JP2004285417A - Tin whisker preventive agent, and method for manufacturing whisker preventive tinned work - Google Patents
Tin whisker preventive agent, and method for manufacturing whisker preventive tinned work Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
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- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、スズメッキ物におけるスズホイスカを防止するためのスズホイスカ防止剤、及びこれを用いたホイスカ防止性スズメッキ物の製造方法に関する。
【０００２】
【従来の技術】
スズメッキは、はんだ付け性及び耐食性が良好であり、電気・電子部品（例えば、電気部品の端子やプリント配線基板等）のメッキに適していることから、広く利用されている。
【０００３】
しかし、スズメッキ物は、スズメッキ後にメッキ表面にホイスカと呼ばれる髭状のスズ結晶が発生することが知られている。このスズホイスカは、特に電気・電子部品においては短絡を引き起こすことがあるため、スズメッキ物においてこのスズホイスカの発生を防止することが望まれている。
【０００４】
このようなスズホイスカの発生は被スズメッキ物表面の凹凸に起因すると考えられることから、被スズメッキ物表面を平滑化することが試みられており、特許文献１では酸、過酸化物、及び硫酸基あるいは燐酸基を親水基とし直鎖または環状炭化水素基を疎水基とする有機高分子化合物を含有する処理液にて被スズメッキ物表面を処理して平滑化することが提案されている。
【０００５】
【特許文献１】
特開平５−１４８６５８号公報（特許請求の範囲等）
【０００６】
【発明が解決しようとする課題】
しかしながら、特許文献１に記載の処理液では、被スズメッキ物表面を平滑化するのに被スズメッキ物表面を２μｍ乃至それ以上の厚みでエッチングしなければならなかった。このため、このような処理液を年々高集積化が進む電子部品における線幅の細い回路銅などの被スズメッキ物に使用すると、被スズメッキ物自体の形状安定性が保てないという問題があった。
【０００７】
従って本発明の目的は、僅かなエッチング量であっても十分に被スズメッキ物表面を平滑化して効果的にスズホイスカの発生を防止することのできるスズホイスカ防止剤を提供することにある。
【０００８】
また、本発明の他の目的は、微細な被スズメッキ物であっても僅かなエッチング量にて被スズメッキ物の形状安定性を保ったままスズメッキが施されたホイスカ防止性スズメッキ物の製造方法を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者らは上記課題を解決すべく鋭意研究した結果、本発明を完成するに至った。
【００１０】
即ち、本発明は、ｐＨ５以下であり、鉄化合物系酸化剤、非イオン性界面活性剤、及び銅イオンを含有する水溶液であることを特徴とするスズホイスカ防止剤である。
【００１１】
本発明のスズホイスカ防止剤においては、非イオン性界面活性剤が、以下の一般式（１）及び／又は一般式（２）、
Ａ〔（Ｃ３Ｈ６Ｏ）ｎ（Ｃ２Ｈ４Ｏ）ｍ Ｈ〕ｋ （１）
Ａ〔（Ｃ２Ｈ４Ｏ）ｍ（Ｃ３Ｈ６Ｏ）ｎ Ｈ〕ｋ （２）
（式中、Ａはｋ価の活性水素含有化合物の残基、ｋは１〜４の数、ｎは３〜３５の数、ｍは１〜７０の数である）で表される化合物であることが好ましく、また、鉄化合物系酸化剤が、塩化第二鉄、硫酸第二鉄及び硝酸第二鉄からなる群から選ばれる１種以上であることが好ましい。
【００１２】
また、本発明は、被スズメッキ物表面を前記本発明のスズホイスカ防止剤にて処理した後、スズメッキを施すことを特徴とするホイスカ防止性スズメッキ物の製造方法である。
【００１３】
本発明の製造方法においては、好ましくは被スズメッキ物が電子デバイスの配線銅である。
【００１４】
【発明の実施の形態】
以下、本発明の実施の形態について具体的に説明する。
本発明のスズホイスカ防止剤は、ｐＨ５以下、好ましくはｐＨ４以下の酸性水溶液である。水溶液のｐＨが５を超えると被スズメッキ物、特に銅のエッチング性が悪化し、またスラッジも発生しやすくなる。一方、ｐＨの下限は特になく、工業化適性の許す限り、低いほうが好ましい。
【００１５】
水溶液を上記のｐＨに調整する方法は何ら限定されるものではなく、周知の方法によればよく、例えば、酸を含有させることにより達成することができる。酸としては、有機酸でも無機酸でもよく、例えば、塩酸、硫酸、硝酸、燐酸、ギ酸、酢酸等を単独で又は混合して用いることができるが、粘性等のハンドリングの観点から、塩酸、リン酸又はギ酸等が好ましい。
【００１６】
本発明のスズホイスカ防止剤は、鉄化合物系酸化剤を含有するものである。鉄化合物系酸化剤は、被スズメッキ物の表面、特には銅の表面を激しくエッチングすることなく僅かにエッチングし、且つ均一にエッチングするという観点から、本発明において使用する。このような観点から使用し得る鉄化合物系酸化剤は特に限定されるものではなく、酸化剤として公知の鉄化合物であればどのようなものでも使用することができ、例えば、塩化第二鉄、硫酸第二鉄、硝酸第二鉄等を例示することができる。
【００１７】
本発明に使用する鉄化合物系酸化剤の使用量も特に限定されるものではなく、被スズメッキ物の表面、特には銅の表面を１．０μｍ／分〜５．０μｍ／分程度エッチングできる程度であればよく、概ね０．５〜１０重量％、好ましくは１〜５重量％程度であれば好適に用いることができる。
【００１８】
また、本発明のスズホイスカ防止剤は、非イオン性界面活性剤を含有するものである。非イオン性界面活性剤であればどのようなものでもよいが、本発明の効果が良好に得られるという点で、好ましくは、以下の一般式（１）及び／又は一般式（２）、
Ａ〔（Ｃ３Ｈ６Ｏ）ｎ（Ｃ２Ｈ４Ｏ）ｍ Ｈ〕ｋ （１）
Ａ〔（Ｃ２Ｈ４Ｏ）ｍ（Ｃ３Ｈ６Ｏ）ｎ Ｈ〕ｋ （２）
（式中、Ａはｋ価の活性水素含有化合物の残基、ｋは１〜４の数、ｎは３〜３５の数、ｍは１〜７０の数である）で表される化合物が好ましい。
【００１９】
上記一般式中、Ａに対応する活性水素含有化合物としては、炭素原子数３〜１８のアルコール、炭素原子数３〜１８のアルキル基を有するアルキルフェノール、エチレングリコール、プロピレングリコール、ブチレングリコール等の如きグリコール、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトール等のポリオール等で代表される水酸基含有化合物、或いはエチレンジアミン、ジエチレントリアミン等のアルキレンアミン等を挙げることができ、特にはエチレンジアミン等のアルキルアミンが好ましい。
【００２０】
また、上記一般式中、ポリオキシエチレン鎖、ポリオキシプロピレン鎖は、上述の如き活性水素含有化合物にエチレンオキサイド或いはプロピレンオキサイドを常法によって付加させることにより得ることができる。その付加モル数（上記一般式中のｎ及びｍ）については、本発明の所期の目的を達成する上で、ｎは３〜３５、より好ましくは６〜１５であり、ｍは１〜７０、より好ましくは２〜２０の数である。尚、これらは平均値として表される。
【００２１】
本発明に使用する非イオン性界面活性剤の使用量も特に限定されるものではないが、概ね０．１〜７重量％、好ましくは０．５〜３重量％程度であれば好適に用いることができる。
【００２２】
更に、本発明のスズホイスカ防止剤は、銅イオンを含有するものである。銅イオンとしては、塩化銅、硫酸銅、硝酸銅等の銅塩を溶解させてもよく、或は酸化剤が系に存在する段階で金属銅を溶解させてもよい。尚、銅塩を溶解させる場合、上記鉄化合物や酸等と同様のアニオンとの塩とすることが取り扱い上好ましい。
【００２３】
このような銅イオンは、好ましくは銅濃度として０．０５〜１０ｇ／Ｌ、より好ましくは０．５〜５ｇ／Ｌ、最も好ましくは１．５〜５ｇ／Ｌ程度であれば好適に用いることができる。
【００２４】
本発明のスズホイスカ防止剤には、上記配合物の他に本発明の目的を阻害しない範囲内で所望により可溶化剤や濡れ性向上剤等を配合することができる。
【００２５】
次に、本発明のスズメッキ物の製造方法について説明する。本発明のスズメッキ物の製造方法は、被スズメッキ物表面を上記本発明のスズホイスカ防止剤にて処理した後、スズメッキを施すものである。
【００２６】
被スズメッキ物は金属であればよく、特に限定されないが、被スズメッキ物が特に銅又は銅合金であると本発明の効果を顕著に得ることができるので好ましい。また、被スズメッキ物が微細な、電子デバイスの配線銅等である場合にも本発明の効果を顕著に得ることができ、好ましい。
【００２７】
本発明のスズホイスカ防止剤による被スズメッキ物表面の処理手段は、特に限定されるものではなく、例えば、浸漬法やスプレー法などの公知の方法によって被スズメッキ物表面に本発明のスズホイスカ防止剤を接触させればよい。
【００２８】
また、処理条件も特に限定されるものではないが、僅かなエッチング量であっても十分に被スズメッキ物表面を平滑化するという本発明の効果を顕著に得る観点から、本発明のスズホイスカ防止剤による被スズメッキ物表面のエッチング量は０．１〜１．５μｍ、好ましくは０．３〜１μｍ程度となるように、例えば、１０〜４０℃で１０〜１２０秒、好ましくは２０〜６０秒程度処理すればよい。
【００２９】
【実施例】
以下に実施例を挙げ本発明をさらに説明するが、本発明はこれに限定されるものではない。
【００３０】
〔実施例１〕
４０重量％塩化第二鉄８２．１重量部、２０重量％塩酸１１７．４重量部、７６重量％ギ酸１０．５重量部、８５重量％リン酸１０．８重量部、濡れ性向上剤としてのジプロピレングリコールモノメチルエーテル１０．７重量部、一般式（１）においてＡがエチレンジアミン残基であり、ｎ＝１１．６、ｍ＝１０．５、ｋ＝４である化合物１１．０重量部、一般式（１）においてＡがエチレンジアミン残基であり、ｎ＝１１．６、ｍ＝４．０、ｋ＝４である化合物１．１重量部、純水８５６．４重量部を混合し、これに銅チップ３．８重量部を溶解させ、本発明のスズホイスカ防止剤（１）を得た。
【００３１】
得られたスズホイスカ防止剤（１）は、ｐＨ０．１２、塩化第二鉄含量３．０重量％、合計非イオン性界面活性剤含量１．１重量％、銅濃度３．０ｇ／Ｌであった。
【００３２】
一方、１０ｃｍ×１０ｃｍで厚さ１７０μｍのポリイミドフィルムを絶縁基材とし、この上にセミアディティブ法によりリード幅２５μｍ、リードスペース幅２５μｍ、リード厚さ８μｍの銅配線回路を形成し、テストピースを得た。
【００３３】
次に、このテストピースを２５℃の上記スズホイスカ防止剤（１）中に３０秒間浸漬した後、水洗して乾燥した。次いで、無電解スズメッキ処理を行い、銅配線回路上に０．５μｍ厚のスズメッキ皮膜を設けた。
【００３４】
このように処理したテストピースを大気中に放置し、ホイスカの発生状況を６０日経過後及び９０日経過後に顕微鏡で観察したところ、いずれにおいても全くホイスカは観察されず、銅配線回路の形状も良好に保たれていた。尚、スズホイスカ防止剤（１）による処理によって減少した当該テストピースにおける銅配線回路のリード厚は０．７μｍであった。
【００３５】
〔実施例２〕
４０重量％塩化第二鉄８２．１重量部、２０重量％塩酸１１７．４重量部、７６重量％ギ酸１０．５重量部、８５重量％リン酸１０．８重量部、濡れ性向上剤としてのジプロピレングリコールモノメチルエーテル１０．７重量部、一般式（２）においてＡがエチレンジアミン残基であり、ｎ＝１１．６、ｍ＝１０．５、ｋ＝４である化合物１１．０重量部、一般式（２）においてＡがエチレンジアミン残基であり、ｎ＝１１．６、ｍ＝４．０、ｋ＝４である化合物１．１重量部、純水８５６．４重量部を混合し、これに銅チップ３．８重量部を溶解させ、本発明のスズホイスカ防止剤（２）を得た。
【００３６】
スズホイスカ防止剤（２）は、ｐＨ０．１２、塩化第二鉄含量３．０重量％、合計非イオン性界面活性剤含量１．１重量％、銅濃度３．０ｇ／Ｌであった。
【００３７】
実施例１と同様のテストピースを用いて、実施例１と同様にして試験したところ、６０日経過後及び９０日経過後のいずれにおいても全くホイスカは観察されず、銅配線回路の形状も良好に保たれていた。尚、スズホイスカ防止剤（２）による処理によって減少した該テストピークにおける銅配線回路のリード厚は０．７μｍであった。
【００３８】
〔実施例３〕
４０重量％塩化第二鉄８２．１重量部、２０重量％塩酸１１７．４重量部、７６重量％ギ酸１０．５重量部、８５重量％リン酸１０．８重量部、濡れ性向上剤としてのジプロピレングリコールモノメチルエ−テル１０．７重量部、一般式（１）においてＡがエチレンジアミン残基であり、ｎ＝１１．６、ｍ＝１０．５、ｋ＝４である化合物１１．０重量部、一般式（２）においてＡがエチレンジアミン残基であり、ｎ＝１１．６、ｍ＝４．０、ｋ＝４である化合物１．１重量部、純水８５６．４重量部を混合し、これに銅チップ３．８重量部を溶解させ、本発明のスズホイスカ防止剤（３）を得た。
【００３９】
スズホイスカ防止剤（３）は、ｐＨ０．１２、塩化第二鉄含量３．０重量％、合計非イオン性界面活性剤含量１．１重量％、銅濃度３．０ｇ／Ｌであった。
【００４０】
実施例１と同様のテストピースを用いて、実施例１と同様にして試験したところ、６０日経過後及び９０日経過後のいずれにおいても全くホイスカは観察されず、銅配酸回路の形状も良好に保たれていた。尚、スズホイスカ防止剤（３）による処理によって減少した該テストピースにおける銅配線回路のリード厚は０．７μｍであった。
【００４１】
【発明の効果】
以上説明してきたように、本発明のスズホイスカ防止剤によれば、僅かなエッチング量であっても十分に被スズメッキ物表面を平滑化して効果的にスズホイスカの発生を防止することができる。また、本発明のホイスカ防止性スズメッキ物の製造方法によれば、微細な被スズメッキ物であってもエッチング量を僅かとし被スズメッキ物の形状安定性を保ったままスズメッキを施すことができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a tin whisker inhibitor for preventing tin whiskers in a tin-plated product, and a method for producing a whisker-preventive tin-plated product using the same.
[0002]
[Prior art]
Tin plating is widely used because it has good solderability and corrosion resistance and is suitable for plating electric and electronic components (for example, terminals of electric components and printed wiring boards).
[0003]
However, it is known that tin-plated products generate whisker-like tin crystals called whiskers on the plating surface after tin plating. Since this tin whisker may cause a short circuit particularly in electric / electronic parts, it is desired to prevent the generation of the tin whisker in a tin-plated product.
[0004]
Since the occurrence of such tin whiskers is considered to be caused by irregularities on the surface of the tin-plated object, attempts have been made to smooth the surface of the tin-plated object. In Patent Document 1, acid, peroxide, and sulfuric acid groups or It has been proposed to treat the surface of a tin-plated object with a treatment solution containing an organic polymer compound having a phosphoric acid group as a hydrophilic group and a linear or cyclic hydrocarbon group as a hydrophobic group to smooth the surface.
[0005]
[Patent Document 1]
JP-A-5-148658 (Claims, etc.)
[0006]
[Problems to be solved by the invention]
However, with the treatment liquid described in Patent Document 1, the surface of the tin-plated object has to be etched with a thickness of 2 μm or more in order to smooth the surface of the tin-plated object. For this reason, when such a processing liquid is used for tin-plated objects such as circuit copper having a small line width in electronic components that are becoming highly integrated year by year, there is a problem that the shape stability of the tin-plated object itself cannot be maintained. .
[0007]
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a tin whisker inhibitor which can sufficiently smooth the surface of a tin-plated object even with a small etching amount and can effectively prevent the generation of tin whiskers.
[0008]
Another object of the present invention is to provide a method for producing a tin-plated whisker-preventive tin-plated product which is tin-plated while maintaining the shape stability of the tin-plated product with a small etching amount even for a fine tin-plated product. To provide.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention.
[0010]
That is, the present invention is a tin whisker inhibitor, which is an aqueous solution containing an iron compound-based oxidizing agent, a nonionic surfactant, and copper ions at a pH of 5 or less.
[0011]
In the tin whisker inhibitor of the present invention, the nonionic surfactant comprises the following general formula (1) and / or general formula (2):
A [(C 3 H 6 O) n (C 2 H 4 O) m H] k (1)
A [(C 2 H 4 O) m (C 3 H 6 O) n H] k (2)
Wherein A is a residue of a k-valent active hydrogen-containing compound, k is a number of 1 to 4, n is a number of 3 to 35, and m is a number of 1 to 70. It is preferable that the iron compound oxidizing agent is at least one selected from the group consisting of ferric chloride, ferric sulfate, and ferric nitrate.
[0012]
Further, the present invention is a method for producing a whisker-preventive tin-plated material, comprising treating the surface of a tin-plated product with the tin whisker-preventing agent of the present invention, and then applying tin plating.
[0013]
In the manufacturing method of the present invention, the tin-plated object is preferably wiring copper of an electronic device.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described.
The tin whisker inhibitor of the present invention is an acidic aqueous solution having a pH of 5 or less, preferably pH 4 or less. If the pH of the aqueous solution exceeds 5, the etching property of the tin-plated product, particularly copper, deteriorates, and sludge tends to be generated. On the other hand, there is no particular lower limit of the pH, and a lower one is preferable as long as industrial suitability is allowed.
[0015]
The method for adjusting the pH of the aqueous solution to the above-mentioned pH is not limited at all, and may be a known method, for example, it can be achieved by including an acid. The acid may be an organic acid or an inorganic acid.For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid and the like can be used alone or as a mixture. Acids or formic acid are preferred.
[0016]
The tin whisker inhibitor of the present invention contains an iron compound-based oxidizing agent. The iron compound-based oxidizing agent is used in the present invention from the viewpoint that the surface of the object to be tin-plated, in particular, the surface of copper is slightly etched without being violently etched and is uniformly etched. The iron compound-based oxidizing agent that can be used from such a viewpoint is not particularly limited, and any iron compound known as an oxidizing agent can be used, for example, ferric chloride, Ferric sulfate, ferric nitrate and the like can be exemplified.
[0017]
The amount of the iron compound-based oxidizing agent used in the present invention is not particularly limited, either, and the surface of the object to be tin-plated, particularly the surface of copper, can be etched by about 1.0 μm / min to 5.0 μm / min. Any amount may be used as long as it is about 0.5 to 10% by weight, preferably about 1 to 5% by weight.
[0018]
Further, the tin whisker inhibitor of the present invention contains a nonionic surfactant. Any non-ionic surfactant may be used, but from the viewpoint that the effects of the present invention can be favorably obtained, preferably, the following general formula (1) and / or general formula (2):
A [(C 3 H 6 O) n (C 2 H 4 O) m H] k (1)
A [(C 2 H 4 O) m (C 3 H 6 O) n H] k (2)
(Wherein, A is a residue of a k-valent active hydrogen-containing compound, k is a number of 1 to 4, n is a number of 3 to 35, and m is a number of 1 to 70). .
[0019]
In the above general formula, the active hydrogen-containing compound corresponding to A includes alcohols having 3 to 18 carbon atoms, alkylphenols having an alkyl group having 3 to 18 carbon atoms, glycols such as ethylene glycol, propylene glycol, butylene glycol and the like. And hydroxyl-containing compounds typified by polyols such as trimethylolpropane, glycerin, pentaerythritol and sorbitol; and alkyleneamines such as ethylenediamine and diethylenetriamine. Particularly preferred are alkylamines such as ethylenediamine.
[0020]
In the above general formula, the polyoxyethylene chain and the polyoxypropylene chain can be obtained by adding ethylene oxide or propylene oxide to the active hydrogen-containing compound as described above by a conventional method. With respect to the number of moles added (n and m in the above general formula), n is from 3 to 35, more preferably from 6 to 15, and m is from 1 to 70, in order to achieve the intended object of the present invention. And more preferably a number of 2 to 20. These are represented as average values.
[0021]
Although the amount of the nonionic surfactant used in the present invention is not particularly limited, it is preferably about 0.1 to 7% by weight, preferably about 0.5 to 3% by weight. Can be.
[0022]
Further, the tin whisker inhibitor of the present invention contains copper ions. As the copper ions, copper salts such as copper chloride, copper sulfate, and copper nitrate may be dissolved, or metallic copper may be dissolved at a stage where an oxidizing agent is present in the system. When dissolving a copper salt, it is preferable from the viewpoint of handling that a salt with the same anion as the above iron compound or acid is used.
[0023]
Such a copper ion is preferably used in a copper concentration of preferably 0.05 to 10 g / L, more preferably 0.5 to 5 g / L, and most preferably about 1.5 to 5 g / L. it can.
[0024]
To the tin whisker inhibitor of the present invention, a solubilizing agent, a wettability improver, and the like can be optionally added in addition to the above-mentioned compounds, as long as the object of the present invention is not impaired.
[0025]
Next, a method for producing a tin-plated product of the present invention will be described. In the method for producing a tin-plated product of the present invention, the surface of the tin-plated product is treated with the tin whisker inhibitor of the present invention, and then tin-plated.
[0026]
The material to be tin-plated is not particularly limited as long as it is a metal, but it is preferable that the material to be tin-plated is particularly copper or a copper alloy since the effects of the present invention can be remarkably obtained. In addition, the effect of the present invention can be remarkably obtained even when the tin-plated object is fine wiring copper or the like for an electronic device, which is preferable.
[0027]
The means for treating the surface of the tin-plated object with the tin whisker inhibitor of the present invention is not particularly limited. For example, the tin whisker inhibitor of the present invention is brought into contact with the tin-plated object surface by a known method such as an immersion method or a spray method. You can do it.
[0028]
Further, the treatment conditions are not particularly limited, but from the viewpoint of remarkably obtaining the effect of the present invention of sufficiently smoothing the surface of the tin-plated object even with a small etching amount, the tin whisker inhibitor of the present invention is used. For example, treatment is performed at 10 to 40 ° C. for 10 to 120 seconds, preferably for about 20 to 60 seconds, so that the amount of etching of the surface of the object to be tin-plated is about 0.1 to 1.5 μm, preferably about 0.3 to 1 μm. do it.
[0029]
【Example】
Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.
[0030]
[Example 1]
82.1 parts by weight of 40% by weight ferric chloride, 117.4 parts by weight of 20% by weight hydrochloric acid, 10.5 parts by weight of 76% by weight formic acid, 10.8 parts by weight of 85% by weight phosphoric acid, as a wettability improver 10.7 parts by weight of dipropylene glycol monomethyl ether, 11.0 parts by weight of a compound of the general formula (1) wherein A is an ethylenediamine residue and n = 11.6, m = 10.5, k = 4 In the formula (1), 1.1 parts by weight of a compound in which A is an ethylenediamine residue, n = 11.6, m = 4.0, and k = 4, and 856.4 parts by weight of pure water are mixed. 3.8 parts by weight of the copper chips were dissolved to obtain a tin whisker inhibitor (1) of the present invention.
[0031]
The obtained tin whisker inhibitor (1) had a pH of 0.12, a ferric chloride content of 3.0% by weight, a total nonionic surfactant content of 1.1% by weight, and a copper concentration of 3.0 g / L. .
[0032]
On the other hand, a copper wiring circuit having a lead width of 25 μm, a lead space width of 25 μm, and a lead thickness of 8 μm was formed on the insulating substrate of a polyimide film of 10 cm × 10 cm and a thickness of 170 μm by a semi-additive method to obtain a test piece. Was.
[0033]
Next, the test piece was immersed in the tin whisker inhibitor (1) at 25 ° C. for 30 seconds, washed with water and dried. Next, an electroless tin plating process was performed to provide a tin plating film having a thickness of 0.5 μm on the copper wiring circuit.
[0034]
The test piece treated in this manner was left in the air, and the occurrence of whiskers was observed with a microscope after 60 days and 90 days. No whiskers were observed in any case, and the shape of the copper wiring circuit was good. Was kept in In addition, the lead thickness of the copper wiring circuit in the test piece which was reduced by the treatment with the tin whisker inhibitor (1) was 0.7 μm.
[0035]
[Example 2]
82.1 parts by weight of 40% by weight ferric chloride, 117.4 parts by weight of 20% by weight hydrochloric acid, 10.5 parts by weight of 76% by weight formic acid, 10.8 parts by weight of 85% by weight phosphoric acid, as a wettability improver 10.7 parts by weight of dipropylene glycol monomethyl ether, 11.0 parts by weight of a compound in which A is an ethylenediamine residue in the general formula (2), and n = 11.6, m = 10.5, and k = 4, In the formula (2), 1.1 parts by weight of a compound in which A is an ethylenediamine residue, n = 11.6, m = 4.0, and k = 4, and 856.4 parts by weight of pure water are mixed. 3.8 parts by weight of the copper chips were dissolved to obtain a tin whisker inhibitor (2) of the present invention.
[0036]
The tin whisker inhibitor (2) had a pH of 0.12, a ferric chloride content of 3.0% by weight, a total nonionic surfactant content of 1.1% by weight, and a copper concentration of 3.0 g / L.
[0037]
When a test was performed in the same manner as in Example 1 using the same test piece as in Example 1, no whiskers were observed after 60 days and 90 days, and the shape of the copper wiring circuit was well maintained. I was dripping. The lead thickness of the copper wiring circuit at the test peak, which was reduced by the treatment with the tin whisker inhibitor (2), was 0.7 μm.
[0038]
[Example 3]
82.1 parts by weight of 40% by weight ferric chloride, 117.4 parts by weight of 20% by weight hydrochloric acid, 10.5 parts by weight of 76% by weight formic acid, 10.8 parts by weight of 85% by weight phosphoric acid, as a wettability improver 10.7 parts by weight of dipropylene glycol monomethyl ether, 11.0 parts by weight of a compound of the general formula (1) wherein A is an ethylenediamine residue, n = 11.6, m = 10.5, and k = 4 In the general formula (2), 1.1 parts by weight of a compound in which A is an ethylenediamine residue, n = 11.6, m = 4.0, k = 4, and 856.4 parts by weight of pure water are mixed, 3.8 parts by weight of the copper chips were dissolved in this to obtain a tin whisker inhibitor (3) of the present invention.
[0039]
The tin whisker inhibitor (3) had a pH of 0.12, a ferric chloride content of 3.0% by weight, a total nonionic surfactant content of 1.1% by weight, and a copper concentration of 3.0 g / L.
[0040]
When a test was performed in the same manner as in Example 1 using the same test piece as in Example 1, no whiskers were observed after 60 days and after 90 days, and the shape of the copper distribution circuit was excellent. Was kept. The lead thickness of the copper wiring circuit in the test piece which was reduced by the treatment with the tin whisker inhibitor (3) was 0.7 μm.
[0041]
【The invention's effect】
As described above, according to the tin whisker inhibitor of the present invention, even with a small etching amount, the surface of the tin-plated object can be sufficiently smoothed to effectively prevent the generation of tin whiskers. Further, according to the method for producing a tin-plated material having anti-whisker properties of the present invention, even a fine tin-plated product can be tin-plated while maintaining the shape stability of the tin-plated product with a small etching amount.
Claims (5)
Ａ〔（Ｃ３Ｈ６Ｏ）ｎ（Ｃ２Ｈ４Ｏ）ｍ Ｈ〕ｋ （１）
Ａ〔（Ｃ２Ｈ４Ｏ）ｍ（Ｃ３Ｈ６Ｏ）ｎ Ｈ〕ｋ （２）
（式中、Ａはｋ価の活性水素含有化合物の残基、ｋは１〜４の数、ｎは３〜３５の数、ｍは１〜７０の数である）で表される化合物である請求項１記載のホイスカ防止剤。The nonionic surfactant is represented by the following general formula (1) and / or general formula (2):
A [(C 3 H 6 O) n (C 2 H 4 O) m H] k (1)
A [(C 2 H 4 O) m (C 3 H 6 O) n H] k (2)
Wherein A is a residue of a k-valent active hydrogen-containing compound, k is a number of 1 to 4, n is a number of 3 to 35, and m is a number of 1 to 70. The whisker inhibitor according to claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003079529A JP4162217B2 (en) | 2003-03-24 | 2003-03-24 | Tin whisker inhibitor and method for producing whisker preventive tin plating using the same |
| TW093105750A TWI319605B (en) | 2003-03-24 | 2004-03-04 | Tin whisker generation-preventing agent and method of producing a whiskerless tin-plated product by using the same |
| KR1020040017944A KR101059487B1 (en) | 2003-03-24 | 2004-03-17 | Tin whisker inhibitor and manufacturing method of whisker-resistant tin plating material using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003079529A JP4162217B2 (en) | 2003-03-24 | 2003-03-24 | Tin whisker inhibitor and method for producing whisker preventive tin plating using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004285417A true JP2004285417A (en) | 2004-10-14 |
| JP4162217B2 JP4162217B2 (en) | 2008-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003079529A Expired - Lifetime JP4162217B2 (en) | 2003-03-24 | 2003-03-24 | Tin whisker inhibitor and method for producing whisker preventive tin plating using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4162217B2 (en) |
| KR (1) | KR101059487B1 (en) |
| TW (1) | TWI319605B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006213938A (en) * | 2005-02-01 | 2006-08-17 | Ebara Udylite Kk | Whisker preventive for tin or tin alloy plating and whisker preventing method using the same |
| JP2018521223A (en) * | 2015-06-16 | 2018-08-02 | スリーエム イノベイティブ プロパティズ カンパニー | Plating polymer article comprising a tin / copper bond / seed layer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4186029B2 (en) * | 1998-10-05 | 2008-11-26 | 石原薬品株式会社 | Abnormal crystal precipitation inhibitor in tin or tin alloy plating film on copper foil substrate and method for preventing the same |
-
2003
- 2003-03-24 JP JP2003079529A patent/JP4162217B2/en not_active Expired - Lifetime
-
2004
- 2004-03-04 TW TW093105750A patent/TWI319605B/en not_active IP Right Cessation
- 2004-03-17 KR KR1020040017944A patent/KR101059487B1/en active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006213938A (en) * | 2005-02-01 | 2006-08-17 | Ebara Udylite Kk | Whisker preventive for tin or tin alloy plating and whisker preventing method using the same |
| JP2018521223A (en) * | 2015-06-16 | 2018-08-02 | スリーエム イノベイティブ プロパティズ カンパニー | Plating polymer article comprising a tin / copper bond / seed layer |
| US11066753B2 (en) | 2015-06-16 | 2021-07-20 | 3M Innovative Properties Company | Plated polymeric article including tin/copper tie/seed layer |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200425363A (en) | 2004-11-16 |
| KR101059487B1 (en) | 2011-08-25 |
| JP4162217B2 (en) | 2008-10-08 |
| TWI319605B (en) | 2010-01-11 |
| KR20040084653A (en) | 2004-10-06 |
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