JP3972127B2 - Metal-coated fiber body and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal-coated fiber body that is excellent in adhesion and corrosion resistance of a metal coating provided on a fiber body, is lightweight, can be manufactured at low cost, and has little influence on human skin, and a method for manufacturing the metal-coated fiber body.
[0002]
[Prior art]
Conventionally known are conductive fibers or yarns 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, and various methods are available for improving the adhesion of the metal coating film. Has been tried. For example, when coating copper sulfide, a method of pre-treating a polymer material with a dye having a copper ion-trapping group, and then sulfiding after binding copper ions to this (Japanese Patent Publication No. 01-37513) or alkali treatment For example, a method of attaching a copper ion capturing group to a roughened fiber surface and then bonding copper sulfide to the copper ion capturing group is known (Japanese Patent Laid-Open No. 06-298973). For materials that are difficult to be metal-plated, such as aramid fiber, a method of forming metal plating by attaching metal ions using polyvinylpyrrolidone (PVP) and reducing the metal ions (JP-A 06-506267) No.) is known.
[0003]
[Problems to be solved by the invention]
However, the plating method using PVP is not general because the types of fibers are limited. Further, the coating method for introducing a copper ion capturing group has a problem that the metal coating is limited to copper or a compound thereof, and the adhesion strength of the metal coating is not always sufficient. Note that if the fiber is roughened by alkali treatment, the adhesion strength of the metal coating can be generally increased, but sufficient effects 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 wear. Furthermore, from the viewpoint of electrical conductivity, the metal coating is required to have a highly reliable adhesion strength because a disconnection state is caused even by partial peeling of the metal coating. In addition, metal-coated fibers, particularly silver-coated fibers, have a problem of causing surface corrosion or discoloration due to oxides or detergents in the atmosphere.
[0004]
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. In general, metal-coated fiber bodies often show surface corrosion due to chlorine and sulfide. In order to prevent this, there is a double metal-coated fiber body in which an anticorrosion metal coating is provided on the upper side of the underlying metal coating. However, this has a concern that the amount of metal is large and the cost is increased. The present invention provides a metal-coated fibrous 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]
[Means for solving the problems]
The present invention is a fiber body having a metal coating, in which a metal coating provided on the surface of the fiber body is used as a base, and a surface coating of a fluorine compound is provided thereon, and it is excellent by providing a conductive metal coating on the base. A metal-coated fiber body having high electrical conductivity and high corrosion resistance by coating with a fluorine compound on the surface, less irritation to the skin, relatively light weight, and low in production cost.
[0006]
The present invention relates to a metal-coated fiber body having the following configuration and a method for producing the same.
(1) A metal coating is provided on the surface of a base fiber made of acrylic fiber, nylon fiber, polyester fiber, high-strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber, or aramid fiber, and the surface of the metal coating Is coated with a fluorine compound coating, and is heat-treated at a temperature not lower than the melting temperature of the substrate fiber and lower than the melting temperature after the metal coating is provided. A metal-coated fiber body, which is formed.
(2) The metal-coated fiber body described in (1) above, wherein the fluorine compound coating is 0.01 to 5% of the weight of the metal-coated fiber body.
(3) The metal-coated fiber body according to (1) or (2) above, wherein the surface of the fluorine compound coating is paraffin-treated or wax-treated.
(4) The metal coating according to any one of (1) to (3) above, wherein the metal coating is a conductive metal coating made of one or more of gold, silver, copper, nickel, tin, or an alloy thereof. Fiber body.
(5) A metal coating is provided on the surface of a base fiber made of acrylic fiber, nylon fiber, polyester fiber, high-strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber, or aramid fiber, and the crystallization temperature of the base fiber A method for producing a metal-coated fibrous body, wherein the heat treatment is performed at a temperature lower than the melting temperature and then a fluorine compound coating is formed on the surface of the metal coating at a temperature lower than the crystallization temperature of the base fiber.
(6) After providing a metal coating on the surface of the base fiber, the metal-coated fiber body is heat-treated at a temperature higher than the crystallization temperature of the base fiber and lower than the melting temperature. The metal-coated fibrous body according to (5) above, wherein after circulating the solution and contacting, pressurized water vapor is introduced, and drying and heat treatment is performed below the crystallization temperature of the base fiber to form a fluorine compound coating on the metal-coated surface Manufacturing method.
[0007]
Furthermore, this invention relates to the following manufacturing methods.
(7) After providing a metal coating on the surface of the base fiber, this is heat-treated at a temperature that is higher than the crystallization temperature of the base fiber and lower than the melting temperature. The manufacturing method of the metal-coated fiber body formed below the crystallization temperature.
(8) The method for producing a metal-coated fibrous body according to the above (7), wherein an organic fluorine-based surfactant or an alkoxysilane-based fluorine compound solution is used as the fluorine-based compound coating forming solution.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be specifically described based on embodiments.
The metal-coated fiber body of the present invention is characterized by having a base metal coating on the surface layer of the base fiber and a fluorine compound coating thereon. In the present invention, the fiber body refers to short fibers (staples), long fibers (filaments), and various processed yarns (filament yarns, spun yarns, etc.) made of these fibers, and these are broadly referred to as fiber bodies. .
[0009]
As a fiber (called a base fiber) as a base of the metal-coated fiber body of the present invention, a synthetic fiber mainly composed of a polymer material such as polyester, polyamide, acrylic, polyolefin, nylon, natural fiber such as cotton, rayon, etc. In addition to these organic fibers, inorganic fibers such as glass fibers, or composite fiber bodies thereof can be used. These fiber bodies may be a mixture of two or more, or may be a mixture of synthetic fibers and natural fibers.
[0010]
Furthermore, the present invention includes those using high-strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber, or aramid fiber as the base fiber. The high-strength nylon fiber is a highly polymerized nylon fiber marketed under the trade name of XYLON. These fibers are high polymers, have a high melting temperature, and are excellent in heat resistance. Conductive resins containing metal-coated single fibers using the base fibers are suitable for use in a high temperature environment.
[0011]
The base 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 an alloy thereof. The coating method or means is not limited. Electrolytic plating, chemical (electroless) plating, vacuum deposition, or the like can be used. It is preferable to provide the metal coating 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 fiber body is etched in advance with an alkali or the like to roughen the surface because the plated metal to be coated enters the rough surface of the surface of the fiber body and exhibits an anchor effect. This metal coating may be a single layer or two or more layers.
[0012]
The metal coating preferably has orange peel on the surface. The adhesion strength is improved by having an orange peel in the metal coating. An orange peel is a state similar to an orange peel and has a surface roughness of about 0.01 to 1 μm, and is called yuzu skin or pear skin. When the thickness of the metal coating is approximately several hundred nanometers (nm) or less, the metal coating having an orange peel is in a rough state up to the back side of the coating, and the surface of the base fiber is a metal in the rough state. Since it enters the back surface of the coating and exhibits an anchor effect, the adhesive strength between the base fiber and the metal coating is improved. Furthermore, since the metal coating surface has orange peel, the adhesive strength with the fluorine compound coating on the upper side is also improved.
[0013]
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 can be obtained by this fluorine compound coating. In order to have long-lasting water repellency, the amount of the fluorine compound coating is preferably 0.5% by weight or more. Even if the coating amount exceeds 5% by weight, the water repellency does not change greatly. Therefore, the coating amount is suitably 5% by weight or less.
[0014]
This fluorine compound coating is preferably formed using an organic fluorine-based surfactant or an alkoxysilane-based fluorine compound. For example, a solution containing the above compound is applied to the metal-coated surface, or a metal-coated fiber body is immersed in these solutions to adhere the fluorine compound solution to the metal-coated surface, which is dried and heat-treated to obtain a fluorine-based surface activity. A fluorine compound coating is formed on the surface of the metal coating by reacting an agent or by hydrolysis of alkoxysilicone.
[0015]
A commercially available fluorine-based surfactant can be used as the fluorine compound solution. As an example of this, an aqueous solution in which a fluorine-containing surfactant having a concentration of 1 to 10%, a melamine resin having a concentration of 0.1 to 1%, and a catalyst compound of 0.05 to 1% is mixed is known. In addition, when the density | concentration of a fluorine-type surfactant is deeper than 10%, since the surface of a metal covering fiber body will change into brown, it is unpreferable. Further, when the concentration is less than 1%, the water repellent effect is low, and the discoloration preventing effect for chlorine and sulfur compounds is also low.
[0016]
The metal-coated fiber body of the present invention has a fluorine-based compound coating on the surface, and this serves as a protective layer for the underlying metal coating, thereby improving the corrosion resistance. Specifically, for example, when this metal-coated fibrous body is washed with a chlorine-based cleaning agent, penetration of the chlorine-based cleaning agent is prevented by this surface coating, so that the corrosion resistance to the chlorine-based cleaning agent is excellent. In addition, it exhibits excellent corrosion resistance against corrosion caused by sulfides contained in dust, sweat, etc., or oxidation reaction in the 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 possibility of causing metal allergy or the like. In addition, since these fluorine compound coatings are highly transparent, the color tone of the underlying metal coating appears on the coating surface under an appropriate film thickness. Therefore, by providing a white conductive metal coating, it is possible to obtain a white conductive fiber body that is excellent in corrosion resistance and does not cause metal allergy.
[0017]
The metal-coated fiber body of the present invention includes those obtained by further surface-treating the surface of the fluorine-based compound coating. As the surface treatment, rust prevention treatment or oil treatment (oiling) with paraffin or wax can be performed. In addition, this rust prevention treatment can prevent a decrease in whiteness over time and a decrease in adhesion (peeling strength). Moreover, the slipperiness of the fiber body surface improves by performing an oil process. This oil treatment improves slipping when the fiber body is processed by a loom or a knitting machine, and thus also protects the adhesion of the metal coating. When the metal-coated fiber body is actually used, it receives physical forces such as friction, shearing force, bending, and the like, and the metal coating is peeled or missing depending on its strength and frequency. The degree thereof is directly based on the adhesion strength between the metal coating and the fibrous body, but by applying the surface treatment, friction, shearing force and the like are buffered, and as a result, peeling of the metal coating is prevented.
[0018]
The metal-coated fiber body of the present invention is used as various yarns such as short fibers and long fibers, or spun yarn and processed yarn. In addition to using the metal-coated fiber alone, it can be used as a synthetic fiber, a natural fiber, or a mixed fiber blended with a synthetic fiber and a natural fiber. Furthermore, 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 or a knitted material. In this case, those using silver, tin, nickel, etc. have high whiteness, so that they have excellent color developability when dyed and are suitable for textiles and clothing materials. Furthermore, what coated silver etc. can be utilized as an antimicrobial fiber body and antimicrobial clothing. Specific applications include antibacterial socks, underwear, outerwear, lab coats, bedding, sheets, napkins, gloves, shirts, trousers, carpets, mats, curtains or work clothes.
[0019]
In addition, the metal-coated fiber body of the present invention is not limited to a fabric material or the like, and uses its conductivity to prevent an electromagnetic wave shielding material, dust-free clothing, gloves, shoes, covers, work clothes, and other antistatic materials, or electrodes or It can be used as an alternative material for reducing the weight of electric wires. Further, it can be used as a composite conductive material by kneading with an organic material, a conductive reinforcing material of a fiber reinforced plastic, or the like.
[0020]
In addition, as a means for producing the metal-coated fiber body of the present invention, the base fiber may be installed in a tank in a cheese winding state and plated so that a plating solution flows from the inside to the outside of the cheese winding. Specifically, a shaft for supporting the base fiber is provided in the tank, a large number of small holes through which the plating solution flows are provided on the peripheral surface of the shaft, and an introduction pipe for the plating solution is connected to the shaft. A base fiber of cheese winding is inserted into this shaft, and a plating solution is supplied. The plating solution flows inside the shaft, flows out from the small holes, and passes through the base fiber from the inside toward the outside. According to such a manufacturing means, the gap between the fibers is pushed outward by the plating solution, and the plating solution penetrates into the details of the mutual fibers. The plating is formed uniformly.
[0021]
After the metal coating (plating) is applied, the fiber body is dried and subjected to a heat treatment within the above temperature range (a temperature higher than the crystallization temperature of the base fiber and lower than the melting temperature) . This heat treatment may be performed by introducing pressurized water vapor into the plating tank. Alternatively, the wound body may be taken out from the plating tank and transferred to an electric furnace or the like for heat treatment. Note that the heat treatment atmosphere may be air, but in order to prevent discoloration due to oxidation of the metal coating, the heat treatment may be performed in an inert atmosphere such as nitrogen or argon. After forming the metal coating, a fluorine compound coating is further formed below the crystallization temperature of the base fiber. After the metal coating (plating) and heat treatment have been finished, the fiber body is again placed in the tank of the plating process, and after circulating the fluorine-based compound solution and contacted, pressurized water vapor is introduced, dried, and heat treated. The fluorine compound can be uniformly coated on the upper layer of the coating.
[0022]
【Example】
Hereinafter, the present invention will be specifically described by way of examples.
Using the above-described plating means, the base fiber (150 denier) 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 solution (Ascreen A-220: Okuno Pharmaceutical 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, 20 wt% sodium hydroxide solution is circulated in the plating tank for 20 minutes at 70 ° C., and after thoroughly washing with ion exchange water, 5 wt% concentrated hydrochloric acid solution is placed in the plating tank at room temperature for 2 minutes. It was circulated.
(C) Activation treatment: After alkali treatment, concentrated hydrochloric acid solution and palladium chloride mixed solution (Catalyst C: Hadano Pharmaceutical Co., Ltd. product) was circulated through the plating bath at room temperature for 3 minutes and then thoroughly washed with ion-exchanged water. . Further, a 10 wt% sulfuric acid solution was circulated through the plating tank at 45 ° C. for 3 minutes for activation.
(D) Formation of the first layer metal coating: After the catalyst is attached to the surface of the fiber body by the above pretreatment, the base fiber is immersed in each of silver, nickel and copper plating solutions, and the base layer is coated by electroless plating. A single metal coating was formed.
(E) Heat treatment: A part of the metal-coated fiber body produced through the above steps was placed in an electric furnace and heat-cooled under a temperature condition not lower than the crystallization temperature of the base fiber and lower than the melting temperature.
[0023]
[Example 1]
The metal-coated fiber body obtained by the steps (a) to (e) above was prepared using a fluorosurfactant (0.05% concentration, 1% concentration, 3% concentration, 5% concentration), melamine resin (0.3). % Concentration) and an organic amine (0.1% concentration) in an aqueous solution, taken out, dried, and heat-treated for 4 hours.
[0024]
[Example 2]
The metal-coated fiber body obtained by the steps (a) to (e) above was prepared by using an alkoxysilane surfactant (0.05% concentration, 1% concentration, 3% concentration, 5% concentration), acetic acid (0.1%). % Concentration) was taken out, taken out and dried, followed by heat treatment for 4 hours.
[0025]
These metal-coated fiber bodies were subjected to whiteness and chlorine bleaching tests to examine the presence or absence of corrosion. In the chlorine bleaching test, the silver-coated fiber of the sample was immersed in 100 cc of an aqueous chlorine solution (an aqueous solution containing 50% of the trade name Hiter) for 10 minutes at room temperature, and the generated bubbles were observed and evaluated in three stages. The whiteness was left in the atmosphere at room temperature (1 month, 3 months), and the L value was determined based on the Hunter equation. These results are shown in Table 1. In addition, as a comparative example, a fiber body not formed with a fluorine compound coating is shown in comparison.
[0026]
As shown in this result, all the metal-coated fiber bodies belonging to the preferred range of the present invention have excellent corrosion resistance against chlorine corrosion, and also have high discoloration resistance, and high whiteness in silver coating. . On the other hand, all the comparative examples were corroded by chlorine and the whiteness was also lowered.
[0027]
【The invention's effect】
The metal-coated fiber body of the present invention is excellent in corrosion resistance and has high coating strength. Specifically, it has excellent chlorine corrosion resistance in the chlorine bleaching test. Furthermore, it maintains whiteness without discoloration even when left in the atmosphere. In addition, the stretch 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 a field that could not be applied due to insufficient adhesion and discoloration resistance of the metal coating.
[0028]
[Table 1]

Claims (6)

A base fiber made of acrylic fiber, nylon fiber, polyester fiber, high-strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber, or aramid fiber has a metal coating, and the surface of the metal coating is a fluorine compound. And having a coating, heat-treated at a temperature not lower than the melting temperature of the substrate fiber and lower than the melting temperature after the metal coating is provided, and the fluorine compound coating is formed at a temperature lower than the crystallization temperature of the substrate fiber. A metal-coated fibrous body characterized by comprising:   The metal-coated fiber body according to claim 1, wherein the fluorine compound coating is 0.01 to 5% of the weight of the metal-coated fiber body. The metal-coated fiber body according to claim 1 or 2, wherein the surface of the fluorine compound coating is paraffin-treated or wax-treated.   The metal-coated fiber body according to any one of claims 1 to 3, wherein the metal coating is a conductive metal coating composed of one or more of gold, silver, copper, nickel, tin, or an alloy thereof. A metal coating is provided on the surface of the base fiber made of acrylic fiber, nylon fiber, polyester fiber, high-strength nylon fiber, polyphenylene sulfide fiber, polycarbonate fiber, or aramid fiber, and the crystallization temperature of the substrate fiber is exceeded. A method for producing a metal-coated fiber body, in which a heat treatment is performed at a temperature lower than the melting temperature, and then a fluorine compound coating is formed on the surface of the metal coating at a temperature lower than the crystallization temperature of the base fiber.   After providing a metal coating on the surface of the substrate fiber, the metal-coated fiber body is heat-treated at a temperature higher than the crystallization temperature of the substrate fiber and lower than the melting temperature, and then placed in a tank to circulate the fluorine compound solution. 6. The method for producing a metal-coated fibrous body according to claim 5, wherein after the contacting, pressurized water vapor is introduced, and drying and heat treatment is performed at a temperature lower than the crystallization temperature of the base fiber to form a fluorine compound coating on the surface of the metal coating.