JP6938605B2 - Conductive fabric and its manufacturing method - Google Patents

Description

The present invention relates to a conductive cloth having a conductive pattern coated with an insulating resin film, which is formed on at least a part of the cloth while holding the internal voids of the cloth, and a method for producing the same. More specifically, the present invention relates to a conductive fabric having sufficient conductivity without impairing the original moisture permeability and breathability of the fabric, and having excellent followability and durability to shape changes such as bending, and a method for producing the same.

The conductive fabric can be used as a wearable device by mounting electronic components and sensors. By wearing a wearable device using the conductive fabric of the present invention, it is possible to measure biological signals and movements of humans and animals, which are used in the medical and healthcare fields, as well as in the environment and construction fields. Its usefulness is attracting attention in various industries such as.

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

However, the method of weaving or knitting a conductive thread has problems such as requiring a special device and a low degree of freedom in the shape of the conductive pattern. Since the method of printing a conductive paste may have insufficient conductivity, there is a problem that the fabric tends to be hard and heavy because it is necessary to increase the amount of paste to be printed in order to increase the conductivity. There was also a risk of cracking because the flexibility of the fabric could not be followed.

So far, a method of forming a thin metal layer on a cloth through an adhesive or the like has been proposed for decorative purposes (Patent Documents 3 and 4). Further, an electronic garment in which an electronic circuit or the like is formed on a cloth by an inkjet printing method has been proposed (Patent Document 5). However, in these methods, the internal voids existing between the threads of the fabric are not retained, and the original moisture permeability and breathability of the fabric tend to be impaired.

Japanese Unexamined Patent Publication No. 2013-019064 Japanese Unexamined Patent Publication No. 2014-151018 Japanese Unexamined Patent Publication No. 07-216765 Japanese Unexamined Patent Publication No. 2003-073982 Japanese Unexamined Patent Publication No. 2005-146499

An object of the present invention is to provide a conductive fabric having sufficient conductivity without impairing the original moisture permeability and breathability of the fabric and a method for producing the same.

As a result of diligent studies, the present inventors have a conductive pattern formed on a part of the fabric while retaining the internal voids of the fabric, and insulate the conductive pattern while retaining the internal voids of the fabric. We have found that a conductive fabric coated with a resin film can solve the above problems, and have completed the present invention.

That is, the present invention relates to the following conductive fabric and a method for producing the conductive fabric.
(1) At least a part of the cloth has a conductive pattern portion and an insulating resin film having a thickness of 10 to 15 μm that covers the conductive pattern portion, and is a JIS-L-1099 A-1 method (calcium method). ), The conductive fabric having a moisture permeability of 50 g / m ² · h or more in the conductive pattern portion.

(2) The conductive fabric according to (1), which is for a wearable device.

(3) At least a part of the cloth has a conductive pattern portion and an insulating resin film having a thickness of 10 to 15 μm that covers the conductive pattern portion, and JIS-L-1099 A-1 method (calcium method). A method for producing a conductive fabric having a moisture permeability of 50 g / m2 · h or more measured in accordance with the above, which comprises the following steps.
(A) Step of forming a conductive pattern portion on at least a part of the cloth (B) Step of coating the conductive pattern portion with an insulating resin film

(4) The step (A) for forming the conductive pattern portion includes a weaving or knitting step using at least a part of the conductive threads or the threads containing the conductive fibers, according to the description of (3). Production method.

(5) The production method according to (3) or (4 ), wherein the step (A) for forming the conductive pattern portion includes an electroless plating treatment step.
(6) The manufacturing method according to (5) , wherein the electroless plating treatment step includes a step of printing a plating resist on a cloth to form a resist layer having a pattern opposite to a desired conductive pattern.
(7) In the electroless plating treatment step, a plating resist is printed on the cloth to form a resist layer having a pattern opposite to the desired conductive pattern, and then the electroless plating catalyst ink is applied to the cloth. The production method according to (6), which comprises a step.
(8) The production method according to any one of (3) to (7) , wherein the step (B) of coating the insulating resin film includes an electrodeposition coating step.
(9) The production method according to (8), wherein an anionic polyester electrodeposition coating material is used in the electrodeposition coating step.

Although the conductive fabric of the present invention has the conductive pattern and the coating of the insulating resin film, the internal voids of the fabric are retained, and as a result, sufficiently high moisture permeability is maintained.
Since the conductive pattern of the present invention is formed while maintaining the internal voids of the fabric, the conductive fabric has sufficient conductivity without impairing the original moisture permeability and breathability of the fabric, and is resistant to shape changes such as bending. It has excellent followability and flexibility.

1. 1. Conductive cloth The conductive cloth of the present invention has a conductive pattern and an insulating resin film having a thickness of 10 to 15 μm that covers the conductive pattern in at least a part of the cloth.

(1) Cloth The cloth used in the present invention is mainly composed of non-conductive threads. The yarn may be a monofilament yarn or a multifilament yarn in which a large number of fibers are bundled. The thickness of the yarn is not particularly limited, but in the case of monofilament, it is preferably 10 to 70 dtex, and in the case of multifilament, it is preferably 10 to 170 dtex.

Specific examples of the fabric include fiber fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics. Examples of the fiber material include natural fibers such as cotton, hemp, wool and silk, recycled fibers such as rayon and cupra, semi-synthetic fibers such as acetate and triacetate, polyamide (nylon 6, nylon 66, etc.) and polyester (nylon 6, nylon 66, etc.). (Polyester terephthalate, polytrimethylene terephthalate, etc.), synthetic fibers such as polyurethane and polyacrylic, and the like can be mentioned, and two or more of these may be combined. Among them, a cloth made of synthetic fibers having excellent overall fiber properties is preferable, and a cloth made of generally used synthetic fibers such as polyester fiber and nylon fiber is preferable.

The fiber fabric may be dyed, antistatic processed, flame-retardant processed, calendar processed or the like, if necessary. The thickness of the fabric is not particularly limited, but is preferably 0.02 to 1 mm.

(2) Conductive pattern The conductive pattern formed on the cloth in the present invention is a non-conductive thread forming the cloth even if it is composed of conductive threads or threads containing conductive fibers. May be subjected to electroless plating treatment.

In the production method of the present invention described later, when a conductive pattern is formed by weaving or knitting using at least a part of a conductive yarn or a yarn containing a conductive fiber, the conductive pattern is a conductive yarn. Consists of threads or threads containing conductive fibers. When the conductive pattern is formed by a method including an electroless plating treatment step, the non-conductive yarn forming the fabric is electrolessly plated.

As the conductive yarn or the yarn containing the conductive fiber, a metal yarn, a yarn made of a fiber made of a conductive polymer, and a yarn made of a fiber made of a conductive polymer are used as a part of the yarn (multifilament). In the case of thread, etc.).

When the conductive pattern is obtained by subjecting an electroless plating treatment, the metal for electroless plating is at least one metal selected from the group consisting of copper, nickel, tin, and silver, or an alloy thereof ( For example, an alloy of copper and tin). Copper and nickel are preferred, and copper is particularly preferred.

Of these, a conductive pattern obtained by subjecting the non-conductive threads forming the fabric to an electroless plating treatment is more preferable because the degree of freedom of the conductive pattern is higher.
The film thickness of the plating film (conductive pattern) formed by the electroless plating treatment is preferably 0.1 to 10 μm, more preferably 0.2 to 7 μm.

(3) Insulating Resin Film The conductive pattern in the conductive fabric of the present invention is at least partially covered with an insulating resin film. Specific examples of the insulating resin include acrylic resin, melamine resin, epoxy resin, urethane resin, polyester resin, polyurethane resin, and polyamine resin. Of these, particularly preferable ones are acrylic resins, polyester resins, and polyurethane resins. The most preferable is a polyester resin.

The conductive pattern needs to be at least partially covered with an insulating resin film, but more preferably, almost the entire surface of the conductive pattern is covered with an insulating resin film. Preferably, 100% of the surface of the conductive pattern is coated with an insulating resin film.

The thickness of the insulating resin film is 10 to 15 μm. If the film thickness is within this range, there is no possibility that the film thickness is too thin and the insulating property is insufficient, or that the film thickness is too thick and the texture of the fabric becomes hard. In the present invention, by forming the thickness of the insulating resin film thin, it becomes easy to maintain the internal voids of the fabric.

(4) Internal Voids of Fabric The conductive fabric of the present invention has a feature that it retains the internal voids of the fabric even though it has the conductive pattern and the coating of the insulating resin film. Usually, there is a gap between the threads that make up the fabric. The "internal void of the fabric" in the present invention means the void between the threads originally possessed by such a fabric. Due to the presence of internal voids, the fabric has physical characteristics peculiar to the fabric such as moisture permeability, breathability, and flexibility.

Regarding the retention of the internal voids of the fabric in the conductive fabric of the present invention, the moisture permeability can be used as a guide. Specifically, the moisture permeability is measured in accordance with JIS-L-1099 A-1 method (calcium method), the conductive pattern portions on the fabric 50g / ^{m 2} · h or more, preferably 100 g / ^{m 2} -H or more, more preferably 200 g / m ² · h or more.

That is, although the conductive fabric of the present invention has a conductive pattern and an insulating resin film formed on the conductive pattern, the conductive pattern portion has ^{a high moisture permeability of 50 g / m 2} · h or more. It is being held. Here, the conductive pattern portion refers to a portion on the fabric in which the conductive pattern and the insulating resin film covering the conductive pattern are formed.

It is considered that the high moisture permeability of the conductive fabric of the present invention is realized by forming the insulating resin film without filling the internal voids of the fabric. That is, as will be described later, the conductive fabric of the present invention has a rate of change in moisture permeability of the fabric of 90% or less, preferably 80% or less, more preferably 70% before and after the formation of the insulating resin film at the time of its manufacture. In the following cases, it can be said that the conductive fabric of the present invention retains the original internal voids of the fabric.

In the conductive fabric of the present invention, since the conductive pattern portion is formed while retaining the internal voids of the fabric, the inherent properties of the fabric (for example, moisture permeability) are maintained.

2. Method for Producing Conductive Fabric The conductive fabric of the present invention is not particularly limited in its production method, but is preferably (A) a step of forming a conductive pattern on at least a part of the fabric, and (B) the conductive pattern. Manufactured by a method including a step of coating an insulating resin film.

(1) Step of forming a conductive pattern (A)
In the step (A), a conductive pattern is formed on at least a part of the above-mentioned fabric.

Examples of the method for forming the conductive pattern include a method including a weaving or knitting step using at least a part of a conductive yarn or a yarn containing a conductive fiber, or a method including an electroless plating treatment step. .. Of these, a method of electroless plating the non-conductive threads forming the fabric is more preferable because the degree of freedom of the conductive pattern is higher.

Examples of the conductive yarn used in the method including the weaving or knitting step include a metal yarn, a conductive resin-coated yarn and the like. Examples of the metal used for the metal thread include copper, nickel, tin, silver and the like. Specific examples of the conductive resin-coated yarn include a conductive yarn (trade name: Metallian, manufactured by Teijin Limited) in which nylon fibers are coated with carbon.
The thickness of the conductive yarn is not particularly limited, but is preferably 10 to 170 dtex.

Examples of the conductive fiber include a fiber made of a conductive polymer, a metal fiber, a carbon fiber and the like. Specific examples of the conductive polymer include polyacetylene, poly (p-phenylene vinylene), polypyrrole, polythiophene, polyaniline, poly (p-phenylene) and the like. The thickness of the conductive fiber is not particularly limited, but is preferably 10 to 170 dtex.

Examples of the thread (multifilament) containing the conductive fiber include a thread made of the conductive fiber and a thread using a part of the conductive fiber. The thickness of the thread containing the conductive fiber is not particularly limited, but is preferably 10 to 170 dtex.
The weaving or knitting method is not particularly limited, and conventionally known methods are used.

Examples of the method including the electroless plating treatment step include a method in which a fabric having a pattern having plating catalytic activity is subjected to an electroless plating treatment to form a conductive pattern.
More specifically, a plating resist is printed on the cloth to form a resist layer having a pattern opposite to the desired conductive pattern, and then an electroless plating catalyst ink is applied to the cloth and then reduced to perform plating. It forms the desired pattern of metal with catalytic activity.

Then the resist layer is removed. The method for removing the resist layer is not particularly limited, and a known method can be used. For example, the bath temperature is about 25 to 35 ° C. (more preferably about 30 ° C.) by immersing in a 0.1% NaOH aqueous solution and using an ultrasonic cleaner (for example, trade name; US CLEANER, manufactured by AS ONE Co., Ltd.). The resist layer can be removed in a washing time of 1 to 2 minutes.
Then, by subjecting this to an electroless plating treatment, a desired conductive pattern can be formed on the fabric.

The plating resist is not particularly limited as long as it has chemical resistance to the plating solution used in the electroless plating process.
As a method for forming the reverse-patterned plating resist layer, it is preferable to cure the reverse-patterned plated resist. The curing method may be either thermosetting or ultraviolet curing. Therefore, the plating resist of the present invention may be a thermosetting type or an ultraviolet curable type.

The plating resist is usually mixed with a solvent, a binder resin, a coloring component, an additive and the like as needed.
As the binder resin, resins such as epoxy-based, polyester-based, acrylic-based, and isocyanate-based resins can be used. The binder resin may be a thermosetting type or an ultraviolet curable type.

Examples of the thermosetting binder resin include epoxy resins and acrylic carboxylic acid polymers.
Examples of the epoxy resin include bisphenol A type liquid epoxy resin, cresol novolac type epoxy resin, and phenol novolac type epoxy resin. Specifically, the epoxy resin is "EPICLON 850" (epoxy equivalent 188), and the cresol novolac type epoxy resin is "EPICLON N-665" (epoxy equivalent 202-212), "EPICLON N-680" (epoxy equivalent 206). ~ 216), "EPICLON N-695" (epoxy equivalent 209 to 219), as a phenol novolac type epoxy resin, "EPICLON N-775" (epoxy equivalent 184 to 194) (both trade names, manufactured by DIC Co., Ltd.), etc. Can be mentioned

As the carboxylic acid acrylic polymer, "JONCRYL 682" (molecular weight 1700, solid acid value 240 mgKOH / g), "JONCRYL 683" (molecular weight 8000, solid acid value 165 mgKOH / g) (both trade names, BASF Japan Co., Ltd.) , "ARUFON UC-3000" (molecular weight 10000, solid acid value 74 mgKOH / g), "ARUFON UC-3900" (molecular weight 4600, solid acid value 108 mgKOH / g) (all trade names, Toa Synthetic Co., Ltd. (Made) and so on.

As the ultraviolet curable binder resin, a monomer or oligomer 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 trimethylrol propane. Examples thereof include triacrylate, trimethylol EO-modified propane triacrylate, and dipentaerystol hexaacrylate.

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

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, Glycos such as dipropylene glycol, 1,3-butylene glycol, tripropylene glycol; ethylene glycol monomethyl ether acetate, propylene 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-propyl ether, propylene glycol-n-butyl ether, dipropylene glycol methyl ether, diethylene glycol-n-propyl ether, dipropylene Glycol esters such as glycol-n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol-n-butyl ether; glycol ethers; glycol ester ethers; dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone and the like Can be mentioned.

As the coloring component, known pigments and dyes conventionally used for inks can be used regardless of whether they are inorganic or organic.
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.

Examples of the surface conditioner include BYK-300, BYK-301, BYK-306 and the like as silicone-based surface conditioners (all trade names are manufactured by Big Chemie Japan Co., Ltd.), and BYK-350 as an acrylic surface conditioner. , BYK-352, BYK-354, etc. (all trade names, manufactured by Big Chemie Japan Co., Ltd.).

Examples of the defoaming agent include BYK-051, BYK-052, BYK-053 and the like (trade names, all manufactured by Big Chemie Japan Co., Ltd.).
Examples of the leveling agent include BYKETOL-OK, BYKETOL-SPECIAL and the like (both are trade names, manufactured by Big Chemie Japan Co., Ltd.).

Examples of the rheology control agent include BYK-405, BYK-410 and the like (both are trade names, manufactured by Big Chemie Japan Co., Ltd.).
The solvent and various additives can be appropriately used, for example, to adjust the viscosity and printability of the plating resist.

In particular, it is preferable to add a curing accelerator to the plating resist. By adding a curing 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 quickly after printing, and the bleeding and spreading of the pattern due to the flow of the ink is suppressed as compared with the case where the curing accelerator is not added, and a more delicate resist pattern can be obtained. It is considered that this is because a precise patterned metal foil can be obtained by performing the plating treatment.

The curing accelerator needs to be selected according to the binder resin. Specifically, for the epoxy resin, an imidazole compound, an amine compound and the like are preferably used. Examples of the imidazole compound include the Curesol series (trade names) manufactured by Shikoku Chemicals Corporation, such as "SIZ", "2MZ-H", and "2MZ-OK". Examples of the amine compound include Ajinomoto Fine-Techno Co., Ltd.'s Amicure series (trade names) such as "PN-23", "PN-H", and "PN-31".

Examples of the isocyanate-based binder resin 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 (manufactured by BASF, trade name; Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF, trade name; Irgacure 369), 2,4,6 Examples thereof include a photopolymerization initiator such as -trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, trade name; Lucillin TPO) and a sensitizer such as diethylthioxanthone.

The mixing ratio of the curing accelerator to the plating resist is not particularly limited and can be adjusted as appropriate.

As a printing method for printing the plating resist on the fabric, known methods such as gravure printing, screen printing, photolithography, gravure offset printing, flexographic printing, and inkjet printing can be applied.
Of these, screen printing, inkjet printing and the like are preferable.

Examples of the metal having plating catalytic activity include copper, nickel, silver, tin, rhodium, palladium, gold and platinum, but palladium having high plating catalytic activity is preferably used.

Examples of the electroless plating catalyst ink include a solution containing metal ions that can be reduced to become a metal having plating catalytic activity. Examples of such metal ions include palladium ions, and examples of compounds that generate palladium ions include palladium chloride, palladium bromide, palladium acetate, palladium sulfate, palladium nitrate, palladium acetylacetonate, and palladium oxide. Among them, palladium chloride, which is widely used as a general catalyst, is preferably used because it is relatively easy to obtain.

The solvent used for the metal ion-containing solution is not particularly limited, but water is preferable.
The metal ion concentration in the metal ion-containing solution is preferably 30 to 80 g / L, more preferably 30 to 50 g / L.

The reaction temperature when the fabric is brought into contact with the metal ion-containing solution is 10 ° C to 80 ° C, preferably 10 ° C to 50 ° C. The contact time of the metal ion-containing solution is preferably 10 seconds to 800 seconds, more preferably 30 seconds to 500 seconds.

After contacting with the metal ion-containing solution, it is preferable to wash the cloth with water to remove non-specifically attached metal ions. As a washing method with water, a known washing method can be applied.

As the reduction method, a method in which the cloth on which the metal ions are adsorbed is brought into contact with an acidic treatment liquid containing a reducing agent (hereinafter referred to as a reduction treatment liquid) is preferable. Examples of the reducing agent used in the acidic treatment liquid containing the reducing agent include dimethylamine borane, sodium hypophosphite, hydrazine, diethylamine, ascorbic acid, borofluoric acid (tetrafluoroboric acid) and the like.

The reducing agent concentration of the reduction treatment liquid is preferably 5 to 20 g / L. The solvent used in the reduction treatment liquid is not particularly limited, but water or the like is preferable. The pH of the reduction treatment liquid is preferably 6 or less, more preferably 2 to 6, and even more preferably 3 to 5.9.

The time for contacting the fabric with the reduction treatment liquid is 30 seconds to 600 seconds, preferably 60 seconds to 300 seconds. The contact temperature is 10 ° C to 80 ° C, preferably 30 ° C to 50 ° C. After contacting with the reducing treatment liquid, the fabric is washed with water to remove the non-specifically attached reducing agent. After the reduction treatment, it is washed and dried as necessary to obtain a fabric having a desired pattern having plating catalytic activity.

As a method of electroless plating treatment, a known electroless plating method can be used. Examples of the metal for electroless plating include at least one metal selected from the group consisting of copper, nickel, tin, and silver, or an alloy thereof (for example, an alloy of copper and tin). Copper and nickel are preferred, and copper is particularly preferred.

An existing plating bath can be used for electroless plating, and the fabric may be immersed in this plating bath. The reaction time and temperature of electroless plating can be appropriately adjusted according to the plating film thickness, but the preferred plating time is 5 to 20 minutes, and the preferred temperature is 40 to 50 ° C.

The film thickness of the electroless plating film (conductive pattern) thus obtained is preferably 0.1 to 10 μm, more preferably 0.2 to 7 μm.

After forming the electroless plating film, the fabric can be washed with water to remove the non-specifically attached plating solution, if necessary.

In the step (A), it is desirable to form the conductive pattern while maintaining the internal voids of the fabric. As described above, the internal voids of the fabric refer to the voids between the threads originally possessed by the fabric, and in the present invention, it is desirable that the moisture permeability of the fabric before the formation of the conductive pattern does not significantly decrease after the formation of the conductive pattern. As described above, in the present invention, the conductive pattern can be formed while maintaining the internal voids in the weaving or knitting process using at least a part of the conductive threads or the threads containing the conductive fibers. By adopting the method including or the method including the electroless plating treatment step. Weaving or knitting tends to form voids, and electroless plating tends to form internal voids because the film thickness is easy to control.

Further, the conductive pattern may be formed on at least a part of the cloth, and may be the entire surface or only a part of the cloth.

(2) Step of coating the insulating resin film (B)
In the step (B), the conductive pattern is coated with an insulating resin film. The coating method is not particularly limited, but an electrodeposition coating method is preferably used. In the electrodeposition coating method, the cloth is immersed in a resin liquid for electrodeposition coating, and electricity is passed through the conductive pattern in this state, so that the resin film can be applied only to the conductive portion. By using the electrodeposition coating method, it is possible to form an extremely thin and uniform resin film only on the conductive pattern portion, and by adjusting the film thickness, it is possible to sufficiently maintain the voids in the fabric.

Examples of the resin liquid used for electrodeposition coating include acrylic resin, melamine resin, epoxy resin, urethane resin, polyester resin, and polyamine resin. Of these, particularly preferable ones are acrylic resins, polyester resins, and polyurethane resins. The most preferable is a polyester resin. The electrodeposition coating treatment temperature is preferably 20 to 30 ° C., the voltage is preferably 10 to 150 V, the conduction time is preferably 30 to 180 seconds, and the distance between the poles is 50 to 200 mm. In addition, after conduction, pre-drying and baking are performed.

In the step (B), it is preferable to form an insulating resin film on the conductive pattern while maintaining the internal voids of the fabric. As described above, the internal voids of the fabric refer to the voids between the threads originally possessed by the fabric, and in the present invention, it is desirable that the moisture permeability of the fabric before coating the insulating resin film does not significantly decrease after coating.

In the present invention, the insulating resin film can be formed on the conductive pattern while maintaining the internal voids because the electrodeposition coating method is adopted as the method for forming the insulating resin film. According to the electrodeposition coating method, it is easy to control the thickness of the insulating resin film by selecting the conditions, so that the insulating resin film is formed so as to cover the conductive pattern without filling the voids of the fabric. It is easy to do.

The thickness of the insulating resin film thus formed is 10 μm or more, and the preferable film thickness is 10 to 15 μm. If the film thickness is within this range, there is no possibility that the film thickness is too thin and the insulating property is insufficient, or that the film thickness is too thick and the texture of the fabric becomes hard. In the present invention, by forming the thickness of the insulating resin film thin, it becomes easy to maintain the internal voids of the fabric.

In the manufacturing method of the present invention, as a guideline for the state in which the internal voids are retained, the rate of change in moisture permeability in the conductive pattern portion is 90% or less before and after the step (B) of coating the insulating resin film. Can be mentioned. Specifically, the rate of change of the moisture permeability in the conductive pattern portion measured in accordance with the JIS-L-1099 A-1 method (calcium method) before and after the formation of the insulating resin film is 90% or less, preferably 90% or less. It is preferably 80% or less, more preferably 70% or less, particularly preferably 50% or less, and most preferably 30% or less.

The rate of change in moisture permeability of the conductive pattern portion in the present invention is expressed as follows.
"Humidity change rate (%) = {(moisture permeability of the conductive pattern part before forming the insulating resin film)-(moisture permeability of the conductive pattern part after forming the insulating resin film)} ÷ (before forming the insulating resin film) Moisture permeability of the conductive pattern part) x 100 "

Here, the methods for determining the moisture permeability of the conductive pattern portion before forming the insulating resin film are the moisture permeability of the fabric before the conductive pattern formation (unprocessed), the moisture permeability of the fabric after the conductive pattern formation (after processing), and. It is obtained by the following calculation from the area ratio (%) that the conductive pattern portion occupies on the cloth.
"Humidity permeability of the conductive pattern portion before forming the insulating resin film = (moisture permeability of the fabric after processing)-(moisture permeability of the unprocessed fabric) x {100-area ratio (%) of the conductive pattern portion on the fabric )} ÷ 100 "
However, if the conductive pattern is formed by weaving or knitting using conductive fibers instead of electroless plating, it is calculated as (moisture permeability of the processed fabric) = (moisture permeability of the unprocessed fabric). Will be done.

The methods for determining the moisture permeability of the conductive pattern portion after forming the insulating resin film are the moisture permeability of the fabric before the conductive pattern is formed (unprocessed), the moisture permeability of the fabric after the insulating resin film is formed (after the film is formed), and It is obtained by the following calculation from the area ratio (%) that the conductive pattern portion occupies on the cloth.
"Moisture permeability of the conductive pattern portion after forming the insulating resin film = (moisture permeability of the fabric after film formation)-(moisture permeability of the unprocessed fabric) x {100-area ratio of the conductive pattern portion on the fabric ( %)} ÷ 100 "

The above calculation is based on the premise that there is no change in moisture permeability in the non-conductive pattern portion on which neither the conductive pattern nor the insulating resin film is formed.

Further, the insulating resin film may be coated on at least a part of the conductive pattern, and may be the whole or only a part of the conductive pattern, but it is preferable that almost the entire surface of the conductive pattern is covered with the insulating resin film. It is desirable to cover with. More preferably, it is desirable to cover 100% of the surface of the conductive pattern with an insulating resin film.

The conductive fabric of the present invention can be suitably used as a base material for wearable devices, a heater, a base material for sensors, and the like.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited by these Examples.
The evaluation methods for various physical properties in this example are as follows.

<Insulation>
Using a high resistivity meter (trade name; Hiresta MCP-HT450, manufactured by Mitsubishi Analytech Co., Ltd.), the resistance value between any two locations (interval 100 mm) on the surface of the conductive fabric was measured.

<Conductivity>
Insulating resin films were removed from both ends of the conductive pattern portion 100 mm, and the resistance value during this period was measured with a measuring instrument (trade name; Digital High Tester 3256-50, manufactured by Hioki Electric Co., Ltd.).

<Humidity permeability>
The moisture permeability (g / m ² · h) was measured according to the JIS-L-1099 textile product moisture permeability test method A-1 method (calcium method).
The rate of change in moisture permeability (%) of the conductive pattern portion before and after the formation of the insulating resin film is the moisture permeability (T ₀ ) of the unprocessed fabric and the moisture permeability of the entire fabric after the formation of the conductive pattern and before the formation of the insulating resin film (%). T _{1 ) and the moisture permeability (T 2} ) of the entire fabric after forming the insulating resin film after forming the conductive pattern were measured by the above methods, respectively, and obtained by calculation based on the following formula (I). The area ratio S (%) of the conductive pattern on the cloth was obtained by taking a photograph of the entire cloth and binarizing it with image processing software (ImageJ; public domain).

[Number 1]
Moisture Permeability Change Rate (%) = (T _3- T ₄ ) ÷ T ₃ × 100 ・ ・ ・ (I)
T ₃ ; Moisture permeability of the conductive pattern portion after forming the conductive pattern and before forming the insulating resin film T ₄ ; Moisture permeability of the conductive pattern portion after forming the conductive pattern and after forming the insulating resin film

In the above mathematical formula (I), T ₃ was obtained by calculation based on the following mathematical formula (II).
[Number 2]
T ₃ = T _1- T ₀ x (100-S) ÷ 100 ... (II)
T ₀ ; Moisture permeability of unprocessed fabric T ₁ ; Moisture permeability of the entire fabric after formation of the conductive pattern and before formation of the insulating resin film S; Area ratio (%) of the conductive pattern on the fabric

However, when the conductive pattern is formed by weaving or knitting using conductive fibers, T ₁ = T ₀ , so “T ₃ = T ₀ × S ÷ 100”.

In the above mathematical formula (I), T ₄ was obtained by calculation based on the following mathematical formula (III).
[Number 3]
T ₄ = T _2- T ₀ × (100-S) ÷ 100 ・ ・ ・ (III)
T _{2 ; Moisture permeability T 0} and S of the entire fabric after the formation of the insulating resin film after the formation of the conductive pattern are the same as those in the above formula (II).

Regarding T ₄ , there is no difference even when the conductive pattern is formed by weaving or knitting using conductive fibers.
Further, the above calculation was performed on the premise that there is no change in moisture permeability in the non-conductive pattern portion where neither the conductive pattern nor the insulating resin film is formed on the fabric.

<Coating>
The conductive cloth on which two independent rows of conductive patterns were formed was immersed in 0.5 wt% saline solution, and in this state, a voltage of 1.58 V was applied between the two rows of conductive patterns. 60 minutes after applying the voltage, the resistance value between the two rows of conductive patterns was measured with a measuring instrument (trade name; Digital High Tester 3256-50, manufactured by Hioki Electric Co., Ltd.). The higher the resistance value, the less leakage there is, indicating that the conductive pattern is sufficiently covered.

[Example 1]
(1) Formation of conductive pattern The plain weave cloth shown below was used as the cloth.
(Plain weave structure)
Vertical: Polyester wooly yarn 33.3dtex / 36f 189 yarns / 25.4mm
Horizontal: Polyester wooly yarn 68.9dtex / 150f 120 yarns / 25.4mm

A mask (protective film) was attached to the back surface of the cloth, and then a resist ink was printed on the front surface (front) of the cloth by screen printing to form a resist layer (a pattern opposite to the desired pattern). The protective film for the mask used was (trade name; "Sanitect MA64", manufactured by Sun A. Kaken Co., Ltd.). The resist resin used was a heat-drying resist ink (trade name: MA-830, manufactured by Taiyo Ink Co., Ltd.).

Next, the cloth was immersed in a plating catalyst ink (an aqueous solution at 20 ° C. containing 0.3 g / L of palladium chloride, 30 g / L of stannous chloride, and 300 ml / L of 36% hydrochloric acid) for 1 minute, and then washed with water. As a result, a desired pattern made of plating catalyst ink was formed on the surface of the fabric where the resist layer was not formed.

Next, the cloth on which the desired pattern made of the plating catalyst ink was formed was immersed in a reduction treatment liquid (borofluoric acid; an aqueous solution having a concentration of 0.1 N) at 40 ° C. for 1 minute and then washed with water. As a result, palladium chloride in the plating catalyst was reduced to obtain a fabric having a pattern having plating catalytic activity.

Next, it was immersed in an electroless copper plating solution (8.6 g / L of cupric chloride, 9 mL / L of formalin, 0.5 g / L of potassium ferrocyanide, 17.3 mL / L of 32% caustic soda) at 45 ° C. for 10 minutes. After that, it was washed with water. The film thickness of the electroless copper plating film (conductive pattern) thus formed is 6 μm.

(2) Coating of Insulating Resin Film Electrodeposition coating is performed using polyester electrodeposition paint (trade name: PEED004BE, manufactured by NTS Co., Ltd .; pH 7.7, anionic), and the conductive pattern is coated with an insulating resin. The membrane was coated. A SUS304 plate was used as the anode plate, and the treatment bath temperature was 25 ° C., voltage, 40 V, time: 60 seconds, and the distance between poles was 50 mm. Then, pre-drying was carried out at 60 ° C. for 15 minutes, and then baking was carried out at 100 ° C. for 30 minutes. The film thickness of the insulating resin film thus formed is 15 μm.

As a result, a fabric having a conductive pattern coated with an insulating resin film was obtained. The obtained fabric was evaluated for insulation, conductivity, moisture permeability, rate of change in moisture permeability, and coating property by the above method. The results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was carried out except that the cloth was changed to a plain weave cloth under the conditions shown below.
(Plain weave structure)
Vertical: Polyester wooly yarn 33.3dtex / 36f 189 yarns / 25.4mm
Horizontal: Polyester thread 55.6dtex / 24f 134 pieces / 25.4mm

In the cloth having a conductive pattern coated with the obtained insulating resin film, the film thickness of the conductive pattern (electroless copper plating film) is 6 μm, and the film thickness of the insulating resin film is 15 μm. The results are shown in Table 1.

[Example 3]
Among the electrodeposition coating conditions, the same procedure as in Example 1 was carried out except that the voltage was changed to 20V. In the cloth having a conductive pattern coated with the obtained insulating resin film, the film thickness of the conductive pattern (electroless copper plating film) is 6 μm, and the film thickness of the insulating resin film is 13 μm. The results are shown in Table 1.

[Comparative Example 1]
As a method for forming the insulating resin film, the same procedure as in Example 1 was carried out except that the entire surface was coated with a bar coat of a polyurethane resin material instead of electrodeposition coating. As a bar coat, bar No. After applying a coating using No. 6 so as to cover the entire one surface of the fabric, the fabric was dried at 80 ° C. for 10 minutes. The entire other surface of the fabric was then similarly coated and dried. The polyurethane resin materials used were 100 parts by weight of the trade name "Hydran WLS-202" (manufactured by DIC Corporation: polyether polyurethane resin) and the trade name "Senka Act Gel NS100" (manufactured by Senka Co., Ltd .: thickener). It consists of 3 parts by weight. In the cloth having a conductive pattern coated with the obtained insulating resin film, the film thickness of the conductive pattern (electroless copper plating film) is 6 μm, and the film thickness of the insulating resin film is 20 μm. The results are shown in Table 1.

[Comparative Example 2]
As a method for forming the insulating resin film, the same procedure as in Example 1 was carried out except that the entire surface was coated with a bar coat of a polyester resin material instead of electrodeposition coating. As a bar coat, bar No. After applying a coating using No. 8 so as to cover the entire one surface of the fabric, the fabric was dried at 80 ° C. for 15 minutes. The entire other surface of the fabric was then similarly coated and dried. The polyurethane resin material used is composed of 40 parts by weight of the trade name "Byron 270" (manufactured by Toyobo Co., Ltd .: amorphous polyester resin) and 60 parts by weight of cyclohexanone (solvent). In the cloth having a conductive pattern coated with the obtained insulating resin film, the film thickness of the conductive pattern (electroless copper plating film) is 6 μm, and the film thickness of the insulating resin film is 25 μm. The results are shown in Table 1.

Since the conductive pattern of the present invention is formed while maintaining the internal voids of the fabric, the conductive fabric has sufficient conductivity without impairing the original moisture permeability and breathability of the fabric, and is resistant to shape changes such as bending. It has excellent followability and flexibility. Such a conductive fabric of the present invention can be suitably used as a base material for a wearable device, a heater, a base material for a sensor, and the like.

Claims (9)

At least a part of the fabric has a conductive pattern portion and an insulating resin film having a thickness of 10 to 15 μm that covers the conductive pattern portion, and conforms to the JIS-L-1099 A-1 method (calcium method). The conductive fabric having a water permeability of 50 g / m ² · h or more measured in the conductive pattern portion. The conductive fabric according to claim 1, which is used for a wearable device. At least a part of the cloth has a conductive pattern portion and an insulating resin film having a thickness of 10 to 15 μm that covers the conductive pattern portion, and conforms to the JIS-L-1099 A-1 method (calcium method). A method for producing a conductive fabric having a water permeability of 50 g / m ^{2 · h or more measured in the conductive pattern portion, which comprises the following steps.}
(A) Step of forming a conductive pattern portion on at least a part of the cloth (B) Step of coating the conductive pattern portion with an insulating resin film The manufacturing method according to claim 3, wherein the step (A) of forming the conductive pattern portion includes a weaving or knitting step using at least a part of the conductive threads or the threads containing the conductive fibers. The manufacturing method according to claim 3 or 4, wherein the step (A) of forming the conductive pattern portion includes an electroless plating treatment step. The manufacturing method according to claim 5, wherein the electroless plating treatment step includes a step of printing a plating resist on a cloth to form a resist layer having a pattern opposite to a desired conductive pattern. The electroless plating treatment step includes a step of printing a plating resist on the cloth to form a resist layer having a pattern opposite to a desired conductive pattern, and then applying an electroless plating catalyst ink to the cloth. , The manufacturing method according to claim 6. The production method according to any one of claims 3 to 7, wherein the step (B) of coating the insulating resin film includes an electrodeposition coating step. The production method according to claim 8, wherein an anionic polyester electrodeposition coating material is used in the electrodeposition coating step.