201224656 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種感光性樹脂組成物，感光性元件， 光阻圖型之形成方法及印刷電路板之製造方法。 【先前技術】 在印刷電路板之製造領域，作爲使用於蝕刻或鍍敷等 之光阻材料係廣泛地使用：具有感光性樹脂組成物或者是 含有該感光性樹脂組成物之層（在以下稱爲「感光性樹脂 組成物層」）形成於支持薄膜上而在感光性樹脂組成物層 上來配置保護薄膜之構造的感光性樹脂組成物層（層合體 )° 向來，印刷電路板係使用前述之感光性元件，藉由例 如以下之程序而進行製造。也就是說，首先，感光性元件 之感光性樹脂組成物層，層壓於貼銅層合板等之電路形成 用基板上。在此時，接觸到.感光性樹脂組成物層之支持薄 膜之面（在以下稱爲感光性樹脂組成物層之「下面」）和 相反側之面（在以下稱爲感光性樹脂組成物層之「上面」 )係密合於形成電路形成用基板之電路之面。因此，在保 護薄膜配置於感光性樹脂組成物層之上面之狀態下，剝離 保護薄膜同時進行該層壓之作業。此外，層壓係藉由感光 性樹脂組成物層來加熱及壓接於基底之電路形成用基板而 進行（常壓層壓法）。 接著，通過遮罩薄膜等而對於感光性樹脂組成物層來 -5- 201224656 進行圖型曝光。在此時，在曝光前或曝光後之任何時間， 來剝離支持薄膜。然後，藉由顯像液而溶解或分散除去感 光性樹脂組成物層之未曝光部。接著，施行蝕刻處理或鎪 敷處理而形成圖型，在最後，剝離及除去硬化部分。 在此所謂蝕刻處理係在蝕刻及除去無藉由形成於顯像 後之硬化光阻所被覆之電路形成用基板之金屬面之後，剝 離硬化光阻之方法。另一方面，所謂鍍敷處理係在無藉由 形成於顯像後之硬化光阻所被覆之電路形成用基板之金屬 面來進行銅及銲錫等之鍍敷處理之後，除去硬化光阻，來 蝕刻藉由該光阻所被覆之金屬面之方法。 但是，作爲前述圖型曝光之方法係向來使用透過以水 銀燈使用作爲光源之光罩而進行曝光之方法。此外，在近 年來，作爲新曝光技術係提議所謂DLP ( Digital Light Processing :數位光製程）之直接地描繪圖型之數位資料 於感光性樹脂組成物層之直接描繪曝光法。該直接描繪曝 光法係對位精度更加良好於透過光罩之曝光方法，並且， 得到微細圖型，因此，正在進行導入而用以製作高密度封 裝基板。 在圖型之曝光，爲了提高生產之良品率，因此，必須 儘可能地縮短曝光時間。在前述之直接描繪曝光法，在使 用相同於習知之透過光罩之曝光方法所使用之感光性樹脂 組成物之相同程度之感度之組成物時，一般需要相當長之 曝光時間。因此，必須提筒曝光裝置側之照度或者是提高 感光性樹脂組成物之感度。 -6- 201224656 此外，感光性樹脂組成物係除了前述之感度以外，解 析度及光阻之剝離特性良好也變得重要。如果感光性樹脂 組成物能夠提供解析度良好之光阻圖型的話，則可以充分 地減低電路間之短路或斷線。此外，在感光性樹脂組成物 能夠形成剝離特性良好之光阻時，藉由縮短化光阻之剝離 時間而提高光阻圖型之形成效率，並且，藉由縮小光阻之 剝離片之大小而減少光阻之剝離殘留，提高電路形成之良 品率。對於此種要求而提議使用特定之黏合劑聚合物、光 聚合引發劑等之感度、解析度及光阻剝離特性良好的感光 性樹脂組成物（例如，參照專利文獻1、2 )。 專利文獻1:日本特開2006-234995號 專利文獻2:日本特開2005-122123號 【發明內容】 [發明所欲解決之課題] 但是，前述專利文獻1及2所記載之感光性樹脂組成 物係解析度及光阻剝離特性尙未充分。 因此，本發明係提供一種在解析度及光阻剝離特性之 提升來具有充分之效果的感光性樹脂組成物、感光性元件 、光阻圖型之形成方法及印刷電路板之製造方法，來作爲 目的。 [用以解決課題之手段] 本發明人們係爲了解決前述之課題，因此，著眼於黏 201224656 合劑聚合物之組成而全心地進行硏究。結果，發現藉由使 用特定構造之黏合劑聚合物而得到在解析度及光阻剝離特 性之提升來具有充分之效果的感光性樹脂組成物，以致於 完成本發明。 也就是說’本發明係一種感光性樹脂組成物，其含有 :(A)具有下述一般式（1)所示之2價基 '下述一般 式（Π )所示之2價基、下述一般式（III )所示之2價基 、下述一般式（IV)所示之2價基的黏合劑聚合物，（B )光聚合性化合物，及（C)光聚合引發劑。 [化學式1]201224656 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a photoresist pattern, and a method for producing a printed circuit board. [Prior Art] In the field of manufacturing printed circuit boards, a photoresist material used for etching or plating is widely used: a photosensitive resin composition or a layer containing the photosensitive resin composition (hereinafter referred to as A photosensitive resin composition layer (laminate) having a structure in which a protective film is formed on a photosensitive resin composition layer in a "photosensitive resin composition layer"), and the printed circuit board is used as described above. The photosensitive element is manufactured by, for example, the following procedure. In other words, first, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. At this time, the surface of the support film of the photosensitive resin composition layer (hereinafter referred to as "underside" of the photosensitive resin composition layer) and the surface opposite thereto (hereinafter referred to as a photosensitive resin composition layer) The "upper" is a surface that is in close contact with the circuit that forms the substrate for circuit formation. Therefore, the protective film is peeled off while the protective film is placed on the upper surface of the photosensitive resin composition layer. Further, the lamination is performed by heating and crimping the substrate for circuit formation on the substrate by a photosensitive resin composition layer (atmospheric pressure lamination method). Next, pattern exposure is performed on the photosensitive resin composition layer by a mask film or the like. At this time, the support film is peeled off at any time before or after the exposure. Then, the unexposed portion of the photosensitive resin composition layer is dissolved or dispersed by the developing solution. Next, an etching process or a smear process is performed to form a pattern, and finally, the hardened portion is peeled off and removed. Here, the etching treatment is a method of peeling off the cured photoresist after etching and removing the metal surface of the circuit-forming substrate which is not coated by the cured photoresist after development. On the other hand, the plating treatment is performed by performing a plating treatment such as copper and solder on the metal surface of the circuit-forming substrate which is formed by the cured photoresist formed after development, and then removing the hardened photoresist. A method of etching a metal surface covered by the photoresist. However, as a method of exposing the pattern described above, a method of performing exposure by using a photomask as a light source with a mercury lamp has been used. In addition, in recent years, as a new exposure technique, a direct drawing exposure method in which a digital material of a direct drawing pattern of DLP (Digital Light Processing) is proposed is directly used for a photosensitive resin composition layer. The direct drawing exposure method has a better alignment accuracy than the exposure method through the photomask, and a fine pattern is obtained. Therefore, introduction is being made to fabricate a high-density package substrate. In the exposure of the pattern, in order to increase the yield of production, it is necessary to shorten the exposure time as much as possible. In the direct drawing exposure method described above, a composition having the same degree of sensitivity as that of the photosensitive resin composition used in the conventional exposure method of the reticle is generally required to have a relatively long exposure time. Therefore, it is necessary to lift the illuminance on the side of the exposure apparatus or to increase the sensitivity of the photosensitive resin composition. -6- 201224656 In addition to the aforementioned sensitivity, the photosensitive resin composition is also important in terms of the resolution and the peeling characteristics of the photoresist. If the photosensitive resin composition can provide a photoresist pattern with good resolution, the short circuit or disconnection between circuits can be sufficiently reduced. Further, when the photosensitive resin composition can form a photoresist having good peeling characteristics, the formation efficiency of the resist pattern can be improved by shortening the peeling time of the photoresist, and the size of the peeling sheet of the photoresist can be reduced. Reduce the peeling residue of the photoresist and improve the yield of the circuit. In view of such a request, it is proposed to use a photosensitive resin composition having excellent sensitivity, resolution, and photoresist peeling properties, such as a specific binder polymer or a photopolymerization initiator (see, for example, Patent Documents 1 and 2). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2005-122123. [Problems to be Solved by the Invention] However, the photosensitive resin compositions described in Patent Documents 1 and 2 The resolution and the peeling characteristics of the photoresist are not sufficient. Therefore, the present invention provides a photosensitive resin composition, a photosensitive element, a method for forming a photoresist pattern, and a method for producing a printed circuit board, which have sufficient effects in improving the resolution and the photoresist peeling property, and purpose. [Means for Solving the Problems] The inventors of the present invention have focused on the above-mentioned problems, and have focused on the composition of the 201224656 mixture polymer. As a result, it has been found that a photosensitive resin composition having a sufficient effect in improving the resolution and the peeling property of the photoresist is obtained by using a binder polymer having a specific structure, so that the present invention has been completed. In other words, the present invention is a photosensitive resin composition containing (A) a divalent group represented by the following general formula (1), a divalent group represented by the following general formula (Π), and A divalent group represented by the general formula (III), a divalent group binder polymer represented by the following general formula (IV), (B) a photopolymerizable compound, and (C) a photopolymerization initiator. [Chemical Formula 1]
[化學式2] [化學式3][Chemical Formula 2] [Chemical Formula 3]
OH («0 201224656 [化學式4] R®OH («0 201224656 [Chemical Formula 4] R®
在此’式（I )、式（II )、式（III )及式（IV )中 ’ R1、R3、R5及R6係各自獨立表示氫原子或甲基，R2及 R4係各自獨立表示碳數1〜3之烷基、碳數1〜3之烷氧基 、OH基或鹵原子，R7係表示碳數1〜6之烷基，„!或„係 各自獨立表示0〜5的整數，m或η爲2〜5時，多個之R2 或R4彼此可相同或不同。 本發明人們係認爲：本發明之感光性樹脂組成物，藉 由使用例如前述（Α)成分之特定構造之黏合劑聚合物， 而在前述解析度及光阻剝離特性之提升，得到充分之效果 。此外’本發明之感光性樹脂組成物係藉由含有前述（A )〜（C)成分而具有良好之感度。 此外’本發明之感光性樹脂組成物係（A )黏合劑聚 合物在總量1 00質量份之該（A )黏合劑聚合物中，該一 般式（I)所示之2價基具有10〜60質量份，該一般式 (Π)所示之2價基具有10〜60質量份，該一般式（III )所示之2價基具有20〜50質量份，該一般式（IV)所 示之2價基具有1質量份以上未達15質量份。藉此而還 更加提高感光性樹脂組成物之解析度及光阻剝離特性。 此外，本發明之感光性樹脂組成物係最好是（C )光 聚合引發劑具有六芳基聯二咪唑化合物。藉此而提高感光 性樹脂組成物之感度及光阻之密合性。 -9 - 201224656 此外，本發明之感光性樹脂組成物係最好是尙含有（ D)增感色素。可以藉此而在以特定之波長範圍內具有波 峰之光來進行曝光之狀態下，於其特定之波長範圍附近， 造成極大吸收，提高感光性樹脂組成物之感度。 此外，本發明之感光性樹脂組成物係最好是尙含有（ E )胺系化合物。藉此而還更加地提高感光性樹脂組成物 之感度。 此外，本發明係一種感光性元件，具備：支持薄膜及 形成於該支持薄膜上之含有前述感光性樹脂組成物的感光 性樹脂組成物層。如果藉由該支持薄膜的話，則具備含有 前述感光性樹脂組成物的感光性樹脂組成物層，因此，即 使是在藉由直接描繪曝光法而形成光阻圖型之狀態下，也 能夠以充分之解析度來進行。此外，也在光阻剝離特性之 提升，具有充分之效果。 此外，本發明係一種光阻圖型之形成方法，具有：在 電路形成用基板上層合含有前述感光性樹脂組成物之感光 性樹脂組成物層的層合步驟，對於感光性樹脂組成物層之 所定部位照射活性光線，使曝光部光硬化之曝光步驟，及 由被層合感光性樹脂組成物層之電路形成用基板，除去感 光性樹脂組成物層之曝光部以外之部分的顯像步驟。如果 藉由該光阻圖型之形成方法的話，則使用含有前述感光性 樹脂組成物之感光性樹脂組成物層而形成光阻圖型，因此 ，即使是藉由曝光時間短之直接描繪曝光法，也可以形成 充分解析度之光阻圖型。此外，也在光阻剝離特性之提升 -10- 201224656 ，具有充分之效果。 此外，本發明係一種印刷電路板之製造方法，具有： 對藉由前述光阻圖型之形成方法，形成光阻圖型之電路形 成用基板進行蝕刻或鑛敷，形成導體圖型的步驟。如果藉 由該印刷電路板之製造方法的話，則使用藉由前述光阻圖 型之形成方法來形成光阻圖型之電路形成用基板，因此’ 可以製造能夠形成高密度之配線同時充分地抑制斷線及短 路的印刷電路板。 [發明之效果] 如果藉由本發明的話，則可以提供一種在解析度及光 阻剝離特性之提升來具有充分之效果的感光性樹脂組成物 、感光性元件、光阻圖型之形成方法及印刷電路板之製造 方法。 【實施方式】 [發明之最佳實施形態] 在以下，就本發明之理想之實施形態而詳細地進行說 明。此外，在本發明，所謂（甲基）丙烯酸係表示丙烯酸 或甲基丙烯酸，所謂（甲基）丙烯酸酯係表示丙烯酸酯或 者是對應於該丙烯酸酯之甲基丙烯酸酯，所謂（甲基）丙 烯醯基係表示丙烯醯基或甲基丙烯醯基 本發明之感光性樹脂組成物係含有：（A )具有前述 一般式（I)所示之2價基（在以下也稱爲「構造單位」 -11 - 201224656 )、前述一般式（II)所示之2價基、前述 所示之2價基、前述一般式（IV)所示之2 聚合物、（B )光聚合性化合物、及（C )光 首先，就成爲（A)成分之黏合劑聚合 〇 (.A)黏合劑聚合物係在前述一般式（ 表示氫原子或甲基，R2係表示碳數1〜3之 〜3之烷氧基、〇H基或鹵原子，m係表示 作爲賦予一般式（I)所示之構造單位之聚 舉苯乙烯或苯乙烯衍生物。此外，在本發明 烯衍生物」係指以取代基（烷基等之有機基 來取代苯乙烯之氫原子。作爲苯乙烯衍生 α -甲基苯乙烯等。 此外’在前述一般式（II)中，R3係表 基，R4係表示碳數1〜3之烷基、碳數1〜 ΟΗ基或鹵原子，m係表示〇〜5的整數。作 (Π )所示之構造單位之聚合性單體係列舉 酸节醋或（甲基）丙烯酸苄基衍生物。作爲 酸节基衍生物係列舉例如（甲基）丙烯酸4-此外’在前述一般式（ΠΙ )中，R5係 甲基。作爲賦予一般式（111)所示之構造單 體係列舉（甲基）丙烯酸。 此外’在前述一般式（IV)中，R6係各 原子或甲基，R7係表示碳數丨〜6之烷基， —般式（III ) 價基的黏合劑 聚合引發劑。 物而進行說明 I )中，R1係 .烷基、碳數1 〇〜5的整數。 合性單體係列 ，所謂「苯乙 或鹵原子等） 物係列舉例如 示氫原子或甲 3之烷氧基、 爲賦予一般式 (甲基）丙烯 (甲基）丙烯 甲基苄基等。 表不氫原子或 位之聚合性單 自獨立表示氫 m或η係各自 -12- 201224656 獨立表示碳數0〜5的整數。由能夠縮短剝離時間以及能 夠提高解析度之觀點來看的話’則R7係最好是碳數1〜4 之烷基、更加理想是碳數1之烷基（甲基）。作爲賦予一 般式（IV )所示之構造單位之聚合性單體係列舉（甲基） 丙烯酸烷酯。 作爲（甲基）丙烯酸烷酯係列舉例如下述一般式（V )所示之化合物等。 CH2 = C ( R8 ) -COOR9 ( V ) 在此，在前述一般式（V)中，R8係表示氫原子或甲 基，R9係表示碳數1〜6之烷基。此外，作爲R9所示之碳 數1〜6之烷基係列舉例如甲基、乙基、丙基、丁基、戊 基、己基、以及這些之構造異性體。作爲前述一般式（V )所示之聚合性單體係列舉例如（甲基）丙烯酸甲基酯、 (甲基）丙烯酸乙基酯、（甲基）丙烯酸丙基酯、（甲基 )丙烯酸丁基酯、（甲基）丙烯酸戊基酯、（甲基）丙烯 酸己基酯等。這些聚合性單體係單獨或者是組合2種以上 而進行使用。 在成爲（A)成分之黏合劑聚合物，前述一般式（I )所示之構造單位之含有比例係最好是相對於（A)成分 之總量1 0 0質量份而成爲1 0〜6 0質量份、更加理想是15 〜55質量份、甚至最好是20〜50質量份、特別最好是20 〜40質量份。可以藉此而使得含有感光性樹脂組成物之感 -13- 201224656 光性樹脂組成物層對於電路形成用基板之密合性以及 剝離特性皆良好。 此外，前述一般式（Π)所示之構造單位之含有 係最好是相對於（A)成分之總量100質量份而成爲 60質量份、更加理想是15〜55質量份、甚至最好是 50質量份、特別最好是25〜45質量份。可以藉此而 含有感光性樹脂組成物之感光性樹脂組成物層對於電 成用基板之密合性以及光阻剝離特性皆良好。 此外，前述一般式（III)所示之構造單位之含有 係最好是相對於（A )成分之總量1 00質量份而成爲 60質量份、更加理想是1 5〜50質量份、甚至最好是 40質量份、特別最好是25〜35質量份。可以藉此而 光阻剝離特性以及顯像性皆良好。 此外，前述一般式（IV)所示之構造單位之含有 係最好是相對於（A)成分之總量100質量份而成爲 量份以上未達1 5質量份、更加理想是2〜1 3質量份 至最好是4〜1 2質量份、特別最好是5〜1 0質量份。 藉此而使得含有感光性樹脂組成物之感光性樹脂組成 對於電路形成用基板之密合性以及光阻剝離特性皆良i 此外，在成爲（A)成分之黏合劑聚合物，前述 式（I)所示之構造單位和前述一般式（II)所示之 單位之含有比例係各自在未達1 〇質量份，有解析度 之傾向發生，在各自超過60質量份時’有剝離片變 剝離時間變長之傾向發生。此外，前述一般式（I〗1 ) 光阻 比例 1 0〜 20〜 使得 路形 比例 1 0〜 20〜 使得 比例 1質 、甚 可以 物層 f。 -般 構造 變差 大而 所示 -14- 201224656 之構造單位之含有比例係在未達10質量份，有鹼溶解性 變差同時剝離片變大而剝離時間變長之傾向發生，在超過 60質量份時，有降低解析度之傾向發生。此外，前述一般 式（IV )所示之構造單位之含有比例係在未達1質量份， 有降低剝離性之傾向發生，在1 5質量份以上，有降低解 析度之傾向發生。 在使用該黏合劑聚合物而調製感光性樹脂組成物之狀 態下，可以單獨使用1種黏合劑聚合物，也可以任意地組 合2種以上之黏合劑聚合物而進行使用。作爲組合2種以 上而進行使用之狀態下之黏合劑聚合物係列舉例如由不同 之共聚物成分所構成之2種以上（包含不同之重複單位來 作爲構成成分）之黏合劑聚合物、不同之重量平均分子量 之2種以上之黏合劑聚合物、不同之分散度之2種以上之 黏合劑聚合物等。此外，也可以使用日本特開平 π -3 27 1 37號公報所記載之具有多重模式分子量分布之聚合物 〇 (A)黏合劑聚合物之重量平均分子量（Mw)及數平 均分子量（Μη)係可以藉由凝膠滲透色譜法（GPC )而進 行測定（藉由使用標準聚苯乙烯之檢量線所造成之換算） 。如果藉由該測定法的話，則黏合劑聚合物之Mw係最好 是5000〜150000、更加理想是10000〜100000、特別最好 是20000〜50000。在Mw未達5000，有降低耐顯像液性 之傾向發生，在超過150000時，有顯像時間變長之傾向 發生。 -15- 201224656 此外，（A )黏合劑聚合物之分散度（Mw/ Μη )係 最好是〗·〇〜3.0、更加理想是1.0〜2.0。在分散度超過 3.0時，有降低密合性及解析度之傾向發生。 此外’可以在（A )黏合劑聚合物，倂用例如苯乙烯 系樹脂、環氧系樹脂、醯胺系樹脂、醯胺環氧系樹脂、醇 酸系樹脂、苯酚系樹脂等。此外，這些樹脂係單獨使用或 者是組合2種以上而使用。 本發明之黏合劑聚合物係例如能夠以常法，來對於聚 合性單體，進行自由基聚合而製造。 前述之（A)黏合> 劑聚合物係可以包含前述一般式（ I )〜（IV )所示之構造單位以外之構造單位。前述之（ A)黏合劑聚合物係最佳理想是僅具有前述一般式（I) 〜（IV)所示之構造單位，但是，在不妨礙本發明目的之 程度下，可以相對於（A)成分之總量而具有這個以外之 構造單位1〜10質量份程度。在該狀態下，作爲賦予前述 一般式（I )〜（IV )所示之構造單位以外之構造單位之 聚合性單體係列舉例如（甲基）丙烯酸庚基酯、（甲基） 丙烯酸辛基酯、（甲基）丙烯酸2-乙基己基酯、（甲基） 丙烯酸壬基酯、（甲基）丙烯酸癸基酯、（甲基）丙烯酸 十一烷基酯、（甲基）丙烯酸十二烷基酯、2-羥基乙酯、 2-羥基丙酯、3-羥基丙酯、4-羥基丁酯、二丙酮丙烯醯胺 等之丙烯醯胺、丙烯腈、乙烯基-η-丁基醚等之乙烯醇之酯 類、（甲基）丙烯酸四氫化糠基酯、（甲基）丙烯酸二甲 胺基乙基酯 '(甲基）丙烯酸二乙胺基乙基酯、（甲基） -16- 201224656 丙烯酸環氧丙基酯、2,2,2-三氟乙基（甲基）丙烯酸酯、 2,2,3,3-四氟丙基（甲基）丙烯酸酯、（甲基）丙烯酸、 溴（甲基）丙烯酸、α -氯（甲基）丙烯酸、々_呋喃基 (甲基）丙烯酸、/3-苯乙烯基（甲基）丙烯酸 '順丁烯 二酸、順丁烯二酸酐、順丁烯二酸單甲酯、順丁烯二酸單 乙酯、順丁烯二酸單異丙酯等之順丁烯二酸單酯、富馬酸 、肉桂酸、〇：-氰基肉桂酸、衣康酸、巴豆酸、丙炔酸等 。這些單體係單獨使用或者是組合2種以上而使用。 由使用鹼溶液而進行鹼顯像之狀態下之顯像性之觀點 來看的話，則本發明之（A )黏合劑聚合物係最好是由具 有羧基之聚合物之1種或2種以上所構成。此種（A)黏 合劑聚合物係例如能夠藉由以常法，來對於（甲基）丙烯 酸其他之具有羧基之聚合性單體和這個以外之聚合性單體 ，進行自由基聚合而製造》 (A)黏合劑聚合物之酸價係最好是80〜250mgKOH /g、更加理想是100〜220mgKOH/g、特別最好是150〜 210mgKOH/g。在該酸價未達80mgKOH/ g，有顯像時間 變長之傾向發生，在超過2 5 0mgK〇H/g時，有降低光硬 化之光阻之耐顯像液性之傾向發生。此外，在進行溶劑顯 像來作爲顯像步驟之狀態下，最好是調製少量之具有羧基 之聚合性單體。 此外，（A )黏合劑聚合物係可以配合於需要而使得 具感光性之特性基，具備在其分子內。 (A )成分之黏合劑聚合物之練合量係相對於（A ) -17- 201224656 成分及（B)成分之總量loo質量份而最好是3〇〜7〇質量 份、更加理想是35〜65質量份、特別最好是40〜60質量 份。在該練合量未達3 0質量份’有無法得到良好形狀之 傾向發生’在超過70質量份時，有無法得到良好感度或 解析度之傾向發生。成爲（A)成分之黏合劑聚合物係單 獨使用1種或者是組合2種以上而使用。 接著，就成爲（B)成分之光聚合性化合物而進行說 明。 成爲（B )成分之光聚合性化合物係列舉例如在多元 醇反應α ,沒-不飽和羧酸所得到之化合物、雙酚a系二（ 甲基）丙烯酸酯化合物、在含環氧丙基化合物反應α>/5-不飽和羧酸所得到之化合物、在分子內具有胺基甲酸乙酯 鍵之（甲基）丙烯酸酯化合物等之胺基甲酸乙酯單體、壬 基苯氧基聚乙烯氧化丙烯酸酯（也稱爲「壬基苯氧基聚乙 二醇丙烯酸酯」）、苯二甲酸系化合物、（甲基）丙烯酸 烷基酯等。這些化合物係單獨使用或者是組合2種以上而 使用。 前述之在多元醇反應α，^ -不飽和羧酸所得到之化合 物係列舉例如乙烯基數成爲2〜1 4之聚乙二醇二（甲基） 丙烯酸酯、丙烯基數成爲2〜14之聚丙二醇二（甲基）丙 烯酸酯、三羥甲基丙烷二（甲基）丙烯酸酯、三羥甲基丙 烷三（甲基）丙烯酸酯、ΕΟ變性三羥甲基丙烷三（甲基 )丙烯酸酯、ΡΟ變性三羥甲基丙烷三（甲基）丙烯酸酯 、Ε0，Ρ0變性三羥甲基丙烷三（甲基）丙烯酸酯、四羥甲 -18- 201224656 基甲烷三（甲基）丙烯酸酯、四羥甲基甲烜 烯酸酯、二季戊四醇五（甲基）丙烯酸酯、 (甲基）丙烯酸酯等。這些化合物係單獨使 2種以上而使用。在此，所謂「E 0」係表示 EO變性之化合物係表示具有乙烯氧化物基 此外，所謂「PO」係表示丙烯氧化物，PO 係表示具有丙烯氧化物基之嵌段構造。 前述雙酚A系二（甲基）丙烯酸酯化合 2.2- 雙（4-((甲基）丙烯氧化聚乙氧基） 2.2- 雙（4-((甲基）丙烯氧化聚丙氧基） 2.2- 雙（4-((甲基）丙烯氧化聚丁氧基） 2.2- 雙（4-((甲基）丙烯氧化聚乙氧基聚 )丙烷等。作爲前述2,2-雙（4-((甲基） 氧基）苯基）丙烷係列舉例如2,2-雙（4_ ( 氧化二乙氧基）苯基）丙烷、2,2-雙（4-( 氧化三乙氧基）苯基）丙烷、2,2-雙（4-( 氧化四乙氧基）苯基）丙烷' 2,2-雙（4-( 氧化五乙氧基）苯基）丙烷、2,2-雙（4-( 氧化六乙氧基）苯基）丙烷、2,2_雙（4-( 氧化七乙氧基）苯基）丙烷、2,2-雙（4-( 氧化八乙氧基）苯基）丙烷、2,2-雙（4-( 氧化九乙氧基）苯基）丙烷、2，2-雙（4-( 氧化十乙氧基）苯基）丙烷、2,2-雙（4-( 氧化十一乙氧基）苯基）丙烷、2,2-雙（4_ 四（甲基）丙 二季戊四醇六 用或者是組合 乙烯氧化物， 之嵌段構造。 變性之化合物 物係列舉例如 苯基）丙烷、 苯基）丙烷、 苯基）丙烷、 丙氧基）苯基 丙烯氧化聚乙 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 (甲基）丙烯 ((甲基）丙 -19- 201224656 烯氧化十二乙氧基）苯基）丙烷、2，2-雙（4-((甲 丙烯氧化十三乙氧基）苯基）丙烷、2,2-雙（4·(( )丙烯氧化十四乙氧基）苯基）丙烷、2,2-雙（4-( 基）丙烯氧化十五乙氧基）苯基）丙烷、2,2-雙（4. 甲基）丙烯氧化十六乙氧基）苯基）丙烷等。 2,2-雙（4-(甲基丙烯氧化五乙氧基）苯基）丙 在商業可得到之ΒΡΕ-500 (新中村化學工業（股）公 、商品名稱）或FA-321MC日立化成工業（股）公司 商品名稱），2,2-雙（4-(甲基丙烯氧化十五乙氧基 基）丙烷係在商業可得到之ΒΡΕ- 1 300 (新中村化學 (股）公司製、商品名稱）。2,2-雙（4-((甲基） 氧化聚乙氧基）苯基）丙烷之1分子內之乙烯氧化物 係最好是4〜2 0、更加理想是8〜1 5。這些化合物係 使用或者是組合2種以上而使用。 在分子內具有胺基甲酸乙酯鍵之（甲基）丙烯酸 合物係列舉例如在Θ位具有ΟΗ基之（甲基）丙烯單 二異氰酸酯化合物（異氰酸酯二異氰酸酯、2,6-甲苯 氰酸酯、2,4-甲苯二異氰酸酯、1，6-六亞甲基二異氰 等）之加成反應物、三（（甲基）丙烯氧化四乙二醇 酸酯）六亞甲基異氰酸酯、ΕΟ變性胺基甲酸乙酯二 基）丙烯酸酯、ΕΟ,ΡΟ變性胺基甲酸乙酯二（甲基） 酸酯等。作爲ΕΟ變性胺基甲酸乙酯二（甲基）丙烯 係列舉例如UA-1 1 (新中村化學工業（股）公司製、 名稱）。此外，作爲前述ΕΟ,ΡΟ變性胺基甲酸乙酯二 基） 甲基 (甲 院係 司製 製、 )苯 工業 丙烯 基數 單獨 酯化 體和 二異 酸酯 異氰 (甲 丙烯 酸酯 商品 (甲 -20- 201224656 基）丙烯酸酯係列舉例如uA-1 3 (新中村化學工業（股） 公司製、商品名稱）。這些化合物係單獨使用或者是組合 2種以上而使用。 壬基苯氧基聚乙烯氧化丙烯酸酯係列舉例如壬基苯氧 基四乙烯氧化丙烯酸酯、壬基苯氧基五乙烯氧化丙烯酸酯 、壬基苯氧基六乙嫌氧化丙稀酸酯、壬基苯氧基七乙稀氧 化丙烯酸酯、壬基苯氧基八乙烯氧化丙烯酸酯、壬基苯氧 基九乙烯氧化丙烯酸酯、壬基苯氧基十乙烯氧化丙烯酸酯 、壬基苯氧基十一乙烯氧化丙烯酸酯。壬基苯氧基八乙烯 氧化丙烯酸酯係列舉例如M_114(東亞合成（股）公司製 、商品名稱）。這些化合物係單獨使用或者是組合2種以 上而使用。 前述苯二甲酸系化合物係列舉例如r -氯- yS-羥丙基-/3，-(甲基）丙烯醯基氧化乙基鄰苯二甲酸酯 '沒-羥 基院基-点’_(甲基）丙烯醯基氧化乙基鄰苯二甲酸酯 等。這些化合物係單獨使用或者是組合2種以上而使用。 此外，由能夠提高硬化膜之可彎曲性之觀點來看的話 ，則最好是在本發明之（Β)成分’將在分子內具有乙二 醇鍵及丙二醇鍵兩者之聚亞院基乙一醇一（甲基）丙稀酸 醋予以包含。該（甲基）丙烯酸酯係如果是具有乙二醇鏈 及丙二醇鏈（η -丙二醇鏈或異丙二醇鏈）兩者來作爲分子 內之亞烷基乙二醇鏈的話’則並無特別限制。此外’該（ 甲基）丙儲酸醋係可以還具有η-丁二醇鏈、異丁二醇鏈、 η -戊二醇鏈、己二醇鏈、成爲這些之構造異性體等之碳數 -21 - 201224656 4〜6程度之亞烷基乙二醇鏈。 在前述乙二醇鏈及丙二醇鏈成爲多個之狀態下，多個 之乙二醇鏈及丙二醇鏈係可以各自連續呈嵌段地存在，也 可以隨機地存在。此外，在前述異丙二醇鏈，丙基之2級 碳可以鍵結於氧原子，1級碳也可以鍵結於氧原子。 在這些（B)成分中之具有至少一個可聚合之乙烯性 不飽和鍵且在分子內具有乙二醇鏈及丙二醇鏈兩者的聚亞 烷基乙二醇二（甲基）丙烯酸酯係列舉例如下列一般式（ VI )： [化學式5] 〇 0 H2C=|~"~〇"tE〇ttP〇^E〇t"~|=CHi (V,) R10 R11 所示之化合物、下列一般式（VI ): [化學式6] ο 〇 H2C=?_i_0 十 〇ME〇^P〇y—?=CH2 R12 R13 所示之化合物、以及下列一般式（VII ) [化學式7] (VIII) H2C=C—C—O—^EO^-Poj-^-C—C=CH RM Π R'5 所示之化合物等。在此，式（VI )、式（VII )及式 (VIII)中，R10、R11、R12、R13、R"及 Rl5 係各自獨立 表示氫原子或碳數1〜3之院基，E0係表示乙二醇鏈，P0 係表示丙二醇鏈’m1〜m4及η1〜η4係各自獨立表示ι〜 -22- 201224656 30的整數。這些化合物係單獨使用或者是組合2種以上而 使用。 作爲前述一般式（VI)〜（VIII)之碳數1〜3之烷 基係列舉例如甲基、乙基、η-丙基、i-丙基。 此外，前述一般式（VI)〜（VIII)之乙二醇鏈之重 複數之總數（n^+m2、m3及m4)係1〜30的整數、最好 是1〜10的整數、更加理想是4〜9的整數 '特別最好是5 〜8的整數。在該重複數超過30時，有傘形可靠性及光阻 形狀惡化之傾向發生。 此外，前述一般式（VI)〜（VIII)之丙二醇鏈之重 複數之總數（η1、η2 + η3及η4)係1〜30的整數 '最好是 5〜20的整數、更加理想是8〜16的整數、特別最好是10 〜14的整數。在該重複數超過30時，有解析度惡化而產 生漿體之傾向發生。 作爲前述一般式（VI )所示之化合物之具體例係列舉 例如成爲RMsR11:甲基、11^+1^=4(平均値）'η1: 12(平均値）之乙烯基化合物（日立化成工業（股）公司 製、商品名稱：FA-OUM)等。此外，作爲前述一般式（ VII)所示之化合物之具體例係列舉例如成爲R12=R13 = 甲基、m3=6 (平均値）、n2+n3 = 12 (平均値）之乙稀 基化合物（日立化成工業（股）公司製、商品名稱：FA-024M )等。此外，作爲前述一般式（VIII )所示之化合物 之具體例係列舉例如成爲R14 = R15 =氫原子、m4 = 1 (平 均値）、η4 = 9 (平均値）之乙烯基化合物（新中村化學 -23- 201224656 工業（股）公司製、樣本名稱：NK酯HEMA-9P)等。這 些化合物係單獨使用或者是組合2種以上而使用。 作爲（B )成分之光聚合性化合物之練合量係最好是 相對於（A)成分及（B)成分之總量100質量份而成爲 30〜70質量份、更加理想是35〜65質量份、特別最好是 40〜6 0質量份。在該練合量未達30質量份，有無法得到 良好之感度或解析度之傾向發生，在超過70質量份時， 有無法得到良好之形狀之傾向發生。 成爲（B)成分之光聚合性化合物係單獨使用1種或 者是組合2種以上而使用。由提高耐鍍敷性及密合性之觀 點來看的話，則該光聚合性化合物係最好是包含雙酚A系 (甲基）丙烯酸酯化合物或者是在分子內具有胺基甲酸乙 酯鍵之（甲基）丙烯酸酯化合物。此外，由提高感度及解 析度之觀點來看的話，則最好是包含雙酚A系（甲基）丙 烯酸酯化合物。 此外，由光阻之剝離片之尺寸變小而縮短剝離時間之 觀點來看的話，則成爲（B )成分之光聚合性化合物係最 好是包含在分子內具有一個可聚合之乙烯性不飽和鍵之光 聚合性不飽和化合物，更加理想是組合在分子內具有一個 可聚合之乙烯性不飽和鍵之光聚合性不飽和化合物和在分 子內具有二個以上之可聚合之乙烯性不飽和鍵之光聚合性 不飽和化合物而進行使用。在該狀態下，例如作爲在分子 內具有一個可聚合之乙烯性不飽和鍵之光聚合性不飽和化 合物係列舉苯氧基聚乙烯氧化（甲基）丙烯酸酯、苯氧基 -24 - 201224656 聚乙烯氧化-聚丙烯氧化（甲基）丙烯酸酯、辛基苯氧基 六乙烯氧化（甲基）丙烯酸酯、辛基苯氧基七乙烯氧化（ 甲基）丙烯酸酯、辛基苯氧基八乙烯氧化（甲基）丙烯酸 酯、辛基苯氧基九乙烯氧化（甲基）丙烯酸酯、辛基苯氧 基十乙烯氧化（甲基）丙烯酸酯、壬基苯氧基聚乙烯氧化 (甲基）丙烯酸酯、壬基苯氧基聚乙烯氧化-聚丙烯氧化 (甲基）丙烯酸酯以及具有（甲基）丙烯基之苯二甲酸衍 生物等。此外，作爲在分子內具有二個以上之可聚合之乙 烯性不飽和鍵之光聚合性不飽和化合物係列舉〗，6-己烷二 元醇二（甲基）丙烯酸酯、1,4-環己烷二元醇二（甲基） 丙烯酸酯、乙烯基數成爲2〜14之聚乙二醇二（甲基）丙 烯酸酯、丙烯基數成爲2〜14之聚丙二醇二（甲基）丙烯 酸酯、前述一般式（VI)〜（VIII)之聚乙烯•聚丙二醇 二（甲基）丙烯酸酯、雙酚A系二（甲基）丙烯酸酯、在 分子內具有胺基甲酸乙酯鍵之二（甲基）丙烯酸酯、雙（ 丙烯氧化乙基）羥乙基異氰酸酯、雙酚A二環氧丙基醚二 (甲基）丙烯酸酯、苯二甲酸環氧丙基酯之（甲基）丙烯 酸加成物等。 此外，由能夠呈平衡良好地提高解析度、剝離時間及 曝光餘地之觀點來看的話，則特別最好是組合1種之在分 子內具有一個可聚合之乙烯性不飽和鍵之光聚合性不飽和 化合物和2種之在分子內具有二個以上之可聚合之乙烯性 不飽和鍵之光聚合性不飽和化合物而進行使用。在該狀態 下，作爲在分子內具有一個可聚合之乙烯性不飽和鍵之光 -25- 201224656 聚合性不飽和化合物係可以使用例如苯氧基聚乙烯氧化（ 甲基）丙烯酸酯、壬基苯氧基聚乙烯氧化（甲基）丙烯酸 酯以及具有（甲基）丙烯基之苯二甲酸衍生物之任何一種 。此外’作爲在分子內具有二個以上之可聚合之乙烯性不 飽和鍵之光聚合性不飽和化合物係可以組合例如由前述一 般式（VI)〜（VIII)之聚乙烯•聚丙二醇二（甲基）丙 烯酸酯、EO變性胺基甲酸乙酯二（甲基）丙烯酸酯及 EO，PO變性胺基甲酸乙酯二（甲基）丙烯酸酯所選出之至 少一種化合物和雙酧A系二（甲基）丙嫌酸酯而進行使用 〇 接著，就成爲（C)成分之光聚合引發劑而進行說明 〇 成爲（C)成分之光聚合引發劑係列舉例如4,4’-雙（ 二乙基胺基）二苯甲酮、二苯甲酮、2-苄基-2-二甲基胺 基-1- ( 4-嗎啉代苯基）-丁酮-1，2-甲基-1-[4-(甲基硫代） 苯基]-2·嗎啉代-丙酮-1等之芳香族酮、烷基蒽醌等之醌類 、苯偶因烷基醚等之苯偶因醚化合物、苯偶因、烷基苯偶 因等之苯偶因化合物、苄基二甲基酮縮醇等之苄基衍生物 、2-(〇-氯苯基）-4,5-二苯基咪唑二聚物、2-(〇-氯苯基 )-4,5-二（甲氧基苯基）咪唑二聚物、2-(〇-氟苯基）-4,5-二苯基咪唑二聚物、2-(〇-甲氧基苯基）-4,5-二苯基 咪唑二聚物、2- (p-甲氧基苯基）-4,5-二苯基咪唑二聚物 等之 2,4,5-三芳基咪唑二聚物、9-苯基吖啶、1,7-雙（ 9,9’-吖啶基）庚烷等之吖啶衍生物等。 -26- 201224656 此外，在前述 2,4,5 -三芳基咪唑二聚物，2個之 2,4,5-三芳基咪唑之芳基之取代基係可以賦予相同之對象 化合物’並且’也可以賦不同之非對稱化合物。此外，由 密合性及感度之觀點來看的話，則光聚合引發劑係最好是 使用成爲2，4,5 -三芳基咪唑二聚物之六芳基二咪唑化合物 。 這些光聚合引發劑係單獨或者是組合2種以上而進行 使用。 此外，成爲（C)成分之光聚合引發劑之練合量係最 好是相對於（A )成分及（B )成分之總量1 00質量份而成 爲0· 1〜1 0質量份、更加理想是2〜6質量份、特別最好 是3.5〜5質量份。在該練合量未達0.1質量份，有不容易 得到良好之感度或解析度之傾向發生，在超過1 0質量份 時，有無法得到正如要求之良好形狀之光阻圖型之傾向發 生。成爲（C)成分之光聚合性化合物係單獨使用1種或 者是組合2種以上而使用。 本發明之感光性樹脂組成物係最好是除了前述（A) 〜（C)成分以外，還含有（D)增感色素及/或（E)胺 系化合物。 成爲本發明之（D )成分之增感色素係能夠有效地利 用曝光所採用之活性光線之吸收波長，最好是極大吸收波 長3 70〜420nm之化合物。在本發明，可以藉由使用此種 增感色素而對於直接描繪曝光法之曝光用光，具有充分高 之感度。在增感色素之極大吸收波長未達3 70nm時，有降 低對於直接描繪曝光用光之感度之傾向發生，在超過 ：*( -27- 201224656 42 Onm時，即使是在黃光環境下，也有降低穩定性之傾向 發生。 作爲增感色素係列舉例如吡唑啉類、蒽類、香豆素類 、咕噸酮類、噁唑類、苯并噁唑類、噻唑類、苯并噻唑類 、三唑類、芪類、三嗪類、噻吩類、萘二甲醯亞胺類等。 由能夠提高解析度、密合性及感度之觀點來看的話，則增 感色素係最好是包含蒽類。此外，增感色素之練合量係最 好是相對於（A)成分及（B)成分之總量100質量份而成 爲0.01〜10質量份、更加理想是0.05〜5質量份、特別最 好是〇」〜2質量份。在該練合量未達0.01質量份，有無 法得到良好之感度或解析度之傾向發生，在超過10質量 份時，有無法得到正如要求之良好形狀之光阻圖型之傾向 發生。成爲（D)成分之增感色素係單獨使用1種或者是 組合2種以上而使用。 作爲成爲（E )成分之胺系化合物係如果是能夠提高 感光性樹脂組成物之感度且在分子內具有胺基之物的話， 則並無特別限定。作爲其具體例係列舉例如雙[4-(二甲基 胺基）苯基]甲烷、雙[4-(二乙基胺基）苯基]甲烷、白結 晶紫等。胺系化合物之練合量係最好是相對於（A )成分 及（B)成分之總量100質量份而成爲0.01〜10質量份、 更加理想是0.05〜5質量份、特別最好是0.1〜2質量份。 在該練合量未達0.01質量份，有無法得到良好之感度之 傾向發生，在超過10質量份時，在形成薄膜後，有（E) 成分容易析出而成爲異物之傾向發生。成爲（E)成分之 -28- 201224656 胺系化合物係單獨使用1種或者是組合2種以上而1 可以在本發明之感光性樹脂組成物，配合於需 對於（A)成分及（B)成分之總量1〇〇質量份，各 0.01〜20質量份程度之在分子內具有至少一個之可 聚合之環狀醚基之光聚合性化合物（氧雜環丁烷化 )、陽離子聚合引發劑、孔雀綠等之染料、三溴苯 白結晶紫等之光發色劑、熱發色防止劑、p-甲苯楓 之可塑劑、顏料、塡充劑、消泡劑、難燃劑、安定 合性賦予劑、平坦劑、剝離促進劑、氧化防止劑、 圖型化劑、熱交聯劑等。這些係單獨使用或者是組· 以上而使用。 此外，本發明之感光性樹脂組成物係可以溶解 、乙醇、丙酮、甲基乙基甲酮、甲基乙二醇乙醚、 二醇乙醚、甲苯、Ν,Ν-二甲基甲醯胺、丙二醇單甲 之溶劑或者是這些之混合溶劑而成爲固態成分3 0 -量％程度之溶液。可以使用該溶液，來作爲用以形 性元件之感光性樹脂組成物層之塗佈液。 此外，前述之塗佈液係除了用以形成感光性元 光性樹脂組成物層以外，例如也可以在金屬板之表 佈成爲液體狀光阻而進行乾燥後，被覆保護薄膜， 使用。作爲金屬板之材質係列舉例如銅、銅系合金 鉻、鐵、不鏽鋼等之鐵系合金、最好是銅、銅系合 系合金等。 接著，就本發明之感光性元件而進行說明。圖 吏用。 要而相 自含有 陽離子 合物等 基颯、 醯胺等 劑、密 香料、 会2種 於甲醇 乙基乙 基醚等 -60質 成感光 件之感 面上塗 來進行 、鎳、 金、鐵 1係顯 -29 - 201224656 示本發明之感光性元件之理想之一實施形態之示意剖面圖 。圖1所示之感光性元件1係藉由支持薄膜2、形成於支 持薄膜2上且含有前述感光性樹脂組成物之感光性樹脂組 成物層3和層合於感光性樹脂組成物層3上之保護薄膜4 所構成。 支持薄膜2係可以使用例如聚乙烯對苯二甲酸酯、聚 丙烯、聚乙烯、聚酯等之具有耐熱性及耐溶劑性之聚合物 薄膜。作爲市面販賣品係列舉例如王子製紙（股）公司製 Arufun MA-410、E-200C (在以上商品名稱）、信越薄膜 (股）公司製等之聚丙烯薄膜、帝人（股）公司製pS系 列（例如商品名稱：PS-25 )等之聚乙烯對苯二甲酸酯薄 膜等，但是，並非限定於此》 此外，支持薄膜2係厚度最好是1〜ΙΟΟμπι、更加理 想是5〜25 μιη。在該厚度未達Ιμιη，有在顯像前之支持薄 膜之剝離時而支持薄膜容易破裂之傾向發生，在超過 1 00 μιη時，有解析度降低之傾向發生。此外，支持薄膜2 係可以使用一個，來作爲感光性樹脂組成物層之支持體， 使用另外一個，來作爲感光性樹脂組成物之保護薄膜而層 合於感光性樹脂組成物層之兩面。 感光性樹脂組成物層3係最好是在前述感光性樹脂組 成物溶解於前述溶劑而成爲固態成分30〜60質量％程度 之溶液（塗佈液）之後，藉由該溶液塗佈於支持薄膜2上， 進行乾燥而形成感光性樹脂組成物層。塗佈係可以藉由例 如使用壓輥塗佈器、逗點塗佈器、照相凹版塗佈器、空氣 -30- 201224656 刀塗佈器、模塗佈器、桿條塗佈器等之習知方法而進行 乾燥係進行於70〜150 °C、5〜30分鐘程度。此外，由 面步驟之防止有機溶劑之擴散之方面來看的話，則感光 樹脂組成物中之殘留有機溶劑量係最好是2質量％以下 此外，感光性樹脂組成物層3之厚度係由於感光性 件之用途而不同，但是，在乾燥後之厚度，最好是1 ΙΟΟμιη、更加理想是1〜50μηι。在該厚度未達Ιμιη，有 佈困難於工業上之傾向發生，在超過ΙΟΟμηι時，有本發 之效果變小而降低接著力、解析度之傾向發生。 此外，感光性樹脂組成物層3係對於波長405 nm之 之透過率，最好是5〜75%、更加理想是7〜60%、特 最好是10〜40%。在該透過率未達5%，有密合性惡化 傾向發生，在超過75%時，有解析度惡化之傾向發生。 述透過率係可以藉由UV分光計而進行測定，作爲前 UV分光計係列舉日立製作所（股）公司製228A型W 分光光度計（商品名稱）等。 保護薄膜4係最好是感光性樹脂組成物層3及保護 膜4間之接著力，小於感光性樹脂組成物層3及支持薄 2間之接著力，並且，最好是低魚眼縮孔之薄膜。此外 所謂「魚眼縮孔」係熱熔融材料，在藉由混練、擠壓， 軸延伸、熔鑄法等而製造薄膜之際，材料之異物、未溶 物、氧化惡化物等，放入至薄膜中。 作爲保護薄膜4係可以使用例如聚乙烯對苯二甲酸 '聚丙烯、聚乙燃、聚醋等之具有耐熱性及耐溶劑性之 後 性 〇 元 塗 明 光 別 之 刖 述 束 薄 膜 解 酯 聚 -31 - 201224656 合物薄膜。作爲市面販賣品係列舉例如王子製紙（股）公 司製Arufun MA-410、E-200C (以上，商品名稱）、信越 薄膜（股）公司製等之聚丙烯薄膜、帝人（股）公司製 PS系列（例如商品名稱：PS-25 )等之聚乙烯對苯二甲酸 酯薄膜等，但是，並非限定於此。 保護薄膜4係厚度最好是1〜100 μπι、更加理想是5〜 50μιη、甚至最好是 5〜30μπι、特別最好是最好是15〜 3〇μηι。在該厚度未達Ιμιη，有在層壓之際而保護薄膜破裂 之傾向發生，在超過ΙΟΟμιη時，有廉價性變差之傾向發生 〇 此外，本發明之感光性元件1係可以還具有緩衝層、 接著層 '光吸收層、氣體障蔽層等之中間層等。此外，得 到之感光性元件1係成爲薄片狀或者是在捲芯來捲繞成爲 壓輥狀而進行保管。此外，在此時，最好是捲繞支持薄膜 1而成爲最外側。由端面保護之觀點來看的話，則最好是 在前述壓輥狀之感光性元件壓輥之端面，設置端面間隔件 ’由耐邊緣熔解性之觀點來看的話，則最好是設置防濕端 面間隔件。此外，作爲捆包方法係最好是包裝於透濕性小 之黑薄片而進行包裝。作爲前述捲芯係列舉例如聚乙烯樹 脂、聚丙烯樹脂、聚苯乙烯樹脂、聚氯乙烯樹脂、ABS樹 脂（丙烯腈-丁二烯-苯乙烯共聚物）等之塑膠等。 接著，就本發明之光阻圖型之形成方法而進行說明。 本發明之光阻圖型之形成方法係至少包含：在電路形 成用基板上層合含有前述感光性樹脂組成物之感光性樹脂 -32- 201224656 組成物層的層合步驟’對於感光性樹脂組成物層之所定部 位照射活性光線’使曝光部光硬化之曝光步驟，及由電路 形成用基板’除去曝光部以外之部分之感光性樹脂組成物 的顯像步驟。此外，所謂「電路形成用基板」係指具備絕 緣層和形成於絕緣層上之導體層的基板。此外，電路形成 用基板係可以在多層化之內部，形成配線，也可以具有小 直徑通孔。 作爲感光性樹脂組成物層來層合於層合步驟之電路形 成用基板上之層合方法係列舉以下之方法。首先，由感光 性樹脂組成物層開始逐漸地剝離保護薄膜，同時於這個而 使得逐漸露出之感光性樹脂組成物層之面部分，密合於形 成電路形成用基板之電路之面。接著，藉由加熱感光性樹 脂組成物層，同時，感光性樹脂組成物層壓接於電路形成 用基板，而進行層合。此外，由提高密合性及追蹤性之觀 點來看的話，則該作業係最好是在減壓下，進行層合。感 光性元件之層合係最好是感_光性樹脂組成物層及/或電路 形成用基板，加熱至70〜130 °C，壓接壓力係最好是〇-1 〜l.OMPa程度（1〜lOkgf/ cm2程度），但是，在這些條 件，並無特別限制。此外’如果正如前面敘述而加熱感光 性樹脂組成物層至70〜130°C的話’則不需要預先對於電 路形成用基板，進行預熱處理，但是’爲了更加地提高層 合性，因此，也可以進行電路形成用基板之預熱處理。 作爲曝光步驟之形成曝光部之方法係列舉通過稱爲原 圖之負型或正型遮罩圖型而照射活性光線於圖像上之方法 -33- 201224656 (遮罩曝光法）。在此時，在存在於感光性樹脂組成物層 上之支持薄膜透過活性光線之狀態下，能夠通過支持薄膜 而照射活性光線，在支持薄膜成爲遮光性之狀態下’在除 去支持薄膜之後，於感光性樹脂組成物層，照射活性光線 。此外，也可以採用藉由雷射直接描繪曝光法或dlp( Digital Light Processing:數位光製程）曝光法等之直接 描繪曝光法而呈圖像狀地照射活性光線之方法。 作爲活性光線之光源係使用習知之光源、例如碳電弧 燈、水銀蒸氣電弧燈、高壓水銀燈、氙燈、氬雷射等之氣 體雷射、YAG雷射等之固體雷射、半導體雷射等之有效地 放射紫外線、可見光等。 作爲顯像步驟之除去曝光部以外之部分之方法係列舉 首先在感光性樹脂組成物層上來存在支持薄膜之狀態下， 除去支持薄膜，然後，藉由濕式顯像、乾式顯像等而除去 曝光部以外之部分，進行顯像之方法。藉此而形成光阻圖 型。 例如在濕式顯像之狀態下，使用對應於鹼性水溶液、 水系顯像液、有機溶劑系顯像液等之感光性樹脂組成物之 顯像液，例如藉由浸漬方式、鬥爭方式、噴射方式、搖動 浸漬、刷擦、洗滌等之習知方法而進行顯像。顯像方式係 爲了提高解析度，因此1最適合爲高壓噴射方式。此外， 也可以配合於需要而倂用2種以上之顯像方法。 作爲顯像液係使用安全且穩定而操作性良好之鹼性水 溶液等。作爲前述鹼性水溶液之鹼係使用例如鋰、鈉或鉀 -34- 201224656 之氫氧化物等之氫氧化鹼、鋰、鈉、鉀或銨之碳酸鹽或者 是重碳酸鹽等之碳酸鉀、磷酸鉀、磷酸鈉等之鹼金屬磷酸 鹽、焦磷酸鈉、焦磷酸鉀等之鹼金屬焦磷酸鹽、硼砂等。 此外，作爲使用於顯像之前述鹼性水溶液係最好是 〇_1〜5質量％之碳酸鈉之稀薄熔液、0.1〜5質量％之碳酸 鉀之稀薄熔液、0.1〜5質量％之氫氧化鈉之稀薄熔液、 0.1〜5質量％之四硼酸鈉（硼砂）之稀薄熔液等。此外， 該鹼性水溶液之pH値係最好是9〜11之範圍，其溫度係 配合於感光性樹脂組成物層之顯像性而進行調整。此外， 可以在鹼性水溶液中，添加表面活性劑、消泡劑及用以促 進顯像之少量之有機溶劑等。 作爲前述水系顯像液係列舉由水或鹼水溶液和一種以 上之有機溶劑所構成之顯像液。在此，作爲鹼性水溶液之 鹼係除了先前敘述之物質以外，還列舉例如矽酸鈉、氫氧 化四甲基銨、乙醇胺、乙烯二胺、二乙烯三胺、2-胺基-2-羥甲基-1,3-丙烷二元醇、1，3-二胺基丙醇-2、嗎啉等。顯 像液之pH値係最好是在可以充分地進行光阻之顯像之範 圍內，儘可能地變小，最好是pH8〜12、更加理想是pH9 ^-10° 作爲前述有機溶劑係列舉例如丙酮、乙酸乙酯、具有 碳數1〜4之烷氧基之烷氧基乙醇、乙醇、異丙醇、丁醇 、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁 基醚等。這些係單獨使用或者是組合2種以上而使用。有 機溶劑之濃度係通常最好是2〜90質量％，其溫度係可以 -35- 201224656 配合於顯像性而進行調整。此外，也可以在水系顯像液φ ’添加少量之界面活性劑、消泡劑等。 此外，作爲單獨使用有機溶劑之有機溶劑系顯像液係、 列舉例如1 ,1，1 -三氯乙烷、Ν-甲基吡咯烷酮、Ν，Ν-二甲基 甲醯胺、環己酮、甲基異丁基酮、r -丁內酯等。這些有 機溶劑系顯像液係爲了防止起火，因此，最好是在1〜2 〇 質量％之範圍，添加水。 作爲顯像後之處理係可以配合於需要，藉由進行60〜 250°C程度之加熱或0.2〜lOJ/cm2程度之曝光，而還硬化 及使用光阻圖型。 接著，就本發明之έ卩刷電路板之製造方法而進行說明 〇 本發明之印刷電路板之製造方法係藉由本發明之光阻 圖型之形成方法而蝕刻或鍍敷形成光阻圖型之電路形成用 基板，來形成導體圖型。 電路形成用基板之蝕刻或鍍敷係以形成之光阻圖型， 作爲遮罩，對於電路形成用基板之導體層等而進行蝕刻或 鑛敷。作爲在進行蝕刻之狀態下之蝕刻液係列舉氯化銅溶 液、氯化鐵溶液、鹼蝕刻溶液、過氧化氫蝕刻液，在這些 當中，由鈾刻因子呈良好之方面來看的話，則最好是使用 氯化鐵溶液。此外，作爲在進行鍍敷之狀態下之鍍敷方法 係列舉例如硫酸銅鍍敷、焦磷酸銅鍍敷等之銅鑛敷、高均 一性（High Throw)銲錫鍍敷等之銲錫鍍敷、瓦特浴（ Watt’s bath :疏酸鎳-氯化鎳）鍍敷、胺基磺酸鎳等之鎳 -36- 201224656 鍍敷、硬金鍍敷、軟金鍍敷等之金鍍敷等。 在蝕刻或鍍敷之結束後，光阻圖型係可以例如藉由更 加強於顯像所使用之鹼性水溶液之強鹼性水溶液而進行剝 離。作爲該強鹼性水溶液係使用例如1〜1 0質量％氫氧化 鈉水溶液、1〜1 〇質量％氫氧化鉀水溶液等。作爲剝離方 式係列舉例如浸漬方式、噴射方式等，可以單獨使用浸漬 方式、噴射方式，也可以倂用浸漬方式、噴射方式》藉由 以上而得到印刷電路板。 在以上，就本發明之理想之實施形態而進行說明，但 是，本發明係並非限定於前述之實施形態。 實施例 在以下，就本發明之理想之實施形態而還更加詳細地 進行說明，但是，本發明係並非限定於這些實施例。 (黏合劑聚合物（（A )成分）之合成）In the 'Formula (I), Formula (II), Formula (III) and Formula (IV), 'R1, R3, R5 and R6 each independently represent a hydrogen atom or a methyl group, and R2 and R4 each independently represent a carbon number. An alkyl group of 1 to 3, an alkoxy group having 1 to 3 carbon atoms, an OH group or a halogen atom, and R 7 represents an alkyl group having 1 to 6 carbon atoms, and „! or „ each independently represents an integer of 0 to 5, m Or when η is 2 to 5, a plurality of R2 or R4 may be the same or different from each other. The present inventors have found that the photosensitive resin composition of the present invention is sufficiently improved in the above-described resolution and photoresist peeling properties by using, for example, a binder polymer having a specific structure of the above (Α) component. effect. Further, the photosensitive resin composition of the present invention has a good sensitivity by containing the components (A) to (C) described above. Further, the photosensitive resin composition of the present invention (A) binder polymer has a total of 10 parts by mass of the (A) binder polymer, and the divalent group represented by the general formula (I) has 10 To 60 parts by mass, the divalent group represented by the general formula (Π) has 10 to 60 parts by mass, and the divalent group represented by the general formula (III) has 20 to 50 parts by mass, and the general formula (IV) The divalent group is shown to have 1 part by mass or more and less than 15 parts by mass. Thereby, the resolution and the photoresist peeling property of the photosensitive resin composition are further improved. Further, it is preferable that the photosensitive resin composition of the present invention has a (C) photopolymerization initiator having a hexaarylbiimidazole compound. Thereby, the sensitivity of the photosensitive resin composition and the adhesion of the photoresist are improved. -9 - 201224656 Further, it is preferable that the photosensitive resin composition of the present invention contains (D) a sensitizing dye. By this, in the state where exposure is performed with light having a peak in a specific wavelength range, it is extremely absorbed in the vicinity of the specific wavelength range, and the sensitivity of the photosensitive resin composition is improved. Further, it is preferable that the photosensitive resin composition of the present invention contains an (E) amine compound. Thereby, the sensitivity of the photosensitive resin composition is further improved. Furthermore, the present invention provides a photosensitive element comprising: a support film; and a photosensitive resin composition layer containing the photosensitive resin composition formed on the support film. When the support film is provided, the photosensitive resin composition layer containing the photosensitive resin composition is provided. Therefore, even in a state in which a photoresist pattern is formed by direct drawing exposure, it is sufficient. The resolution is performed. In addition, it also has a sufficient effect in improving the peeling characteristics of the photoresist. Further, the present invention provides a method for forming a photoresist pattern, comprising: a lamination step of laminating a photosensitive resin composition layer containing the photosensitive resin composition on a circuit formation substrate; and the photosensitive resin composition layer The exposure step of irradiating the active light to the exposed portion, the step of exposing the exposed portion to light, and the step of forming the substrate for forming the photosensitive resin composition layer, and removing the portion other than the exposed portion of the photosensitive resin composition layer. According to the method for forming a photoresist pattern, a photosensitive resin composition layer containing the photosensitive resin composition is used to form a photoresist pattern, and therefore, even a direct drawing exposure method with a short exposure time is used. It is also possible to form a photoresist pattern with sufficient resolution. In addition, it is also effective in improving the peeling characteristics of the photoresist -10- 201224656. Furthermore, the present invention provides a method of manufacturing a printed circuit board, comprising: a step of forming a conductor pattern by etching or mineralizing a circuit formation substrate formed by the photoresist pattern by the method for forming a photoresist pattern. According to the method for producing a printed circuit board, the circuit pattern forming substrate having the photoresist pattern is formed by the above-described patterning method of the photoresist pattern. Therefore, it is possible to manufacture a wiring capable of forming a high density while sufficiently suppressing it. Broken and shorted printed circuit boards. [Effects of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive element, a method for forming a photoresist pattern, and a printing which have sufficient effects in improving the resolution and the photoresist peeling property. The manufacturing method of the circuit board. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a preferred embodiment of the present invention will be described in detail. Further, in the present invention, the term "(meth)acrylic acid means acrylic acid or methacrylic acid, and the term "(meth)acrylate" means acrylate or methacrylate corresponding to the acrylate, so-called (meth) propylene. The bismuth group is a photosensitive resin composition of the basic invention of the acryl fluorenyl group or the methacryl oxime. (A) has a divalent group represented by the above general formula (I) (hereinafter also referred to as "structural unit" - 11 - 201224656), a divalent group represented by the above general formula (II), a divalent group as described above, a 2 polymer represented by the above general formula (IV), (B) a photopolymerizable compound, and (C) Light first, it becomes the binder of (A). A) The binder polymer is in the above general formula (indicating a hydrogen atom or a methyl group, R2 represents an alkoxy group having a carbon number of 1 to 3 to 3, a hydrazine H group or a halogen atom, and m is represented as a general formula ( The polystyrene or styrene derivative of the structural unit shown in I). In addition, the olefin derivative of the present invention means a hydrogen atom substituted with a substituent such as an alkyl group or the like. Further, α-methylstyrene or the like is derived. Further, in the above general formula (II), R3 is a group, and R4 represents an alkyl group having 1 to 3 carbon atoms, a carbon number of 1 to fluorenyl group or a halogen atom, and m is represented by An integer of 〇~5. The polymerizable monomer series of the structural unit shown as (Π) is an acid vinegar or a benzyl derivative of (meth) acrylate. As the acid aryl derivative series, for example, (meth)acrylic acid 4- Further 'in the above general formula (ΠΙ), R5 is a methyl group. As a structural monomer given to the general formula (111), a series of (meth)acrylic acid is added. Further, in the above general formula (IV), R6 is an atom or a methyl group, and R7 is an alkyl group having a carbon number of 丨6, and a bond of a valence group of the general formula (III) Agent polymerization agent. Description of material I), R1 system. An alkyl group having an integer number of carbon atoms of from 1 to 5. The series of the conjugated monomers, such as "benzene or a halogen atom," are, for example, a hydrogen atom or alkoxy group of a methyl group, and a general formula (meth) propylene (meth) propylene methyl benzyl group. The polymerization of a hydrogen atom or a single point of the self-independently means that the hydrogen m or the η system each -12-201224656 independently represents an integer having a carbon number of 0 to 5. As long as the peeling time can be shortened and the resolution can be improved, R7 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group (methyl group) having a carbon number of 1. As a series of polymerizable monomers imparting a structural unit represented by the general formula (IV) (methyl group) As the alkyl (meth)acrylate, for example, a compound represented by the following general formula (V), etc. CH2 = C ( R8 ) -COOR9 ( V ) Here, in the above general formula (V) R8 is a hydrogen atom or a methyl group, and R9 is an alkyl group having 1 to 6 carbon atoms. Further, as an alkyl group having 1 to 6 carbon atoms represented by R9, for example, a methyl group, an ethyl group, a propyl group or a butyl group is mentioned. a base, a pentyl group, a hexyl group, and a structural heterogeneous body thereof. As the above general formula (V) Examples of the monomer series include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. And (meth) hexyl methacrylate, etc. These polymerizable single systems are used alone or in combination of two or more. The structural unit represented by the above general formula (I) is used as the binder polymer of the component (A). The content ratio is preferably 10 to 60 parts by mass, more preferably 15 to 55 parts by mass, even more preferably 20 to 50 parts by mass, based on 100 parts by mass of the total of the component (A). In particular, it is preferably 20 to 40 parts by mass, and the photosensitive composition composition containing the photosensitive resin composition can be excellent in adhesion to the substrate for circuit formation and peeling properties. The content of the structural unit represented by the above general formula (Π) is preferably 60 parts by mass, more preferably 15 to 55 parts by mass, even more preferably 50% by mass based on 100 parts by mass of the total of the component (A). It is particularly preferably 25 to 45 parts by mass. In this case, the photosensitive resin composition layer containing the photosensitive resin composition is excellent in adhesion to the substrate for electrical formation and resist release characteristics. Further, the structure unit of the general formula (III) is the most It is preferably 60 parts by mass, more preferably 15 to 50 parts by mass, even more preferably 40 parts by mass, particularly preferably 25 to 35 parts by mass, per 100 parts by mass of the component (A). In addition, it is preferable that the content of the structural unit represented by the above general formula (IV) is more than 100 parts by mass based on the total amount of the component (A). It is less than 15 parts by mass, more preferably 2 to 13 parts by mass, most preferably 4 to 12 parts by mass, particularly preferably 5 to 10 parts by mass. In this way, the photosensitive resin composition containing the photosensitive resin composition has good adhesion to the circuit-forming substrate and the photoresist peeling property. Further, in the adhesive polymer of the component (A), the above formula (I) The content ratio of the structural unit shown in the above formula (II) and the unit represented by the above general formula (II) are each less than 1 part by mass, and there is a tendency for resolution. When each exceeds 60 parts by mass, the peeling sheet is peeled off. The tendency to become longer occurs. In addition, the above general formula (I 1) has a photoresist ratio of 10 0 to 20 〜 so that the road shape ratio is 10 0 to 20 〜 so that the ratio 1 is qualitative, and even the layer f is. The ratio of the structural unit of the -14 to 201224656 is less than 10 parts by mass, and the alkali solubility is deteriorated, and the peeling sheet becomes large and the peeling time becomes longer. In the case of a part by mass, there is a tendency to lower the resolution. In addition, the content ratio of the structural unit represented by the above formula (IV) is less than 1 part by mass, and the peeling property tends to decrease. When the content is less than 15 parts by mass, the tendency to lower the degree of cleavage tends to occur. In the state in which the photosensitive resin composition is prepared by using the binder polymer, one type of binder polymer may be used singly, or two or more types of binder polymers may be arbitrarily combined and used. The binder polymer in a state in which two or more types are used in combination is, for example, a binder polymer composed of two or more different copolymer components (including different repeating units as a constituent component), and different types thereof. Two or more kinds of binder polymers having a weight average molecular weight, and two or more kinds of binder polymers having different degrees of dispersion. Further, the weight average molecular weight (Mw) and the number average molecular weight (?n) of the polymer ruthenium (A) binder polymer having a multimode molecular weight distribution described in JP-A-2013-37 can also be used. The measurement can be carried out by gel permeation chromatography (GPC) (by conversion using standard polystyrene calibration lines). According to the measurement method, the Mw of the binder polymer is preferably from 5,000 to 150,000, more preferably from 10,000 to 100,000, particularly preferably from 20,000 to 50,000. When the Mw is less than 5,000, the tendency to reduce the liquid resistance is exhibited, and when it exceeds 150,000, the development time tends to be long. -15- 201224656 In addition, the dispersion of (A) binder polymer (Mw / Μη) is preferably 〖·〇~3. 0, more ideal is 1. 0~2. 0. In the degree of dispersion exceeds 3. At 0 o'clock, there is a tendency to lower the adhesion and the resolution. Further, the (A) binder polymer may be, for example, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, or a phenol resin. Further, these resins are used singly or in combination of two or more. The binder polymer of the present invention can be produced, for example, by radical polymerization of a polymerizable monomer by a usual method. The above (A) bonding agent polymer may contain structural units other than the structural unit represented by the above general formulas (I) to (IV). The above (A) binder polymer is preferably one having only the structural unit represented by the above general formulas (I) to (IV), but may be relative to (A) to the extent that the object of the present invention is not impaired. The total amount of the components is about 1 to 10 parts by mass of the structural unit other than this. In this state, a series of polymerizable monomers which are structural units other than the structural unit represented by the above general formulas (I) to (IV) are, for example, heptyl (meth)acrylate or octyl (meth)acrylate. Ester, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, twelve (meth) acrylate Acrylamide, acrylonitrile, vinyl-η-butyl ether, such as alkyl ester, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 3-hydroxypropyl ester, 4-hydroxybutyl ester, diacetone acrylamide Ethyl alcohol esters, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate 'diethylaminoethyl (meth) acrylate, (methyl) - 16- 201224656 Epoxypropyl acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (methyl) Acrylic acid, bromine (meth)acrylic acid, α-chloro(meth)acrylic acid, fluorene-furyl (meth)acrylic acid, /3-styryl (meth)acrylic acid a maleic acid monoester of maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Fumaric acid, cinnamic acid, hydrazine: - cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, and the like. These single systems are used singly or in combination of two or more. The (A) binder polymer of the present invention is preferably one or more selected from the group consisting of a polymer having a carboxyl group, from the viewpoint of the development of the base in the case of performing alkali development. Composition. Such a (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group other than (meth)acrylic acid and a polymerizable monomer other than this in a usual manner. The acid value of the (A) binder polymer is preferably from 80 to 250 mgKOH/g, more preferably from 100 to 220 mgKOH/g, particularly preferably from 150 to 210 mgKOH/g. When the acid value is less than 80 mgKOH/g, the development time tends to become longer, and when it exceeds 250 mgK?H/g, there is a tendency to reduce the photo-resistance resistance of the photo-hardening resist. Further, in the state where solvent imaging is carried out as a developing step, it is preferred to prepare a small amount of a polymerizable monomer having a carboxyl group. Further, the (A) binder polymer may be incorporated in a molecule to provide a photosensitive property group as needed. The amount of the binder polymer of the component (A) is preferably 3 to 7 parts by mass, more preferably 3 to 7 parts by mass, based on the total amount of the components (A) -17 to 201224656 and (B). 35 to 65 parts by mass, particularly preferably 40 to 60 parts by mass. When the amount of the mixture is less than 30 parts by mass, the tendency to obtain a good shape is not more than 70 parts by mass, and there is a tendency that a good sensitivity or resolution is not obtained. The binder polymer which is the component (A) is used singly or in combination of two or more. Next, the photopolymerizable compound of the component (B) will be described. Examples of the photopolymerizable compound which is a component (B) include, for example, a compound obtained by reacting a ?, a non-unsaturated carboxylic acid with a polyol, a bisphenol a bis(meth) acrylate compound, and a glycidyl group-containing compound. a compound obtained by reacting α>/5-unsaturated carboxylic acid, a urethane monomer having a (meth) acrylate compound having a urethane bond in the molecule, or a nonyl phenoxy polyethylene An oxidized acrylate (also referred to as "nonylphenoxy polyethylene glycol acrylate"), a phthalic acid compound, or an alkyl (meth)acrylate. These compounds are used singly or in combination of two or more. The above-mentioned series of compounds obtained by reacting a polyol with an α,^-unsaturated carboxylic acid include, for example, polyethylene glycol di(meth)acrylate having a vinyl number of 2 to 14 and polypropylene glycol having a propylene number of 2 to 14. Di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, decyl trimethylolpropane tri(meth)acrylate, hydrazine Denatured trimethylolpropane tri(meth)acrylate, Ε0, Ρ0 denatured trimethylolpropane tri(meth) acrylate, tetrahydroxymethyl-18- 201224656 methane tri(meth) acrylate, tetrahydroxy Methyl methacrylate, dipentaerythritol penta (meth) acrylate, (meth) acrylate, and the like. These compounds are used alone or in combination of two or more. Here, "E 0" means that the compound which is EO-denatured has an ethylene oxide group. Further, "PO" means a propylene oxide, and PO means a block structure having a propylene oxide group. The aforementioned bisphenol A is a di(meth) acrylate compound. 2-bis(4-((meth) propylene oxide polyethoxy) 2. 2-bis(4-((meth)propene oxide polypropoxy) 2. 2-bis(4-((meth)propene oxide polybutoxy) 2. 2-bis(4-((meth) propylene oxide polyethoxypoly)propane, etc. as the above 2,2-bis(4-((methyl)oxy)phenyl)propane series, for example 2, 2 - bis(4_(diethoxy)phenyl)propane, 2,2-bis(4-(oxytriethoxy)phenyl)propane, 2,2-bis(4-(oxytetraethoxy) Phenyl)propane '2,2-bis(4-(pentaethoxylated)phenyl)propane, 2,2-bis(4-(hexaethoxy)phenyl)propane, 2,2_ Bis(4-(oxyhexaethoxy)phenyl)propane, 2,2-bis(4-(oxygaloxy)phenyl)propane, 2,2-bis(4-(oxyhexaethoxy) Phenyl)propane, 2,2-bis(4-(oxydecaoxy)phenyl)propane, 2,2-bis(4-(oxyundecyloxy)phenyl)propane, 2,2 - bis(4_tetra(methyl)propane dipentaerythritol hexahydrate or a combination of ethylene oxide, block structure. Denatured compounds such as phenyl) propane, phenyl) propane, phenyl) propane, propoxy Phenyl propylene oxidized poly(ethyl) propylene (meth) propylene (meth) propylene (meth) propylene (methyl) propylene (methyl) propylene ( Methyl) propylene (meth) propylene (meth) propylene (meth) propylene (meth) propylene ((methyl) propyl-19 - 201224656 ene oxide dodecyloxy) phenyl) propane, 2, 2 - bis(4-((meth) oxytridecyloxy)phenyl)propane, 2,2-bis(4·(() propylene oxide tetradecyloxy)phenyl)propane, 2,2-double (4-(yl) propylene oxidizes fifteen ethoxy)phenyl)propane, 2,2-bis (4. Methyl) propylene is oxidized to hexadecyloxy)phenyl)propane or the like. 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propene commercially available ΒΡΕ-500 (Xinzhongcun Chemical Industry Co., Ltd., trade name) or FA-321MC Hitachi Chemical Industry (share) company's trade name), 2,2-bis(4-(methacrylic acid pentadecanyloxy)propane is commercially available - 1 300 (New Nakamura Chemical Co., Ltd. The ethylene oxide of one molecule of 2,2-bis(4-((meth) oxidized polyethoxy)phenyl)propane is preferably 4 to 2 0, more preferably 8 to 1 5 These compounds are used singly or in combination of two or more. The (meth) acrylate series having a urethane bond in the molecule is, for example, a (meth) propylene monodiisocyanate having a mercapto group at the oxime position. Addition reaction of compound (isocyanate diisocyanate, 2,6-tolyl cyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.), tris((meth) propylene oxidation Tetraethylene glycolate) hexamethylene isocyanate, decyl urethane diester) acrylate, hydrazine Urethane di (meth) ester and the like. For example, UA-1 1 (manufactured by Shin-Nakamura Chemical Co., Ltd., name) is used as the guanidine-modified urethane di(meth) propylene series. Further, as the aforementioned hydrazine, hydrazine-modified urethane diyl) methyl (manufactured by A. Department of Technology, Benzene), a propylene-based acryl-based ester, and a diiso-isocyanate (methacrylate) (A- 20-201224656 base acrylate series, for example, uA-1 3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). These compounds are used singly or in combination of two or more. Examples of oxidized acrylates include decylphenoxytetraethylene oxidized acrylate, nonylphenoxypentaethylene oxyacrylate, decylphenoxy hexaethylene oxidized acrylate, decyl phenoxy acetylene Oxidized acrylate, nonylphenoxy octaethylene oxidized acrylate, nonyl phenoxy hexaethylene oxidized acrylate, nonyl phenoxy decylene oxidized acrylate, nonyl phenoxy undecylene oxidized acrylate. The phenoxy octaethylene oxidized acrylate series is, for example, M-114 (manufactured by Toagosei Co., Ltd., trade name). These compounds are used singly or in combination of two or more. The series of dicarboxylic acid compounds are, for example, r-chloro-yS-hydroxypropyl-/3,-(meth)acryloyloxyethyl phthalate 'no-hydroxyl-based'-(methyl) Ethyl phthalate oxidized ethyl phthalate, etc. These compounds are used singly or in combination of two or more kinds. In addition, from the viewpoint of improving the flexibility of the cured film, it is preferable. In the (Β) component of the present invention, a poly-methylene glycol mono(meth)acrylic acid vinegar having both a glycol bond and a propylene glycol bond in the molecule is contained. The (meth) acrylate system is included. There is no particular limitation if it has both an ethylene glycol chain and a propylene glycol chain (η-propylene glycol chain or isopropyl glycol chain) as the intramolecular alkylene glycol chain. In addition, the (methyl) propyl group The acid storage vinegar system may further have a carbon number of η-butanediol chain, isobutylene glycol chain, η-pentanediol chain, hexanediol chain, structural anisotropy or the like - 21 - 201224656 4 to 6 degree An alkylene glycol chain. In the state in which the ethylene glycol chain and the propylene glycol chain are plural, a plurality of The ethylene glycol chain and the propylene glycol chain may each exist in a block form continuously or randomly. Further, in the isopropyl glycol chain, the propyl group 2 carbon may be bonded to the oxygen atom, and the first stage carbon may be bonded. a polyalkylene glycol di(methyl) having at least one polymerizable ethylenically unsaturated bond in the component (B) and having both an ethylene glycol chain and a propylene glycol chain in the molecule. The acrylate series is, for example, the following general formula (VI): [Chemical Formula 5] 〇0 H2C=|~"~〇"tE〇ttP〇^E〇t"~|=CHi (V,) R10 R11 The compound of the following formula (VI): [Chemical Formula 6] ο 〇H2C=?_i_0 〇 ME〇^P〇y—?=CH2 R12 R13 The compound shown, and the following general formula (VII) [Chemical Formula 7] (VIII) H2C=C—C—O—^EO^-Poj-^-C—C=CH RM Π Compounds represented by R'5. Here, in the formula (VI), the formula (VII) and the formula (VIII), R10, R11, R12, R13, R" and Rl5 each independently represent a hydrogen atom or a hospital group having a carbon number of 1 to 3, and E0 represents The ethylene glycol chain, P0 means that the propylene glycol chains 'm1 to m4 and η1 to η4 each independently represent an integer of ι to -22-201224656 30. These compounds are used singly or in combination of two or more. Examples of the alkyl group having 1 to 3 carbon atoms of the above general formulae (VI) to (VIII) include a methyl group, an ethyl group, an η-propyl group, and an i-propyl group. Further, the total number of repeating numbers of ethylene glycol chains of the above general formulae (VI) to (VIII) (n^+m2, m3, and m4) is an integer of 1 to 30, preferably an integer of 1 to 10, more preferably It is an integer of 4 to 9 'particularly preferably an integer of 5 to 8. When the number of repetitions exceeds 30, there is a tendency that the reliability of the umbrella shape and the shape of the photoresist deteriorate. Further, the total number of repeating numbers of the propylene glycol chains of the above general formulae (VI) to (VIII) (η1, η2 + η3 and η4) is an integer of from 1 to 30, preferably an integer of from 5 to 20, more preferably 8~ An integer of 16 is particularly preferably an integer of 10 to 14. When the number of repetitions exceeds 30, there is a tendency that the resolution is deteriorated to produce a slurry. As a specific example of the compound represented by the above general formula (VI), for example, a vinyl compound which is RMsR11:methyl, 11^+1^=4 (average 値)'η1: 12 (average 値) (Hitachi Chemical Industry Co., Ltd.) (share) company system, product name: FA-OUM). Further, as a specific example of the compound represented by the above general formula (VII), for example, an ethylene compound which is R12=R13=methyl, m3=6 (average 値), n2+n3 = 12 (average 値) Hitachi Chemical Co., Ltd., product name: FA-024M). Further, as a specific example of the compound represented by the above general formula (VIII), for example, a vinyl compound which is R14 = R15 = hydrogen atom, m4 = 1 (average 値), η4 = 9 (average 値) (Xin Nakamura Chemical) -23- 201224656 Industrial (stock) company, sample name: NK ester HEMA-9P). These compounds are used singly or in combination of two or more. The amount of the photopolymerizable compound as the component (B) is preferably from 30 to 70 parts by mass, more preferably from 35 to 65 parts by mass based on 100 parts by mass of the total of the components (A) and (B). It is particularly preferably 40 to 60 parts by mass. When the amount is less than 30 parts by mass, there is a tendency that a good sensitivity or resolution is not obtained, and when it exceeds 70 parts by mass, there is a tendency that a good shape cannot be obtained. The photopolymerizable compound which is a component (B) is used singly or in combination of two or more. From the viewpoint of improving plating resistance and adhesion, the photopolymerizable compound preferably contains a bisphenol A-based (meth) acrylate compound or has a urethane bond in the molecule. (meth) acrylate compound. Further, from the viewpoint of improving the sensitivity and the degree of resolution, it is preferable to contain a bisphenol A-based (meth) acrylate compound. In addition, when the size of the peeling sheet of the photoresist is reduced and the peeling time is shortened, the photopolymerizable compound which is the component (B) preferably contains a polymerizable ethylenic unsaturated layer in the molecule. The photopolymerizable unsaturated compound of the bond is more preferably a photopolymerizable unsaturated compound having a polymerizable ethylenically unsaturated bond in the molecule and two or more polymerizable ethylenically unsaturated bonds in the molecule. The photopolymerizable unsaturated compound is used. In this state, for example, as a series of photopolymerizable unsaturated compounds having a polymerizable ethylenically unsaturated bond in the molecule, phenoxy polyethylene oxide (meth) acrylate, phenoxy-24 - 201224656 poly Ethylene oxide-polypropylene oxide (meth) acrylate, octylphenoxy hexaethylene oxide (meth) acrylate, octyl phenoxy heptaethylene oxide (meth) acrylate, octyl phenoxy octaethylene Oxidized (meth) acrylate, octylphenoxy hexaethylene oxide (meth) acrylate, octyl phenoxy decylene oxide (meth) acrylate, nonyl phenoxy polyethylene oxidation (methyl) Acrylate, nonylphenoxy polyethylene oxide-polypropylene oxide (meth) acrylate, and phthalic acid derivative having a (meth) propylene group. Further, as a series of photopolymerizable unsaturated compounds having two or more polymerizable ethylenically unsaturated bonds in the molecule, 6-hexanediol di(meth)acrylate, 1,4-ring a hexane diol di(meth) acrylate, a polyethylene glycol di(meth) acrylate having a vinyl group of 2 to 14, a polypropylene glycol di(meth) acrylate having a propylene number of 2 to 14, and the foregoing Polyethylene/polypropylene glycol di(meth)acrylate of the general formula (VI) to (VIII), bisphenol A-based di(meth)acrylate, and urethane bond in the molecule (methyl) Acrylate, bis(propylene oxide ethyl) hydroxyethyl isocyanate, bisphenol A diglycidyl ether di(meth) acrylate, butyl phthalate (meth) acrylate adduct Wait. Further, from the viewpoint of being able to improve the resolution, the peeling time, and the exposure margin in a well-balanced manner, it is particularly preferable to combine one kind of photopolymerizable property having a polymerizable ethylenic unsaturated bond in the molecule. A saturated compound and two kinds of photopolymerizable unsaturated compounds having two or more polymerizable ethylenically unsaturated bonds in the molecule are used. In this state, as a polymerizable unsaturated unsaturated bond having a polymerizable ethylenic unsaturated bond in the molecule, it is possible to use, for example, phenoxy polyethylene oxidized (meth) acrylate or decyl benzene. Any of oxyethylene oxide (meth) acrylate and phthalic acid derivative having a (meth) propylene group. Further, as the photopolymerizable unsaturated compound having two or more polymerizable ethylenically unsaturated bonds in the molecule, for example, polyethylene/polypropylene glycol di(A) of the above general formula (VI) to (VIII) may be combined. At least one compound selected from the group consisting of acrylate, EO modified urethane di(meth) acrylate and EO, PO modified urethane di(meth) acrylate and biguanide A system The photopolymerization initiator which is a component (C) is used as a photopolymerization initiator of the component (C), and the photopolymerization initiator which is a component (C) is exemplified by, for example, 4,4'-bis(diethyl Amino)benzophenone, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1- An aromatic ketone such as [4-(methylthio)phenyl]-2 morpholino-acetone-1, an anthracene such as an alkyl hydrazine, or a benzoin ether compound such as a benzoin alkyl ether a benzylation compound such as a benzoin or an alkyl benzoin or a benzyl derivative such as a benzyldimethylketal or a 2-(indolyl-chlorophenyl)-4,5-diphenylimidazole Dimer 2-(〇-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(〇-fluorophenyl)-4,5-diphenylimidazole dimer, 2 -(〇-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. An acridine derivative such as a 4,5-triaryl imidazole dimer, 9-phenyl acridine or 1,7-bis(9,9'-acridinyl)heptane. -26- 201224656 Further, in the above 2,4,5-triaryl imidazole dimer, the substituent of the aryl group of 2,4,5-triarylimidazole may give the same target compound 'and' Different asymmetric compounds can be assigned. Further, from the viewpoint of adhesion and sensitivity, the photopolymerization initiator is preferably a hexaaryldiimidazole compound which is a 2,4,5-triarylimidazole dimer. These photopolymerization initiators are used singly or in combination of two or more. In addition, it is preferable that the amount of the photopolymerization initiator to be the component (C) is from 0.1 to 10 parts by mass based on the total amount of the components (A) and (B), and is more preferably 0.1 to 10 parts by mass. The ideal is 2 to 6 parts by mass, particularly preferably 3. 5 to 5 parts by mass. The amount of training is less than 0. In the case of 1 part by mass, there is a tendency that a good sensitivity or resolution is not easily obtained, and when it exceeds 10 parts by mass, there is a tendency that a photoresist pattern of a good shape as required is not obtained. The photopolymerizable compound which is a component (C) is used singly or in combination of two or more. The photosensitive resin composition of the present invention preferably contains (D) a sensitizing dye and/or an (E) amine compound in addition to the above components (A) to (C). The sensitizing dye system which is the component (D) of the present invention can effectively utilize the absorption wavelength of the active light used for the exposure, and is preferably a compound which greatly absorbs a wavelength of from 3 to 420 nm. In the present invention, it is possible to sufficiently high sensitivity to the exposure light for direct drawing exposure by using such a sensitizing dye. When the maximum absorption wavelength of the sensitizing dye is less than 3 70 nm, there is a tendency to reduce the sensitivity to directly depicting the light for exposure. When it exceeds: *( -27- 201224656 42 Onm, even in a yellow light environment, there is A tendency to reduce stability occurs. As a series of sensitizing dyes, for example, pyrazolines, guanidines, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, Triazoles, anthraquinones, triazines, thiophenes, naphthoquinones, etc. From the viewpoint of improving the resolution, adhesion, and sensitivity, the sensitizing dye system preferably contains ruthenium. Further, the amount of the sensitizing dye is preferably 0. The mass of the component (A) and the component (B) is 0. 01 to 10 parts by mass, more preferably 0. 05 to 5 parts by mass, particularly preferably 〇" to 2 parts by mass. The amount of training is less than 0. 01 parts by mass, whether or not there is a tendency to obtain a good sensitivity or resolution, and when it exceeds 10 parts by mass, there is a tendency that a photoresist pattern of a good shape as required is not obtained. The sensitizing dye which is the component (D) is used singly or in combination of two or more. The amine-based compound which is the component (E) is not particularly limited as long as it can improve the sensitivity of the photosensitive resin composition and has an amine group in the molecule. As a specific example thereof, for example, bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, white crystal violet or the like can be mentioned. The amount of the amine compound is preferably 0. by mass based on 100 parts by mass of the total of the components (A) and (B). 01 to 10 parts by mass, more preferably 0. 05 to 5 parts by mass, particularly preferably 0. 1 to 2 parts by mass. The amount of training is less than 0. When the amount of the film is more than 10 parts by mass, when the film is formed, the component (E) tends to be precipitated and becomes a foreign matter. -28-201224656 which is the component (E) The amine compound is used singly or in combination of two or more. 1 The photosensitive resin composition of the present invention can be blended with the components (A) and (B). The total amount is 1 part by mass, each 0. 01 to 20 parts by mass of a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule (oxetanization), a cationic polymerization initiator, a dye such as malachite green, and tribromobenzene white a photochromic agent such as crystal violet, a thermochromic preventive agent, a p-toluene maple plasticizer, a pigment, a chelating agent, an antifoaming agent, a flame retardant, a stability imparting agent, a flat agent, a peeling accelerator, An oxidation inhibitor, a patterning agent, a thermal crosslinking agent, and the like. These are used alone or in groups of above. Further, the photosensitive resin composition of the present invention can be dissolved, ethanol, acetone, methyl ethyl ketone, methyl glycol ethyl ether, glycol ether, toluene, hydrazine, hydrazine-dimethylformamide, propylene glycol. The solvent of the monomethyl group or a mixed solvent of these is a solution of a solid content of about 30% by volume. This solution can be used as a coating liquid for a photosensitive resin composition layer of a shape member. Further, the coating liquid described above may be used by, for example, forming a photosensitive photo-resin composition layer, and drying the surface of the metal sheet as a liquid photoresist, and then coating the protective film. The material of the metal plate is, for example, an iron-based alloy such as copper, a copper-based alloy, chromium, iron or stainless steel, preferably a copper or a copper-based alloy. Next, the photosensitive element of the present invention will be described. Figure 吏. In the case of containing a cationic compound or the like, a guanamine or the like, a dense fragrance, and two types of a 60-mass photosensitive member such as methanol ethyl ethyl ether, the surface of the photosensitive member is coated with nickel, gold, and iron.显显-29 - 201224656 A schematic cross-sectional view showing an ideal embodiment of a photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 is formed of a support film 2, a photosensitive resin composition layer 3 formed on the support film 2 and containing the photosensitive resin composition, and laminated on the photosensitive resin composition layer 3. The protective film 4 is composed of. As the support film 2, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. As a series of commercial products, for example, Arufun MA-410, E-200C (in the above product name) manufactured by Oji Paper Co., Ltd., and a polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and the pS series manufactured by Teijin Co., Ltd. (e.g., the product name: PS-25), etc., but not limited to the polyethylene terephthalate film, etc. Further, the thickness of the support film 2 is preferably 1 to ΙΟΟμπι, more preferably 5 to 25 μm. . When the thickness is less than Ιμιη, the support film tends to be easily broken when the support film is peeled off before development, and when it exceeds 100 μm, the resolution tends to decrease. Further, the support film 2 can be used as a support for the photosensitive resin composition layer, and the other one can be laminated on both surfaces of the photosensitive resin composition layer as a protective film of the photosensitive resin composition. The photosensitive resin composition layer 3 is preferably a solution (coating liquid) in which the photosensitive resin composition is dissolved in the solvent to a solid content of about 30 to 60% by mass, and then applied to the support film by the solution. On the 2nd, drying is performed to form a photosensitive resin composition layer. The coating system can be known by, for example, using a roll coater, a comma coater, a gravure coater, an air-30-201224656 knife coater, a die coater, a bar coater, and the like. The drying method is carried out at 70 to 150 ° C for 5 to 30 minutes. In addition, the amount of the residual organic solvent in the photosensitive resin composition is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the surface step. Further, the thickness of the photosensitive resin composition layer 3 is due to the sensitization. The use of the article varies, but the thickness after drying is preferably 1 ΙΟΟ μιη, more preferably 1 to 50 μm. When the thickness is less than Ιμιη, there is a tendency that the fabric is difficult to be industrially generated. When the thickness exceeds ΙΟΟμηι, the effect of the present invention is small, and the tendency of the adhesion and the resolution is lowered. Further, the photosensitive resin composition layer 3 preferably has a transmittance at a wavelength of 405 nm of 5 to 75%, more preferably 7 to 60%, particularly preferably 10 to 40%. When the transmittance is less than 5%, the adhesion tends to deteriorate, and when it exceeds 75%, the resolution tends to deteriorate. The transmittance is measured by a UV spectrometer, and the 228A type W spectrophotometer (trade name) manufactured by Hitachi, Ltd. is used as a front UV spectrometer. The protective film 4 is preferably an adhesive force between the photosensitive resin composition layer 3 and the protective film 4, and is smaller than the adhesion between the photosensitive resin composition layer 3 and the support sheet 2, and is preferably a low fisheye crater. The film. In addition, the "fisheye crater" is a hot-melt material, and when a film is produced by kneading, extrusion, shaft stretching, or casting, a foreign matter, an insoluble matter, an oxidative deterioration, or the like of the material is placed in the film. in. As the protective film 4, for example, polyethylene terephthalic acid 'polypropylene, polyethion, polyacetate, or the like, which has heat resistance and solvent resistance, can be used. - 201224656 Composite film. As a series of commercial products, for example, Arufun MA-410, E-200C (above, trade name) manufactured by Oji Paper Co., Ltd., and polypropylene film produced by Shin-Etsu Film Co., Ltd., and PS series produced by Teijin Co., Ltd. A polyethylene terephthalate film or the like such as, for example, trade name: PS-25, is not limited thereto. The thickness of the protective film 4 is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 30 μm, particularly preferably from 15 to 3 μm. When the thickness is less than Ιμιη, there is a tendency for the protective film to rupture at the time of lamination, and when it exceeds ΙΟΟμηη, there is a tendency that the inexpensiveness is deteriorated. Further, the photosensitive element 1 of the present invention may further have a buffer layer. Then, an intermediate layer such as a light absorbing layer or a gas barrier layer. Further, the photosensitive element 1 obtained is stored in a sheet shape or wound in a roll shape in a winding core. Further, at this time, it is preferable to wind the support film 1 to be the outermost side. From the viewpoint of the end face protection, it is preferable that the end face spacer is provided on the end face of the pressure roller-shaped photosensitive member pressure roller. From the viewpoint of edge melting resistance, it is preferable to provide moisture prevention. End spacer. Further, it is preferable that the packaging method is packaged in a black sheet having a small moisture permeability. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). Next, a method of forming the photoresist pattern of the present invention will be described. The method for forming a photoresist pattern of the present invention includes at least a laminating step of laminating a photosensitive resin-32-201224656 composition layer containing the photosensitive resin composition on a circuit-forming substrate. An exposure step of irradiating the active light with a predetermined portion of the layer to light-curing the exposed portion, and a developing step of removing the photosensitive resin composition of the portion other than the exposed portion by the substrate for forming the circuit. In addition, the "circuit formation substrate" means a substrate including an insulating layer and a conductor layer formed on the insulating layer. Further, the substrate for circuit formation may be formed inside a plurality of layers, or may have a small-diameter through hole. The following method is used as a series of lamination methods for laminating a circuit formation substrate as a photosensitive resin composition layer. First, the protective film is gradually peeled off from the photosensitive resin composition layer, and at this time, the surface portion of the photosensitive resin composition layer which is gradually exposed is adhered to the surface of the circuit for forming the circuit-forming substrate. Next, the photosensitive resin composition layer is heated, and the photosensitive resin composition is laminated on the circuit-forming substrate to be laminated. Further, in view of improving the adhesion and the traceability, it is preferable that the operation is carried out under reduced pressure. Preferably, the laminate of the photosensitive element is a photosensitive resin composition layer and/or a substrate for forming a circuit, and is heated to 70 to 130 ° C, and the pressure is preferably 〇-1 〜1. The degree of OMPa (about 1 to 10 kgf/cm2), however, there are no particular restrictions on these conditions. In addition, if the photosensitive resin composition layer is heated to 70 to 130 ° C as described above, it is not necessary to perform preheating on the substrate for circuit formation in advance, but in order to further improve the lamination property, Preheating of the substrate for circuit formation can be performed. A method of forming an exposure portion as an exposure step is a series of methods of irradiating active light onto an image by a negative or positive mask pattern called an original image -33 - 201224656 (mask exposure method). At this time, in a state in which the support film existing on the photosensitive resin composition layer transmits the active light, the active light can be irradiated through the support film, and in the state where the support film is light-shielding, after the support film is removed, The photosensitive resin composition layer is irradiated with active light. Further, a method of irradiating the active light in an image form by a direct drawing exposure method such as a laser direct drawing exposure method or a dlp (Digital Light Processing) exposure method may be employed. As the light source of the active light, a conventional light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, an argon laser or the like, a solid laser such as a YAG laser, or a semiconductor laser is used. The ground emits ultraviolet light, visible light, and the like. In the method of removing the portion other than the exposed portion as the development step, the support film is removed in the state where the support film is present on the photosensitive resin composition layer, and then removed by wet development, dry development, or the like. A method of developing a portion other than the exposure portion. Thereby, a photoresist pattern is formed. For example, in the state of wet development, a developing liquid corresponding to a photosensitive resin composition such as an aqueous alkaline solution, a water-based developing liquid, or an organic solvent-based developing liquid is used, for example, by dipping method, struggle mode, and spraying. Development is carried out by a conventional method such as shaking, rubbing, washing, or the like. The development method is to improve the resolution, so 1 is most suitable for the high pressure injection method. Further, two or more types of development methods may be used in combination with the need. As the developing liquid system, an alkaline aqueous solution which is safe and stable and has good workability is used. As the base of the alkaline aqueous solution, for example, an alkali hydroxide such as lithium, sodium or potassium-34-201224656, a carbonate of lithium, sodium, potassium or ammonium or a potassium carbonate or phosphoric acid such as a bicarbonate is used. An alkali metal pyrophosphate such as potassium or sodium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate, or borax. Further, as the aqueous alkaline solution used for development, it is preferably a thin melt of sodium carbonate of 〇_1 to 5% by mass, 0. 1 to 5 mass% of a thin melt of potassium carbonate, 0. 1 to 5 mass% of a thin melt of sodium hydroxide, 0. 1 to 5 mass% of a thin melt of sodium tetraborate (borax) or the like. Further, the pH of the alkaline aqueous solution is preferably in the range of from 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be added to the alkaline aqueous solution. The water-based developing liquid series is a developing liquid composed of water or an aqueous alkali solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, sodium citrate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxyl Methyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine, and the like. The pH of the developing solution is preferably as small as possible within a range in which the development of the photoresist can be sufficiently performed, and it is preferably pH 8 to 12, more preferably pH 9 - 10 ° as the above organic solvent system. For example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , diethylene glycol monobutyl ether, and the like. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably from 2 to 90% by mass, and the temperature can be adjusted in accordance with the development property of -35 to 201224656. Further, a small amount of a surfactant, an antifoaming agent or the like may be added to the aqueous developing solution φ '. Further, examples of the organic solvent-based developing liquid system using an organic solvent alone include, for example, 1,1,1-trichloroethane, fluorene-methylpyrrolidone, hydrazine, hydrazine-dimethylformamide, and cyclohexanone. Methyl isobutyl ketone, r - butyrolactone, and the like. In order to prevent ignition, these organic solvent-based developing liquids are preferably added in a range of 1 to 2% by mass. The processing system after the development can be combined with the need to perform heating at a temperature of 60 to 250 ° C or 0. 2~lOJ/cm2 exposure, but also hardened and used photoresist pattern. Next, a method of manufacturing the brush circuit board of the present invention will be described. The method of manufacturing the printed circuit board of the present invention is etched or plated to form a photoresist pattern by the method for forming a photoresist pattern of the present invention. A circuit forming substrate is used to form a conductor pattern. The circuit forming substrate is etched or plated to form a photoresist pattern, and is used as a mask for etching or mineralizing a conductor layer or the like of the circuit forming substrate. As a series of etching liquids in the state of etching, a copper chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution are used, and among these, when the uranium engraving factor is good, the most It is good to use a ferric chloride solution. In addition, as a series of plating methods in the state of plating, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as high-throw solder plating, and watts are used. Bath (Watt's bath: nickel-nickel chloride-nickel chloride), nickel-36-201224656 such as nickel sulfonate, gold plating such as hard gold plating, soft gold plating, etc. After the end of the etching or plating, the photoresist pattern can be peeled off, for example, by a strong alkaline aqueous solution which is more enhanced in the alkaline aqueous solution used for development. As the strongly alkaline aqueous solution, for example, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 1% by mass aqueous potassium hydroxide solution, or the like is used. As the detachment method, for example, a immersion method, a blast method, or the like may be used, and the immersion method or the blast method may be used singly, or the dicing method or the blast method may be used to obtain a printed circuit board. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the embodiments described above. EXAMPLES Hereinafter, the preferred embodiments of the present invention will be described in more detail, but the present invention is not limited to these examples. (Composition of binder polymer ((A) component)
在具備攪拌機、回流冷卻器、溫度計、滴下漏斗及氮 氣導入管之燒瓶，加入質量比3:2之甲基乙二醇乙醚及 甲苯之練合物45 0g，吹入氮氣，同時，進行攪拌，加熱至 8〇°C爲止。另一方面，作爲共聚單體係準備混合甲基丙烯 酸150g、甲基丙烯酸甲酯25g、甲基丙烯酸苄酯125g及 苯乙烯200g、和偶氮二氮丁腈9.0g之溶液（在以下稱爲 「溶液a」），在預先準備之質量比3: 2之甲基乙二醇乙 醚及甲苯之練合物經過4小時而滴下溶液a之後，於80°C -37- 201224656 進行攪拌，同時，保溫2小時。此外，在質量比3:2之 甲基乙二醇乙醚及甲苯之練合物100g，經過10分鐘而滴 下溶解偶氮二氮丁腈1.2g之溶液》在攪拌滴下後之溶液 同時於80°C保溫3小時之後，經過30分鐘而加溫至90°C 。在90°C保溫2小時之後，進行冷卻而得到黏合劑聚合物 (A-1 )。 黏合劑聚合物（A- 1 )之非揮發性成分（固態成分） 係47.8質量％，重量平均分子量係30,000。此外，重量 平均分子量係藉由凝膠滲透色譜法而進行測定，藉由使用 標準聚苯乙烯之檢量線，來進行換算而導引出重量平均分 子量。GPC之條件顯示於以下。 幫浦：日立L-6000型（日立製作所（股）公司製、 商品名稱） 柱.G e 1 p a ck G L - R 4 2 0 + G e 1 p a c k GL-R430 + Gelpack GL-R440 (合計3條）（在以上、曰立化成工業（股）公 司製、商品名稱） 洗提液：四氫化呋喃 測定溫度：40t 流量：2.05mL/分鐘 檢測器：日立L-3 300型RI (日立製作所（股）公司 製、商品名稱） 此外’藉由相同於前述黏合劑聚合物（A-1)之合成 方法之同樣方法來合成黏合劑聚合物（A-2)〜（A-10) 而成爲下述表1所示之組成。 -38- 201224656 【IM A-10 1 1 1 〇 Ό Ο r—H 30000 A-9 〇 1 1 1 〇 m Τ""Η 30000 A-8 1 1 1 CN m v〇 T-H 1 30000 ! | A-7 咖 1 1 宕 <5 ON i-H 30000 A-6 <Ν iTi 1 1 00 cn s (N 1 30000 A-5 m Ο 1 1 宕 m \o 30000 A-4 t 1 in m VO Os Π 30000 <N m c〇 T"H \ 1 CN VO ON 30000 A-2 CN 1 1 ο v〇 ON 1 30000 1- i LA-1 in cs 1 1 ο VO ON 30000 Γ 甲基丙烯酸 甲基丙烯酸苄酯 甲基丙烯酸甲酯 甲基丙烯酸丁酯 甲基丙烯酸2-羥乙基 苯乙烯 酸價(mgKOH/g) 重量平均分子量 黏合劑 聚合物( 質量比) (％S.A 寸：¾¾¾链趟画 ® 键((Ν\ε#&-\·Κ1觀 ΠΚ1糊El·* -39- 201224656 (感光性樹脂組成物之調製） 以表2所示之値量比，來練合前述黏合劑聚合物（A_ 1 )〜（A -1 0 )和以下之材料，調製實施例1〜6及比較例 1〜5之感光性樹脂組成物之溶液》 <光聚合性化合物（（B)成分）> B-1: 2,2-雙（4-(甲基丙烯醯基五乙氧基）苯基）丙 烷（日立化成工業（股）公司製、商品名稱·· FA-321M ) B-2:藉由前述一般式（VII)所示之化合物、Ri2及 R13分別爲甲基、m3 = 6 (平均値）、n2+ n3= 12 (平均値 )之乙烯基化合物（曰立化成工業（股）公司製、商品名 稱：FA-024M ) B-3 : 4-正壬基苯氧基八乙烯羥基丙烯酸酯（東亞合 成（股）公司製、商品名稱：Μ-1 1 4 ) <光聚合引發劑（（C)成分）> 01:2,2’-雙（2-氯苯基）-4,4’，5,5’-四苯基雙咪唑（ Hampford公司製、商品名稱：BCIM ) <增感色素（（D)成分）> D-1 : 9,10-二丁氧基蒽（川崎化成工業（股）公司製 、商品名稱：DBA、顯示極大吸收之波長[λ n] = 3 68nm、 388nm、4 1 0nm ) -40- 201224656 < (E )發色劑（胺化合物）> E-1 :白結晶紫（山田化學（股）公司製） <染料> 孔雀綠（大阪有機化學工業（股）公司製） <溶劑> 丙酮 甲苯 甲醇 -41 - 201224656 【(NS 比較例5 咖 I I 1 1 1 1 1 1 〇 o 1 卜 ΓΟ 00 ο 1 0.25 1 0.03 〇\ 比較例4 I I I 1 1 1 1 1 1 卜 rn 00 ο 0.25 0.03 〇\ in 比較例3 I I I 咖 咖 1 1 1 1 〇 1 o 卜 rn οο Ο 0.25 0.03 〇\ in 比較例2 I I 1 1 1 1 1 1 1 CS o 卜 rn 00 ο 0.25 0.03 〇\ iT) 比較例I I I t 1 1 1 1 1 1 CN ^Ti o 卜 Γ〇 00 ο 0.25 0.03 〇\ 實施例6 I I 1 1 1 1 唯 1 1 Ο cn 00 ο 0.25 0.03 〇\ 實施例5 I I 1 1 1 1 1 1 1 CN o 卜 cn 00 ο 0.25 0.03 ON ^T) 實施例4 I 1 1 1 1 1 1 1 1 卜 ΓΟ 00 ο 0.25 0.03 〇\ yn in 實施例3 I I 1 1 1 1 1 1 1 卜 rn οο ο 0.25 0.03 〇\ m 實施例2 I 1 1 1 1 1 1 1 1 m T·^ 1 卜 cn 00 ο 0.25 0.03 〇\ 實施例I I 1 1 1 1 1 1 1 1 to (N o 卜 rn 00 ο 0.25 0.03 σ\ <n A-l A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 | 1 CQ B-2 1 B-3 C-l »^Η 1 Q ώ 孑L雀綠 丙酮 甲苯 甲醇 (A)成分 (B)成分 1 (c戚分 (D)成分1 (Ε)成分 染料 溶劑 。丑_»长嗽雄·}鐮^尔链_砟* _φ^锻晅长漱张Kf1s(v) -42- 201224656 (感光性元件之製作） 得到之各種感光性樹脂組成物之溶液，塗佈在成爲支 持薄膜之16 μιη厚度之聚乙烯對苯二甲酸酯薄膜上。然後 ，使用70°C及1 l〇t之熱風對流式乾燥機而進行乾燥，形 成乾燥後之膜厚25 μπι之感光性樹脂組成物層。接著，在 感光性樹脂組成物層上，藉由壓輥加壓而層合保護薄膜， 得到各個實施例1〜6及比較例1〜5之感光性元件。 (試驗片之製作） 接著，使用具有相當# 600之刷子之硏磨機（三啓（ 股）公司製），硏磨在銅箔（厚度3 5mm)層合於兩面之 玻璃環氧材料之貼銅層合板（日立化成工業（股）公司製 、商品名稱：MCL-E-67)之銅表面，在進行水洗後，以 空氣流，來進行乾燥，得到貼銅層合板（基板）。然後， 在貼銅層合板加溫至80°C之後，於貼銅層合板上，除去前 述之各個感光性元件之保護薄膜，同時，各個感光性樹脂 組成物層密合於貼銅層合板之表面上’在！20°C、4kgf/ cm2之壓力下，進行層壓（層合）’製作試驗片》 (特性評價） <光感度> 冷卻層合各個感光性元件之貼銅層合板，在成爲23 °C 之時間點，於支持薄膜，將具有濃度區域〇·〇〇〜2.00、濃 度階梯0.05、薄片尺寸20mmxl87mm、各個階梯之尺寸 -43- 201224656 3 mmx 1 2 mm之41段之階梯薄片之光工具予以密合 以40 5 nm之藍紫色雷射二極體作爲光源之日 Mechanics (股）公司製之直描機DE-1AH(商品名 以50mJ/cm2之曝光量，透過光工具及支持薄膜.而 描繪）於感光性樹脂組成物層。此外，照度之測定 適用405nm對應探針之紫外線照度計（USHIO電 )公司製、商品名稱：UIT-150)而進行。 接著，剝離支持薄膜，噴射30°C、1質量％碳 溶液24秒鐘，除去感光性樹脂組成物層之未曝光 進行顯像’。然後，藉由測定形成於貼銅層合板上之 膜之階梯薄片之段數，而評價感光性樹脂組成物之 。光感度之評價係由階梯薄片之段數所表示，該階 之段數越高而表示光感度越高。得到之結果顯示於; <解析度> 解析度係使用具有線幅寬/空間幅寬：6/ 6〜 (單位：mm)來作爲解析度評價用負底片之光工 行曝光。在此，’解析度係在藉由曝光後之顯像所形 阻圖型，以完美地除去未曝光部之部分之線幅寬間 幅寬中之最小値（單位：μιη )，來作爲解析度之指 析度之評價係數値越小而越加成爲良好値。得到之 示於表4。 <光阻形狀> 。使用 立 Via 稱）， 曝光（ 係使用 機（股 酸鈉水 部分， 光硬化 光感度 梯薄片 隻4 ° 30/30 具，進 成之光 之空間 標。解 結果顯 -44 - 201224656 顯像後之光阻形狀係使用掃描型電子顯微鏡（商品名 稱：日立掃描型電子顯微鏡s-5 00A )而進行觀察。光阻 形狀係最好是接近於矩形。 <剝離性> 剝離性係藉由以下之方法而進行評價。首先，各個實 施例及比較例之感光性樹脂組成物層形成於貼銅層合板上 ，曝光及顯像各個感光性樹脂組成物層，製作40mm X 50mm大小之光硬化膜。接著，使用3 %氫氧化鈉水溶液 而進行剝離。剝離性之評價係以由貼銅層合板上開始剝離 光硬化膜之結束時之時間，作爲剝離時間。此外，藉由目 視而觀察在剝離結束後之剝離片之尺寸。就表3所示之剝 離製程之條件及剝離片尺寸之指標而進行顯示。得到之結 果顯示於表4。 [表3] 製程等 條件等 曝光 曝光量:60mJ/cm2、尺寸:40mmx50mm 顯像 顯像液:l%Na2C03、液溫:30〇C、噴射式 剝離 剝離液:3%NaOH、液溫:50〇C、浸漬攪拌 剝離片之尺寸 L:薄片狀、M:30〜40mm、S:30mm角以下 -45- 201224656 【i 比較例5 CN cn 矩形 比較例4 〇 100 矩形 比較例3 o 220 矩形 比較例2 r-H jrj 00 矩形 比較例1 (N v〇 00 矩形 實施例6 o zn 矩形 實施例5 Τ-Η o 00 矩形 實施例4 o (N 00 κη 矩形 實施例3 o 00 v〇 in 矩形 實施例2 τ·Ή o On 〇0 ! 矩形 實施例1 1_ o § ϋ0 矩形 光感度* 解析度(μπι) 剝離時間⑻ ^ 1 剝離片之尺寸 光阻形狀 銳襲 #-Nssss 塞w* -46- 201224656 <評價結果> 正如表4所示’各個實施例丨〜6係解析度1 〇μηι及高 解析度，適度地縮短剝離時間，並且，剝離片之尺寸也變 小，達到解析度和剝離性之平衡。另一方面，在比較例1 、2、5 ’剝離性良好之解析度係變低。此外，在比較例3 、4 ’高解析度之剝離時間係變長，剝離片之尺寸變大。 正如以上，確認本發明之感光性樹脂組成物之效果。 [產業上之可利用性] 如果藉由本發明的話，則能夠提供一種在解析度及光 阻剝離特性之提升來具有充分之效果的感光性樹脂組成物 、感光性元件、光阻圖型之形成方法及印刷電路板之製造 方法。 【圖式簡單說明】 圖1係顯示本發明之感光性元件之理想之一實施形態 之示意剖面圖。 【主要元件符號說明】 1 :感光性元件 2 :支持薄膜 3 :感光性樹脂組成物層 4 :保護薄膜 -47-In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, 45 g of a mixture of methyl glycol ether and toluene having a mass ratio of 3:2 was added, and nitrogen gas was blown while stirring. Heat to 8 ° ° C. On the other hand, a solution of 150 g of methacrylic acid, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, 200 g of styrene, and 9.0 g of azodiazepine was prepared as a copolymerization system (hereinafter referred to as a solution). "solution a"), after preliminarily preparing a mixture of methyl glycol ether and toluene having a mass ratio of 3:2, and then dropping the solution a after 4 hours, stirring at 80 ° C -37 - 201224656, Keep warm for 2 hours. In addition, in a mass ratio of 3:2 of methyl glycol ether and toluene 100g, after 10 minutes, a solution of 1.2 g of dissolved azodiazepine was added dropwise. The solution after stirring and dropping was simultaneously at 80 °. After 3 hours of C incubation, it was heated to 90 ° C over 30 minutes. After keeping at 90 ° C for 2 hours, it was cooled to obtain a binder polymer (A-1 ). The nonvolatile component (solid component) of the binder polymer (A-1) was 47.8% by mass, and the weight average molecular weight was 30,000. Further, the weight average molecular weight is measured by gel permeation chromatography, and the weight average molecular weight is guided by conversion using a standard polystyrene calibration curve. The conditions of GPC are shown below. Pump: Hitachi L-6000 (Hitachi Manufacturing Co., Ltd., product name) Column. G e 1 pa ck GL - R 4 2 0 + G e 1 pack GL-R430 + Gelpack GL-R440 (Total 3 (In the above, 曰立化成工业股份有限公司), the product name) Eluent: Tetrahydrofuran Determination temperature: 40t Flow rate: 2.05mL / min Detector: Hitachi L-3 300 RI (Hitachi Manufacturing Co., Ltd. (Company, product name) In addition, the binder polymer (A-2) to (A-10) is synthesized by the same method as the synthesis method of the above-mentioned binder polymer (A-1). The composition shown in Table 1. -38- 201224656 [IM A-10 1 1 1 〇Ό Ο r-H 30000 A-9 〇1 1 1 〇m Τ""Η 30000 A-8 1 1 1 CN mv〇TH 1 30000 ! | A- 7 咖1 1 宕<5 ON iH 30000 A-6 <Ν iTi 1 1 00 cn s (N 1 30000 A-5 m Ο 1 1 宕m \o 30000 A-4 t 1 in m VO Os Π 30000 <N mc〇T"H \ 1 CN VO ON 30000 A-2 CN 1 1 ο v〇ON 1 30000 1- i LA-1 in cs 1 1 ο VO ON 30000 苄 benzyl methacrylate methacrylate Methyl methacrylate butyl methacrylate 2-hydroxyethyl styrene acid methacrylate (mgKOH / g) Weight average molecular weight binder polymer (mass ratio) (% SA inch: 3⁄43⁄43⁄4 chain ® ®® key ( Ν\ε#&-\·Κ1 ΠΚ1 1 paste El·* -39- 201224656 (Preparation of photosensitive resin composition) The binder polymer (A_ 1) was blended in the amount ratio shown in Table 2 (A -1 0 ) and the following materials, the solutions of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared. <Photopolymerizable compound (component (B)) > B- 1: 2,2-bis(4-(methacryloyl)pentaethylene Phenyl)propane (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-321M) B-2: The compound represented by the above general formula (VII), Ri2 and R13 are respectively methyl group, m3 = 6 (average 値), n2+ n3 = 12 (average 値) vinyl compound (manufactured by 曰立化成股份有限公司), trade name: FA-024M) B-3 : 4-n-decyl phenoxy octaethylene Hydroxy acrylate (manufactured by Toagosei Co., Ltd., trade name: Μ-1 1 4 ) <Photopolymerization initiator ((C) component)> 01:2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetraphenylbisimidazole (manufactured by Hampford Co., Ltd., trade name: BCIM) <sensitizing dye ((D) component)> D-1 : 9,10-dibutoxy Based on Kawasaki Chemical Co., Ltd., trade name: DBA, wavelength showing maximum absorption [λ n] = 3 68 nm, 388 nm, 4 1 0 nm ) -40- 201224656 < (E ) coloring agent (amine) Compound) > E-1: White Crystal Violet (manufactured by Yamada Chemical Co., Ltd.) <Dye> Malachite Green (Osaka Organic Chemical Industry Co., Ltd.) <Solvent> Acetone Toluene Methanol-41 - 2012246 56 [(NS Comparative Example 5 Coffee II 1 1 1 1 1 1 〇o 1 ΓΟ 00 ο 1 0.25 1 0.03 〇 \ Comparative Example 4 III 1 1 1 1 1 1 卜 rn 00 ο 0.25 0.03 〇 \ in Comparative Example 3 III 咖咖1 1 1 1 〇1 o rn οο Ο 0.25 0.03 〇\ in Comparative Example 2 II 1 1 1 1 1 1 1 CS o rn 00 ο 0.25 0.03 〇\ iT) Comparative Example III t 1 1 1 1 1 1 CN ^Ti o Γ〇 00 ο 0.25 0.03 〇\ Example 6 II 1 1 1 1 Only 1 1 Ο cn 00 ο 0.25 0.03 〇\ Example 5 II 1 1 1 1 1 1 1 CN o cn 00 ο 0.25 0.03 ON ^T) Example 4 I 1 1 1 1 1 1 1 1 Divination 00 ο 0.25 0.03 〇 yn in Example 3 II 1 1 1 1 1 1 1 Bu rn οο ο 0.25 0.03 〇\ m Implementation Example 2 I 1 1 1 1 1 1 1 1 m T·^ 1 卜 00 ο 0.25 0.03 〇\ Example II 1 1 1 1 1 1 1 1 to (N o rn 00 ο 0.25 0.03 σ\ <n Al A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 | 1 CQ B-2 1 B-3 Cl »^Η 1 Q ώ 孑L Green Acetone Toluene methanol (A) component (B) component 1 (c 戚 (D) component 1 (Ε) component dye solvent. Ugly _»长嗽雄·}镰^ 尔 chain_砟* _φ^ 晅 晅 K K Kf1s (v) -42- 201224656 (Production of photosensitive elements) A solution of various photosensitive resin compositions obtained, coated On a polyethylene terephthalate film having a thickness of 16 μm supporting the film. Then, it was dried using a hot air convection dryer at 70 ° C and 1 l〇t to form a photosensitive resin composition layer having a film thickness of 25 μm after drying. Then, a protective film was laminated on the photosensitive resin composition layer by pressurization with a press roll to obtain photosensitive elements of Examples 1 to 6 and Comparative Examples 1 to 5. (Preparation of test piece) Next, using a honing machine (manufactured by Sanqi Co., Ltd.) having a brush of #600, honing the paste of the glass epoxy material laminated on both sides of the copper foil (thickness 35 mm) The copper surface of the copper laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67) was subjected to water washing, and then dried by air flow to obtain a copper-clad laminate (substrate). Then, after the copper-clad laminate is heated to 80 ° C, the protective film of each of the photosensitive elements described above is removed on the copper-clad laminate, and each photosensitive resin composition layer is adhered to the copper-clad laminate. On the surface 'at! Lamination (lamination) 'production test piece> (characteristic evaluation) under pressure of 20 ° C and 4 kgf / cm 2 <Photosensitivity> Cooling laminated copper-bonded laminate of each photosensitive element at 23 ° At the time point of C, in the supporting film, a light tool having a concentration region of 〇·〇〇~2.00, a concentration step of 0.05, a sheet size of 20 mm×l87 mm, and a size of each step of -43-201224656 3 mmx 1 2 mm The direct-drawing machine DE-1AH made by Mechanics Co., Ltd., which is a light source with a blue-violet laser diode of 40 5 nm, is used. The product name is 50mJ/cm2, and the light tool and the supporting film are transmitted. And depicted in the photosensitive resin composition layer. In addition, the measurement of the illuminance was carried out by using an ultraviolet illuminometer (USHIO Electric Co., Ltd., product name: UIT-150) manufactured by 405 nm corresponding probe. Then, the support film was peeled off, and a carbon solution of 30% by weight and 1% by mass was sprayed for 24 seconds to remove the exposure of the photosensitive resin composition layer to perform development. Then, the photosensitive resin composition was evaluated by measuring the number of the step sheets of the film formed on the copper-clad laminate. The evaluation of the light sensitivity is represented by the number of segments of the stepped sheet, and the higher the number of segments of the step, the higher the light sensitivity. The results obtained are shown in the following: <Resolution> The degree of resolution is an optical exposure using a line width/space width: 6/6 to (unit: mm) as a negative film for resolution evaluation. Here, 'the resolution is the shape of the image formed by the exposure after exposure, so as to perfectly remove the minimum 値 (unit: μιη) among the widths of the line widths of the unexposed portions as an analysis. The evaluation coefficient of the degree of degree of analysis is smaller and becomes more good. The results are shown in Table 4. <Photoresist shape>. Use Li (called Via), exposure (use the machine (sodium sulphate water part, light-hardened light sensitivity ladder sheet only 4 ° 30/30, the space of the light into the light. Solution results -44 - 201224656 after imaging The photoresist shape was observed using a scanning electron microscope (trade name: Hitachi Scanning Electron Microscope s-5 00A). The photoresist shape is preferably close to a rectangular shape. <Peelability> The evaluation was carried out by the following methods. First, the photosensitive resin composition layers of the respective examples and comparative examples were formed on a copper-clad laminate, and each photosensitive resin composition layer was exposed and developed to prepare a photohardening of 40 mm X 50 mm. Then, the film was peeled off using a 3% aqueous sodium hydroxide solution, and the peeling property was evaluated as the peeling time as the peeling time from the end of the peeling of the photocured film on the copper-clad laminate, and it was observed by visual observation. The size of the release sheet after the completion of the peeling was displayed on the conditions of the peeling process and the size of the release sheet shown in Table 3. The results obtained are shown in Table 4. [Table 3] Process, etc. Conditions, etc. Exposure exposure: 60mJ/cm2, size: 40mmx50mm Imaging solution: l% Na2C03, liquid temperature: 30 〇C, spray stripping stripping solution: 3% NaOH, liquid temperature: 50 〇C, immersion stirring stripping The size of the sheet L: flaky, M: 30 to 40 mm, S: 30 mm or less - 45 - 201224656 [i Comparative Example 5 CN cn Rectangular Comparative Example 4 〇 100 Rectangular Comparative Example 3 o 220 Rectangular Comparative Example 2 rH jrj 00 Rectangular Comparative Example 1 (N v〇00 Rectangular Example 6 o zn Rectangular Example 5 Τ-Η o 00 Rectangular Example 4 o (N 00 κη Rectangular Example 3 o 00 v〇in Rectangular Example 2 τ·Ή o On 〇0 ! Rectangular Example 1 1_ o § ϋ0 Rectangular Light Sensitivity* Resolution (μπι) Peeling Time (8) ^ 1 Size of the Peeling Sheet Resistive Shape Sharp Attack #-Nssss Plug w* -46- 201224656 <Evaluation Results> As shown in Table 4, 'Each Embodiment 丨~6 is a resolution of 1 〇μηι and a high resolution, the peeling time is moderately shortened, and the size of the release sheet is also small, achieving a balance between resolution and peelability. On the other hand, in Comparative Examples 1, 2, and 5, the resolution of good peelability is low. In addition, in the comparative examples 3 and 4', the peeling time of the high-resolution peeling time was long, and the size of the peeling sheet became large. As described above, the effect of the photosensitive resin composition of the present invention was confirmed. [Industrial Applicability] According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive element, a method for forming a photoresist pattern, and a method for producing a printed wiring board, which have sufficient effects in improving the resolution and the peeling resistance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. [Explanation of main component symbols] 1 : Photosensitive element 2 : Support film 3 : Photosensitive resin composition layer 4 : Protective film -47-