201127238 六、發明說明: 【發明所屬之技術領域】 本發明係關於印刷配線板及其製造方法,尤$胃,@ 具有細密電路圖案之高密度印刷配線板及其製造方法相關 【先前技術】 以安裝電子機器所使用之半導體構件等電子構件爲目 的之印刷配線板,隨著半導體電路之超高密度化,更爲要 求其電路導體寬度與電路間之絕緣間隔更爲極細線化(精 細圖案化)。 傳統上,印刷配線板之電路圖案形成方法,係使用將 銅箔或銅合金箔(本說明書將其統稱爲銅箔)與絕緣用樹 脂進行接著之形態的敷銅層板,於銅箔表面形成感光性抗 蝕膜後,進行選擇性曝光、顯影來除去抗蝕膜,其次,以 倉虫刻除去銅箱之露出部分的方法,所謂触刻法,係於形成 著薄於5 // m之銅膜的絕緣用樹脂表面形成感光性抗蝕膜後 ,進行選擇性曝光、顯影來除去電路形成部分之抗蝕膜, 其次,將露出之薄銅膜當做電鍍電極使用,以電銅鍍將銅 塡埋於抗蝕膜除去部分,其次,除去抗蝕膜後,以對全表 面進行均一蝕刻來完全除去絕緣用樹脂表面之薄銅膜,而 形成由以電銅鍍形成之部分所構成之電路,所謂半減量( semisubtractive)法或半加量(semiadditive)法,係對絕 緣用樹脂表面提供無電解電鍍觸媒後,形成感光性抗蝕膜 -5- 201127238 ’其次,以選擇性曝光、顯影除去電路形成部分之抗蝕膜 後’只以無電解銅鑛而於抗蝕膜除去部分形成銅電路,所 謂全加量(fulladditive )法,係進一步於當做電鑛電極使 用之金屬板表面’選擇性地形成電鍍抗蝕膜,其次,以電 鍍於未形成抗蝕膜之部分形成鍍銅層,以除去抗蝕膜或未 除去抗蝕膜之方式,同時進行半硬化性樹脂之層合成形, 其次’藉由去除金屬板,而形成於樹脂塡埋銅電路之形態 之電路的方法等,係大家所熟知(例如,參照專利文獻i 4 ) 0 然而,前述傳統之任一方法,因爲係以受到限制之區 域的選擇性蝕刻或選擇性電鍍來形成銅電路圖案,電路之 寬度精度、經濟性、量產性等受到限制,故要求可以更經 濟且更合理之方法來製造高密度銅電路圖案的技術。 [專利文獻] [專利文獻1]日本特開2003-249751公報 [專利文獻2]日本特開2003-298243公報 [專利文獻3]日本特開2004-193458公報 [專利文獻4]日本特開2007-242975公報 【發明內容】 有鑑於如前面所述之傳統技術,本發明之目的係在提 供一種印刷配線板之製造方法,可以於各種熱硬化性樹脂 組成物層合板或熱硬化性樹脂組成物薄膜等之基板之表面 -6- 201127238 ,製作高精度且更經濟之極細線的銅電路圖案。 此外,本發明之目的係在提供一種高密度印刷配線板 ,具有以此種方法所製造之高精度且極細密之銅電路圖案 0 爲了達成前述目的,依據本發明所提供之印刷配線板 之製造方法,其特徵爲含有: (a )對形成著感光性抗蝕膜之基板表面進行選擇性 曝光及顯影,來形成已形成著電路形成部分之溝圖案之可 以無電解銅鍍來形成鍍銅層之圖案化抗蝕膜的製程; (b) 於前述溝圖案部分之基板之露出表面及圖案化 之抗蝕膜表面整體進行無電解銅鍍,其次,至表面成爲大 致平滑爲止進行電解銅鏟,來形成覆蓋上述抗蝕膜之鍍銅 層的製程;以及 (c) 至前述抗蝕膜之表面露出爲止,以機械硏磨及/ 或化學硏磨或蝕刻使鍍銅層均一地減少,來使銅電路圖案 從表面露出的製程。 其他實施形態時,於前述製程(C )之後,更含有(d )以表面層部分只爲銅電路圖案之方式除去前述抗蝕膜的 製程。該製程(d )時,應以鹼性水溶液剝離前述抗蝕膜 、或去膠處理去除。 良好之實施形態時,前述基板,應具有蝕刻除去敷銅 層板之銅箔全部而轉錄著銅箔之凹凸面的表面。 其他良好實施形態時,前述抗蝕膜,形成圖案後,執 行從由紫外線照射、加熱處理及電漿處理所構成之群組所 201127238 選取之任一種之至少1種處理,可以無電解銅鍍來形成鍍 銅層之抗蝕膜。 其他良好實施形態之前述製程(a)時,對形成於基 板表面之感光性抗蝕膜以紫外線之圖案曝光或紫外線之直 接描繪來實施選擇性曝光,其次,進行顯影,而形成電路 形成部分的溝圖案。此外,前述製程(a)所使用之基板 •調合需要·具有貫通孔。 進一步製作多層之印刷配線板時,前述製程(c )後 ,於形成層間樹脂絕緣層後進一步形成感光性抗蝕膜,其 次,重複前述製程(a) 、(b)及(c)。或者,前述製 程(d )後,於形成層間樹脂絕緣層後進一步形成感光性 抗蝕膜,其次,重複前述製程(a) 、(b)及(c),用 以製作多層印刷配線板。此時,重複前述製程(a ) 、( b )及(c),亦可進一步以表面層部分只爲銅電路圖案之 方式來實施前述(d)之抗蝕膜除去製程。 此外,依據本發明,係提供一種印刷配線板,其特徵 爲,具有以前述任一種方法所製作之塡埋於表面層部分之 銅電路圖案與該圖案間之樹脂絕緣層,以該等銅電路圖案 與樹脂絕緣層形成平坦之表面。 本發明之印刷配線板之製造方法,不同於傳統之利用 受限制之區域之選擇性蝕刻或選擇性電鍍來形成銅電路之 方法,於形成於基板表面之感光性抗蝕膜進行選擇性曝光 及顯影來形成電路形成部分之溝圖案之可以無電解銅鍍來 形成鍍銅層之圖案化抗蝕膜,對溝圖案部分之基板之露出 -8 - 201127238 表面及圖案化之抗蝕膜表面整體覆蓋無電解鍍銅層,其次 ’至表面成爲大致平滑爲止進行電解銅鍍,於形成覆蓋於 上述抗蝕膜之鍍銅層後,至上述抗蝕膜表面露出爲止,以 機械硏磨及/或化學硏磨或蝕刻使鍍銅層整體均一地減少 ’來使銅電路圖案從表面露出,故全部製程無需特別之製 程或材料,卻可以良好生産性來形成高精度之細密電路圖 案。利用此種方法,可以容易地形成至5^m寬度程度爲止 之極細銅電路,此外,即使重複用以形成上述溝圖案之抗 蝕膜形成製程、無電解銅鍍之電解銅鍍製程、以及整體硏 磨或蝕刻製程來製作多層印刷配線板時,因爲電路圖案區 域之規制而使用感光性抗蝕,亦可以獲得良好之上下層銅 電路圖案的對位精度。此外,所得到之印刷配線板,具有 優良之電路之寬度精度及信賴性優,亦適合使用於半導體 晶片安裝用之基體及超高密度印刷配線板的製造。 【實施方式】 如前面所述,本發明之印刷配線板之製造方法,不同 於傳統之利用區域受到限制之選擇性蝕刻或選擇性電鍍來 形成銅電路之方法,係對形成於基板表面之感光性抗蝕膜 進行選擇性曝光及顯影,來形成電路形成部分之溝圖案, 故可以進行無電解銅鍍,亦即,可以無電解銅鍍來形成鍍 銅層,對圖案化之抗蝕膜,於溝圖案部分之基板之露出表 面及圖案化之抗蝕膜表面整體進行無電解銅鍍,其次,至 表面成爲大致平滑爲止進行電解銅鍍,形成覆蓋上述抗蝕 -9 - 201127238 膜之鍍銅層後,至使上述抗蝕膜之表面露出爲止,以機械 硏磨及/或化學硏磨或蝕刻來使鍍銅層整體均一減少,而 使銅電路圖案從表面露出者。 一般而言,傳統之銅電路圖案之形成方法時,係以電 鍍(觸媒)不會附著於由市販之電鍍抗蝕所形成之抗触膜 表面爲前提,而以於不存在抗蝕膜之部分形成電鍍之方式 來進行設計。相對於此種傳統之先入觀,本發明者等,針 對於含有抗蝕膜之基材之樹脂表面形成電鏟層,進行審慎 地檢討,結果,發現只要適度處理即可實施無電解銅鍍, 尤其是,照射強於曝光時之紫外線、或以抗蝕膜之玻璃轉 移溫度(Tg)以上之溫度進行加熱、或氬、氧等之電漿處 理等前處理係有效的方法。藉由實施此種前處理,不但於 抗蝕膜上析出無電解銅鍍,也可減少溶析等及抑制電鍍液 之污染,亦可以實現無電鍍表面之變色、光澤不良、針孔 之電鍍析出。此外,可抑制耐鹼性及抗蝕膜之潤脹,形成 之電路形狀亦較爲安定,亦獲得証實。其可獲得料想不到 之令人驚奇的效果。 以下,針對本發明之印刷配線基板之製造方法,參照 附錄圖式,進行具體說明。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring board and a method of manufacturing the same, and more particularly to a high-density printed wiring board having a fine circuit pattern and a method of manufacturing the same. A printed wiring board for the purpose of mounting an electronic component such as a semiconductor member used in an electronic device, and the ultra-high density of the semiconductor circuit, the wiring width between the circuit conductor and the circuit is required to be further thinned (fine patterning) ). Conventionally, a circuit pattern forming method of a printed wiring board is a copper-clad laminate in which a copper foil or a copper alloy foil (collectively referred to as copper foil in this specification) and an insulating resin are used to form a copper-clad laminate on the surface of the copper foil. After the photosensitive resist film, selective exposure and development are performed to remove the resist film, and secondly, the exposed portion of the copper box is removed by squeezing, and the so-called etch method is formed to be thinner than 5 // m. After forming a photosensitive resist film on the surface of the resin for insulating the copper film, the resist film is removed by selective exposure and development to remove the circuit formation portion. Next, the exposed thin copper film is used as a plating electrode, and copper is plated by electric copper plating. The ruthenium is buried in the resist removal portion, and after the resist film is removed, the entire surface is uniformly etched to completely remove the thin copper film on the surface of the insulating resin, thereby forming a circuit composed of a portion formed by electroplating. The so-called semi-subtractive method or semi-adjusted method is to form an electroless resist film on the surface of the insulating resin to form a photosensitive resist film -5, 201127238' Selective exposure, development removes the resist film forming part of the circuit, and then forms a copper circuit only in the portion of the resist removed by electroless copper ore. The so-called fulladditive method is further used as an electrode for electric ore. The surface of the metal plate is selectively formed with a plating resist film, and secondly, a copper plating layer is formed by plating on a portion where the resist film is not formed, to remove the resist film or the resist film is not removed, and the semi-curable resin is simultaneously performed. The method of forming a circuit in the form of a resin-embedded copper circuit by removing a metal plate is known (for example, refer to Patent Document i 4). However, any of the aforementioned conventional In the method, since the copper circuit pattern is formed by selective etching or selective plating in a restricted area, the width precision, economy, mass productivity, and the like of the circuit are limited, so that it is required to be manufactured in a more economical and rational manner. High density copper circuit pattern technology. [Patent Document 1] JP-A-2003-249751 [Patent Document 2] JP-A-2003-298243 [Patent Document 3] JP-A-2004-193458 (Patent Document 4) JP-A-2007- 242 975 SUMMARY OF THE INVENTION In view of the conventional techniques as described above, an object of the present invention is to provide a method for producing a printed wiring board which can be used for various thermosetting resin composition laminates or thermosetting resin composition films. The surface of the substrate is -6-201127238, and a copper circuit pattern of extremely fine lines with high precision and economy is produced. Further, an object of the present invention is to provide a high-density printed wiring board having a high-precision and extremely fine copper circuit pattern manufactured by such a method. In order to achieve the aforementioned object, the manufacture of a printed wiring board according to the present invention is provided. The method comprises the following steps: (a) selectively exposing and developing a surface of a substrate on which a photosensitive resist film is formed to form a groove pattern in which a circuit forming portion has been formed, and forming a copper plating layer by electroless copper plating (b) electroless copper plating is performed on the exposed surface of the substrate of the groove pattern portion and the entire surface of the patterned resist film, and then the electrolytic copper shovel is performed until the surface is substantially smooth. a process for forming a copper plating layer covering the resist film; and (c) until the surface of the resist film is exposed, and the copper plating layer is uniformly reduced by mechanical honing and/or chemical honing or etching. A process in which a copper circuit pattern is exposed from a surface. In other embodiments, after the above process (C), (d) a process of removing the resist film such that the surface layer portion is only a copper circuit pattern. In the process (d), the resist film is peeled off with an alkaline aqueous solution or removed by a stripping treatment. In a good embodiment, the substrate should have a surface on which the copper foil of the copper-clad laminate is etched to transcribe the surface of the copper foil. In another preferred embodiment, after the resist film is patterned, at least one of the treatments selected from the group consisting of ultraviolet irradiation, heat treatment, and plasma treatment 201127238 may be performed, and electroless copper plating may be used. A resist film of a copper plating layer is formed. In the above-described process (a) of the other preferred embodiment, the photosensitive resist film formed on the surface of the substrate is subjected to selective exposure by direct exposure of ultraviolet pattern or ultraviolet light, and secondly, development is performed to form a circuit forming portion. Ditch pattern. In addition, the substrate used in the above process (a) needs to be blended and has a through hole. When a multilayer printed wiring board is further produced, after the process (c), a photosensitive resist film is further formed after the interlayer resin insulating layer is formed, and the processes (a), (b) and (c) are repeated. Alternatively, after the above process (d), a photosensitive resist film is further formed after the formation of the interlayer resin insulating layer, and then the processes (a), (b) and (c) are repeated to form a multilayer printed wiring board. At this time, the above-described processes (a), (b), and (c) are repeated, and the resist film removing process of the above (d) may be further carried out so that the surface layer portion is only a copper circuit pattern. Further, according to the present invention, there is provided a printed wiring board characterized by having a resin insulating layer which is formed by any of the above methods and which is buried between a copper circuit pattern of a surface layer portion and the pattern, and the copper circuit The pattern and the resin insulating layer form a flat surface. The method for manufacturing a printed wiring board of the present invention is different from the conventional method of forming a copper circuit by selective etching or selective plating using a restricted region, and selectively exposing the photosensitive resist film formed on the surface of the substrate. The pattern of the groove forming the circuit forming portion can be formed by electroless copper plating to form a patterned resist film of the copper plating layer, and the substrate of the groove pattern portion is exposed -8 - 201127238 surface and the entire surface of the patterned resist film is covered The electroless copper plating layer is subjected to electrolytic copper plating until the surface is substantially smooth, and after the copper plating layer covering the resist film is formed, the surface of the resist film is exposed, and mechanical honing and/or chemistry is performed. The honing or etching uniformly reduces the overall copper plating layer to expose the copper circuit pattern from the surface, so that the entire process requires no special processes or materials, but good precision can be used to form a high-precision fine circuit pattern. According to this method, an extremely fine copper circuit up to a width of 5 μm can be easily formed, and the resist film forming process for forming the groove pattern, the electrolytic copper plating process for electroless copper plating, and the whole can be repeated. When a honing or etching process is used to fabricate a multilayer printed wiring board, since the photosensitive resist is used for the regulation of the circuit pattern region, the alignment accuracy of the upper upper layer copper circuit pattern can be obtained. Further, the obtained printed wiring board has excellent circuit width accuracy and reliability, and is also suitable for use in the manufacture of a substrate for mounting a semiconductor wafer and an ultrahigh-density printed wiring board. [Embodiment] As described above, the method for manufacturing a printed wiring board of the present invention is different from the conventional method of forming a copper circuit by selective etching or selective plating using a limited area, and is sensitive to the surface formed on the substrate. The selective resist film is selectively exposed and developed to form a groove pattern of the circuit forming portion, so that electroless copper plating can be performed, that is, a copper plating layer can be formed by electroless copper plating, and the patterned resist film can be formed. Electroless copper plating is performed on the exposed surface of the substrate on the groove pattern portion and the entire surface of the patterned resist film, and then electrolytic copper plating is performed until the surface is substantially smooth, thereby forming a copper plating covering the resist-9 - 201127238 film. After the layer, until the surface of the resist film is exposed, the entire copper plating layer is uniformly reduced by mechanical honing and/or chemical honing or etching, and the copper circuit pattern is exposed from the surface. In general, the conventional copper circuit pattern formation method is based on the premise that plating (catalyst) does not adhere to the surface of the anti-touch film formed by the commercially available electroplating resist, so that no resist film exists. Part of the plating is formed to design. The inventors of the present invention have made an electric shovel layer on the surface of a resin containing a base material of a resist film, and have carefully reviewed it. As a result, it has been found that electroless copper plating can be performed as long as it is moderately treated. In particular, the irradiation is stronger than the ultraviolet rays at the time of exposure, or the pretreatment such as heating at a temperature equal to or higher than the glass transition temperature (Tg) of the resist film, or plasma treatment such as argon or oxygen. By performing such pretreatment, electroless copper plating can be deposited not only on the resist film, but also dissolution and the like, and contamination of the plating solution can be reduced, and discoloration of the electroless plating surface, poor gloss, and plating of pinholes can be achieved. . Further, it is possible to suppress the alkali resistance and the swelling of the resist film, and the shape of the formed circuit is also relatively stable and confirmed. It can achieve unexpected results that are unexpected. Hereinafter, a method of manufacturing the printed wiring board of the present invention will be specifically described with reference to the attached drawings.
首先,如第1 (C)圖所示,準備於表面形成有感光性 抗蝕膜4之基板1。此外,第1 (C)圖中,係兩表面形成著 感光性抗蝕膜4之基板1,然而,亦可以爲單面形成著感光 性抗蝕膜4之基板。基板1,若爲使用做爲印刷配線板之眾 所皆知的基板,並無特別限制。具體而言,例如,於JIS -10- 201127238 所規定之E、N E、D、S、T玻璃等之一般眾所皆知之玻璃 纖維之不織布、織布等,含浸例如環氧樹脂、聚醯亞胺樹 脂、氰酸酯樹脂、馬來亞醯胺樹脂、雙鍵結合附加聚苯醚 樹脂、該等樹脂之含溴或磷化合物等之樹脂組成物等之1 種或2種以上,必要時,含浸調合著眾所皆知之觸媒、硬 化劑、硬化促進劑等之熱硬化性樹脂組成物,並硬化之基 板。此外’亦可以使用聚醯亞胺蕋板、雙馬來亞醯胺-三 氮雜苯樹脂基板、氟樹脂基板等之樹脂基板、及聚醯亞胺 薄膜、PET薄膜、陶瓷基板、晶圓基板等。該等基板,爲 了於其表面形成有微細凹凸狀之平坦面來提高與感光性抗 蝕膜之密貼性,亦可以實施眾所皆知之粗化處理,例如, 利用氫氧化鈉水溶液等鹼性溶液之潤脹、利用含有過錳酸 鹽、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等氧化劑之 液的處理、以及利用硫酸水溶液、鹽酸水溶液等之酸的處 理等一連串之化學處理(氧化劑處理)。粗化處理,亦可 以使用市販之去膠液(粗化劑)。 然而,尤其是,最好使用第1 (A)圖所示之於基板1 之兩面貼合著銅箔2之敷銅層板3,蝕刻除去全部銅箔2, 而爲具有如第1(B)圖所示之轉錄著銅箔凹凸面之表面的 基板1。此時,無需前述粗化處理,蝕刻除去全部銅箔2之 基板表面可直接以良好密貼性來形成感光性抗蝕膜4,故 配線板可以得到充份之信賴性。此種敷銅層板3可以使用 傳統眾所皆知之所有敷銅層板,然而,亦適合使用以下之 層合成形敷銅層板,亦即,於銅箱或樹脂複合銅箱,例如 -11 - 201127238 ,於日本特開2007-242975號公報所記載之銅箔的單面形 成著含有嵌段共聚合聚醯亞胺樹脂及聚馬來亞醯胺化合物 之樹脂層之樹脂複合銅箔的樹脂層面,疊合B層樹脂組成 物層。使用於樹脂複合銅箔之銅箔’,只要爲使用於印刷配 線板之眾所皆知的銅箔,並無特別限制,然而,最好使用 電解銅箔、軋製銅箔、該等之銅合金等。該等之銅箔,亦 可以使用實施例如鎳、鈷處理、矽烷處理劑等之眾所皆知 之表面處理者。銅箔之厚度並無特別限制,以3 5 /z m以下 爲佳。形成有樹脂層之銅箔面表面粗細度(Rz ),以4 y m 以下爲佳,最好爲2#m以下。此處,「Rz」係JIS B0601 所規定之十點平均粗細度。此外,亦可以於銅箔形成眾所 皆知之接著層。 蝕刻除去敷銅層板3之全部銅箔2的方法,可以眾所皆 知之方法來實施。蝕刻液並無特別限制,然而,適合使用 硫酸-過氧化氫之水溶液、過硫酸銨、過硫酸鈉、過硫酸 鉀等過硫酸鹽水溶液、以及三氯化鐵、三氯化銅之水溶液 等。 如前面所述,於形成有微細凹凸狀平坦面之基板1表 面,形成有感光性抗蝕膜4。形成感光性抗蝕膜4所使用之 感光性樹脂組成物,可以爲於載體膜上形成乾燥塗膜之乾 薄膜的形態,亦可以爲稀釋於溶劑之液狀的狀態。乾薄膜 時,於約40〜130 °C之溫度範圍,以熱輥式貼合機及真空 貼合機貼合於基板上,爲液狀時,以網版印刷、噴灑塗佈 器、壓鑄塗佈器、縫隙塗佈器、簾幕塗佈器、滾軸塗佈器 -12- 201127238 等進行塗佈,以約60〜150 °C溫度之熱風循環式 遠紅外線實施約1〜3 0分鐘之乾燥來使溶劑揮發 燥),可形成不黏著之感光性抗蝕膜4。此時所 光性抗鈾膜4的膜厚應在約3〜3 0 # m之範圍,以 成之電路的最小線寬之2倍以下更佳,最好爲等 此外,感光性抗蝕膜4,以於後面之無電解銅鍍 電解銅鍍觸媒固接而具有充份耐鹼性及密貼性爲 製作乾薄膜所使用之薄膜,以聚對苯二甲酸 熱可塑性樹脂薄膜爲佳,可以使用10〜50 v m之 ,爲了有良好之處理性,以25〜5〇//m之膜厚爲 得到良好之解析度,以1 0〜2 5 /z m之膜厚爲佳。 其差異,應設計成感光性抗蝕膜之折射率爲1 . 1.55〜1.60之範圍更佳的乾薄膜,即使載體膜較 到良好解析度。 形成感光性抗蝕膜4所使用之感光性樹脂組 以使用:使曝光部(活性能量線所照射之部分) 顯影除去未曝光部之負型感光性樹脂組成物;或 具有交聯構造而不溶於顯影液,但,曝光部會因 性能量線而發生之酸的化合物所發生之酸而分解 影除去之正型感光性樹脂組成物之任一種。該等 脂組成物,從考慮環境問題之觀點而言,以使用 液做爲顯影液之鹼性顯影型感光性樹脂組成物爲 ,以含有具羧基之樹脂爲佳。 例如,正型感光性樹脂組成物,可以使用如 乾燥爐或 (暫時乾 形成之感 電鍍所形 倍以下。 製程使無 佳。 乙二酯等 厚度範圍 佳,爲了 爲了消除 5 0以上、 厚亦可得 成物,可 硬化而以 未曝光部 爲照射活 ,並被顯 感光性樹 驗性水溶 佳,所以 曰本特開 -13- 201127238 平6-295064號公報所記載之皮膜形成性含羧基樹脂, ,含有羧基之聚合物之不飽和單體的均聚合物,該含 單體及其他可共聚合之單體的共聚合物,含有分子鏈 分子末端有羧基之聚酯系、聚胺甲酸酯系、聚醯胺系 含羧基樹脂及一分子中含有2個以上乙烯醚基之化合 及含有活性能量線照射會發生酸之化合物(光酸發生 做爲必要成份之感光性樹脂組成物,如日本特開2 72923號公報所記載之含有使單乙烯醚化合物與聚羧 脂反應而得到之樹脂及光酸發生劑做爲必要成份之感 樹脂組成物、如日本特許第403 1 5 93號公報所記載之 二羧酸及二乙烯醚化合物之加成聚合反應所得到之聚 醛酯(P〇ly hemiacetal ester)及光酸發生劑做爲必要 之感光性樹脂組成物、如國際公開w 0 9 9 - 1 5 9 3 5 A所 之含有酣性經基(phenolic hydroxyl group)或竣基 性可溶性聚合物、乙烯醚化合物、以及光酸發生劑做 要成份之感光性樹脂組成物等。然而,殘留有因活性 線照射而硬化之曝光部的負型感光性樹脂組成物,因 使用之含羧基樹脂,因爲不實施後面所述之前處理程 可實施無電解銅鍍而較佳。 此種負型感光性樹脂組成物,含有(A )含羧基 、(B)光聚合起始劑、(C)感光性單體,未剝離存 銅電路間之感光性抗蝕膜而殘留做絕緣層來使用時, 加(D )熱硬化性樹脂及(E )塡料爲佳。 前述含羧基樹脂(A ),可以使用以賦予鹼性顯 例如 羧基 中或 等之 物以 劑) P 10- 酸樹 光性 含有 半縮 成份 記載 之鹼 爲必 能量 爲所 序也 樹脂 在於 應增 影性 -14- 201127238 爲目的而使分子中具有羧基之傳統眾所皆知之各種含殘基 樹脂。尤其是,從光硬化性及兩顯影性而言’以分子中具 有乙烯性不飽和雙鍵結合之含羧基感光性樹脂(Α·1)爲 佳。其次,其不飽和雙鍵結合,應爲緣自丙烯酸或甲基丙 烯酸或該等之衍生物者。此外,只使用沒有乙烯性不飽和 雙鍵結合之含羧基樹脂(Α-2 )時’爲了使組成物成爲光 硬化性,必須倂用後述之分子中具有2個以上乙烯性不飽 和基之化合物(C ),亦即,必須倂用感光性單體。 此外,以折射率爲1.50〜1.60而言,以使用分子內具 有芳環之構造的含羧基樹脂(Α)爲佳,因爲接近前面所 述之載體膜的折射率,而有良好的解析度。具有芳環之含 羧基樹脂,可以使用於苯乙烯及其衍生物、茚構造、二苯 基乙二酮(甲基)丙烯酸酯等之含芳環(甲基)丙烯酸酯 及各種(甲基)丙烯酸酯之共聚合物及各種酸改性環氧( 甲基)丙烯酸酯、各種酚樹脂之環氧烷改性物添加酸酐者 〇 含羧基樹脂(A )之具體實例,如以下列舉之化合物 (亦可以爲寡聚物及聚合物之任一)。 (1) (甲基)丙烯酸等之不飽和羧酸、及苯乙烯、 α -甲苯乙烯、低烷基(甲基)丙烯酸酯、異丁烯等之含 不飽和基化合物之共聚合所得到之含羧基樹脂。 (2) 脂肪族二異氰酸酯、分歧脂肪族二異氰酸酯、 指環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯、 及二羥甲基丙酸、二羥甲基丁酸等之含羧基二乙醇化合物 -15- 201127238 、以及聚碳酸酯系聚醇、聚醚系聚醇、聚酯系聚醇、聚烯 系聚醇、丙烯系聚醇、雙酚A系環氧烷衍生物二醇、具有 酚性羥基及乙醇性羥基之化合物等二醇化合物之加成聚合 反應所得到之含羧基氨基鉀酸酯樹脂》 (3) 脂肪族二異氰酸酯、分歧脂肪族二異氰酸酯、 指環式二異氰酸酯、芳香族二異氰酸酯等之二異氰酸酯化 合物、及聚碳酸酯系聚醇、聚醚系聚醇、聚酯系聚醇、聚 烯系聚醇、丙烯系聚醇、雙酚A系環氧烷衍生物二醇、有 酚性羥基及乙醇性羥基之化合物等二醇化合物之加成聚合 反應所得到之氨基鉀酸酯樹脂之末端與酸酐反應所得之末 端含羧基氨基鉀酸酯樹脂。 (4) 二異氰酸酯、及雙酚A型環氧樹脂、加氫雙酚A 型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙二 甲酚型環氧樹脂、雙酚型環氧樹脂等2官能環氧樹脂之( 甲基)丙烯酸酯或其部分酸酐改性物、含羧基二乙醇化合 物及二醇化合物之加成聚合反應所得到之含羧基感光性氨 基鉀酸酯樹脂。 (5) 上述(2)或(4)之樹脂之聚合中,添加羥烷 基(甲基)丙烯酸酯等之分子中有1個羥基及1個以上之( 甲基)丙烯醯基之化合物,而爲末端(甲基)丙烯化之含 羧基氨基鉀酸酯樹脂。 (6) 上述(2)或(4)之樹脂之聚合中,添加異佛 酮二異氰酸醋及季戊四醇三丙稀酸酯(pentaerythritol triacrylate)之等莫耳反應物等之分子中有1個異氰酸基( -16- 201127238 isocyanate group)及1個以上之(甲基)丙烯醯基之化合 物,而爲末端(甲基)丙烯化之含羧基氨基鉀酸酯樹脂。 (7) 使(甲基)丙烯酸與後面所述之2官能或其以上 之多官能(固態)環氧樹脂產生反應,將酞酐、四氫化酞 酐、六氫化酞酐等2鹽基酸酐附加至存在於側鍵之羥基而 爲含羧基感光性樹脂。 (8) 使(甲基)丙烯酸與後面所述之進一步以環氧 氯丙烷使2官能(固態)環氧樹脂之羥基產生環氧化之多 官能環氧樹脂產生反應,對所生成之羥基附加2鹽基酸酐 而爲含羧基感光性樹脂。 (9 )對如酚醛之多官能酚化合物附加如環氧乙烷之 環狀醚、如碳酸丙烯酯之環狀碳酸鹽,以(甲基)丙烯酸 使所得到之羥基部分酯化,使多鹽基酸酐與殘留之羥基產 生反應而成爲含羧基感光性樹脂。 (1 〇 )對上述(1 )〜(9 )之樹脂進一步附加於縮水 甘油基(甲基)丙烯酸酯、α -甲基縮水甘油基(甲基) 丙烯酸酯等之分子中含有1個環氧基及1個以上之(甲基) 丙烯醯基的化合物,而成爲含羧基感光性樹脂。 該等含羧基樹脂(A )之使用,不受前述列舉之限制 ,可以使用1種或混合數種來使用。 此外,本說明書時,(甲基)丙烯酸酯係用以統稱丙 烯酸酯、甲基丙烯酸酯及其混合物的用語,其他類似用語 亦相同。 如上所述之含羧基樹脂(A),因爲於主鏈·聚合物 -17- 201127238 之側鍵具有多數之遊離羧基,故可以利用鹼性水溶液進行 顯影。 此外,前述含羧基樹脂(A )之酸値,應在30〜150 mgKOH/g之範圍爲理想,更理想是40〜110mgKOH/g之範 圍。含羧基樹脂之酸値低於30mgKOH/g時,對於鹼性水溶 液之溶解性降低,所形成之塗膜難以顯影。另一方面,高 於150mgK:OH/g,因爲顯影液對曝光部之溶解過度,而使 線過細,或曝光部及未曝光部無法區別而被顯影液溶解刹 離,有時難以形成正常之抗蝕圖案。 此外,上述含羧基樹脂(A)之重量平均分子量,因 樹脂基材而不同,一般而言,以2,000〜1 50,000爲佳,最 好在5,000〜100,000之範圍。重量平均分子量爲2,000以下 ,不黏著性能可能較差,曝光後之塗膜之耐濕性不好,顯 影時可能發生膜減少,而使解析度大幅降低。另一方面’ 重量平均分子量若超過1 50,000,有時顯影性會顯著惡化 ,且貯存安定性變差。 此種含羧基樹脂(A)之調合量,全組成物中,應爲 20〜80質量%,最好在30〜60質量%之範圍。含羧基樹脂 (B)之調合量少於上述範圍時,皮膜強度降低而不佳° 另一方面,多於上述範圍時,組成物之黏性較高’將導致 塗佈性等降低而不佳。 光聚合起始劑(B ),可以使用慣用之眾所皆知者’ 此外,亦可以使用慣用之眾所皆知之光起始助劑、增感齊IJ 。具體之光聚合起始劑、光起始助劑及增感劑之實例’例 -18- 201127238 如,安息香化合物、苯乙酮化合物、蒽醌化合物、噻噸酮 化合物、縮酮化合物、二苯基酮化合物、咕噸酮化合物、 三級胺化合物等。 安息香化合物之具體實例,例如,安息香、安息香甲 醚、安息香***、安息香膠異丙醚。 苯乙酮化合物之具體實例,例如,苯乙酮、2,2 -二甲 氧基-2-苯基乙醯苯、2,2·二乙氧基-2-苯基乙醯苯、1,1-二 氯乙醯苯酮。 蒽醌化合物之具體實例,例如,2 -甲基蒽醌、2 -乙基 蒽醌、2-t-丁基蒽醌、1-氯蒽醌。 噻噸酮化合物之具體實例,例如,2,4 -二甲基噻噸酮 、2,4 -二乙基噻噸酮、2 -氯噻噸酮、2,4 -二異丙基噻噸酮 〇 縮酮化合物之具體實例,例如,苯乙酮二甲基縮酮、 二苯基乙二酮二甲基縮酮。 二苯基酮化合物之具體實例,例如,二苯基酮、4-苯 甲醯基二苯硫、4-苯甲醯基- 4’-甲基二苯硫、4_苯甲醯基_ 4’-乙基二苯硫、4-苯甲醯基-4’-丙基二苯硫。 三級胺化合物之具體實例,例如,乙醇胺化合物、具 有二烷基苯胺構造之化合物,例如,4,4’·二甲基胺二苯基 酮(日本曹達株式會社製NISSO CURE-MABP) 、4,4、二 乙基胺二苯基酮(HODOGAYA CHEMICAL CO.,LTD.製 EAB )等之二烷基胺二苯基酮、7_ (二乙基胺)-4-甲基· 2H-1-苯并哌喃-2-酮(7-(二乙基胺)-4_甲基豆香素)等 -19- 201127238 含有二烷基胺基之豆香素化合物、4_二甲基胺安息香酸乙 基(NIPPON KAYAKU CO., L T D 製 K A Y A C U R E - E P A )、 2-二甲基胺安息香酸乙基(INTERNATIONAL BIO-SYNTHETICS 製 Quantacure DΜB ) 、4-二甲基胺安息香酸 (n-丁氧基)乙基(INTERNATIONAL BIO-SYNTHETICS 製Quantacure BEA) 、p-二甲基胺安息香酸異戊基乙基醋 (NIPPON KAYAKU CO.,LTD.製 KAYACURE-DMBI ) 、4- 二甲基胺安息香酸2-乙基己基(Van Dyk公司製Esolol507 )、4,4’-二乙基胺二苯基酮(HODOGAYA CHEMICAL CO·,LTD·製 EAB )。 前述光聚合起始劑以外,亦可以使用α-胺苯乙酮系 光聚合起始劑、acyl phosphine oxide系光聚合起始劑、 oxime ester系光聚合起始劑等。α-胺苯乙酮系光聚合起 始劑,例如,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙酮-1,2-二苯基乙二酮-2-二甲基胺-1-( 4-嗎啉苯基)-丁烷-1-酮、2-(二甲基胺)-2-[(4-甲基苯基)甲基]·1-[4-(4-嗎 啉基)苯基]-1-丁酮、Ν,Ν-二甲基胺苯乙酮等。市販品, CIBA JAPAN 公司製 IRGACURE-907、IR G A C U R E - 3 6 9、 IRGACURE-379 等。acyl phosphine oxide系光聚合起始劑 ’例如2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三 甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基 )-2,4,4-三甲基-戊基氧化膦等,市販品,例如,BASF公 司製之 Lucirin TPO、CIBA J A P AN 公司製之 IR G A C U R E-819等。oxime ester系光聚合起始劑’例如,2-(乙醯基異 -20- 201127238 亞硝基甲基)噻噸-9 -酮等,市販品’例如,C IB A J A P A N 公司製之 CGI-325 、 IRGACURE-OXEOl 、 IRGACURE-OXE02、ADEKA 公司製之 N-1919 等。 上面列舉了具代表性的光聚合起始劑類,然而,只要 以光照射可發生基活性中心者、或有助於其成長種之運作 者即可,不受限於前面所述之物。此外,其本身雖然不會 產生基,然而,亦可使用對前述光聚合起始劑有增感效果 之慣用之眾所皆知的增感劑。前述光聚合起始劑、光起始 助劑及增感劑,可以單獨使用,亦可以組合2種以上來使 用。此外,光聚合起始劑、光起始助劑及增感劑之調合量 ,以通常量之比例即足夠,一般而言,相對於含羧基樹脂 (A ) 1 00質量% (使用2種以上之含羧基樹脂時爲其合計 量,以下相同),應爲0.01〜30質量%,最好在0.5〜15質 量%之範圍。光聚合起始劑(B )之調合量爲〇 · 〇 1質量%以 下,光硬化性不足,塗膜會剝離、或耐藥品性等之塗膜特 性會降低而不佳。另一方面,超過3 0質量%,則光聚合起 始劑(B )之塗膜表面的光吸收激增,有深部硬化性降低 的傾向而不佳。 本發明之感光性樹脂組成物所使用之分子中具有2個 以上之乙烯性不飽和基的化合物(C ),因爲活性能量線 照射而光硬化,而使前述含羧基樹脂(A )不溶或協助其 不溶於鹼性水溶液。此種化合物,例如,乙二醇、甲氧基 四伸乙甘醇、聚乙二醇、丙二醇等甘醇之二丙烯酸酯類; 己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、三羥基 -21 - 201127238 乙基異氰尿酸酯等之多元醇或該等之環氧乙烷加成產物或 環氧丙烷加成產物等多價丙烯酸酯類;苯氧基丙烯酸酯、 雙酚A二丙烯酸酯、及該等酚類之環氧乙烷加成產物或環 氧丙烷加成產物等多價丙烯酸酯類;甘油二縮水甘油醚、 甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、異氰尿 酸三縮水甘油酯等縮水甘油醚之多價丙烯酸酯類;及三聚 氰胺丙烯酸酯及/或對應上述丙烯酸酯之各甲基丙烯酸酯 類等,可以單獨或組合2種以上來使用。 此外,例如,使丙烯酸與甲酚酚醛型環氧樹脂等多官 能環氧樹脂產生反應之環氧丙烯酸酯樹脂,此外,使季戊 四醇三丙烯酸酯等羥基丙烯酸酯及二異氰酸異佛爾酮等二 異氰酸酯之半胺甲酸酯化合物與該環氧丙烯酸酯樹脂之羥 基產生反應之環氧胺甲酸酯丙烯酸酯化合物等。此種環氧 丙烯酸酯系樹脂,無塵性不會降低,而可提高光硬化性。 此種分子中具有2個以上之乙烯性不飽和基之化合物 (C)的調合量,相對於前述含羧基樹脂(A) 100質量% ,應爲5〜100質量%、最好爲1〜7〇質量%之比例。前述調 合量爲5質量%以下時,光硬化性會降低,活性能量線照射 後之鹼性顯影難以形成圖案而不佳。另一方面,超過100 質量%時,對鹼性水溶液之溶解性降低,塗膜變脆而不佳 〇 此外,本發明所使用之感光性樹脂組成物,爲了賦予 耐熱性,可以添加熱硬化性成份(D )。熱硬化成份(D ),可以使用三聚氰胺樹脂、苯胍肼樹脂等胺樹脂、雙馬 -22- 201127238 來亞醯胺化合物、氧代氮苯并環己烷化合物 '噁唑啉化合 物 '碳化二亞胺樹脂、杜塞型異氰酸鹽(blocked isocyanate)化合物、cyclocarbonate化合物、多官能環氧 化合物、多官能氧環丁烷化合物、episulphide樹脂、三聚 氰胺衍生物等眾所皆知之慣用熱硬化性樹脂。該等當中, 最好之熱硬化成份(D),係1分子中具有2個以上之環狀 醚基及/或環狀乙硫醚基(以下,簡稱爲環狀(硫)ether group )之熱硬化性成份,例如,分子中具有2個以上之環 氧基的多官能環氧化合物、分子中具有2個以上之環氧丁 基的多官能氧環丁烷化合物、分子中具有2個以上之乙硫 醚基的episulphide樹脂。熱硬化性成份(D )之調合量, 相對於前述含羧基樹脂(A )之羧基1當量,應爲〇·6〜2.5 當量,最好在0.8〜2.0當量範圍。 感光性樹脂組成物含有如前面所述之熱硬化性成份( D)時。應進一步含有熱硬化觸媒。此種熱硬化觸媒,例 如,咪唑、2 -甲基咪唑、2 -乙基咪唑、2 -乙基-4-甲基咪唑 、2-苯基咪唑、心苯基咪唑、1-氰乙基-2-苯基咪唑、1-( 2-氰乙基)-2·乙基-4-甲基咪唑等咪唑衍生物;二氰二胺 、二苯基乙二酮二甲基胺、4-(二甲基胺)-Ν,Ν-二甲基 二苯基苯甲胺、4-甲氧基-Ν,Ν-二甲基二苯基苯甲胺、4-甲 基-Ν,Ν-二甲基二苯基苯甲胺等胺化合物、己二酸二醯、 癸二酸二醯胼等醯肼化合物;三苯膦等磷化合物等。此外 ,市販物,例如,四國化成工業社製之2ΜΖ-Α、2ΜΖ-0Κ 、2ΡΗΖ、2Ρ4ΒΗΖ、2P4MHZC皆爲咪唑系化合物之商品名 -23- 201127238 稱)、SAN-APRO LIMITED 製之 U-CAT (登錄商 3 5 03N、U-CAT3502T (皆爲二甲基胺之杜塞型異氰酸 合物的商品名稱)、DBU、DBN、U-CATSA102 CAT5 002 (皆爲二環式脒化合物及其鹽)。尤其是, 受限於上述,只要爲環氧樹脂及氧環丁烷化合物之熱 觸媒、或可促進環氧基及/或環氧丁基及羧基之反應 可,可單獨使用,亦可2種以上混合使用。此外,亦 用胍胺、乙胍(哄)(acetoguanamine)、苯胍肼、 氰胺、2,4-二胺-6-甲基丙烯酰氧基乙基酯-S-三氮雜苯 乙烯基-2,4-二胺-S-三氮雜苯、2-乙烯基-4,6-二胺-S-雜苯·異三聚氰酸加成產物、2,4-二胺-6-甲基丙烯酰 乙基酯-S-三氮雜苯·異三聚氰酸加成產物等S-三氮雜 生物,最好將具有該等密貼性賦予劑機能之化合物與 熱硬化觸媒倂用。該等熱硬化觸媒之調合量,通常量 例即足夠,例如,相對於含羧基樹脂(A )或分子中# 個以上之環狀(硫)ether group之熱硬化性成份(D) 質量%,應爲〇 . 1〜2 0質量%,最好爲0.5〜1 5.0質量% » 本發明所使用之感光性樹脂組成物,爲了提高其 之物理強度等,配合需要,可調合塡料(E)。此種 ,可以使用眾所皆知之慣用無機或有機塡料,然而, 使用硫酸鋇、球狀矽石及滑石爲佳。此外,爲了得到 外觀及難燃性,亦可將氧化鈦、金屬氧化物、氫氧化 金屬氫氧化物當做體質顏料塡料使用。塡料之調合量 爲組成物整體量之75質量%以下,最好爲0.1〜60質量 標) 鹽化 、U-並未 硬化 者即 可使 三聚 、2-三氮 氧基 苯衍 前述 之比 I:有2 1 00 塗膜 塡料 又以 白色 鋁等 ,應 :%之 -24- 201127238 比例。塡料之調合量,超過組成物整體量之7 5質量%時, 絕緣組成物之黏度較高,塗佈、成形性降低而硬化物較脆 ,故不佳。 本發明所使用之感光性樹脂組成物,爲了調製組成物 ,或爲了調整塗佈於基板及載體膜之黏度,可以調合酮類 、芳香族碳化氫類、二醇醚類、glycol ether acetate類、 酯類、乙醇類、脂肪族碳化氫、石油系溶劑等各種有機溶 劑。此外,必要時,可以調合苯二酚、苯二酚單甲基醚、 t-丁基鄰苯二酚、苯三酚、硫二苯胺等眾所皆知之慣用聚 合抑制劑、微粉矽石、有機皂土、蒙脫土等眾所皆知之慣 用增黏劑、顏料、染料、矽系、氟系、高分子系等防沫劑 及/或勻染劑、咪唑系、噻唑系、***系等矽烷偶合劑、 氧化防止劑、防鏽劑等眾所皆知之慣用添加劑類。 (1 )圖案化之抗蝕膜形成製程 如前述第1 (C)圖所示,於表面形成著感光性抗蝕膜 4之基板1,配合需要,進行開孔而形成貫通孔6後,實施 選擇性曝光及顯影,如第2 ( A )圖所示,用以形成形成著 電路形成部分之溝圖案之可以無電解銅鍍形成鍍銅層之圖 案化抗蝕膜(以下,簡稱爲抗蝕膜或抗蝕圖案)5。使用 負型感光性樹脂組成物形成感光性抗蝕膜4時,以顯影除 去未曝光部,使用正型感光性樹脂組成物時,以顯影除去 曝光部。選擇性曝光,可以接觸式(或非接觸方式),透 過形成著圖案之光罩選擇性地以活性能量線進行曝光,或 -25- 201127238 者,亦可以雷射直接曝光機,直接進行圖案曝光。此外’ 形成感光性抗蝕膜所使用之感光性樹脂組成物,含有熱硬 化性成份(D )時,可以進一步進行加熱硬化,來提高抗 蝕膜之耐熱性、耐藥品性、耐吸濕性、密貼性、電氣特性 等諸特性。 上述活性能量線照射所使用之曝光機,可以使用直接 描繪裝置(例如,利用來自電腦之CAD資料,以直接雷射 描繪影像之雷射直接成像裝置)、配載金屬鹵素燈之曝光 機、配載(超)高壓水銀燈之曝光機、配載水銀弧光燈之 曝光機、或使用(超)高壓水銀燈等紫外線燈之直接描繪 裝置。活性能量線,只要使用最大波長爲3 5 0〜41 Onm範圍 之雷射光,可以爲氣體雷射、固體雷射之任一種。此外, 其曝光量係因膜厚等而不同,然而,一般爲5〜200mJ/cm2 、5〜100mJ/cm2更好、最好爲5〜50mJ/cm2之範圍內。上 述直接描繪裝置,可以使用例如日本ORB OTECH公司製、 PENTAX公司製等之物,只要振盪最大波長爲3 50〜410nm 之雷射光的裝置,任何裝置皆可使用。 前述顯影方法,可以採用浸漬法、淋浴法、噴灑法、 刷法等。顯影,可以爲溶劑顯影,然而,最好使氫氧化鉀 、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨水、 胺類等鹼性水溶液來實施。 (2)無電解銅鍍電解銅鍍製程 於前述溝圖案部分之基板1之露出表面及抗蝕圖案5之 -26- 201127238 表面整體,以眾所皆知之方法,如第2 ( B )圖所示,實施 無電解銅鍍,其次,至表面大致平滑爲止,實施電解銅鍍 ,形成覆蓋上述抗蝕圖案5之鍍銅層7。 此時,於無電解銅鍍之前,以於抗蝕圖案5之表面形 成無電解銅鍍爲目的之前處理,應爲對顯影後之抗蝕圖案 5,以比曝光時更強之紫外線照射,或者,加熱至抗触膜 之玻璃轉移溫度(Tg )以上的溫度,或者,實施氬、氧等 之電漿處理。藉由實施上述前處理,不但可以於抗蝕圖案 5上析出無電解銅鍍,亦可減少溶析等,抑制電鎪液之污 染,也可實現無電鍍表面之變色、光澤不良、針孔電鍍析 出。此外,亦可抑制耐鹼性及抗蝕膜之潤脹,所形成之電 路形狀也較爲安定。 無電解銅鍍’一般而言,係對基板之露出表面及圖案 化之抗蝕膜表面整體供應鉋觸媒,接著,浸漬於無電解銅 鍍液中來形成銅層。無電解鍍銅層之厚度,一般約爲〇.5 〜2 // m之範圍。此外’配合需要,形成無電解鍍銅層後, 以1 00 °C〜2 00 °C進行加熱處理。加熱時間並無特別限制, 可以在30分鐘〜5小時之間進行選擇。爲了不使銅箔氧化 ,以在真空中或惰性氣體中進行加熱爲佳。其次,浸漬於 電解銅鍍液中,如第2(B)圖所示,形成覆蓋抗蝕圖案5 且鍍銅層7表面大致平滑之電解鍍銅層。電解鍍銅層之厚 度可以任意選擇。 (3 )蝕刻製程 -27- 201127238 如第2 ( B )圖所示,形成鍍銅層7後,如第2 ( C )圖 示,至前述抗蝕圖案5表面露出爲止,以機械硏磨及/或化 學硏磨或蝕刻使鍍銅層7均一減少,而使銅電路圖案8從表 面露出。藉此,上下銅電路圖案8處於介由電鍍貫通孔9連 結之狀態。機械硏磨及/或化學硏磨可以使用傳統眾所皆 知之方法,此外,蝕刻液,並無特別限制,可以使用硫 酸-過氧化氫之水溶液、過硫酸銨或過硫酸鈉、過硫酸鉀 等過硫酸鹽水溶液、三氯化鐵或三氯化銅之水溶液等。 (4 )抗蝕膜剝離製程 以塡埋於銅電路圖案8間之狀態存在之抗蝕圖案5,可 以直接保留做爲絕緣層而不剝離,配合需要,以鹼性水溶 液、溶劑等只使抗蝕圖案5潤脹剝離及/或以過錳酸鹼性鹽 等實施所謂去膠處理來進行去除,如第2圖(D)所示,成 爲基板1上只形成著銅電路圖案8之配線板。 (5 )層間樹脂絕緣層形成製程 此外,製作多層印刷配線板時,對如前述第2(C)圖 所示之具有抗蝕圖案5及銅電路圖案8之基板、或如第2圖 (D)所示之只具有銅電路圖案8之基板表面,例如,進行 環氧樹脂、聚醯亞胺樹脂、氰酸酯樹脂、馬來亞醯胺樹脂 、雙鍵結合附加聚苯醚樹脂、該等樹脂之含溴或磷化合物 等樹脂組成物等之1種或2種以上與配合需要調合著眾所皆 知之觸媒、硬化劑、硬化促進劑等熱硬化性樹脂組成物之 -28- 201127238 塗佈,加熱硬化、或含浸於玻璃纖維之不織布、織 硬化性樹脂組成物,貼合半硬化之半固態的半固化 熱壓著貼合薄膜狀樹脂,如第3 ( A)圖所示,形成 脂絕緣層10,配合需要,對其表面實施如前面所述 處理。此時,最好於銅箔或樹脂複合銅箔,例如, 特開2007-242975號公報所記載之銅箔單面形成著 段共聚聚醯亞胺樹脂及聚馬來亞醯胺化合物之樹脂 脂複合銅箔的樹脂層面,疊合B層樹脂組成物層, 合成形之敷銅層板,其次,蝕刻除去全部銅箔,來 有轉錄著銅箔之微細凹凸面之表面的層間樹脂絕緣 此時,無需前述粗化處理,其後製程可以於層間樹 層1 〇表面形成密貼性良好之感光性抗蝕膜,而得到 賴之配線板。此種敷銅層板,可以使用傳統眾所皆 有敷銅層板。此外,於上述基板表面,塗佈含有前 化性成份(D )及塡料(E )之感光性樹脂組成物, 貼合該乾薄膜,對整體照射活性能量線使其光硬化 進行加熱使其熱硬化,可形成層間樹脂絕緣層1 0。 於B層樹脂組成物層所使用之樹脂組成物,在 成物原本之特性的範圍,可以配合需要調合各種添 該等添加物,可以適度使用不飽和聚酯等含有聚合 結合單體類及其預聚合物類;聚丁二烯、馬來化丁 丁二烯-丙烯腈共聚合物、聚氯丁二烯、丁二烯-苯 聚合物、聚異戊二烯、丁基橡膠、氟橡膠、天然橡 分子量液狀〜高分子量之彈性橡膠類;聚乙烯、聚 布等熱 片、或 層間樹 之粗化 於曰本 含有嵌 層之樹 貼合層 形成具 層1 0。 脂絕緣 値得信 知之所 述熱硬 或者, 後,再 無損組 加物。 性雙鍵 二烯、 乙烯共 膠等低 丙烯、 -29- 201127238 聚丁烯、聚-4-甲基戊烯、聚苯乙烯、AS樹脂、ABS樹脂、 MBS樹脂、苯乙烯-異戊二烯橡膠、丙烯橡膠、該等之核 殼(core-shell )橡膠、聚乙烯-丙烯共聚合物、4-氟化乙 烯-6-氟化乙烯共聚合物類;聚碳酸酯、聚苯醚、聚颯、聚 酯、聚苯硫等之高分子量預聚合物或寡聚物:聚胺甲酸酯 等,可以適度選用。其他,眾所皆知之有機或無機之充塡 劑、染料、顏料、增黏劑、滑劑、防沫劑、分散劑、勻染 劑、光增感劑、難燃劑、光澤劑、聚合抑制劑、搖變性賦 予劑等各種添加劑,可以配合需要,適度地組合使用。尤 其是,以碳酸氣體雷射開孔時,爲了良好之孔形狀,應適 度添加無機充塡劑。例如,矽石、球狀矽石、氧化鋁、滑 石、燒結滑石、矽灰石、合成雲母、氧化鈦、氫氧化鋁等 之一般眾所皆知之物。該等塡料之形狀可以爲針狀、球狀 等任意之形狀。 (6)抗蝕圖案形成製程 如前述第3 ( A)圖所示,於形成有層間樹脂絕緣層1 〇 之基板1,如前面所述,形成感光性抗蝕膜,配合需要, 形成通孔1 1後,與前述製程(1 )相同,對感光性抗蝕膜 實施選擇性曝光及顯影,如第3(B)圖所示,形成形成有 電路形成部分之溝圖案之可以無電解銅鍍形成鍍銅層之外 層抗蝕圖案12。形成感光性抗蝕膜所使用之感光性樹脂組 成物含有熱硬化性成份(D )時,例如,進一步以約1 40〜 18 0°C之溫度加熱進行熱硬化,使前述含羧基樹脂(A)之 -30- 201127238 殘基與分子中具有2個以上之環狀(硫)ether group的熱 硬化性成份(D )產生反應’而形成耐熱性、耐藥品性、 耐吸濕性、密貼性、電氣特性等諸特性優良之硬化皮膜。 此外,未含有熱硬化性成份(D )時,亦可藉由熱處理, 使曝光時爲未反應狀態而殘存之光硬化性成份之乙烯性不 飽和結合產生熱自由基聚合,來提升皮膜特性,故可依目 的·用途來實施熱處理(熱硬化)。 (7 )無電解銅鍍-電解銅鍍製程 其後,於前述層間樹脂絕緣層1 〇之露出表面及抗蝕圖 案I2之表面整體,與前述製程(2)相同,如第3(C)圖 所示,實施無電解銅鍍,其次,至表面大致平滑爲止,實 施電解銅鍍,形成覆蓋上述抗蝕圖案12之外層鍍銅層13» 此時,亦與前述製程(2 )相同,於無電解銅鑛之前,以 於抗蝕圖案12表面形成無電解銅鍍爲目的之前處理,可以 於顯影後對抗蝕圖案1 2,進一步照射比曝光時更強之紫外 線、或加熱至抗蝕膜玻璃轉移溫度(Tg )以上之溫度、或 實施氬、氧等之電漿處理。 (8 )蝕刻製程 如第3 (C)圖所示’形成外層鍍銅層13後,與前述製 程(3)相同,至前述抗蝕圖案12表面露出爲止,以機械 硏磨及/或化學硏磨或蝕刻均一地使鍍銅層1 3減少,如第3 圖(D)所示’使外層銅電路圖案14從表面露出。以塡埋 -31 - 201127238 於銅電路圖案14間之狀態存在之抗蝕圖案12,可以不剝離 而直接保留做爲絕緣層使用,配合需要,只針對抗餓圖案 1 2以鹼性水溶液、溶劑等進行潤脹剝離、及/或實施所謂 去膠處理進行去除’而成爲表層部,只形成外層銅電路圖 案14之配線板。 此外,多層印刷配線板,重複前述製程(5 )〜(8 ) 可以良好生産性來進行製作。 以如前面所述之本發明方法所形成之電路圖案,即使 線與間隔小於5 /z m時,電路圖案間亦不會有導電體存在, 而爲絕緣信賴性優良之電路。 [實施例] 以下,係利用實施例及比較例針對本發明進行具體說 明,然而,本發明並未受限於下述實施例。此外,以下’ 「%」等在未特別聲明之情形下,全部爲質量基準。 感光性抗蝕組成物之調製; 以下述表1所示之比例(質量% )調合下述表1所示各 種成份,以撹絆機進行預混合後,以3支滾子進行揉合’ 調製感光性抗蝕組成物。 -32- 201127238 表1 組成(質量%) 抗蝕A 抗蝕B 感光性樹脂-I·1 222 感光性樹脂-2” 154 感光性聚合物 40 20 光聚合起始劑Μ 5 5 熱硬化性樹脂*5 25 顏料膏·6 3 無機塡料” 70 熱硬化觸媒 0.5 備註 *1 : CYCLOMERP (ACA) Ζ254 (DAICEL-CYTEC COMPANY LTD.製感 光性共聚合物,固態部分50%、酸値l〇〇mgKOH/g) *2 : UE-9210 (DIC公司製酸改性環氧丙烯酸酯、 固態部分65%、酸値80mgKOH/g) *3 :三羥甲基丙烷三丙烯酸酯 *4 : TPO-L (BASF公司製acyl phosphine oxide系光聚合起始劑) *5 : NC-3000 (NIPP〇NKAYAKUCO.,LTD.製二苯基酚醛環氧樹脂) *6 :酞花青藍及丙二醇甲醚醋酸酯之1 : 9之膏 *7 :矽石膏(ADMATECHS公司製球狀矽石、固態部分70% :丙二醇甲醚 醋酸酯溶液) *8 : 1B2PZ (四國化成工業社製咪唑化合物) 乾薄膜之製作 將所得到之各感光性抗蝕組成物進一步以丙二醇甲醚 醋酸酯稀釋,得到1 OdPa . S之抗蝕溶液。將其以薄膜塗佈 器塗佈於1 6 M m厚之聚對苯二甲酸乙二酯薄膜,慢慢使溫 度從50 °C上昇至80 °C來進行乾燥,得到抗蝕厚度10 // m之 乾薄膜。將所得到之乾薄膜分別視爲乾薄膜A及乾薄膜B。 實施例1 -33- 201127238 將絕緣層厚0.2mm、12ym兩面銅箔(銅箔之外型3.3 A m )之BT樹脂敷銅層板(三菱瓦斯化學(股)製,商品 名稱:CCL-HL830 )當做敷銅層板,以金屬鑽頭形成孔徑 75 之貫通孔’以去膠處理(過錳酸鉀系去膠溶液(奧 野製藥(股)製)進行潤脹、去膠(溶解)、中和、水洗 後’蝕刻表面之全部銅箱層,其次,利用NICHIGO-MORTON公司製真空貼合機,以7〇〇c、〇5Mpa、3〇秒之條 件’貼合乾薄膜A。其後,利用雷射直接曝光裝置( ORBOTECH公司製、parag0n ),以1 〇〇mJ/cm2之條件照射 3 5 5nm之紫外線’描繪最小線及間隔爲10私m之圖案。其 後,利用30°C之1 wt%碳酸鈉水溶液,以2氣壓之噴灑壓進 行顯影,重複2次水洗,得到形成著感光性抗蝕圖案之基 板。 利用配載著高壓水銀燈之UV輸送帶裝置以300mJ/cm2 之條件進行UV硬化後,利用氧電漿以500W、250mTorr、 60秒之條件實施電漿處理。 其次,使用無電解銅鍍液(奧野製藥(股)製、ATS ADD COPPER CT)進行無電解銅鍍,全面形成厚l#m之 銅層,利用1 30°C之加熱爐進行2小時加熱後,利用硫酸銅 鍍液以1.5安培/dm2實施70分鐘之電解電鍍,形成約10/zm 厚之銅層。將形成有該銅層之基板,利用蝕刻液(瓦斯化 學(股)製、SE-07 ),至可以看到乾薄膜表面爲止,蝕 刻銅箔使其成爲平坦。將形成有電路之基板,利用鹼性剝 離液(三菱瓦斯化學(股)製、R-200) ’以50°C、3分鐘 -34- 201127238 之條件進行剝離’再以去膠製程完全除去感光性抗蝕,得 到最小線及間隔爲1 ο // m之電路基板。 實施例2 對實施例1所得到之電路基板實施Μ E C公司之C Z處理 後,將附有銅箔(銅箔外型爲3 · 3 m )之Β層樹脂組成物 片(三菱瓦斯化學(股)製,C R S - 4 0 1 )貼合於兩面,加 熱條件:110°Cx30分 +180°Cx90分、加壓條件:5kgf/cm2x 1 5分+20kgf/cm2 ’在最後條件、真空度3〇mmHg以下,以2 小時之條件進行層合成形。蝕刻所得到之4層板之表面銅 箔’以碳酸氣體雷射(輸出1 3mJ )進行1次照射來形成孔 徑6 0 /z m之盲孔。其次,以前述條件貼合乾薄膜a,以後 ’與實施例1相同,實施電路形成,得到最小線及間隔爲 10# m之4層電路基板。 實施例3 實施例1時,以乾薄膜B取代乾薄膜A,同樣貼合於表 面之銅箔層全部蝕刻之敷銅層板,其後,同樣使用雷射直 接曝光裝置(ORBOTECH公司製、Paragon)以200mJ/cm2 之條件照射3 5 5nm之紫外線,描繪最小線及間隔爲20 μ m 之圖案。其後,使用30 °C之lwt%碳酸鈉水溶液,以2氣壓 之噴灑壓進行顯影,重複2次水洗,得到形成著感光性抗 蝕圖案之基板。 以熱風乾燥爐實施1 5 0 °c、1小時硬化後,以氧電漿在 -35- 201127238 500w、250mTorr、60秒之條件下實施電發處理。 其次,使用無電解銅鍍液(奧野製藥(股)製、ATS ADD COPPER CT)進行無電解銅鍍,形成厚i#m之銅層 ,利用1 3 0 °C之加熱爐進行2小時加熱後,利用硫酸銅鍍液 以1.5安培/dm2實施70分鐘之電解銅鍍,形成約厚之 銅層。將形成有該銅層之基板,利用蝕刻液(三菱瓦斯化 學(股)製、SE-07 ),至可以看到乾薄膜表面爲止,蝕 刻銅箔使其成爲平坦,得到最小線及間隔爲20 ^ m之電路 基板。 實施例4 對實施例3所得到之電路基板實施MEC公司之CZ處理 ,實施密貼性處理後,與實施例1相同,於其上貼合乾薄 膜B,實施防焊層圖案之曝光、顯影後,利用熱風乾燥爐 實施150°C、1小時之熱硬化,得到形成防焊層之電路基板 實施例5 對實施例2所得到之4層電路基板實施MEC公司之CZ處 理後,與實施例1相同,貼合乾薄膜防焊層(TAIYO INK MFG.CO., LTD.製、AUS410、膜厚 20#m品),使用高壓 水銀燈以600 mJ/cm2之條件進行防焊圖案之曝光、顯影後 ,使用熱風乾燥爐實施1 50°C、1小時之熱硬化’得到形成 著防焊層之電路基板。 -36- 201127238 比較例1 將絕緣層厚〇.2mm、12// m兩面銅箔(銅箔之外型3.3 Vm)之BT樹脂敷銅層板(三菱瓦斯化學(股)製、商品 名CCL-HL8 3 0 )當做敷銅層板,使用金屬鑽頭形成孔徑75 # m之貫通孔,其次,以蝕刻液(三菱瓦斯化學(股)製 、SE-〇7)將表面之銅箔層蝕刻至平坦的2.0"m爲止,以 去膠處理(過錳酸鉀系去膠溶液(奧野製藥(股)製)進 行潤脹、去膠(溶解)、中和、水洗後,實施無電解銅鍍 ’形成約1 # m之銅層,其後,實施1 3 0 °C、2小時之加熱處 理’其次,使用NICHIGO-MORTON公司製真空貼合機以7〇 °C、〇.5Mpa ' 3〇秒之條件貼合半加量用乾薄膜(日立化成 (股)製、RY-3515 )。其後,使用紫外線曝光裝置(伯 東(股)製、HAP-5 020 )以100mJ/Cm2之條件照射紫外線 ’描繪最小線及間隔爲1 0 // m之圖案。其後,利用3 0 °C之 lwt%碳酸鈉水溶液,以2氣壓之噴灑壓進行顯影,重複2次 水洗’得到形成著感光性抗蝕圖案之基板。其次,使用硫 酸銅鍍液,以1.5安培/dm2實施70分鐘之電解銅鍍,於未形 成抗蝕層之部分形成約10#ιη厚之銅圖案。其次,使用鹼 性剝離液(三菱瓦斯化學(股)製、R - 2 0 0 ),以5 0。(:、3 分鐘之條件,剝離半加量用乾薄膜後,使用蝕刻液(三菱 瓦斯化學(股)製、SE-07 ),至形成著該銅圖案之基板 之形成有半加量用乾薄膜的部分消失爲止,蝕刻銅電路, 得到最小線及間隔爲1 0以m之電路基板。 -37- 201127238 比較例2 對比較例1所製作之電路板實施MEC公司之CZ處理後 ’將熱硬化性乾薄膜(Ajinomoto Fine-Techno Co.,Inc.製 ' ABF-GX13)貼合於兩面,使用NICHIGO-MORTON公司 製真空貼合機以7〇°C、〇.5Mpa、30秒之條件貼合後,使用 熱風乾燥爐實施170 °C、60分鐘之熱硬化來進行層合成形 。所得到之基板,使用碳酸氣體雷射(輸出1 3mJ )以1次 照射來形成孔徑60 // m之肓孔。其次,以去膠處理(過錳 酸鉀系去膠溶液(日本MacDermid (股)製)進行潤脹、 去膠(溶解)、中和,除去肓孔之塗污及實施熱硬化乾薄 膜之硬化面的凹凸處理。此時之樹脂表面的凹凸爲Rz5.3 μπι。對該基板,使用無電解銅鍍液(奧野製藥(股)製 、ATS ADD COPPER CT)進行無電解銅鏟,形成厚ljam 之銅層,以1 30 °C之加熱爐進行2小時加熱後,使用 NICHIGO-MORTON公司製真空貼合機以70°C、0.5Mpa、 3 0秒之條件貼合半加量用乾薄膜。其後,使用紫外線曝光 裝置(0RC社製),以lOOnU/cm2之條件照射紫外線,描繪 最小線及間隔爲1 〇 Μ m之圖案。其後,使用3 0 °c之1 w t %碳 酸鈉水溶液,以2氣壓之噴灑壓進行顯影,重複2次水洗, 得到形成有感光性抗蝕圖案之基板。其次,對該基板,使 用硫酸銅鍍液,以1.5安培/dm2實施70分鐘之電解銅鑛,於 形成有抗蝕層之部分形成約10// m厚之銅圖案。其次,使 用鹼性剝離液(三菱瓦斯化學(股)製、R-200 ),以50 °C、3分鐘之條件,剝離半加量用乾薄膜後,使用触刻液 -38- 201127238 (三菱瓦斯化學(股)製,SE-07)蝕刻銅電路,至形成 著該銅圖案之基板之形成著半加量用乾薄膜之銅部分消失 爲止,得到最小線及間隔爲1 〇 β m之多層電路基板。 此外,於該基板,與實施例5相同,形成乾薄膜防焊 層(TAIYO INK MFG.CO., LTD.製、AUS410)之防焊圖案 ,得到形成著防焊層之基板。 針對前述各實施例及比較例所製作之電路基板,實施 如後面所述之特性試驗。結果如表2所示。 表2First, as shown in Fig. 1(C), the substrate 1 on which the photosensitive resist film 4 is formed is prepared. Further, in the first (C) drawing, the substrate 1 on which the photosensitive resist film 4 is formed on both surfaces is used. However, the substrate on which the photosensitive resist film 4 is formed on one side may be used. The substrate 1 is not particularly limited as long as it is a substrate known as a printed wiring board. Specifically, for example, non-woven fabrics, woven fabrics, etc. of glass fibers, such as E, NE, D, S, and T glass, which are defined in JIS-10-201127238, are impregnated with, for example, epoxy resin and polyfluorene. One or more of an imide resin, a cyanate resin, a maleimide resin, a double bond-bonded polyphenylene ether resin, a resin composition containing a bromine or a phosphorus compound, or the like, if necessary The substrate is cured by impregnating a thermosetting resin composition such as a catalyst, a hardener, a hardening accelerator, or the like which is well known. Further, a resin substrate such as a polyimide, a bismaleimide-triazole resin substrate, a fluororesin substrate, or a polyimide film, a PET film, a ceramic substrate, or a wafer substrate can be used. Wait. In order to improve the adhesion to the photosensitive resist film by forming a flat surface having fine irregularities on the surface thereof, it is also possible to carry out a well-known roughening treatment, for example, using a base such as an aqueous sodium hydroxide solution. Swelling of a solution, treatment with a solution containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and a series of chemistry such as treatment with an aqueous solution of sulfuric acid or hydrochloric acid Treatment (oxidant treatment). For the roughening treatment, it is also possible to use a commercially available degumming solution (roughening agent). However, in particular, it is preferable to use the copper-clad laminate 3 to which the copper foil 2 is bonded to both surfaces of the substrate 1 as shown in Fig. 1 (A), and to remove all the copper foils 2, and to have the first (B) The substrate 1 on which the surface of the copper foil uneven surface is transcribed is shown. In this case, the surface of the substrate on which all the copper foils 2 are removed by etching is removed without the need for the roughening treatment, and the photosensitive resist film 4 can be formed directly with good adhesion. Therefore, the wiring board can be sufficiently reliable. The copper-clad laminate 3 can use all of the copper-clad laminates conventionally known, however, it is also suitable to use the following composite-shaped copper-clad laminates, that is, in a copper box or a resin composite copper box, for example - A resin composite copper foil containing a resin layer of a block copolymerized polyimine resin and a polymaleimide compound is formed on one surface of a copper foil described in Japanese Laid-Open Patent Publication No. 2007-242975. On the resin layer, a layer B resin composition layer is laminated. The copper foil used in the resin composite copper foil is not particularly limited as long as it is a copper foil known for use in a printed wiring board. However, it is preferable to use an electrolytic copper foil, a rolled copper foil, or the like. Alloys, etc. As the copper foil, a surface treatment person known as, for example, nickel, cobalt treatment, decane treatment agent or the like can be used. The thickness of the copper foil is not particularly limited, and is preferably 3 5 /z m or less. The surface roughness (Rz) of the surface of the copper foil on which the resin layer is formed is preferably 4 μm or less, more preferably 2 #m or less. Here, "Rz" is the ten-point average thickness specified in JIS B0601. In addition, it is also possible to form a well-known layer of the copper foil. The method of etching away all of the copper foil 2 of the copper-clad laminate 3 can be carried out by a well-known method. The etching liquid is not particularly limited. However, an aqueous solution of sulfuric acid-hydrogen peroxide, an aqueous solution of persulfate such as ammonium persulfate, sodium persulfate or potassium persulfate, and an aqueous solution of ferric chloride or copper trichloride are suitably used. As described above, the photosensitive resist film 4 is formed on the surface of the substrate 1 on which the fine uneven surface is formed. The photosensitive resin composition used for forming the photosensitive resist film 4 may be in the form of a dry film in which a dried coating film is formed on the carrier film, or may be in a liquid state diluted in a solvent. When the film is dry, it is attached to the substrate by a hot roll laminator and a vacuum laminator at a temperature of about 40 to 130 ° C. When it is in a liquid state, it is screen-printed, spray-coated, and die-cast. Cloth, slit coater, curtain coater, roller coater -12- 201127238, etc., coating, at a temperature of about 60~150 °C, the hot air circulation type far infrared ray is carried out for about 1 to 30 minutes. The photosensitive resist film 4 which is not adhered can be formed by drying to evaporate the solvent. At this time, the film thickness of the light anti-uranium film 4 should be in the range of about 3 to 30 # m, preferably 2 times or less of the minimum line width of the circuit, preferably, etc. Further, the photosensitive resist film 4, for the subsequent electroless copper plating electrolytic copper plating catalyst fixed with sufficient alkali resistance and adhesion for the film used for the production of dry film, polyethylene terephthalate thermoplastic resin film is preferred, It is possible to use 10 to 50 vm. In order to have good rationality, a film thickness of 25 to 5 Å/m is obtained for good resolution, and a film thickness of 10 to 2 5 /zm is preferred. The difference should be designed such that the refractive index of the photosensitive resist film is 1. 1. 55~1. A dry film of a better range of 60, even if the carrier film is of good resolution. The photosensitive resin group used for forming the photosensitive resist film 4 is used by developing an exposed portion (the portion irradiated with the active energy ray) to remove the negative photosensitive resin composition of the unexposed portion; or having a crosslinked structure and being insoluble. In the developer, the exposed portion may be any one of the positive photosensitive resin compositions which are decomposed by the acid generated by the acid compound which is generated by the energy ray. In view of environmental problems, the lipid composition is preferably an alkali-developable photosensitive resin composition using a liquid as a developing solution, and preferably a resin having a carboxyl group. For example, the positive-type photosensitive resin composition can be used, for example, in a drying oven or (temporarily dry-formed by electroplating.) The process is not good. The thickness range of ethylenediester is good, in order to eliminate 50 or more, thick A film-forming carboxyl group-containing film described in Japanese Unexamined Patent Application Publication No. Hei No. Hei No. Hei. a resin, a homopolymer of an unsaturated monomer containing a carboxyl group polymer, a copolymer of a monomer and other copolymerizable monomer, a polyester system having a carboxyl group at a molecular chain molecule end, and a polyamine a compound containing a carboxyl group-containing resin and a polyamine-containing carboxyl group-containing resin, and a compound containing two or more vinyl ether groups in one molecule, and a compound containing an acid generated by irradiation with an active energy ray (photoacid-based photosensitive resin composition is required as a component) A resin composition containing a resin obtained by reacting a monovinyl ether compound with a polycarboxylate and a photoacid generator as an essential component, as exemplified by Japan, as disclosed in Japanese Laid-Open Patent Publication No. 2 72923 A polyacetal ester (P〇ly hemiacetal ester) obtained by an addition polymerization reaction of a dicarboxylic acid and a divinyl ether compound described in the publication No. 403 1 5, and a photoacid generator are used as a photosensitive resin composition. Such as the international publication w 0 9 9 - 1 5 9 3 5 A containing phenolic hydroxyl group or sulfhydryl soluble polymer, vinyl ether compound, and photoacid generator as the photosensitive resin A negative photosensitive resin composition having an exposed portion which is cured by irradiation with an active wire remains, and the carboxyl group-containing resin used can be subjected to electroless copper plating without performing the previous treatment described later. The negative photosensitive resin composition contains (A) a carboxyl group-containing, (B) photopolymerization initiator, and (C) a photosensitive monomer, and remains without removing the photosensitive resist film between the copper circuits. When the insulating layer is used, it is preferable to add (D) a thermosetting resin and (E) a coating material. The carboxyl group-containing resin (A) can be used to impart an alkalinity, for example, a carboxyl group or the like. 10- Acid tree light contains half shrinkage The base described is a must-have energy, and the resin is a residue-containing resin which is known in the art to have a carboxyl group in the molecule for the purpose of photoinhibition-14-201127238. In particular, from photohardenability and In terms of both developability, it is preferred that the carboxyl group-containing photosensitive resin (Α·1) having an ethylenically unsaturated double bond in its molecule is bonded. Secondly, its unsaturated double bond should be derived from acrylic acid or methacrylic acid or In addition, when only the carboxyl group-containing resin (Α-2) having no ethylenic unsaturated double bond is used, in order to make the composition photohardenable, it is necessary to use two or more of the molecules described later. The ethylenically unsaturated group compound (C), that is, the photosensitive monomer must be used. In addition, the refractive index is 1. 50~1. In the case of 60, a carboxyl group-containing resin (Α) having a structure having an aromatic ring in the molecule is preferred because it has a good resolution in view of the refractive index of the carrier film described above. The carboxyl group-containing resin having an aromatic ring can be used for styrene-containing (meth) acrylates such as styrene and its derivatives, oxime structure, diphenylethylenedione (meth) acrylate, and various (meth) groups. A conjugate of an acrylate copolymer and various acid-modified epoxy (meth) acrylates, an alkylene oxide modification of various phenol resins, an acid anhydride, and a carboxyl group-containing resin (A), such as the compounds listed below ( It can also be either an oligomer or a polymer). (1) A carboxyl group obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid or an unsaturated group-containing compound such as styrene, α-methylstyrene, a low alkyl (meth) acrylate or isobutylene Resin. (2) a diisocyanate such as an aliphatic diisocyanate, a divalent aliphatic diisocyanate, a ring-shaped diisocyanate or an aromatic diisocyanate, and a carboxyl group-containing diethanol compound such as dimethylolpropionic acid or dimethylolbutanoic acid- 15-201127238, and polycarbonate-based polyalcohol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, propylene-based polyol, bisphenol A-based alkylene oxide derivative diol, and phenolic A carboxyl group-containing urethane resin obtained by addition polymerization of a diol compound such as a hydroxyl group and an alcoholic hydroxyl group (3) Aliphatic diisocyanate, divalent aliphatic diisocyanate, ring diisocyanate, aromatic diisocyanate a diisocyanate compound, a polycarbonate-based polyalcohol, a polyether-based polyalcohol, a polyester-based polyalcohol, a polyolefin-based polyalcohol, a propylene-based polyalcohol, a bisphenol A-based alkylene oxide derivative diol, or the like A terminal carboxyl group-containing urethane resin obtained by reacting a terminal of a urethane resin obtained by an addition polymerization reaction of a diol compound such as a phenolic hydroxyl group and an alcoholic hydroxyl group with an acid anhydride. (4) Diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, A carboxyl group-containing photosensitive potassium compound obtained by addition polymerization of a (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing diethanol compound, and a diol compound, such as a bisphenol type epoxy resin Acid ester resin. (5) In the polymerization of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth)acryl fluorenyl groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. It is a terminal (meth) acrylated carboxylated urethane resin. (6) In the polymerization of the resin of the above (2) or (4), one of the molecules such as isophorone diisocyanate and pentaerythritol triacrylate is added. An isocyanate group (-16-201127238 isocyanate group) and one or more (meth)acryloyl group-based compounds, and a terminal (meth) acrylated carboxyl group-containing urethane resin. (7) reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin of a bifunctional or higher functional group described later, and adding a 2-basic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrofurfuric anhydride A carboxyl group-containing photosensitive resin is present in the hydroxyl group present in the side bond. (8) reacting (meth)acrylic acid with a polyfunctional epoxy resin which further epoxidizes a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin described later, and attaches 2 to the generated hydroxyl group. A salt-based acid anhydride is a carboxyl group-containing photosensitive resin. (9) adding a cyclic ether such as a cyclic ether of ethylene oxide to a polyfunctional phenol compound such as phenolic acid, such as a cyclic carbonate of propylene carbonate, and partially esterifying the obtained hydroxyl group with (meth)acrylic acid to make a multi-salt The base acid anhydride reacts with the residual hydroxyl group to form a carboxyl group-containing photosensitive resin. (1) The resin of the above (1) to (9) is further added to a molecule such as glycidyl (meth) acrylate or α-methyl glycidyl (meth) acrylate. A compound containing one or more (meth) acrylonitrile groups and a carboxyl group-containing photosensitive resin. The use of the carboxyl group-containing resin (A) is not limited to the above-described examples, and may be used alone or in combination of several kinds. Further, in the present specification, the term "(meth)acrylate" is used collectively to refer to the terms of acrylate, methacrylate and a mixture thereof, and the like is the same. Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the main chain·polymer-17-201127238, it can be developed with an aqueous alkaline solution. Further, the acid-containing oxime of the carboxyl group-containing resin (A) should preferably be in the range of 30 to 150 mgKOH/g, more preferably 40 to 110 mgKOH/g. When the acid hydrazide of the carboxyl group-containing resin is less than 30 mgKOH/g, the solubility in the alkaline aqueous solution is lowered, and the formed coating film is difficult to develop. On the other hand, if it is higher than 150 mg K: OH/g, the developer is excessively dissolved in the exposed portion, and the line is too thin, or the exposed portion and the unexposed portion are indistinguishable from being dissolved by the developer, and sometimes it is difficult to form a normal one. Resist pattern. Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin substrate, and is generally preferably 2,000 to 150,000, more preferably 5,000 to 100,000. The weight average molecular weight is 2,000 or less, the non-adhesive property may be inferior, the moisture resistance of the coating film after exposure is not good, and film reduction may occur at the time of development, and the resolution is greatly lowered. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is deteriorated. The blending amount of the carboxyl group-containing resin (A) should be 20 to 80% by mass, preferably 30 to 60% by mass based on the total composition. When the blending amount of the carboxyl group-containing resin (B) is less than the above range, the film strength is lowered. On the other hand, when the amount is more than the above range, the viscosity of the composition is high, which may result in a decrease in coatability or the like. . The photopolymerization initiator (B) can be used by a person skilled in the art. Further, it is also possible to use a conventionally known photoinitiator and a sensitization IJ. Examples of specific photopolymerization initiators, photoinitiating aids, and sensitizers 'Example-18- 201127238 For example, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, diphenyl A ketone compound, a xanthone compound, a tertiary amine compound, and the like. Specific examples of benzoin compounds, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. Specific examples of the acetophenone compound, for example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2·diethoxy-2-phenylethyl benzene, 1, 1-Dichloroacetone. Specific examples of the hydrazine compound are, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-t-butylhydrazine, 1-chloroindole. Specific examples of thioxanthone compounds, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone Specific examples of the ketal compound are, for example, acetophenone dimethyl ketal, diphenylethylenedione dimethyl ketal. Specific examples of the diphenyl ketone compound, for example, diphenyl ketone, 4-benzylidene diphenyl sulphide, 4-benzylidene-4'-methyldiphenyl sulphide, 4-phenylidene fluorenyl _ 4 '-Ethyl diphenyl sulfide, 4-benzylidene-4'-propyl diphenyl sulfide. Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaniline structure, for example, 4,4'-dimethylamine diphenyl ketone (NISSO CURE-MABP, manufactured by Nippon Soda Co., Ltd.), 4 , 4, diethylamine diphenyl ketone (HODOGAYA CHEMICAL CO. ,LTD. Dialkylamine diphenyl ketone, 7-(diethylamine)-4-methyl-2H-1-benzopipene-2-one (7-(diethylamine)-4) _Methyl bean fragrant), etc. -19- 201127238 Soybean compound containing dialkylamine group, ethyl 4-dimethylamine benzoate acid (NIPPON KAYAKU CO. , LTD. KAYACURE - EPA ), 2-dimethylamine benzoic acid ethyl (INTERCATIONAL BIO-SYNTHETICS Quantacure DΜB), 4-dimethylamine benzoic acid (n-butoxy) ethyl (INTERNATIONAL BIO-SYNTHETICS Quantacure BEA), p-dimethylamine benzoic acid isoamyl ethyl vinegar (NIPPON KAYAKU CO. ,LTD. KAYACURE-DMBI), 4-dimethylamine benzoic acid 2-ethylhexyl (Esolol 507 manufactured by Van Dyk Co., Ltd.), 4,4'-diethylamine diphenyl ketone (EADOGAYA CHEMICAL CO·, LTD. ). In addition to the photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, an acyl phosphine oxide photopolymerization initiator, an oxime ester photopolymerization initiator, or the like can be used. α-Aminoacetophenone photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinone-1,2-diphenylethylenedione -2-dimethylamine-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamine)-2-[(4-methylphenyl)methyl]· 1-[4-(4-morpholino)phenyl]-1-butanone, hydrazine, hydrazine-dimethylamine acetophenone, and the like. City merchandise, IRGACURE-907, IR G A C U R E - 3 6 9, IRGACURE-379, etc., manufactured by CIBA JAPAN. Acyl phosphine oxide photopolymerization initiator 'for example 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl oxidation Phosphine, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, etc., commercially available, for example, Lucirin TPO, CIBA JAP AN, manufactured by BASF The system of IR GACUR E-819 and so on. An oxime ester photopolymerization initiator 'for example, 2-(ethenyliso-20- 201127238 nitrosomethyl) thioxan-9-one, etc., commercially available product 'for example, CGI-325 manufactured by C IB AJAPAN Co., Ltd. , IRGACURE-OXEOl, IRGACURE-OXE02, N-1919 made by ADEKA. Representative photopolymerization initiators are listed above. However, those which can generate a base active center or contribute to the growth of the species by light irradiation are not limited to those described above. Further, although the base itself does not generate a base, it is also possible to use a conventionally known sensitizer which has a sensitizing effect on the above photopolymerization initiator. The photopolymerization initiator, the photoinitiator, and the sensitizer may be used singly or in combination of two or more. In addition, the blending amount of the photopolymerization initiator, the photoinitiating aid, and the sensitizer is sufficient in a usual amount, and generally, it is 100% by mass based on the carboxyl group-containing resin (A) (two or more types are used). The carboxyl group-containing resin is the total amount, the same as the following), and should be 0. 01 to 30% by mass, preferably at 0. A range of 5 to 15% by mass. When the photopolymerization initiator (B) is blended in an amount of 〇·〇 of 1% by mass or less, the photocurability is insufficient, and the coating film is peeled off, or the coating properties such as chemical resistance are lowered. On the other hand, when the amount is more than 30% by mass, the light absorption on the surface of the coating film of the photopolymerization initiator (B) is sharply increased, and the deep curing property tends to be lowered. The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photosensitive resin composition of the present invention is photohardened by irradiation with an active energy ray, and the carboxyl group-containing resin (A) is insoluble or assisted. It is insoluble in an aqueous alkaline solution. Such a compound, for example, a diacrylate of ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, three Hydroxy-21 - 201127238 Polyols such as ethyl isocyanurate or polyvalent acrylates such as these ethylene oxide addition products or propylene oxide addition products; phenoxy acrylate, bisphenol A a polyvalent acrylate such as a diacrylate or an ethylene oxide addition product or a propylene oxide addition product of the phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane tricondensate A polyvalent acrylate of a glycidyl ether such as a glyceryl ether or a triglycidyl isocyanurate; and a melamine acrylate and/or each methacrylate corresponding to the above acrylate may be used alone or in combination of two or more. . Further, for example, an epoxy acrylate resin in which acrylic acid is reacted with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and a hydroxy acrylate such as pentaerythritol triacrylate or isophorone diisocyanate. An epoxy urethane acrylate compound in which a half-isocyanate compound of a diisocyanate reacts with a hydroxyl group of the epoxy acrylate resin. Such an epoxy acrylate-based resin can improve the light-hardenability without lowering the dust-free property. The blending amount of the compound (C) having two or more ethylenically unsaturated groups in the molecule should be 5 to 100% by mass, preferably 1 to 7 based on 100% by mass of the carboxyl group-containing resin (A).比例% by mass. When the blending amount is 5% by mass or less, the photocurability is lowered, and it is difficult to form a pattern by alkaline development after the active energy ray irradiation. On the other hand, when the content is more than 100% by mass, the solubility in the alkaline aqueous solution is lowered, and the coating film becomes brittle. In addition, the photosensitive resin composition used in the present invention may be provided with thermosetting property in order to impart heat resistance. Ingredient (D). For the thermosetting component (D), an amine resin such as a melamine resin or a benzoquinone resin, a double horse-22-201127238, a sulfonium compound, an oxoazobenzoic compound, an oxazoline compound, a carbonized secondary product can be used. A commonly known thermosetting resin such as an amine resin, a blocked isocyanate compound, a cyclocarbonate compound, a polyfunctional epoxy compound, a polyfunctional oxycyclobutane compound, an episulphide resin, a melamine derivative, and the like . Among these, the most preferable thermosetting component (D) has two or more cyclic ether groups and/or cyclic ethyl sulfide groups (hereinafter, simply referred to as a cyclic (ether) ether group) in one molecule. The thermosetting component is, for example, a polyfunctional epoxy compound having two or more epoxy groups in the molecule, a polyfunctional oxycyclobutane compound having two or more epoxy butyl groups in the molecule, and two or more molecules in the molecule. Ethyl sulfide based episulphide resin. The blending amount of the thermosetting component (D) should be 〇·6~2 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). 5 equivalents, preferably at 0. 8~2. 0 equivalent range. When the photosensitive resin composition contains the thermosetting component (D) as described above. It should further contain a heat hardening catalyst. Such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, cardiophenylimidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenylimidazole and 1-(2-cyanoethyl)-2·ethyl-4-methylimidazole; dicyandiamide, diphenylethylenedione dimethylamine, 4- (dimethylamine)-oxime, Ν-dimethyldiphenylbenzylamine, 4-methoxy-oxime, Ν-dimethyldiphenylbenzylamine, 4-methyl-oxime, Ν- An amine compound such as dimethyldiphenylbenzylamine, an anthracene acid adipate or a phosphonium azelate or the like; a phosphorus compound such as triphenylphosphine or the like. In addition, the city's goods, for example, manufactured by Shikoku Chemical Industry Co., Ltd., 2ΜΖ-Α, 2ΜΖ-0Κ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2P4MHZC are all known as imidazole compounds, -23-201127238), U-made by SAN-APRO LIMITED CAT (registered trademarks 3 5 03N, U-CAT3502T (all trade names of dextro-isocyanate dimethylamine), DBU, DBN, U-CATSA102 CAT5 002 (all are bicyclic hydrazine compounds and In particular, it is limited to the above, and may be used alone as long as it is a thermal catalyst of an epoxy resin and an oxycyclobutane compound, or may promote an epoxy group and/or an epoxybutyl group and a carboxyl group. It is also possible to use a mixture of two or more kinds. In addition, guanamine, acetoguanamine, benzoquinone, cyanamide, 2,4-diamine-6-methacryloyloxyethyl ester are also used. -S-triazastyryl-2,4-diamine-S-triazabenzene, 2-vinyl-4,6-diamine-S-heterobenzene-isocyanuric acid addition product, An S-triaza complex such as a 2,4-diamine-6-methacryloylethyl ester-S-triazabenzene-iso-cyanuric acid addition product, preferably having such a close adhesion property Compound function and thermosetting For the use of the catalyst, the amount of the thermosetting catalyst is usually sufficient, for example, the thermosetting property of the carboxyl group-containing resin (A) or more than # cyclic (sulfur) ether groups in the molecule. Ingredient (D)% by mass, should be 〇. 1 to 2 0% by mass, preferably 0. 5~1 5. 0% by mass» The photosensitive resin composition used in the present invention is blended with the material (E) in order to improve the physical strength and the like. In this case, conventionally known inorganic or organic tanning materials can be used, however, barium sulfate, spheroidal vermiculite and talc are preferred. Further, in order to obtain an appearance and flame retardancy, titanium oxide, a metal oxide or a metal hydroxide hydroxide can also be used as a body pigment pigment. The blending amount of the dip material is 75 mass% or less, preferably 0. 1~60 mass standard) Salinization, U- is not hardened, then the ratio of trimeric and 2-triazobenzene can be increased by I: there are 2 1 00 coating film and white aluminum, etc., should: %-24 - 201127238 ratio. When the blending amount of the coating material exceeds 75 mass% of the total amount of the composition, the viscosity of the insulating composition is high, and the coating and moldability are lowered, and the cured product is brittle, which is not preferable. The photosensitive resin composition used in the present invention may contain a ketone, an aromatic hydrocarbon, a glycol ether, a glycol ether acetate, or the like, in order to prepare a composition or to adjust the viscosity of the substrate and the carrier film. Various organic solvents such as esters, ethanols, aliphatic hydrocarbons, and petroleum solvents. In addition, if necessary, it is possible to mix conventional polymerization inhibitors such as hydroquinone, benzenediol monomethyl ether, t-butyl catechol, benzenetriol, thiodiphenylamine, and fine powdered vermiculite. Organic bentonite, montmorillonite, etc. commonly known as tackifiers, pigments, dyes, lanthanides, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole, thiazole, triazole It is a conventionally known additive such as a decane coupling agent, an oxidation inhibitor, and a rust inhibitor. (1) The patterned resist film forming process is as shown in the above-mentioned first (C) diagram, and the substrate 1 on which the photosensitive resist film 4 is formed on the surface is formed, and the through hole 6 is formed by opening the hole. Selective exposure and development, as shown in Fig. 2(A), a patterned resist film for forming a copper plating layer by electroless copper plating to form a groove pattern forming a circuit forming portion (hereinafter, simply referred to as resist Film or resist pattern) 5. When the photosensitive resist film 4 is formed using the negative photosensitive resin composition, the unexposed portion is removed by development, and when the positive photosensitive resin composition is used, the exposed portion is removed by development. Selective exposure, contact (or non-contact), selective exposure to the active energy line through the patterned mask, or -25-201127238, can also be directly exposed by laser direct exposure machine . In addition, when the photosensitive resin composition used for forming the photosensitive resist film contains the thermosetting component (D), it can be further heat-hardened to improve the heat resistance, chemical resistance, and moisture absorption resistance of the resist film. Characteristics such as adhesion and electrical characteristics. The exposure machine used for the above active energy ray irradiation can use a direct drawing device (for example, a laser direct imaging device that uses a CAD data from a computer to directly image a laser), an exposure machine equipped with a metal halide lamp, and a matching machine. An exposure machine for carrying (ultra) high-pressure mercury lamps, an exposure machine equipped with a mercury arc lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp. The active energy ray can be either a gas laser or a solid laser as long as it uses laser light having a maximum wavelength of 3 5 0 to 41 Onm. Further, the exposure amount varies depending on the film thickness or the like, but is usually in the range of 5 to 200 mJ/cm 2 , more preferably 5 to 100 mJ/cm 2 , and most preferably 5 to 50 mJ/cm 2 . For the direct drawing device, for example, a product manufactured by ORB OTECH Co., Ltd., PENTAX Corporation, or the like can be used, and any device can be used as long as it oscillates laser light having a maximum wavelength of 3 50 to 410 nm. As the developing method, a dipping method, a shower method, a spraying method, a brush method, or the like can be employed. The development may be a solvent development, but it is preferably carried out by using an aqueous alkaline solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, aqueous ammonia or an amine. (2) The electroless copper plating electrolytic copper plating process is performed on the exposed surface of the substrate 1 of the groove pattern portion and the surface of the resist pattern 5 -26-201127238 as a whole, by a well-known method such as the second (B) As shown in the figure, electroless copper plating is performed, and secondly, until the surface is substantially smooth, electrolytic copper plating is performed to form a copper plating layer 7 covering the resist pattern 5. At this time, before the electroless copper plating, the treatment is performed for the purpose of forming electroless copper plating on the surface of the resist pattern 5, and the resist pattern 5 after development should be irradiated with ultraviolet rays stronger than that at the time of exposure, or It is heated to a temperature higher than the glass transition temperature (Tg) of the anti-contact film, or subjected to plasma treatment such as argon or oxygen. By performing the above pretreatment, not only electroless copper plating can be deposited on the resist pattern 5, but also elution can be reduced, and the contamination of the electroplating liquid can be suppressed, and the discoloration of the electroless plating surface, poor gloss, and pinhole plating can be achieved. Precipitate. Further, it is also possible to suppress alkali resistance and swelling of the resist film, and the shape of the formed circuit is also relatively stable. Electroless copper plating 'Generally, a planing medium is supplied to the exposed surface of the substrate and the entire surface of the patterned resist film, and then immersed in an electroless copper plating solution to form a copper layer. The thickness of the electroless copper plating layer is generally about 〇. 5 ~ 2 / m range. In addition, after forming an electroless copper plating layer, it is heat-treated at 100 ° C to 200 ° C. The heating time is not particularly limited and can be selected between 30 minutes and 5 hours. In order not to oxidize the copper foil, it is preferred to carry out heating in a vacuum or in an inert gas. Next, immersed in an electrolytic copper plating solution, as shown in Fig. 2(B), an electrolytic copper plating layer covering the resist pattern 5 and having a substantially smooth surface of the copper plating layer 7 is formed. The thickness of the electrolytic copper plating layer can be arbitrarily selected. (3) Etching Process -27- 201127238 As shown in the second (B) diagram, after the copper plating layer 7 is formed, as shown in the second (C), the surface of the resist pattern 5 is exposed, mechanically honed and / or chemical honing or etching to uniformly reduce the copper plating layer 7 to expose the copper circuit pattern 8 from the surface. Thereby, the upper and lower copper circuit patterns 8 are in a state of being connected via the plating through holes 9. Mechanical honing and/or chemical honing can be carried out by a conventionally known method. Further, the etching solution is not particularly limited, and an aqueous solution of sulfuric acid-hydrogen peroxide, ammonium persulfate or sodium persulfate or potassium persulfate can be used. Wait for an aqueous solution of a sulfate solution, ferric chloride or copper trichloride, and the like. (4) The resist pattern peeling process is a resist pattern 5 which is present in a state in which the copper circuit pattern 8 is buried between the copper circuit patterns 8 and can be directly left as an insulating layer without being peeled off, and the mixture is required to be resistant only by an alkaline aqueous solution or a solvent. The etching pattern 5 is swelled and peeled off and/or removed by a so-called degumming treatment using a permanganic acid alkaline salt or the like, and as shown in FIG. 2(D), the wiring board in which only the copper circuit pattern 8 is formed on the substrate 1 is formed. . (5) Interlayer Resin Insulation Layer Forming Process Further, when a multilayer printed wiring board is produced, the substrate having the resist pattern 5 and the copper circuit pattern 8 as shown in the second (C) above, or FIG. 2 (D) The surface of the substrate having only the copper circuit pattern 8 shown, for example, an epoxy resin, a polyimide resin, a cyanate resin, a maleimide resin, a double bond-bonded polyphenylene ether resin, etc. One or two or more kinds of resin compositions such as a bromine-containing or phosphorus-containing compound, and a thermosetting resin composition such as a catalyst, a hardener, or a hardening accelerator which are well-known to be blended, -28-201127238 Coated, heat-hardened, or impregnated with glass fiber, non-woven fabric, woven curable resin composition, semi-cured semi-cured semi-cured laminated film resin, as shown in Figure 3 (A), The grease insulating layer 10 is formed, and the surface thereof is subjected to the treatment as described above for the purpose of blending. In this case, it is preferable to form a resin emulsion of a copolymerized polyimine resin and a polymaleimide compound on one side of a copper foil described in Japanese Laid-Open Patent Publication No. 2007-242975, for example, in the copper foil or the resin composite copper foil. The resin layer of the composite copper foil is laminated with the B layer resin composition layer, the composite shape of the copper layer plate, and secondly, all the copper foil is removed by etching, and the interlayer resin in which the surface of the fine uneven surface of the copper foil is transcribed is insulated at this time. The roughening treatment is not required, and the subsequent process can form a photosensitive resist film having good adhesion on the surface of the interlayer tree layer 1 to obtain a wiring board. Such a copper-clad laminate can be used with conventional copper-clad laminates. Further, a photosensitive resin composition containing the pre-formation component (D) and the pigment (E) is applied onto the surface of the substrate, and the dry film is bonded to the entire surface, and the entire active energy ray is irradiated to cause photohardening and heating. Thermally hardened, an interlayer resin insulating layer 10 can be formed. The resin composition used for the layer B resin composition layer may be blended with various additives in the range of the properties of the original composition, and the polymerizable monomer may be appropriately used, such as an unsaturated polyester. Prepolymers; polybutadiene, maleated butadiene-acrylonitrile copolymer, polychloroprene, butadiene-benzene polymer, polyisoprene, butyl rubber, fluororubber, Natural rubber molecular weight liquid ~ high molecular weight elastic rubber; polyethylene, poly cloth and other hot sheets, or interlaminar tree roughening in the layer containing the layer of the layer of the layer of the layer formed into a layer 10. The grease is insulated and the heat is hardened or, afterwards, the additive is not damaged. Low double propylene such as diene, ethylene co-gel, -29- 201127238 polybutene, poly-4-methylpentene, polystyrene, AS resin, ABS resin, MBS resin, styrene-isoprene Rubber, propylene rubber, core-shell rubber, polyethylene-propylene copolymer, 4-fluorinated ethylene-6-fluorinated ethylene copolymer; polycarbonate, polyphenylene ether, poly High molecular weight prepolymers or oligomers such as hydrazine, polyester, polyphenylene sulfide, etc.: polyurethanes, etc., can be suitably selected. Other, well-known organic or inorganic filling agents, dyes, pigments, tackifiers, slip agents, antifoaming agents, dispersing agents, leveling agents, photosensitizers, flame retardants, gloss agents, polymerization Various additives such as an inhibitor and a rheological property imparting agent can be used in combination as appropriate. In particular, when opening a hole with a carbon dioxide gas, an inorganic filler should be added appropriately for a good hole shape. For example, vermiculite, spheroidal vermiculite, alumina, talc, sintered talc, ash stone, synthetic mica, titanium oxide, aluminum hydroxide, and the like are generally known. The shape of the dip may be any shape such as a needle shape or a spherical shape. (6) Resist pattern forming process As shown in the above-mentioned 3rd (A), the substrate 1 on which the interlayer resin insulating layer 1 is formed is formed as described above, and a photosensitive resist film is formed, and a through hole is formed as needed. After 1 1 , the photosensitive resist film is subjected to selective exposure and development in the same manner as the above-described process (1), and as shown in FIG. 3(B), an electroless copper plating may be formed to form a groove pattern in which a circuit forming portion is formed. A copper plating layer outer layer resist pattern 12 is formed. When the photosensitive resin composition used for forming the photosensitive resist film contains the thermosetting component (D), for example, it is further heated and cured at a temperature of about 140 to 180 ° C to form the carboxyl group-containing resin (A). -30- 201127238 The residue reacts with the thermosetting component (D) having two or more cyclic (sulfur) ether groups in the molecule to form heat resistance, chemical resistance, moisture absorption, and adhesion. A hardened film with excellent properties such as electrical characteristics. Further, when the thermosetting component (D) is not contained, the ethylenic unsaturated bonding of the photocurable component remaining in an unreacted state at the time of exposure may be thermally radically polymerized by heat treatment to enhance the film properties. Therefore, heat treatment (thermosetting) can be performed depending on the purpose and application. (7) Electroless copper plating-electrolytic copper plating process, after the exposed surface of the interlayer resin insulating layer 1 and the entire surface of the resist pattern I2 are the same as the above-mentioned process (2), as shown in Fig. 3(C) As shown in the figure, electroless copper plating is performed, and secondly, until the surface is substantially smooth, electrolytic copper plating is performed to form a copper plating layer 13 covering the outer surface of the resist pattern 12. In this case, the same as the above process (2), Before the copper ore is electrolyzed, the electroless copper plating is formed on the surface of the resist pattern 12, and the resist pattern 12 may be further irradiated with ultraviolet rays stronger than that during exposure or heated to the resist glass. Temperatures above temperature (Tg) or plasma treatment of argon, oxygen, etc. (8) The etching process is as shown in Fig. 3(C), after forming the outer copper plating layer 13, the same as the above process (3), until the surface of the resist pattern 12 is exposed, mechanically honing and/or chemical enthalpy The grinding or etching uniformly reduces the copper plating layer 13 as shown in Fig. 3(D) to expose the outer copper circuit pattern 14 from the surface. The resist pattern 12 existing in the state between the copper circuit patterns 14 can be directly used as an insulating layer without being peeled off, and is only required for an anti-hungry pattern 1 2 with an alkaline aqueous solution or a solvent. The wiring sheet which forms the outer layer copper circuit pattern 14 is formed by swelling and peeling, and/or performing a so-called stripping process and removing it to become a surface layer part. Further, the multilayer printed wiring board can be produced by repeating the above processes (5) to (8) with good productivity. With the circuit pattern formed by the method of the present invention as described above, even when the line and the interval are less than 5 /z m, there is no electric conductor between the circuit patterns, and the circuit is excellent in insulation reliability. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, however, the present invention is not limited to the examples described below. In addition, the following '%' and the like are all based on quality unless otherwise stated. Preparation of photosensitive resist composition; The various components shown in the following Table 1 were blended at a ratio (% by mass) shown in Table 1 below, and pre-mixed by a machine, and then twisted by three rollers. Photosensitive resist composition. -32- 201127238 Table 1 Composition (% by mass) Resist A A resist B Photosensitive resin - I·1 222 Photosensitive resin - 2" 154 Photosensitive polymer 40 20 Photopolymerization initiator Μ 5 5 Thermosetting resin *5 25 pigment paste·6 3 inorganic coating” 70 heat curing catalyst 0. 5 Remarks *1 : CYCLOMERP (ACA) Ζ254 (DAICEL-CYTEC COMPANY LTD. Photosensitive copolymer, solid part 50%, acid 値l〇〇mgKOH/g) *2 : UE-9210 (acid-modified epoxy acrylate manufactured by DIC Corporation, solid portion 65%, acid strontium 80 mgKOH/g) *3 : Trimethylolpropane triacrylate*4 : TPO-L (acyl phosphine oxide photopolymerization initiator manufactured by BASF) *5 : NC-3000 (NIPP〇NKAYAKUCO. ,LTD. Diphenylphenolic epoxy resin) *6 : Indigo blue and propylene glycol methyl ether acetate 1: 9 paste *7 : 矽 gypsum (ADMATECHS globular vermiculite, solid part 70%: propylene glycol methyl ether Acetate solution) *8 : 1B2PZ (Imidazole compound manufactured by Shikoku Kasei Kogyo Co., Ltd.) Preparation of dry film Each of the obtained photosensitive resist compositions was further diluted with propylene glycol methyl ether acetate to obtain 1 OdPa. S resist solution. It was applied to a film of polyethylene terephthalate having a thickness of 16 Mm by a film coater, and the temperature was gradually raised from 50 ° C to 80 ° C to obtain a resist thickness of 10 //. a dry film of m. The obtained dry film was regarded as dry film A and dry film B, respectively. Example 1 -33- 201127238 The thickness of the insulating layer is 0. 2mm, 12ym two-sided copper foil (copper foil shape 3. 3 A m ) BT resin copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., trade name: CCL-HL830) is used as a copper-clad laminate, and a metal drill bit is used to form a through-hole of the aperture 75 to be degummed (permanganese) The potassium acid-based degumming solution (manufactured by Okuno Pharmaceutical Co., Ltd.) is used to swell, remove (dissolve), neutralize, and wash, and then etch all the copper layer of the surface, and secondly, use a vacuum laminating machine manufactured by NICHIGO-MORTON Co., Ltd. The dry film A was bonded to the conditions of 7〇〇c, 〇5Mpa, and 3〇 seconds. Thereafter, it was irradiated under the condition of 1 〇〇mJ/cm2 by a laser direct exposure apparatus (param0n manufactured by ORBOTECH Co., Ltd.). 5 5nm ultraviolet rays 'depicted the minimum line and the interval is 10 private m pattern. Thereafter, using a 1 wt% sodium carbonate aqueous solution at 30 ° C, the development is carried out at a pressure of 2 atmospheres, and the water washing is repeated twice to obtain a photosensitive film. The substrate of the resist pattern was subjected to UV curing under the conditions of 300 mJ/cm 2 by a UV conveyor belt device equipped with a high-pressure mercury lamp, and then subjected to plasma treatment under conditions of 500 W, 250 mTorr, and 60 seconds using oxygen plasma. Electroless copper plating solution (Okuno Pharmaceutical Co., Ltd.) ATS ADD COPPER CT) Electroless copper plating is carried out to form a copper layer with a thickness of l#m. After heating for 2 hours in a heating furnace at 30 ° C, a copper sulfate plating solution is used. 5 amps/dm2 was subjected to electrolytic plating for 70 minutes to form a copper layer of about 10/zm thick. The substrate on which the copper layer was formed was etched with an etching solution (SE-07, manufactured by Gas Chemicals Co., Ltd.) to etch the copper foil to make it flat. The substrate on which the circuit is formed is peeled off by an alkaline stripping solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., R-200) at 50 ° C, 3 minutes - 34 - 201127238, and the photosensitive process is completely removed by a stripping process. Scratch, get the minimum line and the circuit board with a spacing of 1 ο // m. Example 2 The circuit board obtained in Example 1 was subjected to CZ treatment by EC, and a layer of a resin layer containing a copper foil (a copper foil profile of 3 · 3 m) was attached (Mitsubishi Gas Chemical Co., Ltd. ), CRS - 4 0 1 ) is applied to both sides, heating conditions: 110 ° C x 30 minutes + 180 ° C x 90 minutes, pressurization conditions: 5 kgf / cm 2 x 1 5 points + 20 kgf / cm 2 'In the final condition, vacuum 3 〇 Below the mmHg, the layer was formed in a two hour condition. The surface copper foil of the 4-layered plate obtained by etching was irradiated with a carbon dioxide gas laser (output of 13 mJ) to form a blind hole having a pore diameter of 6 0 /z m. Then, the dry film a was bonded under the above-described conditions, and the circuit was formed in the same manner as in the first embodiment, and a four-layer circuit substrate having a minimum line and a space of 10 mm was obtained. [Example 3] In the case of Example 1, the dry film A was replaced with a dry film B, and the copper layer of the copper foil layer which was entirely etched on the surface was bonded, and thereafter, a laser direct exposure apparatus (ArBOTECH, Paragon, Inc.) was used in the same manner. The ultraviolet rays of 355 nm were irradiated under the conditions of 200 mJ/cm2, and the pattern of the minimum line and the interval of 20 μm was drawn. Thereafter, development was carried out at a pressure of 2 atm using a 1 wt% aqueous sodium carbonate solution at 30 ° C, and water washing was repeated twice to obtain a substrate on which a photosensitive resist pattern was formed. After curing in a hot air drying oven at 150 ° C for 1 hour, the electric hair treatment was carried out under the conditions of -35 - 201127238 500 w, 250 mTorr, and 60 seconds. Next, electroless copper plating was performed using an electroless copper plating solution (ATS ADD COPPER CT) to form a copper layer having a thickness of i#m, and heating was performed for 2 hours in a heating furnace at 130 °C. , using copper sulfate plating solution to 1. 5 amps/dm2 was subjected to electrolytic copper plating for 70 minutes to form a copper layer of about thick thickness. The substrate on which the copper layer was formed was etched (Mitsubishi Gas Chemical Co., Ltd., SE-07) until the surface of the dry film was visible, and the copper foil was etched to be flat, and the minimum line and interval were 20. ^ m circuit board. [Example 4] The circuit board obtained in Example 3 was subjected to a CZ treatment by MEC Co., Ltd., and after the adhesion treatment, the dry film B was bonded thereto in the same manner as in Example 1, and the solder resist pattern was exposed and developed. After that, a hot air drying oven was used to perform heat curing at 150 ° C for one hour to obtain a circuit board on which a solder resist layer was formed. Example 5 After performing a CZ treatment on a four-layer circuit board obtained in Example 2, the same procedure as in Example 1 identical, fit dry film solder mask (TAIYO INK MFG. CO. , LTD. , AUS410, film thickness 20#m), after exposure and development of the solder resist pattern using a high-pressure mercury lamp at 600 mJ/cm2, and then hot-drying at 150 ° C for 1 hour using a hot air drying oven A circuit board with a solder mask. -36- 201127238 Comparative Example 1 The insulation layer is thick. 2mm, 12// m double-sided copper foil (copper foil shape 3. 3 Vm) BT resin copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., trade name CCL-HL8 3 0 ) is used as a copper-clad laminate, using a metal drill to form a through hole with a hole diameter of 75 # m, and secondly, an etching solution (Mitsubishi Gas Chemical Co., Ltd., SE-〇7) etches the copper foil layer on the surface to a flat surface. 0"m, after degumming treatment (potassium permanganate-based degumming solution (made by Okuno Pharmaceutical Co., Ltd.) for swelling, degumming (dissolving), neutralizing, and washing, electroless copper plating is formed. 1 # m of the copper layer, followed by the implementation of 1 30 ° C, 2 hours of heat treatment 'Second, using NICHIGO-MORTON company vacuum laminator to 7 ° ° C, 〇. 5Mpa '3 sec. conditions for the semi-additive dry film (Hitachi Chemical Co., Ltd., RY-3515). Thereafter, ultraviolet rays were irradiated under conditions of 100 mJ/cm 2 using an ultraviolet exposure apparatus (manufactured by Bodo Co., Ltd., HAP-5 020) to draw a pattern of minimum lines and intervals of 10 // m. Thereafter, development was carried out by using a lwt% sodium carbonate aqueous solution at 30 °C under a spray pressure of 2 atm, and the water washing was repeated twice to obtain a substrate on which a photosensitive resist pattern was formed. Secondly, use copper sulphate plating solution to 1. 5 amps/dm2 was subjected to electrolytic copper plating for 70 minutes, and a copper pattern of about 10#ιη thick was formed on the portion where the resist layer was not formed. Next, an alkali stripping solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., R - 2 0 0) was used, and 50 was used. (:, a condition of 3 minutes, after peeling off a half-size dry film, an etching solution (made by Mitsubishi Gas Chemical Co., Ltd., SE-07) was used, and the substrate on which the copper pattern was formed was semi-added. Before the film portion disappeared, the copper circuit was etched to obtain a circuit board having a minimum line and a spacing of 10 m. -37- 201127238 Comparative Example 2 After the CZ process of MEC Co., Ltd. was performed on the circuit board produced in Comparative Example 1 Hardening dry film (Ajinomoto Fine-Techno Co. , Inc. The system 'ABF-GX13' is attached to both sides, using a vacuum laminating machine made by NICHIGO-MORTON Co., Ltd. at 7 °C, 〇. After bonding at a condition of 5 MPa and 30 seconds, the layer was formed by hot-hardening at 170 ° C for 60 minutes using a hot air drying oven. The obtained substrate was irradiated with a carbon dioxide gas (output of 13 mJ) in one shot to form a pupil having a pore diameter of 60 // m. Next, the gel removal treatment (potassium permanganate-based degumming solution (manufactured by Japan MacDermid Co., Ltd.) is used to swell, remove (dissolve), neutralize, remove the smear of the pupil, and perform hardening of the heat-hardened dry film. Concave and convex treatment of the surface. At this time, the unevenness of the surface of the resin is Rz5. 3 μπι. On the substrate, an electroless copper plating solution (ATS ADD COPPER CT) was used to form an electroless copper shovel to form a copper layer having a thickness of 1 jam, and the mixture was heated in a heating furnace at 130 ° C for 2 hours. Using a vacuum laminator made by NICHIGO-MORTON Co., Ltd. at 70 ° C, 0. A dry film is applied to a half-added amount of 5 Mpa and 30 seconds. Thereafter, ultraviolet rays were irradiated under the conditions of 100 nU/cm 2 using an ultraviolet exposure apparatus (manufactured by OC Corporation), and a pattern of a minimum line and an interval of 1 〇 Μ m was drawn. Thereafter, development was carried out using a 1 w t % sodium carbonate aqueous solution at 30 ° C at a spray pressure of 2 atm, and the water washing was repeated twice to obtain a substrate on which a photosensitive resist pattern was formed. Next, using a copper sulfate plating solution for the substrate, 1. 5 amps/dm2 was subjected to electrolytic copper ore for 70 minutes, and a copper pattern of about 10//m thick was formed in the portion where the resist layer was formed. Next, using an alkaline stripping solution (Mitsubishi Gas Chemical Co., Ltd., R-200), peeling the semi-added dry film at 50 ° C for 3 minutes, using a contact engraving solution -38- 201127238 (Mitsubishi Gas Chemicals Co., Ltd., SE-07) etching a copper circuit until the copper portion of the substrate on which the copper pattern is formed forms a semi-added dry film disappears, and a multilayer having a minimum line and a spacing of 1 〇β m is obtained. Circuit board. Further, on the substrate, a dry film solder resist layer (TAIYO INK MFG.) was formed in the same manner as in Example 5. CO. , LTD. The solder resist pattern of the system, AUS410), obtains a substrate on which the solder resist layer is formed. The circuit board produced in each of the above examples and comparative examples was subjected to a characteristic test as described later. The results are shown in Table 2. Table 2
特性 實施例 比較例 1 2 3 4 5 1 2 剝離強度(N/cm) 9.3 10.1 8.9 9.2 9.8 7.8 5.9 焊接耐熱性 〇 〇 〇 〇 〇 〇 〇 細線形成性 〇 〇 〇 〇 〇 X Δ 無電解電鍍適性 〇 〇 〇 〇 〇 〇 X (1 )剝離強度 依據JIS C 6 4 8 1,以3次測定之剝離強度的平均値。 (2 )焊接耐熱性 以1 2 1 °C、2 0 3 kP a實施4小時處理後,浸漬於2 6 0 °C之 焊接夜中30秒鐘,觀察是否有電路剝離、樹脂剝離等之異 常,依以下基準進行評估。 〇:異常 X :部分膨脹 (3 )細線形成性 -39- 201127238 以顯微鏡觀察確認是否形成L/S (線/間隔)=1 〇/1 〇 a m 或L/S = 2 0/2〇em之細線,依以下基準進行評估。 〇:形成而沒有問題。 A :極小部分發現剝離。 X :可見剝離。 (4 )無電解電鍍適性 對各配線板實施無電解鎳鍍,再進行無電解電鍍,確 認電路形成時之蝕刻殘渣是否有導致電鍍之異常析出,依 以下基準進行評估。 〇:無異常析出。 X :電鍍析出沒有配線之樹脂上。 如表2所示之結果,實施例1〜5時,配線板因爲蝕刻 全部銅箔,而在銅箔之外型具有表面粗細度的狀態下形成 電路,故得到剝離強度高之結果。此外,於基材及感光性 抗蝕膜之表面整體以無電解銅鍍形成電解銅鍍之種層(導 通層),其次,全面形成電解鍍銅層後,至感光性抗飩膜 表面露出爲止並成爲平坦進行蝕刻,所形成之配線板具高 精細度,因爲完成之電路間沒有導電層形成之痕跡,沒有 飩刻不良所導致之鎳及電鍍異常析出的可能性。 此外,實施例3及實施例4所得到之配線板,電路與絕 緣層爲平坦,防焊層亦可以均一膜厚來形成,係高精度之 形成方法。 另一方面,比較例1時,與實施例相同,配線板之銅 箔全部進行蝕刻而在銅箔之外型表面具有粗細度的情形下 -40- 201127238 形成電路,故到剝離強度相對較高的結果。然而,因爲基 材樹脂上之外型較大,可以看見剝離銅箔層時之過蝕刻所 導致的細線釗離。另一方面,比較例2時,未利用銅箔之 外型而以去膠製程於樹脂上形成凹凸,故完成之電路之剝 離強度較實施例爲低。此外,形成配線板之後處理的無電 解鎳鍍、無電解電鍍時,配線以外之樹脂上也有電鍍之異 常析出。應該是因爲於細線間(感光性抗蝕膜之下)形成 無電解銅鏟,即使進行蝕刻,無電解銅鍍之觸媒的鈀未被 蝕刻而殘留下來。 本發明之印刷配線板之製造方法,適合於基板表面形 成高精度且極細密之銅電路圖案之高密度印刷配線板及多 層印刷配線板的製造。 【圖式簡單說明】 第1圖係至於基板表面形成感光性抗蝕膜爲止之製程 之良好實施形態的槪略部分剖面圖。 第2圖係包含對形成於基板表面之感光性抗蝕膜之溝 圖案形成製程、無電解銅鍍-電解銅鍍製程、整體硏磨或 蝕刻製程、及抗蝕膜剝離製程之本發明之印刷配線板製造 方法的實施形態槪略部分剖面圖。 第3圖係更包含針對第2圖所示之印刷配線板依本發明 之從樹脂絕緣層形成至銅電路圖案形成爲止之製程之印刷 配線板製造方法的實施形態槪略部分剖面圖。 -41 - 201127238 【主要元件符號說明】 1 :基板 2 :銅箔 3 :敷銅層板 4 :感光性抗蝕膜 5 :抗触圖案 6 :貫通孔 7 :鑛銅層 8 :銅電路圖案 9 :電鍍貫通孔 1 〇 :層間樹脂絕緣層 1 1 :通孔 1 2 :外層之抗蝕圖案 1 3 :外層之鍍銅層 14:外層之銅電路圖案 -42Characteristic Example Comparative Example 1 2 3 4 5 1 2 Peel strength (N/cm) 9.3 10.1 8.9 9.2 9.8 7.8 5.9 Solder heat resistance 〇〇〇〇〇〇〇 Thin line forming 〇〇〇〇〇X Δ Electroless plating suitability 〇〇〇〇〇〇X (1) Peel strength According to JIS C 6 4 8 1, the average enthalpy of the peel strength measured three times. (2) Solder heat resistance was treated at 1 2 1 ° C and 2 0 3 kP a for 4 hours, and then immersed in a soldering night at 260 ° C for 30 seconds to observe whether there was an abnormality such as circuit peeling or resin peeling. The evaluation is based on the following criteria. 〇: Abnormal X: Partial expansion (3) Thin line formation -39- 201127238 Observed by microscope observation whether L/S (line/space) = 1 〇/1 〇am or L/S = 2 0/2〇em Thin lines are evaluated on the basis of the following criteria. 〇: Formed without problems. A: A very small part was found to be peeled off. X: visible peeling. (4) Electroless plating suitability Electroless nickel plating was applied to each wiring board, and electroless plating was performed to confirm whether or not the etching residue at the time of circuit formation caused abnormal precipitation of the plating, and was evaluated according to the following criteria. 〇: No abnormal precipitation. X: Electroplating is performed on a resin without wiring. As a result of the results shown in Table 2, in the first to fifth embodiments, the wiring board formed a circuit in a state in which the surface of the copper foil had a surface roughness by etching all of the copper foil, and as a result, the peel strength was high. Further, a layer (electroconducting layer) of electrolytic copper plating is formed on the entire surface of the substrate and the photosensitive resist film by electroless copper plating, and then, after the electrolytic copper plating layer is formed in total, the surface of the photosensitive anti-crack film is exposed. The flat wiring is etched, and the formed wiring board has high definition, because there is no trace of the formation of the conductive layer between the completed circuits, and there is no possibility of abnormal precipitation of nickel and plating due to poor etching. Further, in the wiring board obtained in the third embodiment and the fourth embodiment, the circuit and the insulating layer are flat, and the solder resist layer can be formed to have a uniform film thickness, which is a method of forming a high precision. On the other hand, in the case of Comparative Example 1, as in the case of the embodiment, the copper foil of the wiring board was entirely etched, and in the case where the surface of the copper foil had a thickness, the circuit was formed in the case of -40 to 201127238, so that the peeling strength was relatively high. the result of. However, since the base resin is large in appearance, the fine line separation caused by the overetching when the copper foil layer is peeled off can be seen. On the other hand, in Comparative Example 2, the unevenness of the copper foil was not used and the unevenness was formed on the resin by the stripping process, so that the peeling strength of the completed circuit was lower than that of the examples. Further, in the case of electroless nickel plating or electroless plating which is processed after forming the wiring board, plating on the resin other than the wiring is also abnormally deposited by plating. It should be because an electroless copper shovel is formed between the thin wires (below the photosensitive resist film), and even if etching is performed, palladium of the catalyst for electroless copper plating is not etched and remains. The method for producing a printed wiring board of the present invention is suitable for producing a high-density printed wiring board and a multi-layer printed wiring board having a highly precise and extremely fine copper circuit pattern on the surface of the substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic partial cross-sectional view showing a preferred embodiment of a process for forming a photosensitive resist film on a substrate surface. 2 is a printing process of the present invention including a groove pattern forming process for a photosensitive resist film formed on a surface of a substrate, an electroless copper plating-electrolytic copper plating process, an overall honing or etching process, and a resist peeling process. A cross-sectional view of an embodiment of a method of manufacturing a wiring board. Fig. 3 is a schematic partial cross-sectional view showing an embodiment of a method of manufacturing a printed wiring board according to the process of forming a printed wiring board according to the present invention from the formation of a resin insulating layer to the formation of a copper circuit pattern. -41 - 201127238 [Description of main component symbols] 1 : Substrate 2 : Copper foil 3 : Copper-clad laminate 4 : Photosensitive resist film 5 : Anti-contact pattern 6 : Through hole 7 : Mineral copper layer 8 : Copper circuit pattern 9 : plating through hole 1 〇: interlayer resin insulating layer 1 1 : through hole 1 2 : outer layer resist pattern 1 3 : outer layer copper plating layer 14: outer layer copper circuit pattern - 42