JP2019052355A - Electrolytic Sn or Sn alloy plating solution and method for producing Sn or Sn alloy plating product - Google Patents
Electrolytic Sn or Sn alloy plating solution and method for producing Sn or Sn alloy plating product Download PDFInfo
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- JP2019052355A JP2019052355A JP2017178077A JP2017178077A JP2019052355A JP 2019052355 A JP2019052355 A JP 2019052355A JP 2017178077 A JP2017178077 A JP 2017178077A JP 2017178077 A JP2017178077 A JP 2017178077A JP 2019052355 A JP2019052355 A JP 2019052355A
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- salts
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- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 89
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- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- VRPKUXAKHIINGG-UHFFFAOYSA-N biphenyl-4,4'-dithiol Chemical compound C1=CC(S)=CC=C1C1=CC=C(S)C=C1 VRPKUXAKHIINGG-UHFFFAOYSA-N 0.000 description 1
- LEDIWWJKWAMGLD-UHFFFAOYSA-N bis(2-methylundecan-2-yl) disulfide Chemical compound CCCCCCCCCC(C)(C)SSC(C)(C)CCCCCCCCC LEDIWWJKWAMGLD-UHFFFAOYSA-N 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
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- 229940050410 gluconate Drugs 0.000 description 1
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- 229960003180 glutathione Drugs 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- ZTVZLYBCZNMWCF-UHFFFAOYSA-N homocystine Chemical compound [O-]C(=O)C([NH3+])CCSSCCC([NH3+])C([O-])=O ZTVZLYBCZNMWCF-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- OSZKBWPMEPEYFU-UHFFFAOYSA-N methyl 3-[(3-methoxy-3-oxopropyl)disulfanyl]propanoate Chemical compound COC(=O)CCSSCCC(=O)OC OSZKBWPMEPEYFU-UHFFFAOYSA-N 0.000 description 1
- AYEQJLOHMLYKAV-UHFFFAOYSA-N n-(4-sulfanylphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(S)C=C1 AYEQJLOHMLYKAV-UHFFFAOYSA-N 0.000 description 1
- ZHMIOPLMFZVSHY-UHFFFAOYSA-N n-[2-[(2-benzamidophenyl)disulfanyl]phenyl]benzamide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1SSC1=CC=CC=C1NC(=O)C1=CC=CC=C1 ZHMIOPLMFZVSHY-UHFFFAOYSA-N 0.000 description 1
- AAPAGLBSROJFGM-UHFFFAOYSA-N naphthalene-1,5-dithiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1S AAPAGLBSROJFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229960003703 sodium thiosalicylate Drugs 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明は、はんだ接合に供されるめっき物形成のための電解Ｓｎ又はＳｎ合金めっき液及びはんだ接合に供されるめっき物を製造するＳｎ又はＳｎ合金めっき物の製造方法に関する。 The present invention relates to an electrolytic Sn or Sn alloy plating solution for forming a plated product to be used for solder bonding and a method for manufacturing a Sn or Sn alloy plated material to manufacture a plated material to be used for solder bonding.
デバイスの高密度化及び高容量化にともない、半導体チップとの接合に用いられるはんだ材料から生じるアルファ線によるデバイスの動作不良への影響は無視できない問題となっている。アルファ線は、はんだ材料中（正確にはＳｎ金属中）に不純物として含まれるＰｂ金属から主に発生することが知られている。よって従来からＰｂ濃度を低くすることが求められている。 As the density of devices increases and the capacity increases, the influence of the alpha rays generated from the solder material used for bonding to the semiconductor chip on the malfunction of the device has become a problem that cannot be ignored. It is known that alpha rays are mainly generated from Pb metal contained as an impurity in the solder material (exactly Sn metal). Therefore, it has been conventionally required to reduce the Pb concentration.
例えば、特許文献１では、実装基板と接続するために半導体チップの主面にはＳｎ−Ａｇ−Ｃｕめっきから成るＰｂ濃度を低くした複数の半田バンプを設けることが記載されている。また、特許文献２では、接合構造に無鉛はんだを使用し接合することが記載されている。 For example, Patent Document 1 describes that a plurality of solder bumps made of Sn—Ag—Cu plating with a low Pb concentration are provided on the main surface of a semiconductor chip for connection to a mounting substrate. Moreover, in patent document 2, it is described using a lead-free solder for joining structure and joining.
しかしながら、半導体業界の進歩を考えると、デバイスのさらなる小型化、高密度化及び高容量化が進むと考えられ、より一層の低アルファ線への対応が必須となり、さらなる低濃度Ｐｂ化が可能なＳｎめっきが求められる。 However, considering the advancement of the semiconductor industry, it is considered that devices will be further miniaturized, densified, and increased in capacity, and it will be necessary to cope with further lower alpha rays, and further reduction in Pb concentration is possible. Sn plating is required.
そこで、本発明は低濃度Ｐｂ化に可能なＳｎ又はＳｎ合金めっき液を提供することを目的とする。 Accordingly, an object of the present invention is to provide a Sn or Sn alloy plating solution capable of reducing the concentration of Pb.
本発明の一態様に係る電解Ｓｎ又はＳｎ合金めっき液は、はんだ接合に供されるめっき物形成のための電解Ｓｎ又はＳｎ合金めっき液であって、少なくとも、硫黄系化合物と、Ｓｎ塩と、無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、界面活性剤とを含有し、前記硫黄系化合物は、下記の一般式であらわされるチオール化合物（式Ａ）、チオール化合物（式Ａ）の塩、又はジスルフィド化合物（式Ｂ）であることを特徴とする。 The electrolytic Sn or Sn alloy plating solution according to an aspect of the present invention is an electrolytic Sn or Sn alloy plating solution for forming a plated article to be used for solder joining, and includes at least a sulfur compound, an Sn salt, One or more acids selected from inorganic acids, organic acids, or water-soluble salts thereof, or water-soluble salts thereof, and a surfactant, and the sulfur compound is a thiol compound represented by the following general formula (formula A), a salt of a thiol compound (formula A), or a disulfide compound (formula B).
式Ａ：
Ｒ２：
このようにすれば、各成分の働きにより、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能なＳｎめっき物を提供することができる。 By doing so, it is possible to provide an Sn plated product that can suppress the eutectoid of Pb and reduce the concentration of Pb by the action of each component.
このとき、本発明の一態様では前記硫黄系化合物と、前記Ｓｎ塩のＳｎと、前記酸又はその水溶性塩と、前記界面活性剤との濃度比は、重量比で１：０．２〜７００：１〜３０００：０．０１〜１０００としても良い。 At this time, in one aspect of the present invention, the concentration ratio of the sulfur compound, Sn of the Sn salt, the acid or water-soluble salt thereof, and the surfactant is 1: 0.2 to It is good also as 700: 1-3000: 0.01-1000.
このようにすれば、各成分の濃度比が最適となり、さらなる低濃度Ｐｂ化が可能となる。 In this way, the concentration ratio of each component is optimized, and a further reduction in concentration Pb is possible.
また、本発明の一態様では、前記Ｒ１は前記一般式（Ｉ）〜（ＩＩＩ）のいずれかであり、前記Ｒ２は前記一般式の（ＩＶ）又は（Ｖ）であり、前記式Ａ又は前記式Ｂが前記Ｒ１又は前記Ｒ２の２位又は６位と結合するとしても良い。 In one embodiment of the present invention, R 1 is any one of Formulas (I) to (III), R 2 is Formula (IV) or (V), and Formula A Alternatively, the formula B may be bonded to the 2-position or the 6-position of the R 1 or the R 2 .
このようにすれば、Ｐｂの共析を抑制し、さらなる低濃度Ｐｂ化が可能となる。 In this way, it is possible to suppress the eutectoid of Pb and further reduce the concentration of Pb.
また、本発明の一態様では、前記酸又はその水溶性塩が、硫酸、塩酸、硝酸、りん酸、スルファミン酸、有機スルホン酸、カルボン酸又はその塩から選ばれる１種以上の酸又はその塩であり、かつ前記界面活性剤が、アニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤から選ばれる１種以上としても良い。 In one embodiment of the present invention, the acid or a water-soluble salt thereof is one or more acids or salts thereof selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid, organic sulfonic acid, carboxylic acid, or a salt thereof. And the surfactant may be at least one selected from an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
このようにすれば、最適な成分の選択となり、Ｐｂの共析を抑制し、さらなる低濃度Ｐｂ化が可能となる。 In this way, it is possible to select an optimum component, suppress the eutectoid of Pb, and further reduce the concentration of Pb.
さらにＡｇ塩、Ｃｕ塩、Ｂｉ塩、Ｉｎ塩、Ａｕ塩、Ｓｂ塩、Ｚｎ塩、Ｎｉ塩から選ばれる１種以上のＳｎ塩以外の金属塩を含有しても良い。 Furthermore, you may contain metal salts other than 1 or more types of Sn salt chosen from Ag salt, Cu salt, Bi salt, In salt, Au salt, Sb salt, Zn salt, and Ni salt.
このようにすれば、ＳｎＡｇ、ＳｎＣｕ、ＳｎＢｉ、ＳｎＩｎ，ＳｎＡｕ，ＳｎＳｂ，ＳｎＺｎ，ＳｎＮｉにも適用可能なＳｎ合金めっき液となり、低濃度Ｐｂ化に可能なＳｎ合金めっき液を提供することができる。 If it does in this way, it will become Sn alloy plating solution applicable also to SnAg, SnCu, SnBi, SnIn, SnAu, SnSb, SnZn, SnNi, and Sn alloy plating solution which can be made low concentration Pb can be provided.
また、本発明の一態様では、はんだ接合に供されるめっき物を製造するＳｎ又はＳｎ合金めっき物の製造方法であって、電解Ｓｎ又はＳｎ合金めっき液を作製するめっき液作製工程と、前記めっき液を用いて前記Ｓｎ又はＳｎ合金めっき物を製造するめっき工程とを有し、前記めっき液作製工程において、前記電解Ｓｎ又はＳｎ合金めっき液は、少なくとも、硫黄系化合物と、Ｓｎ塩と、無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、界面活性剤とを含有させて作製し、前記硫黄系化合物は、下記の一般式であらわされるチオール化合物（式Ａ）、チオール化合物（式Ａ）の塩、又はジスルフィド化合物（式Ｂ）であることを特徴とする。 Moreover, in one aspect of the present invention, there is provided a manufacturing method of a Sn or Sn alloy plating product for manufacturing a plating product to be subjected to solder joining, a plating solution preparation step for preparing an electrolytic Sn or Sn alloy plating solution, A plating step of producing the Sn or Sn alloy plating product using a plating solution, and in the plating solution preparation step, the electrolytic Sn or Sn alloy plating solution includes at least a sulfur compound, an Sn salt, One or more acids selected from inorganic acids, organic acids or water-soluble salts thereof, or water-soluble salts thereof, and a surfactant are prepared, and the sulfur compound is a thiol represented by the following general formula: It is a compound (formula A), a salt of a thiol compound (formula A), or a disulfide compound (formula B).
式Ａ：
Ｒ２：
このようにすれば、各成分の働きにより、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能なＳｎめっき物を提供することができる。 By doing so, it is possible to provide an Sn plated product that can suppress the eutectoid of Pb and reduce the concentration of Pb by the action of each component.
また、本発明の一態様では、前記Ｓｎ又はＳｎ合金めっき物の被膜が低アルファグレードＳｎ又はＳｎ合金めっき被膜（０．０１ｃｏｕｎｔｓ／ｈｒ／ｃｍ２未満）としても良い。 In one embodiment of the present invention, the Sn or Sn alloy plating film may be a low alpha grade Sn or Sn alloy plating film (less than 0.01 counts / hr / cm 2 ).
このようにすれば、低濃度Ｐｂ化が可能となり、デバイスの動作不良への影響を防止できる。 In this way, it is possible to reduce the concentration of Pb, and it is possible to prevent an influence on device malfunction.
以上説明したように本発明によれば、各成分の働きにより、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能な電解Ｓｎ又はＳｎ合金めっき液を提供することができる。 As described above, according to the present invention, it is possible to provide an electrolytic Sn or Sn alloy plating solution capable of suppressing the eutectoid of Pb and reducing the concentration of Pb by the action of each component.
以下、本発明の好適な実施の形態について詳細に説明する。なお、以下に説明する本実施形態は、特許請求の範囲に記載された本発明の内容を不当に限定するものではなく、本実施形態で説明される構成の全てが本発明の解決手段として必須であるとは限らない。
１．電解Ｓｎ又はＳｎ合金めっき液
１−１．硫黄系化合物
１−２．Ｓｎ塩、Ｓｎ以外の塩
１−３．酸又はその水溶性塩
１−４．界面活性剤
１−５．結晶調整剤
１−６．有機溶媒
１−７．酸化防止剤
１−８．キレート剤
２．Ｓｎ又はＳｎ合金めっき物の製造方法
２−１．めっき液作製工程
２−２．めっき工程
Hereinafter, preferred embodiments of the present invention will be described in detail. The present embodiment described below does not unduly limit the contents of the present invention described in the claims, and all the configurations described in the present embodiment are essential as means for solving the present invention. Not necessarily.
1. 1. Electrolytic Sn or Sn alloy plating solution 1-1. Sulfur-based compound 1-2. Sn salt, salt other than Sn 1-3. Acid or water-soluble salt thereof 1-4. Surfactant 1-5. Crystal modifier 1-6. Organic solvent 1-7. Antioxidant 1-8. Chelating agent2. 2. Manufacturing method of Sn or Sn alloy plated article 2-1. Plating solution preparation process 2-2. Plating process
［１．電解Ｓｎ又はＳｎ合金めっき液］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、はんだ接合に供されるめっき物形成のための電解Ｓｎ又はＳｎ合金めっき液であって、少なくとも、硫黄系化合物と、Ｓｎ塩と、無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、界面活性剤とを含有する。そして少なくとも添加される硫黄系化合物、Ｓｎ塩、酸又はその水溶性塩及び界面活性剤は下記の特徴を有する。以下詳細に説明する。
[1. Electrolytic Sn or Sn alloy plating solution]
An electrolytic Sn or Sn alloy plating solution according to an embodiment of the present invention is an electrolytic Sn or Sn alloy plating solution for forming a plated article to be used for solder joining, and includes at least a sulfur-based compound, an Sn salt, 1 type or more acids chosen from inorganic acid, organic acid, or its water-soluble salt, or its water-soluble salt, and surfactant. At least the sulfur-based compound, Sn salt, acid or water-soluble salt thereof and surfactant that are added have the following characteristics. This will be described in detail below.
ここでめっき液とは、めっきをするために用いられる液であって、各種金属及び成分が一つの容器に濃縮されたもの、各種金属及び成分が複数の容器に分かれ各容器に各種金属及び成分が濃縮されたもの、上記濃縮されたもの等を水で調整し建浴したもの、及び各種金属及び成分を添加し調整し建浴したものをいう。 Here, the plating solution is a solution used for plating, in which various metals and components are concentrated in one container, various metals and components are divided into a plurality of containers, and various metals and components are contained in each container. Concentrated, prepared and prepared with water, and those prepared by adding various metals and components.
［１−１．硫黄系化合物］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する硫黄系化合物は、下記の一般式であらわされるチオール化合物（式Ａ）、チオール化合物（式Ａ）の塩、又はジスルフィド化合物（式Ｂ）であることを特徴とする。
[1-1. Sulfur compounds]
The sulfur-based compound contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention is a thiol compound (formula A), a salt of a thiol compound (formula A), or a disulfide compound ( Formula B).
式Ａ：
Ｒ２：
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する硫黄系化合物は、Ｐｂの共析防止剤として含有され、上記のように式Ａに示すようなチオール化合物、チオール化合物の塩、又は式Ｂに示すようなジスルフィド化合物である。そしてＲ１は、アニリン（Ｉ）、ピリジン（ＩＩ）又はピリジンＮオキシド（ＩＩＩ）のいずれかである。また、Ｒ２は、アニリン（ＩＶ）、ピリジン（Ｖ）、ベンゼン（ＶＩ）、ブタン（ＶＩＩ）、トルエン（ＶＩＩＩ）のいずれかである。また、式Ｂで表記したように、左右に同じ構造のもののＲ２が結合される。 The sulfur-based compound contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention is contained as a Pb eutectoid inhibitor, and as described above, a thiol compound or a salt of a thiol compound as shown in Formula A Or a disulfide compound as shown in Formula B. R1 is aniline (I), pyridine (II), or pyridine N oxide (III). R2 is any one of aniline (IV), pyridine (V), benzene (VI), butane (VII), and toluene (VIII). Moreover, as represented by Formula B, R 2 having the same structure is bonded to the left and right.
少なくとも、後述する、Ｓｎ塩、酸又はその塩、界面活性剤とを含有しためっき液とすることで、各成分の働きにより、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能な電解Ｓｎ又はＳｎ合金めっき液を提供することができる。 By using a plating solution containing at least an Sn salt, an acid or salt thereof, and a surfactant, which will be described later, electrolytic Sn capable of suppressing the eutectoid of Pb and reducing the concentration of Pb by the action of each component. Alternatively, an Sn alloy plating solution can be provided.
また、本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する、硫黄系化合物、Ｓｎ塩のＳｎ、酸又はその水溶性塩、界面活性剤との濃度（ｇ／Ｌ）の比は、最適な濃度比が存在し、重量比で１：０．０５〜１００００：０．５〜５００００：０．０００５〜１００００である。好ましくは、重量比で、１：０．２〜７００：１〜３０００：０．０１〜１０００であり、より好ましくは１：０．２〜１４０：２〜４００：０．０１〜２００である。さらに好ましくは１：４〜１６：１５〜６２：０．５〜２であることが好ましい。例えば、さらに好ましい比の範囲において、硫黄系化合物を１とすると、重量比でＳｎ塩のＳｎが４〜１６、酸又はその水溶性塩が１５〜６２、界面活性剤が０．５〜２の割合である。 Moreover, ratio (g / L) of the concentration with the sulfur type compound, Sn of Sn salt, acid or its water-soluble salt, and surfactant contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention. There is an optimum concentration ratio, and the weight ratio is 1: 0.05 to 10000: 0.5 to 50000: 0.0005 to 10000. Preferably, it is 1: 0.2-700: 1-3000: 0.01-1000 by weight ratio, More preferably, it is 1: 0.2-140: 2-400: 0.01-200. More preferably, it is 1: 4-16: 15-62: 0.5-2. For example, in a more preferable ratio range, assuming that the sulfur-based compound is 1, Sn by weight ratio is 4 to 16, Sn or water-soluble salt thereof is 15 to 62, and surfactant is 0.5 to 2. It is a ratio.
硫黄系化合物の重量の濃度に対し、Ｓｎ塩、酸又はその水溶性塩、界面活性剤の重量の濃度比が上記の範囲を外れる場合には、Ｐｂ防止能力が低下する可能性があるからである。このような範囲とすることで、上記の各成分の濃度比が最適となり、共析防止能力が高まり、さらなる低濃度Ｐｂ化が可能となる。 If the concentration ratio of the Sn salt, acid or its water-soluble salt, and surfactant is out of the above range with respect to the concentration of the sulfur-based compound weight, the ability to prevent Pb may be reduced. is there. By setting it as such a range, the density | concentration ratio of said each component becomes optimal, eutectoid prevention capability increases, and the further low density | concentration Pb is attained.
さらに本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する硫黄系化合物の濃度は、０．０１〜１００ｇ／Ｌとすることが好ましい。上記濃度が０．０１ｇ／Ｌ未満となると共析防止能力が低下する可能性がある。一方、１００ｇ／Ｌを超えると、コスト的に好ましくない。より好ましくは０．１〜５０ｇ／Ｌであり、さらに好ましくは０．５〜５０ｇ／Ｌである。 Furthermore, it is preferable that the density | concentration of the sulfur type compound contained in the electrolytic Sn or Sn alloy plating solution which concerns on one Embodiment of this invention shall be 0.01-100 g / L. If the concentration is less than 0.01 g / L, the ability to prevent eutectoid may be reduced. On the other hand, if it exceeds 100 g / L, it is not preferable in terms of cost. More preferably, it is 0.1-50 g / L, More preferably, it is 0.5-50 g / L.
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する硫黄系化合物は、上述したようにＰｂの共析防止剤として作用する。それは、めっき液中に加わった上記の硫黄系化合物がＳｎ、Ｐｂの析出電位を貴または卑にシフトさせるからである。（硫黄化合物の種類によって卑側にシフトさせたり貴側にシフトさせる。）Ｓｎの析出電位を卑側にシフトさせる化合物はＰｂの析出電位も卑側にシフトさせる傾向があり、Ｓｎの析出電位を貴側にシフトさせる化合物はＰｂの析出電位も貴側にシフトさせる傾向があるからである。この際、Ｓｎの析出電位がＰｂの析出電位よりも貴になり、かつ電位差が０．０６Ｖ以上に広がるためであると考えられる。 The sulfur compound contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention acts as a Pb eutectoid preventing agent as described above. This is because the sulfur-based compound added to the plating solution shifts the Sn and Pb deposition potential to noble or base. (Depending on the type of sulfur compound, it shifts to the base side or to the noble side.) A compound that shifts the Sn precipitation potential to the base side also tends to shift the Pb precipitation potential to the base side. This is because the compound shifted to the noble side tends to shift the precipitation potential of Pb to the noble side. At this time, it is considered that the Sn deposition potential becomes nobler than the Pb deposition potential and the potential difference spreads to 0.06 V or more.
ここでＳｎ又はＳｎ合金めっき被膜中には、上述したようにＰｂが不純物として含まれる。これはＳｎめっき液の作製に際し、めっき液に加えられるＳｎ塩中にＰｂが含有するためである。このＰｂがめっきの際にＳｎ又はＳｎ合金めっき中に取り込まれる。よって従来は、Ｓｎ又はＳｎ合金めっき被膜中のＰｂ量を低くするために、Ｓｎ塩の精製段階でＰｂ濃度を低くさせた低濃度ＰｂのＳｎ塩を使用している。しかし、上述したようにさらなるデバイスの小型化、高密度化及び高容量化に伴い、一層のＰｂの低濃度化が必要となることが予想される。そうした場合に、これ以上の低濃度Ｐｂ化にするためには、さらなるＳｎの精製技術が必要となり、コストも増加するため、困難である。 Here, as described above, Sn or Sn alloy plating film contains Pb as an impurity. This is because Pb is contained in the Sn salt added to the plating solution during the production of the Sn plating solution. This Pb is taken in during Sn or Sn alloy plating during plating. Therefore, conventionally, in order to reduce the amount of Pb in the Sn or Sn alloy plating film, a low-concentration Pb Sn salt in which the Pb concentration is lowered in the purification step of the Sn salt is used. However, as described above, it is expected that further reduction in the Pb concentration will be required as the device is further reduced in size, increased in density, and increased in capacity. In such a case, in order to make the concentration of Pb lower than this, it is difficult because further Sn purification technology is required and the cost increases.
そこで、本発明者らは、前述した本発明の目的を達成するために鋭意検討を重ねた結果、本発明の一実施形態に用いられる硫黄系化合物は、Ｐｂ共析を防止し、その他の成分がＰｂ共析防止を補助できることが分かった。すなわち本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液のように、少なくとも、硫黄系化合物と、Ｓｎ塩と、酸又はその水溶性塩と、界面活性剤とを含有することで、硫黄系化合物がＰｂの共析を防止し、上記のＳｎ塩と、酸又はその水溶性塩と、界面活性剤とがＰｂの共析防止を補助することで、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能なＳｎ又はＳｎ合金めっき液を提供することができることとなる。よって、上記の硫黄系化合物と上記のＳｎ塩と、酸又はその水溶性塩と、界面活性剤とを組み合わせることによって、総合的に上記の目的を達成できる。以下詳細に説明する。 Therefore, as a result of intensive studies to achieve the above-described object of the present invention, the present inventors have found that the sulfur-based compound used in one embodiment of the present invention prevents Pb eutectoid and other components. Was found to be able to assist in preventing Pb eutectoid. That is, like the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention, at least a sulfur compound, an Sn salt, an acid or a water-soluble salt thereof, and a surfactant are contained. Compound prevents Pb eutectoid, and the Sn salt, acid or its water-soluble salt, and surfactant assist in preventing Pb eutectoid, thereby suppressing Pb eutectoid It is possible to provide a Sn or Sn alloy plating solution that can be made to have a concentration Pb. Therefore, the above object can be comprehensively achieved by combining the above sulfur compound, the above Sn salt, an acid or a water soluble salt thereof, and a surfactant. This will be described in detail below.
上記硫黄系化合物中の上記Ｒ１は上記一般式（Ｉ）〜（ＩＩＩ）のいずれかであり、上記Ｒ２は上記一般式の（ＩＶ）又は（Ｖ）であり、上記式Ａ又は上記式Ｂが上記Ｒ１又は上記Ｒ２の２位又は６位と結合することが好ましい。このような分子構造とすることで、水溶液中の上記分子構造中の硫黄原子や窒素原子が、ＳｎやＰｂイオンを他の１，３，４，５位と比べより強く保持することができる。そのため電位に関しても、より大きな効果が発揮され、Ｐｂの共析をさらに防止できる。 The R 1 in the sulfur compound is any one of the general formulas (I) to (III), the R 2 is (IV) or (V) in the general formula, and the formula A or the formula It is preferable that B is bonded to the 2-position or 6-position of R 1 or R 2 . By setting it as such a molecular structure, the sulfur atom and nitrogen atom in the said molecular structure in aqueous solution can hold | maintain Sn and Pb ion more strongly than other 1,3,4,5-positions. Therefore, a greater effect is exhibited with respect to the potential, and Pb eutectoid can be further prevented.
上記硫黄系化合物のチオールとしては、下記に限定されるわけではないが、具体的には、ベンゼンチオール、１，４−ベンゼンジチオール、１，３−ベンゼンジチオール、１，２−ベンゼンジチオール、１，３，５−ベンゼントリチオール、２−ナフタレンチオール、１，５−ナフタレンジチオール、４−メチルベンゼンチオール、２−メチルベンゼンチオール、３−メチルベンゼンチオール、３，５−ジメチルベンゼンチオール、４−アミノベンゼンチオール、２，４−ジメチルベンゼンチオール、３，４−ジメチルベンゼンチオール、４−ヒドロキシベンゼンチオール、３−アミノベンゼンチオール、４−ｔｅｒｔ−ブチルベンゼンチオール、２，５−ジメチルベンゼンチオール、４−エチルベンゼンチオール、３−ヒドロキシベンゼンチオール、４−イソプロピルベンゼンチオール、４−メトキシベンゼンチオール、２−アミノベンゼンチオール、４−（ジメチルアミノ）ベンゼンチオール、３−メトキシベンゼンチオール、トルエン−３，４−ジチオール、２−ヒドロキシベンゼンチオール、２−エチルベンゼンチオール、２−イソプロピルベンゼンチオール、２−メトキシベンゼンチオール、３，４−ジメトキシベンゼンチオール、５−ｔｅｒｔ−ブチル−２−メチルベンゼンチオール、２，５−ジアミノ−１，４−ベンゼンジチオール、３−エトキシベンゼンチオール、４−ニトロベンゼンチオール、４，４’−ビフェニルジチオール、チオキシレノール、３−メルカプト安息香酸、チオサリチル酸ナトリウム、４−アセトアミドベンゼンチオール、２−メルカプトピリジン、２−メルカプトピリジンＮ−オキシド、２−メルカプトピリジンＮ−オキシドナトリウム、２−メルカプト−５−ニトロピリジン、２−メルカプトニコチン酸、及び上記化合物の塩などが挙げられる。 Examples of the thiol of the sulfur compound include, but are not limited to, benzenethiol, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol, 1, 3,5-benzenetrithiol, 2-naphthalenethiol, 1,5-naphthalenedithiol, 4-methylbenzenethiol, 2-methylbenzenethiol, 3-methylbenzenethiol, 3,5-dimethylbenzenethiol, 4-aminobenzene Thiol, 2,4-dimethylbenzenethiol, 3,4-dimethylbenzenethiol, 4-hydroxybenzenethiol, 3-aminobenzenethiol, 4-tert-butylbenzenethiol, 2,5-dimethylbenzenethiol, 4-ethylbenzenethiol , 3-hydroxybenzene All, 4-isopropylbenzenethiol, 4-methoxybenzenethiol, 2-aminobenzenethiol, 4- (dimethylamino) benzenethiol, 3-methoxybenzenethiol, toluene-3,4-dithiol, 2-hydroxybenzenethiol, 2 -Ethylbenzenethiol, 2-isopropylbenzenethiol, 2-methoxybenzenethiol, 3,4-dimethoxybenzenethiol, 5-tert-butyl-2-methylbenzenethiol, 2,5-diamino-1,4-benzenedithiol, 3 -Ethoxybenzenethiol, 4-nitrobenzenethiol, 4,4'-biphenyldithiol, thioxylenol, 3-mercaptobenzoic acid, sodium thiosalicylate, 4-acetamidobenzenethiol, 2-mercaptopi Jin, 2-mercaptopyridine N- oxide, 2-mercaptopyridine N- oxide sodium, 2-mercapto-5-nitropyridine, 2-mercapto nicotinic acid, and salts of the above compounds.
また、上記硫黄系化合物のジスルフィド化合物としては、下記に限定されるわけではないが、具体的には、ジメチルジスルフィド、ジメチルトリスルフィド、ジ−ｔｅｒｔ−ブチルジスルフィド、ジエチルジスルフィド、ジイソプロピルジスルフィド、アリルメチルジスルフィド、ジアリルジスルフィド、ジイソブチルジスルフィド、ジプロピルジスルフィド、メチルプロピルジスルフィド 、ビス（２，２−ジエトキシエチル）ジスルフィド、ジブチルジスルフィド、ジイソアミルジスルフィド、ビス（２−ジメチルアミノエチル）ジスルフィド、ビス（２−ヒドロキシエチル）ジスルフィド、シスタミン、ジアミルジスルフィド、ジ−ｔｅｒｔ−オクチルジスルフィド、ジデシルジスルフィド、アリルプロピルジスルフィド、テトラメチルチウラムジスルフィド、ジ−ｔｅｒｔ−ドデシルジスルフィド、ジシクロヘキシルジスルフィド、ジチオジグリコール酸、テトラエチルチウラムジスルフィド、２，２’−ジチオジプロピオン酸、３，３’−ジチオジプロピオン酸、４，４’−ジチオニ酪酸、３，３’−ジチオジプロピオン酸ジメチル、ホルムアミジンジスルフィド、テトライソプロピルチウラムジスルフィド、ジベンジルジスルフィド、メチル２−メチル−３−フリルジスルフィド、テトラブチルチウラムジスルフィド、ビス（２−メチル−３−フリル）ジスルフィド、ビス（フェニルアセチル）ジスルフィド、Ｌ−（−）−シスチン、２，２’−ジチエニルジスルフィド、ＤＬ−ホモシスチン、２−メチル−３−フリルプロピルジスルフィド、４，４’−ジチオジモルホリン、ジフルフリルジスルフィド、３，３’−ジチオジプロピオン酸ジ（Ｎ−スクシンイミジル）、フルフリルメチルジスルフィド 、ビス（２−ベンズアミドフェニル）ジスルフィド、Ｎ，Ｎ’−ジカルボベンゾキシ−Ｌ−シスチン、２，２’−ジチオビス（５−ニトロピリジン）、６，６’−ジチオジニコチン酸、４，４’−ジ（１，２，３−トリアゾリル）ジスルフィド水和物、グルタチオン、３−（２−ピリジルジチオ）プロピオン酸Ｎ−スクシンイミジル、４−（２−ベンゾチアゾリルジチオ）モルホリン、２，２’−ジベンゾチアゾリルジスルフィド、Ｏ−イソブチロイルチアミンジスルフィド、アノイリンジスルフィド、ジフェニルジスルフィド、ジ−ｐ−トリルジスルフィド、ビス（４−ヒドロキシフェニル）ジスルフィド、３，３−ジチオビス（１−プロパンスルホン酸）、４，４’−ジチオジアニリン、２，２’−ジチオジアニリン、ビス（３−ヒドロキシフェニル）ジスルフィド、ビス（６−ヒドロキシ−２−ナフチル）ジスルフィド、ビス（４−ニトロフェニル）ジスルフィド、ビス（３−ニトロフェニル）ジスルフィド、ビス（２−ニトロフェニル）ジスルフィド、ビス（２，４−ジニトロフェニル）ジスルフィド、２，２’−ジチオ二安息香酸、５，５’−ジチオビス（２−ニトロ安息香酸）、２，２’−ジピリジルジスルフィド、４，４’−ジピリジルジスルフィド、２，２’−ジチオビス（５−ニトロピリジン）、６，６’−ジチオジニコチン酸、及び上記化合物の塩などが挙げられる。また、トリスルフィドとして、ジイソプロピルトリスルフィド、などが挙げられる。 Further, the disulfide compound of the sulfur compound is not limited to the following, but specifically, dimethyl disulfide, dimethyl trisulfide, di-tert-butyl disulfide, diethyl disulfide, diisopropyl disulfide, allyl methyl disulfide , Diallyl disulfide, diisobutyl disulfide, dipropyl disulfide, methylpropyl disulfide, bis (2,2-diethoxyethyl) disulfide, dibutyl disulfide, diisoamyl disulfide, bis (2-dimethylaminoethyl) disulfide, bis (2-hydroxyethyl) ) Disulfide, cystamine, diamyl disulfide, di-tert-octyl disulfide, didecyl disulfide, allylpropyl disulfide, tetramethyl Thiuram disulfide, di-tert-dodecyl disulfide, dicyclohexyl disulfide, dithiodiglycolic acid, tetraethylthiuram disulfide, 2,2′-dithiodipropionic acid, 3,3′-dithiodipropionic acid, 4,4′-dithionibutyric acid, Dimethyl 3,3′-dithiodipropionate, formamidine disulfide, tetraisopropyl thiuram disulfide, dibenzyl disulfide, methyl 2-methyl-3-furyl disulfide, tetrabutyl thiuram disulfide, bis (2-methyl-3-furyl) disulfide Bis (phenylacetyl) disulfide, L-(−)-cystine, 2,2′-dithienyl disulfide, DL-homocystine, 2-methyl-3-furylpropyl disulfide, 4,4′-dithiodimorpho Difurfuryl disulfide, 3,3′-dithiodipropionic acid di (N-succinimidyl), furfurylmethyl disulfide, bis (2-benzamidophenyl) disulfide, N, N′-dicarbobenzoxy-L-cystine, 2,2′-dithiobis (5-nitropyridine), 6,6′-dithiodinicotinic acid, 4,4′-di (1,2,3-triazolyl) disulfide hydrate, glutathione, 3- (2- Pyridyldithio) propionate N-succinimidyl, 4- (2-benzothiazolyldithio) morpholine, 2,2'-dibenzothiazolyl disulfide, O-isobutyroylthiamine disulfide, anoline disulfide, diphenyl disulfide, di- p-tolyl disulfide, bis (4-hydroxyphenyl) disulfide, , 3-dithiobis (1-propanesulfonic acid), 4,4′-dithiodianiline, 2,2′-dithiodianiline, bis (3-hydroxyphenyl) disulfide, bis (6-hydroxy-2-naphthyl) disulfide Bis (4-nitrophenyl) disulfide, bis (3-nitrophenyl) disulfide, bis (2-nitrophenyl) disulfide, bis (2,4-dinitrophenyl) disulfide, 2,2′-dithiodibenzoic acid, 5 , 5′-dithiobis (2-nitrobenzoic acid), 2,2′-dipyridyl disulfide, 4,4′-dipyridyl disulfide, 2,2′-dithiobis (5-nitropyridine), 6,6′-dithiodinicotine Examples include acids and salts of the above compounds. Examples of the trisulfide include diisopropyl trisulfide.
また、上記硫黄系化合物は、具体的に、２，２−ジチオジアニリン、２−アミノベンゼンチオール、２，２−ジピリジルジスルフィド、２−メルカプトピリジン、２−メルカプトピリジンＮ−オキシドであることがさらに好ましい。このようにすれば、Ｐｂの共析を抑制し、さらなる低濃度Ｐｂ化が可能となる。 Further, the sulfur compound is specifically 2,2-dithiodianiline, 2-aminobenzenethiol, 2,2-dipyridyl disulfide, 2-mercaptopyridine, 2-mercaptopyridine N-oxide. preferable. In this way, it is possible to suppress the eutectoid of Pb and further reduce the concentration of Pb.
［１−２．Ｓｎ塩、Ｓｎ以外の塩］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有するＳｎ塩は、第１Ｓｎ塩（Ｓｎ塩（ＩＩ））、第２Ｓｎ塩（Ｓｎ塩（ＩＶ））を用いることが好ましい。
[1-2. Sn salt, salt other than Sn]
As the Sn salt contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention, it is preferable to use a first Sn salt (Sn salt (II)) or a second Sn salt (Sn salt (IV)).
第１Ｓｎ塩（Ｓｎ塩（ＩＩ））として、下記に限定されるわけではないが、具体的には、メタンスルホン酸Ｓｎ（ＩＩ）等のアルカンスルホン酸Ｓｎ（ＩＩ）、イセチオン酸Ｓｎ（ＩＩ）等のアルカノールスルホン酸Ｓｎ（ＩＩ）などの有機スルホン酸Ｓｎ（ＩＩ）、硫酸Ｓｎ（ＩＩ）、ホウフッ化Ｓｎ（ＩＩ）、塩化Ｓｎ（ＩＩ）、臭化Ｓｎ（ＩＩ）、ヨウ化Ｓｎ（ＩＩ）、酸化Ｓｎ（ＩＩ）、リン酸Ｓｎ（ＩＩ）、ピロリン酸Ｓｎ（ＩＩ）、酢酸Ｓｎ（ＩＩ）、クエン酸Ｓｎ（ＩＩ）、グルコン酸Ｓｎ（ＩＩ）、酒石酸Ｓｎ（ＩＩ）、乳酸Ｓｎ（ＩＩ）、コハク酸Ｓｎ（ＩＩ）、スルファミン酸Ｓｎ（ＩＩ）、ギ酸Ｓｎ（ＩＩ）、ケイフッ化Ｓｎ（ＩＩ）などが挙げられる。 Examples of the first Sn salt (Sn salt (II)) include, but are not limited to, alkanesulfonic acid Sn (II) such as methanesulfonic acid Sn (II), and isethionic acid Sn (II). Organic sulfonic acid Sn (II) such as alkanol sulfonic acid Sn (II), Sn (II) sulfate, Sn (II) borofluoride, Sn (II) chloride, Sn (II) bromide, Sn (II) iodide ), Sn (II) oxide, Sn (II) phosphate, Sn (II) pyrophosphate, Sn (II) acetate, Sn (II) citrate, Sn (II) gluconate, Sn (II) tartrate, Sn lactate (II), succinic acid Sn (II), sulfamic acid Sn (II), formic acid Sn (II), silicofluorinated Sn (II) and the like.
第２Ｓｎ塩（Ｓｎ塩（ＩＶ））として、下記に限定されるわけではないが、具体的には、Ｓｎ酸ナトリウム、Ｓｎ酸カリウムなどが挙げられる。 The second Sn salt (Sn salt (IV)) is not limited to the following, but specific examples include sodium Sn acid and potassium Sn acid.
特にメタンスルホン酸Ｓｎ（ＩＩ）等のアルカンスルホン酸Ｓｎ（ＩＩ）、イセチオン酸Ｓｎ（ＩＩ）等のアルカノールスルホン酸Ｓｎ（ＩＩ）などの有機スルホン酸Ｓｎ（ＩＩ）が好ましい。 In particular, alkanesulfonic acid Sn (II) such as methanesulfonic acid Sn (II) and organic sulfonic acid Sn (II) such as alkanol sulfonic acid Sn (II) such as isethionic acid Sn (II) are preferable.
また、Ｓｎ塩の濃度は、Ｓｎとして５〜１００ｇ／Ｌとすることが好ましい。５ｇ／Ｌ未満となると、Ｓｎ濃度が低すぎるためヤケやコゲが生じる原因になる場合がある。一方、１００ｇ／Ｌを超えると、コストが増加する問題や浴の安定性が不安定になり、沈殿を生じる可能性がある。さらに好ましくは１０〜７０ｇ／Ｌである。 Moreover, it is preferable that the density | concentration of Sn salt shall be 5-100 g / L as Sn. If it is less than 5 g / L, the Sn concentration may be too low, which may cause burns and burns. On the other hand, if it exceeds 100 g / L, the problem of increased cost and the stability of the bath may become unstable and precipitation may occur. More preferably, it is 10-70 g / L.
さらにＰｂ濃度の低い、例えば、Ｐｂ濃度が１．０ｐｐｍ以下の低濃度ＰｂのＳｎ塩を使用することも可能である。特にＰｂ濃度が低いＳｎめっき物を得るためのめっき液となり、さらなる低濃度Ｐｂ化が可能となる。代表的なＳｎ塩及び濃度は、上記で挙げられた物質及び濃度である。 Furthermore, it is also possible to use Sn salt having a low Pb concentration, for example, a low concentration Pb having a Pb concentration of 1.0 ppm or less. In particular, it becomes a plating solution for obtaining a Sn plated product having a low Pb concentration, and a further reduction in Pb concentration is possible. Typical Sn salts and concentrations are the materials and concentrations listed above.
また、Ｓｎめっきばかりでなく、Ｓｎ合金めっきにも適用可能である。すなわち、本発明の他の実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、さらにＡｇ塩、Ｃｕ塩、Ｂｉ塩、Ｉｎ塩、Ａｕ塩、Ｓｂ塩、Ｚｎ塩、Ｎｉ塩等から選ばれる１種以上のＳｎ塩以外の金属塩を含有させることが好ましい。このようにすれば、Ｓｎめっきの他、Ｓｎ合金めっき（ＳｎＡｇ、ＳｎＣｕ、ＳｎＢｉ、ＳｎＩｎ，ＳｎＡｕ，ＳｎＳｂ，ＳｎＺｎ，ＳｎＮｉ等）にも適用可能なＳｎ合金めっき液となり、低濃度Ｐｂ化に可能なＳｎ合金めっき液を提供することができる。 Moreover, it is applicable not only to Sn plating but also to Sn alloy plating. That is, the electrolytic Sn or Sn alloy plating solution according to another embodiment of the present invention is further selected from Ag salt, Cu salt, Bi salt, In salt, Au salt, Sb salt, Zn salt, Ni salt and the like. It is preferable to contain a metal salt other than the above Sn salt. If it does in this way, it will become Sn alloy plating solution applicable also to Sn alloy plating (SnAg, SnCu, SnBi, SnIn, SnAu, SnSb, SnZn, SnNi etc.) besides Sn plating, and it is possible to make low concentration Pb. An Sn alloy plating solution can be provided.
［１−３．酸又はその水溶性塩］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する酸又はその水溶性塩は、無機酸、有機酸又その水溶性塩から選ばれる１種以上である。上記の酸又はその水溶性塩は、Ｐｂの共析防止を補助するために含有される。上記の酸又はその水溶性塩により、被めっき物表面やＳｎ表面のｐＨを一定に保ち、均一な表面電位とするからである。
[1-3. Acid or water-soluble salt thereof]
The acid or its water-soluble salt contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention is at least one selected from inorganic acids, organic acids, and water-soluble salts thereof. The above acid or a water-soluble salt thereof is contained in order to help prevent Pb eutectoid. This is because the acid or the water-soluble salt thereof keeps the pH of the surface of the object to be plated or the Sn surface constant, thereby obtaining a uniform surface potential.
上記の酸又はその水溶性塩は、下記に限定されるわけではないが、具体的には、硫酸、塩酸、硝酸、りん酸、スルファミン酸、有機スルホン酸（メタンスルホン酸等のアルカンスルホン酸、イセチオン酸等のアルカノールスルホン酸）、カルボン酸（芳香族カルボン酸、脂肪族飽和カルボン酸、アミノカルボン酸）などが挙げられる。必要に応じて上記水溶性塩の中和塩を使用することもできる。 The acid or water-soluble salt thereof is not limited to the following, but specifically, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid, organic sulfonic acid (alkanesulfonic acid such as methanesulfonic acid, Alkanol sulfonic acids such as isethionic acid), carboxylic acids (aromatic carboxylic acids, aliphatic saturated carboxylic acids, aminocarboxylic acids) and the like. If necessary, a neutralized salt of the above water-soluble salt can be used.
また、上記の酸又はその水溶性塩の濃度は、５０〜５００ｇ／Ｌとすることが好ましい。５０ｇ／Ｌ未満となるとめっき液の安定性が悪くなり、沈殿物が発生しやすくなる。Ｐｂ析出電位に影響を与える可能性がある。一方、５００ｇ／Ｌを超えるとコストが増加する。より好ましくは５０〜３００ｇ／Ｌであり、さらに好ましくは、１００〜２００ｇ／Ｌである。 Moreover, it is preferable that the density | concentration of said acid or its water-soluble salt shall be 50-500 g / L. When it is less than 50 g / L, the stability of the plating solution is deteriorated and precipitates are easily generated. There is a possibility of affecting the Pb deposition potential. On the other hand, if it exceeds 500 g / L, the cost increases. More preferably, it is 50-300 g / L, More preferably, it is 100-200 g / L.
［１−４．界面活性剤］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する界面活性剤は、アニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤から選ばれる１種以上を用いることができる。中でも非イオン界面活性剤が好ましく、アルキレンオキサイド系のものが好適である。上記の界面活性剤は、Ｐｂの共析防止を補助するために含有される。界面活性剤は、被めっき物やＳｎ又はＳｎ合金結晶表面の電流密度を均一にし、表面での均一な析出電位を保つからである。
[1-4. Surfactant]
As the surfactant contained in the electrolytic Sn or Sn alloy plating solution according to one embodiment of the present invention, one or more selected from an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used. Of these, nonionic surfactants are preferred, and alkylene oxides are preferred. Said surfactant is contained in order to assist prevention of eutectoid of Pb. This is because the surfactant makes the current density on the surface of the object to be plated and the Sn or Sn alloy crystal uniform, and maintains a uniform precipitation potential on the surface.
アルキレンオキサイド系のものとして、下記に限定されるわけではないが、具体的には、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルアミド、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン多価アルコールエーテル、酸化エチレン酸化プロピレンブロック重合型、酸化エチレン酸化プロピレンランダム重合型、酸化プロピレン重合型などが挙げられる。中でも特にポリオキシエチレンアルキルフェニルエーテルが好ましい。 Examples of alkylene oxides are not limited to the following, but specific examples include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and polyoxyethylene. Examples include fatty acid esters, polyoxyethylene polyhydric alcohol ethers, ethylene oxide / propylene oxide block polymerization types, ethylene oxide / propylene oxide random polymerization types, and propylene oxide polymerization types. Of these, polyoxyethylene alkylphenyl ether is particularly preferable.
また、上述した酸又はその水溶性塩が、硫酸、塩酸、硝酸、りん酸、スルファミン酸、有機スルホン酸、カルボン酸又はその塩から選ばれる１種以上の酸又はその塩であり、かつ上記界面活性剤が、アニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤から選ばれる１種以上であることがさらに好ましい。 The acid or the water-soluble salt thereof is at least one acid selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid, organic sulfonic acid, carboxylic acid or a salt thereof, and the interface. More preferably, the activator is at least one selected from an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
また、上記の界面活性剤の濃度は、０．０５〜１００ｇ／Ｌとすることが好ましい。０．０５ｇ／Ｌ未満となると、めっき時間を減らすため高電流密度でめっきした場合、高電流密度になる部分でヤケやコゲが発生する場合がある。一方、１００ｇ／Ｌを超えると、Ｓｎめっき被膜が黒色化し、色むらが発生するなどの不良を生じる場合がある。よってＳｎ又はＳｎ合金めっきそのものの被膜に影響を与える場合がある。より好ましくは０．５〜１００ｇ／Ｌである。 Moreover, it is preferable that the density | concentration of said surfactant shall be 0.05-100 g / L. If it is less than 0.05 g / L, when plating is carried out at a high current density in order to reduce the plating time, burns and burns may occur at the portion where the high current density is reached. On the other hand, if it exceeds 100 g / L, the Sn plating film may be blackened, resulting in defects such as uneven color. Therefore, the film of Sn or Sn alloy plating itself may be affected. More preferably, it is 0.5-100 g / L.
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、上記の通り、少なくとも、硫黄系化合物と、Ｓｎ塩と、無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、界面活性剤とを含有する。このようにめっき液に上記の成分を含有させれば、各成分によりめっき表面が均一な析出電位となるため、Ｐｂ共析を防止するのに最適となる。また、１つの構成・成分が欠落すると上記の目的を達成することが困難となる。 As described above, the electrolytic Sn or Sn alloy plating solution according to an embodiment of the present invention is at least one acid selected from a sulfur compound, an Sn salt, an inorganic acid, an organic acid, or a water-soluble salt thereof. Or the water-soluble salt and surfactant are contained. If the above components are contained in the plating solution in this way, the plating surface becomes uniform deposition potential by each component, which is optimal for preventing Pb eutectoid. Further, if one component / component is missing, it becomes difficult to achieve the above object.
少なくとも上記の構成・成分を説明したが、本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液に含有する電解Ｓｎ又はＳｎ合金めっき液は、さらに下記の構成・成分が含有されることも好ましい。以下説明する。 Although at least the above-described configuration / component has been described, the electrolytic Sn or Sn alloy plating solution contained in the electrolytic Sn or Sn alloy plating solution according to an embodiment of the present invention may further include the following configuration / component. preferable. This will be described below.
［１−５．結晶調整剤］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、さらに結晶調整剤が含有されることが好ましい。結晶調整剤は析出した被膜の平滑化をもたらす効果がある。よって、Ｓｎ又はＳｎ合金結晶が成長するに際し、Ｓｎ又はＳｎ合金結晶をより平滑にすることで、結晶表面の局所的な電位の偏りを減らし、Ｐｂ共析防止を補助する。また、上記の結晶調整剤は、アルデヒド類、ケトン類、ベンゾチアゾール類等を使用することができる。
[1-5. Crystal modifier]
The electrolytic Sn or Sn alloy plating solution according to an embodiment of the present invention preferably further contains a crystal modifier. The crystal modifier has an effect of smoothing the deposited film. Therefore, when the Sn or Sn alloy crystal grows, the Sn or Sn alloy crystal is made smoother, thereby reducing local potential bias on the crystal surface and assisting in preventing Pb eutectoid. In addition, aldehydes, ketones, benzothiazoles, and the like can be used as the crystal modifier.
［１−６．有機溶媒］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、さらに有機溶媒を添加されることが好ましい。また、上記の有機溶媒は、下記に限定されるわけではないが、具体的には、メタノール、２−プロパノールなどの１価アルコール類、エチレングリコール、ジエチレングリコール、トリエチレングリコールなどの２価アルコール類などが挙げられる。
[1-6. Organic solvent]
It is preferable that an organic solvent is further added to the electrolytic Sn or Sn alloy plating solution according to an embodiment of the present invention. In addition, the organic solvent is not limited to the following, but specifically, monohydric alcohols such as methanol and 2-propanol, dihydric alcohols such as ethylene glycol, diethylene glycol, and triethylene glycol. Is mentioned.
［１−７．酸化防止剤］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、さらに酸化防止剤が含有されることが好ましい。酸化防止剤は、浴中の２価Ｓｎイオンの酸化と、他のめっき液成分の酸化を防ぎ、液を安定化させる効果がある。よって酸化防止剤の含有により、Ｓｎの酸化還元電位をより一定にすることを補助するので、結果としてＰｂ共析防止を補助できる。上記の酸化防止剤としては、下記に限定されるわけではないが、具体的には、カテコール、ヒドロキノン、４−メトキシフェノール、アスコルビン酸などが挙げられる。
[1-7. Antioxidant]
It is preferable that the electrolytic Sn or Sn alloy plating solution according to the embodiment of the present invention further contains an antioxidant. The antioxidant has an effect of stabilizing the solution by preventing oxidation of divalent Sn ions in the bath and oxidation of other plating solution components. Therefore, the inclusion of the antioxidant helps to make the Sn oxidation-reduction potential more constant, and as a result, the prevention of Pb eutectoid can be assisted. Examples of the antioxidant include, but are not limited to, catechol, hydroquinone, 4-methoxyphenol, and ascorbic acid.
また、上記の酸化防止剤濃度は、０．１〜１００ｇ／Ｌとすることが好ましい。濃度が０．１ｇ／Ｌ未満となると、酸化防止の効果が低下する可能性がある。一方、１００ｇ／Ｌを超えると、コストが増加する傾向にある。さらに好ましい範囲は、０．１〜１０ｇ／Ｌである。 Moreover, it is preferable that said antioxidant density | concentration shall be 0.1-100 g / L. When the concentration is less than 0.1 g / L, the antioxidant effect may be reduced. On the other hand, when it exceeds 100 g / L, the cost tends to increase. A more preferable range is 0.1 to 10 g / L.
［１−８．キレート剤］
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液は、さらにキレート剤が含有されることも可能である。上記のキレート剤は、下記に限定されるわけではないが、具体的には、シュウ酸、コハク酸、マロン酸、グリコール酸、グルコン酸、グルコノラクトン、グリシン、エチレンジアミン酢酸、ピロリン酸、トリポリリン酸などが挙げられる。
[1-8. Chelating agent]
The electrolytic Sn or Sn alloy plating solution according to an embodiment of the present invention may further contain a chelating agent. The above chelating agents are not limited to the following, but specifically, oxalic acid, succinic acid, malonic acid, glycolic acid, gluconic acid, gluconolactone, glycine, ethylenediamineacetic acid, pyrophosphoric acid, tripolyphosphoric acid Etc.
また、上記のキレート剤濃度は、０，１〜２００ｇ／Ｌとすることが好ましい。０．１ｇ／Ｌ未満となると、キレート効果が低下する場合があり、一方２００ｇ／Ｌを超えるとコストが増加する傾向にある。さらに好ましい範囲は０．１〜１００ｇ／Ｌである。 Moreover, it is preferable that said chelating agent density | concentration shall be 0.1-200 g / L. If it is less than 0.1 g / L, the chelate effect may be reduced, while if it exceeds 200 g / L, the cost tends to increase. A more preferable range is 0.1 to 100 g / L.
［２．Ｓｎ又はＳｎ合金めっき物の製造方法］
本発明の一実施形態に係るＳｎ又はＳｎ合金めっき物の製造方法は、図１に示すように、はんだ接合に供されるめっき物を製造するＳｎ又はＳｎ合金めっき物の製造方法であって、電解Ｓｎ又はＳｎ合金めっき液を作製するめっき液作製工程Ｓ１と、上記めっき液を用いて前記Ｓｎ又はＳｎ合金めっき物を製造するめっき工程Ｓ２とを有する。以下工程順に説明する。
[2. Method for producing Sn or Sn alloy plating product]
The method for producing a Sn or Sn alloy plated article according to an embodiment of the present invention is a method for producing a Sn or Sn alloy plated article for producing a plated article to be subjected to solder bonding, as shown in FIG. It has plating solution preparation process S1 which produces electrolytic Sn or Sn alloy plating solution, and plating process S2 which manufactures said Sn or Sn alloy plating thing using the above-mentioned plating solution. This will be described in the order of steps.
［２−１．めっき液作製工程］
本発明の一実施形態に係るＳｎ又はＳｎ合金めっき物の製造方法は、図１に示すように、めっき液作製工程Ｓ１を有する。上記めっき液作製工程Ｓ１において、上記電解Ｓｎ又はＳｎ合金めっき液は、少なくとも、硫黄系化合物と、Ｓｎ塩と、無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、界面活性剤とを含有させて作製する。そして、上記硫黄系化合物は、下記の一般式であらわされるチオール化合物（式Ａ）、チオール化合物（式Ａ）の塩、又はジスルフィド化合物（式Ｂ）とする。
[2-1. Plating solution preparation process]
The manufacturing method of Sn or Sn alloy plated article according to an embodiment of the present invention includes a plating solution preparation step S1 as shown in FIG. In the plating solution preparation step S1, the electrolytic Sn or Sn alloy plating solution is at least one or more acids selected from a sulfur compound, an Sn salt, an inorganic acid, an organic acid, or a water-soluble salt thereof, or a water solution thereof. It is prepared by containing a functional salt and a surfactant. The sulfur-based compound is a thiol compound (formula A) represented by the following general formula, a salt of a thiol compound (formula A), or a disulfide compound (formula B).
式Ａ：
Ｒ２：
本発明の一実施形態に係るＳｎ又はＳｎ合金めっき物の製造方法に使用されるめっき液に含有する硫黄系化合物は、Ｐｂの共析防止剤として含有され、上記の式Ａに示すようなチオール化合物、チオール化合物の塩であり、又は式Ｂに示すようなジスルフィドである。そしてＲ１は、アニリン、ピリジン又はピリジンＮオキシドのいずれかである。また、Ｒ２は、アニリン（ＩＶ）、ピリジン（Ｖ）、ベンゼン（ＶＩ）、ブタン（ＶＩＩ）、トルエン（ＶＩＩＩ）のいずれかである。 The sulfur-based compound contained in the plating solution used in the method for producing a Sn or Sn alloy plated article according to an embodiment of the present invention is contained as a Pb eutectoid inhibitor, and a thiol as shown in Formula A above Compound, a salt of a thiol compound, or a disulfide as shown in Formula B. R1 is aniline, pyridine, or pyridine N oxide. R2 is any one of aniline (IV), pyridine (V), benzene (VI), butane (VII), and toluene (VIII).
少なくとも上述したように、Ｓｎ塩と、酸又はその塩、界面活性剤とを含有しためっき液とすることで、各成分の働きにより、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能なＳｎ又はＳｎ合金めっき物を提供することができる。 As described above, by using a plating solution containing an Sn salt, an acid or a salt thereof, and a surfactant, the eutectoid of Pb is suppressed by the action of each component, and a low concentration Pb can be achieved. An Sn or Sn alloy plated article can be provided.
また、上記の硫黄系化合物、Ｓｎ塩、酸又はその塩、界面活性剤の濃度比、濃度、好ましい化合物は上記に説明した通りである。また、Ｓｎ塩として、上述Ｐｂ濃度が１．０ｐｐｍ以下の上記のＳｎ塩を使用することも可能である。硫黄系化合物、Ｓｎ塩、酸又はその塩、界面活性剤の他にさらに、上述した結晶調整剤、有機溶媒、酸化防止剤、キレート剤を含有させることも好ましい。Ｓｎ合金めっき液とするために、上述したように、さらにＡｇ塩、Ｃｕ塩、Ｂｉ塩、Ｉｎ塩、Ａｕ塩、Ｓｂ塩、Ｚｎ塩、Ｎｉ塩等から選ばれる１種以上のＳｎ以外の金属塩を含有することが好ましい。 Further, the above-described sulfur-based compound, Sn salt, acid or salt thereof, surfactant concentration ratio, concentration, and preferred compounds are as described above. Moreover, it is also possible to use said Sn salt whose said Pb density | concentration is 1.0 ppm or less as Sn salt. In addition to the sulfur compound, Sn salt, acid or salt thereof, and surfactant, it is also preferable to contain the above-mentioned crystal modifier, organic solvent, antioxidant, and chelating agent. In order to obtain a Sn alloy plating solution, as described above, one or more metals other than Sn selected from Ag salt, Cu salt, Bi salt, In salt, Au salt, Sb salt, Zn salt, Ni salt, etc. It is preferable to contain a salt.
［２−２．めっき工程］
本発明の一実施形態に係るＳｎ又はＳｎ合金めっき物の製造方法は、図１に示すように、めっき工程Ｓ２を有する。上記のめっき液作製工程Ｓ１で作製しためっき液を用いて、Ｓｎ又はＳｎ合金めっき物を製造する。電流密度は、特に限定されないが、１〜２０A／ｄｍ２の範囲でめっきを行うことが好ましい。さらに好ましい範囲は２〜６Ａ／ｄｍ２である。また、必要な前処理や後処理を行い、Ｓｎ又はＳｎ合金めっき物を得る。
[2-2. Plating process]
The manufacturing method of Sn or Sn alloy plated article according to an embodiment of the present invention includes a plating step S2 as shown in FIG. An Sn or Sn alloy plating product is manufactured using the plating solution prepared in the plating solution preparation step S1. The current density is not particularly limited, but the plating is preferably performed in the range of 1 to 20 A / dm2. A more preferable range is 2 to 6 A / dm 2 . Further, necessary pre-treatment and post-treatment are performed to obtain a Sn or Sn alloy plated product.
また、Ｓｎ又はＳｎ合金めっき物の製造方法によれば、上記めっき物の被膜が低アルファグレードＳｎ又はＳｎ合金めっき被膜（０．０１ｃｏｕｎｔｓ／ｈｒ／ｃｍ２未満）であることを特徴とする。ここで図２に、Ｓｎ中のＰｂ含有量とα線量（ｃｏｕｎｔｓ／ｈｒ／ｃｍ２）の関係を示す。このようにＳｎ中のＰｂ含有量とα線量は比例関係にあり、Ｐｂ含有量が増加するとα線量も増加する。これらのデータから近似式を算出すると、α線量（ｃｏｕｎｔｓ／ｈｒ／ｃｍ２）＝０．００４８×Ｐｂ含有量（ｐｐｍ）＋０．０００５である。この近似式から０．０１ｃｏｕｎｔｓ／ｈｒ／ｃｍ２に相当するＰｂ含有量は、２．０ｐｐｍとなる。つまり、上記の低アルファグレードＳｎめっき被膜は、Ｐｂ濃度が２．０ｐｐｍ未満であることを特徴とする。このようにすれば、低濃度Ｐｂ化が可能となり、デバイスの動作不良への影響を防止できる。 Moreover, according to the manufacturing method of Sn or Sn alloy plated material, the film of the plated material is a low alpha grade Sn or Sn alloy plated film (less than 0.01 counts / hr / cm 2 ). FIG. 2 shows the relationship between the Pb content in Sn and the α dose (counts / hr / cm 2 ). Thus, the Pb content in Sn and the α dose are in a proportional relationship, and as the Pb content increases, the α dose also increases. When an approximate expression is calculated from these data, α dose (counts / hr / cm 2 ) = 0.0048 × Pb content (ppm) +0.0005. From this approximate expression, the Pb content corresponding to 0.01 counts / hr / cm 2 is 2.0 ppm. That is, the low alpha grade Sn plating film is characterized in that the Pb concentration is less than 2.0 ppm. In this way, it is possible to reduce the concentration of Pb, and it is possible to prevent an influence on device malfunction.
次に、本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液及びＳｎ又はＳｎ合金めっき物の製造方法について実施例により詳しく説明する。なお、本発明は、これらの実施例に限定されるものではない。 Next, an electrolytic Sn or Sn alloy plating solution and a method for producing a Sn or Sn alloy plated product according to an embodiment of the present invention will be described in detail with reference to examples. The present invention is not limited to these examples.
［実施例１］
実施例１では、電解Ｓｎめっき液として、硫黄系化合物、Ｓｎ塩、有機酸、界面活性剤を加えた。硫黄系化合物として、ジベンジルジスルフィドを５ｇ／Ｌ加えた。Ｓｎ塩としてアルカンスルホン酸Ｓｎ（ＩＩ）をＳｎ（Ｓｎ２＋）として４０ｇ／Ｌ、有機酸として有機スルホン酸を１５５．３ｇ／Ｌ、界面活性剤としてポリオキシエチレンアルキルフェニルエーテルを５ｇ／Ｌ加えた。また、結晶調整剤として、２−メルカプトベンゾチアゾールを０．１５ｇ／Ｌ加えた。めっき液の液温を３０℃、電流密度を４Ａ／ｄｍ２とした。さらに、実施例１ではＰｂ濃度が１．０ｐｐｍ以下の低濃度ＰｂのＳｎ塩を用いためっき液も作製した。
[Example 1]
In Example 1, a sulfur compound, an Sn salt, an organic acid, and a surfactant were added as an electrolytic Sn plating solution. As a sulfur compound, 5 g / L of dibenzyl disulfide was added. 40 g / L of alkanesulfonic acid Sn (II) as Sn (Sn 2+ ) as Sn salt, 155.3 g / L of organic sulfonic acid as organic acid, and 5 g / L of polyoxyethylene alkylphenyl ether as surfactant were added. . Further, 0.15 g / L of 2-mercaptobenzothiazole was added as a crystal modifier. The temperature of the plating solution was 30 ° C., and the current density was 4 A / dm 2 . Furthermore, in Example 1, a plating solution using a low-concentration Pb Sn salt having a Pb concentration of 1.0 ppm or less was also produced.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．４５４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.454 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。なお、以下Ｓｎ塩を使用した際のＰｂ析出量は日立ハイテクサイエンス製ＺＡ３３００を用いて測定し、低濃度ＰｂのＳｎ塩はＡｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ製Ａｇｉｌｅｎｔ ７７００ ＳｅｒｉｅｓのＩＣＰ−ＭＳを用いて測定した。また、析出電位はＢＡＳ社製のモデル２３２５バイポテンショスタットを使用した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured. In the following, the amount of Pb deposited when using Sn salt was measured using ZA3300 manufactured by Hitachi High-Tech Science, and the Sn salt of low concentration Pb was measured using ICP-MS of Agilent 7700 Series manufactured by Agilent Technologies. Moreover, the model 2325 bipotentiostat made from BAS was used for the precipitation potential.
［実施例２］
実施例２では、硫黄系化合物として、４，４’−ジピリジルジスルフィドを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 2]
In Example 2, 5 g / L of 4,4′-dipyridyl disulfide was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．４５４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.454 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例３］
実施例３では、硫黄系化合物として、ジフェニルジスルフィドを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 3]
In Example 3, 5 g / L of diphenyl disulfide was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．４５４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.454 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例４］
実施例４では、硫黄系化合物として、２，２−ジチオジアニリンを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 4]
In Example 4, 5 g / L of 2,2-dithiodianiline was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は２５．８８５ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the source metal Sn of the Sn salt was 25.885 ppm, and the Pb concentration in the source metal Sn of the Sn salt of the low concentration Pb was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例５］
実施例５では、硫黄系化合物として、２−アミノベンゼンチオールを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 5]
In Example 5, 5 g / L of 2-aminobenzenethiol was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．４５４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.454 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例６］
実施例６では、硫黄系化合物として、２，２−ジピリジルジスルフィドを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 6]
In Example 6, 5 g / L of 2,2-dipyridyl disulfide was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は２６．２３６ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 26.236 ppm, and the Pb concentration in the raw material Sn of the Sn salt of the low concentration Pb was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例７］
実施例７では、硫黄系化合物として、２−メルカプトピリジンを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 7]
In Example 7, 5 g / L of 2-mercaptopyridine was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．４５４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.454 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例８］
実施例８では、硫黄系化合物として、２−メルカプトピリジンＮ−オキシドＮａ塩を５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 8]
In Example 8, 5 g / L of 2-mercaptopyridine N-oxide Na salt was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．４５４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.454 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例９］
実施例９では、硫黄系化合物として、２，２−ジチオジアニリンを５ｇ／Ｌ加えた。さらにＳｎ−Ａｇ合金めっきとするため、Ａｇ塩を０．５ｇ／Ｌ加えた。Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 9]
In Example 9, 5 g / L of 2,2-dithiodianiline was added as a sulfur compound. Furthermore, in order to make Sn—Ag alloy plating, 0.5 g / L of Ag salt was added. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は４０．３０１ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．８２６ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 40.301 ppm, and the Pb concentration in the raw metal Sn of the Sn salt of the low concentration Pb was 0.826 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［実施例１０］
実施例１０では、硫黄系化合物として、２，２−ジピリジルジスルフィドを５ｇ／Ｌ加えた。さらにＳｎ−Ａｇ合金めっきとするため、Ａｇ塩を０．５ｇ／Ｌ加えた。Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Example 10]
In Example 10, 5 g / L of 2,2-dipyridyl disulfide was added as a sulfur compound. Furthermore, in order to make Sn—Ag alloy plating, 0.5 g / L of Ag salt was added. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は６５．４３１ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 65.431 ppm, and the Pb concentration in the raw metal Sn of the Sn salt of the low concentration Pb was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［比較例１］
比較例１では、硫黄系化合物を加えなかった。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 1]
In Comparative Example 1, no sulfur compound was added. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は２５．８０７ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 25.807 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［比較例２］
比較例２では、硫黄系化合物として、３，６−ジチア１，８−オクタンジオールを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 2]
In Comparative Example 2, 5 g / L of 3,6-dithia 1,8-octanediol was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は２１．５８４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 21.484 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［比較例３］
比較例３では、硫黄系化合物として、チオ尿素を５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 3]
In Comparative Example 3, 5 g / L of thiourea was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１６．７９４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 16.794 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［比較例４］
比較例４では、硫黄系化合物として、ビス（２−アミノフェニル）スルフィドを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 4]
In Comparative Example 4, 5 g / L of bis (2-aminophenyl) sulfide was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１５．０６５ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 15.065 ppm, and the Pb concentration in the raw material Sn of the low concentration Pb Sn salt was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［比較例５］
比較例５では、硫黄系化合物として、３−アミノピリジンを５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。なお比較例５では、低濃度ＰｂのＳｎ塩を用いためっき液は作製しなかった。
[Comparative Example 5]
In Comparative Example 5, 5 g / L of 3-aminopyridine was added as a sulfur compound. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1. In Comparative Example 5, a plating solution using a low concentration Pb Sn salt was not produced.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は１６．０６８ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 16.068 ppm.
そして上記のめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量を測定した。 Then, using the above plating solution, electrolytic Sn plating was performed, and the Pb eutectoid rate (%) and the Pb eutectoid amount were measured.
［比較例６］
比較例６では、硫黄系化合物として、実施例４と同じ２，２−ジチオジアニリンを５ｇ／Ｌ加えたが、有機酸、界面活性剤を加えなかった。その他Ｓｎ塩、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 6]
In Comparative Example 6, 5 g / L of the same 2,2-dithiodianiline as in Example 4 was added as a sulfur compound, but no organic acid or surfactant was added. In addition, the conditions of Sn salt, crystal adjusting agent, liquid temperature, and current density were the same as in Example 1.
［比較例７］
比較例７では、硫黄系化合物として、実施例４と同じ２，２−ジチオジアニリンを５ｇ／Ｌ加えたが、界面活性剤を加えなかった。その他Ｓｎ塩、有機酸、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 7]
In Comparative Example 7, 5 g / L of the same 2,2-dithiodianiline as Example 4 was added as a sulfur compound, but no surfactant was added. In addition, the conditions of Sn salt, organic acid, crystal adjusting agent, liquid temperature, and current density were the same as in Example 1.
［比較例８］
比較例８では、硫黄系化合物として、３，６−ジチア１，８−オクタンジオールを５ｇ／Ｌ加えた。さらにＳｎ−Ａｇ合金めっきとするため、Ａｇ塩を０．５ｇ／Ｌ加えた。Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。
[Comparative Example 8]
In Comparative Example 8, 5 g / L of 3,6-dithia 1,8-octanediol was added as a sulfur compound. Furthermore, in order to make Sn—Ag alloy plating, 0.5 g / L of Ag salt was added. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は２６．７３４ｐｐｍ、低濃度ＰｂのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は０．４０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 26.734 ppm, and the Pb concentration in the raw metal Sn of the Sn salt of the low concentration Pb was 0.407 ppm.
そして上記の２つのめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the two plating solutions described above, and the Pb eutectoid rate (%), the Pb eutectoid amount, and the deposition potential were measured.
［比較例９］
比較例９では、硫黄系化合物として、チオ尿素を５ｇ／Ｌ加えた。さらにＳｎ−Ａｇ合金めっきとするため、Ａｇ塩を０．５ｇ／Ｌ加えた。また、Ｓｎ塩、有機酸、界面活性剤、結晶調整剤、液温、電流密度の条件は実施例１と同様とした。なお比較例９では、低濃度ＰｂのＳｎ塩を用いためっき液は作製しなかった。
[Comparative Example 9]
In Comparative Example 9, 5 g / L of thiourea was added as a sulfur compound. Furthermore, in order to make Sn—Ag alloy plating, 0.5 g / L of Ag salt was added. The conditions of Sn salt, organic acid, surfactant, crystal modifier, liquid temperature, and current density were the same as in Example 1. In Comparative Example 9, a plating solution using a low-concentration Pb Sn salt was not produced.
このときのＳｎ塩の原料金属Ｓｎ中のＰｂ濃度は２５．８０７ｐｐｍであった。 At this time, the Pb concentration in the raw material Sn of the Sn salt was 25.807 ppm.
そして上記のめっき液を用いて、それぞれ電解Ｓｎめっきを行い、Ｐｂの共析率（％）、Ｐｂ共析量、析出電位を測定した。 Then, electrolytic Sn plating was performed using the above plating solution, and Pb eutectoid rate (%), Pb eutectoid amount, and precipitation potential were measured.
なおＰｂ共析率（％）は、めっき被膜中Ｐｂ含有量（ｐｐｍ）／Ｓｎ原材料中のＰｂ含有量（ｐｐｍ）×１００として算出した。その結果を表１に示す。 The Pb eutectoid rate (%) was calculated as Pb content in plating film (ppm) / Pb content in Sn raw material (ppm) × 100. The results are shown in Table 1.
全ての実施例では、全ての比較例よりも共析率が低い値となり、Ｐｂ共析量も低い値となった。さらに低濃度ＰｂのＳｎ塩を用いた全ての実施例におけるめっき液でも、全ての比較例よりも小さい値となり、Ｐｂ共析量も極めて低い値となった。また、本発明の一実施形態に係る電解Ｓｎめっき液に用いられる硫黄系化合物を加えた実施例では、比較例と比べ、Ｐｂ，Ｓｎの析出電位を貴または卑にシフトさせＰｂ，Ｓｎの析出電位差が０．０６Ｖ以上に広がった。よって上記の硫黄系化合物が共析防止剤として働いたことが分かる。 In all the examples, the eutectoid rate was lower than in all the comparative examples, and the Pb eutectoid amount was also lower. Furthermore, even in the plating solutions in all the examples using the Sn salt of low concentration Pb, the values were smaller than in all the comparative examples, and the amount of Pb eutectoid was extremely low. In addition, in the example in which the sulfur-based compound used in the electrolytic Sn plating solution according to one embodiment of the present invention was added, the precipitation potential of Pb and Sn was shifted to noble or base as compared with the comparative example, and the precipitation of Pb and Sn. The potential difference spread over 0.06V. Therefore, it turns out that said sulfur type compound worked as a eutectoid inhibitor.
また、上記式Ａ又は上記式Ｂが上記Ｒ１又は上記Ｒ２の２位又は６位と結合した硫黄系化合物、すなわち２，２−ジチオジアニリン、２−アミノベンゼンチオール、２，２−ジピリジルジスルフィド、２−メルカプトピリジン、２−メルカプトピリジンＮ−オキシドを加えた実施例４〜７では、２位又は６位以外と結合した実施例１〜３と比べ、Ｓｎ塩のめっき液及び低濃度ＰｂのＳｎ塩を用いためっき液において、共析率が低い値となった。 In addition, a sulfur compound in which the formula A or the formula B is bonded to the 2-position or the 6-position of the R 1 or the R 2 , that is, 2,2-dithiodianiline, 2-aminobenzenethiol, 2,2-dipyridyl In Examples 4 to 7 to which disulfide, 2-mercaptopyridine, and 2-mercaptopyridine N-oxide were added, compared with Examples 1 to 3 bonded to positions other than 2-position or 6-position, Sn salt plating solution and low concentration Pb In the plating solution using the Sn salt, the eutectoid rate was low.
有機酸及び界面活性剤を加えていない比較例６と、界面活性剤を加えていない比較例７は、被膜が成り立たなかったため、共析率、Ｐｂ濃度は測定できなかった。被膜が成り立たなかった理由としては、被めっき物表面やＳｎ表面のｐＨを一定に保てず、均一な表面電位とはならなかったため、及び被めっき物やＳｎ結晶表面の電流密度を均一できず、表面での均一な析出電位を保つことができなかったためと考えられる。よって、上記硫黄系化合物とＳｎ塩の他、無機酸、有機酸又その水溶性塩や界面活性剤を加えることは重要であり、上記化合物との組み合わせることは重要であった。 In Comparative Example 6 in which no organic acid and a surfactant were added and in Comparative Example 7 in which no surfactant was added, the eutectoid rate and the Pb concentration could not be measured because the film was not formed. The reason why the film was not formed was that the surface of the object to be plated or the Sn surface could not be kept constant and the surface potential was not uniform, and the current density of the object to be plated or Sn crystal surface could not be made uniform. This is probably because a uniform deposition potential on the surface could not be maintained. Therefore, in addition to the sulfur compound and Sn salt, it is important to add an inorganic acid, an organic acid, a water-soluble salt thereof, and a surfactant, and it is important to combine with the above compound.
またＳｎ−Ａｇ合金めっき液でも同様に、実施例９及び１０では、比較例８及び９よりも共析率が低い値となり、Ｐｂ共析量も低い値となった。さらに低濃度ＰｂのＳｎ塩を用いた全ての実施例におけるめっき液でも、全ての比較例よりも低い値となり、Ｐｂ共析量も極めて低い値となった。また、本発明の一実施形態に係る電解Ｓｎめっき液に用いられる硫黄系化合物を加えた実施例では、比較例と比べ、Ｐｂ，Ｓｎの析出電位を貴または卑にシフトさせＰｂ，Ｓｎの析出電位差が０．０６Ｖ以上に広がった。よって上記の硫黄系化合物が共析防止剤として働いたことが分かる。 Similarly, in the Sn-Ag alloy plating solution, in Examples 9 and 10, the eutectoid rate was lower than in Comparative Examples 8 and 9, and the Pb eutectoid amount was also lower. Furthermore, even in the plating solutions in all Examples using Sn salt of low concentration Pb, the values were lower than in all Comparative Examples, and the amount of Pb eutectoid was extremely low. In addition, in the example in which the sulfur-based compound used in the electrolytic Sn plating solution according to one embodiment of the present invention was added, the precipitation potential of Pb and Sn was shifted to noble or base as compared with the comparative example, and the precipitation of Pb and Sn. The potential difference spread over 0.06V. Therefore, it turns out that said sulfur type compound worked as a eutectoid inhibitor.
本発明の一実施形態に係る電解Ｓｎ又はＳｎ合金めっき液及びＳｎ又はＳｎ合金めっき物の製造方法を適用することによって、各成分の働きにより、Ｐｂの共析を抑制し、低濃度Ｐｂ化が可能なＳｎ又はＳｎ合金めっき液を提供することができた。 By applying the electrolytic Sn or Sn alloy plating solution and the Sn or Sn alloy plating product manufacturing method according to one embodiment of the present invention, the eutectoid of Pb is suppressed by the action of each component, and the low concentration Pb is reduced. A possible Sn or Sn alloy plating solution could be provided.
なお、上記のように本発明の各実施形態及び各実施例について詳細に説明したが、本発明の新規事項及び効果から実体的に逸脱しない多くの変形が可能であることは、当業者には、容易に理解できるであろう。従って、このような変形例は、全て本発明の範囲に含まれるものとする。 Although the embodiments and examples of the present invention have been described in detail as described above, it will be understood by those skilled in the art that many modifications can be made without departing from the novel matters and effects of the present invention. It will be easy to understand. Therefore, all such modifications are included in the scope of the present invention.
例えば、明細書又は図面において、少なくとも一度、より広義又は同義な異なる用語と共に記載された用語は、明細書又は図面のいかなる箇所においても、その異なる用語に置き換えることができる。また、電解Ｓｎ又はＳｎ合金めっき液及びＳｎ又はＳｎ合金めっき物の製造方法の構成、動作も本発明の各実施形態及び各実施例で説明したものに限定されず、種々の変形実施が可能である。 For example, a term described with a different term having a broader meaning or the same meaning at least once in the specification or the drawings can be replaced with the different term in any part of the specification or the drawings. Further, the configuration and operation of the electrolytic Sn or Sn alloy plating solution and the Sn or Sn alloy plated product are not limited to those described in the embodiments and examples of the present invention, and various modifications can be made. is there.
Ｓ１ めっき液作製工程 Ｓ２ めっき工程 S1 Plating solution preparation process S2 Plating process
Claims (7)
少なくとも、硫黄系化合物と、
Ｓｎ塩と、
無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、
界面活性剤とを含有し、
前記硫黄系化合物は、下記の一般式であらわされるチオール化合物（式Ａ）、チオール化合物（式Ａ）の塩、又はジスルフィド化合物（式Ｂ）であることを特徴とする電解Ｓｎ又はＳｎ合金めっき液。
式Ａ：
Ｒ２：
At least a sulfur compound,
Sn salt,
One or more acids selected from inorganic acids, organic acids or water-soluble salts thereof, or water-soluble salts thereof;
Containing a surfactant,
The sulfur-based compound is a thiol compound (formula A) represented by the following general formula, a salt of a thiol compound (formula A), or a disulfide compound (formula B). .
Formula A:
かつ前記界面活性剤が、アニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤から選ばれる１種以上であることを特徴とする請求項１乃至３の何れか１項に記載の電解Ｓｎ又はＳｎ合金めっき液。 The acid or water-soluble salt thereof is one or more acids or salts thereof selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid, organic sulfonic acid, carboxylic acid or salts thereof,
4. The electrolytic Sn according to claim 1, wherein the surfactant is at least one selected from an anionic surfactant, a cationic surfactant, and a nonionic surfactant. 5. Or Sn alloy plating solution.
電解Ｓｎ又はＳｎ合金めっき液を作製するめっき液作製工程と、
前記めっき液を用いて前記Ｓｎ又はＳｎ合金めっき物を製造するめっき工程とを有し、
前記めっき液作製工程において、前記電解Ｓｎ又はＳｎ合金めっき液は、少なくとも、硫黄系化合物と、Ｓｎ塩と、無機酸、有機酸又その水溶性塩から選ばれる１種以上の酸又はその水溶性塩と、界面活性剤とを含有させて作製し、
前記硫黄系化合物は、下記の一般式であらわされるチオール化合物（式Ａ）、チオール化合物（式Ａ）の塩、又はジスルフィド化合物（式Ｂ）であることを特徴とするＳｎ又はＳｎ合金めっき物の製造方法。
式Ａ：
Ｒ２：
A plating solution preparation step of preparing an electrolytic Sn or Sn alloy plating solution;
A plating process for producing the Sn or Sn alloy plating product using the plating solution,
In the plating solution preparation step, the electrolytic Sn or Sn alloy plating solution is at least one or more acids selected from sulfur compounds, Sn salts, inorganic acids, organic acids, and water-soluble salts thereof, or water-soluble salts thereof. Made by containing salt and surfactant,
The sulfur-based compound is a thiol compound (formula A) represented by the following general formula, a salt of a thiol compound (formula A), or a disulfide compound (formula B). Production method.
Formula A:
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| KR1020207010094A KR20200053534A (en) | 2017-09-15 | 2018-07-26 | Electrolytic Sn or Sn alloy plating solution and Sn or Sn alloy plating method |
| PCT/JP2018/028003 WO2019054060A1 (en) | 2017-09-15 | 2018-07-26 | Electrolytic sn or sn alloy plating solution and method for producing electrolytic sn or sn alloy plated article |
| US16/646,990 US20200208285A1 (en) | 2017-09-15 | 2018-07-26 | Electrolytic sn or sn alloy plating solution and method for producing sn or sn alloy plated article |
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| JP2021188112A (en) * | 2020-06-04 | 2021-12-13 | 上村工業株式会社 | Tin or tin alloy plating bath |
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| CN115917789A (en) * | 2020-05-11 | 2023-04-04 | 科罗拉多州立大学研究基金会 | Electrodeposition of phase-pure SnSb from eutectic ethaline solution for anodes of Na-ion and Li-ion batteries |
| CN114214677A (en) * | 2021-12-30 | 2022-03-22 | 佛山亚特表面技术材料有限公司 | Acidic copper plating deep hole agent, preparation method thereof and electroplating method |
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| JP3301707B2 (en) * | 1997-01-20 | 2002-07-15 | ディップソール株式会社 | Tin-silver alloy acid electroplating bath |
| DE10026680C1 (en) * | 2000-05-30 | 2002-02-21 | Schloetter Fa Dr Ing Max | Electrolyte and method for depositing tin-silver alloy layers and use of the electrolyte |
| JP5158303B2 (en) * | 2006-04-14 | 2013-03-06 | 上村工業株式会社 | Tin electroplating bath, tin plating film, tin electroplating method and electronic device component |
| JP5649805B2 (en) | 2009-08-12 | 2015-01-07 | ルネサスエレクトロニクス株式会社 | Manufacturing method of semiconductor device |
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| EP3711955A2 (en) | 2019-03-20 | 2020-09-23 | Seiko Epson Corporation | Liquid ejecting unit and liquid ejecting apparatus |
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