CN1015554B - Utilize tungsten-tungsten-diol complexes 2 dissolution of metals - Google Patents
Utilize tungsten-tungsten-diol complexes 2 dissolution of metalsInfo
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- CN1015554B CN1015554B CN 85101736 CN85101736A CN1015554B CN 1015554 B CN1015554 B CN 1015554B CN 85101736 CN85101736 CN 85101736 CN 85101736 A CN85101736 A CN 85101736A CN 1015554 B CN1015554 B CN 1015554B
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Abstract
Come dissolution of metals with a kind of solution that contains the tungsten-tungsten-diol complexes 2 of sulfuric acid, hydrogen peroxide and catalytic amount, just can accelerate the dissolution rate of metal.
Description
The present invention relates to dissolution of metals in containing the moisture etching solution of sulfuric acid-hydrogen peroxide.Be particularly related to a kind of raising dissolving metal etching solution prescription ability, that form novelty that has.Important use of the present invention is an etch copper in producing printed-wiring board (PWB).
Known on the technology, produce printed wiring and will and hinder corrosion material (generally being to use plastics) with the copper layer.The general production method of printed wiring is on the surface of copper layer, covers on the figure that designs with the resistance corrosion material (this material is not subjected to the effect of etching solution) of protective part.Touch when carving, not protected copper layer is etched, and the zone that covers then remains intact, so can obtain required plastic plate circuit.The resistance corrosion material can be plastics, printing ink or solder flux.
In recent years, industrially more and more tend to adopt hydrogen peroxide one sulfate system to come etched circuit board, because etching solution is with low cost, method is simple, the copper of consumption can reclaim from etching solution.
Yet, also there are a lot of problems with hydrogen peroxide as the composition of etching solution, well-known, in sulfuric acid-superoxol, if exist heavy metal ion such as cupric ion can endanger stability of peroxide.In etching, carry out along with etched, content of copper ion increases in the etching reagent, and the hydrogen peroxide in the etching solution decomposes gradually even exhausts, and causes etching speed to reduce greatly.In order to improve the effect of etching reagent, once proposed to reduce the Decomposition of cupric ion to hydrogen peroxide with various stablizers (wherein some was successfully used).
Although adding suitable stabilizers is to significantly reduce the hydrogen peroxide decomposition that metal ion causes, in general, the etching speed of the hydrogen peroxide that is stabilized-sulfuric acid etchant agent is very low, especially under the high situation of copper ion concentration, more need be improved.Once proposed adding catalyzer and promotor in the prior art and improve etching speed, wherein the special case of catalyzer is exactly a United States Patent (USP) 3,597, and 290 disclosed metal ions resemble silver, mercury, palladium, gold and platinum ion.These ionic oxidation potentials all are higher than copper.Other example has United States Patent (USP) 3,293, and 093 N-ethanoyl is to one aniline, Sulphathiazole and silver ions; Or the combination (United States Patent (USP) 3,341,384) of these three kinds of components and diprotic acid.Become phenylurea or phenylformic acid (United States Patent (USP) 3,407,141); Or urea or thiocarbamide (United States Patent (USP) 3,668,131).
Another problem that adopts hydrogen peroxide-sulfuric acid etchant agent often to run into is: even a spot of chlorion or bromide anion also can produce adverse influence to etching speed, so can not be with common tap water preparation etching solution, must precipitate in the water impurities ionic way and remove these ions by sloughing the water intermediate ion or for example adding soluble silver salt (utilizing silver ions).
Though silver ions seems to have provided the low etching speed of a kind of solution and by chlorine, the general way of the problem that bromide anion causes.But when preparation hydrogen peroxide-sulfuric acid etchant solution, still there are some shortcomings, the one, the price height of silver, the 2nd, silver ions can not improve etching speed ideally.
For this reason, the purpose of this invention is to provide a kind of newly, the high-level efficiency water-soluble composition comes dissolution of metals.
Another purpose provides an improved way, to dissolve the such metal of alloy that resembles copper and copper at a high speed.
Also will be conspicuous in other purpose of the present invention detailed description hereinafter.
The invention provides a kind of composition, said composition comprises the sulfuric acid of about 0.2-4.5 mol.0.25-8 the aqueous solution of the tungsten of the hydrogen peroxide of mol and effective catalyst amount-dibasic alcohol plural components.
If the concentration of composite catalyst maintain 2 mmoles/liter and higher, then dissolving metal speed is accelerated greatly, concentration range be preferably in the 5-50 mmole/liter, if use excessive concentration, superiority does not increase yet.
The concentration of plural components can be: dibasic alcohol: 0.1-10%(weight), and 0.5-5% preferably.Tungsten: 5-5000PPM.Preferably 50-2000PPM(is as the criterion with the gross weight of dissolving metal).In order to obtain optimum, dibasic alcohol 1-3%, tungsten 100-1000PPM.
The dibasic alcohol that the present invention uses can be a primary alconol, for example, 1,4-butyleneglycol and 1, the 6-hexylene glycol, the available suitable compound at United States Patent (USP) 4,141, proves that operable binary primary alconol has following structural formula in 850 and 4,174,253:
R wherein
1Be to be selected from (a) :-(CR
2R
3)
n-, R here
2And R
3Be respectively the alkyl of H or 1-4C atom, n is at least 2, or (b): the cycloalkyl of 5-7 carbon atom or the cycloalkyl that has the 1-4C atom alkyl to replace.
The used suitable uncle's glycol promotor of the present invention comprises 1,4-butyleneglycol, 1,5-pentanediol 1,6-hexylene glycol, 1,7-heptanediol etc.; The 2-methyl isophthalic acid, 4-butyleneglycol, 2-ethyl-1,5-pentanediol, 3-propyl group-1,5-pentanediol or the like, 1,4-cyclohexyl dimethanol, 2-methyl isophthalic acid, 3-cyclopentyl dimethanol or the like.
Also can use: (a): the naphthenic hydrocarbon of the 5-7C atom that replaces by monohydroxy or dihydroxyl, or the alkyl naphthene of the 5-7C atom that (b) replaces by monohydroxy or dihydroxyl, wherein alkyl contains 1-4 C atom, and is attached to and does not have in the ring on the substituent C atom.
The naphthenic hydrocarbon that the used suitable hydroxyl of the present invention replaces is cyclopentanol, hexalin, suberyl alcohol, 1,2-encircles pentanediol, and 1,3-encircles pentanediol, 1, the 2-cyclohexanediol, 1, the 3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-encircles heptanediol, and 1,3-encircles heptanediol, 1,4-encircles heptanediol, and the C of other various alkyl replacements
5-C
7Cycloalkanol and cycloalkanes glycol, for example methyl-cyclohexanol.The compound preferably of this type is that ring is gone up the compound that no alkyl replaces.
Also can use second type dibasic alcohol, such compound is 525 in Application No., and 078(1983 applied for August 22) in existing the disclosure.The structural formula of this dibasic alcohol promotor is:
Wherein, R
1, R
2, R
3And R
4Can be H, CH
3, OC
2H
5Or OC
3H
7
The example of the suitable dibasic alcohol that the present invention uses has 2-butyne-1, the 4-glycol; 3-hexin-2, the 5-glycol; One propoxy-generation-2-butyne-1, the 4-glycol; With 21 Ji Dai-2-butyne-1,4 glycol.
Sulfuric acid concentration should remain between the 0.2-4.5 mol in the solution, is preferably between the 0.3-4 mol.The concentration of hydrogen peroxide of solution can be in the width range of about 0.25-8 mol.Preferably be limited in the 1-4 mol.
Remaining part of solution is made up of water, needn't make any particular processing to water, so that free chlorine bromide anion drops to 2PPM or lower level, also needn't in solution, add component and precipitate other and be harmful to the chlorine of etching process and the impurity of bromine resemble the soluble silver salt.The present invention allows to contain relatively large impurity such as 50PPM in the composition, even higher, and etching speed is not had obvious influence.
Solution also can contain other composition, for example adds stablizer to prevent owing to heavy metal ion makes the hydrogen peroxide minimizing.United States Patent (USP) U.S.P.3,537,895; U.S.P.3,597,290; U.S.P.3,649,194; U.S.P.3,801,512 and U.S.P.3,945,865, enumerated a series of suitable stabilizers (example.) above-mentioned patent lists in this explanation as a reference.Any compound that acid hydrogen peroxide metal treatment fluid is played stabilization all can use, and has same advantage.
In addition, as needs, also can add the known additive as side direction and horizontal etchback that can prevent etchback.United States Patent (USP) 3,597,290 and 3,773,577 to disclose this compound be nitrogen compound.But, in the present invention, because the etching catalyst in the etch combination has improved etching speed widely, so needn't use this additive.
Above-mentioned each solution is effective especially to the etching of chemical grinding, copper and copper alloy.But other metal and alloy such as iron, nickel, zinc and steel also can adopt solution of the present invention to dissolve.
When using this solution dissolving Special Metal, can use common operational condition.For example, during etch copper, temperature is remained between about 105-104 °F.Preferably 120-135 °F.
Solution of the present invention is very suitable for as dipping and sprays etched etching reagent.When carrying out etching with composition of the present invention, speed is exceedingly fast, and for example the copper layer of every square feet of 1 ounce of copper of etching only needs 0.5-1 minute.Because fast like this etching speed is arranged, it is very tempting using this composition to produce printed-wiring board (PWB), adopts composition of the present invention to process a large amount of printed wiring workpiece in the unit time, is very economical therefore.Also can reduce in addition resistance below the corrosion material deleterious lateral etches and the etchback at edge.Another significant advantage of the present invention is that the etched plate that obtains is very clean.
Following Example is as explanation of the present invention.
Example 1-19
In this group contrast experiment, with every square feet of lamination copper coin (2 * 3 inches) of coating that one ounce copper is arranged, be immersed in the solution that 300ml stirring and carry out etching, maintain the temperature at 120 °F.Every kind of etching solution all contains the sulfuric acid (1.8 mol) of (66 ° of the degree Beaume) of 10% volume, the hydrogen peroxide of 10% volume (50%W/W) (1.76 mol), and 11.8 ounces/adding the copper sulfate pentahydrate of human relations, remaining is deionized water or distilled water.Solution is stablized with 2.5 grams per liter sodium sulfocarbolates.Do not having in the presence of the catalyzer, adding chlorion (example 1), removing the copper required time fully from stratified base is 9 minutes and 15 seconds.
Every kind of solution of example 2-19, except by with example 1 identical forming, also contain just like dibasic alcohol and/or the tungsten promotor of table shown in-1.Experimental result shows that all additives all have obvious effects to improving etching speed.
(referring to table 1) example 20-25
Second group of experiment carried out with butyleneglycol and tungsten.Except the sodium sulfocarbolate consumption rose with 4g/ liter replacement 2g/, other parameter of its etching solution was all identical.
(referring to table 2) when tungsten and organic additive combine, compared during with independent use tungsten or organic additive from the test-results of above-mentioned example 20-25 as can be seen, and etching speed is obviously accelerated.
Table 1
The concentration etching speed of experiment organic additive tungsten
Sequence number concentration of organic additive (% weight) (PPM) (divides: second)
21,6-hexylene glycol 0.75-7: 30
3 - - 100 7∶30
41,6-hexylene glycol 0.75 100 5: 55
5 - - 775 4∶10
61,6-hexylene glycol 0.75 775 4: 45
7 - - - 9∶15
8 one propoxy-generation-2-
Butine-1,4-glycol 1.0-9: 30
9-propoxy-generation-2-
Butine-1,4-glycol 3.0-11: 24
10 3-hexins-2,5-glycol 1.0-8: 47
11 3-hexins-2,5-glycol 3.0-8: 31
12 diethoxy generation-2-fourths
Alkynes-1,4-glycol 1.0-10: 23
13 diethoxy generation-2-fourths
Alkynes-1,4-glycol 3.0-14: 21
14 1 propoxy-generation-2-fourths
Alkynes-1,4-glycol 1.0 775 5: 15
15 3-hexins-2,5-glycol 1.0 775 3: 54
16 diethoxy generation-2-fourths
Alkynes-1,4-glycol 1.0 775 4: 33
17 - - 100 6∶40
18 1,4-butyleneglycol 0.75 100 5: 00
19 1,4-butyleneglycol 0.75-5: 45
Example 20-25
Second group of experiment carried out with butyleneglycol and tungsten.Except the sodium sulfocarbolate consumption rose with 4g/ liter replacement 2g/, other parameter of its etching solution was all identical.
Table 2
The concentration etching speed of experiment butyleneglycol concentration tungsten
Sequence number (% weight) (PPM) (is divided: second)
20 - - 10∶39
21 - 100 8∶44
22 - 775 6∶40
23 1.0 - 10∶22
24 1.0 100 7∶00
25 1.0 775 3∶45
From the test-results of above-mentioned example 2-25 as can be seen, when tungsten and organic additive combine, compare during with independent use tungsten or organic additive, etching speed is obviously accelerated.
Claims (11)
1, a kind ofly contacts in the technology of dissolution of metals with metallographic phase with the aqueous solution that contains sulfuric acid (about 0.2-4.5 mol) and hydrogen peroxide (about 0.25-8 mol), increase the method for solution to dissolving metal speed, this method comprises the promotor that adds significant quantity, promotor is made up of the tungsten of about 5-5000PPM and the dibasic alcohol of about 0.1-10% (weight), and dibasic alcohol is earlier from the binary primary alconol with following structural formula:
R wherein
1Be selected from: (a)-(CR
2R
3)
n-, R here
2And R
3It is respectively the alkyl of hydrogen or 1-4C atom, n is 2 at least, (b) cycloalkyl that the cycloalkyl of 5-7C atom is arranged or have the 1-4C atom alkyl to replace, or the cycloalkyl of the substituent 5-7C atom of monohydroxy or dihydroxyl arranged (c), or the alkyl-cycloalkyl of the 5-7C atom that monohydroxy or dihydroxyl replace arranged (d), each alkyl contains the 1-4C atom, and is attached to and does not have in the ring on the substituent C atom, or the dibasic alcohol that (e) has following structure:
Wherein, R
1, R
2, R
3And R
4Can be H, CH
3, OC
2H
5Or OC
3H
7
2, according to the process of claim 1 wherein that the consumption of tungsten is about 5-5000PPM in the promotor, the dibasic alcohol consumption is a 0.5-5.0%(weight).
3, according to the process of claim 1 wherein that the said aqueous solution has also contained stabilizer function, to reduce the sodium sulfocarbolate of heavy metal ion to the Decomposition of hydrogen peroxide.
4, according to the process of claim 1 wherein that the concentration of hydrogen peroxide remains between the 1-4 mol.
5, according to the process of claim 1 wherein that sulfuric acid concentration remains between about 0.3-4 mol.
6, according to the process of claim 1 wherein that promotor is 1, the 4-butyleneglycol.
7, according to the process of claim 1 wherein that promotor is 1, the 6-hexylene glycol.
8, according to the process of claim 1 wherein that promotor is 2-butyne-1, the 4-glycol.
9, according to the process of claim 1 wherein that promotor is 3-hexin-1, the 4-glycol.
10, according to the process of claim 1 wherein that promotor is a propoxy-generation-2-butyne-1, the 4-glycol.
11, according to the process of claim 1 wherein that metal is the alloy of copper or copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101736 CN1015554B (en) | 1984-01-12 | 1985-04-01 | Utilize tungsten-tungsten-diol complexes 2 dissolution of metals |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/570,056 US4522683A (en) | 1984-01-12 | 1984-01-12 | Dissolution of metals utilizing tungsten-diol combinations |
| CN 85101736 CN1015554B (en) | 1984-01-12 | 1985-04-01 | Utilize tungsten-tungsten-diol complexes 2 dissolution of metals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101736A CN85101736A (en) | 1987-01-31 |
| CN1015554B true CN1015554B (en) | 1992-02-19 |
Family
ID=25741484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101736 Expired CN1015554B (en) | 1984-01-12 | 1985-04-01 | Utilize tungsten-tungsten-diol complexes 2 dissolution of metals |
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| Country | Link |
|---|---|
| CN (1) | CN1015554B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368598C (en) * | 2005-08-09 | 2008-02-13 | 广东省石油化工研究院 | Copper or copper alloy surface tiny-etching treatment fluid for smoothing |
| CN110050516B (en) | 2016-12-07 | 2023-06-02 | D-波系统公司 | System, method and apparatus relating to superconducting printed circuit boards |
| CN108251840B (en) * | 2018-02-08 | 2019-10-29 | 皆利士多层线路版(中山)有限公司 | Chemistry stripping copper liquid medicine and stripping copper method |
| US11678433B2 (en) | 2018-09-06 | 2023-06-13 | D-Wave Systems Inc. | Printed circuit board assembly for edge-coupling to an integrated circuit |
| US11647590B2 (en) * | 2019-06-18 | 2023-05-09 | D-Wave Systems Inc. | Systems and methods for etching of metals |
| CN113981447A (en) * | 2021-11-10 | 2022-01-28 | 纳然电子技术(苏州)有限公司 | Etching solution |
-
1985
- 1985-04-01 CN CN 85101736 patent/CN1015554B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85101736A (en) | 1987-01-31 |
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