JP3310702B2 - Stabilization of acidic aqueous hydrogen peroxide solution. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for pickling, etching,
The present invention relates to a method for increasing the stability of an acidic hydrogen peroxide aqueous solution used in performing a chemical treatment such as chemical polishing.

[0002]

2. Description of the Related Art Since an acidic hydrogen peroxide aqueous solution has an excellent dissolving power for a copper-based metal material, for example, a pickling for dissolving and removing an oxide scale on a copper alloy surface, a part of a copper alloy. Etching to dissolve and remove
Conventionally, copper alloy surfaces have been widely used for chemical dissolution treatments such as chemical polishing for brightening treatment.

[0003] However, hydrogen peroxide is a compound that is very easily decomposed, and particularly in a system in which copper ions are present, catalytic decomposition occurs within a short time and the oxidation activity is lost. Therefore, in order to solve such problems, a method of adding phenacetin, an aliphatic alcohol, an aliphatic amine, glycols, glycol ethers, arylsulfonic acid, phenol, phenolsulfonic acid, or the like as a stabilizer to an aqueous hydrogen peroxide solution has been proposed. Has been adopted.

[0004]

However, such a stabilizer as described above has an insufficient stabilizing effect in a high temperature range of about 50 ° C. or higher, and emits a bad smell by volatilization at the time of use or has an undesirable side effect. There is a problem that a reaction is caused to form a precipitate. For example, in a pickling treatment step for dissolving and removing oxide scale of a copper-based metal material, a treatment temperature of about 50 ° C. or more is often used because of the need to increase treatment efficiency, and a large amount of Of copper peroxide is eluted, and the decomposition of hydrogen peroxide becomes extremely severe in combination with the effect of temperature, so that the stabilization purpose is hardly achieved by the above stabilizer. As a result, a large amount of acid fog is generated by oxygen gas generated by violent decomposition of hydrogen peroxide, which significantly deteriorates the working environment.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide an acidic solution in which copper ions having a decomposition promoting action are mixed even under a considerably high temperature condition. In addition, the present invention aims to establish a technology capable of minimizing the decomposition of hydrogen peroxide and maximally and effectively exerting the cleaning or dissolving treatment effect of the aqueous solution of acidic hydrogen peroxide.

[0006]

Means for Solving the Problems The stabilization method according to the present invention which can solve the above problems is represented by the following general formula [1] in an aqueous solution of acidic hydrogen peroxide mixed with copper ions. From one or more phenyl glycol ethers and a glycol ether represented by the following general formula [2], a glycol represented by the following general formula [3], and an ethylene oxide-added aliphatic amine represented by the following general formula [4] The gist of the present invention resides in that at least one compound selected from the group consisting of:

[0007]

Embedded image

[0008]

The present inventors have conducted various studies to solve the problems of the prior art as described above. As a result, the phenyl glycol ether represented by the above formula [1] was added to an acidic aqueous solution containing hydrogen peroxide. For example, if one or more of ethylene glycol phenyl ether (hereinafter abbreviated as EPH) and diethylene glycol phenyl ether (hereinafter abbreviated as DPH) are contained, it is known that decomposition of hydrogen peroxide is significantly suppressed. Was.

However, phenyl glycol ethers combine with copper ions to form precipitates. Therefore, when phenyl glycol ethers are used for, for example, dissolution treatment of a copper alloy and copper ions are eluted into the treatment solution, the phenyl glycol ethers become stable. Not only does the phenyl glycol ether, which should act as an agent, bind to the copper ions, losing the stabilizing effect, but also contaminates the copper alloy surface with the resulting precipitate.

[0010] The solution for chemically dissolving the copper alloy is usually 10 to 150 g / l of hydrogen peroxide and 100 to 20 g / l.
An acidic aqueous hydrogen peroxide solution containing 0 g / liter of sulfuric acid is used, and a large amount of copper ions are eluted in the treatment liquid in the dissolution treatment step. Therefore, the stabilizing effect of the fernyl glycol ethers cannot be effectively exerted in the acidic hydrogen peroxide aqueous solution in which copper ions are eluted in the treatment liquid.

[0011] Therefore, it was considered whether or not the stabilizing effect of the phenyl glycol ethers could be effectively exhibited by preventing the reaction between the phenyl glycol ethers and copper ions, and further research was conducted in that direction. As a result, the glycol ethers represented by the above formula [2] together with the phenyl glycol ethers,
When a glycol represented by [3] and at least one compound selected from the group consisting of ethylene oxide-added aliphatic amine represented by the general formula [4] are contained, copper ions and phenyl glycol ethers can be obtained. It was found that an excellent stabilizing effect on hydrogen peroxide was exhibited without precipitation even in a relatively high temperature range, and the present invention was completed here.

The phenyl glycol ethers used herein are the compounds represented by the above formula [1], specifically, EPH and DPH, which can be used alone or in combination of two or more. Can be used in combination. The amount used is 0.1 to the aqueous solution of acidic hydrogen peroxide.
1 to 10 g / liter, more preferably 0.5 to 2 g / liter
When the amount is less than 0.1 g / liter, a sufficient stabilizing effect is hardly exhibited, and the effect is saturated at about 10 g / liter, so that further addition is economically useless.

The glycol ethers represented by the general formula [2] used in combination with the above phenyl glycol ethers are compounds having an ether group and a hydroxyl group in one molecule, and specific examples thereof include ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Propylene glycol monoethyl ether, dipropylene glycol monobutyl ether and the like. You.

The compound represented by the general formula [3] includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Dipropylene glycol, tripropylene glycol and the like are exemplified as preferable ones.

Representative examples of the ethylene oxide-added aliphatic amine represented by the general formula [4] include monooxyethylene octylamine, dioxyethylene octylamine, polyoxyethylene octylamine, monooxyethylene laurylamine, Examples thereof include dioxyethylene laurylamine, polyoxyethylene laurylamine, polyoxyethylene oleylamine, and polyoxyethylene stearylamine.

The compounds represented by the above general formulas [2], [3], and [4] prevent the reaction between copper ions and phenyl glycol ethers, as described above, and effectively exhibit the stabilizing effect. The effect is effectively exerted not only when the above compound is added alone, but also when two or more kinds are used in combination at an arbitrary ratio.

The preferred addition amount of these compounds is represented by the general formula
The range of 0.5 to 2 times the weight of the phenyl glycol ethers represented by [1] is preferable. If the amount is less than 0.5 times the effect is not sufficiently exhibited, and the effect is 2 times.
Further addition is economically useless because it saturates twice.

The present invention is constituted as described above, and a phenyl glycol ether represented by the above general formula [1] and a phenyl glycol ether represented by the above general formula [2] to an aqueous solution of acidic hydrogen peroxide into which copper ions are mixed. By containing the compound represented by [4], hydrogen peroxide can be stably maintained even under relatively high temperature conditions, and the chemical treatment effect on the copper or copper alloy of the acidic aqueous hydrogen peroxide solution Can be exerted as effectively as possible.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples, and may be modified within a range that can be adapted to the above and following points. It is of course possible to carry out them, and all of them are included in the technical scope of the present invention.

Example 1 A stabilizer shown in Table 1 was added to an aqueous solution containing 30 g / L of hydrogen peroxide and 160 g / L of sulfuric acid, and 1 g / L of Cu ²⁺ ion was added thereto. Was kept at 75 ° C. for 6 hours, the presence or absence of a precipitate was observed, and the amount of hydrogen peroxide was quantified. The results shown in Table 1 were obtained.
In addition, A to L in Table 1 (and Table 2) mean the following compounds, respectively.

A: ethylene glycol methyl ether B: diethylene glycol butyl ether C: propylene glycol ethyl ether D: ethylene glycol E: dipropylene glycol F: monooxyethylene laurylamine G: ethylene glycol butyl ether H: dipropylene glycol methyl ether I: tri Ethylene glycol J: dioxyethylene octylamine K: polyoxyethylene laurylamine L: polyoxyethylene oleylamine

[0022]

[Table 1]

Example 2 A stabilizer shown in Table 2 was added to an aqueous solution containing 30 g / L of hydrogen peroxide and 160 g / L of sulfuric acid, and 30 g / L of Cu ²⁺ ions were added thereto. After maintaining at 75 ° C. for 6 hours, the presence or absence of a precipitate was observed, and the amount of hydrogen peroxide was quantified. The results shown in Table 2 were obtained.

[0024]

[Table 2]

As is evident from Tables 1 and 2, No. satisfying the requirements of the present invention. 1-10 and 27-36
Indicates that no precipitate is formed and the decomposition rate of hydrogen peroxide is low. On the other hand, No. 11 to 19 and 37 to 45 are EPH and / or D as stabilizers.
Although only PH was used, some of which had good results in the decomposition rate of hydrogen peroxide,
In all cases, the formation of a precipitate is observed, and the object of the present invention cannot be achieved. No. 20-25 and 46-51
No EPH or DPH was added, and only the compounds of the general formulas [2] to [4] were added. No formation of a precipitate was observed, but decomposition of hydrogen peroxide was remarkable.
Again, the object of the present invention cannot be achieved.

[0026]

The present invention is constituted as described above and suppresses the decomposition of hydrogen peroxide in an acidic aqueous hydrogen peroxide solution into which copper ions are mixed, and produces a precipitate which causes contamination of the liquid to be treated. Therefore, the performance as a processing solution for performing chemical processing such as pickling, etching, and chemical polishing on copper, a copper alloy, or the like can be significantly improved.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-109296 (JP, A) JP-B-54-2607 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01B 15/00

Claims (2)

(57) [Claims] 1. An aqueous solution of acidic hydrogen peroxide containing copper ions, wherein at least one of phenyl glycol ethers represented by the following general formula [1] and glycol ethers represented by the following general formula [2]: At least one compound selected from the group consisting of glycols represented by the following general formula [3] and ethylene oxide-added aliphatic amines represented by the following general formula [4]: A method for stabilizing an aqueous hydrogen oxide solution. Embedded image 2. An aqueous solution of an acidic hydrogen peroxide having the general formula [1]
One or more phenyl glycol ethers represented by the formula: 0.1 to 10 g / liter, the glycol ethers represented by the general formula [2], the glycols represented by the general formula [3], and the glycols represented by the general formula [4] The acidic hydrogen peroxide aqueous solution according to claim 1, wherein at least one compound selected from the group consisting of ethylene oxide-added aliphatic amines is contained in an amount of 0.5 to 2 times the weight of the phenyl glycol ethers. Stabilization method.