WO2021019862A1 - 酸化第一錫の溶解方法 - Google Patents
酸化第一錫の溶解方法 Download PDFInfo
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- WO2021019862A1 WO2021019862A1 PCT/JP2020/018453 JP2020018453W WO2021019862A1 WO 2021019862 A1 WO2021019862 A1 WO 2021019862A1 JP 2020018453 W JP2020018453 W JP 2020018453W WO 2021019862 A1 WO2021019862 A1 WO 2021019862A1
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- tin
- methanesulfonic acid
- msa
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- aqueous solution
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- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 238000000034 method Methods 0.000 title claims abstract description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 272
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 88
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 33
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims description 68
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 48
- 238000004090 dissolution Methods 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 24
- 238000007747 plating Methods 0.000 claims description 17
- PGGZKNHTKRUCJS-UHFFFAOYSA-N methanesulfonic acid;tin Chemical compound [Sn].CS(O)(=O)=O PGGZKNHTKRUCJS-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- -1 methanesulfonic acid ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
Definitions
- the present invention relates to a method for producing an aqueous tin methanesulfonate solution by dissolving stannous oxide in an aqueous solution of methanesulfonic acid.
- an insoluble electrode platinum, precious metal oxide, etc.
- an insoluble electrode platinum, precious metal oxide, etc.
- a divalent tin ion solution is often added as a tin ion supplement that is consumed from the plating solution.
- a tin methanesulfonate solution in which stannous oxide is dissolved in an aqueous solution of methanesulfonic acid is used. Since this tin methanesulfonate solution is a solution for replenishing tin ions, it is preferable that the tin ion concentration is high.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2003-96590 discloses a solution in which the concentration of tin methanesulfonic acid is 100 g / L as tin and the concentration of methanesulfonic acid is 150 g / L in Examples. ..
- Patent Document 2 Japanese Unexamined Patent Publication No. 2005-314799 discloses a solution having a Sn 2+ ion concentration of 20 g / L and a methanesulfonic acid concentration of 30 mL / L in Examples.
- Patent Document 3 Japanese Unexamined Patent Publication No. 2010-163667 discloses a solution in which the concentration of tin methanesulfonic acid is 15 g / L as tin and the concentration of methanesulfonic acid is 115 g / L as free acid in Examples. doing.
- Patent Document 4 Patent No. 5104253 discloses that SnO: 20 g was dissolved in 300 mL of 25 ° C. methanesulfonic acid in Comparative Test 1 of Examples.
- Patent Document 5 Patent No. 5458555 discloses that SnO: 20 g was dissolved in 300 mL of 25 ° C. methanesulfonic acid in Example 1.
- the tin methanesulfonate solution is a solution for replenishing tin ions, so it is better that the tin ion concentration is high.
- the tin ion concentration in the tin methanesulfonate solution disclosed in the prior art is low.
- an object of the present invention is to provide a method for dissolving stannous oxide in an aqueous solution of methanesulfonic acid, which can achieve a high tin ion concentration.
- the present inventor has been diligently researching to solve the above problems. Then, they have found that when stannous oxide is dissolved in an aqueous solution of methanesulfonic acid by a method described later, a higher tin ion concentration than before can be achieved, and the present invention has been reached.
- the present invention includes the following (1).
- (1) A method for producing an aqueous solution of tin methanesulfonic acid by dissolving stannous oxide in an aqueous solution of methanesulfonic acid.
- tin methanesulfonate solution which is a tin methanesulfonate solution which can be suitably used for replenishing tin ions and has a high tin ion concentration.
- FIG. 1 compares MSA 1.03 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, and MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA). Then, it is a graph which showed the relationship between the Sn concentration (g / L) expected from the SnO input amount, and the Sn concentration (g / L) actually achieved.
- FIG. 2 compares MSA 1.11 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, and MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA).
- FIG. 3 shows 98% MSA 1.03 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA).
- MSA methanesulfonic acid
- MSA 4 compares MSA 1.01 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, and MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA). Then, it is a graph which showed the relationship between the Sn concentration (g / L) expected from the SnO input amount, and the Sn concentration (g / L) actually achieved.
- FIG. 5 compares MSA 1.05 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, and MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA).
- FIG. 6 compares MSA 1.3 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, and MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA). Then, it is a graph which showed the relationship between the Sn concentration (g / L) expected from the SnO input amount, and the Sn concentration (g / L) actually achieved.
- MSA methanesulfonic acid
- MSA 7 compares MSA 1.4 times, MSA 1.5 times, MSA 2.0 times, MSA 2.5 times, and MSA 3.0 times in the dissolution experiment of stannous oxide in an aqueous solution of methanesulfonic acid (hereinafter referred to as MSA). Then, it is a graph which showed the relationship between the Sn concentration (g / L) expected from the SnO input amount, and the Sn concentration (g / L) actually achieved.
- the value of B / 2A is an index indicating how many times the number of moles of methanesulfonic acid was used with respect to the number of moles of methanesulfonic acid required according to the stoichiometric ratio of the reaction.
- the value of B / 2A when the value of B / 2A is n, it may be expressed as MSA n times.
- the number of moles A of stannous oxide used for dissolution is the total number of moles of stannous oxide used for dissolution, and the number of moles of methanesulfonic acid used for dissolution.
- the number B is the total number of moles of methanesulfonic acid used for dissolution.
- the value of B / 2A is, for example, in the range of 1.00 to 1.40, preferably in the range of 1.01 to 1.40, or in the range of 1.02 to 1.40, or 1. It can be in the range of .03 to 1.40.
- the value of B / 2A is, for example, in the range of 1.00 to 1.30, preferably in the range of 1.01 to 1.30, or in the range of 1.02 to 1.30, or 1. It can be in the range of .03 to 1.30.
- the B / 2A value is, for example, in the range 1.00 to 1.20, preferably in the range 1.01 to 1.20, or in the range 1.02 to 1.20, or 1. It can be in the range of .03 to 1.20.
- the value of B / 2A is, for example, in the range of 1.00 to 1.15, preferably in the range of 1.01 to 1.15, or in the range of 1.02 to 1.15, or 1. It can be in the range of .03 to 1.15.
- the value of B / 2A is, for example, in the range 1.00 to 1.12, preferably in the range 1.01 to 1.12, or in the range 1.02 to 1.12, or 1. It can be in the range of .03 to 1.12.
- the value of B / 2A is, for example, in the range of 1.00 to 1.11, preferably in the range of 1.01 to 1.11, or in the range of 1.02 to 1.11, or 1. It can be in the range of .03 to 1.11.
- the value of B / 2A is, for example, in the range of 1.00 to 1.10, preferably in the range of 1.01 to 1.10, or in the range of 1.02 to 1.10, or 1. It can be in the range of .03 to 1.10.
- the value of B / 2A is, for example, in the range of 1.00 to 1.09, preferably in the range of 1.01 to 1.09, or in the range of 1.02 to 1.09, or 1. It can be in the range of .03 to 1.09.
- the value of B / 2A is, for example, in the range of 1.00 to 1.08, preferably in the range of 1.01 to 1.08, or in the range of 1.02 to 1.08, or 1. It can be in the range of .03 to 1.08.
- the value of B / 2A is, for example, in the range of 1.00 to 1.07, preferably in the range of 1.01 to 1.07, or in the range of 1.02 to 1.07, or 1. It can be in the range of .03 to 1.07.
- the value of B / 2A is, for example, in the range of 1.00 to 1.06, preferably in the range of 1.01 to 1.06, or in the range of 1.02 to 1.06, or 1. It can be in the range of .03 to 1.06.
- the value of B / 2A is, for example, in the range of 1.00 to 1.05, preferably in the range of 1.01 to 1.05, or in the range of 1.02 to 1.05, or 1 It can be in the range of .03 to 1.05.
- the value of B / 2A is, for example, in the range of 1.00 to 1.04, preferably in the range of 1.01 to 1.04, or in the range of 1.02 to 1.04, or 1. It can be in the range of .03 to 1.04.
- the value of B / 2A is, for example, in the range of 1.00 to 1.03, preferably in the range of 1.01 to 1.03, or in the range of 1.02 to 1.03. Can be done.
- stannous oxide used is not particularly limited, and commercially available stannous oxide can be used.
- stannous oxide can be in powder form.
- the form of the powder can be used without particular limitation as long as it is suitable for the dissolution operation, and for example, a powder having an average particle size in the range of 1 ⁇ m to 100 ⁇ m can be used.
- the methanesulfonic acid used is not particularly limited, and commercially available methanesulfonic acid can be used.
- the methanesulfonic acid can be used in the form of an aqueous solution of methanesulfonic acid.
- the concentration of methanesulfonic acid in the aqueous solution of methanesulfonic acid is determined depending on the target dissolved tin ion concentration and the value of B / 2A, as described above.
- the tin methanesulfonic acid aqueous solution can be produced by putting the stannous oxide powder into the methanesulfonic acid aqueous solution and stirring and dissolving the powder.
- the charging and stirring can be performed using known means.
- the charging and stirring operations are carried out until the stannous oxide powder is dissolved. Dissolution can be detected visually because the black stannous oxide powder becomes colorless and transparent upon dissolution.
- the loading and stirring operations are carried out over, for example, 0.1 to 60 minutes, 1 to 30 minutes, or 1 to 10 minutes, depending on the total amount. Can be done.
- the temperature of the solution during dissolution is not particularly limited, but may be, for example, in the range of 10 to 80 ° C, or in the range of, for example, 20 to 60 ° C.
- stannous oxide can be dissolved in an aqueous solution of methanesulfonic acid to produce an aqueous solution of tin methanesulfonic acid.
- the obtained tin aqueous solution of methanesulfonate contains a high concentration of tin in the form of Sn 2+ ions.
- the content of tin present as Sn 2+ ions in the tin methanesulfonate aqueous solution is, for example, in the range of 200 to 450 g / L, preferably in the range of 250 to 450 g / L, preferably 300.
- the content of methanesulfonic acid in the tin methanesulfonic acid aqueous solution is determined from the above-mentioned B / 2A value and the tin content.
- the content of methanesulfonic acid present as methanesulfonic acid ions in the tin methanesulfonate aqueous solution is, for example, in the range of 0.1 to 100 g / L, or 0.1 to 70 g / L. Range, or 0.1 to 50 g / L, 0.1 to 40 g / L, 0.1 to 30 g / L, 0.1 to 25 g / L, or 0.1. It can be in the range of ⁇ 20 g / L.
- the tin methanesulfonate aqueous solution produced by the present invention has a high content of tin present as Sn 2+ ions.
- tin plating is performed using an insoluble electrode (platinum, noble metal oxide, etc.) instead of metallic tin as the anode, tin ions are consumed from the plating solution. Therefore, tin ions are added to such a tin plating solution. For replenishment, it can be suitably used by taking advantage of the characteristic of high concentration of Sn 2+ ions.
- the present invention includes a method of adding a tin methanesulfonate aqueous solution produced by the present invention to a tin plating solution to replenish tin ions to the tin plating solution. Furthermore, the present invention includes a method for producing a tin plating solution supplemented with tin ions in this way.
- the present invention may include the following (1) and below.
- (1) A method for producing an aqueous solution of tin methanesulfonic acid by dissolving stannous oxide in an aqueous solution of methanesulfonic acid.
- (2) The production method according to (1), wherein the stannous oxide is a stannous oxide powder.
- a method of replenishing tin ions to a tin plating solution including.
- Example 1 Preparation of high-concentration tin methanesulfonate solution by dissolving stannous oxide
- a high-concentration tin methanesulfonic acid solution the operation of putting the stannous oxide powder into the aqueous solution of methanesulfonic acid and dissolving it was performed by setting the conditions as follows.
- stannous oxide powder a commercially available stannous oxide powder (HK0040 active stannous oxide manufactured by JX Metals Trading Co., Ltd.) was prepared.
- methanesulfonic acid aqueous solution As a methanesulfonic acid aqueous solution, a commercially available methanesulfonic acid aqueous solution (manufactured by JX Metals Trading Co., Ltd., product name: NSP-A700M, methanesulfonic acid concentration 68% by mass) was prepared.
- the liquid volume of the high-concentration tin methanesulfonate solution to be adjusted was set to 100 mL.
- a plurality of concentrations (for example, 300 g / L) were set as the target high-concentration tin concentration (Sn 2+ ion concentration).
- the amount of Sn required to achieve each of the above-targeted tin concentrations was calculated.
- the amount of Sn required to bring the tin concentration to 300 g / L in 100 mL is 30 g.
- the mass of stannous oxide powder required to achieve each of the above tin concentrations was determined.
- the number of moles of tin is determined from the value of the amount of tin required to achieve each target tin concentration, the number of moles of methanesulfonic acid required for the reaction is determined according to the above stoichiometric ratio. ..
- the amount of methanesulfonic acid used is expressed as MSA 1.0 times in the present application. I have something to do.
- the methane used in the present application when 1.1 times the number of moles of methanesulfonic acid is used with respect to the number of moles of methanesulfonic acid required according to the chemical quantity theory ratio, the methane used in the present application.
- the amount of sulfonic acid may be expressed as MSA 1.1 times. These MSA 1.0 times, MSA 1.1 times, etc. are collectively referred to as MSA n times in the present application.
- MSA amount set corresponding to the tin amount required to achieve each target tin concentration a plurality of MSA amounts are set for each of the required tin amounts, and each of them is set.
- the amount of MSA corresponding to each set amount of MSA was calculated. For example, when the MSA is 1.0 times the tin amount of 30 g, the specific gravity is 1.38 when the concentration of the MSA solution is 68%, the tin atomic weight is 118.7, and the MSA molecular weight is 96.1.
- the tin methanesulfonate solution (MSA-Sn solution) was recovered, and pure water was appropriately added to make a scalpel, and the volume was adjusted to the specified amount (100 mL).
- the tin concentration (Sn 2+ ion concentration) of the obtained specified amount of tin methanesulfonate solution was measured by redox titration by iodine starch reaction.
- Example 2 Preparation of a high-concentration tin methanesulfonic acid solution by dissolving stannous oxide in a high-concentration aqueous solution of methanesulfonic acid]
- MSA 1.03 using a higher concentration methanesulfonic acid aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, methanesulfonic acid concentration 98% by mass) instead of the methanesulfonic acid aqueous solution used in Example 1.
- the same experiment was conducted under the condition of doubling.
- FIGS. 1 to 7 The results obtained by the experiments of Examples 1 and 2 are shown in FIGS. 1 to 7. Each point in the graph shows the measured value obtained by the dissolution experiment by the combination of the amount of stannous oxide powder used and the amount of methanesulfonic acid used set by the above procedure.
- the horizontal axis of the graphs of FIGS. 1 to 7 is the Sn 2+ ion concentration [g / L] in the solution calculated assuming that the entire amount of the charged stannous oxide powder is dissolved.
- the vertical axis of the graphs of FIGS. 1 to 7 is the Sn 2+ ion concentration [g / L] measured by titrating the actually obtained solution. For example, the MSA 1.03 times shown in FIG.
- the stannous oxide charged in the methanesulfonic acid aqueous solution has the Sn 2+ ion concentration expected from the charged amount.
- the total amount of the charged amount was dissolved as it was, but if it exceeds that, not only does it not dissolve, but the dissolved amount decreases, and the Sn 2+ ion concentration expected from the input amount becomes
- the Sn 2+ ion concentration of the tin methanesulfonate aqueous solution decreased to about 50 [g / L].
- the stannous oxide charged in the methanesulfonic acid aqueous solution has the Sn 2+ ion concentration expected from the charged amount.
- the Sn 2+ ion concentration expected from the input amount is 300.
- the Sn 2+ ion concentration of the tin methanesulfonate aqueous solution decreased to about 50 [g / L].
- the stannous oxide added into the methanesulfonic acid aqueous solution has a Sn 2+ ion concentration of 200 [, which is expected from the input amount.
- the Sn 2+ ion concentration expected from the input amount is 230 [g].
- the Sn 2+ ion concentration of the tin methanesulfonate aqueous solution decreased to about 100 [g / L].
- the stannous oxide charged in the methanesulfonic acid aqueous solution has a Sn 2+ ion concentration of 100 [expected from the charged amount].
- the Sn 2+ ion concentration expected from the input amount is 190 [g].
- the Sn 2+ ion concentration of the tin methanesulfonate aqueous solution decreased to about 40 [g / L].
- stannous oxide dissolves in an aqueous solution of tin methanesulfonate as a solvent, in order to increase the amount of stannous oxide dissolved in a certain amount of aqueous solution, methane is more than the number of moles required as a chemical quantity theory ratio. It was predicted before the experiment that sufficient dissolution of stannous oxide should be expected by preparing an excessive amount of tin sulfonate. However, contrary to this expectation, the presence of a sufficient excess of methanesulfonic acid rather inhibits the dissolution of stannous oxide, rather than the Sn 2+ ion concentration obtained by adding less stannous oxide.
- methanesulfonic acid should be as close as possible after satisfying the equivalent in the equivalent ratio. It is clear that it is desirable to keep the tin concentration low, and that a high concentration of Sn 2+ ion concentration: 450 [g / L] can be easily achieved by adopting a low tin concentration of methanesulfonate, for example, which is 1.03 times MSA. It became.
- the present invention it is possible to provide a stannous oxide solution that can be suitably used for tin ion supplementation and has a high tin ion concentration.
- the present invention is an industrially useful invention.
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Abstract
Description
(1)
酸化第一錫をメタンスルホン酸水溶液中で溶解して、メタンスルホン酸錫水溶液を製造する方法であって、
酸化第一錫のモル数をAとし、メタンスルホン酸のモル数をBとした場合に、
B/2Aの値が、1.0~1.4の範囲にある、製造方法。
本発明によれば、酸化第一錫をメタンスルホン酸水溶液中で溶解して、メタンスルホン酸錫水溶液を製造する方法であって、酸化第一錫のモル数をAとし、メタンスルホン酸のモル数をBとした場合に、B/2Aの値が、1.0~1.4の範囲にある製造方法によって、高い錫イオン濃度を有するメタンスルホン酸錫水溶液を製造することができる。
溶解に使用する酸化第一錫のモル数をAとし、溶解に使用するメタンスルホン酸のモル数をBとする。この場合に、目標とする錫濃度を達成するために必要となる錫のモル数を決定すれば、溶解反応での化学量論比に従って、反応に必要となるメタンスルホン酸のモル数が定まる。
SnO+2CH3SO3H→Sn(CH3SO3)2+H2O
使用される酸化第一錫には、特に制限はなく、市販の酸化第一錫を使用することができる。好適な実施の態様において、酸化第一錫は、粉末の形態とすることができる。粉末の形態としては、溶解の操作に適していれば特に制限なく使用することができるが、例えば平均粒径が、1μm~100μmの範囲の粉末を使用することができる。
使用されるメタンスルホン酸には、特に制限はなく、市販のメタンスルホン酸を使用することができる。好適な実施の態様において、メタンスルホン酸は、メタンスルホン酸水溶液の形態で使用することができる。好適な実施の態様において、メタンスルホン酸水溶液におけるメタンスルホン酸の濃度は、上述のように、目標とする溶解後の錫イオン濃度と、B/2Aの値に依存して決定される。
好適な実施の態様において、メタンスルホン酸水溶液中へ、酸化第一錫粉末を投入して、攪拌して溶解することによって、メタンスルホン酸錫水溶液を製造することができる。投入と攪拌は、公知の手段を使用して行うことができる。投入と攪拌の操作は、酸化第一錫粉末が溶解するまで行われる。溶解は、黒色の酸化第一錫粉末が溶解によって無色透明となるために、目視によって検出することができる。好適な実施の態様において、投入と攪拌の操作は、その全体量にも依存するが、例えば0.1分間~60分間、あるいは1分間~30分間、あるいは1分間~10分間をかけて行うことができる。好適な実施の態様において、溶解の際の溶液の温度は、特に制限はないが、例えば10~80℃の範囲、あるいは例えば20~60℃の範囲とすることができる。
本発明によれば、酸化第一錫をメタンスルホン酸水溶液中で溶解して、メタンスルホン酸錫水溶液を製造することができる。得られたメタンスルホン酸錫水溶液は、高い濃度の錫を、Sn2+イオンの形態で含有する。
好適な実施の態様において、本発明によって製造されるメタンスルホン酸錫水溶液は、Sn2+イオンとして存在する錫の含有量が、高い含有量となっている。錫めっきを行うにあたって、陽極を金属錫ではなく不溶性電極(白金、貴金属酸化物等)を使用する場合には、めっき液から錫イオンが消耗するから、このような錫めっき液への錫イオンの補給のために、Sn2+イオンが高濃度であるという特性を活かして、好適に使用することができる。したがって、本発明は、本発明によって製造されるメタンスルホン酸錫水溶液を、錫めっき液へ添加して、錫めっき液へ錫イオンを補給する方法を含む。さらに、本発明は、このように錫イオンが補給された錫めっき液を製造する方法を含む。
好適な実施の態様において、本発明は、次の(1)以下を含んでもよい。
(1)
酸化第一錫をメタンスルホン酸水溶液中で溶解して、メタンスルホン酸錫水溶液を製造する方法であって、
酸化第一錫のモル数をAとし、メタンスルホン酸のモル数をBとした場合に、
B/2Aの値が、1.0~1.4の範囲にある、製造方法。
(2)
酸化第一錫が、酸化第一錫粉末である、(1)に記載の製造方法。
(3)
B/2Aの値が、1.01~1.4の範囲にある、(1)~(2)のいずれかに記載の製造方法。
(4)
メタンスルホン酸水溶液中へ、酸化第一錫粉末を投入して、攪拌して溶解することによって、メタンスルホン酸錫水溶液を製造する、(1)~(3)のいずれかに記載の製造方法。
(5)
酸化第一錫が、メタンスルホン酸水溶液中へ全て溶解した場合に、Sn2+イオンとして存在する錫の含有量が、300~450g/Lの範囲である、(1)~(4)のいずれかに記載の製造方法。
(6)
酸化第一錫のモル数Aが、溶解のために使用される酸化第一錫の全量のモル数であり、
メタンスルホン酸のモル数Bが、溶解のために使用されるメタンスルホン酸の全量のモル数である、(1)~(5)のいずれかに記載の製造方法。
(7)
(1)~(6)のいずれかに記載の製造方法によって製造されたメタンスルホン酸錫水溶液を、錫めっき液へ添加する工程、
を含む、錫めっき液へ錫イオンを補給する方法。
(8)
(7)に記載の錫イオンの補給方法によって、錫イオンが補給された錫めっき液を製造する方法。
(9)
Sn2+イオンとして存在する錫の含有量が、300~450g/Lの範囲にある、メタンスルホン酸錫水溶液。
(10)
メタンスルホン酸錫水溶液が、錫めっき液への錫イオン補給用メタンスルホン酸錫水溶液である、(9)に記載のメタンスルホン酸錫水溶液。
高濃度メタンスルホン酸錫溶液を調整するために、メタンスルホン酸水溶液中へ酸化第一錫粉末を投入して、溶解する操作を、以下のように条件を設定して行った。
酸化第一錫粉末として、市販の酸化第一錫粉末(JX金属商事株式会社製 HK0040 活性酸化第一錫)を用意した。
メタンスルホン酸水溶液として、市販のメタンスルホン酸水溶液(JX金属商事株式会社製、製品名:NSP-A700M、メタンスルホン酸濃度68質量%)を用意した。
調整する高濃度メタンスルホン酸錫溶液の液量を100mLとした。
目標とする高濃度の錫濃度(Sn2+イオン濃度)として、複数の濃度(例えば、300g/L)を設定した。
例えば、100mL中に錫濃度を300g/Lとするために必要となるSn量は、30gである。
例えば、100mL中に錫濃度を300g/Lとするために必要となる酸化第一錫粉末の質量はこれが湿潤品であってSn品位86%となる場合に、30.0g÷0.86=34.88→約34.9gとなる。
酸化第一錫(以下SnOと記す場合がある)は、メタンスルホン酸(CH3SO3H、)と、次のように反応して溶解する。
SnO+2CH3SO3H→Sn(CH3SO3)2+H2O
このように、SnO:MSA=1:2のモル比で、SnOはMSAへ溶解する。
例えば、錫量30gに対してMSA1.0倍とする場合、MSAの溶液の濃度が68%である場合に比重が1.38となり、錫原子量118.7、MSA分子量96.1であるから、MSAの溶液の投入量は、30.0g÷118.7×192.2÷1.38÷0.98×1.0=51.76mL→約51.8mLと算出される。
上記の手順によって算出された、投入すべき酸化第一錫粉末の各質量、使用されるべきMSAの液体の各体積に加えて、上記の目標とする各錫濃度を達成するためには、適宜、純水の添加が必要となった。この純水の添加にあたっては、100mLからMSAの液体の各体積を引いた値を、純水添加量の最大値の概算としていったん算出しておき、酸化第一錫の投入に先立って、使用される純水の大部分を予めMSAを液体へ混合して使用し、さらに酸化第一錫の投入後に最終的に100mLとなるようにメスアップして調整することで、反応後の溶液を所定の体積(100mL)とした。
所定の体積のMSAの液体へ、純水を適宜添加した後に自然冷却で約30℃とした。
このMSA水溶液へ、所定の質量の酸化第一錫粉末を順に添加しながら攪拌して、全体で3分間をかけて溶解した。この間の温度は約30~50℃の範囲へ維持されていた。黒色の酸化第一錫粉末が、全量溶解すれば、その時点で溶解終了時間とした。3分間をかけても溶解しなかった場合にも、さらに溶解操作を継続して、5分間の経過時に溶解操作の終了であることとした。
溶解操作の終了後に、メタンスルホン酸錫溶液(MSA-Sn溶液)を回収して、適宜純水を添加してメスアップし、規定液量(100mL)へと調整した。得られた規定液量のメタンスルホン酸錫溶液について、ヨウ素でんぷん反応による酸化還元滴定で錫濃度(Sn2+イオン濃度)を測定した。
例1で用いたメタンスルホン酸水溶液に代えて、より高濃度のメタンスルホン酸水溶液(富士フイルム和光純薬株式会社製、和光特級、メタンスルホン酸濃度98質量%)を使用して、MSA1.03倍となる条件で、同様に実験を行った。
例1及び例2の実験によって得られた結果を、図1~図7に示す。グラフの各点は、上記の手順によって設定した酸化第一錫粉末の使用量、メタンスルホン酸の使用量の組みあわせによる溶解実験によって得られた測定値を示している。図1~図7のグラフの横軸は、投入した酸化第一錫粉末の全量が溶解するとして計算した溶液中のSn2+イオン濃度[g/L]である。図1~図7のグラフの縦軸は、実際に得られた溶液を滴定して測定したSn2+イオン濃度[g/L]である。例えば、図1に記載されたMSA1.03倍とは、上述したメタンスルホン酸量においてMSA1.03倍量の場合を意味し、投入した酸化第一錫がメタンスルホン酸と反応してメタンスルホン酸錫となる場合の化学量論比から必要となるメタンスルホン酸のモル数に対して、1.03倍のモル数のメタンスルホン酸が使用された場合を意味する。MSA1.5倍、MSA2.0倍、MSA2.5倍、MSA3.0倍も同様である。図3に記載された98%MSA1.03倍とあるデータは、例2によって高濃度(98質量%)のメタンスルホン酸濃度で実験を行った場合の結果であり、特に記載のないデータは、いずれも例1によって実験を行った場合の結果である。図1~図7では、対比のために、比較例のデータについてはいずれも同内容を記載している。
40[g/L]程度にまで減少した。
Claims (10)
- 酸化第一錫をメタンスルホン酸水溶液中で溶解して、メタンスルホン酸錫水溶液を製造する方法であって、
酸化第一錫のモル数をAとし、メタンスルホン酸のモル数をBとした場合に、
B/2Aの値が、1.0~1.4の範囲にある、製造方法。 - 酸化第一錫が、酸化第一錫粉末である、請求項1に記載の製造方法。
- B/2Aの値が、1.01~1.4の範囲にある、請求項1~2のいずれかに記載の製造方法。
- メタンスルホン酸水溶液中へ、酸化第一錫粉末を投入して、攪拌して溶解することによって、メタンスルホン酸錫水溶液を製造する、請求項1~3のいずれかに記載の製造方法。
- 酸化第一錫が、メタンスルホン酸水溶液中へ全て溶解した場合に、Sn2+イオンとして存在する錫の含有量が、300~450g/Lの範囲である、請求項1~4のいずれかに記載の製造方法。
- 酸化第一錫のモル数Aが、溶解のために使用される酸化第一錫の全量のモル数であり、
メタンスルホン酸のモル数Bが、溶解のために使用されるメタンスルホン酸の全量のモル数である、請求項1~5のいずれかに記載の製造方法。 - 請求項1~6のいずれかに記載の製造方法によって製造されたメタンスルホン酸錫水溶液を、錫めっき液へ添加する工程、
を含む、錫めっき液へ錫イオンを補給する方法。 - 請求項7に記載の錫イオンの補給方法によって、錫イオンが補給された錫めっき液を製造する方法。
- Sn2+イオンとして存在する錫の含有量が、300~450g/Lの範囲にある、メタンスルホン酸錫水溶液。
- メタンスルホン酸錫水溶液が、錫めっき液への錫イオン補給用メタンスルホン酸錫水溶液である、請求項9に記載のメタンスルホン酸錫水溶液。
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