TW201216002A

TW201216002A - Photosensitive resin composition, and photosensitive element, method for producing resist pattern, method for producing lead frame and method for producing printed wiring board using the same

Info

Publication number: TW201216002A
Application number: TW100122602A
Authority: TW
Inventors: Kenichi Iwashita; Masataka Kushida
Original assignee: Hitachi Chemical Co Ltd
Priority date: 2010-07-30
Filing date: 2011-06-28
Publication date: 2012-04-16
Also published as: KR20130095631A; JPWO2012014580A1; CN102597877A; CN102854750B; WO2012014580A1; TWI507820B; JP4849197B1; CN102854750A

Abstract

A photosensitive resin composition comprising: a binder polymer which contains a structural unit derived from a (meth)acrylic acid and a structural unit derived from a benzyl (meth)acrylate ester or a benzyl (meth)acrylate ester derivative; a polymerizable compound which has at least one ethylenically unsaturated bond; and a photopolymerization initiator which contains an acylphosphine oxide compound and a hexaarylbiimidazole derivative.

Description

201216002 六、發明說明：【發明所屬之技術領域】本發明係關於感光性樹脂組成物，以及使用其之感光性元件、光阻圖型之製造方法、引線框架之製造方法、印刷電路板及印刷電路板之製造方法。【先前技術】印刷電路板之製造領域中，廣泛使用具有於支撐薄膜上形成感光性樹脂組成物，或含有該感光性樹脂組成物之層（以下稱爲「感光性樹脂層」），且於感光性樹脂層上配置保護薄膜之構造之感光性元件（層合體）作爲蝕刻或鍍敷等所用之光阻材料。過去’印刷電路板係使用上述感光性元件，以例如以下順序製造。亦即，首先將感光性元件之感光性樹脂層層合於貼銅之層合板等之電路形成用基板上》此時，與感光性樹脂層之支撐薄膜接觸之面（以下稱爲感光性樹脂層之「下面」）爲相反側之面（以下稱爲感光性樹脂層之「上面」）成爲密著於形成電路形成用基板之電路之面上。因此，於感光性樹脂層之上面配置保護薄膜時，一邊剝離保護薄膜一邊進行該層合之作業。又，層合體係藉由將感光性樹脂層加熱壓著於下層之電路形成用基板上進行（常壓層合法）。接著，通過光罩薄膜等使感光性樹脂層圖型曝光。此時，在曝光前或曝光後之任何時點剝離支撐薄膜。隨後， -5- 201216002 以顯像液使感光性樹脂層之未曝光部份溶解或分散去除。接著，施以蝕刻處理或鍍敷處理形成圖型，最後剝離去除硬化部份。此處所謂蝕刻處理爲鈾刻去除於顯像後未被形成之硬化光阻被覆之電路形成用基板之金屬面後，剝離硬化光阻之方法。另一方面，所謂鍍敷處理爲於顯像後未被形成之硬化光阻被覆之電路形成用基板之金屬面上進行銅及焊料等之鍍敷處理後，去除硬化光阻，而蝕刻由該光阻所被覆之金屬面之方法。此處，上述之圖型曝光方法，過去係使用利用水銀燈作爲光源，透過光罩曝光之方法。又，近年來，已提案有稱爲DLP (數位光加工）之新曝光技術，係將圖型之數位數據直接描繪在感光性樹脂層上之直接描繪曝光法。該直接描繪曝光法相較於透過光罩之曝光方法其位置精準度更良好，且由於可獲得微細圖型，故已導入以製作高密度封裝基板。另一方面，伴隨著近年來之印刷電路板之高密度化，對於感光性樹脂組成物之高解像性及高密著性之要求亦增高。尤其在封裝基板製作中，要求可形成L/S (線寬/間隔寬）爲1 0/ 1 0 (單位：μηι )以下之光阻圖型之感光性樹脂組成物。高密度封裝基板由於電路間之寬度狹窄，故重要的是光阻形狀須優異。若光阻之剖面形狀爲梯形或倒梯形，且 -6- 201216002 光阻有拖尾時，由於隨後之藉由蝕刻處理或鍍敷處理形成之電路有發生短路或斷線之可能性故並不被期望，而期望光阻形狀爲矩形且無拖尾。另外，爲了提高感光性樹脂層之解像度，有效的是使感光性樹脂層薄膜化。然而，在形成印刷電路板時需要某種程度之電路厚度（銅厚等）時，藉蝕刻工法，由於會有蝕刻時之側蝕刻之影響，故細線部之光阻線容易脫落，於印刷電路板之高密度化（電路厚度與電路寬度兼具）有其界限。又，藉由鍍敷工法，由於若使感光性樹脂層薄膜化則難以獲得必要之電路厚度（銅厚），故印刷電路板之高密度化有其界限》近年來，對於不使感光性樹脂層之薄膜化而達成高解像度已進行各種嘗試。例如，於曝光前在剝離了支撐薄膜之感光性樹脂層上直接密著光學工具（Photo Tool)之方法。通常，感光性樹脂層係以密著於基材之方式維持某種程度之黏著性，使用該方法時，產生之問題爲光學工具與感光性樹脂層始終密著，難以剝離光學工具而使作業性低，有因感光性樹脂組成物污染光學工具，因氧阻礙之影響使感度降低等。因此，作爲改良該方法之嘗試，於特開平卜22 1 73 5號公報、特開平2-230149號公報中，係進行有使感光性樹脂層設爲兩層以上’使與光學工具直接接觸之層爲非黏著性樹脂層。然而，該方法由於使感光性樹脂層多層化，故塗佈時費工，對於感度降低係不具有效果者。 201216002 另外，爲達成印刷電路板之高密度化，作爲製造方法之半加成法（semi-additive method)受到囑目》本方法係藉由依序進行利用無電解鍍敷等而於基材上形成極薄膜導體層、形成光阻圖型、鍍敷、剝離光阻及快速蝕刻（去除不必要之極薄膜導體層），而形成印刷電路板。該工法之優點列舉爲由於幾乎不會有側蝕刻之影響故可獲得良好之電路，使印刷電路板之高密度化成爲可能。又，感光性樹脂組成物，除上述感度以外，重要的是解像度、光阻之剝離特性及密著性亦須優異。若感光性樹脂組成物可提供解像度及密著性優異之光阻圖型，則可充分降低電路間之短路或斷線。又，若感光性樹脂組成物可形成剝離特性優異之光阻，則可藉由使光阻之剝離時間縮短化而提高光阻圖型之形成效率，且，藉由減小光阻剝離片之大小而減少光阻之剝離殘留，提高電路形成之良率。對於該等要求，於特開平1 1 -3 27 1 37號公報中，提案使用特定之黏合劑聚合物、光聚合起始劑等之優異感度、解像度及光阻剝離特性之感光性樹脂組成物。另外，於特開2003-2 1 5799號公報、特開2000-1 62767 號公報中，揭示爲了使曝光部份與未曝光部份之對比（呈像性）變良好，而使用兒茶酚、氫醌等聚合抑制劑之感光性樹脂組成物。【發明內容】 [發明欲解決之課題] -8- 201216002 然而，特開平丨1·327137號公'報中記載之感光性樹脂組成物具有良好之剝離性’但相反地有解像度方面不足之情況。另外於特開2003-2 15799號公報及特開2000-162767號公報中所記載之感光性樹脂組成物’雖然解像度及呈像性方面良好，但若聚合抑制劑之添加量過多則有使感度下降，進而使密著性下降之情況。如此，過去之感光性樹脂組成物針對感度、解像度、密著性、光阻形狀及硬化後之剝離特性之所有特性，並非充分滿足所要求之特性者。再者，透過光罩之圖型曝光若爲了展現深部硬化性而增大曝光量，則圖型剖面之表面部（上部）對光罩之線寬變大，而有解像性下降之問題。因此，本發明之課題係提供一種感度、解像度、密著性、光阻形狀及硬化後之剝離特性之任一者均優異之感光性樹脂組成物，以及使用該等之感光性元件、光阻圖型之製造方法、引線框架之製造方法、印刷電路板及印刷電路板之製造方法。 [解決課題之手段] 本發明包含以下之樣態：本發明之第一樣態爲一種感光性樹脂組成物，其含有下列成分：（A) 具有源自（甲基）丙烯酸之構成單位及源自（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物 -9- 201216002 之構成單位之黏合劑聚合物，及（B) 具有至少一個乙烯性不飽和鍵之聚合性化合物，及（C) 含有醯基氧化膦系化合物及六芳基聯咪唑衍生物之光聚合起始劑。上述構成之感光性樹脂組成物之感度、解像度、密著性、光阻形狀及硬化後之剝離特性之任一者均優異。前述醯基氧化膦系化合物較好爲以下述通式（I)或通式（II)表示之化合物。據此，可進一步提高解像度，且獲得更優異之光阻形狀。【化1】 ο 〇 R1 C—P—R2 R4 C一P—C——R6201216002 VI. [Technical Field] The present invention relates to a photosensitive resin composition, a photosensitive member using the same, a method for producing a photoresist pattern, a method for manufacturing a lead frame, a printed circuit board, and printing The manufacturing method of the circuit board. [Prior Art] A layer having a photosensitive resin composition formed on a support film or a composition containing the photosensitive resin composition (hereinafter referred to as "photosensitive resin layer") is widely used in the field of manufacturing a printed circuit board. A photosensitive element (laminate) having a structure of a protective film disposed on the photosensitive resin layer is used as a photoresist for etching or plating. In the past, printed circuit boards were produced using the above-described photosensitive elements in the following order. In other words, the photosensitive resin layer of the photosensitive element is first laminated on a circuit-forming substrate such as a copper-clad laminate. In this case, the surface in contact with the support film of the photosensitive resin layer (hereinafter referred to as photosensitive resin) The "upper side" of the layer is the surface on the opposite side (hereinafter referred to as "upper surface" of the photosensitive resin layer) which is adhered to the surface of the circuit on which the circuit formation substrate is formed. Therefore, when a protective film is placed on the upper surface of the photosensitive resin layer, the lamination is performed while peeling off the protective film. Further, the laminate system is carried out by heating and pressing the photosensitive resin layer on the substrate for circuit formation of the lower layer (normal pressure layering). Next, the photosensitive resin layer is pattern-exposed by a photomask film or the like. At this time, the support film is peeled off before or at any time after the exposure. Subsequently, -5 - 201216002 dissolves or disperses the unexposed portion of the photosensitive resin layer with a developing liquid. Next, an etching 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 uranium engraving is removed from the metal surface of the circuit-forming substrate coated with the hard photoresist which is not formed after development, and the cured photoresist is removed. On the other hand, the plating treatment is performed by performing a plating treatment of copper, solder, or the like on the metal surface of the circuit-forming substrate on which the cured resist is not formed after development, and then removing the cured photoresist, and etching is performed. A method of coating a metal surface with a photoresist. Here, in the above-described pattern exposure method, a method of exposing through a reticle using a mercury lamp as a light source has been used. Further, in recent years, a new exposure technique called DLP (Digital Photographic Processing) has been proposed, which is a direct drawing exposure method in which digital data of a pattern is directly drawn on a photosensitive resin layer. The direct drawing exposure method has better positional accuracy than the exposure method by the reticle, and since a fine pattern is available, it has been introduced to produce a high-density package substrate. On the other hand, with the recent increase in the density of printed circuit boards, the demand for high resolution and high adhesion of photosensitive resin compositions has also increased. In particular, in the production of a package substrate, it is required to form a photosensitive resin composition having a resist pattern of L/S (line width/space width) of 10/100 (unit: μηι) or less. Since the high-density package substrate has a narrow width between circuits, it is important that the photoresist shape is excellent. If the cross-sectional shape of the photoresist is trapezoidal or inverted trapezoidal, and the photoresist of -6-201216002 has a tailing, the circuit formed by the etching treatment or the plating treatment may have a short circuit or a disconnection. It is expected that the shape of the photoresist is expected to be rectangular and without smearing. Further, in order to improve the resolution of the photosensitive resin layer, it is effective to thin the photosensitive resin layer. However, when a certain degree of circuit thickness (copper thickness, etc.) is required in forming a printed circuit board, the etching process may cause the photoresist of the thin line portion to fall off due to the etching effect at the time of etching. The high density of the board (both circuit thickness and circuit width) has its limits. In addition, it is difficult to obtain a necessary circuit thickness (copper thickness) by thinning the photosensitive resin layer by the plating method, so that the density of the printed circuit board is limited. In recent years, the photosensitive resin is not required. Various attempts have been made to achieve a high resolution by thinning the layers. For example, a method in which an optical tool (Photo Tool) is directly adhered to a photosensitive resin layer from which a support film has been peeled off before exposure. In general, the photosensitive resin layer maintains a certain degree of adhesion so as to adhere to the substrate. When this method is used, the problem arises in that the optical tool and the photosensitive resin layer are always adhered to each other, and it is difficult to peel off the optical tool and work. The property is low, and the optical tool is contaminated by the photosensitive resin composition, and the sensitivity is lowered due to the influence of oxygen inhibition. Therefore, as a result of the improvement of the method, the photosensitive resin layer is made of two or more layers in direct contact with the optical tool, in Japanese Laid-Open Patent Publication No. Hei. The layer is a non-adhesive resin layer. However, in this method, since the photosensitive resin layer is multi-layered, it is laborious to apply, and it does not have an effect on sensitivity reduction. 201216002 In addition, in order to achieve a high density of printed circuit boards, a semi-additive method as a manufacturing method has been attracting attention. This method is formed on a substrate by electroless plating or the like in sequence. The thin film conductor layer, the photoresist pattern, the plating, the stripping photoresist, and the rapid etching (removing the unnecessary thin film conductor layer) form a printed circuit board. The advantage of this method is that a good circuit can be obtained because there is almost no influence of side etching, which makes it possible to increase the density of the printed circuit board. Further, in addition to the above-described sensitivity, the photosensitive resin composition is important in that the resolution, the peeling property of the photoresist, and the adhesion are also excellent. If the photosensitive resin composition provides a resist pattern with excellent resolution and adhesion, it can sufficiently reduce short circuits or disconnection between circuits. Further, when the photosensitive resin composition can form a photoresist having excellent peeling properties, the formation efficiency of the resist pattern can be improved by shortening the peeling time of the photoresist, and the resist release sheet can be reduced. The size reduces the peeling residue of the photoresist and improves the yield of the circuit formation. In the above-mentioned Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. 1 -3 27 1 37 proposes to use a photosensitive resin composition having excellent sensitivity, resolution and photoresist peeling properties such as a specific binder polymer or a photopolymerization initiator. . Further, in Japanese Laid-Open Patent Publication No. 2003-2 1799, JP-A-2000-1 62767, it is disclosed that catechol is used in order to improve the contrast (imageability) between the exposed portion and the unexposed portion. A photosensitive resin composition of a polymerization inhibitor such as hydroquinone. [Problems to be Solved by the Invention] -8-201216002 However, the photosensitive resin composition described in the Japanese Patent Publication No. Hei. No. 1,327,137 has good peelability, but conversely, there is a lack of resolution. . In addition, the photosensitive resin composition described in the Japanese Patent Laid-Open Publication No. JP-A No. 2000-162767 is excellent in resolution and imageability. However, if the amount of the polymerization inhibitor added is too large, the sensitivity is obtained. Decline, which in turn reduces the adhesion. As described above, in the past, all of the characteristics of the photosensitive resin composition for the sensitivity, the resolution, the adhesion, the photoresist shape, and the peeling property after hardening do not sufficiently satisfy the required characteristics. Further, when the exposure of the reticle is increased to reveal the deep sclerosing property, the surface portion (upper portion) of the cross-section of the pattern has a large line width with respect to the reticle, and the resolution is lowered. Therefore, the subject of the present invention is to provide a photosensitive resin composition which is excellent in any of sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing, and photosensitive members and photoresists using the same. A method of manufacturing a pattern, a method of manufacturing a lead frame, a printed circuit board, and a method of manufacturing a printed circuit board. [Means for Solving the Problem] The present invention contains the following aspects: The first aspect of the present invention is a photosensitive resin composition containing the following components: (A) having a constituent unit derived from (meth)acrylic acid and a source thereof a binder polymer composed of benzyl (meth) acrylate or benzyl (meth) acrylate derivative -9 - 201216002, and (B) a polymerizable compound having at least one ethylenically unsaturated bond, and C) A photopolymerization initiator containing a fluorenylphosphine oxide-based compound and a hexaarylbiimidazole derivative. The photosensitive resin composition having the above configuration is excellent in sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing. The above fluorenylphosphine oxide-based compound is preferably a compound represented by the following formula (I) or formula (II). According to this, the resolution can be further improved, and a more excellent resist shape can be obtained. 【化1】 ο 〇 R1 C—P—R2 R4 C—P—C—R6

[通式（I)中，R1、R2及R3各獨立表示碳數卜20之烷基或芳基，式（II)中，R4、R5及R6各獨立表示碳數1〜20之烷基或芳基]。前述六芳基聯咪唑衍生物較好爲2，4,5-三芳基咪唑二聚物。據此，可進一步提高感度及解像度。本發明之第二樣態爲一種感光性元件，其具備支撐體、形成於前述支撐體上之上述感光性樹脂組成物的塗膜之感光性樹脂層。本發明之第三樣態爲一種光阻圖型之製造方法，其具有下列步驟：於基板上形成上述之感光性樹脂組成物的塗膜之感光性樹脂層的感光性樹脂層形成步驟，對前述感光性樹脂層之至少一部份照射活性光線而使之光硬化之曝光 -10- 201216002 步驟，及自基板上去除前述感光性樹脂層之未硬化部份，形成由前述感光性樹脂層之硬化物所成之光阻圖型之顯像步驟。本發明之第四樣態爲一種引線框架之製造方法，其包含使上述之光阻圖型之製造方法所得之形成有光阻圖型之基板進行鍍敷處理，而形成導體圖型之步驟。本發明之第五樣態爲一種印刷電路板之製造方法，其包含使由上述光阻圖型之製造方法所得之形成有光阻圖型之基板進行鍍敷處理，形成導體圖型之步驟。依據該製造方法，可精度良好、尤其是有效率地製造如高密度封裝基板之高密度化印刷電路板。本發明之第六樣態爲一種印刷電路板，其係由上述印刷電路板之製造方法而製造。 [發明效果] 依據本發明，可提供一種感度、解像度、密著性、光阻形狀及硬化後之剝離特性之任一者均優異之感光性樹脂組成物’以及使用該等之感光性元件、光阻圖型之製造方法、引線框架之製造方法、及印刷電路板之製造方法。【實施方式】本說明書中「步驟」一詞不僅爲獨立之步驟，於無法與其他步驟明確區分時，只要可達成該步驟所期望之作用亦包含於本用語。 -11 - 201216002 另本說明中使用「〜」表示之數値範圍係表示包含「〜」之前後所述之數値分別作爲最小値及最大値之範圍。進而提及本說明書中之組成物中之各成分之量時，組成物中之各成分複數存在該物質時，只要沒有特別說明，則意指組成物中存在之該複數物質之合計量。〈感光性樹脂組成物〉本發明之感光性樹脂組成物含有（A)具有源自（甲基）丙烯酸之構成單位及源自（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物之構成單位之黏合劑聚合物之至少一種，及（B)具有至少一個乙烯性不飽和鍵之聚合性化合物之至少一種，及（C)含有醯基氧化膦系化合物及六芳基聯咪唑衍生物之光聚合起始劑。藉由該構成，而顯示感度、解像度、密著性、光阻形狀及硬化後之剝離特性之任一者均優異之特性。 (A) 黏合劑聚合物本發明中之黏合劑聚合物只要具有源自（甲基）丙烯酸之構成單位，及源自（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物之構成單位者即無特別限制。又前述黏合劑聚合物除前述源自（甲基）丙烯酸之構成單位，及源自 (甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物之構成單位以外，亦可視需要進一步具有源自（甲基）丙烯酸烷酯之構成單位或源自苯乙烯或苯乙烯衍生物之構成單位之 -12- 201216002 其他構成單位所構成。前述（甲基）丙烯酸苄酯衍生物可列舉爲例如於苄基之芳香環上經碳數1〜6之烷氧基、鹵素、碳數1〜6之烷基取代之化合物。具體而言，列舉爲（甲基）丙烯酸乙氧基苄酯、（甲基）丙烯酸甲氧基苄酯、（甲基）丙烯酸氯苄酯、（甲基）丙烯酸甲基苄酯、（甲基）丙烯酸乙基苄酯等〇又，（甲基）丙烯酸 '及（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物以外之其他聚合性單體列舉爲例如苯乙烯；乙烯基甲苯、α-甲基苯乙烯等α-位或芳香環中經取代之可聚合之苯乙烯衍生物；二丙酮丙烯醯胺等之丙烯醯胺；丙烯腈；乙烯基-正丁基醚等乙烯醇之酯類；（甲基）丙烯酸烷酯、（甲基）丙烯酸環烷酯、（甲基）丙烯酸糠酯、（甲基）丙烯酸四氫糠酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸金剛烷酯、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯酸二甲胺基乙酯、（甲基）丙烯酸二乙胺基乙酯、（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸2,2,2-三氟乙酯、（甲基）丙烯酸2,2,3,3_四氟丙酯、（甲基）丙烯酸β-呋喃酯、（甲基）丙烯酸β-苯乙烯酯、馬來酸、馬來酸酐、馬來酸單甲酯、馬來酸單乙酯、馬來酸單異丙酯等馬來酸單酯，富馬酸、桂皮酸、α -氰基桂皮酸、衣康酸、巴豆酸、丙酸。該等可單獨使用或任意組合兩種以上使用。前i述（a )黏合劑聚合物就提高鹼顯像性及剝離特性 -13- 201216002 之觀點而言，較好含有源自（甲基）丙烯酸烷酯之構成單位之至少一種》至於（甲基）丙烯酸烷酯列舉爲以下述通式（IV)表示之化合物。下述通式（IV)中，R9表示氫原子或甲基’ 且R1()表示碳原子數1~12之烷基。【化2】 R9 Ο I II in H2C =C一C—Ο—R10 (|V) 上述通式（IV)中之以R1()表示之碳原子數1〜12之烷基列舉爲甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基及該等之構造異構體。就更提高剝離特性之觀點而言，上述烷基較好爲碳原子數1~4者。以上述通式（IV )表示之化合物之具體例列舉爲例如 (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）丙烯酸己酯、（甲基）丙烯酸庚酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸十一烷酯、 (甲基）丙烯酸十二烷酯。該等可單獨使用或任意的組合兩種以上使用。又前述黏合劑聚合物就使解像度及密著性良好之觀點而言’較好進一步含有源自苯乙烯或其衍生物之構成單位之至少一種。 -14- 201216002 構成前述黏合劑聚合物之各構成單位之含有率並無特別限制。例如，源自（甲基）丙烯酸之構成單位之含有率以使黏合劑聚合物之酸價成爲10 0mgKOH/g〜2 5 0mgKOH/g 之含有率較佳，更好成爲120mgKOH/g〜240mgKOH/g之含有率，又更好爲140mgKOH/g~23 0mgKOH/g之含有率，最好爲150mg KOH/g〜230mgKOH/g之含有率。藉由使黏合劑聚合物之酸價成爲10 0mgKOH/g以上可抑制顯像時間變長。又，藉由使酸價爲250mgKOH/g以下，可提高感光性樹脂組成物之硬化物之耐顯像液性（密著性）。又，進行溶劑顯像時，亦較好少量調製（甲基）丙烯酸等具有羧基之聚合性單體（monomer)。又，（A)黏合劑聚合物中之源自（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物之構成單位之含有率以黏合劑聚合物分子之總質量爲準，較好爲5質量％〜6 5質量％，更好爲10質量％~5 5質量％，又更好爲20質量％〜50質量％〇該含有率在5質量％以上時可進一步提高解像度。又藉由使該含有率在65質量％以下，可抑制剝離片變大，且可抑制剝離時間變長。又前述黏合劑聚合物含有源自（甲基）丙烯酸烷酯之構成單位時，其含有率以黏合劑聚合物分子之全部質量作爲基準，較好爲1質量％〜5〇質量％，更好爲2質量％~30質量％，又更好爲3質量％〜20質量％。藉由使其含量爲1質量％以上，可抑制剝離片變大， -15- 201216002 且可抑制剝離時間變長。又藉由使其含量爲50質量％以下，可進一步提高解像度及密著性。再者前述黏合劑聚合物爲分子內具有源自苯乙烯或其衍生物之構成單位時，其含有率以黏合劑聚合物分子之總質量爲準，較好爲5質量％〜65質量％，更好爲10質量％~6〇質量％，又更好爲15質量％~55質量％，最好爲20質量％~50 質量％。該含有率在5質量。/。以上時可進一步提高密著性。又藉由使該含有率爲65質量％以下，可抑制剝離片變大’且可抑制剝離時間變長。前述黏合劑聚合物之重量平均分子量（Mw)較好爲 10000〜100000 ，更好爲20000〜80000 ，又更好爲25000〜 60000 〇[In the formula (I), R1, R2 and R3 each independently represent an alkyl group or an aryl group of a carbon number; in the formula (II), R4, R5 and R6 each independently represent an alkyl group having 1 to 20 carbon atoms or Aryl]. The above hexaarylbiimidazole derivative is preferably a 2,4,5-triarylimidazole dimer. According to this, the sensitivity and the resolution can be further improved. According to a second aspect of the invention, there is provided a photosensitive element comprising a support and a photosensitive resin layer of a coating film of the photosensitive resin composition formed on the support. The third aspect of the present invention is a method for producing a photoresist pattern having the steps of forming a photosensitive resin layer of a photosensitive resin layer of a coating film of the photosensitive resin composition described above on a substrate, At least a portion of the photosensitive resin layer is irradiated with active light to cause photohardening exposure -10-201216002, and the uncured portion of the photosensitive resin layer is removed from the substrate to form a photosensitive resin layer The imaging step of the photoresist pattern formed by the hardened material. According to a fourth aspect of the invention, there is provided a method of manufacturing a lead frame comprising the step of forming a conductor pattern by subjecting a substrate having a resist pattern obtained by the above-described method for manufacturing a photoresist pattern to a plating process. According to a fifth aspect of the invention, there is provided a method of producing a printed circuit board comprising the step of forming a conductor pattern by subjecting a substrate having a photoresist pattern obtained by the above-described photoresist pattern manufacturing method to a plating pattern. According to this manufacturing method, a high-density printed circuit board such as a high-density package substrate can be manufactured with high precision and particularly high efficiency. A sixth aspect of the invention is a printed circuit board manufactured by the above-described method of manufacturing a printed circuit board. [Effect of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in any of sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing, and a photosensitive element using the same, A method of manufacturing a photoresist pattern, a method of manufacturing a lead frame, and a method of manufacturing a printed circuit board. [Embodiment] The term "step" in this specification is not only an independent step, but also cannot be clearly distinguished from other steps, as long as the desired effect of the step can be achieved. -11 - 201216002 The number range indicated by "~" in this description means the range of the number 値 before and after the "~" is the minimum 値 and the maximum 値 respectively. When the amount of each component in the composition in the present specification is further mentioned, when the component is present in plural in the composition, unless otherwise specified, it means the total amount of the plural substances present in the composition. <Photosensitive Resin Composition> The photosensitive resin composition of the present invention contains (A) a constituent unit derived from (meth)acrylic acid and derived from benzyl (meth)acrylate or benzyl (meth)acrylate derivative. At least one of a binder polymer of the constituent unit, and (B) at least one of a polymerizable compound having at least one ethylenically unsaturated bond, and (C) a fluorenylphosphine oxide-containing compound and a hexaarylbiimidazole derivative Photopolymerization initiator. According to this configuration, any of excellent characteristics such as sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing is exhibited. (A) Adhesive polymer The binder polymer in the present invention has a constituent unit derived from (meth)acrylic acid, and a composition derived from benzyl (meth)acrylate or benzyl (meth)acrylate derivative. There is no special restriction on the unit. Further, in addition to the above-mentioned constituent unit derived from (meth)acrylic acid, and a constituent unit derived from benzyl (meth)acrylate or benzyl (meth)acrylate derivative, the binder polymer may further have a source as needed. It consists of a constituent unit of alkyl (meth)acrylate or a constituent unit derived from styrene or a styrene derivative, -12-201216002. The benzyl (meth) acrylate derivative may, for example, be a compound substituted with an alkoxy group having 1 to 6 carbon atoms, a halogen or an alkyl group having 1 to 6 carbon atoms on an aromatic ring of a benzyl group. Specifically, it is exemplified by ethoxybenzyl (meth)acrylate, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, methylbenzyl (meth)acrylate, (methyl) Ethyl benzyl acrylate or the like, and other polymerizable monomers other than (meth)acrylic acid' and (benzyl) (meth) acrylate or benzyl (meth) acrylate derivative are exemplified by, for example, styrene; vinyl toluene; a polymerizable styrene derivative substituted in the α-position or an aromatic ring such as α-methylstyrene; a acrylamide such as diacetone acrylamide; acrylonitrile; vinyl alcohol such as vinyl-n-butyl ether Esters; alkyl (meth)acrylate, cycloalkyl (meth)acrylate, decyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, (a) Adamantyl acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate , 2,2,2-trifluoroethyl (meth)acrylate, (methyl 2,2,3,3_tetrafluoropropyl acrylate, β-furyl (meth)acrylate, β-styrene (meth)acrylate, maleic acid, maleic anhydride, monomethyl maleate, A maleic acid monoester such as monoethyl maleate or monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propionic acid. These may be used singly or in combination of two or more. The above-mentioned (a) binder polymer preferably contains at least one of constituent units derived from alkyl (meth)acrylate from the viewpoint of improving alkali developability and peeling property-13-201216002. The alkyl acrylate is exemplified by the compound represented by the following formula (IV). In the following general formula (IV), R9 represents a hydrogen atom or a methyl group, and R1() represents an alkyl group having 1 to 12 carbon atoms. [Chem. 2] R9 Ο I II in H2C = C - C - Ο - R10 (|V) The alkyl group having 1 to 12 carbon atoms represented by R1 () in the above formula (IV) is exemplified as a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl and such structural isomers. From the viewpoint of further improving the peeling property, the above alkyl group is preferably one having a carbon number of from 1 to 4. Specific examples of the compound represented by the above formula (IV) are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (A) Ethyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, Ethyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate. These may be used singly or in combination of two or more. Further, the binder polymer preferably contains at least one of constituent units derived from styrene or a derivative thereof from the viewpoint of satisfactory resolution and adhesion. -14- 201216002 The content ratio of each constituent unit constituting the above-mentioned binder polymer is not particularly limited. For example, the content of the constituent unit derived from (meth)acrylic acid is preferably such that the acid value of the binder polymer is from 10 mgKOH/g to 250 mgKOH/g, more preferably from 120 mgKOH/g to 240 mgKOH/ The content of g is more preferably a content of 140 mgKOH/g to 23 mgKOH/g, and is preferably a content of 150 mg KOH/g to 230 mgKOH/g. By setting the acid value of the binder polymer to 100 mgKOH/g or more, the development time can be suppressed from becoming long. Further, by setting the acid value to 250 mgKOH/g or less, the development resistance of the cured product of the photosensitive resin composition can be improved (adhesiveness). Further, in the case of performing solvent development, a polymerizable monomer having a carboxyl group such as (meth)acrylic acid is preferably prepared in a small amount. Further, the content of the constituent unit derived from the benzyl (meth) acrylate or the benzyl (meth) acrylate derivative in the (A) binder polymer is preferably based on the total mass of the binder polymer molecule. It is 5% by mass to 6.55% by mass, more preferably 10% by mass to 5% by mass, and still more preferably 20% by mass to 50% by mass. When the content ratio is 5% by mass or more, the resolution can be further improved. When the content is 65 mass% or less, the release sheet can be prevented from becoming large, and the peeling time can be suppressed from becoming long. Further, when the binder polymer contains a constituent unit derived from an alkyl (meth)acrylate, the content thereof is preferably from 1% by mass to 5% by mass based on the total mass of the binder polymer molecule. It is 2% by mass to 30% by mass, and more preferably 3% by mass to 20% by mass. When the content is 1% by mass or more, the release sheet can be prevented from becoming large, and -15 to 201216002 can be suppressed from becoming longer. Further, by setting the content to 50% by mass or less, the resolution and the adhesion can be further improved. Further, when the binder polymer has a constituent unit derived from styrene or a derivative thereof in the molecule, the content thereof is preferably 5% by mass to 65% by mass based on the total mass of the binder polymer molecule. More preferably, it is 10% by mass to 6% by mass, more preferably 15% by mass to 55% by mass, and most preferably 20% by mass to 50% by mass. The content rate is 5 mass. /. The above can further improve the adhesion. When the content is 65 mass% or less, the release sheet can be prevented from becoming large, and the peeling time can be suppressed from becoming long. The weight average molecular weight (Mw) of the binder polymer is preferably from 10,000 to 100,000, more preferably from 20,000 to 80,000, still more preferably from 25,000 to 60000 〇.

Mw爲1 0000以上時，會有感光性樹脂組成物之硬化物之耐顯像液性（密著性）優異之傾向，若爲looooo以下時，會有顯像時間優異之傾向。又，黏合劑聚合物之重量平均分子量係以凝膠滲透層析儀（GPC )測定（由使用標準聚苯乙烯之校正線換算）〇前述黏合劑聚合物之分散度（Mw/Mn )並無特別限制，但較好爲1 ·〇〜3.0，更好爲1 .5〜2.5。分散度若爲3.0以下則可更提高密著性及解像度》且，前述黏合劑聚合物亦可視需要，於其分子內具有對於具有3 50nm~440nm範圍之波長之光具有感光性之特性 -16- 201216002 基。本發明中之黏合劑聚合物較好爲在黏合劑聚合物中含有源自（甲基）丙烯酸之構成單位，及源自（甲基）丙烯酸苄酯或其衍生物之構成單位5質量％〜65質量％，及源自 (甲基）丙烯酸烷酯之構成單位1質量％〜50質量％，與源自苯乙烯及其衍生物之構成單位5質量％〜65質量％，且酸價爲100mgKOH/g〜250mgKOH/g，重量平均分子量爲 10000-100000 〇更好爲含有源自（甲基）丙烯酸之構成單位，及源自 (甲基）丙烯酸苄酯之構成單位1〇質量5質量％，及源自具有碳數1〜4之烷基之（甲基）丙烯酸烷酯之構成單位2 質量％〜3 0質量％，與源自苯乙烯及其衍生物之構成單位10 質量％〜60質量％，且酸價爲120mgKOH/g〜23 0mgKOH/g，重量平均分子量爲20000〜80000。進而更好爲含有源自（甲基）丙烯酸之構成單位，及源自（甲基）丙烯酸苄酯之構成單位20質量％〜50質量％，及源自具有碳數1〜4之烷基之（甲基）丙烯酸烷酯之構成單位3質量％〜20質量％，與源自苯乙烯及其衍生物之構成單位15質量°/。~55質量％，且酸價爲140mgKOH/g〜 230mgKOH/g，重量平均分子量爲25 000~60000。本發明中之黏合劑聚合物可以通常方法製造。具體而言，可以例如使（甲基）丙烯酸、與（甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物、及視需要使用之其他聚合性單體經自由基聚合而製造8 -17- 201216002 本發明之感光像性樹脂組成物中之黏合劑聚合物可單獨使用一種黏合劑聚合物，亦可任意組合兩種以上之黏合劑聚合物。組合兩種以上使用時之黏合劑聚合物列舉爲由不同之共聚合成分所組成之兩種類以上（包含以不同之單體單位作爲共聚合成分）之黏合劑聚合物、不同重量平均分子量之兩種類以上之黏合劑聚合物、不同分散度之兩種類以上之黏合劑聚合物。又，亦可使用具有特開平11-327137號公報中所述之多態分子量分布之聚合物。本發明之感光性樹脂組成物中之（A)黏合劑聚合物之含有率較好爲感光性樹脂組成物中之20質量％〜90質量％，更好爲30質量％〜80質量％，又更好爲40質量％~65質量％〇黏合劑聚合物之含有率爲20質量％以上時，會有薄膜之成形性優異之傾向，又爲9〇質量％以下時，會有感度及解像度優異之傾向》又前述感光性樹脂組成物中之（A)黏合劑聚合物之含有率較好爲（A)黏合劑聚合物成分及（B)聚合性化合物成分之總量1〇〇質量份中之質量份〜7〇質量份’較好爲35質量份~65質量份，最好爲40質量份〜60質量份。藉由使該含有率爲30質量份以上’可更提高薄膜之成形性。且，爲70質量份以下時’可更提高感度及解像度。 (B ) 聚合性化合物 -18- 201216002 本發明之敏輻射線性樹脂組成物含有具有至少一烯性不飽和鍵之聚合性化合物之至少一種》前述聚合性化合物之含有率較好爲感光性樹脂組中之3質量％~7〇質量％，更好爲1〇質量％〜60質量。/。，好爲25質量％〜50質量％。聚合性化合物之含有率爲3質量％以上時，會有及解像度優異之傾向。又爲70質量％以下時，會有薄成形性優異之傾向。前述聚合性化合物只要具有至少一個乙烯性不飽，且爲可聚合之化合物則無特別限制。其中，就提高像性、解像度及硬化後之剝離特性之觀點而言，較好至少一種雙酚A型（甲基）丙烯酸酯化合物，更好含少一種以下述通式（ΙΠ)表示之化合物。【化3】When the Mw is at least 10,000, the cured product of the photosensitive resin composition tends to be excellent in image liquid resistance (adhesiveness), and when it is below the looooo, the development time tends to be excellent. Further, the weight average molecular weight of the binder polymer is measured by a gel permeation chromatography (GPC) (converted from a calibration line using standard polystyrene), and the dispersion of the above binder polymer (Mw/Mn) is not It is particularly limited, but preferably 1 · 〇 ~ 3.0, more preferably 1. 5 ~ 2.5. When the degree of dispersion is 3.0 or less, the adhesion and the resolution can be further improved. Further, the binder polymer may have a property of being photosensitive in a molecule having a wavelength in the range of 3 50 nm to 440 nm as needed. - 201216002 base. The binder polymer in the present invention preferably contains a constituent unit derived from (meth)acrylic acid in the binder polymer, and a constituent unit derived from benzyl (meth)acrylate or a derivative thereof of 5% by mass. 65% by mass, and a constituent unit derived from an alkyl (meth)acrylate: 1% by mass to 50% by mass, and a constituent unit derived from styrene and a derivative thereof, 5% by mass to 65% by mass, and an acid value of 100 mgKOH /g~250 mgKOH/g, the weight average molecular weight is 10,000 to 100,000 〇, more preferably, it comprises a constituent unit derived from (meth)acrylic acid, and a constituent unit derived from benzyl (meth)acrylate, 1 〇 mass 5 mass%, And a constituent unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, 2% by mass to 30% by mass, and a constituent unit derived from styrene and a derivative thereof, 10% by mass to 60% by mass %, and the acid value is 120 mgKOH/g to 23 mg/KOH, and the weight average molecular weight is 20,000 to 80,000. Further, it is more preferably contained in a constituent unit derived from (meth)acrylic acid, and a constituent unit derived from benzyl (meth)acrylate: 20% by mass to 50% by mass, and derived from an alkyl group having a carbon number of 1 to 4. The constituent unit of the alkyl (meth)acrylate is 3% by mass to 20% by mass, and the constituent unit derived from styrene and its derivative is 15% by mass. ~55 mass%, and the acid value is 140 mgKOH/g to 230 mgKOH/g, and the weight average molecular weight is 25 000 to 60,000. The binder polymer in the present invention can be produced by a usual method. Specifically, for example, (meth)acrylic acid, benzyl (meth) acrylate or benzyl (meth) acrylate derivative, and other polymerizable monomers used as needed may be subjected to radical polymerization to produce 8- 17-201216002 The binder polymer in the photosensitive resin composition of the present invention may be a binder polymer alone or in combination of two or more binder polymers. The binder polymer used in combination of two or more kinds is exemplified by a binder polymer composed of two or more kinds of different copolymerized components (including copolymer units having different monomer units), and two different weight average molecular weights. More than one type of binder polymer, two or more types of binder polymers with different degrees of dispersion. Further, a polymer having a polymorphic molecular weight distribution as described in JP-A-11-327137 can also be used. The content of the (A) binder polymer in the photosensitive resin composition of the present invention is preferably from 20% by mass to 90% by mass, more preferably from 30% by mass to 80% by mass, based on the amount of the photosensitive resin composition. More preferably, it is 40% by mass to 65% by mass. When the content of the binder polymer is 20% by mass or more, the moldability of the film tends to be excellent, and when it is 9% by mass or less, the sensitivity and the resolution are excellent. The content of the (A) binder polymer in the photosensitive resin composition is preferably (A) the binder polymer component and (B) the total amount of the polymerizable compound component in 1 part by mass. The parts by mass to 7% by mass part is preferably from 35 parts by mass to 65 parts by mass, more preferably from 40 parts by mass to 60 parts by mass. By setting the content to 30 parts by mass or more, the formability of the film can be further improved. Further, when it is 70 parts by mass or less, the sensitivity and the resolution can be further improved. (B) Polymerizable Compound -18-201216002 The radiation sensitive linear resin composition of the present invention contains at least one of polymerizable compounds having at least one ethylenically unsaturated bond. The content of the polymerizable compound is preferably a photosensitive resin group. 3% by mass to 7〇% by mass, more preferably 1% by mass to 60% by mass. /. , good for 25 mass% to 50 mass%. When the content of the polymerizable compound is 3% by mass or more, the resolution tends to be excellent. When the amount is 70% by mass or less, the formability is excellent. The polymerizable compound is not particularly limited as long as it has at least one ethylenic unsaturated and is a polymerizable compound. Among them, at least one bisphenol A type (meth) acrylate compound, more preferably one compound represented by the following formula (ΙΠ), is preferable from the viewpoint of improving the imageability, the resolution, and the peeling property after hardening. . [化3]

上述通式（III)中，R7及R8各獨立表示氫原子基，X各獨立表示碳數2〜6之伸烷基。m及η表示 m + n = 2〜10之整數。X爲兩種以上之伸烷基時，-(X-之構造單位可無規地存在’亦可嵌段地存在。上述通式（ΠΙ)中，R7及R8較好均爲甲基。又，一分子中複數存在之X各獨E爲碳數2〜6之基（例如’伸乙基、伸丙基、伸異丙基、伸丁基、伸個乙成物又更感度膜之和鍵鹼顯含有有至 (III) 或甲滿足〇)- 伸烷異丁 -19- 201216002 基、伸戊基及伸己基），但就使鍍敷貴金屬之耐性及光阻圖型之解像度成良好之觀點而言，X較好爲伸乙基、伸丙基或伸異丙基，更好爲伸乙基。 m及η在2以上時，分子內鄰接之兩個以上之X可分別相同亦可不同。且，X爲兩種以上之伸烷基時，·（ Χ-0) -之構造單位可無規地存在，亦可嵌段地存在。且，上述通式（III)中，m及η爲滿足m + n = 2〜10之整數，藉由使m + n = 3〜6，由於抑制了由含有以上述通式（III )表示之化合物之感光性樹脂組成物形成之光阻對於顯像液之膨潤，故解像性提高而較佳。又使m + n = 8〜10由於進而提高光阻之剝離性故而較佳。 (m + n)爲2以上時，有提高（A)黏合劑聚合物成分與（B)聚合性化合物成分之相溶性之傾向。又（m + n ) 爲10以下時，可抑制由含有以上述通式（ΙΠ)表示之化合物之感光性樹脂組成物形成之光阻對於顯像液之膨潤，而有更提高密著性之傾向。· 前述感光性樹脂組成物組合以上述通式（111 )表示之化合物中之m + n = 3~6之化合物、及m + n = 8~10之化合物之兩種類而使用時，可均衡性良好地提高解像度及剝離特性故而更佳。前述感光性樹脂組成物含有m + n = 3~6之化合物（Ilia )與m + n = 8~10之化合物（Illb)作爲以上述通式（ΙΠ)表示之化合物時，其含有比（Illa/IIIb )較好爲1/10〜1/1 ’ 更好爲1/7-1/3。 -20- 201216002 且前述雙酚A系（甲基）丙烯酸酯化合物具體而言列舉爲2,2-雙（4·((甲基）丙烯醯氧基多乙氧基）苯基）丙烷' 2,2-雙（4-((甲基）丙烯醯氧基多丙氧基）苯基 )丙烷、2,2·雙（4-((甲基）丙烯醯氧基多丁氧基）苯基）丙烷、2，2·雙（4·((甲基）丙烯醯氧基多乙氧基多丙氧基）苯基）丙烷等。其中就進一步提高解像性及剝離特性之觀點而言，以2,2-雙（4·((甲基）丙烯醯氧基聚乙氧基）苯基）丙烷較佳。該等中，2，2-雙（4-((甲基）丙烯醯氧基二丙氧基 )苯基）丙烷可以ΒΡΕ-200 (新中村化學工業（股）製造，製品名）商業獲得，2,2-雙（4-(甲基丙烯醯氧基五乙氧基）苯基）丙烷可以ΒΡΕ-5 00 (新中村化學工業（股）製造，製品名）或FA-321MC曰立化成工業（股）製造，製品名）商業獲得。該等雙酚Α系（甲基）丙烯酸酯化合物可單獨使用一種或任意組合兩種以上使用。前述感光性樹脂組成物中，前述雙酚A系（甲基）丙烯酸酯化合物（較好爲以通式（ΠΙ )表示之化合物）之含有率於（B )聚合性化合物成分之總質量中較好爲30質量％~100質量％，更好爲50質量％〜90質量％。藉由使前述含有率在該範圍內可提高光阻之解像度。前述感光性樹脂組成物中，較好更含有分子內具有（聚）氧伸乙基鏈及（聚）氧伸丙基鏈之至少一者之聚烷二醇二（甲基）丙烯酸酯之至少一種，更好進一步含有分子 -21 - 201216002 內具有（聚）氧伸乙基鏈及（聚）氧伸丙基鏈二者之聚烷二醇二（甲基）丙烯酸酯作爲（B)聚合性化合物成分。藉此，提高感光性樹脂組成物之硬化物（硬化膜）之可撓性。前述聚烷二醇二（甲基）丙嫌酸酯之分子內，（聚）氧伸乙基鏈及（聚）氧伸丙基鏈可分別連續嵌段地存在，亦可無規地存在。又，（聚）氧伸異丙基鏈中，伸異丙基之二級碳可鍵結於氧原子，亦可係一級碳鍵結於氧原子。前述聚烷二醇二（甲基）丙烯酸酯最好爲以下述通式 (V)、通式（VI )或通式（VII )表示之化合物。該等係單獨或組合兩種以上使用。【化4】In the above formula (III), R7 and R8 each independently represent a hydrogen atom group, and X each independently represents an alkylene group having 2 to 6 carbon atoms. m and η represent an integer of m + n = 2 to 10. When X is two or more kinds of alkylene groups, -(the structural unit of X- may exist randomly) may also exist in blocks. In the above formula (ΠΙ), R7 and R8 are preferably all methyl groups. X in the presence of a plurality of molecules in a molecule is a group having a carbon number of 2 to 6 (for example, 'extended ethyl group, propyl group, isopropyl group, butyl group, butyl group, and a more sensitive film. The bond base contains either (III) or a satisfying 〇)-alkylene isobuty-19- 201216002 base, pentyl group and hexyl group, but the resolution of the plated precious metal and the resolution of the photoresist pattern are good. From the viewpoint of viewpoint, X is preferably an ethyl group, a propyl group or an extended isopropyl group, more preferably an ethyl group. When m and η are 2 or more, two or more X adjacent to each other in the molecule may be the same or different. Further, when X is two or more kinds of alkylene groups, the structural unit of ((-0)- may be present randomly or in blocks. Further, in the above formula (III), m and η are integers satisfying m + n = 2 to 10, and by m + n = 3 to 6, since the inclusion of the formula (III) is suppressed The photoresist formed by the photosensitive resin composition of the compound is swollen to the developing liquid, so that the resolution is improved. Further, it is preferable to make m + n = 8 to 10 to improve the peeling property of the photoresist. When (m + n) is 2 or more, the compatibility of the (A) binder polymer component and the (B) polymerizable compound component tends to be improved. When (m + n ) is 10 or less, it is possible to suppress swelling of the developing solution by the photoresist formed of the photosensitive resin composition containing the compound represented by the above formula (ΙΠ), and to improve adhesion. tendency. - The balance of the photosensitive resin composition can be used when the combination of the compound of the formula (111) and the compound of m + n = 3 to 6 and the compound of m + n = 8 to 10 are used. It is better to improve the resolution and the peeling property satisfactorily. The photosensitive resin composition contains a compound (Ilia) of m + n = 3 to 6 and a compound (Illb) of m + n = 8 to 10 as a compound represented by the above formula (ΙΠ), and its content ratio (Illa) /IIIb) is preferably 1/10 to 1/1' and more preferably 1/7-1/3. -20- 201216002 and the aforementioned bisphenol A-based (meth) acrylate compound is specifically exemplified as 2,2-bis(4.((meth)acryloxypolyethoxy)phenyl)propane ' 2 , 2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, 2,2·bis(4-((meth)propenyloxy)oxy)phenyl ) Propane, 2,2.bis(4.((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, etc. Among them, 2,2-bis(4·((meth)acryloxycarbonyloxy)phenyl)propane is preferred from the viewpoint of further improving the resolution and the peeling property. Among these, 2,2-bis(4-((meth)propenyloxydipropoxy)phenyl)propane can be commercially obtained from ΒΡΕ-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane can be ΒΡΕ-5 00 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name) or FA-321MC 曰立化成工业(share) manufacturing, product name) commercial acquisition. These bisphenol oxime (meth) acrylate compounds may be used singly or in combination of two or more. In the photosensitive resin composition, the content of the bisphenol A-based (meth) acrylate compound (preferably, the compound represented by the formula (ΠΙ)) is higher than the total mass of the (B) polymerizable compound component. It is preferably from 30% by mass to 100% by mass, more preferably from 50% by mass to 90% by mass. The resolution of the photoresist can be improved by making the aforementioned content ratio within this range. Preferably, the photosensitive resin composition further contains at least one of a polyalkylene glycol di(meth)acrylate having at least one of a (poly)oxyethylidene chain and a (poly)oxypropoxypropyl chain in the molecule. a polyalkylene glycol di(meth)acrylate having a (poly)oxyethylidene chain and a (poly)oxypropanyl chain in the molecule 21 - 201216002 as (B) polymerizable Compound ingredient. Thereby, the flexibility of the cured product (cured film) of the photosensitive resin composition is improved. In the molecule of the polyalkylene glycol di(methyl)propionate, the (poly)oxyethylidene chain and the (poly)oxypropanyl propyl chain may be present in a continuous block, or may be present in a random manner. Further, in the (poly)oxy-extension isopropyl chain, the secondary carbon of the isopropyl group may be bonded to the oxygen atom, or may be bonded to the oxygen atom by the primary carbon. The polyalkylene glycol di(meth)acrylate is preferably a compound represented by the following formula (V), formula (VI) or formula (VII). These systems are used singly or in combination of two or more. 【化4】

Μ 0 H2C=r 一。~(p〇HE〇yp〇y 了 ⑶2 ⑽Μ 0 H2C=r One. ~(p〇HE〇yp〇y (3)2 (10)

〇 II〇 II

H2C=C—C—0 R 上述通式（V)、通式（VI)及通式（VII)中，R分別獨立表示氫原子或甲基’且EO表示氧伸乙基，p〇表示氧伸丙基。mi、m2、m3及ι«4表示由氧伸乙基所組成之構成單位之重複數，iM、n2、ns及〜表示由氧伸丙基所組成之構成單位之重複數’氧伸乙基之重複總數„11+„12、⑴及 -22- 201216002 m4(平均値）分別獨立表示1〜3 0之整數，氧伸丙基之重複總數ru、η2 + η3及η4 (平均値）分別獨立表示1〜30之數。以上述通式（V )、通式（VI )及通式（VII )之任一者表示之化合物中，氧伸乙基之重複總數1^+012、m3及m4 (平均値）爲1〜30之數，但較好爲1〜10之數，更好爲4〜9 之數，最好爲5〜8之數。藉由使該重複數之總數爲30以下，可更提高解像度、密著性及光阻形狀。又，氧伸丙基之重複總數ηι、Π2+Ι13及平均値）爲 1〜30之數，較好爲5~20之數，更好爲8〜16之數，最好爲 10〜14之數。藉由使該重複數之總數爲30以下，可提高解像度，抑制淤渣之發生。以上述通式（V)表示之化合物具體而言列舉爲R=甲基，mi + m2 = 6 (平均値）、iM = 12 (平均値）之乙烯化合物（日立化成工業（股）製造，商品名FA-023M)等。且以上述通式（VI)表示之化合物具體而言列舉爲R=甲基，m3 = 6 (平均値）、n2 + n3 = 12 (平均値）之乙烯化合物（日立化成工業（股）製造’商品名FA_024M)等。進而以上述通式（VII)表示之化合物具體而言列舉爲11"1氫原子，m4=l (平均値）、n4 = 9 (平均値）之乙烯化合物（新中村化學工業（股）製造’樣品名NK Ester HEMA_9P )等。該等可單獨使用一種’或組合兩種以上使用。本發明中之前述聚烷二醇二（甲基）丙烯酸酯之含有率在（B)聚合性化合物成分之總質量中較好爲5質量 5 0質量％，更好爲5質量％〜1 5質量％。 -23- 201216002 藉由使前述含有率爲5質量％以上，可提高可撓性。又藉由使前述含有率爲50質量％以下，可提高解像性。本發明中之感光性樹脂組成物可進一步含有前述雙酚 Α系（甲基）丙烯酸酯化合物及聚烷二醇二（甲基）丙烯酸酯以外之其他聚合性化合物作爲（B )聚合性化合物。至於其他聚合性化合物列舉爲壬基苯氧基聚伸乙基氧基丙烯酸酯、苯二甲酸系化合物、（甲基）丙烯酸多元醇酯、（甲基）丙烯酸烷酯等。其中，就均衡性良好地提高解像度、密著性、光阻形狀及硬化後之剝離特性之觀點而言，較好爲由壬基苯氧基聚伸乙基氧基丙烯酸酯及苯二甲酸系化合物選出之至少一種。前述壬基苯氧基聚伸乙基氧基丙烯酸酯列舉爲例如壬基苯氧基三伸乙基氧基丙烯酸酯、壬基苯氧基四伸乙基氧基丙烯酸酯、壬基苯氧基五伸乙基氧基丙烯酸酯、壬基苯氧基六伸乙基_基丙烯酸酯、壬基苯氧基七伸乙基氧基丙烯酸酯、壬基苯氧基八伸乙基氧基丙烯酸酯、壬基苯氧基九伸乙基氧基丙烯酸酯、壬基苯氧基十伸乙基氧基丙烯酸酯、壬基苯氧基十一伸乙基氧基丙烯酸酯。該等可單獨使用一種，或任意組合兩種以上使用。又苯二甲酸系化合物列舉爲例如γ-氯-β-羥基丙基-β’-(甲基）丙烯醯氧基乙基-鄰-苯二甲酸酯、β-羥基乙基-Ρ’-(甲基）丙烯醯氧基乙基-鄰-苯二甲酸酯、及β-羥基丙基-β’-(甲基）丙烯醯氧基乙基-鄰-苯二甲酸酯。其中，較好爲γ-氯- β-羥基丙基-β’-(甲基）丙烯醯氧基乙基-鄰- -24- 201216002 苯二甲酸酯。γ-氯-β_羥基丙基- β’_ (甲基）丙烯醯氧基乙基-鄰-苯二甲酸酯爲以FA-MECH (日立化成工業（股）製造’製品名）而商業獲得。該等可單獨使用一種或組合兩種以上使用。再者（甲基）丙烯酸多元醇酯列舉爲例如三羥甲基丙烷聚乙氧基三（甲基）丙烯酸酯、三羥甲基丙烷聚丙氧基三（甲基）丙烯酸酯、三羥甲基丙烷聚丁氧基三（甲基）丙烯酸酯、三羥甲基丙烷聚乙氧基聚丙氧基三（甲基）丙烯酸酯、三羥甲基乙烷聚乙氧基三（甲基）丙烯酸酯、三羥甲基乙烷聚丙氧基三（甲基）丙烯酸酯、三羥甲基乙烷聚丁氧基三（甲基）丙烯酸酯、三羥甲基乙烷聚乙氧基聚丙氧基三（甲基）丙烯酸酯、季戊四醇聚乙氧基三（甲基 )丙烯酸酯、季戊四醇聚丙氧基三（甲基）丙烯酸酯、季戊四醇聚丁氧基三（甲基）丙烯酸酯、季戊四醇聚乙氧基聚丙氧基三（甲基）丙烯酸酯、甘油聚乙氧基三（甲基）丙烯酸酯、甘油聚丙氧基三（甲基）丙烯酸酯、甘油聚丁氧基三（甲基）丙烯酸酯、甘油聚乙氧基聚丙氧基三（甲基）丙烯酸酯。該等可單獨使用一種或組合兩種以上使用。本發明之感光性樹脂組成物含有其他聚合性化合物作爲（B )聚合性化合物時，其含有率就均衡性良好地提高解像度、密著性、光阻形狀及硬化後之剝離特性之觀點而言，其含有率於（B)聚合性化合物成分之總質量中較好爲1質量％〜30質量％，更好爲3質量％~25質量％，又更好爲 -25- 201216002 5質量％〜20質量％。 (C ) 光聚合起始劑前述感光性樹脂組成物含有含（C-1)醯基氧化膦系化合物之至少一種，及（C-2)六芳基聯咪唑衍生物之至少一種之光聚合起始劑。藉由含有至少兩種化合物作爲光聚合起始劑，可提高感度、解像度’進而亦可使光阻形狀變好。又由於光阻圖型之線寬値對於曝光量之變化小，故製程寬裕度變廣，而爲良好。前述感光性樹脂組成物中’前述光聚合起始劑之含有率較好爲感光性樹脂組成物之總質量中之質量％~20質量％，更好爲1質量1 〇質量％，又更好爲3質量％~7質量 %。光聚合起始劑之含有率爲0.1質量％以上時’會有獲得足夠之感度、解像度之傾向。又爲20質量％以下時’會有薄膜之成形性更良好之傾向° 前述（C-1 )醯基氧化膦系化合物較好爲以下述通式 (I)或通式（II)表示之化合物。【化5】H2C=C—C—0 R In the above formula (V), formula (VI) and formula (VII), R independently represents a hydrogen atom or a methyl group, and EO represents an oxygen-extended ethyl group, and p〇 represents an oxygen group. Prolonged propyl. Mi, m2, m3, and ι «4 represent the number of repetitions of the constituent units composed of the oxygen-extended ethyl group, and iM, n2, ns, and 〜 represent the repeating number of the constituent units composed of the oxygen-extended propyl group. The total number of repetitions „11+„12, (1) and -22- 201216002 m4 (average 値) are independent of the integers from 1 to 30, respectively, and the total number of repetitions of oxy-propyl groups ru, η2 + η3 and η4 (average 値) are independent Indicates the number from 1 to 30. In the compound represented by any one of the above formula (V), formula (VI) and formula (VII), the total number of repeats of oxygen-extended ethyl groups 1^+012, m3 and m4 (average 値) is 1~ The number of 30, but preferably from 1 to 10, more preferably from 4 to 9, preferably from 5 to 8. By making the total number of the repeats 30 or less, the resolution, the adhesion, and the resist shape can be further improved. Further, the total number of repetitions of oxygen-extended propyl groups ηι, Π2+Ι13 and average 値) is from 1 to 30, preferably from 5 to 20, more preferably from 8 to 16, most preferably from 10 to 14. number. By making the total number of the repeats 30 or less, the resolution can be improved and the occurrence of sludge can be suppressed. The compound represented by the above formula (V) is specifically a vinyl compound of R = methyl group, mi + m2 = 6 (average 値), iM = 12 (average 値) (manufactured by Hitachi Chemical Co., Ltd., commodity Name FA-023M) and so on. Further, the compound represented by the above formula (VI) is specifically exemplified by a vinyl compound of R = methyl group, m3 = 6 (average 値), and n2 + n3 = 12 (average 値) (manufactured by Hitachi Chemical Co., Ltd.) Product name FA_024M) and so on. Further, the compound represented by the above formula (VII) is specifically an ethylene compound (manufactured by Shin-Nakamura Chemical Co., Ltd.) of 11 "1 hydrogen atom, m4=l (average 値), n4 = 9 (average 値) Sample name NK Ester HEMA_9P) and so on. These may be used alone or in combination of two or more. The content of the polyalkylene glycol di(meth)acrylate in the present invention is preferably 5 mass% by mass, more preferably 5% by mass to 15%, based on the total mass of the (B) polymerizable compound component. quality%. -23-201216002 The flexibility can be improved by setting the content rate to 5% by mass or more. Further, by setting the content rate to 50% by mass or less, the resolution can be improved. The photosensitive resin composition of the present invention may further contain, as the (B) polymerizable compound, a polymerizable compound other than the bisphenol fluorene (meth) acrylate compound and polyalkylene glycol di(meth) acrylate. The other polymerizable compound is exemplified by a nonylphenoxy polyethyl acrylate, a phthalic acid compound, a (meth)acrylic acid polyol ester, or an (meth)acrylic acid alkyl ester. Among them, from the viewpoint of improving the resolution, the adhesion, the shape of the photoresist, and the peeling property after hardening, it is preferred to use a mercaptophenoxy polyethyl acrylate and a phthalic acid. At least one of the compounds is selected. The above mercaptophenoxy polyethyl acrylate is exemplified by, for example, nonylphenoxytriethyloxyacrylate, mercaptophenoxytetraethyloxyacrylate, mercaptophenoxy Pentaethyloxy acrylate, nonylphenoxy hexaethyl acrylate, decyl phenoxy heptaethyl acrylate, decyl phenoxy octaethyloxy acrylate , nonylphenoxy hexaethyloxy acrylate, decyl phenoxy decyl ethyl acrylate, decyl phenoxy eleven ethyl acrylate. These may be used alone or in combination of two or more. The phthalic acid-based compound is exemplified by, for example, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-o-phthalate, β-hydroxyethyl-Ρ'- (Meth)acryloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloxyethyl-o-phthalate. Among them, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-o--24-201216002 phthalate is preferred. Γ-chloro-β-hydroxypropyl-β'_(meth)acrylomethoxyethyl-o-phthalate is commercially available as FA-MECH (product name manufactured by Hitachi Chemical Co., Ltd.) obtain. These may be used alone or in combination of two or more. Further, the (meth)acrylic polyol ester is exemplified by, for example, trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxytri(meth)acrylate, trimethylol Propane polybutoxy tri(meth) acrylate, trimethylolpropane polyethoxypolypropoxy tri(meth) acrylate, trimethylolethane polyethoxy tri(meth) acrylate , trimethylolethane polypropoxy tri(meth)acrylate, trimethylolethane polybutoxy tri(meth)acrylate, trimethylolethane polyethoxypolypropoxy three (meth) acrylate, pentaerythritol polyethoxy tri (meth) acrylate, pentaerythritol polypropoxy tri (meth) acrylate, pentaerythritol polybutoxy tri (meth) acrylate, pentaerythritol polyethoxylate Polypropoxy tri(meth)acrylate, glycerol polyethoxy tri(meth)acrylate, glycerol polypropoxy tri(meth)acrylate, glycerol polybutoxy tri(meth)acrylate, glycerin Polyethoxylated polypropoxy tri(meth)acrylateThese may be used alone or in combination of two or more. When the photosensitive resin composition of the present invention contains a polymerizable compound as the (B) polymerizable compound, the content ratio thereof is excellent in balance, adhesion, photoresist shape, and peeling property after curing. The content of the component (B) of the polymerizable compound component is preferably from 1% by mass to 30% by mass, more preferably from 3% by mass to 25% by mass, even more preferably from -25 to 201216002% by mass. 20% by mass. (C) Photopolymerization initiator The photopolymerization of the photosensitive resin composition containing at least one of (C-1) fluorenylphosphine oxide-based compound and at least one of (C-2) hexaarylbiimidazole derivative Starting agent. By containing at least two kinds of compounds as photopolymerization initiators, sensitivity and resolution can be improved, and the shape of the photoresist can be improved. Further, since the line width of the photoresist pattern is small for the change in the exposure amount, the process width is widened and is good. In the photosensitive resin composition, the content of the photopolymerization initiator is preferably from 5% by mass to 20% by mass based on the total mass of the photosensitive resin composition, more preferably 1% by mass, and more preferably It is 3 mass% to 7 mass%. When the content of the photopolymerization initiator is 0.1% by mass or more, sufficient sensitivity and resolution tend to be obtained. When the amount is 20% by mass or less, the moldability of the film tends to be better. The (C-1) fluorenylphosphine oxide compound is preferably a compound represented by the following formula (I) or formula (II). . 【化5】

〇 II 0 R4—C—P—C —R6 R1—C—P—R2 (Ν) 0 k3 (丨）通式（I)中，R1、r2&r3各獨立表示碳數1 ~20之院基或芳基。通式（11)中’ r4、r5及&6各獨立表示碳數 -26- 201216002 1〜20之烷基或芳基。通式（I)中之R1、R1或R3爲碳數1〜2 0之烷基時，該烷基可爲直鏈狀、分支狀及環狀之任一者。又該烷基之碳數更好爲5〜10。又通式（II)中之R4、R5或R6爲碳數1〜20 之烷基時，該烷基可爲直鏈狀、分支狀及環狀之任一者。又該烷基之碳數更好爲5~10。通式（I )中之R1、R2或R3爲芳基時，該芳基亦可具有取代基。該取代基可列舉爲例如碳數1〜6之烷基及碳數 1~4之烷氧基。又通式（II)中之R4、R5或R6爲芳基時，該芳基亦可具有取代基。該取代基可列舉爲例如碳數1〜6 之烷基及碳數1〜4之烷氧基。以通式（II )表示之化合物具體而言列舉爲例如雙（ 2,6-二甲氧基苯甲醯基）-2,4,4-三甲基-戊基氧化膦。以前述通式（I)或通式（II)表示之化合物可單獨使用一種或組合兩種以上使用。前述（C-1)醯基氧化膦系化合物較好爲以上述通式 (I)或通式（II)表示之化合物，更好爲以下述通式（ VIII)或通式（IX)表示之化合物。【化6】〇II 0 R4—C—P—C—R6 R1—C—P—R2 (Ν) 0 k3 (丨) In the general formula (I), R1, r2, and r3 each independently represent a yard number of 1 to 20 carbon atoms. Or aryl. In the formula (11), 'r4, r5 and & 6 each independently represent an alkyl group or an aryl group having a carbon number of -26 to 201216002 1 to 20. When R1, R1 or R3 in the formula (I) is an alkyl group having 1 to 20 carbon atoms, the alkyl group may be any of a linear chain, a branched chain and a cyclic group. Further, the alkyl group preferably has a carbon number of 5 to 10. When R4, R5 or R6 in the formula (II) is an alkyl group having 1 to 20 carbon atoms, the alkyl group may be any of a linear chain, a branched chain and a cyclic group. Further, the alkyl group preferably has a carbon number of 5 to 10. When R1, R2 or R3 in the formula (I) is an aryl group, the aryl group may have a substituent. The substituent may, for example, be an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. When R4, R5 or R6 in the formula (II) is an aryl group, the aryl group may have a substituent. The substituent may, for example, be an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The compound represented by the formula (II) is specifically exemplified by, for example, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide. The compounds represented by the above formula (I) or (II) may be used alone or in combination of two or more. The (C-1) fluorenylphosphine oxide-based compound is preferably a compound represented by the above formula (I) or formula (II), more preferably represented by the following formula (VIII) or formula (IX). Compound. 【化6】

-27- 1 及R13各獨立表示碳數 201216002 1~6之烷基或碳數1~4之烷氧基，pi、p2及p3各獨立表示〇〜5之整數。pi、p2及p3爲2以上時，複數存在之R11、R1: 及R13可分別相同亦可不同。上述碳數1〜6之烷基列舉爲例如甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基。上述碳數1〜4之烷氧基列舉爲例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第三丁氧基。 R11較好爲碳數1~4之烷基，更好爲甲基。pi較好爲 1〜4之整數，更好爲3。又，p2及p3較好爲0。-27- 1 and R13 each independently represent a carbon number 201216002 an alkyl group of 1 to 6 or an alkoxy group having a carbon number of 1 to 4, and pi, p2 and p3 each independently represent an integer of 〇~5. When pi, p2, and p3 are 2 or more, R11, R1: and R13 in the plural may be the same or different. The alkyl group having 1 to 6 carbon atoms is exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group or a hexyl group. The above alkoxy group having 1 to 4 carbon atoms is exemplified by a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a third butoxy group. R11 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. The pi is preferably an integer of 1 to 4, more preferably 3. Further, p2 and p3 are preferably 0.

【化7】 Ο Ο II Ο II【化7】 Ο Ο II Ο II

上述通式（IX)中，R14、R15及Rl6各獨立表示碳數 1〜6之烷基或碳數1〜4之烷氧基’ ql、q2及q3各獨立表示〇〜5之整數。ql、q2及q3爲2以上時’複數存在之R14、R15 及R16可分別相同亦可不同。上述碳數1〜6之烷基列舉爲例如甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基。上述碳數1〜4之烷氧基列舉爲例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第三丁氧基。 R14及R15較好各獨立爲碳數1〜4之烷基’更好爲甲基。ql及q2較好爲1〜4之整數’更好爲3。又，q3較好爲〇。 201216002 以上述通式（VIII )表示之化合物就更有效地提高感度及光阻形狀之觀點而言，較好爲2,4,6 -三甲基苯甲醯基-二苯基氧化膦。2,4,6-三甲基苯甲醯基-二苯基氧化膦爲例如可以DAROCUR-TPO (日本BASF公司製造，商品名）而商業獲得。又以上述通式（IX)表示之化合物就更有效地提高感度及光阻形狀之觀點而言，較好爲雙（2，4,6-三甲基苯甲醯基）-苯基氧化膦。雙（2,4,6-三甲基苯甲醯基）-苯基氧化膦爲例如以IRGACURE-819 (日本BASF公司製造，商品名）而商業獲得。本發明中以上述通式（VIII)或通式（IX)表示之化合物可單獨使用一種或組合兩種以上使用。前述感光性樹脂組成物中，該等（C-1 )醯基氧化膦系化合物之含有率，相對於（C)光聚合起始劑之總量，較好爲20質量％〜60質量％，更好爲30質量％〜45質量％。前述（C-2)六芳基聯咪唑衍生物就提高感度及密著性之觀點而言，較好含有2,4,5-三芳基咪.唑二聚物之至少 —種。前述2，4,5-三芳基咪唑二聚物可爲構造對稱亦可非對稱。前述2,4,5-三芳基咪唑二聚物列舉爲例如2-(鄰-氯苯基）-4,5-二苯基咪唑二聚物、2-(鄰-氯苯基）-4,5-雙-( 間-甲氧基苯基）咪唑二聚物、2-(對-甲氧基苯基）-4,5-二苯基咪唑二聚物。其中，以2-(鄰-氯苯基）-4,5-二苯基咪唑二聚物較佳。 -29- 201216002 前述感光性樹脂組成物中，前述（C-2 )六芳基聯咪唑衍生物之含有率，相對於（C)光聚合起始劑成分之總量，較好爲30質量％〜70質量％，更好爲45質量％〜65質量％〇前述感光性樹脂組成物中，（C-1 )醯基氧化膦系化合物對（C-2)六芳基聯咪唑衍生物之含有比率（C-1/C-2 )並無特別限制。就感度、解像度及密著性之觀點而言，前述含有比率（C-1/C-2)較好爲0.1〜0.9，更好爲0.3~0.9 ，又更好爲0.5〜0.8。前述感光性樹脂組成物亦可進一步含有前述醯基氧化膦系化合物及六芳基聯咪唑衍生物以外之其他光聚合起始劑。其他光聚合起始劑列舉爲例如二苯甲酮、2-苄基-2-二甲胺基-1- ( 4-嗎啉基苯基）-丁酮- l，2-甲基- l-[4-(甲硫基）苯基]-2-嗎啉基·丙酮-1等之芳香族酮類，烷基蒽醌等醌類，苯甲偶因烷基醚等苯偶因醚化合物，苯偶因、烷基苯偶因等苯偶因化合物、苄基二甲基縮酮等苄基衍生物，9-苯基吖啶、1,7- (9,9’-吖啶基）庚烷等吖啶衍生物。該等可單獨使用一種或組合兩種以上使用。前述感光性樹脂組成物中之（C )光聚合起始劑之含量相對於（A )黏合劑聚合物成分及（B )聚合性化合物成分之總量100質量份，較好爲0.1質量份〜10質量份，更好爲1質量份〜7質量份，又更好爲2質量份〜6質量份，最好爲3質量份〜5質量份。藉由使前述光聚合起始劑之含量成爲0.1質量份以上 -30- 201216002 ’而更提高感度、解像度及密著性》又，藉由成爲10質量份以下，可獲得更優異之光阻形狀。前述感光性樹脂組成物較好爲前述黏合劑聚合物之含有率爲20質量％〜90質量％，前述聚合性化合物之含有率爲 3質量％〜70質量％，前述光聚合起始劑之含有率爲0.1質量 %〜2 0質量％。更好前述黏合劑聚合物之含有率爲30質量％〜80質量％，前述聚合性化合物之含有率爲10質量％〜60質量％，前述光聚合起始劑之含有率爲1質量％〜1〇質量％。又更好前述黏合劑聚合物之含有率爲40質量5質量％，前述聚合性化合物之含有率爲25質量％~50質量％，前述光聚合起始劑之含有率爲3質量％〜7質量％。前述感光性樹脂組成物較好進而含有（D)增感色素。據此，使感光性樹脂組成物之硬化感度變得更良好。 (D )增感色素列舉爲例如二烷胺基二苯甲酮類、吡唑啉類、蒽類、香豆素類、咕噸酮類、噁唑類、苯并噁唑類、噻唑類、苯并噻唑類、***類、二苯乙烯類、三嗪類、噻吩類、萘二醯亞胺類、三芳基胺類。該等可單獨使用 —種或組合兩種以上使用。尤其，於使用390nm〜420nm之活性光線進行感光性樹脂層之曝光時，就感度及密著性之觀點而言’ （D)增感色素較好包含由吡唑咐類、蒽類、香豆素類及三芳基胺類所組成群組選出之至少一種’其中更好爲由吡唑啉類、蒽類及三芳基胺類所組成群組選出之至少一種。 -31 - 201216002 (D)增感色素之含量相對於（A)黏合劑聚合物成分及（B )聚合性化合物成分之總量1 00質量份，較好爲 0.01質量份~1〇質量份，更好爲0.05質量份〜5質量份，又更好爲0.1質量份~3質量份。藉由使前述（D)增感色素之含量爲0.01質量份以上，可更提高感度及解像度。又藉由爲10質量份以下，可抑制光阻形狀成爲倒梯形，提高密著性。前述感光性樹脂組成物較好進而含有（E )胺系化合物。據此，可使感光性樹脂組成物之感度變得更良好。前述（E )胺系化合物列舉爲例如雙[4-(二甲胺基）苯基]甲烷、雙[4-(二乙胺基）苯基]甲烷、隱色結晶紫（ Leuco Crystal Violet)。該等可單獨使用一種或組合兩種以上。前述感光性樹脂組成物含有（E)胺系化合物成分時，其含量相對於（A)黏合劑聚合物成分及（B)聚合性化合物成分之總量1〇〇質量份，較好爲〇.〇1質量份~1〇質量份，更好爲〇.〇5質量份~5質量份，最好爲0.1質量份〜2質量份。藉由使前述（E)胺系化合物之含量爲0.01質量份以上，可更提高感度。又藉由爲10質量份以下，可抑制過量之（E)胺系化合物在形成薄膜後以異物析出。前述感光性樹脂組成物除上述成分以外，可視需要含有其他成分。其他成分可列舉爲例如分子內具有至少一個可陽離子聚合之環狀醚基之光聚合性化合物（氧雜環丁烷 • 32 - 201216002 化合物等）、陽離子聚合起始劑、孔雀石綠（malachite green )等染料、三溴苯基颯、光發色劑、熱發色防止劑、對-甲苯磺醯胺等可塑劑、顏料、塡充劑、消泡劑、難燃劑、安定劑、密著性賦予劑、平流劑、剝離促進劑、抗氧化劑、香料、呈像劑、熱交聯劑。該等可單獨使用一種或組合兩種以上使用。又該等其他成分之含量相對於（A)黏合劑聚合物成分及（B )聚合性化合物成分之總量1 〇〇質量份，較好各爲〇.〇1質量份〜20質量份左右。前述感光性樹脂組成物可含有至少一種有機溶劑。前述有機溶劑可無特別限制地使用通常使用之有機溶劑。具體而言列舉爲例如甲醇、乙醇、丙酮、甲基乙基酮、甲基溶纖素、乙基溶纖素、甲苯、N，N-二甲基甲醯胺、丙二醇單甲基醚、及該等之混合溶劑。例如，可使用將前述（A )黏合劑聚合物、（B )聚合性化合物、及（C)光聚合起始劑溶解於前述有機溶劑中，作爲固體成分3 0質量％〜60質量％左右之溶液（以下稱爲「塗佈液」）使用。又，固體成分意指自前述溶液（感光性樹脂組成物）去除揮發性成分而殘留之成分。前述塗佈液可用於形成如下之感光性樹脂層。將前述塗佈液塗佈於後述之支撐薄膜或金屬板等支撐體之表面上，並經乾燥，藉此可於支撐體上形成源自前述感光性樹脂組成物之感光性樹脂層。 -33- 201216002 至於金屬板列舉爲銅、銅系合金、鎳、鉻、鐵、不銹鋼等鐵系合金’較好爲銅、銅系合金、鐵系合金等。形成之感光性樹脂層之厚度隨其用途而不同，但以乾燥後之厚度爲Ιμιη〜ΙΟΟμιη左右較佳。感光性樹脂層之與支撐體對向之面成相反側之面（表面）亦可經保護薄膜被覆。至於保護薄膜列舉爲聚乙烯、聚丙烯等聚合物薄膜等。前述感光性樹脂組成物可使用於例如後述之光阻圖型製造方法中。其中’適於應用於利用鍍敷處理形成電路之製造方法中。〈感光性元件〉本發明之感光性元件1 0係如於圖1中其一例之槪略剖面圖所示，爲具備支撐體2、於前述支撐體上形成之前述感光性樹脂組成物之塗膜之感光性樹脂層4，且具備視需要設置之保護薄膜6等之其他層而構成。前述支撐體可使用聚對苯二甲酸乙二酯、聚丙烯、聚乙烯、聚酯等具有耐熱性及耐溶劑性之聚合物薄膜。前述支撐體（以下有時稱爲「支撐薄膜」）之厚度較好爲 1μηι~100μιη，更好爲 5μηι~50μιη，又更好爲 5μιη~30μιη 。藉由使支撐體之厚度成爲1 μιη以上，可抑制剝離支撐薄膜時支撐薄膜之破裂。又藉由在ΙΟΟμιη以下，可抑制解像度降低。前述感光性元件10可視需要具有被覆感光性樹脂層4 之與支撐體2相對之面爲相反側之面（表面）上之保護膜6 -34- 201216002 前述保護膜對感光性樹脂層之接著力較好比感光性樹脂層對於支撐薄膜之接著力小者，又，較好爲低魚眼之薄膜。此處，所謂「魚眼」意指使構成保護薄膜之材料利用熱熔融、混練、擠出、二軸延伸、澆鑄法等製造薄膜時，材料之異物、未融解物、氧化劣化物等納入薄膜中而成者。亦即，所謂「低魚眼」意指薄膜中之上述異物等較少。具體而言，保護薄膜可使用聚對苯二甲酸乙二酯、聚丙烯、聚乙烯、聚酯等具有耐熱性及耐溶劑性之聚合物薄膜。市售者列舉爲王子製紙公司製造之ARUFUN MA-410 、E-2 00C，信越薄膜公司製造等之聚丙烯薄膜，帝人公司製造之PS-25等之PS系列等之聚對苯二甲酸乙二酯薄膜等。又，保護薄膜亦可爲與前述支撐體相同者。保護薄膜之厚度較好爲Ιμιη〜ΙΟΟμιη，更好爲5μκι ~50μιη，又更好爲5μιη〜30μιη，最好爲15μπι~30μηι。藉由使保護薄膜之厚度爲1 μιη以上，於一邊剝離保護薄膜，一邊將感光性樹脂層及支撐薄膜層合於基板上時，可抑制保護薄膜之破裂。又藉由爲100μιη以下可提高生產性。前述感光性元件可例如如下述般製造。可以包含下列之製造方法製造：將（Α)黏合劑聚合物、（Β)聚合性化合物、及（C )光聚合性起始劑溶解於有機溶劑中，調製固體成分30質量％〜60質量％左右之塗佈液，將前述塗佈液塗佈於支撐體上’形成塗佈層，及使前述塗佈層乾燥形 -35- 201216002 成感光性樹脂層。前述塗佈液塗佈於支撐體上之塗佈可藉由例如輥塗佈器、科馬塗佈器、凹版塗佈器、空氣刀塗佈器、模嘴塗佈器、棒塗佈器之習知方法進行。又前述塗佈層之乾燥只要是可自塗佈層去除有機溶劑之至少一部份即無特別限制。例如，較好於70°C〜150°C進行5分鐘〜30分鐘左右。乾燥後，感光性樹脂層中之殘留有機溶劑量就防止後續步驟中之有機溶劑擴散之觀點而言，較好爲2質量％以下。前述感光性元件中之感光性樹脂層之厚度可依據用途適宜選擇，但乾燥後之厚度較好爲1μπι~100μιη，更好爲 1μιη~50μηι，又更好爲 5μπι~40μιη。藉由使感光性樹脂層之厚度爲1 μιη以上，使工業上塗佈變得容易，而提高生產性。又藉由爲ΙΟΟμηι以下，可提高密著性及解像度。前述感光性樹脂層對於紫外線之透過率，對於波長 365nm之紫外線較好爲5%~75%，更好爲10%〜65%，最好爲 1 5%〜55 %。藉由使該透過率爲5%以上，可更提高密著性。又藉由使透過率爲75%以下，可更提高解像度。又，上述透過率可利用UV分光計測定。UV分光計列舉爲日立製作所製造之22 8 A型W Beam分光光度計。前述感光性元件可視需要進而具有緩衝層、接著層、光吸收層、氣體阻隔層等公知中間層等。 -36- 201216002 前述感光性元件之形態並無特別限制，可爲薄片狀，或亦可捲於捲芯上成滾筒狀之狀態。捲成滾筒狀時，較好以使支撐薄膜成爲外側之方式捲取。捲芯列舉爲聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、聚氯化乙烯樹脂、ABS樹脂（丙烯腈-丁二烯-苯乙烯共聚物）等塑膠等。如此獲得之滾筒狀之感光性元件滾筒之端面就端面保護之觀點而言較好設置端面隔離物，就耐邊緣融著之觀點而言較好設置防濕端面隔離物。又，捆包方法較好爲包在透濕性小之黑色薄片中之包裝。前述感光性元件可適當使用於後述之光阻圖型製造方法中。其中，適宜應用於藉由鍍敷處理形成電路之製造方法。〈光阻圖型之製造方法〉本發明之光阻圖型之製造方法具備有（i)於基板上形成前述之感光性樹脂組成物的塗膜之感光性樹脂層之感光性樹脂層形成步驟，（Π )對前述感光性樹脂層之至少 —部份照射活性光線而使之光硬化之曝光步驟，及（iii ) 自基板上去除前述感光性樹脂層之未硬化部份，形成由源自前述感光性樹脂層之硬化物所成之光阻圖型之顯像步驟，且視需要包含其他步驟之構成。 (i ) 感光性樹脂層形成步驟感光性樹脂層形成步驟中，係於基板上形成前述感光 -37- 201216002 性樹脂組成物之塗膜的感光性樹脂層。前述基板並無特別限制，但可使用通常具備絕緣層與絕緣層上形成之導體層之電路形成用基板，或合金基材等之晶粒焊墊（引線框架用基材）。於基板上形成感光性樹脂層之方法可藉由例如自前述感光性元件去除保護薄膜後，邊加熱感光性元件之感光性樹脂層邊壓著上述基板而進行。據此，獲得以由基板與感光性樹脂層及支撐體之順序層合而成之層合體。該感光性樹脂層形成步驟，就密著性及服貼性之觀點而言，較好在減壓下進行。壓著時之感光性樹脂層及/或基板之加熱較好在70°C〜13(TC之溫度下進行。又壓著較好在 O.IMPa〜l.OMPa左右（lkgf/cm2~10kgf/cm2左右）之壓力下進行，但該等條件可視需要適當選擇。又，若將感光性樹脂層加熱至70°C〜130°C，則雖無必要預先使基板經預熱處理，但爲了進一步提高密著性及服貼性，亦可進行基板之預熱處理。 (ϋ ) 曝光步驟曝光步驟係藉由對形成於基板上之感光性樹脂層之至少一部份照射活性光線，使照射活性光線之部份光硬化，形成潛像。此時，存在於感光性樹脂層上之支撐體（支撐薄膜）對於活性光線爲透過性時，可通過支撐薄膜照射活性光線，但當支撐薄膜爲遮光性時，係對去除支撐薄膜後之感光 -38- 201216002 性樹脂層照射活性光線。至於曝光方法列舉爲稱爲ARTWORK之透過負型或正型光罩圖型照射活性光線成圖像狀之方法（光罩曝光法）。另外，亦可採用LDI (雷射直接呈像）曝光法或DLP ( 數位光製程）曝光法等之藉由直接描繪曝光法照射活性光線成圖像狀之方法》作爲活性光線之光源可使用習知之光源，例如使用碳電弧燈、水銀蒸汽電弧燈、高壓水銀燈、氙氣燈、氬氣雷射等氣體雷射、YAG雷射等固體雷射、半導體雷射等之有效放射出紫外線.、可見光者。 C ίϋ) 顯像步驟· 顯像步驟係藉由自基板上去除前述感光性樹脂層之未硬化部份，於基板上形成由使前述感光性樹脂層光硬化而成之硬化物所構成之光阻圖型。感光性樹脂層上存在有支撐薄膜時，係在去除支撐薄膜後，進行上述曝光部份以外之未曝光部份之去除（顯像 )。顯像方法有濕式顯像與乾式顯像，但廣泛使用濕式顯像。利用濕式顯像時，係使用對應於感光性樹脂組成物之顯像液，利用習知顯像方法顯像。至於顯像方法列舉爲使用浸漬方式、槳攪方式、噴霧方式、刷洗、快速拍打（ slapping )、剝落(scrapping )、搖動浸漬等方法，就提高解像度之觀點而言，以高壓噴霧方式最適合。亦可組合 -39- 201216002 該等兩種以上進行顯像。顯像液之構成係依據前述感光性樹脂組成物之構成適當選擇。列舉爲例如鹼性水溶液、水系顯像液及有機溶劑系顯像液。鹼性水溶液作爲顯像液使用時，較好爲安全且安定，且操作性良好。至於鹼性水溶液之鹼係使用鋰、鈉或鉀之氫氧化物等之氫氧化鹼金屬鹽；鋰、鈉、鉀或銨之碳酸鹽或碳酸氫鹽之碳酸鹼金屬鹽；磷酸鋰、磷酸鈉、等鹼金屬磷酸鹽；焦磷酸鈉、焦磷酸鉀等鹼金屬焦磷酸鹽等。至於鹼性水溶液較好爲0.1質量質量％之碳酸鈉之稀薄溶液、0.1質量質量％之碳酸鉀之稀薄溶液、0.1 質量％〜5質量％之氫氧化鈉之稀薄溶液、0.1質量％~5質量 %之四硼酸鈉之稀薄溶液等。鹼性水溶液之pH較好爲9〜11 之範圍，其溫度係配合感光性樹脂層之鹼顯像性調節。鹼性水溶液中亦可混入表面活性劑、消泡劑、促進顯像用之少量有機溶劑等。水系顯像液爲例如由水或鹼性水溶液與一種以上之有機溶劑所組成之顯像液。鹼性水溶液之鹼除先前所述之物質以外，列舉爲例如硼砂或偏矽酸鈉、氫氧化四甲基銨、乙醇胺、乙二胺、二乙三胺、2-胺基-2-羥基甲基·ι，3_丙二醇、1，3-二胺基丙醇-2及嗎啉等。水系顯像液之pH在可充分的進行顯像之範圍內儘可能小愈好，較好爲pH8~12，更好爲PH9〜10。水系顯像液中使用之有機溶劑列舉爲丙酮、乙酸乙酯 -40- 201216002 、具有碳原子數1〜4之烷氧基之烷氧基乙醇、乙醇、異丙醇、丁醇、二乙二醇單甲基醚、二乙二醇單乙基醚及二乙二醇單丁基醚等。該等可單獨或組合兩種以上使用。水系顯像液中之有機溶劑之濃度通常較好爲2質量％~90質量％，其溫度可配合鹼性顯像液而調整。水系顯像液中亦可少量混入界面活性劑、消泡劑等。有機溶劑系顯像液列舉爲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、甲基異丁基酮及γ· 丁內酯等有機溶劑。該等有機溶劑爲了防止起火，較好添加1~20質量％範圍之水。本發明中，於顯像步驟中去除未曝光部份後，可視需要進行60°C〜250°C左右之加熱或0.2J/cm2〜10J/cm2左右之曝光，藉此使光阻圖型進一步硬化。〈引線框架之製造方法〉本發明之引線框架之製造方法包含使利用前述光阻圖型之製造方法形成有光阻圖型之基板進行鍍敷處理，形成導體圖型之步驟，視需要包含光阻去除步驟、蝕刻處理步驟等其他步驟之構成。至於前述基板係使用合金基材等晶粒焊墊（引線框架用基材）。本發明中，係以於支撐體上形成之光阻圖型作爲光罩，對支撐體進行鍍敷處理。鍍敷處理之方法可爲電解鏟敷處理，亦可爲無電解鍍 -41 - 201216002 敷處理’但較好爲無電解鍍敷處理。無電解鍍敷處理列舉爲例如硫酸銅鍍敷、焦磷酸銅鍍敷等銅鍍敷，HIGH THROW焊料鍍敷等焊料鍍敷，瓦特鍍浴（Watts bath )( 硫酸鎳-氯化鎳）鍍敷、胺磺酸鎳等鎳鍍敷、硬質金鍍敷、軟金鍍敷等金鍍敷。前述鑛敷處理之後，去除支撐體上之光阻圖型。光阻圖型之去除可藉由例如比前述顯像步驟中使用之鹼性水溶液更強之鹼性水溶液剝離。該強鹼性水溶液係使用例如1 質量1 0質量％之氫氧化鈉水溶液.、1質量％〜1 0質量％氫氧化鉀水溶液等。其中，以使用1質量1 〇質量％之氫氧化鈉水溶液或氫氧化鉀較佳，更好使用1質量％〜5質量％之氫氧化鈉水溶液或氫氧化鉀。光阻圖型之剝離方式列舉爲浸漬方式、噴霧方式等，該等可單獨使用亦可倂用。去除光阻圖型後，進而進行蝕刻處理，去除不要之金屬層而製造引線框架。蝕刻處理之方法係依據欲去除之金屬層適當選擇。例如，蝕刻液列舉爲氯化銅溶液、氯化鐵溶液、鹼性蝕刻溶液及過氧化氫蝕刻液。該等中，就使蝕刻因子良好方面而言較好使用氯化鐵溶液。〈印刷電路板之製造方法〉本發明之印刷電路板之製造方法包含使藉由前述光阻 -42- 201216002 Η型之製造方法之形成有光阻圖型之基板經鍍敷處理，形成導體圖型之步驟，且視需要包含光阻去除步驟、蝕刻處理步驟等其他步驟而構成。本發明中係以於基板上形成之光阻圖型作爲光罩，對基板上設置之導體層進行鍍敷處理。印刷電路板之製造方法中，有關鍍敷處理之方法、光圖型之去除方法、蝕刻處理，係與前述引線框架之製造方法相同。利用本發明之印刷電路板之製造方法製造之印刷電路板可爲多層印刷電路板，且亦可具有小直徑通孔。又前述印刷電路板可利用包含使由前述光阻圖型之製造方法之形成有光阻圖型之基板進行蝕刻處理，形成導體圖型之步驟之製造方法製造。該製造方法係以於基板上形成之光阻圖型作爲光罩，對設置於基板上之導體層進行蝕刻處理。日本專利申請案2010-173083號之揭示將其全文以參照之方式倂入本說明書中。本說明書中所述之全部文獻、專利申請案及技術規格 ’各文獻、專利申請案、及技術規格均以參照之方式倂入 ’具體且與個別敘述時相同之程度，倂入本說明書中供參考0 [實施例] 以下，以實施例具體說明本發明但本發明並不受該等 -43- 201216002 實施例之限制。又，若無特別說明，則「份」及「％」均爲質量基準》〈合成例〉 (黏合劑聚合物（A-1)之合成）混合聚合性單體（Monomer)的甲基丙嫌酸150g、甲基丙烯酸苄酯125g、甲基丙烯酸甲酯25g及苯乙烯2 00g( 質量比3 0/25/5/40 )、及偶氮雙異丁腈9.0g，調製溶液a。將偶氮雙異丁腈1.2g溶解於甲基溶纖素60g及甲苯40g 之混合液（質量比3 : 2) 100g中，調製溶液b。於具備攪拌機、回流冷凝管、溫度計、滴加漏斗及氮氣導入管之燒瓶中倒入甲基溶纖素2 7 0g及甲苯180g之混合液（質量比3 : 2 ) 450g，邊於燒瓶內吹拂氮氣邊攪拌，加熱升溫至80°C » 於燒瓶內之上述混合液中，於4小時內滴加上述溶液a 後，邊攪拌邊於80°C保溫2小時。接著’在10分鐘內將上述溶液b滴加於燒瓶內之溶液中之後’邊攪拌燒瓶內之溶液邊在80°C保溫3小時。接著，於30分鐘內將燒瓶內之溶液升溫至90°C，於90°C保溫2小時後’經冷卻獲得黏合劑聚合物（A-1 )之溶液。黏合劑聚合物（A-1)之不揮發份（固體成分）爲 47.8質量％ )，重量平均分子量爲30,000，酸價爲 196mgKOH/g。又，重量平均分子量係以凝膠滲透層析法 (GPC )測定，且使用標準聚苯乙烯校正線換算而導出。 -44- 201216002 GPC之條件示於下。 GPC之條件泵：日立L-6000型（日立製作所（股）製造）管柱：以下之合計三根 Gelpack GL-R420 Gelpack GL-R43 0In the above formula (IX), R14, R15 and R16 each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and q1, q2 and q3 each independently represent an integer of 〇~5. When ql, q2, and q3 are 2 or more, R14, R15, and R16 in the plural may be the same or different. The alkyl group having 1 to 6 carbon atoms is exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group or a hexyl group. The above alkoxy group having 1 to 4 carbon atoms is exemplified by a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a third butoxy group. R14 and R15 are each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. Ql and q2 are preferably an integer of from 1 to 4, more preferably 3. Also, q3 is preferably 〇. 201216002 The compound represented by the above formula (VIII) is preferably 2,4,6-trimethylbenzylidene-diphenylphosphine oxide from the viewpoint of more effectively improving the sensitivity and the shape of the photoresist. 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide is commercially available as DAROCUR-TPO (manufactured by BASF Corporation, Japan). Further, in view of the compound represented by the above formula (IX), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide is preferred from the viewpoint of more effectively improving the sensitivity and the shape of the photoresist. . Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide is commercially available, for example, as IRGACURE-819 (trade name, manufactured by BASF Corporation, Japan). In the present invention, the compound represented by the above formula (VIII) or (IX) may be used alone or in combination of two or more. In the photosensitive resin composition, the content of the (C-1) fluorenylphosphine oxide-based compound is preferably from 20% by mass to 60% by mass based on the total amount of the (C) photopolymerization initiator. More preferably 30% by mass to 45% by mass. The above (C-2) hexaarylbiimidazole derivative preferably contains at least one of 2,4,5-triarylmazoleazole dimer from the viewpoint of improving sensitivity and adhesion. The aforementioned 2,4,5-triarylimidazole dimer may be structurally symmetric or asymmetrical. The aforementioned 2,4,5-triarylimidazole dimer is exemplified by, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4. 5-bis-(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred. -29-201216002 The content of the (C-2) hexaarylbiimidazole derivative in the photosensitive resin composition is preferably 30% by mass based on the total amount of the (C) photopolymerization initiator component. ～70% by mass, more preferably 45% by mass to 65% by mass 〇In the photosensitive resin composition, (C-1) fluorenylphosphine oxide-based compound is contained in (C-2) hexaarylbiimidazole derivative The ratio (C-1/C-2) is not particularly limited. The content ratio (C-1/C-2) is preferably from 0.1 to 0.9, more preferably from 0.3 to 0.9, still more preferably from 0.5 to 0.8, from the viewpoints of sensitivity, resolution and adhesion. The photosensitive resin composition may further contain a photopolymerization initiator other than the above-described mercaptophosphine oxide-based compound and hexaarylbiimidazole derivative. Other photopolymerization initiators are exemplified by, for example, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-l- An aromatic ketone such as [4-(methylthio)phenyl]-2-morpholinylacetone-1, an anthracene such as an alkyl hydrazine, or a benzoin ether compound such as a benzoin alkyl ether; a benzylation compound such as a benzoin or an alkyl benzoin or a benzyl derivative such as a benzyldimethylketal, a 9-phenyl acridine or a 1,7-(9,9'-acridinyl)g An acridine derivative such as an alkane. These may be used alone or in combination of two or more. The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.1 part by mass based on 100 parts by mass of the total of (A) the binder polymer component and (B) the polymerizable compound component. 10 parts by mass, more preferably 1 part by mass to 7 parts by mass, still more preferably 2 parts by mass to 6 parts by mass, more preferably 3 parts by mass to 5 parts by mass. By setting the content of the photopolymerization initiator to 0.1 part by mass or more to -30 to 201216002', the sensitivity, the resolution, and the adhesion are further improved, and by 10 parts by mass or less, a more excellent resist shape can be obtained. . In the photosensitive resin composition, the content of the binder polymer is preferably 20% by mass to 90% by mass, and the content of the polymerizable compound is 3% by mass to 70% by mass, and the photopolymerization initiator is contained. The ratio is 0.1% by mass to 20% by mass. More preferably, the content of the binder polymer is 30% by mass to 80% by mass, the content of the polymerizable compound is 10% by mass to 60% by mass, and the content of the photopolymerization initiator is 1% by mass to 1%. 〇% by mass. Further, the content of the binder polymer is preferably 40% by mass and 5% by mass, the content of the polymerizable compound is 25% by mass to 50% by mass, and the content of the photopolymerization initiator is 3% by mass to 7 mass%. %. The photosensitive resin composition preferably further contains (D) a sensitizing dye. According to this, the hardening sensitivity of the photosensitive resin composition is further improved. (D) sensitizing dyes are exemplified by, for example, dialkylaminobenzophenones, pyrazolines, anthraquinones, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, Benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalene diimines, triarylamines. These may be used alone or in combination of two or more. In particular, when the photosensitive resin layer is exposed to light using active light of 390 nm to 420 nm, the (D) sensitizing dye preferably contains pyrazoles, anthraquinones, and fragrant beans from the viewpoint of sensitivity and adhesion. At least one selected from the group consisting of a steroid and a triarylamine is at least one selected from the group consisting of pyrazolines, anthraquinones, and triarylamines. -31 - 201216002 (D) The content of the sensitizing dye is preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the total of (A) the binder polymer component and (B) the polymerizable compound component. More preferably, it is 0.05 part by mass to 5 parts by mass, and more preferably 0.1 part by mass to 3 parts by mass. By setting the content of the (D) sensitizing dye to 0.01 parts by mass or more, the sensitivity and the resolution can be further improved. Further, when it is 10 parts by mass or less, the shape of the photoresist can be suppressed to be an inverted trapezoid, and the adhesion can be improved. The photosensitive resin composition preferably further contains (E) an amine compound. According to this, the sensitivity of the photosensitive resin composition can be made better. The above (E) amine compound is exemplified by bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, and Leuco Crystal Violet. These may be used alone or in combination of two or more. When the photosensitive resin composition contains the (E) amine compound component, the content thereof is preferably 1 part by mass based on the total amount of the (A) binder polymer component and the (B) polymerizable compound component. 1 part by mass to 1 part by mass, more preferably 5 parts by mass to 5 parts by mass, more preferably 0.1 part by mass to 2 parts by mass. By setting the content of the above (E) amine compound to 0.01 part by mass or more, the sensitivity can be further improved. Further, by using 10 parts by mass or less, it is possible to suppress excessive (E) amine-based compound from being deposited as a foreign matter after forming a film. The photosensitive resin composition may contain other components as needed in addition to the above components. The other component may, for example, be a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule (oxetane • 32 - 201216002 compound, etc.), a cationic polymerization initiator, malachite green (malachite green) ) dyes, tribromophenyl hydrazine, photochromic agent, thermal hair color preventive agent, p-toluene sulfonamide and other plasticizers, pigments, chelating agents, defoamers, flame retardants, stabilizers, adhesion A sex-imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an image-forming agent, and a thermal crosslinking agent. These may be used alone or in combination of two or more. Further, the content of the other components is preferably from about 1 part by mass to about 20 parts by mass per part by mass of the (A) binder polymer component and (B) the polymerizable compound component. The photosensitive resin composition may contain at least one organic solvent. The organic solvent to be used in general can be used without particular limitation. Specifically, for example, methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and These mixed solvents. For example, the (A) binder polymer, the (B) polymerizable compound, and the (C) photopolymerization initiator may be dissolved in the organic solvent to obtain a solid content of about 30% by mass to about 60% by mass. The solution (hereinafter referred to as "coating liquid") is used. Further, the solid content means a component remaining from the solution (photosensitive resin composition) by removing volatile components. The coating liquid described above can be used to form a photosensitive resin layer as follows. The coating liquid is applied onto the surface of a support such as a support film or a metal plate to be described later, and dried to form a photosensitive resin layer derived from the photosensitive resin composition on the support. -33- 201216002 The metal plate is exemplified by an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron or stainless steel, and is preferably a copper, a copper-based alloy, or an iron-based alloy. The thickness of the photosensitive resin layer to be formed varies depending on the use thereof, but it is preferably about ιμηη to ΙΟΟμιη after drying. The surface (surface) of the photosensitive resin layer opposite to the surface opposite to the support may be covered with a protective film. The protective film is exemplified by a polymer film such as polyethylene or polypropylene. The photosensitive resin composition can be used, for example, in a photoresist pattern manufacturing method to be described later. Wherein ' is suitable for use in a manufacturing method for forming a circuit by a plating process. <Photosensitive element> The photosensitive element 10 of the present invention is a schematic cross-sectional view of an example of FIG. 1 and is provided with a support 2 and a coating of the photosensitive resin composition formed on the support. The photosensitive resin layer 4 of the film is provided with another layer such as the protective film 6 to be provided as needed. As the support, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene or polyester can be used. The thickness of the support (hereinafter sometimes referred to as "support film") is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 5 μm to 30 μm. By setting the thickness of the support to 1 μm or more, it is possible to suppress cracking of the support film when the support film is peeled off. Further, by lowering ΙΟΟμηη, the resolution reduction can be suppressed. The photosensitive element 10 may have a protective film 6-34-201216002 on the surface (surface) on the opposite side of the surface of the photosensitive resin layer 4 facing the support 2, and the adhesion of the protective film to the photosensitive resin layer. It is preferable that the photosensitive resin layer has a small adhesion to the supporting film, and is preferably a film of a low fisheye. Here, the term "fisheye" means that when a film constituting the protective film is produced by heat fusion, kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, unmelted matter, oxidative degradation or the like of the material is incorporated into the film. Founder. That is, the "low fisheye" means that the foreign matter or the like in the film is small. Specifically, as the protective film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The commercial products are listed as ARUFUN MA-410, E-2 00C manufactured by Oji Paper Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and PS series such as PS-25 manufactured by Teijin Co., Ltd. Ester film and the like. Further, the protective film may be the same as the support described above. The thickness of the protective film is preferably Ιμιη~ΙΟΟμιη, more preferably 5μκι to 50μιη, still more preferably 5μιη to 30μιη, and most preferably 15μπι~30μηι. When the thickness of the protective film is 1 μm or more, the protective film is peeled off, and when the photosensitive resin layer and the supporting film are laminated on the substrate, cracking of the protective film can be suppressed. Further, productivity can be improved by being 100 μm or less. The photosensitive element can be produced, for example, as follows. It can be produced by the following production method: a (Α) binder polymer, a (Β) polymerizable compound, and (C) a photopolymerizable initiator are dissolved in an organic solvent to prepare a solid content of 30% by mass to 60% by mass. The coating liquid on the left and right sides is applied onto the support by applying the coating liquid to form a coating layer, and the coating layer is dried to form a photosensitive resin layer of -35 to 201216002. The coating of the coating liquid applied to the support may be performed by, for example, a roll coater, a Koma applicator, a gravure coater, an air knife coater, a die coater, a bar coater. The conventional method is carried out. Further, the drying of the coating layer is not particularly limited as long as it can remove at least a part of the organic solvent from the coating layer. For example, it is preferably from about 70 ° C to 150 ° C for about 5 minutes to 30 minutes. After the drying, the amount of the organic solvent remaining in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The thickness of the photosensitive resin layer in the photosensitive member may be appropriately selected depending on the use, but the thickness after drying is preferably from 1 μm to 100 μm, more preferably from 1 μm to 50 μm, and even more preferably from 5 μm to 40 μm. When the thickness of the photosensitive resin layer is 1 μm or more, industrial coating is facilitated, and productivity is improved. Further, by being ΙΟΟμηι or less, the adhesion and the resolution can be improved. The transmittance of the photosensitive resin layer to ultraviolet rays is preferably from 5% to 75%, more preferably from 10% to 65%, most preferably from 15% to 55%, for ultraviolet rays having a wavelength of 365 nm. By making the transmittance 5% or more, the adhesion can be further improved. Further, by making the transmittance 75% or less, the resolution can be further improved. Further, the above transmittance can be measured by a UV spectrometer. The UV spectrometer is exemplified by a 22 8 A W Beam spectrophotometer manufactured by Hitachi. The photosensitive element may further include a known intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, or a gas barrier layer, as needed. -36- 201216002 The form of the photosensitive element is not particularly limited, and may be in the form of a sheet or may be wound on a winding core in a roll shape. When it is rolled into a roll shape, it is preferable to take up the support film so that it may become outer side. The core is exemplified by a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS resin (acrylonitrile-butadiene-styrene copolymer). The end face of the roller-shaped photosensitive member roller thus obtained is preferably provided with an end face spacer from the viewpoint of end face protection, and a moisture-proof end face spacer is preferably provided from the viewpoint of edge edge fusion. Further, the packaging method is preferably a package wrapped in a black sheet having a small moisture permeability. The photosensitive element can be suitably used in a photoresist pattern manufacturing method to be described later. Among them, it is suitably applied to a manufacturing method of forming a circuit by a plating process. <Method for Producing Photoresist Pattern> The method for producing a resist pattern of the present invention includes a step of forming a photosensitive resin layer of (i) a photosensitive resin layer on which a coating film of the photosensitive resin composition is formed on a substrate (Π) an exposure step of irradiating at least a portion of the photosensitive resin layer with active light to photoharden, and (iii) removing an uncured portion of the photosensitive resin layer from the substrate, forming a source The step of developing the photoresist pattern formed by the cured product of the photosensitive resin layer, and including other steps as necessary. (i) Photosensitive resin layer forming step In the photosensitive resin layer forming step, a photosensitive resin layer on which a coating film of the photosensitive-37-201216002 resin composition is formed is formed on a substrate. The substrate is not particularly limited, and a circuit pad for forming a conductor layer formed on an insulating layer and an insulating layer, or a die pad (a substrate for a lead frame) such as an alloy substrate can be used. The method of forming the photosensitive resin layer on the substrate can be carried out by, for example, removing the protective film from the photosensitive member and then pressing the photosensitive resin layer of the photosensitive member while pressing the substrate. According to this, a laminate in which the substrate and the photosensitive resin layer and the support are laminated in this order is obtained. The photosensitive resin layer forming step is preferably carried out under reduced pressure from the viewpoint of adhesion and conformability. The heating of the photosensitive resin layer and/or the substrate during pressing is preferably carried out at a temperature of 70 ° C to 13 (TC), and is preferably pressed at about O.IMPa to 1.0 MPa (lkgf/cm 2 to 10 kgf / It is carried out under the pressure of about cm2, but these conditions may be appropriately selected as needed. Further, if the photosensitive resin layer is heated to 70 ° C to 130 ° C, it is not necessary to pre-heat the substrate in advance, but further The adhesion and the conformability are improved, and the substrate may be pre-heat treated. (ϋ) Exposure step The exposure step is performed by irradiating at least a portion of the photosensitive resin layer formed on the substrate with active light to make the irradiation activity. Part of the light is hardened to form a latent image. At this time, the support (support film) existing on the photosensitive resin layer is permeable to the active light, and the active light can be irradiated through the support film, but when the support film is shielded In the case of the sensitization, the sensitized light-38-201216002 resin layer is irradiated with active light. The exposure method is exemplified as a method of illuminating the active light into an image by a negative or positive reticle pattern called ARTWORK. (mask Exposure method). Alternatively, an LDI (laser direct image) exposure method or a DLP (digital photo process) exposure method may be used to directly illuminate the active light into an image by direct drawing exposure. The light source can 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, which emits ultraviolet rays. C. In the development process, the development step is performed by removing the uncured portion of the photosensitive resin layer from the substrate, and forming a hardening by photohardening the photosensitive resin layer on the substrate. The pattern of the photoresist formed by the object. When the support film is present on the photosensitive resin layer, the removal of the unexposed portion other than the exposed portion (development) is performed after the support film is removed. The development methods include wet development and dry development, but wet imaging is widely used. In the case of wet development, a developing liquid corresponding to a photosensitive resin composition is used, and development is carried out by a conventional development method. As for the development method, the method of using the immersion method, the paddle stirring method, the spraying method, the brushing, the slapping, the scapping, the shaking immersion, and the like is preferable, and the high pressure spraying method is most suitable from the viewpoint of improving the resolution. Can also be combined -39- 201216002 These two or more are used for imaging. The constitution of the developing liquid is appropriately selected in accordance with the constitution of the above-mentioned photosensitive resin composition. For example, it is an alkaline aqueous solution, an aqueous developing solution, and an organic solvent-based developing solution. When an alkaline aqueous solution is used as a developing solution, it is preferably safe and stable, and has good handleability. As the base of the alkaline aqueous solution, an alkali metal hydroxide such as lithium, sodium or potassium hydroxide; an alkali metal carbonate of lithium, sodium, potassium or ammonium carbonate or hydrogencarbonate; lithium phosphate or sodium phosphate; And alkali metal phosphate; alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate. As for the alkaline aqueous solution, preferably 0.1% by mass of a thin solution of sodium carbonate, 0.1% by mass of a thin solution of potassium carbonate, 0.1% by mass to 5% by mass of a thin solution of sodium hydroxide, 0.1% by mass to 5 mass A thin solution of % tetraborate or the like. The pH of the alkaline aqueous solution is preferably in the range of from 9 to 11, and the temperature is adjusted in accordance with the alkali developability of the photosensitive resin layer. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed into the alkaline aqueous solution. The aqueous developing solution is, for example, a developing liquid composed of water or an aqueous alkaline solution and one or more organic solvents. The base of the alkaline aqueous solution is exemplified by, for example, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxyl, in addition to the materials previously described. Base, 3, propylene glycol, 1,3-diaminopropanol-2, and morpholine. The pH of the aqueous imaging solution is as small as possible within a range in which sufficient development can be performed, preferably from pH 8 to 12, more preferably from pH 9 to 10. The organic solvent used in the aqueous imaging solution is exemplified by acetone, ethyl acetate-40-201216002, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. These may be used alone or in combination of two or more. The concentration of the organic solvent in the aqueous developing solution is usually preferably from 2% by mass to 90% by mass, and the temperature can be adjusted in accordance with the alkaline developing solution. A small amount of a surfactant, an antifoaming agent, or the like may be mixed into the aqueous developing solution. The organic solvent-based developing solution is exemplified by 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ·butyl An organic solvent such as a lactone. These organic solvents are preferably added in an amount of from 1 to 20% by mass in order to prevent ignition. In the present invention, after removing the unexposed portion in the developing step, it is possible to perform heating at about 60 ° C to 250 ° C or exposure at about 0.2 J/cm 2 to 10 J/cm 2 as needed, thereby further forming the photoresist pattern. hardening. <Manufacturing Method of Lead Frame> The method for manufacturing a lead frame according to the present invention includes a step of forming a conductor pattern by forming a substrate having a resist pattern formed by the above-described photoresist pattern manufacturing method, and optionally including light. The steps of the other steps such as the removal step, the etching process step, and the like. As the substrate, a die pad (a substrate for a lead frame) such as an alloy substrate is used. In the present invention, the support is subjected to a plating treatment by using a photoresist pattern formed on the support as a photomask. The plating treatment method may be electrolytic shovel treatment, or electroless plating - 41 - 201216002, but preferably electroless plating treatment. The electroless plating treatment is, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as HIGH THROW solder plating, and Watts bath (nickel sulfate-nickel chloride) plating. Gold plating such as nickel plating such as nickel sulfamate, hard gold plating, and soft gold plating. After the aforementioned mineral deposit treatment, the photoresist pattern on the support is removed. The removal of the photoresist pattern can be removed by, for example, an alkaline aqueous solution stronger than the alkaline aqueous solution used in the above development step. For the strong alkaline aqueous solution, for example, a 1 mass% aqueous sodium hydroxide solution, a 1 mass% to 10 mass% aqueous potassium hydroxide solution, or the like is used. Among them, a sodium hydroxide aqueous solution or potassium hydroxide having a mass of 1% by mass is preferably used, and a sodium hydroxide aqueous solution or potassium hydroxide of 1% by mass to 5% by mass is more preferably used. The peeling pattern of the photoresist pattern is exemplified by a dipping method, a spraying method, and the like, and these may be used alone or in combination. After removing the photoresist pattern, etching is further performed to remove the unnecessary metal layer to fabricate the lead frame. The etching process is suitably selected depending on the metal layer to be removed. For example, the etching liquid is exemplified by a copper chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide etching solution. Among these, it is preferred to use a ferric chloride solution in terms of a good etching factor. <Manufacturing Method of Printed Circuit Board> The method of manufacturing a printed circuit board according to the present invention includes forming a conductor pattern by plating a substrate having a resist pattern formed by the above-described photoresist manufacturing method of the photoresist type 42-201216002 The step of the type is configured to include other steps such as a photoresist removal step and an etching treatment step as needed. In the present invention, the photoresist pattern formed on the substrate is used as a photomask, and the conductor layer provided on the substrate is plated. In the method of manufacturing a printed circuit board, the method of plating treatment, the method of removing the pattern, and the etching treatment are the same as the method of manufacturing the lead frame. The printed circuit board manufactured by the method of manufacturing a printed circuit board of the present invention may be a multilayer printed circuit board, and may have a small-diameter through hole. Further, the printed circuit board can be manufactured by a manufacturing method including a step of forming a conductor pattern by etching a substrate having a photoresist pattern formed by the above-described photoresist pattern forming method. In the manufacturing method, the photoresist pattern formed on the substrate is used as a photomask, and the conductor layer provided on the substrate is etched. The disclosure of Japanese Patent Application No. 2010-173083 is incorporated herein in its entirety by reference. All documents, patent applications and technical specifications referred to in this manual 'all documents, patent applications, and technical specifications are incorporated by reference to the extent that they are specific and the same as the individual descriptions. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples of the -43-201216002. In addition, unless otherwise specified, "parts" and "%" are quality standards" <Synthesis Example> (Synthesis of Adhesive Polymer (A-1)) Methyl propylene of mixed polymerizable monomer (Monomer) Solution a was prepared by 150 g of acid, 125 g of benzyl methacrylate, 25 g of methyl methacrylate, 200 g of styrene, 200 g of styrene (mass ratio of 3 0/25/5/40), and 9.0 g of azobisisobutyronitrile. 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a mixed liquid of 60 g of methyl cellosolve and 40 g of toluene (mass ratio 3:2) to prepare a solution b. Into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, a mixture of 270 mg of methyl cellulolytic solution and 180 g of toluene (mass ratio: 3:2) was poured into a flask, and was blown in a flask. The mixture was stirred under nitrogen and heated to 80 ° C. The solution a was added dropwise to the mixture in the flask over 4 hours, and then kept at 80 ° C for 2 hours while stirring. Then, the solution b was added dropwise to the solution in the flask over 10 minutes, and the solution in the flask was stirred while maintaining the solution at 80 ° C for 3 hours. Next, the solution in the flask was heated to 90 ° C in 30 minutes, and kept at 90 ° C for 2 hours, and then cooled to obtain a solution of the binder polymer (A-1). The binder polymer (A-1) had a nonvolatile content (solid content) of 47.8% by mass, a weight average molecular weight of 30,000, and an acid value of 196 mgKOH/g. Further, the weight average molecular weight was measured by gel permeation chromatography (GPC) and derived using standard polystyrene calibration line conversion. -44- 201216002 The conditions of GPC are shown below. GPC conditions Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.) Pipe column: The following total three Gelpack GL-R420 Gelpack GL-R43 0

Gelpack GL-R440 (以上爲日立化成工業（股）製造，商品名）溶離液：四氫呋喃測定溫度：4 0 °C 流量：2.05mL/分鐘檢測器：日立L-3 3 00型RI (日立製作所（股）製造） (黏合劑聚合物（A-2)〜（A-6)之合成）黏合劑聚合物（A_l)之合成中，除使用下表1所示之材料，以該表中所示之質量比作爲聚合性單體（Monomer )以外，與獲得黏合劑聚合物（A-1)之溶液同樣地，分別獲得黏合劑聚合物（A-2 )〜（A-6 )之溶液。 -45 - 201216002 [表i] 黏合劑衆合物之構成 (A-1) 甲基丙烯酸/甲基丙烯酸节醋/甲基丙烯酸甲酯/苯乙烯 (質&匕30/25/5/40) 酸價：196mgKOH/g，雷景平均分子量：30000 (A-2) 甲基丙烯酸/甲基丙烯酸节醋/甲基丙烯酸甲醋/苯乙烯 (質量比27/23/5/45) 酸價：176mgKOH/g，重量平均分子量：30000 (A-3) 甲基丙烯酸/甲基丙烯酸苄酯/甲基丙烯酸甲酯/苯乙烯 (質量比25/35/10/30) 酸價：163mgKOH/g，重量平均分子量：30000 (A-4) 甲基丙烯酸/甲基丙烯酸苄酯/甲基丙烯酸甲酯/苯乙烯 (質量比35/25/5/35) 酸價：228mgKOH/g，重量平均分子量：30000 (A-5) 甲基丙烯酸/甲基丙烯酸苄酯/苯乙烯 (質量比30/50/20) 酸價：196mgKOH/g，重量平均分子量：30000 (A-6) 甲基丙烯酸/甲基丙烯酸苄酯/苯乙烯 (質量比25/50/25) 酸價：163mgKOH/g，重量平均分子量：30000 〈實施例1〜1 1及比較例1〜4〉 [感光性樹脂組成物之調製] 分別使用作爲（A )黏合劑聚合物之上述獲得之A-1〜A-6、作爲（B )聚合性化合物之以下所示之B-1〜B-4，作爲（C)光聚合起始劑之以下所示之C-1A、C-1B、C-2 ，作爲其他成分之以下所示之成分，以下表2所示之調配量（調配份數）混合，藉此分別調製實施例1〜1 1及比較例 1〜4之感光性樹脂組成物。又，表2中所示之（A )黏合劑聚合物之調配量（調配份數）爲不揮發份之質量（固體成 -46 - 201216002 分量）。 (B ) 光聚合性化合物 B-l: 2,2-雙（4-(甲基丙烯醯氧基五乙氧基）苯基）丙烷[FA-321M (日立化成工業（股）製造，製品名） B-2: 2,2-雙（4-((甲基）丙烯醯氧基二丙氧基）苯基）丙烷[BPE-200 (新中村化學工業（股）製造，製品名 ) B-3:上述通式（V)中，R=甲基，ΠΜ+ιηπόί：平均値 )，m = 12 (平均値）之化合物[FA-023M (日立化成工業 (股）製造，製品名）] B-4:上述通式（VI)中，R =甲基，πΐ3 = 6(平均値），η2 + η3=12 (平均値）之化合物[FA-0 24MC日立化成工業 (股）製造，製品名）] (C ) 光聚合起始劑 C-1A : 2,4,6-三甲基苯甲醯基-二苯基-氧化膦 [DAROCUR-TPO (曰本BASF公司製造，商品名） C-1B :雙（2,4,6-三甲基苯甲醯基）-苯基氧化膦 [IRGACURE-819 (曰本BASF公司製造，商品名）] C-2A: 2,2’-雙（2-氯苯基）-4,4’，5,5’ -四苯基聯味哩 [B-CIM ( Hampford公司製造，商品名）] (D ) 增感色素 -47- 201216002 D-1: 4,4’-雙（二乙胺基）二苯甲酮 (E) 胺系化合物 E-1 :隱色結晶紫[LCV (山田化學公司製造，商品名染料 MKG (大阪有機化學工業公司製造，商品名）：孔雀石綠表2 成分實施列 Μ m 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 (A) A-1 60 60 60 eo A-2 - 60 - - - - 60 - 60 eo 60 - - - A-3 - A-4 - A-5 - A-6 - (B) B-1 30 30 30 30 30 30 30 30 30 30 25 30 3D 30 30 B—2 5 5 5 5 5 5 5 5 5 5 10 5 5 5 5 B-3 5 5 5 5 5 5 5 5 5 - 5 5 5 5 5 B-4 - (C) C-1A 2 2 2 2 2 - - - - 2 - - 2 - C-1B - - - - - 2 2 2 1.5 2 - 2 - - 2 C-2A 3 3 3 3 3 3 3 3 2.5 3 3 3 3 - - (D) D-1 0.1 0.1 αι 0.1 0.1 0.1 αι 0.1 0.1 0.1 0.1 0.1 0.15 0.15 0.15 (E) E-1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 染料 MKG 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.0S 0.05 0.05 0.05 0.05 溶劑丙酮 5 5 5 S 5 5 -5 5 5 5 5 5 5 5 5 甲苯 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 甲醇 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 〈感光性元件之調製〉將上述獲得之感光性樹脂組成物分別均勻地塗佈於厚度16μιη之聚對苯二甲酸乙二酯薄膜（帝人（股）製造，蔺品名「HTF-01」）上，以7〇。(：及ll〇°C之熱風對流式乾 -48- 201216002 燥器乾燥，形成乾燥後之膜厚爲2 5μιη之感光性樹脂層。於該感光性樹脂層上貼合保護薄膜（Tamapoly (股）製造，製品名「NF-15」），分別獲得依序層合聚對苯二甲酸乙二酯（支撐薄膜）與感光性樹脂層及保護薄膜之感光性元件P1〜PI 1及Pic〜P4c。〈層合體之製作〉使用表面粗化處理液「MERCK ETCH BOND CZ-8100 」（Merck公司製造，商品名）對於兩面層合銅箔（厚度 :35μπι)而成之玻璃環氧材料的貼銅層合板（基板，日立化成工業公司製造，商品名「MLC-E-679」）進行表面處理，經水洗、酸洗及水洗後，以空氣流乾燥。將經表面處理之貼銅層合板加溫至80 °C，邊剝離保護薄膜邊以使感光性樹脂層接觸銅表面之方式，分別層合上述獲得之感光性元件。據此，分別獲得依序層合貼銅層合板、感光性樹脂層、支撐薄膜而成之層合體。所得層合體使用作爲以下所示試驗中之試驗片。又，層合係使用120°C之熱滾筒，以〇.4MPa之壓著壓力、1.0m/分鐘之滾筒速度進行。〈評價〉 (光感度測定試驗）於上述獲得之試驗片之支撐薄膜上，載置具有作爲負型光罩之濃度區域0.00〜2.00、濃度階變0.05、密度階變圖 -49- 201216002 大小爲20mmx 187mm、各階變大小爲3mm x 12mm共41段密度階變圖（step tablet )之光學工具，使用具有高壓水銀燈之曝光機（OAK公司製造，商品名「EXM-1201」），以70mJ/cm2之照射能量使感光性樹脂層曝光。接著，剝離支撐薄膜，以30°C之1質量％碳酸鈉水溶液，以最少顯像時間（去除未曝光部份之最少時間）之兩倍時間噴霧顯像，去除未曝光部份而進行顯像處理。顯像處理後，藉由測定形成於基板上之光硬化膜之密度階變圖之段數，評價感光性樹脂組成物之光感度。光感度係以密度階變圖之段數表示，該密度階變圖之段數愈高，則顯示光感度高。結果示於表3。 (解像度及密著性之測定試驗）爲了調查解像度及密著性，而於上述獲得之試驗片之支撐薄膜上密著使用密著性評價用負型之具有線寬/間隔寬爲2/2〜30/30 (單位：μιη)之電路圖型之玻璃鉻型之光學工具，使用具有高壓水銀燈之曝光機，以41段之密度階變圖之剩餘段數成爲14段之能量對上述層合體之感光性樹脂層進行曝光。曝光後，與上述感光度測定試驗同樣進行顯像處理。於顯像處理後，徹底去除間隔部份（未曝光部份），且線部份（曝光部份）並未產生蛇行或缺陷所形成之光阻圖型中，利用最小線寬/間隔寬之値，評價解像度•密著性。其數値愈小意指解像度及密著性均良好，結果示於表3 -50- 201216002 (光阻形狀之評價）上述解像度•密著性之評價中，使用日立掃描型電子顯微鏡S-500A觀察所得光阻形狀（光阻圖型之剖面形狀）〇光阻形狀爲梯型或倒梯型時，或有光阻之拖尾或龜裂時，會有由隨後之蝕刻處理或鍍敷處理所形成之電路容易產生短路或斷線之傾向。據此，以光阻形狀爲矩形（長方形），且沒有光阻拖尾或龜裂者較適宜。結果示於表3。又，所謂「龜裂」意指光阻圖型之線部份（曝光部份 )出現裂縫或龜裂，或者伴隨著出現線部份之缺陷或斷裂 (光阻之線寬精度之評價）於上述獲得之試驗片之支撐薄膜上密著作爲用以評價光阻之線寬精度之解像度評價用負型之具有線寬/間隔寬爲10/10(單位：μηι)之配線圖型之玻璃鉻型之光學工具，使用具有高壓水銀燈之曝光機，以使4 1段密度階變圖之殘留段數成爲14段及17段之能量，對上述層合體之感光性樹脂層進行曝光。曝光後，與上述光感度測定試驗同樣地進行顯像處理。針對所得光阻圖型，使用日立掃描型電子顯微鏡s_ 5 00A測定光阻最上部之線寬値。此處’線寬値愈接近 -51 - 201216002 ΙΟμιη之値，則顯示線寬精度愈高。結果示於表3。 (剝離特性之評價）將試驗片切成40mmx50mm之四方形大小，以使41段之階段板之剩餘段數成爲14段之能量對上述層合體之感光性樹脂層進行全面曝光。曝光後，與上述光感度測定試驗同樣進行顯像處理。將如此獲得之剝離特性評價用之各試驗片浸漬於邊以攪拌子攪拌之50°C之3質量％氫氧化鈉水溶液中，以目視觀察各試驗片之光阻表面。自攪拌開始，至使硬化膜自基板完全剝離去除之時間作爲剝離時間》又，以目視觀察剝離後之剝離片之尺寸，以下列評價基準進行評價。剝離時間愈短，剝離片尺寸愈小’則意指剝離特性愈良好。結果示於表3。〜評價基準〜 L:剝離片尺寸爲薄片狀。 Μ ·剝離片尺寸爲邊長30mm以上未達40mm。 S·剝離片之尺寸小於邊長30mm。 -52- 201216002 ε撇比較例4 〇 2 1 1 1 1 l 1 比較例3 〇 ε 1 1 1 1 1 1 比較例2 CO CM 倒梯形 12.5 LO Έ 比較例1 〇 Q： CM 矩形 CO Ο V·. s Έ 實施侧1 Ε CO 矩形 10.2 00 實施例10 〇〇〇矩形 10.3 CM 00 co 實施例9 〇> Ο 矩形' 10.3 〇 P c/> 實施例8 0〇 CO 矩形 10,3 Ύ— V- p 00 實施例7 £ GO 矩形 10.4 CSI P co 實施例6 〇〇矩形 10.3 s CO 實施例5 o 矩形 10.4 r·· τ- CO CO 實施例4 2 •<r σ> 矩形 10.2 CM IA CO 實施例3 2 o 矩形 10.5 CO CO 實施例2 2 寸 00 矩肜 10.3 CO Y~ T- CO 實施例1 Ξ：寸 CO 矩形 10.3 CM T- r- o CO 感光性樹脂雛物感光性元件感光度(段數)*1 解像度·密著性 (//m) 光阻形狀 14段之線寬値(jam) 17段之線寬値(//m) 剝離時間(秒）剝離片尺寸鋪 smeiv)函親塑¾¾¾ 寸-B-iBU/i 日 0/._米_—1* -53- 201216002 由表3可了解，由實施例1〜11之感光性樹脂組成物調製之感光性元件爲感度、解像度、密著性、光阻形狀及硬化後之剝離特性均優異者。又4 1段密度階變圖之剩餘段數爲1 4段時之線寬値接近1 Ομηι，1 7段時即使增加曝光量線寬値之變化量仍小。另一方面，由比較例1〜2之感光性樹脂組成物調製之感光性元件之解像度、密著性、光阻形狀、光阻之線寬精度、或剝離特性均差。又，由比較例3~4之感光性樹脂組成物調製之感光性元件光感度低而無法形成圖型。 [產業上之可能利用性] 本發明之感光性樹脂組成物適用作爲形成製造印刷電路板用之光阻圖型之材料。尤其，上述感光性樹脂組成物由於感度、解像度、密著性、光阻形狀及硬化後之剝離特性均優異，故亦適用於形成製造高密度封裝基板等之具有細線化•高密度化配線之印刷電路板用之光阻圖型。【圖式簡單說明】圖1爲顯示本發明之感光性元件之一實施形態之模式剖面圖。【主要元件符號說明】 2 :支撐體 -54- 201216002 4 :感光性樹脂層 6 :保護薄膜 1 0 :感光性元件 -55-Gelpack GL-R440 (The above is manufactured by Hitachi Chemical Co., Ltd., trade name) Solvent: Tetrahydrofuran Measurement temperature: 40 °C Flow rate: 2.05 mL/min Detector: Hitachi L-3 00 type RI (Hitachi Manufacturing Co., Ltd. ( (manufacturing)) (Composition of binder polymer (A-2) ~ (A-6)) In the synthesis of binder polymer (A-1), except the materials shown in Table 1 below, as shown in the table A mass ratio of the binder polymer (A-2) to (A-6) was obtained in the same manner as the solution for obtaining the binder polymer (A-1), except for the polymerizable monomer (Monomer). -45 - 201216002 [Table i] Composition of adhesive composition (A-1) Methacrylic acid/methacrylic acid vinegar/methyl methacrylate/styrene (mass & 匕30/25/5/40 Acid value: 196mgKOH/g, average molecular weight of Leijing: 30000 (A-2) methacrylic acid/methacrylic acid vinegar/methyl methacrylate/styrene (mass ratio 27/23/5/45) : 176 mgKOH/g, weight average molecular weight: 30000 (A-3) methacrylic acid / benzyl methacrylate / methyl methacrylate / styrene (mass ratio 25/35/10/30) Acid value: 163 mgKOH / g , Weight average molecular weight: 30000 (A-4) methacrylic acid / benzyl methacrylate / methyl methacrylate / styrene (mass ratio 35 / 25 / 5 / 35) Acid value: 228mgKOH / g, weight average molecular weight :30000 (A-5) methacrylic acid/benzyl methacrylate/styrene (mass ratio 30/50/20) Acid value: 196 mgKOH/g, weight average molecular weight: 30000 (A-6) methacrylic acid/A Benzyl acrylate/styrene (mass ratio: 25/50/25) Acid value: 163 mgKOH/g, weight average molecular weight: 30,000 <Examples 1 to 1 1 and Comparative Examples 1 to 4> [Modulation of photosensitive resin composition Use separately As the (A) binder polymer, A-1 to A-6 obtained above, and (B) a polymerizable compound, B-1 to B-4 shown below, as (C) photopolymerization initiator C-1A, C-1B, and C-2 shown below are mixed as the components shown below in the other components, and the blending amounts (the number of blending portions) shown in Table 2 below are mixed, whereby Examples 1 to 1 are separately prepared. 1 and photosensitive resin compositions of Comparative Examples 1 to 4. Further, the amount of the (A) binder polymer shown in Table 2 (the number of blending) is the mass of the nonvolatile matter (solid content -46 - 201216002). (B) Photopolymerizable compound B1: 2,2-bis(4-(methylpropenyloxypentaethoxy)phenyl)propane [FA-321M (manufactured by Hitachi Chemical Co., Ltd., product name) B -2: 2,2-bis(4-((meth)propenyloxydipropoxy)phenyl)propane [BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) B-3: In the above formula (V), R = methyl, ΠΜ+ιηπόί: average 値), m = 12 (average 値) of the compound [FA-023M (manufactured by Hitachi Chemical Co., Ltd., product name)] B-4 : In the above formula (VI), R = methyl, π ΐ 3 = 6 (average 値), η2 + η3 = 12 (average 値) of the compound [FA-0 24MC manufactured by Hitachi Chemical Co., Ltd., product name)] (C) Photopolymerization initiator C-1A : 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide [DAROCUR-TPO (manufactured by BA本BASF, trade name) C-1B : Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide [IRGACURE-819 (manufactured by Sakamoto BASF, trade name)] C-2A: 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenyl-linked miso [B-CIM (manufactured by Hampford, trade name)] (D) sensitizing dye-47- 20 1216002 D-1: 4,4'-bis(diethylamino)benzophenone (E) Amine compound E-1 : leuco crystal violet [LCV (manufactured by Yamada Chemical Co., Ltd., trade name dye MKG (Osaka Organic) Manufactured by Chemical Industry Co., Ltd., trade name: Malachite Green Table 2 Ingredients Implementation Μ m 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 (A) A-1 60 60 60 eo A-2 - 60 - - - - 60 - 60 eo 60 - - - A-3 - A-4 - A-5 - A-6 - (B) B-1 30 30 30 30 30 30 30 30 30 30 30 3D 30 30 B— 2 5 5 5 5 5 5 5 5 5 5 10 5 5 5 5 B-3 5 5 5 5 5 5 5 5 5 - 5 5 5 5 5 B-4 - (C) C-1A 2 2 2 2 2 - - - - 2 - - 2 - C-1B - - - - - 2 2 2 1.5 2 - 2 - - 2 C-2A 3 3 3 3 3 3 3 3 2.5 3 3 3 3 - - (D) D-1 0.1 0.1 αι 0.1 0.1 0.1 αι 0.1 0.1 0.1 0.1 0.1 0.15 0.15 0.15 (E) E-1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Dye MKG 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.0S 0.05 0.05 0.05 0.05 Solvent Acetone 5 5 5 S 5 5 -5 5 5 5 5 5 5 5 5 Toluene 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Methanol 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 <Preparation of photosensitive element> The photosensitive resin composition obtained above was uniformly applied to a polyphenylene terephthalate having a thickness of 16 μm. The ethylene formate film (manufactured by Teijin Co., Ltd., under the product name "HTF-01") was 7 〇. (: and hot air convection dry type □ - 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 Manufactured, product name "NF-15"), respectively obtained by sequentially laminating polyethylene terephthalate (support film) and photosensitive resin layer and protective film photosensitive elements P1 ~ PI 1 and Pic ~ P4c [Production of Laminated Fabrics] Copper paste of glass epoxy material obtained by using a surface roughening treatment liquid "MERCK ETCH BOND CZ-8100" (manufactured by Merck) for a double-sided laminated copper foil (thickness: 35 μm) The laminate (substrate, manufactured by Hitachi Chemical Co., Ltd., trade name "MLC-E-679") is surface-treated, washed with water, pickled, and washed with water, and dried by air flow. The surface-treated copper laminate is heated. The photosensitive member obtained above was laminated by peeling off the protective film to expose the photosensitive resin layer to the copper surface at 80 ° C. Accordingly, the laminated copper laminate and the photosensitive resin layer were sequentially obtained. Supporting film The laminate obtained was used as a test piece in the test shown below. Further, the laminate was carried out using a 120 ° C hot roll at a press pressure of MPa4 MPa and a roll speed of 1.0 m/min. Evaluation> (Photosensitivity Test) On the support film of the test piece obtained above, the concentration region having a negative mask was placed at 0.00 to 2.00, the concentration step was changed to 0.05, and the density step was changed to -49-201216002 and the size was 20 mmx. 187mm, optical tool with a step size of 3mm x 12mm and a 41-step density step (step tablet), using an exposure machine with a high-pressure mercury lamp (manufactured by OAK, trade name "EXM-1201"), at 70mJ/cm2 Irradiation energy exposes the photosensitive resin layer. Next, the support film is peeled off and sprayed with a 1% by mass aqueous solution of sodium carbonate at 30 ° C for twice the time of the minimum development time (minimum time to remove the unexposed portion). The development process was performed by removing the unexposed portion. After the development process, the light sensitivity of the photosensitive resin composition was evaluated by measuring the number of stages of the density step change pattern of the photocured film formed on the substrate. The degree is expressed by the number of segments of the density step map, and the higher the number of segments of the density step change chart, the higher the light sensitivity is. The results are shown in Table 3. (Measurement of resolution and adhesion) In order to investigate the resolution and density The glass film of the circuit pattern having a line width/space width of 2/2 to 30/30 (unit: μιη) having a negative adhesion evaluation type is used for adhesion to the support film of the test piece obtained above. In the optical tool of the type, an exposure machine having a high-pressure mercury lamp was used to expose the photosensitive resin layer of the laminate by the energy of the remaining number of segments of the 41-stage density step. After the exposure, the development process was carried out in the same manner as the above sensitivity measurement test. After the image processing, the spacer portion (unexposed portion) is completely removed, and the line portion (exposed portion) is not formed into a photoresist pattern formed by a meander or a defect, and the minimum line width/space width is utilized. Hey, evaluate the resolution and the adhesion. The smaller the number, the better the resolution and the adhesion. The results are shown in Table 3 - 50 - 201216002 (Evaluation of the shape of the photoresist). In the above resolution and adhesion evaluation, the Hitachi scanning electron microscope S-500A was used. Observe the shape of the photoresist (the cross-sectional shape of the photoresist pattern). When the photoresist shape is a ladder type or an inverted ladder type, or there is a tail or crack of the photoresist, it may be treated by subsequent etching or plating. The resulting circuit is prone to shorts or breaks. Accordingly, it is preferable that the shape of the photoresist is rectangular (long square), and there is no photoresist tailing or cracking. The results are shown in Table 3. Further, the term "crack" means that a crack or crack occurs in a line portion (exposed portion) of a photoresist pattern, or a defect or a break in a line portion (evaluation of line width accuracy of a photoresist) is The support film of the test piece obtained above is a glass chrome having a wiring pattern having a line width/space width of 10/10 (unit: μηι) for the evaluation of the resolution for determining the line width of the photoresist. In the optical tool of the type, an exposure machine having a high-pressure mercury lamp is used to expose the photosensitive resin layer of the laminate to the energy of 14 segments and 17 segments in the number of remaining segments of the density step pattern. After the exposure, development processing was carried out in the same manner as the above-described photometric measurement test. For the obtained photoresist pattern, the line width 値 of the uppermost portion of the photoresist was measured using a Hitachi scanning electron microscope s_500A. Here, the line width is closer to -51 - 201216002 ΙΟμιη, the higher the line width accuracy is. The results are shown in Table 3. (Evaluation of Peeling Characteristics) The test piece was cut into a square shape of 40 mm x 50 mm so that the remaining number of stages of the 41-stage stage plate was 14 pieces of energy to fully expose the photosensitive resin layer of the above laminate. After the exposure, development processing was carried out in the same manner as the above-described photometric measurement test. Each test piece for evaluation of the peeling property thus obtained was immersed in a 3 mass% sodium hydroxide aqueous solution at 50 ° C stirred by a stirrer to visually observe the photoresist surface of each test piece. The time from the start of stirring to the time when the cured film was completely peeled off from the substrate was taken as the peeling time. The size of the peeled sheet after peeling was visually observed, and evaluated based on the following evaluation criteria. The shorter the peeling time, the smaller the peeling sheet size' means the better the peeling property. The results are shown in Table 3. ~ Evaluation criteria ~ L: The peeling sheet size is a sheet shape. Μ · The size of the release sheet is 30mm or more and less than 40mm. The size of the S· peeling sheet is smaller than the side length of 30 mm. -52- 201216002 ε撇Comparative Example 4 〇2 1 1 1 1 l 1 Comparative Example 3 〇ε 1 1 1 1 1 1 Comparative Example 2 CO CM Inverted trapezoid 12.5 LO Έ Comparative example 1 〇Q: CM Rectangular CO Ο V· s 实施 Implementation side 1 Ε CO rectangle 10.2 00 Example 10 〇〇〇 Rectangular 10.3 CM 00 co Example 9 〇> Ο Rectangular ' 10.3 〇P c/> Example 8 0〇CO Rectangular 10,3 Ύ— V-p 00 Example 7 £ GO Rectangular 10.4 CSI P co Example 6 〇〇Rectangle 10.3 s CO Example 5 o Rectangular 10.4 r·· τ-CO CO Example 4 2 •<r σ> Rectangular 10.2 CM IA CO Example 3 2 o Rectangular 10.5 CO CO Example 2 2 inch 00 moment 肜 10.3 CO Y~ T- CO Example 1 Ξ: Inch CO Rectangular 10.3 CM T- r- o CO Photosensitive resin prototype photosensitive element sensitization Degree (segment number)*1 Resolution/adhesiveness (//m) Resistance of the 14-segment line width ja (jam) 17-segment line width / (//m) Peeling time (seconds) Peeling sheet size smeiv ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) As sensitivity, resolution, adhesion, peeling property after the resistance, resist shape and are excellent in hardening. In addition, the number of remaining segments of the density gradient map of the 4 1 segment is close to 1 Ομηι when the segment is 1 4 segments, and the amount of change in the width of the exposure line is still small when the segment is 7-7. On the other hand, the photosensitive elements prepared by the photosensitive resin compositions of Comparative Examples 1 to 2 were inferior in resolution, adhesion, photoresist shape, line width accuracy of the photoresist, and peeling characteristics. Further, the photosensitive element prepared by the photosensitive resin compositions of Comparative Examples 3 to 4 had a low light sensitivity and could not form a pattern. [Industrial Applicability] The photosensitive resin composition of the present invention is suitably used as a material for forming a photoresist pattern for producing a printed circuit board. In particular, since the photosensitive resin composition is excellent in sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing, it is also suitable for forming fine-line/high-density wiring for manufacturing a high-density package substrate or the like. Photo resistive pattern for printed circuit boards. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element of the present invention. [Main component symbol description] 2 : Support -54- 201216002 4 : Photosensitive resin layer 6 : Protective film 1 0 : Photosensitive element -55-

Claims

201216002 七、申請專利範園： 1. 一種感光性樹脂組成物，其含有下列成分： (A ) 具有源自（甲基）丙烯酸之構成單位及源自 (甲基）丙烯酸苄酯或（甲基）丙烯酸苄酯衍生物之構成單位之黏合劑聚合物， (B ) 具有至少一個乙烯性不飽和鍵之聚合性化合物，及 (C ) 含有醯基氧化膦系化合物及六芳基聯咪唑衍生物之光聚合起始劑。 2. 如申請專利範圍第1項之感光性樹脂組成物’其中前述醯基氧化膦系化合物爲以下述通式（1)或通式（11 )表示之化合物，【化1】 0 , II 2 R1一C—P——R2201216002 VII. Application for Patent Park: 1. A photosensitive resin composition containing the following components: (A) having a constituent unit derived from (meth)acrylic acid and derived from benzyl (meth)acrylate or (methyl) a binder polymer of a constituent unit of a benzyl acrylate derivative, (B) a polymerizable compound having at least one ethylenically unsaturated bond, and (C) a fluorenylphosphine oxide-containing compound and a hexaarylbiimidazole derivative Photopolymerization initiator. 2. The photosensitive resin composition of the first aspect of the invention, wherein the sulfhydryl phosphine oxide compound is a compound represented by the following formula (1) or (11), [Chemical Formula 1] 0, II 2 R1 - C - P - R2

Ο p4-C—P—C-R6 II I IIΟ p4-C-P-C-R6 II I II

〇 R5 0 [通式（I)中，R1、R2及R3各獨立表不碳數1〜20之院基或芳基，式（II)中，R4、R5及R6各獨立表示碳數1 ~20之院基或芳基]。 3 .如申請專利範圍第1項之感光性樹脂組成物’其中前述六芳基聯咪唑衍生物爲2,三芳基咪唑一聚物。 4·—種感光性元件，其具備有支撐體、形成於那述支撐體上之如申請專利範圍第1項之感光性樹脂組成物的塗膜之感光性樹脂層。 -56- 201216002 5. —種光阻圖型之製造方法，其具有下列步驟：於基板上形成如申請專利範圍第1至3項中任一項之感光性樹脂組成物的塗膜之感光性樹脂層的感光性樹脂層形成步驟，對前述感光性樹脂層之至少一部份照射活性光線而使之光硬化之曝光步驟，及自基板上去除前述感光性樹脂層之未硬化部份，形成由前述感光性樹脂層之硬化物所成之光阻圖型之顯像步驟〇 6. —種引線框架之製造方法，其包含使由如申請專利範圍第5項之光阻圖型之製造方法所得之形成有光阻圖型之基板進行鍍敷處理，而形成導體圖型之步驟。 7·—種印刷電路板之製造方法，其包含使由如申請專利範圍第5項之光阻圖型之製造方法所得之形成有光阻圖型之基板進行鍍敷處理，形成導體圖型之步驟。 8 · —種印刷電路板’其係由如申請專利範圍第7項之印刷電路板之製造方法而製造。 -57-〇R5 0 [In the formula (I), R1, R2 and R3 each independently represent a hospital group or an aryl group having a carbon number of 1 to 20, and in the formula (II), R4, R5 and R6 each independently represent a carbon number of 1 to ~ 20 yard base or aryl base]. 3. The photosensitive resin composition of claim 1, wherein the hexaarylbiimidazole derivative is a diarylimidazole monomer. A photosensitive element comprising a support and a photosensitive resin layer formed on the support of the photosensitive resin composition of the first aspect of the invention. -56-201216002 5. A method for producing a photoresist pattern, comprising the steps of: forming a photosensitive film of a photosensitive resin composition according to any one of claims 1 to 3 on a substrate a photosensitive resin layer forming step of the resin layer, an exposure step of irradiating at least a portion of the photosensitive resin layer with active light to photoharden, and removing an uncured portion of the photosensitive resin layer from the substrate to form A method for producing a photoresist pattern formed by the cured product of the photosensitive resin layer, a method for producing a lead frame, comprising a method for producing a photoresist pattern according to claim 5 The resulting step of forming a substrate having a photoresist pattern is subjected to a plating process to form a conductor pattern. 7. A method of manufacturing a printed circuit board, comprising: plating a substrate formed with a resist pattern obtained by the method for manufacturing a photoresist pattern according to claim 5 of the patent application, forming a conductor pattern step. A printed circuit board is manufactured by a method of manufacturing a printed circuit board as claimed in claim 7. -57-