JP2016160480A - Plated fiber and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an electroless plating film excellent in adhesion between a fiber and a metal coating without reducing the strength of a polymer fiber material and using a palladium catalyst.SOLUTION: The method for manufacturing a plated fiber comprises: subjecting an organic polymer fiber to electron beam irradiation treatment to graft polymerize a carboxyl group, sulfonic group or phosphate group containing monomer to 0.1-40 wt.% of the organic polymer fiber; depositing metal salt on the organic polymer fiber by immersing the organic polymer fiber in a metal salt solution; reducing and activating the metal salt deposited on the surface of the organic polymer fiber; immersing the organic polymer fiber in a plating solution to perform electroless plating; and forming an electroless plating film excellent in adhesion between a fiber and a metal coating without reducing the strength of a polymer fiber material by forming a metal plating layer.SELECTED DRAWING: None

Description

  The present invention relates to a technique for improving the adhesion of a plating film in a method for plating a polymer fiber material.

  The process of plating on ordinary polymer materials is a degreasing process (removes oil and fat components adhering to the surface to improve wettability), an etching process (chemical roughening of the surface with chromic acid, etc.) ) And then removing the remaining chromium compound with hydrochloric acid or the like) Catalyst process (adsorbing a catalytic metal such as Pd-Sn complex), accelerator process (activation treatment by oxidation-reduction reaction), plating process (metal) To produce a film).

  In addition, the process of plating on the polymer fiber material is also manufactured through substantially the same process as the process of plating on the polymer material. However, in Patent Document 1, the first process of plasma treatment or electron beam irradiation on the filament bundle is performed. A second step of immersing in a supercritical fluid containing an organometallic complex and attaching the organometallic complex to the filament surface; a third step of reducing and activating the organometallic complex attached to the filament surface; A method for producing a conductive fiber yarn is disclosed, which includes a fourth step of forming a metal plating layer by performing an electroless plating treatment by dipping in a plating solution.

  Furthermore, in Patent Document 2, the step of fixing the silane coupling agent to the fiber surface with the organic polymer fiber, the silane coupling agent fixed to the fiber surface is metallized, and the metal particles are transferred to the fiber surface via the silane coupling agent. And a step of forming an organic polymer fiber fixed to the metal, and a step of electroless plating the metallized organic polymer fiber using a plating metal compound having a higher ionization tendency than the above metal. A method for producing metal-plated organic polymer fibers is disclosed.

  Further, in Patent Document 3, an organometallic complex is dissolved in a supercritical carbon dioxide fluid, impregnated in a polymer fiber material, and then the impregnated organometallic complex is reduced by setting the reduction temperature with a heater. A technique is disclosed in which a metal catalyst for plating is deposited on the surface of the material, and this is used as a plating nucleus.

However, in these techniques, the adhesion between the fiber and the metal film is poor, and the metal film is easily peeled off or the strength of the fiber is lowered.
JP2010-1000093 JP2003-171869 JP2007-56287A

  The present invention has been made in view of such a technical background, and the object thereof is to improve the adhesion between the fiber and the metal film without reducing the strength of the polymer fiber material and without using a palladium catalyst. Another object is to form an electroless plating film.

  As a result of intensive studies to solve such problems, the present inventor conducted an electron beam irradiation treatment on the organic polymer fiber to graft polymerize a carboxyl group, sulfonic acid group, or phosphoric acid group-containing monomer, and then a metal salt. The metal salt is attached to the organic polymer fiber by dipping in the solution, then the metal salt adhering to the surface of the organic polymer fiber is reduced and activated, and then the organic polymer fiber is immersed in the plating solution. By performing an electroless plating process and forming a metal plating layer, it is possible to form an electroless plating film having excellent adhesion between the fiber and the metal film without reducing the strength of the polymer fiber material. The present invention has been reached. The present invention provides the following means.

  [1] A first step of subjecting an organic polymer fiber to electron beam irradiation treatment to graft-polymerize a carboxyl group, sulfonic acid group, or phosphoric acid group-containing monomer in an amount of 0.1 to 40% of the weight of the organic polymer fiber; Or a second step in which a metal salt is attached to an organic polymer fiber graft-polymerized with a sulfonic acid group- or phosphate group-containing monomer, and a metal salt attached to the surface of the organic polymer fiber is reduced and activated. A method for producing a plated fiber comprising three steps and a fourth step of forming an electroless plating process by immersing the activated organic polymer fiber in a plating solution to form a metal plating layer.

  [2] A plated fiber obtained by the production method according to item 1 above.

  In the invention of [1], the carboxyl group, sulfonic acid group, or phosphate group-containing monomer is graft-polymerized to the organic polymer fiber in the first step in an amount of 0.1 to 40% of the weight of the organic polymer fiber. Since the group is covalently bonded to the fiber, the bonding force is strong, and an electroless plating film having excellent adhesion between the fiber and the metal film and high durability can be formed. Moreover, the amount of functional groups introduced into the organic polymer fiber can be adjusted by changing conditions such as irradiation dose and monomer concentration in graft polymerization.

  Furthermore, in the second step, the functional group introduced into the organic polymer fiber by graft polymerization can attach the metal salt, so the adhesion between the plating film produced in the subsequent step and the surface of the organic polymer fiber Can be improved. In addition, since the introduced functional group can selectively adsorb the metal salt, the concentration of the metal salt solution in which the organic polymer fiber is immersed is different from that in the case of performing electroless plating on the raw organic polymer fiber. In comparison, a lower concentration is possible with graft polymerized organic polymer fibers.

  In the third step, since the metal salt adhering to the surface of the organic polymer fiber is reduced and activated, a plating film can be formed by a subsequent plating treatment. Furthermore, by plating the organic polymer fiber that has undergone the above-mentioned step in the fourth step, it is possible to form an electroless plating film having excellent adhesion and durability, light weight and good conductivity with high productivity. it can. Moreover, an electroless plating film having excellent adhesion between the fiber and the metal film can be formed without using a palladium catalyst.

  In the invention of [2], a plated fiber is provided in which an electroless plated film excellent in adhesion between the fiber and the metal film is formed without reducing the strength of the polymer fiber material.

  Examples of the organic polymer fiber in the present invention include polypropylene, cellulose, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, polyethylene, polyisoprene, polyvinyl chloride, polyisoprene, wool, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, and nylon. And polyester fibers.

  The carboxyl group, sulfonic acid group, or phosphoric acid group-containing monomer may be a compound having a vinyl group and a functional group containing a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples include acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, vinyl benzoic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 2- (methacryloyloxy) ethyl phosphate. Graft polymerization is carried out in order to copolymerize a carboxyl group, sulfonic acid group, or phosphoric acid group-containing polymer around the organic polymer fiber and to stably deposit a large amount of metal salt in the next step.

  First, in the first step, an organic polymer fiber is subjected to an electron beam irradiation treatment to graft-polymerize a carboxyl group, a sulfonic acid group, or a phosphate group-containing monomer. At normal temperature, the organic polymer fiber may be irradiated with an electron beam and immersed in a carboxyl group, sulfonic acid group, or phosphoric acid group-containing monomer solution and heated, or the carboxyl group, sulfonic acid group, or phosphoric acid group-containing monomer After immersing the organic polymer fiber in the solution, it may be subjected to electron beam irradiation treatment and heated to cause graft polymerization. The electron beam irradiation may be performed on the yarn wound in a cone shape, but it is slightly stretched with a single yarn or a parallel running yarn so that the electron beam irradiation treatment is performed uniformly. The state is preferably irradiated with an electron beam, and it is preferable to apply a slight load to the take-up reel and perform the electron beam irradiation while winding at a constant speed. In the graft polymerization, it is preferable to perform electron beam irradiation, monomer application, and heating reaction in a nitrogen atmosphere.

  Next, in the second step, a metal salt is attached to the organic polymer fiber graft-polymerized with the carboxyl group, sulfonic acid group, or phosphate group-containing monomer. As a method, the graft polymerized organic polymer fiber may be immersed in a metal salt solution. The immersion temperature is preferably 20 ° C. to 60 ° C., and the immersion time may be about 1 minute to 10 minutes. Thereby, the metal salt can be bonded to the surface of the organic polymer fiber. Further, as in the first step, it is preferable that the metal salt is adhered while winding the metal salt solution at a constant speed by applying a slight load to the take-up reel. The metal salt is not particularly limited, but silver salts such as silver nitrate, silver oxide, silver sulfate, silver chloride, silver sulfite, silver carbonate, silver acetate, copper nitrate, copper oxide, copper sulfate, copper chloride, copper sulfite, Copper salts such as copper carbonate and copper acetate; nickel salts such as nickel sulfate, nickel chloride, nickel nitrate, nickel sulfite and nickel carbonate; cobalt salts such as cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate and cobalt carbonate; tin nitrate And tin salts such as tin sulfate, tin acetate, tin oxide, tin chloride and tin carbonate.

  In the third step, the metal salt adhering to the surface of the organic polymer fiber is reduced and activated. Examples of the treatment liquid include an aqueous solution of sodium borohydride, aldehyde, glucose, hydrazine, ascorbic acid, and the like. Moreover, the activation process reduced by electron beam irradiation may be sufficient. Thereby, a metal can be combined with the surface of the organic polymer fiber by reducing the metal salt adsorbed in the second step. That is, a catalytically active metal can be formed. In the third step, it is preferable to perform the activation treatment while winding the reel around the reel at a constant speed as in the first step and the second step.

  In the fourth step, the organic polymer fiber obtained in the third step is immersed in a plating solution, and an electroless plating treatment is performed to form a metal film. In electroless plating, metal ions in the plating solution are reduced by the electrons released when the reducing agent contained in the plating solution is oxidized on the catalytically active metal surface bonded to the surface of the organic polymer fiber. The metal is deposited on the surface of the organic polymer fiber as a metal film. As electroless plating, a commonly used plating solution can be used. Examples thereof include electroless copper plating, electroless nickel plating, electroless silver plating, electroless cobalt plating, and electroless tin plating.

    The thickness of the plating film is preferably 0.2 μm or more, and more preferably 0.4 μm or more. 0.5 μm to 3.0 μm is the most preferable. If the thickness is less than 0.2 μm, sufficient conductivity and adhesion may not be obtained. If the thickness exceeds 3.0 μm, the flexibility of the fiber is lost and hard. This is not preferable.

  The fourth step is also preferably performed while being wound around the reel at a constant speed, as in the previous step. Of course, there are a washing step, a drying step, etc. between each of the first step to the fourth step, which are not described here. Moreover, it is also possible to process as a continuous process by processing including the 1st process to the 4th process, winding up.

  In addition, electroplating is a method in which metal ions contained in the plating solution are reduced by energizing the object to be plated as an electrode on a metal surface with strong catalytic activity, and the metal is deposited on the object as a metal film. is there. Since electroplating is easier to control the thickness of the plating film than electroless plating, electroplating may be performed after electroless plating in the present invention.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples. In addition, the implementation method of each process, the test method, and evaluation were performed as follows.

(Electron beam graft polymerization process)
Electron beam irradiation was performed with an irradiation dose of 100 kGy using an electron beam irradiation apparatus manufactured by I. Electron Beam. Subsequent monomer application and heating reaction (6 minutes) were performed by a method of continuously treating in a nitrogen atmosphere. Moreover, the kind of monomer, the monomer concentration, the graft ratio, etc. were performed as described in Table 1.

(Catalyst application process)
The organic polymer fiber that has been subjected to electron beam graft polymerization is wound around the bobbin for dyeing, and the flow of water from the inside to the outside of the bobbin for dyeing is created using a liquid feed pump (10 L / min), and the fiber is washed and washed. Monomer-derived compounds not directly bound to were removed. Next, using a liquid feed pump, the catalyst was applied by immersing in a 1% solution of an aqueous silver nitrate solution at 25 ° C. for 5 minutes. Thereafter, the solution was sufficiently washed with ion exchange water using a liquid feed pump.

(Activation process)
The organic polymer fiber to which silver nitrate ions were attached was immersed in a 0.5% solution of an aqueous sodium borohydride solution to reduce the silver ions. Thereafter, it was thoroughly washed with ion exchange water.

(Electroless plating process)
The activated organic polymer fiber is immersed in an electroless plating solution (Muden Silver SS: Okuno Pharmaceutical Co., Ltd.) for 1 hour at 60 ° C. using a liquid feed pump. A metal coating was formed on top. The fiber on which the metal film was formed was washed with ion exchange water and then heated to dry.

(Strength measurement and evaluation of polymer fiber materials)
Strength (cN) and elongation (%) were measured under the conditions of a sample length of 25 cm and a tensile speed of 30 cm / min using a tensile tester of TENSORAPID3 manufactured by USTER. The strength (cN / dtex) is a value obtained by dividing the strength (cN) by the total fineness. In comparison with the unprocessed product, the strength reduction rate was evaluated as ◎, 5% to 10% as ○, 10% to 20% as Δ, and 20% or more as ×.

(Fiber-to-metal coating adhesion test and evaluation tape peeling method)
This was performed according to JIS H8504. After attaching a commercially available cellophane tape to the plated polymer fiber material, peel it off, and visually observe the ratio of "the area of the plating film attached to the tape after peeling the tape" to "the plating area before sticking the tape". I went. Those less than 2% were evaluated as ◎, those from 2% to less than 10% were evaluated as ◯, those from 10% to less than 15% were evaluated as Δ, and those from 15% or more were evaluated as ×.

(Fiber and metal coating adhesion test and evaluation wear test method)
The prepared electroless-plated fibers were subjected to coating adhesion (peeling) strength in accordance with JIS L 0849 “Test Method for Dye Fastness to Friction”. Specifically, a white cloth was layered on the electroless plated fiber of the test material, a load of 200 g was applied, and friction was performed at a reciprocating speed of 30 times per minute. 100 measures the conductivity of after friction reciprocating conductivity after friction those less than 10 ¹ Ω / cm ◎, ○ a of less than ^{10 1 Ω / cm~10 3 Ω /} cm, 10 3 Ω / cm~10 of less than ^{5 Ω} / cm things △, was evaluated as × of not less than 10 ^{5 Ω} / cm.

(Appearance evaluation)
Observe the appearance of the electroless plating fiber created inside and outside of the dyed bobbin, and the appearance of the middle point of the yarn. If the plating is uniform, there is no uneven plating. When there was, it evaluated with plating unevenness existence.

<Example 1>
Nylon fiber yarn (2760 dtex 151f) is prepared as an organic polymer fiber, irradiated with an electron beam at an irradiation dose of 100 kGy in a nitrogen atmosphere, immersed in a 50% monomer solution of acrylic acid, and at a temperature of 80 ° C. for 6 minutes. After heating, it was washed with water and dried to obtain a grafted yarn. The graft rate was 4%. The strength reduction rate is 2%. The obtained yarn was wound around a dyed paper tube, immersed in a 1% silver nitrate aqueous solution, and using a liquid feed pump (5 L / min), a liquid flow from the inside to the outside of the paper tube was created and grafted. Silver ions were selectively adsorbed on the functional group. Next, after washing with water, the silver ions selectively adsorbed by immersion in a 0.1% sodium borohydride aqueous solution were reduced to silver. Next, after washing with water, silver plating by electroless plating was performed at a temperature of 60 ° C. using the reduced silver as a catalyst. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 1%, and the conductivity after friction was 0.8Ω / cm.

<Examples 2 to 7>
Although it implemented and evaluated by the content described in Table 1, all got favorable evaluation. In Example 6, polyester fiber yarn (560 dtex 96f) was prepared as the organic polymer fiber, and in Example 7, polypropylene fiber yarn (540 dtex 120f) was prepared.

<Comparative Examples 1 and 2>
It implemented by the content described in Table 1 by said implementation method, and evaluated. Satisfactory evaluation was not obtained in either Comparative Example 1 or Comparative Example 2.

  The polymer fiber material coated with a plating film according to the present invention is, for example, knitted or woven and incorporated into a fabric to obtain a fabric having a current-carrying performance, and its application range is wide.

Claims (2)

A first step of subjecting the organic polymer fiber to electron beam irradiation treatment and graft polymerization of a carboxyl group, sulfonic acid group or phosphoric acid group-containing monomer in an amount of 0.1 to 40% of the weight of the organic polymer fiber;
A second step of attaching a metal salt to the organic polymer fiber graft-polymerized with the carboxyl group, sulfonic acid group or phosphoric acid group-containing monomer;
A third step of reducing and activating the metal salt adhering to the organic polymer fiber surface;
A method for producing a plated fiber, comprising a fourth step of forming a metal plating layer by immersing the activated organic polymer fiber in a plating solution and performing an electroless plating treatment.   A plated fiber obtained by the production method according to claim 1.