JP6514942B2 - Conductive cloth - Google Patents

Description

  The present invention relates to a conductive fabric having a pattern (circuit) or the like of metal foil transferred onto a fabric made of nonconductive fibers. More particularly, the present invention relates to a conductive fabric having sufficient conductivity without impairing the flexibility inherent to the fabric, and having excellent followability to the shape change such as bending and durability, and a method for producing the same.

  A cloth having conductivity can be used as a wearable device by mounting electronic components and sensors. By mounting the wearable device using the conductive fabric of the present invention, it is possible to measure biological signals and motions of humans and animals, and it is used in the medical field and healthcare field, as well as in the environment and architecture fields. Its usefulness has attracted attention in various industries such as Japan.

  Conventional techniques for imparting conductivity to a fabric include a method of weaving or knitting a conductive yarn (for example, Patent Document 1), a method of printing a conductive paste (for example, Patent Document 2), and the like. .

  However, in the method of weaving or weaving the conductive yarn, there are problems such as requiring a special device and that the degree of freedom of the conductive pattern shape is low. Since the conductivity may be insufficient in the method of printing the conductive paste, there is a problem that the cloth tends to be hard and heavy because it is necessary to increase the amount of the paste to be printed in order to increase the conductivity. There is also a possibility that a crack may occur due to the inability to follow the softness of the fabric.

  Heretofore, methods have been proposed in which a thin metal layer is formed on a fabric via an adhesive or the like for the purpose of decoration or the like (Patent Documents 3 and 4). In addition, an electronic garment has been proposed in which an electronic circuit or the like is formed on a cloth by an inkjet printing method (Patent Document 5).

JP, 2013-019064, A JP, 2014-151018, A JP 07-216765 A Japanese Patent Application Publication No. 2003-073982 JP 2005-146499 A

  An object of the present invention is to provide a conductive fabric having sufficient conductivity without impairing the softness inherent to the fabric and having excellent followability to the shape change such as bending and durability, and a method for producing the same.

  As a result of intensive studies, the present inventors have found that a conductive fabric having an undercoating layer, an adhesive layer, a metal foil and a cover coat on the fabric can solve the above-mentioned problems, and complete the present invention. It reached. Moreover, about this conductive fabric, after forming a plating resist layer which has a pattern reverse to a desired conductive pattern with a plating resist on a support body, after forming a pattern-like metal foil layer by electroplating, this is used as a fabric By sticking and peeling a support body, it discovered that the electroconductive fabric which has a desired conductive pattern was obtained, and came to complete this invention.

That is, the present invention relates to a conductive cloth and a method for producing a conductive cloth described below.
(1) On the fabric, a base coating layer formed of a resin material composed of a urethane resin or a silicone resin , a patterned adhesive layer, and a patterned metal foil are sequentially laminated in this order, and at least a patterned metal foil A conductive coat having a cover coat for covering the base coating layer, wherein the peel strength of the resin material forming the underlying coating layer makes the resin material a film of 20 .mu.m in thickness, at a tensile speed of 50 mm / min according to JIS-C5016. A conductive fabric having a peel strength of at most 0.05 N / mm when peeled off from a PET film having a thickness of 100 μm at 90 °.

(2) The conductive fabric according to (1), wherein the peel strength of the resin material forming the adhesive layer is 0.1 N / mm or more.
(3) The conductive fabric according to (1), wherein the metal foil is a copper foil.
(4) The conductive fabric according to (1), wherein the thickness of the metal foil is 1 to 30 μm.

(5) A method of producing a conductive fabric comprising a base coating layer, a patterned adhesive layer, and a patterned metal foil sequentially laminated in this order on a fabric and having a cover coat covering at least the patterned metal foil. A method for producing a conductive fabric, comprising the following steps (a), (b) and (c):
(A) A supported metal pattern having a base coating layer on at least one side, a support, a patterned metal foil, and a patterned adhesive layer formed on the surface of the patterned metal foil; Bonding the base coating layer and the patterned adhesive layer so as to overlap with each other,
(B) peeling the support from the patterned metal foil with support, transferring the patterned metal foil onto the fabric, and (c) applying a cover coat so as to cover at least the patterned metal foil

(6) The patterned metal foil with a support prints a plating resist on the release layer of a support having a substrate and a release layer, and has a plating resist layer having a pattern reverse to the desired conductive pattern. After formation, the support is subjected to electroplating to form a patterned metal foil layer having a desired conductive pattern, and then a resin material for adhesive layer is selectively applied on the patterned metal foil layer. (5), which is obtained by forming a patterned adhesive layer.

(7) The method according to (6), wherein the release layer is a nickel-tin thin film layer formed on a substrate by an electric nickel-tin plating treatment.

  In the present invention, conductivity can be easily imparted on the fabric by attaching a thin metal foil to the fabric via the adhesive layer. By selecting the type and thickness of the metal foil or adhesive to be used, it is possible to obtain a conductive fabric having high durability to bending following the flexibility without losing the flexibility of the fabric.

It is the schematic (cross-sectional structure) which shows an example of the electroconductive fabric of this invention.

1 ··· Patterned metal foil 2 · · · Patterned adhesive layer 3 · · · Fabric 4 · Undercoating layer 5 · · · Cover coat

1. Conductive Fabric FIG. 1 shows a schematic view of the cross-sectional configuration of the conductive fabric of the present invention. According to FIG. 1, in the conductive fabric of the present invention, (i) the base coating layer 4 is laminated on the fabric 3 as a layer structure, and (ii) the pattern-like adhesive layer 2 and (iii) the pattern The metal foil 1 is sequentially laminated, and the cover coat 5 is formed so as to cover at least the (iii) pattern metal foil 1.

(1) Cloth As a cloth used for the present invention, textiles, such as textiles, a knit, and a nonwoven fabric, can be mentioned, for example. Moreover, as the fiber material, for example, natural fibers such as cotton, hemp, wool and silk, regenerated fibers such as rayon and cupra, semi-synthetic fibers such as acetate and triacetate, polyamide (nylon 6, nylon 66 etc.), polyester ( Examples thereof include polyethylene terephthalate, polytrimethylene terephthalate and the like), synthetic fibers such as polyurethane and polyacryl, and the like, and two or more of these may be combined. Among them, a fabric made of synthetic fibers excellent in all fiber properties is preferable, and a fabric made of polyester fibers is particularly preferable.
The fiber cloth may be subjected to dyeing, antistatic treatment, flame retardant treatment, calendering, etc., as necessary. The thickness of the fabric is not particularly limited, but is preferably about 0.02 to 1 mm.

(2) Base Coating Layer The base coating layer in the present invention is responsible for the function of chemical protection such as waterproofing and mechanical protection for preventing tearing of metal foil. The undercoating layer may be formed as a layer on the surface of the fabric, or may be in the form of covering the entire fabric.

  In the case of using a relatively dense structure fabric such as a plain weave fabric or a fabric having few surface irregularities, the base coating is mainly provided for the purpose of waterproofing (chemical protection) of the fabric. In that case, for example, the fabric is dipped in a resin material (hereinafter, may be referred to as a "base coating agent") forming the base coating layer, and the base coating layer is formed by filling the base coating agent in the gaps between the yarns. be able to. At this time, the entire fabric is covered with a thin undercoating layer (film), and the undercoating layer may not necessarily be formed as a separate layer on the cloth.

  On the other hand, in the case of a fabric having a large surface asperity and a relatively rough fiber structure such as a knitted fabric, the base coating is mainly provided for the purpose of smoothing the surface of the fabric. In that case, it is preferable to laminate the base coating layer having a certain thickness to the surface of the fabric as a separate layer. The purpose is not only waterproofing of the fabric but also mechanical protection to prevent tearing of the metal foil.

  Since the fabric is formed by overlapping and entanglement of yarns, the surface has fine irregularities. On the other hand, since the metal foil layer is formed on the fabric so as to bridge the convex portions of the fabric, when the fabric is bent, the overlapping and entangled yarns are displaced, and the distance between the convex portions of the fabric is greatly varied. Directly, the metal foils torn are broken. The base coating is considered to have the effect of preventing tearing of the metal foil by eliminating unevenness on the surface of the fabric to make it flat and suppressing individual movement (displacement) of the yarns constituting the fabric.

  The preferred thickness of the undercoating layer is 1 to 50 μm. By providing the base coating layer having such a thickness, it is possible to maintain conductivity while having flexibility, without tearing the metal foil even if the conductive fabric is bent.

As the resin material for forming the underlying coating layer state, and are not without impairing the soft texture of and fabric in those with waterproof (having a function of protecting the metal foil to form a circuit and the like), urethane resins or a resin material is used made of silicone resin. More specifically, polyurethane resin such as polyether polyurethane resin, polyester polyurethane resin, urethane modified epoxy resin, urethane modified acrylic resin, urethane modified resin such as urethane modified polyester resin, silicone resin, silicone modified epoxy resin, silicone Silicone modified resin, such as a modified polyester resin and a silicone modified phenol resin, etc. are mentioned.

  The underlying coating layer preferably does not have such strong adhesion as the adhesive layer. Specifically, in the undercoating layer of the present invention, the peeling strength of the resin material forming the same is 100 μm thick at a tensile speed of 50 mm / min according to JIS-C5016, using the resin material as a film of 20 μm thick. The peel strength at the time of peeling off from the PET film at 90 ° is required to be 0.05 N / mm or less, preferably 0.01 N / mm or less. As described above, in the present invention, such a low adhesion resin material is used to form the base coating layer.

This is because the conductive fabric of the present invention is produced by the method specific to the present invention described later.
That is, the conductive fabric of the present invention comprises (a) a fabric having a base coating layer on at least one side, a support, a patterned metal foil, and a patterned adhesive layer formed on the surface of the patterned metal foil. Bonding the body-like patterned metal foil so that the base coating layer and the pattern-like adhesive layer overlap, (b) peeling the support from the support-like patterned metal foil, and patterning the fabric It can be manufactured by the method including the steps of transferring the metal foil and (c) applying a cover coat so as to cover at least the pattern metal foil.

  In such a manufacturing method, it is important that the base coating layer of the fabric is not adhered to the support when the cloth and the support-attached pattern-like metal foil are attached to each other in the step (a). If the base coating layer adheres to the support, the support may not be easily peeled off from the patterned metal foil with a support in the next step (b).

  The peel strength between the underlying coating layer and the support needs to be sufficiently smaller than the peel strength between the adhesive layer and the patterned metal foil, specifically 0.05 N / mm or less, preferably 0.01 N / Mm or less.

  If the adhesion of the resin material for the base coating layer is strong and the value of the peel strength is too large, the base coating layer adheres to the support during the production of the conductive fabric, and the support is simply pulled from the patterned metal foil. There is a possibility that the conductive cloth of the present invention can not be obtained. Alternatively, the plating resist layer or the peeling layer on the support may break and adhere to the fabric side (the surface of the base coating layer), which may cause a problem of contamination and / or foreign matter adhesion.

The peeling strength in the present invention is peeling according to JIS-C5016 “Peeling strength of conductor” (90 ° peel peeling test) at a tensile speed of 50 mm / min and a tensile length of 50 mm for 1 minute. The test was conducted, and the maximum value of the peel strength in the measurement range (the maximum value of the peel strength measured within this peel time) was evaluated as the peel strength in the present invention. Specifically, after a resin material to be an adhesive layer or a base coating layer is formed on a PET film to a thickness of 20 μm, another PET film is overlapped and bonded, and then a PET film on one side is fixed to The maximum value of the peel strength when one PET film is peeled at 90 ° is taken as the peel strength (N / mm) of the present invention. The PET film used for measurement of peel strength is a 100 μm thick diafoil (made by Mitsubishi resin).
As a resin material of the base coating layer used by this invention, the thing whose peeling strength calculated | required by the said peeling test is 0.05 N / mm or less, Preferably 0.01 N / mm or less is used.

(3) Adhesive layer The adhesive layer in the present invention is selectively formed on the side of the patterned metal foil, and is used to bond the fabric and the patterned metal foil. The adhesive material constituting the adhesive layer is particularly good as long as it has good adhesion to both the fabric (including the base coating layer) and the patterned metal foil and does not impair the feel of the fabric. For example, a urethane resin or an acrylic resin can be used without limitation. From the viewpoint of workability, those having hot melt properties are preferably used. In the case where waterproofing is the main purpose, urethane resins are particularly preferred. More specifically, a one-part moisture-curable urethane adhesive is preferred.
The thickness of the adhesive layer is not particularly limited, but preferably about 1 to 50 μm.

The adhesive layer preferably has high adhesion to a certain extent unlike the base coating layer. Specifically, in the adhesive layer of the present invention, the peeling strength of the resin material forming the PET film makes the resin material a film with a thickness of 20 μm, and the PET with a thickness of 100 μm at a tensile speed of 50 mm / minute according to JIS-C5016. It is preferable that it is 0.1 N / mm or more as peeling strength at the time of tearing off at 90 degrees from a film, More preferably, it is 0.5 N / mm or more.
In the present invention, the adhesive layer is formed of a resin material having adhesiveness sufficiently higher than that of the resin material forming the base coating layer.

  This is because, as described above, the conductive fabric of the present invention is produced by the method specific to the present invention described later. That is, in the production method of the present invention, in the step (a), the cloth and the patterned metal foil with a support are bonded with the adhesive layer interposed therebetween, and then in the step (b) The body is peeled off and the patterned metal foil is transferred onto the fabric. It is important to ensure that the pattern metal foil is transferred after peeling off the support by firmly adhering the fabric and the support pattern metal foil.

  The peel strength between the underlying coating layer and the support needs to be sufficiently smaller than the peel strength between the adhesive layer and the patterned metal foil, specifically 0.05 N / mm or less, preferably 0.01 N / Mm or less.

  When the adhesiveness of the resin material for adhesive layer is weak and the value of the peel strength is too small, the pattern metal foil simultaneously peels when peeling the support from the pattern metal foil, and the pattern metal foil is reliably transferred to the fabric. It may not be possible to transfer.

(4) Metal foil As a metal which comprises metal foil, copper, nickel, tin, zinc, chromium, silver, gold etc. are mentioned. Particularly preferably, copper foil is used. The thickness of the metal foil is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm.

(5) Cover Coat The cover coat of the present invention is formed to cover at least the patterned adhesive layer and the patterned metal foil formed on the base coating layer. This is mainly formed for the purpose of insulation, waterproof, tear prevention, etc. of the pattern-like metal layer formed on the fabric.

  The resin material used for the cover coat is not particularly limited, but urethane resins and silicone resins are preferable. More specifically, polyurethane resin, silicone resin and the like can be mentioned. More specifically, polyether polyurethane and the like can be mentioned. The same resin material as that of the underlying coating layer may be used.

  The thickness of the cover coat is about 5 to 20 μm. When the thickness of the cover coat is too thick, the feeling may be lowered, and when it is too thin, the effect of preventing insulation and breakage may be insufficient. Here, the thickness of the cover coat is from the surface of the base coating layer of the fabric to the surface of the cover coat layer.

2. Method for Producing Conductive Fabric The conductive fabric of the present invention is not particularly limited in the method for producing the conductive fabric, but is preferably produced by a method including the following steps (a), (b) and (c).

(A) A supported metal pattern having a base coating layer on at least one side, a support, a patterned metal foil, and a patterned adhesive layer formed on the surface of the patterned metal foil; Bonding the base coating layer and the patterned adhesive layer so as to overlap with each other,
(B) peeling the support from the patterned metal foil with support and transferring the patterned metal foil onto the fabric, and (c) covering the patterned adhesive layer and the patterned metal foil so as to cover at least the patterned adhesive layer and the patterned metal foil. Process of applying

(1) Fabric having base coating layer The fabric used in step (a) of the method of the present invention has a base coating layer on at least one side, and the base coating layer is formed as a layer on the surface of the fabric It may be in the form of covering the entire fabric.

  Examples of the method of forming the undercoating layer on the fabric include a method of immersing the cloth in the undercoating agent, and a method of coating by an applicator, knife, roller, brush, dispenser, ink jet printing, screen printing and the like. In the case of the method of immersing the fabric in the base coating agent, the fabric is dipped and then dried by a conventional method.

(2) Patterned metal foil with a support The patterned metal foil with a support used in the method of the present invention has a support, a patterned metal foil, and a patterned adhesive layer formed on the surface of the patterned metal foil. It can be produced by the following method. That is, the patterned metal foil with a support is formed by printing a plating resist on the release layer of a support having a substrate and a release layer to form a plating resist layer having a pattern reverse to the desired conductive pattern. Then, the support is subjected to electroplating to form a patterned metal foil layer having a desired conductive pattern, and then the resin material for adhesive layer is selectively applied on the patterned metal foil layer. It is obtained by forming a patterned adhesive layer.

1) Support (base and release layer)
The support used in the present invention has a substrate and a release layer. As a base material, a metal laminated body etc. which laminated a metal on a metal thin film, a resin film, etc. are mentioned. An organic film or an inorganic film is used as the peeling layer.

  The patterned metal foil of the present invention is formed on the release layer of the support. The release layer prevents the pattern-like metal foil from being bonded too strongly to the substrate of the support, and easily peels off when peeling the support from the pattern-like metal foil in the step (b) in the above-mentioned manner. This has the effect of enabling the metal layer to be transferred to the fabric side. The thickness of the release layer is not particularly limited, but preferably about 0.05 to 1 μm, more preferably about 0.1 to 0.5 μm.

  As an organic type film which can form a exfoliation layer, films, such as a nitrogen content organic compound, a sulfur content organic compound, carboxylic acid, etc. are mentioned, and 1 type or 2 types or more can be mixed and used among these.

Specifically, as the nitrogen-containing organic compound, 1,2,3-benzotriazole which is a triazole compound having a substituent, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H -1,2,4-triazole and 3-amino-1H-1,2,4-triazole etc. are mentioned. Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid and 2-benzimidazolethiol. As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid and the like.
As a method of forming an organic type film on a substrate, a conventionally known application method such as an immersion method, a spray method and the like can be adopted according to the type of the compound.

As an inorganic type film which can form a exfoliation layer, a film made of an alloy mainly composed of nickel or aluminum, an oxide of nickel or aluminum, or an inorganic compound such as a sulfide is mentioned.
As a method of forming an inorganic type film | membrane on a base material, the electroplating method, the electroless-plating method, the vapor deposition method etc. are employable according to the kind of film | membrane material, for example.

  Among these, inorganic films are preferable, and further, a nickel-tin thin film formed by electric nickel-tin plating is preferable. The method of electro nickel-tin plating is not particularly limited, and a conventionally known method can be adopted.

  As the substrate used in the present invention, the surface roughness is Ra = 0.5 μm or less in order to ensure the releasability between the release layer formed on one side and the pattern-like metal foil layer formed thereon by plating treatment It is desirable to use If the roughness of the substrate surface is too large, the irregularities on the surface of the release layer formed on the substrate tend to be large, and the surface of the release layer having the irregularities is plated to form a patterned metal foil layer In this case, the plating metal intrudes into the irregularities, so the adhesion between the patterned metal foil layer and the peeling layer becomes too high due to the anchor effect, and as a result, the peeling property of the patterned metal foil layer from the peeling layer decreases. There is. The lower limit of the surface roughness is not particularly limited, but preferably Ra = 0.005 μm or more.

  Moreover, when forming a nickel-tin thin film layer by an electric nickel-tin plating process as a peeling layer on the base material used by this invention, it is preferable that the said base material has electroconductivity in the at least single side | surface. . More preferably, a substrate having a surface resistance of 0.3 Ω / □ or less is preferable. If the conductivity is low, the electro nickel-tin plating process can not be performed sufficiently, and it may be difficult to form a nickel-tin thin film layer as a release layer. The lower limit of the surface resistance is not particularly limited, but is preferably 0.001 Ω / □ or more.

In the present invention, it is desirable to select a metal thin film, a metal laminate, and the like provided with the conditions as described above as the base material of the support.
Examples of the metal used for the base metal thin film include copper, aluminum, nickel, titanium and stainless steel. Of these, copper is particularly preferred. When aluminum is used, it is preferable to perform known pretreatment such as zincate treatment so that the aluminum thin film is not dissolved in the plating solution.

  The thickness of the base metal thin film is not particularly limited, but preferably about 18 to 500 μm. In addition, when using the metal thin film for base materials which consists of a single metal as a base material, and using an alloy or a metal compound (oxide, sulfide etc.) as a peeling layer, only the surface part of the metal thin film for substrates is oxidized and this An oxide film can also be used as a release layer. As an example, using metal aluminum as a metal thin film for a substrate, oxidizing only the surface part, and using this oxide film as a exfoliation layer etc. is mentioned.

  The metal laminate for a substrate of the present invention is various films in which a metal is laminated on at least one surface of a lamination base film such as a resin film. Examples of the metal include copper and aluminum. As a base film for lamination, PET (polyethylene terephthalate), polyimide, PEN (polyethylene naphthalate) and the like can be mentioned. The thickness of the laminating base film is not particularly limited, but preferably about 25 to 125 μm. Although the thickness in particular of the metal layer laminated | stacked is not restrict | limited, Preferably it is about 0.05-20 micrometers.

  The conditions for lamination are not particularly limited, and conventionally known methods such as a method of bonding a metal thin film and a base film for lamination, a method of forming a metal layer on the resin film surface by metal plating or metal deposition, etc. it can. Moreover, a commercially available vapor deposition film can also be used.

2) Plating Resist In the present invention, a plating resist is printed on the peeling layer of the above-mentioned support to form a plating resist layer having a pattern reverse to the desired conductive pattern (hereinafter, simply referred to as "reverse pattern").

  The plating resist used in the present invention is not particularly limited as long as it adheres to the peeling layer, has chemical resistance to a plating solution used in a plating process described later, and does not have conductivity.

  As a method of forming a reverse pattern-like plating resist layer, it is preferable to cure the plating resist printed in the reverse pattern. The curing method may be either thermal curing or ultraviolet curing. Therefore, the plating resist of the present invention may be a thermosetting type or an ultraviolet curing type.

In the plating resist, usually, a solvent, a binder resin, a coloring component, an additive and the like are appropriately blended as needed.
As the binder resin, resins such as epoxy resins, polyester resins, acrylic resins and isocyanate resins can be used. The binder resin may be thermosetting or ultraviolet curing.

An epoxy resin, carboxylic acid acrylic polymer, etc. are mentioned as a thermosetting type binder resin.
Examples of the epoxy resin include bisphenol A liquid epoxy resin, cresol novolac epoxy resin, and phenol novolac epoxy resin. Specifically, "EPICLON 850" (epoxy equivalent 188) as the epoxy resin, "EPICLON N-665" (epoxy equivalent 202-212) as the cresol novolac epoxy resin, "EPICLON N-680" (epoxy equivalent 206) ~ 216), “EPICLON N-695” (epoxy equivalent 209 to 219), and as a phenol novolac epoxy resin, “EPICLON N-775” (epoxy equivalent 184 to 194) (all are trade names, manufactured by DIC Corporation), etc. Is mentioned

  As a carboxylic acid acrylic polymer, “JONCRYL 682” (molecular weight 1700, solid content acid number 240 mg KOH / g), “JON CRYL 683” (molecular weight 8000, solid content acid number 165 mg KOH / g) (all are trade names, BASF Japan Ltd.) Product), "ARUFON UC-3000" (molecular weight 10000, solid content acid number 74 mg KOH / g), "ARUFON UC-3 900" (molecular weight 4600, solid content acid number 108 mg KOH / g) (all are trade names, Toagosei Co., Ltd. And the like.

  As the UV-curable binder resin, monomers or oligomers containing a double bond such as an acryloyl group or a methacryloyl group can be used. Specific examples include monofunctional acrylates such as 2-hydroxy-3-phenoxypropyl acrylate and nonylphenol EO-modified acrylate, bifunctional acrylates such as bisphenol AEO-modified diacrylate and tripropylene glycol diacrylate, pentaerythritol triacrylate and trimethylolpropane Examples include triacrylate, trimethylol EO-modified propane triacrylate, dipentaerythritol hexaacrylate and the like.

  The binder component can be in the range of 10% to 100% as the solid content concentration of the resist ink.

  The solvent is not particularly limited, but water; hydrocarbons such as hexane, cyclohexane and heptane; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum naphtha; methanol, ethanol, n-propyl alcohol, isopropyl alcohol and the like Alcohols; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate, isopropyl acetate, butyl acetate and γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol, diethylene glycol, propylene glycol, Glycols such as dipropylene glycol, 1,3-butylene glycol and tripropylene glycol; ethylene glycol monomethyl ether acetate, pro Pyrene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate (BCA; butyl carbitol acetate), dipropylene glycol monomethyl ether acetate (DPMA), propylene glycol monomethyl ether, propylene glycol n- Glycol esters such as propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, diethylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, etc. Glicor Ethers; glycol esters ethers; dimethyl sulfoxide, N, N- dimethylformamide, N- methylpyrrolidone and the like.

As the coloring component, whether it is an inorganic type or an organic type, known pigments and dyes which have been conventionally used in inks can be used.
In addition, various additives can be added as needed. Specific examples of such various additives include surface conditioners, antifoaming agents, leveling agents, rheology control agents, curing accelerators and the like.

  As a surface conditioner, for example, BYK-300, BYK-301, BYK-306 etc. (all are trade names, made by BIC Chemie Japan KK) as a silicone type surface conditioner, BYK-350 as an acrylic type surface conditioner. , BYK-352, BYK-354, etc. (all are trade names, manufactured by Big Chemie Japan Ltd.).

As an antifoamer, BYK-051, BYK-052, BYK- 053 grade | etc., (All are brand names and BIC Chemie Japan KK-made) are mentioned.
As a leveling agent, BYKETOL-OK, BYKETOL-SPECIAL, etc. (all are brand names and BIC Chemie Japan KK-made) are mentioned.

As a rheology control agent, BYK-405, BYK-410 grade | etc., (All are a brand name and BIC Chemie Japan KK-made) are mentioned.
The solvent and various additives can be used as appropriate, for example, to adjust the viscosity, printability, etc. of the plating resist.

  In particular, it is preferable to add a curing accelerator to the plating resist. By adding a hardening accelerator to the plating resist, a patterned metal foil having a more precise pattern can be obtained. This is because the resist ink is cured immediately after printing, and the spread and spread of the pattern due to the flow of the ink are suppressed, and a more delicate resist pattern is obtained, compared with the case where the curing accelerator is not added. It is considered that the plating process gives a precise patterned metal foil.

  The curing accelerator should be selected in accordance with the binder resin. Specifically, for epoxy resins, imidazole compounds, amine compounds and the like are preferably used. Examples of the imidazole compound include cuazole series (all trade names) manufactured by Shikoku Kasei Kogyo Co., Ltd. such as "SIZ", "2MZ-H", and "2MZ-OK". Examples of the amine compound include Amicure series (all trade names) manufactured by Ajinomoto Fine Techno Co., Ltd. such as "PN-23", "PN-H" and "PN-31".

  Examples of isocyanate-based binder resins include amines such as triethylamine, triethylenediamine, and diazabicycloundecene, and tributyltin dilaurate.

  For UV-curable resins, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, trade name: Irgacure 184), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On (BASF, trade name; Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (BASF, trade name; Irgacure 369), 2, 4, 6 -Photopolymerization initiators such as trimethyl benzoyl diphenyl phosphine oxide (manufactured by BASF, trade name: Lucirin TPO), and sensitizers such as diethyl thioxanthone.

  The compounding ratio of the curing accelerator to the plating resist is not particularly limited, and can be appropriately adjusted.

  The plating resist used in the present invention is preferably one that can form a plating resist layer having high adhesion to the release layer. In addition, the plating resist preferably has chemical resistance to a plating solution used in a plating process described later.

The plating resist preferably has a volume resistivity of 10 ⁸ Ω · cm or more. If the volume resistivity is less than 10 ⁸ Ω · cm, the plated metal may be deposited on the surface of the plating resist layer during electroplating, so that a precise patterned metal foil may not be obtained. . For the same reason, it is preferable that the coloring component used for the plating resist does not contain a conductive component such as metal fine particles.

3) Printing of plating resist As a printing method when printing a plating resist on the release layer, it is possible to apply known methods such as gravure printing, screen printing, photolithography, gravure offset printing, flexographic printing, inkjet printing, etc. it can. Among these, inkjet printing, screen printing and the like are preferable.

  The thickness of the plating resist layer formed on the peeling layer can ensure insulation and is preferably thinner than the thickness of the metal foil formed in a later step, and more preferably about 0.1 μm to 2 μm.

  The thickness of the plating resist layer can be adjusted, for example, in the case of screen printing, by optimizing the plate emulsion thickness and the ink viscosity. In the case of gravure and gravure offset printing, adjustment can be made by optimizing the engraving depth of the gravure plate recess and the viscosity of the ink. In the case of inkjet printing, adjustment can be performed by controlling the size and the number of ejections of ink droplets ejected from the inkjet nozzle.

  After printing the plating resist, the formed plating resist layer is cured. When a thermosetting type plating resist is used, it is preferable that the temperature be low and the heating time (drying time) be short, from the industrial viewpoint such as production cost. Curing is preferably performed at 50 to 150 ° C. for 5 to 60 minutes. In the case of using a UV-curable plating resist, UV light having a wavelength of 200 nm to 400 nm may be irradiated so as to be an integrated light amount necessary for curing of the plating resist.

4) Plating Treatment In the present invention, after forming a plating resist layer on the release layer, the support is plated to form a metal foil layer on the portion other than the plating resist layer on the release layer. At this time, since the plating resist layer is formed in a reverse pattern to the desired conductive pattern, a patterned metal foil layer having the desired conductive pattern is formed.

The plating treatment may, for example, be electroplating or electroless plating. As an example of the plating process, the electrolytic copper plating process will be described below.
As the electrolytic copper plating treatment, conventionally known methods such as a method using a copper sulfate plating bath can be appropriately used. The conditions for the plating treatment may be those conventionally known.
The thickness of the copper foil formed on the release layer can be adjusted by changing the current density and the reaction time based on known techniques.

In the case where a copper foil plating process is adopted as the plating process of the present invention to form a patterned copper foil layer on a peeling layer of a support, copper electroplating such that the thickness of the copper foil satisfies the above conditions Preferred conditions for treatment include, for example, current density: 0.2 to 5 A / dm ² , reaction time: 0.5 minutes to 30 minutes, and the like.

  The thickness of the patterned metal foil layer thus formed is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm.

5) Formation of adhesive layer After forming a patterned metal foil layer having a desired conductive pattern on the release layer of the support, a resin material for adhesive layer is selectively applied on the patterned metal foil layer To form a patterned adhesive layer. As a method of forming an adhesive layer, a method of selectively applying a resin material for an adhesive layer only on the patterned metal foil layer can be used using known techniques such as various printing techniques, dispensers, and inkjets. . As a result, an adhesive layer having the same desired conductive pattern as the patterned metal foil is formed on the patterned metal foil, and the “support, the patterned metal foil and the pattern formed on the patterned metal foil surface according to the present invention are formed. A patterned metal foil with a support having the adhesive layer is obtained.

(3) Bonding In the present invention, the "fabric having a base coating layer on at least one surface" obtained by the above-described method, "a support, a patterned metal foil, and a patterned shape formed on the surface of the patterned metal foil. The support-attached pattern-like metal foil having an adhesive layer is pasted so that the base coating layer and the pattern-like adhesive layer overlap (step (a)). That is, the patterned metal foil on the support is bonded to the cloth with the adhesive layer interposed therebetween.

As a method of bonding, thermocompression bonding is preferable. The conditions for the thermocompression bonding are not particularly limited, but preferably the temperature is 80 to 150 ° C., the pressure is 0.5 to 2.0 kgf / cm ² , and the time is 1 to 5 minutes.

(4) Peeling of Support After laminating the patterned metal foil with a support and the fabric, the support is peeled from the patterned metal foil, and the patterned metal foil is transferred onto the cloth (step (b )). The peel strength between the fabric and the patterned metal foil bonded by the adhesive layer is preferably sufficiently larger than the peel strength between the patterned metal foil and the support.

  In the present invention, the above-described support contains a release layer, and the release layer and the patterned metal foil have appropriate release properties and can be easily removed. Can be easily peeled off from the patterned metal foil in the peeling layer. The release layer remains on the support side. By making the support easily peelable in this manner, a precise patterned metal foil can be easily transferred to the fabric.

(5) Formation of Cover Coat In the method of the present invention, after the support is peeled off and the patterned metal foil is transferred to a fabric, a cover coat is applied so as to cover at least the patterned metal foil (step (c)) . The cover coat is mainly intended to insulate, waterproof, and prevent breakage of the pattern-like metal layer formed on the fabric. Preferably, the cover coat is formed to cover at least the pattern-like adhesive layer and the pattern-like metal foil formed on the base coating layer, and may be formed to cover the entire conductive fabric.

  The method for forming the cover coat is not particularly limited, but for example, it may be formed by applying a resin material (cover coat agent) for a cover coat using an applicator on the surface of the fabric to which the pattern copper foil has been transferred. it can.

  The conductive fabric obtained by the method of the present invention is excellent in flexibility (flexibility) and followability, has high durability to bending, and is resistant to tearing of the patterned metal foil, so the high conductivity lasts for a long time. Therefore, it can utilize suitably for an information terminal, a sensor cloth, a sheet material etc.

EXAMPLES The present invention will be described by way of examples, but the present invention is not limited by these examples.
The evaluation method of various physical properties in this example is as follows.

<Flexibility (flexibility)>
The conductive fabric was bent 10 times, and the resistance value before and after the bending was measured to confirm the presence or absence of breakage. Specifically, first, the resistance between any two points on the conductive fabric is measured, and then the metal foil transfer surface is inside at any place between the two points, and a bending tester (manufactured by Yasuda Seiki Seisakusho) Was carried out 10 times (bending speed 1 time / sec) using 180 degrees of bending. After that, the resistance between the same two places was measured again and evaluated according to the following criteria.
;: The resistance did not change even after bending 10 times.
X: The resistance value changed (increased) after bending 10 times.
In addition, the measurement of resistance value was performed using Hioki Electric Co., Ltd. 3256-50 digital high tester.

<Water resistance>
The conductive fabric was immersed in brine (NaCl; 0.5 wt%) and a voltage of 1.58 V was applied between the two rows of patterned copper foil. The resistance between the two lines of the pattern 5 minutes after the application of the voltage was measured using a 3254-50 digital high tester manufactured by Hioki Electric Co., Ltd.

Example 1
(1) Preparation of Patterned Metal (Copper) Foil with Support Using the following plating solution 1 (pH 10.5) with a copper-deposited polyimide film (made by Toray KP film: copper thickness 1 μm) as the base layer of the support The electrolytic nickel-tin plating process was performed, and the peeling layer was formed in the copper vapor deposition side of the base layer. The plating processing temperature is 40 ° C., and the current density is lowered in the order of 0.085 A / dm ² , 0.055 A / dm ² and 0.030 A / dm ² , and the processing time at each current density is 74 seconds, 74 seconds and 74 It was in seconds. No aeration was performed using an insoluble electrode at the anode. The thickness of the obtained release layer was 0.1 μm.

(Plating solution 1)
Nickel (II) sulfate, hexahydrate; 30 g / L
Tin (II) sulfate; 6 g / L
Sodium gluconate; 75 g / L
Glycine; 15 g / L

  Next, pattern printing was performed on the release layer by an inkjet method using a plating resist, and a plating resist layer having a pattern reverse to the desired conductive pattern was formed. The plating resist used here is 90% by weight of acrylic monomer (trade name "2-hydroxyethyl acrylate", manufactured by Kyoeisha Chemical Co., Ltd.) as a resin, and photopolymerization initiator (trade name "1-hydroxy" as a polymerization initiator. What contained 10 weight% of "cyclohexyl phenyl ketone" (made by BASF Corporation) was used. Thus, a support having a plating resist layer having a pattern reverse to the target conductive pattern formed on the release layer was obtained.

Subsequently, the support was subjected to electrolytic plating for 5 minutes at a current density of 2 A / dm ² using a copper sulfate plating solution to form a patterned copper foil layer having a desired conductive pattern. As the copper sulfate plating solution, 120 g / l of copper sulfate, 150 g / l of sulfuric acid and 50 mg / l of chlorine ions were used. According to the above process, a patterned copper foil was formed on the support in which copper foils with a line width of 5 mm, a line length of 150 mm, and a metal (copper) film thickness of 5 μm were arranged in parallel in parallel at 5 mm intervals.

  Next, on the surface of the patterned copper foil, a one-component moisture-curable polyurethane resin solution (trade name "NH320" manufactured by DIC Corporation), which is a hot-melt adhesive material, is dispensed with a dispenser (trade name "Made by Iwashita Engineering Co., Ltd." It applied selectively using AD3300C "), and made it solidify at 23 degreeC for 5 minutes, and formed the pattern-like adhesive layer. Thus, a patterned metal (copper) foil with a support of the present invention was obtained.

(2) Preparation of conductive fabric A polyester plain woven fabric as a fabric is dipped in a polyurethane resin aqueous coating agent and then dried at 80 ° C. for 10 minutes to form a base on the fabric including the gaps of the yarns constituting the fabric. A coating layer was formed. Here, as the polyester plain weave used, a plain weave made of polyethylene terephthalate fibers, having a vertical yarn density of 114 / inch and a weft yarn density of 84 / inch was used. Moreover, as a polyurethane resin aqueous coating agent, it is composed of 50% by weight of "Hydran WLS-202" manufactured by Dainippon Chemical Co., Ltd. and 50% by weight of water, and the viscosity is 3 mPa · s (B type rotational viscometer, 25 (50 ° C.) was used. The polyurethane resin is a polyether-based polyurethane having water resistance, thereby obtaining a fabric having a water-resistant base coating layer (average thickness: 3 μm).

Next, the above-described patterned copper foil with a support and a fabric are stacked so that the surface of the pattern-like adhesive layer formed on the patterned copper foil and the undercoat coating layer of the fabric are in contact with each other. The bonding temperature was 120 ° C., the pressure was 1 kgf / cm ² , and the time was 1 minute. The support was then peeled off from the patterned copper foil and the patterned copper foil was transferred onto the fabric.

  The peel strength of each of the base coating layer and the resin material used to form the adhesive layer was evaluated by the following method. The peel strength in this example is the maximum value within the measurement range by carrying out a peel test at a tensile speed of 50 mm / min according to JIS-C5016 "Peel-off strength of conductor" (90 peel peel test). It is evaluated by asking for.

First, on a PET film for evaluation (Mitsubishi Resins Co., Ltd., trade name "Diafoil", thickness 100 μm), resin material for base coating layer (polyurethane resin aqueous coating agent) and resin material for adhesive layer (1 The liquid moisture curing type polyurethane resin was separately applied to form a resin film having a thickness of 20 μm. Subsequently, another PET film was laminated | stacked on each, and it bonded together by the bonding temperature of 120 degreeC, and the pressure of 1 kgf / cm < ² >. Thereafter, the PET film on one side was fixed and the other PET film was peeled off at an angle of 90 °, and the maximum value of the peeling strength at that time was taken as the peeling strength.

  The resin material for base coating layers showed almost no adhesiveness, and the peel strength was 0.001 N / mm. On the other hand, the resin material for adhesive layer showed strong adhesiveness and peel strength was 0.7 N / mm.

  Subsequently, a polyurethane resin was applied using an applicator (trade name "Baker-type applicator" manufactured by Tester Sangyo Co., Ltd.) on the surface of the above-mentioned fabric on which the patterned copper foil was transferred, and a cover coat was applied. The polyurethane resin used here contains 97% by weight of "Hydran WLS-202" manufactured by Dainippon Chemical Co., Ltd., and 3% by weight of "Senka Actogel NS100" manufactured by Senka Co., Ltd. as a thickener. It is a thing.

In addition, it was confirmed that the surface resistance value of the polyurethane resin for cover coat is 10 ¹³ Ω / □ or more (measuring device: “Hiresta UP” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and that it has insulation.

  As a result, a conductive fabric of the present invention having a cover coat made of a polyurethane resin having a water resistance and an insulating resin film thickness of 10 μm was obtained. Even if it bent, the obtained conductive fabric did not tear a copper foil, but had flexibility (flexibility evaluation "(circle)"). Moreover, in water resistance evaluation, the resistance value 5 minutes after voltage application is 42 M (ohm) (measurement upper limit of an apparatus), and it was shown that there is sufficient water resistance.

Example 2
As the fabric, a warp-knitted material (material: polyethylene terephthalate fiber, thickness: 300 μm) was used, and the base coating agent was filled and solidified on the fabric including the gaps of the yarns constituting the fabric. In addition, since the texture of the knitted fabric is coarser than that of the plain woven fabric, when forming the base coating layer, the gap between the yarns was sufficiently filled with the resin using an applicator to form a smooth flat surface.

  As a base coating agent, 97% by weight of a polyurethane resin (trade name; "Hydran WLS-202") manufactured by Dainippon Chemical Industry Co., Ltd. and a thickener (trade name: Senka Actogel NS100 manufactured by Senka Co., Ltd.) And a viscosity of 10 Pa · s (B-type rotational viscometer, 25 ° C., 50 rpm). In addition, this resin material for base coating layers showed hardly adhesiveness, and the peeling strength measured by the method similar to Example 1 was 0.001 N / mm.

  Others were performed in the same manner as in Example 1. As a result, a fabric having a water resistant underlying coating layer (average thickness: 15 μm) was obtained. Even if it bent, the obtained conductive fabric did not tear a copper foil, but had flexibility (flexibility evaluation "(circle)"). Moreover, in water resistance evaluation, the resistance value 5 minutes after voltage application is 42 M (ohm) (measurement upper limit of an apparatus), and it was shown that there is sufficient water resistance.

Comparative Example 1
The same fabric as in Example 1 was used. A one-part, moisture-curable polyurethane resin solution (made by DIC, trade name "NH320"), which is a hot-melt adhesive material as a resin material for the base coating layer, is coated on the fabric using an applicator and solidified, and cured. A fabric having a primer coating layer with a thickness of 20 μm was obtained. This hot-melt adhesive material was the same as the resin used for the adhesive layer of Example 1, and its peel strength was 0.7 N / mm.

  Next, using the same support pattern-formed copper foil as in Example 1, the support pattern-formed copper so that the surface of the pattern-like adhesive layer formed on the pattern-form copper foil is in contact with the base coating layer of the fabric. The foil and the fabric were stacked, and heat and pressure were applied in the same manner as in Example 1 to bond them together. Next, the support was peeled off from the patterned copper foil on the peeling layer side and transfer of the patterned copper foil layer was tried on the fabric, but the support is firmly adhered to the fabric side, and if it is peeled off forcibly, The plating resist layer and the peeling layer were broken and transferred to the fabric side, and a conductive fabric to which only the target pattern-like copper foil was transferred could not be obtained.

Comparative Example 2
The same procedure as in Example 2 was carried out except that the undercoating layer was not formed. The conductive cloth thus obtained was easily broken when bent, and the properties of the conductive cloth could not be maintained (flexibility evaluation "x"). Further, in the water resistance evaluation, the resistance value after 5 minutes of voltage application was 685 Ω, and the water resistance was insufficient.

The conductive fabric of the present invention is excellent in flexibility (flexibility) and followability, has high resistance to bending, and is difficult to be broken in the patterned metal foil, so high conductivity lasts for a long time.
Therefore, it can be suitably used as a base material or the like for wearable devices.

Claims (7)

A base coating layer formed of a resin material composed of a urethane resin or a silicone resin , a patterned adhesive layer, and a patterned metal foil are sequentially laminated in this order on a fabric, and a cover covering at least the patterned metal foil A conductive fabric having a coat, wherein the peel strength of the resin material forming the base coating layer is 100 μm thick at a tensile speed of 50 mm / min according to JIS-C5016, using the resin material as a film of 20 μm thick A conductive cloth having a peel strength of at most 0.05 N / mm when peeled off from a PET film at 90 °.   The conductive fabric according to claim 1, wherein the peel strength of the resin material forming the adhesive layer is 0.1 N / mm or more.   The conductive fabric according to claim 1, wherein the metal foil is a copper foil.   The conductive fabric according to claim 1, wherein the thickness of the metal foil is 1 to 30 μm. A method for producing a conductive fabric comprising a base coating layer, a patterned adhesive layer, and a patterned metal foil sequentially laminated in this order on a fabric, and having a cover coat covering at least the patterned metal foil. A method for producing a conductive fabric, comprising steps (a), (b) and (c).
(A) A supported metal pattern having a base coating layer on at least one side, a support, a patterned metal foil, and a patterned adhesive layer formed on the surface of the patterned metal foil; Bonding the base coating layer and the patterned adhesive layer so as to overlap with each other,
(B) peeling the support from the patterned metal foil with support, transferring the patterned metal foil onto the fabric, and (c) applying a cover coat so as to cover at least the patterned metal foil   After the plating resist is printed on the release layer of the support having the base material and the release layer, the pattern-formed metal foil with support formed a plating resist layer having a pattern reverse to the desired conductive pattern. And electroplating the substrate to form a patterned metal foil layer having a desired conductive pattern, and then selectively applying a resin material for an adhesive layer on the patterned metal foil layer to form a pattern. The method according to claim 5, which is obtained by forming an adhesive layer. The manufacturing method according to claim 6, wherein the release layer is a nickel-tin thin film layer formed on a substrate by an electric nickel-tin plating treatment.

Images