TW200848930A

TW200848930A - Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board

Info

Publication number: TW200848930A
Application number: TW96146127A
Authority: TW
Inventors: Yukiko Muramatsu; Masahiro Miyasaka; Hanako Nankawa
Original assignee: Hitachi Chemical Co Ltd
Priority date: 2006-12-19
Filing date: 2007-12-04
Publication date: 2008-12-16
Also published as: KR20090084941A; KR20130049836A; JPWO2008075531A1; KR101289569B1; KR20120068988A; JP5136423B2; CN101558356B; TWI370951B; CN101558356A; WO2008075531A1

Abstract

This invention provides a photosensitive resin composition comprising (A) a binder polymer comprising a divalent group represented by general formula (I), a divalent group represented by general formula (II), and a divalvent group represented by general formula(III), (B) a photopolymerizable compound, and (C) a photopolymerization initiator comprising a hexaarylbiimidazole compound containing at least one alkoxy group having 1 to 5 carbon atoms. (I) (II) (III) wherein R<1>, R<3>, and R<5> each independently represent a hydrogen atom or a methyl group; R<2> and R<4> each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an OH group, or a halogen atom; and m and n are each independently an integer of 0 to 5.

Description

200848930 九、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，光阻圖型之形成方法及印刷電路板之製造方法。 '【先前技術】於印刷電路板之製造領域中，作爲蝕刻和鍍層等所用之光阻材料，乃廣泛使用感光性樹脂組成物，和於支持薄膜上形成含有此感光性樹脂組成物之層（以下，稱爲「感光性樹脂組成物層」），並於感光性樹脂組成物層上具有配置保護薄膜構造的感光性元件（層合體）。先前，印刷電路板爲使用上述感光性元件，例如依下列手續製造。即，首先，於貼銅層合板等之電路形成用基板上層合感光性元件之感光性樹脂組成物層。此時，感光性樹脂組成物層之支持薄膜接觸面（以下，稱爲感光性樹脂組成物層之「下面」）與反側面（以下，稱爲感光性樹脂組成物層之「上面」），爲密黏至形成電路形成用基板之電路面。因此，於感光性樹脂組成物層之上面配置保護薄膜時，此層合作業爲一邊剝落保護薄膜一邊進行。又，層合爲將感光性樹脂組成物層於底層之電路形成用基板上加熱壓黏而進行（常壓層合法）。其次，透過光罩薄膜等令感光性樹脂組成物予以圖型曝光。此時，以曝光前或曝光後之任何時機剝離支持薄膜。其後，將感光性樹脂組成物層之未曝光部以顯像液予以 -6- 200848930 溶解或分散除去。其次，施以飩刻處理或鍍敷處理形成圖型’最終將硬化部分剝離除去。此處所謂蝕刻處理，係於顯像後將未被所形成之硬化光阻覆被之電路形成用基板的金屬面予以蝕刻除去後，將硬化光阻剝離的方法。另一方面，所謂鍍敷處理，係於顯像後將未被所形成之硬化光阻覆被之電路形成用基板的金屬面進行銅及焊料等之鍍敷處理後，除去硬化光阻並將此光阻所覆被之金屬面予以蝕刻之方法。然而’上述之圖型曝光手法，自以往，使用水銀燈作爲光源並且使用透過光罩予以曝光之手法。又，近年，作爲新曝光技術的DLP ( Digital Light Processing，數碼光加工）’已提案將圖型的數碼數據直接描畫至感光性樹脂組成物層的直接描畫曝光法。此直接描畫曝光法比透過光的曝光方法之位置配合精細度更加良好，且可取得精細圖型，故被持續導入用以製作高密度封裝基板。圖型曝光中，爲了提高生產的效率，乃必須縮短曝光時間。上述之直接描畫曝光法中，若使用與先前透過光罩之曝光方法所用之感光性樹脂組成物同程度感度的組成物，則一般上需要許多的曝光時間。因此，必須提高曝光裝置側的照度和提高感光性樹脂組成物的感度。又，感光性樹脂組成物除了上述之感度，其重要爲解像度及密黏性均優良。於形成精細的配線電路上，特別要求圖型化之光阻膜中之圖型線的剖面形狀爲良好。對於此類要求，提案使用特定之光聚合啓始劑等之高感度、高解 -7- 200848930 像度及高密黏性的感光性樹脂組成物（例如，參照專利文獻1 )。更且，形成光阻圖型之顯像步驟中所發生的泥漿，具有再附著至基板的問題。若泥漿再附著至基板，則於顯像步驟後施行蝕刻時，欲經蝕刻除去的金屬箔被泥漿所保護並且於基板上殘存，故容易發生配線間的短路。又，於顯像步驟後施行鍍層時，殘存於基板上的泥漿阻礙鍍層的形成，故易發生斷線。因此，於顯像步驟中，亦要求充分抑制泥漿的發生。專利文獻1 ··國際公開第06/3 82 79號公報【發明內容】 (發明所欲解決之課題）但是，先前之感光性樹脂組成物之情況，經由直接描畫曝光法形成高密度之光阻圖型的情況中，解像度及光阻圖型對於電路形成用基板的密黏性仍未充分。更且，亦期望提高顯像步驟時所發生之泥漿的除去性。又，於顯像後之光阻圖型表面，亦期望抑制小片物附著的顯像殘渣。於是，本發明爲以提供提高解像度、密黏性、顯像步驟時發生之泥漿的除去性及抑制顯像殘渣上具有充分效果的感光性樹脂組成物，感光性元件，光阻圖型之形成方法及印刷電路板之製造方法爲其目的。 (解決課題之手段） -8- 200848930 本發明者等人爲了解決上述課題，著眼於膠黏劑聚合物及光聚合啓始劑的組成並且進行致力檢討。其結果’發現經由使用特定的膠黏劑聚合物，並於其中組合特定構造之光聚合啓始劑，則不損害充分的高感度，具有充分高的解像度及密黏性，更且對於顯像時發生之泥漿的除去性及顯像殘渣的抑制具有充分效果的感光性樹脂組成物’並且達到完成本發明。即，本發明爲含有（A)具有下述一般式（I)所示二價基，下述一般式（H)所示二價基’與下述一般式（ΠΙ )所示二價基的膠黏劑聚合物’ （Β )光聚合性化合物’ 及（C)含有具有1個以上碳數1〜5之院氧基之六芳基雙咪唑化合物的光聚合啓始劑的感光性樹脂組成物。 [化1] R1BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a photoresist pattern, and a method for producing a printed circuit board. [Prior Art] In the field of manufacturing of printed circuit boards, as a photoresist material used for etching and plating, a photosensitive resin composition is widely used, and a layer containing the photosensitive resin composition is formed on a support film ( Hereinafter, it is referred to as a "photosensitive resin composition layer", and a photosensitive element (laminate) having a protective film structure is disposed on the photosensitive resin composition layer. Previously, the printed circuit board was manufactured using the above-described photosensitive element, for example, according to the procedure below. In other words, first, a photosensitive resin composition layer of a photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. In this case, the support film contact surface of the photosensitive resin composition layer (hereinafter referred to as "lower surface" of the photosensitive resin composition layer) and the reverse side surface (hereinafter referred to as "upper surface" of the photosensitive resin composition layer), It is densely bonded to the circuit surface on which the substrate for forming a circuit is formed. Therefore, when a protective film is placed on the upper surface of the photosensitive resin composition layer, this layer is carried out while peeling off the protective film. Further, lamination is carried out by heating and pressure-bonding the photosensitive resin composition layer on the circuit-forming substrate of the underlayer (normal pressure layering). Next, the photosensitive resin composition is exposed to light through a mask film or the like. At this time, the support film is peeled off at any timing before or after the exposure. Thereafter, the unexposed portion of the photosensitive resin composition layer is dissolved or dispersed by a developing solution at -6 - 200848930. Next, an engraving treatment or a plating treatment is applied to form a pattern, and finally the hardened portion is peeled off. Here, the etching treatment is a method in which the metal surface of the circuit-forming substrate which is not formed by the cured photoresist is removed after development, and the cured photoresist is peeled off. On the other hand, in the plating treatment, after the development, the metal surface of the substrate for circuit formation which is not formed by the cured photoresist is subjected to a plating treatment such as copper or solder, and then the hard photoresist is removed and The method in which the photoresist is etched by the metal surface is etched. However, the above-mentioned pattern exposure method has conventionally used a mercury lamp as a light source and a method of exposing through a reticle. In addition, in recent years, DLP (Digital Light Processing), which is a new exposure technology, has proposed a direct drawing exposure method in which digital data of a pattern is directly drawn to a photosensitive resin composition layer. This direct drawing exposure method is more excellent in positional fineness than the light exposure method, and a fine pattern can be obtained, so that it is continuously introduced to produce a high-density package substrate. In the pattern exposure, in order to improve the efficiency of production, it is necessary to shorten the exposure time. In the above direct drawing exposure method, when a composition having the same sensitivity as that of the photosensitive resin composition previously used for the exposure method of the photomask is used, a large amount of exposure time is generally required. Therefore, it is necessary to increase the illuminance on the side of the exposure device and to improve the sensitivity of the photosensitive resin composition. Further, in addition to the above sensitivity, the photosensitive resin composition is excellent in both resolution and adhesion. In forming a fine wiring circuit, it is particularly preferable that the cross-sectional shape of the pattern line in the patterned photoresist film is good. For such a requirement, it is proposed to use a photosensitive resin composition having a high sensitivity and a high resolution of a photopolymerization initiator such as a specific photopolymerization initiator (for example, refer to Patent Document 1). Further, the slurry which occurs in the developing step of forming the photoresist pattern has a problem of reattaching to the substrate. When the slurry is attached to the substrate, the metal foil to be removed by the etching is protected by the slurry and remains on the substrate when the etching is performed after the developing step, so that short-circuiting between the wirings is likely to occur. Further, when the plating is applied after the developing step, the mud remaining on the substrate hinders the formation of the plating layer, so that the wire breakage is liable to occur. Therefore, in the developing step, it is also required to sufficiently suppress the occurrence of mud. [Patent Document 1] International Publication No. 06/3 82 79 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) However, in the case of the conventional photosensitive resin composition, a high-density photoresist is formed by direct drawing exposure. In the case of the pattern, the resolution and the pattern of the photoresist pattern are insufficient for the substrate for circuit formation. Further, it is also desired to improve the removal of the slurry which occurs when the developing step. Further, it is also desirable to suppress the development residue of the adhesion of the small pieces on the surface of the photoresist pattern after development. Therefore, the present invention provides a photosensitive resin composition having a sufficient effect of improving the resolution, the adhesion, the removal property of the slurry which occurs when the developing step is performed, and the effect of suppressing the development residue, and the formation of the resistive pattern. The method and method of manufacturing a printed circuit board are for its purpose. (Means for Solving the Problem) -8-200848930 In order to solve the above problems, the inventors of the present invention have focused on the composition of the adhesive polymer and the photopolymerization initiator and conducted a review. As a result, it was found that by using a specific adhesive polymer and combining a photopolymerization initiator having a specific structure therein, sufficient high sensitivity is not impaired, a sufficiently high resolution and adhesion are obtained, and The removal of the mud and the suppression of the development residue have a sufficiently effective photosensitive resin composition' and the completion of the present invention has been achieved. That is, the present invention contains (A) a divalent group represented by the following general formula (I), a divalent group represented by the following general formula (H) and a divalent group represented by the following general formula (ΠΙ). Adhesive polymer '(Β) photopolymerizable compound' and (C) photosensitive resin composition containing a photopolymerization initiator of hexaarylbisimidazole compound having one or more oxy groups of 1 to 5 carbon atoms Things. [Chemical 1] R1

(I) [化2] R3(I) [Chemical 2] R3

R5 I -ch2—c- (R4)n (Μ) (III)R5 I -ch2—c- (R4)n (Μ) (III)

、OH -9- 200848930 式（I)、式（II)、及式（III)中，R1、：^3、及R5各獨立表示氫原子或甲基，R2及R4各獨立表示碳數1〜3的烷基、烷氧基、OH基或鹵素原子，㈤或n各獨立表示〇〜5的整數，m或η爲2〜5時，複數的R2或R4彼此可相同或相異。本發明之感光性樹脂組成物爲經由組合如上述之特定成分所構成，即使於直接描畫曝光法形成光阻圖型中，亦可於充分的解像度及密黏性下進行，又，對於顯像步驟時所發生之泥漿的除去性具有充分效果。經由使用含有具有上述（Α)成分般之特定基的膠黏劑聚合物，和上述（C) 成分般之特定之六芳基雙咪唑化合物的光聚合啓始劑，則可在提高如上述之解像度、密黏性、泥漿之除去性及顯像殘渣之抑制上取得充分效果之情事係爲本發明者等人所考慮的。又，本發明之感光性樹脂組成物，其光聚合啓始劑爲含有一種以上之下述一般式（IV )所示化合物爲佳。 ZJ-Z2 (IV) 式（IV)中，Z1及z2各自獨立，表示以下述一般式（v) 或（VI )所示之1價基。 -10- 200848930 [化4]OH -9- 200848930 In the formula (I), the formula (II), and the formula (III), R1, :3, and R5 each independently represent a hydrogen atom or a methyl group, and R2 and R4 each independently represent a carbon number of 1~ The alkyl group, the alkoxy group, the OH group or the halogen atom of 3, (5) or n each independently represent an integer of 〇~5, and when m or η is 2 to 5, the plural R2 or R4 may be the same or different from each other. The photosensitive resin composition of the present invention is composed of a specific component as described above, and can be formed under a sufficient resolution and adhesion even in a photoresist pattern formed by direct drawing exposure. The removal of the mud which occurs during the step has a sufficient effect. By using a photopolymerization initiator containing an adhesive polymer having a specific group as the above (Α) component and a specific hexaaryldiimidazole compound of the above (C) component, the above can be improved The fact that the resolution, the stickiness, the removal of the mud, and the suppression of the development residue are sufficiently effective are considered by the inventors and the like. Further, in the photosensitive resin composition of the present invention, the photopolymerization initiator is preferably one or more compounds represented by the following general formula (IV). ZJ-Z2 (IV) In the formula (IV), Z1 and z2 are each independently and represent a monovalent group represented by the following general formula (v) or (VI). -10- 200848930 [Chemical 4]

(V) [化5](V) [Chemical 5]

(VI) 式（v)及式（VI)中，R6〜R3 5各獨立表示氫原子、鹵素原子或碳數1〜5的烷氧基，同一分子中R6〜R35以複數形式存在時，彼等可爲相同或相異，R6〜R35的至少1個表示碳數1〜5的烷氧基。如此’提高感光性樹脂組成物的解像度，並且進一步提高密黏性及泥漿除去性。又’本發明之感光性樹脂組成物爲更含有（D )增感色素爲佳。如此，以特定之波長範圍內具有波峰之光予以曝光時，在其特定之波長範圍附近具有極大吸收，並且提高感光性樹脂組成物的感度。又，本發明之感光性樹脂組成物爲更含有（E )胺系 -11 - 200848930 化合物爲佳。如此，更加提高感光性樹脂組成物的感度。又，本發明爲具備支持薄膜及於該支持薄膜上所形成之含有上述感光性樹脂組成物之感光性樹脂組成物層的感光性元件。若根據此支持薄膜，因爲具備含有上述感光性樹脂組成物之感光性樹脂組成物層，故即使以直接描畫曝光法形成光阻圖型時，亦可於充分的解像度及密黏性下進行，又，對於提高顯像步驟時所發生之泥漿的除去性及顯像殘渣的抑制上亦具有效果。又，本發明爲具有在電路形成用基板上，層合含有上述感光性樹脂組成物之感光性樹脂組成物層的層合步驟，於感光性樹脂組成物層的指定部分以活性光線照射而使曝光部光硬化之曝光步驟，及由層合感光性樹脂組成物層之電路形成用基板，除去感光性樹脂組成物層之曝光部以外的部分之顯像步驟之光阻圖型的形成方法。若根據此光阻圖型的形成方法，因爲使用含有上述感光性樹脂組成物之感光性樹脂組成物層形成光阻圖型，故即使以曝光時間短的直接描畫曝光法，亦可形成充分之解像度及密黏性的光阻圖型。又，可確實除去顯像步驟時發生的泥漿。又，本發明爲具有將藉由上述光阻圖型之形成方法形成光阻圖型之電路形成用基板，經餽刻或鍍敷而形成導電圖型之步驟之印刷電路板的製造方法。若根據此印刷電路板的製造方法，因爲使用藉由上述光阻圖型之形成方法形成光阻圖型的電路形成用基板，故可形成高密度的配線，並且可製造斷線及短路被充分抑制的印刷電路板。 -12- 200848930 (發明之效果）若根據本發明，則可提供提高解像度、密黏性、顯像步驟時發生之泥漿的除去性及抑制顯像殘渣上具有充分效果的感光性樹脂組成物，感光性元件，光阻圖型之形成方法及印刷電路板之製造方法。【實施方式】以下’詳細說明關於本發明的實施形態。另外，於本發明中’所謂（甲基）丙烯酸爲表示丙烯酸或甲基丙烯酸 ’且（甲基）丙烯酸酯爲意指丙烯酸酯或其對應之甲基丙烯酸酯’所謂（甲基）丙烯醯基爲意指丙烯醯基或甲基丙烯醯基。本發明之感光性樹脂組成物爲含有（A )上述一般式 (I )所示2價基（以下，亦稱爲「構造單位」），上述一般式（Π )所示之構造單位，上述一般式（m)所示之構造單位的膠黏劑聚合物，（B )光聚合性化合物，及（C ) 含有具有1個以上碳數1〜5的烷氧基之六芳基雙咪唑化合物之光聚合啓始劑的感光性樹脂組成物。首先，說明關於（A )成分之膠黏劑聚合物。 (A )成分之膠黏劑聚合物爲含有根據上述一般式（I )所示之苯乙烯或苯乙烯衍生物的構造單位，根據上述一般式（II )所示之（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物的構造單位，及根據上述一般式（III )所示之 -13- 200848930 (甲基）丙烯酸的構造單位。如此，以感光性樹脂組成物作爲構成材料之感光性樹脂組成物層對於電路形成用基板的密黏性及剝離特性均爲良好。此處，上述式（I)中，R1爲表示氫原子或甲基’ r2 爲表示碳數1〜3的烷基，碳數1〜3的烷氧基，OH基或鹵素原子，m爲表示0〜5之整數。又，上述式（II)中，R3爲表示氫原子或甲基’ r4爲表示碳數1〜3的烷基，碳數1〜3的烷氧基，〇H基或鹵素原子，m爲表示0〜5之整數。又，上述式（III)中，R5爲表示氫原子或甲基’具體而言，根據丙烯酸或甲基丙烯酸的構造單位。上述一^般式（I)所不之構造單位的含有比例爲（A) 成分之總量中10〜60質量％爲佳，且以15〜50質量％爲更佳，以2 0〜5 0質量％爲特佳。又，上述一般式（Π )所示之構造單位的含有比例爲（A )成分之總量中1 〇〜60質量 %爲佳，且以15〜50質量％爲更佳，以20〜50質量％爲特佳。又，上述一般式（III)所不之構造卓位的含有比例爲（ A)成分之總量中20〜50質量％爲佳，且以23〜40質量％爲更佳，以2 5〜3 5質量％爲特佳。根據苯乙烯或苯乙烯衍生物之構造單位，根據（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物之構造單位的配合量分別未滿1 0質量％ ’則具有解像性差的傾向’若其配合量爲超過60質量％則剝離片變大，具有剝離時間變長的傾向。又，根據（甲基）丙烯酸之構造單位的配合量未滿2 0質量％ ’則鹼溶解性差’ -14- 200848930 剝離片變大，具有剝離時間變長的傾向’若其配合量超過 5 0質量％則解像性有降低之傾向。使用本發明之膠黏劑聚合物的感光性樹脂組成物，對於密黏性、解像度、顯像時發生之泥漿的除去性及顯像殘渣的抑制上具有優良的效果〇另外，於本發明中，所謂「苯乙烯衍生物」係指苯乙烯中氫原子被取代基（烷基等之有機基和鹵素原子等）所取代者。使用此膠黏劑聚合物形成感光性樹脂組成物層時，可單獨使用一種膠黏劑聚合物，且亦可任意組合使用二種以上之膠黏劑聚合物。組合使用二種以上時之膠黏劑聚合物，可列舉例如，不同之共聚成分所構成之二以上之（含有不同之重複單位作爲構成成分）膠黏劑聚合物，不同之重量平均分子量之二種以上之膠黏劑聚合物，不同分散度之二種以上之膠黏劑聚合物等。又，亦可使用特開平11-3 27 1 3 7號公報中記載之具有多型式分子量分佈的聚合物。 (A)膠黏劑聚合物之重量平均分子量（Mw)及數平均分子量（Μη)可根據膠滲透層析（GPC)測定（以使用標準聚苯乙烯之檢量線換算）。若根據此測定法，則膠黏劑聚合物的Mw爲5000〜150000爲佳，且以10000〜 1 000000爲更佳，以20000〜50000爲特佳。Mw未滿5000則耐顯像液性有降低的傾向，若超過1 5 0 0 0 0則顯像時間有變長的傾向。又，（A )膠黏劑聚合物的分散度（Mw/Mn )爲1 ·〇〜 -15- 200848930 3 · 0爲佳，且以1 · 〇〜2 · 0爲更佳。分散度若超過3 · 0則密黏性及解像度有降低的傾向。本發明之膠黏劑聚合物可例如令聚性性單體進行自由基聚合而製造。提供上述一般式（I)〜（III)所示之構造單位的聚合性單體，可列舉例如，苯乙烯及/或苯乙烯衍生物、（甲基）丙烯酸苄酯及/或（甲基）丙烯酸苄酯衍生物、（甲基）丙烯酸。上述（Α)膠黏劑聚合物亦可含有上述一'般式（I)〜 (III )所示之構造單位以外的構造單位。此時，提供上述一般式（I )〜（III )所示之構造單位以外之構造單位的聚合性單體，可列舉例如，雙丙酮丙烯醯胺等之丙烯醯胺、丙烯腈、乙烯基-正丁醚等之乙烯醇的酯類、（甲基）丙烯酸烷酯、（甲基）丙烯酸四氫糠酯、（甲基）丙燒酸二甲胺i乙酯、（甲基）丙烯酸二乙胺基乙酯、（甲基）丙烯酸縮水甘油酯、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）丙燦酸、 α-漠基（甲基）丙傭酸、α-氯基（甲基）丙嫌酸、0_咲喃基（甲基）丙烯酸、Θ -苯乙烯基（甲基）丙嫌酸、順丁烯二酸、順丁烯二酸酐、順丁烯二酸單甲酯、順丁條二酸單乙酯、順丁烯二酸單異丙酯等之順丁烯二酸單酯、反丁嫌一酸、肉桂酸、α -氰基肉桂酸、衣康酸、丁烯酸、丙炔酸等。其可單獨或組合使用二種以上。又，上述（甲基）丙烯酸烷酯可列舉例如，下述一般式（VII )所示之化合物，於此等化合物之烷基以經基、 -16 - 200848930 環氧基、鹵基等所取代的化合物等。 CH2 = C(R36)-COOR37 (VII) 此處，上述一般式（VII)中，R36爲表示氫原子或甲基，R3·7爲表示碳數1〜12之烷基。又，R3 7所示之碳數1〜 1 2的烷基可列舉例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基及其構造異構物。上述一般式（VII )所示之單體可列舉例如，（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基 )丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸乙酯、（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）丙烯酸十一烷酯、（甲基）丙烯酸十二烷酯等。此等單體可單獨或組合使用二種以上。本發明中之（A )膠黏劑聚合物，由使用鹼溶液進行鹼顯像時之顯像性的觀點而言，以具有羧基之聚合物一種或二種以上所構成爲佳。此類（A )膠黏劑聚合物例如，令具有羧基之聚合性單體與其他聚合性單體進行自由基聚合則可製造。 (A)膠黏劑聚合物之酸價爲80〜25 0 mgKOH/g爲佳，且以 100 〜220 mgKOH/g 爲更佳，以 150 〜210 mgKOH/g 爲特佳。此酸價未滿80 mgKOH/g則顯像時間有變長的傾 -17- 200848930 向，若超過250 mgKOH/g則光硬化之光阻的耐顯像液性降低的傾向。又，顯像步驟爲進行溶劑顯像時，調製少具有羧基之聚合性單體爲佳。又，（A )膠黏劑聚合物爲視需要亦可令其分子內有具感光性的特性基。 (A )成分之膠黏劑聚合物的配合量，相對於（A 成分及（B)成分之總量100質量份以30〜70質量份爲佳且以35〜65質量份爲更佳，以40〜60質量份爲特佳。此合量未滿3 0質量份則具有無法良好形狀的傾向，若超過質量％則具有無法取得良好之感度和解像性的傾向。（ )成分可單獨使用一種或組合使用二種以上。又，於本發明之感光性樹脂組成物中，亦可倂用上 (A )成分以外之樹脂，例如，可倂用丙烯酸系樹脂、乙烯系樹脂、環氧系樹脂、醯胺系樹脂、醯胺環氧系樹、醇酸系樹脂、酚系樹脂等。其中亦由鹼顯像性之觀點言，以丙烯酸系樹脂爲佳。又，此等樹脂可單獨或組合用二種以上。其次，說明關於（B )成分之光聚合性化合物。 (B )成分之光聚合性化合物可列舉例如，令多元以α，θ-不飽和羧酸反應所得之化合物、雙酚a系（甲 )丙烯酸酯化合物、含縮水甘油基之化合物以αΘ -不和羧酸反應所得之化合物、分子內具有胺基甲酸乙酯鍵 (甲基）丙烯酸酯化合物等之胺基甲酸乙酯單體、壬苯基聚乙烯氧基丙烯酸酯、苯二甲酸系化合物、（甲基）有量具 ) 配 70 A 述苯脂而使醇基飽之氧丙 -18- 200848930 烯酸烷酯等。此等化合物可單獨或組合使用二種以上。令上述多元醇以α，0 -不飽和羧酸反應所得之化合物，可列舉例如，伸乙基數爲2〜1 4之聚乙二醇二（甲基）丙烯酸酯、伸丙基數爲2〜14之聚丙二醇二（甲基）丙烯酸酯、伸乙基數爲2〜14且伸丙基數爲2〜14之聚乙烯-聚丙二醇二（甲基）丙烯酸酯、三羥甲基丙烷二（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、ΕΟ改質三羥甲基丙烷三（甲基）丙烯酸酯、ΡΟ改質三羥甲基丙烷三（甲基）丙烯酸酯、ΕΟ、ΡΟ改質三羥甲基丙烷三（甲基）丙烯酸酯、四羥甲基甲烷三（甲基）丙烯酸酯、四羥甲基甲烷四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯等。此等化合物可單獨或組合使用二種以上。此處，所謂「Ε〇」爲表示環氧乙烷，經ΕΟ改質之化合物爲表示具有環氧乙烷基之分段構造者。又，所謂「Ρ〇」爲表示環氧丙烷，經ρ0改質之化合物爲表示具有環氧丙烷基之分段構造者。上述雙酚Α系（甲基）丙烯酸酯化合物可列舉例如’ 2,2-雙（4-((甲基）丙烯醯氧基聚乙氧基）苯基）丙院、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）丙烯醯氧基聚丁氧基）苯基）丙院、2，2 -雙（4-((甲基）丙烯醯氧基聚乙氧基聚丙氧基）苯基）丙烷等。上述2,2-雙（4-((甲基）丙烯醯氧基聚乙氧基）苯基）丙烷可列舉例如’ 2,2-雙（4-((甲基）丙烯醯氧基二乙氧基）苯基）丙烷、2,2-雙（4-(( -19- 200848930 甲基）丙烯醯氧基三乙氧基）苯基）丙烷、2,2-雙（4-( (甲基）丙烯醯氧基四乙氧基）苯基）丙烷、2,2-雙（4_ ((甲基）丙烯醯氧基五乙氧基）苯基）丙烷、2，2-雙（ 4-((甲基）丙烯醯氧基六乙氧基）苯基）丙烷、2,2-雙 (4-((甲基）丙烯醯氧基五乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基八乙氧基）苯基）丙烷、 2,2-雙（4-((甲基）丙烯醯氧基九乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基十乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基十一乙氧基）苯基 )丙烷、2,2-雙（4-((甲基）丙烯醯氧基十二乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基十三乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基十四乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基十五乙氧基）苯基）丙烷、2,2-雙（4-((甲基）丙烯醯氧基十六乙氧基）苯基）丙烷等。上述2，2-雙（4-(甲基丙烯醯氧基五乙氧基）苯基）丙烷可爲ΒΡΕ-5 00 (新中村化學工業（股）製，商品名或 FA-321M (日立化成工業（股）製，商品名）型式於商業上取得，上述2，2-雙（4-(甲基丙烯醯氧基十五乙氧基）苯基）丙烷可爲ΒΡΕ- 1300(新中村化學工業（股）製，商品名）型式於商業上取得。上述2,2-雙（4-((甲基）丙烯醯氧基聚乙氧基）苯基）丙烷於一分子內之環氧乙烷基數爲4〜2 0爲佳，且以8〜1 5爲更佳。此等化合物可單獨或組合使用二種以上。 -20- 200848930 上述分子內具有胺基甲酸乙酯鍵之（甲基）丙烯酸酯化合物，可列舉例如，於A位具有OH基之（甲基）丙烯基單體與二異氰酸酯化合物（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、1，6-己二異氰酸酯等）之加成反應物、三（（甲基）丙烯醯氧基四乙二醇異氰酸酯）伸乙基異氰脲酸酯、EO改質胺基甲酸乙酯二（甲基）丙烯酸酯、EO、PO改質胺基甲酸乙酯二（甲基）丙烯酸酯等。上述EO改質胺基甲酸乙酯二（甲基）丙烯酸酯可列舉例如，UA-1 1 (新中村化學工業（股）製，商品名）。又，上述EO、PO改質胺基甲酸乙酯二（甲基）丙烯酸酯可列舉例如，UA-1 3 (新中村化學工業（股）製，商品名）。此等化合物可單獨或組合使用二種以上。上述壬苯氧基聚乙烯氧基丙烯酸酯可列舉例如，壬苯氧基四乙烯氧基丙烯酸酯、壬苯氧基五乙烯氧基丙烯酸酯、壬苯氧基六乙烯氧基丙烯酸酯、壬苯氧基七乙烯氧基丙烯酸酯、壬苯氧基八乙烯氧基丙烯酸酯、壬苯氧基九乙烯氧基丙烯酸酯、壬苯氧基十乙烯氧基丙烯酸酯、壬苯氧基十一乙烯氧基丙烯酸酯。此等化合物可單獨或組合使用二種以上。上述苯二甲酸系化合物可列舉例如，r -氯-/3 -羥丙基- yS’-(甲基）丙烯醯氧乙基苯二甲酸酯、羥烷基-/3 (甲基）丙烯醯氧烷基苯二甲酸酯等。此等化合物可單獨或組合使用二種以上。又，本發明之（B )成分由耐鍍敷性及密黏性之觀點 -21 - 200848930 而言，以含有雙酚A系（甲基）丙烯酸酯化合物或分子內具有胺基甲酸乙酯鍵之（甲基）丙烯酸酯化合物爲佳。又，由提高感度及解像度之觀點而言，以含有雙酚A系（甲基）丙烯酸酯化合物爲佳。更且，於本發明之（B)成分中，由提高硬化膜之可撓性的觀點而言，以含有分子內具有乙二醇鏈及丙二醇鏈兩者之聚伸烷基二元醇二（甲基）丙烯酸酯爲佳。此（甲基）丙烯酸酯於分子內的伸烷基二元醇鏈，若爲具有乙二醇鏈及丙二醇鏈（正丙二醇鏈或異丙二醇鏈）兩者，則無特別限制。又，此（甲基）丙烯酸酯亦可再具有正丁二醇鏈、異丁二醇鏈、正戊二醇鏈、己二醇鏈，彼等之構造異構物等之碳數4〜6左右的伸烷基二元醇鏈。上述乙二醇鏈及丙二醇鏈爲複數時，複數的乙二醇鏈及丙二醇鏈並非必要以各別連續且以分段性存在，以無規性存在亦可。又，於上述異丙二醇鏈中，伸丙基的二級碳可結合至氧原子，且一級碳爲結合至氧原子亦可。此等（B)成分中之分子內具有乙二醇鏈及丙二醇鏈兩者之聚伸烷基二元醇二（甲基）丙烯酸酯，可列舉例如，下述一般式（VIII)所示之化合物： [化6] 和 fc(p0ttE0t(VI) In the formula (v) and the formula (VI), R6 to R3 5 each independently represent a hydrogen atom, a halogen atom or an alkoxy group having a carbon number of 1 to 5, and when R6 to R35 are present in a plural form in the same molecule, The same may or may not be the same, and at least one of R6 to R35 represents an alkoxy group having 1 to 5 carbon atoms. Thus, the resolution of the photosensitive resin composition is improved, and the adhesion and the mud removal property are further improved. Further, the photosensitive resin composition of the present invention preferably contains (D) a sensitizing dye. Thus, when light having a peak in a specific wavelength range is exposed, it has a maximum absorption in the vicinity of its specific wavelength range, and the sensitivity of the photosensitive resin composition is improved. Further, the photosensitive resin composition of the present invention is preferably a compound further containing (E) an amine-based group - 200848930. In this way, the sensitivity of the photosensitive resin composition is further improved. Moreover, the present invention is a photosensitive element comprising a support film and a photosensitive resin composition layer containing the photosensitive resin composition formed on the support film. According to the support film, since the photosensitive resin composition layer containing the photosensitive resin composition is provided, even when the resist pattern is formed by direct drawing exposure, it can be carried out under sufficient resolution and adhesion. Moreover, it also has an effect in improving the removal property of the mud which occurs at the time of a development process, and suppression of a developing residue. Moreover, the present invention is a laminating step of laminating a photosensitive resin composition layer containing the photosensitive resin composition on a circuit-forming substrate, and irradiating with a reactive light at a predetermined portion of the photosensitive resin composition layer. The exposure step of the photocuring of the exposed portion, and the method of forming the resist pattern of the developing step of the portion other than the exposed portion of the photosensitive resin composition layer by the circuit-forming substrate in which the photosensitive resin composition layer is laminated. According to the method for forming the photoresist pattern, since the photoresist pattern is formed using the photosensitive resin composition layer containing the photosensitive resin composition, even if the direct exposure method is short in exposure time, it can be sufficiently formed. Resolution and adhesion of the photoresist pattern. Moreover, the mud which occurs when the developing step is removed can be surely removed. Further, the present invention is a method of manufacturing a printed circuit board having a step of forming a conductive pattern by feeding or plating a circuit-forming substrate formed by the above-described pattern of the resist pattern. According to the method of manufacturing a printed circuit board, since the resistive pattern-formed circuit-forming substrate is formed by the above-described patterning method, a high-density wiring can be formed, and disconnection and short-circuiting can be sufficiently performed. Suppressed printed circuit boards. -12-200848930 (Effect of the Invention) According to the present invention, it is possible to provide a photosensitive resin composition which improves the resolution, the adhesion, the removal property of the slurry which occurs during the development step, and the suppression of the sufficient effect on the development residue. A photosensitive element, a method of forming a photoresist pattern, and a method of manufacturing a printed circuit board. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. Further, in the present invention, 'the so-called (meth)acrylic acid means acrylic acid or methacrylic acid' and (meth)acrylic acid ester means acrylate or its corresponding methacrylate ester' so-called (meth)acryl fluorenyl group. To mean propylene fluorenyl or methacryl fluorenyl. The photosensitive resin composition of the present invention contains (A) a divalent group represented by the above general formula (I) (hereinafter also referred to as "structural unit"), a structural unit represented by the above general formula (Π), and the above-mentioned general An adhesive polymer of the structural unit represented by the formula (m), (B) a photopolymerizable compound, and (C) a hexaarylbisimidazole compound having one or more alkoxy groups having 1 to 5 carbon atoms; A photosensitive resin composition of a photopolymerization initiator. First, the adhesive polymer for the component (A) will be explained. The adhesive polymer of the component (A) is a structural unit containing a styrene or a styrene derivative represented by the above general formula (I), and benzyl (meth)acrylate represented by the above general formula (II) Or a structural unit of a benzyl (meth) acrylate derivative, and a structural unit of -13-200848930 (meth)acrylic acid according to the above general formula (III). In this manner, the photosensitive resin composition layer containing the photosensitive resin composition as a constituent material is excellent in adhesion and peeling properties to the circuit-forming substrate. Here, in the above formula (I), R1 represents a hydrogen atom or a methyl group 'r2 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group or a halogen atom, and m is a An integer from 0 to 5. Further, in the above formula (II), R3 represents a hydrogen atom or a methyl group 'r4 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorene H group or a halogen atom, and m is a An integer from 0 to 5. Further, in the above formula (III), R5 represents a hydrogen atom or a methyl group. Specifically, it is a structural unit based on acrylic acid or methacrylic acid. The content ratio of the structural unit which is not in the above formula (I) is preferably 10 to 60% by mass in the total amount of the component (A), and more preferably 15 to 50% by mass, more preferably 2 to 50%. The mass % is particularly good. Further, the content ratio of the structural unit represented by the above general formula (Π) is preferably 1 〇 to 60% by mass in the total amount of the component (A), and more preferably 15 to 50% by mass, and more preferably 20 to 50% by mass. % is especially good. Further, the content ratio of the structure of the above formula (III) is preferably 20 to 50% by mass based on the total amount of the component (A), and more preferably 23 to 40% by mass, more preferably 2 5 to 3 5% by mass is particularly good. According to the structural unit of the styrene or the styrene derivative, the compounding amount of the structural unit of the benzyl (meth) acrylate or the benzyl (meth) acrylate derivative is less than 10% by mass, respectively, and the dissolving property is poor. When the blending amount is more than 60% by mass, the release sheet becomes large, and the peeling time tends to be long. In addition, when the amount of the structural unit of (meth)acrylic acid is less than 20% by mass, the alkali solubility is poor. -14-200848930 The release sheet becomes large, and the peeling time tends to become longer. The mass % has a tendency to reduce the resolution. The photosensitive resin composition using the adhesive polymer of the present invention has excellent effects on adhesion, resolution, removal of mud which occurs during development, and suppression of development residue. Further, in the present invention The term "styrene derivative" means a hydrogen atom in styrene which is substituted by a substituent (organic group such as an alkyl group or a halogen atom). When the photosensitive resin composition layer is formed using the adhesive polymer, one type of the adhesive polymer may be used alone, and two or more kinds of the adhesive polymers may be used in any combination. When two or more types of adhesive polymers are used in combination, for example, two or more different copolymerized components (including different repeating units as constituent components) of the adhesive polymer may be mentioned, and two different weight average molecular weights are used. More than one type of adhesive polymer, two or more kinds of adhesive polymers with different degrees of dispersion. Further, a polymer having a polytype molecular weight distribution described in JP-A No. 11-3 27 137 can also be used. (A) The weight average molecular weight (Mw) and the number average molecular weight (?n) of the adhesive polymer can be measured by gel permeation chromatography (GPC) (converted using a standard polystyrene calibration line). According to this measurement method, the Mw of the adhesive polymer is preferably from 5,000 to 150,000, more preferably from 10,000 to 1,000,000, and particularly preferably from 20,000 to 50,000. When the Mw is less than 5,000, the liquid resistance of the image is lowered, and if it exceeds 1,500, the development time tends to be long. Further, the (A) adhesive polymer has a degree of dispersion (Mw/Mn) of 1 · 〇〜 -15 - 200848930 3 · 0 is preferable, and 1 · 〇〜 2 · 0 is more preferable. When the degree of dispersion exceeds 3,000, the adhesion and resolution tend to decrease. The adhesive polymer of the present invention can be produced, for example, by subjecting a polymerizable monomer to radical polymerization. The polymerizable monomer having the structural unit represented by the above general formulas (I) to (III) may, for example, be styrene and/or a styrene derivative, benzyl (meth)acrylate, and/or (methyl). Benzyl acrylate derivative, (meth)acrylic acid. The above (Α) adhesive polymer may also contain structural units other than the structural units represented by the above general formulas (I) to (III). In this case, a polymerizable monomer having a structural unit other than the structural unit represented by the above general formulas (I) to (III) is provided, and examples thereof include acrylamide, acrylonitrile, and vinyl group such as diacetone acrylamide. An ester of vinyl alcohol such as n-butyl ether, an alkyl (meth)acrylate, a tetrahydrofurfuryl (meth)acrylate, a methyl methacrylate (ethyl) acrylate, and a diethyl (meth)acrylate Aminoethyl ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (methyl)propionic acid, α-glycine (methyl) propyl mercenic acid, α-chloro (methyl) propionic acid, 0-fluorenyl (meth)acrylic acid, anthracene-styryl (A Base) propylene, maleic acid, maleic anhydride, monomethyl maleate, monoethyl succinate, monoisopropyl maleate, etc. Diacid monoester, anti-butyric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. They may be used alone or in combination of two or more. Further, the alkyl (meth)acrylate may, for example, be a compound represented by the following general formula (VII), wherein the alkyl group of the compound is substituted with a trans group, an epoxy group such as -16 - 200848930, a halogen group or the like. Compounds, etc. CH2 = C(R36)-COOR37 (VII) Here, in the above general formula (VII), R36 represents a hydrogen atom or a methyl group, and R3·7 represents an alkyl group having 1 to 12 carbon atoms. Further, examples of the alkyl group having 1 to 12 carbon atoms represented by R3 7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, and a decyl group. Monoalkyl, dodecyl and structural isomers thereof. The monomer represented by the above general formula (VII) may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, or (methyl). Ethyl acrylate, ethyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, ( Oxyl methacrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. These monomers may be used alone or in combination of two or more. In the (A) adhesive polymer of the present invention, it is preferred to use one or two or more kinds of polymers having a carboxyl group from the viewpoint of developing the alkali image by using an alkali solution. Such a (A) adhesive polymer can be produced, for example, by subjecting a polymerizable monomer having a carboxyl group to radical polymerization of another polymerizable monomer. (A) The acid value of the adhesive polymer is preferably from 80 to 25 mgKOH/g, more preferably from 100 to 220 mgKOH/g, and particularly preferably from 150 to 210 mgKOH/g. When the acid value is less than 80 mgKOH/g, the development time is prolonged. -17-200848930, if it exceeds 250 mgKOH/g, the photocuring resistance of the photohardenable film tends to decrease. Further, in the developing step, it is preferred to prepare a polymerizable monomer having a carboxyl group when performing solvent development. Further, the (A) adhesive polymer may have a photosensitive characteristic group in its molecule as needed. The amount of the binder polymer of the component (A) is preferably 30 to 70 parts by mass and more preferably 35 to 65 parts by mass based on 100 parts by mass of the total of the components A and (B). 40 to 60 parts by mass is particularly preferable. When the amount is less than 30 parts by mass, the shape tends to be inferior in shape, and if it exceeds the mass %, good sensitivity and resolution tend not be obtained. Further, in the photosensitive resin composition of the present invention, a resin other than the component (A) may be used, and for example, an acrylic resin, an ethylene resin, or an epoxy resin may be used. A amide-based resin, a guanamine-based epoxy resin, an alkyd-based resin, a phenol-based resin, etc. Among them, an acrylic resin is preferred from the viewpoint of alkali developability. Further, these resins may be used alone or in combination. The photopolymerizable compound of the component (B) is described. The photopolymerizable compound of the component (B) may, for example, be a compound obtained by reacting a plurality of α,θ-unsaturated carboxylic acids, or bisphenol. a series (meth) acrylate compound, containing shrinkage a glyceryl-based compound obtained by reacting αΘ with a carboxylic acid, a urethane monomer having a urethane bond (meth) acrylate compound or the like in the molecule, and fluorenyl phenyl ethoxy acrylate Ester, phthalic acid-based compound, (meth) metering tool) 70 A phenylene ester, and alcoholic group oxypropyl -18-200848930 alkylate. These compounds may be used alone or in combination of two or more. The compound obtained by reacting the above polyol with an α,0-unsaturated carboxylic acid may, for example, be a polyethylene glycol di(meth)acrylate having an ethyl group number of 2 to 14 and a propyl group of 2 to 14 Polypropylene glycol di(meth)acrylate, polyethylene-polypropylene glycol di(meth)acrylate, trimethylolpropane di(methyl) having an ethyl group number of 2 to 14 and a propyl group of 2 to 14 Acrylate, trimethylolpropane tri(meth)acrylate, hydrazine-modified trimethylolpropane tri(meth)acrylate, hydrazine-modified trimethylolpropane tri(meth)acrylate, hydrazine, Lanthanum modified trimethylolpropane tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, tetramethylol methane tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate Ester, dipentaerythritol hexa(meth) acrylate, and the like. These compounds may be used alone or in combination of two or more. Here, "Ε〇" is an ethylene oxide, and the ruthenium-modified compound is a segmented structure having an oxirane group. Further, "Ρ〇" is a propylene oxide, and the compound modified by ρ0 is a segmented structure having an oxypropylene group. The above bisphenol oxime (meth) acrylate compound may, for example, be a '2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl) propyl), 2,2-bis ( 4-((Meth)acryloxylated polypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypolybutoxy)phenyl) propyl, 2, 2-bis(4-((meth)acryloxypolyethoxypolypropyloxy)phenyl)propane or the like. The above 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane may, for example, be '2,2-bis(4-((methyl) propylene oxy) Oxy)phenyl)propane, 2,2-bis(4-((-19-200848930)methyl decyloxytriethoxy)phenyl)propane, 2,2-bis(4-((A) Acryloxytetraki)phenyl)propane, 2,2-bis(4-((methyl)propenyloxypentaethoxy)phenyl)propane, 2,2-bis(4- ((Meth)propenyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethoxy)phenyl)propane, 2,2- Bis(4-((meth)propenyloxy octaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)pentaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxylethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy eleven ethoxy) Phenyl)propane, 2,2-bis(4-((meth)propenyloxydodecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy) Thirteen ethoxy)phenyl)propane, 2,2-bis(4-((methyl) Acryloxytetradecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentadecane)ethoxy)phenyl)propane, 2,2-bis ( 4-((meth)acryloxylhexadecyloxy)phenyl)propane or the like. The above 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane may be ΒΡΕ-5 00 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name or FA-321M (Hitachi Chemical Co., Ltd.) The industrial (stock) system, trade name) type is commercially available, and the above 2,2-bis(4-(methacryloxylpentadecane)ethoxy)phenyl)propane can be ΒΡΕ-1300 (Xinzhongcun Chemical) The industrial (stock) system, the trade name) is commercially available. The above 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane is in one molecule of epoxy B. The alkyl group is preferably 4 to 20, and more preferably 8 to 15. The compounds may be used alone or in combination of two or more. -20- 200848930 The above molecule has a urethane bond (methyl group) The acrylate compound may, for example, be a (meth) propylene monomer having an OH group at the A site and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene) Addition reaction of isocyanate, hexamethylene diisocyanate, etc., tris((meth) propylene methoxytetraethylene isocyanate) Ethyl isocyanurate, EO modified ethyl urethane di(meth) acrylate, EO, PO modified urethane di(meth) acrylate, etc. The above EO modified amine group The ethyl formate di(meth)acrylate may, for example, be UA-1 1 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). Further, the above EO, PO modified urethane di(methyl) For example, UA-1 3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) may be used. These compounds may be used alone or in combination of two or more. Examples of the above-mentioned nonylphenoxypolyoxyacrylate include , nonylphenoxytetraethyleneoxy acrylate, nonylphenoxypentavinyloxyacrylate, nonylphenoxy hexaethyleneoxy acrylate, nonylphenoxy pentyleneoxy acrylate, decyloxy VIII Ethylene oxy acrylate, nonylphenoxy hexaethyleneoxy acrylate, nonylphenoxy decyloxy acrylate, decyloxy undecyl oxy acrylate. These compounds may be used singly or in combination. The above phthalic acid compound may, for example, be mentioned. R-chloro-/3-hydroxypropyl-yS'-(meth)acryloyloxyethyl phthalate, hydroxyalkyl-/3 (meth) propylene oxyalkyl phthalate, etc. These compounds may be used alone or in combination of two or more. Further, the component (B) of the present invention contains bisphenol A (methyl) from the viewpoint of plating resistance and adhesion. An acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule is preferred. Further, from the viewpoint of improving sensitivity and resolution, a bisphenol A-based (meth) acrylate compound is used. Further, in the component (B) of the present invention, from the viewpoint of improving the flexibility of the cured film, a polyalkylene glycol having both an ethylene glycol chain and a propylene glycol chain in the molecule is contained. Di(meth)acrylate is preferred. The alkyl diol chain of the (meth) acrylate in the molecule is not particularly limited as long as it has both an ethylene glycol chain and a propylene glycol chain (n-propylene glycol chain or isopropyl glycol chain). Further, the (meth) acrylate may further have a n-butylene glycol chain, an isobutylene glycol chain, a n-pentanediol chain, a hexanediol chain, and a carbon number of 4 to 6 of the structural isomers thereof. A chain of alkyl diols. When the above-mentioned ethylene glycol chain and propylene glycol chain are plural, it is not necessary that the plural ethylene glycol chain and the propylene glycol chain are present continuously and in a segmental manner, and may be present in a random manner. Further, in the above isopropyl glycol chain, the secondary carbon of the propyl group may be bonded to the oxygen atom, and the primary carbon may be bonded to the oxygen atom. In the (B) component, the polyalkylene glycol di(meth)acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule may, for example, be represented by the following general formula (VIII). Compound: [Chemical 6] and fc(p0ttE0t

h2c=c——C——0 R36 -22- 200848930 下述一般式（IX )所示之化合物： [化7] II H2〇=C—C—0 R38 十0rcH2 R39 (IX) 及，下述一般式（X)所示之化合物 [化8] h2c=c—C—0H2c=c——C——0 R36 -22- 200848930 The compound of the following general formula (IX): [Chem. 7] II H2〇=C—C—0 R38 十 0rcH2 R39 (IX) and, the following The compound of the general formula (X) [Chemical 8] h2c=c-C-0

(X) R40 此處，式（VIII )、式（IX )及式（X )中，R36〜r41各獨立表示氫原子或碳數1〜3的烷基，EO爲表示乙二醇鍵’ PO爲表示丙二醇鏈，m1〜m4及η1〜η4各獨立表示1〜30之整數。此等化合物可單獨或組合使用二種以上。上述一般式（VIII)〜（X)中之碳數1〜3的丨完基可列舉例如，甲基、乙基、正丙基、異丙基。又，上述一般式（VIII )〜（X )中之乙二醇鏈的重複數總數（mkm2、m3及m4)爲1〜30之整數’以1〜之整數爲佳，且以4〜9之整數爲更佳，以5〜8之整數爲特佳。此重複數若超過30則傳導信賴性及光阻形狀有惡化的傾向。又，上述一般式（VIII )〜（X )中之丙二醇鏈的重 -23- 200848930 複數總數（η1、η2+ n3及η4)爲1〜30之整數，以5〜20之整數爲佳，且以8〜16之整數爲更佳，以10〜14之整數爲特佳。此重複數若超過3 0則解像度惡化，且有發生泥漿的傾向。上述一般式（VIII )所示化合物之具體例可列舉例如，R36 = R37==甲基、11^+1112 = 4 (平均値），n1 = 12 (平均値）之乙烯基化合物（日立化成工業（股）製，商品名FA-023M)等。又，上述一般式（IX)所示化合物之具體例可列舉例如，R38 = R39=甲基，m3 = 6 (平均値），n2 + n3 = 12 (平均値）之乙烯基化合物（日立化成工業（股）製，商品名FA-024M)等。更且，上述一般式（X)所示化合物之具體例可列舉例如，R4G = R41 =氫原子，m4=l (平均値），n4 = 9 (平均値）之乙烯基化合物（新中村化學工業（股 )製，樣品名NK Ester HEMA-9P )等。此等化合物可單獨或組合使用二種以上。 (B )成分之光聚合性化合物的配合量爲相對於（A ) 成分及（B )成分之總量1〇〇質量份，以30〜70質量份爲佳，且以35〜65質量份爲更佳，以40〜60質量份爲特佳。此配合量未滿30質量份則具有無法取得良好感度和解像性的傾向，若超過70質量份則具有無法取得良好形狀的傾向。 (B )成分可單獨一種或組合使用二種以上。其次，說明關於（C )成分之光聚合啓始劑。 (C)成分之光聚合啓始劑爲含有具有一個以上碳數爲1〜5之烷氧基的六芳基雙咪唑化合物。具體而言，於上 -24- 200848930 述式（IV)所示，上述式（V)及上述式（VI)中’式中，R6〜R3 5各獨立表示氫原子、鹵素原子或碳數1〜5的烷氧基，此R6〜R35的至少一者爲含有碳數1〜5的^71:¾基爲佳。六芳基雙咪唑化合物若爲具有1個以上碳數1〜5的院氧基即可，且以具有2個以上爲較佳，以具有4個以上爲更佳。若不含有此碳數1〜5的烷氧基’則無法取得密黏性、解像度、泥漿除去性及顯像殘渣之抑制效果。此碳數1〜5 的烷氧基可列舉甲氧基、乙氧基、丙氧基、丁氧基、戊氧基及其構造異構物。其中亦以碳數1，即甲氧基爲佳。又，六芳基雙咪唑化合物由進一步提高密黏性、解像度、泥漿除去性及顯像殘渣之抑制效果的觀點而言’以含有碳數 1〜5的院氧基及鹵素原子兩者爲佳。又，同一分子中R6〜 R35以複數形式存在時’彼等可爲相同或相異。另外，本說明書中「R6〜R35」所示之基爲表示R6、R7、R8、R9、 R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20 、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、 R31、R32、R33、R34、或 R35之基。此具有1個以上碳數1〜5的烷氧基之六芳基雙咪唑化合物可列舉例如，2 -(鄰-氯苯基）-4，5 -雙（間-甲氧苯基 )咪唑二聚物、2-(鄰-甲氧苯基）-4,5-二苯基咪唑二聚物、2,4-雙（鄰-氯苯基）-5-(3，4-二甲氧苯基）咪唑二聚物等。又，使用由交叉偶合反應所得之含有具有一個以上碳數1〜5的院氧基之六芳基雙咪哩化合物的化合物爲佳，可列舉例如2-(鄰-氯苯基）-4,5 -二苯基咪哩單體及2,4 -雙 -25- 200848930 (鄰-氯苯基）-5_ (3,4-二甲氧苯基）咪唑單體之偶合反應所得之化合物，2,2’，4-三（鄰-氯苯基）-4，，5，-二苯基-5- ( 3,4-二甲氧苯基）咪唑等。又，於本發明之感光性樹脂組成物中，在不損害特性之程度中，可合倂配合上述之具有1個以上碳數1〜5的烷氧基之六芳基雙咪唑化合物以外的光聚合啓始劑。具有一個以上烷氧基之六芳基雙咪唑化合物以外的光聚合啓始劑可列舉二苯酮、2-苄基-2-二甲胺基-1- ( 4-嗎啉苯基）-丁酮-1，2-甲基- l-[4-(甲硫基）苯基]-2-嗎啉基-丙酮-1等之芳香族酮、烷基蒽醌等之醌類、苯偶姻烷醚等之苯偶姻醚化合物、苯偶姻、烷基苯偶姻等之苯偶姻化合物、苄基二甲基縮醛等之苄基衍生物、2-(鄰-氯苯基）-4,5 -二苯基咪唑二聚物、2-(鄰-氟苯基）-4,5 -二苯基咪唑二聚物等之不含有烷氧基之2,4,5-三芳基咪唑二聚物、9-苯基吖丙啶、1，7- ( 9，9’-吖丙啶基）庚烷等之吖丙啶衍生物。 (C)成分之光聚合啓始劑中之具有一個以上碳數1〜 5的烷氧基之六芳基雙咪唑化合物的含有比例，於（C )成分之總量中，以10〜100質量％爲佳，且以30〜100質量％爲更佳，以50〜100質量％爲特佳。此配合量未滿10質量％，則具有無法取得高感度及高解像度的傾向。又，（C )成分之光聚合啓始劑的配合量，相對於（A )成分及（B )成分之總量1 0 0質量份，以0 · 1〜1 〇質量份爲佳，且以2〜6質量份爲更佳，以3 .5〜5質量份爲特佳。 -26- 200848930 此配合量未滿0 .1質量份則具有無法取得良好之感度和解像性的傾向，若超過1 〇質量份則具有無法取得良好形狀的傾向。（C )成分可爲單獨一種或組合使用二種以上。本發明之感光性樹脂組成物爲於上述（A )〜（C )成分，加上含有（D )增感色素及/或（E )胺系化合物爲佳。（D )成分之增感色素可列舉例如，二烷胺基二苯酮類、吡唑啉類、蒽類、香豆素類、咕噸酮類、噚唑類、苯并噚唑類、噻唑類、苯并噻唑類、三唑類、芪類、三嗪類、噻吩類、酞醯亞胺類等。又，上述增感色素以極大吸收波長爲370〜420nm之化合物爲佳，經由使用此類增感色素，則可對於直接描畫曝光法之曝光光線，具有充分的感度。若增感色素的極大吸收波長爲未滿3 7 0 n m，則對於直接描畫曝光光線的感度有降低的傾向，若超過42 Onm，則即使在黃色光環境下亦有安定性降低的傾向。極大吸收波長爲 3 70〜42 Onm的增感色素，例如，吡唑啉類、蒽類、香豆素類、咕噸酮類爲佳。上述增感色素的配合量相對於（A ) 成分及（B)成分之總量100質量份，以0.01〜1〇質量份爲佳，且以〇 . 〇 5〜5質量份爲更佳，以0 · 1〜2質量份爲特佳。此配合量未滿〇 · 〇 1質量份則具有無法取得良好感度和解像性的傾向，若超過1 〇質量份則具有無法取得良好形狀的傾向。（D)成分可爲單獨一種或組合使用二種以上。 (E )成分之胺系化合物可列舉例如，雙[4-(二甲胺基）苯基]甲烷、雙[4-(二乙胺基）苯基]甲烷、無色結晶紫等。配合量爲相對於（A )成分及（B )成分之總量1 00 -27- 200848930 質量份，以0.01〜10質量份爲佳，且以0.05〜5質量份爲更佳，以0.1〜2質量份爲特佳。此配合量未滿〇. 〇 1質量份則具有無法取得良好感度的傾向，若超過1 0質量份則於薄膜形成後’具有以異物型式析出的傾向。（E )成分可爲單獨一種或組合使用二種以上。於本發明之感光性樹脂組成物中，視需要，可將分子內具有至少一個可陽離子聚合之環狀醚基的光聚合性化合物（噚丁烷化合物等）、陽離子聚合啓始劑、孔雀綠等之染料、三溴苯基颯、無色結晶紫等之光發色劑、防止熱發色劑、對-甲苯磺醯胺等之可塑劑、顏料、充塡劑、消泡劑、難燃劑、安定劑、密黏性附著劑、勻塗劑、促進剝離劑、抗氧化劑、香料、影像劑、熱交聯劑等，相對於（A )成分及（B)成分之總量100質量份各別含有0.01〜20質量份左右。其可單獨或組合使用二種以上。又，本發明之感光性樹脂組成物爲於甲醇、乙醇、丙醇、甲基乙基醇、甲基溶纖劑、乙基溶纖劑、甲苯、N，N-二甲基甲醯胺、丙二醇單甲醚等之溶劑或其混合溶劑中以固形成分3 0〜6 0質量％左右之溶液型式亦可。此溶液可使用作爲形成感光性元件之感光性樹脂組成物層用之塗佈液〇又，上述塗佈液除了可使用於形成感光性元件之感光性樹脂組成物層以外，例如’於金屬板之表面上，以液狀光阻型式塗佈且乾燥後，被覆保護薄膜供使用亦可。金屬板的材質可列舉例如，銅、銅系合金、鎳、鉻、鐵、不鏽 -28- 200848930 鋼等之鐵系合金，較佳爲銅、銅系合金、鐵系合金等。其次，說明關於本發明之感光性元件。圖1爲示出本發明之感光性元件之適當的一實施形態的模式剖面圖。圖 1所示之感光性元件1爲由支持薄膜2、支持薄膜2上所形成之含有上述感光性樹脂組成物的感光性樹脂組成物層3、和感光性樹ΐ旨組成物層3上所層合的保護薄膜4所構成。支持薄膜2可例如使用聚對苯二甲酸乙二酯、聚丙烯、聚乙烯、聚酯等之具有耐熱性及耐溶劑性的聚合物薄膜。市售物質可列舉例如，王子製紙（股）公司製Alfun MA-410、E-2 00C (以上，商品名）、信越薄膜（股）公司製之聚丙烯薄膜、帝人（股）公司製PS系列（例如， PS-25，商品名）、帝人Dupont (股）公司製HTF-01、 HTR-02 (以上，商品名）等之聚對苯二甲酸乙二醇薄膜等〇又，支持薄膜2爲厚度爲1〜100 //m爲佳，且以5〜 25 // m爲更佳。其厚未滿1 // m則在顯像前剝離支持薄膜時，具有易令支持薄膜破裂的傾向，若超過1 0 0 // m則解像度有降低之傾向。另外，支持薄膜2，可將一者作爲感光性樹脂組成物層的支持體，且另一者作爲感光性樹脂組成物之保護薄膜並於感光性樹脂組成物層的兩面層合供使用亦可。感光性樹脂組成物層3爲將上述感光性樹脂組成物溶解於如上述之溶劑，作成固形成分3 0〜6 0質量°/〇左右之溶液（塗佈液）後，將此溶液於支持薄膜2上塗佈乾燥形成 -29- 200848930 爲佳。塗佈爲例如以使用輥塗器、科馬塗層器、照相凹版塗層器、空氣刀塗層器、型板塗層器、棒塗器等之公知方法進行。乾燥可在70〜150 °C、5〜30分鐘左右進行。又，感光性樹脂組成物中之殘存有機溶劑量，由防止其後步驟之有機溶劑擴散的觀點而言，以2質量％以下爲佳。又，感光性樹脂組成物層3之厚度爲根據感光性元件的用途而異，乾燥後之厚度爲1〜100 //m爲佳，且以1〜 50 // m爲更佳。此厚度未滿1 // m則有工業上塗佈困難的傾向，若超過1 0 0 // m則本發明之效果變小，接黏力、解像度有降低之傾向。又，感光性樹脂組成物層3，對於波長405 nm光的穿透率爲5〜75%爲佳，且以7〜60%爲更佳，以10〜40%爲特佳。其穿透率未滿5%則密黏性有惡劣之傾向，若超過75 %則解像度有惡劣的傾向。上述穿透率可以UV分光計測定，且上述UV分光計可列舉（股）日立製作所製228A型W束分光光度計等。保護薄膜4，比感光性樹脂組成物層3及支持薄膜2之接黏力，以感光性樹脂組成物層3及保護薄膜4之接黏力更小爲佳，又，以低魚眼的薄膜爲佳。另外，所謂「魚眼」 ’係將材料熱熔融，並且以混練、押出、雙軸延拉、澆鑄法等製造薄膜時，材料的異物、未溶解物、氧化惡化物等被攝入薄膜中之情況。保護薄膜4可使用例如，聚對苯二甲酸乙二酯、聚丙烯、聚乙烯、聚酯等之具有耐熱性及耐溶劑性的聚合物薄 -30- 200848930 膜。市售物質可列舉例如，TAMAPOLY (股）公司製NF-13、NF-15 (以上，商品名）等之聚乙烯薄膜、王子製紙 (股）公司製Alfun MA-410、E-200C (以上，商品名）、信越薄膜（股）公司製等之聚乙烯薄膜、帝人（股）公司製P S系列（例如，P S -2 5，商品名）等之聚對苯二甲酸乙二酯等，但並非限於此。保護薄膜4爲厚度爲1〜100 //m爲佳，且以5〜50//m 爲更佳，以5〜30 //m爲再佳，以15〜30 //m爲特佳。此厚度未滿1 // m則在層合時，保護薄膜有破裂之傾向，若超過1 00 // m則有廉價性差的傾向。又，本發明之感光性元件1亦可再具有緩衝層、接黏層、光吸收層、阻氣層等之中間層。又，所得之感光性元件1可爲薄片狀，或於捲芯以滾筒狀捲取並且保管。另外，此時以支持薄膜1爲最外側般捲纏爲佳。於上述滾筒狀之感光性元件的邊緣面，由保護邊緣面的觀點而言，設置邊緣面間隔件爲佳，且由耐邊緣熔合的觀點而言，設置防濕邊緣面間隔件爲佳。又，捆包方法以透濕性小的黑色薄片包住予以包裝爲佳。上述捲芯可列舉例如，聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、聚氯乙烯樹脂、ABS樹脂 (丙烯腈-丁二烯-苯乙烯共聚物）等之塑料等。其次，說明關於本發明之光阻圖型之形成方法。本發明之光阻圖型之形成方法爲至少包含於電路形成用基板上，層合含有上述感光性樹脂組成物之感光性樹脂組成物層之層合步驟，於感光性樹脂組成物層的指定部分 -31 - 200848930 以活性光線照射而使曝光部光硬化之曝光步驟’及由電路形成用基板，除去曝光部以外之部分中的感光性樹脂組成物層的顯像步驟。另外，所謂「電路形成用基板」’係指具備絕緣層和絕緣層上所形成之導體層的基板。又’電路形成用基板於多層化之內部亦可形成配線，且亦可具有小徑的直通孔。層合步驟中感光性樹脂組成物層對於電路形成用基板上的層合方法，可列舉例如，令保護薄膜由感光性樹脂組成物層慢慢剝離，並將同時慢慢露出的感光性樹脂組成物層之面部分密黏至電路形成用基板的形成電路面，一邊將感光性樹脂組成物層加熱一邊將感光性樹脂組成物層密黏至電路形成用基板予以層合之方法。另外，此作業由密黏性及追從性的觀點而言，於減壓下層合爲佳。感光性元件的層合爲將感光性樹脂組成物層及/或電路形成用基板於 70〜130 °C中加熱爲佳，壓黏壓力爲〇·1〜1·〇 MPa左右（1 〜10 kgf/cm2左右）爲佳，但並非特別限制於此等條件。又，感光性樹脂組成物層若如上述於7〇〜130 °C中加熱，則不必要預先將電路形成用基板予以預熱處理，但爲了更加提高層合性，亦可進行電路形成用基板的預熱處理。曝光步驟中形成曝光部的方法，可列舉透過所謂之原圖負型或正型光罩圖型於畫像上照射活性光線的方法（光罩曝光法）。此時，感光性樹脂組成物層上存在之支持薄膜爲活性光線穿透之情形中，可透過支持薄膜照射活性光線，於支持薄膜爲具遮光性之情形中，除去支持薄膜後對 -32- 200848930 感光性樹脂組成物層照射活性光線。又，亦可採用以雷射直接描畫曝光法和DLP ( Digital Light Processing，數碼光加工）曝光法等之直接描畫曝光法將活性光線以畫像狀照射之方法。活性光線之光源可使用公知之光源，例如，碳弧燈、水銀蒸氣弧燈、高壓水銀燈、氙燈、氬雷射等之氣體雷射、YAG雷射等之固體雷射、半導體雷射等之可有效放射紫外線、可見光等者。顯像步驟中除去曝光部以外之部分的方法，首先，於感光性樹脂組成物層上存在支持薄膜之情形中，可列舉除去支持薄膜，其後，以濕式顯像、乾式顯像等除去曝光部以外之部分予以顯像的方法。如此形成光阻圖型。例如’濕式顯像之情況，使用鹼性水溶液、水系顯像液、有機溶劑系顯像液等之對應感光性樹脂組成物的顯像液，例如，以浸漬方式、漿葉方式、噴霧方式、搖動浸漬、刷塗、磨擦等之公知方法予以顯像。顯像方式於提高解像度上，以高壓噴霧方式爲最適當。又，視需要亦可倂用二種以上之顯像方法。顯像液可使用鹼性水溶液等之安全且安定，操作性良好者。上述鹼性水溶液之鹼，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酸鹽、焦磷酸鈉、焦磷酸鉀等之鹼金屬焦磷酸鹽、硼砂等。又’顯像所用之上述鹼性水溶液以0 · 1〜5質量％碳酸 -33- 200848930 鈉之稀薄溶液，0 · 1〜5質量％碳酸鉀之稀薄溶液，〇 · 1〜5 質量％氫氧化鈉之稀薄溶液，0.1〜5質量％四硼酸鈉（硼砂 )之稀薄溶液等爲佳。又，此鹼性水溶液之pH爲9〜1 1之範圍爲佳，其溫度爲配合感光性樹脂組成物層之顯像性而調節。又，於鹼性水溶液中，亦可添加表面活性劑、消泡劑，用以促進顯像之少量的有機溶劑等。上述水系顯像液可列舉水或鹼水溶液與一種以上之有機溶劑所構成的顯像液。此處，鹼性水溶液之鹼除了上述之物質以外，可列舉例如，偏矽酸鈉、氫氧化四甲基銨、乙醇胺、乙二胺、二伸乙基三胺、2-胺基-2-羥甲基-1，3-丙二醇、1，3-二胺基丙醇-2、嗎啉等。顯像液之pH於光阻可充分顯像之範圍中儘可能小者爲佳，以pH8〜12爲佳，且以p 9〜1 0更佳。上述有機溶劑可列舉例如，丙酮、醋酸乙酯、具有碳數1〜4之烷氧基的烷氧基乙醇、乙醇、異丙醇、丁醇、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚等。其可單獨或組合使用二種以上。有機溶劑之濃度通常爲2〜 90質量％爲佳，其溫度可配合顯像性而調整。又’於水系顯像液中，亦可添加少量界面活性劑、消泡劑等。又，單獨使用有機溶劑之有機溶劑系顯像液可列舉例如，1，1，1-三氯乙烷、N-甲基吡咯烷酮，N，N-二甲基甲醯胺、環己酮、甲基異丁基酮、r - 丁內酯等。此等有機溶劑系顯像液爲了防止引火’以1〜2〇質量％之範圍添加水爲佳。 -34- 200848930 顯像後之處理，視需要進行6 0〜2 5 0 °C左右之加熱或 0.2〜10 J/cm2左右之曝光，令光阻圖型進一步硬化供使用亦可。其次，說明關於本發明之印刷電路板的製造方法。本發明之印刷電路板的製造方法，係將根據上述本發明之光阻圖型之形成方法，形成光阻圖型之電路形成用基板予以蝕刻或鍍敷形成導體圖型。電路形成用基板之蝕刻及鍍敷爲以所形成的光阻圖型作爲光罩，並且對電路形成用基板之導體層等進行。進行餓刻時之触刻液可列舉氯化銅溶液、氯化鐵溶液、鹼餓刻溶液、過氧化氫蝕刻液，其中，由蝕刻因素良好之觀點而言以使用氯化鐵溶液爲佳。又，進行鍍敷時之鍍敷方法可列舉例如，硫酸銅鍍敷、焦磷酸銅鍍敷等之銅鍍敷、快慢焊料鍍敷等之焊料鍍敷、瓦特浴（硫酸鎳、氯化鎳）鍍敷、胺磺酸鎳等之鎳鍍敷、硬金鍍敷、軟金鍍敷等之鍍金等〇蝕刻或鍍敷終了後，光阻圖型可例如以顯像所用之鹼性水溶液更強鹼性的水溶液予以剝離。此強鹼性水溶液例如可使用1〜1 0質量％氫氧化鈉水溶液、1〜1 〇質量％氫氧化鉀水溶液等。剝離方式可列舉例如，浸漬方式、噴霧方式等，且可單獨使用浸漬方式、噴霧方式，且亦可倂用。根據上述則取得印刷電路板。以下，雖然說明本發明之較佳的實施形態’但本發明並非被限定於上述實施形態。 -35- 200848930 實施例以下’進一步詳細說明本發明之較佳的實施發明並非被限定於此等實施例。 (感光性樹脂組成物之調製）配合以下之材料，調製實施例i〜4及比較例光性樹脂組成物的溶液。 <膠黏劑聚合物> 膠黏劑聚合物溶液（固形成分：表2所示之和質量比，溶劑（質量比）：甲基溶纖劑/甲苯聚合物重量平均分子量：3 0000，固形成分酸價〜4，比較例1、2、6爲1 96 mgKOH/g，比較例3 mgKOH/g ) : 1 13克（固形成分54克）。另外，聚合物重量平均分子量爲根據膠滲 GPC )測定，並且使用標準聚苯乙烯之檢量線換出。以下示出GPC的條件。泵··日立L-6000型（（股）日立製作所製）柱：Gelpack G1-R420 + Gelpack G1-R43 0 η GL-R 440 (計3根）（以上，日立化成工業（股品名）(X) R40 Here, in the formula (VIII), the formula (IX) and the formula (X), R36 to r41 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and EO represents an ethylene glycol bond 'PO To represent the propylene glycol chain, m1 to m4 and η1 to η4 each independently represent an integer of 1 to 30. These compounds may be used alone or in combination of two or more. The ruthenium group having a carbon number of 1 to 3 in the above general formulae (VIII) to (X) may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group. Further, the total number of repetitions (mkm2, m3, and m4) of the ethylene glycol chain in the above general formulas (VIII) to (X) is an integer of from 1 to 30, preferably in an integer of from 1 to 4, and is from 4 to 9 The integer is better, and the integer of 5 to 8 is particularly good. If the number of repetitions exceeds 30, the conduction reliability and the shape of the photoresist are deteriorated. Further, the total number (η1, η2 + n3, and η4) of the weight of the propylene glycol chain in the above general formulae (VIII) to (X) is an integer of 1 to 30, preferably an integer of 5 to 20, and An integer of 8 to 16 is more preferable, and an integer of 10 to 14 is particularly preferable. If the number of repetitions exceeds 30, the resolution deteriorates and the mud tends to occur. Specific examples of the compound represented by the above general formula (VIII) include, for example, a vinyl compound having R36 = R37 ==methyl, 11^+1112 = 4 (average 値), and n1 = 12 (average 値) (Hitachi Chemical Industry Co., Ltd. (share) system, trade name FA-023M) and so on. Further, specific examples of the compound represented by the above general formula (IX) include, for example, a vinyl compound having R38 = R39 = methyl group, m3 = 6 (average 値), and n2 + n3 = 12 (average 値) (Hitachi Chemical Industry Co., Ltd. (share) system, trade name FA-024M), etc. Further, specific examples of the compound represented by the above general formula (X) include, for example, a vinyl compound having R4G = R41 = hydrogen atom, m4 = 1 (average 値), and n4 = 9 (average 値) (Xinzhongcun Chemical Industry) (stock) system, sample name NK Ester HEMA-9P) and so on. These compounds may be used alone or in combination of two or more. The amount of the photopolymerizable compound of the component (B) is preferably 1 to 30 parts by mass based on the total amount of the components (A) and (B), and is preferably 30 to 70 parts by mass, and is 35 to 65 parts by mass. More preferably, it is particularly preferred from 40 to 60 parts by mass. When the amount is less than 30 parts by mass, the feeling of goodness and resolution is not obtained, and if it exceeds 70 parts by mass, the shape tends not to be obtained. The component (B) may be used alone or in combination of two or more. Next, a photopolymerization initiator for the component (C) will be described. The photopolymerization initiator of the component (C) is a hexaarylbisimidazole compound containing one or more alkoxy groups having 1 to 5 carbon atoms. Specifically, in the above formula (V) and the above formula (VI), R6 to R3 5 each independently represent a hydrogen atom, a halogen atom or a carbon number 1 as shown in the above formula (IV). Preferably, at least one of R6 to R35 is a ^71:3⁄4 group having a carbon number of 1 to 5. The hexaarylbisimidazole compound may have one or more oxy groups having 1 to 5 carbon atoms, and preferably 2 or more, more preferably 4 or more. If the alkoxy group having 1 to 5 carbon atoms is not contained, the effect of suppressing the adhesion, the resolution, the mud removal property, and the development residue can not be obtained. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a structural isomer thereof. Among them, a carbon number of 1, that is, a methoxy group is preferred. Further, from the viewpoint of further improving the adhesion, the resolution, the mud removal property, and the effect of suppressing the development residue, the hexaarylbisimidazole compound is preferably selected from the group having a carbon number of 1 to 5 and a halogen atom. . Further, when R6 to R35 exist in the plural form in the same molecule, they may be the same or different. In the present specification, the radicals represented by "R6 to R35" mean R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, A group of R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, or R35. The hexaarylbisimidazole compound having one or more alkoxy groups having 1 to 5 carbon atoms may, for example, be 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole. Polymer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxybenzene Base) imidazole dimer and the like. Further, a compound containing a hexaaryl bisphosphonium compound having one or more oxy groups having 1 to 5 carbon atoms, which is obtained by a cross-coupling reaction, is preferably used, and examples thereof include 2-(o-chlorophenyl)-4. a compound obtained by coupling of 5 - diphenylimidonomer and 2,4 -bis-25- 200848930 (o-chlorophenyl)-5-(3,4-dimethoxyphenyl)imidazole monomer, 2 2',4-tris(o-chlorophenyl)-4,5,-diphenyl-5-(3,4-dimethoxyphenyl)imidazole. Further, in the photosensitive resin composition of the present invention, light other than the above-described hexaarylbisimidazole compound having one or more alkoxy groups having 1 to 5 carbon atoms may be blended to the extent that the properties are not impaired. Polymerization initiator. The photopolymerization initiator other than the hexaarylbisimidazole compound having one or more alkoxy groups may, for example, be benzophenone or 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane. An aromatic ketone such as keto-1,2-methyl-l-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, an anthracene such as an alkyl hydrazine, or a benzoin a benzoin ether compound such as an alkyl ether, a benzoin compound such as benzoin or an alkyl benzoin, a benzyl derivative such as a benzyl dimethyl acetal, or a 2-(o-chlorophenyl)- 2,5,5-triarylimidazole which does not contain alkoxy groups, such as 4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer An aziridine derivative such as a dimer, 9-phenyl aziridine or 1,7-(9,9'-aziridinyl)heptane. The content ratio of the hexaarylbisimidazole compound having one or more alkoxy groups having 1 to 5 carbon atoms in the photopolymerization initiator of the component (C) is 10 to 100 by mass in the total amount of the component (C) % is preferable, and it is more preferably 30 to 100% by mass, and particularly preferably 50 to 100% by mass. When the amount is less than 10% by mass, the high sensitivity and the high resolution tend not to be obtained. Further, the amount of the photopolymerization initiator of the component (C) is preferably 0. 1 to 1 part by mass based on 100 parts by mass of the total of the components (A) and (B). 2 to 6 parts by mass is more preferably, and is preferably 3.5 to 5 parts by mass. -26- 200848930 If the blending amount is less than 0.1 part by mass, there is a tendency that good sensitivity and resolution are not obtained, and if it exceeds 1 〇 by mass, a good shape tends not to be obtained. The component (C) may be used alone or in combination of two or more. The photosensitive resin composition of the present invention is preferably the component (A) to (C), and preferably contains (D) a sensitizing dye and/or an (E) amine compound. Examples of the sensitizing dye of the component (D) include dialkylaminobenzophenones, pyrazolines, anthraquinones, coumarins, xanthones, oxazoles, benzoxazoles, and thiazoles. Classes, benzothiazoles, triazoles, anthraquinones, triazines, thiophenes, quinones, and the like. Further, the sensitizing dye is preferably a compound having a maximum absorption wavelength of 370 to 420 nm, and by using such a sensitizing dye, it is possible to sufficiently absorb the exposure light of the direct exposure method. When the maximum absorption wavelength of the sensitizing dye is less than 370 nm, the sensitivity for directly drawing the exposure light tends to decrease, and if it exceeds 42 Onm, the stability tends to decrease even in a yellow light environment. A sensitizing dye having a maximum absorption wavelength of 3 70 to 42 Onm, for example, a pyrazoline, an anthracene, a coumarin, or a xanthone is preferred. The amount of the sensitizing dye to be added is preferably 0.01 to 1 part by mass based on 100 parts by mass of the total of the components (A) and (B), and more preferably 5 to 5 parts by mass. 0 · 1 to 2 parts by mass is particularly good. When the amount is less than 〇, 〇 1 part by mass has a tendency to be inferior in sensitivity and resolution, and if it exceeds 1 part by mass, it has a tendency to fail to obtain a good shape. The component (D) may be used alone or in combination of two or more. Examples of the amine compound of the component (E) include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, and colorless crystal violet. The compounding amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on the total amount of the components (A) and (B) of 1 00 -27 to 200848930 parts by mass, and 0.1 to 2 parts by mass. The mass portion is exceptional. When the amount of the compound is less than 质量1 parts by mass, the feeling of goodness is not obtained, and if it exceeds 10 parts by mass, it tends to precipitate in a foreign form after the film is formed. The component (E) may be used singly or in combination of two or more. In the photosensitive resin composition of the present invention, if necessary, a photopolymerizable compound (inium butane compound, etc.) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and malachite green can be used. Photochromic agents such as dyes, tribromophenylphosphonium, colorless crystal violet, thermal plasticizers, p-toluenesulfonamides, plasticizers, pigments, eliminants, defoamers, flame retardants , a stabilizer, a viscous adhesive, a leveling agent, a release promoting agent, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, etc., each of which is 100 parts by mass based on the total amount of the components (A) and (B) Do not contain about 0.01 to 20 parts by mass. They may be used alone or in combination of two or more. Further, the photosensitive resin composition of the present invention is methanol, ethanol, propanol, methyl ethyl alcohol, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, In a solvent such as propylene glycol monomethyl ether or a mixed solvent thereof, a solution form having a solid content of about 30 to 60% by mass may be used. This solution can be used as a coating liquid for forming a photosensitive resin composition layer of a photosensitive element. The coating liquid can be used in addition to a photosensitive resin composition layer for forming a photosensitive element, for example, a metal plate. On the surface, after coating and drying in a liquid photoresist pattern, the protective film may be coated and used. The material of the metal plate may, for example, be an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron or stainless steel -28-200848930 steel, and is preferably copper, a copper-based alloy or an iron-based alloy. Next, the photosensitive element of the present invention will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. The photosensitive element 1 shown in Fig. 1 is a photosensitive resin composition layer 3 containing the above-mentioned photosensitive resin composition formed on the support film 2 and the support film 2, and a photosensitive composition layer 3 The laminated protective film 4 is composed of. The support film 2 can be, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester. For example, the Alfun MA-410, E-2 00C (above, trade name) manufactured by Oji Paper Co., Ltd., the polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and the PS series manufactured by Teijin Co., Ltd. (for example, PS-25, trade name), polyethylene terephthalate film such as HTF-01, HTR-02 (trade name) manufactured by Teijin Dupont Co., Ltd., etc. The thickness is preferably from 1 to 100 //m, and more preferably from 5 to 25 // m. When the thickness is less than 1 // m, the support film is peeled off before development, and the support film tends to be broken. If it exceeds 100 μm, the resolution tends to decrease. Further, the support film 2 may be one as a support for the photosensitive resin composition layer, and the other may be used as a protective film for the photosensitive resin composition and laminated on both surfaces of the photosensitive resin composition layer. . The photosensitive resin composition layer 3 is a solution (coating liquid) in which the photosensitive resin composition is dissolved in a solvent as described above to form a solid content of about 30 to 60 mass % / Torr, and the solution is applied to a support film. 2 coating drying to form -29-200848930 is preferred. The coating is carried out, for example, by a known method using a roll coater, a Koma coater, a gravure coater, an air knife coater, a plate coater, a bar coater or the like. Drying can be carried out at 70 to 150 ° C for 5 to 30 minutes. In addition, the amount of the organic solvent remaining in the photosensitive resin composition is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. Further, the thickness of the photosensitive resin composition layer 3 varies depending on the use of the photosensitive element, and the thickness after drying is preferably from 1 to 100 //m, and more preferably from 1 to 50 // m. If the thickness is less than 1 / m, the coating tends to be difficult in the industrial application. When the thickness exceeds 100 μm, the effect of the present invention is small, and the adhesion and the resolution tend to be lowered. Further, the photosensitive resin composition layer 3 preferably has a transmittance of 5 to 75% for light having a wavelength of 405 nm, more preferably 7 to 60%, and particularly preferably 10 to 40%. If the penetration rate is less than 5%, the adhesion tends to be bad, and if it exceeds 75%, the resolution tends to be bad. The above-mentioned transmittance may be measured by a UV spectrometer, and the UV spectrometer may be a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd., or the like. The protective film 4 has a higher adhesion than the photosensitive resin composition layer 3 and the support film 2, and the photosensitive resin composition layer 3 and the protective film 4 have a smaller adhesion force, and a low fisheye film. It is better. In addition, when the film is produced by kneading, extrusion, biaxial stretching, casting, or the like, the "fisheye" is taken into the film by foreign matter, undissolved matter, or oxidative deterioration of the material. Happening. As the protective film 4, for example, a polymer thin film of -30-200848930 having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. For example, a polyethylene film such as NF-13, NF-15 (trade name) manufactured by TAMAPOLY Co., Ltd., Alfun MA-410, E-200C manufactured by Oji Paper Co., Ltd. (above, Product name), polyethylene film such as Shin-Etsu Film Co., Ltd., and polyethylene terephthalate such as PS series (for example, PS-25, trade name) manufactured by Teijin Co., Ltd., but not Limited to this. The protective film 4 preferably has a thickness of 1 to 100 //m, and is preferably 5 to 50//m, more preferably 5 to 30 //m, and particularly preferably 15 to 30 //m. If the thickness is less than 1 / m, the protective film tends to crack when laminated, and if it exceeds 100 / m, the price tends to be poor. Further, the photosensitive element 1 of the present invention may further have an intermediate layer of a buffer layer, an adhesive layer, a light absorbing layer, a gas barrier layer or the like. Further, the obtained photosensitive member 1 may be in the form of a sheet or may be wound up and stored in a roll shape in a winding core. Further, at this time, it is preferable that the support film 1 is wound as the outermost side. In the edge surface of the above-mentioned roller-shaped photosensitive member, it is preferable to provide an edge-face spacer from the viewpoint of protecting the edge surface, and it is preferable to provide a moisture-proof edge surface spacer from the viewpoint of edge fusion resistance. Further, the packing method is preferably carried out by wrapping it in a black sheet having a small moisture permeability. Examples of the winding core include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS resin (acrylonitrile-butadiene-styrene copolymer). Next, a method of forming the photoresist pattern of the present invention will be described. The method for forming a photoresist pattern of the present invention is a lamination step of laminating a photosensitive resin composition layer containing the photosensitive resin composition at least on a circuit-forming substrate, and designing a photosensitive resin composition layer Part-31 - 200848930 The exposure step of photocuring the exposed portion by irradiation with active light and the development step of the photosensitive resin composition layer in the portion other than the exposed portion by the substrate for circuit formation. In addition, the "circuit forming substrate" means a substrate including a conductive layer and a conductor layer formed on the insulating layer. Further, the circuit-forming substrate may be formed with wiring inside the multilayer, and may have a through-hole having a small diameter. In the lamination step, the method of laminating the photosensitive resin composition layer on the circuit-forming substrate is, for example, a photosensitive resin in which the protective film is gradually peeled off from the photosensitive resin composition layer and is gradually exposed at the same time. A method in which the surface of the layer of the material layer is adhered to the circuit surface of the circuit-forming substrate, and the photosensitive resin composition layer is adhered to the circuit-forming substrate while the photosensitive resin composition layer is heated. Further, this work is preferably laminated under reduced pressure from the viewpoint of adhesion and followability. The lamination of the photosensitive element is preferably performed by heating the photosensitive resin composition layer and/or the circuit formation substrate at 70 to 130 ° C, and the pressure of the pressure is about 1 to 1 〇 MPa (1 to 10 kgf). It is preferable that it is about /cm2, but it is not particularly limited to these conditions. In addition, when the photosensitive resin composition layer is heated at 7 to 130 ° C as described above, it is not necessary to preheat the substrate for circuit formation in advance, but in order to further improve the laminate property, the substrate for circuit formation may be used. Preheat treatment. The method of forming the exposed portion in the exposure step may be a method of irradiating the active light onto the image through a so-called negative pattern or a positive mask pattern (mask exposure method). At this time, in the case where the support film present on the photosensitive resin composition layer is transparent to the active light, the active light can be irradiated through the support film, and in the case where the support film is light-shielding, after the support film is removed, the -32- 200848930 The photosensitive resin composition layer illuminates the active light. Further, a method in which the active light is irradiated in an image form by a direct drawing exposure method such as a laser direct drawing exposure method or a DLP (Digital Light Processing) exposure method may be employed. The light source of the active light may use a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, an argon laser or the like, a solid laser such as a YAG laser, or a semiconductor laser. Effectively emit ultraviolet light, visible light, etc. In the case where the portion other than the exposed portion is removed in the developing step, first, in the case where the supporting film is present on the photosensitive resin composition layer, the support film is removed, and then removed by wet development or dry development. A method of developing a portion other than the exposure portion. The photoresist pattern is thus formed. For example, in the case of the wet development, a developing liquid corresponding to the photosensitive resin composition such as an aqueous alkaline solution, an aqueous developing solution, or an organic solvent-based developing liquid is used, for example, by a dipping method, a paddle method, or a spraying method. A known method such as shaking, brushing, rubbing, or the like is used for development. The high-pressure spray method is most suitable for improving the resolution. Also, two or more types of development methods can be used as needed. The developing solution can be safe and stable using an alkaline aqueous solution or the like, and is excellent in workability. As the base of the alkaline aqueous solution, for example, an alkali hydroxide of lithium, sodium or potassium hydroxide, a carbonate of lithium, sodium, potassium or ammonium or a carbonate of a bicarbonate, potassium phosphate or sodium phosphate may be used. Alkali metal pyrophosphate such as alkali metal phosphate, sodium pyrophosphate or potassium pyrophosphate, borax, and the like. Further, the above alkaline aqueous solution used for image development is a thin solution of 0. 1 to 5 mass% of carbonic acid-33-200848930 sodium, a thin solution of 0. 1 to 5 mass% of potassium carbonate, 〇·1 to 5 mass% of hydroxide. A thin solution of sodium, a thin solution of 0.1 to 5% by mass of sodium tetraborate (borax) or the like is preferred. Further, the pH of the alkaline aqueous solution is preferably in the range of 9 to 1 1 , and the temperature thereof is adjusted in accordance with the developability of the photosensitive resin composition layer. Further, a surfactant or an antifoaming agent may be added to the alkaline aqueous solution to promote a small amount of an organic solvent or the like for development. The aqueous developing solution may, for example, be a developing solution comprising water or an aqueous alkali solution and one or more organic solvents. Here, the base of the alkaline aqueous solution may, for example, be sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine or 2-amino-2-, in addition to the above-mentioned substances. Hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine, and the like. The pH of the developing solution is preferably as small as possible in the range in which the photoresist can be sufficiently imaged, preferably pH 8 to 12, and more preferably p 9 to 1 0. Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, and the like. They may be used alone or in combination of two or more. The concentration of the organic solvent is usually from 2 to 90% by mass, and the temperature can be adjusted in accordance with the developability. Further, a small amount of a surfactant, an antifoaming agent, or the like may be added to the aqueous developing solution. Further, examples of the organic solvent-based developing solution using an organic solvent alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and A. Isobutyl ketone, r - butyrolactone and the like. It is preferable that these organic solvent-based developing liquids are added in an amount of 1 to 2% by mass in order to prevent ignition. -34- 200848930 After the development, the heating of about 60 to 250 °C or the exposure of about 0.2 to 10 J/cm2 may be performed as needed to further harden the photoresist pattern. Next, a method of manufacturing the printed circuit board of the present invention will be described. In the method of manufacturing a printed wiring board according to the present invention, a circuit pattern forming substrate having a photoresist pattern is formed by etching or plating in accordance with the method for forming a photoresist pattern of the present invention. The etching and plating of the circuit-forming substrate are performed by using the formed photoresist pattern as a mask, and the conductor layer of the circuit-forming substrate or the like. The contact liquid for the purpose of being hungry can be exemplified by a copper chloride solution, a ferric chloride solution, an alkali-stricken solution, and a hydrogen peroxide etching solution. Among them, a ferric chloride solution is preferred from the viewpoint of good etching factor. Moreover, the plating method at the time of plating, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as fast and slow solder plating, and Watt bath (nickel sulfate, nickel chloride). After plating or plating such as nickel plating such as plating or nickel sulfonate nickel plating, hard gold plating, or soft gold plating, etc., the photoresist pattern can be made stronger, for example, by using an alkaline aqueous solution for development. The alkaline aqueous solution is peeled off. For the strong alkaline aqueous solution, for example, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 1% by mass aqueous potassium hydroxide solution, or the like can be used. Examples of the peeling method include a dipping method, a spray method, and the like, and a dipping method or a spraying method may be used alone or in combination. According to the above, a printed circuit board is obtained. Hereinafter, the preferred embodiments of the present invention will be described, but the present invention is not limited to the above embodiments. -35-200848930 EXAMPLES The following detailed description of the preferred embodiments of the present invention is not intended to be limited thereto. (Preparation of photosensitive resin composition) A solution of the examples i to 4 and the comparative photosensitive resin composition was prepared by blending the following materials. <Adhesive Polymer> Adhesive Polymer Solution (solid content: mass ratio in Table 2, solvent (mass ratio): methyl cellosolve/toluene polymer weight average molecular weight: 3 0000, The solid form acid value was ~4, Comparative Examples 1, 2, and 6 were 1 96 mgKOH/g, and Comparative Example 3 mgKOH/g): 1 13 g (solid content: 54 g). Further, the weight average molecular weight of the polymer was measured according to the infiltration GPC, and was exchanged using a standard polystyrene calibration line. The conditions of GPC are shown below. Pump··Hitachi L-6000 (manufactured by Hitachi, Ltd.) Column: Gelpack G1-R420 + Gelpack G1-R43 0 η GL-R 440 (3 pieces) (above, Hitachi Chemical Industry Co., Ltd.)

溶離液：四氫呋喃測定溫度：40°C 例，但本 1〜6之感固形成分 (3/2 )， :實施例1 〜5爲163 透層析（算則可算卜 Gelpack )製，商 -36- 200848930 流量：2.0 5毫升/分鐘檢測器：日立L-3 3 00型RI ((股）日立製作所製） <光聚合性化合物> 2，2_雙（4-(甲基丙烯氧基五乙氧基）苯基）丙烷（ •.FA-321M，日立化成工業（股）製）：31克上述一般式（IX)所示之化合物，R38吸R39各爲甲基，m3 = 6 (平均値），n2 + n3 = 12 (平均値）之乙烯基化合物 (FA-024M，日立化成工業（股）製）：15克 <光聚合啓始劑> 表2所示之光聚合啓始劑與質量比（各光聚合啓始劑的組成爲不於表3〜表5。表3爲表Tf^TCDM-HABI的組成，表4爲表不CDM-HABI的組成，表5爲表示B-CIM( Hampford公司製，商品名）的組成） <增感色素> 9,10-二丁氧基蒽（川崎化成工業（股）製，表示吸收極大之波長[λ n] = 368 nm' 388 nm、410 nm) : 〇·8 克 <發色劑> 無色結晶紫（山田化學（股）製）：〇 · 2 5克 <染料> -37- 200848930 孔雀綠（大阪有機化學工業（股）製）：〇·〇3克 <溶劑> 丙酮9克甲苯5克甲醇5克 (感光性元件之製作）將所得之各感光性樹脂組成物的溶液，於作爲支持薄膜之16 // m厚的聚對苯二甲酸乙二酯薄膜（帝人Dupont (股）製，商品名：HTF-01 )上均勻塗佈。其後，使用70 °C及1 1 〇 °C之熱風對流式乾燥機予以乾燥，形成乾燥後之膜厚爲25 // m的感光性樹脂組成物層。接著，於感光性樹脂組成物層上將保護薄膜（TAMA POLY (股）製’商品名：NF-1 5 )以輥加壓予以層合’取得各實施例1〜4及比較例1〜6之感光性元件。 (試驗片之製作）接著，將兩面層合銅箔（厚度35mm )之玻璃環氧材貼銅層合板（日立化成工業（股）製’商品名MCL_E-6 7 )的銅表面，使用具備相當#600刷的硏磨機（三啓（股）製）予以硏磨，水洗後，以空氣流將其乾燥，取得貼銅層合板（基板）。其後’將貼銅層合板於8〇°C中加溫後’於貼銅層合板上一邊除去上述各感光性元件的保護薄膜’ > -38- 200848930 邊令各感光性樹脂組成物層爲於貼銅層合板的表面上密黏，並於120 °C下以4 kgf/cm2的壓力下層合，製作試驗片。 (特性評價） <光感度> 將各感光性元件層合的貼銅層合板冷卻並且於23 °C 之時刻，令支持薄膜，濃度範圍0.00〜2.00，濃度階段 0.05，藥片大小20 mmxl87 mm，各階段之大小爲3mmxl2 mm之具有41段階段藥片的光學工具。使用405 nm之藍紫色雷射二極管作爲光源的日立Bemechanix (股）製直描機 DE-1AH，以50 mJ/cm2之曝光量透過光學工具及支持薄膜於感光性樹脂組成物層曝光（描畫）。另外，照度之測定爲使用應用405 nm對應探針之紫外線照度計（UCO電機（股）製，商品名：「UIT-150」）進行。接著，剝離支持薄膜，於30 °C下噴霧1質量％碳酸鈉水溶液2 4秒鐘，並將感光性樹脂組成物層之未曝光部分除去且顯像。其後，經由測定貼銅層合板上所形成之光硬化膜的階段藥片的段數，則可評價感光性樹脂組成物的光感度。光感度之評價爲以階段藥片的段數表示，此階段藥片的段數愈高，則顯示光感度愈高。所得之結果示於表2。 <解像度（除去性）> 解像度爲使用具有線寬/空間寬6/6〜3 0/3 0 (單位： mm )之配線圖型的光學工具作爲評價用負型並且曝光。 •39- 200848930 此處’解像度爲於曝光後之顯像所形成的光阻圖型中，以未曝光部被美麗除去部分中之線寬間的空間寬中最小値（單位··// m )作爲解像度的指標。解像度的評價爲以數値愈小則爲愈良好之値。所得之結果示於表2。 <密黏性> 密黏性爲使用具有線寬/空間寬爲6/6〜3 0/3 0 (單位： // m )之配線圖型的光學工具作爲密黏性評價用負型並且曝光。此處，密黏性爲以經由曝光後之顯像處理可美麗除去未曝光部，且線不會產生蛇行，碎片且所生成之線寬/ 空間寬的最小値（單位··// m )作爲密黏性的指標。密黏性的評價爲以數値愈小則爲愈良好之値。所得之結果示於表2。 <光阻形狀> 顯像後之光阻形狀爲使用掃描型電子顯像鏡（商品名 :日立掃描型電子顯微鏡S-500A )觀察。光阻形狀期望接近矩形。 <泥漿除去性> 泥漿除去性爲以下列方法評價。首先，將各感光性元件中除去保護薄膜的感光性樹脂組成物層0 · 6 m 2溶解於1公升之1 % Na2C03水溶液中，並以小型顯像噴霧循環器攪拌 90分鐘。其後，將攪拌之溶液移至聚乙烯瓶中並且放置1 -40- 200848930 週後，比較聚乙烯瓶振盪前後底部泥漿（堆積物）的流走程度，並以表1所示之四階段判定除去性。泥漿除去性以數値愈高則除去性愈良好，4爲意指完全除去。 [表1] 程度判定基準 4 泥漿爲完全流走 3 泥漿爲幾乎完全流走 2 一部分泥漿流走 1 泥漿未流走 <顯像殘渣> 顯像殘渣爲使用掃描型電子顯微鏡（商品名：日立掃描型電子顯微鏡S-5 00A)，如下判定顯像後光阻圖型表面。期望幾乎完全無顯像殘渣。 A :幾乎完全無小片物附著般的顯像殘渣 β :有若干小片物附著般的顯像殘渣 C :有多數小片物附著般的顯像殘渣 -41 - 200848930 【(Ns 比較例6 〇 Ο m m TCDM -HABI 18.5 ι—Η 矩形寸 < 比較例5 (N ο (Ν ο 二苯甲酮 11.5 异矩形 cn < 比較例4 (N ο ^Τ) (Ν ο TCDM- HABI 18.5 (Ν (Ν Η 矩形寸 < 比較例3 (Ν ο (Ν ο B-CIM r- <rJ 18.7 r-H 矩形 m U 比較例2 § ο 〇 ο B-CIM rn 17.9 Ο (Ν t—H 矩形 (N PQ 比較例1 (Ν 〇 ο B-CIM 卜 rn r-H Ο (Ν τ-Η 矩形 PQ 實施例4 Ο S 〇 ο TCDM- HABI 17.8 Ο (Ν r-H 矩形寸 < 實施例3 § ο 〇 ο TCDM- HABI 18.5 ο Ο 1—Η 矩形寸 < 實施例2 (Ν 〇 ο CDM- HABI ^T) — 17.1 ο Ο Τ-Η 矩形寸 < 實施例1 (Ν 〇 ο TCDM- HABI 17.7 00 Ο τ—Η 矩形寸 < 苯乙烯甲基丙烯酸苄酯甲基丙烯酸甲基丙烯酸甲酯甲基丙烯酸2-乙基己酯光聚合啓始劑光聚合啓始劑量(質量比）光感度* 密黏性(L/SXpm) 解像度(除去性)(μιη) 光阻形狀泥漿除去性顯像殘渣膠黏劑聚合物 (質量比） -42- 200848930 [表3] TCDM-HABI之組成 Z1 Z2 含有量 (質量份）式(V) 式(V) R17及R18=甲氧基 R17及R18=甲氧基 R6及Ru=氯基 R6及Ru=氯基式(V) 式(VI) R17及R18=甲氧基 R32及R33=甲氧基 38 R6及Ru=氯基 R21及R26=氯基式(VI) 式(VI) R32及R33=甲氧基 R32及R33=甲氧基 R21及R26=氯基 R21及R26=氯基式(V) 式(V) R17及R18=甲氧基 R6及Ru=氯基 R6=氯基式(V) 式(VI) R17及R18=甲氧基 R6及RI1=氯基 R21:氯基 46 式(VI) 式(V) R32及R33=甲氧基 R21及R26=氯基 r6=氯基式(VI) 式(VI) R32及R33=甲氧基 R21及R26=氯基 r21=氯基式(V) 式(V) R6:氯基 r6=氯基式(V) 式(VI) 16 R6:氯基 r21=氯基式(VI) 式(VI) r21=氯基 r21=氯基 *關於R6〜R35未特別記載之情況，表示氫原子。 -43- 200848930 [表4] CDM-HABI之組成 Z1 Z2 含有量 (質量份）式(V) R12及R17=甲氧基 r6=氯基式(V) R12及R17=甲氧基 r6=氯基 100 式(V) R12及R17=甲氧基 R6及Ru=氯基式(VI) R27及R32=甲氧基 R21=氯基式(VI) R27及r32=甲氧基 R21=氯基式(VI) R27及R32=甲氧基 R21=氯基 *關於R6〜R35未特別記載之情況，表示氫原子。 [表5] B-CIM之組成 Z1 Z2 含有量 (質量份）式(V) 式(V) r6=氯基 r6=氯基式(V) 式(VI) 100 R6:氯基 r21=氯基式(VI) 式(VI) r21=氯基 r21=氣基 *關於R6〜R35未特別記載之情況，表示氫原子。 <評價結果> 如表2所示般，實施例1〜4之感光性樹脂組成物爲於階段段數感度、密黏性、解像性、泥漿除去性及光阻形狀的全部評價中取得良好的結果。另一方面，比較例1〜6之感 -44- 200848930 光性樹脂組成物爲於階段段數感度、密黏性、解像性、泥漿除去性及光阻形狀的評價中至少一個評價，比實施例差之結果。 (產業上之可利用性）若根據本發明，則可提供提高解像度、密黏性、顯像步驟時發生之泥漿的除去性及顯像殘渣之抑制上具有充分效果的感光性樹脂組成物，感光性元件，光阻圖型之形成方法及印刷電路板之製造方法。【圖式簡單說明】圖1爲示出本發明之感光性元件之適當的一實施形態的模式剖面圖。【主要元件符號說明】 1 :感光性元件，2 :支持薄膜，3 :感光性樹脂組成物，4 :保護薄膜 -45-Isolation liquid: tetrahydrofuran measurement temperature: 40 ° C, but the sensible solid content of this 1 to 6 (3/2), : Example 1 to 5 is 163 permeation chromatography (calculation can be calculated as Gelpack), commerce -36 - 200848930 Flow rate: 2.0 5 ml/min Detector: Hitachi L-3 00 type RI (manufactured by Hitachi, Ltd.) <Photopolymerizable compound> 2,2_bis(4-(methacryloxy) Pentaethoxy)phenyl)propane (•.FA-321M, manufactured by Hitachi Chemical Co., Ltd.): 31 g of the compound of the above general formula (IX), R38 is each a methyl group, m3 = 6 ( Average 値), n2 + n3 = 12 (average 値) vinyl compound (FA-024M, manufactured by Hitachi Chemical Co., Ltd.): 15 g <photopolymerization initiator> Photopolymerization shown in Table 2 The ratio of the initiator to the mass (the composition of each photopolymerization initiator is not in Table 3 to Table 5. Table 3 is the composition of the table Tf^TCDM-HABI, Table 4 is the composition of the CDM-HABI, Table 5 is the representation B-CIM (composition of product name, manufactured by Hampford Co., Ltd.) <sensitizing dye> 9,10-dibutoxy fluorene (manufactured by Kawasaki Chemical Industry Co., Ltd.), indicating the wavelength of absorption maximum [λ n] = 368 Nm' 388 Nm, 410 nm) : 〇·8 g <chromogen > colorless crystal violet (manufactured by Yamada Chemical Co., Ltd.): 〇· 2 5 g <dye> -37- 200848930 Malachite Green (Osaka Organic Chemical Industry) (manufactured by the company): 〇·〇3 g <solvent> Acetone 9 g of toluene 5 g of methanol 5 g (production of photosensitive element) A solution of each of the obtained photosensitive resin compositions was used as a support film 16 The m-thick polyethylene terephthalate film (manufactured by Teijin Dupont Co., Ltd., trade name: HTF-01) was uniformly coated. Thereafter, it was dried using a hot air convection dryer at 70 ° C and 1 1 〇 ° C to form a photosensitive resin composition layer having a film thickness of 25 // m after drying. Then, a protective film (trade name: NF-1 5 manufactured by TAMA POLY Co., Ltd.) was laminated on a photosensitive resin composition layer by roll pressurization to obtain each of Examples 1 to 4 and Comparative Examples 1 to 6. Photosensitive element. (Preparation of the test piece) Next, the copper surface of the copper epoxy board (trade name MCL_E-6 7 by Hitachi Chemical Industry Co., Ltd.) which laminated the copper foil of the double-sided copper foil (35 mm thickness) is used suitably. The #600 brush honing machine (Sanqi (share) system) was honed, washed with water, and dried by air flow to obtain a copper-clad laminate (substrate). Then, 'the copper-clad laminate is heated at 8 ° C, and the protective film of each of the photosensitive elements is removed on the copper-clad laminate'. -38- 200848930 A test piece was prepared by adhering to the surface of the copper-clad laminate and laminating at 120 ° C under a pressure of 4 kgf/cm 2 . (Characteristics evaluation) <Photosensitivity> The copper-clad laminate laminated with each photosensitive element was cooled and at 23 ° C, the support film was allowed to have a concentration range of 0.00 to 2.00, a concentration stage of 0.05, and a tablet size of 20 mm x 87 mm. An optical tool with a 41-stage stage tablet of 3 mm x 12 mm in each stage. A Hitachi Bemechanix direct-drawing machine DE-1AH using a 405 nm blue-violet laser diode as a light source is exposed (photographed) through an optical tool and a supporting film at a photosensitive resin composition layer at an exposure amount of 50 mJ/cm2. . Further, the measurement of the illuminance was carried out using an ultraviolet illuminometer (manufactured by UCO Motor Co., Ltd., trade name: "UIT-150") using a probe of 405 nm. Next, the support film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C for 24 seconds, and the unexposed portion of the photosensitive resin composition layer was removed and developed. Thereafter, the light sensitivity of the photosensitive resin composition can be evaluated by measuring the number of stages of the step of the photocured film formed on the copper clad laminate. The evaluation of the light sensitivity is expressed by the number of segments of the stage tablets, and the higher the number of tablets in this stage, the higher the light sensitivity is. The results obtained are shown in Table 2. <Resolution (Removability)> The resolution is an optical tool having a wiring pattern having a line width/space width of 6/6 to 3 0/3 0 (unit: mm) as a negative type for evaluation and exposure. •39- 200848930 Here, the resolution is the minimum of the space width between the line widths in the portion where the unexposed portion is beautifully removed, in the resist pattern formed by the exposure after exposure (unit··// m ) as an indicator of resolution. The resolution is evaluated as the number is smaller and the better is the better. The results obtained are shown in Table 2. <Adhesiveness> The adhesiveness is an optical tool having a wiring pattern having a line width/space width of 6/6 to 3 0/3 0 (unit: //m) as a negative type for evaluation of adhesion. And exposure. Here, the adhesion is such that the unexposed portion can be beautifully removed by the development process after exposure, and the line does not generate meandering, and the minimum line width/space width generated by the fragments (unit··//m) As an indicator of adhesion. The evaluation of the dense viscosity is such that the smaller the number, the better the flaw. The results obtained are shown in Table 2. <Photoresist shape> The shape of the photoresist after development was observed using a scanning electron microscope (trade name: Hitachi Scanning Electron Microscope S-500A). The photoresist shape is expected to be close to the rectangle. <Mud removal property> Mud removal property was evaluated by the following method. First, the photosensitive resin composition layer from which the protective film was removed in each photosensitive member was dissolved in 1 liter of a 1% Na2CO3 aqueous solution, and stirred in a small development spray circulator for 90 minutes. Thereafter, the stirred solution was transferred to a polyethylene bottle and placed for 1 -40 - 200848930 weeks, and the degree of flow of the bottom mud (stack) before and after the oscillation of the polyethylene bottle was compared, and the four stages shown in Table 1 were determined. Remove sex. The mud removal property is higher as the number is higher, and the removal is better, and 4 means complete removal. [Table 1] Degree of Judgment Criteria 4 Mud is completely flowed away 3 Mud is almost completely flowed away 2 Part of mud is flowing away 1 Mud is not flowing away> Development residue> Image residue is scanned electron microscope (trade name: Hitachi Scanning Electron Microscope S-5 00A), the surface of the photoresist pattern after development is determined as follows. It is expected that there is almost no visible residue. A: The image-forming residue is almost completely free of small pieces of film β: There are a few small pieces attached to the image-forming residue C: There are many small pieces attached to the image-forming residue -41 - 200848930 [(Ns Comparative Example 6 〇Ο mm TCDM -HABI 18.5 ι-Η Rectangular inch < Comparative Example 5 (N ο (Ν ο benzophenone 11.5 hetero- rectangle cn < Comparative Example 4 (N ο ^Τ) (Ν ο TCDM-HABI 18.5 (Ν (Ν矩形 Rectangular inch < Comparative Example 3 (Ν ο (Ν ο B-CIM r- <rJ 18.7 rH Rectangle m U Comparative Example 2 § ο 〇ο B-CIM rn 17.9 Ο (Ν t—H Rectangle (N PQ Comparison Example 1 (Ν Bο B-CIM 卜 r r Ο (Ν τ-Η Rectangular PQ Example 4 Ο S 〇ο TCDM-HABI 17.8 Ο (Ν rH Rectangle inch < Example 3 § ο 〇ο TCDM- HABI 18.5 ο Ο 1—Η Rectangular inch< Example 2 (Ν 〇ο CDM-HABI ^T) — 17.1 ο Ο Τ-Η Rectangular inch < Example 1 (Ν 〇ο TCDM- HABI 17.7 00 Ο τ—Η Rectangular Inch < styrene methacrylate methacrylate methacrylic acid methyl methacrylate 2-ethylhexyl methacrylate photopolymerization initiator photopolymerization initiator Quantity (mass ratio) Light sensitivity* Density (L/SXpm) Resolution (removability) (μιη) Photoresist shape mud removal imaging residue adhesive polymer (mass ratio) -42- 200848930 [Table 3] Composition of TCDM-HABI Z1 Z2 Content (parts by mass) Formula (V) Formula (V) R17 and R18 = methoxy R17 and R18 = methoxy R6 and Ru = chloro group R6 and Ru = chloro group (V Formula (VI) R17 and R18 = methoxy R32 and R33 = methoxy 38 R6 and Ru = chloro group R21 and R26 = chloro group (VI) Formula (VI) R32 and R33 = methoxy R32 and R33 = methoxy R21 and R26 = chloro group R21 and R26 = chloro group (V) formula (V) R17 and R18 = methoxy group R6 and Ru = chloro group R6 = chloro group (V) formula (VI) R17 And R18 = methoxy R6 and RI1 = chloro group R21: chloro group 46 Formula (VI) Formula (V) R32 and R33 = methoxy group R21 and R26 = chloro group r6 = chloro group (VI) Formula (VI) R32 and R33=methoxyl R21 and R26=chloro group r21=chloro group (V) formula (V) R6: chloro group r6=chloro group (V) formula (VI) 16 R6: chloro group r21=chlorine group Formula (VI) Formula (VI) r21 = chloro group r21 = chloro group * The case where R6 to R35 are not specifically described means a hydrogen atom. -43- 200848930 [Table 4] Composition of CDM-HABI Z1 Z2 Content (parts by mass) Formula (V) R12 and R17 = methoxy group r6 = chloro group (V) R12 and R17 = methoxy group r6 = chlorine Base 100 Formula (V) R12 and R17 = methoxy R6 and Ru = chloro (VI) R27 and R32 = methoxy R21 = chloro (VI) R27 and r32 = methoxy R21 = chloro (VI) R27 and R32 = methoxy group R21 = chloro group * The hydrogen atom is not specifically described for R6 to R35. [Table 5] Composition of B-CIM Z1 Z2 Content (parts by mass) Formula (V) Formula (V) r6 = Chlorine group r6 = Chlorine group (V) Formula (VI) 100 R6: Chloro group r21 = Chlorine group Formula (VI) Formula (VI) r21 = chloro group r21 = gas group * The case where R6 to R35 are not particularly described means a hydrogen atom. <Evaluation Results> As shown in Table 2, the photosensitive resin compositions of Examples 1 to 4 were evaluated in all stages of the stage number sensitivity, adhesion, resolution, mud removal property, and photoresist shape. Good results. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 6-44-200848930 were evaluated in at least one of the evaluation of the stage number sensitivity, the adhesion, the resolution, the mud removal property, and the photoresist shape. The result of the poor implementation. (Industrial Applicability) According to the present invention, it is possible to provide a photosensitive resin composition which has sufficient effects for improving the resolution, the adhesion, the removal property of the slurry which occurs during the development step, and the suppression of the development residue. A photosensitive element, a method of forming a photoresist pattern, and a method of manufacturing a printed circuit board. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. [Main component symbol description] 1 : Photosensitive element, 2: Support film, 3: Photosensitive resin composition, 4: Protective film -45-

Claims

200848930 X. Patent Application No. 1. A photosensitive resin composition comprising (A) a divalent group represented by the following general formula (I), a divalent group represented by the following general formula (II), and The divalent group of the adhesive polymer represented by the following general formula (III), (B) the photopolymerizable compound, and (C) a hexaaryl double having one or more alkoxy groups having 1 to 5 carbon atoms Photopolymerization initiator of imidazole compound; [Chemical 1]

[Chemical 2]

R5 I ——CH 2 —C — 0 丄 OH (丨丨丨) [In the formula (I), the formula (II) and the formula (III), each of RhR 3 and R 5 independently represents a hydrogen atom or a methyl group. R2 and R4 each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a 0H group or a halogen atom, and m or η each independently -46-200848930 represents an integer of 0 to 5, m or When η represents 2 to 5, the plural R 2 or R 4 may be the same or different from each other]. 2. The photosensitive resin composition of claim 1, wherein the photopolymerization initiator contains one or more compounds represented by the following general formula (IV); Z]-Z2 (IV) [Formula (IV) In the above, each of Z1 and Z2 independently represents a monovalent group represented by the following general formula (V) or (VI)] [Chemical 4]

[Chemical 5]

-47- 200848930 [In the formulae (V) and (VI), 'R6 to R35 each independently represent a hydrogen atom, a halogen atom or an alkoxy group having 1 to 5 carbon atoms, and when R6 to R35 are present in a plural form in the same molecule, They may be the same or different, and at least one of R6 to R35 represents an alkoxy group having a carbon number of 1 to 5. 3. The photosensitive resin composition of claim 1 or 2, which further comprises (D) a sensitizing dye. 4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (E) an amine compound. 5. A photosensitive member comprising a support film and a photosensitive resin composition formed on the support film and comprising the photosensitive resin composition according to any one of claims 1 to 4 Layer of matter. 6. A method of forming a photoresist pattern, comprising: forming a photosensitive resin composition comprising the photosensitive resin composition according to any one of claims 1 to 4 on a substrate for forming a circuit; The step of laminating the material layer, the exposure step of photocuring the exposed portion by irradiation with active light, and the substrate forming circuit for forming the photosensitive resin composition layer A developing step of a portion of the photosensitive resin composition layer other than the exposed portion. 7. A method of manufacturing a printed circuit board, comprising: forming a circuit pattern forming substrate of a photoresist pattern by a method for forming a photoresist pattern according to claim 6 of the patent application, by etching or plating; The step of forming a conductor pattern. -48-