201127987 六、發明說明： 【發明所屬之技術領域】 本發明係關於用於非電解金屬電鍍之預處理溶液，尤 指用於預處理印刷電路基板之樹脂基板，以及印刷電路基 板之製造製程。 【先前技術】 於印刷電路基板中’層間電連接一般係經由稱為通孔 之細小貫穿孔達成。-般係於使用含有陽離子性表面活化 劑之預處理溶液（調質劑）進行預處理後，使用濕式製程作 為用以於該等通孔（玻璃布/樹月旨斷面）内形成導電膜之製 程’於該濕式製程中’係使用涉及含有纪作為主要成份之 催化劑的非電解電鑛製程來形成電鑛膜。此外’係於以高 效能半導體封裝基板為代表之高密度印刷電路基板上使用 增層（build-up)製程，該增層製程係使用高效能絕緣樹脂 材料，以及係使用加成製程（additive pr〇cess)，尤指其 中使用非電鍍之銅鍍層作為晶種層（seed layer)之半力9口成 製程（semi-additive process)作為電路形成製程。 為了提升濕式製程中樹脂基板與導電膜之黏合性，於 使用含有溶劑作為主要成份之處理溶液實施樹脂膨潤步驟 後，使用涉及含有高錳酸鹽作為主要成份之處理溶液的粗 糙化步驟來氧化並分解該樹脂以形成粗糙形狀。使用一 '左 俊之中和步称移除I孟，以經由一系歹彳’之去汗/粗链化步驟/ 成錨固。使用預處理及藉由催化劑賦予步驟之非電解電:v 實施隨後之調質，並形成已結合之導電膜。具有優異催= 4 94883 ❻ 201127987 活性之纪係廣泛用作該非電解電鍍催化劑。藉由將樹脂基 板浸泡於催化劑溶液（錫鈀（SnPd)膠體混合物）中，該SnPd 膠體混合物被吸附於該樹脂基板之表面上。而加速劑之處 理活化了該催化劑’並經由非電解電鍍處理於該樹脂基板 之表面上形成導電膜^ 然而’當樹脂基板表面之粗輕度下降以及該基板與金 屬膜間之黏合性下降時，主要依賴於錨固效果之結合製程 難以獲得良好結合之電频。此外，黏合性受該預處理溶 液中酸、驗及陽離子性表面活化劑之麵、該樹脂材料等 的廣泛影響。高效能半導體封裝尤其受伴隨著IG晶片效能 提升之增加域號妓賴率所影響，且正尋求經封裝之 基板中電路及具有平整表面之電路的最小化。然而，半加 成製程中之傳統非電__難以形成良好雜至不太粗 i之表面上的導電膜’且對於材料表面可變成多麼平整有 限制。基於該背景訊息’㈣研發能賦予基板及金屬膜優 ” σ。強度而該;^材料及樹脂表面粗糙度不會影響結果 之表面處理製程及非電解電鍍製程。 於寻利麥考文獻 _-_3號中，係提供電：：二丰导利申請案第 奴仏電路基板之製造製程，其中， ==!成指定厚度之金屬層:藉由使於樹脂層(包含 =絕緣樹脂，㈣性崎樹脂係含有細 上具Λ導體圖案的表面進行親水性提升處理如電聚 處理寻、貫施破璃蝕刻處理 疋 合物溶液接觸以移除存在於接樹脂層與氫氟酸化 禪近月丨j述形成導體圖形之表呻 ϋ W- 94883 5 201127987 處的該顆粒添加劑、以及再實施非電解電鍍及電解電鍍。 然而，於專利參考文獻丨中闡述之該製裎需要 =、 臭氧處理、電暈放電處理等來產生親水性表面，且必需要 特殊設備。 @ 於專利參考文獻2--日本專利國内發表案第 H06-505770號中，係闡述包含下列之溶液：（a)約 至50g/L之聚鱗酸鈉，（b) 0至約5g/L之Na-EDTA，（c)約 5g/L至20g/L之磷酸三鉀，（d) 0. 5g/L至約2g/L之 ANTAROX™ BL300，（e) 0 至約 2g/L 之 SYNPERONIC™ NP-10， (f )約1 g/L至約5g/L之基於咪°坐衍生物的四級錄化合 物，以及（g) 〇至約2g/L之二氟化（氫？）銨，使用無機酸 將其pH調節為約1.0至4.0之範圍’該溶液係於將金屬塗 層塗覆於所述基板上之前，用於非金屬基板之清潔及調 質。然而，專利參考文獻2根本不關注黏合性，且如後文 之比較例中所闡述者，即使當加入於專利參考文獻2中闡 述量的二氟化氫銨時，僅得到不充分之黏合性。 於專利參考文獻3——未審查之曰本專利申請案第 2002-38197號中，係闡述含有一種或多種二醇鱗、水、氟 化物鹽及視需要之添加劑且設計為用以自基板移除聚合性 物質的組成物。然而，專利參考文獻3並未闡述本發明之 預處理溶液及印刷電路基板製造製程。 【發明内容】 本發明之目標係提供當非電解地對樹脂基板進行金 屬電鍍時用於非電解電鍍之預處理溶液，從而可在不需實 6 94883 201127987 施乾式黏合性促進預處理製程或形成金屬膜下，獲得良好 黏附於樹脂基板之不太粗糙表面上的金屬電鍍膜；以及提 供使用前述預處理溶液之表面處理製程、金屬電鍍膜形成 製程以及印刷電路基板製造製程。 本毛明之發明人發現，上揭問題可藉由預處理溶液中 陽離子性聚合物、水及敎量之雙氟化物鹽之存在予以解 決，且基於該發現完成本發明。 本申請案之發明係提供設計為用於非電解電鍍之樹 脂基板之表面上的預處理溶液，其特徵在於陽離子性聚合 物、水及5 g/L至2〇〇 g/L之雙氟化物鹽之存在。該雙氟 化物鹽較佳係選自氟化氫銨、氟化氫鉀及氟化氫鈉組成之 群組中之至少一種鹽。該預處理溶液可進一步含有非離子 性表面活性劑及/或螯合劑。再者，前述樹脂基板可為用於 印刷電路基板之樹脂基板，以及用於此印刷電路基板之樹 脂基板可含有通孔、盲孔或兩者。此外，本申請案之發明 亦提供印刷電路基板製造製程，該製程係包括於執行非電 解電鍍製程之前，使用前述預處理溶液處理樹脂基板表 面。此外，本申請案之發明亦提供用以於樹脂基板上形成 金屬電鍍膜之製程，該製程係包括藉由將樹脂基板與前述 預處理溶液接觸來處理該樹脂基板表面之步驟，藉由將業 已使用預處理溶液處理之該樹脂基板與催化劑溶液接觸而 使該催化劑吸附於該樹脂基板表面上之步驟，以及對吸附 催化劑之該樹脂基板進行非電解電鍍處理之步驟。 與使用其中不含有該特定量之雙氟化物鹽之本發明 94883 7 201127987 之預處理溶液之例或不使用本發明之預處理溶液之例相 比，當使財發明之預處理溶液作為用於非電解電鑛之預 處理溶液㈣電解地電_脂基板時，其優勢在於，即使 當樹脂基板表面*太粗料，藉_非電解電賴得之金 屬電錢膜更佳地黏附於該樹脂基板上。 【實施方式】 除了特別明確註明者外，本說明書通篇所使用之縮寫 係具有如下意義：g=公克，mg=毫克，卜攝氏度，m=米， L=公升，mL=毫升，dm2=平方分米，m〇le=莫耳以及_牛頓。 所有數子範圍係包括邊界值且可以任意順序組合。 本發明之預處理溶液係電鍍預處理溶液，某些時候稱 為調質劑’其特徵在於陽離子性聚合物、水以及5 g/L至 200 g/L之雙氟化物鹽的存在。 雙氟化物鹽係分子中含有可電解地離解之FHF_的化 合物。對於構成該雙氟化物鹽之陽離子成份並無特別限 制。更具體而言’可例舉氟化氫銨⑽4FHF)、氣化氮鉀 (KFHF)、氟化氫鈉⑽HF)等作為該雙氟化物鹽。本發明之 預處理溶液係含有5g/L至2〇〇g/L、較佳5g/L至5〇g/L、 更佳 7. 5g/L 至 15g/L 之範圍或 〇. 09ra〇le/L 至 3· 5m〇le/L、 較佳 0· 09m〇le/L 至 〇. 9m〇le/L、更佳 〇. 13m〇le/L 至 0.26m〇le/L之範圍的雙氟化物鹽。當存在低於“几之雙 氟化物鹽時，由於後文之比較例中所述般獲得不充分之黏 a J·生所以此選擇不文吾好。此外，一旦存在超過2〇〇忌几 之該鹽時’由於將非離子性表面活性料溶解於該預處理 94883 8 201127987 溶液時非離子性表面活性劑等難以溶解，所 喜好。 此邊擇不受 本發明之預處理溶液係含有陽離子性聚合物作為主 要構成元素。該陽離子性聚合物某些時候稱為陽離子性表 面活性劑，且係於水中電解地解離以形成有機陽離子、 劑:該陽離子性聚合物具有中和電荷並騎予預= 〆合液中之树脂基板表面正電荷之角色。該陽離子性y人斗 之分子量較佳係約至U00。作為較佳之陽離二二勿 合物實例，可例舉聚（二胺基二甲基）銨鹽、聚（二烯丙武队 =基）銨鹽、聚合物四級胺化合物如聚（乙稀基^定）四= 專、聚丙烯酸胺、聚（伸乙基亞胺）等。此等實例中力， 氯化聚（二稀丙基二甲基）銨、氯化聚（二稀两基 = == 共Γ及聚(伸乙基亞胺)為較佳者。該_子： 佳：°.5g/L 至 Ug/L，或更佳以。.5g/L 1. 〇 g/L的置加入預處理溶液中。 ::存在於本發明之預處理溶液十之水 舉洛餾水、去離子水等。 』例 本發明之預處理溶液可進一步含有非 料性表面活性劑某些時候係稱為非離面 該非於水中顯示離子性性質。於預處理溶液中， 面活性°作為該非離子性表 伸乙幻炫基越、聚氣衍生物如聚（氧 、 Λ申乙基）辛基苯基峻、聚（氧伸乙基r)r 94883 9 201127987 壬基苯基醚等，聚乙二醇及烷基醇乙氧基化物。該非離子 性表面活性劑較佳係以1 g/L至10 g/L，更佳係以1 g/L 至5 g/L的量加入預處理溶液中。 本發明之預處理溶液可進一步含有螯合劑。螯合劑係 含有多個一旦與金屬原子結合即形成螯合化合物之供體原 子的試劑，並扮演與溶解於該預處理溶液中之金屬離子於 該預處理溶液中形成螯合物化合物之角色。作為螯合劑之 較佳實例，可例舉單烷基胺類如單曱醇胺、單乙醇胺、單 丙醇胺、異丙醇胺等；二烷基胺類；三烷基胺類如三乙醇 胺、三丁醇胺等；氨及乙二胺四乙酸鹽（EDTA)。此等實例 中，單乙醇胺、三乙醇胺、異丙醇胺及氨係尤佳者。現在， 該預處理溶液之ρ Η係根據該螯合劑之類型及量而變化。螯 合劑係較佳以2. 0 g/L至20 g/L，更佳以2. 0 g/L至15 g/L 加入該預處理溶液中。 普通添加劑如pH調節劑等可根據需要如同其他視需 要之成份加入本發明之預處理溶液。 本發明之預處理溶液係用作預處理溶液以實施樹脂 基板表面之非電解電鐘。該樹脂基板係含有作為該構成成 份之一的樹脂，且只要於樹脂基板表面上發生非電解電 鐘，則對該基板之構建材料、形狀、尺寸等皆無特別限制。 舉例而言，可例舉印刷電路基板作為該樹脂基板。印刷電 路基板可含有玻璃布/樹脂斷面。此外，印刷電路基板可含 有稱為通孔之細小貫穿孔，稱為盲孔之細小非貫穿孔，或 兩者。通孔及盲孔之平均直徑並無限制。然而，通孔之平 10 94883 201127987 均直徑通#係0. 2毫米（mm)至〇. 9賴，而盲孔之平均直徑 通常係50微米（，）至1〇〇_。此外，功能性絕緣樹脂材 料基板係用作以高效能半導體封裝基板為代表之高密度印 刷電路基板_脂基板。出現在樹脂基板之孔的内壁^面 亦涵蓋於本發明樹脂基板之“表面” Θ。舉例而言，孔的 内壁表面（例如出現在印刷電路基板中之通孔及盲孔）係涵 蓋於印刷電路基板之“表面，’内。 作為用以構建樹脂基板之樹脂，可例舉環氧樹脂、氰 酸酯樹脂、雙馬.來醯亞胺三畊樹脂、聚醯亞胺、ABs、聚苯 醚、聚砜、氟樹脂、聚碳酸酯、聚縮醛、聚對苯醚 質、紙等構建之複合基板 (poly(phenyleneoxide))、聚丙烯、液晶聚合物等。該樹 脂基板可僅使用一種樹脂構建，或可係自以一種樹脂及一 種除樹脂外之物質如玻璃纖維、玻璃纖維布、其他^機物 本發明之非電解電鍍製程係允許於電鍍浴中使用 原劑將金屬沈積於經催化性地活化之表面上而無免、 對電鑛浴施加電能的電錢製程，且係熟識該技藝二 知之製程。舉例而言’非電解電鑛製程可含有二 鍍之樹脂基板與催化劑溶液接觸而將催化劑吸匕 板表面之步驟，以及對其上業已吸附催化劑之榭二树1 订非電解⑽處㈣於_脂基板上形成金屬 驟。此外，非電解電鍍製程可含有 *朕之^ 步驟之前去油脂及洗㈣=:;:r= 链化樹脂基板表面讀糙化㈣、軟_步料使用酸^ 94883 11 201127987 洗滌步驟等。此去汙步驟、粗糙化步驟、軟蝕刻步驟及使 用酸之洗條步驟可使用所述技術領域中已知之普通處理溶 液。 於本發明中，短語“係用作用於樹脂基板表面之非電 解電鑛之預處理溶液”係表示，本發明之預處理溶液係作 為於非電解電鑛製程中將催化劑吸附於樹脂基板表面上之 步驟之剛的步驟之一中使用處理樹脂基板之處理溶液。舉 例而言’當於非電解電鍍製程中實施額外步驟如去汙步 驟、粗链化步驟、軟餘刻步驟及/或洗滌步驟等時，本發明 之預處理溶液係作為預處理溶液於此等步驟中之視需要步 驟之前及/或之後的任意階段使用。 於本發明之另一態樣中，係提供樹脂基板表面處理製 私，於該製程中使用本發明之預處理溶液處理樹脂基板之 表面。於本發明之用於樹脂基板之表面處理製程中，一種 將树脂基板與該預處理溶液接觸之視需要製程可應用於 使用本發明之預處理溶液處理樹脂基板表面”，只要於 對藉由所述處理製程獲得之樹脂基板進行非電解電鍍處理 之後最終獲仔之该樹脂基板上的金屬電鑛膜具備本發明之 有盃效果即可。舉例而言，藉由將經處理之樹脂基板浸泡 於該預處理溶液中或將該預處理溶液噴灑於經處理之樹脂 基板來實施使用本發明之預處理溶液的樹脂基板表面之處 理。對使用本發明之樹脂基板表面處理製程處理的樹脂基 板並無特別限制，只要其為隨後進行非電解電鐘處理之樹 脂基板即可。該樹脂基板可為藉由實施上揭去汙步驟、粗BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment solution for electroless metal plating, particularly a resin substrate for pretreatment of a printed circuit board, and a manufacturing process of a printed circuit board. [Prior Art] In the printed circuit board, the interlayer electrical connection is generally achieved through a small through hole called a through hole. Generally, after pretreatment with a pretreatment solution (tempering agent) containing a cationic surfactant, a wet process is used as a conductive layer for forming the through holes (glass cloth/tree section) The membrane process 'in this wet process' uses an electroless ore process involving a catalyst containing a component as a main component to form an electrodeposited film. In addition, a build-up process is used on a high-density printed circuit board represented by a high-performance semiconductor package substrate, which uses a high-performance insulating resin material and an additive process (additive pr). 〇cess), especially a semi-adhesive process in which an electroless copper plating layer is used as a seed layer as a circuit formation process. In order to improve the adhesion between the resin substrate and the conductive film in the wet process, after the resin swelling step is carried out using a treatment solution containing a solvent as a main component, the roughening step involving a treatment solution containing permanganate as a main component is used to oxidize. The resin is decomposed to form a rough shape. Use a 'Zuo Junzhong step to remove I Meng to go through the sweat/thick chaining step/ anchoring through a series of 歹彳'. The pretreatment and the electroless electricity imparted by the catalyst are used: v to carry out subsequent quenching and tempering, and to form a bonded conductive film. It has excellent urging = 4 94883 ❻ 201127987 The activity of the system is widely used as the electroless plating catalyst. The SnPd colloidal mixture was adsorbed on the surface of the resin substrate by immersing the resin substrate in a catalyst solution (tin palladium (SnPd) colloidal mixture). The treatment of the accelerator activates the catalyst and forms a conductive film on the surface of the resin substrate via electroless plating treatment. However, when the thickness of the surface of the resin substrate is lowered and the adhesion between the substrate and the metal film is lowered. It is difficult to obtain a good combined frequency by relying on a combination of anchoring effects. Further, the adhesiveness is widely affected by the acid in the pretreatment solution, the surface of the cationic surfactant, the resin material, and the like. High performance semiconductor packages are particularly affected by the increased domain number dependency associated with improved IG die performance and are seeking to minimize the circuitry in the packaged substrate and the circuitry having a flat surface. However, the conventional non-electrical __ in the semi-additive process is difficult to form a conductive film on the surface of the substrate which is not too coarse, and there is a limit to how flat the surface of the material can become. Based on the background message '(4) R & D can give the substrate and metal film excellent σ. Strength; ^ material and resin surface roughness will not affect the results of the surface treatment process and electroless plating process. In the _3, the system provides the electricity:: The manufacturing process of the circuit board of the second slave of the application of the second franchise application, wherein ==! is the metal layer of the specified thickness: by making the resin layer (including = insulating resin, (4) sex The resin is composed of a surface having a fine conductor pattern on the surface for hydrophilic lifting treatment such as electropolymerization treatment, and a glass etching treatment to contact the solution to remove the presence of the resin layer and the hydrofluoric acid. The description of the formation of the conductor pattern 呻ϋ W- 94883 5 201127987 at the particle additive, and the implementation of electroless plating and electrolytic plating. However, the preparation of the system described in the patent reference 裎 needs =, ozone treatment, electricity A corona discharge treatment or the like is used to produce a hydrophilic surface, and special equipment is required. @ Patent Reference 2 - Japanese Patent Publication No. H06-505770, the following solution is described: (a)至约5. 5g / L to 5g / L of sodium sulphate, (b) 0 to about 5g / L of Na-EDTA, (c) about 5g / L to 20g / L of tripotassium phosphate, (d) 0. 5g / L to Approximately 2 g/L of ANTAROXTM BL300, (e) 0 to about 2 g/L of SYNPERONICTM NP-10, (f) from about 1 g/L to about 5 g/L of a quaternary derivative based on a derivative And (g) bismuth to about 2 g/L of difluorinated (hydrogen) ammonium, the pH of which is adjusted to a range of about 1.0 to 4.0 using a mineral acid. The solution is applied to a metal coating on the substrate. Previously, it was used for cleaning and tempering of non-metal substrates. However, Patent Reference 2 does not pay attention to adhesion at all, and as explained in the comparative examples hereinafter, even when added in Patent Reference 2 In the case of ammonium dihydrogen fluoride, only insufficient adhesion is obtained. In the patent reference 3 - Unexamined Patent Application No. 2002-38197, it is stated that one or more diol scales, water, fluoride salts are contained. And an additive as needed and designed to remove the polymerizable substance from the substrate. However, Patent Reference 3 does not describe the pretreatment solution and printing of the present invention. [Technical Field] The object of the present invention is to provide a pretreatment solution for electroless plating when metal plating of a resin substrate is performed non-electrolyticly, so that it is possible to carry out dry adhesion promotion without the need of real 6 94883 201127987 A metal plating film which adheres well to a less rough surface of the resin substrate is obtained under a pretreatment process or a metal film; and a surface treatment process using the foregoing pretreatment solution, a metal plating film formation process, and a printed circuit board manufacturing process are provided. The inventors of the present invention have found that the above problems can be solved by the presence of a cationic polymer, water and a dibasic difluoride salt in a pretreatment solution, and the present invention has been completed based on this finding. The invention of the present application provides a pretreatment solution designed on the surface of a resin substrate for electroless plating, characterized by a cationic polymer, water and a difluoride of 5 g/L to 2 g/L. The existence of salt. The bisfluoride salt is preferably at least one salt selected from the group consisting of ammonium hydrogen fluoride, potassium hydrogen fluoride and sodium hydrogen fluoride. The pretreatment solution may further contain a nonionic surfactant and/or a chelating agent. Further, the resin substrate may be a resin substrate used for a printed circuit board, and the resin substrate used for the printed circuit board may include a through hole, a blind hole, or both. Further, the invention of the present application also provides a printed circuit board manufacturing process including processing the surface of the resin substrate using the aforementioned pretreatment solution before performing the electroless plating process. In addition, the invention of the present application also provides a process for forming a metal plating film on a resin substrate, the process comprising the steps of treating the surface of the resin substrate by contacting the resin substrate with the pretreatment solution, by a step of contacting the resin substrate with the catalyst solution by using the pretreatment solution to adsorb the catalyst on the surface of the resin substrate, and performing an electroless plating treatment on the resin substrate adsorbing the catalyst. The pretreatment solution of the invention is used as compared with the case of using the pretreatment solution of the invention 94883 7 201127987 which does not contain the specific amount of the difluoride salt or the example of the pretreatment solution of the invention is not used. Pretreatment solution for electroless ore (4) Electrolytic galvanic _ grease substrate, the advantage is that even when the surface of the resin substrate * is too coarse, the metal electric film deposited by the non-electrolytic electricity is better adhered to the resin. On the substrate. [Embodiment] Unless otherwise specified, the abbreviations used throughout this specification have the following meanings: g = g, mg = mg, b, c = m, L = liter, mL = ml, dm2 = square Decimeter, m〇le=mole and _newton. All number subranges include boundary values and can be combined in any order. The pretreatment solution of the present invention is a plating pretreatment solution, sometimes referred to as a tempering agent, which is characterized by the presence of a cationic polymer, water, and a difluoride salt of from 5 g/L to 200 g/L. The difluoride salt-based molecule contains a compound which is electrolytically dissociable FHF_. There is no particular limitation on the cationic component constituting the difluoride salt. More specifically, as the difluoride salt, ammonium hydrogen fluoride (10) 4FHF, vaporized nitrogen potassium (KFHF), sodium hydrogen fluoride (10) HF, or the like can be exemplified. The pretreatment solution of the present invention contains 5g/L to 2〇〇g/L, preferably 5g/L to 5〇g/L, more preferably 7.5g/L to 15g/L or 〇. 09ra〇le /L to 3·5m〇le/L, preferably 0·09m〇le/L to 〇. 9m〇le/L, more preferably 13. 13m〇le/L to 0.26m〇le/L range of difluoro Salt. When there is less than a few of the difluoride salts, the selection is not as good as described in the comparative example below. Therefore, this choice is not good. In addition, once there are more than 2 jealousy In the case of the salt, it is preferred that the nonionic surfactant is difficult to dissolve due to the dissolution of the nonionic surfactant in the pretreatment 94883 8 201127987 solution. The pretreatment solution of the present invention is not cationic. The polymer is a main constituent element. The cationic polymer is sometimes referred to as a cationic surfactant and is electrolytically dissociated in water to form an organic cation: the cationic polymer has a neutralizing charge and is pre-charged. = the role of the positive charge on the surface of the resin substrate in the chelating solution. The molecular weight of the cationic y- hopper is preferably about U00. As an example of the preferred cation, the poly(diamino group) is exemplified. Methyl)ammonium salt, poly(diene-propane group=yl) ammonium salt, polymer quaternary amine compound such as poly(ethylene group) four = specialty, polyacrylic acid amine, poly(extended ethylenimine) Etc. In these examples , poly(dipropyldimethyl)ammonium chloride, chlorinated poly(diuret two base === conjugated and poly(extended ethylenimine) is preferred. The _ sub: good: °. 5g / L to Ug / L, or more preferably.. 5g / L 1. 〇g / L is added to the pretreatment solution. :: Pretreatment solution present in the present invention, the water of the water, go to Ionic water, etc. The pretreatment solution of the present invention may further contain an undesired surfactant, which is sometimes referred to as non-offset surface, which exhibits ionic properties in water. In the pretreatment solution, surface activity is regarded as the nonionic Sexually expressed in the form of polyethylene, such as poly(oxygen, oxime ethyl) octyl phenyl sulphide, poly(oxyethylidene) r 94883 9 201127987 decyl phenyl ether, etc., polyethylene glycol And the alkyl alcohol ethoxylate. The nonionic surfactant is preferably added to the pretreatment solution in an amount of from 1 g/L to 10 g/L, more preferably from 1 g/L to 5 g/L. The pretreatment solution of the present invention may further contain a chelating agent, which is a reagent containing a plurality of donor atoms which form a chelate compound upon binding to a metal atom, and acts as a solvent. The metal ions in the pretreatment solution form a chelate compound in the pretreatment solution. As preferred examples of the chelating agent, monoalkylamines such as monosterolamine, monoethanolamine, monopropanol can be exemplified. Amines, isopropanolamines, etc.; dialkylamines; trialkylamines such as triethanolamine, tributylamine, etc.; ammonia and ethylenediaminetetraacetate (EDTA). In these examples, monoethanolamine, three The chelating agent is preferably 2.0 g/L to 20 g/, and the amount of the chelating agent is preferably 2. 0 g/L to 20 g/. L, more preferably added to the pretreatment solution at 2.0 g/L to 15 g/L. A common additive such as a pH adjuster or the like may be added to the pretreatment solution of the present invention as needed as needed. The pretreatment solution of the present invention is used as a pretreatment solution to carry out an electroless electric clock on the surface of a resin substrate. The resin substrate contains a resin as one of the constituent components, and if a non-electrolytic clock is generated on the surface of the resin substrate, the material, shape, size, and the like of the substrate are not particularly limited. For example, a printed circuit board can be exemplified as the resin substrate. The printed circuit substrate may contain a glass cloth/resin cross section. Further, the printed circuit board may include a fine through hole called a through hole, a small non-through hole called a blind hole, or both. The average diameter of the through hole and the blind hole is not limited. However, the through hole flat 10 94883 201127987 average diameter through # 0. 2 mm (mm) to 〇. 9 赖, and the average diameter of the blind hole is usually 50 microns (,) to 1 〇〇 _. Further, the functional insulating resin material substrate is used as a high-density printed circuit board _ grease substrate typified by a high-performance semiconductor package substrate. The inner surface of the hole which appears in the resin substrate is also covered by the "surface" of the resin substrate of the present invention. For example, the inner wall surface of the hole (for example, the through hole and the blind hole appearing in the printed circuit board) is included in the "surface," of the printed circuit board. As the resin for constructing the resin substrate, an epoxy resin is exemplified. Resin, cyanate resin, double horse, yttrium imide resin, polyimine, ABs, polyphenylene ether, polysulfone, fluororesin, polycarbonate, polyacetal, polyparaphenylene, paper a composite substrate (poly(phenyleneoxide)), a polypropylene, a liquid crystal polymer, etc. The resin substrate may be constructed using only one resin, or may be a resin and a material other than a resin such as glass fiber or glass fiber. The electroless plating process of the present invention allows the use of an agent to deposit a metal on a catalytically activated surface in an electroplating bath, and is inevitably used to apply electric energy to the electric ore bath, and For example, the process of the non-electrolytic electrowinning process may include the step of contacting the two-plated resin substrate with the catalyst solution to adsorb the surface of the catalyst, and adsorbing the catalyst thereon.榭二树1 order non-electrolytic (10) (4) to form a metal on the _ grease substrate. In addition, the electroless plating process can contain * 朕 ^ before the steps to remove grease and wash (four) =:;: r = chained resin substrate surface read Roughening (four), soft _ step material using acid ^ 94883 11 201127987 washing step, etc. This decontamination step, roughening step, soft etching step and acid stripping step can use common processing solutions known in the art. In the present invention, the phrase "serving as a pretreatment solution for electroless ore of a resin substrate surface" means that the pretreatment solution of the present invention is used as a catalyst for adsorbing a catalyst on a surface of a resin substrate in an electroless electrolytic process. The treatment solution for treating the resin substrate is used in one of the steps of the above step. For example, when additional steps such as a decontamination step, a thick chaining step, a soft residue step, and/or washing are performed in the electroless plating process When the step is the same, the pretreatment solution of the present invention is used as a pretreatment solution at any stage before and/or after the optional steps in the steps. In another aspect of the present invention, Providing a surface treatment of the resin substrate, in which the surface of the resin substrate is treated with the pretreatment solution of the present invention. In the surface treatment process for a resin substrate of the present invention, a resin substrate is contacted with the pretreatment solution. The process may be applied to the surface of the resin substrate using the pretreatment solution of the present invention as long as the metal oxide on the resin substrate is finally obtained after the electroless plating treatment of the resin substrate obtained by the treatment process The film may have the cup effect of the present invention. For example, the resin substrate surface treatment using the pretreatment solution of the present invention is carried out by immersing the treated resin substrate in the pretreatment solution or spraying the pretreatment solution onto the treated resin substrate. The resin substrate to be subjected to the surface treatment process of the resin substrate of the present invention is not particularly limited as long as it is a resin substrate which is subsequently subjected to electroless electric clock treatment. The resin substrate can be subjected to a decontamination step by implementation
94883 12 201127987 糙化步驟、軟蝕刻步驟及/或酸洗等步驟獲得者，或可為未 實施此等步驟所獲得之樹脂基板。 於本發明之另一態樣中，係提供一種藉由下述步驟於 樹脂基板上形成金屬電鍍膜之製程，包括： 將樹脂基板與本發明之預處理溶液接觸以處理該樹 脂基板之表面的步驟， 藉由將業已使用該預處理溶液處理之樹脂基板與催 化劑溶液接觸而將催化劑吸附於該樹脂基板表面上的步 驟，以及 對其上已吸附催化劑之該樹脂基板進行非電解電鑛 處理的步驟。 於某些例中，於本發明之該製程中，係於該將催化劑 吸附於樹脂基板表面的步驟之前，以及於該藉由將樹脂基 板與本發明之預處理溶液接觸來處理該樹脂基板之表面的 步驟之如或之後，實施上揭去汙步驟、粗縫化步驟、軟姓 刻步驟及/或酸洗步驟等，以於樹脂基板上形成金屬電鍍 膜。此外，於某些例中，可在催化劑吸附後實施活化催化 劑的加速劑處理。 可藉由下列步驟於樹脂基板表面上形成具有優異結 合之導電膜：於使用本發明之預處理溶液進行預處理之 後’將樹脂基板如印刷電路基板浸泡於催化劑溶液中以允 許將催化劑吸附於樹脂基板表面上，經視需要之加速劑處 理活化催化劑’再實施非電解電鍵。於此例中，較佳係使 用具有優異催化活性之催化劑作為該非電解電鑛催化劑， 94883 13 201127987 舉例而言，可使用含有ί巴之催化劑。 於本發明中，非電解電鍍可稱為銅、鎳或銅-鎳合金 之非電解電鍍，儘管非電解電鍍並不限於此等金屬。 ' 作為使用本發明之預處理溶液進行表面處理製程之 非電解銅電鍍之實例，可例舉下列製程。 首先，將樹脂基板於加熱至45°C之上揭本發明之預處 理溶液中浸泡5分鐘，以實施將催化劑施加於待處理之材 料表面之表面調節。使用30°C過硫酸鈉對該樹脂基板之表 面軟蝕刻1分鐘，接著於室溫酸洗該表面1分鐘，移除因 蝕刻所產生之汙物鹽。隨後將該待處理之材料浸泡，舉例 而言，於45°C之SnPd膠體催化劑溶液中浸泡4分鐘以將 催化劑施加於該待處理材料之表面。然後，於藉由將該待 處理材料於室溫之加速劑溶液中浸泡5分鐘的步驟中，移 除Sn等並將Pd金屬化。藉由於經催化劑活化之待處理材 料上實施普通非電解電鍍，舉例而言，於25°C進行非電解 電鍍20分鐘，而於該樹脂基板上形成銅膜。 接著，藉由例舉實施例及比較例更詳細地闡述本發 明。下文中該實施例及比較例中之黏合強度及表面粗糙度 係如下述般予以評估。 (1)黏合強度 藉由非電解銅電鍍獲得之樹脂基板上之含有銅電鍍 膜的經電鍍材料之表面係進一步於室溫使用去離子水洗滌 三次，並使用加熱（120°C，30分鐘）乾燥。將經電鍍之材 料表面上之該非電解銅膜的表面浸泡於酸清洗劑中（液體 14 94883 201127987 溫度35°C，2分鐘），隨後酸洗，再使用（ELECTR0P0SIT™ EP1100)進行非電解銅電鍍處理。於室溫使用去離子水將該 電解銅電鍍之表面洗蘇3次，於升高之溫度下乾燥 (180°C ’ 60分鐘）。所獲得之銅電鍍膜厚度係2〇 am至25 //m。將該電鍍膜切割為1公分（cm)寬之條，根據印刷電路 板測試方法JIS™ C5012使用INSTR0N™ 5564於90。角及5〇 mm/分鐘之牽引速度（pull up rate)測量該電鑛臈對該基材 樹脂之黏合強度。 (2)表面粗链度（Ra) 將待處理之樹脂基板於液體溫度為70°C至80°C之含 有溶劑作為主要成份的樹脂膨潤溶液 (CIRCUPOSIT™ MLB211)中浸泡5至10分鐘，隨後藉由將其 於液體溫度為70°C至80°C之含有高錳酸鹽作為主要成份 之溶液（CIRCUPOSIT™ MLB213)中浸泡5至2 0分鐘予以粗M 化。藉由將其與液體溫度為45°C之中和處理溶液 (CIRCUPOSIT™ MLB 216-5)中浸泡5至10分鐘移除猛，隨 後使用表面粗糙度測量裝置WYKO NT8000測量經處理之樹 脂基板的表面粗綠度（Ra)。 實施例1至10 使用下列樹脂基板1至3作為待處理之樹脂基板。 樹脂基板 樹脂基板1 : Ra : 590至630奈米（nm) 樹脂基板2 : Ra : 480至500(nm) 環氧樹脂基板3 : Ra : 900至1000(nm) 15 94883 201127987 使用下揭含有陽離子性聚合物、螯合劑、非離子性表 面活性劑及水之預處理母液（A)&(D)，並藉由以表丨中顯 示之比例加入氟化氫錢作為該雙氟化物鹽來製備預處理溶 液浴。使用高錳酸鹽對樹脂基板丨至3進行去汙及粗糙化， 並於45°C將樹脂基板1至3浸泡於表3中顯示之預處理溶 液中5分鐘。隨後使用過硫酸鈉軟蝕刻該等基板並用酸洗 滌。使用SnPd混合膠體（CATAP〇SIT™ 44催化劑）沈積催化 劑，使用加速劑溶液（ACCELERATOR™ 19E)活化該催化劑。 隨後於25 C將該等基板於非電解銅電鑛溶液· (CUP0SIT™ 328銅混合濃縮物）中浸泡2〇分鐘，以允許非 電解銅電鍍發生。隨後實施電解電鍍製程，再對該基板進 行黏合性測試。評估結果亦於表丨中報告。 預處理母液 下揭之溶液（A)至（D)係全部由羅門哈斯公司（Rohm and Haas Denshi Zairyo K. K.)製造，且係含有陽離子性 聚合物、螯合劑、非離子性表面活性劑及水。 (A) 调質劑中和劑 3320 (Conditioner neutralizer 3320) (B) 清洗劑調質劑 231 (Cleaner conditioner 231) (C) CIRCUPOSIT™ 860 (D) 清洗劑調質劑 ΧΡ2285 (Cleaner conditioner XP2285) 16 94883 d 201127987 表1 實施 例1 實施 例2 實施 例3 货施 例4 實施 例5 實施 例6 實施 實施 實施 例9 實施 例10 樹脂基板 樹脂 基板I 樹脂 基板1 〜· 樹脂 基板2 環氣 樹脂 基板3 樹脂 基板1 樹脂 基桎1 1y'J I 樹脂 基板] 例8 樹脂 基板】 樹脂 基板] 樹脂 基板1 預處理母液 之類型 A D A "ΤΓΓ~ D 1ΓΤ- A D A ~~10~' D 1 η D NH.HF (g/L) 11.4 0 2 ΓΤΓΡ pH —4. 04—~ u, z ~~689^" 0.2 ΙΤ〇~7 ΓΤ〇67 0.2 〕.85 795 0.088 飞15 _662 0.088 ~5.54 671 0.175 ~ΎΪ8~' ~652~~ 0.175 ~Χ39~ 70Γ~ 】5 0.26 ^ 15 _ 0.26 ITrP 剝離強度M/m 673 704 682 實施例11至13 藉由以表2中顯示之比例向上揭預處理母液中加入氟 化氫銨來製備預處理溶祕。使㈣孔器於兩側皆層壓Μ ㈣鋼箱之含有玻璃布之環氧樹脂兩側之厚度為I 6曰随的 鍍層（Hitachi Kasei KogyoK.K.製造之FR-4)上產生直护 ，0.9咖之通孔，以所獲得之樹脂基板4作為待處理材料 實施非電解銅電鍍，除此之外，以實施例丨闡述之方式實 施操作。隨後拋光該通孔基板，使用背光製程檢查通孔内 化學銅均鍍能力。結果顯示於第！圖至第3圖中。 表294883 12 201127987 The steps of the roughening step, the soft etching step, and/or the pickling are obtained, or may be a resin substrate obtained by not performing the steps. In another aspect of the present invention, there is provided a process for forming a metal plating film on a resin substrate by the following steps, comprising: contacting a resin substrate with a pretreatment solution of the present invention to treat a surface of the resin substrate; a step of adsorbing a catalyst on a surface of the resin substrate by contacting a resin substrate which has been treated with the pretreatment solution with a catalyst solution, and performing electroless ore treatment on the resin substrate on which the catalyst has been adsorbed step. In some embodiments, in the process of the present invention, the resin substrate is treated by contacting the resin substrate with the pretreatment solution of the present invention before the step of adsorbing the catalyst on the surface of the resin substrate. After or after the surface step, a decontamination step, a roughing step, a soft surrogate step, and/or a pickling step are performed to form a metal plating film on the resin substrate. Further, in some instances, an accelerator treatment of the activated catalyst may be carried out after adsorption of the catalyst. A conductive film having excellent bonding can be formed on the surface of the resin substrate by the following steps: after pretreatment using the pretreatment solution of the present invention, a resin substrate such as a printed circuit substrate is immersed in a catalyst solution to allow adsorption of the catalyst to the resin On the surface of the substrate, the activated catalyst is treated with an accelerator as needed to perform electroless electrolysis. In this case, a catalyst having excellent catalytic activity is preferably used as the electroless ore catalyst, and 94883 13 201127987, for example, a catalyst containing κB can be used. In the present invention, electroless plating may be referred to as electroless plating of copper, nickel or a copper-nickel alloy, although electroless plating is not limited to such metals. As an example of the electroless copper plating which is subjected to the surface treatment process using the pretreatment solution of the present invention, the following processes can be exemplified. First, the resin substrate was immersed in the pretreatment solution of the present invention heated to 45 ° C for 5 minutes to carry out surface conditioning for applying the catalyst to the surface of the material to be treated. The surface of the resin substrate was soft-etched for 1 minute using sodium persulfate at 30 ° C, and then the surface was pickled at room temperature for 1 minute to remove the salt of the dirt resulting from the etching. The material to be treated is then immersed, for example, by soaking for 4 minutes in a SnPd colloidal catalyst solution at 45 ° C to apply a catalyst to the surface of the material to be treated. Then, in the step of immersing the material to be treated in an accelerator solution at room temperature for 5 minutes, Sn or the like is removed and Pd is metallized. By performing ordinary electroless plating on the material to be treated which is activated by the catalyst, for example, electroless plating is performed at 25 ° C for 20 minutes to form a copper film on the resin substrate. Next, the present invention will be explained in more detail by way of examples and comparative examples. The adhesive strength and surface roughness in the examples and comparative examples below were evaluated as follows. (1) Bonding strength The surface of the plated material containing the copper plating film on the resin substrate obtained by electroless copper plating was further washed three times with deionized water at room temperature, and heated (120 ° C, 30 minutes). dry. The surface of the electroless copper film on the surface of the electroplated material is immersed in an acid cleaning agent (liquid 14 94883 201127987 temperature 35 ° C, 2 minutes), followed by pickling, and then using (ELECTR0P0SITTM EP1100) for electroless copper plating deal with. The surface of the electrolytic copper plating was washed 3 times with deionized water at room temperature and dried at an elevated temperature (180 ° C '60 minutes). The thickness of the copper plating film obtained is from 2 〇 am to 25 //m. The plated film was cut into strips of 1 cm (cm) width, and INSTR0NTM 5564 was used at 90 according to the printed circuit board test method JISTM C5012. The bonding strength of the electric ore to the substrate resin was measured at an angle and a pull up rate of 5 〇 mm/min. (2) Surface Thickness (Ra) The resin substrate to be treated is immersed in a resin swelling solution (CIRCUPOSITTM MLB211) containing a solvent as a main component at a liquid temperature of 70 ° C to 80 ° C for 5 to 10 minutes, followed by It is coarsely mashed by immersing it in a solution containing a permanganate as a main component (CIRCUPOSITTM MLB213) at a liquid temperature of 70 ° C to 80 ° C for 5 to 20 minutes. The smear was removed by soaking it for 5 to 10 minutes with a liquid temperature of 45 ° C and a treatment solution (CIRCUPOSITTM MLB 216-5), and then the treated resin substrate was measured using a surface roughness measuring device WYKO NT8000. Surface roughness (Ra). Examples 1 to 10 The following resin substrates 1 to 3 were used as the resin substrate to be treated. Resin substrate Resin substrate 1 : Ra : 590 to 630 nm (nm) Resin substrate 2 : Ra : 480 to 500 (nm) Epoxy substrate 3 : Ra : 900 to 1000 (nm) 15 94883 201127987 Use cation containing Prepolymerized mother liquor (A) & (D) of a polymer, a chelating agent, a nonionic surfactant and water, and prepared by adding hydrogen fluoride as the difluoride salt in the proportions shown in the Table Treat the solution bath. The resin substrates 丨 to 3 were decontaminated and roughened using permanganate, and the resin substrates 1 to 3 were immersed in the pretreatment solution shown in Table 3 at 45 ° C for 5 minutes. The substrates are then soft etched using sodium persulfate and washed with acid. The catalyst was deposited using a SnPd mixed colloid (CATAP® SITTM 44 catalyst) and the catalyst was activated using an accelerator solution (ACCELERATORTM 19E). The substrates were then immersed in an electroless copper electromineral solution (CUP0SITTM 328 copper mixed concentrate) at 25 C for 2 minutes to allow electroless copper plating to take place. Subsequently, an electrolytic plating process was carried out, and the substrate was tested for adhesion. The results of the assessment are also reported in the table. The solutions (A) to (D) of the pretreatment mother liquor are all manufactured by Rohm and Haas Denshi Zairyo KK and contain a cationic polymer, a chelating agent, a nonionic surfactant and water. . (A) Conditioner Neutralizer 3320 (Conditioner neutralizer 3320) (B) Cleaner Conditioner 231 (Cleaner conditioner 231) (C) CIRCUPOSITTM 860 (D) Cleaner Conditioner ΧΡ 2285 (Cleaner conditioner XP2285) 16 94883 d 201127987 Table 1 Example 1 Example 2 Example 3 Cargo Example 4 Example 5 Example 6 Embodiment Example 9 Example 10 Resin substrate Resin substrate I Resin substrate 1 to resin substrate 2 Ring resin substrate 3 Resin substrate 1 Resin based 桎1 1y'JI resin substrate] Example 8 Resin substrate] Resin substrate] Resin substrate 1 Type of pretreatment mother liquid ADA "ΤΓΓ~ D 1ΓΤ- ADA ~~10~' D 1 η D NH.HF (g/L) 11.4 0 2 ΓΤΓΡ pH —4. 04—~ u, z ~~689^" 0.2 ΙΤ〇~7 ΓΤ〇67 0.2 〕.85 795 0.088 Fly 15 _662 0.088 ~5.54 671 0.175 ~ΎΪ8~ ' ~652~~ 0.175 ~Χ39~ 70Γ~ 】5 0.26 ^ 15 _ 0.26 ITrP Peel Strength M/m 673 704 682 Examples 11 to 13 By adding the ammonium hydrogen fluoride to the pretreatment mother liquor by the ratio shown in Table 2 To prepare the pretreatment solution. (4) The hole is laminated on both sides. (4) The thickness of the steel plate containing the glass cloth on both sides of the epoxy resin is the thickness of the coating (the FR-4 manufactured by Hitachi Kasei Kogyo K.K.). The via hole of 0.9 was used, and the obtained resin substrate 4 was subjected to electroless copper plating as a material to be processed, and the operation was carried out in the manner described in the examples. The via substrate is then polished, and the chemical copper plating ability in the via is checked using a backlight process. The result is shown in the first! Figure to Figure 3. Table 2
1--- 實施例 11 實施例 12 霄施例 1 〇 樹脂基板 樹脂基板 4 樹脂基板 4 —丄 ύ 樹脂基板 Λ __赛處理母液之類型 B C — ---^ Γ) NH4FHF (g/L) 11.4 11.4 1/ 11.4 —-- (raole/L) 0· 2 0. 2 JZHJ 基於實施例Π至13 ’本發明之預處理溶液可用於含 94883 17 201127987 有通孔之基板上而沒有任何電鍍之問題。 實施例14至19 藉由以表3中顯示之比例加入各別的雙氟化物鹽來代 替實施例1之11.4 g/L(0. 2 mole/L)氟化氫銨來製備預處 理溶液浴。以實施例1中闡述之方式實施非電解鋼電鍍。 各別的測試結果係於表3中顯示。 表 樹脂基板 預處理母液類型 添加 劑1---Example 11 Example 12 Example 1 Resin substrate Resin substrate 4 Resin substrate 4 - 树脂 Resin substrate _ __赛Processing mother liquid type BC — ---^ Γ) NH4FHF (g/L) 11.4 11.4 1/ 11.4 —-- (raole/L) 0· 2 0. 2 JZHJ Based on the examples Π to 13 'The pretreatment solution of the present invention can be used on a substrate having a through hole of 94883 17 201127987 without any plating problem. Examples 14 to 19 A pretreatment solution bath was prepared by substituting 11.4 g/L (0.2 mole/L) of ammonium hydrogen fluoride of Example 1 by adding the respective difluoride salts in the proportions shown in Table 3. Electroless steel plating was carried out in the manner set forth in Example 1. The individual test results are shown in Table 3. Table resin substrate pretreatment mother liquor type additive
NMHFNMHF
NaFHFNaFHF
KFHFKFHF
pH 剝離強度（N/m) 實施例 14 樹脂基 板1 L10 660 實施例 、15 樹脂基 板1pH Peel Strength (N/m) Example 14 Resin Base Plate 1 L10 660 Example, 15 Resin Base Plate 1
D ).25 4. 57 651 貫施例 :攻 Λ〇Γ~ J 實施例 貫施例 實施例 17 18 19 樹脂基 樹脂基 樹脂基 板1 板1 板1 D A D 0. 25 L 0.25 0.25 4.34 4.12 4.55 660 670 660 比較例1至16 藉由加入表4中顯示之各別化合物來代替實施例丨之 11.4g/L(0.2mole/L)氟化氫錢來製備預處理溶液浴，以實 施例1中闡述之方式實施非電解鋼電鍍。各別的測試結果 係於表4中顯示。於此使用、、或氫氧化鈉調整比較例13 至16之pH。 94883 18 201127987 表4 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 2 3 4 5 6 7 8 樹脂基板 樹脂基 板1 樹脂基 板1 樹脂基 板1 樹脂基 板1 樹脂基 板2 環氧樹 脂基板 3 樹脂基 板1 樹脂基 板1 預處理母液類型 A B C D A D A D NHJHF (g/L) 2.5 2.5 (mole/L) 0.044 0. 044 NaF (g/L) (mole/L) 添加 劑 NH-Cl (g/L) (raole/L) nh3 (g/L) (mole/L) (g/L) NaBr (mole/L) pH 2.05 11.41 9.96 11.21 2. 05 11.21 2.82 8. 11 剝離強度 599 568 537 606 916 718 613 630 表4續 比較 例9 比較 例10 比較 例11 比較 例12 比較 例13 比較 例]4 比較 例15 比較 例16 樹脂基板 樹脂 基板1 樹脂 基板1 樹脂 基板1 樹脂 基板1 樹脂 基板1 樹脂 基板1 樹脂 基板1 樹脂 基板] 預處理母液類型 A A A A A A A A 添加 劑 NftFHF (g/L) (mole/L) NaF (g/L) 8.4 8.4 (m〇le/L) 0.2 0.2 Cl (g/L) 10.7 10.7 (mole/L) 0.2 0.2 NHa (g/L) 3.4 3.4 (mole/L) 0.2 0.2 NaBr (g/L) 20.6 20.6 (mole/L) 0.2 0.2 P H 4.19 2.28 3.77 2.26 4. 25 4.13 4.13 4. 17 剝離強度 629 579 614 629 603 518 572 60] 比較例17及18 藉由加入表5中顯示之各別的化合物來代替實施例1 之11.4 g/L (0. 2 mo 1 e/L)敦化氫銨來製備預處理溶液浴， 以實施例1中闡述之相同方式實施非電解銅電鍍。各別的 19 94883 201127987 使用硫酸或氫氧化鈉調整預處理溶液浴之pH。 ’ < 表5D).25 4. 57 651 Example: Attack ~ J Example Example 17 17 19 Resin-based resin-based resin substrate 1 Plate 1 Plate 1 DAD 0. 25 L 0.25 0.25 4.34 4.12 4.55 660 670 660 Comparative Examples 1 to 16 A pretreatment solution bath was prepared by adding the respective compounds shown in Table 4 instead of the 11.4 g/L (0.2 mole/L) hydrogen fluoride of the Example, as described in Example 1. The method implements electroless steel plating. The individual test results are shown in Table 4. The pH of Comparative Examples 13 to 16 was adjusted using this, or sodium hydroxide. 94883 18 201127987 Table 4 Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 2 3 4 5 6 7 8 Resin Substrate Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate 2 Epoxy Resin Substrate 3 Resin substrate 1 Resin substrate 1 Pretreatment mother liquid type ABCDADAD NHJHF (g/L) 2.5 2.5 (mole/L) 0.044 0. 044 NaF (g/L) (mole/L) Additive NH-Cl (g/L) (raole /L) nh3 (g/L) (mole/L) (g/L) NaBr (mole/L) pH 2.05 11.41 9.96 11.21 2. 05 11.21 2.82 8. 11 Peel strength 599 568 537 606 916 718 613 630 Table 4 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 4 Comparative Example 15 Comparative Example 16 Resin Substrate Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate 1 Resin Substrate] Pretreatment mother liquor type AAAAAAAA Additive NftFHF (g/L) (mole/L) NaF (g/L) 8.4 8.4 (m〇le/L) 0.2 0.2 Cl (g/L) 10.7 10.7 (mole/L) 0.2 0.2 NHa (g/L) 3.4 3.4 (mole/L) 0.2 0.2 NaBr (g/L) 20.6 20.6 (mole/ L) 0.2 0.2 PH 4.19 2.28 3.77 2.26 4. 25 4.13 4.13 4. 17 Peel strength 629 579 614 629 603 518 572 60] Comparative Examples 17 and 18 Substituting Example 1 by adding the respective compounds shown in Table 5 11.4 g/L (0.2 mol 1 e/L) of ammonium hydride was prepared to prepare a pretreatment solution bath, and electroless copper plating was carried out in the same manner as described in Example 1. Individual 19 94883 201127987 Adjust the pH of the pretreatment solution bath using sulfuric acid or sodium hydroxide. ‘ < Table 5
5結果亦於表5中顯示。於此，加人前述化合物後 處理母液A的pH為3.93,而預處理母液DipHg9^ 根據實施例1至19 t獲得之結果，當使用本發明之 預處理，谷液時，無論樹脂基板之表面粗糙度及預處理母液 之類型如何，皆達成優異之黏合性。此外，當將業已加入 氟化氫銨之預處理溶液與不加入氟化氫銨之實例（比較例 1)及加入非雙氟化物鹽之化合物之實例（比較例9至12)相 比時可知，與比較例丨及9至12相比，實施例丨之剝離強 度優異且黏合性傑出。此外，當於比較例13至18中加入 非雙氟化物鹽之化合物代替氟化氫銨時，即使該預處理溶 液之pH與實施例之pH相當，仍無法達成優異黏合性。此 外，將實施例5之結果與比較例7之結果相比，以及將實 施例6之結果與比較例8之結果相比，發現當氟化氫銨二 加入量低於5 g/L時，黏合性不良。當使用氟化氫鉀或氟 化氫鈉作為該雙氟化物鹽時，無法獲得與氟化氫銨相關之 優異剝離強度及黏合性。 94883 20 201127987 【圖式簡單說明】 第1圖·此照片係顯示當使用於實施例11 預處，溶液時，通孔内之化學銅均鐘能力； 第2圖：此照片係顯示當使用於實施例12 預處理溶液時，通孔内之化學鋼均難力的照片 第3圖.此照片係顯不當使用於實施例丄3 預處理溶㈣，通孔内之化學鋼，能力的照片 【主要元件符號說明】 4\%\ 中製備之 中製備之 ;以及 中製備之 948835 Results are also shown in Table 5. Here, the pH of the mother liquor A after the addition of the aforementioned compound is 3.93, and the pretreatment mother liquor DipHg9^ is obtained according to the results of Examples 1 to 19 t, when the pretreatment of the present invention is used, regardless of the surface of the resin substrate. Excellent roughness is achieved by the roughness and the type of pretreatment mother liquor. Further, when the pretreatment solution to which ammonium hydrogen fluoride has been added is compared with the example in which no ammonium hydrogen fluoride is added (Comparative Example 1) and the compound to which the non-difluoride salt is added (Comparative Examples 9 to 12), it is known that the comparative example is compared with the comparative example. Compared with 9 to 12, the examples have excellent peel strength and excellent adhesion. Further, when a compound other than the difluorinated salt was added to Comparative Examples 13 to 18 instead of ammonium hydrogen fluoride, excellent adhesion could not be obtained even if the pH of the pretreatment solution was comparable to the pH of the Example. Further, the results of Example 5 were compared with the results of Comparative Example 7, and the results of Example 6 were compared with those of Comparative Example 8, and it was found that when the amount of ammonium hydrogen fluoride added was less than 5 g/L, the adhesion was observed. bad. When potassium hydrogen fluoride or sodium hydrogen fluoride is used as the difluoride salt, excellent peel strength and adhesion to ammonium hydrogen fluoride cannot be obtained. 94883 20 201127987 [Simple description of the drawing] Fig. 1 This photo shows the chemical copper uniformity in the through hole when used in the solution of Example 11; Figure 2: This photo shows when used in Example 12 When the pretreatment solution was used, the chemical steel in the through hole was difficult to photograph. Fig. 3. This photograph was improperly used in the example 丄3 Pretreatment solution (4), chemical steel in the through hole, photo of ability [ The main component symbol description] prepared in the preparation of 4\%\; and the prepared 94883