JP2017052975A - Plated fiber and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an electroless plating film excellent in adhesion between fibers and a metallic film.SOLUTION: A production method of plated fibers includes a first step for coating the surface of organic polymer fibers with metal particle-containing polyester elastomer resin solution, a second step for drying the organic polymer fibers coated with the metal particle-containing polyester elastomer resin solution to thereby form a sheath structure, and a third step for immersing the organic polymer fibers (core sheath structure fibers) on which the sheath structure is formed by drying into electroless plating solution, to thereby form a metal film.SELECTED DRAWING: Figure 1

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

  This invention is made | formed in view of this technical background, The objective is to form the electroless-plating membrane | film | coat excellent in the adhesiveness of a fiber and a metal membrane | film | coat.

  As a result of intensive studies to solve such problems, the present inventor applied a metal particle-containing polyester elastomer resin solution to the surface of the organic polymer fiber, and then dried to form a sheath structure, Next, the organic polymer fiber (core-sheath structure fiber) having a sheath structure formed by the drying treatment is immersed in an electroless plating solution to form a metal film, thereby providing excellent adhesion between the organic polymer fiber and the metal film. The present inventors have found that an electroless plating film can be formed and have reached the present invention. The present invention provides the following means.

  [1] A first step of applying a metal particle-containing polyester elastomer resin solution to the surface of the organic polymer fiber, and applying the metal particle-containing polyester elastomer resin solution to dry the organic polymer fiber to form a sheath structure. A second step and a third step in which an organic polymer fiber (core-sheath structure fiber) having a sheath structure formed by the drying treatment is immersed in an electroless plating solution in a temperature range of 40 ° C. to 100 ° C. to form a metal film. A process for producing a plated fiber, comprising: a step.

  [2] The method for producing a plated fiber according to [1], wherein in the first step, the polyester elastomer resin is a polyester-polyether elastomer resin, and the metal particles have a particle size of 10 nm to 5000 nm.

  [3] The plated fiber produced by the method for producing a plated fiber as described in [1] or [2] above, wherein the organic polymer fiber is one or a plurality of fibers selected from nylon, polyester, and polypropylene.

  In the invention of [1], in the first step, the metal particle-containing polyester elastomer resin solution can be applied to the surface of the organic polymer fiber. Since the metal particles are contained, the catalytic action is exhibited, so that the catalyst application step and the activation step required in the prior art are not required. Since the polyester elastomer resin is dissolved in the solvent, the metal particles can be dispersed in the polyester elastomer resin, so there is no need to knead the metal particles in the organic polymer fiber in advance, but only in the polyester elastomer resin. Therefore, metal particles are not wasted.

  Furthermore, in the second step, the metal particle-containing polyester elastomer resin solution can be applied and the organic polymer fiber can be dried to form a sheath structure. That is, when the solvent volatilizes, the metal particle-containing polyester elastomer resin layer can be firmly formed on the surface of the organic polymer fiber, and the adhesion with the metal film to be formed later by the solvent volatilization trace. To improve.

  In the third step, a metal film is formed by immersing the organic polymer fiber (core-sheath structure fiber) having a sheath structure formed by the drying treatment in an electroless plating solution in a temperature range of 40 ° C to 100 ° C. can do. Since the metal particles are dispersed not only in the outer layer of the sheath structure but also in the inner layer of the sheath structure, the metal coating formed by the catalytic action of the metal particles has excellent adhesion and excellent durability. It becomes a plating film.

  In the invention of [2], since the polyester elastomer resin is a polyester-polyether elastomer resin in the first step, the polyester elastomer resin can be easily laminated by being applied to the surface of the organic polymer fiber in a state dissolved in a solvent. In addition, since the particle size of the metal particles is 10 nm to 5000 nm, the metal particles have good dispersibility and can be sufficiently dispersed on the fiber surface of the organic polymer fiber.

  In the invention of [3], since the organic polymer fiber is one or a plurality of fibers selected from nylon, polyester and polypropylene, it is insoluble in the solvent of the polyester-polyether elastomer resin solution and forms a core-sheath structure fiber. Therefore, it is possible to obtain a plated fiber having excellent adhesion and durability, light weight and good conductivity.

It is sectional drawing which shows the structure of the plating fiber which concerns on one Embodiment of this invention. It is sectional drawing which shows the structure by which the drying process was performed on the organic polymer fiber to which the drying process which concerns on one Embodiment of this invention was performed, and the sheath structure was formed.

  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; Examples thereof include polyalcohol fibers such as fluorine fibers and organic fibers such as fluorine fibers. Among them, it is effective to apply the method for producing plated fibers of the present invention to general-purpose fibers such as nylon, polyester, and polypropylene.

  First, in the first step, a metal particle-containing polyester elastomer resin solution prepared in advance is applied to the surface of the organic polymer fiber. As the method, after immersing the organic polymer fiber in the metal particle-containing polyester elastomer resin solution, the organic polymer fiber may be pulled up, but the method of application is not particularly limited. The metal particle-containing polyester elastomer resin solution is allowed to pass through in a cheese state. The temperature of the metal particle-containing polyester elastomer resin solution when immersed is preferably 0 ° C. to 35 ° C., and the immersion time may be about 1 minute to 10 minutes. The concentration of the polyester elastomer resin solution is preferably 0.05 to 30% by mass. Thus, the metal particle-containing polyester elastomer resin solution can be applied to the surface of the organic polymer fiber.

  The polyester elastomer resin is preferably a polyester-polyether elastomer resin. The solvent for dispersing the polyester elastomer resin is not particularly limited, but for example, methylene chloride is preferable because it can easily dissolve the polyester elastomer resin and does not dissolve the organic polymer fiber.

  The metal particles are not particularly limited as long as they exhibit a catalytic action on the plated metal, and examples thereof include Ag, Cu, Ni, Co, Au, Pd, Rh, Pt, In, and Sn. Can do. In the case of silver plating, Ag and Pd are preferable since the reactivity of plating is good. The particle size of the metal particles is not particularly limited, but is preferably in the range of 10 nm to 1000 nm. By setting the particle size within this range, the metal particles can be dispersed well and sufficiently dispersed on the fiber surface of the organic polymer fiber. The concentration of the metal particles in the polyester elastomer resin solution is preferably 0.05 to 15% by mass.

  Next, in the second step, the metal particle-containing polyester elastomer resin solution is applied and the organic polymer fiber is dried to form a sheath structure. The drying temperature does not need to be particularly high and may be processed at about 50 ° C. In addition, preferable drying process temperature is 40 to 70 degreeC. In this range, for example, when the solvent methylene chloride volatilizes, a small cavity is formed in the polyester elastomer resin that formed a sheath structure, and this cavity reaches the surface of the sheath structure, so the formation of a metal film in the subsequent process A metal film sometimes enters or closes these cavities, so that an anchor effect is exhibited and adhesion of plating is improved, which is preferable. Thus, a sheath structure is formed around the organic polymer fiber, so that a core-sheath structure fiber is obtained. The solvent evaporates to form the metal particle-containing polyester elastomer resin layer firmly on the surface of the organic polymer fiber, and the adhesion with the metal film to be formed later due to the volatile trace of the solvent. improves.

  In the third step, an organic polymer fiber (core-sheath structure fiber) having a sheath structure formed by the drying treatment is immersed in an electroless plating solution, and an electroless plating treatment is performed to form a metal film. The temperature of the electroless plating solution is 40 ° C to 100 ° C, and the immersion time is preferably 10 minutes to 90 minutes.

  Electroless plating is an electron released when the reducing agent contained in the plating solution is oxidized by the strong catalytic action of the metal particles contained in the polyester elastomer resin at the sheath part formed on the surface of the organic polymer fiber. Thus, the metal ions in the plating solution are reduced, and the metal is deposited on the surface of the organic polymer fiber as a metal film. In particular, since the metal particles are deposited toward the metal particles, the formed metal film is firmly adhered. That is, a metal film is formed with metal particles in the vicinity of the surface of the polyester elastomer resin as a nucleus, the metal particles are buried in the polyester elastomer resin, and a part of the metal particles is exposed on the surface of the polyester elastomer resin. Therefore, combined with the anchor effect, the adhesion of the metal film layer is improved. As electroless plating, a commonly used plating solution can be used. Examples thereof include electroless copper plating, electroless nickel plating, and electroless silver plating.

  Thereafter, the core-sheath structure fiber on which the metal coating was formed was washed with ion-exchanged water (water washing step) and then heated to dry (drying step).

  The thickness of the plating film of the plating fiber thus obtained is preferably 0.2 μm or more, 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.

  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. Moreover, the kind of organic polymer fiber, metal particle concentration, metal particle diameter, etc. were performed as described in Table 1. Moreover, it shows about the evaluation of a tape peeling method, a friction test method, and external appearance evaluation (plating nonuniformity).

(Core-sheath fiber creation process)
The organic polymer fiber is coated with a metal particle-containing polyester elastomer resin solution (polyester-polyether elastomer resin, 100 nm metal particles dispersed in methylene chloride as a solvent, 10 wt% solution).

(Drying process)
Thereafter, the organic polymer fiber coated with the metal particle-containing polyester elastomer resin is dried at 50 ° C. to produce a core-sheath structure fiber.

(Electroless plating process)
On the core-sheath fiber including the metal-sheathed fiber, an electroless plating solution (Muden Silver SS: Okuno Pharmaceutical Co., Ltd. product) is immersed at 50 ° C. for 1 hour using a feed pump. A metal film is formed on.

(Washing / drying process)
The fiber on which the metal film has been formed is washed with ion exchange water and then heated to dry.

<Fiber and 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 Abrasion test method>
The adhesion (peeling) strength of the coating of the produced electroless-plated fiber was measured according to 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.

<Evaluation by plating unevenness appearance>
Observe the appearance of the electroless plated fiber on the inside and outside of the dyed bobbin and the middle point of the yarn. If the plating is uniform, the plating unevenness is not found. When there was no part, the presence of uneven plating was evaluated as x.

<Example 1>
After passing through a polyester yarn (167 dtex / 50f) wound around a dyed bobbin, a silver particle-containing polyester-polyether elastomer resin 10% by weight solution (methylene chloride solvent, 100 nm silver particle concentration 0.1%), It dried at the temperature of 50 degreeC, and produced the core-sheath structure fiber (initial stage volume resistivity 6.8 * 1013 ohm * cm). Next, an electroless plating solution (Muden Silver SS: Okuno Pharmaceutical Co., Ltd. product) is supplied to the core-sheath structure fiber with a liquid feed pump and immersed at a temperature of 50 ° C. (plating processing temperature) for 1 hour. A metal film was formed on the core-sheath fiber. Thus, a plating fiber by electroless plating was obtained using the silver particles contained in the sheath portion of the core-sheath structure fiber 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.

<Example 2>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that nylon yarn (156 dtex / 48f) was used instead of polyester yarn. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 1%, and the conductivity after friction was 1.2 Ω / cm.

<Example 3>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that polypropylene yarn (178 dtex / 60f) was used instead of polyester yarn. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 1%, and the conductivity after friction was 1.0 Ω / cm.

<Example 4>
In Example 1, silver particles having a particle size of 2000 nm were used. A core-sheath plated fiber was obtained in the same manner as in Example 1 except that the silver particle concentration was 1%. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 1.5%, and the conductivity after friction was 1.8 Ω / cm.

<Example 5>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the silver particle concentration was 8%. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 1.1%, and the conductivity after friction was 6.2 Ω / cm.

<Example 6>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that silver particles having a particle size of 4000 nm were used. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 9.2%, and the electrical conductivity after friction was 14Ω / cm.

<Example 7>
In Example 1, silver particles having a particle size of 1000 nm were used. Further, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the plating temperature was 70 ° C. In the adhesion test, the area ratio of the tape peeling portion of the plating film was evaluated as ◎ when the ratio was 1.4%, and the conductivity after friction was evaluated as ○ when 43 Ω / cm.

<Example 8>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the silver particle concentration was 13%. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 1.3%, and the conductivity after friction was 6.3 Ω / cm.

<Example 9>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the plating temperature was 90 ° C. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 3.8%, and the electrical conductivity after friction was 38Ω / cm.

<Example 10> A plating fiber having a core-sheath structure was obtained in the same manner as in Example 1 except that silver particles having a particle size of 10,000 nm were used. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 13%, and the conductivity after friction was 1.8 × 10 ⁴ Ω / cm.

<Example 11>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the silver particle concentration was 20%. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 14%, and the conductivity after friction was 6.2 × 10 ⁴ Ω / cm.

<Comparative Example 1>
In Example 1, a 10% by weight polyester-polyether elastomer resin solution containing no metal particles (methylene chloride solvent) was passed through, followed by drying at a temperature of 50 ° C. to form a core-sheath fiber (initial volume resistivity) Electroless plating was performed in the same manner as in Example 1 except that 6.8 × 10 13 Ω · cm) was formed. However, although a metal film was formed somewhat, adhesion was insufficient and it was difficult to say that it was a plated fiber. It was.

<Comparative example 2>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the plating temperature was 20 ° C. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 25%, and the conductivity after friction was 9.2 × 10 ⁶ Ω / cm.

<Comparative Example 3>
In Example 1, a core-sheath plated fiber was obtained in the same manner as in Example 1 except that the plating temperature was 110 ° C. In the adhesion test, the area ratio of the tape peeling portion of the plating film was 18%, and the electric conductivity after friction was 5.2 × 10 ⁶ Ω / cm.

  As shown in Table 1, good evaluation was obtained for all of Examples 1 to 11.

  On the other hand, in Comparative Examples 1 to 3, a satisfactory evaluation was not obtained in any of the adhesion tests of the plating film tape peeling method and the friction test method. Furthermore, the evaluation by appearance evaluation (plating unevenness) was x with plating unevenness because there was a portion where plating could not be performed uniformly or not. None of the comparative examples gave satisfactory evaluation.

  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.

1 ... Plating fiber 2 ... Sheath 3 ... Core (organic polymer fiber)
4 ... Plating (metal coating)
5 ... Core sheath fiber

Claims (3)

  A first step of applying a metal particle-containing polyester elastomer resin solution to the surface of the organic polymer fiber, and a second step of forming a sheath structure by applying the metal particle-containing polyester elastomer resin solution and drying the organic polymer fiber And a third step of immersing the organic polymer fiber (core-sheath structure fiber) having a sheath structure formed by the drying treatment in an electroless plating solution in a temperature range of 40 ° C. to 100 ° C. to form a metal film. The manufacturing method of the plating fiber characterized by including.   2. The method for producing a plated fiber according to claim 1, wherein in the first step, the polyester elastomer resin is a polyester-polyether elastomer resin, and a particle diameter of the metal particles is 10 nm to 5000 nm.   3. The plated fiber manufactured by the method for manufacturing a plated fiber according to claim 1, wherein the organic polymer fiber is one or more fibers selected from nylon, polyester, and polypropylene.