JP2003247076A - Method for depositing electroless plating film, and plated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for depositing an electroless plating film by which a film with excellent adhesion can be deposited onto the surface of a material to be plated without performing etching. <P>SOLUTION: When depositing the electroless plating film by immersion in an electroless plating solution onto the material to be plated on which a catalyst layer is formed, the material to be plated is immersed in a pretreating liquid containing a nitrate ion, a zinc ion, an indium ion and an amine borane complex to undergo formation of a substrate treatment layer for electroless plating, then immersed in a treating liquid containing water-soluble metallic salt, and successively immersed in the above electroless plating solution to undergo deposition of the electroless plating film. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electroless plating method capable of forming a coating film having excellent adhesion on an object to be plated, and an undercoating layer for electroless plating on the object to be plated. The present invention relates to a plated product on which an electroless plating layer having excellent adhesion is formed.

[0002]

2. Description of the Related Art Conventionally, when an electroless plating film is formed on an object to be plated such as a non-conductive base material such as a glass base material or a resin base material, high adhesion is required. In order to obtain a film having, after the glass substrate is subjected to chromium sputtering and etching with hydrofluoric acid, on the other hand,
In the resin base material, after etching with an alkaline solution, a catalyst layer was formed on the surface of the base material, and subsequently electroless plating was performed to form a film.

However, in the above-mentioned conventional method, since spattering or etching treatment using a harmful substance is required, there is not only a safety problem, but also a large amount of waste liquid containing it is generated, which is also environmentally friendly. There's a problem.

Further, in various fields, by forming an electroless plating film on an object to be plated, various functions such as conductivity, rust prevention, abrasion resistance, decorativeness, and a base for electroplating are imparted. Has been developed, the adhesion of the coating to the object to be plated is still insufficient, despite the above etching treatment,
The reliability of the article on which the electroless plating film was formed was also insufficient. Therefore, it has been desired to develop a method of forming an electroless plating film capable of forming a film having higher adhesiveness and a plated product having the electroless plating film having higher adhesiveness.

The present invention has been made in view of the above circumstances, and a method for forming an electroless plating film capable of forming a film having excellent adhesion on an object to be plated without etching treatment, and It is an object of the present invention to provide a more reliable plated product on which an electroless plating film having excellent adhesion is formed.

[0006]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that nitrate ions are formed before the electroless plating on the object to be plated. An electroless plating film having excellent adhesion even if etching treatment is not performed by forming a base treatment layer for electroless plating by treating with a pretreatment liquid containing a zinc ion, an indium ion, and an amine borane complex. It has been found that can be formed.

It has also been found that the use of a zinc-containing indium hydroxide plating layer as a base treatment layer for forming an electroless plating film on an object to be plated makes it possible to form an electroless plating film having excellent adhesion. The present invention has been completed.

That is, the present invention provides the following method for forming an electroless plating film and a plated product. Claim 1: Water-soluble after forming a base treatment layer for electroless plating using a pre-treatment liquid containing nitrate ions, zinc ions, indium ions and amine borane complex on an object to be plated having a catalyst layer formed thereon. A method for forming an electroless plating film, which comprises performing treatment using a treatment liquid containing a metal salt and subsequently forming an electroless plating film using an electroless plating liquid. [2] The method for forming an electroless plating film according to [1], wherein after the pre-treatment with the pre-treatment liquid, heat treatment is performed and then treatment is performed using a treatment liquid containing a water-soluble metal salt. Claim 3: A base treatment layer for electroless plating on an object to be plated,
A plated product in which an electroless plated layer is laminated in this order, wherein the electroless plated undercoat layer is a zinc-containing indium hydroxide plated layer. Claim 4: A base treatment layer for electroless plating on an object to be plated,
A plated product in which an electroless plated layer is laminated in this order, wherein the electroless plated undercoat layer is a zinc-containing indium hydroxide plated layer subjected to a heat treatment. Claim 5: The zinc-containing indium hydroxide plating layer,
It is produced by an electroless plating method.
Alternatively, the plated product according to item 4.

The present invention will be described in more detail below. As the object to be plated of the present invention, one having an electroless plating film formed on the entire surface of the object to be plated and one having an electroless plating film formed on a part of the surface of the object to be plated can be employed. The shape of the object to be plated is not particularly limited, and examples thereof include a plate shape, a sheet shape, and a powder. The material of the object to be plated is not particularly limited, but when it is a material such as ceramics such as glass, resins such as plastics, oxides such as ITO, etc., which usually have poor adhesion with the electroless plating film, The effect of the invention becomes remarkable, and other metals may be used. Hereinafter, the present invention will be described by taking as an example the case where an electroless plating film is formed on the entire surface of the object to be plated, but the invention is not limited thereto.

These objects to be plated are washed with a known degreasing agent, an organic solvent or the like, and then a known surface conditioner such as a surfactant or a silane coupling agent is used to impart an electric charge to the surface and then a catalyst is applied. Perform processing.

Regarding the method of applying the catalyst onto the object to be plated, an aqueous solution application method such as a sensitizing-activating method, an alkaline catalyst method, a catalyzing-accelerating method, or an organometallic complex is applied. Then, a thermal decomposition method, a dry method such as a sputtering method, or the like can be used.

In this case, the sensitizer is a water-soluble stannous salt such as tin chloride (stannous chloride) of 1 to 50 g / L,
Especially 5 to 30 g / L, acid such as hydrochloric acid 5 to 100 ml / L,
It is particularly preferable to use a solution containing 20 to 60 ml / L and adjusted to pH 1 to 5, particularly 1.5 to 3.

As the activator, a water-soluble palladium salt such as palladium chloride 0.01 to 1 g / L, particularly 0.02 to 0.5 g / L, an acid such as hydrochloric acid 0.01 to 1 m
1 / L, especially 0.02-0.5 ml / L, pH
It is preferable to use a solution adjusted to 1 to 5, particularly 1.5 to 3.

On the other hand, as a catalyst, a water-soluble stannous salt such as tin chloride (stannous chloride) is in the range of 10 to 100 g / L, particularly 20 to 50 g / L, and a water-soluble palladium salt such as palladium chloride is 0.01. ~ 1 g / L, especially 100-500 mg /
A solution containing L and adjusted to pH 1 to 5, particularly 1.5 to 3, is preferable. Known accelerators are used as the accelerator.

As the processing conditions, known conditions are adopted, but in the sensitizing-activating method,
In the catalyzing-accelerating method, in which the dipping treatment is repeated twice at 25 ° C. for 1 minute each time,
It is preferable to immerse in the catalyst solution at 25 ° C. for 10 minutes and then in the accelerator solution at 25 ° C. for 3 minutes.

In particular, it is preferable to form a catalyst layer containing Sn, Ag, and Pd, and the method of applying sensitizing-silver activity-palladium activity using an aqueous solution controls the steps, aqueous solution, and treatment conditions. Can be applied more easily.

Examples of the sensitizing solution include divalent tin ions such as SnCl ₂ and SnSO ₄ dissolved in an acid solution such as hydrochloric acid and sulfuric acid in an amount of 1 to 50 g / divalent tin ion.
An acidic solution containing L and having a pH of about 0.1 to 1.5 is used, and the object to be plated is added to the solution at 10 to 60 ° C. for 10 seconds to
The immersion treatment is carried out for 5 minutes, and the silver ion-containing activator is, for example, silver ion 0.0001 to 0.5.
Mol / L is used, pH is set to 5 to 11, liquid temperature is set to 15 to 60 ° C., and the plated object is set to 10 seconds to 5 seconds.
Immersion treatment may be performed for a minute.

As the activator containing palladium,
Divalent palladium salts such as PdCl ₂ and PdSO ₄ are added with hydrochloric acid,
Dissolve in an acid solution such as sulfuric acid and add divalent Pd ion to 0.01
Using a solution containing ~ 1 g / L and having a pH of 1-3,
It is preferable to perform the immersion treatment at 10 to 60 ° C. for 1 second to 5 minutes. If it is soaked for too long, Pd nuclei may be aggregated and agglomerated.

In the present invention, Sn, Ag, and Pd are thus deposited on the surface of the object to be plated, Sn: Ag: Pd = (1
-10): (1-10): (1-10) is recommended to be applied in a weight ratio. Particularly, in the case of an application method using an aqueous solution, considering that fine catalyst nuclei are obtained at a high density, it is preferable. Sn: Ag: Pd = (1-5) :( 1-5):
(1-5), more preferably Sn: Ag: Pd = (1
4) :( 1-3) :( 1-2), and Sn
It is desirable that ≧ Ag ≧ Pd.

Further, by applying sensitizing treatment and Ag activating treatment to about Sn: Ag = 3: 2, fine catalyst nuclei can be imparted at high density. Further, as the ratio of Pd to be applied after that, it is particularly preferable that the ratio of Pd is smaller than Ag.
It is preferable that g: Pd = 2: 1 or so, and if Pd is larger than this ratio, the particle size is likely to be large.
If the amount of Pd is too small, the function as a catalyst for electroless plating deteriorates. That is, Sn: Ag: Pd = 3: 2: 1
The vicinity is the optimum condition for obtaining fine catalyst nuclei at a high density.

Here, in order to obtain the optimum conditions as described above, it is preferable to repeat sensitizing-silver activity-palladium activity a plurality of times as one step, whereby fine catalyst nuclei are provided at high density. can do.

Although the reason for this is not clear, very fine catalyst nuclei are formed by first performing sensitizing-silver activity-palladium activity once, and then it is first provided by repeating the above steps. It is considered that this is because the catalyst nuclei are formed at a high density around the catalyst nuclei.

Therefore, a large amount of catalyst particles can be deposited even on the object to be plated, which is a material such as glass or resin to which normal catalyst particles are difficult to deposit, and the subsequent pretreatment can surely form the undercoat layer. it can.

The same applies to the cases where the sensitizing-palladium activation method and the sensitizing-silver activation method are used.

Setting Sn, Ag, and Pd within the above range
From 1500 nuclei / μm²Or more, preferably
Is 2000 nuclei / μm²Above, more preferably 2500 nuclei
/ Μm ²Above, especially 3000 nuclei / μm²With the above nuclear density
can do.

In this case, the high density Pd nucleus dispersion layer can have an average surface roughness of 0.5 nm or less, particularly 0.3 nm or less, and a catalyst nucleus particle diameter of 2 nm or less, preferably 1.5 nm. The thickness is more preferably 1 nm or less, and a dense and dense layer can be formed. When such a high-density Pd nucleus dispersion layer is used as the catalyst layer of the undercoat layer for electroless plating, the particle size of the catalyst nucleus is 0.0
It is preferably 3 nm or more.

The nucleus density, average roughness, and average particle size can be measured by AFM (atomic force microscope) observation.
The weight ratio of n, Ag, and Pd can be analyzed by ICP (inductively coupled plasma optical emission spectroscopy analyzer).

In the present invention, after the catalyst layer is formed on the object to be plated in this way, a zinc-containing indium hydroxide plating layer is formed on the catalyst layer by using a pretreatment liquid as described later. It is formed as a base treatment layer for electroless plating, and then treated with a treatment solution containing a water-soluble metal salt, and subsequently, an electroless plating film is formed using the electroless plating solution.

In this zinc-containing indium hydroxide plating layer, not all of the indium in the layer may be present as indium hydroxide, but some of the indium is a metal, oxide or other compound, or an alloy with zinc. And so on. Further, the indium hydroxide is not limited to one composed only of indium hydroxide, and may be one in which indium hydroxide and another compound are bonded. On the other hand, zinc is
It means that the element zinc should be contained, and it may be contained as a metal, a hydroxide or an oxide or other compound, or an alloy with indium. These can be understood by measuring the undercoat layer for electroless plating by an X-ray diffraction method, an X-ray photoelectron light splitting method (XPS), or the like. Here, in the present invention, it is important that zinc is contained in the indium hydroxide plating layer which is the undercoating layer for electroless plating. When zinc is not present, the deposition rate of the electroless plating film becomes slower during formation,
Further, the formed electroless plating film may have poor adhesion.

The amount of zinc contained in the zinc-containing indium hydroxide plating layer may be smaller than that of indium. There is a possibility that zinc will be eroded by the complexing agent and the like and the adhesion of the formed electroless plating film will deteriorate. The amounts of indium and zinc in the zinc-containing indium hydroxide plating layer can be measured by an atomic absorption method or the like.

As a method for forming the zinc-containing indium hydroxide plating layer, a dry plating method such as a sputtering method can be adopted, but from the aspects of economical efficiency, productivity and adhesion of the coating, a wet plating method, particularly electroless plating is used. It is preferable to adopt the dipping electroless plating method. When the dry plating method is used, it is not necessary to form the above catalyst layer.

When the electroless plating method is used, a catalyst layer is formed on the object to be plated by the method described above, and then a pretreatment liquid containing nitrate ions, zinc ions, indium ions and amine borane complex is used. Just process it.

The pretreatment liquid containing nitrate ion, zinc ion, indium ion and amine borane complex is not particularly limited as long as it contains each of these components, but zinc ion is 0 .0
01-5 mol / L, especially 0.05-0.5 mol / L
L, indium ion 0.00001-0.1 mol
/ L, in particular 0.0001 to 0.01 mol / L, and an amine borane complex such as dimethylamine borane to 0.
0001 to 1 mol / L, especially 0.001 to 0.1 mo
A treatment liquid containing 1 / L and having a pH of 2 to 7, particularly 3 to 6, can be preferably used. In this case, the nitrate ion concentration is 0.001 to 5 mol / L, particularly 0.01 to 1 mo.
It becomes 1 / L.

The zinc ion and indium ion may be supplied by any of these nitrates and sulfates. However, when zinc ion or indium ion is added as a sulfate, nitric acid such as potassium nitrate or sodium nitrate is added. Ions are adjusted to fall within the above range.

Here, when the zinc ion concentration in the pretreatment liquid is lower than 0.001 mol / L and the indium ion concentration is higher than 0.1 mol / L, the formed undercoat layer is formed. Zinc may not be co-deposited, and the adhesion of the electroless plating film may be deteriorated. In addition, the indium ion concentration is 0.00001mo
When it is lower than 1 / L, indium is not sufficiently codeposited in the undercoat layer, and the adhesion of the electroless plating film may be deteriorated.

Then, the object to be plated is placed in the treatment liquid at 50 to 90 ° C., particularly 60 to 85 ° C. for 1 minute or more, especially 1
The treatment may be performed by immersing it for 0 minutes or more. The upper limit of the treatment time is not particularly limited, but is usually 90 minutes or less, and particularly 60 minutes or less.

The thickness of the zinc-containing indium hydroxide plating layer formed by the above electroless plating method is not particularly limited and is usually 0.01 to 1 μm, particularly 0.1 to 0.5.
The thickness can be about 0.2 μm, for example. Further, in the above zinc-containing indium hydroxide plating, whether indium or zinc is deposited as a coating, whether it is deposited as a coating as a result of dense crystal grains, or is it deposited in another state? Although it is unknown, as shown in FIG. 1, it suffices if it substantially covers the portion of the object to be plated that forms the electroless plating film,
Also, the cross section may be substantially layered.

Further, after the zinc-containing indium hydroxide plating layer of the present invention is formed, it is exposed to 20 atmospheres or nitrogen atmosphere.
You may heat-process at 0-400 degreeC for 5 to 30 minutes. When this heat treatment is performed, the indium hydroxide in the zinc-containing indium hydroxide plating layer is partially or wholly converted to indium oxide, but the zinc-containing indium hydroxide plating layer is subjected to the heat treatment without electrolysis. Also in the undercoating layer for plating, it is possible to form an electroless plating film having excellent adhesion as in the zinc-containing indium hydroxide layer.

An object to be plated on which a zinc-containing indium hydroxide plating layer (primary treatment layer for electroless plating) is formed by treatment with a pretreatment liquid containing the above nitrate ions, zinc ions, indium ions and amine borane complex is formed. , A treatment liquid containing a water-soluble metal salt. In this case, the treatment liquid is not particularly limited as long as it is a treatment liquid containing a metal salt capable of forming a catalytic metal layer capable of forming an electroless plated film, and a colloid type can also be used.

Specific water-soluble metal salts include water-soluble Pd salts such as palladium chloride, water-soluble Ag salts such as silver chloride, water-soluble Cu salts such as copper nitrate, and water-soluble Pt salts such as chloroplatinic acid. Among these, water-soluble Pd salt can be preferably used.

The concentration of the water-soluble metal salt in the treatment liquid is
It is preferably 0.01 to 1 g / L, particularly 0.05 to 0.5 g / L, in which case the pH of the aqueous solution is 1 to 5,
It is particularly preferably 2 to 4.

In the dipping step in this treatment liquid, the object to be plated treated with the above-mentioned pretreatment liquid is at room temperature to 80 ° C., especially 25
To a treatment liquid containing a water-soluble metal salt adjusted to -60 ° C,
Immersion may be performed for 15 seconds to 5 minutes, especially 15 seconds to 1 minute. The treatment method with this treatment liquid may be other than the above-mentioned immersion method,
A spray method or a coating method can be adopted.

The object to be plated on which the catalytic metal layer is formed after the treatment with the pretreatment liquid as described above is subjected to electroless plating, but the conditions in this case are not particularly limited, and are usually The plating conditions used can be used. Also, the plating metal is not particularly limited,
For example, an electroless Cu coating, an electroless Ni-P coating, an electroless Ni-B coating, an electroless Ag coating, an electroless Au coating, an electroless Co coating, various electroless alloy coatings, an eutectoid coating, etc. are appropriately selected. Can be used.

As an example, when forming an electroless Cu plating film, a water-soluble copper salt such as copper sulfate 0.01 to 0.5 is used.
mol / L, especially 0.03 to 0.1 mol / L, a reducing agent such as formaldehyde 0.1 to 1 mol / L, especially 0.1.
3 to 0.8 mol / L, complexing agent such as EDTA 0.01 to
A solution containing 1 mol / L, particularly 0.05 to 0.5 mol / L, and adjusted to pH 9 to 14, particularly 10 to 13,
A method of immersing at 30 to 70 ° C. for 5 to 60 minutes can be adopted.

Further, the electroless plating film may be further electroplated, and in this case also, good adhesion between the base material and the electroless plating layer can be maintained.

In this case, the conditions for electroplating are 0.1 to 0.5 mol / L of water-soluble copper salt such as copper sulfate,
Especially 0.2 to 0.4 mol / L, acid such as sulfuric acid 1.5 to 3
containing mol / L, immersed in a solution of pH 0.1-2,
20 to 30 ° C., cathode current density 1 to 4 A / dm ² , particularly 2
A method of electrolyzing at 3 A / dm ² for 5 to 60 minutes can be adopted.

The electroless plating film formed on the object to be plated by the above-mentioned treatment has excellent adhesion. Also, when forming an electroless plating film on a part of the surface of the object to be plated by masking with a resist or photosensitive patterning of the catalyst layer, the adhesion between the electroless plating film and the object to be plated Is excellent. Therefore, the plated product of the present invention can be effectively used as a plated product or part having various functions provided by the electroless plating film, or a material thereof, in which peeling of the plating film is prevented as much as possible. For example, it is effective for decorative plated products or their materials that perform precious metal plating such as gold plating on plastics, electronic components such as glass substrates with copper-plated wiring or printed boards with copper-plated wiring, or their materials. Can be used.

[0048]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. [1] Application of catalyst [Examples 1 to 3, Comparative Examples 1 to 3] Soda lime glass was used as the object to be plated, and a film was formed on the object to be plated with the catalyst in the following steps. i. Degreasing / Surface Conditioning It was immersed in the following surface conditioner solution at 50 ° C. for 5 minutes. Asahi Cleaner C-4000 (manufactured by Uemura Industry Co., Ltd.)
50 g / L ii. Rinse with water at 25 ° C. for 15 seconds iii. Sensitizing It was immersed in the following sensitizing solution at 20 ° C. for 1 minute. Tin chloride 15 g / L hydrochloric acid 45 mL / L pH 1.5 iv. Washing with water 25 ° C, 15 seconds v. Catalytic Immersion It was immersed in the following palladium activating solution at 20 ° C. for 1 minute. Palladium chloride 0.15 g / L hydrochloric acid 0.15 mL / L pH 2.8 vi. Washing with water, 25 ° C., 15 seconds In Example 3, the operations of iii to vi were repeated twice. In addition, in Comparative Example 1, etching treatment with hydrofluoric acid was performed before applying the catalyst.

[Examples 4 to 6] Soda lime glass was used as the object to be plated, and a film was formed on the object to be plated with the catalyst in the following steps. i. Degreasing / Surface Conditioning It was immersed in the following surface conditioner solution at 50 ° C. for 5 minutes. Asahi Cleaner C-4000 (manufactured by Uemura Industry Co., Ltd.)
50 g / L ii. Rinse with water at 25 ° C. for 15 seconds iii. Sensitizing It was immersed in the following sensitizing solution at 20 ° C. for 1 minute. Tin chloride 15 g / L hydrochloric acid 45 mL / L pH 1.5 iv. Washing with water 25 ° C, 15 seconds v. Catalysis Addition The above silver activating solution was dipped at 20 ° C. for 1 minute. Silver nitrate 0.96 g / L pH 7.0 vi. Rinse with water at 25 ° C for 15 seconds vii. Catalytic Immersion It was immersed in the following palladium activating solution at 20 ° C. for 1 minute. Palladium chloride 0.15 g / L hydrochloric acid 0.15 mL / L pH 2.8 viii. The above operation of iii to viii was repeated twice at 25 ° C. for 15 seconds.

[2] Pretreatment [Examples 1 to 6, Comparative Examples 2 and 3] The pretreated liquid (aqueous solution) shown in Table 1 was treated with the catalyst-added object to be plated at 80 ° C. It was immersed for 20 minutes. In Comparative Example 1, no pretreatment was performed. In Example 6, after the pretreatment, heat treatment was performed at 300 ° C. for 10 minutes in the atmosphere.

Table 2 also shows the results of measurement of the underlayers for electroless plating of Examples 1 to 6 and Comparative Examples 2 and 3 by X-ray diffraction and atomic absorption. Further, FIG. 1 shows a SEM photograph of the base treatment layer according to Example 1, and FIG. 2 shows a SEM photograph of the base treatment layer according to Comparative Example 2.

[0052]

[Table 1]

[3] Pd adsorption [Examples 1 to 6, Comparative Examples 2 and 3] Palladium chloride 0.15 g /
L, hydrochloric acid 0.15 mL / L, a treatment solution (aqueous solution) of pH 3.0 was immersed at 25 ° C. for 30 seconds to adsorb Pd.
In Comparative Example 1, this Pd adsorption treatment was not performed.

[4] Electroless Plating [Examples 1 to 6 and Comparative Examples 1 to 3] Electroless Cu plating was performed by immersing in a Cu plating solution having the following composition for 20 minutes at 60 ° C. Plating solution composition: Copper sulfate 0.06 mol / L EDTA 0.12 mol / L HCHO 0.5 mol / L pH 12.5

[5] Electroplating, heat treatment [Examples 2 to 4] In Examples 2 to 4, the object to be plated on which the electroless Cu plating film was formed as described above was used as a through cup AC-90 (Uemura Kogyo). 25)
After Cu electroplating was performed under conditions of 50 ° C., 2 A / dm ² for 30 minutes, heat treatment was performed for 30 minutes at 250 ° C.

With respect to the electroless plated coatings obtained in each of the above Examples and Comparative Examples, the adhesion between the object to be plated and the coating was evaluated. The results are shown in Table 2.

The adhesion was evaluated by cross-cutting at intervals of 2 mm in a grid pattern and then using a 3M Scotch tape to perform a peeling test to visually confirm the peeling of the coating. ◯: No peeling of the coating was observed. X: Peeling of the film was observed.

[0058]

[Table 2]

As shown in Table 2, the electroless plating undercoat layers of Examples 1 to 6 were zinc-containing indium hydroxide plating layers or zinc-containing indium oxide in which indium hydroxide was changed to indium oxide by heat treatment. Since it is a plating layer, it can be seen that the electroless Cu coating formed thereon has excellent adhesion to the object to be plated. Further, it is found that even when the electroplating film is formed on the surface of the electroless Cu plating film, the adhesion between the film and the object to be plated can be maintained.

On the other hand, in Comparative Example 1, the object to be plated was previously subjected to etching treatment, but the pretreatment was not performed and the undercoating layer for electroless plating was not formed. You can see that it is getting worse. Further, in Comparative Example 2, the indium hydroxide plating layer which is the base treatment layer for electroless plating is not used, and in Comparative Example 3, zinc is contained in the indium hydroxide plating layer which is the base treatment layer for electroless plating. It can be seen that the adhesiveness is inferior to that of each of the Examples, since the alloy does not contain any of.

[0061]

As described above, according to the present invention,
A zinc-containing indium hydroxide plating layer is formed as a pretreatment layer for electroless plating by treating with a pretreatment liquid containing nitrate ions, zinc ions, indium ions and amine borane complex on the object to be plated on which the catalyst layer has been formed. After that, since electroless plating is performed to form a coating, it is possible to perform etching treatment on the object to be plated in advance.
It is possible to form a film having excellent adhesion to the object to be plated. Further, since the electroless plating film (layer) having excellent adhesion to the object to be plated can be formed, the plated product obtained by the present invention can prevent the peeling of the plating film as much as possible, and various plated products and It can be effectively used as the material.

[Brief description of drawings]

FIG. 1 is an electron micrograph of a base treatment layer in Example 1.

2 is an electron micrograph of a base treatment layer in Comparative Example 2. FIG.

Continued front page    F-term (reference) 4K022 AA02 AA03 AA04 AA05 AA11                       BA01 BA03 BA08 BA10 BA14                       BA31 BA33 BA36 CA03 CA06                       CA07 CA13 DA03 DB06 EA01

Claims (5)

[Claims] 1. A pretreatment liquid containing nitrate ions, zinc ions, indium ions, and amine borane complex is used on the object to be plated on which the catalyst layer is formed, to form a base treatment layer for electroless plating, and then a water-soluble solution is prepared. A method for forming an electroless plating film, comprising the steps of: treating with a treatment liquid containing an organic metal salt, and subsequently forming an electroless plating film with an electroless plating liquid. 2. The method for forming an electroless plating film according to claim 1, wherein the pretreatment with the pretreatment liquid is followed by heat treatment and then treatment with a treatment liquid containing a water-soluble metal salt. 3. A plating-processed product in which an electroless plating undercoat layer and an electroless plating layer are laminated in this order on an object to be plated, wherein the electroless plating undercoat layer is zinc-containing indium hydroxide plating. A plated product characterized by being a layer. 4. A plating-processed product in which an electroless plating undercoat layer and an electroless plating layer are laminated in this order on an object to be plated, wherein the electroless plating undercoat layer is zinc-containing indium hydroxide plating. A plated product, characterized in that the layer is heat-treated. 5. The plated product according to claim 3, wherein the zinc-containing indium hydroxide plating layer is produced by an electroless plating method.