JPS61245369A - Production of conductive yarn - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing conductive yarn.

More specifically, the present invention relates to a method for industrially stably producing yarn having uniform force conductivity.

[Conventional technology]

In recent years, with the development and spread of the electronics industry, the demand for conductive materials has increased, and various new products have been proposed in response. Among them, conductive fibers have been proposed in which copper sulfide is attached to acrylic fibers, polyamide fibers, polyester fibers, or natural animal or vegetable fibers containing cyan groups (I !# Kaisho 56-
No. 128311, No. 56-169808 and No. 57
-21570 Publication). These conductive fibers are e.g.
The fibers can be made by treating the fiber yarn in a solution containing a copper salt and a reducing sulfur compound, or by bringing it into contact with a reducing sulfur compound such as hydrogen sulfide under pressure and then treating it with a solution containing copper ions. A conductive layer made of copper sulfide is formed on the surface, thereby making it possible to obtain conductive fibers. As a method for producing these conductive fiber yarns containing copper sulfide, short fibers (stable) are A method in which copper sulfide formation treatment is applied and the resulting short fibers having a conductive layer are made into yarn, a method in which filament yarn or p-fiber yarn is subjected to copper sulfide formation treatment in the form of cheese, and filament yarn. There is a method in which a thread or a spun yarn is wound by mK and the whole is subjected to a copper sulfide forming treatment. However, with these methods, it is difficult to uniformly apply copper sulfide formation treatment to fibers or yarns, and the conductivity of the resulting yarns is low, and the yarns may become entangled or There are problems such as yarn breakage and unsatisfactory stability in processing the yarn, and therefore it is not suitable for mass production.

[Problem that the invention seeks to solve]

It is an object of the present invention to provide a method for industrially producing a conductive yarn in which a conductive layer containing copper sulfide is uniformly formed, the conductivity of the obtained product is uniform, and the workability is excellent. This is the object of the present invention.

[Means for solving problems]

The aforementioned problems can be solved by the method of the invention. The method for producing conductive yarn of the present invention involves producing a knitted fabric from the fiber yarn, and subjecting the knitted fabric to a copper sulfide forming treatment so that the surface of the fibers constituting the knitted fabric does not contain copper sulfide. The method is characterized by forming a conductive layer consisting of the following: and disassembling the obtained copper sulfide-containing knitted fabric.

There are no particular limitations on the type of fiber yarn used in the method of the present invention, but examples include polyamide fibers (including aromatic polyamide fibers), polyester fibers, polyacrylic fibers, polyolefin fibers, and polyurethane fibers. , polyester ether fiber, polyvinyl alcohol fiber,
Preferably, the fiber is made of at least one type of fiber selected from polyvinyl chloride fiber, polyvinylidene chloride fiber, rayon fiber, cupra fiber, cellulose acetate fiber, animal fiber, vegetable fiber, and the like. These fiber yarns are used in the form of spun yarn, monofilament yarn, or multifilament yarn, and may be mixed fiber yarn or composite yarn.

There are no particular limitations on the thickness of the fiber yarns used in the method of the present invention, but in general, a thickness of 10 to 100 denier is preferred, and a thickness of 10 to 755'' denier is more preferred.

There are no particular restrictions on the knitting method or knitting structure of the knitted fabric in the method of the present invention, and any knitting method and knitting structure such as known jersey knitting, rubber knitting, double-sided knitting, Milanorip knitting, etc. can be adopted. However, in the method of the present invention, it is preferable to use jersey knitting, which has good yarn disassembly properties.Although there is no particular limitation on the density of the 0-knitted fabric, if it is made too coarse, the knitted fabric will twitch during the copper sulfide forming process. In addition, the yarn may easily break during the knitting process, resulting in a decrease in productivity. Furthermore, if the density of the knitted fabric is moderately high, the fluidized copper conductive layer formed on the fiber surface tends to adhere unevenly, and therefore uniform conductivity may not be obtained.

The preferred density of the knitted fabric varies depending on the type of yarn denier knitting machine used, but for example, when a knitted fabric is knitted with fiber yarns of 10 to 100 denier as mentioned above, the density at the end of elongation is 10. It is preferable to set the density to ~100 rouf/25.4wm. To be more specific, for example, for a yarn with a thickness of about 30 denier,
Using a knitting machine with 400 to 200 knitting needles with a can diameter of 3/, ~31/231/, the elongation density is 20 to 80 loops/
Preferably, it is within inches.

There is also no particular limitation on the method of depositing the conductive agent containing copper sulfide onto the knitted fabric. For example, in accordance with the method described in Japanese Patent Application Laid-Open No. 57-35078, a knitted fabric of fiber yarn made of synthetic 4-limer is brought into contact with a reducing sulfur compound such as hydrogen sulfide under pressure, and then Treatment with an aqueous solution of copper salts, simultaneously with or following this treatment,
A method in which a reducing agent is used can be used. Alternatively, after adsorbing -valent steel ions to the knitted fabric, sulfur atoms and/or sulfur ions may be released in accordance with the method described in JP-A-56-128311. A method of treatment with a compound may also be used. Alternatively, according to the method described in JP-A-57-21570, divalent copper ions, a reducing agent capable of reducing the divalent copper ions to monovalent ones, sulfur atoms and/or A method of treating a knitted fabric using a treatment liquid containing a compound capable of releasing sulfur ions can be used.

Copper salts used in the above method include divalent copper salts such as cupric chloride, steel sulfate, steel nitrate, cupric acetate, and copper oxalate; cuprous chloride, cuprous iodide, and cyanide. There are copper salts such as cuprous oxide and cuprous thiocyanate.

In addition, as reducing sulfur compounds, sulfoxylates,
Nithionite, thiosulfate, sulfite, bisulfite, pyrosulfite, thiourea, etc. can be used.

Further, examples of reducing agents capable of reducing divalent copper ions to monovalent copper ions include metal steel, hydroxylamine sulfate, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphite, glucose, etc. I can do it.

Furthermore, compounds that can release both or either one of sulfur atoms and sulfur ions include sodium sulfide, sulfite, dithionite, sodium dithionite,
Sodium thiosulfate, acidic sodium sulfite, sodium pyrosulfite, sulfur disulfide, di-thiourea, hydrogen sulfide,
Examples include Rongarit C10 and Rongarit 2.

Among the treatment methods described above in which a conductive agent containing copper sulfide is deposited on a knitted fabric, for example, in the case of a method in which the knitted fabric is treated in one bath with an aqueous solution containing a copper salt and a reducing sulfur compound, the treatment conditions are as follows: Usually 20-150℃, preferably 30-100℃
℃ temperature for 10 minutes to 5 hours, and a bath ratio of 1:10 to 200 is adopted. When heat treatment is used in combination with this deposition treatment, it is preferable to heat the treatment bath to a temperature of t-0.5 to b. The value of the treatment bath is usually 1.5 to 6. If necessary, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, organic acids such as citric acid and acetic acid, and disodium hydrogen phosphate, sodium citrate, and acetic acid are added. A voice conditioning agent consisting of at least 1111 selected from salts such as sodium is used. It is also effective to add a nitrile group-containing compound and/or a mercat group-containing compound to the treatment bath for the purpose of promoting the formation of copper sulfide.

Generally for copper sulfide formation? During the i& treatment, it is preferable to place the knitted fabric to be treated in a coarse net bag for the treatment in order to prevent the knitted fabric from becoming taut and causing defects such as eye distortion.

In the method of the present invention, the conductivity of the copper sulfide conductive layer obtained in the conductive layer forming treatment step and contained in the copper non-sulfide-containing knitted fabric is determined by the conductivity required for the intended conductive yarn, the intended use, and the type of yarn. Although the amount can be arbitrarily determined in consideration of the risk of thickness, it is generally preferable that the amount is in the range of 0.5 to 10% by weight.

For knitted fabrics containing copper sulfide, apply an appropriate amount of / before the unraveling process.
The disassembly property can also be improved by impregnating and adhering a graphine-based smoothing oil agent and/or a silicone-based smoothing oil agent.

In addition, in order to impart high resistance and durability against physical friction, abrasion, rubbing, etc. to the conductive yarn obtained by the unraveling process, during or after the unraveling process, An abrasion-resistant agent for the running yarn, such as a resin that forms a film and becomes water-insoluble after drying, such as a polyester-based, polyamide-based, or polyacrylic acid-based polymer. may be provided, preferably in an amount of 3 to 40% by weight.

In the method of the present invention, since the conductive agent containing copper sulfide is applied to the knitted fabric, a continuous conductive layer is uniformly formed on the surface of the fibers constituting the knitted fabric. Therefore, the conductivity of the obtained conductive yarn is also uniform. Furthermore, in the method of the present invention, the unraveling process of the copper sulfide-containing knitted fabric is carried out smoothly, and the resulting conductive yarn can be processed, such as winding, unwinding, gold thread, twisting, weaving, knitting, etc. The process is easily carried out.

〔Example〕

The method of the present invention will be further explained by Examples. Example 1 and Comparative Examples 1 and 2 Nylon 66 filament yarn, 30d/10f (trade name: Leona, manufactured by Asahi Kasei Kogyo Co., Ltd.) raw yarn with 300 needles, 3
A knitted fabric having a stretched density of 50 loops/25.4 g was produced by knitting using a one-piece knitting machine having a can diameter of q inches. Pack 500 I of each of these knitted fabrics into net bags made of polypropylene fiber, put 10 bags (5 to 9 in terms of weight of knitted fabric) into a no-arm dyeing machine (capacity 2001), and add 29/L to the treatment solution. A score roll Fc-250 (manufactured by Kao Atlas Co., Ltd.) was added, and scouring was performed at 60° C. for 10 minutes. After scouring, sulfuric acid steel 201/l, sodium thiosulfate 201/l
1/II) 180 g of a treatment solution containing 3011/It of disodium citrate and 12ν11 of citric acid was added to the J? The temperature of the treatment liquid was raised from room temperature to 50°C over 20 minutes while rotating and stirring the paddle dyeing machine stirring blade loaded into the dollar dyeing machine, and further treated at 50°C for 20 minutes. After treatment, the knitted fabric was dehydrated and washed with water. After dewatering, the knitted fabric was taken out of the polypropylene bag and spread on a dryer screen to dry. After drying,
3.5 weight of copper sulfide was evenly adhered to the copper sulfide-containing knitted fabric, and no scratches such as twitching occurred. The surface electrical resistance of the obtained copper sulfide-containing knitted fabric was 2×1
It was within the range of 0-5×10 3 Ω/mouth. This knitted fabric was disassembled in order to recover the yarn. At this time, in order to improve the durability of the conductivity, the disassembled yarn was immersed in a 25% Hytran AP-20 (I-lysester-based abrasion resistance additive manufactured by Dainippon Ink Co., Ltd.) aqueous solution at a yarn speed of 100 m.
41107 passed through a 200°C heater zone in 5 seconds at a speed of 7 minutes, was further brought into contact with a 210°C contact heater for 2 seconds, and was then wound into 500g portions using a pern winder.
4- Stoppage due to thread cutting during formation of yarn is only Q, 4/
The conductive yarn was obtained in a very high yield.

The obtained conductive thread exhibited an electrical resistance of 3×10Ω·rust.

In Comparative Example 1, the same yarn as in Example 1 was used at a density (15
It was rolled up in 8,500,9 pieces of cheese. This cheese is attached to a cheese dyeing machine (manufactured by Nichikin Seisakusho), and the score roll F
Scouring with a scouring solution containing a-25021//l at a processing temperature of 60°C for 10 minutes while passing the solution from the inside to the outside of the cheese for 3 minutes and from the outside to the inside of the cheese for 3 minutes each. did.

After scouring and water washing, 20 f of copper sulfate was added in the same manner as in Example-1.
1/l, sodium thiosulfate 201/l, disodium phosphate disodium 30 Vl, and citric acid 129/l, a total amount of 201 treatment liquid was prepared, and using this treatment liquid, cheese was treated in the same manner as in Example-1. The treatment was carried out. The temperature of the treatment liquid was raised from room temperature to 50°C over 20 minutes, and then further raised for 50 minutes.
Treatment was performed at 0°C for 20 minutes.

After treatment and washing with water, vacuum dehydration and drying were performed. After drying, the cheese threads were divided into cones of 10 tl each and the state of adhesion of copper sulfide was observed. 100 each for the innermost and outermost layers of cheese
Copper sulfide was found to be attached to the threads of grade I, but no copper sulfide was attached to the 300 g inner layer of the cheese, indicating that it is difficult to uniformly attach copper sulfide with this cheese processing method. There was found.

In Comparative Example 2, the same raw yarn as in Example 1 was wound up to a T-length by soog, and pierced in five places to fix the yarn so that it would not be disturbed. This rope was subjected to the same copper sulfide processing treatment as in Example 1 using a jet-type skein yarn dyeing machine (manufactured by Shinko Seisakusho).

The composition of the processing liquid used, processing temperature, time, etc. were the same as in Example 1. After treatment, it was washed with water, dehydrated using a Certre dehydrator, and then dried at 90° C. for 60 minutes using a gKg dryer. After the copper sulfide treatment, the entire surface was removed to see how the copper sulfide had adhered, and it was found that no copper sulfide had adhered to the expanded area, and the shape of the rug had deteriorated considerably. The resistance value of the obtained yarn was on the side of 1.5×10 Ω·, and the portion to which copper sulfide was not attached was not conductive at all. I tried to rewind this whole material into a cone using a wine goo to obtain a conductive thread, but it turned out to be 1
At a yarn speed of 00 m/min, yarn breakage occurred frequently and it was not possible to rewind the yarn around the cone. Therefore, we used the tin drum method to wind the yarn from the ground onto a tin drum for the purpose of winding it once and then rewinding it around the cone, but the yarn speed was about 5 m/min, and it took a very long time to untangle the yarn by hand. In short, it turned out that this was not a method that could be produced industrially.

Example 2 Acrylic long fiber yarn, 5C1d/25f (trade name Pieuron, manufactured by Mukasei Kogyo Co., Ltd.) was knitted using a single knitting machine in the same manner as in Example 1, with an elongation of 9 and a density of 40 loops/25. 4
A knitted fabric of m was manufactured. Each of these 5009 pieces of knitted fabric was packed into a polypropylene net bag, and then put into a rotary dyeing machine.
(manufactured by Tokyo Washiki Co., Ltd.), put 5 bags (2.5 to 9 in weight of Buron knitted fabric) into water and add sulfuric acid steel 2011/l,
thiosulfate) IJium2 Q 11/It.

A treatment solution with a total volume of 10011 was prepared by adding 2 G Ii/ll of sodium bisulfite. The temperature of this treatment solution was raised from room temperature to 70°C over 30 minutes, and then further raised to 70°C for 30 minutes.
The treatment was carried out for a minute. After that, the knitted fabric was immersed in a treatment solution containing 0.5971 Poron MR (manufactured by Shin-Etsu Silicone Co., Ltd.) as a smoothing agent in order to improve the disassembly property of the knitted fabric after washing and washing, and after dehydration, the knitted fabric was heated to 100°C. It was dried for 40 minutes. This knitted fabric contained 8.2% by weight of copper sulfide, had an electrical resistance of 5 Q/D, and exhibited excellent electrical conductivity. This knitted fabric was unknitted using a corn wine gourd at a yarn speed of 200 m/min. Yarn breakage occurred twice in this unraveling process.
2.5 - A knitted fabric and a yarn having very stable and uniform conductivity was obtained.

The electrical resistance of the obtained conductive yarn was 2.5- [Effects of the Invention] The method of the present invention makes it possible to efficiently produce conductive yarn Togane having uniform conductivity and excellent workability. It is something that can be done. Furthermore, the conductive yarn produced by the method of the present invention is
It can be used in antistatic textile products in all electronics industry fields, such as antistatic carpets, antistatic clothing, and antistatic gloves.

Claims (1)

[Scope of Claims] 1. A knitted fabric is produced from fiber yarns, and this knitted fabric is subjected to a copper sulfide forming treatment to form a conductive material containing copper sulfide on the surface of the fibers constituting the knitted fabric. Forming a layer, and then disassembling the obtained copper sulfide-containing knitted fabric, method 2 for producing conductive yarn, wherein the fiber yarn is polyamide fiber, polyester fiber, polyacrylic fiber, polyolefin fiber. , polyurethane fiber, polyester ether fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, cellulose acetate fiber, rayon fiber, cupro fiber, animal natural fiber, and vegetable natural fiber. Manufacturing method 3 according to claim 1, in which the knitted fabric is made of seed fibers, and the knitted fabric is made of yarn having a thickness of 10 to 100 deniers, and the stretched density is 10 to 100 loops/25.4 mm. Claim 1 falling within the scope of
Manufacturing method 4 according to Claim 1, wherein the copper sulfide-containing knitted fabric contains 0.5 to 10% by weight of a conductive layer.