JPH03215699A - Electrodeposition coated member and production thereof - Google Patents

Abstract

PURPOSE:To produce the above electrodeposition coated member having excellent corrosion resistance by successively forming a chemically colored film and an electrodeposition coated film on a nonmetallic base material having a thin film of copper on a surface and curing the electrodeposition coated film at a low temp. CONSTITUTION:The nonmetallic base material 1 is subjected to etching and catalytic treatment and thereafter, the thin film 2 of copper plating of about 1 to 10mu thickness is formed by electroless plating on this substrate. After the chemically colored film 3 of a thin oxide film is formed on the thin film 2 of the copper plating by a copper oxide method, etc., using an alkali, the electrodeposition coated film 4 of an acrylic, melamine system, etc., of low-temp. curing resins on the chemically colored film 3 and is subjected to a curing treatment for about 20 to 180 min. at about 90 to 100 deg.C. The electrodeposition coated film 4 is formed with a good adhesive property on the non-metallic base material 1 in this way and the electrodeposition coated member useful for optical apparatus, such as cameras, is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an electrodeposition coating material and a coating material suitable for forming rough surfaces used in optical equipment such as cameras, office machines, audio products, home appliances, instruments, etc. This invention relates to electrodeposition coated members.

[Conventional technology]

Conventionally, the method of forming an electrodeposition coated member was to apply nickel plating on a zinc phosphate member or copper on the surface of the base material, and then perform chromate treatment with chromate or chromium plating to form a coating film.

Additionally, spray painting includes a special treatment such as fogging treatment.

However, the conventional method has the following drawbacks. When forming a coating film on a substrate, if it is applied directly to the copper surface, the corrosion resistance of the copper itself is extremely poor, which poses a major quality problem. Next, although painting the nickel-plated surface solves the problem of corrosion resistance, it has extremely poor adhesion, which is still a quality problem. Furthermore, chemical treatment using chromate or electrolytic chromate treatment to improve adhesion, or chromium plating, etc., increases the number of steps, worsens the working environment, and poses problems such as pollution, making mass production difficult. isn't it.

In addition, in spray painting, a coating film is formed on the nickel plating film, but it is formed using a special treatment such as a silane coupling agent treatment or an expensive paint with limited special specifications, so the complexity of the process also increases the It requires a lot of technology and is expensive, so it cannot be mass-produced.

On the other hand, in recent years, the curing method for electrodeposited coatings has also been changed to
A transition is being made from the high temperature curing type described in Japanese Patent No. 99 to the low temperature curing type. This is because the base material for exterior use has become plastic, and the need for surface modification has increased, making it necessary to develop products for high-end products. For this reason, several electrodeposition coating methods have been proposed for the purpose of surface modification as well as low-temperature curing, but all of them have coating film characteristics that are lower in adhesion to the substrate than high-temperature curing types. The product lacks versatility and is limited.

[Problems to be solved by the invention] The present invention has been made in view of the above problems, and its purpose is to provide an electrodeposition coated member with excellent corrosion resistance and a method for manufacturing the same. . Another object of the present invention is to provide an electrocoated member and a method for producing the same, which exhibits good adhesion between the base material and the electrocoated film even when the electrocoated film is cured by a low-temperature curing method. It is something to do.

[Means for solving problems]

The electrodeposition coated member of the present invention is characterized by having a metal base material or a non-metal base material having a copper thin film on the surface thereof, a chemically colored film, and an electrodeposition coated film on the chemically colored film. It is something.

Further, the method for manufacturing an electrodeposition coated member of the present invention involves forming a chemically colored film on a metal base material or a nonmetallic base material having a copper thin film on its surface, and then applying an electrodeposition coated film on the chemically colored film. After being formed, the electrodeposited coating is cured at a low temperature.

That is, according to the present invention, a copper thin film is formed on a substrate, a chemically colored layer is formed on the copper thin film, and then an electrodeposition coating film is formed, thereby improving the corrosion resistance of the copper itself and improving the corrosion resistance of the electrodeposition coating film. It has improved adhesion to base materials, and is effective for application to exterior painting of plastic plating that is designed to shield electromagnetic waves, such as OA equipment and home appliances.

The structure of the electrocoated member according to the present invention is shown in FIG.

FIG. 2 is a cross-sectional view of an embodiment in which the nonmetallic member in FIG. 1 is plated with copper, further a chemically colored film is formed, and then an electrodeposition coating film is formed. As a non-metallic member, ABS resin is subjected to electroless copper plating or electrolytic plating, and then a chemically colored film is formed to form an electrodeposition coating film.The method for forming this chemically colored film is as follows: There are copper oxide methods, copper carbonate methods, copper sulfide methods, cupric ammonia hydroxide methods, cuprous oxide methods, etc., but according to the present invention, as a method that satisfies adhesion and corrosion resistance, the copper oxide method using alkali is the most effective method. Also, when an electrodeposition coating film is formed directly on copper, copper dissolves and accumulates in the electrodeposition paint, which affects the physical properties of the coating, but formation of an electrodeposition coating film on an oxide film is due to the presence of copper ions. It is not allowed. Next, the processing conditions for chemical coloring are as follows:
This goal can be achieved by forming a thin oxide film. Regarding electrodeposition coating, anionic or cationic coatings can be applied.

Next, the curing temperature is 90 to 10 degrees depending on the plastic material.
It is desirable to bake in an oven at 0°C for 20 to 180 minutes.

FIG. 2 is a cross-sectional view of an embodiment in which a chemically deposited/colored film is formed on a metal base material and an electrodeposition coating film is formed. In this case as well, copper oxide using alkali was the most effective chemical coloring method.

In this way, by forming an oxide film on the metal base material of the electrodeposition coated member, the adhesion with the electrodeposition coating film and the corrosion resistance are significantly improved, which has the effect of increasing the commercial value. Particularly, the present invention is effective in curing electrodeposition coating films at low temperatures.

In a typical configuration of the present invention, the base material is an ABS material or a metal material, and the ABS material is etched and treated with a catalyst, followed by electroless plating to a thickness of 1 to 10 μm using a commonly known plastic plating method. . Next, copper oxide (thickness of 1 μm or less) is formed using a copper member or alkali, and later the plated member is coated with a generally known low-temperature curing resin such as acrylic/melamine, acrylic, epoxy, urethane, or alkyd resin. Forms an electrodeposition coating. The strength of the coating can be improved by dispersing ceramic particles in the coating as necessary. Resin concentration as paint is 7-15wt%
is preferable (1 to 3 wt% is added as a pigment for coloring).The electrolytic conditions are 20 to 25°C, pH 8.5 to
9 and 50-170v is desirable.

Next, the curing temperature is 22 in an oven at 90 to 100℃.
It is cured for 0 to 180 minutes to complete. This specimen is JISK
5400, and was evaluated by adhesion and salt water resistance tests. The results are shown in Table 11 and Table 2.

As described above, the present invention solves problems regarding adhesion or corrosion resistance of electrodeposition coatings by forming an oxide film, and also enables application to exteriors, and greatly contributes to cost reduction by abolishing Ni plating.

Hereinafter, the present invention will be explained in more detail according to Examples, but the present invention is not limited to the Examples.

〔Example〕

Example I Cr03H using ABS (manufactured by Denki Kagaku Kogyo Co., Ltd.) substrate
After treatment with 2S04-H20 type etching solution for 1 minute and washing with water, 30 g of stannous chloride/I2 as sensitizer solution,
Hydrochloric acid 20mf/I! Treat for 2 minutes at room temperature using
Then, as an activator liquid, palladium chloride 0.3
g/A, and treated with 3 ml/I of hydrochloric acid at room temperature for 2 minutes to conductivity. Thereafter, plating was performed for 30 minutes at an electroless copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd.) with a pH of 13.0 and a bath temperature of 70°C to obtain a thickness of 2 μm. Then sodium hydroxide 5
% and potassium persulfate for 1 minute at 70° C. to form a chemically colored copper oxide film. and,
Acrylic/melamine resin (product name: Honeybright C-
After dispersing 100 parts by weight of alumina with an average particle size of 1 μm and electroless nickel plating of 2 μm on the surface of alumina (IL, manufactured by Honey Kasei Co., Ltd.) in a Pall mill for 30 hours, 15 parts by weight was added to demineralized water. Add 2.0 parts by weight of carbon black for coloring, and use the coating solution at a bath temperature of 25%.
℃ and pH 8 to 9, using the object to be coated as an anode and a 0.5t stainless steel plate as a counter electrode, apply a voltage of 150 V, 3
It was electrodeposited for a minute. After electrodeposition, it was washed with water and cured in an oven at 97°C±1°C for 60 minutes to complete the process. The adhesion (according to JISK5400 grid test) and corrosion resistance (according to JISK5400 salt spray test) of the formed electrocoated coating were compared with those of the electrocoated coating on copper and the electrocoated coating on nickel. As shown in (Tables 1 and 2), the adhesion is 100/1.
00, corrosion resistance was very effective when the width of one side blistering was 1 mm or less.

Example 2 Cr03H using ABS (manufactured by Denki Kagaku Kogyo Co., Ltd.) substrate
Treated with 2SO4-H20 etching solution for 1 minute, washed with water, and then treated with 30g/I of stannous chloride as a sensitizer solution! ,
Hydrochloric acid 20mi! /I! was treated for 2 minutes at room temperature, washed with water, and then treated with 0.0% palladium chloride as an activator solution.
3g/I! , hydrochloric acid 3rrl/j! was used for 2 minutes at room temperature to make it conductive. After that, electroless copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd.), pH 13.0, bath temperature 70°C, 30
Plating was performed for minutes to obtain a thickness of 2 μm. Then, at 70°C with an aqueous solution of 5% sodium hydroxide and 1% potassium persulfate,
After processing for 1 minute, the formation of an oxide film was completed. And acrylic/melamine resin (product name: Honeybly) C-IL
(manufactured by Honey Kasei Co., Ltd.) Average particle size 1 per 100 parts by weight
After dispersing 10 parts by weight of μm alumina in a ball mill for 30 hours, it was diluted to 15 parts by weight with demineralized water, and 2.0 parts by weight of carbon plaque was added for coloring. Under the conditions of ~9, the object to be coated was used as an anode, a 0.5t stainless steel plate was used as a counter electrode, and an applied voltage of 150V was applied.
, electrodeposited for 3 minutes. After electrodeposition, it was washed with water and cured in an oven at 97°C±1°C for 60 minutes to complete the process. The adhesion (according to JIS.K5400 grid test) and corrosion resistance (according to JIS.K5400 salt spray test) of the formed electrocoated coating were evaluated for the electrocoated coating on copper and the electrocoated coating on nickel. As a result of comparison, results similar to those of Example-1 were obtained, and it was recognized that the results were very effective.

Example 3 Cr03H using ABS (manufactured by Denki Kagaku Kogyo Co., Ltd.) substrate
After treatment with 2SO4-H20 based etching solution for 1 minute and washing with water, 30g/It of stannous chloride was added as a sensitizer solution.
Hydrochloric acid 20mj7/I! was treated for 2 minutes at room temperature, washed with water, and then treated with 0.0% palladium chloride as an activator solution.
3g/I! , hydrochloric acid 3ml/I! was used for 2 minutes at room temperature to make it conductive. After that, electroless copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd.), pH 13.0, bath temperature 70°C, 30
Plating was performed for minutes to obtain a thickness of 2 μm.

Next, it was treated with an aqueous solution of 5% sodium hydroxide and 1% potassium persulfate at 70° C. for 1 minute to complete the formation of an oxide film. Then, 100 parts by weight of acrylic/melamine resin (trade name: Honeybrite C-IL, manufactured by Honey Kasei Co., Ltd.) was diluted to 15 parts by weight with demineralized water, and 2.0 parts by weight of carbon black was added for coloring. Using a bath temperature of 25℃, pH
Under conditions 8 to 9, the object to be coated was used as the anode and the counter electrode was used as the 0.
Electrodeposition was performed using a 5t stainless steel plate at an applied voltage of 150V for 3 minutes. After electrodeposition, wash with water and place in an oven at 97℃±1℃ for 6 days.
It was cured for 0 minutes and completed.

Adhesion of the formed electrodeposited coating (JIS.K5400
Corrosion resistance 01S. As a result of comparing the electrodeposited coating on copper and the electrocoated coating on nickel (according to K5400 salt spray test), the same results as in Example 1 were obtained, and it was recognized that it was very effective. .

Example 4 Using a brass plate (100 x 50 x 0.7), solvent degreasing,
Plating pretreatment such as electrolytic degreasing was performed. Next, using an aqueous solution of 5% sodium hydroxide and 1% potassium persulfate, treatment was performed at 70°C for 1 minute to form a copper oxide film. The average particle size is 1 μm per 100 parts by weight of acrylic/melamine resin (trade name: Elecoat, manufactured by Shimizu Co., Ltd.)
After dispersing the alumina surface with 2 μm of electroless nickel plating in a ball mill with 10 parts by weight for 30 hours,
Dilute to 15 parts by weight with demineralized water, add 2.0 parts by weight of carbon black for coloring, and use a coating solution at a bath temperature of 25°C, p.
Under the conditions of H8-9, the object to be coated is the anode and the counter electrode is 0.
．． Electrodeposition was performed using a 5t stainless steel plate at an applied voltage of 150V for 3 minutes. After electrodeposition, it was washed with water and cured in an oven at 97°C±1°C for 60 minutes to complete the process. Regarding the adhesion (based on JIS.K5400 grid test) and corrosion resistance (based on JIS.K5400 salt spray test) of the formed electrodeposition coating film,
As shown in Table 1, the adhesion was 100/100, and the corrosion resistance was 1 mm or less in terms of blistering width on one side, making it very effective. was required.

Table 1 Adhesion evaluation results Table 2 Corrosion resistance evaluation results [Effects of the invention] As explained above, the present invention provides copper plating on a metal member or a member to be metallized, and then forms a chemically colored film. By applying electrodeposition coating to this surface, we provide an electrodeposition coated member that can significantly contribute to the improvement of the physical properties of the coating film and the economic effect of shortening the process.

Further, according to the present invention, even when the electrodeposition coating film is cured at a low temperature, it is possible to obtain an electrodeposition coating member having extremely excellent adhesion to a substrate.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of an embodiment in which a nonmetallic base material is copper plated, an oxide film is formed, and then an electrodeposition coating is formed. FIG. 2 is a cross-sectional view of an embodiment in which a chemically colored coating was formed on a metal substrate and then an electrodeposition coating was formed. l...Non-metal base material 2...Plating member 3...Chemical color coating 4...Electrodeposition coating member 5...Metal base material) 1! ;B [S≧;) Room-2-Figure

Claims (4)

[Claims] (1) An electrocoated member comprising a metal substrate or a nonmetallic substrate having a copper thin film on its surface, a chemically colored film, and an electrodeposited coating on the chemically colored film. (2) The electrocoated member according to claim 1, wherein the copper thin film is a copper plating film. (3) The electrocoated member according to claim 1, wherein the chemically colored film is a copper oxide film. (4) Forming a chemically colored film on a metal base material or a nonmetallic base material having a thin copper film on the surface, then forming an electrodeposition coating on the chemically colored film, and then curing the electrodeposition coating at a low temperature. 1. A method for manufacturing an electrodeposition coated member, the method comprising: