LOW alpha-RAY EMISSION STANNOUS OXIDE AND METHOD OF PRODUCING THE SAME

Abstract

What is provided is stannous oxide having an α-ray emission amount of 0.002 cph/cm.sup.2 or less after heating in an atmosphere at 100° C. for 6 hours. Tin containing lead as an impurity is dissolved in a sulfuric acid aqueous solution to prepare a tin sulfate aqueous solution, and lead sulfate is precipitated in the aqueous solution and removed. While stirring the tin sulfate aqueous solution from which lead sulfate has been removed, a lead nitrate aqueous solution containing lead having an α-ray emission amount of 10 cph/cm.sup.2 or less is added to cause lead sulfate to be precipitated in the tin sulfate aqueous solution, and simultaneously the tin sulfate aqueous solution is circulated while removing the lead sulfate from the aqueous solution. A neutralizing agent is added to the tin sulfate aqueous solution to collect stannous oxide.

Claims

1. Stannous oxide having a low α-ray emission amount, wherein an α-ray emission amount after heating in an atmosphere at 100° C. for 6 hours is 0.002 cph/cm.sup.2 or less.

2. The stannous oxide having a low α-ray emission amount according to claim 1, wherein an α-ray emission amount of the stannous oxide after heating in the atmosphere at 200° C. for 6 hours is 0.002 cph/cm.sup.2 or less.

3. A method of producing stannous oxide having a low α-ray emission amount, the method comprising: a step (a) of dissolving tin containing lead as an impurity in a sulfuric acid aqueous solution to prepare a tin sulfate aqueous solution and cause lead sulfate to be precipitated in the tin sulfate aqueous solution; a step (b) of filtering the tin sulfate aqueous solution containing the lead sulfate in the step (a) to remove the lead sulfate from the tin sulfate aqueous solution; a step (c) of adding a lead nitrate aqueous solution containing lead having an α-ray emission amount of 10 cph/cm.sup.2 or less to a first tank for over 30 minutes while stirring the tin sulfate aqueous solution from which the lead sulfate has been removed in the step (b) at a rotation speed of at least 100 rpm to cause lead sulfate to be precipitated in the tin sulfate aqueous solution, simultaneously circulating the tin sulfate aqueous solution so that a circulation flow rate is at least 1 vol %/min with respect to a total liquid amount in the first tank while filtering the tin sulfate aqueous solution to remove the lead sulfate from the tin sulfate aqueous solution; and a step (d) of adding a neutralizing agent to the tin sulfate aqueous solution obtained in the step (c) to collect stannous oxide.

4. The method of producing stannous oxide having a low α-ray emission amount according to claim 3, wherein a concentration of lead nitrate in the lead nitrate aqueous solution in the step (c) is 10 mass % to 30 mass %.

5. The method of producing stannous oxide having a low α-ray emission amount according to claim 3, wherein an addition rate of the lead nitrate aqueous solution in the step (c) is 1 mg/sec to 100 mg/sec with respect to 1 L of the tin sulfate aqueous solution.

6. The method of producing stannous oxide having a low α-ray emission amount according to claim 4, wherein an addition rate of the lead nitrate aqueous solution in the step (c) is 1 mg/sec to 100 mg/sec with respect to 1 L of the tin sulfate aqueous solution.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0026] FIG. 1 is a flowchart showing each step of a method of producing stannous oxide having a low α-ray emission amount according to the present embodiment.

[0027] FIG. 2 is a diagram showing a decay chain (uranium-radium decay series) in which uranium (U) decays until .sup.206Pb is reached.

[0028] FIG. 3 is a diagram showing a part of an apparatus for producing the stannous oxide having a low α-ray emission amount according to the present embodiment.

DESCRIPTION OF EMBODIMENTS

[0029] Next, embodiments of the present invention will be described with reference to the drawings.

[0030] There are many radioactive elements that emit α-rays, but many do not actually pose a problem because their half-lives are either very long or very short. As indicated by the broken line frame in FIG. 2, α-rays, which actually pose a problem, are kinds of radiation emitted when a decay from .sup.210Po, which is an isotope of Polonium after β decay occurs like .sup.210Pb.fwdarw..sup.210Bi.fwdarw..sup.210Po in the decay chain of U, into .sup.206Pb, which is an isotope of lead, occurs. In particular, regarding the emission mechanism of α-rays of tin used for a solder, this has been clarified by past investigation. Here, Bi has a short half-life, and thus can be ignored in terms of management. In summary, an α-ray source of tin is primarily .sup.210Po and the amount of .sup.210Pb, which is the emission source of .sup.210Po, is attributed to the emission amount of α-rays.

[0031] First, a method of producing stannous oxide having a low α-ray emission amount according to an embodiment of the present invention will be described in order of steps shown in FIG. 1 and based on a production apparatus shown in FIG. 3.

<Step (a) and Step (b)>

[Metal Raw Material]

[0032] A metal raw material for obtaining the stannous oxide (SnO) having a low α-ray emission amount according to the embodiment of the present invention is tin, and selection of this raw material tin is not restricted by the Pb content of impurities or the magnitude of the α-ray emission amount. For example, even with a metal such as a commercially available tin in which the concentration of Pb is about 320 mass ppm and the α-ray emission amount of Pb is about 9 cph/cm.sup.2, stannous oxide finally obtained by the production method and the production apparatus described below can achieve an α-ray emission amount of 0.002 cph/cm.sup.2 or less after heating in the air at 100° C. or 200° C. for 6 hours. The shape of the raw material tin is not limited and may be powdery or lumpy. To accelerate the dissolution rate, there is also an electrolytic elution method using a hydrogen ion exchange membrane.

[Preparation of Tin Sulfate Aqueous Solution and Precipitation Separation of Lead Sulfate]

[0033] In step (a) and step (b) shown in FIG. 1, as shown in FIG. 3, a sulfuric acid aqueous solution (H.sub.2SO.sub.4) is put in a tin sulfate preparation tank 11 through a supply port 11a to be stored in the tank 11, and a raw material tin is added thereto through a supply port 11b and stirred by a stirrer 12 to dissolve the raw material tin in the sulfuric acid aqueous solution, whereby a tin sulfate (SnSO.sub.4) aqueous solution 13 of the raw material tin is prepared. At this time, in the tin sulfate preparation tank 11, lead (Pb) in the raw material tin is precipitated as lead sulfate (PbSO.sub.4). There are cases where lead sulfate (PbSO.sub.4) is precipitated on the bottom portion of the tin sulfate preparation tank 11. By a pump 14 provided outside the tin sulfate preparation tank 11, the tin sulfate aqueous solution is passed (hereinafter, referred to as filtered) through a filter 16 and is also transferred to a subsequent first tank 21 via a transfer pipeline 17. The lead sulfate precipitated in the tin sulfate preparation tank 11 by the filter 16 is removed from the tin sulfate aqueous solution. A membrane filter is preferable as the filter 16. The pore size of the filter is preferably in a range of 0.1 μm to 10 μm, and more preferably in a range of 0.2 μm to 1 μm. Lead sulfate may contain impurities.

<Step (c)>

[Reduction of Lead (.SUP.210.Pb)]

[0034] In step (c) shown in FIG. 1, the first tank 21 shown in FIG. 3 stores a tin sulfate aqueous solution 23 which is transferred by the pump 14 and from which the lead sulfate has been removed. When a predetermined amount of the tin sulfate aqueous solution 23 is stored in the first tank 21, a lead nitrate aqueous solution having a predetermined concentration and containing lead (Pb) having an α-ray emission amount as low as 10 cph/cm.sup.2 or less is added to the first tank 21 through a supply port 21a, and the tin sulfate aqueous solution 23 is stirred by a stirrer 22 at a rotation speed (stirring speed) of at least 100 rpm. Here, the tin sulfate aqueous solution 23 of the raw material tin from which the lead sulfate has been removed is adjusted to a temperature of 10° C. to 50° C., and more preferably 20° C. to 40° C., and the lead nitrate aqueous solution containing lead having the low α-ray emission amount is added at a predetermined rate for over 30 minutes. As a result, lead sulfate (PbSO.sub.4) is precipitated in the tin sulfate aqueous solution. There are cases where lead sulfate (PbSO.sub.4) is precipitated on the bottom portion of the first tank 21. This lead nitrate aqueous solution is prepared, for example, by mixing Pb having a surface α-ray emission amount of 10 cph/cm.sup.2 and a purity of 99.99% in a nitric acid aqueous solution. Accordingly, lead (.sup.210Pb), which is a radioisotope in impurities and is contained in the raw material tin and cause a high α-ray emission amount and ions of lead (Pb) which is a stable isotope, are removed after being mixed in the liquid, and the amount of lead (.sup.210Pb) which is the radioisotope in the liquid gradually decreases. The concentration of tin sulfate in the tin sulfate aqueous solution of the raw material tin is preferably 100 g/L or more and 250 g/L or less, and more preferably 150 g/L or more and 200 g/L or less. The concentration of sulfuric acid (H.sub.2SO.sub.4) in the tin sulfate aqueous solution is set to preferably 10 g/L or more and 50 g/L or less, and more preferably 20 g/L or more and 40 g/L or less.

[0035] When a stirring speed of the tin sulfate aqueous solution is less than 100 rpm, lead ions in the tin sulfate aqueous solution and the lead nitrate aqueous solution are precipitated as lead sulfate before being sufficiently mixed, so that ions of lead (.sup.210Pb) which is the radioisotope in the tin sulfate aqueous solution cannot be substituted with ions of lead (Pb) which is the stable isotope. The upper limit of the stirring speed is a rotation speed at which the liquid is not scattered by stirring, and is determined by the size of the first tank 21 which is a reaction tank, and the size and shape of the blades of the stirrer 22. Here, regarding the size of the first tank 21, a cylindrical container having a diameter of about 1.5 m can be used, the size of the blade of the stirrer 22 is a radius of about 0.5 m (a diameter of about 1 in), and the shape thereof can be a propeller shape.

[0036] The α-ray emission amount of lead contained in the lead nitrate aqueous solution is an α-ray emission amount as low as 10 cph/cm.sup.2 or less. The α-ray emission amount is set to 10 cph/cm.sup.2 or less because the α-ray emission amount of the finally obtained stannous oxide cannot be set to 0.002 cph/cm.sup.2 or less. The concentration of lead nitrate in the lead nitrate aqueous solution is preferably 10 mass % to 30 mass %. When the concentration thereof is less than 10 mass %, the reaction time between the tin sulfate aqueous solution and the lead nitrate aqueous solution is prolonged and the production efficiency tends to deteriorate, and when the concentration thereof exceeds 30 mass %, lead nitrate is not efficiently utilized and tends to be wasted.

[0037] An addition rate of the lead nitrate aqueous solution is preferably 1 mg/sec to 100 mg/sec, and more preferably 1 mg/sec to 10 mg/sec with respect to 1 L of the tin sulfate aqueous solution. This addition rate depends on the concentration of lead nitrate in the lead nitrate aqueous solution. When the addition rate is less than 1 mg/sec, the reaction time between the tin sulfate aqueous solution and the lead nitrate aqueous solution is prolonged and the production efficiency tends to deteriorate, and when the addition rate exceeds 100 mg/sec, lead nitrate is not efficiently utilized and tends to be wasted. Furthermore, it takes 30 minutes or longer to add the lead nitrate aqueous solution because even if the concentration and the addition rate of the lead nitrate aqueous solution are increased, the reduction in lead (.sup.210Pb) as the radioisotope proceeds only at a constant rate, and it is necessary to add the lead nitrate aqueous solution for over a certain period of time for a sufficient reduction. Therefore, when the addition time is shorter than 30 minutes, the α-ray emission amount of the raw material tin cannot be reduced to a desired value.

[0038] Returning to FIG. 3, in step (c) shown in FIG. 1, simultaneously with the above addition, the tin sulfate aqueous solution 23 in the first tank 21 at a temperature of 10° C. to 50° C. is sent to a circulation pipeline 27 through a filter 26 by a pump 24 provided outside the first tank 21, or transferred to a subsequent second tank (not illustrated) via a transfer pipeline 28. The circulation pipeline 27 and the transfer pipeline 28 are respectively provided with on-off valves 27a and 28a. While removing the residual lead sulfate (PbSO.sub.4) from the tin sulfate aqueous solution 23 by the filter 26 in the first tank 21 by operating the pump 24, the valve 27a is opened and the valve 28a is closed, whereby the tin sulfate aqueous solution 23 is circulated through the circulation pipeline 27 at a circulation flow rate of at least 1 vol %/min with respect to the total liquid amount in the first tank. That is, 1 vol % or more of the total liquid amount in the first tank is circulated per minute. For example, in a case where the total liquid amount in the first tank is 100 L, 1 L/min or more of the liquid is circulated. By the circulation of the tin sulfate aqueous solution, excess lead sulfate in the liquid is removed, and substitution between ions of lead (.sup.210Pb) which is the radioisotope and ions of lead (Pb) which is the stable isotope in the tin sulfate aqueous solution is smoothly performed. The circulation flow rate is set to at least 1 vol %/min (1 vol %/min or more) because when the circulation flow rate is less than 1 vol %/min, the liquid amount of the tin sulfate aqueous solution passing through the filter 26 becomes small, the efficiency of collecting lead sulfate suspended in the liquid by the filter 26 decreases, a large amount of lead sulfate remains in the tin sulfate aqueous solution, and substitution between ions of lead (.sup.210Pb) which is the radioisotope and ions of lead (Pb) which is the stable isotope in the tin sulfate aqueous solution is not smoothly performed. The circulation flow rate is adjusted by a flow meter (not illustrated) installed in the pump 24 and the circulation pipeline 27. The circulation flow rate is more preferably set to 5 vol %/min or more. The circulation flow rate is set to preferably 50 vol %/min or less, and more preferably 30 vol %/min or less. As the filter 26, the above-mentioned membrane filter can be used. In step (c), the tin sulfate aqueous solution 23 may be circulated in the first tank 21 with bubbling using an inert gas such as nitrogen gas. By circulating the tin sulfate aqueous solution 23 with bubbling, the generation of Sn.sup.4+ in the liquid can be suppressed. Accordingly, the proportion of Sn.sup.4+ contained in the stannous oxide obtained in step (d), which will be described below, can be reduced, so that when the plating liquid is replenished with the stannous oxide, the generation of sludge in the plating liquid and suspension of the plating liquid can be suppressed. The flow rate of the inert gas is preferably set to 5 L/min or more and 30 L/min or less.

<Step (d)>

[Collection of Stannous Oxide (SnO)]

[0039] Subsequently, in step (d) shown in FIG. 1, a neutralizing agent is added to the tin sulfate aqueous solution in which the amount of lead (.sup.210Pb) is reduced, the resultant is subjected to solid-liquid separation such as filtering in an inert gas atmosphere, for example, a nitrogen gas atmosphere, and a stannous oxide precursor of the separated slurry is washed with pure water. After the washing with water, solid-liquid separation is performed again and washing with water is performed again. This is repeated 3 to 5 times. The stannous oxide subjected to the final solid-liquid separation is dried in a vacuum at a temperature of 20° C. or higher to obtain powdery stannous oxide (SnO). Examples of the neutralizing agent include sodium hydrogen carbonate, sodium hydroxide, potassium hydrogen carbonate, potassium hydroxide, ammonium hydrogen carbonate, and ammonia water. Solid-liquid separation and washing with water are performed in an inert gas atmosphere in order to prevent the stannous oxide precursor in the slurry from being oxidized to stannic oxide. In addition, drying of the stannous oxide in a vacuum is also to prevent the stannous oxide from being oxidized to stannic oxide.

[0040] The powdery stannous oxide obtained in the above embodiment is characterized in that the α-ray emission amount is 0.002 cph/cm.sup.2 or less at the initial stage of the production and after a long period of time elapsed from the production, and the α-ray emission amount is 0.002 cph/cm.sup.2 or less even after heating in the air at 100° C. or 200° C. for 6 hours.

EXAMPLES

[0041] Next, examples of the present invention will be described in detail together with comparative examples.

Example 1

[0042] A commercially available Sn powder having an α-ray emission amount of 10 cph/cm.sup.2 and a Pb concentration of 15 ppm was used as a metal raw material, and this was added to a sulfuric acid aqueous solution at a concentration of 130 g/L stored in a tin sulfate preparation tank, mixed therein, and dissolved at 50° C., whereby 1 m.sup.3 of a 200 g/L (as tin sulfate) tin sulfate aqueous solution was prepared. The concentration of sulfuric acid (H.sub.2SO.sub.4) of the tin sulfate aqueous solution was about 40 g/L. Accordingly, Pb contained in the metal raw material tin was precipitated as lead sulfate. The tin sulfate aqueous solution was filtered through a membrane filter (pore size: 0.2 μm) manufactured by Yuasa Membrane Systems Co., Ltd. to remove lead sulfate. Next, in the first tank, the tin sulfate aqueous solution from which lead sulfate had been removed was adjusted to 40° C. and then stirred at a rotation speed of 100 rpm. In the meanwhile, to this aqueous solution, a lead nitrate aqueous solution (lead nitrate concentration: 20 mass %) containing Pb having an α-ray emission amount of 10 cph/cm.sup.2 was added at a rate of 1 mg/sec.Math.L (1000 mg/sec) for over 30 minutes. As the first tank, a cylindrical container having a diameter of 1.5 m with a propeller-shaped stirrer having a blade with a radius of about 0.5 m (a diameter of about 1 m) was used. Simultaneously with this addition, the tin sulfate aqueous solution was passed through the same membrane filter as above to remove lead sulfate from the tin sulfate aqueous solution, and with nitrogen bubbling performed at 10 L/min in the first tank, the tin sulfate aqueous solution was circulated so that the circulation flow rate was 1 vol %/min with respect to the total liquid amount in the first tank. Thereafter, sodium hydrogen carbonate was directly added to the tin sulfate aqueous solution after filtering the tin sulfate aqueous solution from the first tank as a neutralizing agent in a nitrogen gas atmosphere, and the obtained slurry was filtered. Solid contents obtained by the filtration in the nitrogen gas atmosphere were washed with pure water. After repeating filtration and washing with water three times, the solid contents were dried in a vacuum at a temperature of 20° C. or higher to obtain powdery stannous oxide.

[0043] The production conditions of Example 1 described above are shown in Table 1 below. The addition rate of the lead nitrate aqueous solution is the addition rate to 1 L of the tin sulfate aqueous solution. The total addition amount of the lead nitrate aqueous solution is the amount added to 1 L of the tin sulfate aqueous solution.

TABLE-US-00001 TABLE 1 Lead nitrate aqueous solution Pb Tin sulfate aqueous α-ray concentration solution emission Total in raw Stirring Circulation amount of Lead nitrate Addition Addition addition material Sn speed flow rate Pb concentration rate time amount (mass ppm) (rpm) (vol %/min) (cph/cm.sup.2) (mass %) (mg/sec .Math. L) (min) (mg/L) Example 1  15 100 1 10 20 1 30 360 Example 2  15 500 1 10 20 1 30 360 Example 3  15 1000 1 10 20 1 30 360 Example 4  15 500 1 10 10 1 30 180 Example 5  15 500 1 10 20 1 30 360 Example 6  15 500 1 10 30 1 30 540 Example 7  15 500 1 10 40 1 30 720 Example 8  15 500 1 10 20 1 30 360 Example 9  15 500 1 10 20 10 30 3600 Example 10 15 500 1 10 20 100 30 36000 Example 11 150 500 1 10 20 1 30 360 Example 12 240 500 1 10 20 1 30 360 Example 13 320 500 1 10 20 1 30 360 Example 14 15 500 1 10 5 1 60 180 Example 15 15 500 1 10 1 1 300 180 Example 16 15 500 1 10 20 0.5 60 360 Comparative 15 50 1 10 20 1 30 360 Example 1 Comparative 15 500 0.5 10 20 1 30 360 Example 2 Comparative 15 500 1 10 40 1 20 480 Example 3 Comparative 15 500 1 10 20 1 20 240 Example 4 Comparative 15 500 1 10 20 10 20 2400 Example 5 Comparative 15 500 1 10 20 100 20 24000 Example 6 Comparative 15 500 1 12 20 1 30 360 Example 7

Examples 2 to 16 and Comparative Examples 1 to 7

[0044] In Examples 2 to 16 and Comparative Examples 1 to 7, the raw material tin, the stirring speed and circulation flow rate of the tin sulfate aqueous solution, the α-ray emission amount of Pb in the lead nitrate aqueous solution, lead nitrate concentration, addition rate, addition time, and total addition amount described in Example 1 were changed as shown in Table 1 above. Hereinafter, in the same manner as in Example 1, stannous oxides as final products were obtained.

Comparative Example 8

[0045] In Comparative Example 8, stannous oxide was obtained by the method according to Example 2 of Patent Document 1 described in the background art of the present specification. Specifically, a raw material tin (Sn) in a level of 4N was used as the anode. As the electrolytic solution, an ammonium sulfate aqueous solution was used and adjusted to a pH of 6 to a pH of 7. Methanesulfonic acid was added as a complex ion forming agent to adjust the pH to 3.5. The resultant was subjected to electrolysis under the conditions of an electrolysis temperature of 20° C. and a current density of 1 A/dm.sup.2. By the electrolysis, stannous oxide (SnO) was precipitated. The resultant was filtered and dried to be purified after the electrolysis, whereby powdery stannous oxide having an α-ray emission amount of 0.001 cph/cm.sup.2 was finally obtained.

Comparative Example 9

[0046] In Comparative Example 9, stannous oxide was obtained by the method according to an example of Patent Document 2 described in the background art of the present specification. Specifically, first, an acidic aqueous solution was prepared by an electrolysis method under the following conditions.

[0047] Sn plate: 180×155×1 mm, about 200 g, α-ray emission amount: 0.002 cph/cm.sup.2 or less, purity: 99.995% or more

[0048] Tank: Diaphragm electrolyzer

[0049] Anode tank: 2.5 L of 3.5 N (3.5 mol/L) hydrochloric acid was used

[0050] Cathode tank: 2.5 L of 3.5 N (3.5 mol/L) hydrochloric acid was used

[0051] Electrolysis amount: Electrolyzed at a constant voltage of 2 V for 30 hours.

[0052] Target Sn composition after completion of electrolysis: Sn concentration 200 g/L

[0053] HCl concentration after completion of electrolysis: Normality 1 N (1 mol/L)

[0054] As a Sn.sup.4+ reduction treatment, after electrolysis, a Sn plate (180×155×1 mm, about 200 g, α-ray emission amount: 0.002 cph/cm.sup.2 or less, purity: 99.995% or more) was immersed in an acidic aqueous solution at 80° C. for 3 days and subjected to a reflux treatment (a treatment in which a liquid overflowing from an electrolyzer (anode tank or cathode tank) is returned to the electrolyzer with a pump), and a free acid (FA) reduction treatment of causing the concentration of hydrochloric acid to be 0.5 N (0.5 mol/L) or less was performed by repeating boiling the liquid until the amount of the liquid was halved and diluting the liquid after the boiling with pure water to return the amount of the liquid to the original amount.

[0055] Next, the acidic aqueous solution was neutralized under the following conditions to prepare stannous hydroxide.

[0056] Atmosphere: N.sub.2 gas

[0057] Alkaline aqueous solution: 40 mass % ammonium carbonate aqueous solution

[0058] Liquid temperature of acidic aqueous solution: 30° C. to 50° C.

[0059] pH during neutralization: 6 to 8

[0060] Next, the stannous hydroxide was dehydrated under the following conditions.

[0061] Atmosphere: N.sub.2 gas

[0062] Liquid temperature: 80° C. to 100° C.

[0063] Time: 1 to 2 hours

[0064] In addition, filtration was performed by a suction filtration method, and washing with water was performed twice with warm water (70° C.) and once with pure water. Furthermore, drying in a vacuum was performed at 25° C. overnight to obtain powdery stannous oxide.

<Comparative Test and Evaluation>

[0065] Regarding the stannous oxides which were 25 kinds of final products obtained in Examples 1 to 16 and Comparative Examples 1 to 9, the Pb concentration in the stannous oxide and the α-ray emission amount by Pb before heating, after heating, and 1 year after slow cooling after heating were measured by the methods described below. The results are shown in Table 2 below.

(a) Pb Concentration in Stannous Oxide

[0066] Regarding the Pb concentration in the stannous oxide, the powdery stannous oxide was used as a sample, this was dissolved in hot hydrochloric acid, the obtained liquid was analyzed by ICP (plasma optical emission spectrometer, limit of quantification: 1 mass ppm), and the amount of impurity Pb was measured.

(b) α-Ray Emission Amount by Pb in Stannous Oxide

[0067] First, the obtained powdery stannous oxide was used as Sample 1 before heating. The α-ray emission amount emitted from Sample 1 before heating was measured for 96 hours by a gas flow type α-ray measuring device (MODEL-1950, limit of measurement: 0.0005 cph/cm.sup.2) manufactured by Alpha Sciences Inc. The limit of measurement of this device is 0.0005 cph/cm.sup.2. The α-ray emission amount at this time was defined as the α-ray emission amount before heating. Next, Sample 1 measured before heating was heated in the air at 100° C. for 6 hours and then gradually cooled to room temperature to obtain Sample 2. The α-ray emission amount of Sample 2 was measured by the same method as Sample 1. The α-ray emission amount at this time was defined as “after heating (100° C.)”. Next, Sample 2 after the measurement of the α-ray emission amount was heated in the air at 200° C. for 6 hours and then gradually cooled to room temperature to obtain Sample 3. The α-ray emission amount of Sample 3 was measured by the same method as Sample 1. The α-ray emission amount at this time was defined as “after heating (200° C.)”. Furthermore, Sample 3 was vacuum-packed to prevent contamination and stored for 1 year to obtain Sample 4, and the α-ray emission amount of Sample 4 was measured by the same method as Sample 1. The α-ray emission amount at this time was defined as “after 1 year”.

TABLE-US-00002 TABLE 2 Final product Pb α-ray emission amount (cph/cm.sup.2) concentration Before After heating After heating After Kind (mass ppm) heating (100° C.) (200° C.) 1 year Example 1  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 2  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 3  SnO 3 <0.0005 <0.0005 <0.0005 <0.0005 Example 4  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 5  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 6  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 7  SnO 3 <0.0005 <0.0005 <0.0005 <0.0005 Example 8  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 9  SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 10 SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 11 SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 12 SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 13 SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 14 SnO 3 <0.0005 <0.0005 <0.0005 <0.0005 Example 15 SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Example 16 SnO 2 <0.0005 <0.0005 <0.0005 <0.0005 Comparative SnO 3 0.0007 0.0021 0.0025 0.0112 Example 1 Comparative SnO 2 <0.0005 0.0023 0.0027 0.0152 Example 2 Comparative SnO 2 <0.0005 0.0024 0.0023 0.0039 Example 3 Comparative SnO 3 <0.0005 0.0021 0.0027 0.0032 Example 4 Comparative SnO 2 0.0005 0.0022 0.0023 0.0035 Example 5 Comparative SnO 2 <0.0005 0.0025 0.0025 0.0031 Example 6 Comparative SnO 3 0.0006 0.0023 0.0025 0.0056 Example 7 Comparative SnO <1 0.0006 0.0022 0.0026 0.0052 Example 8 Comparative SnO 3 0.0009 0.0027 0.0029 0.0082 Example 9

[0068] As is clear from Table 2, in Comparative Example 1, since the stirring speed of the tin sulfate aqueous solution when the lead nitrate aqueous solution was added was set to 50 rpm, lead (.sup.210Pb) as the radioisotope of the raw material tin was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was 0.0007 cph/cm.sup.2, the α-ray emission amount was increased to 0.0021 cph/cm.sup.2 after heating at 100° C., to 0.0025 cph/cm.sup.2 after heating at 200° C., and further to 0.0112 cph/cm.sup.2 after 1 year.

[0069] In Comparative Example 2, since the circulation flow rate of the tin sulfate aqueous solution during the addition and after the addition of the lead nitrate aqueous solution was set to 0.5 vol %/min, lead (.sup.210Pb) as the radioisotope in the raw material was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was less than 0.0005 cph/cm.sup.2, the α-ray emission amount was increased to 0.0023 cph/cm.sup.2 after heating at 100° C., to 0.0027 cph/cm.sup.2 after heating at 200° C., and further to 0.0152 cph/cm.sup.2 after 1 year.

[0070] In Comparative Example 3, since the addition time was set to 20 minutes even though the lead nitrate concentration of the lead nitrate aqueous solution was as high as 40 mass %, lead (.sup.210Pb) as the radioisotope of the raw material tin was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was less than 0.0005 cph/cm.sup.2, the α-ray emission amount was increased to 0.0024 cph/cm.sup.2 after heating at 100° C., to 0.0023 cph/cm.sup.2 after heating at 200° C., and further to 0.0039 cph/cm.sup.2 after 1 year.

[0071] In Comparative Example 4, since the lead nitrate concentration of the lead nitrate aqueous solution was set to 20 mass % and the addition time was set to 20 minutes, lead (.sup.210Pb) as the radioisotope of the raw material tin was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was less than 0.0005 cph/cm.sup.2, the α-ray emission amount was increased to 0.0021 cph/cm.sup.2 after heating at 100° C., to 0.0027 cph/cm.sup.2 after heating at 200° C., and further to 0.0032 cph/cm.sup.2 after 1 year.

[0072] In Comparative Example 5, since the addition time was set to 20 minutes even though the addition rate of the lead nitrate aqueous solution was as fast as 10 mg/sec, lead (.sup.210Pb) as the radioisotope of the raw material tin was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was 0.0005 cph/cm.sup.2, the α-ray emission amount was increased to 0.0022 cph/cm.sup.2 after heating at 100° C., to 0.0023 cph/cm.sup.2 after heating at 200° C., and further to 0.0035 cph/cm.sup.2 after 1 year.

[0073] In Comparative Example 6, since the addition time was set to 20 minutes even though the addition rate of the lead nitrate aqueous solution was as fast as 100 mg/sec, lead (.sup.210Pb) as the radioisotope of the raw material tin was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was less than 0.0005 cph/cm.sup.2, the α-ray emission amount was increased to 0.0025 cph/cm.sup.2 after heating at 100° C., to 0.0025 cph/cm.sup.2 after heating at 200° C., and further to 0.0031 cph/cm.sup.2 after 1 year.

[0074] In Comparative Example 7, since the lead nitrate aqueous solution in which the α-ray emission amount of Pb contained in the lead nitrate aqueous solution was 12 cph/cm.sup.2 was used, lead (.sup.210Pb) as the radioisotope of the raw material tin was insufficiently reduced. In addition, although the α-ray emission amount of the metal tin before heating was 0.0006 cph/cm.sup.2, the α-ray emission amount was increased to 0.0023 cph/cm.sup.2 after heating at 100° C., to 0.0025 cph/cm.sup.2 after heating at 200° C., and further to 0.0056 cph/cm.sup.2 after 1 year.

[0075] The α-ray emission amount of the metal tin produced under the conditions described in Example 1 of Patent Document 1 of Comparative Example 8 was 0.0006 cph/cm.sup.2 before heating, but increased to 0.0022 cph/cm.sup.2 after heating at 100° C., to 0.0026 cph/cm.sup.2 after heating at 200° C., and further to 0.0052 cph/cm.sup.2 after 1 year.

[0076] The α-ray emission amount of the metal tin produced under the conditions described in Example 1 of Patent Document 2 of Comparative Example 9 was 0.0009 cph/cm.sup.2 before heating, but increased to 0.0027 cph/cm.sup.2 after heating at 100° C., to 0.0029 cph/cm.sup.2 after heating at 200° C., and further to 0.0082 cph/cm.sup.2 after 1 year.

[0077] Contrary to this, in the metal tins obtained in Examples 1 to 16 satisfying the production conditions of the fifth aspect of the present invention, the α-ray emission amount of the metal tin before heating was less than 0.0005 cph/cm.sup.2. In addition, the α-ray emission amount of the metal tin after heating at 100° C. was less than 0.0005 cph/cm.sup.2, and the α-ray emission amount of the metal tin after heating at 200° C. was less than 0.0005 cph/cm.sup.2. Furthermore, the α-ray emission amount of the metal tin after 1 year was less than 0.0005 cph/cm.sup.2.

[0078] That is, in the metal tins obtained in Examples 1 to 16, the α-ray emission amount before heating was less than 0.002 cph/cm.sup.2, the α-ray emission amount after heating at 100° C. was 0.002 cph/cm.sup.2 or less, the α-ray emission amount after heating at 200° C. was 0.002 cph/cm.sup.2 or less, and the α-ray emission amount of the metal tin after 1 year was less than 0.002 cph/cm.sup.2.

INDUSTRIAL APPLICABILITY

[0079] The stannous oxide having a low α-ray emission amount of the present invention can be used for replenishing tin or a tin alloy plating liquid with a Sn component for forming a solder bump for joining a semiconductor chip of a semiconductor device in which a soft error is a problem due to the influence of α-rays.

REFERENCE SIGNS LIST

[0080] 11 Tin sulfate preparation tank [0081] 12, 22 Stirrer [0082] 13 Tin sulfate aqueous solution [0083] 14, 24 Pump [0084] 16, 26 Filter [0085] 17, 28 Transfer pipeline [0086] 21 First tank [0087] 23 Tin sulfate aqueous solution [0088] 27 Circulation pipeline