JP4817166B2 - Tin-copper alloy plating solution - Google Patents
Tin-copper alloy plating solution Download PDFInfo
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- JP4817166B2 JP4817166B2 JP2004122110A JP2004122110A JP4817166B2 JP 4817166 B2 JP4817166 B2 JP 4817166B2 JP 2004122110 A JP2004122110 A JP 2004122110A JP 2004122110 A JP2004122110 A JP 2004122110A JP 4817166 B2 JP4817166 B2 JP 4817166B2
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- 238000007747 plating Methods 0.000 title claims description 119
- 229910000597 tin-copper alloy Inorganic materials 0.000 title claims description 31
- 239000000243 solution Substances 0.000 claims description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- -1 aromatic carbonyl compound Chemical class 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 12
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 238000002845 discoloration Methods 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910001128 Sn alloy Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004002 naphthaldehydes Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 2
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Description
本発明は、スズ−銅合金めっき液、スズ−銅合金めっき方法及びスズ−銅合金めっき皮膜が形成された物品に関する。 The present invention relates to a tin-copper alloy plating solution, a tin-copper alloy plating method, and an article on which a tin-copper alloy plating film is formed.
スズ−鉛合金めっきは、外観が良好で、はんだ付け性に優れ、更に、めっき浴の管理も比較的容易であり、従来から、はんだめっきと称されて、電気・電子部品のめっきに広く利用されている。しかしながら、近年、環境保全対策として、人体に有害な鉛を含有しない、はんだめっきに代わり得る鉛フリーのスズ合金めっきの開発が強く要望されている。 Tin-lead alloy plating has a good appearance, excellent solderability, and relatively easy management of the plating bath. Conventionally, it has been called solder plating and is widely used for plating of electrical and electronic parts. Has been. However, in recent years, there has been a strong demand for development of lead-free tin alloy plating that does not contain lead harmful to the human body and can replace solder plating as an environmental protection measure.
フレキシブル基板などのプリント配線板では、基板上にチップ部品を装着する際に、めっき皮膜を溶解させた後固化させてチップ部品を基板に接合するリフロー処理が広く行われている。この方法で用いる基板に対して鉛フリ−のスズ合金めっきを行う場合には、めっき皮膜が良好な光沢を有し、リフロー処理後においても変色しないことが要求される。更に、鉛フリーのスズ合金めっき液は、安価であることも重要な要件である。 In a printed wiring board such as a flexible substrate, when a chip component is mounted on the substrate, a reflow process is widely performed in which the plating film is dissolved and then solidified to bond the chip component to the substrate. When lead-free tin alloy plating is performed on a substrate used in this method, it is required that the plating film has good gloss and does not change color even after reflow treatment. Furthermore, it is an important requirement that the lead-free tin alloy plating solution is inexpensive.
近年、スズ−鉛合金に代わる鉛フリーの低融点のスズ合金めっきとして、比較的安価なスズ−銅合金が、コネクター部品などの接合材料として使用されている。 In recent years, a relatively inexpensive tin-copper alloy has been used as a bonding material for connector parts and the like as a lead-free low melting point tin alloy plating instead of a tin-lead alloy.
例えば、下記特許文献１には、添加剤としてＮ，Ｎ−ビス（ポリオキシエチレン）アルキルアミン化合物を含有するスズ−銅合金めっき浴が記載されている。しかしながら、このめっき浴を用いる場合には、形成されるめっき皮膜の光沢性が劣るためにめっき後に物理研磨等が必要となる。 For example, Patent Document 1 below discloses a tin-copper alloy plating bath containing an N, N-bis (polyoxyethylene) alkylamine compound as an additive. However, when this plating bath is used, since the gloss of the plating film formed is inferior, physical polishing or the like is required after plating.
また、下記特許文献２には、有機スルホン酸、有機スルホン酸の２価錫塩と２価銅塩、分散剤及び光沢剤を含有する光沢錫／銅合金めっき浴が記載されている。しかしながら、このめっき浴では、形成されるめっき皮膜の外観は良好であるものの、有機スルホン酸を酸成分として含有するために、硫酸を用いる場合と比べてコストが高いという欠点がある。更に、リフロー処理後に変色を生じ易く、部品の実装不良を引き起こし易いという問題点もある。
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、良好な光沢を有するめっき皮膜を形成でき、しかもリフロー処理後にめっき皮膜の変色が少ない、安価なスズ−銅合金めっき液を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main purpose is to form an inexpensive tin film which can form a plating film having a good gloss and has little discoloration of the plating film after reflow treatment. -To provide a copper alloy plating solution.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、スズ−銅合金の硫酸浴を基本浴として用い、これに塩化物、芳香族カルボニル化合物及び界面活性剤を添加しためっき液によれば、上記した目的を達成できることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, it was found that a tin-copper alloy sulfuric acid bath was used as a basic bath, and a plating solution to which a chloride, an aromatic carbonyl compound and a surfactant were added could achieve the above-described purpose. The invention has been completed.
即ち、本発明は、下記のスズ−銅合金めっき液、スズ−銅合金めっき方法、及びスズ−銅合金めっき皮膜が形成された物品を提供するものである。
１． 硫酸第一スズ、硫酸銅（II）、硫酸、塩化物、芳香族カルボニル化合物及び界面活性剤を有効成分として含有する水溶液からなるスズ−銅合金めっき液であって、
硫酸第一スズを５〜１００ｇ／ｌ、硫酸銅（II）を５水和物の濃度として０．１〜５ｇ／ｌ、硫酸を９８％硫酸の濃度として５０〜２５０ｇ／ｌ、塩化物としてアルカリ金属の塩化物及びアルカリ土類金属の塩化物からなる群から選択された少なくとも一種を０．０１〜１ｇ／ｌ、芳香族カルボニル化合物を０．０１〜１ｇ／ｌ及び界面活性剤を１〜５０ｇ／ｌ含有する水溶液からなるスズ−銅合金めっき液。
２． 上記項１に記載されたスズ−銅合金めっき液中で、被めっき物を陰極として電解することを特徴とするスズ−銅合金めっき方法。
３． 上記項２に記載の方法によってスズ−銅合金めっき皮膜が形成された物品
本発明のスズ−銅合金めっき液は、硫酸第一スズ、硫酸銅（II）、硫酸、塩化物、芳香族カルボニル化合物及び界面活性剤を有効成分として含有する水溶液からなるものである。
That is, the present invention provides the following tin-copper alloy plating solution, tin-copper alloy plating method, and an article on which a tin-copper alloy plating film is formed.
1. A tin-copper alloy plating solution comprising an aqueous solution containing stannous sulfate, copper (II) sulfate, sulfuric acid, chloride, an aromatic carbonyl compound and a surfactant as active ingredients ,
Stannous sulfate 5-100 g / l, copper (II) sulfate pentahydrate concentration 0.1-5 g / l, sulfuric acid 98% sulfuric acid concentration 50-250 g / l, chloride as alkali 0.01-1 g / l of at least one selected from the group consisting of metal chlorides and alkaline earth metal chlorides, 0.01-1 g / l of aromatic carbonyl compounds and 1-50 g of surfactants. A tin-copper alloy plating solution composed of an aqueous solution containing / l .
2 . A tin-copper alloy plating method, wherein electrolysis is performed using the object to be plated as a cathode in the tin-copper alloy plating solution described in the above item 1 .
3 . Article in which a tin-copper alloy plating film is formed by the method according to item 2 above
The tin-copper alloy plating solution of the present invention comprises an aqueous solution containing stannous sulfate, copper (II) sulfate, sulfuric acid, chloride, an aromatic carbonyl compound and a surfactant as active ingredients.
この様な組成を有するスズ−銅合金めっき液は、酸成分として硫酸を用い、金属成分として硫酸塩、即ち、硫酸第一スズと硫酸銅（II）を用いたものであり、有機スル
ホン酸と有機スルホン酸塩を用いた、いわゆる有機スルホン酸浴と比較して、非常に安価なめっき液である。
The tin-copper alloy plating solution having such a composition uses sulfuric acid as an acid component, and uses sulfates as metal components, that is, stannous sulfate and copper (II) sulfate. Compared with a so-called organic sulfonic acid bath using an organic sulfonate, the plating solution is very inexpensive.
本発明めっき液中における硫酸第一スズの濃度については、特に限定的ではないが、濃度が低すぎると析出効率が低下して、所定の膜厚を得ることが困難になる。一方、濃度が高すぎると、めっき液中に溶解させることが困難となり、コスト的にも好ましくない。これらの点から、硫酸第一スズの濃度は、通常、５〜１００ｇ／ｌ程度とすることが好ましく、１５〜６０ｇ／ｌ程度とすることがより好ましい。 The concentration of stannous sulfate in the plating solution of the present invention is not particularly limited. However, if the concentration is too low, the deposition efficiency is lowered and it is difficult to obtain a predetermined film thickness. On the other hand, if the concentration is too high, it is difficult to dissolve in the plating solution, which is not preferable in terms of cost. From these points, the concentration of stannous sulfate is usually preferably about 5 to 100 g / l, and more preferably about 15 to 60 g / l.
本発明めっき液中の硫酸銅（II）の濃度については、目的とするスズ−銅合金めっき
皮膜の合金組成に応じて決めれば良く、通常、硫酸銅（II）の５水和物の濃度として、
０．１〜５ｇ／ｌ程度の範囲とすることが好ましく、０．３〜３ｇ／ｌ程度の範囲とすることがより好ましい。硫酸第一スズの濃度を上記した範囲とし、硫酸銅（II）の濃度
をこの様な範囲とすることによって、スズ−銅合金めっき皮膜における銅の重量割合を０．５〜５重量％程度の範囲とすることができる。
The concentration of copper sulfate (II) in the plating solution of the present invention may be determined according to the alloy composition of the target tin-copper alloy plating film. Usually, the concentration of copper sulfate (II) pentahydrate ,
The range is preferably about 0.1 to 5 g / l, and more preferably about 0.3 to 3 g / l. By setting the concentration of stannous sulfate in the above range and the concentration of copper (II) sulfate in such a range, the weight ratio of copper in the tin-copper alloy plating film is about 0.5 to 5% by weight. It can be a range.
本発明のめっき液は、酸成分として硫酸を含有するめっき液である。硫酸は金属成分を溶解させ、電導性を維持するために有効な成分であり、有機スルホン酸に比べて非常に安価である。硫酸濃度については、高すぎるとめっき液の粘性が増大し、汲み出し分が増加するため、経済的に好ましくない。また、濃度が低すぎると金属成分、特にスズ塩の溶解性が低下して、不溶性の沈殿物が発生するため好ましくない。これらの点から、通常、硫酸の濃度は、９８％硫酸の濃度として、５０〜２５０ｇ／ｌ程度とすることが好ましく、７０〜２２０ｇ／ｌ程度とすることがより好ましい。 The plating solution of the present invention is a plating solution containing sulfuric acid as an acid component. Sulfuric acid is an effective component for dissolving the metal component and maintaining electrical conductivity, and is very inexpensive compared to organic sulfonic acid. If the sulfuric acid concentration is too high, the viscosity of the plating solution increases and the pumping amount increases, which is not economically preferable. On the other hand, if the concentration is too low, the solubility of metal components, particularly tin salts, is lowered, and insoluble precipitates are generated, which is not preferable. From these points, the concentration of sulfuric acid is usually preferably about 50 to 250 g / l, more preferably about 70 to 220 g / l as the concentration of 98% sulfuric acid.
本発明のめっき液では、芳香族カルボニル化合物をめっき液に配合することによって、析出粒子を微細化し、めっき皮膜の光沢を向上させることができる。芳香族カルボニル化合物としては、特に限定的ではなく、公知のスズめっき液又はスズ合金めっき液において添加剤として知られている成分を用いることができる。具体的には、芳香族アルデヒド、芳香族ケトンなどを用いることができ、芳香族アルデヒドの具体例としては、ベンズアルデヒド、ナフトアルデヒド、これらの誘導体などを挙げることができ、芳香族ケトンの具体例としては、アセトフェノン、ベンゾフェノン、ベンザルアセトン、これらの誘導体などを挙げることができる。これらの芳香族カルボニル化合物は、一種単独又は二種以上混合して用いることができる。 In the plating solution of the present invention, by adding an aromatic carbonyl compound to the plating solution, the precipitated particles can be refined and the gloss of the plating film can be improved. The aromatic carbonyl compound is not particularly limited, and components known as additives in known tin plating solutions or tin alloy plating solutions can be used. Specifically, aromatic aldehydes, aromatic ketones, and the like can be used. Specific examples of aromatic aldehydes include benzaldehyde, naphthaldehyde, and derivatives thereof. Specific examples of aromatic ketones Can include acetophenone, benzophenone, benzalacetone, and derivatives thereof. These aromatic carbonyl compounds can be used singly or in combination of two or more.
芳香族カルボニル化合物の濃度については、低すぎるとめっき皮膜に十分な光沢を付与できず、一方、高すぎるとめっき皮膜の析出を阻害することがある。この様な点から、芳香族カルボニル化合物の濃度は、０．０１〜１ｇ／ｌ程度とすることが好ましく、０．０３〜０．５ｇ／ｌ程度とすることがより好ましい。 If the concentration of the aromatic carbonyl compound is too low, sufficient gloss cannot be imparted to the plating film. On the other hand, if the concentration is too high, precipitation of the plating film may be hindered. From such a point, the concentration of the aromatic carbonyl compound is preferably about 0.01 to 1 g / l, more preferably about 0.03 to 0.5 g / l.
界面活性剤は、析出粒子の素材への密着性を確保し、めっき皮膜のパウダー化を抑制する働きをするものと思われる。使用できる界面活性剤の種類については、特に限定はなく、公知のスズめっき液又はスズ合金めっき液に配合されている各種の界面活性剤を用いることができ、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤などを用いることができる。 The surfactant seems to function to secure the adhesion of the deposited particles to the material and suppress the powder formation of the plating film. The type of surfactant that can be used is not particularly limited, and various surfactants blended in known tin plating solutions or tin alloy plating solutions can be used. Surfactants, cationic surfactants, amphoteric surfactants and the like can be used.
非イオン性界面活性剤の具体例としては、ポリオキシエチレンアルキルフェニルエーテル型界面活性剤、ポリオキシエチレンポリオキシプロピレンエーテル型界面活性剤、ポリオキシエチレンナフトールエーテル型界面活性剤、ポリオキシエチレンポリオキシプロピレンポリアミン型界面活性剤等を挙げることができる。アニオン性界面活性剤の具体例としては、ポリオキシエチレンアルキル硫酸塩などを挙げることができる。カチオン性界面活性剤の具体例としては、アルキルトリメチルアンモニウム塩などを挙げることができる。両性界面活性剤の具体例としては、アルキルベタイン型界面活性剤、アルキルアミドベタイン型界面活性剤等を挙げることができる。これらの界面活性剤は一種単独または二種以上を混合して用いることができる。 Specific examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether type surfactant, polyoxyethylene polyoxypropylene ether type surfactant, polyoxyethylene naphthol ether type surfactant, polyoxyethylene polyoxy A propylene polyamine type surfactant etc. can be mentioned. Specific examples of the anionic surfactant include polyoxyethylene alkyl sulfate. Specific examples of the cationic surfactant include alkyl trimethyl ammonium salt. Specific examples of amphoteric surfactants include alkyl betaine surfactants and alkyl amide betaine surfactants. These surfactants can be used singly or in combination of two or more.
界面活性剤の濃度は、１〜５０ｇ／ｌ程度とすることが好ましく、５〜２０ｇ／ｌ程度とすることがより好ましい。 The concentration of the surfactant is preferably about 1 to 50 g / l, and more preferably about 5 to 20 g / l.
本発明のスズ−銅合金めっき液では、塩化物を添加することによって、上記した界面活性剤と芳香族カルボニル化合物の添加効果を向上させることができ、形成されるめっき皮膜の光沢をより均一なものとすることができる。更に、リフロー処理後のめっき皮膜の変色を抑制することができる。 In the tin-copper alloy plating solution of the present invention, the addition effect of the above-described surfactant and aromatic carbonyl compound can be improved by adding chloride, and the gloss of the formed plating film can be made more uniform. Can be. Furthermore, discoloration of the plating film after the reflow treatment can be suppressed.
一般に、リフロー処理後に変色が発生する場合には、スズ−銅合金めっき皮膜表面の酸化が激しく、厚い酸化皮膜が形成されている。これは、めっき皮膜中に共析した有機物がリフロー処理の際に高温で加熱されて変質、分解などを生じ、大気中の酸素などと反応して酸化物膜が形成されることによるものと思われる。 In general, when discoloration occurs after reflow treatment, the surface of the tin-copper alloy plating film is heavily oxidized, and a thick oxide film is formed. This is thought to be due to the fact that the organic matter co-deposited in the plating film is heated at a high temperature during reflow treatment, causing alteration, decomposition, etc., and reacting with oxygen in the atmosphere to form an oxide film It is.
これに対して、本発明のめっき液から形成されるめっき皮膜は、十分な光沢を有するにもかかわらず、有機物の共析が抑制されており、有機物の含有量が非常に少ないために、リフロー処理後の変色が抑制されている。この様な効果は、めっき液中に塩化物を配合したことによるものと考えられる。 On the other hand, the plating film formed from the plating solution of the present invention has sufficient luster, but the eutectoid of organic matter is suppressed and the content of organic matter is very low. Discoloration after treatment is suppressed. Such an effect is considered to be due to the inclusion of chloride in the plating solution.
本発明のめっき液では、塩化物としては、めっき液中に可溶な塩化物であれば特に限定なく使用できる。例えば、塩酸；塩化ナトリウム、塩化カリウムなどのアルカリ金属塩化物；塩化マグネシウム、塩化カルシウム等のアルカリ土類金属塩化物等を好適に用いることができる。これらの塩化物は、一種単独又は二種以上混合して用いることができる。 In the plating solution of the present invention, any chloride that is soluble in the plating solution can be used as the chloride. For example, hydrochloric acid; alkali metal chlorides such as sodium chloride and potassium chloride; alkaline earth metal chlorides such as magnesium chloride and calcium chloride can be suitably used. These chlorides can be used singly or in combination of two or more.
本発明のめっき液では、塩化物濃度が低すぎると、上記した効果を十分に発揮することができない。一方、塩化物の濃度が過剰となっても、上記した効果がより向上することはない。通常、塩化物の濃度は、０．０１〜１ｇ／ｌ程度とすることが好ましく、０．０３〜０．５ｇ／ｌ程度とすることがより好ましい。 In the plating solution of the present invention, if the chloride concentration is too low, the above-described effects cannot be sufficiently exhibited. On the other hand, even if the concentration of chloride is excessive, the above-described effect is not further improved. Usually, the chloride concentration is preferably about 0.01 to 1 g / l, more preferably about 0.03 to 0.5 g / l.
本発明のめっき液には、更に必要に応じて、酸化防止剤を配合することができる。酸化防止剤を配合することによって、スズ成分の酸化を抑制し、めっき液の安定性を向上させることができる。酸化防止剤としては、例えば、カテコール、ヒドロキノン、アスコルビン酸又はそのアルカリ金属塩、エリソルビン酸又はそのアルカリ金属塩などを使用できる。酸化防止剤は一種単独または二種以上混合して配合することができる。酸化防止剤の濃度については、０．１〜１０ｇ／ｌ程度とすることが好ましい。濃度が高すぎても酸化防止効果がより向上することはほとんどないために、経済的に好ましくない。 The plating solution of the present invention may further contain an antioxidant as necessary. By mix | blending antioxidant, the oxidation of a tin component can be suppressed and stability of a plating solution can be improved. As the antioxidant, for example, catechol, hydroquinone, ascorbic acid or an alkali metal salt thereof, erythorbic acid or an alkali metal salt thereof can be used. Antioxidants can be blended individually or in combination of two or more. The concentration of the antioxidant is preferably about 0.1 to 10 g / l. Even if the concentration is too high, the antioxidant effect is hardly improved, which is economically undesirable.
本発明のめっき液には、更に、必要に応じて、公知のスズめっき液またはスズ合金めっき液で用いられている各種の添加剤を配合してもよい。この様な添加剤の一例として、アミン−アルデヒド反応物等を挙げることができる。 The plating solution of the present invention may further contain various additives used in a known tin plating solution or tin alloy plating solution, if necessary. An example of such an additive is an amine-aldehyde reactant.
本発明のめっき液を用いて電気めっきを行う場合、浴温は、１０〜３０℃程度とすることが好ましく、１５〜２５℃程度とすることがより好ましい。陰極電流密度は、０．１〜１０Ａ／ｄｍ2程度とすることが好ましく、１〜５Ａ／ｄｍ2程度とすることがより好ましい。 When electroplating is performed using the plating solution of the present invention, the bath temperature is preferably about 10 to 30 ° C, and more preferably about 15 to 25 ° C. Cathode current density is preferably set to 0.1 to 10 A / dm 2 about, it is more preferable that the 1-5A / dm 2 about.
本発明のめっき液では、形成されるスズ−銅合金めっき皮膜の合金組成については、めっき液中の硫酸第一スズと硫酸銅（II）の配合割合を調整することによって適宜
設定でき、通常、めっき液中の硫酸銅（II）の割合を多くすることによって、合金
中の銅の比率を高くすることができる。特に、リフロー用のスズ−銅合金皮膜とする場合には、めっき皮膜中の銅の含有量が低すぎても高すぎても融点の上昇につながるため、めっき皮膜中の銅の含有率を０．５〜５重量％程度とすることが好ましい。
In the plating solution of the present invention, the alloy composition of the formed tin-copper alloy plating film can be appropriately set by adjusting the mixing ratio of stannous sulfate and copper (II) sulfate in the plating solution, usually, By increasing the ratio of copper (II) sulfate in the plating solution, the ratio of copper in the alloy can be increased. In particular, when a tin-copper alloy film for reflow is used, the copper content in the plating film is reduced to 0 because the melting point increases if the copper content in the plating film is too low or too high. It is preferably about 5 to 5% by weight.
本発明のスズ−銅合金めっき液によれば、良好な光沢を有し、かつリフロー処理後の変色が非常に少ないスズ−銅合金めっき皮膜を形成できる。更に、該めっき液は、酸成分として安価な硫酸を用いるものであり、非常に低コストのめっき液である。 According to the tin-copper alloy plating solution of the present invention, it is possible to form a tin-copper alloy plating film having good gloss and very little discoloration after the reflow treatment. Further, the plating solution uses an inexpensive sulfuric acid as an acid component, and is a very low cost plating solution.
本発明のめっき液によれば、上記したような優れた特性を有するスズ−銅合金めっき皮膜を形成することが可能であり、形成されるめっき皮膜は、フレキシブル基板などの各種プリント配線板のリフロー処理を行う部分の皮膜として、特に好適に利用できる。 According to the plating solution of the present invention, it is possible to form a tin-copper alloy plating film having excellent characteristics as described above, and the formed plating film can be used for reflow of various printed wiring boards such as flexible substrates. It can be particularly suitably used as a film for a portion to be treated.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
参考例１
下記組成のスズ−銅めっき液を調製した。
硫酸第一スズ ５０ｇ／ｌ
濃硫酸 １５０ｇ／ｌ
硫酸銅（II）・５水和物 ２ｇ／ｌ
ポリオキシエチレンポリオキシプロピレンエーテル １０ｇ／ｌ
ナフトアルデヒド ０．１ｇ／ｌ
３５％塩酸 ０．１ｇ／ｌ（塩酸として）
実施例１
下記組成のスズ−銅めっき液を調製した。
硫酸第一スズ ５０ｇ／ｌ
濃硫酸 １５０ｇ／ｌ
硫酸銅（II）・５水和物 １ｇ／ｌ
ポリオキシエチレンナフトールエーテル ５ｇ／ｌ
ベンザルアセトン ０．１ｇ／ｌ
塩化カリウム ０．４ｇ／ｌ
比較例１及び２
塩化物を含有すること無く、それ以外は、参考例１で調製しためっき液と同様の組成のスズ−銅めっき液（比較例１）と実施例１で調製しためっき液と同様の組成のスズ−銅めっき液（比較例２）を調製した。
上記した参考例１及び実施例１および比較例１、２の各めっき液を用いて形成されためっき皮膜について、下記の方法で各種特性を評価した。結果を下記表１に示す。
Reference example 1
A tin-copper plating solution having the following composition was prepared.
Stannous sulfate 50g / l
Concentrated sulfuric acid 150g / l
Copper (II) sulfate pentahydrate 2g / l
Polyoxyethylene polyoxypropylene ether 10g / l
Naphthaldehyde 0.1 g / l
35% hydrochloric acid 0.1g / l (as hydrochloric acid)
Example 1
A tin-copper plating solution having the following composition was prepared.
Stannous sulfate 50g / l
Concentrated sulfuric acid 150g / l
Copper (II) sulfate pentahydrate 1g / l
Polyoxyethylene naphthol ether 5g / l
Benzalacetone 0.1g / l
Potassium chloride 0.4g / l
Comparative Examples 1 and 2
Without containing chloride, otherwise, tin having the same composition as the plating solution prepared in Reference Example 1 - Tin copper plating solution (Comparative Example 1) The same composition as the plating solution prepared in Example 1 -A copper plating solution (Comparative Example 2) was prepared.
About the plating film formed using each plating solution of above-mentioned reference example 1, Example 1, and comparative examples 1 and 2, various characteristics were evaluated by the following method. The results are shown in Table 1 below.
めっき外観の評価
圧延銅板（１ｃｍ×１ｃｍ）を被めっき物として、液温２０℃、陰極電流密度２Ａ／ｄｍ2で膜厚５μｍとなるようにスズ−銅めっき皮膜を形成した試料について目視による外観の評価を行った。
Evaluation <br/> rolled copper plating appearance (1 cm × 1 cm) as an object to be plated, liquid temperature 20 ° C., tin to a thickness 5μm at cathode current density 2A / dm 2 - to form a copper plating film sample The appearance was visually evaluated.
めっき皮膜中の炭素量の測定
ステンレス板（１０ｃｍ×５ｃｍ）を被めっき物として、液温２０℃、陰極電流密度３Ａ／ｄｍ2で膜厚６０μｍとなるようにスズ−銅めっき皮膜形成した後、皮膜を剥離し、炭素硫黄分析装置（堀場製作所製）によりめっき皮膜中の炭素量を測定した。
Measurements <br/> stainless plate carbon content in the plating film of (10 cm × 5 cm) as an object to be plated, liquid temperature 20 ° C., tin to a thickness 60μm at cathode current density 3A / dm 2 - copper plating film After forming, the film was peeled off, and the amount of carbon in the plating film was measured with a carbon sulfur analyzer (manufactured by Horiba Seisakusho).
リフロー処理後の変色評価
外観評価方法と同様にして圧延銅板に５μｍのめっき皮膜を形成した試料について、ホットプレート上で２３０℃で１分間加熱してめっき皮膜を溶解させた。その後、室温で冷却し、めっき皮膜を固化させたものについて、目視により変色の有無を調べた。
を行った。
Evaluation of discoloration after reflow treatment In the same manner as the appearance evaluation method, a sample in which a 5 μm plating film was formed on a rolled copper plate was heated on a hot plate at 230 ° C. for 1 minute to dissolve the plating film. Then, it was cooled at room temperature, and the presence or absence of discoloration was visually examined for the solidified plating film.
Went.
一方、塩化物を含有しない比較例１及び２のめっき液から形成されたスズ−銅めっき皮膜は、光沢ムラが生じており、リフロー処理後には著しく変色した。 On the other hand, the tin-copper plating film formed from the plating solutions of Comparative Examples 1 and 2 containing no chloride had uneven gloss and remarkably discolored after the reflow treatment.
めっき皮膜中の炭素含有量の測定結果によれば、参考例１及び実施例１のめっき液から形成されたスズ−銅めっき皮膜については、炭素含有量は、それぞれ０．０４％と０．０６％であったのに対して、比較例１及び２のめっき液から形成されためっき皮膜は、参考例１及び実施例１のめっき液から形成されためっき皮膜と比較して、約４倍の炭素を含有するものであった。この結果から、参考例１及び実施例１のめっき液から形成されためっき皮膜は、炭素含有量、即ち有機物の含有量が非常に少なく、このためにリフロー処理後の変色が生じていないものと考えられる。 According to the measurement results of the carbon content in the plating film, for the tin-copper plating films formed from the plating solutions of Reference Example 1 and Example 1 , the carbon contents were 0.04% and 0.06, respectively. In contrast, the plating film formed from the plating solutions of Comparative Examples 1 and 2 was about four times as much as the plating film formed from the plating solutions of Reference Example 1 and Example 1 . It contained carbon. From this result, the plating film formed from the plating solutions of Reference Example 1 and Example 1 has a very low carbon content, that is, the content of organic matter, and therefore no discoloration after reflow treatment has occurred. Conceivable.
Claims (3)
硫酸第一スズを５〜１００ｇ／ｌ、硫酸銅（II）を５水和物の濃度として０．１〜５ｇ／ｌ、硫酸を９８％硫酸の濃度として５０〜２５０ｇ／ｌ、塩化物としてアルカリ金属の塩化物及びアルカリ土類金属の塩化物からなる群から選択された少なくとも一種を０．０１〜１ｇ／ｌ、芳香族カルボニル化合物を０．０１〜１ｇ／ｌ及び界面活性剤を１〜５０ｇ／ｌ含有する水溶液からなるスズ−銅合金めっき液。 A tin-copper alloy plating solution comprising an aqueous solution containing stannous sulfate, copper (II) sulfate, sulfuric acid, chloride, an aromatic carbonyl compound and a surfactant as active ingredients,
Stannous sulfate 5-100 g / l, copper (II) sulfate pentahydrate concentration 0.1-5 g / l, sulfuric acid 98% sulfuric acid concentration 50-250 g / l, chloride as alkali 0.01-1 g / l of at least one selected from the group consisting of metal chlorides and alkaline earth metal chlorides, 0.01-1 g / l of aromatic carbonyl compounds and 1-50 g of surfactants. A tin-copper alloy plating solution composed of an aqueous solution containing / l .
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| JP3655388B2 (en) * | 1996-04-08 | 2005-06-02 | ディップソール株式会社 | Non-acid bath for tin plating and tin-lead alloy plating, and plating method using the plating bath |
| JP4132247B2 (en) * | 1998-07-09 | 2008-08-13 | 株式会社大和化成研究所 | Electrical / electronic circuit components |
| JP3904333B2 (en) * | 1998-09-02 | 2007-04-11 | 株式会社大和化成研究所 | Tin or tin alloy plating bath |
| JP3871013B2 (en) * | 1998-11-05 | 2007-01-24 | 上村工業株式会社 | Tin-copper alloy electroplating bath and plating method using the same |
| JP2000328285A (en) * | 1999-05-14 | 2000-11-28 | Yuken Kogyo Kk | Acidic tin-copper alloy plating bath |
| EP1091023A3 (en) * | 1999-10-08 | 2003-05-14 | Shipley Company LLC | Alloy composition and plating method |
| JP2001262391A (en) * | 2000-03-14 | 2001-09-26 | Ishihara Chem Co Ltd | Tin-copper based alloy plating bath and electronic parts having coating film formed with the same |
| JP4362568B2 (en) * | 2000-06-02 | 2009-11-11 | 奥野製薬工業株式会社 | Tin - copper alloy electroplating solution |
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2004
- 2004-04-16 JP JP2004122110A patent/JP4817166B2/en not_active Expired - Lifetime
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