TW201214041A - Photosensitive resin compound, photosensitive element, method for forming resist pattern, method for producing print wiring board, and print wiring board - Google Patents

Photosensitive resin compound, photosensitive element, method for forming resist pattern, method for producing print wiring board, and print wiring board Download PDF

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Publication number
TW201214041A
TW201214041A TW100125622A TW100125622A TW201214041A TW 201214041 A TW201214041 A TW 201214041A TW 100125622 A TW100125622 A TW 100125622A TW 100125622 A TW100125622 A TW 100125622A TW 201214041 A TW201214041 A TW 201214041A
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Taiwan
Prior art keywords
photosensitive resin
mass
resin layer
component
resist pattern
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TW100125622A
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Chinese (zh)
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TWI563342B (en
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Junichi Iso
Yoshiki Ajioka
Mitsuru Ishi
Manami Usuba
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Hitachi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/0285—Silver salts, e.g. a latent silver salt image
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/0325—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polysaccharides, e.g. cellulose
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0272—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers for lift-off processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

A photosensitive resin composition includes (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenic unsaturated bond, (C) a photopolymerization initiator and (D) a sensitizing dye. The (B) component includes a (meth)acrylate compound having a structure derived from a dipentaerythritol, and the (D) component includes a pyrazoline compound.

Description

.201214041 六、發明說明： 【發明所屬之技術領域】 本發明係關於感光性樹脂組成物、感光性元件、抗蝕 圖型之製造方法、引線框架之製造方法、印刷電路板之製 ' 造方法及印刷電路板。 【先前技術】 以往，於印刷電路板之製造領域中，作爲蝕刻或鍍敷 等所用之抗蝕材料之感光性樹脂組成物，或具有將含有此 感光性樹脂組成物之層（以下，稱爲「感光性樹脂層」） 形成於支持薄膜上，並於感光性樹脂層上配置保護薄膜而 成之構造的感光性元件（層合體）受到廣泛使用。 自此，印刷電路板係使用上述感光性元件，例如藉由 以下之順序而製造。即，首先將感光性元件之感光性樹脂 層層合於貼銅層合板等之電路形成用基板上。此時，與感 光性樹脂層之支持薄膜接觸之面（以下，稱爲感光性樹脂 層之「下面」）相反對側之面（以下，稱爲感光性樹脂層 之「上面」），係與形成電路形成用基板之電路之面密著 。因此，將保護薄膜配置於感光性樹脂層之上面時，係一 • 邊剝離保護薄膜並同時進行此層合作業。又，層合係藉由 將感光性樹脂層加熱壓著於基底之電路形成用基板上而進 行（常壓層合法）。 其次，經由遮罩薄膜等而施行感光性樹脂層之圖型曝 光。此情況時，係於曝光前或曝光後之任何時點剝離支持 -3- 201214041 薄膜。其後，將感光性樹脂層之未曝光部以顯像液溶解或 分散去除。其後，施以蝕刻處理或鍍敷處理而使圖型形成 ，而最後將硬化部分剝離除去。 然而，作爲上述之圖型曝光之手法，近年來則係不經 由遮罩薄膜而使用數位資料將活性光線直接照射成圖像狀 之雷射直接描繪法受到實用化。作爲直接描繪法所用之光 源，由安全性或操作性等之面觀之，係使用YAG雷射及半 導體雷射等，而最近亦有提出使用長壽命且高輸出之氮化 鎵系藍色雷射等之技術。 並且，近年來伴隨印刷電路板之高精細化、高密度化 ，而逐漸改採用可形成比以往更精細圖型之被稱爲DLP ( Digital Light Processing)曝光法之直接描繪法。一般而 言，DLP曝光法係使用將藍紫色半導體雷射作爲光源之波 長390~430nm之活性光線。 又，在主要泛用之印刷電路板中，亦採用使用可對應 少量多品種之將YAG雷射作爲光源之波長3 55nm之多邊多 光束（polygon multi-beam)的曝光法。 伴隨此般各種之圖型曝光方法之開發，爲了可對應各 曝光波長，亦探討著於感光性樹脂組成物中適用各種增感 劑（例如，參考專利文獻1〜5 )。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2004-301996號公報 [專利文獻2]日本特開2005-107191號公報 201214041 [專利文獻3]日本特開2005-215142號公報 [專利文獻4]日本特開2007_101941號公報 [專利文獻5]日本特開2007-101940號公報 【發明內容】 [發明所欲解決之課題] 抗蝕圖型近年來逐漸更加微細化之中，特別係於蝕刻 步驟中，要求具有充分蓋孔可靠性並同時要求滿足形成 L/S (線寬度/間距寬度）=2〇/20 (單位：μπι )以下之圖型 之高解像度性。 在此，蓋孔可靠性係指將通孔以抗蝕膜覆蓋時，直至 顯像處理等之抗蝕剝離步驟前之段階中，抗蝕膜難以裂斷 之性能。 又，對於用以形成抗蝕圖型之感光性樹脂層亦要求有 密著性。在密著性之提升上，使感光性樹脂層柔軟化係爲 有效，藉此基材之朝凹凸之追隨性亦提升。然而，其結果 在剝離步驟下之抗蝕之剝離變得需要更長時間而有導致生 產效率降低之情形。又，感光性樹脂層之柔軟化亦會使由 捲取感光性元件之製品輥之端部產生感光性樹脂層滲出之 現象（熔邊，Edge Fusion)，而有污染層合輕之憂慮。 又，在使感光性樹脂層之解像度提升上，感光性樹脂 層之薄膜化係爲有效。然而，在印刷電路板形成時必須有 一定程度之電路厚（銅厚等）時，由於有蝕刻工法中有鈾 刻時之蓋孔可靠性容易變得不足之傾向，而被覆通孔之部 -5- 201214041 分之抗蝕膜容易變得脫落。故，藉由使感光性樹脂層變薄 而使抗蝕圖型之寬度變狹窄而進行提高解像度之方法則有 其界限。 更且’使雷射高速移動而進行曝光之直接描繪法，若 與使用碳弧燈、水銀蒸汽弧燈、超高壓水銀燈、高壓水銀 燈及氙氣燈等之有效放射紫外線之光源進行全面曝光之以 往之曝光方法相比，每個點之曝光能量爲小致使生產效率 變低。故’對直接描繪法要求有更高感度之感光性樹脂組 成物。 因此’爲了使光感度提升，若增加感光性樹脂組成物 中所含之光開始劑或增感劑之量，由於感光性樹脂層之表 層部局部性地進行光反應且層底部之硬化性降低，而有光 硬化後所得之解像度及抗蝕形狀惡化之傾向。 本發明係有鑑於上述問題點而完成者，係以提供光感 度優良，且可使所形成之抗蝕膜之蓋孔可靠性或密著性及 所形成之抗蝕圖型之解像度提升之感光性樹脂組成物、使 用此之感光性元件、抗蝕圖型之製造方法、引線框架之製 造方法及印刷電路板之製造方法爲目的者。 [用以解決課題之手段] 本發明者們發現一種含有（Α)成分之黏合劑聚合物 、（Β)成分之具有至少一個乙烯性不飽和鍵結之光聚合 性化合物、（C )成分之光聚合開始劑、（D )成分之增感 色素，且其中上述（Β)成分含有具有源自二季戊四醇之 -6- 201214041 骨架之（甲基）丙烯酸酯化合物，上述（D)成分含有吡 唑啉化合物之感光性樹脂組成物，其光感度優良，可使所 形成之抗蝕膜之蓋孔可靠性或密著性及所形成之抗蝕圖型 之解像度提升一事，進而完成本發明。 又，本發明係關於具有支持體，與於上述支持體上所 形成之源自上述感光性樹脂組成物之感光性樹脂層的感光 性元件。藉此，可提供上述特性皆優之感光性元件。 並且，本發明係關於具有於基板上形成源自上述感光 性樹脂組成物之感光性樹脂層的感光性樹脂層形成步驟、 對上述感光性樹脂層之至少一部分照射活性光線而使曝光 部光硬化之曝光步驟、藉由顯像將上述感光性樹脂層之未 硬化部分由基板上除去之顯像步驟之抗蝕圖型之製造方法 。藉此，可形成上述特性皆優之抗蝕圖型。 又，本發明係關於含有對藉由上述抗蝕圖型之製造方 法而形成有抗蝕圖型之基板施予蝕刻處理或鎪敷處理而形 成導體圖型之步驟的印刷電路板之製造方法及藉此所得之 印刷電路基板。所使用之感光性樹脂組成物由於上述特性 皆優，故可提供適於印刷電路板之高密度化的製造法。 更進一步，本發明係關於含有對藉由上述抗蝕圖型形 成方法而形成有抗蝕圖型之基板施予鍍敷處理而形成導體 圖型之步驟的引線框架之製造方法。所使用之感光性樹脂 組成物由於上述特性皆優，故可提供適於引線框架之高密 度化的製造法。 201214041 [發明之效果] 依據本發明，可提供光感度優良且所形成之抗蝕膜之 蓋孔可靠性或密著性及所形成之抗蝕圖型之解像性皆優之 感光性樹脂組成物、使用此之感光性元件、抗蝕圖型之形 成方法、引線框架之製造方法、印刷電路板之製造方法及 印刷電路板。 【實施方式】 以下，詳細說明關於本發明之適宜實施例。尙且，本 發明中之（甲基）丙烯酸係丙烯酸及對應其之甲基丙烯酸 ’（甲基）丙烯酸酯係指丙烯酸酯及對應其之甲基丙烯酸 酯’（甲基）丙烯醯基係指丙烯醯基及對應其之甲基丙烯 醯基* 又，本發明中「步驟」之用語不僅單指獨立之步驟， 在與其他步驟無法明確區別時，只要係可達成該步驟之所 期望之作用者，亦被本用語所包含。 並且，本明細書中使用「〜」所表示之數値範圍係分 別表示包含記載於「〜」之前後之數値的最小値及最大値 之範圍。 <感光性樹脂組成物> 本發明之感光性樹脂組成物係含有（A )黏合劑聚合 物、（B )具有至少一個乙烯性不飽和鍵結之光聚合性化 合物' (C)光聚合開始劑、（D )增感色素而成。 -8 - 201214041 以下’更詳細說明本發明之感光性樹脂組成物所使用 之各成分。 [(A)成分··黏合劑聚合物] 作爲本發明可使用之（A)成分：黏合劑聚合物，例 如可舉出丙烯酸系樹脂、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、及酚系樹脂。 由鹼顯像性之觀點，以丙烯酸系樹脂爲佳。此等可單獨使 用或將2種以上組合使用。 上述（A )黏合劑聚合物係例如可藉由使聚合性單體 自由基聚合而製造。上述聚合性單體，例如可舉出苯乙烯 、乙烯甲苯、及α-甲基苯乙烯等之於α-位或芳香族環中經 取代之可聚合之苯乙烯衍生物、二丙酮丙烯醯胺等之丙烯 醯胺、丙烯腈及乙烯-η -丁基醚等之乙烯醇之酯類、（甲基 )丙烯酸烷酯、（甲基）丙烯酸苄基酯、（甲基）丙烯酸 四氫呋喃基酯、（甲基）丙烯酸二甲基胺基乙酯、（甲基 )丙烯酸二乙基胺基乙基酯'(甲基）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、α-溴丙烯酸、α-氯丙 烯酸、β -呋喃基（甲基）丙烯酸、β -苯乙烯基（甲基）丙 烯酸、馬來酸、馬來酸酐、馬來酸單甲酯、馬來酸單乙酯 、馬來酸單異丙酯等之馬來酸單酯、富馬酸、桂皮酸、α-氰基桂皮酸、伊康酸、巴豆酸、及丙炔酸。此等可單獨使 用或將2種以上組合使用。 201214041 作爲上述（甲基）丙烯酸烷酯，例如可舉出下述一般 式（IV) H2C = C(R6)-COOR7 (IV) [式（IV)中，R6表示氫原子或甲基，R7表示碳數 1~12之烷基]所表示之化合物、及此等化合物之烷基被羥 基、環氧基、鹵基等所取代之化合物。 上述一般式（IV)中之R7所示之碳數1〜12之烷基，例 如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、 辛基、壬基、癸基、十一基、十二基、苄基及此等之構造 異構物。 上述一般式（IV)所表示之單體，例如可舉出（甲基 )丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙 酯、（甲基）丙烯酸丁基酯、（甲基）丙烯酸戊酯、（甲 基）丙烯酸己酯、（甲基）丙烯酸庚酯、（甲基）丙烯酸 辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸壬酯 、（甲基）丙烯酸癸酯、（甲基）丙烯酸十一酯、及（甲 基）丙烯酸十二酯、（甲基）丙烯酸苄酯。此等可單獨使 用或將2種以上組合使用。 又’本發明中之（A)成分之黏合劑聚合物，由鹼顯 像性之觀點’係以含有羧基爲佳，例如，可藉由使具有羧 基之聚合性單體與其他聚合性單體自由基聚合而製造。上 述具有羧基之聚合性單體係以（甲基）丙烯酸爲佳，其中 亦以甲基丙烯酸爲更佳。 上述（A)黏合劑聚合物之羧基含有量（相對於所使 -10- 201214041 用之全聚合性單體之具有羧基之聚合性單體之配合率）， 由鹼顯像性與鹼耐性之平衡性之觀點，以1 2〜5 0質量％爲佳 ’ 12~40質量％爲較佳，15〜35質量％爲更佳，15~30質量％ 爲特佳。此羧基含有率爲1 2質量％以上時鹼顯像性提升， 5 0質量％以下時則有鹼耐性優異之傾向。 尙且’源自上述（A)黏合劑聚合物中之具有羧基之 聚合性單體之構造單位之含有率，係與上述含有羧基之單 體之配合率有所相關，故係以12~5 0質量％爲佳，12〜40質 量％爲較佳，15〜35質量％爲更佳，15〜30質量％爲特佳》 又’本發明中之（A)成分之黏合劑聚合物，由密著 性及耐藥品性之觀點，以使其含有苯乙烯或苯乙烯衍生物 作爲聚合性單體爲佳。 將上述苯乙烯或苯乙烯衍生物作成共聚合成分時，其 含有量（相對於所使用之全聚合性單體之苯乙烯或苯乙烯 衍生物之配合率）由使密著性及耐藥品性變爲良好之觀點 ，係相對於（A)成分全體之固形分以含有1〇質量％〜60質 量％爲佳，含有15質量％〜50質量％爲更佳。此含有量爲10 質量％以上時有密著性上升之傾向，50質量％以下時可抑 制因剝離片變大所造成之剝離所需時間之長時間化。 尙且，源自上述（A)黏合劑聚合物中之苯乙烯或苯 乙烯衍生物之構造單位之含有率，係與苯乙烯或苯乙烯衍 生物之上述配合率有所相關，以10質量％~60質量％爲佳， I5質量％〜50質量％爲更佳。 此等黏合劑聚合物可單獨使用或將2種類以上組合使 -11 - 201214041 用。作爲將2種類以上予以組合使用時之黏合劑聚合物， 例如可舉出由不同共聚合成分所構成之2種類以上之黏合 劑聚合物、不同重量平均分子量之2種類以上之黏合劑聚 合物’及不同分散度之2種類以上之黏合劑聚合物。 上述（A)黏合劑聚合物係可藉由通常之方法而製造 。具體而言’例如，可藉由使（甲基）丙烯酸烷基酯與（ 甲基）丙烯酸與苯乙烯等自由基聚合而製造。 上述（A)黏合劑聚合物之重量平均分子量，由機械 強度及鹼顯像性之平衡之觀點，以20,000〜3 00,000爲佳， 40,〇〇〇〜150,000爲較佳，40,000〜120,000爲更佳，50,000〜 80,000爲特佳。重量平均分子量若在20,000以上則有耐顯 像液性優良之傾向，在300,000以下則有可抑制顯像時間 變長之傾向。尙且，本發明之重量平均分子量係依據凝膠 滲透層析法而測定，並依據使用標準聚苯乙烯而作成之檢 量線所換算之値。 上述（A)黏合劑聚合物之含有量係相於（A)成分 及後述之（B)成分之總量100質量份，以30質量份〜80質 量份爲佳，以40質量份〜75質量份爲較佳，以50質量份~70 質量份爲更佳。（A)成分之含有量若在此範圍時，感光 性樹脂組成物之塗膜性及光硬化物之強度可變得更良好。 [(B)成分：具有至少一個乙烯性不飽和鍵結之光聚合性 化合物] 作爲本發明所用之（B)成分之具有至少一個乙烯性 -12- 201214041 不飽和鍵結之·光聚合性化合物，由平衡地提升解像度及蓋 孔可靠性之觀點，係至少含有具有源自二季戊四醇之骨架 之（甲基）丙烯酸酯化合物。在此，具有源自二季戊四醇 之骨架之（甲基）丙烯酸酯係指二季戊四醇與（甲基）丙 烯酸之酯化物者，而該酯化物係定義爲含有經伸烷基氧基 改質之化合物者。又，一分子中之酯鍵之數係以6爲佳， 亦可混合酯鍵之數爲1〜5之化合物。 作爲具有源自二季戊四醇之骨架之（甲基）丙烯酸酯 ，更具體可舉出例如下述一般式（I)所表示之化合物。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a photosensitive element, a method for producing a resist pattern, a method for producing a lead frame, and a method for producing a printed circuit board. And printed circuit boards. [Prior Art] In the field of the manufacture of printed circuit boards, a photosensitive resin composition as a resist material for etching or plating, or a layer containing the photosensitive resin composition (hereinafter referred to as "Photosensitive Resin Layer" A photosensitive element (laminate) having a structure in which a protective film is formed on a support film and is provided with a protective film is widely used. From then on, the printed circuit board is manufactured using the above-described photosensitive element, for example, by the following procedure. In other words, the photosensitive resin layer of the photosensitive element is first laminated on a circuit-forming substrate such as a copper-clad laminate. In this case, the surface opposite to the support film of the photosensitive resin layer (hereinafter referred to as "underside" of the photosensitive resin layer) is opposite to the opposite side (hereinafter referred to as "upper surface" of the photosensitive resin layer). The surface of the circuit forming the circuit-forming substrate is adhered. Therefore, when the protective film is disposed on the photosensitive resin layer, the protective film is peeled off and the layer is simultaneously bonded. Further, the lamination is carried out by heating and pressing the photosensitive resin layer on the substrate for circuit formation (normal pressure lamination). Next, pattern exposure of the photosensitive resin layer is performed via a mask film or the like. In this case, support -3- 201214041 film is peeled off before or after exposure. Thereafter, the unexposed portion of the photosensitive resin layer is dissolved or dispersed in the developing solution. Thereafter, an etching treatment or a plating treatment is applied to form a pattern, and finally the hardened portion is peeled off. However, as a method of exposure of the pattern described above, in recent years, a direct laser direct drawing method in which active light is directly irradiated into an image using a digital material without using a mask film has been put into practical use. As a light source used in the direct drawing method, YAG lasers and semiconductor lasers are used in terms of safety or operability, and recently, a long-life and high-output GaN-based blue ray has been proposed. Shooting and other technologies. In addition, in recent years, with the high definition and high density of printed circuit boards, a direct drawing method called DLP (Digital Light Processing) exposure method which can form a finer pattern than the conventional one has been gradually adopted. In general, the DLP exposure method uses active light of a wavelength of 390 to 430 nm using a blue-violet semiconductor laser as a light source. Further, in the main general-purpose printed circuit board, an exposure method using a polygon multi-beam having a wavelength of 3 55 nm using a YAG laser as a light source in a small number of varieties is also employed. With the development of various pattern exposure methods, various sensitizers have been proposed for use in photosensitive resin compositions in order to respond to respective exposure wavelengths (for example, refer to Patent Documents 1 to 5). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-215142 [Patent Document 3] JP-A-2005-215191 (Patent Document 3) JP-A-2005-215142 [Patent Document 5] JP-A-2007-101940 [Patent Document 5] JP-A-2007-101940 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The pattern of the resist pattern has been further refined in recent years, particularly In the etching step, it is required to have sufficient cap hole reliability and at the same time, it is required to satisfy the high resolution which forms a pattern of L/S (line width/pitch width) = 2 〇 / 20 (unit: μπι ) or less. Here, the reliability of the cap hole refers to a performance in which the resist film is hardly broken in the step before the resist stripping step such as development processing when the via hole is covered with a resist film. Further, adhesion to the photosensitive resin layer for forming a resist pattern is also required. In the improvement of the adhesion, it is effective to soften the photosensitive resin layer, whereby the followability of the substrate toward the unevenness is also improved. However, as a result, the peeling of the resist under the peeling step becomes longer and there is a case where the productivity is lowered. Further, the softening of the photosensitive resin layer causes a phenomenon in which the photosensitive resin layer bleeds out from the end portion of the product roll from which the photosensitive element is taken up (Edge Fusion), and there is a concern that the contamination layer is light. Moreover, the thinning of the photosensitive resin layer is effective in improving the resolution of the photosensitive resin layer. However, when a certain degree of circuit thickness (copper thickness, etc.) must be formed when the printed circuit board is formed, there is a tendency that the reliability of the cap hole when the uranium engraving is apt to become insufficient in the etching method, and the part of the through hole is covered - 5-201214041 The resist film is easy to fall off. Therefore, there is a limit to the method of increasing the resolution by narrowing the width of the resist pattern by thinning the photosensitive resin layer. Furthermore, the direct drawing method of exposing the laser to high-speed movement is a comprehensive exposure to a light source that uses ultraviolet light, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp. Compared with the exposure method, the exposure energy at each point is small, resulting in low production efficiency. Therefore, a photosensitive resin composition requiring a higher sensitivity to the direct drawing method is required. Therefore, in order to increase the light sensitivity, if the amount of the light-initiating agent or the sensitizer contained in the photosensitive resin composition is increased, the surface layer portion of the photosensitive resin layer partially undergoes photoreaction and the hardenability of the bottom portion of the layer is lowered. However, there is a tendency that the resolution obtained by photohardening and the shape of the resist deteriorate. The present invention has been made in view of the above problems, and is excellent in providing light sensitivity, and can improve the reliability or adhesion of the formed resist film and the resolution of the formed resist pattern. A resin composition, a photosensitive element using the same, a method for producing a resist pattern, a method for producing a lead frame, and a method for producing a printed circuit board are intended. [Means for Solving the Problem] The present inventors have found a binder polymer having a (Α) component, a photopolymerizable compound having at least one ethylenically unsaturated bond, and a component (C) a photopolymerization initiator, a sensitizing dye of the component (D), wherein the (Β) component contains a (meth) acrylate compound having a skeleton derived from dipentaerythritol -6-201214041, and the component (D) contains a pyrazole The photosensitive resin composition of the porphyrin compound has excellent photosensitivity, and the reliability or adhesion of the formed resist film and the resolution of the formed resist pattern can be improved, and the present invention has been completed. Further, the present invention relates to a photosensitive element having a support and a photosensitive resin layer derived from the photosensitive resin composition formed on the support. Thereby, a photosensitive element excellent in the above characteristics can be provided. Furthermore, the present invention relates to a photosensitive resin layer forming step of forming a photosensitive resin layer derived from the photosensitive resin composition on a substrate, and irradiating at least a part of the photosensitive resin layer with an active light to cure the exposed portion. The exposure step is a method for producing a resist pattern of a developing step of removing the uncured portion of the photosensitive resin layer from the substrate by developing. Thereby, a resist pattern having the above characteristics can be formed. Moreover, the present invention relates to a method of manufacturing a printed circuit board including a step of forming a conductor pattern by applying an etching process or a ruthenium treatment to a substrate on which a resist pattern is formed by the above-described resist pattern manufacturing method. The printed circuit board thus obtained. Since the photosensitive resin composition to be used is excellent in the above characteristics, it is possible to provide a production method suitable for increasing the density of a printed circuit board. Furthermore, the present invention relates to a method of manufacturing a lead frame comprising a step of forming a conductor pattern by applying a plating process to a substrate on which a resist pattern is formed by the resist pattern forming method. Since the photosensitive resin composition to be used is excellent in the above characteristics, it is possible to provide a production method suitable for high density of the lead frame. 201214041 [Effects of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in light sensitivity and which is excellent in the reliability or adhesion of the formed resist film and the resolution of the formed resist pattern. And a photosensitive element using the same, a method of forming a resist pattern, a method of manufacturing a lead frame, a method of manufacturing a printed circuit board, and a printed circuit board. [Embodiment] Hereinafter, a preferred embodiment of the present invention will be described in detail. Moreover, the (meth)acrylic acrylic acid in the present invention and the corresponding methacrylic acid '(meth)acrylate means acrylate and the corresponding methacrylate '(meth)acryloyl group means Acryl fluorenyl group and corresponding methacryl oxime group * In addition, the term "step" in the present invention refers not only to an independent step, but also to the desired effect of the step when it is not clearly distinguishable from other steps. Also included in this term. Further, the range of numbers indicated by "~" in the present specification indicates the range including the minimum 値 and the maximum 记载 of the number 记载 before and after the "~". <Photosensitive Resin Composition> The photosensitive resin composition of the present invention contains (A) a binder polymer, and (B) a photopolymerizable compound having at least one ethylenically unsaturated bond' (C) photopolymerization Starting agent, (D) sensitized pigment. -8 - 201214041 Hereinafter, each component used in the photosensitive resin composition of the present invention will be described in more detail. [(A) component·················· A guanamine epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of alkali developability, an acrylic resin is preferred. These may be used singly or in combination of two or more. The above (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include a polymerizable styrene derivative substituted with an α-position or an aromatic ring, such as styrene, vinyl toluene, and α-methylstyrene, and diacetone acrylamide. Ethyl alcohol esters such as acrylamide, acrylonitrile and ethylene-η-butyl ether, alkyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate 'p-propyl methacrylate, 2,2,2-trifluoroethyl (A) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth)acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, Maleic acid monoester of β-styryl (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Acid, cinnamic acid, α-cyano cinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These may be used singly or in combination of two or more. 201214041 The above-mentioned (meth)acrylic acid alkyl ester is, for example, the following general formula (IV): H2C = C(R6)-COOR7 (IV) [In the formula (IV), R6 represents a hydrogen atom or a methyl group, and R7 represents A compound represented by an alkyl group having 1 to 12 carbon atoms and a compound in which an alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group or the like. The alkyl group having 1 to 12 carbon atoms represented by R7 in the above general formula (IV) may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a decyl group. , fluorenyl, undecyl, dodecyl, benzyl and these structural isomers. Examples of the monomer represented by the above general formula (IV) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Amyl methacrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate , (meth) methacrylate, eleven (meth) acrylate, and (meth) acrylate, benzyl (meth) acrylate. These may be used singly or in combination of two or more. Further, the binder polymer of the component (A) in the present invention preferably contains a carboxyl group from the viewpoint of alkali developability, and for example, a polymerizable monomer having a carboxyl group and another polymerizable monomer can be used. Manufactured by radical polymerization. The above polymerizable single system having a carboxyl group is preferably (meth)acrylic acid, and more preferably methacrylic acid. The carboxyl group content of the above (A) binder polymer (combination ratio of the polymerizable monomer having a carboxyl group of the wholly polymerizable monomer used in -10-201214041), and alkali developability and alkali resistance From the viewpoint of balance, it is preferable that 12 to 50% by mass is 12 to 40% by mass, 15 to 35% by mass is more preferable, and 15 to 30% by mass is particularly preferable. When the carboxyl group content is 12% by mass or more, the alkali developability is improved, and when it is 50% by mass or less, the alkali resistance tends to be excellent. Further, the content ratio of the structural unit derived from the polymerizable monomer having a carboxyl group in the above (A) binder polymer is related to the compounding ratio of the above carboxyl group-containing monomer, so that it is 12 to 5 0% by mass is preferable, 12 to 40% by mass is preferable, 15 to 35% by mass is more preferable, and 15 to 30% by mass is particularly preferable. Further, the binder polymer of the component (A) in the present invention is composed of From the viewpoint of adhesion and chemical resistance, it is preferred to contain a styrene or a styrene derivative as a polymerizable monomer. When the styrene or the styrene derivative is used as a copolymerization component, the content (the compounding ratio of the styrene or the styrene derivative with respect to the wholly polymerizable monomer used) is such that the adhesion and the chemical resistance are obtained. In view of the fact that the solid content of the entire component (A) is preferably from 1% by mass to 60% by mass, more preferably from 15% by mass to 50% by mass. When the content is 10% by mass or more, the adhesion tends to increase, and when it is 50% by mass or less, the time required for peeling due to the increase in the release sheet can be suppressed. Further, the content ratio of the structural unit derived from the styrene or styrene derivative in the (A) binder polymer is related to the above-mentioned compounding ratio of the styrene or the styrene derivative, and is 10% by mass. More preferably, it is 60% by mass, and more preferably I5 mass% to 50% by mass. These binder polymers may be used singly or in combination of two or more types for use in -11 - 201214041. When the binder polymer is used in combination of two or more types, for example, two or more types of binder polymers composed of different copolymerization components and two or more types of binder polymers having different weight average molecular weights may be mentioned. And 2 or more types of binder polymers with different degrees of dispersion. The above (A) binder polymer can be produced by a usual method. Specifically, for example, it can be produced by radically polymerizing an alkyl (meth)acrylate with (meth)acrylic acid and styrene. The weight average molecular weight of the above (A) binder polymer is preferably from 20,000 to 30,000,000 in terms of balance between mechanical strength and alkali developability, preferably from 40, 〇〇〇 to 150,000, and more preferably from 40,000 to 120,000. Good, 50,000~80,000 is especially good. When the weight average molecular weight is 20,000 or more, the liquid crystal resistance tends to be excellent, and when it is 300,000 or less, the development time tends to be suppressed. Further, the weight average molecular weight of the present invention is determined by gel permeation chromatography and is calculated based on a calibration line prepared using standard polystyrene. The content of the (A) binder polymer is preferably 30 parts by mass to 80 parts by mass, and preferably 40 parts by mass to 75 parts by mass based on 100 parts by mass of the component (A) and the component (B) described later. The portion is preferably more preferably 50 parts by mass to 70 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured material can be further improved. [Component (B): Photopolymerizable compound having at least one ethylenically unsaturated bond] Photopolymerizable compound having at least one ethylenic -12-201214041 unsaturated bond as the component (B) used in the present invention From the viewpoint of balancedly improving the resolution and the reliability of the cap hole, it contains at least a (meth) acrylate compound having a skeleton derived from dipentaerythritol. Here, the (meth) acrylate having a skeleton derived from dipentaerythritol means an esterified product of dipentaerythritol and (meth)acrylic acid, and the esterified product is defined as a compound having a modified alkylidene group. By. Further, the number of ester bonds in one molecule is preferably 6 or a compound having 1 to 5 ester bonds. The (meth) acrylate having a skeleton derived from dipentaerythritol is more specifically, for example, a compound represented by the following general formula (I).

h2c 一般式（I)中，R4各自獨立表示氫原子或甲基，A表 示碳數2〜6之伸烷基，複數存在之A可互爲相同異可爲相異 。！1爲0~20之整數。 —般式（〇中，R4各自獨立表示氫原子或甲基，由 可使感度、密著性及解像度更加提升之觀點，以甲基爲佳 〇 一般式（I)中，A表示碳數2〜6之伸烷基，以碳數2〜5 之伸烷基爲佳’碳數2〜4之伸烷基爲更佳。 •13- 201214041 —般式（I)中，η爲0〜20之整數，以〇~15爲佳，0〜10 爲較佳，0〜5爲更佳。 又，上述具有源自二季戊四醇之骨架之（甲基）丙烯 酸酯化合物之含有量，由蓋孔可靠性及解像性之平衡性之 觀點，相對於（A )成分及（Β )成分之總量1 00質量份而 言，係以3質量份~25質量份爲佳，5質量份〜20質量份爲更 佳。 (B)成分除了上述具有源自二季戊四醇之骨架之（ 甲基）丙烯酸酯化合物以外，亦可使用其他之光聚合性化 合物。 其他光聚合性化合物，例如可舉出，使多元醇與α，β-不飽和羧酸反應而得之化合物、雙酚Α系（甲基）丙烯酸 酯化合物、具有胺基甲酸酯鍵之（甲基）丙烯酸酯化合物 等之胺基甲酸酯單體、壬基苯氧基四乙烯氧（甲基）丙烯 酸酯、壬基苯氧基八乙烯氧（甲基）丙烯酸酯、γ-氯-β-羥 基丙基-β’-(甲基）丙烯醯氧基乙基-〇-酞酸酯、（3-羥基乙 基-β’-(甲基）丙烯醯氧基乙基-〇-酞酸酯、β-羥基丙基-β’-(甲基）丙烯醯氧基乙基-0-酞酸酯、及（甲基）丙烯 酸烷酯。此等可單獨使用或將2種類以上組合使用。 上述之中，由平衡地提升蓋孔可靠性及解像性之觀點 ，以含有雙酚Α系（甲基）丙烯酸酯化合物爲佳。作爲上 述雙酚A系（甲基）丙烯酸酯化合物，可舉出2,2-雙（4-(( 甲基）丙烯醯氧基聚乙氧基）苯基）丙烷、2,2-雙（4-((甲基 )丙烯醯氧基聚丙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙 -14- 201214041 烯醯氧基聚丁氧基）苯基）丙烷、2,2_雙（4-((甲基）丙烯醯 氧基聚乙氧基聚丙氧基）苯基）丙烷等。此等可單獨使用 或將2種類以上組合使用。 雙酚A系（甲基）丙烯酸酯化合物，例如2,2-雙（4-(( 甲基）丙烯醯氧基二丙氧基）苯基）丙烷係可由商業上取得 如BPE-200 (新中村化學工業（股）製、製品名），2,2-雙（ 4-(甲基丙烯醯氧基五乙氧基）苯基）丙烷係由商業上取 得如BPE-500 (新中村化學工業（股）製、製品名）或FA-321M(日立化成工業（股）製、製品名）。並且，2,2-雙（ 4-(甲基丙烯醯氧基十五乙氧基）苯基）丙烷係可由商業 上取得如ΒΡΕ- 1 3 00 (新中村化學工業（股）製、製品名）。 雙酚Α系（甲基）丙烯酸酯化合物之含有率係相對於 (A )成分及（B )成分之總量而言，以5質量％〜2 5質量％ 爲佳，7質量％〜15質量％爲更佳。 作爲使上述多元醇與（Χ，β-不飽和羧酸反應而得之化合 物，例如可舉出乙烯基之數爲2〜14之聚乙二醇二（甲基） 丙烯酸酯、丙烯基之數爲2〜14之聚丙二醇二（甲基）丙烯 酸酯、乙烯基之數爲2~ 14且丙烯基之數爲2〜14之聚乙烯聚 丙二醇二（甲基）丙烯酸酯、乙烯基之數爲1〜21之三羥甲 基丙烷聚乙烯三（甲基）丙烯酸酯、乙烯基之數爲1〜2 1之 四羥甲基甲烷聚乙烯三（甲基）丙烯酸酯、及乙烯基之數 爲1〜30之四羥甲基甲烷聚乙烯四（甲基）丙烯酸酯。此等 可單獨使用或將2種類以上組合使用。 上述之中，由蓋孔可靠性及解像性優異之觀點，係含 -15- 201214041 有以乙烯基之數爲1〜2 1之三羥甲基丙烷聚乙烯三（甲基） 丙烯酸酯爲佳。 使多元醇與α，β-不飽和羧酸反應而得之化合物之含有 率，係相對於（Α)成分及（Β)成分之總量而言，以5質 量％〜25質量％爲佳，7質量％~15質量％爲更佳》 上述胺基甲酸酯單體，例如可舉出於Ρ位具有羥基之 (甲基）丙烯酸基單體與異佛爾酮二異氰酸酯、2，6-甲苯 二異氰酸酯、2,4-甲苯二異氰酸酯、及1,6-六亞甲基二異 氰酸酯等之二異氰酸酯化合物之加成反應物、參（（甲基） 丙烯醯氧基四乙二醇異氰酸酯）六亞甲基三聚異氰酸酯、 ΕΟ改質胺基甲酸酯二（甲基）丙烯酸酯、及ΕΟ、ΡΟ改質 胺基甲酸酯二（甲基）丙烯酸酯。 尙且，ΕΟ表示環氧乙烷，ΕΟ改質之化合物係具有環 氧乙烷基之嵌段構造。又，ΡΟ表示環氧丙烷，ΡΟ改質之 化合物係具有環氧丙烷基之嵌段構造。 ΕΟ改質胺基甲酸酯二（甲基）丙烯酸酯，例如可舉出 新中村化學工業（股）製、製品名UA-U。又，ΕΟ、ΡΟ改質 胺基甲酸酯二（甲基）丙烯酸酯，例如可舉出新中村化學 工業（股）製、製品名UA-13。又，參（（甲基）丙烯醯氧基四 乙二醇異氰酸酯）六亞甲基三聚異氰酸酯，例如可舉出新 中村化學工業（股）製、製品名UA-21。其中，由可更使蓋 孔可靠性提升之觀點’以具有異三聚氰酸環骨架之胺基甲 酸酯單體爲佳，以參（甲基丙烯醯氧基四乙二醇異氰酸酯 六亞甲基）三聚異氰酸酯之UA_21 (新中村化學工業（股） -16- 201214041 製、製品名）爲更佳。 具有異三聚氰酸環骨架之胺基甲酸酯單體之含有率， 係相對於（A)成分及（B)成分之總量而言，以5質量 %~25質量％爲佳，7質量％~15質量％爲更佳。 上述之其他光聚合性化合物可單獨使用或將2種類以 上組合使用。 上述（B)成分之含有量係相對於（A)成分及（B) 成分之總量100質量份而言，以設爲20質量份〜60質量份爲 佳，30質量份〜55質量份爲更佳，35質量份〜50質量份爲特 佳。（B )成分之含有量若在此範圍時，感光性樹脂組成 物之光感度及塗膜性可變得更良好。 [(C )成分：光聚合開始劑] (C)成分之光聚合開始劑，可舉出二苯甲酮、2-苄 基-2-二甲基胺基-1- ( 4·嗎啉基苯基丁酮-1,2-甲基-1-[4-(甲基硫代）苯基]-2-嗎啉基-丙酮-1等之芳香族酮、烷 基蒽醌等之醌類、安息香烷基醚等之安息香醚化合物、安 息香、烷基安息香等之安息香化合物、苄基二甲基縮酮等 之苄基衍生物、2- ( 〇-氯苯基）-4,5-二苯基咪唑二聚物、 2- ( 〇-氟苯基）-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-(9,9’-吖啶基）庚烷等之 吖啶衍生物等。此等可單獨使用或將2種類以上組合使用 〇 上述之中，亦以含有2,4,5-三芳基咪唑二聚物爲佳。 -17- 201214041 作爲上述2,4,5 -三芳基咪唑二聚物’例如可舉出2_( 〇 -氯 苯基）-4,5-二苯基咪唑二聚物、2-(〇-氯苯基）-4,5-雙· (m -甲氧基苯基）咪唑二聚物、及2- (p -甲氧基苯基）-4,5 -二苯基咪唑二聚物β其中，亦以2-(〇 -氯苯基）-4,5-二苯基咪唑二聚物爲佳。 2,4,5 -三芳基咪唑二聚物，例如’ 2,2’-雙（2-氯苯基 )-4,4’，5,5’-四苯基雙咪唑係可由商業上取得，如8-(：11^ (保土谷化學製、製品名）。 (C) 成分之含有量係相對於（A)成分及（B)成分 之總量100質量份而言，以0.01質量份〜30質量份爲宜，0.1 質量份〜10質量份爲佳，1質量份〜7質量份爲較佳，0.1質 量份〜20質量份爲更佳，2質量份〜6質量份爲更較佳，3質 量份〜5質量份爲特佳。此配合量爲0.1質量份以上時，有 光感度、解像度或密著性提升之傾向，1 〇質量份以下時有 抗蝕形狀優良之傾向。 [(D)成分：增感色素] (D) 成分之增感色素係具有吡唑啉化合物。光聚合 性化合物藉由與具有源自二季戊四醇之骨架之（甲基）丙 烯酸酯化合物組合使用，而可得到光感度優良，且所形成 之抗蝕膜之蓋孔可靠性或密著性及所形成之抗蝕圖型之解 像性皆優之感光性樹脂組成物。 吡唑啉化合物可適用作爲增感色素所使用者。例如可 舉出具有在吡唑啉環含有苯乙烯基、噻吩基、呋喃基、聯 -18- 201214041 苯基或萘基之基的化合物，以具有含有選自苯乙烯基、噻 吩基及呋喃基之至少一種之基爲佳。 吡唑啉環上之含有苯乙烯基、噻吩基或呋喃基之基所 鍵結之位置可爲1位〜5位之任一者，以在3位及5位之至少 一處鍵結者爲更佳。 吡唑啉化合物係以更具有苯基爲佳。吡唑啉環上之苯 基之取代位置可在1位~5位之任一者皆可，以1位爲更佳。 上述吡唑啉化合物係以含有下述一般式（II)所表示 之化合物爲佳。 【化2】H2c In the general formula (I), R4 each independently represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 6 carbon atoms, and A in the plural may be the same or different. ! 1 is an integer from 0 to 20. - In the general formula, R4 independently represents a hydrogen atom or a methyl group, and the viewpoint of improving the sensitivity, the adhesion, and the resolution is further improved by a methyl group. In the general formula (I), A represents a carbon number of 2 The alkyl group of ~6 is preferably an alkyl group having a carbon number of 2 to 5, and the alkyl group having a carbon number of 2 to 4 is more preferably. • 13-201214041 In the general formula (I), η is 0 to 20 The integer is preferably 〇~15, preferably 0~10, more preferably 0~5. Further, the content of the (meth) acrylate compound having a skeleton derived from dipentaerythritol is reliable by the cap hole. The viewpoint of the balance between the sex and the resolution is preferably 3 parts by mass to 25 parts by mass, and 5 parts by mass to 20 parts by mass based on the total amount of the (A) component and the (Β) component of 100 parts by mass. (B) Component Other than the (meth) acrylate compound having a skeleton derived from dipentaerythritol, other photopolymerizable compounds may be used. Other photopolymerizable compounds include, for example, a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, a bisphenol fluorene (meth) acrylate compound, A urethane monomer such as a urethane bond (meth) acrylate compound, decyl phenoxytetraethylene oxy (meth) acrylate, nonyl phenoxy octaethylene oxy (methyl) Acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-anthracene phthalate, (3-hydroxyethyl-β'-(meth) propylene oxime Oxyethyl-indenyl phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-0-decanoate, and alkyl (meth)acrylate. These may be separate Two or more types are used in combination. Among the above, it is preferable to contain a bisphenol fluorene-based (meth) acrylate compound from the viewpoint of balancedly improving the reliability and resolution of the cap hole. The (meth) acrylate compound may, for example, be 2,2-bis(4-((methyl)propenyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((methyl) Acetyleneoxypolypropoxy)phenyl)propane, 2,2-bis(4-((methyl)propane-14-201214041 olefinoxypolybutoxy)phenyl)propane, 2,2_ Bis(4-((meth)propenyloxypolyethoxypolypropoxy) Phenyl)propane, etc. These may be used singly or in combination of two or more kinds. Bisphenol A is a (meth) acrylate compound such as 2,2-bis(4-((methyl)propenyloxy) Dipropoxy)phenyl)propane is commercially available as BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), 2,2-bis(4-(methacryloxy)pentaethoxylate The phenyl)propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi Chemical Co., Ltd.), and 2, 2 - Bis(4-(methacryloxylpentadecyl hexadecyloxy)phenyl)propane is commercially available as ΒΡΕ- 1 3 00 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). The content of the bisphenol fluorene (meth) acrylate compound is preferably 5% by mass to 25% by mass, and 7 mass% to 15% by mass based on the total of the components (A) and (B). % is better. Examples of the compound obtained by reacting the above polyol with (Χ, β-unsaturated carboxylic acid) include polyethylene glycol di(meth)acrylate and propylene group having a vinyl group number of 2 to 14. The number of polypropylene glycol di(meth)acrylates of 2 to 14 and the number of vinyl polypropylene glycol di(meth)acrylates having 2 to 14 vinyl groups and 2 to 14 propylene groups, and the number of vinyl groups is 1 to 21 dimethylolpropane polyethylene tri(meth) acrylate, vinyl number 1 to 2 1 tetramethylol methane polyethylene tri(meth) acrylate, and vinyl number 1 to 30 hydroxymethylmethane polyethylene tetra(meth) acrylate. These may be used singly or in combination of two or more kinds. Among the above, from the viewpoint of excellent reliability and resolution of the lid hole, Containing -15- 201214041 It is preferred to use trimethylolpropane polyethylene tri(meth) acrylate having a vinyl number of 1 to 2 1 . The polyol is reacted with an α,β-unsaturated carboxylic acid. The content of the compound is 5% by mass to 25 based on the total amount of the (Α) component and the (Β) component. % is preferably, and 7 mass% to 15 mass% is more preferable. The above urethane monomer may, for example, be a (meth)acrylic monomer having a hydroxyl group in the oxime and isophorone diisocyanate. Addition reaction of diisocyanate compound such as 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate, ginseng ((meth) propylene oxytetrazide Glycol isocyanate) hexamethylene trimer isocyanate, hydrazine urethane di(meth) acrylate, and hydrazine, hydrazine urethane di(meth) acrylate. ΕΟ represents ethylene oxide, and the ruthenium-modified compound has a block structure of an oxirane group. Further, ΡΟ represents propylene oxide, and the ruthenium-modified compound has a block structure of an oxypropylene group. The urethane di(meth) acrylate may, for example, be manufactured by Shin-Nakamura Chemical Co., Ltd., product name UA-U. Further, hydrazine, hydrazine-modified urethane di(methyl) The acrylate may, for example, be manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name UA-13. The hexamethylene tripolyisocyanate of ginseng ((meth) propylene oxime tetraethylene glycol isocyanate), for example, the product name UA-21, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. From the viewpoint of improving the reliability of the cap hole, it is preferable to use a urethane monomer having an iso-cyanuric acid ring skeleton, and a methacrylic acid oxytetraethylene glycol isocyanate hexamethylene trimeric isocyanate. UA_21 (New Nakamura Chemical Industry Co., Ltd. -16- 201214041, product name) is more preferable. The content of the urethane monomer having a hetero-cyanuric ring skeleton is relative to the component (A). The total amount of the component (B) is preferably 5% by mass to 25% by mass, more preferably 7% by mass to 15% by mass. The other photopolymerizable compounds described above may be used singly or in combination of two or more kinds. . The content of the component (B) is preferably 20 parts by mass to 60 parts by mass, and 30 parts by mass to 55 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). More preferably, 35 parts by mass to 50 parts by mass is particularly preferred. When the content of the component (B) is within this range, the photosensitivity and coating properties of the photosensitive resin composition can be further improved. [(C) component: photopolymerization initiator] The photopolymerization initiator of the component (C) may, for example, be benzophenone or 2-benzyl-2-dimethylamino-1-(4·morpholinyl) Aromatic ketones such as phenylbutanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, and the like a benzoin compound such as a benzoin alkyl ether, a benzoin compound such as a benzoin or an alkyl benzoin, a benzyl derivative such as a benzyl dimethyl ketal, or a 2-( 〇-chlorophenyl)-4,5-di a 2,4,5-triarylimidazole dimer such as a phenylimidazole dimer or a 2-(non-fluorophenyl)-4,5-diphenylimidazole dimer, 9-phenyl acridine, An acridine derivative such as 1,7-(9,9'-acridinyl)heptane, etc. These may be used singly or in combination of two or more kinds, and may also contain 2,4,5- The triaryl imidazole dimer is preferred. -17- 201214041 As the above 2,4,5-triaryl imidazole dimer, for example, 2_(〇-chlorophenyl)-4,5-diphenylimidazole is exemplified. Polymer, 2-(〇-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5- Diphenyl imi The azole dimer β is preferably 2-(anthracene-chlorophenyl)-4,5-diphenylimidazole dimer. 2,4,5-triaryl imidazole dimer, for example, '2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole is commercially available, such as 8-(:11^ (manufactured by Hodogaya Chemical Co., Ltd.). The content of the component (C) is preferably 0.01 parts by mass to 30 parts by mass, and preferably 0.1 parts by mass to 10 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). The mass part is preferably 7 parts by mass, more preferably 0.1 part by mass to 20 parts by mass, more preferably 2 parts by mass to 6 parts by mass, more preferably 3 parts by mass to 5 parts by mass. The compounding amount is 0.1 mass. When the amount is more than the above, there is a tendency that the light sensitivity, the resolution, or the adhesion are improved. When the amount is less than 1 part by mass, the shape of the resist is excellent. [(D) component: sensitizing dye] (D) Sensitizing dye system A pyrazoline compound is used. The photopolymerizable compound is used in combination with a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and is excellent in light sensitivity and formed by a resist film. A photosensitive resin composition excellent in reliability, adhesion, and resolution of the formed resist pattern. The pyrazoline compound can be suitably used as a sensitizing dye. For example, it has a pyrazoline. The compound having a styrene group, a thienyl group, a furyl group, a phenyl group of -18-201214041 phenyl or a naphthyl group is preferably a group having at least one selected from the group consisting of a styryl group, a thienyl group and a furyl group. The position of the group containing a styryl group, a thienyl group or a furyl group on the oxazoline ring may be any one of positions 1 to 5, and is bonded to at least one of the 3 and 5 positions. good. The pyrazoline compound is more preferably a phenyl group. The substitution position of the phenyl group on the pyrazoline ring may be any one of the 1st to the 5th positions, and more preferably 1 position. The above pyrazoline compound is preferably a compound represented by the following general formula (II). [Chemical 2]

上述一般式（II)中，R1及R2各自獨立表示取代或無 取代之苯基 '噻吩基或呋喃基，由使解像度更加提升之觀 點，係以取代或無取代之苯基爲佳。 作爲R1及R2所表示之苯基、噻吩基或呋喃基之取代基 ，可舉出碳數1〜10之烷基、碳數1~10之烷氧基或碳數1~10 之酯基，以碳數1~10之烷基或碳數1〜10之烷氧基爲佳，碳 數3〜8之烷基或碳數1〜5之烷氧基爲更佳。 R1及R2所表示之苯基、噻吩基或呋喃基之取代基爲烷 -19- 201214041 基時，該烷基可爲直鏈狀、分支狀、環狀之任—者’以直 鏈狀或分支狀爲佳，以分支烷基爲佳。 R1及R2所表示之苯基、噻吩基或呋喃基之取代基爲烷 氧基時，該烷氧基可爲直鏈狀、分支狀、環狀之任—者， 以直鏈狀或分支狀爲佳。 R1或R2爲可取代之苯基時，苯基中之取代基之結合位 置係以對位（4位）爲佳。 —般式（Π )中，R3表示碳數卜10之烷基、碳數1~1〇 之烷氧基或碳數1~1〇之酯基，以碳數1~1〇之烷基或碳數 1~1〇之烷氧基爲佳，碳數3〜8之烷基或碳數1~5之烷氧基爲 更佳。 R3所表之上述碳數1~1〇之烷基或碳數1〜1〇之烷氧基可 爲直鏈狀亦可爲分支狀。碳數1〜1〇之烷基，例如可舉出甲 基、乙基、異丙基、η-丁基、tert-丁基、異戊基、及tert-辛基，但並受限於此等。 —般式（II )中之m表示0~5之整數，以0〜4爲佳，0~3 爲較佳，0爲更佳。 尙且，m爲2〜5時，複數之R3可互爲相同亦可爲相異。 —般式（II )中之a表示0〜2之整數，以1爲更佳* 一般式（II)中之b表示0〜2之整數，以0或1爲較佳， 〇爲更佳。 又，一般式（II)中之a及b之和爲1〜4，以1~3爲佳， 1或2爲較佳，1爲更佳。 作爲上述一般式（Π )所表示之化合物，例如可舉出 -20- 201214041 1-苯基-3- ( 4-甲氧基苯乙烯基）-5- ( 4-甲氧基苯基）-口比 唑啉、1-苯基-3-(4-異丙基苯乙烯基）-5-( 4-異丙基苯基 )-吡唑啉、1-苯基- 3-(3,5-二甲氧基苯乙烯基）-5-(3，5-二甲氧基苯基）-吡唑啉、1-苯基-3-( 3，4-二甲氧基苯乙烯 基）-5- (3,4 -二甲氧基苯基）-吡唑啉、1-苯基-3- (2,6-二 甲氧基苯乙烯基）-5- (2,6-二甲氧基苯基）-吡唑啉、I-苯 基-3-( 2,5-二甲氧基苯乙烯基）-5- (2,5-二甲氧基苯基 )-吡唑啉、卜苯基-3- (2,3-二甲氧基苯乙烯基）-5-( 2,3-二甲氧基苯基）-吡唑啉、1-苯基- 3-(2，4-二甲氧基苯乙烯 基）-5- ( 2,4-二甲氧基苯基）-吡唑啉、1- ( 4-tert-丁基-苯基）_3_苯乙烯基-5-苯基-吡唑啉、1_苯基·3-(4-tert-丁 基-苯乙烯基）-5-(44 61^-丁基-苯基）-吡唑啉、1，5-雙-(4-tert-丁基-苯基）-3-(4-tert-丁基-苯乙烯基）-吡唑啉 、l-(4-tert-辛基-苯基）-3-苯乙烯基-5-苯基-吡唑啉、1-苯基-3-( 4-tert-辛基-苯乙烯基）-5- ( 4-tert-辛基-苯基 )-吡唑啉、1 ,5-雙-(4-tert-辛基-苯基）-3- ( 4-tert-辛基-苯乙烯基）-吡唑啉、1-(4-月桂基-苯基）-3-苯乙烯基-5-苯基-吡唑啉、1-苯基- 3-(4-月桂基-苯乙烯基）-5-(4-月 桂基-苯基）-吡唑啉、1-(4-月桂基-苯基）-3- (4-月桂 基-苯乙烯基）-5-(4-月桂基-苯基）-吡唑咐、1-(4-16 1^-辛基-苯基）-3- ( 4-tert-丁 基-苯乙烯基）-5- ( 4-tert-丁 基-苯基）-吡唑啉、1-( 4-tert-丁基-苯基）-3- (4-tert-辛 基-苯乙烯基）-5-(4-以1^-辛基-苯基）-吡唑啉、1-(4-月 桂基-苯基）-3- ( 4-tert-丁 基-苯乙烯基）-5- ( 4-tert-丁 -21 - 201214041 基-苯基）-啦哩琳、1- ( 4-tert -丁基-本基）-3- ( 4 -月桂 基-苯乙烯基）-5-(4-月桂基-苯基）·吡唑啉、卜（4-月桂 基-苯基）-3- ( 4-tert -辛基-苯乙烁基）( 4-tert -辛基_ 苯基）-吡唑啉、l-(4-tert-辛基-苯基）_3_(4-月桂基-苯 乙烯基）-5-(4-月桂基-苯基）-吡唑啉、1-苯基- 3-(4-甲 氧基苯基）-5-(4-tert-丁基苯基）吡唑啉、1-苯基-3-(2-噻吩基）-5-( 4-tert-丁基苯基）-吡唑啉、1-苯基-3-( 2-噻吩基）乙烯基- 5-(2-噻吩基）-吡唑啉、1-苯基-3-(2-噻吩基）-5- (2-噻吩基）-吡唑啉、1-苯基-3- (2-噻吩基 )-5 -苯乙嫌基卩比哩琳、1-苯基-3- ( 4 -聯本基）-5- ( 4-tert-丁基-苯基）-吡唑啉、及1-苯基-3- ( 4-聯苯基）-5-( 4-tert-辛基-苯基）-吡唑啉。此等可單獨使用或將2種以上 組合使用。 上述一般式（II)所表示之化合物中，由合成之容易 度及使光感度提升之觀點，以1-苯基-3- (4-甲氧基苯乙烯 基）-5- ( 4-甲氧基苯基）-吡唑爲特佳，由合成之容易度 及使對溶劑之溶解性提升之觀點，以1-苯基-3- ( 4-異丙基 苯乙烯基）-5- (4-異丙基苯基）吡唑啉爲特佳。 又，本發明之感光性樹脂組成物中，只要係在不損及 本發明之效果的程度內，亦可一倂配合上述一般式（II) 所表示之化合物以外之增感色素。 上述一般式（IV)所表示之化合物以外之增感色素， 例如可舉出二烷基胺基二苯甲酮類、蔥類、香豆素類、氧 葱酮類、噁唑類、苯并噁唑類、噻唑類、苯并噻唑類、三 -22- 201214041 唑類、芪類、三嗪類、噻吩類、萘二甲醯亞胺基類、及三 芳基胺類。此等可單獨使用或將2種以上組合使用。 (D)成分之增感色素中之上述一般式（II)所表示 之化合物之含有比例，在（D )成分之總量中係以1 〇質量 %〜100質量％爲佳，30質量％〜100質量％爲更佳，50〜100質 量％爲特佳。此配合量在10質量％以上時，有容易高感度 化及高解像度化之傾向。 (D)成分之含有量係相對於（A)成分及（B)成分 之總量100質量份而言，以設爲0.01質量％〜1〇質量份爲佳 ，0.05質量％~5質量份爲較佳，0.1質量％〜3質量份爲更佳 。此含有量爲〇.〇1質量份以上時，有容易得到光感度及解 像度之傾向，1 〇質量份以下時，則有容易得到充分良好之 抗蝕形狀的傾向。 [其他成分] 又，本發明之感光性樹脂組成物，可因應必要配合孔 雀綠、維多利亞純藍、亮綠、及甲基紫等之染料、三溴苯 基颯、隱色結晶紫、二苯基胺、苄基胺、三苯基胺、二乙 基苯胺、〇-氯苯胺及第三丁基兒茶酚等之光發色劑、防熱 發色劑、P-甲苯磺胺等之可塑劑、顏料、充塡劑、消泡劑 、難燃劑、密著性賦予劑、調平劑、剝離促進劑、防氧化 劑、香料、顯像劑、熱交聯劑、聚合禁止劑等，其含有量 係相對於（A)成分及（B)成分之總量100質量份而各自 含有〇.〇1質量份〜2 0質量份之程度。此等可單獨使用或將2 -23- 201214041 種類以上組合使用。 本發明之感光性樹脂組成物可因應必要含有至少一種 有機溶劑。上述有機溶劑並無特別受限，可使用通常所用 之有機溶劑。具體而言，可舉出甲醇、乙醇、丙酮、甲基 乙基酮、甲基溶纖劑、乙基溶纖劑、甲苯、N，N-二甲基甲 醢胺、丙二醇單甲基醚等之溶劑或此等之混合溶劑。 例如，可使上述（A)黏合劑聚合物、（B)聚合性化 合物、（C)光聚合開始劑與（D)增感色素溶解於上述有 機溶劑而作成固形分30質量％~60質量％程度之溶液（以下 ，稱爲「塗佈液」）後使用。 尙且，固形分係指由上述溶液（感光性樹脂組成物） 去除揮發性成分後所殘留之成分。 上述塗佈液係可如以下般進行而使用於感光性樹脂層 之形成。將上述塗佈液塗佈於後述之支持薄膜、金屬板等 之支持體之表面上，藉由使其乾燥，而可使源自上述感光 性樹脂組成物之感光性樹脂層形成於支持體上。 金屬板例如可舉出銅、銅系合金、鎳、鉻、鐵、不銹 鋼等之鐵系合金，較佳爲銅、銅系合金、鐵系合金。 所形成之感光性樹脂層之厚度雖根據其用途而異，但 以乾燥後之厚度在Ιμιη〜ΙΟΟμηι程度爲佳。亦可將與感光性 樹脂層之支持體相對向之面的相反側之面（表面）以保護 薄膜被覆。保護薄膜可舉出如聚乙烯、聚丙烯等之聚合物 薄膜等。 -24- 201214041 <感光性元件> 本發明之感光性元件1 0係如圖1中所示之一例之略剖 面圖般’其係具備支持體2，與形成於上述支持體上之源 自上述感光性樹脂組成物之感光性樹脂層4，及具備因應 必要而設置之保護薄膜6等之其他之層而構成者。 [支持體] 上述支持體例如可使用聚對酞酸乙二酯、聚丙烯、聚 乙烯、及聚酯等之具有耐熱性及耐溶劑性之聚合物薄膜。 上述支持體（以下’亦有稱爲「支持薄膜」）之厚度 係以 1μιη~100μιη爲佳 ’ ίμιη〜50μιη爲較佳 ’ 1μιη~30μιη爲更 佳。藉有使支持體之厚度在Ιμιη以上，可抑制將支持薄膜 剝離時之支持薄膜破損。又，藉由在ΙΟΟμπι以下而可抑制 解像度之降低。 [保護薄膜] 上述感光性元件10依據需要可更具備被覆與感光性樹 脂層4之支持體2對向之面相反之面（表面）之保護薄膜6 〇 上述保護薄膜係以對感光性樹脂層之接著力比對支持 薄膜之感光性樹脂層之接著力還小者爲佳，又，係以低魚 眼（fisheye)之薄膜爲佳。 在此’ 「魚眼」係指在將構成保護薄膜之材料熱熔融 ’藉由混練、壓出、2軸延伸、澆鑄法等製造薄膜時，材 -25- 201214041 料之異物、未溶解物、氧化劣化物等被混入薄膜中者。即 ，「低魚眼」係指薄膜中之上述異物等爲少之情形。 具體而言，保護薄膜可使用聚對酞酸乙二酯、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 。市售品可舉出如王子製紙公司製Alphan MA-410、E-200C、信越薄膜公司製等之聚丙烯薄膜、帝人公司製PS-25等之 PS系列 等之聚 對酞酸 乙二酯 薄膜等 。尙且 ，保 護薄 膜係亦可與上述支持體爲相同者。 保護薄膜之厚度係以Ιμιη〜ΙΟΟμηι爲佳，5μιη~50μιη爲 較佳，5μηι〜30μιη爲更佳，15μιη~30μηι爲特佳。藉由使保 護薄膜之厚度在Ιμηι以上，可抑制在一邊剝離保護薄膜一 邊將感光性樹脂層及支持薄膜層合於基板上時之保護薄膜 破損。又，在ΙΟΟμιη以下可使生產性提升。 [製造方法] 本發明之感光性元件係可例如以下般實行而製造。可 藉由包含準備使（Α)黏合劑聚合物、（Β)聚合性化合物 、（C)光聚合開始劑、（D)增感色素溶解於上述有機溶 劑之塗佈液的步驟、將上述塗佈液塗佈於支持體上形成塗 佈層之步驟、使上述塗佈層乾燥而形成感光性樹脂層之步 驟的製造方法而製造。 將上述塗佈液塗佈支持體上係可以輥塗法、浮點塗佈 法、凹板塗佈法、氣刀塗佈法、壓鑄模塗法、棒塗法、噴 塗法等之公知之方法進行。 -26- 201214041 又’上述塗佈層之乾燥只要係可由塗佈層去除有機溶 劑之至少一部分則無特別限制。例如，可在7 0 °C ~ 1 5 0°C中 施行5分~3 0分之程度。乾燥後，感光性樹脂層中之殘留有 機溶劑量，由防止於其後之步驟中之有機溶劑擴散之觀點 ，以2質量％以下爲佳。 感光性元件中之感光性樹脂層之厚度可依據用途而適 宜選擇，乾燥後之厚度以1μηι~200μιη爲佳，5μηι~100μιη爲 更佳，10μηι~50μηι特佳。此厚度若爲Ιμιη以上時，工業性 塗佈變得容易，且生產性提升。在200μιη以下時，可充分 得到本發明之效果，並有光感度爲高，且抗蝕底部之光硬 化性優良之傾向。 本發明之感光性元件，依據需要亦可更具有緩衝層、 接著層、光吸收層、或氣體阻隔層等之中間層等。 本發明之感光性元件之形態並無特別限制。例如，可 爲片狀，或亦可爲在捲芯上捲取成輥狀之形狀。 捲取成輥狀時，以使支持薄膜捲取於外側爲佳。 捲芯例如可舉出聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯 樹脂、聚氯乙烯樹脂、或ABS(丙烯腈-丁二烯-苯乙烯共 聚合物）等之塑膠。 於如此般所得之輥狀之感光性元件輥之端面上’由保 護端面之觀點係以設置端面分隔器爲佳，由耐熔邊之觀點 係以設置防濕端面分隔器爲佳。又’梱包方法係以被透濕 性小之黑鋼板進行包裝爲佳。 本發明之感光性元件係例如可適宜使用於後述之抗蝕 -27- 201214041 圖型之製造方法。 <抗蝕圖型之製造方法> 本發明之抗蝕圖型之製造方法係具有（i)於基板上 形成源自上述感光性樹脂組成物之感光性樹脂層的感光性 樹脂層形成步驟、（ii )對上述感光性樹脂層之至少一部 分照射活性光線使曝光部光硬化之曝光步驟、（iii )藉由 顯像將上述感光性樹脂層之未硬化部分由基板上去除之顯 像步驟，且因應必要亦可含有其他步驟。 (i)感光性樹脂層形成步驟 感光性樹脂層形成步驟中，於基板上形成源自上述感 光性樹脂組成物之感光性樹脂層。上述基板並無特別限制 ，通常係使用具備絕緣層與形成於絕緣層上之導體層的電 路形成用基板，或合金基材等之晶粒墊（引線框架用基材 )° 於基板上形成感光性樹脂層之方法，例如，在上述感 光性元件具有保護薄膜之情況時，可將保護薄膜除去後， 藉由將感光性元件之感光性樹脂層一邊加熱一邊壓著至電 路形成用基板而進行。藉此，可得到依順序具備電路形成 用基板與感光性樹脂層與支持體之層合體。 此感光性樹脂層形成步驟由密著性及追隨性之觀點， 係以在減壓下進行爲佳。壓著時之加熱係以在7〇°C〜13 (TC 之溫度下進行爲佳。又’壓著係以在〇.lMPa〜1.0MPa程度 -28- 201214041 (1〜10kgf/cm2程度）之壓力下進行爲佳，且此等之條件 係可依據需要適宜選擇。尙且，若加熱感光性樹脂層至 70°C〜130°C，雖無必要對電路形成用基板施以預熱處理， 但爲了使密著性及追隨性更加提升，亦可實行電路形成用 基板之預熱處理。 (Π)曝光步驟 曝光步驟中，藉由對形成於基板上之感光性樹脂層之 至少一部分照射活性光線，經活性光線照射之曝光部分光 硬化而形成潛像》 此時，存在於感光性樹脂層上之支持體（支持薄膜） 對活性光線爲穿透性之情況時，可通過支持薄膜而照射活 性光線，但在支持薄膜爲遮光性之情況時，係將支持薄膜 除去後才對感光性樹脂層照射活性光線。 曝光方法可舉出如介由被稱爲原圖（artwork)之正型 或負型遮罩圖型將活性光線照射成圖像狀之方法（遮罩曝 光法）。又，亦可藉由採用LDI ( Laser Direct Imaging) 曝光法、或DLP (Dig+ital Light Processing)曝光法等之直 接描繪曝光法而將活性光線照射成圖像狀之方法。 活性光線之光源係使用公知之光源，例如，碳弧燈、 水銀蒸汽弧燈、超高壓水銀燈、高壓水銀燈 '氙氣燈、氙 氣雷射等之氣體雷射、YAG雷射等之固體雷射、半導體雷 射及氮化鎵系青紫色雷射等之可有效放射紫外線者。又， 亦可使用照相用泛光燈球、太陽燈等之可有效放射可見光 -29 - 201214041 者。 本發明之感光性樹脂組成物係可無特別受限於活性光 線之光源而使用，但係以應用至直接描繪曝光用途爲佳。 (iii)顯像步驟 顯像步驟中，藉由以顯像將上述感光性樹脂層之未硬 化部分由基板上去除，而在基板上形成由上述感光性樹脂 層光硬化後之硬化物所構成之抗蝕圖型。 於感光性樹脂層上存在有支持薄膜之情況時，將支持 薄膜除去後，進行去除（顯像）上述曝光部分以外之未曝 光部分。顯像方法則有濕式顯像與乾式顯像。 濕式顯像時，使用對應感光性樹脂組成物之顯像液， 且藉由公知之顯像方法進行顯像》顯像方法可舉出使用浸 漬方式 '盛液方式、噴霧方式、刷洗、速打、刮削、搖動 浸漬等之方法，由提升解像度之觀點，以高壓噴霧方式最 爲適宜。亦可將此等2種以上之方法予以組合而進行顯像 〇 顯像液之構成可因應上述感光性樹脂組成物之構成而 適宜選擇。例如，可舉出鹼性水溶液、水系顯像液、及有 機溶劑系顯像液。 鹼性水溶液在作爲顯像液使用時，係爲安全且安定， 並且操作性良好。作爲鹼性水溶液之鹼，例如可使用鋰、 鈉或鉀之氫氧化物等之氫氧化鹼、鋰、鈉、鉀或銨之碳酸 鹽或重碳酸鹽等之碳酸鹼、磷酸鉀、磷酸鈉等之鹼金屬磷 -30- 201214041 酸鹽、焦磷酸鈉、焦磷酸鉀等之鹼金屬焦磷酸鹽。 顯像所用之鹼性水溶液，係以〇 _ 1質量％〜5質量％碳酸 鈉之稀釋溶液、0_1質量％〜5質量％碳酸鉀之稀釋溶液、〇」 質量％〜5質量％氫氧化鈉之稀釋溶液、0 · 1質量％ ~ 5質量％ 四硼酸鈉之稀釋溶液等爲佳。又，顯像所用之鹼性水溶液 之pH係以設於9〜11之範圍內爲佳，其溫度係可配合感光性 樹脂層之顯像性而調節。又，於鹼性水溶液中亦可混入表 面活性劑、消泡劑、促進顯像用之少量之有機溶劑等。 上述水系顯像液係例如由水或鹼性水溶液與一種以上 之有機溶劑所構成之顯像液。在此，鹼性水溶液之鹼除先 前所述之物質以外，例如，尙可舉出硼砂或偏矽酸鈉、氫 氧化四甲基銨、乙醇胺、乙二胺、二乙三胺、2-胺基-2-羥 基甲基-1、3-丙二醇、1,3-二胺基丙醇-2、及嗎啉。水系 顯像液之pH係在可充分施行顯像之範圍盡可能越小越佳， 以pH8〜12爲佳，pH9〜10爲更佳。 水系顯像液所用之有機溶劑，例如可舉出3-丙酮醇、 丙酮、乙酸乙酯、具有碳數1〜4之烷氧基之烷氧基乙醇、 乙醇、異丙基醇、丁基醇、二乙二醇單甲基醚、二乙二醇 單乙基醚、及二乙二醇單丁基醚。此等可單獨使用或將2 種類以上組合使用。水系顯像液中之有機溶劑之濃度通常 係以設至2質量％〜90質量％爲佳，其溫度係可配合顯像性 而調整。水系顯像液中亦可混入少量界面活性劑、消泡劑 等。 有機溶劑系顯像液，例如可舉出1，1，1-三氯乙烷、N- -31 - 201214041 甲基吡咯啶酮、N，N-二甲基甲醯胺、環己酮、甲基異丁基 酮、及γ-丁內酯。此等有機溶劑爲了防止起火，以在1質 量％~2 0質量％之範圍內添加水爲佳。 本發明中，在顯像步驟中將未曝光部分除去後，因應 必要藉由施行60°c〜2 50°C程度之加熱或0.2J/CIT12〜10J/cm2程 度之曝光，使抗蝕圖型更加硬化而使用亦可。 <印刷電路板之製造方法> 本發明之印刷電路板之製造方法包含、對藉由上述抗 蝕圖型之製造方法而形成有抗蝕圖型之電路形成用基板施 以蝕刻處理或鍍敷處理而形成導體圖型之步驟，因應必要 亦包含去除抗蝕步驟等之其他步驟所構成。本發明之感光 性樹脂組成物可適宜使用於抗蝕圖型之製造，其中，更亦 以應用於藉由鍍敷處理而形成導體圖型之製造方法爲更適 宜。 蝕刻處理係將形成於基板上之抗蝕圖型作爲遮罩，且 蝕刻去除未被抗蝕所被覆之電路形成用基板之導體層而形 成導體圖型。 蝕刻處理之方法係可因應所欲除去之導體層而適宜選 擇。例如，蝕刻液可舉出二氯化銅溶液、三氯化鐵溶液、 鹼蝕刻溶液、過氧化氫系蝕刻液，由蝕刻因子爲良好之觀 點，以使用三氯化鐵溶液爲理想。 另一方面，鍍敷處理係將形成於基板上之抗蝕圖型作 爲遮罩，於未被抗蝕所被覆之電路形成用基板之導體層上 -32- 201214041 鍍敷銅及焊錫等。鍍敷處理後，去除硬化抗蝕，並更對未 被此抗蝕所被覆之導體層予以蝕刻而形成導體圖型。 鍍敷處理之方法可爲電解電鍍處理，亦可爲無電解電 鎪處理，但以無電解電鍍處理爲佳。無電解電鍍處理，例 如可舉出硫酸銅鍍敷及焦磷酸銅鍍敷等之銅鍍敷、高均勻 酸性錫鉛鍍敷等之錫鉛鍍敷、瓦特浴（硫酸鎳-氯化鎳） 鍍敷及磺胺酸鎳鍍敷等之鎳鍍敷、硬鍍金及軟鍍金等之金 鍍敷。 上述蝕刻處理或鍍敷處理之後，基板上之抗蝕圖型被 去除。抗飩圖型之去除，例如，可藉由比上述顯像步驟所 用之鹼性水溶液更爲強鹼性之水溶液而剝離。此強鹼性之 水溶液，例如可使用1質量％〜1 〇質量％氫氧化鈉水溶液、1 質量％〜1 0質量％氫氧化鉀水溶液。其中，以使用1質量 %~1 0質量％氫氧化鈉水溶液或氫氧化鉀水溶液爲佳，以使 用1質量％~5質量％氫氧化鈉水溶液或氫氧化鉀水溶液爲更 佳。 抗蝕圖型之剝離方式，例如可舉出浸漬方式及噴霧方 式，此等可單獨使用或亦可倂用。 在施以鍍敷處理後去除抗蝕圖型之情況時，更以蝕刻 處理對被抗蝕所被覆之導體層予以鈾刻而形成導體圖型， 藉此可製造所期望之印刷電路板。此時之蝕刻處理之方法 ，可因應所欲去除之導體層而適宜選擇。例如，可適用上 述之蝕刻液。 藉由本發明之印刷電路板之製造方法所製造之印刷電 -33- 201214041 路板，不僅可適用於單層印刷電路板亦可適用於多層印刷 電路板之製造，又，亦可適用於具有小徑通孔之印刷電路 板等之製造。 <引線框架之製造方法> 本發明之引線框架之製造方法包含、對藉由上述抗蝕 圖型形成方法而形成有抗蝕圖型之基板施以鍍敷處理而形 成導體圖型之步驟，亦可因應必要包含去除抗蝕步驟、蝕 刻處理步驟等之其他步驟所構成者。 上述基板，例如，基板可使用合金基材等之晶粒墊（ 引線框架用基材）。本發明中將形成於支持體上之抗蝕圖 型作爲遮罩，而於支持體上施行鍍敷處理。 鍍敷處理之方法可舉出在前述之印刷電路板之製造方 法中既已說明者。上述鍍敷處理之後，支持體上之抗蝕圖 型受到去除。抗蝕圖型之去除，例如，可藉由比上述顯像 步驟所用之鹼性水溶液還要更強鹼性之水溶液進行剝離。 此強鹼性之水溶液，可舉出在前述之印刷電路板之製造方 法中所既已說明者。 抗蝕圖型之剝離方式可舉出浸漬方式、噴霧方式等， 此等可單獨使用亦可倂用。將抗蝕圖型除去後，可更藉由 施行蝕刻處理將不要之金屬層去除，而製造成引線框架。 以上，已說明關於本發明適宜之實施形態，但本發明 不受限於上述實施形態任何之限定者。 -34- 201214041 [實施例] 以下’基於實施例更具體地說明本發明，但本發明並 非係侷限於此等實施例者。尙且，若無特別界定時，「份 」及「％」爲質量基準。 [實施例1〜4、比較例1~4] 首先’依照合成例1合成表1所示之黏合劑聚合物（A_ 1 )，並依據合成例2合成（A_2 )。 <合成例1 > 將共聚合單體之甲基丙烯酸125g、甲基丙烯酸甲酯 275g及苯乙烯l〇〇g，與偶氮二異丁腈i.〇g予以混合而調製 成溶液a。 又，使偶氮二異丁腈l.〇g溶解於甲基溶纖劑60g及甲 苯4〇g之配合液（質量比6 : 4 ) 100g中，而調製成溶液b。 另一方面，對具備有攪拌機、迴流冷卻器、溫度計、 滴入漏斗及氮氣導入管之燒瓶，添加質量比6 : 4之甲基溶 纖劑及甲苯之配合物400g，吹入氮氣並同時攪拌，且加熱 至80°C爲止。 在此，將上述溶液a以4小時滴入後，攪拌並同時在 8 〇°C中保溫2小時。其次，將上述溶液b以10分鐘滴入於燒 瓶內之溶液後，攪拌燒瓶內之溶液並在8〇°C中保溫3小時 。並且，使燒瓶內之溶液以30分鐘升溫至90 °C，並在90 °C 中保溫2小時後，使其冷卻而得到黏合劑聚合物（A-1 )之 -35- 201214041 溶液。對此黏合劑聚合物（Ad)之溶液添加丙酮，調製 成爲不揮發成分（固形分）爲50質量％。 <合成例2 > 將共聚合單體之甲基丙烯酸125g、甲基丙烯酸甲酯 25g、苄基甲基丙烯酸酯125g及苯乙烯225g，與偶氮二異 丁腈1.5g予以混合而調製成溶液〇。 又’使偶氮二異丁腈1.2g溶解於甲基溶纖劑60g及甲 苯40g之配合液（質量比6 : 4) l〇〇g中，而調製成溶液d。 另—方面，對裝備有攪拌機、迴流冷卻器、溫度計、 滴入漏斗及氮氣導入管之燒瓶添加質量比6: 4之甲基溶纖 劑及甲苯之配合物4〇〇g，吹入氮氣並同時攪拌，且加熱至 8〇°C爲止。 在此’將上述溶液c以4小時滴入後，攪拌並同時在 8 〇°C中保溫2小時。其次，將上述溶液d以10分鐘滴入於此 燒瓶;內之溶液中後，攪拌燒瓶內之溶液並同時在80°C中保 溫3小時保溫。並且，使燒瓶內之溶液以3 〇分鐘升溫至 90°C ’在90°C中保溫2小時後，使其冷卻而得到黏合劑聚合 物（A-2 )之溶液。對此黏合劑聚合物（A-2 )之溶液添加 丙酮’而調製成不揮發成分（固形分）爲50質量％。 黏合劑聚合物（A-1 )之重量平均分子量爲60,000， 酸價爲163mgKOH/g。又，黏合劑聚合物（A-2)之重量平 均分子量爲50,000，酸價爲163mgKOH/g。尙且，重量平 $分子量係以凝膠滲透層析法而測定，藉有使用標準聚苯 -36- 201214041 乙烯之檢量線所換算而導出者。G P C之條件係如以下所示 -GPC條件- 泵··日立 L-6000型[(股）日立製作所製] 管柱：Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (計3支）[以上，日立化成工業（股）製、製品名] 溶離液：四氫呋喃 測定溫度：25°C 流量：2.05mL /分 檢測器：日立 L-3300型RI[(股）日立製作所製、製品 名] <感光性樹脂組成物之調製> 其次，將表1所示之材料予以配合而得到感光性樹脂 組成物。尙且，表中之數値係表示配合份數（質量基準） 。又，（A)成分及（B)成分係以固形分下之質量表示。 -37- 201214041 [表i] 材料 實施例1 實施例2 實施例3 資施例4 比較例1 比較例2 比較例3 比較例4 CA) (A-1) *1 55 55 55 - 55 55 55 55 (A-2) *2 - - - 55 - - - - (B) (B-1) *3 10 10 10 10 - 10 - - TMPT*4 - - - - 10 - 10 10 FA-321M*5 13 13 13 13 13 13 13 13 TMPT-21*6 10 10 10 10 10 10 10 10 UA-21 *7 12 12 12 12 12 12 12 12 (C) B-CIM*8 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 (D) CD-1) *9 0.25 - - - 0.25 - - - (D-2) *10 - 0.25 - - - - - - (D-3) *n - - 0.25 0.25 - - - 0.25 EAB*12 - - - - - 0.25 0.25 - 添加劑 隱色結晶紫 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 孔雀綠 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 溶劑 丙酮 10 10 10 10 10 10 10 10 甲苯 10 10 10 10 10 10 10 10 甲醇 10 10 10 10 10 10 10 10 上表中之各成分係如以下所示。 -(A)成分：黏合劑聚合物- 氺1: (A-1)甲基丙烯酸/甲基丙烯酸甲酯/苯乙烯 = 25/55/20 (重量比）、重量平均分子量= 60,000、50質量 %甲基溶纖劑/甲苯=6/4 (重量比）溶液 *2: (A-2)甲基丙烯酸/甲基丙烯酸甲酯/苄基甲基丙烯 酸酯/苯乙烯=2 5/5/25/4 5 (重量比）、重量平均分子量 = 50,000、50質量％甲基溶纖劑/甲苯=6/4 (重量比）溶液 -(B )成分：光聚合性化合物- 氺 3 : ( B-1 ) -38- 201214041 —般式（I )中，Π = 0、R4爲甲基之化合物。 * 4 : TMPT [新中村化學（股）製、製品名] 三羥甲基丙烷三丙烯酸酯 * 5 : FA-32 1M[日立化成工業（股）製、製品名] 2,2-雙（4-((甲基）丙烯醯氧基聚乙氧基）苯基） 丙烷 *6: TMPT-21[日立化成工業（股）製、製品名] 乙氧基化三羥甲基丙烷三丙烯酸酯 * 7 : UA-2 1 [新中村化學（股）製、製品名] 參（甲基丙烯醯氧基四乙二醇異氰酸酯六亞甲基）三 聚異氰酸酯 -(C )成分’·光聚合開始劑- * 8 : B-CIM[保土谷化學製、製品名] 2,2’-雙（2-氯苯基）-4,4’，5,5’-四苯基雙咪唑 -(D)成分：增感色素· * 9 : ( D-1 ) 1-苯基-3- (4-甲氧基苯乙烯基）-5- (4-甲氧基苯基） 吡唑啉 氺 10 : ( D-2) 1-苯基-3-(4-異丙基苯乙烯基）-5_(4-異丙基苯基） 吡唑啉 *11: ( D-3) -39 - 201214041 1-苯基-3- ( 4-tert-丁基苯乙烯基）-5- ( 4-tert-丁基苯 基）吡唑啉 * 12 : EAB [保土谷化學製、製品名] 4,4’-雙（二乙基胺基）二苯甲酮 <感光性元件之調製> 將上述所得之感光性樹脂組成物分別均勻塗佈於厚度 1 6 μιη之聚對酞酸乙二酯薄膜（帝人（股）製、製品名「 HTF01」）上，以100°C之熱風對流式乾燥機乾燥10分鐘， 而形成乾燥後之膜厚爲ΙΟμηι之感光性樹脂層。 在此感光性樹脂層上貼合聚丙烯製之保護薄膜（王子 製紙（股）製、製品名「E200C」），而得到依聚對酞酸乙 二酯薄膜（支持薄膜）、感光性樹脂層、與保護薄膜之順 序而層合之感光性元件。 <層合體之製作> 對於兩面層合有厚度12 μιη之銅箔之玻璃環氧材之貼銅 層合板（基板、日立化成工業（股）製、製品名「MCL-E-67 」）之銅表面，使用具備相當於#600之刷的硏磨機（三啓 (股）製）進行硏磨，水洗後，以空氣對流乾燥。將硏磨後 之貼銅層合板加溫至8 0 °C，剝離保護薄膜同時使感光性樹 脂層接觸銅表面，而分別將上述所得之感光性元件予以層 合。層合係使用1 10°c之加熱輥’以〇.4〇MPa之壓著壓力、 1.5m/分之輥速度下進行。 -40- 201214041 藉此分別得到依貼銅層合板、感光性樹脂層、支持薄 膜之順序層合之層合體。將所得之層合體使用作爲以下所 示之試驗中之試驗片。 <評價> (光感度之測定試驗） 於上述所得之試驗片之支持薄膜上設置日立41段階段 式曝光表’使用以波長3 5 5nm之半導體雷射爲光源之直接 描繪曝光裝置（日本Orbotech(股）製、商品名Paragon-9 000m )，以既定之能量進行曝光。 其次’剝離支持薄膜，將30°C之1 ·〇質量％碳酸鈉水溶 液噴霧45秒鐘，去除未曝光部分並施行顯像處理。 顯像處理後，測定貼銅層合板上所形成之光硬化膜之 階段式曝光表之段數，並求得顯像後之殘留階段數爲1 7.0 段之能量（m】/cm2 )。感光性樹脂組成物之光感度係以上 述能量（mJ/cm2 )越少越表顯示高光感度。其結果係如表 2所示。 (密著性及解像度之評價） 於上述所得之試驗片之支持體薄膜上，使用具有線寬 度/間距寬度爲5/5~47/47 (單位：μιη )之配線圖型之描繪 資料作爲解像度評價用圖型，以日立4 1段階段式曝光表之 顯像後之殘留階段數爲1 7 · 0之能量進行曝光。曝光後’進 行上述光感度之測定試驗與同樣之顯像處理。 -41 - 201214041 顯像處理後，使用光學顯微鏡觀察抗蝕圖型。在抗蝕 圖型之間距部分（未曝光部）被完全地去除，且線寬部分 (曝光部）並無蛇行、缺陷產生而形成之抗蝕圖型之中， 決定線寬度間之間距寬度最小者，而作爲密著性（μηι )及 解像度（μιη )進行評價。此之數値越小表示密著性及解像 度越良好。其結果如表2所示。 (蓋孔可靠性之評價） 在0.4mm厚之貼銅層合板上以7mm間隔開孔有直徑 1mm之圓孔的貼銅層合板上，將上述所得之感光性元件層 合於兩面，以日立41段階段式曝光表之顯像後之殘留階段 數爲1 7.0之能量進行曝光。曝光後，使用與光感度之測定 試驗同樣之顯像液，噴霧3 0秒鐘而進行顯像處理。 顯像後，測定合計3 2 0個之圓孔中感光性元件之破損 數（個）’依據下述數式算出蓋孔破損率，並將此作成蓋 孔可靠性。其結果如表2所示。 蓋孔破損率=(孔破損數（個）/)χ 1 00 [表2] 評價項目 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 比較例4 光感度(mJ/cm2) 35 35 35 35 45 75 85 45 密著性（//m) 15 15 15 15 20 20 20 20 解像度（Um) 15 15 15 15 20 20 20 20 蓋孔破損率（％) 0 0 0 0 45 16 60 50 如表2所示般’由實施例丨〜4之感光性樹脂組成物所調 製之感光性元件，與比較例1 ~4相比，顯示光感度、蓋孔 -42- 201214041 可靠性、密著性及解像度皆優之特性。尤其，比較例2中 作爲（B)成分之光聚合性化合物雖係使用具有源自二季 戊四醇之骨架之（甲基）丙烯酸酯化合物，但（D)成分 之增感色素則未使用吡唑琳化合物，於此情況時，與實施 例1及2相，其成爲不僅光感度拙劣，蓋孔可靠性亦爲拙劣 之結果。 由以上可明白得知，實施例1〜4之感光性樹脂組成物 在使用直接描繪曝光法所成之蝕刻工法中，可形成光感度 、蓋孔可靠性、密著性及解像度皆優之印刷電路板一事。 [實施例5〜9] 除了將實施例1中（D)成分之增感色素之種類變更爲 下述表3所示者以外’以與實施例1同樣之方法製作感光性 樹脂組成物及感光性元件，且藉由由上述方法對此進行評 價。其結果如表3所示。尙且，爲了易於比較，在表3中亦 揭載上述比較例2之評價結果。 -43- 201214041 [表3] (D) 實施例5 實施例6 實施例7 實施例8 實施例9 比較例2 (D-4) 0.25 - - 一 - 一 (D-5) - 0.25 - 一 — — (D-6) — - 0.25 - 一 - (D-7) — - 0.25 一 — (D-8) — 一 - - 0.25 - EAB — — — — 一 0.25 光感度 (mJ/cm2) 35 35 35 35 35 75 密著性 ("m) 15 15 15 15 15 20 解像度 ("m) 15 15 15 15 15 20 蓋孔破損率 (%) 0 0 0 0 0 16 上述表中之各成分係如以下所示。 (D - 4 ) : 1 -苯基-3- ( 4 -甲氧基本基）-5- ( 4-tert -丁 基苯基）吡唑啉 (D-5 ) : 1-苯基-3- ( 2-噻吩基）-5- ( 4-tert-丁基苯 基）吡唑啉 (D-6 ) : 1-苯基-3- ( 2-噻吩基）乙烯基-5- ( 2-噻吩 基）吡唑啉 (D-7 ) : 1-苯基-3- (2 -噻吩基）-5- (2 -噻吩基）吡 唑啉 (D-8 ) : 1-苯基-3- ( 2-噻吩基）-5-苯乙烯基吡唑啉 如表3所示般，即使改變（D )成分之增感色素之種類 -44 - 201214041 ，在該當於一般式（II)之化合物時，仍亦顯示光感度、 蓋孔可靠性、密著性及解像度皆優之特性。另一方面’在 使用不該當於一般式（Π)之增感色素之比較例5中’其不 僅光感度拙劣，蓋孔可靠性亦成爲拙劣者。 [實施例10〜13] 實施例2中，除將（B)成分之光聚合性化合物之種類 變更爲下述表4所示般以外，以與實施例2同樣之方法而製 成感光性樹脂組成物及感光性元件’依據上述方法對此進 行評價。其結果如表4所示。 [表4] (B) 實施例10 實施例11 實施例12 實施例13 (B — 2) *13 10 - - - (B-3) *14 — 10 - - (B-4)*15 — — 10 一 (B-5) *16 — — — 10 光感度(mJ/cm2) 35 35 50 50 密著性―） 15 15 15 12.5 解像度（"m) 15 15 15 17.5 蓋孔破損率(％) 0 0 0 0 上述表中之各成分係如以下所示° * 13 : ( B-2 ) —般式（I)中，n=l、A〇 =環氧乙院基、R4舄甲基之 化合物。 -45 - 201214041 * 1 4 : ( B - 3 ) —般式（I)中’ n = 5、AO =環氧乙院基、R爲甲基之 化合物》 *15_ (B-4) —般式（I)中，n=l、AO =環氧丙院基、r4爲甲基之 化合物。 * 16 ： ( B-5 ) —般式（I)中，n = 5、AO =環氧丙烷基、R4爲甲基之 化合物。 如表4所示般，即使改變（B )成分之光聚合性化合物 之種類，在具有源自二季戊四醇之骨架之（甲基）丙烯酸 酯化合物（特別係該當於一般式（I )之化合物）時，亦 顯示光感度、蓋孔可靠性、密著性及解像度皆優異之特性 【圖式簡單說明】 [圖1 ]展示本發明之感光性元件之一實施形態之模式剖 面圖。 【主要元件符號說明】 2 :支持體 4 :感光性樹脂層 6 :保護薄膜 1 0 :感光性元件 -46 -In the above general formula (II), R1 and R2 each independently represent a substituted or unsubstituted phenyl 'thienyl group or a furyl group, and a substituted or unsubstituted phenyl group is preferred from the viewpoint of further improving the resolution. Examples of the substituent of the phenyl group, the thienyl group or the furyl group represented by R1 and R2 include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms is preferred, and an alkyl group having 3 to 8 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is more preferable. When the substituent of the phenyl group, the thienyl group or the furyl group represented by R1 and R2 is an alkane-19-201214041 group, the alkyl group may be linear, branched or cyclic--in a linear or Branching is preferred, and branched alkyl groups are preferred. When the substituent of the phenyl group, the thienyl group or the furyl group represented by R1 and R2 is an alkoxy group, the alkoxy group may be linear, branched or cyclic, and may be linear or branched. It is better. When R1 or R2 is a substitutable phenyl group, the bonding position of the substituent in the phenyl group is preferably the para position (4 position). In the general formula (Π), R3 represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 1 carbon number, or an ester group having 1 to 1 carbon number, and an alkyl group having 1 to 1 carbon number or The alkoxy group having 1 to 1 carbon atoms is preferred, and the alkyl group having 3 to 8 carbon atoms or the alkoxy group having 1 to 5 carbon atoms is more preferred. The alkyl group having 1 to 1 Å of carbon or the alkoxy group having 1 to 1 carbon atoms represented by R3 may be linear or branched. Examples of the alkyl group having 1 to 1 ring carbon atoms include methyl group, ethyl group, isopropyl group, η-butyl group, tert-butyl group, isopentyl group, and tert-octyl group, but are limited thereto. Wait. In the general formula (II), m represents an integer of 0 to 5, preferably 0 to 4, 0 to 3 is preferred, and 0 is more preferred. Moreover, when m is 2 to 5, the plural R3s may be the same or different. In the general formula (II), a represents an integer of 0 to 2, and more preferably 1 is preferable. b in the general formula (II) represents an integer of 0 to 2, preferably 0 or 1, more preferably 〇. Further, the sum of a and b in the general formula (II) is 1 to 4, preferably 1 to 3, 1 or 2 is preferred, and 1 is more preferred. The compound represented by the above general formula (Π) includes, for example, -20-201214041 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)- Oral oxazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(3,5 -dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)- 5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5- (2,6-dimethoxy Phenyl)-pyrazoline, I-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, Phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4- Dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)_3-styryl-5-benzene -Pyrazoline, 1-phenyl-3-(4-tert-butyl-styryl)-5-(44 61^-butyl-phenyl)-pyrazoline, 1,5-bis- (4-tert-butyl-phenyl)-3-(4-tert-butyl-styryl)-pyrazoline , l-(4-tert-octyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-tert-octyl-styryl)- 5-(4-tert-octyl-phenyl)-pyrazoline, 1,5-bis-(4-tert-octyl-phenyl)-3-(4-tert-octyl-styryl) -pyrazoline, 1-(4-lauryl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-lauryl-styryl)- 5-(4-lauryl-phenyl)-pyrazoline, 1-(4-lauryl-phenyl)-3-(4-lauryl-styryl)-5-(4-lauryl-benzene -Pyrazolium, 1-(4-16 1^-octyl-phenyl)-3-(4-tert-butyl-styryl)-5- (4-tert-butyl-phenyl) )-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(4-tert-octyl-styryl)-5-(4- to 1^-octyl-phenyl) -pyrazoline, 1-(4-lauryl-phenyl)-3-(4-tert-butyl-styryl)-5- (4-tert-butyl-21 - 201214041 phenyl-phenyl)-哩哩琳, 1-(4-tert-butyl-benyl)-3-(4-lauryl-styryl)-5-(4-lauryl-phenyl)-pyrazoline, Bu (4 -lauryl-phenyl)-3-(4-tert-octyl-phenethyl) 4-tert-octyl-phenyl)-pyrazoline L-(4-tert-octyl-phenyl)_3_(4-lauryl-styryl)-5-(4-lauryl-phenyl)-pyrazoline, 1-phenyl-3-(4) -Methoxyphenyl)-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3-(2-thienyl)-5-(4-tert-butylphenyl) -pyrazoline, 1-phenyl-3-(2-thienyl)vinyl-5-(2-thienyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5- (2-Thienyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5-phenethyl 卩 卩 、, 1-phenyl-3-(4-linked base) -5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyridyl Oxazoline. These may be used alone or in combination of two or more. Among the compounds represented by the above general formula (II), 1-phenyl-3-(4-methoxystyryl)-5-(4-methyl) is used in view of easiness of synthesis and improvement of light sensitivity. Oxyphenyl)-pyrazole is particularly preferred, and 1-phenyl-3-(4-isopropylstyryl)-5- (from the viewpoint of ease of synthesis and improvement in solubility to a solvent) 4-isopropylphenyl)pyrazoline is particularly preferred. Further, the photosensitive resin composition of the present invention may be blended with a sensitizing dye other than the compound represented by the above general formula (II) as long as it does not impair the effects of the present invention. Examples of the sensitizing dye other than the compound represented by the above general formula (IV) include dialkylaminobenzophenones, onions, coumarins, xanthones, oxazoles, and benzo. Oxazoles, thiazoles, benzothiazoles, tri-22-201214041 azoles, anthraquinones, triazines, thiophenes, naphthylquinone imines, and triarylamines. These may be used alone or in combination of two or more. The content ratio of the compound represented by the above formula (II) in the sensitizing dye of the component (D) is preferably from 1% by mass to 100% by mass based on the total amount of the component (D), and is 30% by mass. 100% by mass is more preferable, and 50 to 100% by mass is particularly preferable. When the blending amount is 10% by mass or more, there is a tendency that the sensitivity is high and the resolution is high. The content of the component (D) is preferably 0.01% by mass to 1% by mass, and 0.05% by mass to 5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). Preferably, 0.1% by mass to 3 parts by mass is more preferably. When the content is 1 part by mass or more, the light sensitivity and the resolution tend to be easily obtained. When the content is 1 part by mass or less, a sufficiently good resist shape tends to be easily obtained. [Other components] Further, the photosensitive resin composition of the present invention may be blended with a dye such as malachite green, Victoria pure blue, bright green, and methyl violet, tribromophenylphosphonium, leuco crystal violet, and diphenyl as necessary. a photochromic agent such as a base amine, a benzylamine, a triphenylamine, a diethylphenylamine, a guanidine-chloroaniline or a tributyl catechol, a heat-resistant color former, a plasticizer such as P-toluenesulfonamide, or the like, Pigment, sputum, antifoaming agent, flame retardant, adhesion imparting agent, leveling agent, peeling accelerator, antioxidant, perfume, developer, thermal crosslinking agent, polymerization inhibitor, etc. Each of the components (A) and (B) is contained in an amount of from 0.1 part by mass to 20,000 parts by mass per 100 parts by mass of the total amount of the component (A). These can be used alone or in combination of 2-23-201214041 types. The photosensitive resin composition of the present invention may contain at least one organic solvent as necessary. The above organic solvent is not particularly limited, and an organic solvent which is usually used can be used. Specific examples thereof include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and the like. A solvent or a mixed solvent of these. For example, the (A) binder polymer, the (B) polymerizable compound, the (C) photopolymerization initiator, and the (D) sensitizing dye are dissolved in the organic solvent to form a solid content of 30% by mass to 60% by mass. A solution of the degree (hereinafter referred to as "coating liquid") is used. Further, the solid fraction refers to a component remaining after removing the volatile component from the above solution (photosensitive resin composition). The coating liquid can be used for the formation of a photosensitive resin layer as follows. The coating liquid is applied onto the surface of a support such as a support film or a metal plate to be described later, and dried to obtain a photosensitive resin layer derived from the photosensitive resin composition on a support. . The metal plate may, for example, be an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron or stainless steel, and is preferably copper, a copper-based alloy or an iron-based alloy. The thickness of the photosensitive resin layer to be formed varies depending on the application, but the thickness after drying is preferably from Ιμηη to ΙΟΟμηι. The surface (surface) on the opposite side to the surface facing the support of the photosensitive resin layer may be covered with a protective film. The protective film may, for example, be a polymer film such as polyethylene or polypropylene. -24- 201214041 <Photosensitive element> The photosensitive element 10 of the present invention has a support 2 as shown in a schematic cross-sectional view of an example shown in Fig. 1, and is derived from the above-mentioned photosensitivity formed on the support. The photosensitive resin layer 4 of the resin composition and other layers including the protective film 6 provided as necessary are formed. [Support] For the support, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The thickness of the support (hereinafter referred to as "support film") is preferably from 1 μm to 100 μm, preferably from 'μμηη to 30 μιηη', preferably from 1 μιη to 30 μιη. By making the thickness of the support Ιμιη or more, it is possible to suppress breakage of the support film when the support film is peeled off. Further, the reduction in resolution can be suppressed by ΙΟΟμπι or less. [Protective Film] The photosensitive element 10 may further include a protective film 6 covering the surface (surface) opposite to the surface of the support 2 of the photosensitive resin layer 4 as needed. The protective film is a photosensitive resin layer. The adhesive force is preferably smaller than the adhesion of the photosensitive resin layer of the support film, and is preferably a film having a low fisheye. Here, 'fisheye' refers to a foreign matter, undissolved material, which is produced by kneading, extruding, 2-axis stretching, casting, etc. when the film constituting the protective film is thermally fused. An oxidized degradation product or the like is mixed into the film. In other words, "low fisheye" means that the foreign matter or the like in the film is small. Specifically, as the protective film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. Commercially available products include a polypropylene film such as Alphan MA-410, E-200C manufactured by Oji Paper Co., Ltd., a polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and a PS series such as PS-25 manufactured by Teijin Co., Ltd. Wait. Further, the protective film system may be the same as the above support. The thickness of the protective film is preferably Ιμηη~ΙΟΟμηι, preferably 5μιη to 50μιη, more preferably 5μηι to 30μιη, and 15μιη to 30μηι is particularly preferred. By making the thickness of the protective film Ιμηι or more, it is possible to suppress breakage of the protective film when the photosensitive resin layer and the support film are laminated on the substrate while peeling off the protective film. Also, productivity can be improved below ΙΟΟμιη. [Production Method] The photosensitive element of the present invention can be produced, for example, by the following method. The coating may be carried out by a step of preparing a coating liquid in which the (Α) binder polymer, the (Β) polymerizable compound, the (C) photopolymerization initiator, and the (D) sensitizing dye are dissolved in the organic solvent. The cloth liquid is applied to a support to form a coating layer, and the coating layer is dried to form a photosensitive resin layer. A known method of coating the support on the coating liquid by a roll coating method, a floating point coating method, a concave plate coating method, an air knife coating method, a die casting method, a bar coating method, a spray coating method, or the like get on. -26- 201214041 Further, the drying of the above coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it can be performed at a rate of 5 minutes to 30 minutes at 70 °C to 150 °C. After the drying, the amount of the organic solvent remaining in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step. The thickness of the photosensitive resin layer in the photosensitive member can be appropriately selected depending on the use, and the thickness after drying is preferably 1 μηι to 200 μηη, more preferably 5 μηι to 100 μιη, and particularly preferably 10 μηι to 50 μηη. When the thickness is Ιμηη or more, industrial coating becomes easy and productivity is improved. When the thickness is 200 μm or less, the effect of the present invention can be sufficiently obtained, and the light sensitivity is high, and the light hardening property of the bottom of the resist tends to be excellent. The photosensitive element of the present invention may further have an intermediate layer such as a buffer layer, a subsequent layer, a light absorbing layer, or a gas barrier layer, as needed. The form of the photosensitive element of the present invention is not particularly limited. For example, it may be in the form of a sheet, or may be wound into a roll shape on the core. When winding up into a roll shape, it is preferable to wind up a support film on the outer side. The core may, for example, be a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin or an ABS (acrylonitrile-butadiene-styrene copolymer). It is preferable to provide the end face separator from the viewpoint of protecting the end face from the viewpoint of protecting the end face, and it is preferable to provide the moisture-proof end face separator from the viewpoint of the refractory edge. Further, the "sling method" is preferably carried out by packaging a black steel sheet having a small moisture permeability. The photosensitive element of the present invention can be suitably used, for example, in the production method of the resist -27-201214041 pattern described later. <Production Method of Resist Patterns> The method for producing a resist pattern of the present invention includes (i) a step of forming a photosensitive resin layer on which a photosensitive resin layer derived from the photosensitive resin composition is formed on a substrate And (ii) an exposure step of irradiating at least a part of the photosensitive resin layer with active light to photoharden the exposed portion, and (iii) a developing step of removing the uncured portion of the photosensitive resin layer from the substrate by development And may include other steps as necessary. (i) Photosensitive resin layer forming step In the photosensitive resin layer forming step, a photosensitive resin layer derived from the photosensitive resin composition is formed on a substrate. The substrate is not particularly limited, and a substrate for circuit formation having an insulating layer and a conductor layer formed on the insulating layer, or a die pad (a substrate for a lead frame) such as an alloy substrate is usually used to form a photosensitive layer on the substrate. In the case where the photosensitive element has a protective film, the photosensitive resin layer can be removed by pressing the photosensitive resin layer of the photosensitive element to the circuit formation substrate while heating, for example. . Thereby, a laminate in which the circuit formation substrate and the photosensitive resin layer and the support are provided in this order can be obtained. The photosensitive resin layer forming step is preferably carried out under reduced pressure from the viewpoint of adhesion and followability. The heating at the time of pressing is preferably performed at a temperature of 7 ° C to 13 (TC). Further, the pressing is performed at a degree of l.lMPa to 1.0 MPa to -28-201214041 (1 to 10 kgf/cm 2 ). It is preferable to carry out under pressure, and such conditions can be appropriately selected as needed. Further, if the photosensitive resin layer is heated to 70 ° C to 130 ° C, it is not necessary to apply a preheat treatment to the substrate for circuit formation. However, in order to further improve the adhesion and followability, pre-heat treatment of the substrate for circuit formation may be performed. (Π) Exposure step In the exposure step, at least a portion of the photosensitive resin layer formed on the substrate is irradiated with an activity. Light, which is photohardened by exposure of the active light to form a latent image. In this case, when the support (support film) present on the photosensitive resin layer is transparent to the active light, it can be irradiated by the support film. Active light, but when the support film is light-shielding, the photosensitive resin layer is irradiated with active light after the support film is removed. The exposure method may be exemplified by a positive type called an artwork or Negative mask A method of irradiating active light into an image (mask exposure method), or directly using an LDI (Laser Direct Imaging) exposure method or a DLP (Dig+ital Light Processing) exposure method A method of irradiating active light into an image. The light source of the active light is a known light source, for example, a gas arc of a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a xenon laser, or the like. Solid-state lasers such as lasers, YAG lasers, semiconductor lasers, and gallium nitride-based blue-violet lasers can effectively emit ultraviolet rays. Also, photographic floodlight balls, solar lamps, etc. can be used for effective radiation. Visible light -29 - 201214041. The photosensitive resin composition of the present invention can be used without being particularly limited to a light source of active light, but is preferably applied to direct drawing exposure. (iii) Development step development step In the case where the uncured portion of the photosensitive resin layer is removed from the substrate by development, a resist formed of a cured product which is photocured by the photosensitive resin layer is formed on the substrate. In the case where a support film is present on the photosensitive resin layer, after the support film is removed, the unexposed portion other than the exposed portion is removed (developed). The development method includes wet development and dry display. In the case of wet development, a development liquid corresponding to a photosensitive resin composition is used, and a development method by a known development method is used, and a method of immersion is used, which is a liquid-filled method, a spray method, and a brushing method. The method of speeding, scraping, shaking, etc. is most suitable for high-pressure spraying from the viewpoint of improving the resolution. It is also possible to combine these two or more methods to form a developing image. The composition of the photosensitive resin composition is appropriately selected. For example, an alkaline aqueous solution, a water-based developing solution, and an organic solvent-based developing solution can be given. When used as a developing solution, the alkaline aqueous solution is safe and stable, and has good handleability. As the base of the alkaline aqueous solution, for example, an alkali hydroxide such as lithium, sodium or potassium hydroxide, a carbonate such as lithium, sodium, potassium or ammonium or a carbonate such as bicarbonate, potassium phosphate or sodium phosphate can be used. Alkali metal phosphate 30- 201214041 alkali metal pyrophosphate such as acid salt, sodium pyrophosphate or potassium pyrophosphate. The alkaline aqueous solution used for development is a diluted solution of 〇_1% by mass to 5% by mass of sodium carbonate, a diluted solution of 0_1% by mass to 5% by mass of potassium carbonate, and 〇% by mass to 5% by mass of sodium hydroxide. It is preferred to dilute the solution, a diluted solution of 0. 1% by mass to 5% by mass of sodium tetraborate. Further, the pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature can be adjusted in accordance with the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. The aqueous developing solution is, for example, a developing liquid composed of water or an aqueous alkaline solution and one or more organic solvents. Here, the base of the alkaline aqueous solution may be exemplified by borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, and 2-amine. Benzyl-2-hydroxymethyl-1, 3-propanediol, 1,3-diaminopropanol-2, and morpholine. The pH of the water-based developing solution is preferably as small as possible in the range in which the development can be sufficiently performed, preferably pH 8 to 12, and pH 9 to 10 is more preferable. Examples of the organic solvent used in the aqueous imaging solution include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropyl alcohol, and butyl alcohol. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These may be used alone or in combination of two or more types. The concentration of the organic solvent in the aqueous developing solution is usually from 2% by mass to 90% by mass, and the temperature can be adjusted in accordance with the developing property. A small amount of a surfactant, an antifoaming agent, etc. may be mixed in the water-based developing solution. Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, N-31 - 201214041 methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and A. Isobutyl ketone, and γ-butyrolactone. In order to prevent ignition, it is preferred to add water in the range of 1% by mass to 20% by mass. In the present invention, after the unexposed portion is removed in the developing step, the resist pattern is required to be heated by a degree of 60 ° C to 2 50 ° C or an exposure of 0.2 J/CIT 12 to 10 J/cm 2 . It can be hardened and used. <Manufacturing Method of Printed Circuit Board> The method of manufacturing a printed wiring board according to the present invention includes etching or plating a circuit forming substrate on which a resist pattern is formed by the above-described resist pattern manufacturing method. The step of forming the conductor pattern by the application process also includes the steps of removing the resist step and the like as necessary. The photosensitive resin composition of the present invention can be suitably used for the production of a resist pattern, and more preferably, it is applied to a production method for forming a conductor pattern by a plating treatment. In the etching treatment, the resist pattern formed on the substrate is used as a mask, and the conductor layer of the substrate for circuit formation not covered by the resist is removed by etching to form a conductor pattern. The etching process can be suitably selected in accordance with the conductor layer to be removed. For example, the etching solution may, for example, be a copper dichloride solution, a ferric chloride solution, an alkali etching solution or a hydrogen peroxide-based etching solution, and it is preferable to use an iron oxide solution because the etching factor is good. On the other hand, in the plating treatment, the resist pattern formed on the substrate is used as a mask, and copper and solder are plated on the conductor layer of the circuit-forming substrate which is not covered by the resist. After the plating treatment, the hardened resist is removed, and the conductor layer not covered by the resist is further etched to form a conductor pattern. The plating treatment may be an electrolytic plating treatment or an electroless electrolytic treatment, but it is preferably an electroless plating treatment. Examples of the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, tin-lead plating such as high uniform acid tin-lead plating, and Watt bath (nickel sulfate-nickel chloride) plating. Gold plating such as nickel plating, hard gold plating, and soft gold plating such as nickel sulfa plating. After the above etching treatment or plating treatment, the resist pattern on the substrate is removed. The removal of the enthalpy pattern can be carried out, for example, by an aqueous solution which is more alkaline than the alkaline aqueous solution used in the above development step. For the strongly alkaline aqueous solution, for example, a 1% by mass to 1% by mass aqueous sodium hydroxide solution and a 1% by mass to 10% by mass aqueous potassium hydroxide solution can be used. In particular, it is preferred to use a 1% by mass to 10% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and it is more preferred to use a 1% by mass to 5% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. The peeling method of the resist pattern may, for example, be a dipping method or a spray method, and these may be used singly or in combination. When the resist pattern is removed after the plating treatment, the conductor layer covered with the resist is etched by etching to form a conductor pattern, whereby a desired printed circuit board can be manufactured. The etching treatment at this time can be suitably selected in accordance with the conductor layer to be removed. For example, the above etching liquid can be applied. The printed electro-33-201214041 circuit board manufactured by the method for manufacturing a printed circuit board of the present invention can be applied not only to a single-layer printed circuit board but also to the manufacture of a multi-layer printed circuit board, and can also be applied to a small-sized printed circuit board. Manufacturing of printed circuit boards and the like of through-holes. <Manufacturing Method of Lead Frame> The method for manufacturing a lead frame according to the present invention includes the step of forming a conductor pattern by subjecting a substrate having a resist pattern formed by the resist pattern forming method to a plating pattern It may also be composed of other steps such as removing the resist step, the etching process step, and the like as necessary. For the substrate, for example, a die pad (a substrate for a lead frame) such as an alloy substrate can be used. In the present invention, the resist pattern formed on the support is used as a mask, and a plating treatment is applied to the support. The method of the plating treatment can be exemplified in the above-described method of manufacturing a printed circuit board. After the above plating treatment, the resist pattern on the support is removed. The removal of the resist pattern can be carried out, for example, by an aqueous solution which is more alkaline than the alkaline aqueous solution used in the above-mentioned developing step. The strongly alkaline aqueous solution can be exemplified in the above-described method for producing a printed circuit board. Examples of the peeling pattern of the resist pattern include a dipping method, a spraying method, and the like, and these may be used alone or in combination. After the resist pattern is removed, the unnecessary metal layer can be removed by performing an etching process to form a lead frame. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to any of the above embodiments. -34-201214041 [Examples] Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited to the examples. Moreover, "parts" and "%" are quality benchmarks unless otherwise defined. [Examples 1 to 4, Comparative Examples 1 to 4] First, the binder polymer (A-1) shown in Table 1 was synthesized in accordance with Synthesis Example 1, and (A_2) was synthesized in accordance with Synthesis Example 2. <Synthesis Example 1 > 125 g of methacrylic acid of a copolymerization monomer, 275 g of methyl methacrylate, and styrene l〇〇g were mixed with azobisisobutyronitrile i.〇g to prepare a solution a . Further, azobisisobutyronitrile 1. 〇g was dissolved in 100 g of a mixture of methyl cellosolve and toluene (mass ratio: 6:4) to prepare a solution b. On the other hand, for a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, 400 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6:4 was added, and nitrogen gas was blown while stirring. And heated to 80 ° C. Here, the above solution a was added dropwise over 4 hours, stirred, and kept at 8 ° C for 2 hours. Next, after the solution b was dropped into the solution in the flask for 10 minutes, the solution in the flask was stirred and kept at 8 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C for 30 minutes, and kept at 90 ° C for 2 hours, and then cooled to obtain a -35 - 201214041 solution of the binder polymer (A-1). To the solution of the binder polymer (Ad), acetone was added to prepare a nonvolatile component (solid content) of 50% by mass. <Synthesis Example 2 > 125 g of methacrylic acid of a copolymerization monomer, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, and 225 g of styrene, and 1.5 g of azobisisobutyronitrile were mixed and prepared. Into the solution 〇. Further, 1.2 g of azobisisobutyronitrile was dissolved in a mixed solution of 60 g of methyl cellosolve and 40 g of toluene (mass ratio: 6:4) to prepare a solution d. On the other hand, adding 4〇〇g of a mixture of methyl cellosolve and toluene having a mass ratio of 6:4 to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, blowing nitrogen gas and Stir at the same time and heat to 8 °C. Here, the above solution c was added dropwise over 4 hours, and stirred while being kept at 8 ° C for 2 hours. Next, the above solution d was dropped into the flask over 10 minutes; after the solution was stirred, the solution in the flask was stirred while maintaining the temperature at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 °C for 3 minutes, and kept at 90 °C for 2 hours, and then cooled to obtain a solution of the binder polymer (A-2). To the solution of the binder polymer (A-2), acetone was added to prepare a nonvolatile component (solid content) to be 50% by mass. The binder polymer (A-1) had a weight average molecular weight of 60,000 and an acid value of 163 mgKOH/g. Further, the binder polymer (A-2) had a weight average molecular weight of 50,000 and an acid value of 163 mgKOH/g. Further, the weight of the molecular weight is measured by gel permeation chromatography and is derived by conversion using a standard polystyrene-36-201214041 ethylene calibration curve. The conditions of GPC are as follows - GPC conditions - Pumps - Hitachi L-6000 type [(Hybrid) Hitachi, Ltd.] Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 pieces) [The above, Hitachi Chemical Industry Co., Ltd., product name] Dissolved solution: Tetrahydrofuran Measurement temperature: 25 ° C Flow rate: 2.05 mL / min. Detector: Hitachi L-3300 type RI [(share) manufactured by Hitachi, Ltd., product name] <Preparation of photosensitive resin composition> Next, the materials shown in Table 1 were blended to obtain a photosensitive resin composition. Moreover, the number in the table indicates the number of parts (quality basis). Further, the components (A) and (B) are represented by the mass of the solid component. -37-201214041 [Table i] Material Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 CA) (A-1) *1 55 55 55 - 55 55 55 55 (A-2) *2 - - - 55 - - - - (B) (B-1) *3 10 10 10 10 - 10 - - TMPT*4 - - - - 10 - 10 10 FA-321M*5 13 13 13 13 13 13 13 13 TMPT-21*6 10 10 10 10 10 10 10 10 UA-21 *7 12 12 12 12 12 12 12 12 (C) B-CIM*8 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 (D) CD-1) *9 0.25 - - - 0.25 - - - (D-2) *10 - 0.25 - - - - - - (D-3) *n - - 0.25 0.25 - - - 0.25 EAB*12 - - - - - 0.25 0.25 - Additive leuco crystal violet 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Malachite 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Solvent Acetone 10 10 10 10 10 10 10 10 Toluene 10 10 10 10 10 10 10 10 10 Methanol 10 10 10 10 10 10 10 10 The components in the above table are as follows. -(A) component: binder polymer - 氺1: (A-1) methacrylic acid / methyl methacrylate / styrene = 25/55/20 (weight ratio), weight average molecular weight = 60,000, 50 mass % methyl cellosolve / toluene = 6 / 4 (by weight) solution * 2: (A-2) methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene = 2 5 / 5 / 25/4 5 (weight ratio), weight average molecular weight = 50,000, 50 mass% methyl cellosolve / toluene = 6 / 4 (weight ratio) solution - (B) component: photopolymerizable compound - 氺 3 : ( B -1 ) -38- 201214041 In the general formula (I), Π = 0 and R4 is a methyl group compound. * 4 : TMPT [Xinzhongcun Chemical Co., Ltd., product name] Trimethylolpropane triacrylate* 5 : FA-32 1M [Hitachi Chemical Industry Co., Ltd., product name] 2,2-double (4 -((Meth)acryloxypolyethoxy)phenyl)propane*6: TMPT-21 [Manufactured by Hitachi Chemical Co., Ltd., product name] Ethoxylated trimethylolpropane triacrylate* 7 : UA-2 1 [Xinzhongcun Chemical Co., Ltd., product name] ginseng (methacryl oxime tetraethylene glycol isocyanate hexamethylene) trimeric isocyanate-(C) component'·photopolymerization initiator - * 8 : B-CIM [Protected by chemical industry, product name] 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole-(D) : sensitizing dye · * 9 : ( D-1 ) 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazolinium 10 : ( D -2) 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)pyrazoline*11: (D-3) -39 - 201214041 1-phenyl -3- (4-tert-butylstyryl)-5- (4-tert-butylphenyl)pyrazoline* 12 : EAB [Protected by chemical industry, product name] 4,4'-double ( Diethylamino)diphenyl Ketone <Preparation of photosensitive element> The photosensitive resin composition obtained above was uniformly applied to a polyethylene terephthalate film (manufactured by Teijin Co., Ltd., product name "HTF01") having a thickness of 16 μm. The film was dried by a hot air convection dryer at 100 ° C for 10 minutes to form a photosensitive resin layer having a film thickness of ΙΟμηι after drying. A protective film made of polypropylene (manufactured by Oji Paper Co., Ltd., product name "E200C") was bonded to the photosensitive resin layer to obtain a polyethylene terephthalate film (support film) and a photosensitive resin layer. A photosensitive element laminated with the order of the protective film. <Production of Laminated Body> A copper-clad laminate of a glass epoxy material having a copper foil having a thickness of 12 μm (a substrate, manufactured by Hitachi Chemical Co., Ltd., product name "MCL-E-67") The surface of the copper was honed using a honing machine (manufactured by Sanqi Co., Ltd.) having a brush equivalent to #600, and after washing with water, it was convectively dried by air. The honed copper-clad laminate was heated to 80 ° C, and the protective film was peeled off while the photosensitive resin layer was brought into contact with the copper surface, and the photosensitive members obtained above were laminated. The lamination was carried out using a heating roll of 1 10 ° C at a press pressure of 〇 4 〇 MPa and a roll speed of 1.5 m / min. -40-201214041 Thereby, a laminate in which the copper laminate, the photosensitive resin layer, and the support film are laminated in this order is obtained. The obtained laminate was used as a test piece in the test shown below. <Evaluation> (Measurement of Light Sensitivity Test) A Hitachi 41-stage staged exposure meter was used on the support film of the test piece obtained above, and a direct drawing exposure apparatus using a semiconductor laser having a wavelength of 35 5 nm as a light source was used. Orbotech (stock), trade name Paragon-9 000m), exposure with a predetermined energy. Next, the support film was peeled off, and a 1% hydrazine mass% sodium carbonate aqueous solution at 30 ° C was sprayed for 45 seconds to remove the unexposed portion and subjected to development processing. After the development processing, the number of stages of the stage exposure meter of the photocured film formed on the copper-clad laminate was measured, and the number of residual stages after development was determined to be 1 7.0-segment energy (m)/cm2). The light sensitivity of the photosensitive resin composition is such that the lower the energy (mJ/cm2), the higher the light sensitivity is. The results are shown in Table 2. (Evaluation of Adhesiveness and Resolution) The image of the wiring pattern having a line width/pitch width of 5/5 to 47/47 (unit: μιη) was used as the resolution on the support film of the test piece obtained above. For the evaluation pattern, the exposure was performed with the energy of the residual phase after the development of the Hitachi 4 1 stage exposure meter was 1 7 · 0. After the exposure, the measurement test of the above light sensitivity and the same development process were carried out. -41 - 201214041 After the development process, the resist pattern was observed using an optical microscope. In the resist pattern in which the distance portion between the resist patterns (unexposed portion) is completely removed, and the line width portion (exposure portion) is not serpentine or defects are formed, the width between the line widths is determined to be the smallest. However, it was evaluated as adhesion (μηι) and resolution (μιη). The smaller the number, the better the adhesion and resolution. The results are shown in Table 2. (Evaluation of Cap Hole Reliability) A copper-clad laminate having a hole having a diameter of 1 mm was opened at a pitch of 7 mm on a 0.4 mm-thick copper-clad laminate, and the photosensitive element obtained above was laminated on both sides to Hitachi The number of residual stages after development of the 41-stage staged exposure meter was 1 7.0 of energy for exposure. After the exposure, the same development solution as the measurement of the light sensitivity was used, and the development was carried out by spraying for 30 seconds. After the development, the number of breakages of the photosensitive elements in the total of 260 round holes was measured. The breakage rate of the cover holes was calculated according to the following formula, and this was made into the reliability of the cover holes. The results are shown in Table 2. Cover hole breakage rate = (hole breakage number (number) /) χ 1 00 [Table 2] Evaluation item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Light sensitivity ( mJ/cm2) 35 35 35 35 45 75 85 45 Adhesion (//m) 15 15 15 15 20 20 20 20 Resolution (Um) 15 15 15 15 20 20 20 20 Cover hole breakage rate (%) 0 0 0 0 45 16 60 50 As shown in Table 2, the photosensitive element prepared by the photosensitive resin composition of Example 丨4 showed light sensitivity and cover hole-42-201214041 compared with Comparative Examples 1-4. Reliability, adhesion and resolution are excellent. In particular, in the photopolymerizable compound as the component (B) in Comparative Example 2, a (meth) acrylate compound having a skeleton derived from dipentaerythritol was used, but the sensitizing dye of the component (D) was not used. In this case, the compound was in contact with Examples 1 and 2, which was not only a poor light sensitivity but also a poor reliability of the cap hole. As apparent from the above, the photosensitive resin compositions of Examples 1 to 4 can be printed in an etching method using a direct drawing exposure method to provide excellent light sensitivity, lid hole reliability, adhesion, and resolution. The board is a thing. [Examples 5 to 9] A photosensitive resin composition and a photosensitive film were produced in the same manner as in Example 1 except that the type of the sensitizing dye of the component (D) in Example 1 was changed to those shown in Table 3 below. The element is evaluated and evaluated by the above method. The results are shown in Table 3. Moreover, for the sake of comparison, the evaluation results of the above Comparative Example 2 are also shown in Table 3. -43- 201214041 [Table 3] (D) Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 2 (D-4) 0.25 - - one - one (D-5) - 0.25 - one - — (D-6) — — 0.25 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 35 35 75 Adhesion ("m) 15 15 15 15 15 20 Resolution ("m) 15 15 15 15 15 20 Cover hole breakage rate (%) 0 0 0 0 0 16 The components in the above table are as Shown below. (D - 4 ) : 1 -Phenyl-3-(4-methoxyphenyl)-5-(4-tert-butylphenyl)pyrazoline (D-5) : 1-phenyl-3- (2-Thienyl)-5-(4-tert-butylphenyl)pyrazoline (D-6) : 1-phenyl-3-(2-thienyl)vinyl-5- (2-thiophene) Pyrazoline (D-7) : 1-phenyl-3-(2-thienyl)-5-(2-thienyl)pyrazoline (D-8) : 1-phenyl-3- ( 2-thienyl)-5-styrylpyrazoline, as shown in Table 3, even if the type of the sensitizing dye of the component (D) is changed - 44 - 201214041, when it is used in the compound of the general formula (II), It also shows the characteristics of light sensitivity, cover hole reliability, adhesion and resolution. On the other hand, in Comparative Example 5 in which a sensitizing dye which should not be used in the general formula was used, it was not only poor in light sensitivity, but also in the reliability of the lid hole. [Examples 10 to 13] In Example 2, a photosensitive resin was produced in the same manner as in Example 2 except that the type of the photopolymerizable compound of the component (B) was changed to the following Table 4. The composition and the photosensitive element 'evaluated according to the above method. The results are shown in Table 4. [Table 4] (B) Example 10 Example 11 Example 12 Example 13 (B-2) *13 10 - - - (B-3) *14 - 10 - - (B-4)*15 — — 10 一(B-5) *16 — — — 10 Light sensitivity (mJ/cm2) 35 35 50 50 Adhesion-) 15 15 15 12.5 Resolution ("m) 15 15 15 17.5 Cover hole breakage rate (%) 0 0 0 0 The components in the above table are as follows: * 13 : ( B-2 ) In the general formula (I), n = l, A 〇 = epoxy phenyl group, R 4 舄 methyl Compound. -45 - 201214041 * 1 4 : ( B - 3 ) General formula (I) ' n = 5, AO = epoxy compound, R is methyl compound * 16_ (B-4) general In (I), n = 1, AO = epoxy propylene, and r4 is a methyl compound. * 16 : (B-5 ) In the general formula (I), n = 5, AO = propylene oxide group, and R4 is a methyl group. As shown in Table 4, even if the kind of the photopolymerizable compound of the component (B) is changed, a (meth) acrylate compound having a skeleton derived from dipentaerythritol (especially a compound of the general formula (I)) In the meantime, the characteristics of the light sensitivity, the lid hole reliability, the adhesion, and the resolution are also excellent. [Brief Description] FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present invention. [Explanation of main component symbols] 2 : Support 4 : Photosensitive resin layer 6 : Protective film 1 0 : Photosensitive element -46 -

Claims (1)

201214041 七、申請專利範圍： 1 . 一種感光性樹脂組成物，其係含有（A )成分：黏 合劑聚合物、（B)成分：具有至少一個乙烯性不飽和鍵 結之光聚合性化合物、（C)成分：光聚合開始劑、及（D )成分：增感色素.；其中 前述（B)成分含有具有源自二季戊四醇之骨架之（ 甲基）丙烯酸酯化合物，而前述（D)成分含有吡唑啉化 合物。 2. —種感光性元件，其係具有 支持體，與 形成於前述支持體上之源自如請求項1之感光性樹脂 組成物之感光性樹脂層。 3. —種抗蝕圖型之製造方法，其係具有以下之步驟 於基板上形成如源自請求項1之感光性樹脂組成物之 感光性樹脂層的感光性樹脂層形成步驟、 對前述感光性樹脂層之至少一部分照射活性光線而使 曝光部光硬化的曝光步驟，與 藉由顯像將前述感光性樹脂層之未硬化部分由基板上 去除的顯像步驟。 4· 一種印刷電路板之製造方法，其係含有對藉由如 請求項3之抗蝕圖型之製造方法而形成有抗蝕圖型之基板 施予蝕刻處理或鍍敷處理而形導體圖型之步驟。 5. —種引線框架之製造方法，其係含有對藉由如請 -47- 201214041 求項3之抗蝕圖型形成方法而形成有抗蝕圖型之基板施予 鍍敷處理而形成導體圖型之步驟。 6. 一種印刷電路板，其係藉由如請求項4之製造方 法而製造者。 -48-201214041 VII. Patent application scope: 1. A photosensitive resin composition comprising (A) component: a binder polymer, and (B) component: a photopolymerizable compound having at least one ethylenically unsaturated bond, ( C) component: a photopolymerization initiator; and (D) component: a sensitizing dye; wherein the component (B) contains a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and the component (D) contains Pyrazoline compound. 2. A photosensitive element comprising a support and a photosensitive resin layer derived from the photosensitive resin composition of claim 1 formed on the support. 3. A method of producing a resist pattern having a photosensitive resin layer forming step of forming a photosensitive resin layer derived from the photosensitive resin composition of claim 1 on a substrate, and the above-mentioned photosensitive The exposing step of irradiating the active light to at least a part of the resin layer to photoharden the exposed portion, and the developing step of removing the uncured portion of the photosensitive resin layer from the substrate by development. 4. A method of manufacturing a printed circuit board, comprising: applying a etching process or a plating process to a substrate on which a resist pattern is formed by a method for forming a resist pattern of claim 3; The steps. A method for producing a lead frame, comprising: forming a conductor pattern by applying a plating process to a substrate on which a resist pattern is formed by a resist pattern forming method according to Item 3 of No. 47-201214041; Type of steps. A printed circuit board produced by the manufacturing method of claim 4. -48-
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