JPH06115909A - Stabilization of acidic aqueous solution of hydrogen peroxide - Google Patents

Abstract

PURPOSE:To minimize the decomposition of H2O2even under a high-temperature condition by adding a specific phenyl glycol ether and a specific compound to an acidic aqueous solution of hydrogen peroxide containing copper ion as an impurity. CONSTITUTION:An acidic aqueous solution of hydrogen peroxide containing 10-150g/l of H2O2 and 100-200g/l of sulfuric acid and contaminated with copper ion is incorporated with 0.1-10g/l of a phenyl glycol ether of formula I ((n) is 1-2) and 0.5-2 times weight (based on the phenyl glycol ether) of at least one kind of compound selected from glycol ethers of formula II (R is 1-2C alkylene; R' is C2H4O or C3H6O; (n) is 1-2), glycols of formula III ((n) is 1-3; R is C2H4O or C3H6O) and ethylene oxide-added aliphatic amine of formula IV (R is 3-18C aliphatic hydrocarbon residue; (x) is 0-5; (y) is 1-5).

Description

Detailed Description of the Invention

[0001]

The present invention relates to pickling, etching, and etching of copper and copper alloys (hereinafter represented by copper alloys).
The present invention relates to a method for enhancing the stability of an acidic hydrogen peroxide aqueous solution used when performing a chemical treatment such as chemical polishing.

[0002]

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

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

[0004]

However, the above-mentioned stabilizers have insufficient stabilizing effect in a high temperature range of about 50 ° C. or higher, and volatilize during use to give off a bad odor, or an undesirable side effect. There is a drawback that a reaction is caused to cause precipitation. 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 higher is often used because it is necessary to improve the treatment efficiency, and a large amount is contained in the treatment liquid. Since the copper ions are eluted, the decomposition of hydrogen peroxide becomes extremely vigorous in combination with the influence of temperature, and the stabilizing purpose as described above hardly achieves the stabilizing purpose. As a result, a large amount of acid mist is generated by the oxygen gas generated by the severe decomposition of hydrogen peroxide, and the working environment is significantly deteriorated.

The present invention has been made in view of the above circumstances, and its purpose is to provide an acidic solution in which copper ions having a decomposition promoting action are mixed even under a considerably high temperature condition. Even among these, it is intended to establish a technique capable of suppressing decomposition of hydrogen peroxide to a minimum and maximally exerting the cleaning or dissolution treatment effect of the acidic hydrogen peroxide aqueous solution.

[0006]

The stabilization method according to the present invention, which has been able to solve the above-mentioned problems, is represented by the following general formula [1] in an acidic aqueous hydrogen peroxide solution containing copper ions. From one or more phenyl glycol ethers, glycol ethers represented by the following general formula [2], glycols represented by the following general formula [3], and ethylene oxide-added aliphatic amine represented by the following general formula [4] The gist is that it contains at least one compound selected from the group consisting of:

[0007]

[Chemical 2]

[0008]

The present inventors have conducted various studies to solve the above-mentioned problems of the prior art, and as a result, in the acidic aqueous solution containing hydrogen peroxide, the phenyl glycol ethers represented by the above formula [1] , For example, it is known that the decomposition of hydrogen peroxide is significantly suppressed if at least one of ethylene glycol phenyl ether (hereinafter abbreviated as EPH) and diethylene glycol phenyl ether (hereinafter abbreviated as DPH) is contained. It was

However, since phenylglycol ethers combine with copper ions to form a precipitate, they are stabilized when they are used for dissolution treatment of copper alloys, for example, where copper ions are eluted into the treatment solution. Not only the phenyl glycol ethers, which should act as agents, bind copper ions and lose the stabilizing effect, but also the precipitates formed contaminate the copper alloy surface.

The chemical dissolution treatment liquid for copper alloys is usually 10 to 150 g / liter of hydrogen peroxide and 100 to 20.
An acidic hydrogen peroxide aqueous 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 above-mentioned fernyl glycol ethers cannot be effectively exhibited in the acidic hydrogen peroxide aqueous solution in which the copper ions are eluted in the treatment liquid as described above.

Therefore, it was thought that the stabilization effect of the phenyl glycol ethers could be effectively exhibited by blocking the reaction between the phenyl glycol ethers and the copper ion, and further research was conducted in that direction. As a result, together with the phenyl glycol ethers, the glycol ethers represented by the above formula [2], the general formula
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 are obtained. The present inventors have found that the reaction of (1) is suppressed and that an excellent stabilizing effect on hydrogen peroxide is exhibited without causing precipitation even in a relatively high temperature range, and thus the present invention has been completed.

The phenyl glycol ethers used here are compounds represented by the above formula [1], specifically EPH and DPH, which may be used alone or in combination of two or more. It can be used together in the ratio of. The amount used is 0.
1-10 g / l, more preferably 0.5-2 g / l
It is in the range of liters, and if it is less than 0.1 g / liter, the sufficient stabilizing effect is difficult to be exhibited, and since the effect is saturated at about 10 g / liter, addition of more than that is economically useless.

Next, 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, di Examples include propylene glycol monoethyl ether and dipropylene glycol monobutyl ether. It

Examples of the compound represented by the above general formula [3] include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Dipropylene glycol, tripropylene glycol and the like are exemplified as preferable ones.

Typical examples of the ethylene oxide-added aliphatic amine represented by the general formula [4] include monooxyethylene octylamine, dioxyethylene octylamine, polyoxyethylene octylamine, monooxyethylene laurylamine, Examples include dioxyethylene lauryl amine, polyoxyethylene lauryl amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine and the like.

The compounds represented by the above general formulas [2], [3] and [4] prevent the reaction between the copper ion and the phenylglycol ethers and effectively exert their stabilizing effect as described above. The effect is effectively exhibited not only when the above compounds are 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 amount is preferably 0.5 to 2 times the weight of the phenyl glycol ether represented by [1], and if the amount is less than 0.5 times, the effect is not sufficiently exhibited, and
It is economically useless to add more than that, since it is saturated with a double amount.

The present invention is constructed as described above, and the phenyl glycol ethers represented by the above general formula [1] and the general formula [2] are previously added to an acidic hydrogen peroxide aqueous solution into which copper ions are mixed. By containing the compound shown in [4], hydrogen peroxide can be kept stable even under relatively high temperature conditions, and the chemical treatment effect on the copper or copper alloy contained in the acidic hydrogen peroxide solution. Can be exerted to the maximum extent.

[0019]

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 compatible with the gist of the above and the following. Of course, it is possible to carry out, 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 / liter of hydrogen peroxide and 160 g / liter of sulfuric acid, and then 1 g / liter of Cu ²⁺ ion was added ^thereto to prepare a mixed solution. Was maintained at 75 ° C. for 6 hours, the presence or absence of a precipitate was observed, and the hydrogen peroxide was quantified to obtain the results shown in Table 1.
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 lauryl amine 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 The stabilizer shown in Table 2 was added to an aqueous solution containing 30 g / liter of hydrogen peroxide and 160 g / liter of sulfuric acid, and then 30 g / liter of Cu ²⁺ ion was added thereto to prepare a mixed solution. Was maintained at 75 ° C. for 6 hours, the presence or absence of a precipitate was observed, and the hydrogen peroxide was quantified to obtain the results shown in Table 2.

[0024]

[Table 2]

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

[0026]

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

Claims (2)

[Claims] 1. An acidic hydrogen peroxide aqueous solution containing copper ions mixed with one or more phenyl glycol ethers represented by the following general formula [1] and glycol ethers represented by the following general formula [2]. An acidic peroxide characterized by containing at least one compound selected from the group consisting of glycols represented by the following general formula [3] and ethylene oxide-added aliphatic amine represented by the following general formula [4]. Stabilization method of aqueous hydrogen oxide solution. [Chemical 1] 2. The general formula [1] in an acidic aqueous hydrogen peroxide solution.
0.1-10 g / liter of one or more of the phenyl glycol ethers represented by the formula, glycol ethers represented by the general formula [2], glycols represented by the general formula [3], and 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.