JP5548870B2 - Pre-plating method for polymer materials - Google Patents

Description

  The present invention relates to a pretreatment method for plating a polymer material, and in particular, the present invention has excellent smoothness and adhesion on the surface of a substrate and forms an excellent appearance of metal plating. The present invention relates to a plating pretreatment method that can be applied.

  Conventionally, when a metal plating film is formed on the surface of a resin substrate, the adhesion of the metal plating film to the surface of the resin substrate has been insufficient. Therefore, in order to improve the adhesion, the surface of the resin substrate is treated with an acid / alkali solution to form irregularities on the surface of the resin substrate, thereby improving the adhesion by the anchor effect ( = Sn-Pd method) has been conventionally employed.

However, in the above method, since the surface of the resin base material can become rough, a surface with excellent smoothness cannot be obtained unless a metal plating film having a certain thickness is provided. In addition, chromic acid, which is widely used as an acid / alkali solution in the treatment for forming irregularities on the surface of the resin base material, is harmful to the human body and has a high risk of contaminating the environment. = Sn-Pd method) is required.
Therefore, as an alternative technique, an electroless plating method in which a reducing polymer layer is formed on a substrate and plating is performed on the reducing polymer layer has been proposed.

  Patent Document 1 discloses plating in which a polymer layer containing a reducing polypyrrole and a binder is formed on a substrate, and a metal film is chemically plated from an electroless plating solution through adsorption of a catalyst such as Pd on the layer. Disclosed is a method for producing a film. The method does not need to provide unevenness on the substrate surface as in the Sn-Pd method described above, and requires a chemical reduction (= de-doping) treatment because polypyrrole having a reducing property is used. Therefore, the problem of a decrease in adhesion between the base material and the metal plating film cannot occur.

JP 2007-270180 A

  However, there are cases where it is difficult to obtain a coating film with even more uniformity (smoothness) depending on the coating film forming method. For example, when spray coating is applied to a substrate made of a resin molded product, if a highly volatile organic solvent is used, the coating film surface uniformity (smoothness) is difficult to obtain, which affects the appearance of the metal plating film. Effect. On the other hand, when a low-volatile organic solvent is used, drying at a high temperature is necessary to eliminate the residual solvent on the substrate, and thus a substrate having poor heat resistance cannot be used. In addition, when spray coating is performed, dust and dirt in the air may be mixed in, and if they adhere to the substrate surface, small blisters (= blisters) occur, which affects the appearance of the metal plating film. Effect.

  Furthermore, a base material that easily contains a solution such as fiber or urethane has a large amount of chemical solution brought into each electroless plating. For example, when there are a large number of steps such as the Sn-Pd method, depending on the step, It was difficult to obtain a reproducible plated product due to concerns such as bringing in (some components derived from chemicals may adversely affect the plating process), and there was a problem in productivity.

Then, this invention makes it a subject to provide the plating pre-processing method which has the smoothness and adhesiveness which were excellent on the base-material surface, and can form the external appearance of the outstanding metal plating. Another object of the present invention is to provide a plating pretreatment method with a simple manufacturing process and high productivity.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventor has (i) a compound having a heterocyclic ring and (ii) a function as an oxidizing agent on a substrate by a specific method. By contacting a metal salt having a catalytic ability for electroplating (hereinafter sometimes referred to as a metal salt), the compound having a heterocyclic ring is in an oxidized state, while the metal salt is in a reduced state. And the compound which has the heterocyclic ring used as the oxidation state superposes | polymerizes on the base-material surface, and becomes a high molecular compound. Further, the metal salt reduced at that time is adsorbed on the surface of the polymer compound and acts as a catalyst for electroless plating. Therefore, since this oxidative polymerization process is performed on the substrate surface, a uniform plating base layer is formed in detail, and therefore, it has been found that the plating film is also uniformly formed in detail, thereby completing the present invention.

That is, the present invention
(1) A method for forming a plating base layer comprising (i) a compound having a heterocyclic ring and (ii) a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating on a substrate,
The plating pretreatment method is characterized in that the plating underlayer is formed by any of the following methods (a) to (c).
(A) A method comprising the steps of immersing the substrate in an aqueous solution containing the compound having a heterocyclic ring and the metal salt and pulling it up (b) immersing the substrate in an aqueous solution containing the compound having a heterocyclic ring And (c) a step of immersing the pulled up substrate in an aqueous solution containing the metal salt (c) immersing the substrate in an aqueous solution containing the metal salt, and Contacting a vapor comprising a compound having:
(2) The plating pretreatment method according to (1), wherein the metal salt is a halide,
It is about.

In the plating pretreatment method of the present invention, the oxidative polymerization step of the compound having a heterocyclic ring is performed on the substrate surface as described above, and therefore a uniform plating base layer is formed on the substrate surface in detail. Further, since the reduced metal salt is adsorbed on the surface of the polymer of the compound having a heterocyclic ring and acts as a catalyst for electroless plating, the plating film can be formed uniformly and in detail as well.
In addition, since the plating pretreatment method of the present invention can simultaneously perform the oxidation polymerization step and the catalyst application step from the above, it is possible to simplify the manufacturing process of the plating underlayer, thus simplifying the manufacturing process. Is possible.
Furthermore, in the plating pretreatment method of the present invention, when the substrate is treated with an aqueous solution containing a compound having a heterocyclic ring and a metal salt, electroless plating treatment is possible immediately after washing with water. A metal plating film can be formed in the process. Moreover, since the plating pretreatment method of the present invention has a small number of steps, the possibility of bringing in a chemical solution is reduced. Furthermore, a plated product with reproducibility can be easily obtained, and the productivity of the plated product is excellent.
Moreover, since an organic solvent is not used, high temperature drying is not required, so even a base material with poor heat resistance can be used.

FIG. 1 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis showing the presence of Pd (zero valence) and Pd (divalent) after application of a Pd catalyst in Example 1 and Comparative Example 2. .

The present invention will be described in detail.
The present invention
A method of forming a plating underlayer comprising (i) a compound having a heterocyclic ring and (ii) a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating on a substrate,
The plating pretreatment method is characterized in that the plating underlayer is formed by any of the following methods (a) to (c).
(A) A method comprising the steps of immersing the substrate in an aqueous solution containing the compound having a heterocyclic ring and the metal salt and pulling it up (b) immersing the substrate in an aqueous solution containing the compound having a heterocyclic ring And (c) a step of immersing the pulled up substrate in an aqueous solution containing the metal salt (c) immersing the substrate in an aqueous solution containing the metal salt, and A method comprising contacting a vapor comprising a compound having:

The base material used in the present invention is not particularly limited. For example, polyester resin, acrylic resin, ABS resin, polypropylene resin, polycarbonate resin, polystyrene resin, polyvinyl chloride resin, polyamide resin, polyimide resin, etc .; acrylic Fiber, polyester fiber, aramid fiber and the like; urethane foam and the like.
Although the shape of a base material is not specifically limited, For example, plate shape and a film form are mentioned. Moreover, as a base material, the resin molded product etc. which shape | molded resin by injection molding etc. are mentioned, for example.

The substrate may be subjected to a hydrophilic treatment on the surface of the substrate before the plating pretreatment. By applying a hydrophilization treatment to the substrate surface, the compound layer having a heterocyclic ring can be improved in adhesion with the compound layer having a heterocyclic ring by hydrogen bonding with a functional group generated from the substrate surface. Therefore, it becomes easy to form a plating base layer (= a layer containing a compound having a heterocyclic ring and a metal salt). As a result, the deposition and adhesion of the metal plating film are improved.
Any appropriate method may be adopted as a method for hydrophilizing the substrate surface. The hydrophilic treatment may be, for example, a dry treatment or a wet treatment. Examples of the dry treatment include discharge treatment such as corona discharge treatment, plasma treatment and glow discharge treatment; ozone treatment; UV ozone treatment; ionizing active ray treatment such as ultraviolet treatment and electron beam treatment. Examples of the wet treatment include ultrasonic treatment using a solvent such as water and acetone; alkali treatment; anchor coat treatment. These processes may be performed independently or in combination of two or more.
Moreover, since the processing temperature of a hydrophilic treatment influences the polymerization rate of the compound which has a heterocyclic ring, it is 10 to 60 degreeC normally.

Examples of the compound having a heterocyclic ring used in the present invention include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl- 3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethylaminopyrrole 3-diethylaminopyrrole, 3-diphenylaminopyrrole Pyrrole derivatives such as 3-methylphenylaminopyrrole and 3-phenylnaphthylaminopyrrole; aniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, Aniline derivatives such as o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline and p-methylaniline; thiophene, 3-methylthiophene, 3-n-butylthiophene, 3- n-pentylthiophene, 3-n-hexylthiophene, 3-n-heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n-decylthiophene, 3-n-undecylthiophene, 3- n-dodecylthiophene, 3-methoxy Examples include thiophene derivatives such as thiophene, 3-naphthoxythiophene, and 3,4-ethylenedioxythiophene, preferably pyrrole, aniline, thiophene, and 3,4-ethylenedioxythiophene. Examples include pyrrole.

  In addition, the treatment temperature for polymerizing the compound having a heterocyclic ring is appropriately selected depending on the type of the compound having a heterocyclic ring used in the present invention, and is preferably 10 ° C to 70 ° C.

  Examples of the metal salt that functions as an oxidizing agent used in the present invention and has a catalytic ability for electroless plating include, for example, silver nitrate, silver acetate, silver sulfate, silver perchlorate, silver fluoride, silver nitrite, silver chloride, odor Silver salts such as silver halide, silver propionate, silver tartrate, silver methylethyl acetate, silver trimethylacetate, silver carbonate, silver oxalate, silver thrombate; copper nitrate, copper sulfate, copper chloride, copper chlorate, perchloric acid Copper salts such as copper, copper bromide, copper acetate, copper carbonate, copper oxalate; nickel salts such as nickel nitrate, nickel sulfate, nickel chloride, nickel bromide, nickel acetate, nickel carbonate, nickel oxalate; palladium sulfate, Examples thereof include palladium salts such as palladium nitrate, palladium acetate, palladium chloride, palladium bromide, palladium iodide and the like. Among these, halides are preferable, and palladium chloride is particularly preferable.

In the method for forming a plating underlayer according to the present invention, a plating base comprising: (i) a compound having a heterocyclic ring; and (ii) a metal salt that functions as an oxidizing agent and has a catalytic ability for electroless plating. As a method of forming the formation, any one of the following methods (a) to (c) is performed.
(A) A method comprising a step of immersing and lifting a substrate in an aqueous solution containing a compound having a heterocyclic ring and a metal salt (b) The substrate is immersed in an aqueous solution containing a compound having a heterocyclic ring and pulled up A method comprising the step of immersing the substrate in an aqueous solution containing a metal salt (c) immersing the substrate in an aqueous solution containing a metal salt, and contacting the pulled up substrate with a vapor containing a compound having a heterocyclic ring; Method including steps Each of the above methods can be performed using means known to those skilled in the art.

In the method (a), when an aqueous solution containing the compound having a heterocyclic ring and a metal salt is prepared, the concentration ratio of the compound having a heterocyclic ring and the metal salt (= compound having a heterocyclic ring / metal salt) is 0. It is 1-80, Preferably it is 0.1-40. When the concentration ratio is less than 0.1, the oxidation state and polymerization of the compound having a heterocyclic ring are insufficient, and the reduction state of the metal salt is also insufficient, so that it can act as a catalyst for electroless plating. It becomes difficult. On the other hand, if the concentration ratio is greater than 80, the metal salt cannot be uniformly deposited on the base material, so that the metal plating film may not be formed uniformly in the subsequent plating treatment.
The treatment temperature in the step of immersing the base material in the aqueous solution containing the compound having a heterocyclic ring and the metal salt is 10 ° C. to 70 ° C., preferably 25 ° C. to 60 ° C., and the treatment time is 0. It is 1 minute to 120 minutes, preferably 20 minutes to 60 minutes.

In the method (b), the concentration of the aqueous solution containing the compound having a heterocyclic ring is 5 × 10 ^{−4 to} 0.9M, preferably 0.01 to 0.5M.
The treatment temperature in the step of immersing the base material in the aqueous solution containing the compound having a heterocyclic ring is 20 ° C. to 50 ° C., preferably 25 ° C. to 40 ° C., and the treatment time is 0.1 minutes to 50 minutes, preferably 1 to 40 minutes.

In the methods (b) and (c), a preferable aqueous solution containing the metal salt is 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3).
The treatment temperature in the step of immersing the substrate in the aqueous solution containing the metal salt is 20 ° C. to 50 ° C., preferably 25 ° C. to 40 ° C., and the treatment time is 0.1 minutes to 50 minutes, Preferably it is 1 minute-40 minutes.

In the method (c), the vapor containing the compound having a heterocyclic ring may be a vaporized aqueous solution containing the compound having a heterocyclic ring, but preferably the vaporized compound itself is vaporized. Is.
The treatment temperature in the step of contacting with the vapor containing the compound having a heterocyclic ring is 20 ° C. to 50 ° C., preferably normal temperature, and the treatment time is 0.1 minutes to 40 minutes, preferably 1 minute to 30. Minutes, and the treatment pressure may be normal or reduced.

The substrate that has been pre-plated by the methods (a) to (c) is immersed in a plating solution for depositing a metal, thereby forming an electroless plating film.
The plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. That is, as a metal that can be used for electroless plating, for example, copper, gold, silver, nickel, chromium, and the like can be applied, but copper is preferable. Specific examples of the electroless plating bath include ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) and the like.
The treatment temperature for electroless plating is 20 ° C. to 50 ° C., preferably 30 ° C. to 40 ° C., and the treatment time is 10 minutes to 40 minutes, preferably 15 minutes to 30 minutes.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.

[Example 1: A method including the steps of immersing and lifting a substrate in an aqueous solution containing a compound having a heterocyclic ring and a metal salt]
<Plating pretreatment method>
Pyrrol monomer 6.5 mM, palladium chloride aqueous solution 0.25 mM, and hydrochloric acid 2 mM were added to ion-exchanged water, and this aqueous solution was mixed. Then, a base material made of ABS resin (Techno 430, manufactured by Techno Polymer Co., Ltd.) was immersed in this mixed solution at 30 ° C. for 30 minutes, then washed with ion-exchanged water and dried to form a plating underlayer. .
<Electroless plating>
Next, the base material made of ABS resin on which the plating base layer has been formed is immersed in an electroless plating bath ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 20 minutes, and then washed with ion-exchanged water. did. As a result, a copper film having a thickness of 0.3 μm was formed on the surface.

[ Reference Example 2: A method including a step of immersing a base material in an aqueous solution containing a compound having a heterocyclic ring, and immersing the pulled up base material in an aqueous solution containing a metal salt]
<Plating pretreatment method>
A base material made of ABS resin (Techno 430, manufactured by Techno Polymer Co., Ltd.) was immersed in an aqueous solution of 0.02M pyrrole monomer at 30 ° C. for 10 minutes, washed with ion-exchanged water, and dried. Subsequently, the substrate was immersed in an aqueous solution containing 1 mM palladium chloride aqueous solution and 3 mM hydrochloric acid at 30 ° C. for 10 minutes, then washed with ion-exchanged water and dried to form a plating underlayer.
<Electroless plating>
Next, the base material made of ABS resin on which the plating base layer has been formed is immersed in an electroless plating bath ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 20 minutes, and then washed with ion-exchanged water. did. As a result, a copper film having a thickness of 0.3 μm was formed on the surface.

[ Reference Example 3: A method including a step of immersing a base material in an aqueous solution containing a metal salt and contacting the pulled base material with a vapor containing a compound having a heterocyclic ring]
<Plating pretreatment method>
A base material made of ABS resin (Techno 430, manufactured by Techno Polymer Co., Ltd.) that has been hydrophilized by plasma treatment is immersed in an aqueous solution containing 1 mM palladium chloride aqueous solution and 3 mM hydrochloric acid at 30 ° C. for 30 minutes, and then It was washed with ion exchange water and dried. Subsequently, only the pyrrole monomer was placed in the glass desiccator, the container was covered and left at 40 ° C. for 10 minutes to vaporize the pyrrole monomer in the container. And the said base material was left to stand in this container at 40 degreeC and the pressure of 0.1 MPa for 5 minutes, and the vapor phase polymerization of the polypyrrole was performed. Thereafter, it was washed with ion-exchanged water and dried to form a plating underlayer.
<Electroless plating>
Next, the base material made of ABS resin on which the plating base layer has been formed is immersed in an electroless plating bath ATS add copper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 20 minutes, and then ion-exchanged water. Washed with. As a result, a copper film having a thickness of 0.3 μm was formed on the surface.

[Example 4: Aramid fiber is immersed in an aqueous solution containing a compound having a heterocyclic ring and a metal salt,
And a method including a pulling step]
A plating underlayer was formed in the same manner as in Example 1 except that the base material of Example 1 was changed to an aramid fiber (Kevlar [registered trademark] manufactured by Toray DuPont Co., Ltd.), and then an electroless plating bath A copper film was formed by immersing in an ATS Adcopper IW bath (Okuno Pharmaceutical Co., Ltd.) for 40 minutes at 35 ° C. The resistance value of the fiber at this time was 5 Ω / m.

[Example 5: Method including immersing urethane foam in aqueous solution containing compound having heterocyclic ring and metal salt, and pulling up]
A plating underlayer was formed in the same manner as in Example 1 except that the base material of Example 1 was changed to a flexible polyurethane foam (Airlon Mac [registered trademark] manufactured by Achilles Co., Ltd.), and then an electroless plating bath A copper film was formed by immersing in an ATS Adcopper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 20 minutes.

[Comparative Example 1: A method including a step of immersing and pulling up a base material in a solution containing only a metal salt]
<Plating pretreatment method>
A base material made of ABS resin (Techno 430, manufactured by Techno Polymer Co., Ltd.) is immersed in an aqueous solution containing 0.25 mM palladium chloride aqueous solution and 2 mM hydrochloric acid at 30 ° C. for 30 minutes, washed with ion-exchanged water, dried and plated. An underlayer was formed.
<Electroless plating>
Next, the base material made of ABS resin on which the plating base layer has been formed is immersed in an electroless plating bath ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 20 minutes, and then washed with ion-exchanged water. did. However, no copper film was formed.

[Comparative Example 2: Conventional Sn-Pd method]
<Plating pretreatment method>
A plating base layer was formed by subjecting a base material made of ABS resin (Techno 430, manufactured by Techno Polymer Co., Ltd.) to the following steps (1) to (5).
(1) Degreasing step After immersing the substrate in an aqueous solution (50 ° C.) consisting of 30 g / L of sodium borate, 20 g / L of sodium phosphate, and 2 g / L of a nonionic surfactant, for 5 minutes, with ion-exchanged water Washed.
(2) Etching Step The substrate was immersed in an aqueous solution (75 ° C.) composed of 420 g / L of chromic acid and 390 g / L of concentrated sulfuric acid for 7 minutes, and then washed with ion exchange water.
(3) Neutralization process The substrate was immersed for 1 minute in an aqueous solution of 50 cc / L concentrated sulfuric acid (room temperature) and then washed with ion-exchanged water.
(4) Catalyst The substrate was immersed for 3 minutes in an aqueous solution (room temperature) consisting of palladium chloride 0.3 g / L, stannous chloride 10 g / L, and concentrated sulfuric acid 200 cc / L, and then washed with ion-exchanged water.
(5) Accelerator The substrate was immersed in an aqueous solution (40 ° C.) of concentrated sulfuric acid 75 cc / L for 3 minutes, washed with ion-exchanged water, and dried to form a plating underlayer.
<Electroless plating>
Next, the base material made of ABS resin on which the plating base layer has been formed is immersed in an electroless plating bath ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 20 minutes, and then washed with ion-exchanged water. did. As a result, a copper film having a thickness of 0.3 μm was formed on the surface.

[Comparative Example 3: Conventional Sn-Pd method]
A plating underlayer was formed in the same manner as in Comparative Example 2 except that the base material of Comparative Example 2 was changed to an aramid fiber (Kevlar [registered trademark] manufactured by Toray DuPont Co., Ltd.), and then an electroless plating bath A copper film was formed by immersing in an ATS Adcopper IW bath (Okuno Pharmaceutical Co., Ltd.) for 40 minutes at 35 ° C.

[Comparative Example 4: Conventional Sn-Pd method]
A plating underlayer was formed in the same manner as in Comparative Example 2 except that the base material of Comparative Example 2 was made of a flexible polyurethane foam (Airlon Mac [registered trademark] manufactured by Achilles Co., Ltd.), and then an electroless plating bath ATS add A copper film was formed by dipping in a copper IW bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 40 minutes.

The plating appearances of the substrates prepared in Examples 1 , 4, 5, Reference Examples 2, 3 and Comparative Examples 1 to 4 were evaluated and shown in Table 1.
In addition, the formation method and evaluation method of a plating base layer are as showing below.
[Pre-plating method]
A: The base material is immersed in an aqueous solution containing pyrrole monomer, palladium chloride and hydrochloric acid. B: The base material is immersed in an aqueous solution containing pyrrole monomer, and then the base material is immersed in an aqueous solution consisting of palladium chloride and hydrochloric acid. C: Palladium chloride After immersing the substrate in an aqueous solution composed of hydrochloric acid and hydrochloric acid, the pyrrole monomer vaporized on the substrate is contacted D: The substrate is immersed in an aqueous solution composed of palladium chloride and hydrochloric acid E: Conventional Sn-Pd method (etching method)
[Evaluation of plating appearance]
○: Plating is deposited on the entire surface, and the uniformity (smoothness) is high and glossy.
Δ: Plating is deposited on the entire surface, but the uniformity is low and there is no gloss.
X: Plating is not deposited.

From the results of Table 1, when the plating pretreatment method of the present invention is used, any substrate subjected to plating treatment has a good plating appearance regardless of the substrate (type and resin) ( See Examples 1 , 4 and 5). In particular, in the case of Example 1, since the base material is immersed in an aqueous solution in which a compound having a heterocyclic ring and a metal salt are mixed and then washed with water, the electroless plating treatment can be performed immediately. It is possible to form a simple metal plating film.
Further, in the plating pretreatment method of the present invention, even when a substrate that easily contains a solution is used, any of the substrates subjected to the plating treatment can have a good plating appearance (Example 4). And 5).
On the other hand, when the substrate was immersed in an aqueous solution not containing a compound having a heterocyclic ring, plating was not deposited (see Comparative Example 1). Further, in the case of the conventional Sn—Pd method, plating was deposited on the entire surface, but the uniformity was low and no gloss was obtained (Comparative Examples 2 to 4).

Using X-ray photoelectron spectroscopy (XPS), the chemical state of the substrate after application of the Pd catalyst in Example 1 and Comparative Example 2 was analyzed.
As a result, in Example 1, a peak appeared at a position different from that in Comparative Example 2 (see FIG. 1). The thing of the comparative example 2 has shown presence of Pd (zero valence), while the thing of Example 1 has a broad peak around 337-338ev. From this result, it is presumed that halides and oxides are mixed in Example 1.

Claims (2)

On a substrate, by contacting the metal salt with a compound (ii) catalytic activity in functional and electroless plating as an oxidizing agent having a (i) heterocycle, on the substrate, was the oxidation state A method of forming a plating underlayer comprising a polymer compound in which a compound having a heterocyclic ring is polymerized on a substrate surface and a metal that acts as a catalyst that is reduced and adsorbed on the surface of the polymer compound ,
The plating underlayer is formed by a method including a step of immersing the substrate in an aqueous solution containing the compound having a heterocyclic ring and the metal salt and pulling it up.
  The plating pretreatment method according to claim 1, wherein the metal salt is a halide.

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