JP5255015B2 - Electroless copper plating method for polymer fiber - Google Patents

Description

The present invention relates to an electroless copper plating method of the polymer textiles, more particularly, by improving the adhesion of the plating film, wire and covered wire was a polymer fiber with a core material, an electromagnetic wave shielding material and a conductive The present invention relates to a technique for producing a polymer fiber with a conductive film suitable as a material such as plastic.

  Conventionally, metal wires have been used as electric wires, but in recent years, in order to reduce weight and cost, research and development has progressed on the assumption that a fiber plating material with a conductive film formed on polymer fibers replaces metal wires. It has been. For example, in the method of plating a polymer material of Patent Document 1, cuprate chloride hydrate 8.75 g / l, Quadrol 20 g / l, sodium hydroxide 15 g / l, formaldehyde 3.6 g / l with an appropriate amount of surface activity. A technique is disclosed in which an aramid fiber is introduced into an electroless plating solution prepared by adding an agent and immersed in the sample at 40 ° C. for 20 minutes to form a copper film on the sample. This aramid fiber (electric wire) with a copper film can be used as an element wire for a covered electric wire, or can be processed into a woven fabric or a knitted fabric and used as an electromagnetic shielding material having various shapes.

  In addition, in Patent Document 2, in order to form a conductor circuit on a polyimide resin film, (1) roughening → (2) neutralization → (3) hydrophilization treatment (immersion in an aqueous sodium hydroxide solution) → ( 4) Catalyst application (immersion in Pd ion-containing catalyst application liquid) → (5) Reduction treatment → (6) Immersion in electroless copper nickel plating liquid → (7) Immersion in copper sulfate electroplating liquid → (8) Conductor circuit formation A method of (etching removal of copper plating film / copper nickel film) is disclosed.

JP2009-242839 JP 2008-231459 A

Therefore, as described in Patent Document 1, to produce a polymer fiber with a conductive film suitable as a material such as an electric wire using a polymer fiber as a core material, a covered electric wire, an electromagnetic shielding material, and a conductive plastic, Various studies have been conducted in the industry to form a conductive film on many polymer fibers. High adhesiveness and strength are required for the polymer fiber with a conductive film for these uses. This is because if the plating (conductive film) is peeled for some reason, the conductive performance is adversely affected.
On the other hand, the plating technique described in Patent Document 2 is a technique related to a conductive film for producing a printed wiring board. This plating technique improves the adhesion property to the polyimide resin by setting the amount of nickel in the film within a certain predetermined range. There is concern about an increase in electrical resistivity due to the inclusion of Ni in the film.

The present invention has been made in view of the above circumstances, an object of the present invention provides an electroless copper plating method of a polymer textiles, which can be provided with good adhesion and conductivity to the plating film There is. As a result, it is intended to realize weight reduction and cost reduction of materials such as an electric wire having a polymer fiber as a core material, a covered electric wire, an electromagnetic shielding material, and a conductive plastic.

  (Delete)

Electroless copper plating method of a polymer textiles according to the present invention in order to solve the above problems, and summarized in that has the following configuration.
(1) The method for electroless copper plating of the polymer fiber is as follows:
An alkali treatment step of immersing the polymer fiber in an alkaline solution for a predetermined time if necessary;
A surface conditioning treatment step in which the polymer fiber A that has undergone the alkali treatment step or the alkali treatment step is omitted is immersed in a surface conditioning agent for a predetermined time;
A Sn-Pd catalyst immersion step of immersing the polymer fiber B that has undergone the surface conditioning treatment step in a colloidal solution of Pd and Sn for a predetermined time;
A heat treatment step of maintaining the polymer fiber C that has undergone the Sn—Pd catalyst immersion step at 120 to 300 ° C. for a predetermined time;
An accelerator treatment step of immersing the polymer fiber D that has undergone the heat treatment step in an acid solution for a predetermined time;
The immersed Accelerator step a predetermined time polymeric fibers E in an electroless copper plating solution which has passed through, the surface of the polymer fiber E, a thickness of more than 0.1 [mu] m 0.707624226Myuemu, and peeling rate ( = " Electroplated copper plating process for forming a conductive film having a ratio of" plated area after tape peeling "to" plated area before tape application "" of 30% or less ,
It has.
(2) The electroless copper plating solution is
(A) 7-15 g / L of CuSO ₄ .5H ₂ O,
(B) 20-35 g / L of EDTA-4Na,
(C) 5-15 g / L of NaOH,
(D) 5-15 cc / L of HCHO,
(E) 0.005 to 0.015 g / L of nonionic surfactant,
(F) 0.05 to 0.15 g / L of KCN, 0-phenanthroline, neocuproin or 2,2-bipyridyl;
_{(G) NiSO 4 · 6H 2} O, CoSO 4 · 7H 2 O, ZnSO 4 · 7H 2 O, SnSO 4, _{and, Na 2 O 3 Sn · 3H} 0 more either one or two or selected from ₂ O Ultra to 0.020 mol / L,
Consists of.

  (Delete)

The electroless copper plating solution of polymer fiber according to the present invention has a predetermined composition, in particular, NiSO ₄ .6H ₂ O, CoSO ₄ .7H ₂ O, ZnSO ₄ .7H ₂ O, SnSO ₄ , and Na. _Since any one or two or more selected from ₂ O ₃ Sn · 3H ₂ O is provided in an amount of more than 0 to 0.020 mol / L, it is possible to form a conductive film having excellent adhesion on the polymer fiber. There is an effect of doing.

  Therefore, if electroless copper plating is performed on polymer fibers using the electroless copper plating solution, a conductive coating is provided that can suppress an increase in resistance value and a decrease in strength due to the low adhesion. There exists an effect that a polymer fiber can be manufactured. Thereby, the polymer fiber with a conductive film suitable as a material of the electric wire which used the polymer fiber as the core material, the covered electric wire, the electromagnetic wave shielding material, and the conductive plastic can be obtained.

  According to the polymer fiber plating method of the present invention, deposits on the surface of the polymer fiber are removed in the alkali treatment step, the surface of the polymer fiber is cationized in the surface conditioning treatment step, and Sn—Pd catalyst immersion is performed. In the process, the anion of the Sn—Pd colloid is firmly adsorbed and bonded to the surface of the polymer fiber. In the heat treatment step, the polymer fiber molecules are opened and Pd—Sn particles (anions composed of Pd and Sn) are taken in and adsorbed / bonded in the molecules, but the catalytic activity is impaired by heat. In the accelerator treatment step, Sn is dissolved in the incorporated Pd—Sn particles, and only Pd is adsorbed and bound in the molecule, and the metal catalyst is reactivated. In the electroless copper plating step, a conductive film is formed on the polymer fiber.

  Therefore, according to the polymer fiber plating method of the present invention, electroless copper is obtained by cationization in the surface conditioning treatment step, incorporation of Pd-Sn particles into the polymer fiber molecule and adsorption / bonding in the heat treatment step. There is an effect of improving the adhesion between the conductive film formed when the plating process is performed and the polymer fiber. Furthermore, since the electroless copper plating solution according to the present invention is used in the electroless copper plating step, this also has the effect of improving the adhesion as described above.

  Therefore, according to this invention, there exists an effect that favorable adhesiveness is acquired by the synergistic effect (The synergistic effect by a surface adjustment process and heat processing, and an electroless copper plating solution). Since the polymer fiber manufacturing method according to the present invention uses the polymer fiber plating method according to the present invention, it has the same effects as the plating method.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In the present specification, “polymer fiber” means both a filament and a bundle which is an assembly of filaments.

(Polymer fiber-Plated fiber)
Examples of the polymer fiber to which the plating method according to one embodiment of the present invention is applied using the electroless copper plating solution according to one embodiment of the present invention include organic polymer fibers having a high melting point (150 ° C. or higher), such as , Polyarylate resins (eg, Vectran®), poly (paraphenylenebenzobisoxazole) (eg, Zylon®), polyparaphenylene terephthalamide (eg, Kevlar®), polyetherimide And high-density polyethylene fibers (for example, Dyneema (registered trademark)) (see Tables 1A to 1F).
As the polymer fiber, one having 1 to 6 decitex (dtex) and a diameter of 10 to 30 μm collected from several tens to several thousand fibers to form a fiber bundle is used. The cross-sectional shape of the fiber bundle is not particularly limited, and may be selected according to the use of the polymer fiber with a conductive film after plating.

(Electroless copper plating solution)
In the electroless copper plating according to this embodiment, the reducing agent (for example, HCHO) contained in the electroless copper plating solution is oxidized on the surface of a metal catalyst (for example, Pd, Ag, Au, Pt, etc.) having high catalytic activity. This is a technology that reduces the "metal ions that become conductive films" contained in the electroless copper plating solution by the electrons emitted when it is applied, and deposits them as a conductive film on the object to be plated with a uniform thickness. .
The electroless copper plating solution according to the present embodiment is preferably a plating solution comprising all of the following components (1) to (7) (see Tables 2A to 2D), but is not limited thereto. Other additives may be contained instead of or in addition to any of the above.
(1) As a hydrate, complex or other compound containing Cu or Cu ions formed as a conductive film, for example, CuSO ₄ .5H ₂ O is 7 to 15 g / L.
(2) In the alkaline plating solution, as a chelating agent that causes the metal to be deposited as a conductive film to exist in the plating solution, for example, EDTA-4Na is 20 to 35 g / L, or as a conductive coating. Cu (or Cu ions) contained in hydrates, complexes, and other compounds containing Cu or Cu ions to be formed and equimolar or more.
(3) As a pH raising agent for making the plating solution alkaline and maintaining it, for example, NaOH is 5 to 15 g / L, or an amount capable of maintaining the pH of the plating solution at 8 or more.
(4) As a reducing agent for reducing metal ions including a metal to be deposited as a conductive film, for example, HCHO is 5 to 15 cc / L.
(5) For example, 0.005 to 0.015 g / L of a nonionic surfactant is used as the surfactant that lowers the surface tension of the plating solution to facilitate the reaction gas.
(6) As a decomposition inhibitor that suppresses decomposition of the plating solution, for example, 0.05 to 0.15 g / L of KCN, 0-phenanthroline, neocuproine, or 2,2-bipyridyl.
(7) As an additive for improving adhesion, any one or two selected from Ni ion (Ni ²⁺ ), Co ion (Co ²⁺ ), Zn ion (Zn ²⁺ ) and Sn ion (Sn ²⁺ , Sn ⁴⁺ ) As an additive containing seeds or more, for example, any one selected from NiSO ₄ · 6H ₂ O, CoSO ₄ · 7H ₂ O, ZnSO ₄ · 7H ₂ O, SnSO ₄ , and Na ₂ O ₃ Sn · 3H ₂ O One type or two or more types is more than 0 to 0.020 mol / L.

The electroless copper plating solution according to the present embodiment is composed of Ni ions (Ni ²⁺ ), Co ions (Co ²⁺ ), Zn ions (Zn ²⁺ ), and Sn ions (Sn ²⁺ , Sn ⁴⁺ ) among the above-described predetermined configurations. Since the additive containing any one kind or two or more kinds selected is contained in an amount of more than 0 to 0.020 mol / L, it is possible to form a conductive film having excellent adhesion on the fiber to be plated. That is, the electroless copper plating solution according to the present embodiment makes it possible to produce a polymer fiber with a conductive film that can suppress an increase in resistance value and a decrease in strength due to low adhesion. Thereby, the polymer fiber with a conductive film suitable as a material of the electric wire which used the polymer fiber as the core, the covered electric wire, the electromagnetic wave shielding material, and the conductive plastic can be obtained.

(Polymer fiber plating method)
The polymer fiber plating method according to an embodiment of the present invention includes (1) alkali treatment, (2) surface conditioning treatment, (3) Sn—Pd catalyst immersion, (4) heat treatment, and (5) in the order of the steps. It consists of each process of an accelerator process and (6) electroless copper plating (refer Table 3A-Table 3D).
Hereinafter, each of these steps will be described.

(1) The alkali treatment step is a step of removing and washing the metal to be plated by immersing the fiber to be plated (polymer fiber) in an alkaline solution at a predetermined temperature for a predetermined time. For example, NaOH or KOH can be used as the alkaline solution. After the alkali treatment, the to-be-plated fiber is washed with water to remove deposits on the to-be-plated fiber such as an alkali treatment solution.
Fig.1 (a) shows the state of the to-be-plated fiber after an alkali treatment process. It can be seen that the dirt on the surface has been removed. In addition, when the stain | pollution | contamination of the to-be-plated fiber is removed from the beginning, you may abbreviate | omit an alkali treatment process.

(2) The surface conditioning treatment step is a step of cationizing the surface of the fiber to be plated by immersing the fiber to be plated in a surface conditioner at a predetermined temperature for a predetermined time so that the catalyst metal is easily attached to the surface of the fiber to be plated. It is. Thereby, the adhesiveness is improved. After the surface conditioning treatment, the fiber to be plated is washed with water, and the deposits on the fiber to be plated such as a surface conditioning agent are removed.
FIG.1 (b) shows the state of the to-be-plated fiber after a surface adjustment process process. It turns out that the surface of the to-be-plated fiber is cationized and the catalyst metal is easy to adhere.

(3) In the Sn—Pd catalyst dipping step, Pd and Sn are immersed on the surface of the fiber to be plated by immersing the fiber to be plated in a catalyst-imparting agent (for example, a colloidal solution of Pd and Sn) at a predetermined temperature. This is a process of adsorption and bonding. The catalyst imparting agent is preferably prepared by dissolving tin (II) chloride and palladium (II) chloride in a hydrochloric acid solution, mixing them with stirring, and aging them while heating.
FIG.1 (c) shows the state of the to-be-plated fiber after a Sn-Pd catalyst immersion process. It can be seen that an anion composed of Pd and Sn is adsorbed and bonded to the surface of the fiber to be plated on which the catalyst is easily attached by the surface conditioning treatment. This adsorption / bonding is considered to be due to van der Waals force (attraction due to interaction between molecules) and Coulomb force (interaction between positive and negative charges).

  The bonding (ionic bonding) is also caused by the Coulomb force because the surface of the fiber to be plated is cationized by the surface conditioning treatment. This contributes to improving the adhesion of plating.

(4) In the heat treatment step, the fibers to be plated are opened by holding the fibers to be plated at 120 to 300 ° C. for a predetermined time (see FIGS. 1D and 1I), and Pd—Sn particles are contained therein. Is taken in, adsorbed and bound (see FIG. 1 (d) (ii)). What is necessary is just to select holding temperature suitably between 120-300 degreeC according to the kind of to-be-plated fiber. For example, 150 to 280 ° C. is particularly preferable in the case of polyarylate resin, 150 to 300 ° C. is particularly preferable in the case of poly (paraphenylene benzobisoxazole), and 120 to 250 ° C. in the case of polyparaphenylene terephthalamide. Is particularly preferable in the case of polyetherimide, and 120 to 250 ° C. is particularly preferable in the case of high density polyethylene fiber.

  FIG.1 (d) (i) shows the state of the to-be-plated fiber in the heat processing process. As shown in the figure, the fiber to be plated opens, and Pd—Sn particles (anions composed of Pd and Sn) are taken in between the molecules of the opened fiber to be plated and adsorbed and bonded. Incorporation, adsorption and bonding of Pd-Sn particles between the fibers to be plated proceed in a state where the bonding force by the Coulomb force is maintained in addition to the adsorption force by the van der Waals force, but the Pd-Sn particles are heated by heat. The catalytic activity of is impaired.

  FIG.1 (d) (ii) shows the state of the to-be-plated fiber after a heat processing process. When the heat treatment step is completed, the temperature drops, and as shown in FIG. As a result, the Pd particles taken in and adsorbed and bonded between the molecules of the fiber to be plated are less likely to be separated from the molecules of the fiber to be plated. This contributes to the improvement of the adhesion of the conductive film formed by the electroless copper plating process described later.

(5) The accelerator treatment step reactivates particles composed of Pd and Sn whose catalytic activity is impaired in the heat treatment step by immersing the fiber to be plated in an activation accelerator (for example, an acid solution) for a predetermined time. In order to make it easier, the Sn is dissolved and only Pd is adsorbed and bonded to the fiber to be plated. The acid solution used as the activation accelerator is not particularly limited as long as it is an acid that dissolves Sn but does not dissolve Pd, and the processing conditions (processing concentration, processing temperature, processing time) are not particularly limited. Examples of suitable acid solutions and treatment conditions include, for example, hydrochloric acid (10%, room temperature, 4 minutes), sulfuric acid (10%, 45 ° C., 5 minutes), hydrofluoric acid (5%, room temperature, 5 minutes) , Borohydrofluoric acid (5-10%, room temperature, 5 minutes).

  FIG.1 (e) shows the state of the to-be-plated fiber after an accelerator process. It can be seen that Pd is strongly adsorbed and bonded to the fiber to be plated. Therefore, the adhesion of the plating applied in the plating process described later is improved. After the accelerator treatment, the fiber to be plated is washed with water to remove deposits on the fiber to be plated such as an accelerator treatment solution.

(6) In the electroless copper plating step, the plated fiber is immersed in an electroless copper plating solution at a predetermined temperature for a predetermined time, whereby a plated film (conductive film) is 0.1 to 2.0 μm on the plated fiber. This is a step of forming with a thickness. As an electroless copper plating solution, it is possible to produce a polymer fiber with a conductive film that can suppress an increase in resistance value and a decrease in strength of a fiber to be plated due to low adhesion. It is not limited. As such an electroless copper plating solution, for example, the above-described electroless copper plating solution and the electroless copper plating solutions shown in Tables 2A to 2D are suitable.

  Processing conditions (processing concentration, processing temperature, processing time) when performing plating using the electroless copper plating solution are not particularly limited, and may be appropriately adjusted according to plating thickness, plating efficiency, and the like. After the electroless copper plating step, the polymer fiber with the conductive film is washed with water, and deposits such as the electroless copper plating solution are removed, followed by hot air drying (60 to 100 ° C.).

  FIG.1 (f) shows the state of the to-be-plated fiber after an electroless copper plating process. It can be seen that the conductive film is formed on Pd adsorbed and bonded to the intermolecular / surface of the fiber to be plated by van der Waals force and / or coulomb force. In particular, Pd that has entered between molecules of the fiber to be plated is firmly fixed to the fiber to be plated by van der Waals force and Coulomb force. Therefore, the conductive film formed by using the Pd as a catalyst metal has excellent adhesion.

  By carrying out the steps (1) to (6) according to one embodiment of the present invention described above, a polymer fiber with a conductive film can be obtained.

Hereinafter, since the plating method according to this embodiment was carried out to produce a polymer fiber with a conductive film, this will be described.
(Electroless copper plating of polymer fiber)
About each Example and each comparative example, the process shown to Table 3A-Table 3F was implemented using the electroless copper plating solution shown to Table 2A-Table 2F with respect to the polymer fiber shown to Table 1A-Table 1F, A polymer fiber with a conductive film was produced. The plating thicknesses shown in Tables 4A to 4F indicate the thicknesses after the electroless copper plating. In addition, the fiber to be plated (polymer fiber) is a bundle of the number of filaments shown in the same table without twisting the filaments shown in Tables 1A to 1F, and is wound and delivered by a roller or the like during the plating process. As a result of the repetition, the cross section becomes a flat shape, and a conductive film is formed in that state. The sum of diameters shown in Tables 1A to 1F assumes a state in which the filaments are flattened until all the filaments are arranged in parallel one by one.

(Adhesion test-procedure)
The adhesion test was carried out using the polymer fiber with a conductive film obtained as described above as a test piece for the adhesion test. The adhesion test was carried out by attaching a commercially available cellophane tape to a test piece, peeling it off, and visually observing the ratio of “plating area after tape peeling” to “plating area before tape application”. . The results are also shown in Tables 4A to 4F.

(Adhesion test-evaluation)
Although the adhesiveness varies depending on what is used as an additive, a high peeling rate is exhibited when no additive is added in the comparative example, but in the example (when the additive is added within a predetermined range). It can be seen that the peel rate is significantly reduced. In particular, it was confirmed that the addition of a small amount of the additive was extremely effective in improving the adhesion. On the other hand, it has been found that addition of a large amount of additive also reduces adhesion. The reason is considered to be that the precipitation rate is extremely increased and the denseness of the plating film is lowered due to an increase in the amount of the additive having a higher ionization tendency than Cu.
The adhesion of the conductive film formed in the electroless copper plating step is preferably less than 30%, more preferably less than 25%, further preferably less than 20%, more preferably less than 15%, and still more preferably less than 10%. . Therefore, the amount of the additive may be appropriately selected so as to satisfy these required characteristics. Since the product is further subjected to electrolytic copper plating, it is sufficient that the adhesiveness is about 30% at the stage of electroless copper plating.

Accordingly, when NiSO ₄ .6H ₂ O is used as an additive, the lower limit of the amount added is essential to exceed 0, and the upper limit is preferably 0.020 mol / L or less, and 0.015 mol / L. The following is more preferable, 0.010 mol / L or less is further preferable, 0.0050 mol / L is further preferable, and 0.0025 mol / L or less is more preferable.

When CoSO ₄ · 7H ₂ O is used as an additive, the lower limit of the amount added is essential to exceed 0, and the upper limit is preferably 0.020 mol / L or less, and 0.015 mol / L or less. More preferably, 0.010 mol / L or less is further preferable, 0.0050 mol / L is further preferable, and 0.0025 mol / L or less is more preferable.

When using ZnSO ₄ · 7H ₂ O as an additive, the lower limit of the amount added is essential to exceed 0, and the upper limit is preferably 0.020 mol / L or less, and 0.015 mol / L or less. More preferably, 0.010 mol / L or less is further preferable, 0.0050 mol / L is further preferable, and 0.0025 mol / L or less is more preferable.

When SnSO ₄ is used as an additive, the lower limit of the amount added is essential to exceed 0, and the upper limit is preferably 0.020 mol / L or less, more preferably 0.015 mol / L or less, and 0 It is more preferably 0.0010 mol / L or less, further preferably 0.0050 mol / L, and further preferably 0.0025 mol / L or less.

(Resistance measurement-method)
Electrolytic copper plating was performed on the test piece used in the adhesion test, and this was used as a test piece for measuring the resistance value. As shown in FIG. 2, the resistance value measurement was carried out by contacting a plated fiber with a conductive film to a terminal attached to a jig and using a commercially available resistance meter manufactured by HIOKI, using a four-terminal method. The measurement length of the resistance value was 30 cm. The results are also shown in Tables 4A to 4F.

(Resistance measurement-evaluation)
The resistance value varies depending on what is used as the additive, but compared to the comparative example (when no additive is added or when there are too many additives), the example (additive was added in a predetermined range). In the case of the same additive, it was found that a relatively low resistance value can be achieved. From this, it was found that a desired resistance value can be obtained if the adhesion (20% in terms of peel rate) confirmed in the examples is satisfied.
Moreover, although it is the reason why the Example achieved a relatively low resistance value compared with the Comparative Example in comparison with those using the same additive, the Example has higher adhesion than the Comparative Example. It is considered that, when electrolytic copper plating is applied thereon, there is little partial peeling and the like and electrical conductivity can be ensured. In addition, since it is a dense film with high adhesion, there may be few defects such as dislocations and crystal grain boundaries and the resistivity may be lowered. In the comparative example, when the additive was not added at all, the reason why a relatively low resistance value was exhibited despite the extremely poor adhesion is considered to be because the additive does not contain a high electrical resistivity.

  Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. Various modifications can be made to the embodiment of the present invention.

  The polymer fiber plating solution according to the present invention, and the polymer fiber plating method using the same and the method for producing the same, improve the adhesion of the plating film, thereby reducing the low resistance value resulting from the low adhesion, Since the strength deficiency can be improved, it is suitable as a material such as an electric wire using a polymer fiber as a core material, a covered electric wire, an electromagnetic shielding material, and a conductive plastic.

It is a figure which shows the process of the plating method of the polymeric fiber which concerns on one Embodiment of this invention. It is a figure for demonstrating the resistance value measuring method of the polymer fiber with a conductive film which concerns on one Embodiment of this invention.

Claims (2)

An electroless copper plating method for polymer fibers having the following configuration.
(1) The method for electroless copper plating of the polymer fiber is as follows:
An alkali treatment step of immersing the polymer fiber in an alkaline solution for a predetermined time if necessary;
A surface conditioning treatment step in which the polymer fiber A that has undergone the alkali treatment step or the alkali treatment step is omitted is immersed in a surface conditioning agent for a predetermined time;
A Sn-Pd catalyst immersion step of immersing the polymer fiber B that has undergone the surface conditioning treatment step in a colloidal solution of Pd and Sn for a predetermined time;
A heat treatment step of maintaining the polymer fiber C that has undergone the Sn—Pd catalyst immersion step at 120 to 300 ° C. for a predetermined time;
An accelerator treatment step of immersing the polymer fiber D that has undergone the heat treatment step in an acid solution for a predetermined time;
The immersion Accelerator step a predetermined time polymeric fibers E in an electroless copper plating solution which has passed through, the surface of the polymer fiber E, a thickness of more than 0.1 [mu] m 0.707624226Myuemu, and peeling rate ( = " Electroplated copper plating process for forming a conductive film having a ratio of" plated area after tape peeling "to" plated area before tape application "" of 30% or less ,
It has.
(2) The electroless copper plating solution is
(A) 7-15 g / L of CuSO ₄ .5H ₂ O,
(B) 20-35 g / L of EDTA-4Na,
(C) 5-15 g / L of NaOH,
(D) 5-15 cc / L of HCHO,
(E) 0.005 to 0.015 g / L of nonionic surfactant,
(F) 0.05 to 0.15 g / L of KCN, 0-phenanthroline, neocuproin or 2,2-bipyridyl;
_{(G) NiSO 4 · 6H 2} O, CoSO 4 · 7H 2 O, ZnSO 4 · 7H 2 O, SnSO 4, _{and, Na 2 O 3 Sn · 3H} 0 more either one or two or selected from ₂ O Ultra to 0.020 mol / L,
Consists of.   2. The method of electroless copper plating of polymer fibers according to claim 1, wherein the conductive film has a thickness of 0.28305 μm or more and 0.707624226 μm or less.

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