CN1178260A - Liquid for separating tin from tin alloy - Google Patents
Liquid for separating tin from tin alloy Download PDFInfo
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- CN1178260A CN1178260A CN 97116133 CN97116133A CN1178260A CN 1178260 A CN1178260 A CN 1178260A CN 97116133 CN97116133 CN 97116133 CN 97116133 A CN97116133 A CN 97116133A CN 1178260 A CN1178260 A CN 1178260A
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- nitric acid
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Abstract
A peeling liquid for stripping tin and tin alloy can effectively control a decrease in the stripping rate with the running of stripping operations. The liquid is an aqueous solution comprising 150 to 300g/l nitric acid, 5 to 25g/l iron ions, 2 to 20g/l chloride ions, and 10 to 500 weight ppm iodine compound.
Description
The present invention relates to can be used for peeling off the tin on the copper matrix and the stripping liquid of tin alloy.More particularly, relate to and can be used for peeling off when making printed circuit board (PCB) the tin that forms as the inhibitor of copper matrix or the stripping liquid of tin alloy (tinsel that for example is called solder flux).
It is a kind of in the board, printed circuit board manufacturing method that solder flux is peeled off method.In the method, on the copper matrix of copper plating film laminated plate, plate postwelding, as resist, copper matrix is carried out etching, form copper pattern, peel off solder flux then with this solder flux pattern with predetermined pattern.As the stripping liquid that is used for this method, known have with nitric acid and iron ion be main component stripping liquid, with hydrogen peroxide and fluorine cpd be the stripping liquid of main component, the aromatics that replaces with mineral acid and nitro is the stripping liquid etc. of main component, but never use fluorine cpd, the tin few equal angles of separating out again on copper matrix of strong toxicity to consider, to being that the use of the stripping liquid of main component increases with nitric acid and iron ion.
Comprising above-mentioned is the stripping liquid of main component with nitric acid and iron ion, and generally speaking, when using stripping liquid, along with the carrying out of strip operation, the solder flux meltage in the liquid increases, and produces the problem that peeling rate descends thus.If can suppress the decline of this peeling rate, then can prolong the life-span of stripping liquid, and very useful on operability and cost.
The present inventor addresses the above problem to have carried out deep research, found that, add at least a in iodine compound, cobalt compound, nickel compound and the zn cpds in the stripping liquid that contains nitric acid, iron ion and chlorion, can suppress the decline of peeling rate, finished the present invention thus.
That is, the present invention is
1. be used for peeling off the stripping liquid of tin and tin alloy, by containing the aqueous solution composition that nitric acid 150-300g/l, iron ion 5-25g/l, chlorion 2-20g/l and iodine concentration are the iodine compound of 10-500ppm (weight, as follows) from copper matrix;
2. be the stripping liquid that the aqueous solution of 0.1-5g/l is formed by the total concn concentration that contains at least a and cobalt, nickel and zinc in nitric acid 150-300g/l, iron ion 5-25g/l, chlorion 2-20g/l and cobalt compound, nickel compound and the zn cpds; With
3. by containing at least a in iodine compound that nitric acid 150-300g/l, iron ion 5-25g/l, chlorion 2-20g/l and iodine concentration are 10-500ppm and cobalt compound, nickel compound and the zn cpds and stripping liquid that the aqueous solution that total concn concentration cobalt, nickel and zinc is 0.1-50g/l is formed.
Concentration of nitric acid in the stripping liquid of the present invention is 150-300g/l, is preferably 230-270g/l.If less than 150g/l, then too small to the solvency power of tin and tin alloy, and if greater than 300g/l, it is fierce that then above-mentioned solvency action becomes, and can not obtain level and smooth copper surface.
The concentration of iron ion is 5-25g/l, is preferably 10-17g/l.If less than 5g/l, then too small to the solvency power of tin and tin alloy, and if greater than 25g/l, it is fierce that then above-mentioned solvency action becomes, and can not obtain level and smooth copper surface, the copper surface can variable color.Above-mentioned iron ion mixes with forms such as molysite such as iron(ic) chloride, iron nitrate, metallic irons usually.
The concentration of chlorion is 2-20g/l, is preferably 5-10g/l.If less than 2g/l, the peeling rate of gun-metal layer at interface that then is present in tin and copper is slow excessively, and if greater than 20g/l, then the erosion of copper becomes big.Above-mentioned chlorion mixes with the form of the compound of muriates such as hydrochloric acid, iron(ic) chloride, sodium-chlor, Repone K, ammonium chloride, cobalt chloride, nickelous chloride, zinc chloride, chloric acid class and their salt etc., the chlorion that can dissociate in stripping liquid usually.
Iodine concentration when mixing iodine compound in stripping liquid of the present invention is 10-500ppm, is preferably 70-150ppm.Iodine can suppress the solder flux peeling rate and descend, and is etched and has unusual effect suppressing copper matrix.If above-mentioned concentration is less than 10ppm, and it is little then to suppress the effect that the solder flux peeling rate descends and copper matrix is etched, and if greater than 500ppm, then the Resins, epoxy that uses in the base material of printed circuit board (PCB) is painted sometimes.Above-mentioned iodine compound is not so long as the compound of can dissociate in stripping liquid iodine or iodide ion then can add particular restriction ground and use, and its object lesson comprises iodide such as sodium iodide, ammonium iodide, potassiumiodide, acid iodide and salt thereof, Periodic acid and salt thereof etc.In the above-mentioned iodine compound, consider preferred acid iodide and salt thereof from the storage stability of stripping liquid.
Cobalt, nickel and zinc concentration when mixing at least a in cobalt compound, nickel compound and the zn cpds in stripping liquid of the present invention are 0.1-50g/l, are preferably 1-10g/l.If if it is little that above-mentioned concentration, then suppresses the effect of solder flux peeling rate decline less than 0.1g/l, and greater than 50g/l, can not obtain increasing with incorporation the raising of corresponding effect, therefore, unfavorable on cost.
Above-mentioned cobalt compound so long as for example cobalt salt or aqueous cobalt coordination compoundes such as Xiao Suangu, cobalt chloride, cobaltous iodide, Cobalt Edetate salt then can not add particular restriction ground and use.Above-mentioned nickel compound so long as for example nickel salt or water-soluble nickel coordination compounds such as nickelous nitrate, nickelous chloride, nickelous iodide, ethylenediamine tetraacetic acid (EDTA) nickel then can not add particular restriction ground and use.Above-mentioned zn cpds so long as for example zinc salt or water-soluble zine coordination compounds such as zinc nitrate, zinc chloride, zinc iodide, ethylenediamine tetraacetic acid (EDTA) zinc then can not add particular restriction ground and use.
The addition of cobaltous iodide, nickelous iodide and zinc iodide is no more than 500ppm for its iodine concentration separately.Therefore, other cobalt compounds, nickel compound, zn cpds can be share.
In stripping liquid of the present invention,, then desirable especially if with at least a the share in iodide and cobalt compound, nickel compound and the zn cpds.
In stripping liquid of the present invention, also can contain other compositions such as inhibitor, sludge preventive.
Above-mentioned inhibitor is the composition for prevent that the copper surface from getting rusty and variable color etc. is added after solder flux is peeled off, preferred example comprises benzotriazole, benzoglyoxaline, imidazoles, their derivative, propylene glycol, quadrol, glycol ether, dihydroxyphenyl propane, their ethylene oxide adduct or oxyethane propylene oxide adduct, the oxyethane propylene oxide adduct that preferred end is a propylene oxide, SYNPERONIC PE/F68 etc.The content of inhibitor is preferably 0.5-20g/l.
Above-mentioned sludge preventive is the composition that the generation of the white depositions that generates when suppressing to carry out tin or tin alloy strip operation is for a long time added, and preferred example comprises Citric Acid, Sodium Citrate, Potassium Citrate, Diammonium citrate, Sodium Glutamate, hydrochloric acid L-arginine etc.The content of sludge preventive is preferably 5-80g/l.
Compound method to stripping liquid of the present invention does not have particular restriction, is dissolved in water as long as will mix composition, preferably gets final product in the deionized water.In addition, the using method of stripping liquid of the present invention there is not particular restriction yet, as long as will spray stripping liquid or treated material is immersed in the stripping liquid at treated material.
Embodiment 1-11 and comparative example 1-2
Copper Foil is being wrapped on the isolator, and the weight ratio of electroplating Sn/Pb again on Copper Foil is on the base material that is used for printed circuit board (PCB) (long 4cm, wide 4cm) that obtains of 6/4 solder flux, in 30 ℃ of liquid temperature, spray pressure 1kgf/cm
2Condition under spray and to have the stripping liquid of forming shown in the table 1-3 (A liquid), peel off solder flux, calculate peeling rate by following formula.The results are shown in Table 1-3.
Then, for the solder flux peeling rate of measuring stripping liquid along with the degree that the carrying out of strip operation descends, be formulated in the liquid (B liquid) that has dissolved in solder flux 150g/l in the above-mentioned A liquid respectively, with this B liquid with above-mentioned same method mensuration solder flux peeling rate.The results are shown in Table 1-3.
In addition,, on the isolator that has only wrapped Copper Foil, spray above-mentioned A liquid, calculate copper dissolution speed by above-mentioned condition for estimating the degree that copper matrix is etched.The results are shown in Table 1-3.
Table 1
| The embodiment number | The composition of stripping liquid (unless otherwise noted, then unit is g/l) | (A liquid) | (B liquid) solder flux peeling rate (μ m/ branch) | Solder flux peeling rate rate of descent (%) | |
| Solder flux peeling rate (μ m/ branch) | Copper dissolution speed (μ m/ branch) | ||||
| Comparative example 1 | 67.5% nitric acid 400, (nitric acid 270) iron nitrate 9 hydrates 125, (iron 21.5) sodium-chlor 15, (chlorine 9.1) benzotriazole 10 deionized water surpluses | ????37.23 | ????5.21 | ????4.85 | ????87.0 |
| 1 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 sodium iodide 150ppm (iodine 127.0ppm) deionized water surplus | ????16.84 | ????0.95 | ????4.73 | ????71.9 |
| 2 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 zinc nitrates, 6 hydrates 32 (zinc 7.0) deionized water surplus | ????33.90 | ????5.03 | ????10.51 | ????69.0 |
| 3 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 nickel nitrates (anhydrous) 22 (nickel 7.1) deionized water surplus | ????35.43 | ????5.32 | ????9.84 | ????72.2 |
| 4 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 cobalt nitrates (II), 6 hydrates 35 (cobalt 7.1) deionized water surplus | ????34.21 | ????4.99 | ????10.16 | ????70.3 |
| ??5 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 sodium iodide 150ppm (iodine 127.0ppm) zinc nitrate 6 hydrates 32 (zinc 7.0) deionized water surplus | ????23.69 | ?????1.47 | ????12.38 | ????47.7 |
| ??6 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 sodium iodide 150ppm (iodine 127.0ppm) nickel nitrates (anhydrous) 22 (nickel 7.1) deionized water surplus | ????20.33 | ?????1.17 | ????11.86 | ????41.7 |
| ??7 | 67.5% nitric acid 400 (nitric acid 270) ferric nitrate 9 hydrates 125 (iron 21.5) sodium chloride 15 (chlorine 9.1) BTA 10 sodium iodide 150ppm (iodine 127.0ppm) cobalt nitrates (II), 6 hydrates 35 (cobalt 7.1) deionized water surplus | ????21.86 | ?????1.23 | ????12.36 | ????43.5 |
Table 2
| The embodiment number | The composition of stripping liquid (unless otherwise noted, then unit is g/l) | (A liquid) | (B liquid) solder flux peeling rate (μ m/ branch) | Solder flux peeling rate rate of descent (%) | |
| Solder flux peeling rate (μ m/ branch) | Copper dissolution speed (μ m/ branch) | ||||
| Comparative example 2 | 67.5% nitric acid 380 (nitric acid 256.5) iron nitrate 9 hydrates 100 (iron 17.3) sodium-chlor 20 (chlorine 12.1) deionized water surplus | ????32.61 | ????6.25 | ????4.57 | ????86.0 |
| 8 | 67.5% nitric acid 380, (nitric acid 256.5) iron nitrate 9 hydrates 100, (iron 17.3) sodium-chlor 20, (chlorine 12.1) ammonium iodide 80ppm, (iodine 70.0ppm) deionized water surplus | ????20.21 | ????2.71 | ????6.11 | ????69.8 |
| 9 | 67.5% nitric acid 380, (nitric acid 256.5) iron nitrate 9 hydrates 100, (iron 17.3) sodium-chlor 20, (chlorine 12.1) ammonium iodide 170ppm, (iodine 148.8ppm) deionized water surplus | ????19.3 | ????1.83 | ????5.84 | ????69.2 |
Table 3
| The embodiment number | The composition of stripping liquid (unless otherwise noted, then unit is g/l) | (A liquid) | (B liquid) solder flux peeling rate (μ m/ branch) | Solder flux peeling rate rate of descent (%) | |
| Solder flux peeling rate (μ m/ branch) | Copper dissolution speed (μ m/ branch) | ||||
| Comparative example 2 | 67.5% nitric acid 380 (nitric acid 256.5) iron nitrate 9 hydrates 100 (iron 17.3) sodium-chlor 20 (chlorine 12.1) deionized water surplus | ????32.61 | ????6.25 | ????4.57 | ???86.0 |
| 10 | 67.5% nitric acid 380 (nitric acid 256.5) ferric nitrate 9 hydrates 100 (iron 17.3) sodium chloride 20 (chlorine 12.1) ammonium iodide 120ppm (iodine 105.1ppm) nickel nitrates (anhydrous) 3 (nickel 1.0) deionized water surplus | ????19.63 | ????1.33 | ????7.69 | ???60.8 |
| 11 | 67.5% nitric acid 380 (nitric acid 256.5) ferric nitrate 9 hydrates 100 (iron 17.3) sodium chloride 20 (chlorine 12.1) ammonium iodide 120ppm (iodine 105.1ppm) nickel nitrates (anhydrous) 30 (nickel 9.7) deionized water surplus | ????22.02 | ????1.09 | ????12.13 | ???44.9 |
The result shows that compare with 2 stripping liquid with comparative example 1, the solder flux peeling rate rate of descent of stripping liquid of the present invention all obtains about inhibition more than 15% shown in the table 1-3.Especially at embodiment 5-7 that share iodine compound and zn cpds, nickel compound or cobalt compound and the stripping liquid of 10-11, compare with 2 stripping liquid with comparative example 1, solder flux peeling rate rate of descent all obtains about inhibition more than 25%, and the degree that copper is etched is also significantly suppressed.
Owing to compare with stripping liquid in the past, the decline of the solder flux peeling rate of stripping liquid of the present invention is less, therefore, but is a kind of very useful stripping liquid on operability and cost of life-time service.
Claims (4)
1. being used for peeling off from copper matrix the stripping liquid of tin and tin alloy, is that the aqueous solution of the iodine compound of 10-500 ppm by weight is formed by containing nitric acid 150-300g/l, iron ion 5-25g/l, chlorion 2-20g/l and iodine concentration.
2. being used for peeling off from copper matrix the stripping liquid of tin and tin alloy, is that the aqueous solution of 0.1-50g/l is formed by the total concn concentration that contains at least a and cobalt, nickel and zinc in nitric acid 150-300g/l, iron ion 5-25g/l, chlorion 2-20g/l and cobalt compound, nickel compound and the zn cpds.
3. be used for peeling off the stripping liquid of tin and tin alloy, form by at least a and aqueous solution that total concn concentration cobalt, nickel and zinc is 0.1-50g/l that contains in iodine compound that nitric acid 150-300g/l, iron ion 5-25g/l, chlorion 2-20g/l and iodine concentration are the 10-500 ppm by weight and cobalt compound, nickel compound and the zn cpds from copper matrix.
4. as claim 1 or 3 described stripping liquids, it is characterized in that described iodine compound is acid iodide or iodate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97116133 CN1178260A (en) | 1996-08-30 | 1997-07-29 | Liquid for separating tin from tin alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP230463/96 | 1996-08-30 | ||
| CN 97116133 CN1178260A (en) | 1996-08-30 | 1997-07-29 | Liquid for separating tin from tin alloy |
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| Publication Number | Publication Date |
|---|---|
| CN1178260A true CN1178260A (en) | 1998-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97116133 Pending CN1178260A (en) | 1996-08-30 | 1997-07-29 | Liquid for separating tin from tin alloy |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311099C (en) * | 2000-10-26 | 2007-04-18 | 美格株式会社 | Corrosion method of metal tin or tin alloy, and corrosion liquor of metal tin or tin alloy |
| CN102094202A (en) * | 2009-12-15 | 2011-06-15 | 同和金属技术有限公司 | Method of detinning Sn plating layer on Cu-based material |
| CN104294273A (en) * | 2014-11-08 | 2015-01-21 | 汕头超声印制板（二厂）有限公司 | Non-toxic gold stripping liquid and method for detecting printed circuit board through non-toxic gold stripping liquid |
| CN106637213A (en) * | 2016-08-04 | 2017-05-10 | 东莞市广华化工有限公司 | Low copper-biting type tin-fading liquid |
| CN107881506A (en) * | 2017-11-21 | 2018-04-06 | 东莞市广华化工有限公司 | A kind of new-type stripping tin liquor |
-
1997
- 1997-07-29 CN CN 97116133 patent/CN1178260A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311099C (en) * | 2000-10-26 | 2007-04-18 | 美格株式会社 | Corrosion method of metal tin or tin alloy, and corrosion liquor of metal tin or tin alloy |
| CN102094202A (en) * | 2009-12-15 | 2011-06-15 | 同和金属技术有限公司 | Method of detinning Sn plating layer on Cu-based material |
| CN102094202B (en) * | 2009-12-15 | 2013-10-09 | 同和金属技术有限公司 | Method of stripping Sn plating layer on Cu-based material |
| CN104294273A (en) * | 2014-11-08 | 2015-01-21 | 汕头超声印制板（二厂）有限公司 | Non-toxic gold stripping liquid and method for detecting printed circuit board through non-toxic gold stripping liquid |
| CN106637213A (en) * | 2016-08-04 | 2017-05-10 | 东莞市广华化工有限公司 | Low copper-biting type tin-fading liquid |
| CN107881506A (en) * | 2017-11-21 | 2018-04-06 | 东莞市广华化工有限公司 | A kind of new-type stripping tin liquor |
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