JPS5864205A - Stabilization of hydrogen peroxide solution - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Hydrogen peroxide-containing solutions have been used in many methods for dissolving metals and gold-butyride. Examples of such methods include pickling, dip polishing17, pre-corrosion, corrosion, and the production of light bulb filaments.

Hydrogen peroxide, which is added to the plate-processing silicon melt for the purpose of promoting dissolution and/or to prevent the production of noxious fumes, is consumed in these ways, and its concentration in the processing solution is
must be replenished on at least a periodic basis to keep it in range. Such heavy metals, mainly especially iron and copper, lead to the destabilization of hydrogen peroxide in solution, because these ions accumulate during use. Rapid catalytic decomposition of hydrogen peroxide occurs, regardless of its consumption, resulting in excess hydrogen peroxide being lost to the process.In the past, hydrogen peroxide was Various stabilizers have been added to hydrogen peroxide to prevent it from being decomposed by these metals.

Other stabilizers have been formulated to stabilize the hydrogen peroxide content of the metal%j1m solution. For example, egg-colored compounds of low molecular weight carboxylic acids and alcohols have been shown to have an III spreading effect on hydrogen peroxide compositions. Other known inhibitors include glycerin, glycols, 4-lyglycols, phenols, p-methoxyphenols, alkyl and aryl sulfonic acids, sulfathiazole, zenacetin, 9-hydroxyquinoline, urea and aminopyridines. . In general, the above hydrogen peroxide stabilizers are used for various reasons, such as insufficient stability at high processing temperatures, unpleasant odors, high volatility, and the formation of insoluble by-products. It has not been completely satisfactory due to undesirable side effects, high cost, toxicity, etc.

Accordingly, it is a primary object of the present invention to provide a new and improved metal dissolution process solution containing aqueous peroxide bulk stabilized against decomposition by dissolved galvanic metals contained therein. It is to provide.

Another object is to provide a method for stabilizing hydrogen peroxide against the degrading effects of ions. Another object is to provide an improved method of rounding metals, such as steel or copper alloys, to melt them at high speed. Yet another object is to provide a new method for corroding or pickling steel and steel alloys.

Other objects 11 will be readily apparent from the specification and description of the range of %M precision.

In accordance with the present invention, it has been found that an effective amount of 3-amino-1,2,4-)riacetic hydrogen peroxide is provided in an aqueous gold-dissolved hydrogen peroxide solution.

3-Aginaw 1. ! , 4-) The lyazole was found to act both as a stabilizer and as a corrosion rate accelerator.

According to the front page of the book @ Ming, it is 3-
Aginault 1.2.4-) Riazole about αil f/j
It has been found that if the dissolved layer contains an amount of about 1"i, it is effectively stabilized against decomposition by heavy metal ion impurities.

In another aspect of the invention, the aqueous hydrogen peroxide solution is
It has been found that the corrosion performance of the melt is substantially improved if the solution contains 1,2,4-) lyazole in amounts ranging from about 10p to the saturation range of the solution. In this context, the term "solution'f4Ii" refers to various metal treatment aqueous solutions that are created on-site by the user and are based on hydrogen peroxide and acids and mixtures of acids. The 1WIlt' shown in this specification is therefore based on the entire scope of the hydrogen peroxide-containing brew.

In the acid-hydrogen peroxide metal treated fg solution, 3-amino-I
I2*4-) The lyazole stability law applies over a wide range up to the dissolution of the stabilizer in the system. Solubility is dependent on the composition and temperature It of the processing solution. To obtain the g-electrifying effect, the added acid ranges from about 0.2 f/1 to saturation. Preferably at least about 0.5 f/l is used, *1 also preferably V'CVt at least about 1 f/l.
l is used. It should be understood that it is also within the scope of this invention to add the 3-amino-1,λ4-triazole in an amount exceeding its solubility V to provide self-controlled storage of the ammonium in the system. .

When used for its catalytic effect as a corrosion rate enhancer, 3-amino-1,2,4-) lyazole is added at about 10p density to saturation. Preferably it is added as a catalyst in an amount of about 90 pjm to about 5OOpp*, most preferably K11t about 150jjfN.

The hydrogen peroxide concentration of the metal processing solution generally varies over a wide range, e.g., from about 5 to 200 f/j at an average temperature. A detergent solution for cleaning metals, such as copper, brass, aluminum, steel, etc., is usually about 5 to about 1 l/l.
Contains 5Of 11J1 of hydrogen peroxide. Concentrations of about 6 to about 40 t/I are commonly used in the immersion polishing of steel and steel alloys, but chemical grinding of steel with #7T
Once is generally about 10 to about Sot/j darkness. In steel rot treatment, ordinary #fVis O~20 Or/
jo [There is f in the song.

Similarly, aI! The components and their at in solution can vary considerably depending on the particular intended use of the solution. However, these are not variables that affect the stabilization of the hydrogen peroxide component.

Thus, the solution can be any of the acids and mixtures of acids used in the maple dissolution process, such as sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, fluoro#1 oxalic acid, etc. , and those acids@# are usually about 2 to about 4002/j
(free acid basis), but higher productions can also be used. For example, cleaning VC for steel, steel, zinc, etc.
Low arousal degrees, typically from about 2 to about 1o
l range is used, but in corrosion treatments about 30
Relatively high reward degrees from 0 to 400 fil are used. In pickling copper and steel alloys, #1 filtration is typically an amount between about 100 and about 400 fil.

Of course, various other additives may be added to these solutions to achieve one's desired results, such as other catalysts and accelerators to increase the melting speed, other stabilizers, and lightening agents. agent,
An immobilizing agent, leveling agent, etc. can also be added in appropriate amounts.

The improved metal processing solution of the present invention has a deteriorating effect on the stability of hydrogen peroxide in metal melting processes, especially those that result in the accumulation of metal ions in the solution.
used to advantage. Examples of such methods include corrosion of metals, chemical grinding, pickling, dip polishing and polishing, and methods of manufacturing tungsten filaments for use in light bulbs and the like. Molten metals in these processes include copper and copper alloys, iron, steel, nickel, cadmium, zinc, aluminum, molybdenum, lead, and the like.

The 3-amino-1,2,4-triazoles used in the present invention have a significant stabilizing effect on hydrogen peroxide, thereby significantly reducing their usefulness in the processes in which they are used. Stretched.

Furthermore, it is an undesirable 1 with metal ions during use.
It also exhibits other highly desirable properties: being a non-biological, readily available, stable, non-volatile, non-toxic, odorless compound.

Furthermore, it has been found that it has a considerable advantageous effect on copper corrosion layers.

In order to better understand the invention, the following examples are presented.

Examples 1-5 These examples demonstrate the excellent stabilizing effect obtained by adding 3-amino-1,2,4-triazole to copper corrosion solutions containing appreciable amounts of steel ions. It shows. Each has a capacity of 5501 and 1
A solution containing B49/j H, 80, 33,6 f/j phosphoric acid and 168 fil copper ions (added as equal gtew 5 liters) was prepared. These solutions were placed in a constant temperature vertical bath maintained at 120"F and sO volume s of hydrogen peroxide and #3 appetizers shown in Table 1. ) After 24 hours of incubation, the VC1 solution was analyzed for hydrogen peroxide.The results are shown in the table.

1 0 10.69% 0.53chi snow Q, s 0
1G, 69% 5.54%j
LISO1 (169% 7.82%4 100
10.69chi 7.45%5 50
0 1a69S L05% From the above examples it can be seen that the effect of the 3-amino-1,2,4-triazole is to stabilize the peracid hydroxide against decomposition.

Examples 6-11 Corrosion tests were conducted using a hydrogen peroxide-sulfur caustic agent in DMA-30 spray saline. A steel laminate with a coating of 1 ounce per square foot of copper was treated with a caustic agent at 125''F'.
It contained 7 tons, 1.12 volumes of mol/j of hydrogen peroxide (24 I mol/j) and 72 volumes of water. Additionally, the solution contains 1 &75 f/I of copper sulfate pentahydrate and 11/I of sodium phenolsulfonate.
4 I was doing it.

- Examples 7 to 11 contain 120 f/l of 3-amino-1,2,
4-) 3-amino-1,2 with rs degree of lyazole
, 4-) Water-soluble oil along Riazole S was used.

The results of consuming 1 ounce of steel phosphate are shown in the table below.

Omotesou @ 0 11:03 〒 I
s8:
45$ 10 6:10 9 115 5:10 10 20 4:15 11 ! i 4:30 From the above example, 1g' eating time is 3-amino-2.4
-) It can be seen that adding lyazole to the corrosive solution significantly shortens the time compared to K.

Many modifications have been made to the above specific aspects. This will be obvious to those who are experts in this industry. All such departures from the foregoing specification are considered to be within the scope of the invention as defined by this specification and claims 13I, j.

% Sunato Kyoda Attorney, Patent Attorney Taikichi Kodejima

Claims (1)

[Scope of Claims] 1. An aqueous hydrogen peroxide solution containing an effective amount of 3-amino-1,2,4-)riazole. 1 3-amino-1,2゜triazole as a stabilizer compound, about α? ! An aqueous hydrogen peroxide solution stabilized against degradation by metal ions containing an amount from f/4 to #V dissolution of the stabilizer compound in the solution. & a stabilized hydrogen peroxide solution according to claim 2, also containing from about 2 to about 400 t/4 mineral acid on a free basis; at least about 0.5 f/j stabilizer. 4. An acidified and stabilized hydrogen peroxide solution according to claim 3, containing the compound.翫 The acidified and stabilized peroxide solution of claim 3 containing at least about 1 f/I of a stabilizer compound. L The mineral acid is sulfuric acid, and the permissible range of % is the acidified and stabilized perbutylated water described in item 3. 7. Peroxide water IIg concentration is about 5 on free vF basis ~about 20
Of, the acidified and stabilized hydrogen peroxide solution described in Section 3 is maintained between %i and 7-%. & An aqueous hydrogen peroxide composition for metal dissolution containing a catalytically effective amount of 3-amino-1,2,4-) lyazole. Claim 8, wherein the t3-amino-1,2,4-) lyazole is present in an amount of at least 10 jpm.
Composition described in the tomb. la 3-amino-1,2,4-triazole is about 9
h'tT presence from 0j5+-m to about 3009'Ptn [7
9. The composition according to claim 8, wherein the composition comprises: IL 3- as a stabilizer compound in an aqueous peroxide solution
Amino-1,2,4-) lyazole from about 0.02 f/l to dissolve the stabilizer compound in solution I [1 in amount]. How to make the game constant. 12 Add 1 beak of about 2 to about 400 f/l on a free basis into the solution, 1. The method listed above in Section 11 of the Enro. 13. The method of claim 12, wherein approximately α5 f/l of stabilizer compound is added to 1 kf/l. 14. The method of claim 12, wherein at least about 1 f/l of the stabilizer compound is added in solution. 1& The method according to claim 12, wherein the mineral acid is sulfuric acid. 11. The method of claim 12, wherein the hydrogen peroxide concentration of the solution is maintained between about 5 and about 100 1/4 degrees on a free basis. 17. A method for dissolving gold, comprising contacting the metal with an aqueous hydrogen peroxide solution containing a catalytically effective amount of 3-amino-1,2,4-triazole. 1 Turtle 3-Anno 1.2.4-) Riazole is about Ij
18. The method of claim 17, wherein there are approximately 300 ppynO keys. The ttAlI hydrogen oxide aqueous solution has a concentration of about 2 to about 400 on a free basis.
Patent i! also contains f/l mineral acids! Blue request range 1
The method described in Section 7. ! The method according to claim 19, wherein the acid is sulfuric acid. ! L Hydrogen peroxide concentration is about 5 to about 200 f/ on a free basis
The method described in the patent claims o tp disciples and claims maintained between l. 2z The method described in claim gIT17, wherein the metal is a copper alloy.