TW200842496A - Printed circuit board and manufacturing method thereof - Google Patents

Printed circuit board and manufacturing method thereof Download PDF

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TW200842496A
TW200842496A TW97109629A TW97109629A TW200842496A TW 200842496 A TW200842496 A TW 200842496A TW 97109629 A TW97109629 A TW 97109629A TW 97109629 A TW97109629 A TW 97109629A TW 200842496 A TW200842496 A TW 200842496A
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Taiwan
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solder resist
alkali
wiring board
printed wiring
type solder
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TW97109629A
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Chinese (zh)
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TWI396041B (en
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Takahiro Yoshida
Takeshi Yoda
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Taiyo Ink Mfg Co Ltd
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  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)

Abstract

Provided is a printed circuit board which can be improved in plating adhesiveness to give high reliability and productivity by reducing development residues in opening portions such as a minute pad formed in a predetermined region of an alkali development type solder resist layer, and a manufacturing method thereof. An alkali development type solder resist layer containing a carboxyl group-containing urethane (meth)acrylate compound as a carboxyl group-containing resin is formed on a substrate surface with a conductor pattern formed thereon, and the alkali development type solder resist layer is exposed in a predetermined opening pattern, developed in a dilute aqueous alkaline solution, washed with water containing 30 to 1,000 ppm of divalent metal ions, and then thermally cured to form an opening portion at a predetermined position of the alkali development type solder resist layer.

Description

200842496 九、發明說明 【發明所屬之技術領域】 本發明有關一種例如軟性印刷配線板或要求柔軟性之 薄板之印刷配線板之製造方法以及印刷配線板。 術 技 前 先 近來隨著半導體零件的急速進步，電子機器逐漸傾向 於小型輕量化、高性能化、多機能化，爲迎合該等傾向， 克正進展印刷配線板之高密度化。對應於該等高密度化， 取代稱爲 QFP(Quad Plat Package，四方扁平封裝）、 SOP(Small Outline Package，小型輪廓封裝）等之1C封 裝，而改由稱爲 BGA(Ball Grid Array，球格柵陣歹ij)、 CSP(Chip Scale Package，晶片級封裝）等之1C封裝上 市。該等封裝基板或車載用印刷配線板中，與半導體等連 接之封裝基板上之墊片等之開口部，爲了施加用以提高可 靠度之鍍金等，故而使用阻焊劑。 進而，隨著該等印刷配線板或封裝基板所用之核心材 之薄片化的進展，已有例如TAB(Tape auto Bonding，捲 帶式自動接合）、T-BQA(Tape Ball Grid Array，捲帶式球 格柵陣列）、T-CSP(Tape Chip Scale Package，捲帶式晶片 級封裝）、UT-CSP(Ultra Thin Chip Scale Package，超薄 晶片級封裝）等上市。如此，藉由核心材變薄，使得阻焊 劑硬化收縮時的彎曲成爲問題。因此，使用該等在捲帶上 之核心材之情況，可使用輥對輥（roll-to-roll)法，由作業 200842496 性、信賴性、膜厚精度、平滑性之觀點觀之，而謀求乾膜 捲帶之阻焊劑。該等乾膜捲帶之阻焊劑係以薄片或輥狀供 給，於其形態之特性上，有必要於樹脂組成物中含有柔軟 性、造膜性優異之樹脂成分。 ^ 至於該等柔軟性、造膜性優異之樹脂成分，可列舉有 ~ 例如使橡膠狀化合物或1分子中具有至少1個羧基及2個 羥基之化合物與二醇化合物、聚異氰酸酯化合物之反應物 Φ 的末端異氰酸酯化合物，與1分子中具有聚合性不飽和 基、羧基以及至少1個羥基之化合物反應而得之感光性樹 脂（例如參考專利文獻1)。 然而，當該等柔軟性、造膜性優異之樹脂成分添加於 阻焊劑，由於顯像性降低、於微小墊片等之開口部產生顯 性殘渣、鍍金等之附著性劣化，而有良率、信賴性降低等 問題。於是’雖有藉由重複顯影而可能去除殘渣之情況， 但生產性降低而成爲問題。 Φ 專利文獻1:日本特開20〇3-192760號公報（申請專利 範圍等） 專利文獻2:日本特開2〇〇2-162739號公報（申請專利 範圍等） 專利文獻3 :日本特開2〇〇4-252485號公報（申請專利 範圍等） 專利文獻4:日本特開2〇〇7-7 1 966號公報（申請專利 範圍等） 200842496 【發明內容】 [本發明欲解決之課題] 鑑於該等先前技術之問題點，本發明之目的在於提供 一種印刷配線板之製造方法以及印刷配線板，該方法藉由 '抑制關於鹼顯影型阻焊劑層之特定部位中所形成之微小墊 "片等之開口部的顯影殘渣，而得以改善電鍍附著性、可獲 得高信賴性、生產性之印刷配線板。 [爲解決問題之手段] 爲達成上述課題，於使用用於UT-CSP等之柔軟性、 造膜性優異之鹼顯影阻焊劑之情況下，發現藉由變更顯影 後之水洗水，使抑制顯影殘渣成爲可能。 亦即，依據本發明之一觀點，其特徵爲：於形成有導 體圖案之基板表面上，形成含有含羧基之胺基甲酸酯（甲 基）丙烯酸酯化合物作爲含羧基之樹脂之鹼顯影型阻焊劑 Φ 層，使該鹼顯影型阻焊劑層經由特定的開口圖案予以曝 光，藉由稀鹼水溶液顯影，使用含30〜lOOOppm的二價金 屬離子的水洗水加以水洗後，藉由熱硬化，在前述鹼顯影 型阻焊劑層之特定位置形成開口部。 又，依據本發明之一觀點，其特徵爲具備形成有導體 圖案之基板、以及形成在該基板上且於特定位置形成有開 口部之鹼顯影型阻焊劑層，該鹼顯影型阻焊劑層含有含羧 基之胺基甲酸酯（甲基）丙烯酸酯化合物以及二價金屬離 子〇 -6 - 200842496 又，金屬離子濃度單位ppm係表示1公升試料中所 含之金屬離子毫克數的單位。 [發明效果] 依據本發明，可提供於鹼顯影型阻焊劑層之特定部位 中所形成之微小墊片等之開口部的顯影殘渣受到抑制，而 得以改善電鍍附著性、可獲得高信賴性、生產性之印刷配 線板。 【實施方式】 以下，就本發明之最佳實施形態加以詳述說明。 首先，本發明之印刷配線板之製造方法適用於對具有 難以顯影之微小墊片部（例如開口直徑爲20〜ΙΟΟμιη者）之 印刷配線板施加採用鹼顯影型阻焊劑之鍍金等之時。 本發明之印刷配線板之製造方法，其特徵爲於形成有 導體圖案之基板表面上，形成含有含羧基之胺基甲酸酯 (甲基）丙烯酸酯化合物作爲含羧基之樹脂之鹼顯影型阻焊 劑層，使該鹼顯影型阻焊劑層經由特定的開口圖案予以曝 光，藉由稀鹼水溶液顯影，使用含30〜lOOOppm的二價金 屬離子的水洗水加以水洗後，藉由熱硬化，在前述鹼顯影 型阻焊劑層之特定位置形成開口部。 亦即，本實施樣態之印刷配線板之製造方法具有以下 步驟。 1 .於形成有導體圖案之基板表面上’形成驗顯影型 -7- 200842496 阻焊劑層之步驟； 2.曝光步驟； 3 .藉由稀鹼水溶液予以顯影之步驟； 4.使用含30〜lOOOppm的二價金屬離子的水洗水之 水洗步驟； 5·(視需要）清洗水洗水之步驟； 6. 使基板乾燥之步驟 (步驟3〜6 —般總稱爲顯影步驟） 7. 熱硬化步驟。 所以，經過該等步驟，形成在形成有導體圖案之基板 表面上具備有在特定位置形成有開口部之鹼顯影型阻焊劑 層之印刷配線板。 首先，於形成有導體圖案之基板表面上形成後述之鹼 顯影型阻焊劑層。於該步驟中，就形成有導體圖案之基板 而言，可舉例如於使用有例如紙酚、紙環氧樹脂、玻璃布 環氧樹脂、玻璃聚醯亞胺、玻璃布/不織布環氧樹脂、玻 璃布/紙環氧樹脂、合成纖維環氧樹脂、氟·聚乙烯· ΡΡ〇·氰酸酯等之高頻電路用貼銅積層板等、全部等級 (FR-4等）之貼銅積層板、其他聚醯亞胺膜、pet膜、玻璃 基板、陶瓷基板、晶片板等上形成導電圖案之基板。 於該等基板表面上形成鹼顯影型阻焊劑層之步驟，有 使用液狀鹼顯影型阻焊劑之方法、以及使用具有鹼顯影型 阻焊劑層之乾膜之方法。 使用液狀鹼顯影型阻焊劑之情況時，以後述之有機溶 200842496 劑（D-1)調整黏度至適於塗佈方法之黏度，於形成有導體 圖案之基板上’於其全面上藉由浸塗法、流塗法、滾塗 法、棒塗佈法、網板印刷法、簾塗法等方法加以塗佈。隨 後，於約60〜100 °C之溫度，使鹼顯影型阻焊劑中所含之 有機溶劑（D-1)揮發乾燥（暫時乾燥）。藉此，形成不黏之鹼 顯影型阻焊劑層。 又’具有鹼顯影型阻焊劑層之乾膜，爲具有載體膜與 將鹼顯影型阻焊劑塗佈於該載體膜（或覆蓋膜）上並乾燥所 得之阻焊劑層以及可自阻焊劑層上剝離之覆蓋層之乾膜。 作爲載體膜，可使用10〜150μπι厚度之PET等之聚酯 膜、聚醯亞胺膜等。 鹼顯影型阻焊劑層係以有機溶劑（D-1 )將鹼顯影型阻 焊劑黏度降低至可塗佈於載體膜或覆蓋膜上之黏度後，使 用刮刀塗佈器、唇模塗佈器、連續塗佈器（comma co ate〇、薄膜塗佈器等，於載體膜（或覆蓋膜）上均一塗佈 例如1 〇〜1 5 0 μ m厚並乾燥所形成者。 至於覆蓋膜，可使用聚乙烯膜、聚丙烯膜等，但較好 其與鹼顯影型阻焊劑層之接著力比載體膜小者。 使用該等鹼顯影型阻焊劑之乾膜時，剝除覆蓋層，將 載體膜上之鹼顯影型阻焊劑層重疊於形成有導體圖案之基 板上。接著，藉由使用積層機等加以層壓，而在形成有導 體圖案之基板上形成驗顯影型阻焊劑層。此時，載體膜較 好.在曝光前或曝光後任一時刻予以剝離。又，層壓係以加 熱積層機，通常在60〜110°C、0.4MPa以上進行。此時， 200842496 藉由使用真空積層機，可抑制孔洞發生。 接著，如此所形成之鹼顯影型阻焊劑層以特定開口圖 案加以曝光。於該曝光步驟中，作爲活性能量腺之照射光 源，一般使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超 高水銀燈、氙氣燈或金屬鹵素燈之接觸或非接觸曝光機。 進而，亦可使用利用雷射光之雷射直接顯影（laser direct imaging)裝置 〇 藉此予以曝光之鹼顯影型阻焊劑層，使用稀鹼水溶液 加以顯影。此顯影步驟中，可使用浸漬法、噴淋法、噴霧 法等，但考慮後續步驟之水洗步驟之情況下，較好使用噴 霧法。 作爲顯影液，可使用例如氫氧化鉀、氫氧化鈉、碳酸 鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之含1價鹼金 屬鹽或銨鹽之稀鹼水溶液。 藉此顯影後之鹼顯影型阻焊劑層立即使用含30〜1000 ppm之2價金屬的水洗水予以水洗。 此水洗步驟中所用之水洗水中所含之2價金屬離子， 可舉例如鈣離子（Ca2 + )、鎂離子（Mg2 + )、緦離子（Sr2 + )、鋇 離子（Ba2 + )等。該等金屬離子對印刷配線板之絕緣性等無 不良影響而適合使用，尤其以鈣離子、鎂離子較好。 至於含該等2價金屬離子之化合物，可舉例如其氯化 物、氫氧化物、硫酸鹽、磷酸鹽、硝酸鹽、乙酸鹽等，但 不對印刷配線板帶來不良影響而言，較宜使用氯化物或氫 氧化物。 -10- 200842496 該等2價金屬離子之濃度，有必要爲3〇〜1〇〇〇ρρϊη。2 價金屬離子濃度小於3 0Ppm時，鹼顯影型阻焊劑之顯影 殘渣去除效果低，會產生顯影殘渣。另一方面，超過 lOOOppm時，引起水洗水中微量溶解之鹼顯影型阻焊劑之 凝集，意外地再附著於墊片部等之上。較好爲 5 0〜lOOOppm。又，使用緦離子（Sr2 + )、鋇離子（Ba2 + )之情 況時，更好爲100〜l〇〇〇ppm。 • 該等2價金屬離子的濃度，可藉由使用原子吸光光度 法、誘導結合電漿發光分光分析法（ICP法）、離子層析法 等測定而加以管理。又，亦可使用簡易型之水質檢查套 組。 藉由設定該水洗步驟，使得降低顯影殘渣成爲可能。 至於其理由，可認爲如下。 含有柔軟性、造膜性優異之含有羧基之胺基甲酸酯 (甲基）丙烯酸酯化合物之鹼顯影型阻焊劑，當以碳酸鈉等 的稀鹼水溶液顯影時，難以溶解而成爲鹼金屬鹽。因此認 爲’以該鹼金屬鹽與水之作用而產生黏附，因此無法傳導 顯影機之噴霧壓而無法去除在微小開口部之附著，而產生 顯影殘渣。 具有此黏附之含有羧基之（甲基）丙烯酸酯化合物之鹼 金屬鹽（通常爲鈉鹽）認爲可藉由以含30〜lOOOppm之2價 金屬離子的水洗水加以水洗，藉由與2價金屬鹽之交換反 應之鹽交聯而轉變成水中不溶物質，而可於水洗水中分散 除去。此時，一部分之2價金屬離子以若干量殘留於鹼顯 -11 - 200842496 影型阻焊劑層表面附近。 此處，於鹼顯影型阻焊劑層表面附近殘存之2價金屬 離子可藉由例如以下順序加以分析。首先，鹼顯影型阻焊 劑層藉由削取等予以分離，於例如1 8M Ω以上之墊傳導度 的純水中，於100〜120 °C加熱處理4〜8小時，熱萃取出離 子成分。接著，該萃取液使用離子層析儀（DIONEX公司 製，型號DXION Chromatograph)等予以分析，藉此檢定 在鹼顯影型阻焊劑層表面附近殘存之2價金屬離子成分。 又，含有羧基之胺基甲酸酯（甲基）丙烯酸酯化合物爲 含有羧基之氨基甲酸酯丙烯酸酯樹脂、含有羧基之胺基甲 酸酯甲基丙烯酸酯以及其混合物之總稱者，於其他類似表 現法亦相同。 再者，依據必要，藉由離子交換水，進行二次洗淨 (清洗）。如此般進行水洗（依據必要的二次洗淨）後之鹼顯 影型阻焊劑層經乾燥後加以硬化。 於如此之熱硬化步驟中，例如使用熱風循環式乾燥爐 或遠紅外線硬化爐等，於設定在例如1 4 0〜1 8 0 °C之溫度加 熱。隨後，使鹼顯影型阻焊劑中所含之羧基與環氧樹脂等 之熱硬化成分反應，形成耐熱性、耐藥品性、耐吸濕性、 密著性、電特性等諸特性優異之硬化塗膜。 又，爲了提高耐電鍍性，亦可在熱硬化前或熱硬化 後，藉由照射紫外線進行硬化。例如，可使用紫外線照射 之傳送爐，於曝光時使未反應之就此殘留的丙烯酸酯基等 的感光基予以硬化。然而，由於會有標記油墨的密著性降 -12- 200842496 低、塗膜的彈性率降低等問題，故較好考慮用途等而選擇 適宜的硬化方法。 所以，於經過該步驟，可形成印刷配線板，其在形成 有銅箔等之導體圖案之基板表面上，於印刷配線板中成爲 墊片部等之部分，具有用以形成鍍金等之開口部之鹼顯影 型阻焊劑層。 此時，開口部之直徑較好爲 20〜ΙΟΟμιη。若小於 20μιη，無法充分獲得曝光時之解像度，故而難以形成精 度良好的開口部。另一方面，若超過1〇〇 μπι，則所搭載的 晶片尺寸變大，而會損及使用CSP、UT-CSP之優點。 又，形成該等小直徑的開口部時，於水洗時水流難以 到達開口部內，容易產生顯影殘渣。然而，藉由使用本實 施形態中之水洗水，即使形成小直徑之開口部，亦可能抑 制顯影殘渣發生。 如此形成之印刷配線板進而藉由例如酸性脫脂液等加 以脫脂、洗淨之後，浸漬於觸媒液中進行觸媒賦予。接 著，藉由進行無電解鎳電鍍、無電解金電鍍而於開口部中 形成墊片。 於該印刷配線板之製造方法中所形成之鹼顯影形阻焊 劑層係使用例如含有下列之鹼顯影型阻焊劑： (Α)含羧基之樹脂； (Β)光聚合起始劑； (C)l分子中含有2個以上環狀醚基及/或環狀硫醚基 之熱硬化性成分； -13- 200842496 (D)稀釋劑。 至於含有羧基之樹脂（A)可使用分子中含有羧酸之樹 脂化合物。進而就光硬化性及耐顯影性方面觀之，較好使 用分子中具有烯屬不飽和雙鍵之含有羧基之感光性樹脂 (A，）。 具體而言，可舉例如下列之樹脂： (1) (甲基）丙燏酸等之不飽和羧酸與其以外之具有不飽 和雙鍵之化合物之1種以上經共聚合而得之含有羧基之樹 脂； (2) 於不飽和羧酸與其以外之具有不飽和雙鍵之化合 物的共聚合體中，部分地加成烯屬不飽和基作爲側鏈（例 如加成有甲基丙烯酸縮水甘油酯）所得之含羧基之樹脂； (3) 於1分子中具有環氧基與不飽和雙鍵之化合物與 其以外之具有不飽和雙鍵之化合物的共聚合體中，使不飽 和單羧酸反應，使所生成之二級羥基與飽和或不飽和多元 酸酐反應所得之含有羧基之樹脂； (4) 使多官能基環氧化合物與不飽和單羧酸反應，使 所生成之羥基與飽和或不飽和多元酸酐反應所得之含有羧 基之樹脂； (5) 使多官能基環氧化合物、不飽和單羧酸、與1分 子中至少具有1個醇性羥基及可與環氧基反應之除醇性羥 基以外之1個反應性基之化合物的反應生成物，與飽和或 不飽和多元酸酐反應所得之含有羧基之樹脂； (6) 使多官能基環氧化合物與不飽和單羧酸反應’使 -14- 200842496 所生成之羥基與飽和或不飽和多元酸酐反應，進而與甲基 丙烯酸縮水甘油酯等之1分子中具有環氧基及不飽和雙鍵 之化合物反應所得之含有羧基之樹脂； (7)使雙酚型雙官能基環氧化合物之羥基與表鹵醇反 應所得之雙酚型多官能基環氧化合物與不飽和單羧酸之反 應生成物，與飽和或不飽和多元酸酐反應所得之線狀含有 羧基之樹脂； 、 • (8)雙酚型環氧樹脂等之雙官能基環氧化合物與具有2 個酚性羥基之芳香族化合物或具有2個羧基之化合物交互. 聚合，所生成之羥基與表鹵醇反應所得之多官能基線狀環 氧化合物與不飽和單羧酸之反應生成物，與飽和或不飽和 多元酸酐反應所得之線狀含有羧基之樹脂； (9)1分子中含有2個以上之酚性羥基之化合物與環氧 烷或環碳酸酯反應所得之反應生成物與含有不飽和基之單 羧酸反應，所得之反應生成物與多元酸酐反應所得之含有 # 羧基之樹脂； (1〇)含有羥基之（甲基）丙烯酸酯化合物（a)、二羥甲基 烷酸（b)以及二異氰酸酯化合物（c)反應所得之化合物，或 者進而與聚合物聚醇（d)反應所得之含有羧基之胺基甲酸 _ (甲基）丙烯酸酯樹脂（以下稱爲「含有羧基之胺基甲酸 酯（甲基）丙烯酸酯化合物」）。 該等含有羧基之樹脂（A)由於在骨架聚合物之側鏈上 具有多數之游離羧基，故而可藉由稀鹼水溶液加以顯影。 該等之中，尤其是（5)〜（10)之含羧基之樹脂較好地適 -15- 200842496 用於UT-CSP等之封裝基板中。其中，藉由含有（10)之含 羧基之胺基甲酸酯（甲基）丙烯酸酯化合物，而可形成更適 於UT-CSP等之封裝基板之柔軟性高的印刷配線板。因 此，該含羧基之胺基甲酸酯（甲基）丙烯酸酯化合物，就賦 予柔軟性之方面而言，相對於含有羧基之樹脂（A) 100質 量份較好含有3 5質量份以上。 該等含有羧基之樹脂（A)可單獨使用亦可組合複數種 加以使用。又，爲了賦予柔軟性，亦可使用羧基端之丁二 烯丙烯腈（CTBN)等之含有羧基之橡膠狀化合物。就賦予 柔軟性之觀點而言，含有羧基之橡膠狀化合物、（7)、（8) 之線狀含有羧基之樹脂、(1 0)之含有羧基之胺基甲酸酯 (甲基）丙烯酸酯化合物，相對於含有羧基之樹脂（A)總 量，較好含有15〜85質量％(含有羧基之樹脂（A) 100質量 份中爲15〜85質量份）。 又，該種含有羧基之胺基甲酸酯（甲基）丙烯酸酯化合 物等以稀鹼水溶液顯影時，容易產生具有黏附性之影像殘 澄。然而，依據本實施形態之使用水洗水，使得抑制顯影 殘渣發生成爲可能。 又’含有羧基之樹脂（A)之酸價較好在 40〜200mg KOH/g之範圍。含有羧基之樹脂酸價若小於40mg KOH/g，貝[J鹼顯影變得困難，另一方面，若超過200mg K〇H/g，貝！]顯影液之曝光部溶解過度，超過必要以上的線 變細’依據情況’曝光部與未曝光部沒有區別地以顯影液 溶解而剝離，正常抗飩劑圖案的描繪變得困難。更好，在 -16- 200842496 45〜120mg KOH/g 之範圍。 又，含有羧基之樹脂（A)之重量平均分子量隨著樹脂 骨架而異，但一般較好在2,000〜1 50,000之範圍。若重量 瓶均分子量小於2,000，則不黏性能劣化’曝光後塗膜之 耐濕性變差，顯影時發生膜減少，解像度大爲劣化。另一 方面，若重量平均分子量超過15 0,000，則有顯影性顯著 劣化且儲存安定性劣化之情況。較好，在5,000〜1 00,000 之範圍^ 此種含有羧基之樹脂（A)之調配比例於全組成物中較 好爲20〜6 0質量％。少於20質量％之情況下，難以獲得充 分的塗膜強度。另一方面，多於60質量％之情況下，黏 性變高，塗佈性降低。較好爲3 0〜5 0質量％。 作爲光聚合起始劑（B)，可舉例如苯偶因、苯偶因甲 基醚 '苯偶因乙基醚、苯偶因異丙基醚等之苯偶因及苯偶 因烷基醚類；苯乙酮、2，2-二甲氧基-2-苯基苯乙酮、2，2-二乙氧基-2-苯基苯乙酮、1，1-二氯苯乙酮等之苯乙酮類； 2-甲基-1-[4-(甲硫基）苯基]-2-嗎啉基丙烷-卜酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基）-丁酮-1、2-(二甲胺基 [(4-甲基苯基）甲基]-1-[4-(4-嗎啉基）苯基]-1-丁酮等之胺 基苯乙酮類；2_甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽 醌、1-氯蒽醌等之蒽醌類；2,4-二甲基噻噸酮、2,4-二乙 基噻噸酮、2-氯噻噸酮、2，4-二異丙基噻噸酮等之噻噸酮 類；苯乙酮二甲基縮酮、苄基二甲基縮酮等之縮酮類；苄 基、二苯甲酮等之二苯甲酮類；或咕噸酮類；（2,6-二甲氧 -17- 200842496 基苯甲醯基）-2,4,4·戊基膦氧化物、雙（2,4,6-三甲基苯甲 醯基）-苯基膦氧化物、2,4,6-三甲基苯甲醯基二苯基膦氧 化物、乙基-2,4,6-三甲基苯甲醯基苯基膦酸酯等之膦氧化 物，以及（2-(乙醯氧基亞胺基甲基）噻噸-9-酮）、1，2-辛二 酮、1-[4·(苯硫基）-、2-(0-苯甲醯基肟）]、乙酮、1·[9-乙 基- 6-(2-甲基苯甲醯基）-9Η-味唑-3-基]-、1-(0-乙醯基肟） 等之肟酯類。 • 此種光聚合起始劑（B)可單獨使用或組合複數種使 用。此種光聚合起始劑（B)之調配比例，相對於含有羧基 之樹脂（A) 100質量份，宜爲0.01〜30質量份。光聚合起 始劑（B)之使用量若低於0.01質量份時，光硬化性降低， 另一方面，多於30質量份時，硬化塗膜特定降低。於肟 系光聚合起始劑時，其調配比例爲0.01〜20質量份，更好 爲0.01〜5質量份。 再者，作爲光起始助劑，可含有三級胺化合物或二苯 # 甲酮化合物。作爲此種三級胺，可舉例如乙醇胺類、4,4’-二甲基胺基二苯甲酮（日本曹達股份有限公司製造之 Nissocure ; MABP)、4-二甲胺基苯甲酸乙酯（日本化藥股 份有限公司製之Cacure ; EPA)、2-二甲胺基苯甲酸乙酯 (International Bio-Synthetics 股份有限公司製之 Quantacure DMB)、4-二甲胺基苯甲酸（正-丁氧基）乙酯 (International B i 〇 - S y ntheti c s 股份有限公司製之 Quant acure BE A)、對-二甲胺基苯甲酸異戊基乙基酯（日本 化藥股份有限公司製之Cacure DMBI)、4-二甲胺基苯甲 -18- 200842496 酸2-乙基己酯（Van Dyk股份有限公司製之Esolol 507)、 4，4’-二乙胺基二苯甲酮（保土谷化學股份有限公司製之 EAB)等。 此等三級胺化合物可單獨使用或作爲混合物使用。較 好三級胺化合物爲4,4’·二乙基胺基二苯甲酮，但並無特 別限制。若係藉由倂用可吸收波長300〜420nm領域之 光、氫牽引型光聚合起始劑可發揮增感效果者，則並不限 定光聚合起始劑（B)、光起始助劑，可單獨使用或複數種 合倂使用。 1分子中含有2個以上環狀醚基及/或環狀硫醚基之熱 硬化性成分（C)係爲了提高硬化物之耐熱性而使用。 至於1分子中含有2個以上環狀醚基及/或環狀硫醚 基之熱硬化性成分（C)，爲1分子中含有2個以上之3、4 或5員環之環狀醚基或環狀硫醚基之任一者或2種類基之 化合物，例如1分子中含有至少2個以上環氧基之化合 物、亦即多官能基環氧化合物（C-1); 1分子內含有至少2 個以上之氧雜環丁烷基之化合物、亦即多官能基氧雜環丁 烷化合物（C-2); 1分子內含有2個以上硫醚基之化合物、 亦即環氧硫化物（episulfide)樹脂等。 至於多官能基環氧化合物（C-1 )，可舉例爲例如日本 環氧樹脂股份有限公司製之Epicote 828、Epieote 834、 Epicote 1001、Epicote 10 04、大日本油墨化學工業股份有 限公司製之 Epiclon 840、Epiclon 850、Epiclon 1 050、 Epiclon 205 5、東都化成股份有限公司製之EpototeYD- -19- 200842496[Technical Field] The present invention relates to a method of manufacturing a printed wiring board such as a flexible printed wiring board or a sheet requiring flexibility, and a printed wiring board. In the past, with the rapid advancement of semiconductor components, electronic devices have become more compact, lighter, higher-performance, and more versatile. To meet these trends, Kezhen is making progress in increasing the density of printed wiring boards. Corresponding to such high density, it replaces the 1C package called QFP (Quad Plat Package), SOP (Small Outline Package), etc., and is called BGA (Ball Grid Array). 1C packages such as 歹 ) )), CSP (Chip Scale Package), etc. are available. In the package substrate or the printed wiring board for a vehicle, a solder resist is used for the opening of a spacer or the like on a package substrate that is connected to a semiconductor or the like in order to apply gold plating or the like for improving reliability. Further, with the progress of the flaking of the core material used for the printed wiring board or the package substrate, for example, TAB (Tape auto Bonding), T-BQA (Tape Ball Grid Array), and tape winding type have been developed. Ball grid arrays, T-CSP (Tape Chip Scale Package), UT-CSP (Ultra Thin Chip Scale Package), etc. are available. Thus, by the thinning of the core material, the bending at the time of hardening and shrinking of the solder resist becomes a problem. Therefore, in the case of using the core material on the web, it is possible to use a roll-to-roll method, and to evaluate the workability, reliability, film thickness accuracy, and smoothness of the work using the roll-to-roll method. Solder resist for dry film tape. The solder resist of the dry film tape is supplied in the form of a sheet or a roll, and it is necessary to contain a resin component excellent in flexibility and film-forming property in the resin composition. For the resin component which is excellent in flexibility and film-forming property, for example, a reaction of a rubber compound or a compound having at least one carboxyl group and two hydroxyl groups in one molecule with a diol compound or a polyisocyanate compound is exemplified. A photosensitive resin obtained by reacting a terminal isocyanate compound of Φ with a compound having a polymerizable unsaturated group, a carboxyl group, and at least one hydroxyl group in one molecule (for example, refer to Patent Document 1). However, when the resin component which is excellent in the flexibility and the film-forming property is added to the solder resist, the development property is lowered, the dominant residue is generated in the opening portion such as the micro spacer, and the adhesion such as gold plating is deteriorated, and the yield is improved. Problems such as reduced reliability. Therefore, although the residue may be removed by repeated development, the productivity is lowered and it becomes a problem. Φ Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 4-252485 (Patent Application No., and the like) Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 2-7-7 No. 966 (Application No., etc.) 200842496 [Summary of the Invention] [Problems to be Solved by the Invention] In view of the problems of the prior art, an object of the present invention is to provide a method of manufacturing a printed wiring board and a printed wiring board by 'suppressing a minute pad formed in a specific portion of an alkali developing type solder resist layer" A developing wiring sheet having an opening portion such as a sheet can be improved in plating adhesion, and a printed wiring board having high reliability and productivity can be obtained. [Means for Solving the Problem] In order to achieve the above-mentioned problem, when an alkali-developing solder resist which is excellent in flexibility and film-forming property such as UT-CSP is used, it is found that the development is suppressed by changing the water washing after development. Residues are possible. That is, according to one aspect of the present invention, it is characterized in that an alkali-developing type containing a carboxyl group-containing urethane (meth) acrylate compound as a carboxyl group-containing resin is formed on the surface of the substrate on which the conductor pattern is formed. a solder resist Φ layer, the alkali developing type solder resist layer is exposed through a specific opening pattern, developed by a dilute aqueous alkali solution, washed with water containing 30 to 1000 ppm of divalent metal ions, and then thermally hardened. An opening is formed at a specific position of the alkali-developing type solder resist layer. Further, according to an aspect of the invention, there is provided a substrate having a conductor pattern formed thereon, and an alkali developing type solder resist layer formed on the substrate and having an opening formed at a specific position, wherein the alkali developing type solder resist layer contains The carboxyl group-containing urethane (meth) acrylate compound and the divalent metal ion 〇-6 - 200842496 Further, the metal ion concentration unit ppm represents a unit of the number of milligrams of metal ions contained in one liter of the sample. According to the present invention, it is possible to suppress the development residue of the opening portion of the minute gasket or the like formed in a specific portion of the alkali-developing type solder resist layer, thereby improving plating adhesion and obtaining high reliability. Productive printed wiring board. [Embodiment] Hereinafter, the best mode for carrying out the invention will be described in detail. First, the method for producing a printed wiring board of the present invention is suitable for applying gold plating or the like using an alkali developing type solder resist to a printed wiring board having a minute pad portion (for example, an opening diameter of 20 to ΙΟΟμη) which is difficult to develop. The method for producing a printed wiring board according to the present invention is characterized in that an alkali-developing type resist containing a carboxyl group-containing urethane (meth) acrylate compound as a carboxyl group-containing resin is formed on a surface of a substrate on which a conductor pattern is formed. a flux layer, the alkali-developable solder resist layer is exposed through a specific opening pattern, developed by a dilute aqueous alkali solution, washed with water containing 30 to 1000 ppm of divalent metal ions, and then subjected to heat hardening, in the foregoing The opening portion is formed at a specific position of the alkali developing type solder resist layer. That is, the method of manufacturing a printed wiring board of this embodiment has the following steps. 1 . The step of forming a solder resist layer on the surface of the substrate on which the conductor pattern is formed; 2. the exposing step; 3. the step of developing by a dilute aqueous alkali solution; 4. using 30 to 1000 ppm a step of washing the water of the divalent metal ion with water; 5) (if necessary) a step of washing the water; 6. a step of drying the substrate (steps 3 to 6 are generally referred to as development steps) 7. A step of heat hardening. Therefore, through these steps, a printed wiring board having an alkali-developing type solder resist layer having an opening formed at a specific position on the surface of the substrate on which the conductor pattern is formed is formed. First, an alkali-developing type solder resist layer to be described later is formed on the surface of the substrate on which the conductor pattern is formed. In this step, as the substrate on which the conductor pattern is formed, for example, paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/non-woven epoxy resin, or the like may be used. Copper-clad laminates of all grades (FR-4, etc.), such as glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluorine-polyethylene, yttrium-cyanate, etc. A substrate on which a conductive pattern is formed on another polyimide film, a pet film, a glass substrate, a ceramic substrate, a wafer plate, or the like. The steps of forming an alkali-developing type solder resist layer on the surface of the substrate include a method of using a liquid alkali-developing type solder resist and a method of using a dry film having an alkali-developing type solder resist layer. When a liquid alkali-developing type solder resist is used, the organic solvent 200842496 (D-1) described later adjusts the viscosity to a viscosity suitable for the coating method, and is formed on the substrate on which the conductor pattern is formed. Coating by a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, or a curtain coating method. Then, the organic solvent (D-1) contained in the alkali developing type solder resist is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 °C. Thereby, a non-stick alkali developing type solder resist layer is formed. Further, a dry film having an alkali-developing type solder resist layer is a solder resist layer having a carrier film and an alkali-developing type solder resist coated on the carrier film (or a cover film) and dried, and a self-resisting solder layer A dry film of the peeled cover. As the carrier film, a polyester film such as PET having a thickness of 10 to 150 μm, a polyimide film or the like can be used. The alkali-developing type solder resist layer is formed by using an organic solvent (D-1) to reduce the viscosity of the alkali-developing type solder resist to a viscosity which can be applied to a carrier film or a cover film, and then using a blade coater, a lip coater, A continuous coater (comma co ate, film coater, etc.) is uniformly coated on the carrier film (or the cover film), for example, to a thickness of 1 〇 to 150 μm and dried. As for the cover film, it can be used. a polyethylene film, a polypropylene film, etc., but preferably has a lower adhesion force to the alkali-developing type solder resist layer than the carrier film. When the dry film of the alkali-developing type solder resist is used, the cover layer is peeled off, and the carrier film is removed. The alkali-developing type solder resist layer is laminated on the substrate on which the conductor pattern is formed. Then, by laminating using a laminator or the like, a proof-developing type solder resist layer is formed on the substrate on which the conductor pattern is formed. The carrier film is preferably stripped at any time before or after the exposure. Further, the lamination is carried out by a heating laminator, usually at 60 to 110 ° C and 0.4 MPa or more. At this time, 200842496, by using a vacuum laminator, Can suppress the occurrence of holes. Then, The formed alkali-developing type solder resist layer is exposed in a specific opening pattern. In the exposure step, as the light source of the active energy gland, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a super-high mercury lamp, a xenon lamp or a metal halogen is generally used. A contact or non-contact exposure machine for a lamp. Further, an alkali-developing type solder resist layer which is exposed by a laser direct imaging device using a laser light can be used for development using a dilute aqueous alkali solution. In the step, a dipping method, a spray method, a spray method, or the like may be used, but in the case of a water washing step of the subsequent step, a spraying method is preferably used. As the developing solution, for example, potassium hydroxide, sodium hydroxide, or sodium carbonate may be used. , a potassium carbonate, sodium phosphate, sodium citrate, ammonia, an amine, etc., a dilute alkali aqueous solution containing a monovalent alkali metal salt or an ammonium salt. The alkali-developed solder resist layer after development is immediately used to contain 30 to 1000 ppm. The water of the divalent metal is washed with water. The divalent metal ion contained in the water wash water used in the water washing step may be, for example, calcium ion (Ca2+). Ions (Mg2 + ), strontium ions (Sr2 + ), cesium ions (Ba2 + ), etc. These metal ions are suitable for use without adversely affecting the insulation properties of the printed wiring board, and particularly preferably calcium ions and magnesium ions. The compound containing the divalent metal ion may, for example, be a chloride, a hydroxide, a sulfate, a phosphate, a nitrate or an acetate. However, chlorine is preferably used without adversely affecting the printed wiring board. Compound or hydroxide. -10- 200842496 The concentration of the divalent metal ion is necessary to be 3〇~1〇〇〇ρρϊη. When the concentration of the metal ion is less than 30Ppm, the development residue of the alkali developing type solder resist is removed. When the effect is low, the development residue is generated. On the other hand, when it exceeds 1000 ppm, aggregation of the alkali-developing type solder resist which causes a slight dissolution in the washing water is accidentally reattached to the gasket portion or the like. It is preferably from 50 to 1000 ppm. Further, in the case of using cerium ions (Sr2 + ) or cerium ions (Ba2 + ), it is more preferably 100 to 1 〇〇〇 ppm. • The concentration of these divalent metal ions can be managed by atomic absorption spectrophotometry, induced plasma spectroscopy (ICP method), ion chromatography, and the like. Also, a simple water quality inspection kit can be used. By setting the water washing step, it is possible to reduce the development residue. As for the reason, it can be considered as follows. An alkali-developing type solder resist containing a carboxyl group-containing urethane (meth) acrylate compound which is excellent in flexibility and film-forming property is difficult to be dissolved into an alkali metal salt when developed with a dilute aqueous alkali solution such as sodium carbonate. . Therefore, it is considered that adhesion occurs by the action of the alkali metal salt and water, so that the spray pressure of the developing machine cannot be conducted, and adhesion to the minute opening portion cannot be removed, and development residue is generated. An alkali metal salt (usually a sodium salt) having a carboxyl group-containing (meth) acrylate compound having such adhesion is considered to be washable by washing with water containing 30 to 1000 ppm of a divalent metal ion, by using a valence The salt of the metal salt exchange reaction is crosslinked to be converted into an insoluble matter in water, and can be dispersed and removed in water washing water. At this time, a part of the divalent metal ions remain in the vicinity of the surface of the base type -11 - 200842496 pattern solder resist layer in a certain amount. Here, the divalent metal ions remaining in the vicinity of the surface of the alkali-developing type solder resist layer can be analyzed by, for example, the following procedure. First, the alkali-developing type solder resist layer is separated by cutting or the like, and is heat-treated at 100 to 120 ° C for 4 to 8 hours in pure water having a pad conductivity of, for example, 18 M Ω or more, to thermally extract the ion component. Then, the extract was analyzed by using an ion chromatograph (manufactured by DIONEX Co., Ltd., model DXION Chromatograph) or the like to thereby determine the divalent metal ion component remaining in the vicinity of the surface of the alkali-developing type solder resist layer. Further, the carboxyl group-containing urethane (meth) acrylate compound is a urethane acrylate resin containing a carboxyl group, a urethane methacrylate containing a carboxyl group, and a mixture thereof, and the like. Similar expressions are the same. Further, secondary washing (washing) is carried out by ion-exchanged water as necessary. The alkali-developing type solder resist layer after being washed in this manner (according to necessary secondary cleaning) is dried and then hardened. In such a heat hardening step, for example, a hot air circulation type drying oven or a far infrared ray hardening furnace or the like is used, and heating is performed at a temperature of, for example, 140 to 180 °C. Then, the carboxyl group contained in the alkali-developing type solder resist is reacted with a thermosetting component such as an epoxy resin to form a hardened coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. . Further, in order to improve the plating resistance, it may be cured by irradiation with ultraviolet rays before or after thermal curing. For example, it is possible to use a transfer furnace for ultraviolet irradiation to cure an unreacted photosensitive group such as an acrylate group remaining after exposure. However, since the adhesion of the marking ink is lowered to -12-200842496, and the elastic modulus of the coating film is lowered, it is preferable to select a suitable curing method in consideration of the use and the like. Therefore, the printed wiring board is formed on the surface of the substrate on which the conductor pattern of copper foil or the like is formed, and is formed as a pad portion or the like in the printed wiring board, and has an opening for forming gold plating or the like. Alkali development type solder resist layer. At this time, the diameter of the opening portion is preferably 20 to ΙΟΟμιη. If the thickness is less than 20 μm, the resolution at the time of exposure cannot be sufficiently obtained, so that it is difficult to form an opening having excellent precision. On the other hand, if it exceeds 1 μm, the size of the wafer to be mounted becomes large, which may impair the advantages of using CSP and UT-CSP. Further, when these small-diameter openings are formed, it is difficult for the water flow to reach the opening during water washing, and development residue is likely to occur. However, by using the water washing water in the present embodiment, even if a small-diameter opening portion is formed, it is possible to suppress the occurrence of development residue. The printed wiring board thus formed is further degreased and washed by, for example, an acidic degreased liquid, and then immersed in a catalyst liquid to provide a catalyst. Next, a spacer is formed in the opening by electroless nickel plating or electroless gold plating. The alkali-developing type solder resist layer formed in the method for producing a printed wiring board uses, for example, an alkali-developing type solder resist containing: (Α) a carboxyl group-containing resin; (Β) a photopolymerization initiator; (C) a thermosetting component containing two or more cyclic ether groups and/or cyclic thioether groups in the molecule; -13- 200842496 (D) Thinner. As the resin (A) having a carboxyl group, a resin compound containing a carboxylic acid in a molecule can be used. Further, in view of photocurability and development resistance, it is preferred to use a carboxyl group-containing photosensitive resin (A,) having an ethylenically unsaturated double bond in its molecule. Specifically, for example, the following resins are used: (1) one or more kinds of unsaturated carboxylic acids such as (meth)propionic acid and other compounds having an unsaturated double bond; Resin; (2) a partial addition of an ethylenically unsaturated group as a side chain (for example, addition of glycidyl methacrylate) to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond; a carboxyl group-containing resin; (3) a copolymer of a compound having an epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond, and reacting the unsaturated monocarboxylic acid to produce a carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride; (4) reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid to react a generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride The obtained carboxyl group-containing resin; (5) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and an alcoholic hydroxyl group having at least one alcoholic hydroxyl group and one epoxy group reactive with an epoxy group One a reaction product of a compound of a reactive group, a carboxyl group-containing resin obtained by reacting with a saturated or unsaturated polybasic acid anhydride; (6) reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid to make it -14-200842496 a carboxyl group-containing resin obtained by reacting a hydroxyl group with a saturated or unsaturated polybasic acid anhydride, and further reacting with a compound having an epoxy group and an unsaturated double bond in one molecule such as glycidyl methacrylate; (7) making a bisphenol type a reaction product of a bisphenol type polyfunctional epoxy compound obtained by reacting a hydroxyl group of a bifunctional epoxy compound with an epihalohydrin and an unsaturated monocarboxylic acid, and a linear form of a carboxyl group obtained by reacting with a saturated or unsaturated polybasic acid anhydride Resin; (8) Bifunctional epoxy compound such as bisphenol epoxy resin interacts with an aromatic compound having two phenolic hydroxyl groups or a compound having two carboxyl groups. Polymerization, generated hydroxyl group and epihalide a reaction product of a polyfunctional base-like epoxy compound obtained by an alcohol reaction and an unsaturated monocarboxylic acid, and a linear carboxyl group-containing resin obtained by reacting with a saturated or unsaturated polybasic acid anhydride (9) A reaction product obtained by reacting a compound containing two or more phenolic hydroxyl groups in one molecule with an alkylene oxide or a cyclic carbonate, and a monocarboxylic acid containing an unsaturated group, and reacting the resulting reaction product with a polybasic acid anhydride The obtained resin having a carboxyl group; (1) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a), a dimethylol alkanoic acid (b), and a diisocyanate compound (c), or further The carboxyl group-containing amino acid carboxylic acid-based (meth) acrylate resin (hereinafter referred to as "carboxyl group-containing urethane (meth) acrylate compound") obtained by the reaction of the polymer polyol (d). The carboxyl group-containing resin (A) can be developed by a dilute aqueous alkali solution because it has a large number of free carboxyl groups in the side chain of the skeleton polymer. Among these, especially the carboxyl group-containing resin of (5) to (10) is preferably used in a package substrate such as UT-CSP. Among them, by containing the carboxyl group-containing urethane (meth) acrylate compound (10), it is possible to form a printed wiring board which is more suitable for a package substrate such as UT-CSP. Therefore, the carboxyl group-containing urethane (meth) acrylate compound preferably contains 35 parts by mass or more based on 100 parts by mass of the carboxyl group-containing resin (A) in terms of flexibility. These carboxyl group-containing resins (A) may be used singly or in combination of plural kinds. Further, in order to impart flexibility, a carboxyl group-containing compound containing a carboxyl group such as a butadiene acrylonitrile (CTBN) having a carboxyl group may be used. From the viewpoint of imparting flexibility, a rubbery compound containing a carboxyl group, a linear carboxyl group-containing resin of (7) and (8), and a carboxyl group-containing urethane (meth)acrylate of (10) The compound is preferably contained in an amount of 15 to 85% by mass based on the total amount of the carboxyl group-containing resin (A) (15 to 85 parts by mass in 100 parts by mass of the carboxyl group-containing resin (A)). Further, when such a carboxyl group-containing urethane (meth) acrylate compound or the like is developed with a dilute aqueous alkali solution, image sticking with adhesion is likely to occur. However, the use of the water washing water according to the present embodiment makes it possible to suppress the occurrence of development residue. Further, the acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mg KOH/g. If the acid value of the resin containing a carboxyl group is less than 40 mg KOH/g, it is difficult to develop the base. On the other hand, if it exceeds 200 mg K〇H/g, the shell! The exposed portion of the developing solution is excessively dissolved, and the line is more than necessary. The film is thinned. Depending on the case, the exposed portion and the unexposed portion are dissolved in the developing solution and peeled off, and the drawing of the normal anti-caries agent pattern becomes difficult. More preferably, it ranges from -16 to 200842496 45~120mg KOH/g. Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but it is usually preferably in the range of 2,000 to 150,000. If the weight average molecular weight of the bottle is less than 2,000, the non-stick property is deteriorated. The moisture resistance of the coating film after exposure is deteriorated, and the film is reduced during development, and the resolution is largely deteriorated. On the other hand, when the weight average molecular weight exceeds 1,500, the developability is remarkably deteriorated and the storage stability is deteriorated. Preferably, in the range of 5,000 to 10,000,000, the proportion of the carboxyl group-containing resin (A) is preferably from 20 to 60% by mass in the total composition. In the case of less than 20% by mass, it is difficult to obtain sufficient coating film strength. On the other hand, when it is more than 60% by mass, the viscosity is high and the coatability is lowered. It is preferably from 30 to 50% by mass. Examples of the photopolymerization initiator (B) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Class; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Acetophenones; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-buxone, 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butanone-1, 2-(dimethylamino[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]- Aminoacetophenones such as 1-butanone; 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole, etc.; 2, 4 - thioxanthones such as dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl a ketal such as a ketal or a benzyl dimethyl ketal; a benzophenone such as a benzyl group or a benzophenone; or a xanthone; (2,6-dimethoxy-17-200842496 Benzamethylene)-2,4,4·pentylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6 a phosphine oxide such as trimethylbenzhydryldiphenylphosphine oxide or ethyl-2,4,6-trimethylbenzimidylphenylphosphonate, and (2-(ethion) Iminoaminomethyl)thioxanthene-9-one), 1,2-octanedione, 1-[4.(phenylthio)-, 2-(0-benzylidenehydrazine), ethyl ketone And an oxime ester such as [9-ethyl-6-(2-methylbenzhydryl)-9-oxazol-3-yl]-, 1-(0-ethenylhydrazine). The photopolymerization initiator (B) may be used singly or in combination of plural kinds. The proportion of the photopolymerization initiator (B) is preferably 0.01 to 100 parts by mass based on the carboxyl group-containing resin (A). When the amount of the photopolymerization initiator (B) used is less than 0.01 parts by mass, the photocurability is lowered. On the other hand, when the amount is more than 30 parts by mass, the cured coating film is specifically lowered. In the case of the initiator, the compounding ratio is 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass. Further, as the photoinitiating aid, a tertiary amine compound or a diphenyl #methanone compound may be contained. A tertiary amine such as ethanolamine or 4,4'-dimethylaminobenzophenone (Japan) Nissocure manufactured by Cao Da Co., Ltd.; MABP), ethyl 4-dimethylaminobenzoate (Cacure, manufactured by Nippon Kayaku Co., Ltd.; EPA), ethyl 2-dimethylaminobenzoate (International Bio-Synthetics) Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester (Quant acure BE A, manufactured by International B i 〇-S y ntheti cs Co., Ltd.), p-two Isoamyl methyl benzoate (Cacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzamide-18- 200842496 2-ethylhexyl acrylate (manufactured by Van Dyk Co., Ltd.) Esolol 507), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like. These tertiary amine compounds can be used singly or as a mixture. The preferred tertiary amine compound is 4,4'.diethylaminobenzophenone, but is not particularly limited. When a sensitizing effect can be exhibited by using a light-absorbing photopolymerization initiator which absorbs light in the wavelength range of 300 to 420 nm, the photopolymerization initiator (B) and the photoinitiator are not limited. It can be used alone or in combination. The thermosetting component (C) containing two or more cyclic ether groups and/or cyclic thioether groups in one molecule is used to improve the heat resistance of the cured product. The thermosetting component (C) containing two or more cyclic ether groups and/or cyclic thioether groups in one molecule is a cyclic ether group containing two or more 3, 4 or 5 membered rings in one molecule. Or a compound of two types of a cyclic thioether group or a group of two types, for example, a compound containing at least two or more epoxy groups in one molecule, that is, a polyfunctional epoxy compound (C-1); a compound having at least two or more oxetanyl groups, that is, a polyfunctional oxetane compound (C-2); a compound containing two or more thioether groups in the molecule, that is, an epoxy sulfide (episulfide) resin and the like. As the polyfunctional epoxy compound (C-1), for example, Epicote 828, Epieote 834, Epicote 1001, Epicote 10 04 manufactured by Nippon Epoxy Co., Ltd., and Epiclon manufactured by Dainippon Ink Chemical Industry Co., Ltd. can be exemplified. 840, Epiclon 850, Epiclon 1 050, Epiclon 205 5. Epotote YD- -19- 200842496, manufactured by Dongdu Chemical Co., Ltd.

011、YD-013、YD-127、YD-128、道化學股份有限公司製 之 D.E.R. 317 、 D.E.R. 331 、 D.E.R. 661 、 D.E.R. 664 、 Ciba Special Chemical 股份有限公司製之 Ararudite 6 0 7 1 、 Ararudite 6084 、 Ararudite GY250 、 Ararudite GY260、住友化學工業股份有限公司製之 Sumi-Epoxy ESA-011、ESA-014、ELA-115、ELA-128、旭化成工業股 份有限公司製之 A.E.R. 330、A.E.R. 331、A.E.R. 661、 A.E.R. 664等（均爲商品名）之雙酚A型環氧樹脂；日本環 氧樹脂股份有限公司製之Epicote 903、大日本油墨化學 工業股份有限公司製之Epiclon 152、Epiclon 165、東都 化成股份有限公司製之Epotote YDB-400、YDB-500、道 化學股份有限公司製之 D.E.R· 542、Ciba Special Chemical股份有限公司製之Ararudite 801 1、住友化學工 業股份有限公司製之Sumi-Epoxy ESB-400、ESB-700、旭 化成工業股份有限公司製之 A.E.R. 711、A.E.R· 714等 (均爲商品名）之溴化環氧樹脂；日本環氧樹脂股份有限公 司製之Epicote 152、Epicote 154、道化學股份有限公司 製之D.E.N. 4 31、D.E.N. 438、大日本油墨化學工業股份 有限公司製之 Epiclon N-730、Epiclon N-770、Epiclon N-865 '東都化成股份有限公司製之Epotote YDCN-701、 YDCN-704、Ciba Special Chemical 股份有限公司製之 Ararudite E CN 1 2 3 5 、 Ararudite ECN1 273 、 Ararudite ECN1 299 ' Ararudite XPY3 07、日本化藥股份有限公司製 之 EPPN-201、EOCN- 1 025、EOCN- 1 020、EOCN-104S、 -20- 200842496 RE-3 06、住友化學工業股份有限公司製之 Sumi-Ep〇xy ESCN-195X、ESCN-220、旭化成工業股份有限公司製之 A.E.R. ECN-23 5、ECN-299等（均爲商品名）之酚醛型環氧 樹脂；大日本油墨化學工業股份有限公司製之Epiclon 830、日本環氧樹脂股份有限公司製之Epicote 807、東都 化成股份有限公司製之 Epotote YDF-170、YDF-175、 YDF-2004、Ciba Special Chemical 股份有限公司製之 Ararudite XPY306等（均爲商品名）之雙酚F型環氧樹脂； 東都化成股份有限公司製之Epotote ST-2004、ST-2007、 ST-3 000(商品名）等之氫化雙酚A型環氧樹脂；日本環氧 樹脂股份有限公司製之Epicote 604、東都化成股份有限 公司製之 Epotote YH-434、Ciba Special Chemical 股份有 限公司製之Ararudite MY720、住友化學工業股份有限公 司製之Sumi-Epoxy ELM-120等（均爲商品名）之縮水甘油 基胺型環氧樹脂；Ciba Special Chemical股份有限♦公司製 之Ararudite CY-3 50(商品名）等之乙內醯脲型環氧樹脂·， Diacell化學工業股份有限公司製之Serokiside 202 1、汽 巴特用化學（Ciba Special Chemical)股份有限公司製之 Ararudite CY175、CY179等（均爲商品名）之脂環式環氧樹 脂；日本環氧樹脂股份有限公司製之YL-93 3、道化學股 份有限公司製之Τ·Ε·Ν· EPPN-501、EPPN-502等（均爲商 品名）之三羥基苯基甲烷型環氧樹脂；日本環氧樹脂股份 有限公司製之YL_6〇56、YX-4000、YL-6121(均爲商品名） 等之雙二甲苯酚型或雙酚型環氧樹脂或其等之混合物；日 -21 - 200842496 本化藥股份有限公司製之EBPS-200、旭電化工股份有限 公司製之EPX-30、大日本油墨化學工業股份有限公司製 之EXA-1514(商品名）等之雙酚S型環氧樹脂；日本環氧 樹脂股份有限公司製之Epicote 157S(商品名）等之雙酹a 酚醛型環氧樹脂；日本環氧樹脂股份有限公司製之 Epic ot e YL-931、CibaSpecial Chemical 股份有限公司製 之Ararudite 1 63等（均爲商品名）之四苯酚乙烷型環氧樹 脂；汽巴特用化學股份有限公司製之Ararudite PT810、 曰產化學工業股份有限公司製之TEPIC等（均爲商品名）之 雜環式環氧樹脂；日本油脂股份有限公司製之Bremer DGT等之二縮水甘油基苯二甲酸酯樹脂；東都化成股份 有限公司製之ZX- 1 0 63等之四縮水甘油基二甲苯酚乙烷樹 脂；新日鐵化學股份有限公司製之ESN-190、ESN-3 60、 大日本油墨化學工業股份有限公司製之HP-4032、EXA-475 0、EXA-47 00等之含有萘基之環氧樹脂；大日本油墨 化學工業股份有限公司製之HP-7200、HP-7200H等之具 有二環戊二烯骨架之環氧樹脂；日本油脂股份有限公司製 之CP-5 0S、CP-5 0M等之縮水甘油基甲基丙烯酸酯共聚物 系環氧樹脂；以及環己基馬來醯亞胺與縮水甘油基甲基丙 烯酸酯之共聚合環氧樹脂；環氧基改性之聚丁二烯橡膠衍 生物（例如 Diacell化學工業股份有限公司製之 PB-3 600 等）、CTBN變性之環氧樹脂（例如東都化成工業股份有限 公司製之 YR_l〇2、YR-450等）等等，但不限於該等。該 等環氧樹脂可單獨使用或組合複數種使用。該等中，尤其 -22- 200842496 較好的是酚醛型環氧樹脂、雜環式環氧樹脂、雙酚A型 環氧樹脂或其等之混合物。 至於多官能基氧雜環丁院化合物（c _ 2 )，可舉例如雙 [(3-甲基-3-氧雜環丁基甲氧基）甲基]醚、雙[(3-乙基-3_氧 雜環丁基甲氧基）甲基]醚、i，4 -雙[(3 -甲基-3 -氧雜環丁基 甲氧基）甲基]苯、1，4-雙[(3-乙基-3-氧雜環丁基甲氧基）甲 基]苯、丙烯酸（3-甲基-3-氧雜環丁基）甲基酯、丙烯酸（3-• 乙基-3-氧雜環丁基）甲基酯、甲基丙烯酸（3-甲基-3-氧雜 環丁基）甲基酯、甲基丙烯酸（3-乙基-3_氧雜環丁基）甲基 酯或其等之寡聚物或共聚物等之多官能基氧雜環丁烷類 等、氧雜環丁烷與酚醛樹脂、聚（對-羥基苯乙烯）、Cal do 型雙酚類、杯芳烴（calixarene)類、杯芳基間苯二酚丙二 烯類或倍半矽氧烷等之具有羥基之樹脂之醚化物等。其他 可舉例如具有氧雜環丁烷環之不飽和單體與（甲基）丙烯酸 烷酯之共聚物等。 ® 至於1分子中含有2個以上之環狀硫醚基之化合物， 可舉例如日本環氧樹脂股份有限公司製之雙酚A型環氧 硫化物樹脂 YL7000等。又，可使用利用相同的合成方 法，將酚醛型環氧樹脂之環氧基的氧原子替換爲硫原子之 環氧硫化物樹脂等。 此種1分子中含有2個以上之環狀醚基及/或環狀硫 醚基之熱硬化性成分（C)之調配比例，相對於含有羧基之 樹脂（A)之羧基合計量1當量，較好爲0.5〜2.0當量。1分 子中含有2個以上之環狀醚基及/或環狀硫醚基之熱硬化 -23- 200842496 性成分（C)之調配比例當少於0.5當量時，有羧基殘留， 使得耐熱性、耐鹼性、電絕緣性等降低。另一方面，當超 過2.0當量時，殘存有1分子中含有2個以上之環狀醚基 及/或環狀硫醚基之熱硬化性成分（C )，故而塗膜強度等降 低。較好在0.8〜1.5當量之範圍。 再者，本實施形態中所用之鹼顯影型阻焊劑中，爲了 成合含有羧基之樹脂（A)或調整組成物、或爲了提高光硬 化性，而使用有稀釋劑（D)。至於稀釋劑（D)，作爲非反應 性稀釋劑則使用有機溶劑（D-1)或作爲反應性稀釋劑則使 用聚合性單體（D-2)。 至於稀釋劑（D-1 )，可舉例如酮類、芳香族烴類、二 醇醚類、二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油 系溶劑等。更具體言之，爲甲基乙基酮、環己酮等酮類； 甲苯、二甲苯、四甲基苯等之芳香族烴類；溶纖劑、甲基 溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必 醇、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二乙醚、 三乙二醇單乙醚等之二醇醚類；二丙二醇甲醚乙酸酯、丙 二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丁醚乙酸酯 等之二醇醚乙酸酯類；乙酸乙酯、乙酸丁酯以及上述二醇 醚類之乙酸酯化物等之酯類；乙醇、丙醇、乙二醇、丙二 醇等之醇類；辛烷、癸烷等之脂肪族烴；石油醚、石油 腦、氫化石油腦、溶劑石腦油等之石油系溶劑等。該等有 機溶劑（D -1)可單獨使用或作爲複數種之混合物使用。 此有機溶劑（D -1)之調配比例並無特別限制’可考慮 -24- 200842496 塗佈性或確保乾燥塗膜的膜厚方面加以決定，但相對於含 有羧基之樹脂（A)與含有羧基之胺基甲酸酯（甲基）丙烯酸 酯化合物之合計量1 0 0質量份，較好爲3 0 0質量份以下。 又，至於作爲反應性稀釋劑之聚合性單體（D-2)，可 舉例如丙烯酸2-羥基乙基酯、丙烯酸2-羥基丙基酯等之 丙烯酸羥基烷基酯類；乙二醇、甲氧基四乙二醇、聚乙二 醇、丙二醇等之二醇的單或二丙烯酸酯類；N，N-二甲基丙 烯醯胺、N-羥甲基丙烯醯胺、N，N-二甲基胺基丙基丙烯醯 胺等之丙烯醯胺類；丙烯酸N，N-二甲基胺基乙基酯、丙 烯酸Ν，Ν·二甲基胺基丙基酯等之丙烯酸胺基烷基酯類； 己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、參-羥 基乙基三聚異氰酸酯等之多價醇或其等之環氧乙烷加成物 或環氧丙烷加成物等之多價丙烯酸酯類·，苯氧基丙烯酸 酯、雙酚Α二丙烯酸酯、以及其等之苯酚類之環氧乙烷 加成物或環氧丙烷加成物等之丙烯酸酯類；甘油二縮水甘 油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、 三縮水甘油基三聚異氰酸酯等之縮水甘油醚之丙烯酸酯 類；以及三聚氰胺丙烯酸酯及/或對應於上述丙烯酸酯之 各甲基丙烯酸酯類等。該等之中，尤其是作爲分子中含有 2個以上烯屬不飽和基之化合物之多官能基（甲基）丙烯酸 酯化合物之光硬化性優異而較佳。 再者，雙酚A、雙酚F型環氧樹脂、酚以及甲酚酚醛 型環氧樹脂等之多官能基環氧樹脂與丙烯酸反應之環氧基 丙烯酸酯樹脂、或使其環氧基丙烯酸酯樹脂之羥基與季戊 -25- 200842496 四醇三丙烯酸酯等之羥基丙烯酸酯與異佛爾酮二異氰酸酯 等之二異氰酸酯之半胺基甲酸酯化合物反應之環氧基胺基 甲酸酯丙烯酸酯化合物等。此等環氧基丙烯酸酯系樹脂可 使指觸乾燥性降低且提高光硬化性。 此等聚合性單體（D-2)之調配比例，相對於含有羧基 之樹脂（A) 100質量份，較好爲120質量份以下。聚合性 單體（D-2)之調配比例若超過120質量份時，會降低電絕 緣性等，塗膜會變脆。更好爲10〜70質量份。 本竇施形態中所用之鹼顯影型阻焊劑，爲了促進含有 羧基之樹脂（A)之羧基與1分子中含有2個以上環狀醚基 及/或環狀硫醚基之熱硬化性成分（C)之硬化反應，較好配 合有硬化觸媒。011, YD-013, YD-127, YD-128, DER 317, DER 331, DER 661, DER 664 manufactured by Dow Chemical Co., Ltd., Ararudite 6 0 7 1 and Ararudite 6084 manufactured by Ciba Special Chemical Co., Ltd. Ararudite GY250, Ararudite GY260, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER 330, AER 331, AER 661, AER manufactured by Asahi Kasei Kogyo Co., Ltd. 664, etc. (both trade names) of bisphenol A epoxy resin; Epicote 903 made by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165, Daido Chemical Co., Ltd. manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epotote YDB-400, YDB-500, DER·542 manufactured by Dow Chemical Co., Ltd., Ararudite 801 manufactured by Ciba Special Chemical Co., Ltd. 1. Sumi-Epoxy ESB-400, ESB manufactured by Sumitomo Chemical Industries, Ltd. -700, brominated epoxy resin of AER 711, AER·714, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd.; Epicote 152, Epicote 154, DEN 4 31, DEN 438, manufactured by Oto Resin Co., Ltd., Epiclon N-730, Epiclon N-770, Epiclon N-made by Dainippon Ink Chemical Industry Co., Ltd. 865 'Epotote YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., Ararudite E CN 1 2 3 5, Ararudite ECN1 273, Ararudite ECN1 299 'Ararudite XPY3 07, manufactured by Ciba Special Chemical Co., Ltd. EPPN-201, EOCN- 1 025, EOCN- 1 020, EOCN-104S, -20- 200842496 RE-3 06, manufactured by Sumitomo Chemical Industries Co., Ltd., Sumi-Ep〇xy ESCN-195X, ESCN- 220, AER ECN-23 5, ECN-299 and other phenolic epoxy resins manufactured by Asahi Kasei Industrial Co., Ltd.; Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Japan Epoxy Epoxy Co., Ltd. Epicote 807, manufactured by Dongdu Chemical Co., Ltd., Epotote YDF-170, YDF-175, YDF-2004, Ararudite XPY30, manufactured by Ciba Special Chemical Co., Ltd. Bisphenol F-type epoxy resin of 6 (both trade names); hydrogenated bisphenol A epoxy resin of Epotote ST-2004, ST-2007, ST-3 000 (trade name) manufactured by Dongdu Chemical Co., Ltd. Resin; Epicote 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotote YH-434 manufactured by Dongdu Chemical Co., Ltd., Ararudite MY720 manufactured by Ciba Special Chemical Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Industries Co., Ltd. Glycidylamine type epoxy resin such as 120 (both trade names); Eiba ureia type epoxy resin such as Ararudite CY-3 50 (trade name) manufactured by Ciba Special Chemical Co., Ltd., Diacell Chemical Serokiside 202 manufactured by Industrial Co., Ltd. 1. Ararudite CY175, CY179, etc. (all trade name) alicyclic epoxy resin manufactured by Ciba Special Chemical Co., Ltd.; Japan Epoxy Resin Co., Ltd. YL-93 3, 化学·Ε·Ν·EPPN-501, EPPN-502, etc. (all trade names) of trihydroxyphenylmethane epoxy resin; Japan epoxy Resin Co., Ltd. YL_6〇56, YX-4000, YL-6121 (all trade names) and other bis-xylenol type or bisphenol type epoxy resin or a mixture thereof; day-21 - 200842496 EBPS-200 manufactured by Pharmaceutical Co., Ltd., EPX-30 manufactured by Asahi Chemical Co., Ltd., and bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Japan Epoxy a phenolic epoxy resin such as Epicote 157S (trade name) manufactured by Epoxy Resin Co., Ltd.; Epic ot e YL-931 manufactured by Japan Epoxy Resin Co., Ltd., Ararudite 1 manufactured by Ciba Special Chemical Co., Ltd. Tetrafluorophenol type epoxy resin of 63 (all of the trade names); Ararudite PT810 manufactured by Kabat Chemical Co., Ltd., TEPIC manufactured by Suga Chemical Industry Co., Ltd. (all are trade names) Epoxy resin; diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil & Fat Co., Ltd.; tetraglycidyl xylenol ethane such as ZX- 1 0 63 made by Dongdu Chemical Co., Ltd. Lipid; ECN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., Naphthalene-based ring of HP-4032, EXA-475 0, EXA-47 00, etc. Oxygen resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals Co., Ltd.; CP-5 0S, CP-5 0M manufactured by Nippon Oil & Fat Co., Ltd. a glycidyl methacrylate copolymer epoxy resin; and a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber Derivatives (such as PB-3 600 manufactured by Diacell Chemical Industry Co., Ltd.), CTBN denatured epoxy resins (such as YR_l〇2, YR-450 manufactured by Dongdu Chemical Industry Co., Ltd.), etc., but not limited to These are the same. These epoxy resins may be used singly or in combination of plural kinds. Among these, in particular, -22-200842496 is preferably a phenolic epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin or a mixture thereof. As the polyfunctional oxetane compound (c _ 2 ), for example, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3) _oxetanylmethoxy)methyl]ether, i,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl) 3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-•ethyl-3-oxetanyl) acrylate Methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or the like a polyfunctional oxetane such as a polymer or a copolymer, an oxetane and a phenol resin, a poly(p-hydroxystyrene), a Cal do type bisphenol, a calixarene, or the like. An etherified product of a resin having a hydroxyl group such as calixyl resorcinol propene or sesquioxane. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate. For the compound containing two or more cyclic thioether groups in one molecule, for example, bisphenol A type epoxy sulfide resin YL7000 manufactured by Nippon Epoxy Resin Co., Ltd., or the like can be mentioned. Further, an epoxy sulfide resin obtained by replacing the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by the same synthesis method can be used. The ratio of the thermosetting component (C) containing two or more cyclic ether groups and/or cyclic thioether groups in one molecule is 1 equivalent to the carboxyl group of the carboxyl group-containing resin (A). It is preferably from 0.5 to 2.0 equivalents. The heat-hardening -23-200842496 component (C) containing two or more cyclic ether groups and/or cyclic thioether groups in one molecule has a carboxyl group residual when less than 0.5 equivalent, so that heat resistance, Alkali resistance, electrical insulation, etc. are reduced. On the other hand, when the amount is more than 2.0 equivalents, the thermosetting component (C) containing two or more cyclic ether groups and/or cyclic thioether groups in one molecule remains, so that the coating film strength and the like are lowered. It is preferably in the range of 0.8 to 1.5 equivalents. Further, in the alkali-developing type solder resist used in the present embodiment, a diluent (D) is used in order to form a resin (A) containing a carboxyl group, to adjust a composition, or to improve photohardenability. As the diluent (D), as the non-reactive diluent, the organic solvent (D-1) is used or as the reactive diluent, the polymerizable monomer (D-2) is used. The diluent (D-1) may, for example, be a ketone, an aromatic hydrocarbon, a glycol ether, a glycol ether acetate, an ester, an alcohol, an aliphatic hydrocarbon or a petroleum solvent. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a cellosolve, a methyl cellosolve, a butyl cellosolve, or a card. a glycol ether of a certain alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether or the like; dipropylene glycol methyl ether acetate a glycol ether acetate such as ester, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate or propylene glycol butyl ether acetate; ethyl acetate, butyl acetate, and an acetate ester of the above glycol ether; Esters; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent naphtha. These organic solvents (D -1) may be used singly or as a mixture of plural kinds. The ratio of the organic solvent (D-1) is not particularly limited. It can be determined by considering the coating property or ensuring the film thickness of the dried coating film, but it is related to the carboxyl group-containing resin (A) and the carboxyl group. The total amount of the urethane (meth) acrylate compound is 100 parts by mass, preferably 300 parts by mass or less. Further, examples of the polymerizable monomer (D-2) as the reactive diluent include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; and ethylene glycol; Mono or diacrylates of diols such as methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; N,N-dimethyl decylamine, N-methylol acrylamide, N,N- Acrylamides such as dimethylaminopropyl propylene decylamine; N,N-dimethylaminoethyl acrylate, hydrazine acrylate, hydrazine dimethylaminopropyl acrylate, etc. a polyvalent alcohol such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol or cis-hydroxyethyltrimeric isocyanate or an ethylene oxide adduct or propylene oxide adduct thereof Acrylates such as polyvalent acrylates, phenoxy acrylates, bisphenol fluorene diacrylates, and phenolic oxirane or propylene oxide adducts thereof; glycerin Diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl trimeric isocyanate An acrylate of a glycidyl ether; and a melamine acrylate and/or a methacrylate corresponding to the above acrylate. Among these, a polyfunctional (meth) acrylate compound which is a compound containing two or more ethylenically unsaturated groups in a molecule is particularly excellent in photocurability. Further, an epoxy-based acrylate resin in which a polyfunctional epoxy resin such as bisphenol A, a bisphenol F-type epoxy resin, a phenol or a cresol novolac type epoxy resin is reacted with acrylic acid, or an epoxy acrylate resin thereof Epoxy urethane reacted with a hydroxyl group of an ester resin and a hydroxy acrylate such as a penta-25-200842496 tetraol triacrylate or a diisocyanate compound of a diisocyanate such as isophorone diisocyanate Acrylate compound, etc. These epoxy acrylate-based resins can reduce the dryness of the touch and improve the photocurability. The blending ratio of the polymerizable monomer (D-2) is preferably 120 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When the proportion of the polymerizable monomer (D-2) exceeds 120 parts by mass, the electrical insulation property and the like are lowered, and the coating film becomes brittle. More preferably 10 to 70 parts by mass. The alkali-developing type solder resist used in the form of the sinus is used to promote the carboxyl group-containing resin (A) carboxyl group and the thermosetting component containing two or more cyclic ether groups and/or cyclic thioether groups in one molecule ( The hardening reaction of C) is preferably combined with a hardening catalyst.

至於此等硬化觸媒，有例如，咪唑、2 -甲基咪唑、2 -乙基咪唑、2 -乙基-4-甲基咪唑、2 -苯基咪唑、4 -苯基咪 唑、1-氰基乙基-2-苯基咪唑、1-(2-氰基乙基）-2-乙基-4-甲基咪唑等之咪唑類；二氰基二醯胺、苄基二甲基胺、4-(二甲基胺基）-N，N-二甲基苄基胺、4-甲氧基-N，N-二甲基 苄基胺、4-甲基-N，N-二甲基苄基胺等之胺化合物；己二 酸醯肼、癸二酸醯肼等之醯肼化合物；三苯基膦等之磷化 合物等，又作爲市售品，有例如四國化成工業股份有限公 司製之 2MZ-A、2-MZ-OK、2PHZ、2P4BHZ、2P4MHZ(各 爲咪唑系化合物之商品名）、San-apro公司製之 U-CAT3 5 03N、U-CAT3 502T(各爲二甲胺之嵌段異氰酸酯化 合物之商品名）、DBU、DBN、U-CATSA102、U-CAT -26- 200842496 5 002(各爲二環式脒化合物以及其鹽）等。尤其是，並不限 定於該等，環氧樹脂或氧雜環丁烷化合物之熱硬化觸媒， 或者若是可促進環氧基及/或氧雜環丁烷基與羧基之反應 者則較佳，即使單獨或混合複數種使用也無妨。又，亦可 使用亦具有作爲密著賦予劑機能之鳥糞胺、乙醯基鳥糞 胺、苯并鳥糞胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧 基乙基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪·三聚異氰酸加成物、2,4·二胺基-6-甲 基丙烯醯氧基乙基-S-三嗪·三聚異氰酸加成物等之S-三 嗪衍生物，較好倂用亦具有作爲密著賦予劑機能之化合物 與熱硬化觸媒。 硬化觸媒之調配比例爲通常量的比例即已足夠，例如 相對於全部樹脂組成物1〇〇質量份，較好爲0.1〜20質量 份。硬化觸媒之調配比例少於〇. 1質量份時，硬化時間變 長，作業性降低同時引起銅箔等之氧化作用。另一方面’ 硬化觸媒之調配比例超過20質量份時，電特性降低，暫 時乾燥後之放置壽命變短。更好爲0.5〜15.0質量份之比 例。 又，本實施形態中使用之鹼顯影型阻焊劑，基於進一 步提高硬化物密著性、機械強度、線膨脹係數等特性之目 的，可調配有無機塡充劑。例如可使用硫酸鋇、鈦酸鋇' 氧化矽粉末、微粉狀氧化矽、無定形二氧化矽、滑石 '黏 土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母等之無機 塡充劑。其調配比例較好爲樹脂組成物之〇〜80質量％ ° -27- 200842496 又，進而依據需要，可調配有下列添加劑類：酞花青 藍、酞花青綠、碘绿、二重氮黃、結晶紫、氧化鈦、碳 黑、萘黑等著色劑；對苯二酚、對苯二酚單甲醚、第三丁 基兒茶酚、焦掊酚、吩噻嗪等的熱聚合抑制劑、微粉氧化 矽、有機膨潤土、蒙脫土等之增黏劑、矽氧系、氟系、高 分子系等之消泡劑及/或勻化劑、咪唑系、噻唑系、三唑 系等之矽烷偶合劑等之添加劑類。 Φ 因此，如此形成的印刷配線板適合用於作爲CSP或 UT-CSP等之封裝基板。 CSP係發揮作爲用以將1C晶片安裝於印刷配線板上 之中間板（插入件）之角色，其尺寸與1C晶片大致相同。 UT-CSP爲CSP的厚度又更薄者。 此種CSP或UT-CSP係例如如下列般加以製造、安裝 者。 首先，於形成有導體半導體之基板兩面上，分別形成 • 鹼顯影型阻焊劑層，該層形成有開口部，形成具有用以與 1C晶片連接之墊片以及用以與印刷配線板連接之墊片之 封裝基板。 接著，於封裝基板之1C晶片連接面上，使用焊線焊 接手法或覆晶手法，連接1C晶片。隨後，以封裝材料（依 據需要之底部塡充劑）將1C晶片固定於封裝基板上。 進而，於封裝基板之印刷配線板連接面上，附著焊錫 球，形成 CSP(UT-CSP)。 所形成之CSP(UT-CSP)設置於印刷配線板上，藉由通 -28- 200842496 過回流焊接爐，使焊錫球熔解，藉由印刷配線板與其施加 有鍍金等之開口部中連接而加以安裝。 [實施例1] 以下顯示實施例以及比較例對本發明之一樣態加以具 體說明，但本發明並不限定於該等實施例。 &lt;含有羧基之樹脂之合成&gt; 置入2200克甲酚酚醛型環氧樹脂（日本化藥股份有限 公司製，EOCN-104S，軟化點92°C，環氧當量220)、134 克二羥甲基丙酸、648.5克丙烯酸、4.6克甲基氫醌、 1131克卡必醇乙酸酯以及484.9克溶劑石油腦，在90°C 加熱攪拌，使反應混合物溶解。接著使反應液冷卻至60 °C，置入13.8克三苯膦，加熱至l〇〇°C，反應約32小 時，獲得酸價爲〇.5mg KOH/g之反應物。接著，置入 3 64.7克四氫苯二甲酸酐、137.5克卡必醇乙酸酯以及 5 8 · 8克溶劑石油腦，加熱至9 5 °C，反應約6小時後，冷 卻，獲得固形物之酸價40mh KOH/g、不揮發份65%之含 有羧基之樹脂。以下，此反應溶液稱爲清漆（A-1)。 &lt;含有羧基之胺基甲酸酯（甲基）丙烯酸酯化合物之合 成&gt; 於配備有溫度計、攪拌裝置以及回流冷凝器之5升可 分離瓶中，置入1，245克作爲聚合物聚醇之聚己內酯二醇 -29- 200842496 (Diacell化學工業股份有限公司製之PLACCEL208，分子 量83 0)、2 01克作爲含有羧基之二羥基化合物之二羥甲基 丙酸、777克作爲聚異氰酸酯之異佛爾酮二異氰酸酯以及 119克作爲含有羥基之（甲基）丙烯酸酯之丙烯酸2-羥基乙 基酯，進而加入平均各0.5克之對-甲氧基苯酚以及二-第 '三丁基-羥基甲苯。攪拌下加熱至60°C後停止，添加0.8 克二丁基錫二月桂酸鹽。反應容器內之溫度開始降低時再 φ 度加熱，在80°C下繼續攪拌，以紅外線吸收光譜確認異 氰酸酯基的吸收光譜（SISOcnr1)消失時爲反應終了，獲得 $ 黏稠液體之胺基甲酸酯丙烯酸酯化合物。此化合物使用卡 必醇乙酸酯調整至不揮發份=56質量％，獲得固形物之酸 價47mg KOH/g、不揮發份50%之含有羧基之胺基甲酸酯 (甲基）丙烯酸酯化合物。以下此反應溶液稱爲清漆（A-2)。 &lt;鹼顯影型阻焊劑之調製&gt; # 使用所得之清漆（A-1)及清漆（A-2)，以三輥硏磨機使 下述調配成分混煉，獲得鹼顯影型阻焊劑。 清漆（A-1) 77份 清漆（A-2) 1〇〇份 2，4,6-三甲基苯偶因二苯基膦氧化物 10份 三聚氰胺 3份 二季戊四醇六丙烯酸酯 20份 -30 - 200842496 25份 2份 10份 RE-3 06(日本化藥股份有限公司 製之酚醛型環氧樹脂） 酞花青綠 黏度調整用溶劑 丙二醇單甲醚乙酸酯 _ &lt;評估用基板之製作〉 1. 鹼顯影型阻焊劑層之形成 使用形成有適當電路之FR-4基板，以磨砂硏磨後， 將所調製之鹼顯影型阻焊劑以絲網印刷法全面印刷，在 8 0 °C乾燥3 0分鐘，形成不黏之鹼顯影型阻焊劑層。 2. 曝光步驟 使用預先形成有鹼顯影型阻焊劑層之基板以及搭載高 壓水銀燈之接觸曝光機（ORC股份有限公司製之 EXP_ φ 2960)，以柯達No.2之階變（Step Tablet)求得成爲6段之 曝光量。 接著，於形成有鹼顯影型阻焊劑層之基板上，搭載特 定圖案之負片膜，設定於所求出之曝光量，以上述接觸曝 光機加以曝光。 3. 顯影步驟 經曝光之基板，使用30°C之1質量％碳酸鈉水溶液， 以噴霧壓力〇.2MPa之顯影機形成經顯影之圖案。又，使 顯影機上所附屬的水洗裝置呈爲停止狀態’顯影後’取出 -31 - 200842496 基板。 4.水洗歩驟 (水洗水之調製） 作爲鈣離子之供給源，使用氯化鈣（分子量=1 1 0 · 9 8， 鈴含量爲36.11質量％)，於1升離子交換水中’溶解氯化 鈣（CaCl2) 2·769毫克，調製含有lppm鈣離子之水洗水。 同樣地，調製含有 10、20、30、100、500、1 000、 ^ 1 0 00 0 ppm齡離子之水洗水。 同時，準備完全不含鈣離子之離子交換水。 (水洗） 於2升燒杯中，加入上述各水洗水並攪拌，以攪拌子 攪拌水洗水，使成有水流之狀態。於放入有此經攪拌水洗 水之燒杯中，置入顯影後之評估用基板並進行水洗。 隨後，省略清洗步驟，以棉屑等去除水分後，予以乾 燥。 φ 5.熱硬化步驟 經乾燥之基板，置入設定於1 5 0 °C之熱風循環式乾燥 爐中歷時60分鐘，使鹼顯影型阻焊劑層硬化。 隨後製作形成有形成開口部之鹼顯影型阻焊劑層之評 估用基板。 &lt;基板之評估&gt; (1)顯影殘渣之評估 形成鹼顯影型阻焊劑層，使用描繪有用以製作直徑 -32- 200842496 8〇μηι虛擬墊片之點狀圖案之負片圖案，經曝光、顯影 後，以各水洗水加以水洗，並經乾燥之熱硬化前的評估用 基板，使用掃描型電子顯微鏡（SEM)，以下列基準評估顯 影殘渣等。其結果示於表1。 〇：無顯影殘渣、附著物者。 1 :有少許顯影殘渣或附著物者。 X :有顯影殘渣或附著物，引起電鍍附著不良者。 Φ (2)焊錫耐熱性評估 形成鹼顯影型阻焊劑層，曝光、顯影後，以各水洗水 加以水洗、經乾燥、熱硬化之評估用基板上，塗佈松香系 助熔劑，於2 6 0 °C之焊錫槽中浸漬3 0秒。以丙二醇單甲 醚洗淨基板後，以下列基準評估塗膜狀態。其結果同時示 於表1。 〇：塗膜全然無膨脹、剝落、變色等異常。 X :辨識出顯著的塗膜膨脹、剝落、變色等。 • (3)鍍金附著性之評估 形成鹼顯影型阻焊劑層，曝光、顯影後，以各水洗水 加以水洗、經乾燥、熱硬化之評估用基板，於3 0 °c之酸 性脫脂液（日本Mac Diarmid股份有限公司製，Metex L-5B之20體積％水溶液）中浸漬3分鐘而脫脂，接著於自來 水中浸漬3分鐘進行水洗。接著，於14.3 wt%過硫酸銨水 溶液中，在室溫浸漬3分鐘，進行軟鈾刻，接著於自來水 中浸漬3分鐘進行水洗。於1 〇體積％硫酸水溶液中，於 室溫，使評估用基板浸漬1分鐘後，於自來水中浸漬3 0 -33- 200842496 秒〜1分鐘進行水洗。進而，於30°C之觸媒溶液（Meltex股 份有限公司製，金屬板活化劑350之10體積％水溶液）中 浸漬7分鐘，進行觸媒賦予後，於自來水中浸漬3分鐘進 行水洗。 如此進行觸媒賦予之評估用基板於8 5 °C之鎳鍍液 (Meltex股份有限公司製，金屬板Ni-865M之20體積％水 溶液，ρΗ4· 6)中浸漬20分鐘，進行無電解鍍鎳。接著， 於1 〇體積％硫酸水溶液中，在室溫浸漬1分鐘，於自來 水中浸漬3 0秒〜1分鐘進行水洗。其次，於9 5 °C之金鍍液 (Meltex股份有限公司製，歐羅斯UP 15體積％與氰化金 鉀3體積％之水溶液，PH6)中浸漬10分鐘進行無電解鍍 金，於自來水中浸漬3分鐘進行水洗，進而於60 °C溫水 中浸漬3分鐘進行熱水洗·。充分水洗後，將水清除乾 淨，乾燥，獲得施以無電解鍍金之評估用基板。 所得之評價用基板以SEM進行觀察，以下列評估基 準進行評估。其結果同時示於表1。 〇：並無因顯影殘渣引起鍍金附著性的問題者。 X :有因顯影殘渣引起鍍金附著性的問題者。 (4)PCT耐性之評估 形成鹼顯影型阻焊劑層，曝光、顯影後，以各水洗水 進行水洗、經乾燥、熱硬化之評估用基板，放入1 2 1 °C、 2大氣壓、溼度100%之高溫高壓高濕槽中歷時168小 時’目視觀察硬化塗膜之狀態變化，以下列基準進行評 估。其結果同時示於表1。 -34- 200842496 〇：未辨識出顯著膨脹、變色者。 △:辨識出少許膨脹、變色者。 X:辨識出顯著膨脹、變色者。 (5) HAST (高度加速升溫及溼度壓力試驗）後之遷移發 生狀態之評估 使用形成有梳型電極（線/間格=5 0 μ m / 5 0 μ m )之F R - 4基 板，形成鹼顯影型阻焊劑層，曝光、顯影後，以各水洗水 進行水洗，乾燥、熱硬化之評估用基板，在1 3 0 °C、溼度 8 5%之環境氛圍下，施加DC5V，進行168小時之HAST。 隨後，以光學顯微鏡觀察遷移發生狀態，以下列基準進行 評估。其結果同時示於表1。 〇：未辨識出顯著遷移發生者。 △:僅辨識出少許遷移發生者。 X:辨識出顯著遷移發生者。 (6) 彎曲之評估 作爲基板，使用厚度60μιη、400mmx300mm之高耐熱 接著絕緣材（日立化成工業股份有限公司），形成鹼顯影型 阻焊劑層，曝光、顯影後，以各水洗水進行水洗、經乾 燥、熱硬化之評估用基板，放置於平面上，測定試驗片之 四角落高度。接著，其合計作爲彎曲變形量，由其變形 量，以下列基準，進行彎曲評估，其結果同時示於表1。 〇：彎曲變形量小於2 0 m m者。 X :彎曲變形量爲20mm以上者。 -35- 200842496 [表1] 實施例 (Ca離子濃度ppm) 比較例 (Ca離子濃度ppm) 30 100 500 1000 0 10 20 10000 ⑴顯影殘渣確認試驗 〇 〇 〇 〇 X X X X (2)焊錫耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 (3)鍍金附著性 〇 〇 〇 〇 X X X X (4)PCT耐性 〇 〇 〇 〇 Δ Δ △ 〇 ⑶遷移發蝴態 〇 〇 〇 〇 Δ Δ Δ 〇 ⑹彎曲評估 〇 〇 〇 〇 〇 〇 〇 〇 由表1所示之結果可以明顯看出，以含30〜i〇〇〇ppm 鈣離子之水洗水進行水洗者，經過一次水洗亦未辨識出顯 影殘渣，其解像性、鍍金附著性、PCT耐性、遷移發生狀 態良好，焊錫耐熱性一良好，也未看到彎曲。 另一方面，以離子交換水、以及含20ppm以下鈣離 子之水洗水進行處理者，進行一次水洗有顯影殘渣殘留， 解像性以及鍍金附著性有問題。又，PCT耐性、遷移發生 狀態亦劣化。又，即使以鈣離子濃度超過lOOOppm者進 行處理，仍殘留有顯影殘渣，解像性、鍍金附著性有問 題。此係認爲於水洗水中溶解的鹼顯影型阻焊劑隨及凝集 之故。 (7)水洗水中離子濃度變化之測定 使用含1 OOppm鈣離子之水洗水，測定每一升水洗水 的基板處理面積與離子濃度之變化。結果示於圖1。 如圖i所示，於含lOOppm鈣離子之水洗水，隨著處 理面積之增大，鈣離子減少，每1升處理約lm2時鈣離子 -36- 200842496 殘留約30ppm，未補充鈣離子，每1生處理達基板面積約 lm2並無問題，確認可水洗。因此，可理解以生產性高地 進行水洗處理是有可能的。 [實施例2] ‘ 製作與實施例1相同的評估基板，水洗水中所含之2 價金屬離子改變成鎂離子，進行同樣水洗。水洗水的鎂離 φ 子濃度調製爲50PPm，進而作爲比較例，則調製鎂離子濃 度爲lOppm、lOOOOppm者。此對於經乾燥之熱硬化前的 評估基板，使用SEM評估顯影殘渣等。 圖2顯示以含50ppm鎂離子之水洗水洗淨時的墊片 部之電子顯微鏡照片。如圖所示，未辨識出顯影殘渣等。 圖3顯不作爲比較例之以含l〇ppm鎂離子之水洗水 洗淨時的墊片部之電子顯微鏡照片。可看出黏著性的顯影 殘渣殘留在岸面（land)周邊以及墊片底部之外周。 φ 圖4顯示作爲比較例之以含lOOOOppm鎂離子之水洗 水洗淨時的墊片部之電子顯微鏡照片。可看出墊片上附著 有樹脂狀附著物。 [實施例3] 如以下般，調製鹼顯影型阻焊劑，與實施例1同樣製 作評估用基板。 &lt;含有羧基之胺基甲酸酯（甲基）丙烯酸酯化合物之合 -37- 200842496 成&gt; 於配備有攪拌裝置、溫度計、回流冷凝器之反應容器 中，置入2400克（3莫耳）之自1,5-戊二醇與1，6-己二醇所 衍生之聚碳酸酯二醇（宇部興產股份有限公司， PDCL800，數平均分子量800)、4 02克（3莫耳）作爲含有 羧基之二羥基化合物之二羥甲基丙酸、1554克（7莫耳）作 爲聚異氰酸酯之異佛爾酮二異氰酸酯以及23 8克（2.05莫 耳）作爲單羥基化合物之丙烯酸2-羥基乙基酯。攪拌下加 熱至60 °C後停止，在反應容器內之溫度開始降低時再度 加熱，在80 °C下繼續攪拌，以紅外線吸收光譜確認異氰 酸酯基的吸收光譜（2280CHT1)消失時爲反應終了，獲得黏 稠液體之胺基甲酸酯丙烯酸酯化合物。接著，以使固形份 成爲50質量％之方式添加卡必醇乙酸酯，獲得數平均分 子量22,000(使用凝膠擔體之液體層析儀（GPC昭和電工股 份有限公司製之GPC-1)，換算爲聚苯乙烯之値）、固形物 之酸價46mg KOH/g之含有羧基之胺基甲酸酯（甲基）丙烯 酸酯化合物。以下此反應溶液稱爲清漆（A-3)。 &lt;含有羧基之樹脂之合成&gt; 於具備有溫度計、兼有氮氣導入裝置之環氧烷導入裝 置以及攪拌裝置之高壓釜中，置入119.4份之酚醛型甲酚 樹脂（商品名「修諾爾CRG951」，昭和高分子股份有限公 司製，OH當量：119.4)、1.09份氫氧化鉀及119.4份甲 苯，一面攪拌一面於反應系內置換氮氣，加熱升溫。接 -38- 200842496 著，緩慢滴加 63 ·8份環氧丙烷，於 125〜132 °C 、 0〜4.8kg/cm2反應16小時。隨後冷卻至室溫’於反應溶液 中，添加混合1.56份之89%磷酸’中和氫氧化鉀’獲得 不揮發份62.1%、羥價爲182.2g/eq之酚醛型甲酚樹脂之 環氧丙烷反應溶液。此爲每1當量酚性羥基平均加成有 1.08莫耳環氧烷者。 所得之酚醛型甲酚樹脂之環氧丙烷反應溶液2 9 3.0 份、丙烯酸43.2份、甲烷磺酸1 1.53份、甲基氫醌0.18 份以及252.9份甲苯’置入具備有攪拌裝置、溫度計以及 空氣吹入管之反應器中。以10毫升/分鐘之速度吹入空 氣，攪拌下，在1 10 °c反應12小時。反應所生成的水’ 以與甲苯之共沸混合物，餾出1 2.6份之水。隨後，冷卻 至室溫，所得之反應溶液以35.35份之15%氫氧化鈉水溶 液中和，接著水洗。隨後，於蒸發器中，以1 1 8 . 1份二乙 二醇單乙醚乙酸酯置換甲苯並餾除，獲得酚醛型丙烯酸酯 樹脂溶液。 接著，所得之酚醛型丙烯酸酯樹脂溶液332.5份及三 苯膦1.22份置入具備有攪拌裝置、溫度計及空氣吹入管 之反應器內，以1〇毫升/分鐘之速度吹入空氣，攪拌下’ 緩慢添加四氫苯二酸酐60·8份，在95〜101 °C反應6小 時，冷卻後，取出。因此獲得不揮發份70.6%、固形物之 酸價87.7mg KOH/g之含有羧基之樹脂。以下，該反應溶 液稱爲清漆（A-4)。 -39- 200842496 &lt;鹼顯影型阻焊劑之調製&gt; 使用所得之含有羧基之胺基甲酸酯（甲基）丙烯酸酯化 合物、包含酚醛型丙烯酸酯化合物之含有羧基之樹脂，以 三輥硏磨機使下述調配成分混煉，獲得鹼顯影型阻焊劑。 清漆（A-3) 170份 清漆（A-4) 23份 2，4,6-三甲基苯偶因二苯基膦氧化物 10份 吩噻嗪 〇·2份 三聚氰胺 3份 二季戊四醇六丙烯酸酯 20份 RE-306 25份 F astgen blue 〇·6份 Cromophtal yellow 〇·6份 丙二醇單甲醚乙酸酯 10份 使用所調製之鹼顯影型阻焊劑，製作與實施例1相同 的評估基板，水洗水中所含之2價金屬離子改變成緦離 子、鋇離子，改變離子濃度，進行水洗。又，作爲比較 例，則使用含3價離子之鋁離子之水洗水進行水洗。接 著，此對於經乾燥之熱硬化前的評估基板，使用SEM評 估顯影殘渣等。 圖5顯示以含115ppm緦離子之水洗水進行洗淨時之 墊片部之電子顯微鏡照片。如圖所示，並未辨識出顯影殘 -40- 200842496 渣等。 圖6顯示作爲比較例之以含1 2ppm緦離子之水洗水 洗淨時的墊片部之電子顯微鏡照片。可看出黏著性的顯影 殘渣殘留在墊片底部之外周。 圖7顯示作爲比較例之以含23 000ppm緦離子之水洗 水洗淨時的墊片部之電子顯微鏡照片。可看出墊片上附著 有樹脂狀附著物。 圖8顯示以含24 Oppm鋇離子之水洗水進行洗淨時之 墊片部之電子顯微鏡照片。如圖所示，並未辨識出顯影殘 渣等。 圖9顯示作爲比較例之以含1 2ppm鋇離子之水洗水 洗淨時的墊片部之電子顯微鏡照片。可看出黏著性的顯影 殘渣殘留在墊片底部之外周。 圖10顯示作爲比較例之以含24000ppm鋇離子之水 洗水洗淨時的墊片部之電子顯微鏡照片。可看出墊片上及 其周邊附著有樹脂狀附著物。 圖1 1顯示作爲比較例之以含5 p p m之3價銘離子之 水洗水洗淨時的墊片部之電子顯微鏡照片。可看出黏著性 顯影殘渣殘留在墊片底部之外周。又，若爲低於5 Oppm 之濃度區域，認爲未發生顯影殘渣而可能以水洗。然而’ 實際上量產時，難以高精度地控制在如此低的濃度，而難 以獲得良好生產性。 因此，於鹼顯影型阻焊劑顯影後之水洗中’藉由利用 含3 0〜lOOOppm之2價金屬離子之水洗水，經一次水洗， -41 - 200842496 於在鹼顯影型阻焊劑層之特定部位中所形成之微小墊片等 之開口部中，抑制顯影殘渣等成爲可能。因此，可以提供 得以改善電鍍附著性，可獲得高信賴性、生產性之印刷配 線板。 【圖式簡單說明】 圖1顯示使用含有lOOppm鈣離子之水洗水時之鈣離 子與每1公升水洗水的處理面積之關係圖。 圖2爲本發明之一樣態中有關之以含50ppm鎂離子 之水洗水洗淨時之墊片部之電子顯微鏡照片。 圖3爲比較例中有關之以含lOppm鎂離子之水洗水 洗淨時之墊片部之電子顯微鏡照片。 圖4爲比較例中有關之以含lOOOOppm鎂離子之水洗 水洗淨時之墊片部之電子顯微鏡照片。 圖5爲本發明之一樣態中有關之以含1 1 5ppm緦離子 之水洗水洗淨時之墊片部之電子顯微鏡照片。 圖6爲比較例中有關之以含12ppm緦離子之水洗水 洗淨時之墊片部之電子顯微鏡照片。 圖7爲比較例中有關之以含23 00 Oppm緦離子之水洗 水洗淨時之墊片部之電子顯微鏡照片。 圖8爲本發明之一樣態中有關之以含240ppm鋇離子 之水洗水洗淨時之墊片部之電子顯微鏡照片。 圖9爲比較例中有關之以含12PPm鋇離子之水洗水 洗淨時之墊片部之電子顯微鏡照片。 -42- 200842496 圖1 0爲比較例中有關之以a 洗水洗淨時之墊片部之電子顯微鏡 圖1 1爲比較例中有關之以# 洗淨時之墊片部之電子顯微鏡照片 24000ppm鋇離子之水 裏片。 5ppm鋁離子之水洗水As such hardening catalysts, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazoles such as phenylethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamine, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl An amine compound such as benzylamine; an anthracene compound such as bismuth adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine, and the like, and a commercially available product, for example, Siguo Chemical Industry Co., Ltd. 2MZ-A, 2-MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade names of imidazole-based compounds), U-CAT3 5 03N, U-CAT3 502T (manufactured by San-apro Co., Ltd.) The trade name of the blocked isocyanate compound, DBU, DBN, U-CATSA102, U-CAT -26-200842496 5 002 (each is a bicyclic hydrazine compound and a salt thereof). In particular, it is not limited to such a thermosetting catalyst of an epoxy resin or an oxetane compound, or preferably a group which can promote the reaction of an epoxy group and/or an oxetane group with a carboxyl group. It can be used even if it is used alone or in combination. Further, it is also possible to use guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxy B, which also functions as a adhesion-imparting agent. Base-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·trimeric isocyanate addition An S-triazine derivative such as an adduct of 2,4·diamino-6-methylpropenyloxyethyl-S-triazine·trimeric isocyanate, or the like A compound that imparts a function to the agent and a heat-hardening catalyst. The proportion of the curing catalyst to the usual amount is sufficient, for example, 0.1 to 20 parts by mass based on 1 part by mass of the total of the resin composition. When the proportion of the hardening catalyst is less than 〇. 1 part by mass, the hardening time becomes long, and the workability is lowered to cause oxidation of the copper foil or the like. On the other hand, when the blending ratio of the hardening catalyst exceeds 20 parts by mass, the electrical characteristics are lowered, and the standing life after temporary drying is shortened. More preferably, it is a ratio of 0.5 to 15.0 parts by mass. Further, the alkali-developing type solder resist used in the present embodiment can be adjusted with an inorganic chelating agent for the purpose of further improving properties such as cured product adhesion, mechanical strength, and linear expansion coefficient. For example, barium sulfate, barium titanate cerium oxide powder, micronized cerium oxide, amorphous cerium oxide, talc 'clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, etc. . The blending ratio is preferably 树脂~80% by mass of the resin composition ° -27- 200842496. Further, according to requirements, the following additives may be added: phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, Coloring agents such as crystal violet, titanium oxide, carbon black, naphthalene black; thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, etc. Antifoaming agent such as micronized cerium oxide, organic bentonite, montmorillonite, antifoaming agent and/or homogenizing agent such as antimony, thiazole, triazole or the like Additives such as coupling agents. Φ Therefore, the thus formed printed wiring board is suitable for use as a package substrate such as CSP or UT-CSP. The CSP functions as an intermediate plate (insert) for mounting a 1C wafer on a printed wiring board, and has a size substantially the same as that of the 1C wafer. UT-CSP is a thinner CSP. Such a CSP or UT-CSP is manufactured and installed, for example, as follows. First, an alkali developing type solder resist layer is formed on both surfaces of a substrate on which a conductor semiconductor is formed, and the layer is formed with an opening portion to form a pad for connecting to the 1C wafer and a pad for connecting to the printed wiring board. The package substrate of the sheet. Next, a 1C wafer was connected to the 1C wafer connection surface of the package substrate by wire bonding or flip chip bonding. Subsequently, the 1C wafer is affixed to the package substrate with an encapsulating material (the bottom sizing agent as needed). Further, a solder ball is attached to the printed wiring board connection surface of the package substrate to form a CSP (UT-CSP). The formed CSP (UT-CSP) is disposed on the printed wiring board, and the solder ball is melted by a reflow soldering furnace of -28-200842496, and is connected by a printed wiring board and an opening portion to which gold plating or the like is applied. installation. [Embodiment 1] The following embodiments and comparative examples are specifically described as the same as the present invention, but the present invention is not limited to the examples. &lt;Synthesis of carboxyl group-containing resin&gt; 2200 g of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220), 134 g of dihydroxy Methylpropionic acid, 648.5 g of acrylic acid, 4.6 g of methylhydroquinone, 1131 g of carbitol acetate, and 484.9 g of solvent naphtha were heated and stirred at 90 ° C to dissolve the reaction mixture. Then, the reaction liquid was cooled to 60 ° C, 13.8 g of triphenylphosphine was placed, and the mixture was heated to 10 ° C for about 32 hours to obtain a reactant having an acid value of 0.5 mg KOH / g. Next, 3 64.7 g of tetrahydrophthalic anhydride, 137.5 g of carbitol acetate, and 58 8 g of solvent naphtha were placed, heated to 95 ° C, and reacted for about 6 hours, and then cooled to obtain a solid matter. A resin containing a carboxyl group having an acid value of 40 mh KOH/g and a nonvolatile content of 65%. Hereinafter, this reaction solution is referred to as varnish (A-1). &lt;Synthesis of carboxyl group-containing urethane (meth) acrylate compound&gt; In a 5 liter separable bottle equipped with a thermometer, a stirring device, and a reflux condenser, 1,245 g was placed as a polymer polymer. Polycaprolactone diol of alcohol -29- 200842496 (PLACCEL 208 manufactured by Diacell Chemical Industry Co., Ltd., molecular weight 83 0), 2 1 g of dimethylolpropionic acid as a dihydroxy compound containing a carboxyl group, 777 g as a poly Isocyanate isophorone diisocyanate and 119 g of 2-hydroxyethyl acrylate as a hydroxyl group-containing (meth) acrylate, further adding an average of 0.5 g of p-methoxyphenol and di-tert-butyl - Hydroxy toluene. After heating to 60 ° C with stirring, the mixture was stopped, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel began to decrease, the temperature was further increased by φ, and stirring was continued at 80 ° C. When the absorption spectrum of the isocyanate group (SISOcnr1) disappeared by the infrared absorption spectrum, the reaction was terminated, and a viscous liquid urethane was obtained. Acrylate compound. This compound was adjusted to a nonvolatile content = 56% by mass using carbitol acetate to obtain a carboxyl group-containing urethane (meth) acrylate having an acid value of 47 mg KOH/g of a solid matter and 50% of a nonvolatile content. Compound. The following reaction solution is referred to as varnish (A-2). &lt;Preparation of alkali-developing type solder resist&gt;# Using the obtained varnish (A-1) and varnish (A-2), the following compounding ingredients were kneaded by a three-roll honing machine to obtain an alkali-developing type solder resist. Varnish (A-1) 77 parts varnish (A-2) 1 part 2,4,6-trimethylphenylene diphenylphosphine oxide 10 parts melamine 3 parts dipentaerythritol hexaacrylate 20 parts -30 - 200842496 25 parts, 2 parts, 10 parts of RE-3 06 (phenolic epoxy resin manufactured by Nippon Kayaku Co., Ltd.) Solvent propylene glycol monomethyl ether acetate for phthalocyanine viscosity adjustment _ &lt;Production of evaluation substrate> 1. Formation of alkali-developed solder resist layer Using an FR-4 substrate formed with a suitable circuit, after honing with a matte, the prepared alkali-developing solder resist is printed in full screen by screen printing and dried at 80 ° C. At 30 minutes, a non-stick alkali-developing solder resist layer was formed. 2. The exposure step was carried out using a substrate on which an alkali-developing type solder resist layer was formed in advance and a contact exposure machine (EXP_ φ 2960 manufactured by ORC Co., Ltd.) equipped with a high-pressure mercury lamp, using a step of Kodak No. 2 (Step Tablet). Become the exposure of 6 segments. Next, a negative film of a specific pattern is placed on the substrate on which the alkali-developing type solder resist layer is formed, and the exposure amount is set, and exposure is performed by the above-mentioned contact exposure. 3. Developing Step The developed substrate was formed using a 1% by mass aqueous sodium carbonate solution at 30 ° C and a developing machine having a spray pressure of 2 2 MPa. Further, the water washing device attached to the developing device is brought into a stopped state. After development, the substrate is taken out -31 - 200842496. 4. Washing step (modulation of washing water) As a source of calcium ions, calcium chloride (molecular weight = 1 1 0 · 9 8 , bell content: 36.11% by mass) is used to dissolve chlorination in 1 liter of ion-exchanged water. Calcium (CaCl2) 2·769 mg, water washing water containing 1 ppm of calcium ions was prepared. Similarly, a water wash containing 10, 20, 30, 100, 500, 1 000, ^ 1 0 00 0 ppm ions was prepared. At the same time, prepare ion-exchanged water that is completely free of calcium ions. (Washing) In a 2-liter beaker, each of the above-mentioned water washing waters was added and stirred, and the water was washed with a stirrer to form a water flow state. The substrate for evaluation after development was placed in a beaker containing the stirred water and washed with water. Subsequently, the washing step is omitted, and after removing moisture with cotton dust or the like, it is dried. φ 5. Thermal hardening step The dried substrate was placed in a hot air circulating type oven set at 150 ° C for 60 minutes to harden the alkali developing type solder resist layer. Subsequently, an evaluation substrate on which an alkali-developing type solder resist layer forming an opening portion was formed was produced. &lt;Evaluation of substrate&gt; (1) Evaluation of development residue An alkali-developing type solder resist layer was formed, and a negative pattern which was used to produce a dot pattern having a diameter of -32 - 200842496 8〇μηι virtual spacer was used for exposure and development. After that, each of the water-washed water was washed with water, and the evaluation substrate before the heat hardening was dried, and a development electron residue (SEM) was used to evaluate the development residue and the like on the following basis. The results are shown in Table 1. 〇: No developer residue or attachment. 1 : There is a little development residue or attachment. X : There is a development residue or deposit, which causes poor plating adhesion. Φ (2) Solder heat resistance evaluation The alkali-developing type solder resist layer is formed, and after exposure and development, a rosin-based flux is applied on a substrate for evaluation of washing, drying, and heat hardening with each water washing water, at 2 60 Immerse for 30 seconds in the solder bath of °C. After the substrate was washed with propylene glycol monomethyl ether, the state of the coating film was evaluated on the following basis. The results are also shown in Table 1. 〇: The coating film has no abnormalities such as swelling, peeling and discoloration. X : Significant coating film swelling, peeling, discoloration, and the like are recognized. • (3) Evaluation of gold plating adhesion The alkali-developing type solder resist layer was formed, and after exposure and development, the substrate for evaluation by washing with water, dried and thermally hardened, and an acidic degreasing solution at 30 ° C (Japan) It was degreased by immersing for 3 minutes in a 20% by volume aqueous solution of Metex L-5B, manufactured by Mac Diarmid Co., Ltd., followed by immersion in tap water for 3 minutes for water washing. Subsequently, it was immersed in a 14.3 wt% aqueous ammonium persulfate solution at room temperature for 3 minutes to carry out soft uranium engraving, followed by immersion in tap water for 3 minutes for water washing. The substrate for evaluation was immersed in a 1% by volume aqueous sulfuric acid solution at room temperature for 1 minute, and then immersed in tap water for 30 - 33 - 200842496 seconds - 1 minute for water washing. Further, the catalyst solution (a 10% by volume aqueous solution of a metal plate activator 350, manufactured by Meltex Co., Ltd.) at 30 ° C was immersed for 7 minutes, and after the catalyst was applied, it was immersed in tap water for 3 minutes and washed with water. The substrate for evaluation by the catalyst was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., a 20-vol% aqueous solution of a metal plate Ni-865M, ρΗ4·6) at 85 ° C for 20 minutes to carry out electroless nickel plating. . Subsequently, the mixture was immersed in a 1% by volume aqueous sulfuric acid solution at room temperature for 1 minute, and immersed in tap water for 30 seconds to 1 minute to carry out water washing. Next, an electroless gold plating was performed on a gold plating solution (manufactured by Meltex Co., Ltd., a 0.15% by volume of Ou Ross UP and a 3 volume% aqueous solution of potassium cyanide, pH 6) at 95 ° C for electroless gold plating, and immersed in tap water. The mixture was washed with water for 3 minutes, and further immersed in warm water of 60 ° C for 3 minutes for hot water washing. After sufficiently washing with water, the water was removed and dried, and a substrate for evaluation by electroless gold plating was obtained. The obtained evaluation substrate was observed by SEM and evaluated by the following evaluation criteria. The results are also shown in Table 1. 〇: There is no problem of gold plating adhesion due to development residue. X : There is a problem of gold plating adhesion due to development residue. (4) Evaluation of PCT resistance The alkali-developing type solder resist layer was formed. After exposure and development, the substrate for evaluation of water washing, drying and heat hardening with each washing water was placed at 1 21 ° C, 2 atm, and humidity 100. The state change of the hardened coating film was visually observed for 168 hours in a high-temperature high-pressure high-humidity tank of %, and was evaluated on the following basis. The results are also shown in Table 1. -34- 200842496 〇: No significant expansion or discoloration was recognized. △: A little expansion or discoloration was recognized. X: A person who notices significant expansion or discoloration is recognized. (5) Evaluation of the state of migration after HAST (highly accelerated temperature rise and humidity pressure test) The FR-4 substrate formed with a comb electrode (line/space grid = 50 μm / 50 μm) was used to form a base. After the development and development of the solder resist layer, the substrate for evaluation was washed with water, dried and thermally cured, and DC5V was applied at 1300 ° C and a humidity of 85% for 168 hours. HAST. Subsequently, the state of migration was observed with an optical microscope and evaluated on the following basis. The results are also shown in Table 1. 〇: No significant migration occurred. △: Only a few migration occurrences were identified. X: A significant migration occurrence is identified. (6) Evaluation of Bending As a substrate, a high-temperature heat-resistant insulating material (Hitachi Kasei Kogyo Co., Ltd.) having a thickness of 60 μm and 400 mm x 300 mm was used to form an alkali-developing type solder resist layer. After exposure and development, each washing water was washed with water. The substrate for evaluation of drying and heat hardening was placed on a flat surface, and the height of the four corners of the test piece was measured. Then, the total amount of the bending deformation was measured by the amount of deformation based on the following basis, and the results are shown in Table 1. 〇: The amount of bending deformation is less than 20 mm. X: The amount of bending deformation is 20 mm or more. -35- 200842496 [Table 1] Example (Ca ion concentration ppm) Comparative example (Ca ion concentration ppm) 30 100 500 1000 0 10 20 10000 (1) Development residue confirmation test 〇〇〇〇XXXX (2) Solder heat resistance 〇〇 〇〇〇〇〇〇(3) Gold-plated adhesion 〇〇〇〇XXXX (4) PCT resistance 〇〇〇〇Δ Δ △ 〇(3) Migration and evolution 蝴Δ Δ Δ 〇(6) Bending evaluation〇〇〇〇 From the results shown in Table 1, it can be clearly seen that the water is washed with a water washing solution containing 30 to i ppm of calcium ions, and the development residue is not recognized after one water washing, and its resolution and gold plating are performed. Adhesion, PCT resistance, migration occurred in a good state, and solder heat resistance was good, and no bending was observed. On the other hand, when it is treated with ion-exchanged water and water washing water containing calcium ions of 20 ppm or less, the washing residue is left once and washed, and the resolution and gold plating adhesion are problematic. Moreover, the PCT tolerance and migration occurrence state also deteriorated. Further, even if the calcium ion concentration exceeds 1,000 ppm, the development residue remains, and there are problems in resolution and gold plating adhesion. This is considered to be caused by agglomeration of the alkali-developing type solder resist dissolved in the water wash water. (7) Measurement of ion concentration change in water wash water The water was washed with water containing 100 ppm of calcium ions, and the change in substrate treatment area and ion concentration of each liter of water wash water was measured. The results are shown in Figure 1. As shown in Fig. i, in the water washing water containing 100 ppm of calcium ions, as the treatment area increases, the calcium ion decreases, and the calcium ion-36-200842496 remains about 30 ppm per liter of about 1 liter of treatment, and no calcium ions are added. 1 raw treatment up to the substrate area of about lm2 no problem, confirmed to be washable. Therefore, it is understood that it is possible to carry out a water washing treatment in a productive manner. [Example 2] 『 The same evaluation substrate as in Example 1 was produced, and the divalent metal ions contained in the water wash water were changed to magnesium ions, and the same water washing was performed. The magnesium ion concentration of the washing water was adjusted to 50 ppm, and as a comparative example, the magnesium ion concentration was adjusted to 10 ppm and 1000 ppm. For the evaluation substrate before the heat curing by drying, the development residue and the like were evaluated using SEM. Fig. 2 shows an electron micrograph of the gasket portion when washed with water containing 50 ppm of magnesium ions. As shown in the figure, development residue or the like is not recognized. Fig. 3 is an electron micrograph showing a gasket portion when washed with water containing 1 〇 ppm of magnesium ions as a comparative example. It can be seen that the adhesive development residue remains on the periphery of the land and the periphery of the bottom of the gasket. φ Fig. 4 shows an electron micrograph of the gasket portion when washed with water containing 100 ppm of magnesium ions as a comparative example. It can be seen that a resin-like deposit adheres to the gasket. [Example 3] An alkali-developing type solder resist was prepared in the same manner as in Example 1 to prepare a substrate for evaluation. &lt;Carboxyl-containing urethane (meth) acrylate compound-37-200842496 </ RTI> 2400 g (3 m) in a reaction vessel equipped with a stirring device, a thermometer, and a reflux condenser Polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (Ube Industries, PDCL800, number average molecular weight 800), 4 02 g (3 m) Dihydroxymethylpropionic acid as a dihydroxy compound containing a carboxyl group, 1554 g (7 mol) of isophorone diisocyanate as a polyisocyanate, and 23 g (2.05 mol) of a 2-hydroxyl acrylate as a monohydroxy compound Ethyl ester. The mixture was heated to 60 ° C with stirring, and then stopped. When the temperature in the reaction vessel began to decrease, the mixture was heated again, and stirring was continued at 80 ° C. The infrared absorption spectrum was confirmed to be the end of the reaction when the absorption spectrum of the isocyanate group disappeared (2280 CHT 1 ). A viscous liquid urethane acrylate compound. Next, carbitol acetate was added so that the solid content was 50% by mass, and a number average molecular weight of 22,000 (a liquid chromatograph using a gel carrier (GPC-1 manufactured by GPC Showa Denko Co., Ltd.) was obtained. A carboxyl group-containing urethane (meth) acrylate compound having an acid value of 46 mg KOH/g in terms of polystyrene. The following reaction solution is referred to as varnish (A-3). &lt;Synthesis of a carboxyl group-containing resin&gt; In an autoclave equipped with a thermometer, an alkylene oxide introducing device having a nitrogen gas introducing device, and a stirring device, 119.4 parts of a phenol novolak type cresol resin (trade name "Shenol" was placed. CRG951", manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4), 1.09 parts of potassium hydroxide and 119.4 parts of toluene, and the nitrogen gas was replaced in the reaction system while stirring, and the temperature was raised by heating. From -38 to 200842496, 63·8 parts of propylene oxide was slowly added dropwise, and reacted at 125 to 132 ° C and 0 to 4.8 kg/cm 2 for 16 hours. Subsequently, it was cooled to room temperature' in the reaction solution, and 1.56 parts of 89% phosphoric acid 'neutralized potassium hydroxide' was added to obtain a propylene oxide resin having a nonvolatile content of 62.1% and a hydroxyl group of 182.2 g/eq. Reaction solution. This is an average addition of 1.08 moles of alkylene oxide per one equivalent of phenolic hydroxyl groups. The resulting phenolic cresol resin has a propylene oxide reaction solution of 2 9 3.0 parts, 43.2 parts of acrylic acid, 1.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene' placed with a stirring device, a thermometer, and air. Blow into the reactor of the tube. Air was blown at a rate of 10 ml/min, and reacted at 10 ° C for 12 hours while stirring. The water produced by the reaction was distilled in an azeotropic mixture with toluene to distill 1 2.6 parts of water. Subsequently, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, followed by water washing. Subsequently, toluene was replaced with 1 1 8 .1 parts of ethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the obtained phenolic acrylate resin solution and 1.22 parts of triphenylphosphine were placed in a reactor equipped with a stirring device, a thermometer, and an air blowing tube, and air was blown at a speed of 1 〇 ml/min, and stirred under ' 60 parts of tetrahydrophthalic anhydride was slowly added, and the mixture was reacted at 95 to 101 ° C for 6 hours, and after cooling, it was taken out. Thus, a carboxyl group-containing resin having a nonvolatile content of 70.6% and an acid value of 87.7 mg KOH/g of the solid matter was obtained. Hereinafter, the reaction solution is referred to as varnish (A-4). -39- 200842496 &lt;Preparation of alkali-developing type solder resist&gt; The obtained carboxyl group-containing urethane (meth) acrylate compound and carboxyl group-containing resin containing a novolac type acrylate compound are used in a three-roller crucible. The mill kneaded the following compounding ingredients to obtain an alkali developing type solder resist. Varnish (A-3) 170 parts varnish (A-4) 23 parts 2,4,6-trimethylphenylene diphenylphosphine oxide 10 parts phenothiazine oxime · 2 parts melamine 3 parts dipentaerythritol hexaacrylic acid Ester 20 parts RE-306 25 parts Fasten blue 〇·6 parts Cromophtal yellow 〇·6 parts propylene glycol monomethyl ether acetate 10 parts The same evaluation substrate as in Example 1 was produced using the prepared alkali developing type solder resist. The divalent metal ions contained in the washing water are changed into cerium ions and cerium ions, and the ion concentration is changed to perform water washing. Further, as a comparative example, water washing was carried out using a washing water containing aluminum ions of trivalent ions. Then, for the evaluation substrate before the heat curing by drying, the development residue and the like were evaluated using SEM. Fig. 5 is an electron micrograph showing the pad portion when it is washed with water containing 115 ppm of cesium ions. As shown in the figure, the development residue -40 - 200842496 slag is not recognized. Fig. 6 is an electron micrograph showing a gasket portion when washed with water containing 12 ppm of cerium ions as a comparative example. It can be seen that the adhesive development residue remains outside the bottom of the gasket. Fig. 7 is an electron micrograph showing a gasket portion when washed with water containing 23 000 ppm of cerium ions as a comparative example. It can be seen that a resin-like deposit adheres to the gasket. Fig. 8 is an electron micrograph showing the pad portion when it is washed with water containing 24 Oppm of cesium ions. As shown in the figure, development residue and the like are not recognized. Fig. 9 is an electron micrograph showing a gasket portion when washed with water containing 12 ppm of cesium ions as a comparative example. It can be seen that the adhesive development residue remains outside the bottom of the gasket. Fig. 10 is an electron micrograph showing a gasket portion when washed with water containing 24,000 ppm of cerium ions as a comparative example. It can be seen that a resinous deposit adheres to the gasket and its periphery. Fig. 1 1 shows an electron micrograph of a gasket portion when washed with water of a 3 valent ion containing 5 p p m as a comparative example. It can be seen that the adhesive development residue remains outside the bottom of the gasket. Further, in the case of a concentration region of less than 5 Oppm, it is considered that the development residue does not occur and may be washed with water. However, in actual production, it is difficult to control such a low concentration with high precision, and it is difficult to obtain good productivity. Therefore, in the water washing after the development of the alkali developing type solder resist, the water is washed by using water containing 30 to 1000 ppm of a divalent metal ion, washed once, and -41 - 200842496 in a specific portion of the alkali developing type solder resist layer. In the opening of a minute gasket or the like formed in the middle, it is possible to suppress development residue and the like. Therefore, it is possible to provide a printed wiring board which can improve plating adhesion and obtain high reliability and productivity. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the calcium ion and the treated area per 1 liter of water washing water when water is washed with water containing 100 ppm of calcium ions. Fig. 2 is an electron micrograph of the gasket portion when washed with water containing 50 ppm of magnesium ions in the same state of the present invention. Fig. 3 is an electron micrograph of the gasket portion of the comparative example in the case of washing with water containing 10 ppm of magnesium ions. Fig. 4 is an electron micrograph of the gasket portion of the comparative example in the case of washing with water containing 1000 ppm of magnesium ions. Fig. 5 is an electron micrograph of the gasket portion when washed with water containing 1 15 ppm of cerium ions in the same state of the present invention. Fig. 6 is an electron micrograph of the gasket portion of the comparative example in the case of washing with water containing 12 ppm of cerium ions. Fig. 7 is an electron micrograph of the gasket portion of the comparative example in the case of washing with water containing 2300 Oppm of cerium ions. Fig. 8 is an electron micrograph of the gasket portion when washed with water containing 240 ppm of cerium ions in the same state of the present invention. Fig. 9 is an electron micrograph of the gasket portion of the comparative example in the case of washing with water containing 12 ppm of cerium ions. -42- 200842496 Fig. 10 is an electron microscope of the gasket portion when washing with a washing water in the comparative example. Fig. 1 is an electron micrograph of the gasket portion when washing with # in the comparative example. 24000 ppm钡Ion water in the piece. 5ppm aluminum ion water wash

-43--43-

Claims (1)

200842496 十、申請專利範圍 1. 一種印刷配線板之製造方法，其特徵爲： 於形成有導體圖案之基板表面上，形成含有含羧基之 胺基甲酸酯（甲基）丙烯酸酯化合物作爲含羧基之樹脂之鹼 顯影型阻焊劑層； 使該鹼顯影型阻焊劑層經由特定的開口圖案予以曝 光，藉由稀驗水溶液顯影，使用含30〜lOOOppm的二價金 屬離子的水洗水加以水洗後，藉由熱硬化，在前述鹼顯影 型阻焊劑層之特定位置形成開口部。 2·如申請專利範圍第1項之印刷配線板之製造方 法，其中前述二價金屬離子係選自 Ca2+、Mg2+、Sr2+、 Ba2 +之至少一種的金屬離子。 3.如申請專利範圍第1或2項之印刷配線板之製造 方法，其中相對於前述含羧基之樹脂100質量份，前述含 羧基之胺基甲酸酯（甲基）丙烯酸酯化合物含有35質量份 以上。 4·如申請專利範圍第1至3項中任一項之印刷配線 板之製造方法，其中藉由於前述形成有導體圖案之基板表 面上’塗佈鹼顯影型阻焊劑並乾燥而形成前述鹼顯影型阻 焊劑層。 5 ·如申請專利範圍第1至3項中任一項之印刷配線 板之製造方法，其中藉由於前述形成有導體圖案之基板表 面上’積層由鹼顯影型阻焊劑所構成之乾膜而形成前述鹼 顯影型阻焊劑層。 -44 - 200842496 6·如申請專利範圍第1至5項中任一項之印刷配線 板之製造方法，其中前述開口部的直徑爲20〜l〇〇Pm。 7.如申請專利範圍第1至6項中任一項之印刷配線 板之製造方法，其中前述導體圖案係包含銅。 8·如申請專利範圍第1至7項中任一項之印刷配線 板之製造方法，其中於前述導體圖案上形成前述開口部。 9· 一種印刷配線板，其特徵爲具有： φ 形成有導體圖案之基板；及 形成於該基板上且於特定位置形成有開口部之鹼顯影 型阻焊劑層，其含有含羧基之胺基甲酸酯（甲基）丙烯酸酯 化合物以及二價金屬離子。 1 〇 ·如申請專利範圍第9項之印刷配線板，其中前述 開口部的直徑爲20〜100 μπι。 1 1 ·如申請專利範圍第9或1 〇項之印刷配線板，其 中前述導體圖案係包含銅。 φ 12 ·如申請專利範圍第9至1 1項中任一項之印刷配 線板，其中於前述導體圖案上形成前述開口部。 13.如申請專利範圍第9至1 2項中任一項之印刷配 線板’其中前述二價金屬離子係藉由使前述驗顯影型阻焊 劑層分離，使經分離的前述鹼顯影型阻焊劑層於水中進行 熱處理而萃取出者。 -45-200842496 X. Patent Application No. 1. A method for manufacturing a printed wiring board, characterized in that a carboxyl group-containing urethane (meth) acrylate compound is formed as a carboxyl group on a surface of a substrate on which a conductor pattern is formed. a resin-developing type solder resist layer; exposing the alkali-developing type solder resist layer to a specific opening pattern, developing it by a rare aqueous solution, and washing with water containing 30 to 1000 ppm of divalent metal ions; An opening is formed at a specific position of the alkali-developing type solder resist layer by thermal curing. 2. The method of producing a printed wiring board according to the first aspect of the invention, wherein the divalent metal ion is a metal ion selected from at least one of Ca2+, Mg2+, Sr2+, and Ba2+. 3. The method for producing a printed wiring board according to claim 1 or 2, wherein the carboxyl group-containing urethane (meth) acrylate compound contains 35 masses based on 100 parts by mass of the carboxyl group-containing resin. More than one. 4. The method of manufacturing a printed wiring board according to any one of claims 1 to 3, wherein the alkali development is formed by coating an alkali-developing type solder resist on the surface of the substrate on which the conductor pattern is formed and drying. Type solder resist layer. The method of manufacturing a printed wiring board according to any one of claims 1 to 3, wherein the surface of the substrate on which the conductor pattern is formed is formed by laminating a dry film composed of an alkali developing type solder resist The alkali-developing type solder resist layer. The method of manufacturing a printed wiring board according to any one of claims 1 to 5, wherein the opening has a diameter of 20 to 1 〇〇 Pm. 7. The method of manufacturing a printed wiring board according to any one of claims 1 to 6, wherein the conductor pattern comprises copper. The method of manufacturing a printed wiring board according to any one of claims 1 to 7, wherein the opening portion is formed in the conductor pattern. 9. A printed wiring board comprising: φ a substrate on which a conductor pattern is formed; and an alkali-developable solder resist layer formed on the substrate and having an opening at a specific position, which contains a carboxyl group-containing amine group A An acid ester (meth) acrylate compound and a divalent metal ion. 1 〇 The printed wiring board of claim 9, wherein the opening has a diameter of 20 to 100 μm. The printed wiring board of claim 9 or claim 1, wherein the conductor pattern comprises copper. The printing wiring board according to any one of claims 9 to 11, wherein the opening portion is formed in the conductor pattern. 13. The printed wiring board of any one of the above-mentioned claims, wherein the divalent metal ion is separated by the aforementioned development-type solder resist layer, and the separated alkali-developing type solder resist is separated. The layer is extracted by heat treatment in water. -45-
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