201236531 六、發明說明： 【發明所屬之技術領域】 本發明係關於印刷佈線板之製造方法。 【先前技術】 伴隨著電子機器之高機能化等的要求，電子零件之高密度 積體化甚至疋尚欲度安裝化等持續發展中。因此，在使用 於電子零件之高密度安裝對應之印刷佈線板等方面，亦較先 前技術增加地，小型薄型化、高密度化及多層化持續發展。 作為在印刷佈線板之基板上以高密度有效形成圖案精度 高之導體電路層，係已開始進行半加成法(SAP法）。 " 依SAP法之電路的形成係例如依下述說明進行。首先， 針對核心基板或層間絕緣層之樹脂表面進行粗化處理。其 次，於經粗化處理過之樹脂表面上，形成為基底之無電解鍍 覆層。接著，藉由鍍覆光阻保護非電路形成部，並藉由電鍍 而針對電路形成部進行電鍍層之增厚。其後，去除光阻，透 過閃蝕將上述電路形成部以外之無電解鍍覆層去除，藉以在 樹脂表面上形成電路。 右根據SAP法，則可將積層在樹脂表面上之金屬層予以 薄膜化。因此，可形成更細微之電路佈線。 然而，於先前技術之針對核心基板或層間絕緣層之樹脂表 面進行SAP法之情形下’在導體電路層與樹脂表面之間並 未獲得充分的密接性’且有導體電路層之剝離強度降低之情 101102469 201236531 形。此時，於例如高溫高濕條件下曝曬印刷佈線板時，會產 生導體電路層剝離、發生加濕膨脹或損害連接可靠性等問 題。 此外，近年來為了兼具封装基板之薄型化與低反翹，而有 以基板之高剛性、低熱膨脹化為目的之高度填充填充材料之 情形。此時，依SAP法之導體電路層與樹脂表面之密接性 問題會明顯化。此係於鑛覆或去除毛邊等而進行化學藥劑處 理時，受到填充材料之影響為一原因。 為了提高樹脂表面與導體電路層之密接性，例如，揭示於 專利文獻1、2之SAP法係依樹脂表面之凹凸成為1〜7 ^爪 之方式針對樹脂表面施以粗化處理。 又，在專利文獻3中，記載有：將矽烷偶合劑層積層於未 施以粗化處理之銅箔，並於其上進一步積層極薄底面樹脂層 而獲得之附有極薄接著劑層之銅结係與基材樹脂之接著強 度優異的主旨。 [先前技術文獻] [專利文獻] 專利文獻1:曰本專利特開2003-69218號公報 專利文獻2:日本專利特開2〇〇3·6〇341號公報 專利文獻3 :日本專利特開2〇〇5·〇53218號公報 【發明内容】 本發明之目的係在於：透過半加成法而對核心基板或層間 101102469 5 201236531 ’而獲得導體 其 若根據本發明，則可提供 係具備有： 種印刷佈線板之製造方法 ^面為由樹脂組成物所構成之基板之上述表面上，藉由 '，，'電解鍍覆形成無電解料層之步驟· 9 ^述無電解鑛覆層上形成具有開口之光阻遮罩之步驟. 在上述開口内，藉由電錄形成電鍍層之步驟； ， 去除上述光阻遮罩之步驟；及 於上述無電解鍍覆層中， ……… 刻選擇性去除依平面視為 與上述電鍵層未重豐之部分之步驟； 在上述形成無電解錢層之步驟後、上述形成電鍍層之步 驟前’具有加熱上述基板之第—加熱步驟，及/或在上述形 成電鑛層後’具有加熱上述基板之第二加熱步驟。 右根據本毛Θ則可透過半加成法而對核心基板或層間絕 緣層之樹脂表面形成密她高之導體電路層，喊得導體電 路層之剝離強度高之印刷佈線板。 【實施方式】 上述目的及其他目的、特徵及優點係可依據以下所說明之 較佳實施形態及隨附之下述圖式而進—步了解。 以下，係針對本發明之實祕態使用圖式進行說明。另 外於所有圖式中，係職予同樣的構成要件相同的元件符 101102469 201236531 號，並適當省略說明。 圖1係朗本實施形態之印顯線板之製造方法例的示 意圖。圖2係說明本實施形態之印刷佈線板之製造方法例的 流程圖。 本實料態之印刷佈線板之製造方法係具備有·在表面為 由樹月日組成物所構成之印刷佈線板用基板1之該表面上，藉 由…、電解鑛覆也成無電解錢覆層2之步驟；在無電解鐘覆層 形成’、有開口之光阻遮罩3之步驟丨在光阻遮罩3之開 口内，藉由電鑛形成電朗4之步驟；去除光阻遮罩3之步 驟；於無電解鍍覆層2中，藉由㈣選擇性去除依平面視為 與電錢層4未重叠之部分之步驟。又，本實施形態之印刷佈 線板之製造方法係麵成無電解鍍㈣2之步驟後、形成電 錢層4之步驟前’具有加熱印刷佈線板用基板i之第-純 步驟，及/或在形成钱層4|，具有力咖卩 狀 板1之第二加熱步驟。 天奴用基 若根據本實施形態，則可以提高印刷佈線板用基板盘導體 電路層之密接性。因此，可提升依本實施形態所獲叙構成 印刷佈線板之導體電路層的剝離強度。 冓成 第二加熱步義可在形錢鍍層4之步驟與切光 罩3之步驟之間、去除光阻遮罩3之步驟與轉 遮 解《層2之步驟之間或選擇性去除無電解鍍覆^電 之後進行。於在選擇性去除無電解料層2之步 101102469 7 201236531 $力17熱步驟時’於選擇性去除無電解鑛覆層2之後，進行 根據第—加熱步驟之加熱處理，而電路層形成階段結束。 藉由第一加熱步驟及第二加熱步驟均進行，則可進一步提 间印刷佈線板用基板料體電路狀密接性。 以下’根據圖1及圖2說明本發明之印刷佈線板之製造方 法例。圖1及圖2解印刷佈線板之製造方法係包含藉由依 序進行準備印刷佈線板用基板1之步驟(步驟⑷）、形成無電 解鍍覆層2之步驟(步驟(b))、形成光阻遮罩3之步驟(步驟 (c))、形成電鍍層4之步驟（步驟、去除光阻遮罩3之步 驟（步驟(e))及選擇性去除無電解鍍覆層2之步驟（步驟⑴)之 /步驟而形成導體電路層的電路層形成階段。第一加熱步 驟係在步驟(b)與步驟⑷之間進行。第二加熱步驟係在步驟 ⑺之後進行。 ，另外’本實施形態之印刷佈線板之製造方法並未限定於上 述方法。第一加熱步驟係可在步驟(b)與步驟(c)之間或步驟 m步驟⑷之間進行。X，第二加熱步驟係可在步驟⑷與 夕^ ^之間、步驟(e)與步驟(f)之間或步驟(f)之後進行。另 加齡軸第二加齡驟兩者，亦可僅進行 較佳為進行第-加熱步驟與第二加熱步驟兩者。 基板^⑷所錢，在步驟⑷中’準騎刷佈線板用 例如可使用 作為印刷佈線板用基板丨，並沒有特別限定， 101102469 201236531 由積層體或金屬張貼積層板等所構成之核心基板，或具有將 内層電路予以覆蓋之絶緣層的多層化基板等。本實施形態之 印刷佈線板之製造方法係透過SAp法將導體電路層形成在 由、、邑、.彖㈣月日組祕所構成之表面的情形時，則可以應用。 本實施形態之㈣佈線板之製造方法侧如可應时形成 核心基板上之導體電路層、或多層印刷佈線板之内層電路或 外層電路的情形。 作為構成核心基板之上述積層體，例如可使用複數片重最 有預浸體者等。職體係沒有特龍定，謂由公知方法: 獲得。預浸體係例如可藉由將含浸有含有熱硬化性樹脂、硬 刮及真充;=|j等之W脂組成物之清漆的玻璃織布等基材予 以加熱乾燥而形成。 作為構成核心基板之上述金屬張貼積層板，例如可使用將 金屬箱重疊於職體或上述積層體之至少—面，並進行加熱 加壓成形者等。料，在將金屬張貼積層板當作為印刷佈線 板用基板1使用時，可採用透過餘刻等方法將設置在表面之 金屬4予以去除的金屬張貼積層板。藉此，則印刷佈線板用 基板1之表面係成為由樹脂組成物所構成。 ★作為多層化基板，例如可使料賴覆通孔法或疊層法 專、、至由層間絕緣層將成為内層電路之導體電路層積声在校 心基板上，並進行多層佈線化途中之積層體，其係於最表面 積層有相絕緣層者等。上述和絕緣層敍有特別限定， 101102469 201236531 例如可藉由未含有預浸體或基材之樹脂組成物等而構成° 上述成為内層電路之導體電路層係可藉由於例如依SAP 法之電路形成階段中，以進行第一加熱步驟為特徼之本實施 形態之電路形成方法而形成。藉此，可提高成為内層電路之 導體電路層的剝離強度。另外，成為内層電路之導體電路層 係可藉由先前所習知之電路形成方法而形成。 又，設置在由上述積層體或上述金屬張貼積層板所構成之 核心基板之兩面的導體電路層，係例如可藉由鑽孔加工或雷 射加工等而將鑛覆層等形成於核心基板上所形成之通孔 内，並藉以可互相電性連接。 成為導體電路層之支撐體的印刷佈線板用基板丨係具有 由絕緣性樹馳錢所構成之表面。構成印刷佈線板用基板 1之表面的樹脂組成物係沒有_限定，例如可為至少含有 熱硬化性樹脂之樹脂組成物。作為上述熱硬化性樹脂，例如 可列舉出脲(尿素)樹脂、三聚氰胺樹脂、順H亞胺化 合物聚胺基曱酸酯樹脂、不飽和聚酯樹脂、具有苯产 :樹脂、雙烯丙基二醢亞胺化合物、乙稀基节_旨、⑽ 基节基嘯脂、苯并環丁烯樹脂、氰_樹脂、環氧樹 熱硬化性㈣細料巾之麵轉移溫度可 ==:中，較佳的是熱硬化性樹脂為玻璃轉 移/皿度可成為200 C以上之組合。 脂，較佳的是使用例如含有螺旋環此s’作為熱硬化性樹 ^雜環式、三經曱基型、 101102469 10 201236531 聯苯基型、萘型、蒽型、酚醛清漆型之2或3官能以上的環 氧樹脂；氰酸酯樹脂（包含氱酸酯樹脂之預聚物）、順丁烯二 醯亞胺化合物、苯并環丁烯樹脂、具有苯并谔畊環之樹脂。 透過使用環氧樹脂及/或氰酸酯樹脂來作為熱硬化性樹 脂’則樹脂組成物之線膨脹小，且可明顯提升樹脂組成物之 耐熱性。又’藉由將環氧樹脂及/或氰酸酯樹脂與高填充董 之填充材料組合’則可以獲得難燃性、耐熱性、耐衝擊性、 高剛性及電氣特性(低介電係數、低介電正切)優越的樹脂組 成物。 於此’耐熱性之提升係可認為是起因於下述原因：硬化反 應後之熱硬化性樹脂之玻璃轉移溫度成為2〇〇〇c以上、硬化 後之樹脂組成物之熱分解溫度變高、於25〇〇c以上之反應殘 渣等低分子量成分減少。 又，難燃性之提升係可認為是起因於：在構造上苯環比例 尚之芳香族系熱硬化性樹脂中，苯環容易碳化(石墨化）而產 生碳化部分。 作為上述環氧樹脂，例如可列舉出雙酚A型環氧樹脂、 雙盼F型環氧樹脂、祕祕清漆型環氧細旨、甲畴酸清 漆型壤氧樹脂、㈣A祕清漆型環氧樹脂、聯苯基盼酸 凊漆型環氧樹脂、蒽型環氧樹脂、二氫蒽型環氧樹脂、3官 能苯酶型環氧樹脂、4官能苯_環氧樹脂、萘型環氧樹 脂、聯苯型環氧樹脂、芳烧基型環氧樹脂、脂環式環氧樹月旨、 101102469 11 201236531 多醇型環氧樹脂、縮水甘油基胺、縮水甘油基醚、丁二烯等 將雙重鍵結予以環氧化之化合物、由含有羥基之聚矽氧樹脂 類與表氯醇之反應所獲得之化合物等。該等之中，環氧樹脂 係以萘型、或芳基伸烷基型環氧樹脂為佳。藉由使用萘型、 或芳基伸烷基型環氧樹脂，則可提高所獲得之積層板之吸濕 焊錫耐熱性（吸濕後之焊錫耐熱性)及難燃性。作為萘型環氧 樹脂’可列舉出DIC(股）製之HP-4700、HP-4770、 HP-4032D、HP-5000、日本化藥（股）製之 NC_73〇〇L、新日 鐵化學(股)製之ESN-375等。又，作為芳基伸烷基型環氧樹 月曰’可列舉出曰本化藥（股）製之NC-3000、NC-3000L、 NC-3000-FH、日本化藥（股）製之NC_73〇〇L、新日鐵化學（股） ESN-375 f。所謂的綠伸絲型環氧樹脂係指重覆 單位中含有-個以上芳香族基與亞甲基等之伸烧基的組合 之環氧樹脂，耐熱性、難燃性及機械性強度優異。 上述氰酸i旨樹脂係例如可藉由❹化氰化合物與苯紛類 進行反應而獲得。作為氰酸酯樹脂之具體例，例如可列舉出 苯驗祕清漆㈣酸賴脂、甲㈣料漆型氰義樹脂等 之祕清漆型1酸g旨樹脂、萘料院基型氰動旨樹脂、二環 戊-稀型氰_旨樹脂、聯苯型純賴脂、雙紛A型氛酸 醋樹脂、雙紛AD型氰酸g旨樹脂、四曱基雙紛F型㈣酉旨樹 脂等雙酚型氰酸酯樹脂等。 。玄4之中，尤其疋以包含酚醛清漆型氰酸酯樹脂、萘酚芳 101102469 12 201236531 烧基型氰酸S旨樹脂、二環戊二稀型氰醆輯脂、或雙紛型氰 酸醋樹脂為佳。此外，較佳的是將上述氰動旨樹脂於樹脂組 成物之全固形分中含有1G重量％以上。藉此，則可提升預 浸體之耐熱，_璃轉移溫度、熱分解溫度）。又，可降低預 浸體之熱膨脹減U其是預㈣在厚度方向之熱膨脹係 數）。透過使賴體在厚度方向之_脹·降低，則可減 輕多層印刷佈線之應力應變。此外，在具有細微層間連接部 之多層印刷佈線板中，可大幅提高其連接可靠性。 作為祕清漆型氰酸賴脂中之較佳者，可舉出有以下述 式⑴所示之祕清漆型氰__卜此情形下，較佳的是 使用重f平均分子#大之祕清漆魏酸㈣脂與重量平 =分子量彳、之祕清漆魏_樹脂的組合。重量平均分子 之祕π漆型氰酸醋樹脂之重量平均分子量係以細〇 ^=^\2(KK)〜_G更佳’以2，細〜3,50G再更佳。 重里平句刀子星小之酚醛清漆型氰酸酯樹脂之重量平均 t子量係以1500以下為佳，以雇〜mo更佳。另外，本實 施形態之重s平均分子量係藉由聚苯乙職算之凝膠層析 法進行測量之數值。 [化1]201236531 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing a printed wiring board. [Prior Art] Along with the demand for high-performance of electronic equipment, high-density integration of electronic components and even the desire for installation have continued to develop. For this reason, in terms of high-density mounting of printed wiring boards for electronic components, etc., the size, thickness, density, and multilayering have been increasing as compared with the prior art. As a conductor circuit layer having high pattern precision at a high density on a substrate of a printed wiring board, a semi-additive method (SAP method) has been started. " The formation of circuits according to the SAP method is carried out, for example, according to the following description. First, the surface of the resin of the core substrate or the interlayer insulating layer is roughened. Next, on the surface of the roughened resin, an electroless plating layer of the substrate is formed. Next, the non-circuit forming portion is protected by plating a photoresist, and the plating portion is thickened by plating. Thereafter, the photoresist is removed, and the electroless plating layer other than the circuit forming portion is removed by flash etching to form a circuit on the surface of the resin. According to the SAP method, the metal layer laminated on the surface of the resin can be thinned. Therefore, a finer circuit wiring can be formed. However, in the case of the SAP method of the resin surface of the prior art for the core substrate or the interlayer insulating layer, 'there is not sufficient adhesion between the conductor circuit layer and the resin surface' and the peeling strength of the conductor circuit layer is lowered.情101102469 201236531 Shape. At this time, when the printed wiring board is exposed to, for example, high-temperature and high-humidity conditions, problems such as peeling of the conductor circuit layer, occurrence of humidification expansion, or deterioration of connection reliability are caused. In addition, in recent years, in order to achieve both a reduction in thickness and a low warpage of the package substrate, there is a case where the filler is highly filled for the purpose of high rigidity and low thermal expansion of the substrate. At this time, the problem of the adhesion between the conductor circuit layer and the resin surface according to the SAP method is conspicuous. This is due to the influence of the filler material when the chemical treatment is carried out in the case of mineral coating or removal of burrs. In order to improve the adhesion between the surface of the resin and the conductor circuit layer, for example, the SAP method disclosed in Patent Documents 1 and 2 applies a roughening treatment to the surface of the resin in such a manner that the unevenness of the surface of the resin is 1 to 7 cm. Further, Patent Document 3 discloses a method in which a ruthenium coupling agent is laminated on a copper foil which is not subjected to roughening treatment, and an extremely thin undercoat layer is further laminated thereon to obtain an extremely thin adhesive layer. The bonding strength between the copper junction and the base resin is excellent. [Prior Art Document] [Patent Document 1] Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-69218 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. 〇〇5·〇53218 SUMMARY OF THE INVENTION The object of the present invention is to obtain a conductor by a semi-additive method for a core substrate or a layer 101102469 5 201236531 ', and according to the present invention, a system is provided: The manufacturing method of the printed wiring board is a step of forming an electroless plating layer by electroplating on the surface of the substrate composed of the resin composition, and forming a non-electrolytic coating layer. a step of forming a photoresist mask with an opening. In the opening, a step of forming a plating layer by electro-recording; a step of removing the photoresist mask; and in the electroless plating layer, ... The step of removing the flat surface is not the same as the above-mentioned electric bond layer; after the step of forming the electroless gold layer, the step of forming the electroplated layer is preceded by the step of heating the substrate, and/or in Later forming electrically seam 'having a second heating step of heating the substrate. According to the present invention, the surface of the resin of the core substrate or the interlayer insulating layer can be formed by a semi-additive method by a semi-additive method, and the printed wiring board having a high peeling strength of the conductor circuit layer can be called. The above and other objects, features and advantages of the present invention will be apparent from the description of the preferred embodiments illustrated herein. Hereinafter, the description will be made using the drawings for the actual state of the present invention. In addition, in all the drawings, the same components are denoted by the same components 101102469 201236531, and the description is omitted as appropriate. Fig. 1 is a view showing an example of a method of manufacturing a printed wiring board of the embodiment of the present invention. Fig. 2 is a flow chart showing an example of a method of manufacturing the printed wiring board of the embodiment. The method for producing a printed wiring board of the present invention is provided on the surface of the substrate 1 for a printed wiring board having a surface composed of a composition of a tree and a moon. Step 2 of layer 2; forming a step of forming a photoresist mask 3 having an opening in an electroless bell coating, forming a step 4 in the opening of the photoresist mask 3 by electrowinning; removing the photoresist The step of the cover 3; in the electroless plating layer 2, the step of selectively removing the portion which is not overlapped with the money layer 4 by the (4) selective removal. Further, the method for producing a printed wiring board according to the present embodiment is a step of forming an electroless plating layer (4) 2, and a step of forming the battery layer 4, which has a first-pure step of heating the substrate i for a printed wiring board, and/or Forming the money layer 4|, having a second heating step of the force coffee plate 1. According to this embodiment, the adhesion of the circuit board conductor circuit layer for a printed wiring board can be improved. Therefore, the peel strength of the conductor circuit layer constituting the printed wiring board according to the present embodiment can be improved. The second heating step can be between the step of forming the money coating 4 and the step of cutting the mask 3, the step of removing the photoresist mask 3 and the step of translating the layer 2 or selectively removing the electroless After plating, it is carried out. After the selective removal of the electroless layer 2, 101102469 7 201236531 $ force 17 thermal step 'after the selective removal of the electroless ore layer 2, the heat treatment according to the first heating step is performed, and the circuit layer formation phase ends. . By performing both the first heating step and the second heating step, it is possible to further improve the circuit-like adhesion of the substrate material for the printed wiring board. Hereinafter, a manufacturing method of the printed wiring board of the present invention will be described with reference to Figs. 1 and 2 . 1 and 2, a method of manufacturing a printed wiring board includes a step of preparing a substrate 1 for a printed wiring board in sequence (step (4)), a step of forming an electroless plating layer 2 (step (b)), and forming light. a step of blocking the mask 3 (step (c)), a step of forming the plating layer 4 (step, step of removing the photoresist mask 3 (step (e)), and step of selectively removing the electroless plating layer 2 (step (1)) / step forming a circuit layer forming phase of the conductor circuit layer. The first heating step is performed between step (b) and step (4). The second heating step is performed after step (7). The manufacturing method of the printed wiring board is not limited to the above method. The first heating step may be performed between step (b) and step (c) or step m step (4). X, the second heating step may be Step (4) and 夕 ^ ^, between step (e) and step (f) or after step (f). Adding the second axis of the second ageing step, or only preferably performing the first - Both the heating step and the second heating step. The substrate ^(4) is used in the step (4). The substrate used for the printed wiring board is not particularly limited, and 101102469 201236531 is a core substrate composed of a laminate or a metal-clad laminate, or a multilayer substrate having an insulating layer covering the inner layer circuit. The manufacturing method of the printed wiring board according to the embodiment can be applied to the case where the conductor circuit layer is formed on the surface composed of the 、, 邑, 彖 (4) 日 组 秘 秘 秘 秘 SA 。 。 四 四 四 四 四 四 四 四 四 四 四The manufacturing method side may be such that the conductor circuit layer on the core substrate or the inner layer circuit or the outer layer circuit of the multilayer printed wiring board can be formed in a timely manner. As the above laminated body constituting the core substrate, for example, a plurality of sheets can be used for the most prepreg. The body system does not have Trondine, which is known by the method: obtained. The prepreg system can be impregnated with, for example, a W-fat composition containing a thermosetting resin, a hard scraping, and a true charge; A substrate such as a glass woven fabric of varnish is formed by heating and drying. As the metal-clad laminate which constitutes the core substrate, for example, a metal case may be overlapped When the metal laminated laminated board is used as the substrate 1 for a printed wiring board, it may be placed on the surface by a method such as a residual film or the like. The metal removed by the metal 4 is placed on the laminate. The surface of the printed wiring board substrate 1 is made of a resin composition. ★ As a multilayer substrate, for example, a through-hole method or a laminate can be used. In the case of the interlayer insulating layer, the conductor circuit of the inner layer circuit is laminated on the core substrate, and the layered body in the middle of the multilayer wiring is formed on the surface layer of the most surface layer, and the like. The insulating layer is specifically limited, and 101102469 201236531 can be formed, for example, by a resin composition not containing a prepreg or a substrate. The above-described conductor circuit layer which becomes an inner layer circuit can be formed in a circuit formation stage by, for example, an SAP method. This is formed by the circuit forming method of this embodiment in which the first heating step is performed. Thereby, the peel strength of the conductor circuit layer which becomes the inner layer circuit can be improved. Further, the conductor circuit layer which becomes the inner layer circuit can be formed by a conventional circuit forming method. Further, the conductor circuit layer provided on both surfaces of the core substrate formed of the laminated body or the metal-clad laminate may be formed on the core substrate by, for example, drilling or laser processing. The through holes are formed and electrically connected to each other. The substrate for a printed wiring board which serves as a support for the conductor circuit layer has a surface composed of an insulating property. The resin composition constituting the surface of the substrate 1 for a printed wiring board is not limited, and may be, for example, a resin composition containing at least a thermosetting resin. Examples of the thermosetting resin include urea (urea) resin, melamine resin, cis-H imine compound polyamino phthalate resin, unsaturated polyester resin, and benzene production: resin, bisallyl II. The surface transfer temperature of the quinone imine compound, the ethylene base group, the (10) ketone group, the benzocyclobutene resin, the cyanide resin, and the epoxy resin thermosetting (four) fine towel can be ==: It is preferred that the thermosetting resin be a glass transfer/dishness of 200 C or more. For the fat, it is preferred to use, for example, a spiral ring containing the s' as a thermosetting tree, a heterocyclic ring, a triterpene group, a 101102469 10 201236531 biphenyl type, a naphthalene type, an anthraquinone type, a novolac type 2 or A trifunctional or higher epoxy resin; a cyanate resin (prepolymer containing a phthalate resin), a maleimide compound, a benzocyclobutene resin, and a resin having a benzofluorene ring. By using an epoxy resin and/or a cyanate resin as the thermosetting resin, the linear expansion of the resin composition is small, and the heat resistance of the resin composition can be remarkably improved. In addition, by combining epoxy resin and/or cyanate resin with high-filled filler material, it can achieve flame retardancy, heat resistance, impact resistance, high rigidity and electrical properties (low dielectric constant, low Dielectric tangent) superior resin composition. Here, the improvement of the heat resistance is considered to be caused by the fact that the glass transition temperature of the thermosetting resin after the curing reaction is 2 〇〇〇 c or more, and the thermal decomposition temperature of the resin composition after curing becomes high. The low molecular weight component such as the reaction residue at 25 〇〇c or more is reduced. In addition, the improvement of the flame retardancy is considered to be due to the fact that in the aromatic thermosetting resin in which the structure is benzene ring, the benzene ring is easily carbonized (graphitized) to produce a carbonized portion. Examples of the epoxy resin include a bisphenol A type epoxy resin, a double-preferred F type epoxy resin, a secret varnish type epoxy resin, a formic acid varnish type earth oxy-resin, and (4) A secret varnish type epoxy. Resin, biphenyl phthalate lacquer epoxy resin, bismuth epoxy resin, indoline oxime epoxy resin, trifunctional benzoic acid epoxy resin, 4-functional benzene epoxy resin, naphthalene epoxy resin , biphenyl type epoxy resin, aryl-based epoxy resin, alicyclic epoxy tree, 101102469 11 201236531 polyol epoxy resin, glycidylamine, glycidyl ether, butadiene, etc. A compound obtained by epoxidizing a double bond, a compound obtained by a reaction of a hydroxyl group-containing polyoxyl resin and epichlorohydrin, and the like. Among these, the epoxy resin is preferably a naphthalene type or an arylalkylene type epoxy resin. By using a naphthalene type or an arylalkylene type epoxy resin, the moisture absorption solder heat resistance (solder heat resistance after moisture absorption) and flame retardancy of the obtained laminate can be improved. As the naphthalene type epoxy resin, HP-4700, HP-4770, HP-4032D, HP-5000, Nippon Chemical Co., Ltd., NC_73〇〇L, Nippon Steel Chemical Co., Ltd. (manufactured by DIC Co., Ltd.) ESN-375, etc. In addition, as the aryl-alkyl-type epoxy resin, the NC-73, NC-3000L, NC-3000-FH, and Nippon Chemical Co., Ltd., NC_73, manufactured by Sakamoto Chemical Co., Ltd. 〇L, Nippon Steel Chemical Co., Ltd. ESN-375 f. The green-stranded epoxy resin is an epoxy resin having a combination of one or more aromatic groups and a stretching group such as a methylene group in a repeating unit, and is excellent in heat resistance, flame retardancy, and mechanical strength. The above-mentioned cyanate-based resin can be obtained, for example, by reacting a cyanide compound with benzene. Specific examples of the cyanate resin include, for example, a benzoic acid varnish (4) acid lyophile, a nail lacquer type cyanide resin, a varnish type 1 acid g resin, and a naphthalene material base type cyanine resin. , Dicyclopentane-dilute cyanide--Resin, biphenyl-type pure lysine, double-type A-type vinegar resin, double-type AD-type cyanate g-resin, tetrakis-based double F-type (four) 酉 resin, etc. A bisphenol type cyanate resin or the like. . Among the mysterious 4, especially the phenolic varnish-type cyanate resin, naphthol aryl 101102469 12 201236531 succinic cyanate S resin, dicyclopentadienyl cyanide resin, or double diced cyanate Resin is preferred. Further, it is preferable that the cyanide resin is contained in an amount of 1 G% by weight or more based on the total solid content of the resin composition. Thereby, the heat resistance of the prepreg, the glass transition temperature, and the thermal decomposition temperature can be improved. Further, the thermal expansion of the prepreg can be reduced by U (the thermal expansion coefficient in the thickness direction). By swelling and lowering the body in the thickness direction, the stress strain of the multilayer printed wiring can be reduced. Further, in the multilayer printed wiring board having the fine interlayer connection portion, the connection reliability can be greatly improved. The preferred one of the secret varnish type cyanate lysate is a varnish type cyanine represented by the following formula (1). In this case, it is preferred to use a heavy averaging molecule #大之秘漆Wei acid (tetra) fat and weight flat = molecular weight 彳, the secret varnish Wei _ resin combination. The weight average molecular weight π lacquer type cyanic acid vinegar resin has a weight average molecular weight of fine 〇 ^ = ^ \ 2 (KK) ~ _ G is better than 2, fine ~ 3, 50 G and more preferably. The weight average of the phenolic phenolic resin of the phenolic varnish is the best. The amount of t is 1500 or less, and it is better to hire ~mo. Further, the weight average s average molecular weight of the present embodiment is a value measured by a gel chromatography method of polyphenylene. [Chemical 1]
OCNOCN
CH·CH·
OCN ⑴ 101102469 201236531 式（1)中，η係表示0以上之整數。 又，作為氰酸酯樹脂，亦可適當使用以下述一般式（2)所 示之氰酸酯樹脂。以下述一般式（2)所示之氰酸酯樹脂係將 依α-萘酚、萘酚等萘酚類與對荏二醇、α，α’-二甲氧基 -對二曱苯、1，4-二(2-羥基-2-丙基）苯等之反應所獲得之萘酚 芳烧基樹脂與氰酸予以縮合而獲得者。一般式(2)之η係1 以上，進一步以10以下為佳。於η為10以下時，因為樹脂 黏度不會增加，對基材之含浸性良好，故而不會使作為積層 板之性能降低。又，於合成時不易引起分子内聚合，可提升 水洗時之分液性，可防止產量降低。 [化2]OCN (1) 101102469 201236531 In the formula (1), the η system represents an integer of 0 or more. Further, as the cyanate resin, a cyanate resin represented by the following general formula (2) can be suitably used. The cyanate resin represented by the following general formula (2) is a naphthol such as α-naphthol or naphthol and p-nonanediol, α,α'-dimethoxy-p-diphenyl, 1 The naphthol aryl-based resin obtained by the reaction of 4-di(2-hydroxy-2-propyl)benzene or the like is obtained by condensation with cyanic acid. The η of the general formula (2) is 1 or more, and more preferably 10 or less. When η is 10 or less, since the resin viscosity does not increase and the impregnation property to the substrate is good, the performance as a laminate is not lowered. Further, it is less likely to cause intramolecular polymerization during the synthesis, and the liquid separation property at the time of washing can be improved, and the yield can be prevented from being lowered. [Chemical 2]
式(2)中，R係表示氫原子或曱基，η係表示1以上之整數。 此外，作為氰酸酯樹脂，亦可適當使用以下述式（3)所示 之二環戊二烯型氰酸酯樹脂。 [化3]In the formula (2), R represents a hydrogen atom or a fluorenyl group, and η represents an integer of 1 or more. Further, as the cyanate resin, a dicyclopentadiene type cyanate resin represented by the following formula (3) can be suitably used. [Chemical 3]
OCNOCN
OCN OCN o〇-6-cx>-0 ⑵ 式（3)中，η係表示0〜8之整數。 又，就耐熱性之觀點而言，亦可於上述熱硬化性樹脂組成 101102469 14 201236531 物中含有順丁烯二醯亞胺化合物。順丁烯二醯亞胺化合物係 一分子中具有一個以上順丁烯二醯亞胺基之化合物，則沒有 特別限定。作為其具體例，係可列舉有N-苯基順丁烯二醯 亞胺、N-羥基苯基順丁烯二醯亞胺、雙(4_順丁烯二醯亞胺 基苯基）甲烷、2,2-雙{4-(4-順丁烯二醯亞胺基苯氧基)_苯基} 丙烷、雙(3,5-二甲基-4-順丁烯二醯亞胺基苯基）曱烷、雙 乙基-5-甲基-4-順丁烯二醯亞胺基苯基）甲烧、雙(3,5_二乙基 -4-順丁烯二醯亞胺基苯基）曱烷、聚苯基甲烷順丁烯二醯亞 胺、該等順丁烯二醯亞胺化合物之預聚物或順丁烯二醯亞胺 化合物與胺化合物之預聚物等。 又’就與金屬箔之密接性觀點而言，亦可於上述熱硬化性 樹脂組成物中含有聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞 胺樹脂或苯氧基樹脂。 樹脂組成物中之熱硬化性樹脂的量係在樹脂组成物之全 固形分中，以10〜90重量％為佳，以20〜70重量％更佳，以 25〜50重量％再更佳。另外，樹脂組成物中之熱硬化性樹脂 的量係可因應其目的而適當調整，沒有特別限定。 又，於使用環氧樹脂及/或氰酸酯樹脂作為熱硬化性樹脂 之情形下，環氧樹脂之含有量係於樹脂組成物之全固形分 中，以5〜50重量％為佳，以5〜25重量％更佳。又，氰酸酯 樹脂之含有量係於樹脂組成物之全固形分中，以5〜5〇重量 %為佳，以10〜25重量％更佳。 101102469 15 201236531 此外’上述熱硬化性樹脂組成物係可就不損及本發明之效 果的範圍含有難燃劑，而由環境觀點而言，則是以非鹵素系 難燃劑為佳。作為關劑’例如可列舉出有機磷系難燃劑、 有機系含氮墙化合物、氮化合物、聚魏系難燃劑、或金屬 氫氧化物等。作為有機磷系難燃劑，可列舉有三光(股)製之 HCA、HCAHQ、HCA-NQ 等膦化合物、clariam(股）製之 OP930、大八化學（股）製之PX2〇〇等磷酸酯化合物、東都化 成（股）製之FX289等含磷環氧樹脂或東都化成（股）製之 ERFOOi等㈣苯氧樹料。作❹齡錢魏合物，可 列舉有大塚化學（股）製之SPB100、SPEl〇〇等磷氮基 (ph〇sphaZene)化合物等。作為金屬氫氧化物，可列舉有住友 化學（股）製之CL310、昭和電工(股)製之Hp_35〇等氫氧化鋁 等。 另外，亦可以於熱硬化性樹脂組成物中並用硬化劑。例 如，若熱硬化性樹脂為環氧樹脂或氰酸酯樹脂，則可使用苯 酚樹脂、或環氧樹脂或氰酸酯樹脂之硬化促進劑。上述苯酚 樹脂並沒有特別限定，例如可列舉有苯酚酚醛清漆樹脂、曱 酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、芳基伸烷基型酚 醛清漆樹脂等酚醛清漆型苯酚樹脂、未改質之可溶酚醛苯酚 樹脂、桐油、亞麻油、核桃油等經改質之油改質可溶酚醛笨 酚樹脂等可溶酚醛型笨酚樹脂等。作為上述笨酚樹脂，較佳 的疋笨酚酚搭清漆樹脂或曱酚酚醛清漆樹脂。其中，就吸濕 101102469 16 201236531 ==?觀點而言，較佳的是聯⑽基改質笨_ 量用該等中之一種，或並用具有相異重量平均分子 1上’或亦可並用—種或兩種以上與該等之預聚 述更化促進劑係沒有特別限定，例如可列舉有環 等之有機金屬鹽、二α丫聯環[2,2,2]辛院等之3級胺類二乙 乙基，等㈣類、壬祕等麵化合物、對甲苯錯 酸等有機酸、鎮(〇nium)鹽化合物等或其混合物。包含节等 中之衍生物，射單獨㈣—種，包含料巾 ^ 亦可並用兩種以上。 ％係 鐵與機械強度之觀點而言，較佳的是於樹脂組成 物中$有無機填充㈣。無魏域料錢有特舰定，例 如可列舉有滑石、燒成黏土、未燒成黏土、雲母、玻璃等石夕 酸鹽、乳化鈦、氧化紹、二氧化石夕、炼融二氧化石夕等氧化物、 碳酸約、碳龍、水滑石等碳酸鹽、氫氧化|S、水銘土 (A1〇(〇H) ’ 一般稱為[擬]水鋁土之水鋁土 (亦即， ΑΙΛ.χΗ2〇，此處之㈣至2))、氫氧化鎮、氨氧簡等 金屬虱氧化物、硫酸鎖、硫㈣、亞硫贿等硫酸鹽或亞硫 酸鹽、餐鋅、甲基石朋酸鋇、硼酸銘、删㈣、石朋酸納等爛 酸鹽、氮化鋁、氣化硼、氮化矽、t化碳等氮化物、鈦酸鏍、 鈦酸鋇等鈦酸㈣。可單獨使_料之-種，亦可並用兩 101102469 17 201236531 種以上。 :等广較佳的是氫氧化鎂、氫氧化銘、水紹土 化矽、熔融二氧彳卜α 、 孔 、滑石、燒成滑石、氧化紹。就低熱膨 脹性及絕緣可靠#少細 ,.>h,3. ^ 觀點而言，特別以二氧化矽為佳，而球 二、° 化夕更佳。又，就耐燃性之觀點而言，較佳的是 虱氧化紹。於樹脂組成物巾高濃度填充有無機填充材料之情 形下，鑽孔磨耗性會牮 μ化，而藉由使用水鋁土作為無機填充 材料，則鑽孔磨耗性變得良好。 。。無機填充材料之_並沒有制限定，可㈣平均粒徑為 早分散之無機填充材料，亦可使用平均粒料多分散之無機 填充材料。此外，也可以並用平均粒徑為單分散及/或多分 散之無機填充材料—種或兩種以上。另外，本案說明書中， 所謂的平均粒徑為單分散係意錄徑之標準偏差在 10%以 下者又戶斤明的平均粒控為多分散係意指粒徑之標準偏差 在10%以上者。 上述無機填充材料之平均粒徑係沒有制限定，較佳的是 l"m 5.0"m特佳的疋〇 ^^3 m。經由將無機填 充材料之粒徑作成上述下限值以上，則可抑制樹脂組成物之 黏度變⑨’可使預浸體製作時之作業性良好。又，透過將無 機填充材料之_作成上述上限似下，則可抑制在樹脂組 成物中引起無機填充材料之沉料現象。另外，平均粒徑係 可使用雷射繞射/散亂式粒度分布測量裝置（島津製作所 101102469 18 201236531 SALD-7000等一般性機器）進行測量。 上述無機填充材料之含有量係沒有特別限定’較佳的是於 樹脂組成物之全固形分中為10〜90重量％，更佳的是3〇〜8〇 重量％ ’再更佳的是50〜75重量％。於樹脂組成物中含有氰 酸酯樹脂及/或其預聚物時，上述無機填充材料之含有量較 佳的是於樹脂組成物之全固形分中為5〇〜75重量％。藉由將 無機填充材料之含有量作成上述上限值以下，則可使樹脂組 成物之流動性良好。又，透過將無機填充材料之含有量作成 上述下限值以上，則可充分提高由樹脂組成物所構成之絕緣 層的強度。 在樹脂組成物中，亦可進一步含有偶合劑。偶合劑係為了 提升熱硬化性樹脂與無機填充材料之界面的濕潤性而加以 調配。藉由提升熱硬化性樹脂與無機填充材料之界面的濕潤 性，則可使樹脂及無機填充材料相對於基材而均勻固定，可 改良耐熱性’尤其是吸濕後之焊錫耐熱性。 上述偶合劑並沒有特別限定，例如可列舉有環氧石夕烧偶合 劑、陽離子性魏偶合劑、胺基㈣偶合劑、鈦㈣系偶合 ^聚發氧油型偶合劑等。藉由使用該等作為偶合劑，則; 提高與無機填充材料之界面的濕潤性。因此，可進一步提升 樹脂組成物之耐熱性。 上述偶合劑之添加量並沒有特靠定，相對於無機填充材 料100重量份，α 〇·〇5〜3重量份為佳，特別以0U重量 101102469 19 201236531 份為佳。透過將偶合劑之含有量設在上述下限值以上，則可 充分覆蓋無機填充材料，而得以充分獲得提升耐熱性之效 果。又，透過將偶合劑之含有量設在上述上限值以下，射 抑制對反應給予影響。藉此，可抑制彎曲強度等之降低。 於樹脂組成物中，因應需要亦可以添加消泡劑、勻平劑、 紫外線吸收劑、發泡劑、抗氧化劑、難燃劑、聚矽氧粉末等 難燃輔助劑、離子捕捉劑等上述成分以外之添加物。 樹脂組成物係就可輕易實現預浸體之低線膨脹化、高剛性 化及高耐熱化之觀㈣言，難的是至少含有環氧樹脂^ 酸s旨樹脂及無機填充材料。其中，在樹脂組成物之固形； 中，較佳的是含有環氧樹脂5〜5G重量％、氰酸g旨樹脂^ 重量％及，機填充材料1G，重量％，更佳的是環氧射 重！％、氰酸酯樹脂10〜25重量%及無機填充材· 30〜80重量％。 印刷佈線板用基板Α之㈣，可進行去造處理 二:=產生於印刷佈線板用基板1之表面的殘渣》 = 別限定’係可藉由使用具有有機物分解作 ==的濕式法、或针對成為對象物者照射直接』 法等乾式料公知叫=)料咖物殘飾 施=去渔處理係例如依下述進行。首先，對_ w处理。其次’進行依驗處理之朗。其後，對掏 101J02469 20 201236531 表面施以中和處理。 接者，如圖1(b)所示般，於步驟⑻中，在表面為由樹脂 、、且成物所構成之印刷佈線板用基板i之該表面上進行無電 解鍍覆，而形成無電解鍍覆層2。無電解鑛覆係在附著有奶 等觸媒之《對象物的表面’可藉由使接觸含有進行鐘覆金 屬離子之電解液（鍍覆液）的化學鍍覆法等公知方法而進 灯。於本實施耗中’作為無電解鍍覆，例如可進行無電解 銅鍍覆。 ‘ 以工 無電解錢覆層2之厚度並沒有特別限定，以〇1_ 且2㈣以下為佳。透過將無電解鍍覆層2之厚度設為0.1 W以上’則可輕易進行下述電錄步驟。又，透過將無電解 鍵覆層2之厚度設為以下，則成為可短時間下進行無 電解鍍覆層2之形成。藉此’可圖謀作業效率的提升。 接下來’進行第-加熱步驟。另外，第一加熱步驟係沒有 限定在㈣⑻與㈣(狀㈣行，也可叫㈣⑷與步驟 ⑷之間進行。就將依下述财所形成之導體電路層5之剝 離強度進—步提升之觀⑽言，第-加熱步驟仙於步驟⑻ 與步驟(c)之間進行為佳。 第力，、、、々驟之加熱處理的加熱温度係以n28〇t>c為 佳，以140〜230〇C為更佳。粒山丄 错由加熱溫度在此範圍内，則可 提升導體電路層5之剝離強度。 第力，、"驟之加熱處理並沒有特別限定，例如可藉由潔 101102469 21 201236531 淨烤爐等可導入氮(n2)之公知裝置進行。 第一加熱步驟之加熱處理係以於氧(〇2)濃度為1 OOOppm 以下之環境下進行為佳，以於氧(〇2)濃度為500ppm以下之 環境下進行為更佳。藉此，可防止構成導體電路層5之銅的 氧化，而可提升導體電路層5之剝離強度。 第一加熱步驟之加熱處理係進一步以於氮（N2)濃度為 78%以上之環境下進行為佳，以於氮(N2)濃度為85%以上之 環境下進行為更佳。藉此，可進一步提升導體電路層5之剝 離強度。 又，第一加熱步驟之加熱處理係可以在大氣壓下進行，也 可以在減壓下進行。例如，於空氣環境下，藉由在3torr以 下之減壓下進行加熱處理，則可減低氧濃度至lOOOppm以 下。又，於以氮取代空氣而在經提高氮濃度之環境下進行減 壓之情形中，即便是在3torr以上，亦可以減低氧濃度至 lOOOppm以下。因此，可防止構成導體電路層5之銅的氧 化，而可提升導體電路層之剝離強度。 此外，在第一加熱步驟中，將印刷佈線板用基板1予以加 熱處理之時間係以30分鐘以上且300分鐘以下為佳。於進 行加熱處理之時間在30分鐘以上之情形下，可充分獲得使 導體電路層5之剝離強度提升的效果。又，於進行加熱處理 之時間在300分鐘以下之情形下，則可實現良好的作業效 率。 101102469 22 201236531 再來，如圖1(c)所示般，在步驟(c)中，將具有開口之光随 遮罩3形成於無電解鍍覆層2上β 藉由光阻遮罩3,而將無電解链覆層2中未形成有導體電OCN OCN o〇-6-cx>-0 (2) In the formula (3), η represents an integer of 0 to 8. Further, from the viewpoint of heat resistance, the maleic imide compound may be contained in the above thermosetting resin composition 101102469 14 201236531. The maleimide compound is not particularly limited as long as it has one or more maleimide groups in one molecule. Specific examples thereof include N-phenyl maleimide, N-hydroxyphenyl maleimide, and bis(4-butyleneiminophenyl)methane. , 2,2-bis{4-(4-maleimidoiminophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-northenylenediamine Phenyl)decane, bisethyl-5-methyl-4-methylene-2-imidazolylphenyl), bis(3,5-diethyl-4-maleimide Phenyl) decane, polyphenylmethane maleimide, a prepolymer of the maleimide compound or a prepolymer of a maleimide compound and an amine compound, etc. . Further, from the viewpoint of the adhesion to the metal foil, the thermosetting resin composition may contain a polyimide resin, a polyamide resin, a polyamide resin or a phenoxy resin. The amount of the thermosetting resin in the resin composition is preferably from 10 to 90% by weight, more preferably from 20 to 70% by weight, still more preferably from 25 to 50% by weight, based on the total solid content of the resin composition. In addition, the amount of the thermosetting resin in the resin composition can be appropriately adjusted depending on the purpose, and is not particularly limited. Further, in the case where an epoxy resin and/or a cyanate resin is used as the thermosetting resin, the content of the epoxy resin is in the total solid content of the resin composition, preferably 5 to 50% by weight, 5 to 25 wt% is more preferable. Further, the content of the cyanate resin is in the total solid content of the resin composition, preferably 5 to 5 % by weight, more preferably 10 to 25% by weight. 101102469 15 201236531 Further, the above thermosetting resin composition may contain a flame retardant in a range that does not impair the effects of the present invention, and is preferably a non-halogen flame retardant from the environmental viewpoint. As the agent, for example, an organic phosphorus-based flame retardant, an organic nitrogen-containing wall compound, a nitrogen compound, a poly-wei flame retardant, or a metal hydroxide can be mentioned. Examples of the organophosphorus-based flame retardant include a phosphine compound such as HCA, HCAHQ, and HCA-NQ manufactured by Sanko Co., Ltd., OP930 manufactured by Clariam Co., Ltd., and PX2® made by Dabashi Chemical Co., Ltd. A compound, a phosphorus-containing epoxy resin such as FX289 manufactured by Tohto Kasei Co., Ltd., or an ERFOOi (tetra) phenoxy tree material manufactured by Tosho Kasei Co., Ltd. The ruthenium-containing sulphate compound, such as SPB100 and SPEl〇〇, which are manufactured by Otsuka Chemical Co., Ltd., may be mentioned. Examples of the metal hydroxide include a water-soluble aluminum oxide such as CL310 manufactured by Sumitomo Chemical Co., Ltd., and Hp_35® manufactured by Showa Denko Electric Co., Ltd. Further, a curing agent may be used in combination with the thermosetting resin composition. For example, if the thermosetting resin is an epoxy resin or a cyanate resin, a curing agent for a phenol resin or an epoxy resin or a cyanate resin can be used. The phenol resin is not particularly limited, and examples thereof include a novolac type phenol resin such as a phenol novolak resin, a nonylphenol novolak resin, a bisphenol A novolak resin, and an arylalkylene novolak resin, which are not modified. Resolved phenolic phenol resin, tung oil, linseed oil, walnut oil and other modified oil modified phenolic phenolic resin and other resol phenolic resin. As the above-mentioned phenol resin, a phenol phenol varnish resin or a nonylphenol phenol varnish resin is preferred. Among them, in terms of moisture absorption 101102469 16 201236531 ==? From the viewpoint, it is preferred to use a combination of one of the above, or a combination of having a different weight average molecular number 1 or may be used in combination - The pre-polymerization accelerator is not particularly limited, and examples thereof include, for example, an organometallic salt such as a ring, and a third-order oxime ring [2, 2, 2] An amine type diethyl ether, an (4) type, a bismuth compound, an organic acid such as p-toluic acid, a sulfonium salt compound, or the like, or a mixture thereof. Including derivatives in knots, etc., shooting alone (four) - species, including a towel ^ can also be used in combination of two or more. From the viewpoint of iron and mechanical strength, it is preferred to have an inorganic filler (4) in the resin composition. There are special ships for the Wei area. For example, there are talc, burnt clay, unfired clay, mica, glass, etc., emulsified titanium, oxidized sulphur, sulphur dioxide, smelting and sulphur dioxide. Oxide oxide, carbonic acid, carbon dragon, hydrotalcite and other carbonates, hydroxide|S, water Ming soil (A1〇(〇H)' is generally called [pseudo] bauxite water bauxite (ie, ΑΙΛ.χΗ2〇, here (4) to 2)), oxidized town, ammonia oxide and other metal bismuth oxides, sulphuric acid locks, sulphur (four), sulphur brittle and other sulfates or sulfites, meal zinc, methyl stone Barium acid, boric acid, delete (four), saponin and other rotten acid, aluminum nitride, vaporized boron, tantalum nitride, t-carbon and other nitrides, barium titanate, barium titanate and other titanic acid (four). It can be used alone or in combination with two types of 101102469 17 201236531. The preferred ones are magnesium hydroxide, hydrazine, water, strontium, molten dioxin, pores, talc, calcined talc, and oxidized. In terms of low thermal expansion and insulation reliability, it is better to use cerium oxide, and the second is better. Further, from the viewpoint of flame resistance, it is preferred to oxidize. In the case where the resin composition is filled with the inorganic filler at a high concentration, the drilling wearability is deteriorated, and by using alumina as the inorganic filler, the drilling wearability is improved. . . The inorganic filler material is not limited, and (4) the inorganic filler having an average particle diameter of early dispersion may be used, and an inorganic filler having an average particle polydisperse may also be used. Further, an inorganic filler having an average particle diameter of monodisperse and/or polydisperse may be used in combination, or two or more kinds thereof may be used in combination. In addition, in the present specification, the average particle diameter is 10% or less of the standard deviation of the monodisperse system. The average particle size of the household is that the standard deviation of the particle size is 10% or more. . The average particle diameter of the above inorganic filler is not limited, and is preferably &^^3 m which is excellent in l"m 5.0" m. When the particle diameter of the inorganic filler is at least the above lower limit value, the viscosity of the resin composition can be suppressed from becoming 9', and the workability at the time of preparation of the prepreg can be improved. Further, by setting the inorganic filler material to the above upper limit, it is possible to suppress the occurrence of a sinking phenomenon of the inorganic filler in the resin composition. Further, the average particle diameter can be measured using a laser diffraction/scatter type particle size distribution measuring device (a general machine such as Shimadzu Corporation 101102469 18 201236531 SALD-7000). The content of the inorganic filler is not particularly limited. It is preferably from 10 to 90% by weight, more preferably from 3 to 8 % by weight, based on the total solid content of the resin composition. More preferably, 50. ~75% by weight. When the cyanoacrylate resin and/or its prepolymer is contained in the resin composition, the content of the inorganic filler is preferably from 5 to 75% by weight based on the total solid content of the resin composition. When the content of the inorganic filler is not more than the above upper limit, the fluidity of the resin composition can be improved. In addition, when the content of the inorganic filler is at least the above lower limit, the strength of the insulating layer composed of the resin composition can be sufficiently increased. Further, a coupling agent may be further contained in the resin composition. The coupling agent is formulated in order to improve the wettability of the interface between the thermosetting resin and the inorganic filler. By improving the wettability at the interface between the thermosetting resin and the inorganic filler, the resin and the inorganic filler can be uniformly fixed to the substrate, and the heat resistance can be improved, in particular, the solder heat resistance after moisture absorption. The coupling agent is not particularly limited, and examples thereof include an epoxy epoxidation coupling agent, a cationic Wei coupling agent, an amine (tetra) coupling agent, and a titanium (tetra) coupling/polyoxygen oil type coupling agent. By using these as a coupling agent, the wettability at the interface with the inorganic filler material is improved. Therefore, the heat resistance of the resin composition can be further improved. The amount of the coupling agent added is not particularly limited, and is preferably 5 to 3 parts by weight based on 100 parts by weight of the inorganic filler, particularly preferably 0U by weight 101102469 19 201236531 parts. When the content of the coupling agent is at least the above lower limit value, the inorganic filler can be sufficiently covered, and the effect of improving heat resistance can be sufficiently obtained. Further, by setting the content of the coupling agent to be equal to or lower than the above upper limit value, the emission suppression affects the reaction. Thereby, the reduction in bending strength or the like can be suppressed. In the resin composition, an antifoaming agent, a leveling agent, a UV absorber, a foaming agent, an antioxidant, a flame retardant, a flame retardant auxiliary agent such as a polyfluorene oxide powder, an ion trapping agent, and the like may be added as needed. Additions other than those. The resin composition can easily realize the low-line expansion, high rigidity, and high heat resistance of the prepreg. (4) It is difficult to contain at least an epoxy resin and an inorganic filler. Among them, in the solid form of the resin composition, it is preferable to contain 5 to 5 g% by weight of the epoxy resin, cyanate g to the resin, % by weight, and 1 G by weight of the machine filler, more preferably epoxy. weight! %, cyanate resin 10 to 25% by weight, and inorganic filler · 30 to 80% by weight. (4) for the printed wiring board substrate (4), it is possible to perform the process 2: = residue generated on the surface of the printed wiring board substrate 1 = "not limited" by using a wet method having organic matter decomposition === Or, it is known that the dry material is directly irradiated to the target person. First, deal with _w. Secondly, carry out the inspection process. Thereafter, the surface of 掏101J02469 20 201236531 was subjected to neutralization treatment. As shown in Fig. 1(b), in the step (8), electroless plating is performed on the surface of the substrate i for a printed wiring board which is made of a resin and an object, and is formed without Electrolytic plating layer 2. The electroless ore coating is carried out by a known method such as an electroless plating method in which an electrolytic solution (plating solution) containing a metal ion is applied in contact with a catalyst having a catalyst such as milk adhered thereto. In the present embodiment, as electroless plating, for example, electroless copper plating can be performed. ‘The thickness of the non-electrolytic coating 2 is not particularly limited, and it is preferably 〇1_ and 2 (four) or less. The following electrographic recording step can be easily performed by setting the thickness of the electroless plating layer 2 to 0.1 W or more. Further, by setting the thickness of the electroless bond layer 2 to be lower, the electroless plating layer 2 can be formed in a short time. This can be used to improve the efficiency of the work. Next, the first heating step is performed. In addition, the first heating step is not limited to (4) (8) and (4) (four (four) rows, also called (four) (4) and step (4). The peeling strength of the conductor circuit layer 5 formed according to the following financial resources is further improved. (10), the first heating step is preferably carried out between step (8) and step (c). The heating temperature of the heat treatment of the first force, the, and the second step is preferably n28〇t>c, and 140~ 230 〇C is more preferable. The heating temperature is within this range, and the peeling strength of the conductor circuit layer 5 can be improved. The heat treatment of the first force, the "step is not particularly limited, for example, by cleaning 101102469 21 201236531 A well-known device that can introduce nitrogen (n2), such as a net oven, is used. The heat treatment in the first heating step is preferably performed in an environment where the concentration of oxygen (〇2) is 10,000 ppm or less. 2) It is more preferable to carry out the environment in which the concentration is 500 ppm or less. Thereby, the oxidation of the copper constituting the conductor circuit layer 5 can be prevented, and the peeling strength of the conductor circuit layer 5 can be improved. The heat treatment in the first heating step is further In an environment where the nitrogen (N2) concentration is 78% or more The behavior is preferably carried out in an environment where the nitrogen (N2) concentration is 85% or more. Thereby, the peeling strength of the conductor circuit layer 5 can be further improved. Further, the heat treatment of the first heating step can be performed under atmospheric pressure. This can also be carried out under reduced pressure. For example, in an air environment, by heating under a reduced pressure of 3 torr or less, the oxygen concentration can be reduced to 1000 ppm or less. In the case where the pressure is reduced in an environment where the nitrogen concentration is increased, the oxygen concentration can be reduced to 100 ppm or less even at 3 torr or more. Therefore, oxidation of copper constituting the conductor circuit layer 5 can be prevented, and the conductor circuit layer can be improved. Further, in the first heating step, the time for heat-treating the printed wiring board substrate 1 is preferably 30 minutes or longer and 300 minutes or shorter. When the heat treatment time is 30 minutes or longer, The effect of improving the peel strength of the conductor circuit layer 5 can be sufficiently obtained. Further, when the heat treatment time is 300 minutes or less, good work can be achieved. 101102469 22 201236531 Then, as shown in FIG. 1(c), in step (c), light having an opening is formed on the electroless plating layer 2 with the mask 3 by a photoresist mask. 3, and no conductor is formed in the electroless chain coating 2
路之區域予以料。亦即，轨麵3之開叫成為形 體電路之區域。 V 作為光阻遮罩3，並沒有特別限定。可使用公知材料 阻遮罩3_如可藉由感紐乾式薄膜等而構成。於使 光性乾式薄麟為光阻鮮3之_下，絲鱗3之形成 係例如依下述進行。首先，將感紐乾式薄膜積層於無電解 鍍覆層2。其次’於感光性乾式薄膜中，針對位於未形成導 體電路之區域的部好以曝絲進行光硬彳卜接著，利用顯 影液將感光性乾式薄膜中之未曝光部予以溶解/去除。此 時，殘存在無電解鍍覆層2上之已硬化的感光性乾式薄膜成 為光阻遮罩3。 接著’如圖1(d)所示般，於步驟⑷中，針對光阻遮罩3 之開口内施以厚厚的電鍍，藉以形成電鍍層4在電路形成 部。 電鍍係可藉由將鍍覆對象物浸潰於鍍覆液中，並通以電流 等公知方法而進行。 再來’如圖1 (e)所示般，於步驟(e)中’去除光阻遮罩3。 接下來，如圖1(f)所示般，於步驟(f)中，利用閃蝕將無電 解鍍覆層2中之依平面視為與電鍍層4未重疊之部分予以選 101102469 23 201236531 擇性去除。亦即，去除掉位於未形成有導體電路之區域的無 電解鍍覆層2。藉此，可使印刷佈線板用基板丨上形成有導 體電路層5。另外，閃蝕係可以藉由將過硫酸鈉等蝕刻液依 喷霧等進行局部性蝕刻等公知方法而進行。 以下，亦將該步驟⑴稱為圖案狀蝕刻步驟。 接著，進行第二加熱步驟。另外，第二加熱步驟係未限定 在步驟⑴之後進行，亦可以於步驟(d)與步驟(e)之間或步驟 ⑷與步驟⑴之間進行。就可更提升導體電路層5之剝離強 度之觀點而言，第二加熱步驟係以於步驟(f)之後進行為佳。 第二加熱步驟之加熱處理的加熱溫度係以130〜280°C為 佳，以140〜230°C為更佳。藉由加熱溫度在此範圍内，則可 提升導體電路層5之剝離強度。 第二加熱步驟之加熱處理並沒有特別限定，可與上述第一 加熱步驟之加熱處理同樣地進行。 第二加熱步驟之加熱處理係以於氧(〇2)濃度為1 〇〇〇ppm 以下之環境下進行為佳，以於氧(〇2)濃度為500ppm以下之 環境下進行為更佳。藉此，可防止構成導體電路層5之銅的 氧化，而可提升導體電路層5之剝離強度。 第二加熱步驟之加熱處理係進一步以於氮（N2)濃度為 78%以上之環境下進行為佳，以於氮(N2)濃度為85%以上之 環境下進行為更佳。藉此，可進一步提升導體電路層5之剝 離強度。 101102469 24 201236531 又 靡下進行，也 下之:成懕下、隹—W如於空氣環境下，藉由在3torr以 下。又，於：熱處理’則可減低氧濃度至1〇〇〇PPm以 壓之产形巾7^空氣而在經提高氮濃度之環境下進行減 ，以下。因此在：以上’亦可以減低氧濃度至 化，而可提__^=^糊5之銅的氧 μ μ #"Γ3〇^Γ! Ep 1 ^ ^ ^ 行加熱處理之，=上且_分鐘以下為佳。於進 導體電路声5之今丨施“里以上之情形下’可充分獲得使 等體電路層5之_強度 之時間在 X，於射加熱處理 率。 下之情形下，則可實現良好的作業效 僅=:::::r__⑽般，不 相電路層於印難線板用基板1之兩面 的情形，亦可_於僅在印刷佈線板縣板丨之單面形成導 體電路層因此，根據本實施形態之印刷佈線板之製造方 法，則可以製造單的刷佈線板、兩面印刷佈線板及多層印 刷佈線板之任一者。 (實施例） 以下，根據實施例及比較例詳細說明本發明，但是本發明 並不限定於此。 101102469 25 201236531 (積層板之製造例i) 將作為環氧樹脂之萘改質曱酚酚醛清漆環氧樹脂(DIC公 司製”〇)8·5重量份、作為苯紛硬化劑之聯苯基芳烧 基i本紛;fsifj曰（明和化成股份有限公司，Μεη7851-4Η)8.5重 置份、苯酚酚醛清漆型氰酸酯樹脂(LONZA公司製，primaset PT_30)17重量份、球狀熔融二氧化矽(Admatechs公司製， SO-25R，平均粒徑〇 5#m)65 5重量份、環氧矽烷(信越化 學工業公司製，KBM-403)0.5重量份混合溶解於曱基乙基 酮。其次’藉由使用高速攪拌裝置進行攪拌，並以不揮發成 分（固形分)成為70重量％之方式調製樹脂清漆。 接著’在將上述樹脂清漆含浸於玻璃織布(厚度87/zm， 曰東紡製E玻璃織布’ WEA-2116)之後，於l5〇t的加熱爐 中進行乾燥2分鐘。藉此，獲得預浸體中之清漆固形分約 50重量％之預浸體。 接下來，於將上述預浸體重疊兩片而成之積層體的兩面 上’重疊12//m銅箔（三井金屬礦業公司製，3EC-VLP箔）， 並於壓力3MPa、溫度220°C下進行加熱加壓成形2小時。 藉此’獲得厚度0.2 0 m m之絕緣層兩面上具有銅箔之積層板。 (積層板之製造例2) 將作為環氧樹脂之聯苯基芳烷基型環氧樹脂（日本化藥公 司製’NC-3000)11重量份、雙順丁烯二醯亞胺化合物(KI 化成工業公司製’ BMI-70)20重量份、4,4 -二胺基二苯基曱 101102469 26 201236531 烧3.5重量份、氫氧化鋁（昭和電工製ηρ·360)65重量份、 環氧石夕炫(信越化學工業公司製，ΚΒΜ-403)0.5重量份混合/ 溶解於曱基乙基_中。其次，藉由使用高速攪拌裝置進行攪 拌’並以不揮發成分（固形分)成為70重量％之方式調製樹脂 清漆。 接著’在將上述樹脂清漆含浸於玻璃織布(厚度87μιη， 曰東紡製Ε玻璃織布，WEA-2116)之後，於15(TC的加熱爐 中進行乾燥2分鐘。藉此，獲得預浸體中之清漆固形分約 50重量％之預浸體。 接下來’於將上述預浸體重疊兩片而成之積層體的兩面， 重疊銅箔（三井金屬礦業公司製，3EC-VLP箔），並 於壓力3MPa、溫度220°C下進行加熱加壓成形2小時。藉 此，獲得厚度0.20mm之絕緣層兩面具有銅箔之積層板。 (實施例1) 將製造例1所獲得之積層板所具有之銅箔予以全面蝕刻 而去除’依目標膜厚l#m形成無電解鍍覆層（上村工業公 司製’ Through-copper PEA製程)於已露出之樹脂表面。接 下來’於空氣環境下（氧濃度約21%，氮濃度約78%，大氣 壓）、150°C下加熱處理30分鐘，藉以進行第一加熱步驟。 第一加熱步驟後，藉由熱滚筒層合機將厚度25//m之紫外 線感光性乾式薄膜(旭化成公司製，SunfortUFG-255)貼附在 該無電解鍍覆層之表面。接著，進行描繪有最小線寬度/線 101102469 27 201236531 間為20/20/zm及lOmmx 150mm(剝離強度測量部位)之圖案 之玻璃遮罩(TOPIC公司製）的位置照合。再者，使用該剝離 遮罩藉由曝光裝置（小野測器EV-0800)將紫外線感光性乾式 薄膜予以曝光。接著，將已曝光之紫外線感光性乾式薄膜利 用碳酸蘇打水溶液進行顯影。藉此，形成光阻遮罩。 接下來，將無電解鍍覆層作為給電層電極，依3A/dm2條 件下進行電解銅鍍覆（奥野製藥公司製81-HL)25分鐘，形成 厚度約20# m之銅佈線的圖案。再者，使用剝離機，藉由 單乙醇胺溶液(三菱氣體化學公司製R-100)將上述光阻遮罩 予以剝離。然後’將屬於給電層之無電解鍍覆層予以閃蝕(接 原電產公司製SAC-702M與SAC-701R35之純水溶液）而加 以去除，形成（圖案狀蝕刻步驟）L/S=20/20 y m及 10mmxl50mm(剝離強度測量部位）之圖案，獲得印刷佈線 板。 (實施例2) 將‘製造例1所獲得之積層板所具有之銅箔予以全面I虫刻 而去除’依目標膜厚l；t/m形成無電解鍍覆層（上村工業公 司製’ Through-copper PEA製程)於已露出之樹脂表面。接 下來，進行作為樹脂表面膨潤處理(SW處理）之將上述積層 板於液溫60°C之市售氫氧化納與乙二醇系溶劑含有液 (Atotech 公司製，Swelling Dip Securiganth P 建浴液）之混合 液(pH12)浸潰2分鐘並水洗3次。接著，進行作為驗性處理 101102469 28 201236531 (ME處理）之將上述積層板於液溫6〇〇c之過錳酸鈉含有粗化 處理液(Atotech公司製，Concentrate Compact CP建浴液）浸 潰5分鐘並水洗3次。再者，進行作為中和處理(Re處理）， 將上述積層板於液溫40°C之中和處理液(Atotech公司製， Reduction Securiganth P500建浴液)浸潰3分鐘後，進行水 洗3次。然後，於空氣環境下（氧濃度約21%，氮濃度約 78%)、150°C下進行加熱處理30分鐘，藉以進行第一加熱 步驟。第一加熱步驟後，與實施例1相同地進行處理，獲得 印刷佈線板。 (實施例3) 於依閃蝕之圖案狀蝕刻步驟之後，於空氣環境下（氧濃度 約21%，氮濃度約78%，大氣壓）、22〇。(：下進行加熱處理 60分鐘，藉以進行第二加熱步驟。除此以外，與實施例i 相同地進行處理’獲得印刷佈線板。 (實施例4) 於依閃蝕之圖案狀蝕刻步驟之後，於空氣環境下（氧濃度 約21%，氮濃度約78%，大氣壓）、22〇。〇下進行加熱處理 60分鐘，藉以進行第二加熱步驟。除此以外，與實施例2 相同地進行處理’獲得印刷佈線板。 (實施例5) 將第-加熱步驟藉由氣環境下（氧濃度45〇ppm，氮濃度約 99%，大氣壓）、220°C下進行加熱處 理60分鐘而進行。除 101102469 29 201236531 此以外，與實施例1相同地進行處理，獲得印刷佈線板。 (實施例6) 將製造例1所獲得之積層板所具有之銅箔予以全面|虫刻 而去除，依目標膜厚1/im形成無電解鍍覆層（上村工業公 司製’ Through-copper PEA製程)於已露出之樹脂表面。接 著，進行作為中和處理(Re處理），將上述積層板於液溫5(rc 之中和處理液(Atotech 公司製 ’ Reduction Securiganth P500 建浴液)浸潰5分鐘後’進行水洗3次。再者，依氮環境丁（氧 濃度450ppm，氮濃度約99%，大氣壓）、22〇。(：下進行加熱 處理60分鐘’藉以進行第一加熱步驟。第一加熱步驟後， 與實施例1相同地進行處理，獲得印刷佈線板。 (實施例7) 將第-加熱步驟藉由氮環境下(氧濃度45〇ppm，氮濃度約 99%，大氣壓）、22Gt下進行加熱處理6()分鐘而進行。除 此以外’與實施例2相同地進行處理，獲得印刷佈線板。 (實施例8) 於依閃钱之圖案狀钮刻步驟之後，於空氣環境下（氧濃产 約21%，氮濃度約78%’大氣壓）、22(rc下進行加熱處= 60分鐘，藉以進行第二加熱步驟。除此以外，與實施例$ 相同地進行處理，獲得印刷佈線板。 (實施例9) 於依閃狀圖案㈣刻步驟之後，於空氣環境下（氧漢度 101102469 30 201236531 約21%，氮濃度約78%，大氣壓）、22(Γ(：τ進行加熱處理 60分鐘，藉以進行第二加熱步驟。除此以外，與實施例6 相同地進行處理，獲得印刷佈線板。 (實施例10) 於依閃蝕之圖案狀蝕刻步驟之後，於空氣環境下（氧濃度 約21% ’ I濃度約78% ’大氣壓）、22(rcir進行加熱處理 6〇分鐘，藉以進行第二加熱步驟。除此以外，與實施例7 相同地進行處理，獲得印刷佈線板。 (實施例11) 將第二加熱步驟藉由氮環境下（氧濃度450卯m，氣濃度約 99%，大氣壓）、22Gt下進行加熱處理⑼分鐘而進行。除 此以外’與實施例8相同地進行處理，獲得印刷佈線板。 (實施例12) 將第^加齡㈣岐環境下(氧濃度45〇鱗，氮濃度約 99%’大^)、22GC下進行加熱處理⑼分鐘而進行。除 二:广例9相同地進行處理，獲得印刷佈線板。 (實施例13) 將第一加熱步驟藉由氮環境下（氧濃度㈣ ，，大氣壓)、22〇ΐ下進行力一。分鐘：。除 行纽，麟 (實施例14) 不使用製造例1所獲得之接 積層板，而使用製造例2所獲捐 101102469 31 201236531 之積層板。除此以外，與實施例8相同地進行處理，獲得印 刷佈線板。 (實施例15) 不使用製造例1所獲得之積層板，而使用製造例2所獲得 之積層板。除此以外，與實施例9相同地進行處理，獲得印 刷佈線板。 (實施例16) 不使用製造例1所獲得之積層板，而使用製造例2所獲得 之積層板。除此以外，與實施例10相同地進行處理，獲得 印刷佈線板。 (實施例17) 除了不進行第一加熱步驟以外，與實施例3相同地進行處 理，獲得印刷佈線板。 (實施例18) 除了不進行第一加熱步驟以外，與實施例4相同地進行處 理，獲得印刷佈線板。 (實施例19) 將第一加熱步驟藉由減壓環境下（氧濃度280ppm， ltorr)、220°C下進行加熱處理00分鐘而進行。除此以外， 與實施例1相同地進行處理，獲得印刷佈線板。 (實施例20) 將第一加熱步驟藉由減壓環境下（氧濃度280ppm， 101102469 32 201236531 ltorr)、220°C下進行加熱處理60分鐘而進行。除此以外， 與實施例2相同地進行處理，獲得印刷佈線板。 (比較例1) 除了不進行第一加熱步驟以外，與實施例1相同地進行處 * 理，獲得印刷佈線板。 * (比較例2) 除了不進行第一加熱步驟以外，與實施例6相同地進行處 理，獲得印刷佈線板。 (比較例3) 除了不進行第一加熱步驟以外，與實施例2相同地進行處 理，獲得印刷佈線板。 (評估） 使用各實施例及比較例所獲得之印刷佈線板，進行導體電 路層之剝離強度測量。剝離強度測量係根據JIS C6481而進 行，測量25t下寬度l〇mm之導體電路層之剝離強度。將 測量結果示於表1。 101102469 33 201236531 [表i] 積 層 板 去渣處理 第一加熱步驟 第二加熱步驟 剝離強度 [kN/m] 實施例1 製 造 例 1 無 空氣環境下 150°C/30 分鐘 (02 約 21%， N2 約 78%) 無 0.55 實施例2 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.58 實施例3 無 空氣環境下 150°C/30 分鐘 (02 約 21%， N2 約 78%) 空氣環境下 220°C/60 分鐘 (02 約 21%， N2 約 78%) 0.60 實施例4 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.55 實施例5 無 氮環境下 220°C/60 分鐘 (〇2450ppm， N2 約 99%) 無 0.77 實施例6 Re50°C/5 分鐘 0.76 實施例7 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.68 實施例8 無 氮環境下 220°C/60 分鐘 (〇2450ppm， N2 約 99%) 空氣環境下 220°C/60 分鐘 (02 約 21%， N2 約 78%) 0.64 實施例9 Re50°C/5 分鐘 0.65 實施例10 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.61 實施例11 無 氮環境下 220°C/60 分鐘 (〇2450ppm， N2 約 99%) 氮環境下 220°C/60 分鐘 (〇2450ppm， N2 約 99%) 0.65 實施例12 Re50°C/5 分鐘 0.70 實施例13 SW60°C/2 分鐘 -ME60°C/5 分鐘 •Re40°C/3 分鐘 0.68 實施例14 製 造 例 2 無 氮環境下 220°C/60 分鐘 (〇2450ppm > N2 約 99%) 空氣環境下 220°C/60 分鐘 (02 約 21%， N2 約 78%) 0.55 實施例15 Re50°C/5 分鐘 0.64 實施例16 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.61 實施例17 製 造 例 1 無 無 空氣環境下 220°C/60 分鐘 (02 約 21 %， N2 約 78%) 0.53 實施例18 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.50 實施例19 無 減壓環境下 220°C/60 分鐘 (ltorr 1 〇2280ppm) 無 0.76 實施例20 SW60°C/2 分鐘 -ME60°C/5 分鐘 •Re40°C/3 分鐘 0.67 比較例1 製 造 例 1 無 無 無 0.48 比較例2 Re50°C/5 分鐘 0.47 比較例3 SW60°C/2 分鐘 -ME60°C/5 分鐘 -Re40°C/3 分鐘 0.39 34 101102469 201236531 關於比較例1〜3，因為未進行第一加熱步驟及第二加熱步 驟，所以所獲得之印刷佈線板的導體電路層之剝離強度較 低。 另一方面，關於實施例1〜20，因為進行第一加熱步驟及/ 或第二加熱步驟，故而所獲得之印刷佈線板的導體電路層之 剝離強度較高。於使用依製造例1所獲得之積層板的實施例 1〜13中，相車乂於在空氣環境下進行第一加熱步驟之實施例 1〜4,在氮環境下進行第一加熱步驟之實施例5〜13的剝離 強度較高。又，實施例14〜16係使用與製造例丨之樹脂清漆 中的成勿不同之依製造例2所獲得之積層板，因為進行第一 加熱步驟及第二加熱步驟’所以所獲得之印刷佈線板的導體 電路層之剝離強度較高。 以上，參照圖式針對本發明之實施形態進行說明，該等係 本發明之例示，而亦可以採用與上述以外之各種構成。 此申請案係主張以2011年1月26日所申請之曰本申請案 特願2011-014105號為基礎之優先權，並將其揭示的全部内 容取入至此說明書中。 【圖式簡單說明】 圖1係說明本實施形態之印刷佈線板之製造方法例的示 意圖。 圖2係說明本實施形態之印刷佈線板之製造方法例的流 程圖。 101102469 35 201236531 【主要元件符號說明】 1 印刷佈線板用基板 2 無電解鍍覆層 3 光阻遮罩 4 電鍍層 5 導體電路層 101102469 36The area of the road is expected. That is, the opening of the rail surface 3 becomes an area of the body circuit. V is not particularly limited as the photoresist mask 3. A known material can be used. The mask 3_ can be formed by a sensible dry film or the like. In the case where the optical dry thin lining is made into the light-resistance 3, the formation of the silk scale 3 is carried out, for example, as follows. First, a sensible dry film is laminated on the electroless plating layer 2. Next, in the photosensitive dry film, the portion which is located in the region where the conductor circuit is not formed is subjected to light hardening, and then the unexposed portion of the photosensitive dry film is dissolved/removed by the developing solution. At this time, the cured photosensitive dry film remaining on the electroless plating layer 2 becomes the photoresist mask 3. Next, as shown in Fig. 1(d), in step (4), thick plating is applied to the opening of the photoresist mask 3, whereby the plating layer 4 is formed in the circuit forming portion. The plating can be carried out by immersing the object to be plated in the plating solution and applying a known method such as electric current. Then, as shown in Fig. 1 (e), the photoresist mask 3 is removed in the step (e). Next, as shown in FIG. 1(f), in the step (f), the plane in the electroless plating layer 2 is regarded as a portion which is not overlapped with the plating layer 4 by means of flash etching. 101102469 23 201236531 Sexual removal. That is, the electroless plating layer 2 located in a region where the conductor circuit is not formed is removed. Thereby, the conductor circuit layer 5 can be formed on the substrate for the printed wiring board. Further, the flash etching can be carried out by a known method such as partial etching using an etching solution such as sodium persulfate by spraying or the like. Hereinafter, this step (1) is also referred to as a pattern etching step. Next, a second heating step is performed. Further, the second heating step is not limited to be carried out after the step (1), and may be carried out between the step (d) and the step (e) or between the step (4) and the step (1). The second heating step is preferably carried out after the step (f) from the viewpoint of further enhancing the peeling strength of the conductor circuit layer 5. The heating temperature of the heat treatment in the second heating step is preferably 130 to 280 ° C, more preferably 140 to 230 ° C. By the heating temperature being within this range, the peel strength of the conductor circuit layer 5 can be improved. The heat treatment in the second heating step is not particularly limited, and can be carried out in the same manner as the heat treatment in the first heating step. The heat treatment in the second heating step is preferably carried out in an environment having an oxygen (〇2) concentration of 1 〇〇〇ppm or less, and more preferably in an environment having an oxygen (〇2) concentration of 500 ppm or less. Thereby, the oxidation of the copper constituting the conductor circuit layer 5 can be prevented, and the peeling strength of the conductor circuit layer 5 can be improved. The heat treatment in the second heating step is preferably carried out in an environment having a nitrogen (N2) concentration of 78% or more, and more preferably in an environment having a nitrogen (N2) concentration of 85% or more. Thereby, the peeling strength of the conductor circuit layer 5 can be further improved. 101102469 24 201236531 靡 进行 进行 , , , , , , : : : 靡 : : : : : : : 。 W W W W W W W W W W W W W W Further, in the case of "heat treatment", the oxygen concentration can be reduced to 1 〇〇〇 PPm, and the air is formed in an environment of increasing the nitrogen concentration. Therefore, in the above: you can also reduce the oxygen concentration to the chemical, but can raise the oxygen of the copper of the __^=^ paste 5, and the Ep 1 ^ ^ ^ heat treatment, = on And _ minutes or less is better. In the case where the current of the conductor circuit 5 is "in the above case", the time of the intensity of the equal-circuit layer 5 can be sufficiently obtained at X, and the heat treatment rate is improved. Under the circumstances, good performance can be achieved. In the case where the operation efficiency is only =:::::r__(10), the non-phase circuit layer is formed on both sides of the substrate 1 for the printed wiring board, and the conductor circuit layer may be formed only on one side of the printed wiring board board. According to the method of manufacturing a printed wiring board of the present embodiment, any of a single brush wiring board, a double-sided printed wiring board, and a multilayer printed wiring board can be manufactured. (Embodiment) Hereinafter, the present invention will be described in detail based on examples and comparative examples. According to the invention, the present invention is not limited thereto. 101102469 25 201236531 (Production Example i of laminated board) The naphthalene-modified phenolic novolac epoxy resin (manufactured by DIC Corporation) as an epoxy resin is 8.5 parts by weight. As a benzene hardening agent, the biphenyl aryl group i is in the same place; fsifj曰 (Minghe Chemical Co., Ltd., Μεη7851-4Η) 8.5 reset parts, phenol novolac type cyanate resin (made by LONZA company, primaset PT_30 ) 17 parts by weight, spherical melting Cerium oxide (manufactured by Admatech Co., Ltd., SO-25R, average particle size 〇5#m) 65 parts by weight, epoxy decane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 parts by weight, mixed and dissolved in mercaptoethyl ketone . Next, the resin varnish was prepared by stirring using a high-speed stirring device and making the nonvolatile component (solid content) 70% by weight. Then, the resin varnish was impregnated into a glass woven fabric (thickness: 87/zm, E-glass woven fabric manufactured by Toray Industries, WEA-2116), and then dried in a heating furnace at 15 Torr for 2 minutes. Thereby, a prepreg having a solid content of the varnish in the prepreg of about 50% by weight was obtained. Next, 12//m copper foil (3EC-VLP foil manufactured by Mitsui Mining & Mining Co., Ltd.) was superposed on both sides of the laminate in which the above-mentioned prepreg was superposed, and the pressure was 3 MPa and the temperature was 220 °C. The heat and pressure molding was carried out for 2 hours. Thereby, a laminate having copper foil on both sides of the insulating layer having a thickness of 0.20 m was obtained. (Production Example 2 of laminated board) 11 parts by weight of a biphenyl aralkyl type epoxy resin (N-Chemistry Co., Ltd. 'NC-3000), which is an epoxy resin, a bis-butylene diimide compound (KI) Chemical Industry Co., Ltd. 'BMI-70) 20 parts by weight, 4,4-diaminodiphenyl sulfonium 101102469 26 201236531 3.5 parts by weight, aluminum hydroxide (ηρ·360 by Showa Denko) 65 parts by weight, epoxy epoxide Xi Xuan (manufactured by Shin-Etsu Chemical Co., Ltd., ΚΒΜ-403) 0.5 parts by weight mixed/dissolved in decylethyl _. Next, the resin varnish was prepared by stirring with a high-speed stirring device and by making the nonvolatile matter (solid content) 70% by weight. Then, the resin varnish was impregnated into a glass woven fabric (thickness: 87 μm, ΕGuangfang woven glass woven fabric, WEA-2116), and then dried in a heating furnace of 15 (TC) for 2 minutes. Thereby, prepreg was obtained. The varnish in the body is solidified into about 50% by weight of the prepreg. Next, the copper foil (made of Mitsui Metal Mining Co., Ltd., 3EC-VLP foil) is superposed on both sides of the laminate in which the above-mentioned prepreg is superposed. And heat-press molding was carried out for 2 hours at a pressure of 3 MPa and a temperature of 220 ° C. Thereby, a laminate having copper foil on both sides of the insulating layer having a thickness of 0.20 mm was obtained. (Example 1) The laminate obtained in Production Example 1 was obtained. The copper foil of the board is completely etched and removed. The electroless plating layer (the Through-copper PEA process manufactured by Uemura Kogyo Co., Ltd.) is formed on the surface of the exposed resin according to the target film thickness l#m. Lower (oxygen concentration about 21%, nitrogen concentration about 78%, atmospheric pressure), heat treatment at 150 ° C for 30 minutes, whereby the first heating step is performed. After the first heating step, the thickness is 25/ by a heat roller laminator. /m ultraviolet photosensitive dry film (Asahi Kasei Co., Ltd., Sunfort UFG-255) is attached to the surface of the electroless plating layer. Next, a pattern with a minimum line width/line 101102469 27 201236531 between 20/20/zm and lOmmx 150mm (peel strength measurement portion) is drawn. The position of the glass mask (manufactured by TOMIC Co., Ltd.) is taken in. Further, the ultraviolet ray-sensitive dry film is exposed by an exposure device (Ono EV-0800) using the peeling mask. Then, the exposed ultraviolet ray is exposed. The dry film is developed by using a carbonated soda aqueous solution to form a photoresist mask. Next, an electroless plating layer is used as an electrode layer electrode, and electrolytic copper plating is performed under conditions of 3 A/dm 2 (81, manufactured by Okuno Co., Ltd.). -HL) A pattern of a copper wiring having a thickness of about 20 mm was formed in 25 minutes. Further, the photoresist mask was peeled off by a monoethanolamine solution (R-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a peeling machine. 'The electroless plating layer belonging to the power supply layer is ablated (supplied with a pure aqueous solution of SAC-702M and SAC-701R35 manufactured by Seiko Corporation) to form (pattern etching step) L/S=20/20 ym And A pattern of 10 mm×l 50 mm (peeling strength measurement site) was obtained to obtain a printed wiring board. (Example 2) The copper foil of the laminated board obtained in Production Example 1 was completely removed and removed according to the target film thickness l; /m forms an electroless plating layer ("through-copper PEA process" manufactured by Uemura Kogyo Co., Ltd.) on the surface of the exposed resin. Next, the above-mentioned laminated plate is subjected to a liquid surface temperature of 60 ° as a resin surface swelling treatment (SW treatment). A commercially available mixture of sodium hydroxide and a glycol-based solvent-containing solution (manufactured by Atotech Co., Ltd., Swelling Dip Securiganth P bath) was immersed for 2 minutes and washed with water three times. Then, the perovskite-containing roughening treatment liquid (Concentrate Compact CP bath solution manufactured by Atotech Co., Ltd.) having the above laminated sheet at a liquid temperature of 6 〇〇c was immersed as an inspection process 101102469 28 201236531 (ME treatment). 5 minutes and washed 3 times. In addition, the laminate was subjected to a neutralization treatment (Re treatment), and the laminate was immersed in a treatment liquid (Reservation Securiganth P500 bath solution manufactured by Atotech Co., Ltd.) at a liquid temperature of 40 ° C for 3 minutes, and then washed with water three times. . Then, heat treatment was carried out for 30 minutes in an air atmosphere (oxygen concentration: about 21%, nitrogen concentration: about 78%) at 150 ° C, whereby the first heating step was carried out. After the first heating step, the same treatment as in Example 1 was carried out to obtain a printed wiring board. (Example 3) After the pattern-like etching step by flashing, in an air atmosphere (oxygen concentration: about 21%, nitrogen concentration: about 78%, atmospheric pressure), 22 Å. (: The heat treatment was performed for 60 minutes, and the second heating step was performed. Otherwise, the treatment was performed in the same manner as in Example i to obtain a printed wiring board. (Example 4) After the etching step in the pattern of flashing, The treatment was carried out in the same manner as in Example 2 except that the second heating step was carried out in an air atmosphere (oxygen concentration: about 21%, nitrogen concentration: about 78%, atmospheric pressure), 22 Torr. 'A printed wiring board was obtained. (Example 5) The first heating step was carried out by heat treatment at 220 ° C for 60 minutes in an atmosphere (oxygen concentration: 45 〇 ppm, nitrogen concentration: about 99%, atmospheric pressure). 101102469 29 201236531 In the same manner as in Example 1, a printed wiring board was obtained in the same manner as in Example 1. (Example 6) The copper foil of the laminated board obtained in Production Example 1 was completely removed by insects, depending on the target film. An electroless plating layer ("through-copper PEA process" manufactured by Uemura Kogyo Co., Ltd.) was formed on the surface of the exposed resin. Then, as a neutralization treatment (Re treatment), the laminated plate was placed at a liquid temperature of 5 ( Rc After washing with a treatment liquid (Reducing Securiganth P500 bath solution manufactured by Atotech Co., Ltd.) for 5 minutes, it was washed three times. Further, it was immersed in a nitrogen atmosphere (oxygen concentration: 450 ppm, nitrogen concentration: about 99%, atmospheric pressure), and 22 Torr. (: Heat treatment was performed for 60 minutes) The first heating step was performed. After the first heating step, the same treatment as in Example 1 was carried out to obtain a printed wiring board. (Example 7) The first heating step was carried out by a nitrogen atmosphere. The process was carried out in the same manner as in Example 2 except that the heat treatment was carried out at a temperature of about 45 ° C, a nitrogen concentration of about 99%, atmospheric pressure, and a heat treatment at 22 Gt for 6 minutes. 8) After the step of engraving with the pattern of the flash money, in the air environment (about 21% oxygen, about 78% 'atmospheric pressure), 22 (heating at rc = 60 minutes) The heating step was carried out in the same manner as in Example #, to obtain a printed wiring board. (Example 9) After the step of the flash pattern (four), in an air atmosphere (oxygen degree 101102469 30 201236531 approximately 21%) , nitrogen concentration is about 78%, large (pressing), 22 (Γ:: τ was heat-treated for 60 minutes, and the second heating step was performed. Otherwise, the same treatment as in Example 6 was carried out to obtain a printed wiring board. (Example 10) After the pattern etching step, the second heating step is performed in an air atmosphere (oxygen concentration of about 21% 'I concentration of about 78% 'atmospheric pressure) and 22 (rcir is heat-treated for 6 minutes). 7 The same processing is performed to obtain a printed wiring board. (Example 11) The second heating step was carried out by heat treatment (9) minutes under a nitrogen atmosphere (oxygen concentration: 450 卯m, gas concentration: about 99%, atmospheric pressure) and 22 Gt. Otherwise, the same treatment as in Example 8 was carried out to obtain a printed wiring board. (Example 12) It was carried out by heat treatment (9) minutes under the conditions of the first age (four) enthalpy (oxygen concentration: 45 〇 scale, nitrogen concentration: about 99%'). Except for the second example: the wide example 9 was processed in the same manner to obtain a printed wiring board. (Example 13) The first heating step was carried out by a force of 1 in a nitrogen atmosphere (oxygen concentration (4), atmospheric pressure) at 22 Torr. minute:. In addition to the line, Lin (Example 14), the laminate obtained in Production Example 1 was not used, and the laminate of 101102469 31 201236531 obtained in Production Example 2 was used. Except for this, the same treatment as in Example 8 was carried out to obtain a printed wiring board. (Example 15) The laminate obtained in Production Example 2 was used instead of the laminate obtained in Production Example 1. Except for this, the same treatment as in Example 9 was carried out to obtain a printed wiring board. (Example 16) A laminate obtained in Production Example 2 was used instead of the laminate obtained in Production Example 1. Otherwise, the same treatment as in Example 10 was carried out to obtain a printed wiring board. (Example 17) A printed wiring board was obtained in the same manner as in Example 3 except that the first heating step was not performed. (Example 18) A printed wiring board was obtained in the same manner as in Example 4 except that the first heating step was not performed. (Example 19) The first heating step was carried out by heat treatment at 220 ° C for 00 minutes under a reduced pressure atmosphere (oxygen concentration: 280 ppm, ltorr). Otherwise, the same treatment as in Example 1 was carried out to obtain a printed wiring board. (Example 20) The first heating step was carried out by heat treatment at 220 ° C for 60 minutes under a reduced pressure atmosphere (oxygen concentration: 280 ppm, 101102469 32 201236531 ltorr). Otherwise, the same treatment as in Example 2 was carried out to obtain a printed wiring board. (Comparative Example 1) A printed wiring board was obtained in the same manner as in Example 1 except that the first heating step was not performed. * (Comparative Example 2) A printed wiring board was obtained in the same manner as in Example 6 except that the first heating step was not performed. (Comparative Example 3) A printed wiring board was obtained in the same manner as in Example 2 except that the first heating step was not performed. (Evaluation) Using the printed wiring board obtained in each of the examples and the comparative examples, the peeling strength measurement of the conductor circuit layer was performed. The peel strength measurement was carried out in accordance with JIS C6481, and the peel strength of the conductor circuit layer having a width of 1 mm at 25 t was measured. The measurement results are shown in Table 1. 101102469 33 201236531 [Table i] Laminate slag treatment First heating step Second heating step Peel strength [kN/m] Example 1 Manufacturing Example 1 150 ° C / 30 minutes without air (02 approximately 21%, N2 About 78%) None 0.55 Example 2 SW60°C/2 minutes-ME60°C/5 minutes-Re40°C/3 minutes 0.58 Example 3 150°C/30 minutes without air (02 approximately 21%, N2 About 78%) 220°C/60 minutes in air (02: 21%, N2 about 78%) 0.60 Example 4 SW60°C/2 minutes-ME60°C/5 minutes-Re40°C/3 minutes 0.55 Implementation Example 5 220 ° C / 60 minutes in a nitrogen-free environment (〇 2450 ppm, N2 about 99%) No 0.77 Example 6 Re50 ° C / 5 minutes 0.76 Example 7 SW60 ° C / 2 minutes - ME 60 ° C / 5 minutes - Re40°C/3 minutes 0.68 Example 8 220°C/60 minutes in a nitrogen-free environment (〇2450ppm, N2 about 99%) 220°C/60 minutes in air (02 about 21%, N2 about 78%) 0.64 Example 9 Re50 ° C / 5 minutes 0.65 Example 10 SW 60 ° C / 2 minutes - ME 60 ° C / 5 minutes - Re 40 ° C / 3 minutes 0.61 Example 11 220 ° C / 60 minutes in a nitrogen-free environment (〇 2450 ppm , N2 about 99%) nitrogen 220 ° C / 60 minutes (〇 2450ppm, N2 about 99%) 0.65 Example 12 Re50 ° C / 5 minutes 0.70 Example 13 SW60 ° C / 2 minutes - ME60 ° C / 5 minutes • Re40 ° C / 3 Minute 0.68 Example 14 Production Example 2 220 ° C / 60 minutes in a nitrogen-free environment (〇 2450 ppm > N2 about 99%) 220 ° C / 60 minutes in an air environment (02 about 21%, N2 about 78%) 0.55 Implementation Example 15 Re50 ° C / 5 minutes 0.64 Example 16 SW 60 ° C / 2 minutes - ME 60 ° C / 5 minutes - Re 40 ° C / 3 minutes 0.61 Example 17 Production Example 1 without air environment 220 ° C / 60 minutes (02 about 21%, N2 about 78%) 0.53 Example 18 SW60°C/2 minutes-ME60°C/5 minutes-Re40°C/3 minutes 0.50 Example 19 220°C/60 minutes without decompression (ltorr 1 〇 2280 ppm) None 0.76 Example 20 SW60°C/2 minutes-ME60°C/5 minutes•Re40°C/3 minutes 0.67 Comparative Example 1 Manufacturing Example 1 No or no 0.48 Comparative Example 2 Re50°C/5 Minute 0.47 Comparative Example 3 SW60°C/2 minutes-ME60°C/5 minutes-Re40°C/3 minutes 0.39 34 101102469 201236531 Regarding Comparative Examples 1 to 3, since the first heating step and the second heating step were not performed Therefore, the peeling strength of the conductor circuit layer of the obtained printed wiring board is low. On the other hand, in Examples 1 to 20, since the first heating step and/or the second heating step were performed, the peeling strength of the conductor circuit layer of the obtained printed wiring board was high. In Examples 1 to 13 in which the laminate obtained in Production Example 1 was used, the first heating step was carried out under a nitrogen atmosphere in Examples 1 to 4 in which the first heating step was carried out in an air atmosphere. The peel strength of Examples 5 to 13 was high. Further, in Examples 14 to 16, the laminate obtained by the production example 2 was used in the resin varnish of the production example, and the printed wiring obtained by the first heating step and the second heating step was used. The peeling strength of the conductor circuit layer of the board is high. The embodiments of the present invention have been described above with reference to the drawings, and the present invention is exemplified, and various configurations other than the above may be employed. This application claims priority based on Japanese Patent Application No. 2011-014105, filed on Jan. 26, 2011, the entire disclosure of which is incorporated herein. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a method of manufacturing a printed wiring board according to the present embodiment. Fig. 2 is a flow chart for explaining an example of a method of manufacturing the printed wiring board of the embodiment. 101102469 35 201236531 [Description of main component symbols] 1 Substrate for printed wiring board 2 Electroless plating layer 3 Photoresist mask 4 Plating layer 5 Conductor circuit layer 101102469 36