TW201009115A - Reduction-type electroless tin plating solution and tin coats formed by using the same - Google Patents

Abstract

Provided is a reduction-type electroless tin plating solution suitable for practical use, which rarely causes replacement reaction on a substrate consisting of either copper or a copper alloy, which enables high-speed stable deposition, which is stable and attains high productivity, and which causes neither breaking of a conductor nor outgrowth of tin even when the conductor has a fine form. The reduction-type electroless tin plating solution is characterized by comprising, as the essential constituents, a water-soluble tin compound, a water-soluble titanium compound, an organic complexing agent, and an organosulfur compound selected from the group consisting of mercaptans and sulfides.

Description

201009115 六、發明說明： 【發明所屬之技術領域】 本發明係關於還原型非電解鍍錫液、使用其之錫膜之製造 方法及使用其所獲得之錫膜。 【先前技術】 參 ❹ 非電解鍍錫係施加在電子零件之端子部份，將錫鹽、有機 磺酸及硫尿素作為基本組成之取代型非電解鍍錫液已被實 用化。 取代型非電解鍍錫液係因為將母體材料之銅或銅合金作 為金屬離子進行溶解，供應電子給鍍敷液中之錫離子而錫螟 進行成長，故在近年來的精細間隔化之電子零件方面，會有 S施以非電解鍍錫處理時，銅或銅合金佈線被溶解，而佈線 斷線導致錫膜無法厚實成長之問題。 為了解決此問題，係將取代型非電解鍍錫液加以改良，雖 然於專利文獻1巾揭示有不使用鹽酸、械等錢用有機續 酸及其一價錫鹽’並進—步使用:欠亞雜峽取代反應與還 原反應平仃地進行’緩和針對母雜料銅或銅合金之侵麵的 非電解鑛錫液’但是會引發母體材料銅或鋼合金的溶解，而 未食匕達到於近年來之已精細間隔化之佈線上使錫膜增 長的階段。 又，於非專利文獻i中 原劑’錯合劑則使用 雖然提案有使用三氣化鈦作為還 EDTA(Ethylenediaminetetraacetic 098120955 2〇l〇〇9li5[Technical Field] The present invention relates to a reduced type electroless tin plating bath, a method for producing a tin film using the same, and a tin film obtained by using the same. [Prior Art] The non-electrolytic tin plating system is applied to the terminal portion of an electronic component, and a substituted electroless tin plating bath containing tin salt, organic sulfonic acid and sulfur urea as a basic component has been put into practical use. The substitution type electroless tin plating solution is obtained by dissolving copper or a copper alloy of a parent material as a metal ion, supplying electrons to tin ions in the plating solution, and growing tin bismuth. Therefore, in recent years, finely spaced electronic parts have been formed. On the other hand, when S is subjected to electroless tin plating treatment, copper or copper alloy wiring is dissolved, and wiring disconnection causes a problem that the tin film cannot grow thickly. In order to solve this problem, the substitution type electroless tin plating solution is improved, although it is disclosed in Patent Document 1 that there is no use of hydrochloric acid, machinery, etc., organic continuous acid and its monovalent tin salt. The heterogorge substitution reaction and the reduction reaction are carried out in a gentle manner to 'mitigate the non-electrolytic tin bath for the intrusion of the mother copper or copper alloy' but cause the dissolution of the parent material copper or steel alloy, and the uncooked meal reaches in recent years. The stage where the tin film is grown on the finely spaced wiring. Further, in Non-Patent Document i, the original agent 'missing agent is used. Although it is proposed to use tri-titanium oxide as EDTA (Ethylenediaminetetraacetic 098120955 2〇l〇〇9li5

Acid，伸乙二胺四乙酸）、NTA(Nitril〇triacetic八灿，氮基三 醋酸)及檸檬酸’且使用碳酸鈉作為pH調整劑之還原型非電 解鍍錫液，但是因為容易產生錫的異常析出，鍍敷液不穩 定，且析出速度緩慢，而難以進行穩定運轉，故並不實用。 [專利文獻1]曰本專利特開昭63-230883號公報 [非專利文獻1]表面技術，Vol. 44，No.11，（1993)第1〇2 至107頁 【發明内容】 (發明所欲解決之問題） 本發明係有鑑於上述先前技術之背景而完成者，其目的係 在於提供一種還原型非電解鍍錫液，其係抑制針對屬於母體 材料之銅或銅合金的取代反應，可進行高速且穩定之析出反 應，鍍敷液穩定且生產性高，即便在形狀細的情形下亦無斷 線’沒有錫滲出，可耐受於實用。 (解決問題之手段） 本發明者係為了解決上述問題而經過仔細檢討結果發 現’透過使用至少以水溶性錫化合物、水溶性鈦化合物、有 機錯合劑及「由硫醇類及硫化物類所組成群中選擇之有機硫 化合物」作為構成成分之還原型非電解鍍錫液，則可抑制針 對屬於母體材料之銅或銅合金的取代反應，具有穩定之錫析 出速度，且可實現優越之浴穩定性等，從而完成本發明。 亦即，本發明係提供一種還原型非電解鍍錫液，其特徵 098120955 4 201009115 為’至少以水溶性錫化合物、水溶性欽化合物、有機錯合 及由硫醇類及硫化物類所組柄巾選擇之有機破化人 作為構成成分。 13 劑 物 j 又，本發明係提供一種踢膜之製造方法，其特徵為 上<還原非電解鍍踢液*進行非電解鐘敷。 — X ’本發明係提供-種錫膜，係藉由採用上述還原型 解鍍錫液來進行非電解鍍敷而獲得。 •(發明效果） 根據本發明，可提供下述還原型非電解鍍錫液，其係抑制 針對母體材料銅或母體材料銅合金的取代反應，可抑制鋼溶 出^鍍敷液中，可進行高速且穩定的錫之析出反應鍵數^ 穩定，且即便在母體材料銅或母體材料銅合金之形狀細的情 形下亦無斷線，沒有錫滲出，即便為精細間隔化的電子零 件，仍可於銅或銅合金上快速且更厚實地使錫膜成長，而可 ® 耐受實用情況。 【實施方式】 以下，針對本發明進行說明，但是本發明並非限定於以下 之實施具體形態，在技術思想的範圍内，係可任意變化 施。 本發明之還原型非電解鍍錫液必須含有水溶性錫化合 物。該水溶性錫化合物只要可成為錫之供應源即可，並無= 別限定，較佳的是由錫之無機酸鹽、羧酸鹽、烷磺酸鹽、烷 098120955 5 201009115 醇增酸鹽、氫氧化物及偏錫酸(metastannicacid)所組成群中 選擇之一種或兩種以上。該等水溶性錫化合物係可使用一種 或混合兩種以上而使用。 作為上述水溶性錫化合物之錫的價數（氧化數），係可使用 一饧或四彳貝之任一者，以析出速度的觀點而言，以二價為 宜。亦即’以亞錫化合物為佳。 具體而言，係可列舉出：氯化亞錫、氯化錫、硫酸亞鍚、 硫酸錫、焦磷酸錫等錫之無機酸鹽；檸檬酸亞錫、檸檬酸錫、 草酸亞錫、草酸錫等錫之羧酸鹽；甲烷磺酸錫、1-乙烷磺酸 錫、2_乙烷磺酸锡、1-丙烷磺酸錫、3-丙烷磺酸錫等錫之烷 績酸鹽；曱醇績酸錫、經基乙烧小績酸錫、1-經基丙烧+ 碩I錫、鉍基乙烷磺酸錫、羥基丙烷-3-磺酸錫等錫之 烧^黃酸鹽；氫氧化亞錫、氫氧化錫等錫之氫氧化物；及偏 錫酸等。該等之中’就鑛敷性能、成本、取得容易度等觀點 而言，特別以氣化亞錫或硫酸亞錫為佳。 本發月之還原型非電解II錫液巾之上述水溶性錫化合物 之3有里並無特別限定，相對於還原型非電解鑛錫液整體， 以金屬錫形式計，通常為〇.5g/L〜l〇0g/L，較佳為 5g/L〜3Gg/L ’特料1Gg/L〜2Gg/L。#還翻非電解鑛錫液 中之金屬錫含有量過少，則錫膜析出速度緩慢，有不實用之 料又’备還原型非電解鑛錫液中之金屬錫含有量過多， 則有作為錫供應源之水溶性錫化合物難以溶解之情形。 098120955 6 201009115 本發明之㈣難電解_液必彡貞含有水溶性鈦化合 物。上述水溶性鈦化合物只要係作為還原劑使用者，則無特 別限制’具體而言，就織性能、取得容易度等觀點來說， 例=有·三氯化鈦、三蛾化鈦、三漠化鈦等_素化鈦；硫酸 鈦等。作為鈦的價數(氧化數），因為二價鈦化合物不穩定， 谷易被氧化而變成四價之情形’且由於四價鈦化合物本身不 會被氧化而無法供應電子，以此情形而言，較佳為三價。該 •等水溶性鈦化合物係可使用一種或混合兩種以上來使用。該 等之中，以鍍敷性能、取得容易度等觀點而言，特佳為三氯 化鈦。 本發明之縣齡電解賴液巾之±述水雜鈦化合物 之含有量並無特別限定，相對於還原型非電解鍍錫液整體， 以金屬鈦形式計，通常為〇.〇lg/L〜l〇〇g/L，較佳為 鏖〇.lg/L〜2〇g/L’特佳為lg/L〜1〇g/L。當還原型非電解錄錫液 中之水溶性鈦化合物含有量過少，則錫膜析出速度緩慢，有 不實用之情形，又’當還非電解鍍錫液中之水溶性鈦化 合物含有量過多，則有作為鍍敷液中之錫供應源異常析出而 使浴穩定性不佳，導致無法進行穩定運轉之情形。 本發明之還原型非電解鍍錫液必須進—步含有有機錯合 劑。作為有機錯合劑，並無特別限制，較佳的是由含胺基之 紐類、含絲之Μ基膦_、含贿之膦_、苯膦酸 類、节基膦_、其鹼金相、胁均金料及其録鹽所 098120955 201009115 組成群中選擇之一種或兩種以上。 作為上述含胺基之羧酸類，並無特别限制，具體而言， 可例舉出：三伸乙基四胺六醋酸、二 ° '、 三胺五醋酸、伸 乙基二胺四醋酸、丙烧二胺四醋酸、_伸乙基二胺三^ 酸、石肖基三醋酸、硝基三丙酸、賴二醋酸、録乙基= 二醋酸、甘胺酸、甘胺基甘胺酸、二_ 险输τ^ 土乙基甘胺酸、麵醯 胺酸、L-麩醯胺酸二醋酸等。 又，作為上述含胺基之亞曱基膦酸類， ^ 项亚無特別限制，具 體而s，係可例舉出：硝基三亞曱基膦酸、伸乙基- 、 甲基膦酸、二伸乙基三胺五亞曱基膦酸、六亞曱基-胺四亞 曱基膦酸、六亞甲基三胺五亞甲基膦酸等。 胺四亞 又’作為上述含羥基之膦酸類，並無特別限制’具體〜 係可例舉出：1_羥基亞乙基-丨，丨·二膦酸等。 、而言’ 又，作為上述苯膦酸類，並無特別限制，具體而一 例舉出：3-曱氧基苯膦酸等。 ° ’係可 又，作為上述苄基膦酸類，並無特別限制，具體而一 可例舉出：3-甲基苄基膦酸、4-氰基苄基膦酸等。β，係 該等有機錯合物係可使用一種或混合兩種以上來使 本發明之還原型非電解鍍錫液中之上述有機錯合 量並沒有特別限制，相對於還原型非電解鍍錫液整體、 為lg/L〜500g/L ’較佳為l〇g/L〜2〇〇g/L，杜 常 特佳為 50g/L〜150g/L。當還原型非電解鍍錫液中之有機錯合 098120955 8 201009115 量過少時’係有錯合力不充分，錄敷液變得不敎等之無法 發揮作為錯合劑之效果，又；若過多，則會產生難以溶解於 水中等之情形’無法見到作為錯合劑之進—步功效的提升， 而有不經濟之情形。 本發明之還原型非電解鍍錫液必須進__步含有由硫醇類 及硫化物類所組成群中選擇之有機硫化合物。所謂「硫醇 類」’係指分子中具有「—SH」之化合物。所謂「硫化物類」， 係指分子中具有「—s—」之化合物，鍵結於s之基係不限 疋在烷基或綠，亦可以是乙縣(aeetyl)(: h 等之烷酼糞埜.β 丄二a ❹ ❹ .硫化物等之 等之烷驢基等，又，亦包含多個二硫化物 「 〇 '」直接鍵結之多硫化物。 作為上述硫醇類，並無特別限制，具體而言，係可例舉有： 1·丙硫醇M-丁硫醇、❻乙二硫醇、u_丙二硫醇、…丁 -硫醇、W戊二硫醇、Μ•己二硫醇、2_胺基乙硫醇、3_ 風硫基-u-丙二醇、Μ_二氫硫基处丁二醇、3•氫硫基丙 酸乙醋、苯硫醇、苯三硫醇、？ ^ ^ + 2,3、二氯基苯硫醇、2,4-二甲 基本硫醇、2-胺基苯硫醇、 奸2蔡碗醇、氫硫基安息香酸、氫 硫基吼咬等。 作為上述硫化物類，並無特別限制，具體而言，係可例舉 有甲爪基醋酉夂(S—甲基硫代經乙酸，⑶3SCH2C〇〇H)、甲 硫基丙酸、甲絲了酸、乙縣―、乙絲㈣、丙硫基 丙酸、丁硫基丙酸、甲硫胺酸、⑽基硫化物、2·胺基苯基 098120955 201009115 苯基硫化物、一歸丙基硫化物、二丁基硫化物、丁基乙基硫 化物、二乙基二硫化物、二異丁基二硫化物、二甲基二硫化 物、二甲基三硫化物等。 該等有機硫化合物係可使用一種或混合兩種以上來使 用。又，由硫醇類及硫化物類所組成群中選擇之有機硫化合 物中’因為可更為顯著達成上述效果，故以硫化物類為特佳。 本發明之非電解鍍錫液係還原型，而取代型鍍錫液之含有 成分的知識在非電解鍍錫液方面是毫無用處的。尤其是本發 明之效果係可抑制因取代反應所導致之銅溶出，即便是經過 精細間隔化之電子零件亦無錫之渗出，且可使錫膜在鋼或铜 合金上快速成長’該等效果均係還原型非電解鍍錫液所特有 的效果。因此，一般不會認為：將在取代型鍍錫液所知曉的 含有成分添加入還原型非電解鍍錫液中，而可達成此類還原 型非電解鍍錫液特有的效果^ ' 本發明之還原型非電解鍍錫液中之上述有機硫化合物含 有量並沒有特別限制，相對於還原型非電解鍍錫液整體，通 常為O.lppm〜l〇〇〇〇〇ppm，較佳為lppm〜1〇〇〇〇ppm，特佳為 5PPm〜1 OOOppm。當還原型非電解鍍錫液中之有機硫化合物 含有量過少時，係析出速度不充分，且於針對内間隔進行鍍 敷處理之情形下，有發生錫滲出等而導致短路之情形。另〜 方面’若過多，則有難以溶解於水中等問題產生之情形，又， 有鍍敷液不穩定之情形。 098120955 10 201009115 關於本發明之還原型非電解鍍锡液，除了上述必須成分之 外，因應需要亦可適當含有下述組成於本發明之還原型非電 解鍍錫液中而使用1以使鍍敷液之pH保持一定的緩衝 劑、用以防止價數(氧德)為二價之錫供應源被氡化成四價 之抗氧化劑、㈣去祕顧之針孔或_使錄液之去泡 效果良好的界面活性劑、心使鍍錫財滑之綺劑等。 / 乍為本發明之還原型非電解鑛錫液中因應需要所含有之 緩衝劑，週知緩衝劑即可，並沒有特別限制，可列舉有：石朋 酸，酸等無機酸；檸檬酸、酒石酸、蘋果酸等氧化叛酸等。 "亥等係可使用一種或混合兩種以上使用。 ^發明之還原型非電解賴液中之緩衝劑含有量並沒有 ❹ 劑含有量射，會有難以發揮緩衝效果之情 濟之情形方面1過多時，會有看不到緩衝效果上升而不經 〇-lg/L~1〇〇g/L^^^ lg/L^50g/L〇 f 獲得抗氧液中之抗氧化劑含有量過少時，會有難以 錫液中之錫供2果的情形，當過多時’則還原型非電解嫉 進行穩技轉析出’而使喊定㈣佳，導致無法 作為本發g月> 還原型非電解鍍錫液中因應需要所含有之 098120955 11 201009115 界面活性劑，週知界面活性劑即可，並沒有特別限制，可採 用非離子系界面活性劑、陰離子系界面活性劑、兩性界面活 性劑或陽離子系界面活性劑。該等係可使用一種或遮合兩種 以上使用。 作為非離子系界面活性劑，係可列舉出：壬苯基聚烧氧 S旨、α-萘醇基聚烷氧酯、二丁基萘醇基聚烷氧酯、苯乙 烯化苯基聚烷氧酯等醚型非離子系界面活性劑；辛基胺聚烷 氧酯、己烯基胺聚烷氧酯、次亞麻油基胺聚烷氧酯等胺型非 離子系界面活性劑等。 作為陰離子系界面活性劑，係可列舉出：月桂基硫酸鈉等 烧基硫酸鹽；聚氧乙烯壬基醚硫酸鈉等聚氧乙烯烷基醚硫酸 鹽；聚氧乙烯烷基苯基醚硫酸鹽；烷基苯磺酸鹽等。 作為兩性界面活性劑，係可列舉出2-十一烧基-1-羧氧基 甲基-1-經基乙基咪唾鏘甜菜臉、Ν-硬酯基_ν，Ν-二甲基-Ν-羧氧基甲基甜菜鹼、月桂基二曱基胺氧化物等。 作為陽離子系界面活性劑，係可列舉出月桂基三曱基銨 鹽、月桂基二曱基銨甜菜鹼、月桂基吡啶鑌鹽、油基咪唑钂 鹽或硬酯基胺醋酸酯等。 s亥等係可使用一種或混合兩種以上使用，較佳的是非離子 系界面活性劑或兩性界面活性劑。 本發明之還原型非電解鍍錫液中之界面活性劑含有量係 以0.01g/L〜20g/L為佳，若可發揮所期望之性能即可，並無 098120955 12 201009115 特別限制含有量。 作為本發明之還原型非電解鍍錫液中因應需要所含有之 光澤劑，週知光澤劑即可，並沒有特別限制，可列舉出：糠 醛；苯亞甲基丙酮；對硝苯甲醛、間氣笨甲醛等甲醛類。該 等係可使用一種或混合兩種以上使用。 本發明之還原型非電解鍍錫液中之光澤_含有量較佳的 是〇.〇lg/L〜20g/L，若可發揮所期望之性能即可，並沒有特 • 別限制含有量。 以上所說明之本發明之還原型非電解鍍錫液的鍍敷條件 並沒有特別限定，溫度條件係以4(TC〜9(TC為佳，以5〇t>c 〜80C為特佳。又，鍍敷時間沒有特別限制，較佳的是30 秒鐘〜5小時，特佳的是1分鐘〜2小時。 ❿ 又’作為本還原型非電解鍍錫液之前處理，亦可實施觸媒 步驟、取代型非電解鍍錫料之活性化。進行活性化時之觸 媒步驟取代型非電解鍍錫液等係無特別限制，可藉由一般 的方法❹市售取代型非電解鍍錫液等。 本發明之本勒輯電解㈣㈣因為可以抑制針對屬 材料之鋼或母騎料之鋼合金的取代反應，所以在鍍 会的❹鋼’即便在母體材料之銅或母體材料之銅合 +裳杜，㈣形下亦無斷線，即使是經過精細間隔化之電 形成在母1时於喊銅合金上射形成賴，故於使錫膜 化成在母體材料之銅或母體材料之鋼合金上方面極為有效。 098120955 13 201009115 透過採用本發明之還原型非電解鍍錫液而進行非電解錢 敷所得到之錫膜的膜厚並沒有特別限制，較佳的是 0·05μπι〜50μιη，特佳的是 〇.5μιη〜20μιη。 [實施例] 以下，列舉實施例及比較例而更進一步說明本發明，惟， 本發明在不超出其主旨的範圍内，並非限定於該等實施例 中。又’還原型非電解鍍錫液之組成中之濃度數值，在其成 分包含結晶水的情形下’係由未包含結晶水之質量所求得之 濃度數值。 <銅溶出量之測量用的鍍敷方法> 使用PAC2〇0(MURATA股份有限公司製，商品名）將 0.1dm2之純銅板五片同時在5(rc下進行脫脂處理5分麵， 其後’進行水洗。其次，使用MEOX(MURATA股份有限八 司製’商品名）在30°C下進行餘刻處理2分鐘，其後，進行 水洗。接著，使用10容量％之稀硫酸，進行25°c下之酸洗 淨30秒鐘’其後，進行水洗。再來，使用JPCAT(日本高純 度化學股份有限公司製，商品名）在6yc下進行活性化處理 2分鐘’其後，進行水洗。 於燒杯中置入下述表1之組成的還原型非電解鍍錫液 lOOmL，並於其中同時將上述五片純銅板浸潰2小時來進行 鍍敷處理。鍍敷處理中之鍍敷液溫度係65〇c，1)11係6 5。 «銅溶出量之測量方法》 098120955 14 201009115 藉由基底之銅溶出量的測量，來確認取代反應之有無。於 上述鑛敷處理之後，針對鍍敷液使用ICp電漿發光分光分析 裝置SPS 3000(精工設備股份有限公司製），並以一般方法測 量鍍敷液中之銅溶出量(銅檢測濃度測量的結果係在檢測 出銅的情形下，將引起銅溶解而針對精細圖案施以鍍敷處理 則會有斷線之可能性的情形判定為「不良」，而未見到銅檢 測出者判定為「良好」，測量結果示於表3，判定結果示於 ❿表4。 <滲出之有無與析出速度之測量用的鍍敷方法> 「滲出之有無」與「析出速度」係針對圖丨所概略表示之 基板（以下稱為「BGA試驗用基板」）進行非電解鍍錫而測 量。使用PAC200(MURATA股份有限公司製，商品名）將bga 試驗用基板一片在50°c下進行脫脂處理5分鐘其後，進 行水洗。其次，使用ME0X(MURATA股份有限公司製商 ❿品名）在3〇〇C下進行钱刻處理2分鐘，其後，進行水洗。接 著，使用10容量％之稀硫酸，進行25°C下之酸洗淨3〇秒鐘， 其後’進行水洗。再來，使肖JPCAT(曰本高純度化學股份 有限公司製，商品名）在机下進行活性化處理2分鐘其 後’進行水洗。 、 於燒杯中置入下述表i之組成的還原型非電解鍵锡液 5〇0mL，並於其中同時將圖1所概略表示之BGA試驗用基 板浸潰1小時來進行鍍敷處理。鍍敷處理中之鍍敷液溫度係 098120955 15 2〇1〇〇9115 65°c ’ pH 係 6 5。 «爹出之有無的測量方法>> ^針ft BGA試驗用基板之鍍數試驗，測量ι⑼帅精細 圖==錫的滲出有無。「滲出之有無」係採用光學顯微鏡 以現進行。將可見到滲出者判定為不良，未見到渗出者判 定為良好，㈣結果示於表3，判定結果示於表4。 «析出速度之測量方法>〉 析出速度」騎對形成有⑽之BGA試驗用基板之膜 厚Λ量用墊’使用螢光X射線分析裝置SFT9255(精工設備 股份有限公司製）’依-般方法測量錫膜之厚度，將產業上 #常有用之錫析出速度為5μιη/1小時以上之析出速度者判 定為良，錫析出速度未滿5μιη/1小時者係因析出速度緩慢 而非為產業上有用者，判定為不良，測量結果示於表3，判 定結果示於表4。 098120955 16 201009115 [表1] 實施例1 實施例2 錫化合物 氯化亞錫 10g/L(以金屬錫形式言 &化亞踢 10g/L(以金屬錫形式計、Acid, ethylenediaminetetraacetic acid), NTA (Nitril〇triacetic octavalent, nitrogen triacetate) and citric acid' and reduced sodium electroless tin plating solution using sodium carbonate as a pH adjuster, but because of the easy generation of tin Abnormal precipitation, the plating solution is unstable, and the deposition rate is slow, and it is difficult to perform stable operation, so it is not practical. [Patent Document 1] Japanese Laid-Open Patent Publication No. SHO63-230883 [Non-Patent Document 1] Surface Technology, Vol. 44, No. 11, (1993) No. 1 to 2, page 107 [Invention] PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the background of the prior art described above, and an object thereof is to provide a reduced-type electroless tin plating bath which suppresses substitution reaction for copper or a copper alloy belonging to a parent material. The high-speed and stable precipitation reaction is carried out, and the plating solution is stable and has high productivity. Even in the case of a fine shape, there is no disconnection 'no tin oozing, and it can withstand practical use. (Means for Solving the Problem) The inventors of the present invention have carefully examined and found that, by using at least a water-soluble tin compound, a water-soluble titanium compound, an organic compounding agent, and "composed of mercaptans and sulfides". The reduced-type electroless tin plating solution selected as a component of the group can suppress substitution reaction of copper or copper alloy belonging to the parent material, has stable tin deposition rate, and can achieve superior bath stability. Sex and the like to complete the present invention. That is, the present invention provides a reduced-type electroless tin plating bath characterized by 098120955 4 201009115 as 'at least a water-soluble tin compound, a water-soluble compound, an organic misalignment, and a handle composed of a mercaptan and a sulfide. The organic selection of the towel is chosen as a constituent. 13 Agent j Further, the present invention provides a method for producing a kick film, characterized in that the upper <reduced electroless plating solution* is subjected to an electroless bell. — X 。 The present invention provides a tin film obtained by electroless plating using the above-described reduced-type tin plating solution. (Effect of the Invention) According to the present invention, it is possible to provide a reduction-type electroless tin plating solution which suppresses a substitution reaction with respect to a copper material of a parent material or a copper material of a parent material, and can suppress a steel elution plating solution and can perform high speed. And the stable number of precipitation reaction bonds of tin is stable, and even if the shape of the parent material copper or the parent material copper alloy is fine, there is no wire breakage, no tin oozing, even for finely spaced electronic parts, The tin film grows fast and thicker on copper or copper alloys, while the ® can withstand practical conditions. [Embodiment] Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily changed within the scope of the technical idea. The reduced type electroless tin plating bath of the present invention must contain a water-soluble tin compound. The water-soluble tin compound may be a supply source of tin, and is not limited thereto, and is preferably a mineral acid salt of a tin, a carboxylate, an alkanesulfonate or an alkane 098120955 5 201009115. One or more selected from the group consisting of hydroxides and metastannic acids. These water-soluble tin compounds may be used alone or in combination of two or more. As the valence (oxidation number) of tin of the above-mentioned water-soluble tin compound, either one or four mussels can be used, and from the viewpoint of the deposition rate, it is preferably bivalent. That is, it is preferable to use a stannous compound. Specific examples thereof include inorganic acid salts of tin such as stannous chloride, tin chloride, arsenic sulfate, tin sulfate, and tin pyrophosphate; stannous citrate, tin citrate, stannous oxalate, and tin oxalate; a carboxylate of tin; a tin alkoxide such as tin methanesulfonate, tin 1-ethanesulfonate, tin 2-ethanesulfonate, tin 1-propanesulfonate or tin 3-propanesulfonate; Alcoholic acid tin, a small amount of acid tin, a base of a propyl group, a tin, a tin, a thiol sulfonate, a tin hydroxypropane sulfonate, a tin sulphate; a hydroxide of tin such as stannous hydroxide or tin hydroxide; and metastannic acid. Among these, in terms of mineralization performance, cost, ease of availability, etc., it is preferable to vaporize stannous or stannous sulfate. The above-mentioned water-soluble tin compound 3 of the reduced-type non-electrolytic tin bath towel of the present month is not particularly limited, and is usually 〇.5 g/ in terms of metal tin as a whole of the reduced-type electroless tin bath liquid. L~l〇0g/L, preferably 5g/L~3Gg/L 'Special material 1Gg/L~2Gg/L. #also turned over the non-electrolytic tin bath liquid tin content is too small, the tin film precipitation rate is slow, there are unpractical materials and 'reduced type non-electrolytic tin bath liquid metal tin content is too much, then there is tin The water-soluble tin compound of the supply source is difficult to dissolve. 098120955 6 201009115 The (four) difficult electrolysis liquid of the present invention contains a water-soluble titanium compound. The water-soluble titanium compound is not particularly limited as long as it is used as a reducing agent. Specifically, in terms of weaving properties and ease of availability, examples include titanium trichloride, trihalide molybdenum, and three deserts. Titanium or the like - titanium nitride; titanium sulfate and the like. As the valence (oxidation number) of titanium, since the divalent titanium compound is unstable, the valley is easily oxidized to become tetravalent, and since the tetravalent titanium compound itself is not oxidized, electrons cannot be supplied, in this case, Preferably, it is trivalent. The water-soluble titanium compound may be used alone or in combination of two or more. Among these, titanium trichloride is particularly preferable from the viewpoints of plating performance and ease of availability. The content of the titanium-containing titanium compound of the county-age electrolyzed liquid towel of the present invention is not particularly limited, and is generally 〇.〇lg/L in terms of titanium metal as a whole of the reduced-type electroless tin plating solution. L〇〇g/L, preferably 鏖〇.lg/L~2〇g/L' is particularly preferably lg/L~1〇g/L. When the content of the water-soluble titanium compound in the reduced non-electrolytic recording liquid is too small, the precipitation rate of the tin film is slow, and it is not practical, and the amount of the water-soluble titanium compound in the electroless tin plating solution is too large. In the case where the supply of tin in the plating solution is abnormally precipitated, the stability of the bath is not good, and stable operation cannot be performed. The reduced electroless tin plating bath of the present invention must further contain an organic binder. The organic complexing agent is not particularly limited, and is preferably an amine group-containing nucleus, a silk-containing fluorenyl phosphine, a bribed phosphine, a phenylphosphonic acid, a stilbene phosphine, an alkali metallurgical phase thereof, The threatening gold material and its recorded salt 098120955 201009115 One or more of the selected groups. The above-mentioned amine group-containing carboxylic acid is not particularly limited, and specific examples thereof include tri-extension ethyltetraamine hexaacetic acid, bis-, triamine pentaacetic acid, ethylidene diamine tetraacetic acid, and propylene. Diamine tetraacetic acid, _ethylidene diamine triacetate, succinyl triacetate, nitrotripropionic acid, lysine diacetate, ethyl acetate = diacetic acid, glycine acid, glycylglycine, two Risky τ^ soil ethylglycine, noiline acid, L-glutamic acid diacetic acid, etc. Further, the above-mentioned amine group-containing mercaptophosphonic acid is not particularly limited, and specifically, s, nitrotrimethylenephosphonic acid, ethylidene, methylphosphonic acid, and Ethyltriamine pentadecylphosphonic acid, hexamethylene-amine tetradecylphosphonic acid, hexamethylenetriamine penta methylene phosphonic acid, and the like. Further, the amine hydroxy group is not particularly limited as the above-mentioned hydroxyl group-containing phosphonic acid. Specific examples thereof include 1-hydroxyethylidene-fluorene, hydrazine diphosphonic acid and the like. Further, the phenylphosphonic acid is not particularly limited, and specific examples thereof include 3-decyloxyphenylphosphonic acid and the like. Further, the benzylphosphonic acid is not particularly limited, and specific examples thereof include 3-methylbenzylphosphonic acid and 4-cyanobenzylphosphonic acid. β, the organic complex compound may be used singly or in combination of two or more kinds to reduce the amount of the above-mentioned organic compound in the reduced electroless tin plating bath of the present invention, and is not particularly limited with respect to the reduced electroless tin plating. The whole liquid is preferably lg/L to 500 g/L', preferably l〇g/L to 2〇〇g/L, and Du Changte is preferably 50 g/L to 150 g/L. When the amount of organic misregistration in the reduced electroless tin plating bath is too small, 098120955 8 201009115 is too small, the mismatching force is insufficient, and the recording fluid becomes unsuccessful, and the effect of the compounding agent is not exhibited, and if too much, There will be cases where it is difficult to dissolve in water, etc. 'The inability to see the progress as a wrong agent is improved, and there is an uneconomic situation. The reduced electroless tin plating bath of the present invention must contain an organic sulfur compound selected from the group consisting of thiols and sulfides. The term "mercaptan" refers to a compound having "-SH" in the molecule. The term "sulfide" refers to a compound having "-s-" in the molecule, and the group bonded to s is not limited to alkyl or green, but may also be aeetyl (: h or the like).酼 酼 . β β β β β β β 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化 硫化There is no particular limitation, and specifically, it may be exemplified by: 1. propanethiol M-butyl mercaptan, decyl dithiol, u-propylene dithiol, ... butyl thiol, W pentanethiol,己• hexanedithiol, 2-aminoethyl ethanethiol, 3_wind thio-u-propylene glycol, Μ_dihydrothio-butanediol, 3-hydroxythiopropyl acetoacetate, benzene thiol, benzene Trithiol, ? ^ ^ + 2,3, dichlorobenzene thiol, 2,4-dimethyl basic thiol, 2-amino phenyl thiol, raccoin 2, thiophene benzoic acid, hydrogen Sulfur-based bites, etc. The above-mentioned sulfides are not particularly limited, and specific examples thereof include methyl-based acetoacetic acid (S-methylthioacetic acid, (3)3SCH2C〇〇H), and methyl sulfide. Propionic acid, methyl sulphuric acid, sulphate, ethene (tetra), propyl thiopropyl Butylthiopropionic acid, methionine, (10)-based sulfide, 2-aminophenyl 098120955 201009115 phenyl sulfide, propyl propyl sulfide, dibutyl sulfide, butyl ethyl sulfide, Diethyl disulfide, diisobutyl disulfide, dimethyl disulfide, dimethyl trisulfide, etc. These organic sulfur compounds may be used alone or in combination of two or more. Among the organic sulfur compounds selected from the group consisting of thiols and sulfides, the above-mentioned effects are more remarkable, so sulfides are particularly preferred. The electroless tin plating solution of the present invention is a reduction type instead of The knowledge of the composition of the tin-plating bath is useless in the electroless tin plating bath. In particular, the effect of the present invention is to suppress the dissolution of copper due to the substitution reaction, even if the electronic components are finely partitioned. Wuxi oozes out and allows the tin film to grow rapidly on steel or copper alloys. These effects are all characteristic of the reduced type electroless tin plating bath. Therefore, it is generally not considered that it will be in the substitution type tin plating bath. Known ingredients The effect of the above-mentioned organic sulfur compound in the reduced type electroless tin plating bath of the present invention is not particularly limited as long as it is added to the reduced type electroless tin plating bath. The total amount of the reduced electroless tin plating solution is usually 0.1 ppm to 1 ppm, preferably 1 ppm to 1 ppm, particularly preferably 5 ppm to 1 0 ppm. When the content of the organic sulfur compound in the tin plating bath is too small, the deposition rate is insufficient, and in the case where the plating treatment is performed on the inner interval, there is a case where a short circuit occurs due to tin bleed out, etc. There are cases where problems such as difficulty in dissolving in water occur, and plating liquid is unstable. 098120955 10 201009115 In addition to the above-mentioned essential components, the reduced-type electroless tin plating bath of the present invention may optionally contain the following composition in the reduced-type electroless tin plating bath of the present invention and use 1 to cause plating. The pH of the liquid is kept constant, and the source of the tin which is used to prevent the valence (oxygen) from being divalent is deuterated into a tetravalent antioxidant, (4) the pinhole of the secret or the defoaming effect of the recording liquid A good surfactant, a tin-plated tincture, and the like.乍 乍 乍 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原Oxidized acid such as tartaric acid and malic acid. "Hai and other systems can be used alone or in combination of two or more. In the case where the amount of the buffer in the reduced-type non-electrolyzed liquid of the invention is not contained in the amount of the buffer, there is a case where it is difficult to exert a buffering effect. When the amount of the buffer is too large, the buffering effect is not observed. 〇-lg/L~1〇〇g/L^^^ lg/L^50g/L〇f When the antioxidant content in the antioxidant liquid is too small, there is a case where it is difficult to supply tin in the tin solution. When there is too much, 'there is a reduction of non-electrolyzed crucibles for stable transfer,' and the call is made (four) is good, which can not be used as the present g month> 098120955 11 201009115 interface included in the reduction type electroless tin plating solution The active agent is not particularly limited as long as it is a known surfactant, and a nonionic surfactant, an anionic surfactant, an amphoteric surfactant or a cationic surfactant may be used. These systems may use one type or cover two or more types. Examples of the nonionic surfactant include fluorenyl phenyl polyoxygen S, α-naphthyl polyalkoxy ester, dibutyl naphthyl polyalkoxy ester, and styrenated phenyl polyalkylene. An ether type nonionic surfactant such as an oxyester; an amine type nonionic surfactant such as an octylamine polyalkoxy ester, a hexenylamine polyalkoxy ester or a linolenic amine polyalkoxy ester. Examples of the anionic surfactant include a calcined sulfate such as sodium lauryl sulfate; a polyoxyethylene alkyl ether sulfate such as polyoxyethylene nonyl ether sulfate; and a polyoxyethylene alkylphenyl ether sulfate. ; alkylbenzene sulfonate and the like. As the amphoteric surfactant, 2-nonylalkyl-1-carboxyoxymethyl-1-pyridylethylpyrene beet face, oxime-stearyl group ν, Ν-dimethyl group can be mentioned. - hydrazine-carboxyoxymethyl betaine, lauryl decylamine oxide, and the like. Examples of the cationic surfactant include lauryl tridecyl ammonium salt, lauryl decyl ammonium betaine, lauryl pyridinium salt, oleyl imidazolium salt or stearylamine acetate. The shai or the like may be used singly or in combination of two or more kinds, and a nonionic surfactant or an amphoteric surfactant is preferred. The amount of the surfactant in the reduced-type electroless tin plating bath of the present invention is preferably 0.01 g/L to 20 g/L, and the desired performance can be exhibited without any 098120955 12 201009115. The brightening agent to be contained in the reduced electroless tin plating bath of the present invention is not particularly limited, and may be exemplified by furfural, benzylideneacetone, and n-benzaldehyde. Formaldehyde and other formaldehyde. These may be used alone or in combination of two or more. The gloss-containing content in the reduced-type electroless tin plating bath of the present invention is preferably 〇.〇lg/L 2 20 g/L, and the desired performance can be exhibited, and the content is not particularly limited. The plating conditions of the reduced electroless tin plating bath of the present invention described above are not particularly limited, and the temperature conditions are 4 (TC to 9 (TC is preferable, and 5 〇 t > c to 80 C is particularly preferable. The plating time is not particularly limited, and is preferably from 30 seconds to 5 hours, particularly preferably from 1 minute to 2 hours. ❿ Also as a pretreatment of the reduced electroless tin plating solution, a catalyst step can also be carried out. The activation of the substituted type electroless tin-plating material is not particularly limited, and the substitution type electroless tin plating liquid is not particularly limited, and a commercially available substituted type electroless tin plating solution can be obtained by a general method. According to the present invention, the electrolysis (4) (4) can suppress the substitution reaction of the steel alloy of the genus material or the mother riding material, so the bismuth steel in the plating process is even in the copper or parent material of the parent material. Du, (4) is also not broken under the shape, even if the finely divided electric is formed on the mother 1 when it is formed on the copper alloy, so that the tin film is formed into the steel alloy of the parent material copper or the parent material. The aspect is extremely effective. 098120955 13 201009115 The film thickness of the tin film obtained by the electroless plating of the reduced electroless tin plating solution of the present invention is not particularly limited, but is preferably from 0.05 μm to 50 μm, particularly preferably from 55 μm to 20 μm. EXAMPLES Hereinafter, the present invention will be further illustrated by way of examples and comparative examples, but the present invention is not limited to the examples within the scope of the invention, and is also a 'reduced type electroless tin plating bath. The concentration value in the composition, when the component contains crystal water, is the concentration value obtained by the mass of the crystal water not included. <Plating method for measuring the copper elution amount> Using PAC2〇0 ( MURATA Co., Ltd., product name) Five sheets of pure copper plate of 0.1 dm2 were simultaneously degreased at 5 (r5, and then washed). Then, MEOX (MURATA Co., Ltd. The residue was treated at 30 ° C for 2 minutes, and then washed with water. Then, using 10% by volume of dilute sulfuric acid, the acid was washed at 25 ° C for 30 seconds. Then, it was washed with water. , using JPCAT (Japan High Purity Chemical Co., Ltd., trade name) was activated at 6 yc for 2 minutes. Thereafter, it was washed with water. In a beaker, 100 mL of a reduced-type electroless tin plating solution having the composition shown in Table 1 below was placed in the beaker. The above five pure copper plates were immersed for 2 hours for plating treatment. The plating solution temperature in the plating treatment was 65 〇c, 1) 11 series 65. «The measurement method of copper dissolution amount 098120955 14 201009115 by The presence or absence of the substitution reaction was measured by measuring the amount of copper eluted from the substrate. After the above-described mineralization treatment, an ICp plasma emission spectroscopic analyzer SPS 3000 (manufactured by Seiko Instruments Co., Ltd.) was used for the plating solution, and measured by a general method. The amount of copper eluted in the plating solution (the result of the copper detection concentration measurement is that when copper is detected, the copper is dissolved and the plating is applied to the fine pattern, and the possibility of disconnection is determined as " "Bad", but the copper tester did not see "good", the measurement results are shown in Table 3, and the results are shown in Table 4. <Plating method for measuring the presence or absence of bleed and the measurement of the deposition rate> "The presence or absence of oozing" and "precipitation rate" are electrolessly performed on the substrate (hereinafter referred to as "BGA test substrate") schematically shown in the figure. Measured by tin plating. One of the bga test substrates was subjected to degreasing treatment at 50 ° C for 5 minutes using PAC200 (manufactured by MURATA Co., Ltd., trade name), and then washed with water. Next, ME0X (manufactured by MURATA Co., Ltd.) was used for the engraving treatment at 3 ° C for 2 minutes, and then washed with water. Subsequently, 10% by volume of dilute sulfuric acid was used, and the acid was washed at 25 ° C for 3 seconds, and then washed with water. In addition, Shaw JPCAT (trade name, manufactured by Sakamoto High Purity Chemical Co., Ltd.) was subjected to activation treatment for 2 minutes, and then washed with water. Into the beaker, 5 〇 0 mL of a reduced-type non-electrolytic bond tin liquid having the composition of the following Table i was placed, and the BGA test substrate schematically shown in Fig. 1 was simultaneously immersed for 1 hour to carry out a plating treatment. The plating solution temperature in the plating treatment is 098120955 15 2〇1〇〇9115 65°c 'pH system 6 5 . «Measurement method for the presence or absence of the &;> ^The number of plating tests for the substrate of the needle ft BGA test, and the measurement of the ι(9) handsome fine figure == the presence or absence of tin bleed. The presence or absence of "exudation" was carried out using an optical microscope. It can be seen that the exudate is judged to be defective, and the exudate is not judged to be good, (4) the results are shown in Table 3, and the judgment results are shown in Table 4. «Measurement method of the deposition rate> The deposition rate is based on the film thickness of the BGA test substrate (10), and the fluorescent X-ray analyzer SFT9255 (manufactured by Seiko Instruments Co., Ltd.) is used. The method measures the thickness of the tin film, and judges that the precipitation rate of the tin which is often used in the industry is 5 μmη / 1 hour or more is good, and the rate of tin deposition is less than 5 μιη / 1 hour because the deposition rate is slow rather than the industry. The above-mentioned useful person was judged to be defective, the measurement results are shown in Table 3, and the determination results are shown in Table 4. 098120955 16 201009115 [Table 1] Example 1 Example 2 Tin compound Stannous chloride 10 g/L (in the form of tin metal & KIA 10g/L (in the form of metal tin,

欽化合物 三氣化鈦 50g/L 三氣化鈦 50g/L 實施例3 氣化亞錫 10g/L(以金屬錫形式計)Qin compound tri-titanized titanium 50g / L three-titanized titanium 50g / L Example 3 gasified stannous 10g / L (in the form of metal tin)

有機錯合劑 硝基三亞甲基膦酸 5〇g/L 硝基三亞甲基膦酸 50g/L 有機硫化合物 氫硫基°比咬 lOOppm 甲硫胺酸 lOOppmOrganic Twisting Agent Nitrotrimethylenephosphonic acid 5〇g/L Nitrotrimethylenephosphonic acid 50g/L Organic sulfur compound Hydrogenthio group ratio bite lOOppm Methionine lOOppm

L氣化鈦 50g/LL gasification titanium 50g/L

硝基三亞甲基膦酸 50g/L 乙酿基硫化物 lOOppm 實施例4 氮化亞錫 10g/L(以金屬錫形式計)Nitrotrimethylenephosphonic acid 50g/L Ethyl sulfide nOOppm Example 4 Stannous nitride 10g/L (as metal tin)

三氣化鈦 50g/LThree gasification titanium 50g/L

硝基三亞甲基膦酸 _50g/L 實施例5 參 甲烷磺酸錫 10g/L(以金屬錫形式計) 二甲基二硫化物 _lOOppmNitrotrimethylenephosphonic acid _50g/L Example 5 Reference Tin sulfonate 10g/L (as metal tin) Dimethyl disulfide _lOOppm

三氣化鈦 50g/LThree gasification titanium 50g/L

硝基三亞甲基膦酸 50g/L 實施例6 實施例 氣化亞錫 10g/L(以金屬錫形式計) 氣化亞錫 10g/L(以金屬錫形式計) 甲硫胺酸 lOOppmNitrotrimethylenephosphonic acid 50g/L Example 6 Example Vaporized gas 10g/L (as metal tin) Gasified stannous 10g/L (as metal tin) Methionine lOOppm

三氣化鈦 50g/L 三氣化鈦 50g/LThree gasification titanium 50g/L three gasification titanium 50g/L

硝基三醋酸 50g/L 甘胺酸 50g/L 甲硫胺酸 lOOppm 甲硫胺酸 lOOppm 實施例8 實施例9 098120955 氣化亞錫 10g/L(以金屬錫形式計) 氣化亞錫 10g/L(以金屬錫形式計）Nitrotriacetic acid 50g/L Glycine 50g/L Methionine 100ppm Methionine 100ppm Example 8 Example 9 098120955 Vaporized stannous 10g/L (as metal tin) Gasified stannous 10g/ L (in terms of metal tin)

氣化鈦 50g/L 三氣化鈦 5〇g/L 17Gasified titanium 50g/L Three-titanium carbide 5〇g/L 17

甲基苄基膦酸 50g/L 1-經基亞乙基-1,1-二膦酸 50g/L 酸 胺 硫 曱 酸 胺 硫 甲Methylbenzylphosphonic acid 50g/L 1-Phenylethylidene-1,1-diphosphonic acid 50g/L acid amine sulfuric acid amine sulfur

m. I 201009115 [表2]m. I 201009115 [Table 2]

No. 錫化合物 欽化合物 有機錯合劑 有機硫化合物 比較例1 氣化亞錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 硝基三亞甲基膦酸 50g/L 無 比較例2 甲烷磺酸錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 硝基三亞甲基膦酸 50g/L 無 比較例3 氣化亞錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 硝基三醋酸 50g/L 無 比較例4 氣化亞錫 10g/L(以金屬錫形式計） 三氣化欽 50g/L 甘胺酸 50g/L 無 比較例5 氣化亞錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 曱基苄基膦酸 50g/L 無 比較例6 氣化亞錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 1-羥基亞乙基-1,1-二膦酸 50g/L 無 比較例7 氣化亞錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 焦磷酸 50g/L 無 比較例8 氣化亞錫 10g/L(以金屬錫形式計） 三氣化鈦 50g/L 硝基三醋酸 50g/L 硫代尿素 80g/L 098120955 18 201009115 [表3]No. tin compound compound organic organic compound sulfur compound comparative example 1 vaporized stannous 10g / L (in terms of metal tin) three gasified titanium 50g / L nitrotrimethylene phosphonic acid 50g / L no comparison example 2 Tin methane sulfonate 10g/L (as metal tin) Trititanized titanium 50g/L Nitrotrimethylene phosphonic acid 50g/L No comparative example 3 Gasified stannous 10g/L (in terms of metal tin) III Gasification Titanium 50g/L Nitrotriacetic Acid 50g/L No Comparative Example 4 Gasified Stannous 10g/L (as Metal Tin) Trigastric 50g/L Glycine 50g/L No Comparative Example 5 Gasification Stannous 10g / L (in the form of metal tin) three gasified titanium 50g / L mercapto benzyl phosphonic acid 50g / L no comparative example 6 gas stannous 10g / L (in the form of metal tin) three gasified titanium 50g/L 1-hydroxyethylidene-1,1-diphosphonic acid 50g/L No comparative example 7 vaporized stannous 10g/L (as metal tin) Tricarbide titanium 50g/L pyrophosphate 50g/L No Comparative Example 8 Gasified stannous 10g/L (as metal tin) Tri-titanized titanium 50g/L Nitrotriacetic acid 50g/L Thioacetate 80g/L 098120955 18 201009115 [Table 3]

No. 銅溶出量 滲出之有無 析出速度 (μτη/1 小時） 實施例1 檢測界限以下 (0.3ppm 以下） 無 8/xm/l小時 實施例2 檢測界限以下 (0.3ppm 以下） 無 小時 實施例3 檢測界限以下 (0.3ppm 以下） 無 6μπι/1小時 實施例4 檢測界限以下 (0.3ppm 以下） 無 7μτη/1小時 實施例5 檢測界限以下 (0.3ppm 以下） 無 8μαι/1小時 實施例6 檢測界限以下 (0.3ppm 以下） 無 9μτη/1小時 實施例7 檢測界限以下 (0_3ppm 以下） 無 6μπι/1小時 實施例8 檢測界限以下 (0_3ppm 以下） 無 6μιη/1小時 實施例9 檢測界限以下 (0.3ppm 以下） 無 7/λπ/Ι小時 比較例1 檢測界限以下 (0.3ppm 以下） 有 2μηι/1小時 比較例2 檢測界限以下 (0.3ppm 以下） 有 2/xm/l小時 比較例3 檢測界限以下 (0.3ppm 以下） 有 1.5/xm/l 小時 比較例4 檢測界限以下 (0.3ppm 以下） 有 2μτη/1小時 比較例5 檢測界限以下 (0.3ppm 以下） 有 2μιη/1小時 比較例ό 檢測界限以下 (0.3ppm 以下） 有 2/xm/l小時 比較例7 5ppm 有 1.5/xm/l 小時 比較例8 53ppm 無 2μην!小時 098120955 19 201009115 [表4]No. The presence or absence of precipitation rate of copper elution amount (μτη/1 hour) Example 1 Detection limit or less (0.3 ppm or less) No 8/xm/l hour Example 2 Detection limit or less (0.3 ppm or less) No hour Example 3 Below detection limit (0.3 ppm or less) No 6 μm / 1 hour Example 4 Detection limit or less (0.3 ppm or less) No 7 μτη / 1 hour Example 5 Detection limit or less (0.3 ppm or less) No 8 μ α / 1 hour Example 6 Detection limit The following (0.3 ppm or less): 9 μτη / 1 hour Example 7 Detection limit or less (0 - 3 ppm or less) No 6 μm / 1 hour Example 8 Detection limit or less (0 - 3 ppm or less) No 6 μm / 1 hour Example 9 Detection limit or less (0.3 ppm The following is not available. 7: λπ / Ι hr. Comparative Example 1 Detected limit or less (0.3 ppm or less) 2 μηι / 1 hour Comparative Example 2 Detection limit or less (0.3 ppm or less) 2/xm/l hr Comparative Example 3 Detected limit or less ( 0.3ppm or less) 1.5/xm/l hours Comparative Example 4 Detection limit or less (0.3ppm or less) 2μτη/1 hour Comparative Example 5 Detection limit or less (0.3ppm or less) 2μιη/1 hour Comparative Example 以下 Below the detection limit (0.3 ppm or less) 2/xm/l hour Comparative Example 7 5ppm 1.5/xm/l hour Comparative Example 8 53ppm None 2μην! Hours 098120955 19 201009115 [Table 4]

No. 銅溶出量 之判定 滲出之有無 之判定 析出速度 之判定 實施例1 良好 良好 良好 實施例2 良好 良好 良好 實施例3 良好 良好 良好 實施例4 良好 良好 良好 實施例5 良好 良好 良好 實施例6 良好 良好 良好 實施例7 良好 良好 良好 實施例8 良好 良好 良好 實施例9 良好 良好 良好 比較例1 良好 不良 不良 比較例2 良好 不良 不良 比較例3 良好 不良 不良 比較例4 良好 不良 不良 比較例5 良好 不良 不良 比較例6 良好 不良 不良 比較例7 不良 不良 不良 比較例8 不良 良好 不良 098120955 20 201009115 如表4所示般，實施例1〜9係在銅溶出量之判定、滲出之 有無之判定、析出速度之判定的任一項目均為良好之判定， 而比較例1〜6係銅溶出量之判定為良好，但在滲出之有無之 判定、析出速度之判定的兩項目中，均為不良。比較例7 及比較例8係銅溶出量之判定為不良，可認為是非還原型之 析出，該等均屬於不可使用者。 (產業上之可利用性） • 本發明之還原型非電解鍍錫液係因為銅溶出量少，沒有斷 線，錫之析出速度快，且沒有錫之滲出而無短路現象，故為 可廣泛利用於近年來之經過精細間隔化的電子零件等。 本案申請係根據2008年6月26日所申請之日本專利申請 案之特願2008-167997，其申請之全部内容均引用至此，並 援用為本案發明之說明書揭示内容。 【圖式簡單說明】 參 圖1係在實施例中為了測量「滲出之有無」與「析出速度」 而所使用之BGA測試用基板之概略圖。 098120955 21No. Determination of the amount of copper elution The determination of the rate of leaching was determined. Example 1 Good and good Example 2 Good and good Good Example 3 Good and good Good Example 4 Good good Good Example 5 Good good Good Example 6 Good Good and good example 7 Good and good Example 8 Good and good Example 9 Good and good Good Comparative Example 1 Good and poor defects Comparative Example 2 Good and poor defects Comparative Example 3 Good and poor defects Comparative Example 4 Good and poor defects Comparative Example 5 Good defects Comparative Example 6 Good Defects Comparative Example 7 Adverse Defects Comparative Example 8 Defective Good Defects 098120955 20 201009115 As shown in Table 4, Examples 1 to 9 were judged in the amount of eluted copper, the presence or absence of exudation, and the deposition rate. Any of the judged items was judged to be good, and the amount of copper elution in Comparative Examples 1 to 6 was judged to be good, but both of the determinations of the presence or absence of bleeding and the determination of the deposition rate were both bad. In Comparative Example 7 and Comparative Example 8, the amount of copper eluted was judged to be defective, and it was considered to be a non-reducing type of precipitation, and all of them were unuserable. (Industrial Applicability) The reduction type electroless tin plating solution of the present invention has a small amount of copper elution, no disconnection, a high deposition rate of tin, and no trace of tin and no short circuit, so that it can be widely used. It is used in electronic parts that have been finely divided in recent years. The application of the present application is based on Japanese Patent Application No. 2008-167997, filed on Jun. 26, 2008, the entire disclosure of which is hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a BGA test substrate used for measuring "the presence or absence of bleeding" and "precipitation rate" in the examples. 098120955 21

Claims (1)

201009115 七、申請專利範圍： γ•種還原型非電解鍍錫液，其特徵為 ，至少以水溶性錫 。物水溶性鈦化合物、有機錯合劑、及由硫醇類與硫化 物類所組成群中選擇之有機硫化合物作為構成成分。 •如申4專利範圍第1項之還原型非電解鍍錫液，其中’ 述水冷性锡化合物係由锡之無機酸鹽、羧酸鹽、烷磺酸 元醇’酸鹽、風氧化物及偏錫酸(metastannicacid)所組 成群中選擇之一種或兩種以上。 3. 如申请專利範圍第1或2項之還原型非電解鍍錫液，其 中，上述水溶性錫化合物係氯化亞錫、氣化錫、硫酸亞錫、 硫酸錫、焦磷酸錫、擰檬酸亞錫、檸檬酸錫、草酸亞錫、草 酸錫、曱烷磺酸錫、1-乙烷磺酸錫、2-乙烷磺酸錫、1-丙烷 ~酸錫、3-丙烷磺酸錫、甲醇磺酸錫、羥基乙烷小磺酸錫、 1-經基丙烷磺酸錫、羥基乙烷_2_磺酸錫、i_羥基丙烷_3_ 磺酸錫、氫氧化亞錫、氫氧化錫或偏錫酸。 4. 如申请專利範圍第1至3項中任一項之還原型非電解鍍 錫液’其中’上述水溶性鈦化合物係函化鈦或硫酸鈦。 5_如申請專利範圍第4項之還原型#電解鍍錫液，其中， 上述齒化鈦係三氯化鈦、三碘化鈦或三溴化鈦。 6.如申請專利範圍第丨至5項中任一項之還原型非電解鍍 錫液’其中’上述有機錯合劑係由含胺基之竣酸類、含胺基 之亞曱基膦酸類、含羥基之膦酸類、苯膦酸類、苄基膦酸類、 098120955 22 201009115 該等之鹼金屬鹽、該等之鹼土類金屬鹽及該等之銨鹽所組成 群中選擇之一種或兩種以上。 7. 如申請專利範圍第6項之還原型非電解鍍錫液，其中， 上述含胺基之羧酸類係三伸乙基四胺六醋酸、二伸乙基三胺 五醋酸、伸乙基二胺四醋酸、丙烷二胺四醋酸、羥基伸乙基 二胺三醋酸、硝基三醋酸、硝基三丙酸、亞胺二醋酸、羥基 m 乙基亞胺二醋酸、甘胺酸、甘胺醯甘胺酸、二羥基乙基甘胺 φ 酸、麩醯胺酸或L-麩醯胺酸二醋酸。 8. 如申請專利範圍第6項之還原型非電解鍍錫液，其中， 上述含胺基之亞甲基膦酸類係硝基三亞甲基膦酸、伸乙基二 胺四亞甲基膦酸、二伸乙基三胺五亞曱基膦酸、六亞甲基二 胺四亞甲基膦酸或六亞甲基三胺五亞甲基膦酸。 9. 如申請專利範圍第6項之還原型非電解鍍錫液，其中， 上述含羥基之膦酸類係1-羥基亞乙基-1,1-二膦酸。 k Ο 10.如申請專利範圍第6項之還原型非電解鍍錫液，其中， 上述苯膦酸類係3-甲氧基苯膦酸。 11. 如申請專利範圍第6項之還原型非電解鍍錫液，其中， 上述苄基膦酸類係3-曱基苄基膦酸或4-氰基苄基膦酸。 12. 如申請專利範圍第1至11項中任一項之還原型非電解 鍍錫液，其中，上述硫醇類係1-丙硫醇、1-丁硫醇、1，2-乙 二硫醇、1,2-丙二硫醇、1,4-丁二硫醇、1,5-戊二硫醇、1，6-己二硫醇、2-胺基乙硫醇、3-氫硫基-1，2-丙二醇、1，4-二氩 098120955 23 201009115 硫基-2,3-丁二醇、3-氫硫基丙酸乙酯、苯硫醇、苯三硫醇、 2,3-二氣基苯硫醇、2,4-二曱基苯硫醇、2-胺基苯硫醇、2-萘硫醇、氫疏基安息香酸、氫硫基定。 13. 如申請專利範圍第1至12項中任一項之還原型非電解 鍍錫液，其中，上述硫化物類係曱硫基醋酸、曱硫基丙酸、 甲硫基丁酸、乙硫基醋酸、乙硫基丙酸、丙硫基丙酸、丁硫 基丙酸、甲硫胺酸、乙醯基硫化物、2-胺基苯基苯基硫化物、 乙醯基硫化物、烯丙基硫化物、丁基硫化物、丁基乙基硫化 物、二乙基二硫化物、二異丁基二硫化物、二曱基二硫化物、 三曱基三硫化物。 14. 一種錫膜之製造方法，其特徵為，採用申請專利範圍 第1至13項中任一項之還原型非電解鍍錫液而進行非電解 鑛敷。 15. —種錫膜，係藉由採用申請專利範圍第1至13項中任 一項之還原型非電解鍍錫液來進行非電解鍍敷而獲得。 098120955 24201009115 VII. Patent application scope: γ• species reduction type electroless tin plating bath, which is characterized by at least water-soluble tin. The water-soluble titanium compound, the organic complexing agent, and the organic sulfur compound selected from the group consisting of thiols and sulfides are used as constituent components. • The reduced electroless tin plating solution according to claim 1 of the scope of claim 4, wherein the water-cooling tin compound is a mineral acid salt of a tin, a carboxylate, an alkanesulfonate, an acid oxide, and One or more selected from the group consisting of metastannic acids. 3. The reduced-type electroless tin plating solution according to claim 1 or 2, wherein the water-soluble tin compound is stannous chloride, tin sulfide, stannous sulfate, tin sulfate, tin pyrophosphate, and lemon Stannous acid, tin citrate, stannous oxalate, tin oxalate, tin decane sulfonate, tin 1-ethane sulfonate, tin 2-ethane sulfonate, 1-propane-tin acid, tin 3-propane sulfonate , tin methoxide sulfonate, tin hydroxyethane sulfonate, tin 1-propylpropane sulfonate, tin hydroxyethane _2 sulfonate, tin i-hydroxypropane _3_ sulfonate, stannous hydroxide, hydroxide Tin or metastannic acid. 4. The reduced-type electroless tin plating solution according to any one of claims 1 to 3, wherein the water-soluble titanium compound is a titanium or titanium sulfate. 5_. The reduced type # electrolytic tin plating solution according to item 4 of the patent application, wherein the above-mentioned toothed titanium is titanium trichloride, titanium triiodide or titanium tribromide. 6. The reduced-type electroless tin plating solution according to any one of the above-mentioned claims, wherein the above-mentioned organic compounding agent is an amine group-containing phthalic acid group, an amine group-containing fluorenylphosphonic acid group, Hydroxyphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, 098120955 22 201009115 One or more selected from the group consisting of the alkali metal salt, the alkaline earth metal salt, and the ammonium salt. 7. The reduced-type electroless tin plating solution according to claim 6, wherein the amino group-containing carboxylic acid is triethylhexylamine hexaacetic acid, di-extended ethyltriamine pentaacetic acid, and ethylidene Amine tetraacetic acid, propane diamine tetraacetic acid, hydroxyl extended ethyl diamine triacetic acid, nitro triacetic acid, nitrotripropionic acid, imine diacetic acid, hydroxyl methyl ethyl imine diacetic acid, glycine acid, glycine Glyceric acid, dihydroxyethylglycine φ acid, glutamic acid or L-glutamic acid diacetic acid. 8. The reduced-type electroless tin plating solution according to claim 6, wherein the amino group-containing methylene phosphonic acid is nitrotrimethylene phosphonic acid or ethylidene diamine tetramethylene phosphonic acid And diethyltriamine pentadecylphosphonic acid, hexamethylenediaminetetramethylenephosphonic acid or hexamethylenetriaminepentamethylenephosphonic acid. 9. The reduced-type electroless tin plating solution according to claim 6, wherein the hydroxyl group-containing phosphonic acid is 1-hydroxyethylidene-1,1-diphosphonic acid. K Ο 10. The reduced-type electroless tin plating solution according to claim 6, wherein the phenylphosphonic acid is 3-methoxyphenylphosphonic acid. 11. The reduced-type electroless tin plating solution according to claim 6, wherein the benzylphosphonic acid is 3-mercaptobenzylphosphonic acid or 4-cyanobenzylphosphonic acid. 12. The reduced type electroless tin plating solution according to any one of claims 1 to 11, wherein the above mercaptan is 1-propanethiol, 1-butanethiol, 1,2-ethanedisulfide Alcohol, 1,2-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 2-aminoethanethiol, 3-hydrogen sulfide Base-1,2-propanediol, 1,4-diargon 098120955 23 201009115 thio-2,3-butanediol, ethyl 3-hydrothiopropionate, benzenethiol, benzenetrithiol, 2,3 - bis-phenylbenzenethiol, 2,4-dimercaptobenzenethiol, 2-aminobenzenethiol, 2-naphthylthiol, hydrocarbyl benzoic acid, thiophanate. 13. The reduced-type electroless tin plating bath according to any one of claims 1 to 12, wherein the sulfides are thiosyl acetic acid, thiosylpropionic acid, methylthiobutyric acid, and ethyl sulfide. Acetate, ethylthiopropionic acid, propylthiopropionic acid, butylthiopropionic acid, methionine, ethyl sulfonium sulfide, 2-aminophenyl phenyl sulfide, ethyl sulfonium sulfide, olefin Propyl sulfide, butyl sulfide, butyl ethyl sulfide, diethyl disulfide, diisobutyl disulfide, dimercapto disulfide, tridecyl trisulfide. A method of producing a tin film, comprising performing a non-electrolytic ore coating using the reduced-type electroless tin plating solution according to any one of claims 1 to 13. A tin film obtained by electroless plating using a reduced type electroless tin plating solution according to any one of claims 1 to 13. 098120955 24