JP2003155574A - Plated product and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plated product in which the discoloration and peeling of a metal-plated layer caused by its corrosion can be suppressed, and to provide a method of producing the product. SOLUTION: In a pretreatment process S41 for silver mirror reaction, tin (II) is supported on the surface of a coat layer by using a tin (II) chloride solution containing tin (II) functioning as a promoter in a process S60, and then, in a washing process S61, the surface of the coat layer is washed, further, in a catalyst supporting process S62, palladium (II) is supported on the surface of the coat layer by using a palladium (II) chloride solution as a catalyst. Thereafter, a washing process S42 and a plating layer forming process S43 utilizing a silver mirror reaction are carried out.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface of a base material layer,
The present invention relates to a plated product having at least a metal plating layer and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, as this type of plated product, one having a base material layer, an undercoat layer, a silver plating layer and a topcoat layer is known. The undercoat layer is formed, for example, by drying an undercoat agent made of a coating material containing at least one of an alkoxy titanium ester, a silane coupling agent having an epoxy group, and an epoxy resin.

When manufacturing this laminated product, for example, the following method may be used. With this method, first, the undercoat agent is applied to the surface of the base material layer and dried to form an undercoat layer. Then, in order to deposit silver by a silver mirror reaction on the surface of the undercoat layer, a tin chloride [II] (SnCl ₂ ) aqueous solution is brought into contact therewith, and tin [II] is supported as a catalyst. Then, an aqueous solution containing silver is applied to the surface of the undercoat layer, and silver is deposited by a silver mirror reaction to form a silver plating layer. Then, after repeatedly washing and drying, a top coat layer is formed on the surface of the silver plating layer.

[0004]

However, in the above-mentioned laminated product having the silver plating layer, Sn ^{2+ which} is a catalyst for the silver mirror reaction is unstable and is absorbed from the dissolved oxygen in the pretreatment chemical liquid or the air. Oxygen is easily oxidized into Sn ⁴⁺ . This Sn ⁴⁺ cannot serve as a catalyst for the silver mirror reaction, and if the oxidation of Sn ²⁺ proceeds as described above, the concentration of Sn ²⁺ naturally decreases, and The catalytic activity will decrease. In addition, in the silver mirror reaction, tin [II], which serves as a catalyst for Ag ⁺ reduction, is
It remains as a catalyst residue between the silver plating layer and the undercoat layer. When water enters the plated product from the outside, tin [0] derived from the catalyst residue may cause so-called battery corrosion, and may oxidize silver and ionize it to solubilize it in water. This causes discoloration of the silver plating layer and peeling between the silver plating layer and the undercoat layer, which is one of the causes of deterioration of the laminated product.

Further, tin [IV] derived from the catalyst residue is
It may be present in the form of SnOCl ₂ in the laminate. This SnOCl ₂ may release O ^{2 −} and Cl ^{− due} to the invasion of water from the outside, and further promote the corrosion of the silver plating layer.

In order to solve such a problem, in the above-mentioned conventional structure, the tin compound remaining after the silver mirror reaction is merely washed with water repeatedly to remove the one adhering to the surface, and also for the washing after the reaction. There is a limit. Therefore, the tin compound may remain in the laminate beyond the expected range, and the oxidation of the silver plating layer remains a problem.

The present invention has been made by paying attention to the problems existing in the prior art as described above. It is an object of the present invention to provide a plated product capable of suitably suppressing discoloration and peeling due to corrosion of a metal plating layer, and a manufacturing method thereof.

[0008]

In order to achieve the above-mentioned object, the invention according to claim 1 of the present invention is a plated product having at least a metal plating layer on the surface of a base material layer. The difference in standard electrode potential between the metal that is carried on the lower layer interposed between the metal plating layer and the base layer and that constitutes the metal plating layer is 0.6 in absolute value.
The gist is that the metal plating layer is formed using a substance of less than 5 eV as a catalyst.

Here, in a plated product, a metal constituting the metal plating layer and an ionizable substance different from the metal (mainly used in forming the metal plating layer, catalyst residue remaining in the same layer) And its conversion product, etc.), electrons may be exchanged between the two, resulting in battery corrosion such as oxidation of the metal forming the metal plating layer. This corrosion is more likely to occur as the difference in standard electrode potential between the metal forming the metal plating layer and the ionizable substance increases.

On the other hand, in the invention according to claim 1 of the present application, a substance whose difference in standard electrode potential from the metal forming the metal plating layer is less than 0.65 eV in absolute value is used as a catalyst, and metal plating is performed. The layer is to be formed on the surface of the lower layer. Therefore, it becomes difficult for electrons to be transferred between the metal forming the metal plating layer and the catalyst residue, and corrosion of the metal forming the metal plating layer is suppressed. As a result,
It is possible to suitably suppress discoloration or peeling of the metal plating layer due to corrosion of the metal forming the metal plating layer.

Further, the invention according to claim 2 of the present application is, in the invention according to claim 1, characterized in that an upper layer which is laminated on the metal plating layer to protect the metal plating layer is provided. Is.

According to the second aspect of the present invention, in addition to the effect of the first aspect of the invention, moisture is less likely to enter between the lower layer and the metal plating layer of the plated product. This makes it difficult for electrons to be exchanged between the metal constituting the metal plating layer and the catalyst residue, and corrosion of the metal constituting the metal plating layer is suppressed. For this reason,
The corrosion resistance of the metal plating layer is improved.

The invention according to claim 3 of the present application is, in the invention according to claim 1 or claim 2, characterized in that the metal forming the metal plating layer is silver.

According to the invention of claim 3 of the present application, in addition to the function of the invention of claim 1 or 2,
It is possible to maintain high brightness of the silver plating layer for a long period of time.
Further, the invention described in claim 4 of the present application, on the surface of the substrate layer,
In the method for producing a plated product including at least a metal plating layer, in forming the metal plating layer, a substance having a difference in standard electrode potential between the metal forming the metal plating layer and an absolute value of less than 0.65 eV is used as a catalyst. A gist is that it has a catalyst supporting step of supporting on the surface of a lower layer on which a metal plating layer is laminated, and a plating layer forming step of forming the metal plating layer on the lower layer supporting the catalyst. is there.

In the invention described in claim 4 of the present application, an action substantially equivalent to that of the invention described in claim 1 is exhibited.
In the invention according to claim 5 of the present application, in the invention according to claim 4, prior to the catalyst supporting step, a promoter for supporting the catalyst on the surface of the lower layer,
The gist of the present invention is to have a step of supporting a promoter on the surface of the lower layer.

According to the fifth aspect of the present invention, in addition to the effect of the fourth aspect of the invention, in addition to having a standard electrode potential close to that of the metal forming the metal plating layer, it directly affects the lower layer. It becomes possible to support a catalyst that is difficult to support by substituting the co-catalyst previously supported in the lower layer. Therefore, it becomes possible to easily form a metal plating layer that is less likely to cause corrosion.

The invention according to claim 6 of the present application is, in the invention according to claim 4 or 5, characterized in that the metal forming the metal plating layer is silver.

According to the invention of claim 6 of the present application, an action substantially equivalent to that of the invention of claim 3 is exhibited.
Further, the invention according to claim 7 of the present application is, in the invention according to claim 6, characterized in that the difference in standard electrode potential between the catalyst and the silver is 0.2 eV or less in absolute value. It is a thing.

In the invention according to claim 7 of the present application, in addition to the function of the invention according to claim 6, the difference in the standard electrode potential from the silver constituting the silver plating layer is small, and silver corrosion is suitable. Can be suppressed. In addition, as described above, examples of the catalyst having a standard electrode potential difference of 0.2 eV or less in absolute value from silver constituting the silver plating layer include palladium [II], iron [III], rhodium [III], Tellurium [V
I], iodine [0], rhenium [VI], osmium [I
V], platinum [II], and mercury [II].

The invention according to claim 8 of the present application is a method for producing a plated product having at least a metal plating layer on the surface of a base material layer, wherein a plating layer forming step of forming the metal plating layer and the metal There is a catalyst supporting step of supporting tin [II] as a catalyst on the surface of the lower layer on which the plating layer is laminated. In the catalyst supporting step, the tin [II] is used.
However, the gist is to use a pretreatment liquid that accounts for 95% or more of all tin.

In the invention according to claim 8 of the present application, since the pretreatment chemical liquid has a high tin [II] concentration in the liquid, the catalyst (tin [II]) supported on the surface of the lower layer is Since the amount is large, the metal forming the metal plating layer can be efficiently deposited. In addition, variations in the deposition of the metal plating layer on the surface of the lower layer are suppressed, and the quality of the plated product can be maintained high.

Further, the pretreatment chemical has a high affinity with substances such as oxygen and chlorine that promote the corrosion of the metal forming the metal plating layer, and among the tin in the pretreatment chemical, tin that does not actually act as a catalyst. It is used for forming a metal plating layer with a small amount of [IV]. Therefore, the amount of tin [IV] remaining between the metal plating layer and the lower layer of the plated product is reduced, and it is possible to suitably suppress discoloration or peeling of the metal plating layer.

Further, in the invention according to claim 9 of the present application, in a method for producing a plated product having at least a metal plating layer on the surface of a base material layer, a plating layer forming step of forming the metal plating layer, and the metal And a catalyst supporting step of supporting a catalyst on the surface of the lower layer on which the plating layer is laminated. In the catalyst supporting step, the oxidation of the active ingredient that actually acts as a catalyst in the plating layer forming step is suppressed. The purpose of the present invention is to use a pretreatment chemical solution that has been subjected to an oxidation suppression treatment.

In the invention according to claim 9 of the present application, the oxidation of the active ingredient in the pretreatment chemical liquid is suppressed by performing the oxidation suppression treatment. Therefore, in forming the metal plating layer, it is possible to use a pretreatment chemical liquid containing a larger amount of active ingredient. Further, the pretreatment chemical liquid can be stably stored for a relatively long period of time while suitably suppressing the concentration decrease of the active ingredient, and its management becomes easy.

Further, in the catalyst supporting step, by using the pretreatment chemical solution subjected to the oxidation suppressing treatment, it becomes possible to easily support a larger amount of the active ingredient on the surface of the lower layer. As a result, it becomes possible to efficiently deposit the metal plating layer on the surface of the lower layer. In addition, variations in the deposition of the metal plating layer on the surface of the lower layer are suppressed, and the quality of the plated product can be maintained high.

Further, since the pretreatment chemical liquid is used for forming the metal plating layer in a state in which the amount of inactive components which do not actually act as a catalyst among the catalyst components in the liquid is small, the metal plating layer and the lower layer of the plated product are The amount of inactive ingredients remaining between and is reduced. In particular, when the inactive component has a high affinity with a substance that promotes corrosion of the metal forming the metal plating layer such as oxygen or chlorine, discoloration or peeling of the metal plating layer is more preferably performed. It becomes possible to suppress.

The invention according to claim 10 is the invention according to claim 9, wherein the oxidation suppressing treatment is an oxidation for suppressing the oxidation of the active ingredient with respect to the pretreatment liquid chemical. The gist of the invention is to include the treatment of adding the suppressing component.

According to the invention of claim 10 of the present application, in addition to the function of the invention of claim 9, a pretreatment chemical liquid is mixed with an oxidation-inhibiting component to prepare a special treatment device. Or, it becomes possible to suppress the oxidation of the active ingredient in the pretreatment chemical liquid without performing a troublesome treatment work. Therefore, it becomes possible to easily obtain a stable pretreatment liquid.

The invention according to claim 11 of the present application is, in the invention according to claim 10, characterized in that the oxidation inhibiting component is a polyhydric alcohol. In the invention according to claim 11 of the present application, in addition to the effect of the invention according to claim 10, by using a polyhydric alcohol as an oxidation inhibiting component, corrosion of the metal forming the metal plating layer is suitably suppressed. It becomes possible to do.

The invention according to claim 12 of the present application is the invention according to any one of claims 9 to 11, wherein the oxidation suppressing treatment is performed by removing the dissolved oxygen from the pretreatment chemical solution. The gist of the present invention is to include the preparation by mixing a solute or a dispersion in a vaporized medium.

The invention according to claim 13 is the invention according to any one of claims 9 to 12, wherein the oxidation suppression treatment is performed on the dissolved oxygen in the pretreatment chemical liquid. The gist is to include degassing treatment for degassing.

The invention according to claim 14 of the present application is the invention according to any one of claims 9 to 13, wherein the oxidation suppressing treatment is carried out by using the pretreatment chemical solution.
The gist of the present invention is to include maintaining the environment in which the pretreatment chemical solution is placed and the flow of oxygen between the environment and the partitioned external environment in a blocked state.

In the inventions according to claims 12 to 14 of the present application, in addition to the action of the invention according to any one of claims 9 to 11, the catalyst in the pretreatment chemical solution is actually used. Oxidation of the active ingredient that acts as the oxygen by dissolved oxygen in the liquid or oxygen supplied from the external environment is suppressed. For this reason, a decrease in the concentration of the active ingredient is suppressed, and the metal plating layer can be efficiently formed when the metal plating layer is formed. In addition, the amount of oxygen taken into the plated product is reduced, and corrosion of the metal forming the formed metal plating layer can be suppressed. Further, if the pretreatment liquid is degassed in advance or stored in a closed container, it can be stored stably for a longer period of time while appropriately suppressing the concentration decrease of the active ingredient. And its management becomes easier.

The invention according to claim 15 of the present application is the method for producing a plated product according to any one of claims 4 to 7, and the method according to claim 9 to 14. The gist is to form the plating layer by using the method for producing a plated product according to any one of the items.

The invention according to claim 16 of the present application is a method for manufacturing a plated product according to claim 8 and a method for manufacturing a plated product according to any one of claims 9 to 14. And a method for forming the plating layer.

In the invention according to claim 15 or claim 16 of the present application, the corrosion of the metal forming the metal plating layer can be suppressed more preferably. Therefore, it can be applied to plated products used in harsh environments.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below in detail with reference to the drawings. As shown in FIG. 1, the plated product 11 includes a base coat layer 13 as a lower layer on the surface (design surface) of a base layer 12 made of synthetic resin.
A (BC layer), a silver plating layer 14 as a metal plating layer, and a top coat layer 15 (TC layer) as an upper layer are formed.

The base material layer 12 is made of, for example, ABS (acrylonitrile / butadiene / styrene copolymer), PC (polycarbonate) / ABS alloy, PP (polypropylene), PMMA (polymethylmethacrylate) or olefinic thermoplastic elastomer (TPO). ) Or the like thermoplastic elastomer (TPE) or the like, and is molded, for example, by a known injection molding method.

The base coat layer 13 is laminated and formed by applying or dipping a base coat agent on the surface of the base material layer 12 and then drying. Examples of the base coat agent include polyester resin, alkyd resin, acrylic resin, and the like, and two-component curing type polyurethane resin is preferably used because it is easy to apply.

The silver plating layer 14 is laminated on the surface of the base coat layer 13 by a chemical plating method (electroless plating method) utilizing a silver mirror reaction. Specifically, an ammoniacal silver nitrate ([Ag (NH ₃ ) ₂ ] ⁺ OH ⁻ ) solution (Tollens reagent) and a reducing agent solution are applied so as to be mixed on the surface of the base coat layer 13 to cause an oxidation-reduction reaction. , Silver (Ag) as a metal forming the metal plating layer is deposited. As the reducing agent solution, an organic compound (R—CHO) having an aldehyde group such as glyoxal,
An aqueous solution such as sodium sulfite or sodium thiosulfate is preferably used.

The top coat layer 15 is formed by laminating a top coat agent on the surface of the silver plating layer 14 in order to protect the silver plating layer 14 or by immersing the top coating agent in the surface and then drying. Examples of the top coat agent include polyester resins and acrylic resins, and a two-component curing type polyurethane resin or an acrylic modified silicone resin is preferably used because it is easy to apply.

Next, a method for manufacturing the plated product 11 will be described below. As shown in FIG. 3, when manufacturing the plated product 11, first, in step S20, the base material layer 12 is injection-molded into a predetermined shape, and then the base coat coating step (BC coating step) of S30 is performed.

The base coat coating step of S30 is a step of forming the base coat layer 13 made of a base coat agent on the surface of the base material layer 12 after molding. In this base coat coating step, first, in the pretreatment step of S31, the surface (design surface) of the base material layer 12 after the molding is thoroughly washed with a cleaning agent such as isopropanol. Subsequently, in the base coating step of S32, the base coat agent is uniformly coated on the design surface of the base material layer 12 after the cleaning. As a method of coating the base coat agent in S32, either coating or dipping may be used.
Spray coating is preferable because of easy coating. As this base coat agent, for example, "EB2854A-5" manufactured by Fujikura Kasei Co., Ltd., "771" manufactured by Ohashi Chemical Co., Ltd. or "E-1" manufactured by Origin Electric Co., Ltd. is preferably used.

Then, in the drying step of S33, the base coating agent coated on the design surface of the base material layer 12 is dried. Here, the above-mentioned "EB
When "2854A-5" or "E-1" is used, it is dried at a temperature of about 80 ° C for about 60 minutes. Or
When “771” is used as the base coat agent, it is dried at a temperature of about 80 ° C. for about 30 minutes. In this way, after performing the drying step of S33, the process of the plating coating step of the next S40 is performed.

The plating coating step of S40 is a step of forming the silver plating layer 14 on the base coat layer 13. In this plating coating step, first, in the silver mirror pretreatment step of S41, a pretreatment chemical liquid containing a catalyst is applied or dipped on the surface of the dried base coat layer 13, and the catalyst is supported on the surface of the base coat layer 13. . This catalyst is for promoting the initial nucleation of silver of the silver plating layer 14 on the surface of the base coat layer 13 and facilitating the precipitation of silver. Then, in the water washing step of S42, the surface of the base coat layer 13 is washed with ion-exchanged water or distilled water (preferably having a conductivity of ³ μS / m ³ or less) to remove excess excess that was not supported on the surface of the base coat layer 13. Remove the pretreatment chemical solution.

Here, tin (Sn) is used as the catalyst,
In addition, tin chloride [II] (SnCl ₂ ) as a pretreatment chemical
If a solution is used, in the solution tin is tin [I
I] and its tin [II] acts as the catalyst. However, this tin [II] is unstable, and due to dissolved oxygen in the tin chloride [II] solution, oxygen in the air, etc.,
It is easily oxidized to tin [IV].

By the way, this tin [IV] is tin [II]
In comparison with, the ionizable substance, especially the silver plating layer 14
Has a high affinity with oxygen, chlorine, etc., which promotes corrosion. Therefore, when tin [IV], oxygen, chlorine, etc. coexist between the base coat layer 13 and the silver plating layer 14, electrons are exchanged between the two, and silver in the silver plating layer 14 is oxidized. It facilitates solubilization in water that has entered the plated product from the outside. Such battery corrosion causes discoloration of the silver plating layer 14,
Peeling between the base coat layer 13 and the silver plating layer 14 occurs, which causes deterioration of the plated product 11. Further, tin has a large difference in standard electrode potential from silver constituting the silver plating layer 14 (in the case of tin [IV], the difference is 0.65 in absolute value).
eV). The large difference between the standard electrode potentials also contributes to the tendency to cause the battery corrosion.

Tin [IV] is used as the base coat layer 13
Between the silver plating layer 14 and the silver plating layer 14 may exist in the form of SnOCl ₂ . This SnOCl ₂ releases O ²⁻ and Cl ⁻ along with the progress of the battery corrosion, which may further promote the corrosion of the silver plating layer 14.

Further, tin [IV] cannot serve as a catalyst in the silver mirror reaction, and tin [I] in a tin chloride [II] solution cannot be used as a catalyst.
As the oxidation of [I] proceeds, the concentration of tin [II] naturally decreases and the catalytic activity of the solution also decreases. When the solution in which the concentration of tin [II] is reduced is used in the silver mirror pretreatment step of S41, the proportion of tin [II] supported on the surface of the base coat layer 13 is decreased, and conversely tin [IV] is decreased. Will increase in proportion. Therefore, in the plating layer forming step of S43 which is the next step, the formation of the silver plating layer 14 is partially hindered by the tin [IV] carried on the surface of the base coat layer 13, and the silver plating layer 14 is formed. It also causes variations in the formation.

In the washing step of S42, most of the tin [IV] on the surface of the base coat layer 13 is removed. However, since it is almost difficult to remove tin [IV] existing inside the plated product by washing, tin [IV] is removed from the base coat layer 13 and the silver plating layer 1.
There is a possibility that it will remain beyond the expected range between 4 and.

Therefore, in the present embodiment, in order to prevent a large amount of tin [IV] from being carried on the surface of the base coat layer 13 or remaining between the base coat layer 13 and the silver plating layer 14, S41 In the silver mirror pretreatment process of
One of the following two methods is used.

First, the first method is a method of carrying out the co-catalyst carrying step of carrying the co-catalyst on the surface of the base coat layer 13 prior to the catalyst carrying step in the silver mirror pretreatment step of S41. The first method will be described below.

As shown in FIG. 2, in the silver mirror pretreatment step of S41, first, in the promoter supporting step of S60, S3
The first pretreatment chemical containing a cocatalyst is applied or dipped on the surface of the base coat layer 13 dried at 0, and the cocatalyst is supported on the surface of the base coat layer 13.

In the co-catalyst loading step of S60, a tin chloride [II] solution, for example, is used as the first pretreatment chemical solution. This tin chloride [II] solution contains tin chloride [II] as a solute and hydrochloric acid. Hydrochloric acid is blended at a ratio of 1 to 2 mol with respect to 1 mol of tin chloride [II], for example. Then, the first pretreatment chemical liquid is prepared with pure water as a medium so that the tin chloride [II] and hydrochloric acid have desired concentrations. Pure water having a conductivity of preferably ³ μS / m ³ or less, more preferably 0.5 μS / m ³ or less, still more preferably 0.05 μS / m ³ or less is used. And this tin chloride [I
The tin [II] present in the solution I] becomes an active ingredient that actually acts as a promoter when the silver plating layer 14 is formed. The first pretreatment chemical is not limited to the tin chloride [II] solution containing the above components, and for example, “K” manufactured by Metal Processing Technology Laboratory Co., Ltd. may be used. .

After the co-catalyst loading step is performed using the first pretreatment chemical solution, ion-exchanged water or distilled water (preferably having a conductivity of 3 μS / m) is added in the washing step of S61.
³ or less) to wash the surface of the base coat layer 13 with water,
Remove excess cocatalyst remaining on the surface.

Next, in the catalyst supporting step of S62, the second pretreatment chemical liquid containing the catalyst is applied or dipped on the surface of the base coat layer 13 on which the co-catalyst is supported, and the catalyst is applied to the surface of the base coat layer 13. Carry it. The catalyst is
By substituting the co-catalyst carried on the surface of the base coat layer 13 in the co-catalyst carrying step of S60, it is carried on the surface of the base coat layer 13. In this embodiment, as the catalyst, a catalyst having a difference in standard electrode potential with respect to silver constituting the silver plating layer 14 of less than 0.65 eV in absolute value is used.
As the catalyst, the smaller the difference in standard electrode potential from the silver constituting the silver plating layer 14, the better, and the difference is an absolute value, preferably 0.2 eV or less, more preferably 0.1 eV or less.
It is preferably eV or less.

In the catalyst loading step of S62, for example, a palladium chloride solution is used as the second pretreatment chemical solution.
The palladium chloride solution contains palladium chloride (PdCl ₂ ) as a solute and hydrochloric acid. Hydrochloric acid is, for example, 1 to 2 with respect to 1 mol of palladium chloride.
It is blended at a ratio of mol. Then, the second pretreatment chemical liquid is prepared with pure water as a medium so that these palladium chloride and hydrochloric acid have desired concentrations. Pure water is
Preferably ³ μS / m ³ or less, more preferably 0.5 μ
Those having a conductivity of S / m ³ or less, more preferably 0.05 μS / m ³ or less are used. Then, palladium [II] present in this palladium chloride solution becomes an active ingredient that actually acts as a catalyst when the silver plating layer 14 is formed. The palladium [II] has a standard electrode potential value of about +0.99 eV, and the difference from the standard electrode potential of silver is about 0.19 eV in absolute value.

The second pretreatment chemical liquid is not limited to the palladium chloride solution containing the above components, and for example, "Activator" manufactured by Okuno Chemical Industries Co., Ltd. may be used.

Next, the second method will be described. In this method, a tin chloride [II] solution having almost the same composition as the first pretreatment chemical is used as the pretreatment chemical, and tin [II] as a catalyst is applied by applying or dipping the pretreatment chemical. It is supported on the surface of the base coat layer 13. When the second method is used, the catalyst loading step of S62 is performed after the drying step of S33, and the step of S60 is performed.
The co-catalyst loading step and the water washing step of S61 are omitted.

However, the pretreatment chemical solution used in the catalyst supporting step of S62 is used in a state where tin [II] in the chemical solution occupies 95% or more of the total tin. In addition,
The pretreatment chemical solution is preferably used in a state where tin [II] accounts for 97% or more of the total tin, and more preferably 99% or more.

Here, when the pretreatment chemical liquid in which tin [II] is less than 95% of all tin is used, the silver plating layer 14
The amount of the non-effective component (tin [IV]) that does not actually act as a catalyst during the formation of a large amount remains between the base coat layer 13 and the silver plating layer 14. Therefore, in the manufactured plated product 11, silver constituting the silver plating layer 14 is easily corroded, and the silver plating layer 14 is easily discolored or peeled off. Further, the formation of the silver plating layer 14 is partially hindered by the tin [IV] carried on the surface of the base coat layer 13, so that the formation of the silver plating layer 14 becomes uneven.

The pretreatment chemical is not limited to the tin chloride [II] solution containing the above components, and for example, "K" manufactured by Metalworking Research Laboratory Co., Ltd. may be used. Good. However, when using the above "K",
The solution in which tin [II] accounts for 95% or more of the total tin is used.

Further, the pretreatment chemical solution used in the catalyst supporting step of S62 is subjected to an oxidation suppressing treatment for suppressing the oxidation of tin [II]. The oxidation suppressing process includes the following processes, for example.

First, as one of the oxidation suppressing treatments, a polyhydric alcohol such as glycerin or glucose as an oxidation suppressing component for suppressing the oxidation of tin [II] is added to a tin chloride [II] solution. It includes processing to do. This polyhydric alcohol is at least equivalent to hydrochloric acid in solution.
1 amount is contained.

Further, as one of the oxidation suppressing treatments, a pretreatment chemical liquid is prepared by mixing tin chloride [II], hydrochloric acid, and an oxidation suppressing component with pure water deaerated of dissolved oxygen. Has been. Here, in the case of preparing the pretreatment liquid, the amount of dissolved oxygen is 1.0 mg / l or less, preferably 0.5 mg / l or less, more preferably 0.2 mg / l or less by degassing treatment. It is desirable to use the purified water.

Further, as one of the oxidation suppressing treatments, there is included a degassing treatment for preparing the predetermined composition of the pretreatment liquid and then degassing the dissolved oxygen in the pretreatment liquid. Here, the amount of dissolved oxygen in the pretreatment chemical solution was 1.0 by this degassing treatment.
It is desirable to set the concentration within the range of mg / l or less, preferably 0.5 mg / l or less, and more preferably 0.2 mg / l or less.

Further, as one of the oxidation suppressing treatments, the pretreatment chemical liquid is held in a state in which the flow of oxygen between the environment in which the chemical liquid is placed and the external environment partitioned by the chemical liquid is blocked. Is included. In order to maintain such a state, for example, a configuration in which the pretreatment chemical solution is stored in a closed container, or a step in which the catalyst supporting step of S62 is performed in an oxygen-free atmosphere, for example, in a nitrogen-purged atmosphere Etc. can be adopted.

In the oxidation suppressing process, any one or more of the above-mentioned processes and other processes may be performed. However, when the plated product 11 to be manufactured is used in a harsh environment, such as an automobile exterior part, it is desirable to use a pretreatment chemical liquid that has been subjected to a plurality of oxidation suppression treatments.

After the silver mirror pretreatment step of S41 is performed by such a method, as shown in FIGS. 2 and 3, S4 is performed.
In the step 2 of washing with water, the surface of the base coat layer 13 is washed with ion-exchanged water or distilled water (preferably having a conductivity of ³ μS / m ³ or less). And the base coat layer 1
Excess catalyst not supported on the surface of 3 is removed.
After the water washing step of S42 is performed, a plating layer forming step of forming the silver plating layer 14 by using a silver mirror reaction is performed in the next S43.

In the plating layer forming step of S43, both solutions are reacted on the base coat layer 13 by simultaneously applying the ammoniacal silver nitrate solution and the reducing agent solution onto the surface of the base coat layer 13 carrying the catalyst. To deposit silver. Then, the deposited silver is deposited and laminated on the surface of the base coat layer 13 centering around palladium [II] or tin [II] carried on the surface of the base coat layer 13 to form a silver plating layer 14. It In this plating layer forming step, for example, “LA” and “LB” manufactured by Metal Processing Technology Laboratory Co., Ltd. are preferably used, and in this plating layer forming step also, a double-headed spray gun or a concentric spray gun. It is convenient to apply the ammoniacal silver nitrate solution and the reducing agent solution by utilizing.

Subsequently, as shown in FIG. 3, in the water washing step of S44, the surface of the silver plating layer 14 is washed with ion-exchanged water or distilled water, and the silver mirror remaining on the surface of the silver plating layer 14 is washed. After removing the solution after the reaction, S45
The post-processing step of silver mirror is performed.

This silver mirror post-processing step of S45 is the same as the above S4.
This is a process for removing impurities on the surface of the silver plating layer 14 which were not removed in the water washing step of No. 4. In this silver mirror post-treatment step, for example, an impurity decomposition and removal step of decomposing and removing the impurities, an impurity adsorption and removal step of adsorbing and removing the impurities, or an antioxidant film forming step of forming an antioxidant film on the surface of the silver plating layer 14. Is done. In addition, you may perform an antioxidant film formation process after performing an impurity decomposition removal process, and may perform an antioxidant film formation process after performing an impurity adsorption removal process.

In the step of decomposing and removing impurities, an acid having a low concentration is applied or dipped on the surface of the silver plating layer 14 to remove the silver plating layer 1.
4 This is a treatment for decomposing and removing impurities on the surface. As the acid, acetic acid, dilute sulfuric acid, dilute hydrochloric acid, formic acid, chromic acid or the like can be used, but since acetic acid has a high effect of decomposing and removing impurities and has a very small negative influence on the mirror surface of the silver plating layer 14, acetic acid is used. Alternatively, dilute sulfuric acid is preferably used.

The impurity adsorption / removal step is a treatment for applying or immersing the protein dispersion liquid on the surface of the silver plating layer 14 so that the impurities on the surface of the silver plating layer 14 are adsorbed to the protein to be removed. As the protein dispersion liquid, milk of various mammals such as milk or milk powder can be used, but a dispersion liquid of casein using water or a low concentration alcohol aqueous solution as a solvent is preferably used.

In the anti-oxidation film forming step, the silver plating layer 14 is used.
Is a treatment of applying or dipping a metal surface treatment agent on the surface of the above to form a thin antioxidant film on the surface of the silver plating layer 14. The metal surface treatment agent is not limited to silver, and known metal surface treatment agents for treating various metal surfaces or plated surfaces can be used. These metal surface treatment agents are applied to the silver plating layer 14
By contacting with, an oxide film having high water repellency is formed on the surface. As this metal surface treatment agent, for example, "Top rinse" manufactured by Okuno Chemical Industries Co., Ltd. is preferably used. When "top rinse" is used as the metal surface treatment agent, it is preferable to use an aqueous solution in the range of 1 to 50% by weight.

Next, in the water washing step of S46, the surface of the silver plating layer 14 is washed with ion-exchanged water or distilled water, and then adhered to the surface of the silver plating layer 14 in the draining and blowing step of S47. Blow off water droplets with an air blow. Then, in the drying step of S48, about 5
After drying at a temperature of 0 ° C. for about 15 minutes, the S50 top coat coating step (TC coating step) is performed.

The topcoat coating step of S50 is a step of forming the topcoat layer 15 made of a topcoat agent on the surface of the silver plating layer 14. In the top coating step, first, the top coating agent is uniformly applied to the surface of the silver plating layer 14 in the top coating step of S51. As this top coat agent, for example, "PTC-02" manufactured by Fujikura Kasei Co., Ltd., "T-7" manufactured by Ohashi Chemical Industry Co., Ltd., or "Origiji Zug # 100" manufactured by Origin Electric Co., Ltd. is preferably used. It

Then, in the drying step of S52, the top coat agent applied on the silver plating layer 14 is dried to form the top coat layer 15. Here, when the above-mentioned “PTC-02” is used as the top coat agent, it is dried at a temperature of about 70 ° C. for about 70 minutes. Alternatively, when the above-mentioned "T-7" or "Origi-Tug # 100" is used as the top coat agent, it is dried at a temperature of about 80 ° C. for about 30 minutes.

The plated product 11 having the above-mentioned structure is, for example, an automobile interior part such as a meter cluster, a center cluster, a register, a center console, an emblem, a wheel cap, a bumper molding, a wheel garnish, a grill radiator, a back panel, an emblem. It can be suitably applied to automobile exterior parts such as. Furthermore, various plated products used for applications other than automobile parts such as air conditioner housings, mobile phones, and notebook computers can also be suitably applied.

The effects exhibited by the above embodiment will be described below. (1) In this embodiment, as one of the methods used in the silver mirror pretreatment step of S41, the difference between the standard electrode potential of silver constituting the silver plating layer 14 and the standard electrode potential is less than 0.2 eV in absolute value. II] as a catalyst, and silver plating layer 1
4 was formed on the surface of the base coat layer 13.
For this reason, it becomes difficult for electrons to be transferred between the silver constituting the silver plating layer 14 and the catalyst residue, its conversion product, and the like, and silver corrosion of the silver plating layer 14 is suppressed. As a result, the silver plating layer 1 caused by the corrosion of the silver of the silver plating layer 14
Discoloration and peeling of No. 4 can be suitably suppressed.

(2) In this embodiment, the silver plating layer 14
A top coat layer 15 that protects the same layer 14 is laminated on. This makes it difficult for moisture to enter between the base coat layer 13 and the silver plating layer 14 in the plated product 11. For this reason, it becomes difficult for electrons to be transferred between the silver of the silver plating layer 14 and the catalyst residue and the like, the corrosion of silver of the silver plating layer 14 is suppressed, and the corrosion resistance of the silver plating layer 14 is improved. be able to.

(3) In this embodiment, the plated product 11
Then, the silver plating layer 14 is formed. Since the corrosion of silver is preferably suppressed as in the above (1) and (2), the silver plating layer 14 can be retained at high brightness for a long period of time.

(4) In this embodiment, when palladium [II] is used as a catalyst in the catalyst supporting step of S62, tin [II] which is a promoter is attached to the surface of the base coat layer 13 in the promoter supporting step. After carrying once, the catalyst palladium [II] is carried in the catalyst carrying step. As a result, it is possible to replace tin [II] with palladium [II], which has a standard electrode potential close to the standard electrode potential of silver of the silver plating layer 14, but which is difficult to support directly on the base coat layer 13. Can be supported on the surface of the base coat layer 13. Therefore, it is possible to easily form the silver plating layer 14 in which corrosion is unlikely to occur.

(5) In this embodiment, when tin [II] is used as a catalyst in the catalyst supporting step of S62, the pretreatment chemical liquid is such that tin [II] accounts for 95% or more of all tin. used. As a result, the concentration of tin [II] in the pretreatment liquid is high, the amount of catalyst supported on the surface of the base coat layer 13 increases, and the silver plating layer 14
The silver can be efficiently deposited. Further, it is possible to suppress variations in the deposition of silver on the surface of the base coat layer 13, and it is possible to maintain high quality of the plated product 11.

Further, the pretreatment chemical liquid is used in a state in which a small amount of inactive components (tin [IV]) which do not actually act as a catalyst among tin in the chemical liquid is small. Therefore, the amount of inactive components remaining between the base coat layer 13 and the silver plating layer 14 of the plated product 11 is reduced, and the silver plating layer 14 is reduced.
It is possible to particularly suitably suppress the discoloration and peeling.

(6) In this embodiment, when tin [II] is used as a catalyst in the catalyst supporting step of S62, one treatment of the oxidation suppressing treatment is that the pretreatment chemical liquid contains an oxidation product of polyhydric alcohol. Inhibitory components are included. Therefore, the oxidation of tin [II] in the pretreatment liquid is suppressed, and a pretreatment liquid containing a larger amount of tin [II] can be used when the silver plating layer 14 is formed. Further, the pretreatment chemical liquid can be stably stored for a comparatively long period of time while appropriately suppressing the decrease in the concentration of tin [II], and the management thereof becomes easy. In addition, by mixing the oxidation-preventing component with the pretreatment chemical to prepare it, oxidation of tin [II] in the pretreatment chemical can be performed without using a special treatment device or performing a troublesome treatment work. Can be suppressed. Therefore, the pretreatment chemical can be easily kept in a stable state.

(7) In this embodiment, when tin [II] is used as a catalyst in the catalyst supporting step of S62, the pretreatment chemical solution is used as one of the oxidation suppressing treatments.
This includes mixing and preparing tin chloride [II], hydrochloric acid, and an oxidation-suppressing component with respect to pure water degassed of dissolved oxygen.
Further, as one of the oxidation suppressing treatments, a degassing treatment for degassing dissolved oxygen in the pretreatment chemical liquid is included. Further, as one of the oxidation suppressing treatments, it is possible to maintain the pretreatment chemical liquid in a state in which the flow of oxygen between the environment in which the chemical liquid is arranged and the external environment partitioned from the environment is blocked. included. This suppresses the oxidation of tin [II] in the pretreatment chemical liquid by dissolved oxygen in the chemical liquid or oxygen from the external environment. For this reason, the decrease in the tin [II] concentration is suppressed, and when the silver plating layer 14 is formed,
Can be formed efficiently. Also, plated product 1
The amount of oxygen taken in 1 is reduced, and silver corrosion of the formed silver plating layer 14 can be suppressed. Further, the pretreatment chemical liquid can be stably stored for a longer period of time while appropriately suppressing the decrease in the concentration of tin [II], and the management thereof is further facilitated.

(8) In this embodiment, when tin [II] is used as a catalyst in the catalyst supporting step of S62, tin [II] occupies 95% or more of the total tin and is subjected to an oxidation suppressing treatment. Pretreatment chemicals will be used. Therefore, silver corrosion of the silver plating layer 14 can be suppressed even more suitably, and the above-described manufacturing method can be applied to a manufacturing method of a plated product used in a harsh environment.

(9) In this embodiment, the silver plating layer 14
Is formed using a chemical plating method utilizing a silver mirror reaction. Therefore, the silver plating layer 14 can be deposited by a very simple method. In addition, the work for depositing the silver plating layer 14 can be performed extremely quickly and easily, which helps reduce the manufacturing cost.

(10) In this embodiment, the base material layer 12 is made of synthetic resin. Therefore, plated product 11
The weight can be reduced, and the degree of freedom in the product shape can be increased.

[0091]

EXAMPLES Examples and comparative examples embodying the above embodiment will be described below. (Example 1) After the base material layer 12 formed in a square plate shape by ABS is injection-molded (S20), isopropanol is spray-washed on the surface (designed surface) of the base material layer 12 to perform S cleaning.
31 pretreatment steps were performed. Subsequently, a base coating agent (“771” manufactured by Ohashi Chemical Industry Co., Ltd.) was spray-coated on the surface of the base material layer 12 to perform a base coating step of S32.
After that, a drying process (S3
By performing 3), the surface of the base material layer 12 will have a thickness of about 20 μm.
A base coat layer 13 having a uniform thickness of m was formed.

Next, on the surface of the base coat layer 13, the first
After the pretreatment chemical solution (tin chloride [II] solution) is spray-coated and the co-catalyst loading step of S60 is performed, the conductivity is 3 μS /
The surface of the base coat layer 13 was spray-washed with m ³ or less of ion-exchanged water, and the water washing step of S61 was performed. The S
In the co-catalyst loading step of 60, the conductivity is 0.05 μS / m
Tin chloride 0.092 mol / l for ^three pure water [I
I] and 0.110 mol / l hydrochloric acid were contained, and a tin chloride [II] solution 72 hours after the preparation was used.

Next, after spraying a second pretreatment chemical solution (palladium chloride solution) on the surface of the base coat layer 13 supporting tin [II] and performing the catalyst supporting step of S62, the conductivity is 3 μS. The surface of the base coat layer 13 was spray-washed with ion-exchanged water of not more than / m ^{3 and} the water washing step of S42 was performed. In the catalyst supporting step of S62, the conductivity is 0.092 mo with respect to pure water having a conductivity of 0.05 μS / m ^3.
A palladium chloride solution containing 1 / l palladium chloride and 0.110 mol / l hydrochloric acid was used.

Subsequently, the Tollens's reagent and glyoxal are simultaneously spray-coated on the surface of the base coat layer 13 using a double-headed spray gun, and the plating layer forming step of S43 is performed, whereby the surface of the base coat layer 13 is reduced to about 0.
The silver plating layer 14 having a uniform thickness of 1 μm was formed. Then, the surface of the silver plating layer 14 was spray-washed with ion-exchanged water, and the water washing step of S44 was performed.

Then, a metal surface treatment agent (10% by weight aqueous solution of "top rinse" manufactured by Okuno Chemical Industries Co., Ltd.) is spray-coated on the surface of the silver plating layer 14 and the silver mirror post-treatment step of S45 is performed. The surface of the silver plating layer 14 was spray-washed with ion-exchanged water, and the water washing step of S46 was performed. Subsequently, the surface of the silver plating layer 14 is blown with compressed air to obtain S4.
After performing the draining blow process of No. 7, the drying process (S48) for 15 minutes was performed in a 50 degreeC drying furnace.

Finally, a top coating agent ("PTC-02" manufactured by Fujikura Kasei Co., Ltd.) is spray-coated on the surface of the silver plating layer 14 to carry out the top coating step of S51, and then at 70 ° C.
By performing the drying step (S52) in the drying furnace for 70 minutes, the top coat layer 15 having a uniform thickness of about 20 μm was formed on the surface of the silver plating layer 14. The obtained plated product 11 has a base coat layer 13 on the surface of the base material layer 12,
A silver plating layer 14 and a top coat layer 15 are formed.

(Comparative Example 1) S60 co-catalyst loading step and S60
61, except that the water washing step of 61 is omitted, and tin chloride [II] solution having the same components as the first pretreatment chemical solution is spray-coated on the surface of the base coat layer 13 in the catalyst supporting step of S62. Similar steps were performed. That is, tin [II] in a tin chloride [II] solution is supported on the surface of the base coat layer 13 as an active ingredient in a state of actually acting as a catalyst when the silver plating layer 14 is formed.
The plating layer forming step of No. 43 was performed. In the obtained plated product, the base coat layer 13, the silver plating layer 14 and the top coat layer 15 are formed on the surface of the base material layer 12. Two plated products of Comparative Example 1 were prepared, and one of them was used as a plated product of Comparative Example 3.

(Example 2) S60 co-catalyst loading step and S60
The water washing step of 61 was omitted, and in the catalyst supporting step of S62, a tin chloride [II] solution was spray-coated on the surface of the base coat layer 13 as a pretreatment chemical. In the catalyst supporting step of S62, the active ingredient (tin [I
I]) was used as a tin chloride [II] solution in which 99% of all catalyst components (tin) were occupied. The manufacturing process other than the above is the same as that of the first embodiment. In the obtained plated product, the base coat layer 13, the silver plating layer 14 and the top coat layer 15 are formed on the surface of the base material layer 12.

(Comparative Example 2) In the catalyst supporting step of S62, a tin chloride [II] solution was spray-coated on the surface of the base coat layer 13 as a pretreatment chemical. In this catalyst loading step of S62, tin chloride in a state where the active ingredient (tin [II]) actually acting as a catalyst in the plating layer forming step in the solution occupies 88% of all the catalyst ingredients (tin) [II]
The solution was used. The manufacturing process other than the above is the same as that of the second embodiment. The obtained plated product has a base layer 1
A base coat layer 13, a silver plating layer 14, and a top coat layer 15 are formed on the surface of No. 2.

(Example 3) S60 co-catalyst loading step and S60
The water washing step of 61 was omitted, and in the catalyst supporting step of S62, a tin chloride [II] solution was spray-coated on the surface of the base coat layer 13 as a pretreatment chemical. In this catalyst loading step, in addition to the components described in Example 1, 0.110 mol / l of glucose, which is an oxidation inhibiting component, was added, and tin chloride [II] 72 hours after the preparation was passed.
The solution was used. The manufacturing process other than the above is the same as that of the first embodiment. The obtained plated product has a base layer 1
A base coat layer 13, a silver plating layer 14, and a top coat layer 15 are formed on the surface of No. 2.

<Corrosion Resistance Accelerated Test> The plated products 11 of Examples 1 to 3 and the plated products of Comparative Examples 1 to 3 were subjected to an accelerated corrosion resistance test by salt spray. That is, 5 wt% sodium chloride was added to the test apparatus in which each plated product was left stationary, and an aqueous solution adjusted to pH 6.5 to 7.2 was sprayed for 240 hours while being kept at 35 ° C. . After that, each plated product is taken out of the test apparatus and washed with running water. The appearance of the plated product thus sprayed with salt water was visually determined by noting the discoloration and white turbidity of the mirror surface as a measure of the progress of corrosion.

Further, with respect to the plated product after the salt spray, the cross-cutting that penetrates the silver plating layer 14 is cut with a needle or a cutter knife, and taping for evaluating the adhesiveness of the silver plating layer 14 using cellophane tape. Test (JIS G02
02) was performed and the state of peeling of the silver plating layer 14 was visually determined. Also, for the plated product after the salt spray,
A taping test (dry taping) for evaluating the adhesion of the silver plating layer 14 was performed using a cellophane tape without cutting the cross-cut, and the state of peeling of the silver plating layer 14 was visually determined. The accelerated corrosion resistance test was performed on the plated products after 3 days from the drying step of S52 for Example 1 and Comparative Example 1 and the drying of S52 for Examples 2 and 3 and Comparative Examples 2 and 3. The process was performed on the plated product 10 days after the process. FIG. 4 shows the evaluation result.

First, from Example 1 and Comparative Example 1, the influence of the corrosion resistance due to the difference in the standard electrode potential between the silver of the silver plating layer 14 and the catalyst will be examined. As shown in FIG. 4, in Example 1 in which the difference between the standard electrode potentials is 0.19 eV in absolute value, good results were obtained in all evaluation items of the appearance and the adhesion of the silver plating layer 14. On the other hand, in Comparative Example 1 in which the difference between the standard electrode potentials is 0.65 eV in absolute value, although good results were obtained in the evaluation items of appearance, good results were obtained in the evaluation items of adhesiveness. Not obtained. In Comparative Example 1, it has been confirmed that the discoloration and the decrease in gloss of the silver plating layer 14 are gradually recognized with the passage of time after the corrosion resistance accelerated test. On the other hand, in Example 1, almost no discoloration or decrease in gloss of the silver plating layer 14 with time was observed.

Next, from Example 2 and Comparative Example 2, the influence of the corrosion resistance by the ratio of the effective component which actually acts as a catalyst to all the catalyst components in the tin chloride [II] solution will be examined. As shown in FIG. 4, when the silver plating layer 14 was formed, in Example 2 in which the tin chloride [II] solution was used in which the active ingredient accounted for 99% of all the catalyst components, the appearance and adhesion were Good results have been obtained in the evaluation items. On the other hand, the active ingredient is 88% of the total catalyst component.
Comparative Example 2 Using a Tin [II] Chloride Solution Occupying
On the other hand, although good results were obtained in the evaluation items of appearance, good results were not obtained in the evaluation items of adhesiveness. In Comparative Example 2, it has been confirmed that the discoloration and the decrease in gloss of the silver plating layer are gradually recognized with the passage of time after the corrosion resistance accelerated test. On the other hand, in Example 2, almost no discoloration or decrease in gloss of the silver plating layer 14 with time was observed.

Next, from Example 3 and Comparative Example 3, the influence of the corrosion resistance depending on the presence or absence of the oxidation inhibiting component in the pretreatment chemical liquid will be examined. As shown in FIG. 4, in the case of forming the silver plating layer 14, in Example 3 in which the pretreatment liquid containing the above-mentioned oxidation inhibiting component was used, good results were obtained in all the evaluation items of appearance and adhesiveness. There is. On the other hand, in Comparative Example 3 in which the pretreatment chemical liquid containing no oxidation inhibiting component was used in forming the silver plating layer 14, good results were obtained in the evaluation items of the appearance, but the adhesiveness was poor. Good results have not been obtained for the evaluation items. In addition,
In Comparative Example 3, it has been confirmed that the discoloration and the decrease in gloss of the silver plating layer are gradually recognized with the lapse of time after the corrosion resistance accelerated test. On the other hand, in Example 3, almost no discoloration or deterioration in gloss of the silver plating layer 14 was observed.

(Modification) The present embodiment can be modified and embodied as follows. -In the above-mentioned embodiment, various shapes of plated products made of various ceramics including rubber, glass, ceramics, wood, paper, etc., and the base coat layer 13 can be directly or indirectly formed on the surface thereof. The base material layer 12 may be made of a possible material. Further, the base material layer 12 may be made of a thermoplastic resin or a thermosetting resin other than those listed in the above embodiment.

In the above embodiment, the top coat layer 15 may be replaced with a film which is attached, pressure-bonded, adhered or adhered on the silver plating layer 14, for example. In this case, the film is replaced with the silver plating layer 1 instead of the top coat coating step of S50.
4 is provided.

In the above embodiment, the top coat coating step of S50 is not limited to be performed immediately after the plating coating step of S40. For example, after the plating coating step of S40, a temporary protective layer that can be contacted and separated from the surface is provided on the silver plating layer 14, the temporary protective layer is discarded as necessary, and then S50 is performed. You may make it perform the top coat painting process of.

In the above embodiment, the plated product 11 has a base coat layer 13 and a top coat layer 15
Alternatively, at least one of them may be omitted. If the base coat layer 13 is omitted, S30
The base coat painting step of the silver plating layer 14 is omitted.
Is directly formed on the surface of the base material layer 12 by the plating coating step of S40.

In the above embodiment, the metal plating layer of the plated product 11 may be made of a metal other than silver. The present invention can be similarly applied as long as a catalyst is used for forming the metal plating layer on the surface of the base material layer when forming the metal plating layer.

In the above embodiment, the silver plating layer 14 is not limited to the method using a spray gun, but may be formed by, for example, an electroplating method or an immersion plating method.
The present invention can be similarly applied as long as a catalyst for forming the metal plating layer on the surface of the base material layer is used in forming the metal plating layer.

In the above embodiment, the co-catalyst supported on the surface of the lower layer (base coat layer 13 or base material layer 12) in the co-catalyst supporting step of S60 is tin [II].
It is not limited to As the co-catalyst, any component can be used as long as it can be supported on the surface of the lower layer in the co-catalyst supporting step of S60 and can be replaced with the catalyst component in the catalyst supporting step of S62.

In the above-described embodiment, the catalyst component that actually acts as a catalyst in the plating layer forming step of S43 may be directly supported on the lower layer (base coat layer 13 or base material layer 12). S if possible
The co-catalyst loading step of 60 and the water washing step of S61 may be omitted.

In the above embodiment, the catalyst used for forming the silver plating layer 14 is not limited to the one containing tin [II] or palladium [II]. As the catalyst, in addition to tin [II] or palladium [II],
For example, vanadium [IV], chromium [VI], iron [II
I], copper [II], arsenic [III], molybdenum [VII],
Ruthenium [II], Ruthenium [III], Rhodium [II
I], antimony [III], tellurium [IV], tellurium [V
I], iodine [0], rhenium [III], rhenium [I
V], rhenium [VI], rhenium [VII], osmium [IV], iridium [III], platinum [II], mercury [I
It may contain any one of I], thallium [III], bismuth [III] and the like. These active ingredients also have a difference in the standard electrode potential with respect to silver of the silver plating layer 14 of less than 0.65 eV in absolute value, so that the silver plating layer 14 is discolored due to corrosion of silver of the silver plating layer 14 or Peeling can be suppressed appropriately.

Among these listed catalysts, iron [II
I], rhodium [III], tellurium [VI], iodine [0], rhenium [VI], osmium [IV], platinum [I
I] and mercury [II] have a difference in standard electrode potential from silver of the silver plating layer 14 of 0.2 eV or less in absolute value. Therefore, if these are used as a catalyst, the corrosion of silver can be suppressed particularly preferably.

In the above embodiment, when a solution containing a catalyst different from palladium [II] is used as the second pretreatment chemical liquid in the catalyst supporting step of S62, the second pretreatment chemical liquid is used. In addition, when the silver plating layer 14 is formed, an oxidation suppression treatment for suppressing the oxidation of the active ingredient that actually acts as a catalyst may be performed. Note that, as the oxidation suppressing treatment, for example, the addition of the oxidation suppressing component to the second pretreatment chemical liquid or the degassing treatment as described above can be performed.

As the oxidation suppressing process, any one or a plurality of the processes described above may be performed. In this case, silver corrosion of the silver plating layer 14 can be suppressed even more suitably, and the above-described manufacturing method should be applied to a manufacturing method of a plated product used in a harsh environment. You can

In the above embodiment, when tin [II] is used as a co-catalyst in the co-catalyst supporting step of S60, the first pretreatment chemical liquid used in the co-catalyst supporting step is not necessarily the oxidation suppressing treatment. Need not have been applied.
However, even in this case, for example, by using the first pretreatment chemical liquid in a state where not much time has passed after the preparation,
It is desirable to use the first pretreatment liquid in a state where tin [II] accounts for 95% or more of all tin.

Further, in the above-mentioned embodiment, the polyhydric alcohol contained in the pretreatment chemical liquid as the oxidation inhibiting component is
It is not limited to glucose or glycerin. As the polyhydric alcohol, in addition to glucose and glycerin, for example,
1,3-propanediol, 1,2-propanediol, ethylene glycol, erythritol, D-erythrulose, D-erythrose, D-threose, D-arabinose, β-D-arabinose, β-L-arabinose, D-xylulose , L-xylulose, D-xylose, α-D-xylose, 2-deoxy-D-ribose, 2-deoxy-β-D-ribose, D-lyxose, α-D-lyxose, α-L-lyxose, D -Ribulose, D-ribose, D-arabilol, ribitol, D-altrose, β-D-altrose, D-allose, β-D-allose, D-idose, D-galactose, α-D-galactose, β-D-galactose, α-L-galactose, D-quinovose, α-D-
Quinobose, D-glucose, α-D-glucose, β
-D-glucose, α-cyclodextrin, β-cyclodextrin and the like may be used.

In addition, the technical ideas that can be understood from the description of the embodiment and the modified examples will be described below together with their effects. (A) The metal plating layer is a silver plating layer formed by a chemical plating method utilizing a silver mirror reaction, and the plating according to any one of claims 4 to 16. Product manufacturing method.

Therefore, according to the invention described in (a), in addition to the effect of the invention described in any one of claims 4 to 16, the silver plating layer is formed by a very simple method. It becomes possible to deposit. Further, the work for depositing the silver plating layer can be performed extremely quickly and easily, which is useful for reducing the manufacturing cost.

(B) The method for producing a plated product according to any one of claims 4 to 16, wherein the base material layer is made of a synthetic resin. Therefore, according to the invention described in (B), in addition to the effect of the invention described in any one of claims 4 to 16, the weight of the plated product can be reduced and the plating can be achieved. The degree of freedom in the shape of the product can be increased.

[0123]

As described above in detail, according to the invention of claim 1, claim 2, claim 4 or claim 11 of the present invention, metal plating caused by corrosion of the metal forming the metal plating layer Discoloration and peeling of the layer can be suitably suppressed.

Further, according to the invention of claim 3 or 6, in addition to the effect of the invention of claim 1 or 2, the silver plating layer is provided with high brightness over a long period of time. Can be held at.

According to the invention of claim 5 of the present application, in addition to the effect of the invention of claim 4, it is possible to easily form a metal plating layer which is unlikely to cause corrosion. Further, according to the invention of claim 7 of the present application, in addition to the effect of the invention of claim 6, corrosion of silver can be suitably suppressed.

Further, according to the invention described in claim 8, the metal constituting the metal plating layer can be efficiently deposited. In addition, the quality of the plated product can be maintained high. Moreover, discoloration and peeling of the metal plating layer can be suitably suppressed.

According to the ninth aspect of the present invention, a pretreatment chemical liquid containing a larger amount of active ingredient can be used when forming the metal plating layer. In addition, the pretreatment chemical liquid can be stably stored for a relatively long period of time while suitably suppressing the concentration decrease of the active ingredient.
The management becomes easy. Also, in the catalyst supporting step,
By using a pretreatment chemical that has been subjected to oxidation suppression treatment,
The metal forming the metal plating layer can be efficiently deposited. In addition, the quality of the plated product can be maintained high. Further, when the non-active ingredient has a high affinity with a substance that promotes corrosion of the metal forming the metal plating layer, such as oxygen or chlorine, the discoloration or peeling of the metal plating layer is particularly preferably suppressed. can do.

According to the invention of claim 10 of the present application, in addition to the effect of the invention of claim 9, the pretreatment chemical can be easily maintained in a stable state. Further, according to the invention of any one of claims 12 to 14 of the present application, in addition to the effects of the invention of any one of claims 9 to 11, an active ingredient It is possible to store it stably for a longer period of time while suitably suppressing the decrease in the concentration thereof, and the management thereof is further facilitated.

According to the fifteenth or sixteenth aspect of the present invention, the corrosion of the metal forming the metal plating layer can be suppressed even more suitably. Further, it can be applied to plated products used in harsh environments.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing a part of a plated product of an embodiment.

FIG. 2 is a diagram showing a flow of a method for manufacturing a plated product according to the embodiment.

FIG. 3 is a diagram showing a flow of a method for manufacturing a plated product according to the embodiment.

FIG. 4 is a diagram showing an evaluation result regarding corrosion resistance of a plated product.

[Explanation of symbols]

11 ... Plated product, 12 ... Base material layer, 13 ... Base coat layer as lower layer, 14 ... Silver plating layer as metal plating layer, 15 ... Top coat layer as upper layer.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor degree meeting Hiroshi             Aichi Prefecture Kasuga-cho, Nishikasugai-gun Ochiai character Nagahata 1             Address: Toyoda Gosei Co., Ltd. (72) Inventor Yasuhiko Ogisu             Aichi Prefecture Kasuga-cho, Nishikasugai-gun Ochiai character Nagahata 1             Address: Toyoda Gosei Co., Ltd. F-term (reference) 4K022 AA13 AA16 AA23 BA01 BA09                       BA18 BA28 CA05 CA14 CA17                       CA18 CA21 CA22 DA01 DB01                       DB08

Claims (16)

[Claims] 1. A plated product having at least a metal plating layer on the surface of a base material layer, which is carried on the base material layer or on a lower layer interposed between the metal plating layer and the base material layer. The difference between the standard electrode potential of the metal forming the metal plating layer and the standard electrode potential is 0.
A plated product, wherein the metal plating layer is formed using a substance of less than 65 eV as a catalyst. 2. The plated product according to claim 1, further comprising an upper layer laminated on the metal plating layer to protect the metal plating layer. 3. The plated product according to claim 1, wherein the metal forming the metal plating layer is silver. 4. A method for producing a plated product comprising at least a metal plating layer on the surface of a base material layer, wherein in forming the metal plating layer, the difference in standard electrode potential between the metal forming the metal plating layer and the absolute value is an absolute value. 0.65 eV
Using a substance of less than a catalyst as a catalyst, a catalyst supporting step of supporting the surface of a lower layer on which the metal plating layer is laminated, and a plating layer forming step of forming the metal plating layer on the lower layer on which the catalyst is supported. A method for producing a plated product, which comprises: 5. A co-catalyst carrying step of carrying, on the surface of the lower layer, a co-catalyst for carrying the catalyst on the surface of the lower layer, prior to the catalyst carrying step. Item 4. A method for producing a plated product according to Item 4. 6. The method for producing a plated product according to claim 4, wherein the metal forming the metal plating layer is silver. 7. The method for producing a plated product according to claim 6, wherein the catalyst has a difference in standard electrode potential from the silver of 0.2 eV or less in absolute value. 8. A method of manufacturing a plated product, which comprises at least a metal plating layer on the surface of a base material layer, comprising: a plating layer forming step of forming the metal plating layer; and a surface of a lower layer on which the metal plating layer is laminated. And a catalyst supporting step of supporting tin [II] as a catalyst, wherein the catalyst supporting step uses a pretreatment chemical solution in which the tin [II] accounts for 95% or more of all tin. Manufacturing method of plated products. 9. A method for producing a plated product, which comprises at least a metal plating layer on the surface of a base material layer, comprising: a plating layer forming step of forming the metal plating layer; and a surface of a lower layer on which the metal plating layer is laminated. And a catalyst supporting step of supporting a catalyst, wherein the catalyst supporting step is performed before the oxidation suppressing treatment for suppressing the oxidation of the active ingredient in a state of actually acting as a catalyst in the plating layer forming step. A method for producing a plated product, which comprises using a treatment chemical. 10. The plating according to claim 9, wherein the oxidation suppressing treatment includes a treatment of adding an oxidation suppressing component for suppressing the oxidation of the effective component to the pretreatment chemical liquid. Product manufacturing method. 11. The method for producing a plated product according to claim 10, wherein the oxidation inhibiting component is a polyhydric alcohol. 12. The oxidation inhibiting treatment includes preparing the pretreatment chemical liquid by blending a solute or a dispersion in a medium in which dissolved oxygen is degassed.
~ The method for manufacturing a plated product according to claim 11. 13. The plating according to claim 9, wherein the oxidation suppressing treatment includes a degassing treatment for degassing dissolved oxygen in the pretreatment chemical liquid. Product manufacturing method. 14. The oxidation inhibiting treatment holds the pretreatment chemical liquid in a state in which the flow of oxygen between the environment in which the pretreatment chemical liquid is placed and the external environment partitioned from the environment is blocked. 14. The method according to claim 9, further comprising:
The method for producing a plated product according to any one of the above. 15. The method for manufacturing a plated product according to claim 4, and the method according to claim 9.
A method for manufacturing a plated product, comprising: forming the plating layer using the method for manufacturing a plated product according to claim 14. 16. The plating layer is formed using the method for producing a plated product according to claim 8 and the method for producing a plated product according to any one of claims 9 to 14. A method for producing a plated product, comprising: