JP2003183980A - Metal coated fiber body and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a metal coated fiber body keeping excellent corrosion resistance and high whiteness and having excellent coating strength. <P>SOLUTION: This metal coated fiber body has metal under coating on the surface of a base fiber and then fluorine compound coating on the metal under coating, and is preferably heat treated at not lower than the crystallization temperature of the base fiber and lower than the melting temperature after forming the metal coating. Consequently, the metal coated fiber body is used in a field in which a conventional metal coated fiber body can not be applied because of insufficient adhesivity of metal coating and color fastness. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal-coated fiber which is excellent in adhesion and corrosion resistance of a metal coating provided on a fibrous body, is lightweight and can be produced at a low price, and has little influence on human skin. The present invention relates to a body and a manufacturing method thereof.

[0002]

2. Description of the Related Art A conductive fiber or conductive thread in which a metal thin film is coated on the surface of a synthetic fiber made of a polymer material such as nylon fiber or polyester fiber has been known in the past, in order to improve the adhesion of the metal coating film. Various methods have been tried. For example, in the case of coating copper sulfide, a method of pretreating a polymer material with a dye having a copper ion-trapping group, binding copper ions to the polymer material, and then sulfiding
(Japanese Patent Publication No. 01-37513) and a method of attaching copper ion-trapping groups to the surface of the fiber roughened by alkali treatment and then binding copper sulfide thereto (Japanese Patent Laid-Open No. 06-298973) and the like. ing. In addition, polyvinylpyrrolidone (PVP) is used for materials that are difficult to apply metal plating such as aramid fiber.
There is known a method of depositing metal ions by utilizing, and reducing the metal ions to form metal plating (Japanese Patent Laid-Open No. 06-506267).

[0003]

However, the above-mentioned PVP
The plating method using is not common because the types of fibers are limited. Further, the coating method of introducing a copper ion-trapping group has a problem that the metal coating is limited to copper or its compound and the adhesion strength of the metal coating is not always sufficient. Although the adhesion strength of the metal coating can be generally increased by roughening the fibers by treating them with an alkali, a sufficient effect cannot be obtained unless the degree of roughening and the state of the metal coating are appropriate. Moreover, when the metal-coated fiber is used for clothing or the like, it is necessary to withstand severe use conditions such as washing and abrasion. Further, from the viewpoint of conductivity, even if the metal coating is partially peeled off, a disconnection state is caused. Therefore, the metal coating is required to have a highly reliable adhesion strength. Further, metal-coated fibers, especially silver-coated fibers, have a problem that surface corrosion and discoloration occur in the atmosphere due to oxides, detergents, and the like.

The present invention solves the above-mentioned problems in conventional metal-coated fibers, and provides a metal-coated fiber body having excellent corrosion resistance and coating strength. Generally, metal-coated fibrous materials are often surface-corroded by chlorine and sulfide. In order to prevent this, there is a double metal-coated fiber body in which an anticorrosive metal coating is provided on the upper side of the underlying metal coating, but this has a large amount of metal, and there is a concern that this will lead to higher costs. The present invention provides a metal-coated fiber body having a small amount of coated metal, excellent corrosion resistance, and less irritation to the skin, by providing a fluorine compound coating on the metal-coated surface.

[0005]

According to the present invention, in a fibrous body having a metal coating, a metal coating provided on the surface of the fibrous body is used as a base, and a surface coating of a fluorine compound is provided thereon, and the base has a conductive property. (EN) Provided is a metal-coated fiber body which has excellent conductivity by providing a metal coating and which has a fluorine compound coating on the surface to enhance corrosion resistance, is less irritating to the skin, is relatively lightweight, and has a low manufacturing cost.

That is, the present invention relates to a metal-coated fiber body having the following constitution and a method for producing the same. (1) A metal-coated fiber body characterized in that a base metal has a metal coating on the surface thereof, and further has a fluorine compound coating thereon. (2) The base fiber is heat-treated at a temperature equal to or higher than the crystallization temperature and lower than the melting temperature after the metal coating is provided.
The metal-coated fiber body of (1). (3) 0.01 to 5% of the weight of the fibrous body is covered with the fluorine compound.
The metal-coated fiber body according to (1) or (2) above, which is (4) The above (1), (2) or (3), wherein the base fiber is an acrylic fiber, nylon fiber, polyester fiber, high strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber or aramid fiber A metal coated fiber body. (5) The metal as described in any one of (1) to (4) above, wherein the underlying metal coating is a conductive metal coating made of one or more of gold, silver, copper, nickel, tin or alloys thereof. Coated fiber body. (6) The metal-coated fiber body according to any one of (1) to (5) above, wherein the underlying metal coating has orange peel, a fluorine compound coating is provided on the upper side, and the paraffin treatment or wax treatment is further performed. .

Furthermore, the present invention relates to the following manufacturing method. (7) After the metal coating is provided on the surface of the base fiber, it is heat-treated at a temperature higher than the crystallization temperature of the base fiber and lower than the melting temperature, and then the base compound fiber is coated with a fluorine compound. A method for producing a metal-coated fiber body which is formed below the crystallization temperature. (8) The method for producing a metal-coated fiber body according to the above (7), wherein an organic fluorine-based surfactant or an alkoxysilane-based fluorine compound solution is used as the solution for forming the fluorine-based compound coating.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on embodiments. The metal-coated fiber body of the present invention is characterized by having an underlying metal coating on the surface layer of the base fiber and a fluorine compound coating thereon. In the present invention, the term "fibrous body" refers to short fibers (staples), long fibers (filaments), and various processed yarns (filament yarns, spun yarns, etc.) made of these fibers, and is broadly referred to as a fibrous body. .

As the fibers (referred to as substrate fibers) as the substrate of the metal-coated fiber body of the present invention, synthetic fibers mainly composed of polymer materials such as polyester, polyamide, acrylic, polyolefin and nylon, natural fibers such as cotton, etc. Fibers, cellulosic fibers such as rayon, in addition to these organic fibers, inorganic fibers such as glass fibers, or composite fibrous bodies thereof may be mentioned. These fiber bodies may be a mixture of two or more kinds, or a mixture of synthetic fibers and natural fibers.

Further, the present invention includes those using high-strength nylon fibers, polyphenylene sulfide fibers, polycarbonate fibers, or aramid fibers as the base fibers. The high-strength nylon fiber is, for example, a highly polymerized nylon fiber marketed under the trade name of Zylon. These fibers are high polymers, have a high melting temperature, and are excellent in heat resistance, and the conductive resin containing the metal-coated single fiber using this base fiber is suitable for use in a high temperature environment.

The underlying metal coating provided on the surface of the base fiber is preferably a conductive metal coating made of one or more of gold, silver, copper, nickel, tin, or alloys thereof. The covering method or means is not limited.
Electrolytic plating, chemical (electroless) plating, vacuum deposition or the like can be used. It is preferable to provide a coating of the above metal on the surface of the base fiber by electrolytic plating or chemical plating. When the metal coating is provided, it is preferable that the surface of the fibrous body is previously subjected to an etching treatment with an alkali or the like to roughen the plated metal to enter the roughened surface of the fibrous body and exert an anchor effect. This metal coating may be a single layer or two or more layers.

The metal coating preferably has orange peel on its surface. Since the metal coating has orange peel, the adhesion strength is improved. Orange peel is a state similar to orange peel and has a surface roughness of about 0.01 to 1 μm.
It is called yuzu skin or satin skin. When the layer thickness of the metal coating is approximately several hundreds of nanometers (nm) or less, the metal coating having orange peel is roughened to the back side of the coating, and the surface of the substrate fiber is a metal in this roughened state. Since it enters the back surface of the coating and exerts an anchor effect, the adhesive strength between the base fiber and the metal coating is improved. Further, since the metal coating surface has orange peel, the adhesive strength with the fluorine compound coating on the upper side is also improved.

The metal-coated fiber body of the present invention has a fluorine compound coating on the surface of the metal coating. The amount of the fluorine compound coating in the metal-coated fiber body is 5% by weight or less, preferably 0.01 to 5% by weight. Excellent water repellency is obtained by this fluorine compound coating. To have long-lasting water repellency, the amount of fluorine compound coating is 0.5% by weight
The above is preferable. Even if the coating amount exceeds 5% by weight, the water repellency does not change significantly, so the coating amount is 5% by weight.
The following are appropriate:

The fluorine compound coating may be formed by using an organic fluorine type surfactant or an alkoxysilane type fluorine compound. For example, a solution containing the above compound is applied to a metal-coated surface, or a metal-coated fiber body is dipped in these solutions to adhere a fluorine compound solution to the metal-coated surface, which is dried and heat-treated to give a fluorine-based surface active agent. A fluorine compound coating is formed on the surface of the metal coating by reacting the agent or by hydrolyzing the alkoxysilicone.

As the fluorine compound solution, a commercially available fluorine type surfactant can be used. As an example of this, 1
An aqueous solution in which a fluorinated surfactant having a concentration of -10%, a melamine resin having a concentration of 0.1 to 1%, and a catalyst compound of 0.05 to 1% are mixed is known. If the concentration of the fluorine-based surfactant is higher than 10%, the surface of the metal-coated fiber body will be discolored to brown, which is not preferable. Also, this concentration is 1
If it is less than%, the water repellent effect is low and the discoloration preventive effect against chlorine and sulfur compounds is also low.

The metal-coated fiber body of the present invention has a fluorine-based compound coating on its surface, which serves as a protective layer for the underlying metal coating, so that the corrosion resistance is improved. Specifically, for example, when the metal-coated fiber body is washed with a chlorine-based cleaning agent, the surface coating prevents penetration of the chlorine-based cleaning agent, and thus the corrosion resistance to the chlorine-based cleaning agent is excellent. Also,
It also has excellent corrosion resistance against sulfide reactions caused by sulfides contained in dust and sweat, and corrosion caused by oxidation reactions in air. Furthermore, since the underlying metal coating is not exposed to the outside, there is almost no irritation to the skin and there is no risk of metal allergy or the like. Further, since these fluorine compound coatings have high transparency, the color tone of the underlying metal coating appears on the coating surface under an appropriate film thickness. Therefore, by providing the white conductive metal coating, it is possible to obtain a white conductive fiber body which is excellent in corrosion resistance and does not cause metal allergy.

The metal-coated fiber body of the present invention includes a surface of a fluorine-based compound coating which is further surface-treated. As the surface treatment, rust prevention treatment with paraffin or wax or oil treatment (oiling) can be applied.
It should be noted that this rust-prevention treatment can prevent a decrease in whiteness over time and a decrease in adhesion (peel strength). Also,
The oil treatment improves the slipperiness of the surface of the fibrous body. This oil treatment improves the slippage of the fibrous body when it is processed by a loom or a knitting machine, and thus protects the adhesion of the metal coating. When the metal coated fiber body is actually used,
When subjected to physical forces such as friction, shearing force, and bending, the metal coating is peeled off or missing depending on its strength and frequency. Although their degree is directly based on the adhesion strength between the metal coating and the fibrous body, the above surface treatment buffers friction, shearing force, etc., and consequently prevents the metal coating from peeling.

The metal-coated fiber body of the present invention is used as various fibers such as short fibers and long fibers, spun yarns and processed yarns. In addition to using the metal-coated fiber alone, it can be used as a mixed fiber obtained by mixing and spinning a synthetic fiber, a natural fiber, or a mixed fiber of a synthetic fiber and a natural fiber. Further, the metal-coated fiber body of the present invention can be used as a fabric material such as a woven fabric or a non-woven fabric, a knitting material, or the like. In this case, those using silver, tin, nickel, etc. have a high whiteness and therefore have excellent coloring properties when dyed, and are suitable for textile materials and cloth materials for clothing. Further, those coated with silver or the like can be used as an antibacterial fiber body and an antibacterial clothing. Specific applications include antibacterial socks, underwear, outerwear, lab coats, bedding, sheets, napkins, gloves, shirts, pants, rugs, mats, curtains or work clothes.

Further, the metal-coated fiber body of the present invention is not limited to a fabric material and the like, but its electric conductivity is utilized to provide an electromagnetic wave shielding material,
It can be used as an antistatic material such as dust-free clothes, gloves, shoes, covers, work clothes, or an alternative material for reducing the weight of electrodes and electric wires. Further, it can be used as a composite conductive material obtained by kneading with an organic material, a conductive reinforcing material for fibrous body reinforced plastic, and the like.

As a means for producing the metal-coated fiber body of the present invention, when the base fiber is placed in a tank in a state of cheese roll and the plating solution is flowed from the inside to the outside of the cheese roll, plating is performed. good. Specifically, a shaft for supporting the base fibers is provided in the tank, a large number of small holes through which the plating solution flows out are provided on the peripheral surface of the shaft, and a pipe for introducing the plating solution is connected to the shaft. Insert the cheese-wound base fiber into this shaft,
Supply plating solution. The plating solution flows inside the shaft, flows out from the small holes to the outside, and passes through the substrate fibers from the inside toward the outside. According to such a manufacturing means, the gap between the fibers is spread outward by the plating solution, and the plating solution penetrates into the details of the fibers, so that even when cheese is wound, the metal on the surface of the fibrous body remains. Plating is formed uniformly.

After applying the metal coating (plating), the fibrous body is dried and subjected to heat treatment within the above temperature range. This heat treatment may be performed by introducing pressurized steam into the plating tank.
Alternatively, the wound body may be taken out of the plating tank and transferred to an electric furnace or the like for heat treatment. The heat treatment atmosphere may be air, but in order to prevent discoloration due to the oxidation of the metal coating, it is preferable to perform the heat treatment under an inert atmosphere such as nitrogen or argon. In addition, metal coating (plating), put the fibrous body that has been subjected to heat treatment again in the tank of the plating process, circulate the fluorine-containing compound solution to make contact, then introduce pressurized steam, and perform drying and heat treatment. Thus, the fluorine compound can be uniformly coated on the upper layer of the metal coating.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples. Base fiber (150 denier) using the plating means
Was placed in a plating tank, and a metal-coated fiber body was obtained through the following treatment steps (a) to (e). (A) Degreasing treatment: A 5 wt% solution of a degreasing liquid (A-screen A-220: product of Okuno Chemical Industries Co., Ltd.) was circulated in a plating tank at 55 ° C. for 5 minutes, and then thoroughly washed with ion-exchanged water. (B) Alkaline treatment: After degreasing treatment, a 20 wt% sodium hydroxide solution was circulated in the plating tank at 70 ° C. for 20 minutes, further thoroughly washed with ion-exchanged water, and then a 5 wt% concentrated hydrochloric acid solution was added to the plating tank at room temperature for 2 minutes. Circulated. (C) Activation treatment: After alkali treatment, a concentrated hydrochloric acid solution and a palladium chloride mixed solution (Catalyst C: a product of Akashino Pharmaceutical Co., Ltd.) were circulated in the plating tank at room temperature for 3 minutes, and then thoroughly washed with ion-exchanged water. . Further, a 10 wt% sulfuric acid solution was circulated in the plating tank at 45 ° C. for 3 minutes for activation. (D) Formation of first-layer metal coating: After the catalyst is attached to the surface of the fibrous body by the above pretreatment, the base fiber is dipped in each plating solution of silver, nickel, and copper, and electroless plating is used to form a base layer. A single layer metallization was formed. (E) Heat treatment: A part of the metal-coated fiber body produced through the above steps was charged into an electric furnace and heat-cooled at a temperature above the crystallization temperature of the base fiber and below the melting temperature.

Example 1 The metal-coated fiber body obtained by the above steps (a) to (e) was treated with a fluorosurfactant (0.05).
% Concentration, 1% concentration, 3% concentration, 5% concentration), immersed in an aqueous solution containing melamine resin (0.3% concentration), organic amine (0.1% concentration), taken out, dried and heated for 4 hours Processed.

Example 2 A metal-coated fiber body obtained by the above steps (a) to (e) was treated with an alkoxysilane-based surfactant (0.05% concentration, 1% concentration, 3% concentration, 5%). concentration),
It was immersed in an aqueous solution containing acetic acid (0.1% concentration), taken out, dried, and heat-treated for 4 hours.

With respect to these metal-coated fibrous bodies, whiteness and chlorine bleaching tests were conducted to examine the presence or absence of corrosion. In the chlorine bleaching test, a sample silver-coated fiber was immersed in 100 cc of an aqueous chlorine solution (an aqueous solution containing 50% of product name Higher) at room temperature for 10 minutes, and bubbles generated were observed to make a three-stage evaluation.
Whiteness is left at room temperature in the atmosphere (1 month, 3 months), then
The L value was calculated based on Hunter's formula. The results are shown in Table 1. In addition, as a comparative example, a fibrous body not coated with a fluorine compound is shown in comparison.

As shown in these results, all of the metal-coated fiber bodies which belong to the preferred range of the present invention have excellent corrosion resistance against chlorine corrosion, have high discoloration resistance, and are white in silver coating. The degree is also high. On the other hand, in each of the comparative examples, corrosion due to chlorine was observed, and the whiteness also decreased.

[0027]

The metal-coated fiber body of the present invention has excellent corrosion resistance and high coating strength. Specifically, it has excellent chlorine corrosion resistance in a chlorine bleaching test. further,
Maintains whiteness without discoloration even when left in the atmosphere. Further, the expansion and contraction rate is small even under heating, and the durability against external force is excellent. Therefore, the metal-coated fiber body of the present invention can also be used in the fields that could not be applied until now because the adhesion and discoloration resistance of the metal coating were insufficient.

[0028]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuo Furuya             Stock Market Association, 3-1, 6 Ibaraki, Akita City, Akita Prefecture             Company Gemco No. 1 Office (72) Inventor Yusuke Maeda             Stock Market Association, 3-1, 6 Ibaraki, Akita City, Akita Prefecture             Company Gemco No. 1 Office F-term (reference) 4L031 AA13 AA17 AA18 AA20 AA21                       AB01 BA04 BA11 CA01 CB12                       DA14 DA15                 4L033 AA05 AA07 AA08 AA10 AC06                       AC15 CA59

Claims (8)

[Claims] 1. A metal-coated fiber body comprising a base fiber and a base metal coating on the surface of the base fiber, and further a fluorine compound coating thereon. 2. The metal-coated fiber body according to claim 1, wherein after the metal coating is provided, the base fiber is heat-treated at a temperature not lower than the crystallization temperature and lower than the melting temperature. 3. The fluorine compound coating is 0.0 in the weight of the fibrous body.
It is 1-5%, The metal-coated fiber body of Claim 1 or 2. 4. The base fiber is an acrylic fiber, a nylon fiber, a polyester fiber, a high strength nylon fiber, a polyphenylene sulfide fiber, a polycarbonate fiber or an aramid fiber.
The metal-coated fiber body as described in 1. 5. The metal coating according to claim 1, wherein the underlying metal coating is a conductive metal coating made of one or more of gold, silver, copper, nickel, tin or alloys thereof. Fibrous body. 6. The metal-coated fiber body according to claim 1, wherein the underlying metal coating has orange peel, a fluorine compound coating is provided on the upper side, and the paraffin treatment or wax treatment is further performed. 7. After providing a metal coating on the surface of the base fiber, this is heat-treated at a temperature higher than the crystallization temperature of the base fiber and lower than the melting temperature, and then the surface of the metal coating is coated with a fluorine compound. A method for producing a metal-coated fiber body which is formed at a crystallization temperature of a base fiber or lower. 8. A solution for forming a fluorine compound coating,
The method for producing a metal-coated fiber body according to claim 7, wherein an organic fluorine-based surfactant or an alkoxysilane-based fluorine compound solution is used.