JP3401846B2 - Method for producing tin (II) hydroxide and method for producing plating solution containing tin ions - Google Patents
Method for producing tin (II) hydroxide and method for producing plating solution containing tin ionsInfo
- Publication number
- JP3401846B2 JP3401846B2 JP17649893A JP17649893A JP3401846B2 JP 3401846 B2 JP3401846 B2 JP 3401846B2 JP 17649893 A JP17649893 A JP 17649893A JP 17649893 A JP17649893 A JP 17649893A JP 3401846 B2 JP3401846 B2 JP 3401846B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- hydroxide
- aqueous solution
- solution
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は水酸化錫（II）の製造方
法及びそれを利用した錫イオン含有メッキ液の製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing tin (II) hydroxide and a method for producing a tin ion-containing plating solution using the same.
【０００２】[0002]
【従来の技術】従来、電気錫メッキ浴として硫酸錫浴な
どの酸性浴が採用されているが、その錫(II)イオン供給
源としては、通常、硫酸錫が採用されている。2. Description of the Related Art Conventionally, an acid bath such as a tin sulfate bath has been adopted as an electric tin plating bath, but tin sulfate is usually adopted as a tin (II) ion supply source.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、錫(II)
イオンは酸性液中でも酸化し易いため時間の経過と共
に、錫(IV)イオンとなり、電気メッキしても金属錫とし
て析出しなくなるという問題がある。また、ハンダメッ
キする場合、浴中にＰb2+イオンとＳn2+を共存させる必
要があるが、錫(II)イオンの供給源として硫酸錫を用い
ると、硫酸基が多量に混入する結果、浴中のＰbイオン
が硫酸鉛として析出、沈澱するという問題があった。こ
れらの問題を避けるためには、錫(II)イオン供給源とし
て水酸化錫（II）を使用することが考えられるが、保存
中に水酸化錫（II）が酸化するという問題があるため市
販されていず、また、水酸化錫（II）を希酸に溶解した
だけでは、錫(II)イオンの酸化を防止できないという問
題があった。他方、水酸化第１錫を酸化第１錫に変換し
て錫メッキ浴の錫イオン供給源として使用する方法が提
案されている。例えば、特開平３−２２３１１２号公報
には、第１錫塩の酸性水溶液と水酸化アルカリ水溶液と
をｐＨ１１〜１２.５の範囲で混合して反応させ、反応
進行中に炭酸アルカリ水溶液を前記水酸化アルカリ水溶
液の２〜１０％添加する方法が開示されている。また、
特開昭６０−２２１３１９号公報には、第１錫塩の酸性
水溶液と炭酸ナトリウム水溶液とをｐＨ６.５〜８.４、
温度７０〜８５の範囲で混合して反応させた後、その反
応液を前記条件下で攪はんする方法が開示されている。
これらの方法で製造された酸化第１錫は、無機酸及び有
機酸に易溶性で,耐酸化性において比較的改善されては
いるが、メッキ浴にした場合の耐酸化性において問題が
あることが明かとなった。[Problems to be Solved by the Invention] However, tin (II)
Since the ions are easily oxidized even in an acidic liquid, they become tin (IV) ions with the passage of time, and there is a problem that they do not precipitate as metallic tin even when electroplating. Further, in the case of solder plating, it is necessary to make Pb 2+ ions and Sn 2+ coexist in the bath. However, when tin sulfate is used as a source of tin (II) ions, a large amount of sulfate groups are mixed in, There was a problem that Pb ions in the bath were precipitated and precipitated as lead sulfate. In order to avoid these problems, it is possible to use tin (II) hydroxide as a tin (II) ion source, but there is a problem that tin (II) hydroxide oxidizes during storage, so it is commercially available. However, there is a problem that the oxidation of tin (II) ions cannot be prevented only by dissolving tin (II) hydroxide in a dilute acid. On the other hand, there has been proposed a method of converting stannous hydroxide into stannous oxide and using it as a tin ion source for a tin plating bath. For example, in JP-A-3-223112, an acidic aqueous solution of stannous salt and an aqueous alkali hydroxide solution are mixed and reacted in a pH range of 11 to 12.5, and an aqueous solution of alkali carbonate is added to the aqueous solution while the reaction is in progress. A method of adding 2 to 10% of an alkali oxide aqueous solution is disclosed. Also,
JP-A-60-221319 discloses that an acidic aqueous solution of stannous salt and an aqueous sodium carbonate solution have a pH of 6.5 to 8.4,
A method is disclosed in which after mixing and reacting at a temperature in the range of 70 to 85, the reaction solution is stirred under the above conditions.
The stannous oxide produced by these methods is easily soluble in inorganic and organic acids and has relatively improved oxidation resistance, but it has a problem in oxidation resistance when used as a plating bath. Became clear.
【０００４】従って、本発明は、硫酸錫を原料として硫
酸基を含有しない水酸化錫（II）を得ると共に、メッキ
浴の保存中に錫(II)イオンの酸化やＰbイオンの析出を
生じることがないようにすることを目的とするものであ
る。Therefore, according to the present invention, tin (II) hydroxide containing no sulfate group is obtained from tin sulfate as a raw material, and tin (II) ions are oxidized or Pb ions are precipitated during storage of the plating bath. The purpose is to ensure that there is no.
【０００５】[0005]
【課題を解決するための手段】本発明は、前記目的を達
成するための手段として、錯化剤を含む硫酸第１錫の水
溶液にアルカリ又は水酸化鉛を添加して反応させ、生成
した水酸化錫（II）を固形分又は溶液として固液分離す
るようにしたものである。[Means for Solving the Problems] As a means for achieving the above object, the present invention provides water produced by adding an alkali or lead hydroxide to an aqueous solution of stannous sulfate containing a complexing agent to cause a reaction. This is a solid-liquid separation of tin (II) oxide as a solid content or solution.
【０００６】また、本発明は、長期保存を可能にするた
め、固形分として得られた水酸化錫（II）は水洗後、錯
化剤の水溶液に溶解する一方、溶液として得られた水酸
化錫（II）はそのまま又は錯化剤水溶液で希釈すること
により、要すれば、その水溶液に水酸化鉛を添加してメ
ッキ浴又はメッキ浴原液とするようにしたものである。Further, according to the present invention, in order to enable long-term storage, tin (II) hydroxide obtained as a solid content is washed with water and then dissolved in an aqueous solution of a complexing agent, while a hydroxide obtained as a solution is obtained. Tin (II) is used as it is or by diluting it with an aqueous solution of a complexing agent, and if necessary, adding lead hydroxide to the aqueous solution to prepare a plating bath or a plating bath stock solution.
【０００７】前記錯化剤としては、クエン酸、グルコン
酸、グルコノヘプトン酸、グルコノラクトン、グルコノ
ヘプトノラクトンからなる群から選ばれた少なくとも一
種を使用すれば良い。また、前記アルカリとしては、狭
義のアルカリ、即ち、アルカリ金属の水酸化物及び水酸
化アンモニウムのみならず、炭酸ナトリウム、炭酸カル
シウム、炭酸アンモニウムなどを含み、水に溶解した
際、アルカリ性を呈するものであれば任意の金属の水酸
化物、炭酸塩を使用できる。As the complexing agent, at least one selected from the group consisting of citric acid, gluconic acid, gluconoheptonic acid, gluconolactone and gluconoheptonolactone may be used. Further, as the alkali, in the narrow sense, that is, not only alkali metal hydroxides and ammonium hydroxides, but also sodium carbonate, calcium carbonate, ammonium carbonate and the like, which exhibits alkalinity when dissolved in water. Any metal hydroxide or carbonate can be used as long as it is present.
【０００８】[0008]
【作用】硫酸錫と錯塩化剤とを水に溶解し、その水溶液
にアンモニア水、炭酸ナトリウム溶液、水酸化ナトリウ
ム、水酸化カリウムなどのアルカリ水溶液又は水酸化鉛
を加えると、水酸化錫（II）が析出する。これを固液分
離して得た水酸化錫（II）を十分に水洗することにより
硫酸根を含まない水酸化錫（II）が得られる。これを錯
化剤水溶液に溶解すると、錯塩を形成して錫イオンの酸
化が防止され、安定した錫(II)イオン含有液が得られ
る。この錫(II)イオン含有液は、そのまま又は希釈して
錫メッキ浴として用いることができるほか、更に水酸化
鉛を添加することによりハンダメッキ浴として用いるこ
とができる。[Function] When tin sulfate and a complex chlorinating agent are dissolved in water and an aqueous solution of ammonia, an aqueous solution of sodium carbonate, an aqueous solution of sodium hydroxide, potassium hydroxide or the like or lead hydroxide is added, tin hydroxide (II ) Is deposited. The tin (II) hydroxide obtained by solid-liquid separation is thoroughly washed with water to obtain tin (II) hydroxide containing no sulfate group. When this is dissolved in a complexing agent aqueous solution, a complex salt is formed to prevent oxidation of tin ions, and a stable tin (II) ion-containing liquid is obtained. This tin (II) ion-containing solution can be used as it is or after dilution as a tin plating bath, and can be used as a solder plating bath by further adding lead hydroxide.
【０００９】なお、アルカリ水溶液として、アンモニア
水を使用した場合、刺激臭があるため、作業場がドラフ
ト内に限定される他、生成した水酸化錫（II）が微細で
あるため、ろ過が困難で遠心分離法により固液分離しな
ければならず、また、反復して水洗しなければならない
為、製造に長時間を要しコスト上昇の原因となるが、こ
れらの問題は、アンモニア水に代えて水酸化ナトリウ
ム、水酸化カリウム、又は水酸化鉛をアルカリ水溶液と
して採用することにより解決され、作業場の制限を受け
たり遠心分離器を使用する必要性も無くなり、作業時間
が短縮される。When ammonia water is used as the alkaline aqueous solution, the work place is limited to the draft because it has an irritating odor, and the tin (II) hydroxide produced is fine, making filtration difficult. Since solid-liquid separation must be carried out by a centrifugal separation method and repeated washing with water results in a long production time and a cost increase, these problems can be solved by replacing ammonia water. This is solved by adopting sodium hydroxide, potassium hydroxide, or lead hydroxide as the alkaline aqueous solution, and the working time is shortened because the work place is not restricted and the necessity of using a centrifuge is eliminated.
【００１０】[0010]
【実施例１】硫酸錫２００gとクエン酸５gを純水２リッ
トルに溶解し、これにアンモニア水１リットルを加えて
十分に撹拌した後、反応液を４本の分離管に７５０mlづ
つ入れて遠心分離機で固液分離し、その上澄み液を排出
する。次いで、各分離管内の固形分に純水３００mlを加
えて撹拌し、再度遠心分離機にかけて固液分離した後、
その上澄み液を排出する操作を２回反復して硫酸根を除
去し、更に各分離管内の固形分に２５重量％クエン酸水
溶液４００mlを加えて撹拌し、錫(II)イオン含有液を得
る。各分離管内の錫(II)イオン含有液を順次６０００ml
の２５重量％クエン酸水溶液に加えて稀釈し、錫メッキ
浴を得た。Example 1 200 g of tin sulfate and 5 g of citric acid were dissolved in 2 liters of pure water, 1 liter of ammonia water was added thereto, and the mixture was sufficiently stirred, and then the reaction solution was put in four separation tubes, 750 ml each, and centrifuged. Solid-liquid separation is performed with a separator, and the supernatant liquid is discharged. Then, add 300 ml of pure water to the solid content in each separation tube, stir, and centrifuge again to perform solid-liquid separation,
The operation of discharging the supernatant liquid is repeated twice to remove sulfate radicals, and 400 ml of a 25 wt% aqueous citric acid solution is added to the solid content in each separation tube and stirred to obtain a tin (II) ion-containing liquid. 6000 ml of tin (II) ion-containing liquid in each separation tube
25% by weight citric acid aqueous solution and diluted to obtain a tin plating bath.
【００１１】この錫メッキ浴８０００mlに水酸化鉛５g
と光沢剤(多価アミン、アルデヒド及びカルボン酸の合
成物)６０mlを添加してハンダメッキ浴を調製した。5 g of lead hydroxide is added to 8000 ml of this tin plating bath.
And 60 ml of a brightener (a compound of polyvalent amine, aldehyde and carboxylic acid) were added to prepare a solder plating bath.
【００１２】このハンダメッキ浴を用い、９０重量％Ｓ
n−１０重量％Ｐb合金からなる電極を陽極として、０.
５Ａ／dm2の電流密度で黄銅上に約４０分メッキしたと
ころ、９０重量％Ｓn−１０重量％Ｐbのハンダ組成の良
好なメッキ皮膜が得られた。メッキ中、メッキ浴の状態
は変化せず、また、従来のメッキ浴と異なり、鉛の優先
析出が抑制され、光沢あるメッキ浴皮膜が得られた。Using this solder plating bath, 90 wt% S
Using an electrode made of an n-10 wt% Pb alloy as an anode,
When a brass was plated at a current density of 5 A / dm 2 for about 40 minutes, a plated film having a solder composition of 90 wt% Sn-10 wt% Pb was obtained. During plating, the state of the plating bath did not change, and unlike the conventional plating bath, preferential deposition of lead was suppressed and a bright plating bath film was obtained.
【００１３】[0013]
【実施例２】硫酸第１錫５０gとグルコン酸１０gを混合
し、これらを純水に溶解して全量を４００ｍｌとし、そ
の水溶液に水酸化カリウム２６ｇを加えて十分に反応さ
せる。その反応液をろ過し、水酸化錫（II）の沈澱物と
硫酸カリウム水溶液とに分離する。得られた水酸化錫
（II）を、０.６モル／ｌ濃度のグルコノ−１、５−ラ
クトン水溶液４００mlに溶解して、錫(II)イオン含有液
を得た。Example 2 50 g of stannous sulfate and 10 g of gluconic acid were mixed and dissolved in pure water to make a total amount of 400 ml, and 26 g of potassium hydroxide was added to the aqueous solution to sufficiently react. The reaction solution is filtered and separated into a tin (II) hydroxide precipitate and an aqueous potassium sulfate solution. The obtained tin (II) hydroxide was dissolved in 400 ml of an aqueous solution of glucono-1,5-lactone having a concentration of 0.6 mol / l to obtain a tin (II) ion-containing liquid.
【００１４】[0014]
【実施例３】硫酸第１錫５０gとグルコヘプトノ−１、
４−ラクトン３gを混合し、これらを純水に溶解して全
量を４００ｍｌとし、その水溶液に水酸化ナトリウム１
８.６４ｇを加えて十分に反応させた後、ろ過し、水酸
化錫（II）からなる固形分と硫酸ナトリウム水溶液とに
分離する。得られた水酸化錫（II）を１.０モル／ｌ濃
度のグルコヘプトノ−１、４−ラクトン水溶液６００ml
に溶解して、錫(II)イオン含有液を得た。Example 3 50 g of stannous sulfate and glucoheptono-1,
3 g of 4-lactone was mixed and dissolved in pure water to make the total volume 400 ml.
After adding 8.64 g and making it fully react, it filters and isolate | separates into the solid content which consists of tin (II) hydroxide, and sodium sulfate aqueous solution. The obtained tin (II) hydroxide was added to 600 ml of a 1.0 mol / l concentration glucoheptono-1,4-lactone aqueous solution.
To obtain a tin (II) ion-containing liquid.
【００１５】[0015]
【実施例４】硫酸第１錫５０gとグルコノ−１、５−ラ
クトン２０gを混合し、これらを純水に溶解して全量を
５００ｍｌとし、その水溶液に水酸化鉛１０８ｇを加え
て十分に反応させた後、ろ過し、水酸化錫（II）溶液と
硫酸鉛からなる固形分とに分離する。得られた水酸化錫
（II）溶液に１.５モル／ｌ濃度のグルコノ−１、５−
ラクトン水溶液８００mlを加えて錫(II)イオン含有液を
得た。ちなみに、実施例１の場合、錫(II)イオン含有液
の調製までに６０分を要したのに対して、実施例２〜実
施例４の方法では、いずれも３０分であった。Example 4 50 g of stannous sulfate and 20 g of glucono-1,5-lactone were mixed and dissolved in pure water to a total volume of 500 ml, and 108 g of lead hydroxide was added to the aqueous solution for sufficient reaction. After that, it is filtered and separated into a tin (II) hydroxide solution and a solid content composed of lead sulfate. Glucono-1,5-concentration of 1.5 mol / l was added to the obtained tin (II) hydroxide solution.
800 ml of an aqueous lactone solution was added to obtain a tin (II) ion-containing liquid. By the way, in the case of Example 1, it took 60 minutes to prepare the tin (II) ion-containing liquid, whereas in the methods of Examples 2 to 4, it was 30 minutes in all cases.
【００１６】[0016]
【発明の効果】以上の説明から明らかなように、本発明
によれば、硫酸第１錫を原料とし、これを錯化剤水溶液
に溶解し、その溶液にアルカリ又は水酸化鉛を添加し
て、水酸化錫（II）を生成させ、これを固液分離するよ
うにしたので、硫酸基を含まない水酸化錫（II）を得る
ことができる。また、この水酸化錫（II）を錯化剤の存
在下で水溶液として保存する、即ち、錯塩の形態で存在
させるようにしたので、錫(II)イオンの酸化を防止で
き、長期に渡って錫(II)イオン含有液として保存、使用
することができる。更に、錫(II)イオン含有液に鉛イオ
ンを共存させたメッキ浴、即ち、ハンダメッキ浴とした
場合でも、硫酸鉛の沈澱を生じることがなく、組成比通
りのハンダメッキ皮膜を形成することができる。しか
も、硫酸基を除去するための添加剤として水酸化ナトリ
ウム、水酸化カリウム又は水酸化鉛を使用することによ
り、遠心分離器を使用すること無く容易に固液分離でき
ると同時に、水酸化錫（II）の製造に要する時間を短縮
できるという優れた効果が得られる。As is apparent from the above description, according to the present invention, stannous sulfate is used as a raw material, this is dissolved in an aqueous solution of a complexing agent, and alkali or lead hydroxide is added to the solution. , Tin (II) hydroxide was generated and solid-liquid separated, so that tin (II) hydroxide containing no sulfate group can be obtained. Further, since this tin (II) hydroxide is stored as an aqueous solution in the presence of a complexing agent, that is, it is made to exist in the form of a complex salt, it is possible to prevent the oxidation of tin (II) ions and to maintain it for a long time. It can be stored and used as a liquid containing tin (II) ions. Further, even when a plating bath in which lead ions coexist in a tin (II) ion-containing liquid, that is, a solder plating bath, lead sulfate is not precipitated and a solder plating film having a composition ratio is formed. You can Moreover, by using sodium hydroxide, potassium hydroxide or lead hydroxide as an additive for removing the sulfate group, solid-liquid separation can be easily performed without using a centrifuge, and at the same time tin hydroxide ( The excellent effect that the time required for the production of II) can be shortened is obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−195101（ＪＰ，Ａ) 特開 昭53−1698（ＪＰ，Ａ) 特開 平３−223112（ＪＰ，Ａ) 特開 昭61−83626（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 1/00 - 23/08 C25D 3/30 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-195101 (JP, A) JP-A-53-1698 (JP, A) JP-A-3-223112 (JP, A) JP-A 61- 83626 (JP, A) (58) Fields surveyed (Int.Cl. 7 , DB name) C01G 1/00-23/08 C25D 3/30
Claims (8)
カリ又は水酸化鉛を添加して反応させ、生成した水酸化
錫（II）を固液分離することを特徴とする水酸化錫（I
I）の製造方法。1. A tin hydroxide characterized in that an alkali or lead hydroxide is added to an aqueous solution of stannous sulfate containing a complexing agent to cause a reaction, and the resulting tin (II) hydroxide is subjected to solid-liquid separation. (I
I) Manufacturing method.
ルコヘプトン酸、グルコノラクトン、グルコノヘプトノ
ラクトンからなる群から選ばれた少なくとも一種である
請求項１記載の水酸化錫（II）の製造方法。2. The tin (II) hydroxide according to claim 1, wherein the complexing agent is at least one selected from the group consisting of citric acid, gluconic acid, glucoheptonic acid, gluconolactone and gluconoheptonolactone. Manufacturing method.
し、生成した水酸化錫（II）を固形分として固液分離し
た後、水洗する請求項１又は請求項２記載の方法。3. The method according to claim 1 or 2, wherein ammonia water is added as the alkali, the produced tin (II) hydroxide is solid-liquid separated as a solid content, and then washed with water.
水酸化カリウム、水酸化ナトリウムからなる群から選ば
れた一種の水酸化物の水溶液を添加し、生成した水酸化
錫（II）を固形分として固液分離した後、水洗する請求
項１又は請求項２記載の方法。4. The alkali is calcium carbonate,
An aqueous solution of one kind of hydroxide selected from the group consisting of potassium hydroxide and sodium hydroxide is added, and the formed tin (II) hydroxide is subjected to solid-liquid separation as solid content, followed by washing with water. Item 2. The method according to Item 2.
水酸化鉛を添加して反応させ、生成した水酸化錫（II）
を溶液として固液分離する請求項１又は請求項２記載の
方法。5. Tin (II) hydroxide produced by adding lead hydroxide to an aqueous solution of stannous sulfate containing the complexing agent and reacting the solution.
The method according to claim 1 or 2, wherein the solid is separated as a solution.
法で得られる固形の水酸化錫（II）を錯化剤水溶液に溶
解することを特徴とする錫イオン含有メッキ液の製造方
法。6. A tin ion-containing plating solution, characterized in that solid tin (II) hydroxide obtained by the method according to claim 1 is dissolved in an aqueous solution of a complexing agent. Method.
に水酸化鉛を溶解することを特徴とする請求項６記載の
方法。7. The method according to claim 6, wherein lead hydroxide is dissolved in a complexing agent aqueous solution in which tin (II) hydroxide is dissolved.
（II）溶液を錯化剤水溶液で希釈することを特徴とする
錫イオン含有メッキ液の製造方法。8. A method for producing a tin ion-containing plating solution, which comprises diluting the tin (II) hydroxide solution obtained by the method of claim 5 with a complexing agent aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17649893A JP3401846B2 (en) | 1993-01-08 | 1993-07-16 | Method for producing tin (II) hydroxide and method for producing plating solution containing tin ions |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-1768 | 1993-01-08 | ||
| JP176893 | 1993-01-08 | ||
| JP17649893A JP3401846B2 (en) | 1993-01-08 | 1993-07-16 | Method for producing tin (II) hydroxide and method for producing plating solution containing tin ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256017A JPH06256017A (en) | 1994-09-13 |
| JP3401846B2 true JP3401846B2 (en) | 2003-04-28 |
Family
ID=26335051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17649893A Expired - Lifetime JP3401846B2 (en) | 1993-01-08 | 1993-07-16 | Method for producing tin (II) hydroxide and method for producing plating solution containing tin ions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3401846B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591266B (en) * | 2014-12-31 | 2016-08-24 | 柳州百韧特先进材料有限公司 | The method extending stannous sulfate shelf life of products |
| CN113184897A (en) * | 2021-06-15 | 2021-07-30 | 江苏好山水环保科技有限公司 | Method for preparing tin hydroxide by using tin-containing waste liquid |
-
1993
- 1993-07-16 JP JP17649893A patent/JP3401846B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06256017A (en) | 1994-09-13 |
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