JP3904333B2 - Tin or tin alloy plating bath - Google Patents

Description

［ここで、 Ｒａは、水素又はアルキル（Ｃ₁〜Ｃ₄）を表し、Ｒｂは、水素、アルキル（Ｃ₁〜Ｃ₄）またはフェニルを表し、Ｒｃは、水素又は水酸基を表し、Ａは単結合、アルキレン、ベンジリデン又はフェニレンを表す。］
で表されるスルファニル酸誘導体およびその塩。
【００３４】
（３）一般式
【化２】

［ここで、Ｒaは、水素又はアルキル（Ｃ₁〜Ｃ₄）を表し、Ｒbは、水素又はメチルを表し、ｎは、２〜１５の整数を表す。］
で表されるキノリン類。
【００３５】
（４)一般式
【化３】

［ここで、Ｘは、水素、ハロゲン、アルキル（Ｃ₁〜Ｃ₄）、アセチル、アミノ基、水酸基、又はカルボキシル基を表し、Ｙは、水素、水酸基を表し、ｎは、０〜１２の整数を表す。］
で表されるトリアゾール及びその誘導体。
【００３６】
（５）一般式
【化４】

［ここで、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ は、それぞれ同一又は異なってもよく、−Ｈ、−ＳＨ、−ＯＨ、−ＯＲ（Ｒは所望により−ＣＯＯＨで置換されていてもよいＣ₁〜Ｃ₆のアルキル基）、ハロゲン、−ＣＯＯＨ、−ＣＯＣＯＯＨ、アリール、−ＳＲ（Ｒは所望により−ＣＯＯＨにて置換されていてもよいＣ₁〜Ｃ₆のアルキル）、
【化５】

、−ＮＨ₂ 、−ＮＲＲ’（Ｒ及びＲ’はＣ₁〜Ｃ₆のアルキル又は一緒になって環を形成してもよい）、−ＮＨＣＯＲ（ＲはＣ₁〜Ｃ₆のアルキル）、−ＮＨＣＯアリール、−ＮＨＮＨ₂、−ＮＯ₂、−ＣＯＮＨアリール、−ＣＳＮＨアリール、−ＣＮ、−ＣＨＯ、−ＳＯ₃Ｈ、−ＳＯ₂ＮＨ₂又は−ＳＯ₂ＮＲＲ’（Ｒ及びＲ’はＣ₁〜Ｃ₆のアルキルまたは一緒になって環を形成してもよい）を表す。］
で表されるベンゾチアゾール及びその誘導体。
【００３７】
（６）一般式
【化６】

［ここで、Ｘ及びＹは、それぞれ独立に水素又は水酸基を表し、Ｒa、Ｒbは、それぞれ独立にアルキル（Ｃ₁〜Ｃ₅）を表す。］
で表されるイミン類。
【００３８】
（７）一般式
【化７】

［ここで、Ｘは、水素、ハロゲン又はアルキル（Ｃ₁ 〜Ｃ₁₈）を表し、Ｙは、水素、水酸基又はアルキル（Ｃ₁ 〜Ｃ₁₈）を表す。］
で表されるトリアジン類。
【００３９】
（８）一般式
【化８】

［ここで、Ｒa、Ｒbは、同一又は異なっていてもよく水素、アルキル（Ｃ₁ 〜Ｃ₁₈）、アルコキシ（Ｃ₁〜Ｃ₁₈）又はシクロアルキル（Ｃ₃〜Ｃ₇）を表し、Ａは、低級アルキレンを表す。]
で表されるトリアジン類。
【００４０】
（９）一般式
【化９】

［ここで、Ｒは、アルキル（Ｃ₁〜Ｃ₄）又はフェニルを表す。]
で表される芳香族オキシカルボン酸のエステル類。
【００４１】
（1０）一般式
Ｒa−ＣＲb＝ＣＨ−ＣＯ−Ｘ−Ｒc
［ここで、Ｒa及びＲcは、フェニル、ナフチル、ピリジル、キノリル、チエニル、フリル、ピロニル、アミノ基、水酸基、もしくは水素から選ばれた基であり、該基は、アルキル（Ｃ₁〜Ｃ₆）、アルキルオキシ（Ｃ₁〜Ｃ₆）、アシル（Ｃ₁ 〜Ｃ₆ ）、アルキルチオ（Ｃ₁〜Ｃ₆）、水酸基，ハロゲン、カルボキシル基、ニトロ基及び−ＮＲdＲe（Ｒd 及びＲｅは、同一又は異なってよく、各々水素又はアルキル（Ｃ₁〜Ｃ₄）を表す）から選ばれた同一又は異なる置換基を１〜４個有してもよく、あるいはＲaとＲcは 結合して環状となってもよく、あるいは、Ｒc はＲa−ＣＲb＝ＣＨ−ＣＯ−に等しくてもよい。Ｘは、単結合もしくはメチレンである。Ｒbは水素又はアルキル（Ｃ₁〜Ｃ₄）である。］
で表されるＣ＝Ｏと共役の位置に二重結合を有する化合物。
【００４２】
（１１）一般式
Ｒ−ＣＨＯ
［ここで、Ｒは、アルキル（Ｃ₁〜Ｃ₆）、アルケニル（Ｃ₂〜Ｃ₆）、アルキニル（Ｃ₂〜Ｃ₆）、フェニル、ナフチル、アセナフチル、ピリジル、キノリル、チエニル、フリル、インドール及びピロニル、アルデヒド基もしくは水素から選ばれた基であり、該基は、アルキル（Ｃ₁〜Ｃ₆）、フェニル、アルキルオキシ（Ｃ₁ 〜Ｃ₆）、アシル（Ｃ₁〜Ｃ₆）、アルキルチオ（Ｃ₁〜Ｃ₆）、水酸基，ハロゲン、ニトロ基及び−ＮＲaＲb（Ｒa及びＲbは、同一又は異なってよく、各々水素又はアルキル（Ｃ₁〜Ｃ₄）を表す）から選ばれた同一又は異なる置換基を１〜４個有してもよい。］
で表されるアルデヒド類。
【００４３】
（１２）一般式
Ｒa−ＣＯ−（ＣＨ₂）ｎ−ＣＯ−Ｒb
［ここで、Ｒa及びＲbは、同一又は異なってもよく、水素、アルキル（Ｃ₁〜Ｃ₆）又は−Ｃ₂Ｈ₄−ＣＯ−ＣＯ−Ｃ₂Ｈ₅を表し、ｎは０〜２の整数である］
で表されるジケトン類。
【００４４】
（１３）一般式
Ｒa−ＮＨ−Ｒb
［ここで、Ｒa は、フェニルを表し、該基は、アルキル（Ｃ₁〜Ｃ₃）、ハロゲン又はアミノ基で置換されてもよい。Ｒb は水素、アルキル（Ｃ₁〜Ｃ₃）、−ＮＨ−ＣＳ−Ｎ＝Ｎ−φ、−ＣＨ₂又は−φ−ＮＨ₂を表す。］
で表されるアニリン誘導体。
【００４５】
（１４）一般式
【化１０】

［ここで、Ｒa 、Ｒｂはそれぞれ独立に水素、低級アルキル、水酸基、ニトロ基、カルボキシル基又はスルホン酸基を表す。］
で表されるニトロ化合物又はそのナトリウム、カリウム又はアンモニウム塩。
【００４６】
（１５）一般式
ＨＯＯＣ−ＣＨＲ−ＳＨ
［ここで、Ｒは、水素又はアルキル（Ｃ₁〜Ｃ₂）を表し、該アルキルの水素はカルボキシル基で置換されていてもよい。］
で表されるメルカプトカルボン酸類。
【００４７】
（１６）下記から選ばれる複素環式化合物類：
１，１０−フェナントロリン、２−ビニルピリジン、キノリン、インドール、イミダゾール、２−メルカプトベンゾイミダゾール、１，２，３−（又は１，２，４−又は１，３，５−）トリアジン、１，２，３−ベンゾトリアジン、２−メルカプトベンゾオキサゾール、２−シンナミルチオフェン、
【００４８】
（１７）アセトフェノン及びハロゲン化アセトフェノン。
【００４９】
（１８）一般式
【化１１】

［ここで、Ｒａ、Ｒｂ及びＲｃは、それぞれ独立に、水素、メチル、エチル又は（ＣＨ₂）ｎ−ＣＨ（Ｒ₄ ）（ＯＨ）を表し、Ｒa、Ｒｂ及びＲｃのうち少なくとも一つは−（ＣＨ₂）ｎ−ＣＨ（Ｒｄ）（ＯＨ）である。Ｒdは水素又はメチルを表し、ｎは１又は２の整数を表す。］
で表されるアミンアルコール類。
【００５０】
（１９）上記（１１）から選ばれたアルデヒドと上記（１３）又は下記一般式（ａ）から選ばれたアミンとの反応生成物。
（ａ）一般式
Ｒａ−ＮＨ−Ｒｂ
［ここで、Ｒａ及びＲｂは水素、アルキル（Ｃ₁ 〜Ｃ₆ ）、又はシクロアルキル（Ｃ₃〜Ｃ₈）を表す。該Ｒａ及びＲｂの水素は、水酸基、アミノ基で置換されていてよく、また、結合して又は−ＮＨ−又は−Ｏ−を介して結合して環を形成してもよい。ただし、該Ｒａ及びＲｂは同時に水素であることはない。］
で表される脂肪族一級又は二級アミン。
【００５１】
これらのうち、特に好適な例を挙げると、
前記式（２）で表されるものとして、
Ｎ−ブチリデンスルファニル酸、Ｎ−（３−ヒドロキシブチリデン）−ｐ−スルファニル酸、アルドール、
【００５２】
前記式（３）で表されるものとして、
８−ヒドロキシキノリンに５モルの酸化プロピレンを付加した生成物、
【００５３】
前記式（４）で表されるものとして、
ベンゾトリアゾール、４−メチルベンゾトリアゾール、４−ヒドロキシベンゾトリアゾール、４−カルボキシベンゾトリアゾール、
【００５４】
前記式（５）で表されるものとして、
ベンゾチアゾール、２−メチルベンゾチアゾール、２−メルカプトベンゾチアゾール、２−アミノ−４−クロロベンゾチアゾール、２−アミノ−６−メトキシベンゾチアゾール、２−ヒドロキシベンゾチアゾール、２−クロロベンゾチアゾール、２−メチル−５−クロロベンゾチアゾール、２，５−ジメチルベンゾチアゾール、５−ヒドロキシ−２−メチルベンゾチアゾール、６−クロロ−２−メチル−４−メトキシベンゾチアゾール、２−（ｎ−ブチル）メルカプト−６−アミノベンゾチアゾール、２−ベンゾチアゾールチオ酢酸、２−ベンゾチアゾールオキシ酢酸、６−エトキシ−２−メルカプトベンゾチアゾール、
【００５５】
前記式（６）で表されるものとして、
Ｎ、Ｎ’ジイソ−ブチリデン−ｏ−フェニレンジアミン、
【００５６】
前記式（７）で表されるものとして、
２，４−ジアミノ−６−［２’−メチルイミダゾリル（１’）エチル−１，３，５−トリアジン、２，４−ジアミノ−６−［２’−エチルイミダゾリル（１’）エチル−１，３，５−トリアジン、２，４−ジアミノ−６−［２’−ウンデシルイミダゾリル（１’）エチル−１，３，５−トリアジン、
【００５７】
前記式（８）で表されるものとして、
β−Ｎ−ドデシルアミノプロピオグアナミン、β−Ｎ−ヘキシルアミノプロピオグアナミン、ピペリジンプロピオグアナミン、シクロヘキシルアミノプロピオグアナミン、モルホリンプロピオグアナミン、β−Ｎ−（２−エチルヘキシロキシプロピルアミノ）プロピオグアナミン、β−Ｎ−（ラウリルオキシプロピルアミノ）プロピオグアナミン、
【００５８】
前記式（９）で表されるものとして、
ｏ−（又はｍ−又はｐ−）安息香酸メチル、サリチル酸フェニル、
【００５９】
前記式（１０）で表されるものとして、
イタコン酸、プロピレン−１，３−ジカルボン酸、アクリル酸、クロトン酸、桂皮酸、アクリル酸メチル、アクリル酸エチル、メタクリル酸、メタクリル酸メチル、メタクリル酸ブチル、エタクリル酸、アクリルアミド、ジアセトンアクリルアミド、ｔ−ブチルアクリルアミド、Ｎ−メトキシジメチルアクリルアミド、クルクミン（１，７−ビス（４−ヒドロキシ−３−メトキシフェラル）−１，６−ヘプタジエン−３，５−ジオン）、イソホロン（３，５，５−トリメチル−２−シクロヘキセノン）、メシチルオキシド、ビニルフェニルケトン、フェニルプロペニルケトン、フェニルイソブテニルケトン、フェニル−１−メチルプロペニルケトン、ベンジリデンアセトフェノン（ｃｈａｌｃｏｎｅ）、２−（ω−ベンゾイル）ビニルフラン、ｐ−フロロフェニルプロペニルケトン、ｐ−クロロフェニルプロペニルケトン、ｐ−ヒドロキシフェニルプロペニルケトン、ｍ−ニトロフェニルプロペニルケトン、ｐ−メチルフェニルプロペニルケトン、２，４，６−トリメチルフェニルプロペニルケトン、ｐ−メトキシフェニルプロペニルケトン、ｐ−メトキシフェニルブテニルケトン、ｐ−メチルチオフェニルプロペニルケトン、ｐ−イソブチルフェニルプロペニルケトン、α−ナフチル−１−メチルプロペニルケトン、４−メトキシナフチルプロペニルケトン、２−チエニルプロペニルケトン、２−フリルプロペニルケトン、１−メチルピロールプロペニルケトン、ベンジリデンメチルエチルケトン、ベンジリデンアセトンアルコール、ｐ−トルイデンアセトン、アニザルアセトン（アニシリデンアセトン）、ｐ−ヒドロキシベンジリデンアセトン、ベンジリデンメチルイソブチルケトン、３−クロロベンジリデンアセトン、ベンザルアセトン（ベンジリデンアセトン）、ベンジリデンアセチルアセトン、４−（１−ナフチル）−３−ブテン−２−オン、ピリジデンアセトン、フルフリジンアセトン、４−（２−チオフェニル）−３−ブテン−２−オン、４−（２−フリル）−３−ブテン−２−オン、アクロレイン（アクリルアルデヒド、プロペナール）、アリルアルデヒド、クロトンアルデヒド、シンナムアルデヒド、ベンジルクロトンアルデヒド、テニリデンアセトン、
【００６０】
前記式（１１）で表されるものとして、
ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ｎ−ブチルアルデヒド、イソブチルアルデヒド、ｎ−バレルアルデヒド（バレラール、ペンタナール）、イソバレルアルデヒド、ｎ−カプロンアルデヒド（ヘキサナール、ヘキシルアルデヒド）、スクシンアルデヒド（スクシンジアルデヒド）、グルタルアルデヒド（１，５−ペンタンジアール、グルタルジアルデヒド）、アルドール（３−ヒドロキシブチルアルデヒド、アセトアルドール）、クロトンアルデヒド、桂皮アルデヒド、プロパギルアルデヒド、ベンズアルデヒド、ｏ−フタルアルデヒド、サリチルアルデヒド（Ｏ−ヒドロキシベンズアルデヒド）、ｐ−ヒドロキシベンズアルデヒド、ｐ−ニトロベンズアルデヒド、ｏ−（又はｐ−）メトキシベンズアルデヒド（アニスアルデヒド）、３−メトキシベンズアルデヒド、バニリン、ｏ−バニリン、ベラトルアルデヒド（３，４−ジメトキシベンズアルデヒド）、２，５−ジメトキシベンズアルデヒド、（２，４−、 ２，６−）ジクロロベンズアルデヒド、１−（又は２−）ナフトアルデヒド、２−（又は４−）クロロ−１−ナフトアルデヒド、２−（又は４−）ヒドロキシ−１−ナフトアルデヒド、５（又は２）−メトキシナフトアルデヒド、２−フルアルデヒド（２−フルアルデヒド＝フルフラール）、３−フルアルデヒド、２（３）−チオフェンカルボキシアルデヒド、ピコリンアルデヒド、３−アセナフトアルデヒド、３−インドールカルボキシアルデヒド、
【００６１】
前記式（１２）で表されるものとして、
グリオキサール（エタンジアール、オキサルアルデヒド、ジホルミル、ビホルミル）、ジアセチル（ビアセチル、ジメチルグリオキサール、ブタンジオン）、ヘキサンジオン−３，４、アセチルアセトン（２，４−ペンタンジオン）、ヘキサンジオン−３，４−アセチルアセトン、
【００６２】
前記式（１３）で表されるものとして、アニリン、ｏ−（又はｍ−又はｐ−）トルイジン、ｏ−（又はｐ−）アミノアニリン、ｏ−（又はｐ−）クロルアニリン、２，５−（又は３，４−）クロルメチルアニリン、Ｎ−モノメチルアニリン、４，４’ジアミノジフェニルメタン、Ｎ−フェニル−（α−又はβ−）ナフチルアミン、ジチゾン、
【００６３】
前記式（１４）で表されるものとして、ｐ−ニトロフェノール、ニトロベンゼンスルホン酸、２，４−ジニトロベンゼンスルホン酸、ｍ−ニトロ安息香酸、
【００６４】
前記式（１５）で表されるものとして、メルカプト酢酸（チオグリコール酸）、メルカプトコハク酸、
【００６５】
前記式（１８）で表されるものとして、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、Ｎ−メチルエタノールアミン、
【００６６】
前記式（１９）で表されるものとして、アミン−アルデヒド縮合物、例えば、ピペラジン、ビペリジン、モルホリン、シクロプロピルアミン、シクロヘキシルアミン、シクロオクチルアミン、エチレンジアミン、モノエタノールアミン、ジエタノールアミン、などの式（ａ）で表される脂肪族第一若しくは第二アミン類又は前記式（１３）で表される芳香族アミン類と前記式（１１）で表されるアルデヒド類との縮合物、
などを挙げることができる。
【００６７】
本発明の錫又は錫合金めっき浴には、ｐＨ緩衝剤を添加して用いることができるが、該ｐＨ緩衝剤には、公知の化合物がいずれも使用でき、例えばリン酸、酢酸、硼酸、クエン酸、酒石酸等のそれぞれナトリウム、カリウム及びアンモニウム塩、さらに多塩基酸の場合には、水素イオンを含む酸性塩等を単独又は適宜混合して用いることができる。該ｐＨ緩衝剤の使用量は、公知の例に従えば良いが、一般には５〜５０ｇ／ｌ程度が用いられ、さらに好ましくは１０〜２０ｇ／ｌ程度が用いられる。
【００６８】
【実施例】
以下に実施例によって、本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではなく、前述の目的に沿って請求した請求項に記載した範囲内でめっき浴の構成或いはめっき処理条件は、適宜、任意に変更することができる。
【００６９】
実施例１
下記（Ａ−１）の錫−銀合金めっき浴を調製し、浴温２５℃で、銅板上に３Ａ／ｄｍ² でめっきを施した。（Ａ−１）の浴からｉ−プロピルアルコールを除いた浴［（Ａ−２）と呼ぶ］、（Ａ−１）の浴からカテコールを除いた浴［（Ａ−３）と呼ぶ］並びに（Ａ−１）の浴からｉ−プロピルアルコール及びカテコールを除いた浴［（Ａ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。

（Ａ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ａ−２）、（Ａ−３）及び（Ａ−４）の浴から得られためっき皮膜は、（Ａ−１）浴からの皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７０】
実施例２
下記（Ｂ−１）の錫−ビスマス合金めっき浴を調製し、浴温２５℃で、銅板上に３Ａ／ｄｍ² でめっきを施した。（Ｂ−１）の浴からｉ−プロピルアルコールを除いた浴［（Ｂ−２）と呼ぶ］、（Ｂ−１）の浴から３，４，５−トリヒドロキシ安息香酸を除いた浴［（Ｂ−３）と呼ぶ］並びに（Ｂ−１）の浴からｉ−プロピルアルコール及び３，４，５−トリヒドロキシ安息香酸を除いた浴［（Ｂ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。

（Ｂ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｂ−２）、（Ｂ−３）並びに（Ｂ−４）の浴から得られためっき皮膜は、（Ｂ−１）浴からの皮膜と比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７１】
実施例３
下記（Ｃ−１）の錫−銅合金めっき浴を調製し、浴温２５℃で、銅板上に３Ａ／ｄｍ² でめっきを施した。（Ｃ−１）の浴からアセトンを除いた浴［（Ｃ−２）と呼ぶ］、（Ｃ−１）の浴からレゾルシノールを除いた浴［（Ｃ−３）と呼ぶ］並びに（Ｃ−１）の浴からアセトン及びレゾルシノールを除いた浴［（Ｃ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。
浴（Ｃ−１） 錫−銅合金めっき浴
硫酸錫（錫として） ３０ ｇ／ｌ
硫酸銅（５水塩）（銅として） １５ ｇ／ｌ
クレゾールスルホン酸 １０ ｇ／ｌ
硫酸 ９８ ｇ／ｌ
エマルゲン４０９ｐ ２ ｇ／ｌ
ベンザルアセトン ０．３ ｇ／ｌ
アセトン ２０ ｇ／ｌ
レゾルシノール ３ ｇ／ｌ
（Ｃ−１）の浴から得られためっき皮膜が平滑均一で良好な光沢があったのに対して、（Ｃ−２）、（Ｃ−３）及び（Ｃ−４）の浴から得られためっき皮膜は、（Ｃ−１）浴からの皮膜と比べて、光沢性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７２】
実施例４
下記（Ｄ−１）の錫−インジウム合金めっき浴を調製し、浴温２５℃で、銅板上に７．５Ａ／ｄｍ² でめっきを施した。（Ｄ−１）の浴からｉ−プロピルアルコールを除いた浴［（Ｄ−２）と呼ぶ］、（Ｄ−１）の浴からヒドロキノンを除いた浴［（Ｄ−３）と呼ぶ］並びに（Ｄ−１）の浴からｉ−プロピルアルコール及びヒドロキノンを除いた浴［（Ｄ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。

（Ｄ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｄ−２）、（Ｄ−３）及び（Ｄ−４）の浴から得られためっき皮膜は、（Ｄ−１）浴から皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７３】
実施例５
下記（Ｅ−１）の錫−亜鉛合金めっき浴を調製し、浴温２５℃で、銅板上に５Ａ／ｄｍ² でめっきを施した。（Ｅ−１）の浴からｉ−プロピルアルコールを除いた浴［（Ｅ−２）と呼ぶ］、（Ｅ−１）の浴からフロログルシンを除いた浴［（Ｅ−３）と呼ぶ］及び（Ｅ−１）の浴からｉ−プロピルアルコール及びフロログルシンを除いた浴［（Ｅ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。
浴（Ｅ−１） 錫−亜鉛合金めっき浴
スルホコハク酸錫（錫として） ５６．４ ｇ／ｌ
スルホコハク酸亜鉛（亜鉛として） ３．６ ｇ／ｌ
スルホコハク酸 １００ ｇ／ｌ
Ｌ−アスコルビン酸 ２．０ ｇ／ｌ
ノイゲンＥＮ１０ ０．３ ｇ／ｌ
ベンズアルデヒド ０．１ ｇ／ｌ
ｉ−プロピルアルコール １０ ｇ／ｌ
フロログルシン ５ ｇ／ｌ
ｐＨ（ＮａＯＨで調整） ４．０
（Ｅ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｅ−２）、（Ｅ−３）及び（Ｅ−４）の浴から得られためっき皮膜は、（Ｅ−１）浴からの皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７４】
実施例６
下記（Ｆ−１）の錫−アンチモン合金めっき浴を調製し、浴温２５℃で、銅板上に２Ａ／ｄｍ² でめっきを施した。（Ｆ−１）の浴からエチルアルコールを除いた浴［（Ｆ−２）と呼ぶ］、（Ｆ−１）の浴からカテコールスルホン酸を除いた浴［（Ｆ−３）と呼ぶ］並びに（Ｆ−１）の浴からエチルアルコール及びカテコールスルホン酸を除いた浴［（Ｆ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。

（Ｆ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｆ−２），（Ｆ−３）及び（Ｆ−４）の浴から得られためっき皮膜は、（Ｆ−１）からの皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７５】
実施例７
下記（Ｇ−１）の錫−金合金めっき浴を調製し、浴温２５℃で、銅板上に１Ａ／ｄｍ² でめっきを施した。（Ｇ−１）の浴からエチレングリコールを除いた浴［（Ｇ−２）と呼ぶ］、（Ｇ−１）の浴からカテコールスルホン酸を除いた浴［（Ｇ−３）と呼ぶ］並びに（Ｇ−１）の浴からエチレングリコール及びカテコールスルホン酸を除いた浴［（Ｇ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。

（Ｇ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｇ−２）、（Ｇ−３）並びに（Ｇ−４）の浴から得られためっき皮膜は、（Ｇ−１）からの皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７６】
実施例８
下記（Ｈ−１）の錫−銀合金めっき浴を調製し、浴温２５℃で、銅板上に２Ａ／ｄｍ² でめっきを施した。（Ｈ−１）の浴からｉ−プロピルアルコールを除いた浴［（Ｈ−２）と呼ぶ］、（Ｈ−１）の浴からヒドロキノンを除いた浴［（Ｈ−３）と呼ぶ］並びに（Ｈ−１）の浴からｉ−プロピルアルコール及びヒドロキノンを除いた浴［（Ｈ−４）と呼ぶ］から同一条件でめっきを施し、それぞっれの浴からのめっき皮膜を比較した。

（Ｈ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｈ−２）、（Ｈ−３）及び（Ｈ−４）の浴から得られためっき皮膜は、（Ｈ−１）浴からの皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。
【００７７】
実施例９
下記（Ｉ−１）の錫−銀合金めっき浴を調製し、浴温２０℃で、銅板上に３Ａ／ｄｍ²でめっきを施した。（Ｉ−１）の浴からエチルアルコールを除いた浴［（Ｉ−２）と呼ぶ］、（Ｉ−１）の浴からカテコールを除いた浴［（Ｉ−３）と呼ぶ］並びに（Ｉ−１）の浴からカテコール及びエチルアルコールを除いた浴［（Ｉ−４）と呼ぶ］から同一条件でめっきを施し、それぞれの浴からのめっき皮膜を比較した。
浴（Ｉ−１） 錫−銀合金めっき浴
フェノールスルホン酸錫（錫として） ２５ ｇ／ｌ
フェノールスルホン酸銀（銀として） ０．４ ｇ／ｌ
フェノールスルホン酸 １００ ｇ／ｌ
トリス（３−ヒドロキシプロピル）
ホスフィン ２０ ｇ／ｌ
２−メルカプトベンゾチアゾール ０．１ ｇ／ｌ
アデカトールＰＣ１０ １ ｇ／ｌ
カチオンＭ １ ｇ／ｌ
エチルアルコール ３０ ｍｌ／ｌ
カテコール ５ ｇ／ｌ
（Ｉ−１）の浴から得られためっき皮膜が平滑均一であったのに対して、（Ｉ−２）、（Ｉ−３）及び（Ｉ−４）の浴から得られためっき皮膜は、（Ｉ−１）浴からの皮膜に比べて、平滑性において劣るばかりでなく、ムラがあり、均一性に欠けるものであった。[0001]
BACKGROUND OF THE INVENTION
The present invention belongs to electroplating technology, and particularly relates to tin or tin alloy electroplating.
[0002]
[Prior art]
Tin or tin alloy plating has a wide range of applications such as soldering, connectors, sliding parts, decoration, and corrosion protection.
[0003]
With regard to the electrodeposition of tin and tin alloys, a dendritic, needle-like, or sponge-like precipitate is formed without an additive, and thus an additive has been regarded as an essential plating bath for a long time. In the beginning, natural polymers such as gelatin and peptone have been used, but at present, surfactants are generally used, and a wide variety of surfactants are used alone or in combination. It is used. Further, an additive called a so-called smoothing agent or brightening agent is often used in combination with the surfactant.
[0004]
To date, there have been countless other types of additives for tin or tin alloy plating, but this fact is a standard that is acceptable to the majority of users. This means that no additional additives have been found. One reason for this is that, generally, a smoothing agent having a high effect has a strong absorption capacity and is often occluded in the electrodeposit, which impairs the physical properties of the electrodeposit, and therefore, a smoothing effect that is as simple as possible with a simple compound. Although there is a demand for a material that shows the above, such a thing has not been found.
[0005]
For example, in order to prevent environmental pollution caused by lead eluted from tin-lead solder currently used for electrical and electronic parts, a tin alloy plating bath for obtaining a lead-free solderable alternative coating However, no suitable additive has been found, and a product that has reached an industrially widely available stage has not yet appeared.
[0006]
[Problems to be solved by the invention]
An effective smoothing additive for tin or tin alloy plating baths, finding as simple a structure as possible and providing a tin or tin alloy plating bath that can be widely used industrially. The purpose of the present invention was to improve the tin or tin alloy plating film as a functional film and to solve the lead-free solderability film problem.
[0007]
[Means for Solving the Problems]
The inventors of the present invention, in particular, as a result of intensive studies on additives for giving a plating film having good characteristics in tin plating or an alloy plating bath of tin and silver, copper, indium, zinc, etc. C in combination with an activator ₁ ~ C ₆ By containing one or more of lower aliphatic saturated alcohols or ketones of the above and one or more of mono (or poly) hydroxybenzene or mono (or poly) hydroxynaphthalene or their derivatives, tin or It has been found that the smoothness of the tin alloy plating film and the uniformity of the plating film appearance are remarkably improved, and as a result, the film characteristics such as solderability and discoloration resistance are improved, and the lead-free soldering film problem is solved. In addition, it has been found that the smoothness of the film is improved even in an alloy plating bath of tin and a metal other than the above, and to improve the tin or tin alloy plating film as a functional film for decoration and corrosion prevention. Successful.
[0008]
That is, the tin or tin alloy plating bath of the present invention includes the following (A) to (E) as essential components:
(A) One or more of tin salts or tin complexes, or one or more of tin salts or tin complexes and one or more of salts or complexes of metals other than tin,
(B) one or more of acid, base and / or complexing agent,
(C) One or more surfactants,
(D) C ₁ ~ C ₆ One or more of lower aliphatic saturated water-soluble alcohols, ketones or ethers, and
(E) A compound in which hydrogen in the benzene ring or naphthalene ring is replaced with a hydroxyl group in the range of 1 to 6 and mono (or poly) hydroxybenzene or mono (or poly) hydroxy in which a carboxyl group or a sulfonic acid group is further introduced to them One or more of naphthalene or their derivatives
Containing.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
For the tin salt or tin complex used in the tin or tin alloy plating bath used in the present invention, any known compound may be used alone or in combination. That is, for example, tin salts of inorganic acids such as sulfuric acid, borofluoric acid, silicic acid, sulfamic acid, hydrochloric acid, pyrophosphoric acid, for example, tin salts of aliphatic sulfonic acids such as methanesulfonic acid, 2-propanolsulfonic acid, sulfosuccinic acid, etc. Tin salt of aromatic sulfonic acid such as phenolsulfonic acid, for example, acetic acid, succinic acid, malonic acid, succinic acid, glycolic acid, tartaric acid, citric acid, gluconic acid, δ-gluconolactone, glycine, mercaptosuccinic acid, ethylenediaminetetraacetic acid , Iminodiacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenedioxybis (ethylamine) -N, N, N ′, N′-tetraacetic acid, glycol ethylenediaminetetraacetic acid, N- (2-hydroxyethyl) ) Carbohydrates such as ethylenediaminetriacetic acid Tin salts or tin complexes of compounds containing a xyl group, for example tin complexes of phosphonic acids such as 1-hydroxyethane-1,1-bisphosphonic acid, such as tris (hydroxymethyl) phosphine, tris (3-hydroxypropyl) phosphine, tri An aliphatic or aromatic phosphine tin complex such as phenylphosphine is preferably used alone or in combination.
[0010]
Of these, tin sulfate, tin chloride, tin methanesulfonate, tin 2-propanolsulfonate, tin phenolsulfonate, tin sulfosuccinate or mercaptosuccinate tin are most preferably used.
[0011]
The amount used varies appropriately depending on the type of plating bath, the type of metal to be alloyed, and the alloy composition, but generally 0.001 g / l to 100 g / l is used as tin. For example, when adding a small amount of tin salt to a gold plating bath to increase the hardness of the gold film, a small amount such as 0.001 g / l is added, and a small amount of silver is added to tin. In order to obtain an alloy film having a tin-silver eutectic composition, about 10 to 100 g / l is preferably used.
[0012]
The component metals that form an alloy with tin include Group IB metals (copper, silver, gold) in the periodic table of elements, Group IIB metals (zinc and cadmium) excluding mercury, and the fifth period excluding tin in groups IIIA to VA And metal salts selected from metals of the 6th period (indium, thallium, lead, antimony, bismuth) or group VIII metals (iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum) Alternatively, one or more of the complexes are used.
[0013]
When these metals are all used as tin alloy plating, the effect of combined use of a surfactant, mono (or poly) hydroxybenzene, mono (or poly) hydroxynaphthalene or derivatives thereof, and alcohol, ketone or ether is effective. Although it appears, the effect when using silver, copper, indium, zinc, gold, nickel, cobalt, palladium, rhodium, bismuth, antimony is remarkable, and the most prominent are silver, copper, indium, zinc It is.
[0014]
These metals are also added and used in the form of salts or complexes. They may be the acids or complexing agents used in the above-mentioned tin salts or complexes and their metal salts or complexes, for example nitric acid, nitrous acid, sulfurous acid, bisulfite, metabisulfite, chloric acid. , Salts or complexes of perchloric acid, bromine, bromic acid, iodine, iodic acid, thiosulfuric acid, thiocyanic acid, ammonia, such as imidazolidinone, 2-imidazolidinethione, thiourea, trimethylthiourea, N, N′-di -N-butylthiourea, tetramethylthiourea, 1-allyl 2-thiourea, N, N'diethylthiourea, 1,3-bis (dimethylaminopropyl) -2-thiourea, N, N dimethylthiourea, N, N -Ureas such as dimethylolurea, thiosemicarbazide, 4-phenyl-3-thiosemicarbazide, 2-thiobarbituric acid, thiourea or thioacetamide and Complexes of these derivatives, such as sulfides or disulfides such as 4,4′-thiodiphenol, 4,4′-aminodiphenyl sulfide, 2,2′-dithiopyridine, such as hydantoin, 5-n-propylhydantoin Hydantoins such as 5,5-dimethylhydantoin, such as 2,2-dimethylsuccinimide, 2-methyl-2-ethylsuccinimide, 2-methylsuccinimide, 2-ethylsuccinimide, 1,1,2, 2-tetramethyl succinimide, 1,1,2-trimethyl succinimide, 2-butyl succinimide, 2-ethyl maleic imide, 1-methyl-2-ethyl maleic imide, 2-butyl maleic imide, etc. Of succinimides (succinimides) or maleic imides and their derivatives, such as e.g. Tylenediamine, ethylamine isopropylamine, n-butylamine, isobutylamine, dipropylamine, dibutylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, 2-amino-2- (hydroxymethyl)- Complexes with amines such as 1,3-propanediol and 2-chloroethylammonium chloride, such as benzotriazole, 2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzobenzo Complexes with nitrogen-containing and / or sulfur-containing complex compounds such as benzotriazole such as oxazole, benzothiazole, benzimidazole or benzoxazole, such as 1-hydroxy Complexes with phosphonic acids such as tan-1,1-bisphosphonic acid, for example, complexes with aliphatic or aromatic phosphines such as tris (hydroxymethyl) phosphine, tris (3-hydroxypropyl) phosphine, triphenylphosphine, etc. It may be.
[0015]
Although the usage-amount of metals other than tin used for the tin or tin alloy plating bath of this invention can be changed suitably according to the objective of this solution, those total amounts are used with the density | concentration of 1-100 g / l in general. For example, in the case of a plating solution such as a gold-tin plating solution used by adding a trace amount of a second metal, the addition amount of the trace metal may be as small as 0.001.
[0016]
As the acid, base and / or complexing agent used in the tin or tin alloy plating bath of the present invention, any known compounds may be used, but any other than the term of tin salt or tin complex, or (A) group tin The acid, base and / or complexing agent described in the section of metal salt or complex is more preferably used alone or in combination.
[0017]
The amount of the acid, base and / or complexing agent used can be appropriately changed depending on the purpose and conditions of use of the solution, starting with the metal concentration. That is, in a pH range bath, an acid or a base may be added so that a desired pH is obtained. In a strongly acidic bath, an acid of about 0.1 to 10 M is generally added, and in a strongly basic bath, approximately 0.1 is added. About 10M base is used. Complexing agents can be used alone or in combination with their acids or bases, but are used in an amount of 1 to 1000 times, more preferably about 1 to 300 times, depending on the concentration of the metal to be complexed. Is used.
[0018]
One or more surfactants are added as essential components to the tin or tin alloy plating bath of the present invention. That is, as the surfactant, any of known nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants may be used alone or in combination, but more preferably. It is desirable to contain at least one nonionic surfactant.
[0019]
Nonionic surfactants preferably used include polyoxyalkylene alkyl ether (or ester), polyoxyalkylene phenyl (or alkylphenyl) ether, polyoxyalkylene naphthyl (or alkyl naphthyl) ether, polyoxyalkylene styrenation Phenyl ether (or polyoxyalkylene styrenated phenyl ether with a polyoxyalkylene chain added to the phenyl group), polyoxyalkylene bisphenol ether, polyoxyethylene polyoxypropylene block polymer, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene Sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyal Lenalkylamine, polyoxyalkylene condensate adduct of ethylenediamine, polyoxyalkylene fatty acid amide, polyoxyalkylene castor (or / and hardened castor oil) oil, polyoxyalkylene alkylphenyl formalin condensate, glycerin (or polyglycerin) fatty acid Ester, pentaerythritol fatty acid ester, sorbitan mono (sesqui, tri) fatty acid ester, higher fatty acid mono (di) ethanolamide, alkyl / alkylolamide, oxyethylene alkylamine, and the like are included.
[0020]
Suitable cationic surfactants include tetra-lower alkyl ammonium halides, alkyl trimethyl ammonium halides, hydroxyethyl alkyl imidazolines, polyoxyethylene alkyl methyl ammonium halides, alkyl benzalkonium halides, dialkyl dimethyl ammonium halides, alkyl dimethyl benzyls. Ammonium halides, alkylamine hydrochlorides, alkylamine acetates, alkylamine oleates, alkylaminoethylglycines, alkylpyridinium halides and the like are included.
[0021]
Suitable anionic surfactants include alkyl (or formalin condensate) -β-naphthalene sulfonic acid (salt), fatty acid soap surfactant, alkyl sulfonate, α-olefin sulfonate, alkyl benzene sulfone. Acid salt, alkyl (or alkoxy) naphthalene sulfonate, alkyl diphenyl ether disulfonate, alkyl ether sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenol ether sulfate, higher Alcohol phosphate monoester salt, polyoxyalkylene alkyl ether phosphate (salt), polyoxyalkylene alkyl phenyl ether phosphate, polyoxyalkylene phenyl ether phosphate, polyoxy Siethylene alkyl ether acetate, alkanoyl sarcosine, alkanoyl sarcosinate, alkanoyl methyl alanine salt, N-acyl sulfocarboxylate, alkyl sulfoacetate, acyl methyl taurate, alkyl fatty acid glycerine sulfate, hydrogenated coconut oil Examples include fatty acid glyceryl sulfate, alkyl sulfocarboxylic acid ester salt, alkyl sulfosuccinate, dialkyl sulfosuccinate, alkyl polyoxyethylene sulfosuccinate, amide polyoxyethylene sulfosuccinate, and sulfosuccinic monooleylamide. The above salts include alkali metal salts, triethanolamine salts, ammonium salts and the like.
[0022]
Amphoteric surfactants preferably used include 2-alkyl-N-carboxymethyl (or ethyl) -N-hydroxyethyl (or methyl) imidazolinium betaine, 2-alkyl-N-carboxymethyl (or ethyl)- N-carboxymethyloxyethyl imidazolinium betaine, 2-alkyl-N-carboxymethyl (or ethyl) -N-hydroxyethyl (or methyl) imidazoline, dimethylalkyl betaine, N-alkyl-β-aminopropionic acid (or its) Salt), alkyl (poly) aminoethylglycine, N-alkyl-N-methyl-β-alanine (or a salt thereof), fatty acid amidopropyldimethylaminoacetic acid betaine, and the like. The above salts include alkali metal salts, triethanolamine salts, ammonium salts and the like.
[0023]
The amount of these surfactants to be used may be determined according to the normal formulation of the surfactant and is appropriately selected depending on the type, but is generally used in a range of approximately 0.001 g / l to 50 g / l, and more preferably. Is used in the range of 0.01 g / l to 50 g / l.
[0024]
In the tin or tin alloy plating bath of the present invention, C is further added as an essential component. ₁ ~ C ₆ 1 type or 2 or more types of lower aliphatic saturated water-soluble alcohols, ketones or ethers are added. Suitable lower aliphatic saturated alcohols, ketones or ethers include methyl alcohol, ethyl alcohol, and n-propyl. Alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, t-butyl alcohol, amyl alcohol, hexyl alcohol, cyclohexyl alcohol, methyl diglycol, ethylene glycol, propylene glycol trimethylene glycol, glycerol, acetone, methyl ethyl ketone, Tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoether Ether or the like is used. More preferably, methyl alcohol, ethyl alcohol, i-propyl alcohol or acetone is used, and most preferably i-propyl alcohol is used.
[0025]
The amount used can be appropriately changed depending on the conditions of the plating bath, but is generally within the range of 0.1 to 300 g / l, and more preferably 1 to 100 g / l. Although there are no clear upper and lower limits, when the amount used is less than about 0.1 g / l, the smoothing action, which is the purpose of addition, is not sufficiently exerted, and the amount of volatilization increases as the alcohol concentration increases, causing odor Alternatively, since the flammability increases, the upper limit is desirably limited to about 300 g / l, more preferably about 100 g / l.
[0026]
The alcohol, ketone or ether may be added independently to the tin or tin alloy plating bath of the present invention, or a surfactant, the hydroxybenzene or hydroxynaphthalene, a smoothing agent, a semi-brightening agent, a brightening agent. Etc. may be added in advance to the plating bath.
[0027]
In the tin or tin alloy plating bath of the present invention, a compound in which hydrogen of a benzene ring or a naphthalene ring is further replaced with a hydroxyl group in the range of 1 to 6 as an essential component, and a monovalent compound further introduced with a carboxyl group or a sulfonic acid group. One or more of (or poly) hydroxybenzene or mono (or) hydroxynaphthalene or their derivatives are added. Among these compounds, catechol, resorcinol, hydroquinone, pyrogallol, oxy Examples include hydroquinone, phloroglucin, 3,4,5-trihydroxybenzoic acid, p-phenolsulfonic acid, cresolsulfonic acid, catecholsulfonic acid, hydroquinonesulfonic acid and the like.
[0028]
Although the usage-amount of these compounds can be suitably changed with the conditions of a plating bath, it is used in 0.01-50 g / l in general, and 0.05-10 g / l is used more suitably. When the amount used is less than about 0.01 g / l, the smoothness or the action that is the purpose of addition is not fully exhibited, and when the amount used exceeds about 50 g / l, the effect becomes excessive and the film is There is a possibility of impairing smoothness.
[0029]
In the tin or tin alloy plating bath of the present invention, one or more of a smoothing agent, a brightening agent, a pH buffering agent and a conductive salt can be further added. These smoothing agents, brightening agents, pH buffering agents and antioxidants can be added with known compounds alone or in combination.
[0030]
These alcohols, ketones or ethers, hydroxybenzenes or hydroxynaphthalenes and surfactants, when combined and added, have shown good smoothing effects over the years It was a surprising result for the inventors of the present application who were involved in alloy plating because it was a combination of compounds that was too simple. The mechanism of its action is not yet clear, but since its effect is manifested only when used in combination with a surfactant, the surfactant micelle state is -OH, C = O or -O- of the compound. I guess that part has some effect.
[0031]
Furthermore, known substances used in tin plating or tin alloy plating can be used as additives such as leveling agents and brighteners that can be used in the tin or tin alloy plating bath of the present invention. As an example, there are the following (1) to (19). These can be used alone or in combination. The amount used is suitably 0.5 to 50 g / l, preferably 1 to 20 g / l when the polymer substance (1) below is used. For additives in the following groups (2) to (19), 0.005 to 30 g / l is appropriate, and 0.02 to 20 g / l is more preferably added.
[0032]
(1) The following polymer compounds
Gelatin, peptone, polyethylene glycol, polyacrylamide, polyethyleneimine, polyvinylpyrrolidone.
[0033]
(2) General formula
[Chemical 1]

[Where Ra is hydrogen or alkyl (C ₁ ~ C _Four Rb represents hydrogen, alkyl (C ₁ ~ C _Four ) Or phenyl, Rc represents hydrogen or a hydroxyl group, and A represents a single bond, alkylene, benzylidene or phenylene. ]
The sulfanilic acid derivative represented by these, and its salt.
[0034]
(3) General formula
[Chemical 2]

[Wherein Ra is hydrogen or alkyl (C ₁ ~ C _Four Rb represents hydrogen or methyl, and n represents an integer of 2 to 15. ]
Quinolines represented by
[0035]
(4) General formula
[Chemical 3]

[Where X is hydrogen, halogen, alkyl (C ₁ ~ C _Four ), Acetyl, an amino group, a hydroxyl group, or a carboxyl group, Y represents hydrogen or a hydroxyl group, and n represents an integer of 0 to 12. ]
And triazoles and derivatives thereof.
[0036]
(5) General formula
[Formula 4]

[Where R ¹ , R ² , R ^Three , R ^Four , R ^Five May be the same or different from each other, and —H, —SH, —OH, —OR (R may optionally be substituted with —COOH; ₁ ~ C ₆ Alkyl group), halogen, -COOH, -COCOOH, aryl, -SR (R is optionally substituted by -COOH) ₁ ~ C ₆ Alkyl),
[Chemical formula 5]

, -NH ₂ , -NRR '(R and R' are C ₁ ~ C ₆ Or may be taken together to form a ring), -NHCOR (R is C ₁ ~ C ₆ Alkyl), -NHCOaryl, -NHNH ₂ , -NO ₂ , -CONHaryl, -CSNHaryl, -CN, -CHO, -SO _Three H, -SO ₂ NH ₂ Or -SO ₂ NRR ′ (R and R ′ are C ₁ ~ C ₆ Or may be taken together to form a ring). ]
And benzothiazole and its derivatives.
[0037]
(6) General formula
[Chemical 6]

[Wherein X and Y each independently represent hydrogen or a hydroxyl group, and Ra and Rb each independently represent alkyl (C ₁ ~ C _Five ). ]
Imines represented by
[0038]
(7) General formula
[Chemical 7]

[Where X is hydrogen, halogen or alkyl (C ₁ ~ C ₁₈ Y represents hydrogen, hydroxyl group or alkyl (C ₁ ~ C ₁₈ ). ]
Triazines represented by
[0039]
(8) General formula
[Chemical 8]

[Wherein, Ra and Rb may be the same or different; hydrogen, alkyl (C ₁ ~ C ₁₈ ), Alkoxy (C ₁ ~ C ₁₈ ) Or cycloalkyl (C _Three ~ C ₇ ) And A represents lower alkylene. ]
Triazines represented by
[0040]
(9) General formula
[Chemical 9]

[Wherein R is alkyl (C ₁ ~ C _Four ) Or phenyl. ]
Aromatic oxycarboxylic acid esters represented by the formula:
[0041]
(10) General formula
Ra-CRb = CH-CO-X-Rc
[Wherein R a and R c are groups selected from phenyl, naphthyl, pyridyl, quinolyl, thienyl, furyl, pyronyl, amino group, hydroxyl group, or hydrogen, which group is alkyl (C ₁ ~ C ₆ ), Alkyloxy (C ₁ ~ C ₆ ), Acyl (C ₁ ~ C ₆ ), Alkylthio (C ₁ ~ C ₆ ), Hydroxyl group, halogen, carboxyl group, nitro group and —NRdRe (Rd and Re may be the same or different and each represents hydrogen or alkyl (C ₁ ~ C _Four May represent 1 to 4 identical or different substituents selected from It may be equal to −. X is a single bond or methylene. Rb is hydrogen or alkyl (C ₁ ~ C _Four ). ]
The compound which has a double bond in the position conjugating with C = O represented by these.
[0042]
(11) General formula
R-CHO
[Wherein R is alkyl (C ₁ ~ C ₆ ), Alkenyl (C ₂ ~ C ₆ ), Alkynyl (C ₂ ~ C ₆ ), Phenyl, naphthyl, acenaphthyl, pyridyl, quinolyl, thienyl, furyl, indole and pyronyl, an aldehyde group or a group selected from the group consisting of alkyl (C ₁ ~ C ₆ ), Phenyl, alkyloxy (C ₁ ~ C ₆ ), Acyl (C ₁ ~ C ₆ ), Alkylthio (C ₁ ~ C ₆ ), Hydroxyl group, halogen, nitro group and —NR a R b (R a and R b may be the same or different and each represents hydrogen or alkyl (C ₁ ~ C _Four 1 to 4) may be the same or different substituents selected from. ]
Aldehydes represented by
[0043]
(12) General formula
Ra-CO- (CH ₂ ) N-CO-Rb
[Wherein Ra and Rb may be the same or different, and may be hydrogen, alkyl (C ₁ ~ C ₆ ) Or -C ₂ H _Four -CO-CO-C ₂ H _Five Where n is an integer from 0 to 2]
Diketones represented by
[0044]
(13) General formula
Ra-NH-Rb
[Wherein Ra represents phenyl and the group is alkyl (C ₁ ~ C _Three ), May be substituted with a halogen or amino group. Rb is hydrogen, alkyl (C ₁ ~ C _Three ), -NH-CS-N = N-φ, -CH ₂ Or -φ-NH ₂ Represents. ]
An aniline derivative represented by:
[0045]
(14) General formula
[Chemical Formula 10]

[Wherein Ra and Rb each independently represent hydrogen, lower alkyl, hydroxyl group, nitro group, carboxyl group or sulfonic acid group. ]
Or a sodium, potassium or ammonium salt thereof.
[0046]
(15) General formula
HOOC-CHR-SH
[Wherein R is hydrogen or alkyl (C ₁ ~ C ₂ And the hydrogen of the alkyl may be substituted with a carboxyl group. ]
Mercaptocarboxylic acids represented by
[0047]
(16) Heterocyclic compounds selected from the following:
1,10-phenanthroline, 2-vinylpyridine, quinoline, indole, imidazole, 2-mercaptobenzimidazole, 1,2,3- (or 1,2,4- or 1,3,5-) triazine, 1,2 , 3-benzotriazine, 2-mercaptobenzoxazole, 2-cinnamylthiophene,
[0048]
(17) Acetophenone and halogenated acetophenone.
[0049]
(18) General formula
Embedded image

[Wherein Ra, Rb and Rc are each independently hydrogen, methyl, ethyl or (CH ₂ ) N-CH (R _Four ) (OH), and at least one of Ra, Rb and Rc is-(CH ₂ ) N-CH (Rd) (OH). Rd represents hydrogen or methyl, and n represents an integer of 1 or 2. ]
An amine alcohol represented by
[0050]
(19) A reaction product of an aldehyde selected from the above (11) and an amine selected from the above (13) or the following general formula (a).
(A) General formula
Ra-NH-Rb
[Where Ra and Rb are hydrogen, alkyl (C ₁ ~ C ₆ ) Or cycloalkyl (C _Three ~ C ₈ ). The hydrogen of Ra and Rb may be substituted with a hydroxyl group or an amino group, and may be bonded or bonded via —NH— or —O— to form a ring. However, Ra and Rb are not simultaneously hydrogen. ]
An aliphatic primary or secondary amine represented by:
[0051]
Among these, a particularly preferable example is as follows:
As represented by the formula (2),
N-butylidenesulfanilic acid, N- (3-hydroxybutylidene) -p-sulfanilic acid, aldol,
[0052]
As represented by the formula (3),
The product of addition of 5 moles of propylene oxide to 8-hydroxyquinoline;
[0053]
As represented by the formula (4),
Benzotriazole, 4-methylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole,
[0054]
As represented by the formula (5),
Benzothiazole, 2-methylbenzothiazole, 2-mercaptobenzothiazole, 2-amino-4-chlorobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-hydroxybenzothiazole, 2-chlorobenzothiazole, 2-methyl -5-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 5-hydroxy-2-methylbenzothiazole, 6-chloro-2-methyl-4-methoxybenzothiazole, 2- (n-butyl) mercapto-6 Aminobenzothiazole, 2-benzothiazolethioacetic acid, 2-benzothiazoleoxyacetic acid, 6-ethoxy-2-mercaptobenzothiazole,
[0055]
As represented by the formula (6),
N, N′diiso-butylidene-o-phenylenediamine,
[0056]
As represented by the formula (7),
2,4-diamino-6- [2'-methylimidazolyl (1 ') ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-ethylimidazolyl (1') ethyl-1, 3,5-triazine, 2,4-diamino-6- [2′-undecylimidazolyl (1 ′) ethyl-1,3,5-triazine,
[0057]
As represented by the formula (8),
β-N-dodecylaminopropioguanamine, β-N-hexylaminopropioguanamine, piperidinepropioguanamine, cyclohexylaminopropioguanamine, morpholinepropioguanamine, β-N- (2-ethylhexyloxypropylamino) pro Pioguanamine, β-N- (lauryloxypropylamino) propioguanamine,
[0058]
As represented by the formula (9),
o- (or m- or p-) methyl benzoate, phenyl salicylate,
[0059]
As represented by the formula (10),
Itaconic acid, propylene-1,3-dicarboxylic acid, acrylic acid, crotonic acid, cinnamic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, ethacrylic acid, acrylamide, diacetone acrylamide, t -Butylacrylamide, N-methoxydimethylacrylamide, curcumin (1,7-bis (4-hydroxy-3-methoxyferral) -1,6-heptadiene-3,5-dione), isophorone (3,5,5-trimethyl) -2-cyclohexenone), mesityl oxide, vinyl phenyl ketone, phenyl propenyl ketone, phenyl isobutenyl ketone, phenyl-1-methylpropenyl ketone, benzylideneacetophenone (chalcone), 2- (ω-benzoyl) vinyl furan p-fluorophenyl propenyl ketone, p-chlorophenyl propenyl ketone, p-hydroxyphenyl propenyl ketone, m-nitrophenyl propenyl ketone, p-methylphenyl propenyl ketone, 2,4,6-trimethylphenyl propenyl ketone, p-methoxyphenyl propenyl Ketone, p-methoxyphenylbutenyl ketone, p-methylthiophenylpropenyl ketone, p-isobutylphenylpropenylketone, α-naphthyl-1-methylpropenylketone, 4-methoxynaphthylpropenylketone, 2-thienylpropenylketone, 2-furyl Propenyl ketone, 1-methylpyrrole propenyl ketone, benzylidene methyl ethyl ketone, benzylidene acetone alcohol, p-toluidene acetone, anisalacetone ( Nisideneacetone), p-hydroxybenzylideneacetone, benzylidenemethylisobutylketone, 3-chlorobenzylideneacetone, benzalacetone (benzylideneacetone), benzylideneacetylacetone, 4- (1-naphthyl) -3-buten-2-one, pyri Dideneacetone, furfuridineacetone, 4- (2-thiophenyl) -3-buten-2-one, 4- (2-furyl) -3-buten-2-one, acrolein (acrylaldehyde, propenal), allylaldehyde , Crotonaldehyde, cinnamaldehyde, benzylcrotonaldehyde, tenylideneacetone,
[0060]
As represented by the formula (11),
Formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde (valeral, pentanal), isovaleraldehyde, n-capronaldehyde (hexanal, hexylaldehyde), succinaldehyde (succindialdehyde), glutar Aldehyde (1,5-pentane dial, glutardialdehyde), aldol (3-hydroxybutyraldehyde, acetoaldol), crotonaldehyde, cinnamic aldehyde, propargyl aldehyde, benzaldehyde, o-phthalaldehyde, salicylaldehyde (O-hydroxy aldehyde) Benzaldehyde), p-hydroxybenzaldehyde, p-nitrobenzaldehyde, o- (or p-) methoxybenzaldehyde ( Varnish), 3-methoxybenzaldehyde, vanillin, o-vanillin, verataldehyde (3,4-dimethoxybenzaldehyde), 2,5-dimethoxybenzaldehyde, (2,4-, 2,6-) dichlorobenzaldehyde, 1- (Or 2-) naphthaldehyde, 2- (or 4-) chloro-1-naphthaldehyde, 2- (or 4-) hydroxy-1-naphthaldehyde, 5 (or 2) -methoxynaphthaldehyde, 2-furaldehyde (2-furaldehyde = furfural), 3-furaldehyde, 2 (3) -thiophenecarboxaldehyde, picolinaldehyde, 3-acenaphthaldehyde, 3-indolecarboxaldehyde,
[0061]
As represented by the formula (12),
Glyoxal (ethanediar, oxalaldehyde, diformyl, biformyl), diacetyl (biacetyl, dimethylglyoxal, butanedione), hexanedione-3,4, acetylacetone (2,4-pentanedione), hexanedione-3,4-acetylacetone,
[0062]
As represented by the formula (13), aniline, o- (or m- or p-) toluidine, o- (or p-) aminoaniline, o- (or p-) chloroaniline, 2,5- (Or 3,4-) chloromethylaniline, N-monomethylaniline, 4,4′diaminodiphenylmethane, N-phenyl- (α- or β-) naphthylamine, dithizone,
[0063]
As represented by the formula (14), p-nitrophenol, nitrobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, m-nitrobenzoic acid,
[0064]
As represented by the formula (15), mercaptoacetic acid (thioglycolic acid), mercaptosuccinic acid,
[0065]
As represented by the formula (18), triethanolamine, diethanolamine, monoethanolamine, N-methylethanolamine,
[0066]
As represented by the formula (19), amine-aldehyde condensates such as piperazine, biperidine, morpholine, cyclopropylamine, cyclohexylamine, cyclooctylamine, ethylenediamine, monoethanolamine, diethanolamine and the like (a A condensate of an aliphatic primary or secondary amine represented by) or an aromatic amine represented by the formula (13) and an aldehyde represented by the formula (11),
And so on.
[0067]
The tin or tin alloy plating bath of the present invention can be used with a pH buffer added thereto, and any known compound can be used for the pH buffer, such as phosphoric acid, acetic acid, boric acid, citric acid. In the case of acid, tartaric acid, and other sodium, potassium, and ammonium salts, and polybasic acids, acidic salts containing hydrogen ions can be used alone or in appropriate combination. The amount of the pH buffer used may be in accordance with known examples, but generally about 5 to 50 g / l is used, more preferably about 10 to 20 g / l.
[0068]
【Example】
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples, and the plating bath is within the scope described in the claims claimed in accordance with the above-mentioned purpose. The configuration or the plating treatment conditions can be arbitrarily changed as appropriate.
[0069]
Example 1
A tin-silver alloy plating bath of the following (A-1) is prepared, and 3 A / dm on a copper plate at a bath temperature of 25 ° C. ² Was plated. A bath obtained by removing i-propyl alcohol from the bath of (A-1) [referred to as (A-2)], a bath obtained by removing catechol from the bath of (A-1) [referred to as (A-3)] and ( Plating was performed under the same conditions from a bath obtained by removing i-propyl alcohol and catechol from the bath A-1) [referred to as (A-4)], and the plating films from the respective baths were compared.

The plating film obtained from the bath (A-1) was smooth and uniform, whereas the plating film obtained from the baths (A-2), (A-3) and (A-4) was (A-1) In addition to being inferior in smoothness as compared with the film from the bath, it was uneven and lacked uniformity.
[0070]
Example 2
The following (B-1) tin-bismuth alloy plating bath was prepared, and the bath temperature was 25 ° C. and 3 A / dm on the copper plate. ² Was plated. A bath obtained by removing i-propyl alcohol from the bath (B-1) [referred to as (B-2)], a bath obtained by removing 3,4,5-trihydroxybenzoic acid from the bath (B-1) [( B-3)] and a bath obtained by removing i-propyl alcohol and 3,4,5-trihydroxybenzoic acid from the bath (B-1) [referred to as (B-4)] and plating under the same conditions. And the plating films from each bath were compared.

The plating film obtained from the bath (B-1) was smooth and uniform, whereas the plating film obtained from the baths (B-2), (B-3) and (B-4) was (B-1) In addition to being inferior in smoothness as compared with the film from the bath, it was uneven and lacked uniformity.
[0071]
Example 3
The following (C-1) tin-copper alloy plating bath was prepared, and the bath temperature was 25 ° C. and 3 A / dm on the copper plate. ² Was plated. A bath obtained by removing acetone from the bath of (C-1) [referred to as (C-2)], a bath obtained by removing resorcinol from the bath of (C-1) [referred to as (C-3)], and (C-1 ) Was removed from the bath obtained by removing acetone and resorcinol from the bath [referred to as (C-4)], and the plating films from the respective baths were compared.
Bath (C-1) Tin-copper alloy plating bath
Tin sulfate (as tin) 30 g / l
Copper sulfate (pentahydrate) (as copper) 15 g / l
Cresol sulfonic acid 10 g / l
Sulfuric acid 98 g / l
Emulgen 409p 2 g / l
Benzalacetone 0.3 g / l
Acetone 20 g / l
Resorcinol 3 g / l
The plating film obtained from the bath (C-1) was smooth and uniform and had a good gloss, whereas it was obtained from the baths (C-2), (C-3) and (C-4). The plated film was not only inferior in gloss as compared with the film from the (C-1) bath, but also had unevenness and lacked uniformity.
[0072]
Example 4
The following (D-1) tin-indium alloy plating bath was prepared, and the temperature was 7.5 A / dm on a copper plate at a bath temperature of 25 ° C. ² Was plated. A bath obtained by removing i-propyl alcohol from the bath of (D-1) [referred to as (D-2)], a bath obtained by removing hydroquinone from the bath of (D-1) [referred to as (D-3)] and ( Plating was performed under the same conditions from a bath [(D-4)] obtained by removing i-propyl alcohol and hydroquinone from the bath of D-1), and the plating films from the respective baths were compared.

The plating film obtained from the bath (D-1) was smooth and uniform, whereas the plating film obtained from the baths (D-2), (D-3) and (D-4) was (D-1) Compared with the film from the bath, the film was not only inferior in smoothness, but also had unevenness and lacked uniformity.
[0073]
Example 5
A tin-zinc alloy plating bath of the following (E-1) is prepared, and 5 A / dm on a copper plate at a bath temperature of 25 ° C. ² Was plated. (E-1) bath obtained by removing i-propyl alcohol [referred to as (E-2)], (E-1) bath obtained by removing phloroglucin [referred to as (E-3)] and ( Plating was performed under the same conditions from a bath obtained by removing i-propyl alcohol and phloroglucin from the bath of E-1) [referred to as (E-4)], and the plating films from the respective baths were compared.
Bath (E-1) Tin-zinc alloy plating bath
Tin sulfosuccinate (as tin) 56.4 g / l
Zinc sulfosuccinate (as zinc) 3.6 g / l
Sulfosuccinic acid 100 g / l
L-ascorbic acid 2.0 g / l
Neugen EN10 0.3 g / l
Benzaldehyde 0.1 g / l
i-propyl alcohol 10 g / l
Phloroglucin 5 g / l
pH (adjusted with NaOH) 4.0
The plating film obtained from the bath (E-1) was smooth and uniform, whereas the plating film obtained from the baths (E-2), (E-3) and (E-4) was (E-1) The film was not only inferior in smoothness but also non-uniformity and lacked uniformity compared to the film from the bath.
[0074]
Example 6
The following (F-1) tin-antimony alloy plating bath was prepared, and the bath temperature was 25 ° C. and 2 A / dm on the copper plate. ² Was plated. A bath obtained by removing ethyl alcohol from the bath (F-1) [referred to as (F-2)], a bath obtained by removing catecholsulfonic acid from the bath (F-1) [referred to as (F-3)] and ( Plating was performed under the same conditions from a bath [(F-4)] obtained by removing ethyl alcohol and catecholsulfonic acid from the bath F-1), and the plating films from the respective baths were compared.

The plating film obtained from the bath (F-1) was smooth and uniform, whereas the plating film obtained from the baths (F-2), (F-3) and (F-4) was , (F-1) was not only inferior in smoothness but also had unevenness and lack of uniformity.
[0075]
Example 7
The following (G-1) tin-gold alloy plating bath was prepared, and the temperature was 1 A / dm on the copper plate at a bath temperature of 25 ° C. ² Was plated. A bath obtained by removing ethylene glycol from the bath (G-1) [referred to as (G-2)], a bath obtained by removing catecholsulfonic acid from the bath (G-1) [referred to as (G-3)] and ( Plating was carried out under the same conditions from a bath [(G-4)] obtained by removing ethylene glycol and catecholsulfonic acid from the bath G-1), and the plating films from the respective baths were compared.

The plating film obtained from the bath (G-1) was smooth and uniform, whereas the plating film obtained from the baths (G-2), (G-3) and (G-4) was , (G-1) was not only inferior in smoothness but also had unevenness and lack of uniformity.
[0076]
Example 8
The following (H-1) tin-silver alloy plating bath was prepared, and 2 A / dm on a copper plate at a bath temperature of 25 ° C. ² Was plated. A bath obtained by removing i-propyl alcohol from the bath of (H-1) [referred to as (H-2)], a bath obtained by removing hydroquinone from the bath of (H-1) [referred to as (H-3)] and ( Plating was performed under the same conditions from a bath obtained by removing i-propyl alcohol and hydroquinone from the bath H-1) [referred to as (H-4)], and the plating films from the respective baths were compared.

While the plating film obtained from the bath (H-1) was smooth and uniform, the plating film obtained from the baths (H-2), (H-3) and (H-4) was (H-1) Compared with the film from the bath, the film was not only inferior in smoothness but also uneven and lacked uniformity.
[0077]
Example 9
The following (I-1) tin-silver alloy plating bath was prepared, and the bath temperature was 20 ° C., and 3 A / dm on the copper plate. ² Was plated. A bath obtained by removing ethyl alcohol from the bath (I-1) [referred to as (I-2)], a bath obtained by removing catechol from the bath (I-1) [referred to as (I-3)], and (I- From the bath of 1) Catechol In addition, plating was performed under the same conditions from a bath excluding ethyl alcohol [referred to as (I-4)], and the plating films from the respective baths were compared.
Bath (I-1) Tin-silver alloy plating bath
Tin phenol sulfonate (as tin) 25 g / l
Silver phenol sulfonate (as silver) 0.4 g / l
Phenolsulfonic acid 100 g / l
Tris (3-hydroxypropyl)
Phosphine 20 g / l
2-mercaptobenzothiazole 0.1 g / l
Adecatol PC10 1 g / l
Cation M 1 g / l
Ethyl alcohol 30 ml / l
Catechol 5 g / l
The plating film obtained from the bath (I-1) was smooth and uniform, whereas the plating film obtained from the baths (I-2), (I-3) and (I-4) was (I-1) The film was not only inferior in smoothness but also non-uniformity and lacked uniformity compared to the film from the bath.

Claims (15)

As essential components: (A) one or more of tin salts or tin complexes, or one or more of tin salts or tin complexes and one or more of salts or complexes of metals other than tin As described above, (B) one or more of acid, base and / or complexing agent, (C) one or more of surfactant, (D) methyl alcohol, ethyl alcohol, n-propyl alcohol , I-propyl alcohol, n-butyl alcohol, i-butyl alcohol, t-butyl alcohol, amyl alcohol, hexyl alcohol, cyclohexyl alcohol, methyl diglycol, ethylene glycol, propylene glycol trimethylene glycol, glycerol, acetone, methyl ethyl ketone, tetrahydrofuran , Dioxane, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, diethylene glycol monomethyl ether, one or more compounds selected from the group consisting of diethylene glycol monoethyl ether, and (E) hydrogen of a benzene ring or a naphthalene ring to a hydroxyl group in the 1-6 range One or more selected from the group consisting of a substituted monohydroxybenzene compound, polyhydroxybenzene compound, monohydroxynaphthalene compound, polyhydroxynaphthalene compound, and a compound having a carboxyl group or a sulfonic acid group introduced thereto A tin or tin alloy plating bath characterized by containing. The tin or tin alloy plating bath according to claim 1, wherein the amount of the compound of group (D) is 0.1 to 300 g / l. The tin or tin alloy plating bath according to claim 1 or 2, wherein the compound of group ( D) is ethyl alcohol. The tin or tin alloy plating bath according to claim 3, wherein an amount of the ethyl alcohol used is 0.1 to 300 g / l. The compound of (E) group is from catechol, resorcinol, hydroquinone, pyrogallol, oxyhydroquinone, phloroglucin, 3,4,5-trihydroxybenzoic acid, p-phenolsulfonic acid, cresolsulfonic acid, catecholsulfonic acid, hydroquinonesulfonic acid. The tin or tin alloy plating bath according to claim 1, which is selected. 6. The tin alloy plating bath according to claim 1 , wherein the metal other than tin of group (A) is gold . (A) tin alloy plating bath of claim 1-5 metals other than group of tin is silver. The tin alloy plating bath according to claim 1, wherein the metal other than tin of group (A) is copper. The tin alloy plating bath according to claim 1, wherein the metal other than tin (A) is selected from indium or zinc. The tin alloy plating bath according to claim 1, wherein the metal other than tin in group (A) is bismuth. The tin according to claim 1, wherein the metal other than tin (A) is selected from cadmium, thallium, lead, antimony, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Alloy plating bath. The tin or tin alloy plating according to any one of claims 1 to 11 , wherein the tin salt is tin sulfate, tin chloride, tin alkane sulfonate, tin alkanol sulfonate, tin phenol sulfonate, tin sulfosuccinate or mercapto succinate. bath. Acids, bases and / or complexing agents are sulfuric acid, hydrochloric acid, aliphatic sulfonic acid, aromatic sulfonic acid, thiourea or derivatives thereof, aliphatic carboxylic acid, compounds having a mercapto group, sulfides, disulfides, fats tin or tin alloy plating bath according to any one of claims 1 to 12, which is a group or an aromatic phosphine or a derivative thereof. The tin or tin alloy plating bath according to any one of claims 1 to 13 , further comprising one or more of a smoothing agent, a semi-brightening agent, a brightening agent, a pH buffering agent, and a conductive salt. Plated subjected to tin or tin alloy plating film using the plating bath of any of claims 1-14.