JP2002194578A - Surface treatment method for metallic material containing copper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment method for a metallic material containing highly versatile copper, which shortens a treatment time, besides keeping a same treatment quality as a conventional one, and easily treats even difficult scale to handle. SOLUTION: The surface treatment method for the metallic material containing copper comprises immersing the metallic material containing copper into a surface treatment agent which contains sulfuric acid of 70 g/liter or more and hydrogen peroxide of 10 g/liter or more as essential components, and applying an ultrasonic vibration to the surface treatment agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a surface of a metal material containing copper, and more particularly to a method for removing silicon oxide formed on the surface of a copper alloy containing silicon. The present invention relates to a surface treatment method for a highly versatile copper-containing metal material that can be easily removed even if it is present.

[0002]

2. Description of the Related Art Conventionally, a metal material containing copper has been widely used as a simple copper or a copper alloy in a printed wiring board manufacturing process and the like. Copper (or copper alloy) -clad laminates in printed wiring boards are treated with surface treatment agents to remove rust inhibitors and oxide films remaining on the copper (or copper alloy) foil surface. For example, Japanese Patent Application No. 2-236289 discloses a surface treating agent containing sulfuric acid, hydrogen peroxide, phosphoric acid, and piperidine as active ingredients. With respect to the surface treatment agents used in these printed wiring board manufacturing processes, further reduction in the processing time while maintaining the processing quality is demanded from the viewpoint of higher definition and higher productivity in recent years. Moreover, 1-6 as a copper alloy
Bronze-based alloys and brass-based alloys containing about 5% by weight of lead are used in faucet fittings, plumbing fittings, plumbing fittings, and valves for water pipes because of their industrially satisfactory machinability. The use of lead has been shunned due to its adverse effects on the human body and the environment, and copper alloys such as brass containing about 1 to 5% by weight of silicon instead of lead have been used. However, brass or the like containing silicon may have scales derived from silicon oxide attached to its surface when subjected to annealing, and such scales are very difficult to remove, and a chemical surface treatment (for example, Treatment with a surface treating agent such as) is insufficient or very time-consuming.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems and to maintain the processing quality as before,
It is another object of the present invention to provide a highly versatile surface treatment method for a copper-containing metal material that can shorten the treatment time and can easily treat even a scale that is difficult to treat.

[0004]

Means for Solving the Problems The present inventors have arrived at the present invention as a result of intensive studies in view of the above. That is, the present invention relates to the first
Immersing a metal material containing copper in a surface treatment agent containing sulfuric acid of 70 g / L or more and hydrogen peroxide of 10 g / L or more as essential components, and applying ultrasonic vibration to the surface treatment agent. A second feature is the surface treatment method for a metal material containing copper, which is a characteristic feature, wherein the copper-containing metal material is a copper alloy containing silicon.

[0005] The surface treating agent used in the present invention contains sulfuric acid and hydrogen peroxide as essential components, and such a sulfuric acid-hydrogen peroxide based surface treating agent is known. Sulfuric acid-hydrogen peroxide-based surface treatment agents are described in, for example,
-236289, but in order to obtain a sufficient synergistic effect with the ultrasonic vibration used in the present invention,
In the present invention, it is necessary that the concentration of sulfuric acid in the surface treatment agent is 70 g / L or more, preferably 90 to 280 g / L, and the concentration of hydrogen peroxide is 10 g / L or more, preferably 50 g / L or more.

[0006] If the sulfuric acid concentration is less than 70 g / liter, the removability of the scale, particularly the removability of the scale derived from silicon oxide, becomes insufficient, and the product becomes versatile. The upper limit of the sulfuric acid concentration is not particularly limited from the viewpoint of the removability of the scale. The more the concentration is, the higher the effect is. Practically, it is preferable to be 280 g / liter or less, since problems such as deterioration of the surface appear. Further, even if the hydrogen peroxide concentration is less than 10 g / liter, similarly, the removability of the scale becomes insufficient, and the versatility is increased. The upper limit of the concentration of hydrogen peroxide is not particularly limited from the viewpoint of the removability of scale. The larger the amount, the higher the effect. Therefore, practically, it is preferably 200 g / liter or less.

As the surface treating agent used in the present invention, known additives can be used in a range of a usual amount as long as the effects of the present invention are not impaired. For example, JP-A-2-23
Additives as described in JP-A-6289 can be blended. As a specific example, phosphoric acid (0.5 g /
Liter or more, preferably 2 to 5 g / liter) and / or
Alternatively, it may contain piberidine (including its derivative, at least 0.1 g / l, preferably 0.1 to 5 g / l).

The present invention has a step of immersing a metal material containing copper in the above-mentioned surface treating agent. Here, the metal material containing copper is a simple substance of copper or a copper alloy, and examples of the copper alloy include bronze, brass, red copper, nickel silver, and the like. Of these, brass containing silicon (for example, 1 to 5% by weight) is used for applications such as water pipes and water valves, and scales derived from silicon oxide are formed on the surface by annealing. May be attached, and it is necessary to remove such scales in order to plate such a copper alloy. However, such a scale derived from silicon oxide is difficult to remove, and the effect is most remarkable as compared with the conventional method.In this respect, the present invention can be used for brass containing silicon. Particularly preferred.

In the present invention, ultrasonic vibration is applied to the above-mentioned surface treatment agent in which a metal material containing copper is immersed. As the ultrasonic vibration, for example, the frequency may be about 20 kHz to 200 kHz, and the output is substantially proportional to the amount of the surface treatment agent liquid,
For example, it may be about 20 to 200 W / liter. If the frequency is outside the above range or if the output is less than the above, the effect of applying ultrasonic vibration may not be sufficient.
Further, it is generally not preferable that the output exceeds the above from the viewpoint of industrialization suitability. In particular, when removing the scale derived from silicon oxide on the surface of brass containing silicon, the frequency is 30 kHz to 50 kHz, and the output is 30 to 1.
It is most preferable that it is 00 W / liter in terms of effect and industrial suitability. In the present invention, the temperature of the surface treatment liquid is not particularly limited, and may be any temperature at which the surface treatment is usually performed, and is usually 10 ° C to 40 ° C, preferably 15 ° C.
Temperatures between 0 ° C and 35 ° C are used.

[0010]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Examples 1 to 21 and Comparative Examples 1 to 5 An aqueous solution having the composition shown in Table 1 was prepared as a surface treatment agent. Annealed, with a diameter of 2 with a scale derived from silicon oxide attached to the surface
A test piece was a silicon-containing brass (Si content: 3% by weight) rod having a length of 0 mm and a length of 10 cm. One liter of the surface treatment agent is placed in a treatment tank in which an ultrasonic vibrator is arranged, and is supplied at 39 kHz and 10 kHz.
Ultrasonic vibration of 0 W or 30 W was applied. Here, the test piece was immersed under the conditions shown in Table 1 to perform a surface treatment. Immediately after the treatment, the test piece was washed with water and dried.
Observation was performed every 1 minute within a treatment time of 10 minutes, and every 10 minutes after that. Table 1 shows the scale removal rate 9 which can be regarded as a practical pass.
The processing time required to reach 0% or more is described.

[0011]

[Table 1]

[Comparative Examples 6 to 8] The same processing conditions as in Example 5 were used (except for Comparative Example 8 at 60 ° C.) except that the composition of the processing solution was changed as shown in Table 2. Table 2 shows the results.

[0013]

[Table 2]

[0014]

According to the present invention, the treatment quality in the surface treatment of a metal material containing copper can be maintained as before, the treatment time can be shortened, and the treatment can be easily performed even on a scale where treatment is difficult. It becomes possible.

Continued on the front page F term (reference) 4K053 PA06 PA12 PA13 QA01 RA13 RA15 SA06 SA18 YA03 5E343 AA01 AA11 BB24 CC33 CC34 CC50 CC52 CC54 EE05 EE06 EE12 GG20

Claims (2)

[Claims] 1. Sulfuric acid of 70 g / l or more and 10 g
Of a copper-containing metal material characterized by immersing a copper-containing metal material in a surface treatment agent containing hydrogen peroxide as an essential component in a volume of not less than / liter and applying ultrasonic vibration to the surface treatment agent. Surface treatment method. 2. The surface treatment method according to claim 1, wherein the metal material containing copper is a copper alloy containing silicon.