated sheet for attaching stretchable clothing fabrics of the present invention is described by taking a female bra as an example in the embodiment, but it can be used for men, women, upper body, or lower body. Applicable to a wide range of biological information measurement clothing with electrodes, and can be applied to protective clothing used in various sports, fighting skills, job sites, and police. Furthermore, the present invention can be applied to hospital clothes and nursing clothes, which are often worn by caregivers and medical personnel when the wearer is sleeping.

1: Stretchable conductive layer 2: Hot melt adhesive layer 3: Release film 4: Surface insulation layer 5: Adhesion promotion layer 11: Stretchable first conductive layer 12: Stretchable second conductive layer 21: The first hot melt adhesive layer 22: The second hot melt adhesive layer 23: The third hot melt adhesive layer 30: Temporary Support 31: 1st release film 32: 2nd release film 41: 1st non-thermoplastic film 42: Second non-thermoplastic film 50: Adhesion Promotion Layer 90: Female buckle (connector) 100: Conductive laminated sheet with base insulation and surface insulation 101: Electrode part 102: Connection part 200: Conductive laminated sheet with connectors, base insulation, and surface insulation

[Fig. 1] Fig. 1 is a schematic diagram showing a cross-sectional structure of a conventional conductive laminate sheet for attaching clothing fabrics. 2] FIG. 2 is a schematic diagram showing a cross-sectional structure of a state in which a portion of the conductive layer is covered by a non-thermoplastic film corresponding to a surface insulating layer in a conventional conductive laminate sheet for attaching clothing fabrics. [ Fig. 3] Fig. 3 is a schematic diagram showing a cross-sectional structure of the conductive laminate sheet for attaching clothing fabrics of the present invention. 4] FIG. 4 is a schematic diagram showing a cross-sectional structure in a state where a portion of the conductive layer is covered by a non-thermoplastic film corresponding to the surface insulating layer in the conductive laminate for attaching clothing fabrics of the present invention. 5] FIG. 5 is a schematic diagram showing a cross-sectional structure when the stretchable conductive layer is composed of two layers of a first conductive layer and a second conductive layer in the conductive laminated sheet for attaching clothing fabrics of the present invention . [FIG. 6] FIG. 6 shows that in the conductive laminate sheet for attaching clothing fabrics of the present invention, when the stretchable conductive layer is composed of two layers of a first conductive layer and a second conductive layer, it is equivalent to a surface covering A schematic diagram of the cross-sectional structure of the state in which the non-thermoplastic film of the insulating layer is partially covered with the conductive layer. [ Fig. 7] Fig. 7 is a schematic step diagram showing an example of the steps in actually producing the conductive laminate sheet for attaching clothing fabrics of the present invention. [ Fig. 8] Fig. 8 is an example of a schematic diagram including electrodes and wires for electrocardiographic measurement, and a connection portion connected to a connector.

11: Stretchable first conductive layer

12: Stretchable second conductive layer

21: The first hot melt adhesive layer

22: The second hot melt adhesive layer

23: The third hot melt adhesive layer

30: Temporary Support

31: 1st release film

32: 2nd release film

41: 1st non-thermoplastic film

42: Second non-thermoplastic film

50: Adhesion Promotion Layer

Claims (6)

A conductive laminate for clothing fabric attachment, comprising in the following order: A stretchable conductive layer composed of at least a flexible resin and a conductive filler, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. A conductive laminated sheet for attaching clothing fabrics, which is a conductive laminated sheet for attaching clothing fabrics with a surface insulating layer, comprising in the following order: Retractable surface insulation, A stretchable conductive layer composed of at least a flexible resin and a conductive filler, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. A conductive laminate for clothing fabric attachment, comprising in the following order: A stretchable first conductive layer composed of at least a flexible resin and a carbon-based conductive filler, A stretchable second conductive layer composed of at least a flexible resin and a metal-based conductive filler, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. A conductive laminate for clothing fabric attachment, comprising in the following order: Retractable surface insulation, A stretchable first conductive layer composed of at least a flexible resin and a carbon-based conductive filler, A stretchable second conductive layer composed of at least a flexible resin and a metal-based conductive filler, Retractable bond-promoting layer, A stretchable layer of hot melt adhesive, and Release film. A method for manufacturing a conductive laminate sheet for attaching clothing fabrics as claimed in claim 1 or 2, comprising at least the following steps: Forming a stretchable conductive layer on a temporary support, forming an adhesion promoting layer on the stretchable conductive layer, and A stretchable hot melt adhesive layer is formed over the adhesion promoting layer. A method for manufacturing a conductive laminate sheet for attaching clothing fabrics as claimed in claim 3 or 4, comprising at least the following steps: A stretchable first conductive layer is formed on the temporary support, Furthermore, a stretchable second conductive layer is formed, forming an adhesion promoting layer over the stretchable second conductive layer, and A stretchable hot melt adhesive layer is formed on the adhesion promoting layer.

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