JP2019085444A - Fabric capable of forming air permeable adhesive layer in conductive member, conductive member and manufacturing method therefor - Google Patents

Abstract

To provide a conductive member having conductivity and/or air permeability and available for various industrial applications.SOLUTION: The inventor found that a conductive member excellent in conductivity and/or air permeability since an adhesive layer obtained by a laminate in a conductive member having a conductive coating existing on a surface of the laminate has air permeability, and available in various industrial applications can be provided. It is also found that the conductive member can be provided by achieving the laminate having the adhesive layer having air permeability by a fabric having a fiber containing an ethylene-unsaturated carboxylic acid copolymer.SELECTED DRAWING: None

Description

  The present invention relates to a fabric capable of forming a breathable adhesive layer in a conductive member, a conductive member and a method of manufacturing the same.

As conductive members applicable to various industrial applications such as electromagnetic wave shields, electrodes or sensors, for example, International Publication WO2010 / 109842 pamphlet (Patent Document 1), on at least one surface of a resin film, ethylene between -A film provided with a metal layer for electronic parts, in which a metal-containing layer such as a metal layer-forming film formed by a plating method or the like is adhered via an adhesive layer containing an unsaturated carboxylic acid copolymer ing.
In Patent Document 1, the ethylene-unsaturated carboxylic acid copolymer is a thermoplastic resin and is excellent in adhesion, and by forming an adhesive film using an extrusion laminating method with a T-die, It is disclosed that the adhesive layer can be formed with high productivity by suppressing the generation of voids.

International Publication WO2010 / 109842 Pamphlet

In order to provide the conductive member, the applicant of the present application examined, with reference to Patent Document 1, a method of manufacturing a conductive member including the following steps.
1. Preparing a precursor laminate formed by laminating in order of first substrate-adhesive film containing ethylene-unsaturated carboxylic acid copolymer-second substrate
2. The first base material and the second base material are bonded and integrated by melting the adhesive film provided in the precursor laminate, and the first adhesive base layer and the second base material are interposed between the adhesive layer derived from the adhesive film. Forming a laminate in which one base layer and the second base layer are bonded and integrated,
3. Forming a conductive coating on the surface of the laminate,
A method of manufacturing a conductive member, comprising:

However, in the conductive member manufactured in this manner, the following problem may occur.
-The first substrate in the prepared conductive member, since there is a layer (adhesive film derived from adhesive film) acting as a non-breathable insulating layer between the first substrate and the second substrate There is a possibility that the conductivity between the side main surface and the second base side main surface is unintentionally low.
-In the process of forming a conductive film on the surface of a layered product by existence of a layer which does not have breathability (adhesive layer derived from adhesive film) between the first substrate and the second substrate The fluid that forms a conductive film, such as a plating solution, does not sufficiently spread to the first substrate and / or the second substrate, and a portion in which the conductive film does not exist is likely to occur in the prepared conductive member. There is a possibility that the conductivity of the conductive member is unintentionally low.
-Since the layer which does not have air permeability (adhesive layer derived from an adhesive film) exists between the 1st substrate and the 2nd substrate, it can not provide the conductive member which is excellent in air permeability.
Therefore, it was thought that there was a limit in diverting the above-mentioned conductive member to various industrial applications.

  An object of the present invention is to provide a conductive member which can be used in various industrial applications, such as excellent conductivity and / or air permeability.

In the first invention, “the laminate having the first base layer and the second base layer bonded and integrated by interposing the air-permeable adhesive layer, and the conductive property existing on at least a part of the surface of the laminate A fabric comprising an ethylene-unsaturated carboxylic acid copolymer-containing fiber capable of forming the air-permeable adhesive layer in a conductive member provided with a coating.
In the second invention, “a laminate in which the first base material layer and the second base material layer are bonded and integrated by interposing an air-permeable adhesive layer containing an ethylene-unsaturated carboxylic acid copolymer, A conductive member comprising the conductive film present on at least a part of the surface of the laminate.
The third invention is described in “1. Process of preparing a precursor laminate formed by laminating in order of first base material—fabric comprising fibers containing ethylene-unsaturated carboxylic acid copolymer” −second base material, 2 The first substrate and the second substrate are bonded and integrated by melting the fabric provided in the precursor laminate, and the first air-permeable adhesive layer derived from the fabric is interposed therebetween. A method of manufacturing a conductive member, comprising: a step of forming a laminate in which a base material layer and the second base material layer are bonded and integrated; and 3. a step of forming a conductive film on the surface of the laminate. It is.

A laminate formed by bonding and integrating a first base material layer and a second base material layer by interposing an adhesive layer containing an ethylene-unsaturated carboxylic acid copolymer, and electrical conductivity existing on the surface of the laminate The applicant continued to study to provide a conductive member with a metallic coating.
As a result, when the adhesive layer in the laminate has air permeability, the following effects are exhibited, and as a result, conductive members usable for various industrial applications such as excellent conductivity and / or air permeability. I found that I could offer.
· The presence of a breathable layer (a breathable adhesive layer derived from a fabric) between the first substrate and the second substrate allows the breathable adhesive layer to have a conductive coating also inside thereof Since it can be, it can prevent that the electroconductivity between the 1st substrate side main surface and the 2nd substrate side main surface in the prepared electroconductive member will become low unintentionally.
-Plating in the step of forming a conductive film on the surface of the laminate by the presence of a breathable layer (a breathable adhesive layer derived from a fabric) between the first substrate and the second substrate A conductive member such as a liquid or the like, since the fluid forming the conductive coating is sufficiently spread over the first substrate and / or the second substrate, and a portion where the conductive coating does not exist in the prepared conductive member is unlikely to occur. Can be prevented from becoming unintentionally low.
-Since the layer which has air permeability (air-permeable adhesive layer derived from cloth) exists between the 1st substrate and the 2nd substrate, the conductive member which is excellent in air permeability can be provided.
And this-application applicant discovered that the laminated body provided with a breathable adhesive layer can be implement | achieved by the fabric provided with the fiber containing an ethylene- unsaturated carboxylic acid copolymer.

  Therefore, the laminate having the air-permeable adhesive layer derived from the fabric according to the present invention and the conductive member provided with the conductive film present on the surface are excellent in the conductivity and / or the air permeability, so that they can be used in various industrial applications. It is an available conductive member.

  In addition, air permeability is obtained by melting the fabric of a precursor laminate formed by laminating in order of a first substrate-a fabric comprising a fiber containing an ethylene-unsaturated carboxylic acid copolymer-a second substrate. According to the method for producing a conductive member including the step of producing a laminate including an adhesive layer, a conductive member that can be used for various industrial applications can be produced because of excellent conductivity and / or air permeability.

  In the present invention, various configurations such as the following configurations can be selected as appropriate.

In describing the present invention, first, a laminate in which the first base material layer and the second base material layer are bonded and integrated by interposing the air-permeable adhesive layer, and at least a part of the surface of the laminate. The conductive member provided with the conductive film which exists is demonstrated.
The first base layer and the second base layer are members described below or layers derived from the members.
The type of the member can be appropriately selected, and for example, a member such as a film, a foam, a porous film, a cloth (refers to a sheet-like structure made of fibers such as a fiber web or nonwoven fabric or a knitted fabric or a woven fabric) can be adopted. In addition, when a 1st base material layer and / or a 2nd base material layer has porosity, the laminated body in which adhesion integration of a 1st base material layer and a 2nd base material is fully performed by a breathable contact bonding layer Can be provided. Moreover, when the first base material layer and / or the second base material layer has air permeability, it is preferable because it is excellent in air permeability and can provide a conductive member that can be used for various industrial applications.

The resin constituting the first base material layer and the second base material layer has, for example, a polyolefin resin (polyethylene, polypropylene, polymethylpentene, a structure in which a part of hydrocarbon is substituted with a cyano group or halogen such as fluorine or chlorine) Polyolefin resins, etc., styrene resins, polyether resins (polyether ether ketone, polyacetal, phenol resin, melamine resin, urea resin, epoxy resin, modified polyphenylene ether, aromatic polyether ketone etc.), Polyester resin (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyarylate, wholly aromatic polyester resin, unsaturated polyester resin Resin, etc.), polyimide resin, polyamideimide resin, polyamide resin (eg, aromatic polyamide resin, aromatic polyetheramide resin, nylon resin, etc.), resin having a tolyl group (eg, polyacrylonitrile, etc.), urethane -Based resin, epoxy resin, polysulfone resin (polysulfone, polyether sulfone, etc.), fluorocarbon resin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), cellulose resin, polybenzimidazole resin, acrylic resin (eg, acrylic resin) Known resins such as polyacrylonitrile resins obtained by copolymerizing acid esters or methacrylates, moda acrylic resins obtained by copolymerizing acrylonitrile with vinyl chloride or vinylidene chloride, etc. can be employed.
The above-mentioned resin may be made of either a linear polymer or a branched polymer, and the resin may be a block copolymer or a random copolymer. Further, the three-dimensional structure of the resin and the presence or absence of crystallinity may be any. Furthermore, a plurality of resins may be mixed.

When the member which constitutes the first base material layer and / or the second base material layer is a fabric or a layer derived from a fabric, its constituent fibers (hereinafter sometimes referred to as fibers) are made of one type of resin Or those composed of a plurality of resins. As a fiber aspect comprised from several types of resin, it can be fiber aspect, such as core-sheath type, a sea island type, a side-by-side type, an orange type, a bimetal type, generally called composite fiber, for example.
Further, as the fibers, in addition to the fibers having a substantially circular cross-sectional shape and the fibers having an elliptical shape, it may contain modified cross-section fibers. In addition, as irregular shape fiber, polygonal shape such as triangular shape, alphabet letter shape such as Y shape, irregular shape, multi-leaf shape, symbol shape such as asterisk shape, or a shape in which a plurality of these shapes are combined Etc. can be exemplified.

  The fiber length of the fiber is not particularly limited, but it may be a short fiber or long fiber having a specific measurable length, or a fiber length having a length that makes it substantially difficult to measure the fiber length. It can be a continuous fiber.

The average fiber diameter of the fibers is appropriately selected, but can be 0.5 to 30 μm, can be 5 to 20 μm, and can be 10 to 15 μm so as to provide conductive members usable for various industrial applications. Can be.
The “average fiber diameter” as referred to herein can be calculated based on a 1000 × electron photomicrograph of a portion to be measured including fibers such as a surface or a cross section. Specifically, 100 points of fibers whose average fiber diameter is to be calculated are selected from electron micrographs, and the arithmetic mean value of the respective fiber diameters of the selected fibers is taken as the average fiber diameter. When the cross-sectional shape of the fiber is non-circular, the diameter of a circle having the same area as the cross-sectional area is regarded as the fiber diameter.

  For example, fibers are melt spinning method, dry spinning method, wet spinning method, direct spinning method (melt blow method, spun bond method, electrostatic spinning method, method of spinning using centrifugal force, JP 2011-012372 A etc.) The method of spinning using the accompanying air stream described in JP-A-2005-264374, etc.), the fiber having a thin fiber diameter by removing one or more kinds of resin components from the composite fiber It can be obtained by a known method such as a method of extraction.

  In addition, it is preferable that the fiber is a fiber that has been mechanically stretched after being spun, because a laminate having a first base layer and a second base layer that are excellent in strength and rigidity can be provided.

  When the fabric is a fiber web or a non-woven fabric, the constituent fibers are entangled with each other, but the method of entanglement can be appropriately selected, and the constituent fibers are entangled by a gas flow such as a needle, water or steam. It can be a woven fabric. Alternatively, the fiber web or non-woven fabric may be prepared by spinning directly using a spinning method and collecting the obtained fibers.

  When the fabric is a woven or knitted fabric, the fabric can be prepared by weaving or knitting the obtained fibers.

  A part of the fibers may be melted and the fibers may be melted and integrated, or the fabric may be configured by bonding and integrating the fibers with a binder. For example, a resin component having a high melting point (A) is used as a core component, and a resin component having a melting point lower than that of the high melting resin component (a melt) Core-sheath type fiber (may be eccentric type fiber) with sheath component as sheath component, (B) high melting point resin component and resin component having melting point lower than this high melting point resin component are attached A side-by-side type fiber, a sea-island type fiber in which a large number of resin components having a melting point higher than that of the low melting point resin component are dispersed in the (C) low melting point resin component can be adopted.

The thickness and basis weight of members constituting the first base material layer and the second base material layer are appropriately selected, but the thickness is 1 to 6 mm so that conductive members usable for various industrial applications can be provided. , And can be 1.5 to 5 mm, can be 2 to 3 mm, and can have a basis weight of 50 to 150 g / m ² .
The thickness refers to the length in the vertical direction of the measurement object when a compressive load of 20 g / cm ² is applied in the direction perpendicular to the surface (main surface) having the largest area of the measurement object, the basis weight refers to mass in terms of per 1 m ² of the main surface of the measurement object.

The breathable adhesive layer is a breathable layer which is interposed between the two layers and plays a role of bonding and integrating the two layers in a laminate including the first base material layer and the second base material layer. It is.
In addition, it can be confirmed with the following method that a breathable contact bonding layer has breathability.
1. If the laminate has breathability across its major surfaces, it can be determined that the breathable adhesive layer has breathability.
2. When the structure after removing the first base material layer or the second base material layer from the laminate has breathability across its both major surfaces, the breathable adhesive layer has breathability It can be judged.
3. In the case where the single breathable adhesive layer taken from the laminate has breathability across its both major surfaces, it can be determined that the breathable adhesive layer has breathability.
In addition, measuring the air permeability between both main surfaces of the measuring object by applying the measuring object to 6.8.1 (Frazil type method) specified in JIS L1913: 2010 “general nonwoven fabric test method”. Can.

The air permeability and the basis weight of the air-permeable adhesive layer in the laminate are appropriately selected, but the air permeability is 0.5 cm ³ / cm ² · sec., So as to provide a conductive member usable for various industrial applications. It is preferable that it is more than 0.8 cm ³ / cm ² · sec. It is preferable that it is more than 1 cm ³ / cm ² · sec. It is preferable that it is more than. On the other hand, the upper limit value of the air permeability is appropriately selected, but 50 cm ³ / cm ² · sec. The following is realistic. Also, the basis weight is preferably from 30~90g / ^{m 2,} is preferably from 40 and 80 g / ^{m 2,} preferably from 50 to 70 g / ^{m 2.}

The breathable adhesive layer of the present invention is a layer containing an ethylene-unsaturated carboxylic acid copolymer.
The ethylene-unsaturated carboxylic acid copolymer referred to herein is a copolymer of ethylene and an unsaturated carboxylic acid. As this unsaturated carboxylic acid, C3-C8 unsaturated carboxylic acid, specifically, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, etc. are used. Be Among these unsaturated carboxylic acids, acrylic acid and methacrylic acid are particularly preferably used. The ethylene-unsaturated carboxylic acid copolymer may be a ternary or higher multicomponent copolymer, and in addition to the above components capable of copolymerizing with ethylene, methyl acrylate, ethyl acrylate, isobutyl acrylate Unsaturated carboxylic acid esters such as n-butyl acrylate, isooctyl acrylate, methyl methacrylate, isobutyl methacrylate, dimethyl maleate and diethyl maleate; vinyl esters such as vinyl acetate and vinyl propionate; propylene, butene, 1 Unsaturated hydrocarbons such as butadiene, 3-butadiene, pentene, 1,3-pentadiene and 1-hexene; oxides such as vinyl sulfuric acid and vinyl nitric acid; halogen compounds such as vinyl chloride and vinyl fluoride; vinyl group-containing 1, 2 A secondary amine compound; carbon monoxide, sulfur dioxide or the like may be copolymerized as a third component.
Further, in the metal salt (ionomer) of the ethylene-unsaturated carboxylic acid copolymer, at least a portion of the carboxyl groups in the above-mentioned ethylene-unsaturated carboxylic acid copolymer can be Na ⁺ , K ⁺ , Li ⁺ , Ca It may be one crosslinked with a metal cation such as a monovalent to trivalent cation such as ²⁺ , Mg ²⁺ , Zn ²⁺ , Cu ²⁺ , Co ²⁺ , Ni ²⁺ , Mn ²⁺ , Al ³⁺ .

  Specific examples of such ethylene-unsaturated carboxylic acid copolymers include nucrel (Mitsui-Dupont Polychemicals Co., Ltd., registered trademark), Aclift (Sumitomo Chemical Co., Ltd., registered trademark), Rexpearl (Mitsubishi, Ltd.) Chemical Co., Ltd., registered trademark) etc. can be adopted.

  The component of the conductive film present on at least a part of the surface of the laminate may be any one having conductivity, for example, nickel, copper, platinum, gold, silver, zinc, cadmium, tin, chromium Various alloys, various metal compounds such as metal oxides, electron conjugated polymers (for example, polymers having conductivity such as polypyrrole), and the like can be adopted. Moreover, the kind of electroconductive film may be comprised only by one type, and several types of mixtures may be sufficient as it.

The form of the conductive film present on at least a part of the surface of the laminate can be appropriately selected, and is present on a part of the exposed surface of the laminate or on the entire exposed surface of the laminate May be It is preferably present on the entire exposed surface of the laminate so as to provide a conductive member usable for various industrial applications. Such a conductive member can be provided by providing the laminate with a method of forming a conductive film using a fluid such as a plating method, as described later.
In addition to the exposed surface of the laminate, the conductive film can be present inside the laminate. Such a conductive member can be provided by providing the laminate according to the present invention to a method of forming a conductive film using a fluid such as a plating method, as described later.

Although the basis weight of the conductive film present on at least a part of the surface of the laminate is appropriately selected, the basis weight is 5 to 30 g / m ² so as to provide a conductive member usable for various industrial applications. Preferably, it is 7 to 25 g / m ² , and preferably 10 to 20 g / m ² .

The thickness, basis weight, porosity and air permeability of the conductive member according to the present invention can be selected as appropriate, but the thickness is preferably 1 to 6 mm so that the conductive member can be used for various industrial applications. , Preferably 1.5 to 5 mm, and more preferably 2 to 3 mm. Basis weight is preferably from 95~270g / ^{m 2,} is preferably from 127~195g / ^{m 2,} preferably from 145~185g / ^{m 2.} The porosity is preferably 70% or more, preferably 80% or more, and more preferably 90% or more. The upper limit of the porosity is appropriately selected, but it is realistic that it is 98% or less. Also, the air permeability is 0.4 cm ³ / cm ² · sec. It is preferable that it is more than 0.6 cm ³ / cm ² · sec. It is more preferable that it is more than 0.9 cm ³ / cm ² · sec. It is most preferable that it is more than. On the other hand, the upper limit value of the air permeability is appropriately selected, but 50 cm ³ / cm ² · sec. The following is realistic.

  The first base material layer and the second base material layer, the air-permeable adhesive layer, and the conductive member carry or bond functional components such as a flame retardant, a water repellent, an antifungal agent, a pigment or the like into the constituent components. You may include in the aspect with which it was kneaded.

  Moreover, although the above-mentioned electroconductive member may be used alone, it may be used by the structure formed by laminating | stacking the support body (for example, foam, a porous film, a fabric, etc.) prepared separately.

The above-described conductive member is a conductive member that can be used for various industrial applications as a result of exhibiting the following effects.
· The presence of a breathable layer (a breathable adhesive layer derived from a fabric) between the first substrate and the second substrate allows the breathable adhesive layer to have a conductive coating also inside thereof Since it can be, it can prevent that the electroconductivity between the 1st substrate side main surface and the 2nd substrate side main surface in the prepared electroconductive member will become low unintentionally.
-Plating in the step of forming a conductive film on the surface of the laminate by the presence of a breathable layer (a breathable adhesive layer derived from a fabric) between the first substrate and the second substrate A conductive member such as a liquid or the like, since the fluid forming the conductive coating is sufficiently spread over the first substrate and / or the second substrate, and a portion where the conductive coating does not exist in the prepared conductive member is unlikely to occur. Can be prevented from becoming unintentionally low.
-Since the layer which has air permeability (air-permeable adhesive layer derived from cloth) exists between the 1st substrate and the 2nd substrate, the conductive member which is excellent in air permeability can be provided.

The fabric capable of constituting the air-permeable adhesive layer of the present invention (hereinafter sometimes referred to as adhesive fabric) is capable of forming the air-permeable adhesive layer in the laminate constituting the above-mentioned conductive member, ethylene-unsaturated It is a fabric provided with a fiber containing a carboxylic acid copolymer.
The configuration of the adhesive fabric can be appropriately selected so as to be able to form a breathable adhesive layer, and the same configuration as the fabric mentioned as being capable of configuring the first base layer and the second base layer described above may be provided. it can. When the adhesive fabric is a member including fibers, the first base layer and the second base layer can be bonded and integrated in the form of a breathable adhesive layer to provide a laminate.

  The fabric is preferably a non-woven fabric so that the effects described above can be exhibited and a breathable adhesive layer can be formed. In addition, when the adhesive fabric is a non-woven fabric having a continuous length (for example, a melt-blown non-woven fabric, a spun bond non-woven fabric, an electrostatic spun non-woven fabric, etc.), adhesion and integration of the first base material layer and the second base material are sufficiently performed. It is preferable because it can form a breathable adhesive layer. In particular, it is more preferable that the adhesive fabric is a melt-blown non-woven fabric, because it can form a breathable adhesive layer in which adhesion and integration of the first substrate layer and the second substrate can be sufficiently performed.

  In addition, although the adhesion | attachment cloth may contain fibers other than the fiber containing an ethylene- unsaturated carboxylic acid copolymer as a constituent fiber, the adhesion integration of a 1st base material layer and a 2nd base material is enough. As can be done, it is preferable that the adhesive fabric is composed only of fibers containing an ethylene-unsaturated carboxylic acid copolymer. Moreover, it is more preferable that the adhesion | pasting fabric is comprised with the fiber comprised only by the ethylene- unsaturated carboxylic acid copolymer from the same reason.

The average fiber diameter, the fabric weight, the thickness, the air permeability and the porosity of the fibers constituting the adhesive fabric are appropriately selected, but are preferably in the following range so that the air-permeable adhesive layer can be formed. The average fiber diameter is preferably 0.5 to 30 μm, preferably 5 to 20 μm, and more preferably 10 to 15 μm. Basis weight is preferably from 30~90g / ^{m 2,} is preferably from 40 and 80 g / ^{m 2,} preferably from 50 to 70 g / ^{m 2.} The thickness is preferably 0.1 to 0.5 mm, preferably 0.2 to 0.4 mm, and more preferably 0.25 to 0.35 mm. The air permeability is preferably 90 to 180 cm ³ / cm ² · sec, preferably 100 to 160 cm ³ / cm ² · sec, and preferably 110 to 140 cm ³ / cm ² · sec. The porosity is preferably 70% or more, preferably 75% or more, and more preferably 80% or more. On the other hand, if the porosity is too high, the first substrate layer and the second substrate may not be sufficiently bonded and integrated, so it is realistic that the porosity is 90% or less.

  Then, the manufacturing method of the electroconductive member concerning this invention is demonstrated. The description of the same items as those described above will be omitted.

Although the manufacturing method of the conductive member concerning this invention can be selected suitably, as an example,
(1) preparing a precursor laminate formed by laminating in the order of a first base material-adhesive fabric (a fabric provided with a fiber containing an ethylene-unsaturated carboxylic acid copolymer) -a second base material;
(2) The first substrate and the second substrate are adhered and integrated by melting the adhesive fabric provided in the precursor laminate, and the air-permeable adhesive layer derived from the adhesive fabric is interposed therebetween. Forming a laminate in which the first base layer and the second base layer are bonded and integrated;
(3) A conductive member can be manufactured by providing a manufacturing method including the step of forming a conductive film on the surface of the laminate.

First, (1) step of preparing a precursor laminate formed by laminating in the order of (1) first base material-adhesive cloth (fabric provided with a fiber containing an ethylene-unsaturated carboxylic acid copolymer) -second base material , Will be described.
Although the preparation method of a precursor laminated body can be selected suitably, a precursor laminated body can be prepared by preparing a 1st base material, a 2nd base material, and an adhesion textile, and laminating each material in the above-mentioned order. . Alternatively, in the case where the adhesive fabric is a direct spun non-woven fabric, the fibers capable of constituting the adhesive fabric can be directly spun on one main surface of the first substrate to form on one main surface of the first substrate. The precursor laminate may be prepared by forming an adhesive fabric and then laminating or directly spinning a second substrate on the exposed main surface on the adhesive fabric side to form a second substrate. .
In addition, you may laminate | stack structural members, such as another porous body, a film, and a foam, on a precursor laminated body.

Next, (2) the first substrate and the second substrate are bonded and integrated by melting the adhesive fabric of the precursor laminate, and the air-permeable adhesive layer derived from the adhesive fabric is interposed therebetween. The step of forming a laminate in which the first base layer and the second base layer are bonded and integrated will be described.
The method for melting the adhesive fabric constituting the precursor laminate can be selected as appropriate, but for example, heating or heating and pressing with a roll, heating to a heater such as an oven dryer, far infrared heater, dry heat dryer, hot air dryer, etc. A method of heating, a method of irradiating infrared rays under no pressure, and a method of heating an ethylene-unsaturated carboxylic acid copolymer contained in the adhesive fabric can be used.
Although the heating temperature and the heating conditions are appropriately selected, it is a temperature at which the ethylene-unsaturated carboxylic acid copolymer contained in the adhesive fabric can be melted to bond and integrate the first base and the second base, The heating temperature is adjusted so that the shapes and functions of constituent members such as the first base and the second base are not unintentionally reduced. In addition, you may pressurize by providing the precursor laminated body after providing to a heating process to a roll apparatus.
After heat treatment, the layer derived from the adhesive fabric containing the melted ethylene-unsaturated carboxylic acid copolymer is cooled. The cooling means is appropriately selected so that the molten ethylene-unsaturated carboxylic acid copolymer can bond and integrate the first substrate and the second substrate, but it is higher than the melting temperature of the ethylene-unsaturated carboxylic acid copolymer. A method of exposing the heat-treated precursor laminate in a low temperature atmosphere can be employed.
As described above, by providing the precursor laminate to the heat treatment step and the cooling step, the first base layer and the second base layer are bonded and integrated by interposing the air-permeable adhesive layer derived from the fabric therebetween. Can be formed.

Finally, (3) a step of forming a conductive film on the surface of the laminate will be described.
Although a method of forming a conductive coating on the surface of the laminate can be selected appropriately, as an example, a method of applying electrolytic plating after electroless plating or electrolytic plating using a fluid (such as an aqueous alkaline solution) or electroless plating In addition, a method by metal deposition processing, a method by sputtering processing, a method by ion plating, a method by metal spraying, etc. can be adopted. Alternatively, after applying a solution containing an oxidizing agent such as iron (III) chloride or copper (II) chloride to the laminate, polymerization is performed by bringing a precursor of an electron conjugated polymer such as pyrrole into contact in a gaseous state, A method of coating the body surface with an electron conjugated polymer can be employed.
As a method of manufacturing a conductive member other than those described above, when laminating the first substrate and the second substrate, the melted ethylene-unsaturated carboxylic acid copolymer is interposed between the main surfaces of both substrates which are in contact during lamination. After the polymer is interposed and laminated, the layer derived from the adhesive fabric containing the melted ethylene-unsaturated carboxylic acid copolymer is cooled, and the air-permeable adhesive layer is interposed between the first base layer and the above. You may form the laminated body which a 2nd base material layer carries out adhesion integration.
Although the method of preparing the melted ethylene-unsaturated carboxylic acid copolymer can be selected as appropriate, it is possible to prepare the ethylene-unsaturated carboxylic acid copolymer melted in the form of fiber or web by using a direct spinning apparatus. it can.

The conductive member according to the present invention can be manufactured as described above. In addition, although the electroconductive member manufactured in this way can also be used as it is, according to the process, use, and a use aspect which laminate the support body (for example, a foam, a porous film, a fabric etc.) prepared separately. It may have various secondary processes such as a process of punching and processing.
Further, it may be subjected to a pressure treatment process such as reliable press treatment.

  Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

Example 1
A wet non-woven fabric (fineness: 1.0 dtex, fiber length: 5 mm, basis weight: 50 g / m ² , air permeability: 17 cm ³ / cm ² · sec., Thickness: 0.25 mm) consisting of polyolefin fibers was prepared.
Next, ethylene-methacrylic acid copolymer resin (Mitsui Dupont Polychemical Co., Ltd., trade name: Nucrel N 1110 H (registered trademark), melting point based on DSC measurement: 95 ° C., melt flow rate: 100 g / 10 min (temperature: 190 ° C.) Melt-blown non-woven fabric composed only of ethylene-methacrylic acid copolymer resin (average fiber diameter: 14 μm, fiber length: continuous length, basis weight: 60 g / l) by applying a load of 2.16 kg) to the melt-blowing method and directly spinning it. m ² , thickness: 0.3 mm, air permeability: 120 cm ³ / cm ² · sec., porosity: 79%).
Then, a foamed polyurethane sponge (weight: 65 g / m ² , air permeability: 480 cm ³ / cm ² · sec., Thickness: 2.8 mm) was prepared.
The respective members prepared as described above were laminated in the order of wet nonwoven fabric-meltblown nonwoven fabric-foamed polyurethane sponge so that the main surfaces are in contact with each other, to prepare a precursor laminate. Then, the precursor laminate was subjected to a heat press apparatus (heating temperature: 110 ° C., pressure: 0.29 MPa), heated and pressurized for 10 seconds to melt the meltblown nonwoven fabric, and then cooled.
Thus, by interposing the ethylene-methacrylic acid copolymer resin, a laminate in which the fiber layer derived from the wet non-woven fabric and the layer derived from the foamed polyurethane sponge are bonded and integrated (weight: 175 g / m ² , thickness) : 2.4 mm, the air permeability between both main surfaces in the laminate: 2 cm ³ / cm ² · sec.) Was produced.

  In addition, since the manufactured laminated body had air permeability over the both main surfaces, the air-permeable adhesive layer derived from the melt-blown nonwoven fabric in the laminated body had air permeability.

(Evaluation method of alkali resistance)
The alkali resistance of the laminate produced in the example was evaluated by using the laminate sample produced as follows for measurement.
From the precursor laminates prepared in the examples, a total of six samples (precursor laminates) each having a size of 50 mm on a short side and 150 mm on a long side were cut out.
And between the meltblown non-woven fabric and the foamed polyurethane sponge in a range (a square range of 50 mm on a side) extending from one end in the long side direction to the other end in each sample (precursor laminate) to the other end Heat-resistant paper was sandwiched between Then, each sample was applied to a heat press apparatus (heating temperature: 110 ° C., pressure: 0.29 MPa) in that state, and heated and pressurized for 10 seconds to melt the meltblown nonwoven fabric, and then cooled.
Thus, by interposing the ethylene-methacrylic acid copolymer resin, a portion (hereinafter referred to as an adhesive integrated portion) in which the fiber layer derived from the wet non-woven fabric and the layer derived from the foamed polyurethane sponge are bonded and integrated. A total of six laminate samples were produced.
In addition, the said range (parts other than an adhesion integrated part) in a laminated body sample is a part by which adhesion integration of the wet nonwoven fabric and ethylene foam polyurethane sponge by ethylene- methacrylic acid copolymer resin is not made.
The maximum value (unit: N / 50 mm) of the stress measured by the end of peeling of the layer derived from the foamed polyurethane sponge from the laminate sample produced as described above was measured. This measurement was performed twice and the average value A (unit: N / 50 mm) of the measured maximum stress was calculated.
Subsequently, after immersing the laminated body sample manufactured as mentioned above in warm water (temperature: 50 degreeC) for 10 minutes, it pulled up from warm water. The maximum value (unit: N / 50 mm) of the stress measured by the end of peeling off the layer derived from the foamed polyurethane sponge was measured from the laminate sample after the main treatment. This measurement was performed twice, and the average value B (unit: N / 50 mm) of the measured maximum stress was calculated.
Furthermore, after immersing the laminated body sample manufactured as mentioned above in sodium hydroxide aqueous solution (temperature: 50 degreeC, pH: 12.5) for 10 minutes, it pulled up from sodium hydroxide aqueous solution. The maximum value (unit: N / 50 mm) of the stress measured by the end of peeling off the layer derived from the foamed polyurethane sponge was measured from the laminate sample after the main treatment. This measurement was performed twice, and the average value C (unit: N / 50 mm) of the measured maximum stress was calculated.
In this measurement, ORIENTEC UCT-500 (between chucks: 30 mm, tensile speed 100 mm / min) was used as a measuring device. In addition, one chuck of the measuring apparatus sandwiches the fiber layer portion derived from the wet non-woven fabric in the laminate sample to which the ethylene-methacrylic acid copolymer resin is attached, and the other chuck is a layer derived from the foamed polyurethane sponge in the laminate sample Measurement was started with the part sandwiched.

It was found that the laminate according to the present invention had alkali resistance since the laminate sample was able to be used for (evaluation method of alkali resistance), and it was subjected to the plating method performed in an alkaline aqueous solution. It turned out that it is a possible laminated body.
Therefore, it was considered that the laminate of the present invention can provide a conductive member provided with a conductive film (plating film formed by the plating method) on at least a part of the surface of the laminate.

Moreover, the average value of each maximum stress of the laminated body sample calculated by (the evaluation method of alkali resistance) is an average value A: 12.3 (N / 50 mm), an average value B: 12.4 (N / 50 mm) Since the average value C: 13.3 (N / 50 mm), and a large difference was not seen in each average value, the laminate according to the present invention exhibited a wet non-woven fabric and a foam even in the alkaline aqueous solution. It has been found that the adhesive integrity of the polyurethane sponge is well maintained.
Therefore, even when the laminate according to the present invention is subjected to a plating method performed under an alkaline aqueous solution, the first substrate and / or the second substrate is prevented from peeling from the laminate, and conductivity is achieved. It was thought that a sex member could be provided.

  In addition, as a further finding, it is possible to manufacture a laminate and a laminate sample by changing the heating and pressing conditions of the heat press apparatus in the manufacturing process of the example to (heating temperature: 110 ° C., pressure: 0.45 MPa). I tried. As a result, in the laminates and laminate samples produced under the present production conditions, as in the results described above, no significant difference was found in the average value of the respective maximum stresses.

Moreover, the adhesive layer in the laminate of the example had air permeability. Therefore, as a result of exhibiting the following effects, the conductive member provided with the laminate according to the present invention was considered to be a conductive member usable for various industrial applications.
· The presence of a breathable layer (a breathable adhesive layer derived from a fabric) between the first substrate and the second substrate allows the breathable adhesive layer to have a conductive coating also inside thereof Since it can be, it can prevent that the electroconductivity between the 1st substrate side main surface and the 2nd substrate side main surface in the prepared electroconductive member will become low unintentionally.
-Plating in the step of forming a conductive film on the surface of the laminate by the presence of a breathable layer (a breathable adhesive layer derived from a fabric) between the first substrate and the second substrate A conductive member such as a liquid or the like, since the fluid forming the conductive coating is sufficiently spread over the first substrate and / or the second substrate, and a portion where the conductive coating does not exist in the prepared conductive member is unlikely to occur. Can be prevented from becoming unintentionally low.
-Since the layer which has air permeability (air-permeable adhesive layer derived from cloth) exists between the 1st substrate and the 2nd substrate, the conductive member which is excellent in air permeability can be provided.

  Therefore, the laminate having the air-permeable adhesive layer derived from the fabric according to the present invention and the conductive member provided with the conductive film present on the surface are excellent in the conductivity and / or the air permeability, so that they can be used in various industrial applications. It is an available conductive member.

  The present invention is a fabric capable of preparing a conductive member applicable to various industrial applications such as an electromagnetic wave shield, an electrode or a sensor, and the conductive member exhibiting the above-mentioned function is provided by using the fabric of the present invention. it can.

Claims (3)

In a conductive member comprising a laminate in which a first base material layer and a second base material layer are bonded and integrated by interposing an air-permeable adhesive layer, and a conductive film present on the surface of the laminate
A fabric comprising fibers containing an ethylene-unsaturated carboxylic acid copolymer capable of forming the breathable adhesive layer.
A laminate formed by bonding and integrating a first base material layer and a second base material layer by interposing an air-permeable adhesive layer containing an ethylene-unsaturated carboxylic acid copolymer, and the surface of the laminate A conductive member comprising the conductive film present in
1. Preparation of a precursor laminate formed by laminating in order of a first substrate-a fabric comprising fibers containing an ethylene-unsaturated carboxylic acid copolymer-a second substrate,
2. The first substrate and the second substrate are adhered and integrated by melting the fabric provided in the precursor laminate, and the air-permeable adhesive layer derived from the fabric is interposed therebetween. Forming a laminate in which one base layer and the second base layer are bonded and integrated,
3. forming a conductive film on the surface of the laminate,
A method of manufacturing a conductive member, comprising: