JPH0681155A - Method for plating laminated member - Google Patents

Abstract

PURPOSE:To enhance the adhesion of a plating layer to a synthetic resin layer by etching the resin layer without causing an excessive reaction and to carry out sure chemical nickel plating on the surface of the resin layer. CONSTITUTION:When a laminated member obtd. by forming a synthetic resin layer by baking on at least one side of a thin metallic sheet etched to a prescribed pattern is plated, it is baked by heating at 100-250 deg.C for 1-5hr, etched with an etching soln. of an inorg. acid at ordinary temp. to 45 deg.C and successively subjected to sensitivity imparting treatment, activation and chemical nickel plating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plating method for a composite member such as an accessory such as an accessory or a pendant, a decorative article such as an emblem, an ornament for Buddhist altar, and other various ornaments.

[0002]

2. Description of the Related Art Conventionally, for use as various ornaments as described above, for example, brass having a thickness of 0.1 mm (a Cu--Zn alloy containing copper as a main component and a yellow color obtained by adding some other elements thereto) Is a general term for alloys of so-called brass) or phosphor bronze (pure copper plus P) metal thin plate, a pattern is formed by applying semiconductor etching technology means, and the metal thin plate on which the pattern is formed is formed. A composite member in which a layer of 6,6-nylon (formally polyamide 66) is formed by baking to give a sense of mass has already been invented.

Therefore, when a chemical plating layer is applied to the surface of the polyamide 66 in the above-mentioned composite member and the composite member after the plating treatment is used as the above-mentioned various ornaments, the pretreatment step of the chemical nickel plating treatment is performed in the composite member. The surface of polyamide 66 is HNO ₃ (nitric acid) or H ₂ S
It is possible to improve the adhesion of the plating layer by etching with an etching solution such as O ₄ (sulfuric acid). However, an oxidizing acid (nitric acid, chromic acid, mixed acid) may be added to the above-mentioned etching treatment in the plating pretreatment step. When sulfuric acid or sulfuric acid is used, an excessive reaction occurs with respect to the polyamide 66, so that there is a problem in that the etching process varies even if the processing time is set.

On the other hand, when the above-mentioned composite member is subjected to surface treatment such as chemical nickel plating, plating is performed due to the difference in thermal expansion coefficient between the brass or phosphor bronze thin metal plate and the polyamide 66 synthetic resin baking layer. There was a problem that the layers peeled off.

[0005]

SUMMARY OF THE INVENTION According to the present invention, a composite member formed by baking on a thin metal plate is subjected to a baking treatment and an etching treatment with an inorganic acid by the above-mentioned baking treatment. Performs heat fixing to the resin layer, prevents shrinkage of the synthetic resin layer under the maximum treatment temperature conditions of the subsequent surface treatment, suppresses alteration of the synthetic resin layer to the minimum, and also prevents excessive reaction by the above-mentioned etching treatment. An object of the present invention is to provide a plating method for a composite member, which can improve the adhesion of the plating layer by etching the synthetic resin layer without causing the above and can perform reliable chemical nickel plating on the surface of the synthetic resin layer.

[0006]

SUMMARY OF THE INVENTION The present invention is a plating method for a composite member having a synthetic resin layer baked on at least one surface of a thin metal plate etched into a predetermined pattern shape. 100-250 ℃,
Baking treatment within the range of heating time 1 to 5 hours 1st
And a second step of etching the composite member after the baking treatment with an etching solution of an inorganic acid having a liquid temperature of room temperature to 45 ° C. for 1 to 15 minutes, and after the etching treatment of the second step. A plating method for a composite member, comprising a step of subjecting the composite member to a sensitization treatment, an activation treatment, and a chemical nickel plating treatment in this order.

[0007]

According to the present invention, a composite member formed by baking a synthetic resin layer on at least one side of a thin metal plate etched into a predetermined pattern is formed by the above-mentioned first step. Heating temperature 100-250 ℃, heating time 1
Since the baking treatment is performed within a range of up to 5 hours to heat-set the synthetic resin layer, the synthetic resin layer is prevented from shrinking under the maximum treatment temperature condition of the subsequent surface treatment, and the deterioration of the synthetic resin layer is prevented. It can be suppressed to a minimum.

In the second step, the composite member after the above baking treatment is treated with an inorganic acid having a liquid temperature of room temperature to 45 ° C.
In particular, since the etching is performed with an etching solution of HCl (hydrochloric acid) for 1 to 15 minutes, an excessive reaction does not occur, the synthetic resin layer can be satisfactorily etched, and the adhesion of the plating layer in the subsequent step can be improved. it can. Therefore, there is an effect that reliable chemical nickel plating can be performed on the surface of the synthetic resin layer in the above-mentioned composite member.

After the above-described chemical nickel plating treatment, gold plating, silver plating,
The plating treatment such as copper plating is performed by the existing plating method, and the composite member is used as various ornaments.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described in detail below with reference to the drawings. The drawing shows a plating method for a composite member. In the first step S1 of the process chart shown in FIG. 1, a predetermined pattern shape is formed on a metal thin plate 1 of brass or phosphor bronze having a thickness of about 0.1 mm (see FIG. 2). It is applied by etching means. That is, when an etching resist is applied to a portion which should be left as a pattern on the above-described metal thin plate 1 by a photographic method and the metal thin plate 1 coated with this resist is etched, the metal thin plate 1 other than the etching resist applied portion is etched. So
After the resist is peeled off, the metal thin plate 1 having a predetermined pattern shape as shown in FIG. 6 can be obtained (see FIG. 3). This thin metal plate 1 has a large number of pattern openings 2 as shown in FIG.

Next, in the second step S2 of the process diagram shown in FIG.
The synthetic resin layer 3 of polyamide 66 (see FIG. 4) is formed on both surfaces of the above-mentioned thin metal plate 1 by baking to form the composite member 4 having a sense of mass.

Next, the third step (S3) of the process chart shown in FIG.
Then, the above-mentioned composite member 4 is heated at a temperature of 100 to 250 ° C., preferably 150 ° C., and a heating time of 1 to 5 hours, preferably 2
Baking is performed under the condition of time. Since the polyamide 66 is heat-set by this baking treatment, it is possible to minimize the deterioration of the polyamide 66 while preventing the polyamide 66 from shrinking under the maximum treatment temperature condition of the subsequent surface treatment.

Next, in a fourth step S4 of the process diagram shown in FIG.
The liquid temperature of the composite member 4 after the above baking treatment is from room temperature to
Etching is performed for 1 to 15 minutes with an inorganic acid etching solution at 45 ° C. More strictly, a simple substance of concentrated hydrochloric acid (HCl) having a concentration of 35% is used as the inorganic acid, and 30 vol.
% Solution as an etching solution, and etching is performed at a liquid temperature of 30 ° C. for about 8 minutes. By using this HCl, it is possible to satisfactorily etch the polyamide 66 without causing an excessive reaction, and it is possible to improve the adhesion of the plating layer in a subsequent step.

Next, in a fifth step S5 of the process chart shown in FIG.
Using palladium chloride and hydrochloric acid, a sensitization treatment for attaching molecules of palladium chloride to the surface of polyamide 66 after the above-described etching treatment is performed.

Next, in a sixth step S6 of the process diagram shown in FIG.
The composite member 4 that has been processed up to the fifth step S5 described above.
Is placed in a liquid containing stannous chloride and hydrochloric acid, and Cl
(Chlorine) is removed to perform an activation treatment for metallizing the palladium pd. Note that this step may be repeated 2-3 times if necessary.

Next, in a seventh step S7 of the process chart shown in FIG.
Composite member 4 for which the processing up to the sixth step S6 described above has been completed
Is dipped in a plating solution having the following composition, and chemical plating (electroless plating) is performed to obtain Ni (nickel) and pd.
(Palladium) to replace the thickness of about 0.1-0.2
A μ chemical nickel plating layer 5 (see FIG. 5) is formed.

Composition of chemical nickel plating solution Nickel sulfate: 5g / l Sodium hypophosphite (reducing agent): 30g / l Stabilizer: ..... As described above, since the above-mentioned baking treatment and etching treatment with hydrochloric acid are executed as the pretreatment step of the chemical nickel plating treatment in the above-mentioned seventh step S7, the composite member 4
It is possible to form a reliable chemical nickel plating layer 5 on the surface of the synthetic resin layer 3 of polyamide 66.

Incidentally, copper sulfate plating is carried out in the next step of the above-mentioned chemical nickel plating, and after this copper sulfate plating is carried out luster nickel plating or matte nickel plating, and then gold plating depending on the purpose of decoration. Since silver plating, black nickel plating or copper plating is performed, each of these plating treatments will be additionally described.

The composition of the plating solution used for the above copper sulfate plating and the plating conditions are as follows. Composition and Conditions of Copper Sulfate Plating Solution Copper Sulfate (CuSO ₄ ) ... 180-200 g / l Sulfuric Acid (H ₂ SO ₄ ) ... 50-70 g / l Solution Temperature ... 25 ° C. Current Density ... 0.5-2 A / dm ² Above When electroplating is performed with the plating solution of, the metal is deposited from the plating solution as the metal salt solution by an electrolytic reaction,
Copper sulfate plating may be applied to the surface of the above-mentioned chemical nickel plating layer 5. The plating time is the time required for the surface gloss to appear, and is usually 15 to 30 minutes.

When forming a nickel plating layer having gloss on the surface of the copper sulfate plating layer, the composition of the plating solution used for this nickel plating and the plating conditions are as follows. The composition and conditions nickel sulfate of nickel plating solution _{(NiSO 4 · 6H 2 O)} ... 240g / l nickel chloride _{(NiCl 2 · 6H 2 O)} ... 45g / l boric acid ... 45 g / l brightener ... qs fluid temperature ... 45 ° C. Current density: 0.5 to 3.0 A / dm ^{2 When} electroplating is performed for about 10 minutes with the above plating solution, a nickel plating layer having a predetermined thickness of gloss is formed on the surface of the copper sulfate plating layer. be able to.

On the other hand, when a matte nickel plating layer is formed on the surface of the above copper sulfate plating layer, the composition of the plating solution used for this nickel plating and the plating conditions are as follows. Nickel Sulfate Composition and Conditions Nickel Sulfate ... 450 g / l Nickel Chloride ... 45 g / l Boric Acid ... 45 g / l Current Density ... 0.5 to 1.5 A / dm ² About 6 to 8 minutes with the above plating solution, electricity By plating, a matte nickel plating layer having a predetermined thickness can be formed on the surface of the copper sulfate plating layer.

When a gold plating layer is formed as a surface plating layer on the surface of the nickel plating or matte nickel plating layer having the above-mentioned luster, the composition and conditions of the plating solution used for this gold plating are as follows. Composition and Conditions of Gold Plating Solution First gold cyanide cyanide… 1.5 g / l citric acid… 30 g / l potassium citrate… 50 g / l PH… 3.8 to 4.5 Solution temperature… 50 ° C. to 60 ° C. Current density 0.2 to 0.5 A / dm ^{2 A} gold plating layer can be formed on the surface of the nickel plating layer by adjusting the plating time with the above plating solution according to the plating layer thickness. For example, if the plating time is set to 20 seconds, a gold plating layer having a thickness of about 0.05μ can be formed.

Furthermore, when a silver plating layer is formed as a surface plating layer on the surface of the above-mentioned glossy nickel plating layer or matte nickel plating layer, the composition and conditions of the plating solution used for this silver plating are as follows. Composition and conditions of silver plating solution 1st silver cyanide (1st silver cyanide) ... 15g / l Sodium blue cyanide (sodium cyanide) ... 30g / l PH ... Uncontrollable liquid temperature ... 30-50 ° C Current density: 0.2 to 0.5 A / dm ^{2 When} electroplating is performed with the above plating solution for, for example, about 30 to 60 seconds, the surface of the nickel plating layer has a thickness of about 1 μm.
The silver plating layer can be formed.

Furthermore, when a black nickel plating layer is formed as a surface plating layer on the surface of the above-mentioned glossy nickel plating layer or matte nickel plating layer,
The composition and conditions of the plating solution used for this black nickel plating are as follows. The composition and conditions nickel ammonium sulfate black nickel plating solution ... 15 g / l Rochelle salt ... 10 g / l solution temperature ... 30 to 35 ° C. Current density ... 0.05~0.2A / dm ² by the above-mentioned plating solution such as about 2 When electroplating is performed for a minute, a black nickel plating layer having a thickness of 1 μm or less can be formed on the surface of the nickel plating layer.

In this way, the seventh step S7 shown in FIG.
The composite member 4 (finished product shown in FIG. 6) that has been subjected to the above processing or the surface plating layer forming processing is used as accessories such as accessories and pendants and various other decorations.

On the other hand, as shown in FIG. 7, the composite member 4 obtained by performing the above-mentioned various treatments on only one surface of the thin metal plate 1 after the etching treatment shown in FIG. 3 is applied to a glass plate 6 or a cloth (not shown). When bonded, it can also be used as an emblem or other decorative article.

In summary, the composite member 4 in which the synthetic resin layer 3 is burned and formed on at least one surface of the metal thin plate 1 etched into a predetermined pattern shape (see FIG. 6),
In the above-described third step S3, the heating temperature of the composite member 4 is 100 to 100
Since the synthetic resin layer 3 is heat-set by baking at 250 ° C. for a heating time of 1 to 5 hours, the synthetic resin layer 3 is prevented from shrinking under the maximum treatment temperature condition of the subsequent surface treatment. The deterioration of the synthetic resin layer 3 can be suppressed to the minimum.

Further, the composite member 4 after the above baking treatment
In the fourth step S4, since the etching is carried out for 1 to 15 minutes with an inorganic acid having a liquid temperature of room temperature to 45 ° C., particularly HCl (hydrochloric acid) for 1 to 15 minutes, an excessive reaction does not occur and the synthetic resin layer 3 is well etched. It is possible to improve the adhesion of the plated layer 5 in the subsequent step. Therefore, there is an effect that the surface of the synthetic resin layer 3 in the above-mentioned composite member 4 can be reliably subjected to chemical nickel plating.

In the correspondence between the configuration of the present invention and the above-described embodiment, the first step of the present invention corresponds to the third step S3 of the above-mentioned embodiment, and the same applies to the second step. Fourth
The invention corresponds to the step S4, the sensitization process corresponds to the fifth process S5, the activation process corresponds to the sixth process S6, and the chemical nickel plating process corresponds to the seventh process S7. However, the configuration is not limited to the above-mentioned embodiment.

[Brief description of drawings]

FIG. 1 is a process drawing showing a plating method for a composite member of the present invention.

FIG. 2 is a sectional view showing a state before etching a thin metal plate.

FIG. 3 is a cross-sectional view showing a state after etching a thin metal plate.

FIG. 4 is a cross-sectional view showing a state after the synthetic resin layer is seized.

FIG. 5 is an enlarged cross-sectional view showing a state after the completion of the chemical nickel plating process.

FIG. 6 is an explanatory diagram showing an example of a pattern shape.

FIG. 7 is an explanatory view showing an example of a completed composite member.

[Explanation of symbols]

 1 ... Metal thin plate 3 ... Synthetic resin layer 4 ... Composite member 5 ... Chemical nickel plating layer

Claims (1)

[Claims] 1. A plating method for a composite member in which a synthetic resin layer is formed by baking on at least one surface of a thin metal plate etched into a predetermined pattern shape, wherein the composite member is heated at a temperature of 100 to 250 ° C. for a heating time of 1 ~ The first step of performing a baking treatment within a range of 5 hours, and the second step of etching the composite member after the baking treatment with an etching solution of an inorganic acid having a liquid temperature of room temperature to 45 ° C for 1 to 15 minutes And a step of subjecting the composite member after the etching treatment of the second step to a sensitivity imparting treatment, an activation treatment and a chemical nickel plating treatment in this order, a plating method for the composite member.