JPH04276082A - Analysis of copper ion concentration in bath for electroless plating of tin, lead, or those alloy - Google Patents
Analysis of copper ion concentration in bath for electroless plating of tin, lead, or those alloyInfo
- Publication number
- JPH04276082A JPH04276082A JP3059643A JP5964391A JPH04276082A JP H04276082 A JPH04276082 A JP H04276082A JP 3059643 A JP3059643 A JP 3059643A JP 5964391 A JP5964391 A JP 5964391A JP H04276082 A JPH04276082 A JP H04276082A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- lead
- tin
- plating bath
- thiourea
- 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.)
- Granted
Links
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 57
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 7
- 239000000956 alloy Substances 0.000 title claims abstract description 7
- 238000007772 electroless plating Methods 0.000 title abstract description 11
- 238000004458 analytical method Methods 0.000 title description 11
- 238000007747 plating Methods 0.000 claims abstract description 70
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 56
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000004737 colorimetric analysis Methods 0.000 claims abstract description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 7
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 18
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 18
- 229910001174 tin-lead alloy Inorganic materials 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000007726 management method Methods 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- LLABTCPIBSAMGS-UHFFFAOYSA-L lead(2+);methanesulfonate Chemical compound [Pb+2].CS([O-])(=O)=O.CS([O-])(=O)=O LLABTCPIBSAMGS-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 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 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Chemically Coating (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、銅又は銅合金に対し無
電解錫、鉛又はそれらの合金めっきを施すめっき浴中の
銅イオン濃度の分析方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for analyzing copper ion concentration in a plating bath for electroless tin, lead, or alloy plating of copper or copper alloys.
【0002】0002
【従来の技術及び発明が解決しようとする課題】従来、
電子工業用部品、回路等の銅又は銅合金部分にはんだ付
け性を付与するため、電気めっき法により錫、鉛又は錫
・鉛合金めっき皮膜を形成することが行なわれているが
、電子装置の小型化に伴なって部品や回路等も微小化又
は複雑化し、電気めっき法ではめっきできない部分も生
じている。そこで、これらの部分にもめっき可能な無電
解錫、鉛又は錫・鉛合金めっき法が検討されている。
例えば、特開平1−184279号公報には、特定の有
機スルホン酸、該有機スルホン酸の錫及び鉛塩、次亜燐
酸ナトリウム(還元剤)及びチオ尿素(錯化剤)を主成
分とする無電解錫・鉛合金めっき浴を用いる方法が提案
されている。しかし、従来の無電解錫、鉛又は錫・鉛合
金めっき法は、めっき浴の金属補給を行なわず、金属濃
度が析出限界以下に低下したらそのまま廃棄する使い捨
てのバッチ方式が多く、このため主にめっき皮膜を薄く
形成する場合に採用されているもので、厚いめっき皮膜
を得る目的でめっき浴を連続使用する提案は殆んどなく
、従って連続使用に必要な連続的に一定の析出量を維持
できるめっき浴の補給管理方法については提案されてい
ない。[Prior art and problems to be solved by the invention] Conventionally,
In order to impart solderability to copper or copper alloy parts of electronic industrial parts, circuits, etc., tin, lead, or tin-lead alloy plating films are formed by electroplating. With miniaturization, components, circuits, etc. have also become smaller or more complex, and there are some areas that cannot be plated using electroplating. Therefore, electroless tin, lead or tin-lead alloy plating methods, which can also plate these parts, are being considered. For example, JP-A-1-184279 discloses a specific organic sulfonic acid, tin and lead salts of the organic sulfonic acid, sodium hypophosphite (reducing agent), and thiourea (complexing agent). A method using an electrolytic tin/lead alloy plating bath has been proposed. However, conventional electroless tin, lead or tin-lead alloy plating methods do not require metal replenishment in the plating bath, and are often disposable batch methods in which the metal concentration drops below the precipitation limit and is discarded as is. This is used when forming a thin plating film, and there are almost no proposals for continuous use of the plating bath for the purpose of obtaining a thick plating film, therefore, maintaining a constant amount of deposit continuously required for continuous use. No proposal has been made regarding a possible plating bath replenishment management method.
【0003】一方、通常の無電解めっき法においては、
随時、めっき浴中の金属成分を分析し、消費された金属
量に比例して金属成分の補給を行なうことにより、めっ
き浴を管理しているが、本発明者らの検討によれば、無
電解錫、鉛又は錫・鉛合金めっき浴の場合は、めっきの
進行と共に被めっき物から溶出した銅がめっき浴中に溶
解、蓄積していくため、めっき浴中で錫及び鉛成分を簡
易にしかも正確に分析することが困難であり、上述した
通常のめっき浴管理方法は無電解錫、鉛又は錫・鉛合金
めっき浴に対しては適用し難いことを知見した。従って
、無電解錫、鉛又は錫・鉛合金めっき浴を容易にかつ確
実に管理できる分析方法を確立することが望まれる。On the other hand, in the usual electroless plating method,
The plating bath is managed by analyzing the metal components in the plating bath from time to time and replenishing the metal components in proportion to the amount of metal consumed. In the case of electrolytic tin, lead, or tin-lead alloy plating baths, as the plating progresses, the copper eluted from the object to be plated dissolves and accumulates in the plating bath, so tin and lead components can be easily removed in the plating bath. Moreover, it is difficult to analyze accurately, and it has been found that the above-mentioned normal plating bath management method is difficult to apply to electroless tin, lead, or tin-lead alloy plating baths. Therefore, it is desired to establish an analysis method that can easily and reliably control electroless tin, lead, or tin-lead alloy plating baths.
【0004】本発明は上記事情に鑑みなされたもので、
無電解錫、鉛又は錫・鉛合金めっき浴中の銅イオン濃度
を容易にかつ正確に分析することができ、このため無電
解錫、鉛又はそれらの合金めっき浴を容易にかつ確実に
管理することができる無電解錫、鉛又は錫・鉛合金めっ
き浴中の銅イオン濃度分析方法を提供することを目的と
する。[0004] The present invention has been made in view of the above circumstances.
The copper ion concentration in electroless tin, lead, or tin/lead alloy plating baths can be easily and accurately analyzed, and therefore electroless tin, lead, or their alloy plating baths can be easily and reliably managed. An object of the present invention is to provide a method for analyzing copper ion concentration in an electroless tin, lead or tin-lead alloy plating bath.
【0005】[0005]
【課題を解決するための手段及び作用】本発明者らは、
上記目的を達成するため種々検討を重ねた結果、銅又は
銅合金用無電解錫、鉛又は錫・鉛合金めっき浴において
は、被めっき物の銅又は銅合金の銅分がめっき浴に溶解
すると同時に錫、鉛又は錫・鉛合金めっき皮膜が析出形
成されるものであり、従ってめっきの進行につれてめっ
き浴中に銅分が蓄積、増加してくるものであるが、この
場合上記溶出銅イオン量と消費される錫及び/又は鉛量
との間に比例関係が存在し、従って溶出銅イオン濃度の
分析結果に基づいて水溶性錫塩及び/又は水溶性鉛塩を
補給することにより、上記無電解めっき浴の管理も容易
にかつ確実に行なうことが可能であることを見出した。
このため、かかる無電解めっき浴中の銅イオン濃度を簡
易にしかも正確に分析する方法につき検討した結果、水
溶性錫塩及び/又は水溶性鉛塩、これらの塩を溶解する
酸、及び錯化剤としてチオ尿素を含む銅又は銅合金用無
電解めっき浴において、溶出銅イオン濃度を分析する場
合、まず浴中のチオ尿素を酸化分解すると共に、1価の
銅イオンを2価の銅イオンに酸化し、この酸化した銅イ
オンを含む全2価の銅イオン濃度を比色法を適用して分
析することにより、めっき浴中の銅イオン濃度が正確に
しかも簡単に定量できることを知見した。[Means and effects for solving the problem] The present inventors have
As a result of various studies to achieve the above objective, we found that in electroless tin, lead or tin-lead alloy plating baths for copper or copper alloys, the copper content of the copper or copper alloy to be plated dissolves in the plating bath. At the same time, a tin, lead, or tin-lead alloy plating film is precipitated and formed, and therefore, as plating progresses, copper content accumulates and increases in the plating bath, but in this case, the above-mentioned amount of eluted copper ions Therefore, by replenishing water-soluble tin salt and/or water-soluble lead salt based on the analysis results of the eluted copper ion concentration, the above-mentioned substances can be reduced. It has been found that the electrolytic plating bath can be easily and reliably controlled. Therefore, as a result of studying a method for easily and accurately analyzing the copper ion concentration in such an electroless plating bath, we found that water-soluble tin salts and/or water-soluble lead salts, acids that dissolve these salts, and complexing When analyzing the concentration of eluted copper ions in an electroless plating bath for copper or copper alloys that contains thiourea as an agent, first thiourea in the bath is oxidized and decomposed, and monovalent copper ions are converted to divalent copper ions. It has been found that the concentration of copper ions in a plating bath can be accurately and easily quantified by oxidizing and analyzing the concentration of all divalent copper ions including the oxidized copper ions using a colorimetric method.
【0006】即ち、上述したように、無電解錫、鉛又は
錫・鉛合金めっきにおいては、めっきの進行につれて被
めっき物から銅が溶出、蓄積してくるが、この場合、本
発明者らの検討によると、上記めっき浴中の銅はチオ尿
素に錯化された状態で存在し、また一部は2価の銅イオ
ンとして存在するが、多くは1価の銅イオンとして存在
する。このような存在状態の銅イオン濃度は原子吸光分
析法等により全銅量を定量することができるものの、本
発明者らはめっき工場現場で簡易に分析を行なう点から
比色法を検討したが、そのままでは良好な比色分析がで
きず、このため更に検討を重ねた結果、上記めっき液に
過酸化水素や亜鉛素酸塩等のチオ尿素を分解可能な酸化
剤を加えてチオ尿素を分解し、更に1価の銅イオンを2
価の銅イオンに酸化した後、比色分析を行なうと、正確
の全銅イオンを定量し得ること、そしてこの全銅イオン
が錫や鉛塩の補給の目安になることを知見し、本発明を
なすに至ったものである。That is, as mentioned above, in electroless tin, lead or tin-lead alloy plating, copper is eluted from the object to be plated and accumulates as the plating progresses. According to studies, the copper in the plating bath is present in a complexed state with thiourea, and some of it is present as divalent copper ions, but most of it is present as monovalent copper ions. Although the concentration of copper ions in this state can be determined by atomic absorption spectrometry, etc., the total amount of copper can be determined, however, the present inventors have considered a colorimetric method for easy analysis at the plating factory site. , it was not possible to perform a good colorimetric analysis as it was, so after further investigation, we added an oxidizing agent that can decompose thiourea, such as hydrogen peroxide or zincate, to the above plating solution to decompose thiourea. and further add 2 monovalent copper ions.
It was discovered that by performing colorimetric analysis after oxidizing to valent copper ions, it was possible to accurately quantify total copper ions, and that this total copper ion could be used as a guide for replenishing tin and lead salts. This is what we have come to do.
【0007】従って、本発明は、水溶性錫塩及び/又は
水溶性鉛塩、これらの塩を溶解する酸、及びチオ尿素を
含む銅又は銅合金用無電解錫、鉛又は錫・鉛合金めっき
浴中の銅イオン濃度を分析する方法において、上記めっ
き浴にチオ尿素を分解可能な酸化剤を加えて該めっき浴
中のチオ尿素を酸化分解すると共に、1価の銅イオンを
2価の銅イオンに酸化し、この酸化した銅イオンを含む
全2価の銅イオン濃度を比色法で測定することを特徴と
する無電解錫、鉛又はそれらの合金めっき浴中の銅イオ
ン濃度の分析方法を提供する。Therefore, the present invention provides electroless tin, lead or tin-lead alloy plating for copper or copper alloys containing water-soluble tin salts and/or water-soluble lead salts, acids that dissolve these salts, and thiourea. In the method of analyzing the copper ion concentration in a bath, an oxidizing agent capable of decomposing thiourea is added to the plating bath to oxidize and decompose the thiourea in the plating bath, and monovalent copper ions are converted to divalent copper. A method for analyzing the concentration of copper ions in an electroless tin, lead or alloy plating bath, characterized by oxidizing to ions and measuring the concentration of all divalent copper ions including the oxidized copper ions using a colorimetric method. I will provide a.
【0008】以下、本発明につき更に詳述すると、本発
明において、分析対象となるめっき浴は、無電解錫、鉛
又はそれらの合金めっき浴であり、水溶性錫塩及び/又
は水溶性鉛塩、これらの塩を溶解する酸、及び錯化剤と
してチオ尿素を含むものが使用される。[0008] The present invention will be described in more detail below. In the present invention, the plating bath to be analyzed is an electroless tin, lead, or alloy plating bath thereof, and water-soluble tin salt and/or water-soluble lead salt. , acids that dissolve these salts, and thiourea as a complexing agent are used.
【0009】上記無電解めっき浴に用いられる水溶性錫
塩としては、例えば硫酸第1錫、アルカンスルホン酸第
1錫、塩化第1錫、アルカノールスルホン酸第1錫、ス
ルホコハク酸第1錫等が挙げられる。また、水溶性鉛塩
としては、例えば塩化鉛、アルカンスルホン酸鉛、酢酸
鉛、アルカノールスルホン酸鉛等等が挙げられる。これ
ら金属塩成分の含有量は通常0.5〜30g/l、特に
1〜20g/lである。酸成分としては、例えばアルカ
ンスルホン酸、塩酸、アルカノールスルホン酸、過塩素
酸、ホウフッ酸、スルホコハク酸等が挙げられる。これ
ら酸成分の含有量は通常50〜250g/l、特に10
0〜200g/lである。また、チオ尿素の含有量は通
常30〜200g/l、特に50〜100g/lである
。Examples of water-soluble tin salts used in the electroless plating bath include stannous sulfate, stannous alkanesulfonate, stannous chloride, stannous alkanolsulfonate, and stannous sulfosuccinate. Can be mentioned. Examples of water-soluble lead salts include lead chloride, lead alkanesulfonate, lead acetate, lead alkanolsulfonate, and the like. The content of these metal salt components is usually 0.5 to 30 g/l, particularly 1 to 20 g/l. Examples of the acid component include alkanesulfonic acid, hydrochloric acid, alkanolsulfonic acid, perchloric acid, borofluoric acid, and sulfosuccinic acid. The content of these acid components is usually 50 to 250 g/l, especially 10
It is 0 to 200 g/l. Further, the content of thiourea is usually 30 to 200 g/l, particularly 50 to 100 g/l.
【0010】なお、上記無電解めっき浴中には、通常還
元剤として次亜リン酸又はその水溶性塩が30〜300
g/l、特に50〜200g/l配合され得るが、更に
EDTA、クエン酸等も添加され得る。なお、めっき浴
のpHは通常0〜3、特に0.5〜2.5である。[0010] The electroless plating bath usually contains 30 to 300% hypophosphorous acid or a water-soluble salt thereof as a reducing agent.
g/l, especially 50 to 200 g/l, and EDTA, citric acid, etc. may also be added. Note that the pH of the plating bath is usually 0 to 3, particularly 0.5 to 2.5.
【0011】而して、上記無電解めっき浴は、表面の少
なくとも一部に銅又は銅合金部分を有する被めっき物を
めっき浴中に浸漬することにより、無電解錫、鉛又は錫
・鉛合金めっき皮膜は上記銅又は銅合金部分上に析出形
成されるが、この際銅又は銅合金部分から銅分が溶出し
、めっき浴中に蓄積していく。[0011]The above-mentioned electroless plating bath can be used to produce electroless tin, lead or tin-lead alloy by immersing the object to be plated, which has a copper or copper alloy part on at least a part of its surface, into the plating bath. A plating film is deposited and formed on the copper or copper alloy part, but at this time, copper content is eluted from the copper or copper alloy part and accumulates in the plating bath.
【0012】本発明はこのめっき浴中の銅イオン濃度を
定量する方法に係るものであるが、このめっき浴中にお
ける銅イオンはチオ尿素によって錯化され、多くは1価
の銅イオンとして存在する(実際、めっき浴は通常無色
である)。[0012] The present invention relates to a method for quantifying the copper ion concentration in this plating bath, and the copper ions in this plating bath are complexed with thiourea and mostly exist as monovalent copper ions. (In fact, plating baths are usually colorless).
【0013】本発明においては、上記めっき浴中の全銅
イオン濃度を測定するため、まずチオ尿素を分解可能な
酸化剤を添加し、チオ尿素を酸化分解して、銅イオンの
チオ尿素による錯化状態をなくすと共に、1価の銅イオ
ンを2価の銅イオンに酸化する。In the present invention, in order to measure the total copper ion concentration in the plating bath, an oxidizing agent capable of decomposing thiourea is first added to oxidize and decompose the thiourea, thereby removing the complexation of copper ions with the thiourea. At the same time, monovalent copper ions are oxidized to divalent copper ions.
【0014】この場合、酸化剤としては、無色でチオ尿
素を分解し得、しかも酸化反応により着色しないもので
あればいずれのものでもよいが、特に過酸化水素等の過
酸化物や亜塩素酸又はその塩などが好適に用いられ、な
かでも過酸化水素が最も好ましい。その添加量は、チオ
尿素を分解し、1価の銅イオンを2価の銅イオンに酸化
し得る量であり、例えば過酸化水素水の場合は通常めっ
き浴1mlに対し0.1〜2g添加される。In this case, any oxidizing agent may be used as long as it is colorless and can decompose thiourea and does not become colored by the oxidation reaction, but in particular peroxides such as hydrogen peroxide and chlorite or its salts are preferably used, with hydrogen peroxide being the most preferred. The amount added is the amount that can decompose thiourea and oxidize monovalent copper ions to divalent copper ions. For example, in the case of hydrogen peroxide solution, 0.1 to 2 g is usually added to 1 ml of plating bath. be done.
【0015】ここで、上記酸化剤の添加でチオ尿素を分
解した場合、同時にチオ尿素によって錯化されていた錫
イオン、特にSn4+や鉛イオンが沈殿し、めっき浴が
白濁する場合があるので、この沈殿の生成を防ぐため、
シュウ酸、酒石酸、クエン酸、EDTAやそれらの塩、
トリエタノールアミン等のSn4+やPb2+を錯化し
得る錯化剤を添加することができる。この場合、その添
加量は通常めっき浴1ml当り1〜40gである。[0015] When thiourea is decomposed by adding the above-mentioned oxidizing agent, tin ions, especially Sn4+ and lead ions complexed by thiourea, may precipitate and the plating bath may become cloudy. To prevent the formation of this precipitate,
Oxalic acid, tartaric acid, citric acid, EDTA and their salts,
A complexing agent capable of complexing Sn4+ and Pb2+, such as triethanolamine, can be added. In this case, the amount added is usually 1 to 40 g per ml of plating bath.
【0016】また、本発明の分析方法は、上記酸化剤の
添加で無色の1価の銅イオンを通常青色の2価の銅イオ
ンに酸化するので、めっき浴は着色し、その着色度合を
比色法により定量するものであるが、2価の銅イオンに
よる着色を更に明確にし、2価の銅イオンの検出感度を
上げるため、発色剤を添加することができる。発色剤と
しては、アンモニアやエチレンジアミン、ジエチレント
リアミン、トリエチレンテトラミン、テトラエチレンペ
ンタミン、アミノエチルモノエタノールアミン等のアミ
ン類が好適に用いられる。これら発色剤の添加量は、め
っき浴1mlに対し通常0.2〜5gとすることができ
る。Furthermore, in the analysis method of the present invention, colorless monovalent copper ions are oxidized into blue divalent copper ions by adding the oxidizing agent, so the plating bath is colored and the degree of coloring is compared. The amount is determined by a color method, but a coloring agent can be added in order to further clarify the coloring caused by divalent copper ions and increase the detection sensitivity of divalent copper ions. As the coloring agent, ammonia and amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and aminoethylmonoethanolamine are preferably used. The amount of these coloring agents added can generally be 0.2 to 5 g per ml of the plating bath.
【0017】更に、本発明に従って分析するに当り、分
析液のpHは4〜11、特に5〜10であることが好ま
しい。pHが4より低いと銅イオンの発色が弱くなる場
合が生じ、またpHが11より高いと、特に酸化剤とし
て過酸化水素を用いた場合、過酸化水素が分解して気泡
が生じ、吸光に影響を及ぼすおそれが生じる。この場合
、pH調整剤、pH緩衝剤として、酢酸やその塩、ヘキ
サエチレンテトラミンなどが使用でき、また上述した錯
化剤、発色剤の添加をpHを上記範囲に調整することも
できる。Furthermore, in performing analysis according to the present invention, the pH of the analysis solution is preferably 4 to 11, particularly 5 to 10. If the pH is lower than 4, the color development of copper ions may be weakened, and if the pH is higher than 11, especially when hydrogen peroxide is used as an oxidizing agent, the hydrogen peroxide decomposes and bubbles are generated, causing light absorption. There is a risk that it will have an impact. In this case, acetic acid, a salt thereof, hexaethylenetetramine, etc. can be used as a pH adjuster or a pH buffering agent, and the pH can also be adjusted to the above range by adding the above-mentioned complexing agent or coloring agent.
【0018】なお、酸化剤、錯化剤、発色剤、pH調整
剤の添加順序に特に制限はなく、これらを同時に添加す
ることもできるが、まず錯化剤を添加し、次いでpH調
整した後に酸化剤を添加することが好ましく、発色剤は
最後に添加すればよい。[0018] There is no particular restriction on the order of addition of the oxidizing agent, complexing agent, coloring agent, and pH adjuster, and they can be added at the same time. It is preferable to add an oxidizing agent, and the coloring agent may be added last.
【0019】以上のようにしてチオ尿素を分解し、1価
の銅イオンを2価の銅イオンに酸化して発色させた分析
サンプルは、これを比色法によって定量する。比色法と
しては、標準サンプルと目視によって比較する方法も採
用し得るが、一般には波長500〜800nmの吸光度
を測定し、予め標準サンプルから作成した検量値と比較
する方法が好適である。[0019] The analytical sample in which thiourea is decomposed and monovalent copper ions are oxidized to divalent copper ions to develop a color is quantified by a colorimetric method. As a colorimetric method, a method of visual comparison with a standard sample may be adopted, but in general, a method of measuring the absorbance at a wavelength of 500 to 800 nm and comparing it with a calibration value prepared in advance from a standard sample is suitable.
【0020】なお、分析は間欠的にめっき浴を試料液と
して採取し、上述した操作を個々に行なう方法、めっき
浴から連続的にポンプによって分析装置に試料液を送り
、この分析装置で上記した前処理操作を自動的に行なっ
た後、フローセルに流して吸光度を連続的に測定する方
法など、常法に従って行なうことができる。The analysis can be carried out by intermittently taking the plating bath as a sample solution and performing the above-mentioned operations individually, or by continuously sending the sample solution from the plating bath to the analyzer using a pump, and using this analyzer to perform the above-described operations. This can be carried out according to a conventional method, such as automatically performing a pretreatment operation and then flowing the sample through a flow cell to continuously measure the absorbance.
【0021】このようにして定量された銅イオン濃度は
、無電解錫、鉛又は錫・鉛合金めっき浴の錫や鉛分の管
理に用いられる。即ち、めっき浴中の銅イオン濃度は消
費される金属量(錫、鉛)と比例関係にあるので、銅イ
オン濃度はこれら金属分の補給の目安になり、銅イオン
濃度の増加分に対して錫塩や鉛塩を補給することにより
めっき浴中の錫塩、鉛塩を管理することができるもので
ある。The copper ion concentration determined in this manner is used to control the tin and lead content in the electroless tin, lead or tin-lead alloy plating bath. In other words, since the copper ion concentration in the plating bath is proportional to the amount of metals consumed (tin, lead), the copper ion concentration serves as a guideline for replenishing these metals, and the increase in copper ion concentration By replenishing tin salt and lead salt, it is possible to control the tin salt and lead salt in the plating bath.
【0022】[0022]
【発明の効果】以上説明したように、本発明方法によれ
ば、無電解錫、鉛又は錫・鉛合金めっき浴の銅イオン濃
度を容易にかつ正確に分析できる。この場合、分析方法
として比色法を採用したので、自動分析に容易に適応さ
せることができ、無電解錫、鉛又は錫・鉛合金めっき浴
の管理に有効に利用することができる。As explained above, according to the method of the present invention, the copper ion concentration of an electroless tin, lead or tin-lead alloy plating bath can be easily and accurately analyzed. In this case, since a colorimetric method was adopted as the analysis method, it can be easily adapted to automatic analysis and can be effectively used for the management of electroless tin, lead or tin-lead alloy plating baths.
【0023】[0023]
【実施例】以下、実施例を示して本発明を具体的に説明
するが、本発明は下記実施例によって限定されるもので
はない。[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples.
【0024】下記めっき浴を使用し下記条件で銅製品に
対し無電解めっきを行ないながら、処理量26μm・d
m2/l毎にめっき浴5mlをサンプリングし、これに
トリエチレンテトラミン20g/l、酢酸100g/l
、クエン酸アンモニウム100g/lの溶液200ml
と35%過酸化水素水2mlを添加した後、その吸光度
を波長620nmで吸光度計(日立製作所製U−321
0)を用いて測定し、全銅量を定量した。結果を表1に
示す。なお、比較のため、原子吸光分析の結果を併記す
る。[0024] While performing electroless plating on copper products using the following plating bath and under the following conditions, the throughput was 26 μm·d.
Sample 5 ml of the plating bath for every m2/l, and add 20 g/l of triethylenetetramine and 100 g/l of acetic acid.
, 200 ml of a solution of 100 g/l ammonium citrate
After adding 2 ml of 35% hydrogen peroxide solution, the absorbance was measured using an absorbance meter (U-321 manufactured by Hitachi, Ltd.) at a wavelength of 620 nm.
0) to quantify the total amount of copper. The results are shown in Table 1. For comparison, the results of atomic absorption spectrometry are also shown.
【0025】なお、めっき浴には、めっきの進行につれ
、分析によつて得られた銅量が0.5g/l増加する毎
に下記補給液(1)〜(3)を下記に示す量において補
給するようにした。
めっき液組成及びめっき条件
メタンスルホン酸
50g/lメタンスルホン酸錫
20g/lメタンスルホ
ン酸鉛 13
g/lチオ尿素
75g/l次亜リン酸ナトリ
ウム 80g/l
クエン酸
15g/l塩化ラウリルピリジニウ
ム 5g/lEDTA
3g/lpH
2.0
浴温
80℃補給液(1) 5
ml/l補給
メタンスルホン酸錫 40
0g/lメタンスルホン酸
180g/l補給液(2) 5ml/l補
給
メタンスルホン酸鉛 38
0g/lメタンスルホン酸
240g/l補給液(3) 15ml/l補給
チオ尿素
120g/l次亜リン酸ナトリウム
3g/lクエン酸
25g/l[0025] As the plating progresses, the following replenishing solutions (1) to (3) are added in the amounts shown below every time the amount of copper obtained by analysis increases by 0.5 g/l. I tried to replenish it. Plating solution composition and plating conditions Methanesulfonic acid
50g/l tin methanesulfonate
20g/l lead methanesulfonate 13
g/l thiourea
75g/l Sodium hypophosphite 80g/l
citric acid
15g/l laurylpyridinium chloride 5g/l EDTA
3g/lpH
2.0
bath temperature
80℃ replenishment liquid (1) 5
ml/l supplementary tin methanesulfonate 40
0g/l methanesulfonic acid
180g/l replenishment liquid (2) 5ml/l replenishment lead methanesulfonate 38
0g/l methanesulfonic acid
240g/l replenishment solution (3) 15ml/l replenishment thiourea
120g/l sodium hypophosphite
3g/l citric acid
25g/l
【
0026】[
0026
【表1】[Table 1]
【0027】表1の結果より、本発明による銅の分析値
は原子吸光分析による分析値とほぼ一致し、従って本発
明により簡易に銅分を分析し得ることが確認された。From the results shown in Table 1, the analytical values for copper according to the present invention almost coincided with the analytical values by atomic absorption spectrometry, and it was therefore confirmed that copper content could be easily analyzed according to the present invention.
Claims (1)
れらの塩を溶解する酸、及びチオ尿素を含む銅又は銅合
金用無電解錫、鉛又は錫・鉛合金めっき浴中の銅イオン
濃度を分析する方法において、上記めっき浴にチオ尿素
を分解可能な酸化剤を加えて該めっき浴中のチオ尿素を
酸化分解すると共に、1価の銅イオンを2価の銅イオン
に酸化し、この酸化した2価銅イオンを含む全2価の銅
イオン濃度を比色法で測定することを特徴とする無電解
錫、鉛又はそれらの合金めっき浴中の銅イオン濃度の分
析方法。Claim 1. Copper in an electroless tin, lead or tin-lead alloy plating bath for copper or copper alloys containing a water-soluble tin salt and/or a water-soluble lead salt, an acid that dissolves these salts, and thiourea. In the method of analyzing ion concentration, an oxidizing agent capable of decomposing thiourea is added to the plating bath to oxidize and decompose the thiourea in the plating bath, and monovalent copper ions are oxidized to divalent copper ions. A method for analyzing copper ion concentration in an electroless tin, lead or alloy plating bath, which comprises measuring the total divalent copper ion concentration including the oxidized divalent copper ions by a colorimetric method.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3059643A JPH0830274B2 (en) | 1991-03-01 | 1991-03-01 | Method for analyzing copper ion concentration in electroless tin, lead or their alloy plating bath |
DE69219924T DE69219924T2 (en) | 1991-03-01 | 1992-02-27 | Analysis of plating solutions containing tin, lead or tin-lead alloy |
EP92103372A EP0501480B1 (en) | 1991-03-01 | 1992-02-27 | Analysis of tin, lead or tin-lead alloy plating solution |
US07/843,199 US5294554A (en) | 1991-03-01 | 1992-02-28 | Analysis of tin, lead or tin-lead alloy plating solution |
KR1019920003430A KR0162905B1 (en) | 1991-03-01 | 1992-03-02 | Analysis of tin, lead or tin-lead alloy plating solution |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3059643A JPH0830274B2 (en) | 1991-03-01 | 1991-03-01 | Method for analyzing copper ion concentration in electroless tin, lead or their alloy plating bath |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04276082A true JPH04276082A (en) | 1992-10-01 |
JPH0830274B2 JPH0830274B2 (en) | 1996-03-27 |
Family
ID=13119108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3059643A Expired - Fee Related JPH0830274B2 (en) | 1991-03-01 | 1991-03-01 | Method for analyzing copper ion concentration in electroless tin, lead or their alloy plating bath |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0830274B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001272389A (en) * | 2000-03-24 | 2001-10-05 | Yoshikazu Kobayashi | Method and device for determination method of copper in acid electroless tin plating |
EP2471977A2 (en) | 2010-12-28 | 2012-07-04 | Rohm and Haas Electronic Materials LLC | Method for removing impurities from plating solution |
EP2481834A1 (en) | 2010-12-28 | 2012-08-01 | Rohm and Haas Electronic Materials LLC | Method for removing impurities from plating solution |
EP2570514A1 (en) | 2011-09-14 | 2013-03-20 | Rohm and Haas Electronic Materials LLC | Method of removing impurities from plating liquid |
-
1991
- 1991-03-01 JP JP3059643A patent/JPH0830274B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001272389A (en) * | 2000-03-24 | 2001-10-05 | Yoshikazu Kobayashi | Method and device for determination method of copper in acid electroless tin plating |
EP2471977A2 (en) | 2010-12-28 | 2012-07-04 | Rohm and Haas Electronic Materials LLC | Method for removing impurities from plating solution |
EP2481834A1 (en) | 2010-12-28 | 2012-08-01 | Rohm and Haas Electronic Materials LLC | Method for removing impurities from plating solution |
EP2570514A1 (en) | 2011-09-14 | 2013-03-20 | Rohm and Haas Electronic Materials LLC | Method of removing impurities from plating liquid |
Also Published As
Publication number | Publication date |
---|---|
JPH0830274B2 (en) | 1996-03-27 |
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