JP2017155383A - Method for producing plated fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a plated fiber excellent in the stability of an electroless plating liquid and further capable of reducing the treatment time of electroless plating.SOLUTION: Provided is a method for producing a plated film comprising: a first step where an organic polymer fiber is subjected to irradiation beam irradiation treatment to graft-polymerize nitrogen-containing monomers; a second step where the organic polymer fiber graft-polymerized with the nitrogen-containing monomers is stuck with a Pd/Sn catalyst; a third step where the Pd/Sn catalyst stuck to the organic polymer fiber surface is reduced, and activation treatment is performed; and a fourth step where the organic polymer fiber plating liquid subjected to the activation treatment is dipped into a plating liquid, and electroless plating treatment is performed to form a metal plating layer, the plating metal in the electroless plating treatment being silver, and also, the concentration of the silver in the plating liquid is 50 to 500 mg/L. The silver is silver nitrate or silber sulfate, and the temperature of the electroless plating treatment is 50 to 65°C.SELECTED DRAWING: None

Description

   The present invention relates to a method for producing a plated fiber.

  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) Producing a coating).

  Moreover, although the process of plating on the polymer fiber material is manufactured through substantially the same process as the process of plating on the polymer material, in Patent Document 1, the filament bundle is subjected to plasma treatment or electron beam irradiation and 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; and plating the filament 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 liquid.

  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, and improvement is required.

Therefore, the applicant has applied for Patent Document 4, and a plated fiber capable of forming an electroless plated film excellent in adhesion between the fiber and the metal film without reducing the strength of the polymer fiber material, and its A manufacturing method is disclosed.
JP2010-1000093 JP2003-171869 JP2007-56287A JP2015-214735A

  The technique described in Patent Document 4 can form an electroless plating film having excellent adhesion between the fiber and the metal film. However, further improvement is required for the stability of the electroless plating solution in the electroless plating treatment process.

  Moreover, although the technique of the said patent document 4 is a manufacturing method of the plating fiber which can process in electroless-plating processing time as short as 15 minutes, the technique which can further shorten the processing time of electroless-plating Development is required.

  The present invention has been made in view of such a technical background, and provides a method for producing a plated fiber that is excellent in the stability of an electroless plating solution and can reduce the processing time of electroless plating. It is.

   In order to achieve the above object, the present invention provides the following means.

[1] A first step of subjecting an organic polymer fiber to electron beam irradiation to graft polymerize a nitrogen-containing monomer, a second step of attaching a Pd / Sn catalyst to the organic polymer fiber grafted with the nitrogen-containing monomer, and A third step of reducing and activating the Pd / Sn catalyst adhering to the surface of the organic polymer fiber, and performing an electroless plating process by immersing the activated organic polymer fiber in a plating solution Including a fourth step of forming a metal plating layer, wherein the plating metal in the electroless plating process is silver, and the concentration of the silver in the plating solution is 50 mg / L to 500 mg / L A method for producing a plated fiber.

[2] The method for producing a plated fiber as described in 1 above, wherein the silver is silver nitrate or silver sulfate.

[3] The method for producing a plated fiber according to item 1 or 2, wherein the temperature in the electroless plating treatment is 50 ° C. to 65 ° C., and the time is 5 minutes to 13 minutes.

  In the invention of [1], since the organic polymer fiber is the first step in which the nitrogen-containing monomer is graft-polymerized by electron beam irradiation treatment, the introduced functional group is covalently bonded to the fiber. An electroless plating film having high strength, excellent adhesion between a fiber and a metal film, and high durability can be formed.

  Furthermore, because this is the second step of attaching a Pd / Sn catalyst to organic polymer fibers grafted with nitrogen-containing monomers, it improves the adhesion between the plating film produced in the subsequent step and the surface of the organic polymer fibers. can do. In addition, since the introduced functional group can selectively adsorb the Pd / Sn catalyst, the concentration of the Pd / Sn colloidal dispersion in which the organic polymer fiber is immersed is equal to that of the raw organic polymer fiber. Compared to the case where electrolytic plating is performed, the organic polymer fiber obtained by graft polymerization can be used at a lower concentration.

  Furthermore, since it is the third step of reducing and activating the Pd / Sn catalyst adhering to the surface of the organic polymer fiber, a plating film can be formed by a subsequent plating treatment.

  Furthermore, this activated organic polymer fiber is immersed in a plating solution to perform an electroless plating process and includes a fourth step of forming a metal plating layer, which is excellent in adhesion and durability, lightweight and conductive A good electroless plating film can be formed with good productivity. Moreover, since the plating metal in the electroless plating treatment is silver and the concentration of the silver in the plating solution is 50 mg / L to 500 mg / L, the electroless plating solution is excellent in stability and electroless plating is performed. The processing time can be shortened.

  In the invention of [2], since silver is silver nitrate or silver sulfate, the electroless plating solution can be made more stable.

  In the invention of [3], since the temperature in the electroless plating treatment is 50 ° C. to 65 ° C. and the time is 5 minutes to 13 minutes, the electroless plating solution can be made more stable and electroless The plating processing time can be shortened.

  The manufacturing method of the plating fiber of this invention is demonstrated in detail. The method for producing a plated fiber according to the present invention includes a first step of subjecting an organic polymer fiber to electron beam irradiation treatment and graft polymerization of a nitrogen-containing monomer, and Pd / Sn on the organic polymer fiber grafted with the nitrogen-containing monomer. A second step of attaching the catalyst, a third step of reducing and activating the Pd / Sn catalyst adhering to the surface of the organic polymer fiber, and immersing the activated organic polymer fiber in the plating solution And a fourth step of forming a metal plating layer, wherein the plating metal in the electroless plating process is silver, and the concentration of the silver in the plating solution is 50 mg / L to 500 mg / It is characterized by being L.

  Examples of the organic polymer fiber in the present invention include aromatic polyamide fiber, polyacrylic fiber, polyester fiber, polyolefin fiber such as polyethylene and polypropylene, nylon, polyvinyl chloride fiber, polyvinylidene chloride fiber, and vinylon. Examples thereof include organic fibers such as polyalcohol fibers and fluorine fibers. Especially, it is effective to apply the manufacturing method of the plating fiber of this invention to nylon, polyester, and polypropylene which are general purpose fibers, and it is especially preferable that it is nylon.

  The nitrogen-containing monomer is not particularly limited, but is preferably a compound having a vinyl group and a functional group containing nitrogen. Specifically, acrylamide, dimethylacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, 4-vinylpyridine, 2-vinylpyridine, N, N- (dimethylamino) ethyl methacrylate, 2- (trimethylammonium) Examples thereof include ethyl methacrylate chloride, N-vinyl 2-vinylpyrrolidone, acrylic amine and the like. The graft polymerization is carried out in order to copolymerize a nitrogen-containing polymer around the organic polymer fiber and to stably deposit a large amount of Pd / Sn in the next step.

  First, in the first step, the organic polymer fiber is subjected to electron beam irradiation treatment to graft-polymerize the nitrogen-containing monomer. At normal temperature, the organic polymer fiber may be subjected to electron beam irradiation treatment and immersed in a nitrogen-containing monomer solution and heated, or after the organic polymer fiber is immersed in the nitrogen-containing monomer solution, electron beam irradiation treatment and heating are performed. And may be graft polymerized. 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 Pd / Sn catalyst is attached to the organic polymer fiber graft-polymerized with the nitrogen-containing monomer. As a method, the graft polymerized organic polymer fiber may be immersed in a Pd / Sn catalyst solution, but a colloidal solution of Pd and Sn is preferable. For example, tin chloride and palladium chloride are dissolved in a hydrochloric acid solution, respectively. What mixed and heated these while stirring is preferable. The immersion temperature is preferably 20 ° C. to 60 ° C., and the immersion time may be about 1 minute to 10 minutes. Thereby, Pd and Sn can be adsorbed and bonded to the surface of the organic polymer fiber. Further, as in the first step, it is preferable that the Pd / Sn catalyst is attached while winding the colloidal solution of Pd and Sn with a slight load on the take-up reel at a constant speed.

  In the third step, the Pd / Sn catalyst adhering to the surface of the organic polymer fiber is reduced and activated. The treatment solution is preferably, for example, an acid or alkali solution that dissolves Sn but does not dissolve Pd. Examples of the acid solution include sulfuric acid, hydrochloric acid, hydrofluoric acid, and the like. Examples of the alkaline solution include sodium hydroxide, potassium hydroxide, ammonia and the like. Thereby, Sn can be dissolved and removed from Pd and Sn adsorbed in the second step, and only Pd can be adsorbed and bonded to the surface of the organic polymer fiber. 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 electrons released when the reducing agent contained in the plating solution is oxidized on the surface of Pd having strong catalytic activity adsorbed and 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.

  The plating metal used for the electroless plating treatment needs to be silver, and the concentration of the silver in the plating solution needs to be 50 mg / L to 500 mg / L. If it is less than 50 mg / L, it is not preferable because the plating treatment time becomes long, and if it exceeds 500 mg / L, the stability of the plating solution is deteriorated, which is not preferable. Of these, 200 mg / L to 400 mg / L is more preferable.

  Examples of the silver include silver nitrate and silver sulfate, and silver nitrate is more preferable.

  The temperature in the electroless plating process is preferably 50 ° C to 65 ° C. If it is less than 50 degreeC, since plating processing time becomes long, it is unpreferable, and even if it exceeds 65 degreeC, stability of a plating solution will worsen and is not preferable. Of these, 50 ° C. to 60 ° C. is more preferable.

  The time in the electroless plating treatment is preferably 5 minutes to 13 minutes. If it is less than 5 minutes, the reaction is not preferable because the reaction is halfway, and if it exceeds 13 minutes, the silver ions in the plating solution disappear, which is not preferable. Of these, 5 to 10 minutes is more preferable.

  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 most preferable, and if it is less than 0.2 μm, sufficient conductivity and adhesion cannot be obtained, and if it exceeds 3.0 μm, the flexibility of the fiber is lost and it becomes hard, which 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.

  Electroplating is a method in which metal ions contained in the plating solution are reduced by energizing the object to be plated on the Pd surface having 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.

<Example 1>
Nylon fiber yarn (2800 dtex 192f) was prepared as the organic polymer fiber. Next, each process was implemented as follows.
(First step: Electron beam graft polymerization step)
In a nitrogen atmosphere, an electron beam irradiation apparatus manufactured by I Electron Beam Co., Ltd. was used, and the nylon fiber yarn was irradiated with an electron beam at an irradiation dose of 50 kGy in a nitrogen atmosphere. Thereafter, the nylon fiber yarn irradiated with the electron beam was immersed in a 10% acrylamide monomer concentration solution, heated at 70 ° C. for 8 minutes, and continuously processed. The graft rate was 21%.
(Second step: catalyst application step)
The organic polymer fiber subjected to the electron beam graft polymerization treatment is immersed in a 0.15% solution of a Pd / Sn catalyst solution (OPC-80 Catalyst ML: Okuno Pharmaceutical Co., Ltd.) for 30 minutes at 25 ° C. Granted. Thereafter, it was thoroughly washed with ion exchange water.
(Third process: Activation process)
The organic polymer fiber provided with the Pd / Sn catalyst was immersed in a 10% solution of a fluorine compound solution (OPC-555 Accelerator M: Okuno Pharmaceutical Co., Ltd.) for 30 minutes at 25 ° C. and activated. Thereafter, it was thoroughly washed with ion exchange water.
(Fourth process: Electroless plating process)
As an electroless plating solution, Muden Silver SS (silver nitrate, manufactured by Okuno Pharmaceutical Co., Ltd.) was used and adjusted with ion-exchanged water so that the concentration of silver was 300 mg / L. The activated organic polymer fiber was immersed in an electroless plating solution with a silver concentration adjusted to 300 mg / L at 50 ° C. for 10 minutes to form a metal film on the organic polymer fiber. The fiber on which the metal film was formed was washed with ion exchange water and then heated to dry.

<Example 2>
A plated fiber was obtained in the same manner as in Example 1 except that the silver concentration was adjusted to 70 mg / L and immersed in an electroless plating solution at 50 ° C. for 13 minutes.

<Example 3>
A plated fiber was obtained in the same manner as in Example 1 except that the silver concentration was adjusted to 450 mg / L and immersed in an electroless plating solution at 50 ° C. for 10 minutes.

<Example 4>
As an electroless plating solution, Muden Silver KSS (silver sulfate, product of Okuno Pharmaceutical Co., Ltd.) was used and adjusted with ion-exchanged water so that the concentration of silver was 300 mg / L. A plated fiber was obtained in the same manner as in Example 1 except that the activated organic polymer fiber was immersed in an electroless plating solution adjusted to a silver concentration of 300 mg / L at 50 ° C. for 10 minutes.

<Comparative Example 1>
A plated fiber was obtained in the same manner as in Example 1 except that the setting did not include the electron beam graft polymerization step of the first step.

<Comparative example 2>
A plated fiber was obtained in the same manner as in Example 1 except that the second step of applying the catalyst was not included.

<Comparative Example 3>
A plated fiber was obtained in the same manner as in Example 1 except that the activation treatment step of the third step was not included.

<Comparative example 4>
A plated fiber was obtained in the same manner as in Example 1 except that the setting was made so as not to include the fourth electroless plating step.

<Comparative Example 5>
A plated fiber was obtained in the same manner as in Example 1 except that the silver concentration was adjusted to 30 mg / L and immersed in an electroless plating solution at 50 ° C. for 30 minutes.

<Comparative Example 6>
A plated fiber was obtained in the same manner as in Example 1 except that the silver concentration was adjusted to 550 mg / L and immersed in an electroless plating solution at 50 ° C. for 10 minutes.

<Fiber and metal coating adhesion test and evaluation wear test method>
The adhesion (peeling) strength of the coating of the produced electroless plated fiber was measured in accordance with JIS L 0849-2013 “Testing method for dyeing 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. The conductivity after 100 reciprocations was measured. As evaluation criteria, the conductivity after friction those less than 10 ¹ Omega / cm "◎", those less than 10 ¹ Omega / cm or more 10 ³ Omega / cm "○", 10 ³ Omega / cm or more 10 ⁵ Those with less than Ω / cm were evaluated as “Δ”, those with 10 ⁵ Ω / cm or more as “x”, and those with “◯” or more as acceptable. Furthermore, a metal plating layer that could not be formed and could not be evaluated was indicated as “−”.

<Evaluation of stability of plating solution>
The state of the plating solution was visually confirmed during the electroless plating process. As evaluation criteria, the case where the plating solution was not turbid was set as “◯”, the case where the plating solution appeared cloudy in black was set as “X”, and the case where “◯” or more was passed.

  As apparent from Table 1, the plated fibers of Examples 1 to 4 of the present invention were excellent in the stability of the plating solution and in the time required for the electroless plating treatment.

  On the other hand, since the comparative example 1 was not performing the electron beam graft polymerization process of the 1st process, it was not able to give a catalyst and was not able to form a metal plating layer in an organic polymer fiber. . Since the comparative example 2 did not perform the catalyst provision process of a 2nd process, the electroless-plating reaction did not occur and the plating metal layer could not be formed in the organic polymer fiber. In Comparative Example 3, since the activation process step of the third step is not performed, the presence of Sn ions originally removed in the plating process step deteriorates the stability of the plating solution, and the organic polymer fiber is plated. A metal layer could not be formed. In Comparative Example 4, since the electroless plating treatment step of the fourth step was not performed, a metal plating layer could not be formed on the organic polymer fiber. In Comparative Example 5, the plating process took time, and the wearability was also inferior. In Comparative Example 6, silver ions in the plating treatment solution were excessively precipitated, the stability of the plating solution was poor, and the wearability was also poor.

  The polymer fiber material coated with a plating film according to the present invention is suitable as a fabric having a current-carrying performance by being incorporated into a knitted or woven fabric, for example, and has a wide range of applications and can be used in various fields. .

Claims (3)

   A first step of subjecting the organic polymer fiber to electron beam irradiation to graft polymerize the nitrogen-containing monomer; a second step of attaching a Pd / Sn catalyst to the organic polymer fiber grafted with the nitrogen-containing monomer; and A third step of reducing and activating the Pd / Sn catalyst adhering to the surface of the organic polymer fiber, and immersing this activated polymer polymer fiber in a plating solution to perform electroless plating treatment, Including a fourth step of forming a plating layer, wherein the plating metal in the electroless plating treatment is silver, and the concentration of the silver in the plating solution is 50 mg / L to 500 mg / L Manufacturing method of plating fiber.   The method for producing a plated fiber according to claim 1, wherein the silver is silver nitrate or silver sulfate.   The method for producing a plated fiber according to claim 1 or 2, wherein a temperature in the electroless plating treatment is 50C to 65C, and a time is 5 minutes to 13 minutes.