TW200936806A - Method of avoiding tin whisker due to electroless plating - Google Patents

Method of avoiding tin whisker due to electroless plating Download PDF

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Publication number
TW200936806A
TW200936806A TW097143674A TW97143674A TW200936806A TW 200936806 A TW200936806 A TW 200936806A TW 097143674 A TW097143674 A TW 097143674A TW 97143674 A TW97143674 A TW 97143674A TW 200936806 A TW200936806 A TW 200936806A
Authority
TW
Taiwan
Prior art keywords
tin
film
coating film
silver
plating
Prior art date
Application number
TW097143674A
Other languages
Chinese (zh)
Other versions
TWI470116B (en
Inventor
Kaoru Tanaka
Takuro Fukami
Hiroshi Asahi
Original Assignee
Ishihara Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ishihara Chemical Co Ltd filed Critical Ishihara Chemical Co Ltd
Publication of TW200936806A publication Critical patent/TW200936806A/en
Application granted granted Critical
Publication of TWI470116B publication Critical patent/TWI470116B/en

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Classifications

    • 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
    • C23C18/48—Coating with alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer

Abstract

The object of the invention is to avoid occurrence of pin holes or tin whiskers on an upper layered tin coating film while in a two-layered electroplating that forms the tin coating film on a base layer. The solution is a method of avoiding tin whiskers due to electroless plating. The method is to form a base coating film consisting of an electroless tin-silver alloy electroplating film on an object to be plated, and then form an electroless tin plating coating film on the base coating film (upper layer coating film). The thickness of the base coating film is 0.025-0.5 μm, and the total film thickness of the base and the upper coating film is 0.1-6 μm. The composition ratio of silver in the base coating film is 5-90 percent by weight, and a copper clad laminated plate is taken as the object to be plated. By forming the extremely thin base coating film, specifying the total thickness of the base and the upper coating film and the ratio of silver in the base coating film, occurence of tin whiskers and pin holes in the tin coating film of the upper layer may be avoided.

Description

200936806 六、發明說明： C發日月所屬之技術_ 3^1 發明領域 本發明係有關於一種防止無電解電鍍造成之錫鬚晶之 5 e 10 15 方法，即提供可簡易防止錫鬚晶又不使鍍錫面產生針孔之 方法。 發明背景 鍛錫塗膜因可焊性高或作為抗蝕阻劑等用途而於弱 電工業及電子工業之零件等中廣泛使用，但眾所皆知其有 容易產生錫鬚晶之缺點。錫鬚晶係造成短路之原因，並使 印刷電路板或薄膜栽體等各種電子零件之可靠性降低，因 此最近配線圖形之高密度化、微細化之發展上，特別加強 對該锡鬚晶之防止之要求。 防止錫鬚晶之方法有：於電锻後進行退火處理或迴焊 處理、使錫系層含有少量鉛或鉍等異極金屬、或形成特定 異極金屬之底層後塗覆錫塗膜…等。 有關防止錫鬚晶之習知技術，可舉例如下。 本申請人首先於專利文獻i中揭示’為以簡便 止錫鬚晶’乃藉由浸潰處理形成由銀、料選出之軍作防 屬之底層薄膜，並於該底層薄膜上形成锡或锡合金金 膜(上層）從而防止鬚晶（申請專利範圍第1項卜 錢塗 又，同樣於專利文獻2中揭示，於薄膜載體等 形上藉由置換鍍形成由銀、Μ等選出之單-金屬之底細阐 20 200936806 膜’並將底層塗膜加熱後’藉由置換鍍形成錫塗膜（上層）， 以防止鬚晶（申請專利範圍第1項）。 專利文獻3中揭示一種為確保焊料潤濕性、同時防止鬚 晶（段落12、84)，乃於基材上形成有摻雜金屬X與金屬γ之 5 電鍍A層（底層V金屬X之塗佈B層（上層）之電子零件材料(金 屬X為錫’金屬γ為銀、鉍、銅等)(申請專利範圍第丨項）。 文中記載，前述塗佈B層（上層）之膜厚為0 〇5〜 1·0μηι(申請專利範圍第4項，段落38)，若為Ι.Ομιη以上將有 產生鬚晶之虞(段落38)，又，前述電鍍Α層（底層）之厚度可 10 為1〜5〇μιη(段落39)。其中並說明電鍍a層（底層）之厚度與 塗佈B層（上層）之厚度之關係，係使電鍍a層（底層）之厚度遠 大於塗佈B層（上層）(段落4〇)。 專利文獻4中揭示一種為於不經過熔融處理等繁複程 序之情形下防止鬚晶（段落1、6、8)，乃於銀、祕等金屬佔5 15 重量％以下且錫佔95重量％以上之錫合金底層塗膜上，形成 錫或錫合金之上層塗膜之方法（申請專利範圍第1項）。 文中記載’前述底層塗膜之膜厚為〇 1〜2〇μιη，上層塗 膜之膜厚為0.025〜5μιη(申請專利範圍第2項），該2層構造 之錫系塗膜’上層宜非常薄(段落12)，上層厚度應為底層之 20 50%以下，若為25%以下更佳（段落2〇)。 專利文獻5中揭示一種由銀或銀合金（中間層）/錫或錫 合金(表面層）/鉍或含銦之錫合金(最表層部）組成、以提升可 焊性(段落卜7、41)之金屬塗層材料（申請專利範圍第1項）。 文中記載，前述銀合金（中間層）係含有錫-銀合金(段落 200936806 14)’中間層之厚度為0·05〜ΙΟμηχ，表層層之厚度因迴焊處 理之關係故為0.05〜20μιη(段落13、is)。 5 ❹ 10 15 e 【專利文獻1】日本專利公開公极特開第2003_129278號 【專利文獻2】日本專利公開公報特開第2〇〇3_332391號 【專利文獻3】日本專利公開公報特許第335〇〇26號 【專利文獻4】日本專利公開公報特開第2〇〇6 9〇3 9號 【專利文獻5】日本專利公開公報特開平第號 【發明内容;J 發明揭示 發明欲解決之課題 上述專利文獻1〜2係形成銀、鉍等單一金屬之底層塗 膜，並於該底層塗媒上形成錫塗膜者，然而若藉由無電解 電鍍於銀之底層上形成錫塗膜，將有該上層之錫塗膜產生 鬚晶，且焊料潤濕性或接合強度降低等择病。 又，專利文獻4之實施例1〜2，係於純錫塗膜(3μιη)之 底層上形成有極薄之錫_銘合金塗膜(上層；1 25μιη)者，由 於該上層並非純錫塗膜，因此在防止鬚晶上固然有效，卻 仍有焊料潤濕性等遜於純錫層之問題。 進而，專利文獻3之實施例1〜2係以錫_銅合金之電鍍Α 層（3·21μηι)為底層’並形成有鍍錫b層（上層；〇 5μιη)者(段 落58)，基本上係將底層及錫塗膜(上層）形成前者較厚、後 者較薄之狀態，因此藉由無電解電鍍形成底層與上層時， 需耗費成本與時間。 本發明係一種於底層上形成錫塗膜之2層電鍵方式，並 20 200936806 以簡易防止錫鬚晶又不使該錫塗膜產生針孔為技術性課 題。 用以欲解決課題之手段 本發明人等發現’若形成一薄的錫-銀合金塗膜作為底 5 層’而非上述習知技術所用之銀塗膜’繼之形成一比底層 厚之純錫塗膜作為底層之上層，並規定底層塗膜之銀含量 在量稍多之適切範圍内，則可確保焊料潤濕性或接合強度 良好而不使上層之錫塗膜產生針孔，並可簡易防止錫鬚晶 之產生’特別是底層塗膜即使做成〇·5μπι以下之極薄狀態， 10 或’即使底層中銀所佔比率極少，仍可充分防止鬚晶產生。 由該發現可知，若限定底層塗膜之膜厚、與底層及上 層之合計塗膜膜厚，且限定底層之錫-銀合金塗膜中之銀成 分，可有效防止上層之錫塗膜產生錫鬚晶與針孔，此外， 若設定適當之底層及上層之塗膜全體中之銀成組分，或， 15 設定特定之底層/上層之膜厚比率，則可使防止錫鬚晶之效 果再提升，從而完成本發明。 即，本發明1係一種防止無電解電鍍造成之錫鬚晶之方 法， 該方法係於被鍍物上形成由無電解錫-銀合金電鍵塗 20 膜組成之底層塗膜後’於該底層塗膜上形成無電解鍍錫塗 膜（上層塗膜）； 該底層塗膜之膜厚係0·025〜’且’底層與上層 塗膜之合計膜厚係0.1〜; 底層之合金塗膜中銀之成分比係5〜90重量％ ; 200936806 • 前述被鍍物係包銅層板、覆晶薄膜(COF)或TAB之薄膜 載體。 本發明2係一種防止無電解電鍍造成之錫鬚晶之方法， 該方法係於被鍍物上形成由無電解錫-鉍合金電鍍塗 5 膜組成之底層塗膜後’於該底層塗膜上形成無電解鍍錫塗 膜(上層塗膜）； 該底層塗膜之膜厚係0.025〜0·5μιη，且，底層與上層 塗膜之合計膜厚係0.1〜6μιη ; 〇 底層之合金塗膜中银之成分比係5〜90重量％ ; 10 前述被鍍物係包銅層板、COF或TAB之薄膜載體。 本發明3係如上述本發明1或2之防止無電解電鍍造成 . 之錫鬚晶之方法，其中底層與上層之塗膜全體中銀之重量 比係0.1〜50重量％ 〇 本發明4係如上述本發明1〜3中任一項之防止無電解 15 電鍍造成之錫鬚晶之方法，其中對於錫-銀合金或錫-鉍合金 所組成之底層塗膜之膜厚A’與錫所組成之上層塗膜之膜厚 ❹ B， 底層塗膜與上層塗膜之膜厚比係B(上層）/A(底層）== 1.2 〜30。 2〇 本發明5係如上述本發明1〜4中任一項之防止無電解 電鍍造成之錫鬚晶之方法’其中形成底層塗膜時無電解電 鍍浴之溫度係5〜60°C。 發明效果 本發明係將底層盡膜之膜厚與底層及上層之合計膜厚 200936806 規定於適當範圍内，且將底層中銀之成分特定於適當範圍 内，因此可妥善確保焊料潤濕性、接合強度及塗膜外觀又 不使上層之錫塗膜產生針孔，並可以簡易方法有效防止錫 鬚晶而不需使用如習知之退火法等繁複之手法。 5 又，將底層及上層之塗膜全體中銀之成分，或底層/上 層之膜厚比規定於適當範圍内，則可使防止鬚晶產生之产 形更加良好。 月 【貧施方式；j 用以實施發明之最佳形態 10 本發明第一項係一種於被鍍物上形成藉由無電解錫 銀合金電鍍做成之底層塗膜，並於該底層塗膜上形成藉由 無電解鍵錫做成之上層塗膜之防止無電解電鍍造成之锡鬚 晶之方法，該方法係以對底層塗膜之膜厚、底層及上層之 合計膜厚、底層之合金塗膜中銀之成分比一一加以規定之 15特定電子零件作為被鑛物(本發明1);第二項係一於相同條 件下’將無電解錫·銀合金電鍍改由無電解錫紐合金電錢形 成底層塗膜，藉以防止錫鬚晶之方法(本發明2)。 ^ 本發明1之底層塗膜係藉由無電解電鍍形成之锡-銀合 金電鑛塗膜’上層塗膜係藉由無電解電鍍形成之錫塗膜。 20 #由無電解電鑛形成底層與上層塗媒之本發日们之第 一特徵，在於將底層與上層之膜厚規定於適當範圍内。 即’底層塗膜之膜厚係0.025〜0 5μιη，理想者為〇 〇3 〜〇.4μιη。底層塗膜之膜厚即使薄至〇 5μιη以下仍可充分 防止鬚晶，另-方面，若薄至低於〇.〇2一則防止鬚晶之效 8 200936806 果降低。 5 ❹ 10 15 ❹ 20 又，底層與上層之合計模厚係0.1〜6μιη ’理想者為0 15 〜4μπι，更理想者為0.2〜3μιη。若較Ο.ίμιη薄，防止鬚晶之 效果降低’即使比6μπι厚’經無電解電鍍後防止錫鬚晶之 效果或焊料潤濕性亦無甚變化，且厚鍍並不適於無電解電 鍍0 進而，如本發明4所示，底層塗膜之膜厚a與上層塗膜 之膜厚B之比率’以B(上層）/A(底層）==1.2〜30為宜，若為2 〜20則更佳。即’本發明係以底層塗膜(錫_銀合金塗膜)極 薄，而上層塗膜(錫塗膜）比底層厚為基本原理，按此點言 之’使底層（電鍍層）之厚度遠大於上層（塗佈8層）之前述專 利文獻3(B/A=0_001〜1)，就與膜厚比率之設計思想相悖。 上述本發明1之第二特徵，在於將錫銀合金所組成之 底層塗膜中銀之成分規定於適當範圍内。 底層塗膜之銀比率係5〜90重量％，又以7〜70重量％為 宜，更理想者為10〜60重量％。 如上所述，因底層塗膜薄，故須增加銀比率以擔保防 止鬚晶之效果，且銀比率在5重量％以下時將使防止鬚晶之 效果降低。再者，若為5重量％以下之比率，則進行無電解 電鍵時’將因電鍍浴之銀濃度過低而必須頻繁補給電鑛 液，故電锻浴管理繁雜之弊病亦須加以考量。另-方面， 銀比率右超過90重量％ ’則恐如前述銀塗膜—般上層之 錫塗膜將有產生針孔之虞。 附帶一提，前述專利文獻4中，底層塗膜之銀、鉍等金 9 200936806 屬成分係設定為5重量％以下。 此外，如本發明3所示，底層與上層之塗膜全體中銀之 重量比宜為0.1〜50重量％，更理想者為0.5〜30重量％。若 超過50重量％，則焊料潤濕性降低，恐有造成接合不良之 5 虞。 本發明1中，形成底層塗膜所用之無電解錫-銀合金電 鍍浴，係以可溶性亞錫鹽與可溶性銀鹽、酸或其鹽、錯合 劑為基本成分。 前述可溶性亞錫鹽及銀鹽並不排除難溶性鹽於外，任 〇 ίο 何鹽類均可使用。 前述可溶性亞錫鹽，以後述有機磺酸之亞錫鹽為首， 可舉氟硼酸亞錫、磺琥珀酸亞錫、氣化亞錫、硫酸亞錫、 _ 氧化亞錫等為例，又以甲磺酸亞錫、乙磺酸亞錫、2-羥乙 烷-1-磺酸亞錫、2-羥丙烷-1-磺酸亞錫、對苯酚磺酸亞錫等 15 有機磺酸之鹽類為宜。 又，前述可溶性銀鹽，可舉硫酸銀、亞硫酸銀、碳酸 銀、磺琥珀酸銀、硝酸銀、有機磺酸銀、氟硼酸銀、擰檬 ® 酸銀、酒石酸銀、葡萄糖酸銀、草酸銀、氧化銀等為例， 難溶性之氣化銀等亦可使用。較宜使用之銀鹽為甲磺酸 20 銀、乙磺酸銀、2-丙醇磺酸銀、酚磺酸銀、氟硼酸銀等。 作為該可溶性亞錫鹽或可溶性銀鹽之金屬鹽者，換算 添加量各為0.0001〜200g/L，理想者為0.1〜80g/L。 構成本發明中無電解錫-銀合金電鍍浴之鹼基之酸，宜 為排水處理較容易之烷磺酸、烷醇磺酸、芳磺酸等有機磺 10 200936806 酸，或，脂族羧酸等有機酸，但即使使用氟硼酸、氟矽酸、 磺胺酸、鹽酸、硫酸、過氣酸等無機酸亦無妨。 前述酸可單獨或合併使用，酸之添加量係0.1〜 300g/L，理想者為20〜120g/L。 5 前述烷磺酸，可使用以化學式CnH2n+1S03H(舉例言之， n=l〜5，理想者為1〜3)表示者，具體言之，除甲磺酸、 乙磺酸、1-丙烷磺酸、2-丙烷磺酸、1-丁烷磺酸、2-丁烷磺 酸、戊烷磺酸等外，尚有己烷磺酸、癸烷磺酸、十二烷磺 Q 酸等。 10 前述烷醇磺酸，可使用以化學式200936806 VI. Description of the invention: Technology of C-issue and sun-moon _ 3^1 FIELD OF THE INVENTION The present invention relates to a method for preventing whisker crystals caused by electroless plating, that is, providing a method for easily preventing tin whisker crystals A method that does not cause pinholes on the tin plated surface. Background of the Invention A wrought tin coating film is widely used in parts of the weak electricity industry and the electronics industry due to high solderability or use as a resist, etc., but it is known that it has a drawback that tin whisker crystals are easily generated. The tin whisker causes a short circuit, and the reliability of various electronic components such as a printed circuit board or a film carrier is lowered. Therefore, in recent developments of high density and miniaturization of the wiring pattern, the tin whisker crystal is particularly strengthened. Prevent the requirements. The method for preventing tin whisker is: annealing or reflowing after electric forging, making the tin layer contain a small amount of a heteropolar metal such as lead or antimony, or forming a bottom layer of a specific heteropolar metal, and then coating a tin coating film, etc. . A conventional technique for preventing tin whisker can be exemplified as follows. The applicant first disclosed in Patent Document i that 'for the convenience of tin whisker' is formed by impregnation to form an underlayer film selected from silver and materials, and tin or tin is formed on the underlying film. Alloy gold film (upper layer) to prevent whiskers (Patent No. 1 of the patent application), also disclosed in Patent Document 2, forming a single selected by silver, ruthenium, etc. by displacement plating on a film carrier or the like - The bottom of the metal is explained 20 200936806 The film 'heats the underlying coating film' to form a tin coating film (upper layer) by displacement plating to prevent whiskers (Patent No. 1). Patent Document 3 discloses a solder for securing Wettability, while preventing whiskers (Sections 12 and 84), is formed on the substrate with a doped metal X and metal γ 5 plating A layer (underlying V metal X coated B layer (upper layer) electronic parts The material (metal X is tin 'metal γ is silver, bismuth, copper, etc.) (the scope of the patent application). The film thickness of the coating layer B (upper layer) is 0 〇5~1·0μηι (application) Patent scope 4, paragraph 38), if Ι.Ομιη above will have The thickness of the electroplated tantalum layer (bottom layer) may be 1 to 5 μm (paragraph 39), and the thickness of the electroplated a layer (bottom layer) and the coating layer B are described. The relationship of the thickness of the (upper layer) is such that the thickness of the electroplated a layer (bottom layer) is much larger than that of the coating layer B (upper layer) (paragraph 4). Patent Document 4 discloses a case where a complicated procedure is not performed by melt processing or the like. The underlying whisker (paragraphs 1, 6, and 8) is formed on a tin alloy or tin alloy overcoat film on a tin alloy undercoat film containing less than 515 wt% of metal such as silver or secret and more than 95 wt% of tin. The method (Patent No. 1 of the patent application). The film thickness of the undercoat film is 〇1 to 2〇μιη, and the film thickness of the upper coating film is 0.025 to 5 μm (the second item of the patent application). The tin-based coating film of the layer structure should be very thin (paragraph 12), and the thickness of the upper layer should be 20% or less of the bottom layer, and more preferably 25% or less (paragraph 2〇). Patent Document 5 discloses a silver or Silver alloy (intermediate layer) / tin or tin alloy (surface layer) / tantalum or tin alloy containing indium (most surface layer a metal coating material which is composed of a metal coating material (paragraph 1 of the patent application). The silver alloy (intermediate layer) contains a tin-silver alloy (paragraph 200936806 14). The thickness of the intermediate layer is from 0.05 to ΙΟμηχ, and the thickness of the surface layer is 0.05 to 20 μm (paragraph 13, is) due to the relationship of the reflow process. 5 ❹ 10 15 e [Patent Document 1] Japanese Patent Publication [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. 335-266 〇〇6 9〇3 9 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. of the Invention. a film, and a tin coating film is formed on the underlying coating medium. However, if a tin coating film is formed on the underlayer of silver by electroless plating, the tin coating film having the upper layer is whiskered, and the solder wettability or Reduced joint strength, etc. Choose a disease. Further, in Examples 1 to 2 of Patent Document 4, a very thin tin-on alloy coating film (upper layer; 1 25 μm) was formed on the underlayer of a pure tin coating film (3 μm) because the upper layer was not pure tin coating. The film is therefore effective in preventing the whisker, but there is still a problem that the solder wettability is inferior to the pure tin layer. Further, in the first to second embodiments of Patent Document 3, the tin-copper alloy plating layer (3·21μηι) is used as the underlayer 'and the tin-plated b layer (upper layer; 〇5μιη) is formed (paragraph 58), basically The bottom layer and the tin coating film (upper layer) are formed in a state where the former is thick and the latter is thin, so that it is costly and time-consuming to form the bottom layer and the upper layer by electroless plating. The present invention is a two-layer electric bond method for forming a tin coating film on a bottom layer, and 20 200936806 is a technical problem for simply preventing tin whisker crystals from causing pinholes in the tin coating film. Means for Solving the Problem The present inventors have found that 'if a thin tin-silver alloy coating film is formed as the bottom 5 layer' instead of the silver coating film used in the above-mentioned prior art', a thicker than the bottom layer is formed. The tin coating film is used as the upper layer of the underlayer, and the silver content of the undercoat film is specified to be within a suitable range of a small amount, thereby ensuring good solder wettability or bonding strength without causing pinholes in the upper tin coating film, and It is easy to prevent the generation of whisker crystals. In particular, even if the undercoat film is made into a very thin state of 〇·5μπι or less, 10 or 'even if the ratio of silver in the underlayer is extremely small, the whisker can be sufficiently prevented. From this finding, it is understood that when the film thickness of the undercoat film is limited, the total coating film thickness of the underlayer and the upper layer is thick, and the silver component in the tin-silver alloy coating film of the underlayer is limited, the tin coating film of the upper layer can be effectively prevented from being tinned. The whisker and the pinhole, in addition, if the silver component in the entire coating film of the bottom layer and the upper layer is set, or 15 is set to a specific film thickness ratio of the bottom layer/upper layer, the effect of the whisker crystal can be prevented. Upgrade to complete the present invention. That is, the present invention 1 is a method for preventing whisker crystals caused by electroless plating, which is formed by forming an undercoat film composed of an electroless tin-silver alloy electroless bond coating film on a substrate to be coated on the primer layer. An electroless tin plating film (upper layer coating film) is formed on the film; the film thickness of the underlying coating film is 0·025~' and the total film thickness of the bottom layer and the upper layer coating film is 0.1~; the alloy film of the bottom layer is silver The composition ratio is 5 to 90% by weight; 200936806 • The above-mentioned object is coated with a copper layer plate, a film on film (COF) or a film carrier of TAB. The present invention is a method for preventing whisker crystals caused by electroless plating, which is formed on an undercoat film composed of an electroless tin-bismuth alloy plating film 5 on a substrate to be coated on the underlying coating film. Forming an electroless tin plating film (upper layer coating film); the film thickness of the underlying coating film is 0.025~0·5μιη, and the total film thickness of the bottom layer and the upper layer coating film is 0.1 to 6 μm; The composition ratio is 5 to 90% by weight; 10 The above-mentioned object to be plated is a copper-clad laminate, a film carrier of COF or TAB. The present invention is directed to the method for preventing tin whisker from electroless plating according to the above invention 1 or 2, wherein the weight ratio of the silver to the entire coating film of the underlayer and the upper layer is 0.1 to 50% by weight. The method for preventing tin whisker caused by electroless plating in any one of the inventions 1 to 3, wherein the film thickness A' and tin of the undercoat film composed of the tin-silver alloy or the tin-bismuth alloy are composed of The film thickness of the upper coating film is ❹ B, and the film thickness ratio of the bottom coating film to the upper coating film is B (upper layer) / A (bottom layer) == 1.2 to 30. 2) The method according to any one of the above Inventions 1 to 4, wherein the electroless plating bath is formed at a temperature of 5 to 60 ° C in the case where the undercoat film is formed. Advantageous Effects of Invention According to the present invention, the film thickness of the underlayer film and the total film thickness of the underlayer and the upper layer 200936806 are set within an appropriate range, and the composition of the silver in the underlayer is specified within an appropriate range, so that solder wettability and bonding strength can be properly ensured. And the appearance of the coating film does not cause pinholes in the upper tin coating film, and the whisker crystal can be effectively prevented by a simple method without using a complicated method such as a conventional annealing method. Further, by setting the composition of the silver in the entire coating film of the bottom layer and the upper layer or the film thickness ratio of the underlayer/upper layer to an appropriate range, it is possible to further improve the production of the whisker. The first method of the present invention is to form an undercoat film formed by electroless tin-silver alloy plating on the object to be plated, and to coat the film on the underlayer. Forming a method for preventing whisker crystals caused by electroless plating by using an electroless bond tin as an overcoat film, which is a film thickness of the undercoat film, a total film thickness of the underlayer and the upper layer, and an alloy of the underlayer The composition of silver in the coating film is specified as the mineral component (the present invention 1); the second item is under the same conditions, and the electroless tin/silver alloy plating is changed from the electroless tin-nickel alloy. The method of forming the undercoat film by money to prevent tin whisker (Invention 2). The undercoat film of the present invention 1 is a tin-silver alloy electric coating film formed by electroless plating. The upper coating film is a tin coating film formed by electroless plating. The first feature of the present invention is that the film thickness of the underlayer and the upper layer is defined within an appropriate range. That is, the film thickness of the undercoat film is 0.025 to 0 5 μmη, and the ideal one is 〇3 to 〇4μιη. The film thickness of the underlying coating film can be sufficiently prevented from being whisker even if it is as thin as 〇 5 μmη, and the other is to prevent the whisker from being thinner than 〇.〇2. 5 ❹ 10 15 ❹ 20 Further, the total thickness of the bottom layer and the upper layer is 0.1 to 6 μm η. The ideal one is 0 15 to 4 μm, and more preferably 0.2 to 3 μm. If it is thinner than Ο.ίμιη, the effect of preventing whisker is reduced 'even if it is thicker than 6μπι', the effect of tin whisker is not changed after electroless plating, and the solder wettability is not changed, and thick plating is not suitable for electroless plating. Further, as shown in the fourth aspect of the invention, the ratio of the film thickness a of the undercoat film to the film thickness B of the upper layer coating film is preferably B (upper layer) / A (bottom layer) == 1.2 to 30, if 2 to 20 It is better. That is, the present invention is based on the fact that the undercoat film (tin-silver alloy coating film) is extremely thin, and the upper coating film (tin coating film) is thicker than the underlying layer, and the thickness of the underlying layer (electroplating layer) is described as follows. The aforementioned Patent Document 3 (B/A = 0_001 to 1) which is much larger than the upper layer (coating 8 layers) is contrary to the design concept of the film thickness ratio. The second feature of the first aspect of the present invention is that the composition of silver in the undercoat film composed of the tin-silver alloy is set within an appropriate range. The silver ratio of the undercoat film is 5 to 90% by weight, preferably 7 to 70% by weight, more preferably 10 to 60% by weight. As described above, since the undercoat film is thin, the silver ratio must be increased to secure the effect of preventing whiskers, and the silver ratio of 5% by weight or less will lower the effect of preventing whiskers. Further, when the ratio is 5% by weight or less, when the electroless electrolysis is performed, the electroless mineral must be frequently replenished because the silver concentration of the electroplating bath is too low, so that the troubles of the electric forging bath management must also be considered. On the other hand, if the silver ratio is more than 90% by weight on the right, it is feared that the tin coating film of the above-mentioned silver coating film will have a pinhole. Incidentally, in the above Patent Document 4, the composition of the gold, ruthenium, and the like 9 200936806 of the undercoat film is set to 5% by weight or less. Further, as shown in the third aspect of the invention, the weight ratio of silver in the entire coating film of the underlayer and the upper layer is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight. If it exceeds 50% by weight, the solder wettability is lowered, which may cause a joint failure. In the first aspect of the invention, the electroless tin-silver alloy electroplating bath for forming the undercoat film is based on a soluble stannous salt, a soluble silver salt, an acid or a salt thereof, and a complexing agent. The above-mentioned soluble stannous salt and silver salt do not exclude the insoluble salts, and any of the salts can be used. The soluble stannous salt is a stannous salt of an organic sulfonic acid described later, and examples thereof include stannous fluoroborate, stannous sulfosuccinate, stannous vapor, stannous sulfate, and stannous oxide. Stannous sulfonate, stannous ethanesulfonate, stannous 2-hydroxyethane-1-sulfonate, stannous 2-hydroxypropane-1-sulfonate, stannous phenolsulfonate, etc. 15 salts of organic sulfonic acid It is appropriate. Further, the soluble silver salt may, for example, be silver sulfate, silver sulfite, silver carbonate, silver sulfosuccinate, silver nitrate, silver silver sulfonate, silver fluoroborate, lemon acid silver, silver tartrate, silver gluconate or silver oxalate. For example, silver oxide, etc., and poorly soluble gasified silver can also be used. The silver salt to be preferably used is methanesulfonic acid 20 silver, silver ethanesulfonate, silver 2-propanolatesulfonate, silver phenolsulfonate, silver fluoroborate or the like. The metal salt of the soluble stannous salt or the soluble silver salt is 0.0001 to 200 g/L, and preferably 0.1 to 80 g/L. The acid constituting the base of the electroless tin-silver alloy plating bath of the present invention is preferably an organic sulfonate such as an alkanesulfonic acid, an alkanolsulfonic acid or an aromatic sulfonic acid which is easily treated by drainage, or an aliphatic carboxylic acid. Organic acids, but even inorganic acids such as fluoroboric acid, fluoroantimonic acid, sulfamic acid, hydrochloric acid, sulfuric acid, and peroxyacid are used. The above acids may be used singly or in combination, and the amount of the acid added is 0.1 to 300 g/L, and preferably 20 to 120 g/L. 5 The aforementioned alkanesulfonic acid can be represented by the chemical formula CnH2n+1S03H (for example, n=l~5, ideally 1~3), specifically, methanesulfonic acid, ethanesulfonic acid, 1-propane Examples of the sulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, and pentanesulfonic acid include hexanesulfonic acid, decanesulfonic acid, and dodecanesulfonic acid. 10 The aforementioned alkanol sulfonic acid can be used in the chemical formula

CmH2m+「CH(0H)-CpH2p-S03H (舉例言之，m=0〜6，p= 1 〜5)表示者，具體言之，除2-羥乙烷-1-磺酸、2-羥丙烷-1-磺酸、2-羥丁烷-1-磺酸、2-羥戊烷-1-磺酸等外，尚有1-羥 丙烷-2-磺酸、3-羥丙烷-1-磺酸、4-羥丁烷-1-磺酸、2-羥己 15 烷-1-磺酸、2-羥癸烷-1-磺酸、2-羥十二烷-1-磺酸等。 前述芳磺酸，基本上為苯磺酸、烷基苯磺酸、萘磺酸、 ® 烷基萘磺酸等，具體言之，可舉1-萘磺酸、2-萘磺酸、甲苯 磺酸、茬磺酸、對酚磺酸、曱苯酚磺酸、磺柳酸、硝基苯 績酸、確苯甲酸、二苯胺-4-續酸等為例。 20 前述脂族羧酸，一般而言可使用碳數1〜6之羧酸。具 體言之，可舉例如：乙酸、丙酸、丁酸、檸檬酸、酒石酸、 葡萄糖酸、磺琥珀酸、三氟乙酸等。 本發明1之無電解錫-銀合金電鍍浴中所含之錯合劑係 用以發揮穩定電鍍浴，並使錫與銀進行共析反應之功能 11 200936806 者，舉例言之有硫脲類、胺類、硫化物類、巯基類等。 _ 前述硫脲類係硫脲與硫脲衍生物。 該硫脲衍生物，可舉例如：1,3-二曱硫脲、三甲硫脲、 二乙硫脲(舉例言之，1，3-二乙基-2-硫脲）、Ν,Ν’-二異丙基 5 硫脲、烯丙硫脲、乙醯硫脲、伸乙硫脲、1，3-二苯硫脲、二 氧化硫脲、硫半卡肼等。 前述胺類，係胺乙酸、胺丙酸、胺戊酸、胺基酸等胺 基羧酸系化合物；伸乙二胺、四亞曱二胺等聚胺系化合物； 單乙醇胺、二乙醇胺等胺醇系化合物等。 © 10 前述胺類中之胺基羧酸系化合物，可舉例如：乙二胺 四乙酸(EDTA)、乙二胺四乙酸二鈉鹽（EDTA · 2Na)、羥乙 基乙二胺三乙酸(HEDTA)、二伸乙三胺五乙酸(DTPA)、三 伸乙四胺六乙酸（TTHA)、乙二胺四丙酸、氮基三乙酸 (NTA)、亞胺二乙酸(IDA)、亞胺二丙酸(IDP)、間苯二胺四 15 乙酸、1,2-二胺基環己烷-Ν,Ν,Ν’,Ν’-四乙酸、二胺丙酸、麩 胺酸、鳥胺酸、半胱胺酸、Ν，Ν-雙(2-羥乙基)甘胺酸等。 又，前述胺類中之聚胺系化合物、胺醇系化合物，可 〇 舉例如：乙二胺四亞甲基磷酸、二伸乙三胺五亞甲基磷酸、 胺基三亞曱基磷酸、胺基三亞甲基磷酸五鈉鹽、單乙醇胺、 20 二乙醇胺、三乙醇胺、單丙醇胺、二丙醇胺、三丙醇胺、 亞曱基二胺、伸乙二胺、四亞曱二胺、戊二胺、己二胺、 二伸乙三胺、四伸乙五胺、五伸乙六胺、六乙烯七胺、桂 皮胺、對曱氧基桂皮胺等。 前述硫化物類、毓基類，可舉例如：2,2’-二硫基二苯 12 200936806 胺、二硫化二吡啶基、硫代二乙酸、β-硫二乙二醇、雙（十 二乙二醇)硫醚、1，2-雙(2-羥乙硫基）乙烷、1，4-雙(2-羥乙硫 基）丁烷、硫甘醇、硫代乙醇酸、巯基琥珀酸等。 本發明1之無電解錫-銀合金電鍍浴中除上述成分外， 5 當可依目的再混合介面活性劑、還原劑、遮蔽錯合劑、pH 值調節劑、緩衝劑、調平劑、應力緩和劑、光澤劑、半光 澤劑、抗氧化劑等一般用於電鐘浴中之添加劑。 前述還原劑係為前述金屬鹽之還原，及其析出速度或 〇 析出合金比率之調整等用途而添加，可將磷酸系化合物、 10 胺硼烷類、硼氫化物、肼衍生物等單獨或合併使用。 前述磷酸系化合物，可舉例如：次磷酸、膦酸、焦磷 .酸、多構酸、或該等之錢、鋰、納、卸、約等鹽。 前述胺硼烷類，可舉二甲胺硼烷、三曱胺硼烷、異丙 胺硼烷、嗎福林硼烷等為例。 15 前述硼氫化物有硼氫化鈉等。前述肼衍生物則可舉水 合肼、甲肼、苯肼等為例。 © 前述還原劑之添加量係0.1〜200g/L，理想者為10〜 150g/L。 前述介面活性劑，有非離子性介面活性劑、兩性介面 20 活性劑.、陽離子性介面活性劑或陰離子性介面活性劑，該 等各種活性劑可單獨或合併使用。 該介面活性劑之添加量係0.01〜100g/L，理想者為0.1 \ 〜50g/L。 前述非離子性介面活性劑，係於烷醇、苯酚、 13 200936806 萘酚、雙酚類、Ci〜(：25烷基酚、芳基烷基酚、Ci〜C25烷基 萘酚、（^〜匸25烷化鱗酸(鹽）、山梨糖醇酯、苯乙缔化酚、 聚烷撐二醇、〇^〜(：22脂族胺、^〜匸]〗脂肪酿胺等中，使環 氧乙烷(EO)及/或環氧丙烷(PO)經2〜3〇〇莫耳加成縮合作用 5 而成者。因此，預定之烷醇、苯酚、萘酚等EO單獨之加成 物、PO單獨之加成物，或EO、P〇共存之加成物中任一皆 可，具體言之，係以α-萘酚或β-萘酚之環氧乙烷加成物（即， α-萘酚聚乙氧基醇等）為宜。 用以使環氧乙烷(ΕΟ)及/或環氧丙烷(ρ〇)產生加成縮合 ◎ 10 作用之Cl〜C2〇烧醇’可舉例如：辛醇、癸醇、月桂醇十 四醇、十六醇、硬脂醇、二十醇、鯨蠟醇、油醇、二十二 醇等。 同樣作用之雙酚類’有雙酚A、雙酚B、雙盼F、雙盼s 等。 - 15 烷基酚，有單、二或三烷基取代酚，可舉例如： 對丁苯酚、對異辛苯酚、對壬苯酚、對己笨酚、2,4二丁苯 酚、2,4,6-三丁苯酚、對十二烷基苯酚、對月桂基笨酚硬 υ 脂醯苯酚等。 芳基烷基酚係可舉2-苯異丙酚等為例。 20 Ci〜Cm烧基萘盼之炫基，有曱基、乙基、丙基、丁基 己基、辛基、癸基、十二基、十八基等，可置於萘核之任 意位置。 烷化磷酸(鹽)係以下列通式(a)表示者。CmH2m+"CH(0H)-CpH2p-S03H (for example, m=0~6, p=1~5), in particular, except 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane 1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentane-1-sulfonic acid, etc., there are still 1-hydroxypropane-2-sulfonic acid, 3-hydroxypropane-1-sulfonate Acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxyhexa-15-sulfonic acid, 2-hydroxydecane-1-sulfonic acid, 2-hydroxydodecan-1-sulfonic acid, etc. The aryl sulfonic acid is basically benzenesulfonic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid, ® alkylnaphthalenesulfonic acid, etc., specifically, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, toluenesulfonic acid For example, hydrazine sulfonic acid, p-phenolsulfonic acid, decyl phenol sulfonic acid, sulfinic acid, nitrobenzene acid, benzoic acid, diphenylamine-4-supply acid, etc. 20 The aforementioned aliphatic carboxylic acid, generally speaking A carboxylic acid having 1 to 6 carbon atoms can be used, and specific examples thereof include acetic acid, propionic acid, butyric acid, citric acid, tartaric acid, gluconic acid, sulfosuccinic acid, trifluoroacetic acid, and the like. The staggering agent contained in the tin-silver alloy plating bath is used to function as a stable electroplating bath and to carry out eutectoid reaction of tin and silver. 11 200936806 There are thioureas, amines, sulfides, sulfhydryls, etc. _ The thiourea type is a thiourea and a thiourea derivative. The thiourea derivative may, for example, be 1,3-dithiourea, Trimethylthiourea, diethylthiourea (for example, 1,3-diethyl-2-thiourea), hydrazine, Ν'-diisopropyl5 thiourea, allylthiourea, acetylthiourea, Ethyl thiourea, 1,3-diphenyl thiourea, thiourea sulphate, sulphide sulphate, etc. The above amines are amine carboxylic acid compounds such as amine acetic acid, acrylic acid, aminovaleric acid, amino acid; A polyamine compound such as ethylenediamine or tetradecanediamine; an amine alcohol compound such as monoethanolamine or diethanolamine, etc. © 10 The aminocarboxylic acid compound in the above amine may, for example, be ethylenediaminetetrazide. Acetic acid (EDTA), ethylenediaminetetraacetic acid disodium salt (EDTA · 2Na), hydroxyethyl ethylenediamine triacetic acid (HEDTA), diethylenetriamine pentaacetic acid (DTPA), triamethylenediamine hexaacetic acid ( TTHA), ethylenediaminetetrapropionic acid, nitrogen triacetic acid (NTA), imine diacetic acid (IDA), imine dipropionic acid (IDP), m-phenylenediamine tetra 15 acetic acid, 1,2-diamine Cyclohexane-Ν,Ν,Ν',Ν'-tetraacetic acid, two Propionic acid, glutamic acid, ornithine, cysteine, hydrazine, hydrazine-bis(2-hydroxyethyl)glycine, etc. Further, the polyamine compound and the amine alcohol compound in the above amines, For example, ethylenediaminetetramethylenephosphoric acid, diethylenetriamine pentamethylphosphoric acid, aminotrimethylenephosphoric acid, aminotrimethylenephosphoric acid pentasodium salt, monoethanolamine, 20 diethanolamine, three Ethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, decylenediamine, ethylenediamine, tetradecanediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, tetrathene Ethyl pentamine, pentaethylene hexamine, hexaethylene heptaamine, cinnamamine, p-methoxy cinnamamine, and the like. Examples of the sulfides and sulfhydryl groups include 2,2'-dithiodiphenyl 12 200936806 amine, dipyridyl disulfide, thiodiacetic acid, β-thiodiethylene glycol, and bis (12 Ethylene glycol) thioether, 1,2-bis(2-hydroxyethylthio)ethane, 1,4-bis(2-hydroxyethylthio)butane, thioglycol, thioglycolic acid, sulfhydryl amber Acid, etc. In addition to the above components, the electroless tin-silver alloy plating bath of the present invention 5 can remix the surfactant, the reducing agent, the masking agent, the pH adjuster, the buffering agent, the leveling agent, and the stress relaxation according to the purpose. Agents, brighteners, semi-gloss agents, antioxidants, etc. are generally used as additives in electric clock baths. The reducing agent is added for the reduction of the metal salt, the precipitation rate thereof, or the adjustment of the ratio of the precipitation of the alloy, and the phosphoric acid compound, the 10 amine borane, the borohydride, the anthracene derivative, or the like may be separately or combined. use. Examples of the phosphoric acid-based compound include hypophosphorous acid, phosphonic acid, pyrophosphoric acid, acid, polymorphic acid, or the like, lithium, sodium, unloading, and the like. Examples of the amine borane include dimethylamine borane, tridecylamine borane, isopropylamine borane, and phofolin borane. 15 The above borohydride has sodium borohydride or the like. The above anthracene derivatives may be exemplified by hydrazine hydrate, formamidine, benzoquinone or the like. © The amount of the reducing agent added is 0.1 to 200 g/L, and preferably 10 to 150 g/L. The aforementioned surfactant may be a nonionic surfactant, an amphoteric interface 20 active agent, a cationic surfactant or an anionic surfactant, and the various active agents may be used singly or in combination. The amount of the surfactant added is 0.01 to 100 g/L, and preferably 0.1 to 50 g/L. The above nonionic surfactant is selected from the group consisting of alkanols, phenols, 13 200936806 naphthols, bisphenols, Ci~(:25 alkylphenols, arylalkylphenols, Ci~C25 alkylnaphthols, (^~)匸25 alkylation of squaric acid (salt), sorbitol ester, phenylethyl phenol, polyalkylene glycol, 〇 ^ ~ (: 22 aliphatic amine, ^ ~ 匸) fat in the amine, etc. Oxygenethane (EO) and/or propylene oxide (PO) are formed by 2 to 3 molar addition condensation. 5 Therefore, predetermined EO separate adducts such as alkanol, phenol, naphthol and the like , PO alone adduct, or any of EO, P〇 coexisting additive, in particular, α-naphthol or β-naphthol ethylene oxide adduct (ie, It is preferred to use α-naphthol polyethoxyl alcohol, etc. to form an addition condensation of ethylene oxide (ΕΟ) and/or propylene oxide (ρ〇). For example: octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, cetyl alcohol, oleyl alcohol, behenyl alcohol, etc. The same effect of bisphenols - bisphenol A, bisphenol B, double hope F, double hope s, etc. - 15 alkyl phenol, there is a single, Or a trialkyl-substituted phenol, for example: p-butyrylphenol, p-isooctylphenol, p-nonylphenol, p-hexylphenol, 2,4 dibutanol, 2,4,6-tributylphenol, p-dodecane Phenolic phenol, p-laury-based phenol, decyl phenol, etc. The arylalkyl phenol is exemplified by 2-propiopropofol, etc. 20 Ci~Cm thiophene, thiol, thiol, B The group, the propyl group, the butyl group, the octyl group, the decyl group, the dodecyl group, the octadecyl group and the like may be placed at any position of the naphthalene nucleus. The alkylated phosphoric acid (salt) is represented by the following formula (a).

Ra · Rb · (MO)P = 〇 14 200936806 (通式(a)中，Ra及Rb係相同或不同之(^〜(：25烷基，惟， 其中之一為Η亦可。Μ係表示Η或鹼金屬。） 山梨糖醇酯，可以單、二或三酯化之1，4-、1，5-或3,6-山梨醇酐為例，舉例言之，如：山梨醇酐單月桂酸酯、山 5 梨醇酐單軟脂酸酯、山梨醇酐二硬脂酸酯、山梨醇酐二油 酸酯、山梨醇酐混合脂肪酸酯等。 脂族胺，有丙胺、丁胺、己胺、辛胺、癸胺、 月桂胺、硬脂醯胺、油胺、乙二胺、丙二胺等飽和及不飽 〇 和脂肪酸胺等。 ίο 脂肪醯胺，有丙酸、丁酸、辛酸、癸酸、月桂 酸、肉豆蔻酸、軟脂酸、硬脂酸、蘿酸等醯胺。 前述陽離子性介面活性劑，舉例言之有下列通式(b)所 表示之四級録鹽， (Rj · R2 · R3 · R4N)+ · X' …(b) 15 (通式(b)中，X係表示鹵素、羥基、烷磺酸或硫 酸，比、R2及R3係表示相同或不同之烷基、R4係表 ® 示烷基或苄基。） 或，下列通式(C)所表示之吡啶鹽等。 R6-(C5H5N-R5)+· X- ...(c) 20 (通式(c)中，C5H5N係表示吡啶環，X係表示鹵素、羥 基、烷磺酸或硫酸，R5係表示烷基，R6係表 示 烷基） 鹽型態之陽離子性介面活性劑，舉例言之有月桂基三 甲基銨鹽、硬脂醯三甲基銨鹽、月桂基二曱基乙基銨鹽、 15 200936806 十八基二甲基乙基銨鹽、二甲节基月桂基銨鹽、鯨蝶基二 曱苄基銨鹽、十八基二甲苄基銨鹽、三甲基苄基銨鹽、三 乙基苄基銨鹽、十六基吡啶鹽、月桂基吡啶鹽、十二基吡 啶鹽、硬脂醯胺乙酸酯、月桂基胺乙酸酯、十八基胺乙酸 5 酯等。 前述陰離子性介面活性劑，有烷硫酸鹽、聚氧乙稀烧 基醚硫酸鹽、聚氧乙烯烷基苯基醚硫酸鹽、烷基苯確酸鹽、 (單、二、三)烷基萘磺酸鹽等。烷基硫酸鹽，可舉月桂硫酸 鈉、油基硫酸鈉等為例。聚氧乙烯烷基醚硫酸鹽，可舉聚 © 10 氧乙烯(E012)壬基醚硫酸鈉、聚氧乙烯(E015)十二基醚硫 酸納等為例。聚氧乙稀烧基笨基醚硫酸鹽，可以聚氧乙婦 (E015)壬基苯基醚硫酸鹽等為例。烷基苯磺酸鹽，可以十 二基苯磺酸鈉等為例。（單、二、三)烷基萘磺酸鹽，可以二 丁基萘磺酸鈉等為例。 15 前述兩性介面活性劑，有羧基甜菜驗、咪嗤淋甜菜驗、 磺酸基甜菜鹼、胺基羧酸等。此外，亦可使用環氧乙烷及/ 或環氧丙烷與烷基胺或二胺之縮合生成物經硫酸化、或磺 © 酸化後之加成物。 具代表性之羧基甜菜鹼或咪唑啉甜菜鹼，有月桂基二 20 曱胺基乙酸甜菜鹼、肉豆蔻基二曱胺基乙酸甜菜鹼、硬脂 醯二甲胺基乙酸甜菜鹼、椰子油脂肪醯胺丙基二甲胺基乙 酸甜菜驗、2-H —基-1-竣甲基-1-經乙基咪0坐(imidazolinium) 甜菜鹼等’硫酸化及磺酸化加成物則有乙氧化烷基胺之硫 酸加成物、績酸化月桂酸衍生物鈉鹽等。 16 200936806 前述磺酸基甜菜鹼，有椰子油脂肪醯胺丙基二曱銨-2-羥丙磺酸、N-椰油醯基(cocoyl)甲基牛磺酸鈉、义軟脂醯基 甲基牛磺酸鈉等。 胺基羧酸則可舉二辛基胺基乙甘胺酸、N-月桂基胺丙 5 酸、辛基二(胺乙基)甘胺酸鈉鹽等為例。 前述遮蔽錯合劑係為提升電鐘浴之穩定性而使用，以 防止從銅等被鍍物之裸金屬溶析出之雜質金屬離子對電鍍 浴造成不良影響者，具體言之，有：EDTA、羥乙基乙二胺 〇 三乙酸(HEDTA)、亞胺二乙酸(IDA)、亞胺二丙酸(IDP)、氮 10 基三乙酸(NTA)、二伸乙三胺五乙酸(DTPA)、三伸乙四胺 六乙酸(TTHA)、乙二胺、六亞曱二胺、二伸乙三胺、檸檬 . 酸、酒石酸、琥珀酸、丙二酸、羥乙酸、葡萄糖甲酸、葡 萄糖酸、焦磷酸、三聚磷酸、1-羥乙烷-1，1-雙膦酸等。 此外，前述本發明1係藉由無電解錫-銀合金電鍍形成 15 底層塗膜，但本發明2係藉由無電解錫-鉍合金電鍍形成底 層塗膜。 ® 本發明2中形成底層塗膜時所用之無電解錫-鉍合金電 鍍浴，係以可溶性亞錫鹽、可溶性鉍鹽、酸或其鹽與錯合 劑為基本成分。 20 前述可溶性鉍鹽係有機磺酸、無機酸之鹽類，具體言 之，有：曱磺酸鉍、乙磺酸鉍、對酚磺酸鉍、硝酸鉍、氯 化叙等。 可溶性鉍鹽之金屬鹽換算含量係0.1〜200g/L，理想者 為 1 〜80g/L。 17 200936806 則述可溶性亞錫鹽、酸或其鹽，係與前述無電解錫·銀 σ金電鍍浴所使用者相同。又無電解錫-叙合金電鑛浴所 使用之錯合射，可使用與前述無電解錫銀合金電鑛相同 之錯合劑’其巾又以硫職或絲紐類尤佳。 5 此外，本發明2之無電解錫-鉍合金電鍍浴中，除上述 基本成分外，更可依目的混合介面活性劑、還原劑、遮蔽 錯合劑、pH值調節劑、緩衝劑、調平劑、應力緩和劑、光 澤劑、半光澤劑、抗氧化劑等各種添加劑，此同於本發明1 之無電解錫·銀合金電鑛浴。 0 10 藉由該無電解錫-鉍合金電鍍形成底層塗膜之本發明2 中，底層塗膜之膜厚、及底層與上層之塗膜全體膜厚之要 件，應符合使用無電解錫_銀合金電鍍之前述本發明丨中第 一特徵之相關要件，底層塗膜中銀比率之要件，應符合同 發明1中第二特徵之相關要件。 15 又，藉由無電解錫·鉍合金電鍍形成底層塗膜時，與進 行無電解錫-銀合金電鑛時相同，基於更妥善防止上層錫塗 膜產生錫鬚晶與針孔之觀點，宜符合底層塗膜之膜厚A與丨 Ο 層塗膜之膜厚B之比率要件(本發明4)，或，底層與上層塗 膜全體中銀之重量比之要件（本發明3)。 2〇 使用本發明1之無電解錫-銀合金電鐘浴、或本發明2之 無電解錫·Μ合金電鐘浴時’浴溫以低於平常之穴〜紙 為宜。 如上所述’本發明中只需將無電解錫·銀合金或無電解 錫姆金之底層塗膜做成厚度僅咖〜〇·_之極薄狀態 18 200936806 5 即足以違到目的，因此無須提高浴溫進行厚鍍。 又，適用本發明之無電解電鍍之被鍍物，係如本發明5 所示’以包銅層板、覆晶薄膜(COF)或TAB之薄膜載體為 宜。前述包銅層板，係指硬式印刷電路板(PCB)、軟式印刷 電路板(FPC)、球柵陣列(BGA)、晶片尺寸封裝(CSP)等。 【實施例】 以下’依序說明本發明之藉由無電解電鍍於被鍍物上 施以底層及上層塗膜之2層電鍍之實施例，與有關防止該實 ❹ 施例因塗膜形成而造成上層錫塗膜產生針孔及錫鬚晶之評 10 價測試例。 前述實施例、測試例之「份」、「％」基本上係重量基 準。 另，本發明並不以下列實施例、測試例為限，凡於本 發明之技術思想範圍内均得以任意變形。 15 《以無電解電鍍形成2層塗膜之實施例》 下列實施例1〜12中，實施例1〜9係底層塗膜為錫-銀 合金塗膜之例，實施例10〜12係底層塗膜為錫-鉍合金塗膜 之例。實施例4、6及11係底層塗膜之膜厚接近本發明之適 當範圍下限(〇.〇25μπι)之例。實施例7係底層與上層之塗腠 20 全體膜厚接近本發明之適當範圍下限(Ο.ίμιη)之例。實施例 8係底層塗膜中銀比率接近本發明之適當範圍下限(5%)之 例。實施例9係底層與上層之塗膜全體中銀比率高於本發明 3所示理想範圍之上限(50%)之例，其他實施例則均為該理 想範圍内之例。 19 200936806 另一方面，下列比較例1〜4中’比較例1係底層塗膜純 - 粹為銀塗膜之例。比較例2係錫·銀合金組成之底層塗膜中 銀比率超過本發明之適當範圍上限(9〇%)之例。比較例3係 同樣之底層塗膜中銀比率比本發明之適當範圍下限(5°/〇)少 5 之例。比較例4係底層塗膜之膜厚比本發明之適當範圍下限 (0.025μιη)薄之例。 (1)實施例1 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4 )所示，藉由無電解錫-銀合金電鍍於 © 1〇 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (4 )以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按不 列（b)之條件於被鍍物上形成下列之錫·銀合金電鍍塗膜 15 (底層）。Ra · Rb · (MO)P = 〇14 200936806 (In general formula (a), Ra and Rb are the same or different (^~(:25 alkyl, only one of them is Η. Η or alkali metal.) Sorbitol ester, which can be mono-, di- or tri-esterified 1,4-, 1,5- or 3,6-sorbitol anhydride, for example, such as: sorbitol single Lauric acid ester, sorbitan monocaprylate, sorbitan distearate, sorbitan dioleate, sorbitan mixed fatty acid ester, etc. Aliphatic amine, propylamine, butylamine , hexylamine, octylamine, decylamine, laurylamine, stearylamine, oleylamine, ethylenediamine, propylenediamine, etc., saturated and unsaturated, fatty acid amines, etc. ίο Fatty amide, propionic acid, butyric acid , octanoic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, abietic acid and the like. The cationic surfactant, for example, has the following four levels of general formula (b) Salt, (Rj · R2 · R3 · R4N) + · X' (b) 15 (In the formula (b), X represents a halogen, a hydroxyl group, an alkanesulfonic acid or a sulfuric acid, and the ratios R2 and R3 are the same or Different alkyl groups, R4 series table Or benzyl.) or a pyridinium salt represented by the following formula (C), etc. R6-(C5H5N-R5)+· X- (c) 20 (In the formula (c), C5H5N represents pyridine a ring, X represents a halogen, a hydroxyl group, an alkanesulfonic acid or a sulfuric acid, R5 represents an alkyl group, and R6 represents an alkyl group. A cationic form of a cationic surfactant, for example, a lauryl trimethylammonium salt, a hard Lipid trimethylammonium salt, lauryl dimercaptoethyl ammonium salt, 15 200936806 octadecyl dimethyl ethyl ammonium salt, dimethyl hexyl ammonium lauryl salt, whale butyl dibenzyl benzyl ammonium salt, Octadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecapyridine salt, lauryl pyridinium salt, dodecyl pyridinium salt, stearylamine acetate , laurylamine acetate, octadecylamine acetate, etc. The anionic surfactants include alkane sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, Alkyl benzene acid salt, (mono, di- or tri) alkylnaphthalene sulfonate, etc. Alkyl sulfate, exemplified by sodium lauryl sulfate, sodium oleate, etc. Polyoxyethylene alkyl ether sulfate, Take the example of polyoxyethylene (E012) sodium decyl ether sulfate, polyoxyethylene (E015) sodium dodecyl ether sulfate, etc. Polyoxyethylene succinyl ether ether sulfate, can be used for polyoxymethylene (E015) Examples of mercaptophenyl ether sulfate, etc. The alkylbenzene sulfonate can be exemplified by sodium dodecylbenzenesulfonate, etc. (mono, di, and tri)alkylnaphthalenesulfonate, which can be dibutylnaphthalene. Sodium sulfonate, etc. are exemplified. 15 The amphoteric surfactants include a carboxyl beet test, a beetine test, a sulfobetaine, an aminocarboxylic acid, etc. In addition, an ethylene oxide and/or a ring may also be used. An addition product of a condensation product of oxypropane with an alkylamine or a diamine, which is sulfated or sulphonated. a representative carboxybetaine or imidazolinium betaine, having lauryl di 20 amidinoacetate betaine, myristyl bis-aminoglycine acetate betaine, stearin dimethylaminoacetate betaine, coconut oil fat Indole propyl dimethylaminoacetic acid beet test, 2-H-yl-1-ylmethyl-1-ethylidene (Iridazolinium), betaine and other 'sulfated and sulfonated adducts A sulfuric acid addition product of an alkylamine oxide, a sodium salt of an acidified lauric acid derivative, or the like. 16 200936806 The aforementioned sulfobetaine has coconut oil fatty amidoxime diammonium chloride 2-hydroxypropanesulfonic acid, N-cocoyl methyl taurate, and a soft base. Sodium taurate and the like. The aminocarboxylic acid may, for example, be dioctylaminoglycine, N-laurylaminepropionic acid or octylbis(aminoethyl)glycine sodium salt. The shielding agent is used to improve the stability of the electric clock bath to prevent the impurity metal ions which are eluted from the bare metal such as copper from being adversely affected by the plating bath. Specifically, there are: EDTA, hydroxy Ethyl ethylenediamine phthalic acid (HEDTA), imine diacetic acid (IDA), imine dipropionic acid (IDP), nitrogen 10 triacetic acid (NTA), diethylenetriamine pentaacetic acid (DTPA), three Ethylenetetraamine hexaacetic acid (TTHA), ethylenediamine, hexamethylenediamine, diamethylenetriamine, lemon, acid, tartaric acid, succinic acid, malonic acid, glycolic acid, gluconic acid, gluconic acid, pyrophosphoric acid , tripolyphosphoric acid, 1-hydroxyethane-1,1-bisphosphonic acid, and the like. Further, in the first aspect of the invention, the undercoat film is formed by electroless tin-silver alloy plating, but in the invention 2, the undercoat film is formed by electroless tin-bismuth alloy plating. The electroless tin-bismuth alloy electroplating bath used in the formation of the undercoat film in the present invention 2 is based on a soluble stannous salt, a soluble sulfonium salt, an acid or a salt thereof and a complexing agent. The above-mentioned soluble sulfonium salt is an organic sulfonic acid or a salt of an inorganic acid, and specifically, cerium sulfonate, cerium ethanesulfonate, cerium phenolsulfonate, cerium nitrate, chlorinated chlorinated or the like. The content of the metal salt of the soluble barium salt is 0.1 to 200 g/L, and the ideal one is 1 to 80 g/L. 17 200936806 The soluble stannous salt, acid or salt thereof is the same as that of the user of the electroless tin/silver iridium gold plating bath described above. Further, the mis-synthesis used in the electroless tin-synthesis electric ore bath can be the same as that of the above-mentioned electroless tin-silver alloy electric ore, and the towel is preferably a sulfur or silk type. Further, in the electroless tin-bismuth alloy plating bath of the present invention 2, in addition to the above basic components, the surfactant, the reducing agent, the masking agent, the pH adjusting agent, the buffering agent, and the leveling agent may be mixed according to the purpose. Various additives such as a stress relieving agent, a glossing agent, a semi-gloss agent, and an antioxidant are the same as the electroless tin/silver alloy electric ore bath of the present invention 1. In the present invention 2 in which the undercoat film is formed by electroless tin-bismuth alloy plating, the film thickness of the undercoat film and the film thickness of the entire underlayer and the upper layer of the coating film should conform to the use of electroless tin_silver. The above-mentioned requirements of the first feature of the present invention in the alloy plating, and the requirement of the silver ratio in the undercoat film, shall comply with the relevant requirements of the second feature of the first invention. 15 Further, when the undercoat film is formed by electroless tin-bismuth alloy plating, it is preferable to prevent the occurrence of whisker crystals and pinholes in the upper tin coating film, as in the case of performing electroless tin-silver alloy electrowinning. The ratio of the film thickness A of the undercoat film to the film thickness B of the ruthenium coating film (the present invention 4), or the weight ratio of the silver layer of the entire underlayer and the upper coating film (invention 3). 2) When the electroless tin-silver alloy electric clock bath of the present invention 1 or the electroless tin/niobium alloy electric clock bath of the present invention 2 is used, the bath temperature is preferably lower than usual. As described above, in the present invention, it is only necessary to make the undercoat film of electroless tin/silver alloy or electroless tin gold into a very thin state of only 18 2009 _ _ _ 2009. Increase the bath temperature for thick plating. Further, the electroless plating to be applied according to the present invention is preferably a film carrier of a copper-clad laminate, a film-coated film (COF) or TAB as shown in Fig. 5 of the present invention. The copper-clad laminate refers to a hard printed circuit board (PCB), a flexible printed circuit board (FPC), a ball grid array (BGA), a chip size package (CSP), or the like. [Embodiment] Hereinafter, an embodiment in which two layers of plating of the underlayer and the upper coating film are applied to the object to be plated by electroless plating according to the present invention will be described in order to prevent the film from being formed by the coating film. A 10-valent test case for the formation of pinholes and tin whiskers in the upper tin coating film. The "parts" and "%" of the foregoing examples and test examples are basically based on the weight basis. Further, the present invention is not limited to the following examples and test examples, and can be arbitrarily modified within the scope of the technical idea of the present invention. 15 "Example of Forming Two Coating Films by Electroless Electroplating" In the following Examples 1 to 12, Examples 1 to 9 are examples in which a primer coating film is a tin-silver alloy coating film, and Examples 10 to 12 are a primer coating layer. The film is an example of a tin-bismuth alloy coating film. The film thicknesses of the undercoat films of Examples 4, 6 and 11 are close to the lower limit of the appropriate range of the present invention (〇. 25 μm). Example 7 is a method in which the film thickness of the underlayer and the upper layer is close to the lower limit of the appropriate range of the present invention (Ο.ίμιη). Example 8 is an example in which the silver ratio in the undercoat film is close to the lower limit (5%) of the appropriate range of the present invention. In the ninth embodiment, the total silver ratio of the coating film of the underlayer and the upper layer is higher than the upper limit (50%) of the ideal range shown in the third embodiment of the present invention, and other examples are examples within the intended range. 19 200936806 On the other hand, in the following Comparative Examples 1 to 4, 'Comparative Example 1 is an example in which the undercoat film is purely a silver coating film. Comparative Example 2 is an example in which the silver ratio in the undercoat film composed of the tin-silver alloy composition exceeds the upper limit (99%) of the appropriate range of the present invention. In Comparative Example 3, the silver ratio in the same undercoat film was 5 less than the lower limit (5°/〇) of the appropriate range of the present invention. In Comparative Example 4, the film thickness of the undercoat film was thinner than the lower limit of the appropriate range (0.025 μm) of the present invention. (1) Example 1 COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) was used as a material to be plated, and was electroplated by electroless tin-silver alloy as shown in the following (4). After the underlayer of the tin-silver alloy coating film is formed on the plating material, a tin coating film (upper layer) is formed on the underlayer by electroless tin plating as shown in the following (mouth). (4) electroless tin-silver alloy electroplating is used to form an electroless tin-silver alloy electroplating bath having the following composition of (a), and the following tin/silver is formed on the object to be plated according to the condition of (b) Alloy plating film 15 (bottom layer).

〇_35莫耳/l ❹ 〇·〇〇5 莫耳/l 0.30莫耳/L 1.40莫耳/L 〇·75莫耳/l :!5.〇g/L (a) 無電解錫-銀合金電鍍浴 甲磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 甲磺酸 20 疏腺 次磷酸 聚氧乙稀辛基苯基趟(E01〇莫耳）〇_35莫耳/l ❹ 〇·〇〇5 Moer/l 0.30 Moh/L 1.40 Moh/L 〇·75 Molar/l :!5.〇g/L (a) Electroless tin-silver Alloy plating bath stannous methanesulfonate (as Sn2+) silver methanesulfonate (as Ag+) methanesulfonic acid 20 phosphatidyl hypophosphite polyoxyethylene octyl phenyl hydrazine (E01 〇 Mo ear)

(b) 浸潰條件 電鍍浴溫：30°C 20 200936806 電鍍時間：45秒 (c)底層 錫-銀合金塗膜之膜厚：0.08μπι 錫-銀合金塗膜之銀比率：46.1% 5 (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜（上層）。下列（f)係顯示底層與上 層塗膜全體之膜厚及銀之比率。 (d)以無電解錫電鍍浴形成上層 10 甲磺酸亞錫(作為Sn2+) :0.30莫耳/L 甲磺酸 :1.00 莫耳/L 紛確酸 :0.50莫耳/L 硫脲 :2.00莫耳/L 次磷酸 :0.50莫耳/L 15 聚氧乙稀十二基苯基醚(E08莫耳） :10.0g/L (e)電鍍條件 電鍍浴溫：65°C 電鍍時間：15分 ⑴上層 20 底層與上層塗膜全體之膜厚：1.15μπι 底層與上層塗膜全體中之銀比率：2.3% (2)實施例2 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 21 200936806 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 建製下列(a)之成分之無電解錫·銀合金電鍍浴，並按下 5 列（b)之條件於被鍍物上形成下列（c)之錫·銀合金電鍍塗膜 (底層）。 (a)無電解錫-銀合金電鍍浴 甲磺酸亞錫（作為Sn2+) :0.35莫耳/L 甲磺酸銀(作為Ag+) :0.007莫耳/L 10 對酚磺酸 :0.10莫耳/L 甲磺酸 :0.20莫耳/L 硫脲 :140莫耳/L 次磷酸 :0.75莫耳/L 聚氧乙稀辛基苯基it(E01〇莫耳） :15.0g/L 15 (b)浸潰條件(b) Immersion conditions Electroplating bath temperature: 30 ° C 20 200936806 Plating time: 45 seconds (c) Film thickness of the underlying tin-silver alloy coating: 0.08 μπι Silver ratio of tin-silver alloy coating: 46.1% 5 ( An electroless tin plating bath having the composition of the following (d) is formed by electroless tin plating, and a tin plating film (upper layer) is formed on the underlayer according to the following condition (e). The following (f) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. (d) Forming the upper layer 10 with an electroless tin plating bath. Stannous methanesulfonate (as Sn2+): 0.30 mol/L methanesulfonic acid: 1.00 mol/L. Acid: 0.50 mol/L Thiourea: 2.00 Mo Ear / L hypophosphorous acid: 0.50 mol / L 15 polyoxyethylene lauryl phenyl ether (E08 Molar): 10.0g / L (e) plating conditions plating bath temperature: 65 ° C plating time: 15 points (1) Thickness of the entire upper layer 20 and the upper coating film: 1.15 μm The silver ratio of the bottom layer to the upper coating film: 2.3% (2) Example 2 COF (Chip on Film; ESPANEX; manufactured by Shinkai Iron Chemical Co., Ltd.) The object to be plated is as shown in the following (4), after electroless tin-silver alloy plating is applied to the underlayer of the tin-silver alloy coating film on 21 200936806, as shown in the following (mouth), by Electroless tin plating is formed on the underlayer to form a tin coating film (upper layer). (彳) Electroless tin-silver alloy plating bath is formed by electroless tin-silver alloy plating, and the following electroless tin/silver alloy plating bath of the following composition (a) is formed, and the following (c) is formed on the object to be plated according to the conditions of column 5 (b). Tin/silver alloy plating film (bottom layer). (a) Electroless tin-silver alloy plating bath Stannous methanesulfonate (as Sn2+): 0.35 mol/L Silver methanesulfonate (as Ag+): 0.007 mol/L 10 p-phenolsulfonic acid: 0.10 mol/ L methanesulfonic acid: 0.20 mol/L Thiourea: 140 mol/L hypophosphorous acid: 0.75 mol/L polyoxyethylene octylphenylit (E01 〇 Moel): 15.0 g/L 15 (b) Immersion condition

電鍍浴溫：30°C 電鍍時間：45秒 (c)底層 錫-銀合金塗膜之媒厚：〇 11μιη 錫-銀合金塗膜之銀比率：49 8% (口）以無電解鍍錫形成上層 建製下列(d)之成分之無電解錫電鍍浴，並按下列…)之 條件於底層上形成鑛錫塗膜(上層）。下列⑴係，顯示底層與上 層塗膜全體之膜厚及銀之比率。 ' 22 200936806Plating bath temperature: 30 ° C Plating time: 45 seconds (c) Base tin-silver alloy coating film thickness: 〇11μιη Tin-silver alloy coating silver ratio: 49 8% (mouth) formed by electroless tin plating An electroless tin plating bath of the following composition (d) is formed on the upper layer, and a tin coating film (upper layer) is formed on the underlayer according to the following conditions. The following (1) shows the film thickness and silver ratio of the entire underlayer and the upper coating film. ' 22 200936806

:0.35莫耳/L :0.50莫耳/L :1.00 莫耳/L :2.30莫耳/L :0.50莫耳/L ：15.0g/L (d) 以無電解錫電鍍浴形成上層 甲磺酸亞錫(作為Sn2+) 曱磺酸 2-羥乙磺酸 硫腺 次磷酸 聚氧乙烯十二基苯基醚(E08莫耳) (e) 電鍍條件 10 15 ⑩ 20 電鍍浴溫：65°C 電鍍時間：15分 (f)上層 底層與上層塗膜全體之膜厚：1.30μιη 底層與上層塗膜全體中之銀比率：1.7% (3)實施例3 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (4)以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。 (a)無電解錫-銀合金電鍍浴: 0.35 mol/L: 0.50 mol/L: 1.00 Mohr/L: 2.30 mol/L: 0.50 mol/L: 15.0 g/L (d) The upper layer of methanesulfonic acid was formed by electroless tin plating bath Tin (as Sn2+) sulfonic acid 2-hydroxyethanesulfonic acid sulfur adenosine polyoxyethylene dodecyl phenyl ether (E08 mol) (e) Plating conditions 10 15 10 20 Plating bath temperature: 65 ° C plating time : 15 minutes (f) Film thickness of the upper layer and the upper coating film: 1.30 μιη Silver ratio of the bottom layer and the upper coating film: 1.7% (3) Example 3 COF (Chip on Film; ESPANEX; Chemical Co., Ltd. is a material to be plated, and as shown in the following (4), an electroless tin-silver alloy is electroplated on the object to be plated to form a bottom layer of a tin-silver alloy coating film, as shown in the following (mouth). A tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (4) Electroless tin-silver alloy plating bath having the following composition of (a) formed by electroless tin-silver alloy plating, and tin of the following (c) is formed on the object to be plated according to the following condition (b) - Silver alloy plating film (bottom layer). (a) Electroless tin-silver alloy plating bath

2-羥乙磺酸亞錫(作為Sn2+) : 0.25莫耳/L 23 200936806Stannous 2-hydroxyethanesulfonate (as Sn2+): 0.25 m/L 23 200936806

0.006 莫耳/L 0.40莫耳/L 1.40莫耳/L 0.75莫耳/L 15.0g/L 甲磺酸銀(作為Ag+) 2-羥乙磺酸 硫脲 次磷酸 5 聚氧乙烯辛基苯基醚(E010莫耳） (b) 浸潰條件 電鍍浴溫：30°C 電鍍時間：45秒0.006 Mohr/L 0.40 Molar/L 1.40 Molar/L 0.75 Molar/L 15.0g/L Silver methanesulfonate (as Ag+) 2-Hydroxyethanesulfonic acid thiourea hypophosphite 5 Polyoxyethylene octylphenyl Ether (E010 Moer) (b) Immersion Condition Plating Bath Temperature: 30 ° C Plating Time: 45 seconds

(c) 底層 10 錫-銀合金塗膜之膜厚：0.15μιη 錫-銀合金塗膜之銀比率：52.6% (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列(e)之 條件於底層上形成鍍錫塗膜（上層）。下列⑴係顯示底層與上 15 層塗膜全體之膜厚及銀之比率。 (d) 以無電解錫電鍍浴形成上層(c) Film thickness of the underlying 10 tin-silver alloy coating: 0.15 μm The ratio of silver to tin-silver alloy coating: 52.6% (mouth) is formed by electroless tin plating to form the upper layer of electroless tin of the following composition (d) A plating bath was formed, and a tin plating film (upper layer) was formed on the underlayer according to the following condition (e). The following (1) shows the film thickness and the ratio of silver of the entire underlayer and the upper 15 coat films. (d) Forming the upper layer with an electroless tin plating bath

2-羥乙磺酸亞錫(作為Sn2+) : 0.40莫耳/LStannous 2-hydroxyethanesulfonate (as Sn2+): 0.40 mol/L

2-羥乙磺酸 ：1.00莫耳/L2-hydroxyethanesulfonic acid: 1.00 mol/L

硫脲 ：2.60莫耳/LThiourea: 2.60 m / L

20 次磷酸 ：0.50莫耳/L20 times phosphoric acid: 0.50 mol/L

聚氧乙烯壬基苯基醚(E012莫耳） ：12.0g/L (e) 電鍍條件 電鍍浴溫：65°C 電鍍時間：15分 24 200936806 (f)上層 底層與上層塗膜全體之膜厚：1.50μιη 底層與上層塗膜全體中之銀比率：2.8% (4)實施例4 5 〇 10 15 20Polyoxyethylene nonylphenyl ether (E012 Molar): 12.0g/L (e) Plating conditions Plating Bath temperature: 65°C Plating time: 15 minutes 24 200936806 (f) Thickness of the upper layer and the upper coating film : 1.50 μιη Silver ratio in the entire underlayer and the upper coating film: 2.8% (4) Example 4 5 〇 10 15 20

以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (4 )以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。 (a) 無電解錫-銀合金電鍍浴 曱磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 曱磺酸 硫脈 次磷酸 聚氧乙烯辛基苯基醚(E010莫耳） (b) 浸潰條件 電鍍浴溫：30°CCOF (Chip on Film; ESPANEX; manufactured by Niigata Iron Chemical Co., Ltd.) is used as a material to be plated, and as shown in the following (4), electroless tin-silver alloy plating is applied to the object to be plated to form a tin-silver alloy coating. After the underlayer of the film, as shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (4) electroless tin-silver alloy plating is used to form an electroless tin-silver alloy plating bath having the following composition of (a), and the following tin (c) is formed on the object to be plated according to the following condition (b) - Silver alloy plating film (bottom layer). (a) Electroless tin-silver alloy plating bath, stannous sulfonate (as Sn2+), silver methane sulfonate (as Ag+), sulfonate sulfuric acid, polyoxyethylene octyl phenyl ether (E010 mol) (b ) Immersion conditions plating bath temperature: 30 ° C

:0.35莫耳/L :0.004莫耳/L :0.30莫耳/L :1.40 莫耳/L :0.75莫耳/L ：15.0g/L 電鍍時間：45秒 (c)底層 錫-銀合金塗膜之膜厚：0.06μιη 25 200936806 錫-銀合金塗膜之銀比率：32.5% (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜(上層）。下列（f)係顯示底層與上 5 層塗膜全體之膜厚及銀之比率。 (d) 以無電解錫電鍍浴形成上層: 0.35 Molar / L : 0.004 Molar / L : 0.30 Molar / L : 1.40 Mohr / L : 0.75 Molar / L : 15.0 g / L Plating time: 45 seconds (c) Underlying tin-silver alloy coating film Film thickness: 0.06μιη 25 200936806 Silver ratio of tin-silver alloy coating film: 32.5% (mouth) An electroless tin plating bath in which the upper layer (d) is formed by electroless tin plating, and is as follows (e) The condition is that a tin plating film (upper layer) is formed on the underlayer. The following (f) shows the film thickness and silver ratio of the entire underlayer and the upper 5 coat films. (d) Forming the upper layer with an electroless tin plating bath

2-羥乙磺酸亞錫(作為Sn2+) : 0.35莫耳/LStannous 2-hydroxyethanesulfonate (as Sn2+): 0.35 mol/L

2-羥乙磺酸 ：1.30莫耳/L2-hydroxyethanesulfonic acid: 1.30 mol/L

硫脲 ：2.00莫耳/LThiourea: 2.00 mole / L

10 次磷酸 ：0.50莫耳/L10 times phosphoric acid: 0.50 mol/L

聚氧乙烯壬基苯基醚(E012莫耳） ：12.0g/L (e) 電鍍條件 電鍍浴溫：65°C 電鍍時間：15分 15 ⑴上層Polyoxyethylene nonylphenyl ether (E012 Molar): 12.0g/L (e) Plating conditions Electroplating bath temperature: 65°C Plating time: 15 minutes 15 (1) Upper layer

底層與上層塗膜全體之膜厚：1·25μιη 底層與上層塗膜全體中之銀比率：2.1% (5)實施例5 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 20 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 26 200936806 列(b)之條件於被鑛物上形成下列卜)之 (底層）。 錫-銀合金電鍍塗膜Film thickness of the entire underlayer and the upper coating film: 1·25 μm η Silver ratio of the entire underlayer and the upper coating film: 2.1% (5) Example 5 COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) was 20 The object to be plated, and as shown in the following (4), after electroless plating of a tin-silver alloy coating film on the object to be plated by an electroless tin-silver alloy, as shown in the following (mouth), by electroless A tin coating film (upper layer) is formed on the underlayer by tin plating. (彳) Electroless tin-silver alloy electroplating bath is formed by electroless tin-silver alloy plating to form the following composition of (a), and the following conditions are formed on the mineral by the conditions of column (b) of 26 200936806; (bottom level). Tin-silver alloy plating film

(a) 無電解錫-銀合金電鍍浴 2-羥乙磺酸亞錫(作為sn2+) 甲磺酸銀(作為Ag+) 2-羥乙磺酸 硫脈 次磷酸 聚氧乙烯辛基苯基_(E01〇莫耳） (b) 浸潰條件 電鍍浴溫：30°C 電鍍時間：45秒 (c) 底層 錫-銀合金塗膜之膜厚：〇.〇9pm 錫-銀合金塗膜之銀比率：45.8% (口）以無電解鍍錫形成上層(a) Electroless tin-silver alloy plating bath Stannous 2-hydroxyethanesulfonate (as sn2+) Silver methanesulfonate (as Ag+) 2-hydroxyethanesulfonic acid sulfur-phosphoric acid polyoxyethylene octylphenyl-( E01〇莫耳) (b) Immersion conditions plating bath temperature: 30 ° C plating time: 45 seconds (c) film thickness of the underlying tin-silver alloy coating: 〇.〇9pm tin-silver alloy coating silver ratio :45.8% (mouth) is formed by electroless tin plating

·· 0.35莫耳/L 0.006 莫耳/L 0.30莫耳/L 1.40莫耳/l 0·75莫耳/L 15.0g/L 建製下列（d)之成分之無電解錫電鍍浴，並按下列（6)之 條件於底層上形成鍍錫塗膜(上層）。下列⑺係顯示底層與上 層塗膜全體之膜厚及銀之比率。 (d)以無電解錫電鍍浴形成上層 2-羥乙磺酸亞錫(作為Sn2+) 2-羥乙磺酸 硫脲 次磷酸················································································································· (6) A tin plating film (upper layer) is formed on the underlayer. The following (7) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. (d) Forming an upper layer of electroless tin plating bath of stannous 2-hydroxyethanesulfonate (as Sn2+) 2-hydroxyethanesulfonic acid Thiourea Hypophosphorous acid

0.30莫耳/L 1.30莫耳/L 2.50莫耳/L 0.70莫耳/L 27 2009368060.30 m / L 1.30 m / L 2.50 m / L 0.70 m / L 27 200936806

聚氧乙烯辛基苯基醚(E010莫耳） ：15.0g/L (e)電鍍條件 電鍍浴溫：65°C 電鍍時間：15分 5 (f)上層 底層與上層塗膜全體之膜厚：1.56μιη 底層與上層塗膜全體中之銀比率：2.7% (6)實施例6Polyoxyethylene octyl phenyl ether (E010 Molar): 15.0g / L (e) Plating conditions Plating bath temperature: 65 ° C Plating time: 15 minutes 5 (f) Film thickness of the upper layer and the upper layer coating film: 1.56μιη Silver ratio of the bottom layer to the upper coating film: 2.7% (6) Example 6

以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 10 被鍍物，並如下列)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 15 列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。COF (Chip on Film; ESPANEX; manufactured by Niigata Iron Chemical Co., Ltd.) was used as a 10 object to be plated, and as shown in the following), a tin-silver alloy coating film was formed by electroless plating of an electroless tin-silver alloy on the object to be plated. After the underlayer, as shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (彳) Electroless tin-silver alloy plating bath having the following composition of (a) formed by electroless tin-silver alloy plating, and the following (c) is formed on the object to be plated under the conditions of column 15 (b) Tin-silver alloy plating film (bottom layer).

(a) 無電解錫-銀合金電鍍浴(a) Electroless tin-silver alloy plating bath

甲磺酸亞錫(作為Sn2+) : 0.35莫耳/LStannous methanesulfonate (as Sn2+): 0.35 mol/L

甲磺酸銀(作為Ag+) : 0.004莫耳/LSilver methane sulfonate (as Ag+): 0.004 mol/L

20 甲磺酸 ：0.30莫耳/L20 methanesulfonic acid: 0.30 mol / L

硫脲 ：1.40莫耳/LThiourea: 1.40 m / L

次磷酸 ：0.75莫耳/LHypophosphorous acid: 0.75 mol/L

聚氧乙烯辛基苯基醚(E010莫耳） ：15.0g/L (b) 浸潰條件 28 200936806 5 電鍍浴溫：30°C 電鍍時間：20秒 (c)底層 錫-銀合金塗膜之膜厚：0.06μπι 錫-銀合金塗膜之銀比率：30.7% (口）以無電解鍍錫形成上層 ❹ 10 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜（上層）。下列（f)係顯示底層與上 層塗膜全體之膜厚及銀之比率。 15⑩ (d) 以無電解錫電鍍浴形成上層 2_羥乙磺酸亞錫(作為Sn2+) 2-羥乙磺酸 硫脲 次磷酸 聚氧乙烯壬基苯基醚(E012莫耳) (e) 電鍍條件 電鍍浴溫：65°C 電鍍時間：3分Polyoxyethylene octyl phenyl ether (E010 Molar): 15.0g / L (b) Impregnation conditions 28 200936806 5 Electroplating bath temperature: 30 ° C Plating time: 20 seconds (c) Underlying tin-silver alloy coating film Film thickness: 0.06μπι Silver ratio of tin-silver alloy coating film: 30.7% (mouth) is formed by electroless tin plating to form upper layer ❹ 10 The electroless tin plating bath of the following component (d) is formed, and is as follows (e) A tin plating film (upper layer) is formed on the underlayer. The following (f) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. 1510 (d) Forming the upper layer of stannous 2-hydroxyethanesulfonate (as Sn2+) 2-electro-ethanesulfonic acid thiourea hypophosphite polyoxyethylene nonylphenyl ether (E012 Moer) (e) Plating conditions plating bath temperature: 65 ° C plating time: 3 points

:0.35莫耳/L :1.30 莫耳/L :1.50 莫耳/L :0.50莫耳/L ：12.0g/L 20 (f)上層 底層與上層塗膜全體之膜厚：〇.35μιη 底層與上層塗膜全體中之銀比率：4.3% (7)實施例7 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 29 200936806 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示 藉由無電解鍍錫於該底層上形成有錫塗臈(上層）。 (4 )以無電解錫-銀合金電鍍形成底層 5 建製下列(a)之成分之無電解錫銀合金電鍵浴並按下 列⑻之條件於被鍍物上形成下列⑷之锡邊合金電錢塗膜 (底層): 0.35 mol / L : 1.30 Mohr / L : 1.50 Mohr / L : 0.50 Mo / L : 12.0g / L 20 (f) The thickness of the upper layer and the upper coating film: 〇.35μιη bottom layer and upper layer Silver ratio in the entire coating film: 4.3% (7) Example 7 COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) was used as the object to be plated, and as shown in the following (4), by electroless plating. Tin-silver alloy plating on 29 200936806 After the underlayer of the tin-silver alloy coating film is formed on the object to be plated, a tin-coated crucible (upper layer) is formed on the underlayer by electroless tin plating as shown in the following (mouth). (4) Electroless tin-silver alloy plating to form the underlayer 5 The electroless tin-silver alloy electric button bath of the following composition (a) is formed and the following (4) tin-side alloy electric coin coating is formed on the object to be plated according to the following condition (8). Membrane

·· 0.35莫耳/L :0.005莫耳/l ’· 〇·3〇莫耳/L :1.40 莫耳/L :0·75莫耳/L :M.Og/L·· 0.35mol/L : 0.005 mol / l ’· 〇·3〇 Moule/L : 1.40 Mohr/L : 0·75 Moh/L : M.Og/L

❹ (a)無電解錫-銀合金電鍍浴 2-羥乙磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 2-羥乙磺酸 硫脲 次磷酸 聚氧乙烯辛基苯基醚(E010莫耳) (b) 浸潰條件 電鍍浴溫：30°C 電鍍時間：20秒 (c) 底層 錫-銀合金塗膜之膜厚：〇.〇7μιη 錫-銀合金塗膜之銀比率：28.2% 2〇 (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列(6)之 條件於底層上形成鍍錫塗膜（上層）。下列⑺係顯示底層與上 層塗膜全體之膜厚及銀之比率。 (d)以無電解錫電鍍浴形成上層 30 200936806❹ (a) Electroless tin-silver alloy plating bath Stannous 2-hydroxyethanesulfonate (as Sn2+) Silver methanesulfonate (as Ag+) 2-hydroxyethanesulfonic acid thiourea hypophosphite polyoxyethylene octyl phenyl ether (E010 Moer) (b) Immersion conditions Electroplating Bath temperature: 30 ° C Plating time: 20 seconds (c) Film thickness of the underlying tin-silver alloy coating: 〇.〇7μιη Tin-silver alloy coating silver ratio : 28.2% 2 〇 (口) An electroless tin plating bath having the composition of the following (d) is formed by electroless tin plating, and a tin plating film (upper layer) is formed on the underlayer according to the following condition (6). The following (7) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. (d) forming an upper layer with an electroless tin plating bath 30 200936806

:0.35莫耳/L :1.30 莫耳/L :1.50 莫耳/L :0.50莫耳/L ：12.0g/L 2-羥乙磺酸亞錫(作為Sn2+) 2-羥乙磺酸 硫脈 次磷酸 聚氧乙烯壬基苯基醚(E012莫耳) (e)電鍍條件 ❹ 10 電鍍浴溫：65°C 電鍍時間：3分 ⑴上層 底層與上層塗膜全體之膜厚：0.30μιη 底層與上層塗膜全體中之銀比率：3.7% (8)實施例8 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 15 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 建製下列(a)之成分之無電解錫-銀合金電鍍浴，並按下 列〇3)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 20 (底層）。: 0.35 mol/L: 1.30 Molar/L: 1.50 Molar/L: 0.50 mol/L: 12.0 g/L stannous 2-hydroxyethanesulfonate (as Sn2+) 2-hydroxyethanesulfonic acid sulfur pulse Polyoxyethylene nonylphenyl ether phosphate (E012 Moer) (e) Plating conditions ❹ 10 Plating bath temperature: 65 ° C Plating time: 3 minutes (1) Film thickness of the upper layer and the upper coating film: 0.30 μm The bottom layer and the upper layer Silver ratio in the entire coating film: 3.7% (8) Example 8 COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) was used as the object to be plated, and as shown in the following (4), by electroless plating. After tin-silver alloy plating is formed on the undercoat layer to form a tin-silver alloy coating film, as shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (彳) electroless tin-silver alloy plating to form an electroless tin-silver alloy plating bath having the following composition of (a), and forming the following tin (c) on the object to be plated according to the following conditions 3) - Silver alloy plating film 20 (bottom layer).

:0.35莫耳/L :0.005莫耳/L :0.30莫耳/L (a)無電解錫-銀合金電鍍浴 曱磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 曱磺酸 31 200936806 硫脲 ：1.40莫耳/L .: 0.35 mol / L : 0.005 m / L : 0.30 mol / L (a) electroless tin - silver alloy plating bath bismuth sulfonate (as Sn2+) silver methane sulfonate (as Ag +) sulfonate 31 200936806 Thiourea: 1.40 mol / L.

次磷酸 ：0.75莫耳/LHypophosphorous acid: 0.75 mol/L

聚氧乙烯辛基苯基醚(E010莫耳）：15_0g/L (b) 浸潰條件Polyoxyethylene octyl phenyl ether (E010 Molar): 15_0g/L (b) Impregnation conditions

5 電鍍浴溫：30°C 電鍍時間：45秒 (c) 底層 錫-銀合金塗膜之膜厚·· 0.08μπι 錫-銀合金塗膜之銀比率：10.1% © 10 (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜（上層）。下列（f)係顯示底層與上 . 層塗膜全體之膜厚及銀之比率。 (d)以無電解錫電鍍浴形成上層 15 甲磺酸亞錫（作為Sn2+) :0.30莫耳/L 甲磺酸 :1.00 莫耳/L 紛確酸 :0.50莫耳/L 硫脲 :2.00莫耳/L 次磷酸 :0.50莫耳/L 20 聚氧乙烯十二基苯基醚(E08莫耳） ：10.0g/L (e)電鍍條件5 Plating bath temperature: 30 ° C Plating time: 45 seconds (c) Film thickness of the underlying tin-silver alloy coating · · 0.08μπι Tin-silver alloy coating silver ratio: 10.1% © 10 (mouth) with no electrolysis Tin plating is performed to form an electroless tin plating bath having the composition of the following (d), and a tin plating film (upper layer) is formed on the underlayer according to the following condition (e). The following (f) shows the film thickness and silver ratio of the entire underlayer and the upper coating film. (d) Forming the upper layer with an electroless tin plating bath. Stannous methanesulfonate (as Sn2+): 0.30 mol/L methanesulfonic acid: 1.00 mol/L. Acid: 0.50 mol/L Thiourea: 2.00 Mo Ear/L hypophosphorous acid: 0.50 mol/L 20 polyoxyethylene dodecylphenyl ether (E08 mol): 10.0 g/L (e) plating conditions

電鍍浴溫：65°C 電鍍時間：5分 ⑴上層 32 200936806 底層與上層塗膜全體之膜厚：〇.85Pm 底層與上層塗膜全體中之銀比率：^% (9)實施例9 以COF(Chip on Film ; ESPANEX ;新日鐵化學社製）為 5 被鍍物，並如下列（^ )所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (4 )以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鑛浴，並按下 1〇 列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。 15Plating bath temperature: 65 ° C Plating time: 5 minutes (1) Upper layer 32 200936806 Film thickness of the entire bottom layer and the upper coating film: 〇.85Pm Silver ratio of the bottom layer and the upper layer coating film: ^% (9) Example 9 with COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) is a 5 object to be plated, and as shown in the following (^), a tin-silver alloy coating film is formed by electroless plating of an electroless tin-silver alloy on the object to be plated. After the underlayer, as shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (4) electroless tin-silver alloy plating is used to form an electroless tin-silver alloy electric ore bath having the following composition of (a), and the following conditions are formed on the object to be plated according to the conditions of column 1 (b) ( c) Tin-silver alloy plating film (bottom layer). 15

20 (a) 無電解錫-銀合金電鍍浴 甲磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 甲磺酸 琉腺 次磷酸 聚氧乙烯辛基苯基醚(E010莫耳） (b) 浸潰條件 電鍍浴溫：50°C 電鍍時間：120秒 (c) 底層 錫·銀合金塗膜之膜厚：0.25μιη 錫-銀合金塗膜之銀比率：8〇 5%20 (a) Electroless tin-silver alloy electroplating bath stannous methanesulfonate (as Sn2+) silver methanesulfonate (as Ag+) methanesulfonic acid pseudophosphoric acid polyoxyethylene octyl phenyl ether (E010 mol) b) Impregnation conditions Electroplating bath temperature: 50 ° C Plating time: 120 seconds (c) Film thickness of the underlying tin/silver alloy coating film: 0.25 μιη Silver ratio of tin-silver alloy coating film: 8〇5%

4·35莫耳/L 0-015 莫耳/L4·35 Moor/L 0-015 Moor/L

0.30莫耳/L0.30 m / L

1.40莫耳/L1.40 mol / L

:〇·75莫耳/L :15.〇g/L 33 200936806 (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜(上層）。下列（f)係顯示底層與上 層塗膜全體之膜厚及銀之比率。 5 (d)以無電解錫電鍍浴形成上層:〇·75mol/L :15.〇g/L 33 200936806 (mouth) An electroless tin plating bath in which the upper layer (d) is formed by electroless tin plating, and is subjected to the following conditions (e) A tin plating film (upper layer) is formed on the underlayer. The following (f) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. 5 (d) Forming the upper layer with an electroless tin plating bath

甲磺酸亞錫（作為Sn2+) : 0.30莫耳/LStannous methanesulfonate (as Sn2+): 0.30 mol/L

曱磺酸 ：1·00莫耳/LSulfonic acid: 1·00 mol/L

酚磺酸 ：0.50莫耳/LPhenolic acid: 0.50 m / L

硫脲 ：2.00莫耳/LThiourea: 2.00 mole / L

10 次磷酸 ：0.50莫耳/L10 times phosphoric acid: 0.50 mol/L

聚氧乙烯十二基苯基醚(Ε08莫耳） ：10.0g/L (e)電鍍條件 電鍍浴溫：65°C 電鍍時間：3分 15 (f)上層Polyoxyethylene dodecyl phenyl ether (Ε08 Moer): 10.0g/L (e) Plating conditions Plating bath temperature: 65°C Plating time: 3 minutes 15 (f) Upper layer

底層與上層塗膜全體之膜厚：〇.61μιη 底層與上層塗膜全體中之銀比率：55.3% (10)實施例10 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 20 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-鉍合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 34 200936806 列(b)之條件於被鍍物上形成下列（c)之錫_銀合金電鍍塗膜 (底層）° ❹ 10 (a) 無電解錫-銀合金電鍍浴 甲磺酸亞錫(作為Sn2+) 甲磺酸鉍(作為Bi3+) 甲磺酸 碰腺 次磷酸 二伸乙三胺五乙酸 聚氧乙婦辛基苯基鍵(E010莫耳) (b) 浸潰條件Film thickness of the entire underlayer and the upper coating film: 〇.61 μιη The silver ratio of the entire underlayer and the upper coating film: 55.3% (10) Example 10 COF (Chip on Film; ESPANEX; manufactured by Niigata Iron Chemical Co., Ltd.) was 20 The object to be plated, and as shown in the following (4), after electroless plating of a tin-silver alloy coating film on the object to be plated by an electroless tin-silver alloy, as shown in the following (mouth), by electroless A tin coating film (upper layer) is formed on the underlayer by tin plating. (彳) Electroless tin-silver alloy plating bath with the following composition of (a) formed by electroless tin-bismuth alloy plating, and the following conditions are formed on the object to be plated under the conditions of 34 200936806 column (b) (c) Tin-silver alloy plating film (bottom layer) ° ❹ 10 (a) Electroless tin-silver alloy plating bath stannous methanesulfonate (as Sn2+) bismuth methanesulfonate (as Bi3+) methanesulfonic acid Diethylenetriamine pentaacetate polyoxyethyl octyl phenyl bond (E010 Mo) (b) Impregnation conditions

:0.35莫耳/L :〇·〇15莫耳/L :〇_3〇莫耳/L :1.40 莫耳/L :〇·75莫耳/L :0·08莫耳/l :15.0g/L 電鍍浴溫：30°C 電鍍時間：45秒 15 (c)底層 錫-鉍合金塗膜之膜厚：〇.1〇μηι: 0.35 Molar / L : 〇 · 〇 15 Moor / L : 〇 _3 〇 Mo / L : 1.40 Mo / L : 〇 · 75 Mo / L : 0 · 08 Mo / l : 15.0g / L plating bath temperature: 30 ° C plating time: 45 seconds 15 (c) underlying tin-bismuth alloy coating film thickness: 〇.1〇μηι

錫-鉍合金塗膜之鉍比率：34 5% (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解锡電鍍洛並按下列（e)之 條件於底層上形成鑛錫塗膜(上層 >下列⑺係顯示底層與上 2〇 層塗膜全體之膜厚及銀之比率。Tin-bismuth alloy coating film ratio: 34 5% (mouth) is formed by electroless tin plating to form the upper layer of the following (d) composition of electroless tin plating and forming tin ore on the bottom layer according to the following conditions (e) Coating film (upper layer) The following (7) shows the film thickness and silver ratio of the entire underlayer and the upper two-layer coating film.

〇·3〇莫耳/L 1.00莫耳/L 0.50莫耳/L (d)以無電解錫電鍍浴形成上層 甲磺酸亞錫(作為Sn2+) 曱磺酸 酚磺酸 35 200936806〇·3〇莫耳/L 1.00 mol/L 0.50 mol/L (d) The upper layer is formed by electroless tin plating bath. Stannous methanesulfonate (as Sn2+) oxime sulfonic acid phenolsulfonic acid 35 200936806

硫脲 ：2.00莫耳/LThiourea: 2.00 mole / L

次磷酸 ：0.50莫耳/LHypophosphorous acid: 0.50 mol / L

聚氧乙烯十二基苯基醚(E08莫耳） ：10.0g/L (e) 電鍍條件Polyoxyethylene dodecyl phenyl ether (E08 Molar): 10.0g / L (e) plating conditions

5 電鍍浴溫：65°C 電鍍時間：15分 (f) 上層 底層與上層塗膜全體之膜厚：1.08μπι 底層與上層塗膜全體中之鉍比率：1.3% 10 (11)實施例11 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍵物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 15 (4 )以無電解錫-鉍合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。 (a)無電解錫-銀合金電鍍浴5 Electroplating bath temperature: 65 ° C Plating time: 15 minutes (f) Film thickness of the upper layer and the upper coating film: 1.08 μπι The ratio of the bottom layer to the upper coating film: 1.3% 10 (11) Example 11 COF (Chip on Film; ESPANEX; manufactured by Shinkai Iron Chemical Co., Ltd.) is a material to be plated, and as shown in the following (4), a tin-silver alloy coating film is formed by electroless plating of an electroless tin-silver alloy on the object to be bonded. After the underlayer, as shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. 15 (4) Electroless tin-silver alloy plating bath with the following composition of (a) formed by electroless tin-bismuth alloy plating, and the following (c) is formed on the object to be plated according to the following conditions (b) Tin-silver alloy plating film (bottom layer). (a) Electroless tin-silver alloy plating bath

20 甲磺酸亞錫（作為Sn2+) : 0.25莫耳/L20 stannous methanesulfonate (as Sn2+): 0.25 m / L

甲磺酸鉍(作為Bi3+) : 0.015莫耳/LBismuth methanesulfonate (as Bi3+): 0.015 mol/L

曱磺酸 ：0.30莫耳/LSulfonic acid: 0.30 mol/L

硫脲 ：1.40莫耳/LThiourea: 1.40 m / L

次磷酸 ：0.75莫耳/L 200936806Hypophosphorous acid: 0.75 mol / L 200936806

二伸乙三胺五乙酸 :0.08莫耳/L 聚氧乙烯辛基苯基醚(Ε010莫耳） (b)浸潰條件 電鍍浴溫：30°C :15.0g/乙 5 電鍍時間：45秒 (c)底層 錫-鉍合金塗膜之膜厚：〇.〇6μηι 錫-叙合金塗膜之祕比率：45.8% (口）以無電解鍍錫形成上層 10 建製下列（d)之成分之無電解錫電鑛浴， 並按下列（e)之 條件於底層上形成鍵錫塗膜(上層）。下列⑺係顯示底層與上 - 層塗膜全體之膜厚及銀之比率。 一 (d)以無電解錫電鍍浴形成上層 2-羥乙磺酸亞錫(作為Sn2+) :0.30莫耳/L 15 2-羥乙磺酸 :1.30 莫耳/L 硫腺 :2.50莫耳/L 次磷酸 :0.70莫耳/L 聚氧乙烯壬基苯基醚(E012莫耳） ：12.0g/L (e)電鍍條件Diethylenetriamine pentaacetic acid: 0.08 mol/L polyoxyethylene octylphenyl ether (Ε010 mol) (b) impregnation conditions plating bath temperature: 30 ° C: 15.0 g / b 5 plating time: 45 seconds (c) Film thickness of the underlying tin-bismuth alloy coating film: 〇.〇6μηι The tin-salt coating film secret ratio: 45.8% (mouth) is formed by electroless tin plating to form the upper layer 10. The following components (d) are formed. An electrolytic tin bath was electrolyzed, and a bond tin coating film (upper layer) was formed on the underlayer according to the following condition (e). The following (7) shows the film thickness and the ratio of silver of the entire underlayer and the upper-layer coating film. One (d) is formed by electroless tin plating bath to form the upper layer of stannous 2-hydroxyethanesulfonate (as Sn2+): 0.30 mol/L 15 2-hydroxyethanesulfonic acid: 1.30 mol/L sulfur gland: 2.50 mol/ L hypophosphorous acid: 0.70 mol/L polyoxyethylene nonylphenyl ether (E012 mol): 12.0 g/L (e) plating conditions

20 電鍍浴溫：65°C 電鍍時間：15分 ⑺上層 底層與上層塗膜全體之膜厚：1.05μιη 底層與上層塗膜全體中之鉍比率：1.5% 37 200936806 (12)實施例12 以COF(Chip on Film ; ESPANEX ;新日鐵化學社製）為 被鍍物，並如下列（<)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後’如下列（口）所示， 5 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫·銀合金電鐘形成底層20 Electroplating bath temperature: 65 ° C Plating time: 15 minutes (7) Film thickness of the upper layer and the upper layer coating film: 1.05 μιη Ratio of the bottom layer to the upper layer coating film: 1.5% 37 200936806 (12) Example 12 with COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) is a material to be plated, and as shown in the following (<), a tin-silver alloy coating film is formed by electroless plating of an electroless tin-silver alloy on the object to be plated. After the bottom layer, as shown in the following (mouth), 5 a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (彳) forming an underlayer with an electroless tin/silver alloy electric clock

建製下列(a)之成分之無電解鍚·銀合金電鍍浴，並按丁 列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。 10 (a)無電解錫-銀合金電鍍浴An electroless yttrium-silver alloy plating bath of the following composition (a) is formed, and a tin-silver alloy plating film (bottom layer) of the following (c) is formed on the object to be plated under the conditions of the column (b). 10 (a) Electroless tin-silver alloy plating bath

〇·35莫耳/l 〇·〇ΐ5 莫耳/l 〇·3〇莫耳/L 1·4〇莫耳/L 0.75莫耳/L 〇·〇8莫耳/L :15.〇g/L 曱磺酸亞錫(作為Sn2+) 曱磺酸鉍(作為Bi3+) 甲磺酸 硫腺 15 次鱗酸〇·35莫耳/l 〇·〇ΐ5 Moer/l 〇·3〇 Mo Er/L 1·4〇 Mo Er/L 0.75 Mo Er/L 〇·〇8 Mo Er/L :15.〇g/ Stannous L sulfonate (as Sn2+) bismuth sulfonate sulfonate (as Bi3+)

二伸乙三胺五乙酸 聚氧乙稀辛基苯基喊(E010莫耳）Diethylenetriamine pentaacetate Polyoxyethylene octylphenyl shrine (E010 Moer)

(b) 浸潰條件 電鍍浴溫：30°C 20 電鍍時間：45秒 (c) 底層 錫-銀合金塗膜之膜厚：〇 〇8μηι 錫-銀合金塗膜之叙比率：38 2〇/。 (口）以無電解鍍錫形成上層 38 200936806 建製下列（d)之成分之無電解錫電鍍浴，並按下列（^之 條件於底膚上形成鍵錫塗膜(上層）。下列⑴係顯示底層與上 層塗膜全體之膜厚及銀之比率。 Ο 10 (d)以無電解錫電鍍浴形成上層 2-羥乙磺酸亞錫(作為Sn2+) 2-羥乙磺酸 硫脲 次磷酸 聚氧乙烯壬基苯基醚(E012莫耳) (e)電鍍條件(b) Immersion conditions Electroplating bath temperature: 30 ° C 20 Plating time: 45 seconds (c) Film thickness of the underlying tin-silver alloy coating: 〇〇8μηι Tin-silver alloy coating ratio: 38 2〇/ . (The mouth) is formed by electroless tin plating to form the upper layer 38 200936806 The electroless tin plating bath of the following component (d) is formed, and a key tin coating film (upper layer) is formed on the substrate according to the following conditions. The following (1) shows Film thickness and silver ratio of the entire underlayer and the upper coating film. Ο 10 (d) Forming the upper layer of stannous 2-hydroxyethanesulfonate (as Sn2+) 2-electro-ethanesulfonic acid thiourea hypophosphorous acid in an electroless tin plating bath Oxyethylene nonylphenyl ether (E012 mol) (e) plating conditions

:0.30莫耳/L :1.30 莫耳/L :2.50莫耳/L :0·70莫耳/L :12.0g/L 電鍍浴溫：65°C 電鍍時間：15分 ⑴上層 15: 0.30 mol / L : 1.30 Mohr / L : 2.50 Mohr / L : 0 · 70 Molar / L : 12.0g / L Plating bath temperature: 65 ° C Plating time: 15 points (1) Upper layer 15

G 20 底層與上層塗膜全體之膜厚：Ι.ΙΙμιη 底層與上層塗膜全體中之鉍比率：1.8% (13)比較例1 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解鍍銀於被鍍物上形 成銀塗膜之底層後，如下列（口）所示，藉由無電解鍍錫於該 底層上形成有錫塗膜(上層）。 (彳）以無電解鍍銀形成底層 建製下列(a)之成分之無電解銀電鍍浴，並按下列(b)之 條件於被鍍物上形成下列(c)之鍍銀塗膜(底層）。 (a)無電解銀電鍍浴 39 200936806 5 甲磺酸銀(作為Ag+) 曱磺酸 硫脈 聚氧乙烯辛基苯基醚(E010莫耳) (b) 浸潰條件 電鍍浴溫：50°C 電鍍時間：60秒 (c) 底層Film thickness of the entire bottom layer and the upper coating film: Ι.ΙΙμιη The ratio of the bottom layer to the upper coating film: 1.8% (13) Comparative Example 1 COF (Chip on Film; ESPANEX; manufactured by Shinkai Iron Chemical Co., Ltd.) As the object to be plated, as shown in the following (4), after the underlayer of the silver coating film is formed on the object to be plated by electroless silver plating, as shown in the following (mouth), electroless tin plating is applied to the bottom layer. A tin coating film (upper layer) is formed thereon. (彳) An electroless silver plating bath having the following composition (a) formed by electroless silver plating, and the following (c) silver plating film (bottom layer) is formed on the object to be plated according to the following condition (b) . (a) Electroless silver plating bath 39 200936806 5 Silver methane sulfonate (as Ag+) Sulfonium sulfonate polyoxyethylene octyl phenyl ether (E010 mol) (b) Immersion conditions plating bath temperature: 50 ° C Plating time: 60 seconds (c) bottom layer

:0.06莫耳/L :1.00 莫耳/L :0.30莫耳/L ：5.0g/L 10 銀塗膜之膜厚：Ο.ΙΟμιη (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜（上層）。下列（f)係顯示底層與上: 0.06 mol / L : 1.00 Mohr / L : 0.30 mol / L : 5.0 g / L 10 Film thickness of silver coating: Ο. ΙΟ μιη (mouth) with electroless tin plating to form the upper layer of the following (d) A tin-free plating bath of the composition is formed, and a tin plating film (upper layer) is formed on the underlayer according to the following condition (e). The following (f) shows the bottom layer and the top

層塗膜全體之膜厚及銀之比率。 (d) 以無電解錫電鍍浴形成上層 15 曱磺酸亞錫(作為Sn2+) : 0.30莫耳/L 曱磺酸 ：1.00莫耳/L 酚磺酸 ：0.50莫耳/L 硫脲 ：2.00莫耳/L 次磷酸 ：0.50莫耳/L 20 聚氧乙烯十二基苯基醚(E08莫耳） ：10.0g/L (e) 電鍍條件The film thickness of the entire coating film and the ratio of silver. (d) Forming the upper layer with an electroless tin plating bath. Stannous sulfonate (as Sn2+): 0.30 mol/L sulfonic acid: 1.00 mol/L phenolsulfonic acid: 0.50 mol/L thiourea: 2.00 Mo Ear/L hypophosphorous acid: 0.50 mol/L 20 polyoxyethylene dodecylphenyl ether (E08 mol): 10.0 g/L (e) plating conditions

電鍍浴溫：65°C 電鍍時間：15分 ⑴上層 40 200936806 底層與上層塗膜全體之膜厚：1.23μηι 底層與上層塗膜全體中之鉍比率：1.3% (14)比較例2 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 5 被鍍物，並如下列)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 Ο 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 10 列（b)之條件於被鍍物上形成下列（C)之錫-銀合金電鍍塗膜 (底層）。 . (a)無電解錫-銀合金電鍍浴Plating bath temperature: 65 ° C Plating time: 15 minutes (1) Upper layer 40 200936806 Film thickness of the entire underlayer and the upper coating film: 1.23 μηι The ratio of the bottom layer to the upper coating film: 1.3% (14) Comparative Example 2 with COF ( Chip on Film; ESPANEX; manufactured by Niigata Iron Chemical Co., Ltd.) is a 5 object to be plated, and as shown in the following), after electroless tin-silver alloy plating on the object to be plated, a bottom layer of a tin-silver alloy coating film is formed. As shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (彳) Electroless tin-silver alloy plating to form the underlayer Ο The electroless tin-silver alloy plating bath of the following composition (a) is formed, and the following conditions are formed on the object to be plated under the conditions of 10 columns (b) (C) Tin-silver alloy plating film (bottom layer). (a) Electroless tin-silver alloy plating bath

:0.15莫耳/L :0.005莫耳/L :1.50 莫耳/L :2.00莫耳/L :0.75莫耳/L ：15.0g/L 甲磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 15 甲磺酸 硫腺 _ 次磷酸 聚氧乙烯辛基苯基醚(E010莫耳） (b) 浸潰條件: 0.15 mol/L: 0.005 mol/L: 1.50 Mohr/L: 2.00 mol/L: 0.75 mol/L: 15.0 g/L stannous methanesulfonate (as Sn2+) silver methanesulfonate (as Ag+) 15 sulfuric acid mesylate _ hypophosphorous octyl phenyl ether (E010 mol) (b) impregnation conditions

20 電鍍浴溫：30°C 電鍍時間：45秒 (c) 底層 錫-銀合金塗膜之膜厚：0.06μιη 錫-銀合金塗膜之鉍比率：98.1% 41 200936806 (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜(上層）。下列（f)係顯示底層與上 層塗膜全體之膜厚及銀之比率。 5 (d)以無電解錫電鍍浴形成上層 10 15 甲磺酸亞錫(作為Sn2+) 甲磺酸 酚磺酸 硫脲 次磷酸 聚氧乙烯十二基苯基醚(E08莫耳) (e)電鍍條件 電鍍浴溫：65°C 電鍍時間：15分 ⑴上層20 Plating bath temperature: 30 ° C Plating time: 45 seconds (c) Film thickness of the underlying tin-silver alloy coating: 0.06 μιη Tin-silver alloy coating film ratio: 98.1% 41 200936806 (mouth) with electroless plating Tin is formed into an electroless tin plating bath in which the composition of the following (d) is formed, and a tin plating film (upper layer) is formed on the underlayer according to the following condition (e). The following (f) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. 5 (d) Forming the upper layer with an electroless tin plating bath 10 15 Stannous methanesulfonate (as Sn2+) Methanesulfonic acid thiourea thiourea hypophosphite polyoxyethylene dodecyl phenyl ether (E08 Mo) (e) Plating conditions plating bath temperature: 65 ° C plating time: 15 points (1) upper layer

:0.30莫耳/L :1.00 莫耳/L :0.50莫耳/L :2.00莫耳/L :0.50莫耳/L ：10.0g/L: 0.30 m / L: 1.00 m / L: 0.50 m / L: 2.00 m / L: 0.50 m / L: 10.0g / L

底層與上層塗膜全體之膜厚：1.25μπι 底層與上層塗膜全體中之銀比率：1.8% (15)比較例3 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 20 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下 42 200936806 列〇3)之條件於被鍍物上形成下列（C)之錫-銀合金電鍍塗膜 (底層）。 5 ❹ 10 (a) 無電解錫-銀合金電鍍浴 甲磺酸亞錫(作為Sn2+) 甲磺酸銀(作為Ag+) 甲磺酸 硫脲 次磷酸 聚氧乙烯辛基苯基醚(E010莫耳） (b) 浸潰條件 電鍍浴溫：30°C 電鍍時間：45秒 (c) 底層Film thickness of the entire underlayer and the upper coating film: 1.25 μm The ratio of the silver content in the entire underlayer and the upper coating film: 1.8% (15) Comparative Example 3 COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) was 20 The plating material, and as shown in the following (4), is formed by electroless tin-silver alloy plating on the substrate to form a tin-silver alloy coating film, as shown in the following (mouth), by electroless plating A tin coating film (upper layer) is formed on the underlayer of tin. (彳) Electroless tin-silver alloy electroplating bath is formed by electroless tin-silver alloy plating to form the following composition of (a), and the following conditions are formed on the object to be plated according to the conditions of 42 200936806, column 3) (C) Tin-silver alloy plating film (bottom layer). 5 ❹ 10 (a) Electroless tin-silver alloy electroplating bath Stannous methanesulfonate (as Sn2+) Silver methane sulfonate (as Ag+) Thiourea methanesulfonate polyoxyethylene octyl phenyl ether (E010 mol) (b) Immersion conditions plating bath temperature: 30 ° C plating time: 45 seconds (c) bottom layer

:0.35莫耳/L :0.003 莫耳/L :1.50 莫耳/L :2.00莫耳/L :0.75莫耳/L ：15.0g/L 15: 0.35 Molar / L : 0.003 Mohr / L : 1.50 Mohr / L : 2.00 Mohr / L : 0.75 Molar / L : 15.0g / L 15

20 錫-銀合金塗膜之膜厚：Ο.ΙΙμιη 錫-銀合金塗膜之銀比率：2.8% (口）以無電解鍍錫形成上層 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜(上層）。下列（f)係顯示底層與上 層塗膜全體之膜厚及銀之比率。 (d)以無電解錫電鍍浴形成上層20 Tin-silver alloy coating film thickness: Ο.ΙΙμιη Tin-silver alloy coating silver ratio: 2.8% (mouth) with electroless tin plating to form the upper layer of the following (d) composition of the electroless tin plating bath, A tin plating film (upper layer) is formed on the underlayer according to the following condition (e). The following (f) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. (d) forming an upper layer with an electroless tin plating bath

:0.30莫耳/L :1.00 莫耳/L :0.50莫耳/L :2.00莫耳/L 曱磺酸亞錫（作為Sn2+) 甲磺酸 紛確酸 硫脲 43 200936806:0.30 mol/L: 1.00 Molar/L: 0.50 mol/L: 2.00 mol/L stannous sulfonate (as Sn2+) methanesulfonic acid, acid, thiourea 43 200936806

次磷酸 ：0.50莫耳/LHypophosphorous acid: 0.50 mol / L

聚氧乙烯十二基苯基醚(E08莫耳） ：10.0g/L (e)電鍍條件 電鍍浴溫：65°C 5 電鍍時間：15分 ⑴上層 底層與上層塗膜全體之膜厚：1.30μιη 底層與上層塗膜全體中之銀比率：0.09%Polyoxyethylene dodecyl phenyl ether (E08 mol): 10.0g / L (e) plating conditions plating bath temperature: 65 ° C 5 plating time: 15 minutes (1) film thickness of the upper layer and the upper layer coating film: 1.30 Μιη The ratio of the silver in the bottom layer to the upper coating film: 0.09%

(16)比較例4 10 以COF(Chip on Film ; ESPANEX ;新曰鐵化學社製）為 被鍍物，並如下列（4)所示，藉由無電解錫-銀合金電鍍於 被鍍物上形成錫-銀合金塗膜之底層後，如下列（口）所示， 藉由無電解鍍錫於該底層上形成有錫塗膜(上層）。 (彳）以無電解錫-銀合金電鍍形成底層 15 建製下列（a)之成分之無電解錫-銀合金電鍍浴，並按下(16) Comparative Example 4 10 COF (Chip on Film; ESPANEX; manufactured by Nippon Steel Chemical Co., Ltd.) was used as a material to be plated, and was electroplated on the object to be plated by an electroless tin-silver alloy as shown in the following (4). After the underlayer of the tin-silver alloy coating film is formed, as shown in the following (mouth), a tin coating film (upper layer) is formed on the underlayer by electroless tin plating. (彳) Electroless tin-silver alloy plating to form the bottom layer 15 The electroless tin-silver alloy plating bath of the following composition (a) is formed and pressed

列（b)之條件於被鍍物上形成下列（c)之錫-銀合金電鍍塗膜 (底層）。The condition of the column (b) forms the tin-silver alloy plating film (bottom layer) of the following (c) on the object to be plated.

:0.35莫耳/L :0.005莫耳/L :0.30莫耳/L :1.40 莫耳/L :0.75莫耳/L :15.0g/L (a)無電解錫-銀合金電鍍浴 甲磺酸亞錫（作為Sn2+) 20 甲磺酸銀(作為Ag+) 甲磺酸 硫脲 次磷酸 聚氧乙烯辛基苯基醚(E010莫耳） 44 200936806 (b) 浸潰條件 電鍍浴溫：30°C 電鍍時間：3秒 (c) 底層 5 錫-銀合金塗膜之膜厚：0.02μπι 錫-銀合金塗膜之銀比率：33.3% (口）以無電解鍍錫形成上層 ❹ 10 建製下列（d)之成分之無電解錫電鍍浴，並按下列（e)之 條件於底層上形成鍍錫塗膜（上層）。下列（f)係顯示底層與上 層塗膜全體之膜厚及銀之比率。 15: 0.35 Molar / L : 0.005 Molar / L : 0.30 Molar / L : 1.40 Mohr / L : 0.75 Molar / L : 15.0 g / L (a) Electroless tin - Silver alloy plating bath Methanesulfonic acid Tin (as Sn2+) 20 silver methane sulfonate (as Ag+) thiourea mesylate polyoxyethylene octyl phenyl ether (E010 mol) 44 200936806 (b) Immersion conditions plating bath temperature: 30 ° C plating Time: 3 seconds (c) Bottom layer 5 Tin-silver alloy coating film thickness: 0.02μπι Tin-silver alloy coating silver ratio: 33.3% (mouth) with electroless tin plating to form the upper layer ❹ 10 The following (d) A tin-free plating bath of the composition is formed, and a tin plating film (upper layer) is formed on the underlayer according to the following condition (e). The following (f) shows the film thickness and the ratio of silver of the entire underlayer and the upper coating film. 15

(d)以無電解錫電鍍浴形成上層 甲磺酸亞錫(作為Sn2+) :0_30莫耳/L 甲磺酸 :1.00 莫耳/L 酴績酸 :0.50莫耳/L 硫脲 :2.00莫耳/L 次磷酸 :0.50莫耳/L 聚氧乙烯十二基苯基醚(E08莫耳） ：10.0g/L (e)電鍍條件 電鍍浴溫：65°C 20 電鍍時間：15分 ⑴上層 底層與上層塗膜全體之膜厚：1.38μιη 底層與上層塗膜全體中之銀比率：1.1% 《上層之錫塗膜之評價測試例》 45 200936806 如上所述，上述實施例1〜12及比較例1〜4中，係藉由 無電解電鍍於底層塗膜上面形成有錫塗膜，關於該上層之 錫塗膜，按下列要點就防止針孔產生之性能及防止錫鬚晶 產生之性能評價如下。 5 (1)防止針孔產生之性能 利用掃描式電子顯微鏡觀察剛完成之上層錫塗膜表 面’並依以下基準評價防止針孔產生之性能之優劣。 〇：上層錫塗膜未產生針孔。 X:上層錫塗膜已產生針孔。 10 (2)防止錫鬚晶產生之性能 利用掃描式電子顯微鏡確認剛完成之上層塗膜表面無 鬚晶產生之狀態後，於室溫下放置500小時，再對試樣之同 一視認部位進行顯微觀察，並依以下基準評價防止鬚晶產 生之性能之優劣。 15 〇：同—視認部位上鬚晶產生之根數為零。 X :同一視認部位上發現產生長度5μιη以上之鬚晶。 下表係上述測試之結果。 實施例1 針孔防止性 〇 鬚晶防止性 〇 實施例2 〇 〇 實施例3 〇 〇 實施例4 〇 〇 實施例5 〇 〇 實施例6 〇 〇 實施例7 〇 〇 200936806(d) Forming the upper layer of stannous methanesulfonate (as Sn2+) with an electroless tin plating bath: 0-30 mol/L methanesulfonic acid: 1.00 mol/L oxime acid: 0.50 mol/L thiourea: 2.00 mol /L hypophosphorous acid: 0.50 mol / L polyoxyethylene dodecyl phenyl ether (E08 Molar): 10.0g / L (e) plating conditions plating bath temperature: 65 ° C 20 plating time: 15 points (1) upper layer Film thickness with the entire upper coating film: 1.38 μm The silver ratio of the entire underlayer and the upper coating film: 1.1% "Evaluation test example of the upper tin coating film" 45 200936806 As described above, the above Examples 1 to 12 and the comparative examples In the first to fourth embodiments, a tin coating film is formed on the undercoat film by electroless plating, and the performance of the tin coating film on the upper layer to prevent pinhole generation and to prevent generation of whisker crystals is evaluated as follows . 5 (1) Performance against pinhole generation The surface of the upper tin coating film was observed by a scanning electron microscope and the performance of pinhole prevention was evaluated according to the following criteria. 〇: The upper tin coating film did not produce pinholes. X: The upper tin coating film has produced pinholes. 10 (2) Preventing the performance of whisker crystals After confirming that the surface of the upper coating film has not been subjected to whisker formation by scanning electron microscopy, it is allowed to stand at room temperature for 500 hours, and then the same visible portion of the sample is subjected to microscopy. Observe and evaluate the merits of the properties of the whisker generation according to the following criteria. 15 〇: The same - the number of roots of the whisker on the visible part is zero. X: A whisker having a length of 5 μm or more was found on the same visual recognition portion. The table below shows the results of the above tests. Example 1 Pinhole prevention 〇 防止 防止 实施 Example 2 〇 实施 Example 3 〇 实施 Example 4 〇 实施 Example 5 〇 实施 Example 6 〇 实施 Example 7 〇 〇 200936806

實施例8 〇 〇 實施例9 〇 〇 實施例10 〇 〇 實施例11 〇 〇 實施例12 〇 〇 比較例1 X 〇 比較例2 X 〇 比較例3 〇 X 比較例4 〇 X 如上表所見，底層塗膜為純粹銀塗膜之比較例1中，雖 於上層之錫塗膜未發現鬚晶產生，但明顯有產生針孔’且 悍接時有損焊料潤濕性或接合強度之虞。 5 相對於此，將底層做成錫-銀合金塗膜之實施例1〜12 中’上層之錫塗膜則無鬚晶及針孔產生。 因此可確定，為妥善防止錫鬚晶又不使上層之錫塗膜 產生針孔，必須將底層形成錫·銀合金塗膜而非銀塗膜。 又，雖以錫-銀合金塗膜做為底層、但底層塗膜之銀比 10 率超過本發明之適當範圍上限(90%)之比較例2，仍與前述 比較例1同樣於上層之錫塗膜產生針孔。反之，底層塗膜之 銀比率低於同一適當範圍下限(5%)之比較例3，上層之錫塗 膜雖未發現針孔，卻產生了錫鬚晶。 因此即可確認，為防止上層之錫塗膜產生針孔及鬚 晶，僅將底層形成錫-銀合金塗膜仍有不足，須將底層之银 比率限定於本發明之適當範圍内。 此外，底層之錫-銀合金塗膜之銀比率於本發明之適卷 47 15 200936806 範圍内、但底層之膜厚比本發明之適當範圍下限(〇〇25μιη) 薄之比較例4，亦與前述比較例3同樣於上層之錫塗膜產生 鬚晶。 由上述清楚可知，為防止上層之錫塗膜產生針孔及鬚 5 晶，須規定底層（錫-銀合金塗膜)之銀比率於本發明之適當 範圍内，並須將底層之膜厚控制在預定之膜厚以上。另外， 底層之膜厚乃如實施例1〜12所見，即使薄如〇·5μιη以下者 仍可善加確保防止鬚晶產生。 繼之，再詳加檢討實施例1〜12，無論底層之種類為錫 ❹ 10 -銀合金塗膜（實施例1〜9)或錫-鉍合金塗膜(實施例1〇〜12) 任一種，皆可防止上層之塗膜產生鬚晶與針孔。由此可知， 無論底層之膜厚、及底層與上層塗膜全體之膜厚於本發明 之適當範圍内有何改變，或，底層之銀比率於本發明之適 當範圍内有何改變，皆可確保防止錫鬚晶性能與防止針孔 15 性能良好。Example 8 〇〇Example 9 〇〇Example 10 〇〇Example 11 〇〇Example 12 〇〇Comparative Example 1 X 〇Comparative Example 2 X 〇Comparative Example 3 〇X Comparative Example 4 〇X As seen in the above table, the bottom layer In Comparative Example 1 in which the coating film was a pure silver coating film, although no whisker was found in the tin coating film of the upper layer, pinholes were formed, and the solder wettability or the bonding strength was impaired during the bonding. 5 In contrast, in the examples 1 to 12 in which the underlayer was made into a tin-silver alloy coating film, the tin coating film of the upper layer was free from whiskers and pinholes. Therefore, it has been confirmed that in order to properly prevent tin whisker without causing pinholes in the upper tin coating film, it is necessary to form a tin-silver alloy coating film instead of a silver coating film. Further, in the case of the comparative example 2 in which the tin-silver alloy coating film was used as the bottom layer but the silver ratio of the undercoat film exceeded the upper limit (90%) of the appropriate range of the present invention, the tin of the upper layer was the same as that of the comparative example 1 described above. The coating film produces pinholes. On the other hand, in Comparative Example 3 in which the silver ratio of the undercoat film was lower than the lower limit (5%) of the same appropriate range, the tin coating film of the upper layer produced tin whisker crystals although pinholes were not found. Therefore, it has been confirmed that in order to prevent pinholes and whiskers from being formed in the upper tin coating film, it is still insufficient to form the tin-silver alloy coating film only on the underlayer, and the silver ratio of the underlayer must be limited to the proper range of the present invention. Further, the silver ratio of the underlying tin-silver alloy coating film is in the range of the present invention in the range of 47 15 200936806, but the film thickness of the underlayer is thinner than the lower limit of the appropriate range of the present invention (〇〇25 μιη), and In the above Comparative Example 3, whiskers were also produced in the upper tin coating film. It is clear from the above that in order to prevent the pinhole and the whisker from being formed on the tin coating film of the upper layer, it is necessary to specify the silver ratio of the underlayer (tin-silver alloy coating film) within the proper range of the present invention, and the film thickness of the underlayer must be controlled. Above the predetermined film thickness. Further, the film thickness of the underlayer is as seen in Examples 1 to 12, and even if it is as thin as 〇·5 μmη or less, it is possible to surely prevent the generation of whiskers. Subsequently, the examples 1 to 12 are reviewed in detail, regardless of the type of the underlayer, which is a tin antimony 10 -silver alloy coating film (Examples 1 to 9) or a tin-bismuth alloy coating film (Examples 1 to 12). It can prevent the coating film of the upper layer from producing whiskers and pinholes. Therefore, it is understood that the film thickness of the underlayer and the film thickness of the entire underlayer and the upper coating film may vary within the appropriate range of the present invention, or the silver ratio of the underlayer may vary within the appropriate range of the present invention. Be sure to prevent tin whisker performance and prevent pinhole 15 from performing well.

特別重要者在於，即使如實施例8所見，形成銀比率少 至之錫-銀合金塗膜作為底層，或如實施例4、6、11所 Q 見’將底層之錫·銀合金塗膜之膜厚做成極薄之〇.〇6pm，仍 可確保上層錫塗膜之鬚晶與針孔防止性能。 20 另，本測試例之對象係對防止鬚晶與針孔產生進行評 價’但除此之外，調査上層錫塗膜之焊料潤濕性後發現， 底層與上層塗膜全體中銀比率在50%以内之實施例（即符合 本發明3之要件之實施例），與不符此要件之實施例9相較之 下’乃得到焊料潤濕性更佳之評價。 48 200936806It is particularly important that, as seen in Example 8, a tin-silver alloy coating film having a small silver ratio is formed as a primer layer, or as in Examples 4, 6, and 11 Q see 'the underlying tin-silver alloy coating film The film thickness is extremely thin. 〇6pm, the whisker and pinhole prevention properties of the upper tin coating film are still ensured. 20 In addition, the object of this test is to evaluate the generation of whiskers and pinholes. However, in addition, after investigating the solder wettability of the upper tin coating film, it was found that the ratio of the silver content of the bottom layer to the upper coating film was 50%. The embodiment (i.e., the embodiment conforming to the requirements of the third aspect of the present invention) is evaluated in comparison with the embodiment 9 which does not conform to the requirement to obtain a better solder wettability. 48 200936806

【圖式簡單說明3 (無） 【主要元件符號說明】 (無） 49[Simple description of the figure 3 (none) [Explanation of main component symbols] (none) 49

Claims (1)

200936806 七、申請專利範圍： 1. 一種防止無電解電鍵造成之錫鬚晶之方法，係於被鑛物 上形成由無電解錫-銀合金電鍍塗膜組成之底層塗膜 後，於該底層塗膜上形成無電解鍍錫塗膜(上層塗膜)之 5 鬚晶防止方法； 該底層塗膜之膜厚係0.025〜0·5μιη，且，底層與上 層塗膜之合計膜厚係0.1〜6μιη ; 底層之合金塗膜中銀之成分比係5〜90重量％ ; 前述被鍍物係包銅層板、覆晶薄膜(COF)或TAB之 10 薄膜載體》 2. —種防止無電解電鍍造成之錫鬚晶之方法，係於被鍍物 上形成由無電解錫-鉍合金電鍍塗膜組成之底層塗膜 後’於該底層塗膜上形成無電解鍍錫塗膜（上層塗膜)之 鬚晶防止方法； 15 該底層塗膜之膜厚係0.025〜0.5μηι，且，底層與上 層塗膜之合計膜厚係0.1〜6μιη ; 底層之合金塗膜中鉍之成分比係5〜90重量％ ; 前述被鍍物係包銅層板、COF或TAB之薄膜載體。 3. 如申請專利範圍第1或2項之防止無電解電鍍造成之錫 20 鬚晶之方法’其中前述底層與上層之塗膜全體中銀或鉍 之重量比係0.1〜50重量％。 4. 如申請專利範圍第丨〜3項中任一項之防止無電解電鍍 造成之錫鬚晶之方法，其中對於錫_銀合金或錫_鉍合金 所組成之前述底層塗膜之臈厚A，與錫所組成之前述上 50 200936806 層塗膜之膜厚B， 前述底層塗膜與前述上層塗膜之膜厚比係B(上層）/ (底層）=1.2〜30。 5.如申請專利範圍第1〜4項中任一項之防止無電解電鍍 5 造成之錫鬚晶之方法，其中形成前述底層塗膜時無電解 電鍍浴之溫度係5〜60°C。200936806 VII. Patent application scope: 1. A method for preventing tin whisker caused by electroless bond, which is formed on the mineral by forming an undercoat film composed of an electroless tin-silver alloy plating film. a method for preventing formation of an electroless tin plating film (upper coating film); the film thickness of the undercoat film is 0.025 to 0.5 μm, and the total film thickness of the underlayer and the upper coating film is 0.1 to 6 μm; The composition ratio of silver in the alloy coating film of the bottom layer is 5 to 90% by weight; the above-mentioned substrate is coated with a copper layer plate, a film on film (COF) or a film carrier of TAB. 2. A tin which is prevented from being electrolessly plated. The whisker method is formed by forming an undercoat film composed of an electroless tin-bismuth alloy plating film on a substrate to form an electroless tin plating film (upper layer coating film) on the underlying coating film. Prevention method; 15 The film thickness of the undercoat film is 0.025~0.5μηι, and the total film thickness of the bottom layer and the upper layer coating film is 0.1~6μιη; the ratio of the composition of the underlying alloy coating film is 5~90% by weight; The above-mentioned object is coated with a copper laminate, COF or TAB thin Carrier. 3. The method of preventing the tin 20 whisker caused by electroless plating according to the first or second aspect of the patent application, wherein the weight ratio of silver or ruthenium in the entire underlayer and the upper coating film is 0.1 to 50% by weight. 4. The method for preventing tin whisker caused by electroless plating according to any one of claims 1-3, wherein the thickness of the foregoing undercoat film composed of tin-silver alloy or tin-bismuth alloy is A And a film thickness B of the above-mentioned upper 50 200936806 layer coating film composed of tin, and a film thickness ratio B (upper layer) / (bottom layer) = 1.2 to 30 of the undercoat film and the upper layer coating film. 5. The method for preventing tin whisker caused by electroless plating according to any one of claims 1 to 4, wherein the temperature of the electroless plating bath is 5 to 60 ° C when the undercoat film is formed. 51 200936806 四、指定代表圖： (一) 本案指定代表圖為：第（ ）圖。（無) (二) 本代表圖之元件符號簡單說明：51 200936806 IV. Designated representative map: (1) The representative representative of the case is: ( ). (none) (2) A brief description of the symbol of the representative figure: 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無)5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (none) 22
TW97143674A 2007-12-27 2008-11-12 To prevent electroless plating caused by tin whisker method TWI470116B (en)

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EP2829637A4 (en) * 2012-03-23 2015-12-09 Jx Nippon Mining & Metals Corp Metallic material for electronic component, connector terminal obtained using same, connector, and electronic component
TWI648151B (en) * 2017-09-13 2019-01-21 國立屏東科技大學 Semiconductor tin-silver bonding structure and manufacturing method thereof

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Publication number Priority date Publication date Assignee Title
US9175400B2 (en) * 2009-10-28 2015-11-03 Enthone Inc. Immersion tin silver plating in electronics manufacture
CN108012449A (en) * 2017-10-28 2018-05-08 惠州市盈海数码电器有限公司 Mounted circuit board location and installation mechanism and alignment system are combined in CD radio reception
CN112291941B (en) * 2019-07-24 2022-02-18 北大方正集团有限公司 Printed circuit board and preparation method thereof

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JP3513709B2 (en) * 2001-10-16 2004-03-31 石原薬品株式会社 Preventing tin whiskers by pretreatment
JP3855161B2 (en) * 2002-05-10 2006-12-06 石原薬品株式会社 Prevention of tin whisker in electronic parts
JP2006009039A (en) * 2004-06-21 2006-01-12 Rambo Chemicals (Hong Kong) Ltd Tin based plating film in which growth of whisker is suppressed and forming method therefor
JP2007053039A (en) * 2005-08-19 2007-03-01 Matsushita Electric Ind Co Ltd Electric connector connection structure and flexible wiring board used for it

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2829637A4 (en) * 2012-03-23 2015-12-09 Jx Nippon Mining & Metals Corp Metallic material for electronic component, connector terminal obtained using same, connector, and electronic component
US9330804B2 (en) 2012-03-23 2016-05-03 Jx Nippon Mining & Metals Corporation Metallic material for electronic components, and connector terminals, connectors and electronic components using same
TWI648151B (en) * 2017-09-13 2019-01-21 國立屏東科技大學 Semiconductor tin-silver bonding structure and manufacturing method thereof

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KR20090071388A (en) 2009-07-01

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