201245870 六、發明說明： 【發明所屬之技術領域】 本發明係關於利祕性水溶液可顯影的感光性樹脂組成 物，含有由該感光性樹脂組成物構成之感光性樹脂組成物層 與支撐層的光阻薄膜，使用該光阻薄膜在基材上形成光阻圖 案的方法，以及使用該光阻薄膜的導體圖案之形成方法。更 詳言之，係關於能提供適用於印刷佈線板之製造、可撓性印 刷佈線板之製造、ic晶片搭載用引線框架（以下稱「引線框 架」）之製造、金屬遮罩製造等金屬箔精密加工、或BGA(球 柵陣列封裝）、CSP(晶片級封裝）等半導體封裝製造、或以 TAB(Tape Automated Bonding，捲帶自動黏合)與 c〇F[Chip[Technical Field] The present invention relates to a photosensitive resin composition developable in a water-soluble aqueous solution, comprising a photosensitive resin composition layer and a support layer composed of the photosensitive resin composition. A photoresist film, a method of forming a photoresist pattern on a substrate using the photoresist film, and a method of forming a conductor pattern using the photoresist film. More specifically, it is possible to provide a printed circuit board, a flexible printed wiring board, a ic wafer mounting lead frame (hereinafter referred to as "lead frame"), and a metal foil manufacturing metal foil. Precision processing, or semiconductor package manufacturing such as BGA (Ball Grid Array Package), CSP (Wafer Level Package), or TAB (Tape Automated Bonding) and c〇F [Chip
On Film(薄膜覆晶）：將半導體IC搭載於薄膜狀細微佈線板 上者]等為代表之帶基板之製造、半導體凸塊之製造、或平 面顯不器領域之ITO電極、位址電極、或電磁波屏蔽等構 件之製造的光阻圖案的感光性樹脂組成物，以及其關聯技 術。 【先前技術】 習知’印刷佈線板係利用光學微影法進行製造。所謂「光 學微影法」係指將感光性樹脂組成物塗佈於基板上，經圖案 曝光而使該感光性樹脂組成物的曝光部進行聚合硬化，再利 用顯景>液除去未曝光部，而在基板上形成光阻圖案，經施行 蝕刻或鍍覆處理，而形成導體圖案後，在將該光阻圖案從該 101106904 , 201245870 基板上剝離除去，藉此在基板上形成導體圖案的方法。 上述光學微影法中，將感光性樹脂組成物塗佈於基板上之 時’可使用例如··將光阻溶液塗佈於基板上再使之乾燥的方 法；或者使用依序積層著支撐層、由感光性樹脂組成物構成 之層（以下亦稱「感光性樹脂組成物層」）、及視需要的保護 層而構成之光阻薄膜，並將該感光性樹脂組成物層側積層於 基板上的方法等任一方法。而且’印刷佈線板之製造時，大 多使用後者的光阻薄膜。 針對上述使用光阻薄膜製造印刷佈線板的方法簡單敘述 如下。 首先，當光阻薄膜具有保護層（例如聚乙烯薄膜）的情況， 係從感光性樹脂組成物層上將其剝離。接著，使用層壓機在 基板(例如貼箔積層板)上’依照該基板、感光性樹脂組成物 層、支撐層的順序積層感光性樹脂組成物層及支撐層。接 著，隔著設有佈線圖案的光罩’對該感光性樹脂組成物層利 用包括由超高壓水銀燈所發出之i射線(365nm)的紫外線等 活性能量線施行曝光，而使曝光部分進行聚合硬化。接著， 將支撐層（例如聚對苯二曱酸乙二酯薄臈）剝離。接著，利用 顯影液(例如具弱鹼性的水溶液），將感光性樹脂組成物層的 未曝光部分予以溶解或分散除去，而在基板上形成光阻圖 案。經光阻圖案形成後，使電路形成的製程大致可區分為2 種方法。第一方法係將未被光阻圖案所覆蓋的基板銅面予以 101106904 4 201245870 钱刻除去後，再將光阻圖案部分利 液予以除去之方法(㈣更強的驗水溶 行使用銅、焊錫、鎳的鑛覆處的鋼面施 除去’進而對露出的基板鋼面施行_的方 用二方面二製作導體形狀均勻且高密度_ 用+添加工法。半添加工法係首先依照上述方法在晶種^吏 膜上形成光阻圖案。接著，對& "s 4 銅佈線，經剝離光阻後，再利用通稱「快速㈣」的： 同時對該鍵銅佈線與晶種銅薄臈施㈣刻。半添加工法係不 =於上述織卫法’其晶種銅薄膜較薄，幾乎沒有因餘刻所 造成的影響’可製成矩形且高密度的佈線。 然而，經顯影後’在硬化光阻與基板的邊界部分會發生所 謂「底腳」（hem)的半硬化光阻(參照目υ。尤其在高^度光 阻圖案間，因底腳而導致在顯影後所出現的晶種銅薄膜:面 積減少，致使藉鍍覆法所形成之鍍銅佈線與銅薄膜間之接地 面積減少。所以，牽涉到鍍銅佈線容易剝落的問題。又，因 為底腳位於鍍銅佈線下，因而亦會在光阻剝離時成為拉扯、 剝離不良的原因。又，即便是蝕刻工法，亦有因底腳而導致 在顯影後所出現的銅薄膜表面積減少，而有蝕刻除去不足之 虞。所以，要求經顯影後的硬化光阻底腳極小之光阻薄膜。 作為解決該等問題的方法，例如專利文獻1提案有藉由使 用三化合物’防止穿透光於基材表面之暈光，抑制底腳發 101106904 5 201245870 生的方法’又專利文獻2提案有藉由使用於分子内具有 架的光聚合性化合物，而抑制半硬化光阻（底腳)發生的= 法。 [先行技術文獻] [專利文獻] 專利文獻1 :日本專利特開2007-114452號公報 專利文獻2:日本專利特開2〇〇9_53388號公報 【發明内容】 (發明所欲解決之問題） 然而，上述專利文獻1所記載的三化合物，雖對減少底 腳可發現效果，但仍然難謂足夠；而上述專利文獻2所記载 之於分子内具有荞骨架的光聚合性化合物，則有因其強疏水 性而導致光阻剝離性大幅惡化的問題。 緣是’本發明在此種背景下，目在於提供：解像性與密接 性均良好，且顯影後的硬化光阻之底腳極小，剝離性亦良好 的感光性樹脂組成物，含有由該感光性樹脂組成物所構成之 感光性樹脂組成物層與支撐層的光阻薄膜，使用該光阻薄膜 在基材上形成光阻圖案的方法，以及使用該光阻薄膜的導體 圖案之形成方法。 (解決問題之手段） 然而’本發明者為解決上述問題經深入鑽研，結果發現於 以黏結劑聚合物為主成分，並含有可光聚合之單體、光聚合 101106904 6 201245870 起始劑的感光性樹脂組成物中，藉由含有作為可光聚合之草 體成分的具有胺基之單體，與作為賦予剝離性成分的具有羧 基之苯并三唑衍生物，則可顯現出高解像性與高密接性，真 經顯影後的硬化光阻之底腳極小，剝離性亦良好，町達成上 述目的’遂完成本發明。 即，本發明要旨係關於一種感光性樹脂組成物，其特徵為 含有：（A)黏結劑聚合物、（B)具胺基且可光聚合之單體、（C) 光聚合起始劑、及(D)具絲之笨并三⑽生物。 再者，本發明係關於一種光阻薄膜，其含有：由本發明之 感光性樹脂組成物所構成之感光性樹脂組成物層、與支樓 層0 再者’本發明係關於-種光阻圖案之形成方法，其包括 #7 用本發明之餘㈣，在基材上形減紐樹脂組成 物層，經曝光、顯影的步驟。 再：’本發明係關於一種導體圖案之形成方法，其包括 用本⑧明光阻賴’在電路形成用基板上形成感光性 =，，經曝光、顯影，而形成光阻圖案的步驟;以 形成上述総㈣的上述電路形·基板施行餘刻 :覆，再將上述光阻圖案予以剝離的步驟。 發明係包括有以下的態樣。 組成物，師徵為含有：⑷黏結劑聚 。（）具胺基且可光聚合之單體、（c)光聚合起始劑、及 101106904 201245870 (D)具叛基之苯并三咬衍生物。 [2]如[1]所記載的感光性樹脂組成物，其中，（b)具胺基且 可光聚合之單體係下述一般式(I)所示之可光聚合的不飽和 化合物； [化1]On Film (film-coated): Manufacture of semiconductor substrates, such as semiconductor wafers, etc., manufacturing of semiconductor bumps, or fabrication of semiconductor bumps, or ITO electrodes and address electrodes in the field of planar display devices. A photosensitive resin composition of a resist pattern produced by a member such as electromagnetic wave shield, and related art. [Prior Art] Conventional printed wiring boards are manufactured by an optical lithography method. The "optical lithography method" is a method in which a photosensitive resin composition is applied onto a substrate, and the exposed portion of the photosensitive resin composition is subjected to polymerization curing by pattern exposure, and the unexposed portion is removed by using a viscous liquid. And forming a photoresist pattern on the substrate, performing etching or plating treatment to form a conductor pattern, and then removing the photoresist pattern from the 101106904, 201245870 substrate, thereby forming a conductor pattern on the substrate . In the above optical lithography method, when a photosensitive resin composition is applied onto a substrate, a method of applying a photoresist solution to a substrate and drying it may be used, or a support layer may be laminated in sequence. a photoresist film composed of a layer composed of a photosensitive resin composition (hereinafter also referred to as "photosensitive resin composition layer") and an optional protective layer, and the photosensitive resin composition layer layer is laminated on the substrate Any method such as the method above. Further, when the printed wiring board is manufactured, the latter photoresist film is mostly used. The method for producing a printed wiring board using the photoresist film described above will be briefly described below. First, when the photoresist film has a protective layer (for example, a polyethylene film), it is peeled off from the photosensitive resin composition layer. Then, the photosensitive resin composition layer and the support layer are laminated in the order of the substrate, the photosensitive resin composition layer, and the support layer by using a laminator on a substrate (for example, a foil-clad laminate). Then, the photosensitive resin composition layer is exposed to an active energy ray including an ultraviolet ray (365 nm) emitted from an ultrahigh pressure mercury lamp via a photomask having a wiring pattern, and the exposed portion is subjected to polymerization hardening. . Next, the support layer (for example, polyethylene terephthalate) is peeled off. Next, the unexposed portion of the photosensitive resin composition layer is dissolved or dispersed by a developing solution (e.g., a weakly alkaline aqueous solution) to form a photoresist pattern on the substrate. After the photoresist pattern is formed, the process of forming the circuit can be roughly divided into two methods. The first method is to remove the copper surface of the substrate not covered by the photoresist pattern by 101106904 4 201245870, and then remove the photoresist pattern part of the liquid solution ((4) stronger water treatment using copper, solder, The steel surface of the nickel ore is removed and further applied to the exposed steel surface of the substrate. The conductor shape is uniform and the density is high. _ The method of adding + is added. The semi-additive method is first used in the seed crystal according to the above method. ^The photoresist pattern is formed on the tantalum film. Then, the &"s 4 copper wiring is stripped of the photoresist, and then the general term "fast (four)" is used: simultaneously the copper wiring of the key and the thin copper of the seed crystal (4) The semi-addition method is not in the above-mentioned weaving method 'the copper film of the seed crystal is thin, and there is almost no influence due to the residuals'. It can be made into a rectangular and high-density wiring. However, after development, it is hardened. A semi-hardened photoresist of the so-called "hem" occurs at the boundary between the photoresist and the substrate (see the target. Especially among the high-resistance photoresist patterns, the seed crystals appear after development due to the feet) Copper film: reduced area, resulting in borrowing The grounding area between the copper-plated wiring formed by the coating method and the copper film is reduced. Therefore, the problem that the copper-plated wiring is easily peeled off is involved. Moreover, since the foot is located under the copper-plated wiring, it also becomes a pull when the photoresist is peeled off. The reason for the poor peeling. Moreover, even in the etching method, there is a decrease in the surface area of the copper film which occurs after development due to the foot, and there is insufficient etching removal. Therefore, the developed hardened photoresist bottom is required. As a method for solving such problems, for example, Patent Document 1 proposes a method of suppressing the light emitted from the surface of the substrate by using the three compound 'suppressing the foot 101106904 5 201245870 ' Further, Patent Document 2 proposes a method of suppressing the occurrence of a semi-cured photoresist (foot) by using a photopolymerizable compound having a carrier in a molecule. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent JP-A-2007-114452 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Although the tri-compound described above is effective in reducing the amount of the foot, it is still difficult to be sufficient. However, the photopolymerizable compound having an anthracene skeleton in the molecule described in Patent Document 2 is highly hydrophobic due to its hydrophobicity. The problem that the photoresist peeling property is greatly deteriorated. The reason is that the present invention provides a good resolution and adhesion, and the base of the hardened photoresist after development is extremely small, and the peeling property is also good. A photosensitive resin composition comprising a photoresist film comprising a photosensitive resin composition layer composed of the photosensitive resin composition and a support layer, a method of forming a photoresist pattern on a substrate using the photoresist film, and using A method of forming a conductor pattern of the photoresist film. (Means for Solving the Problem) However, the present inventors have intensively studied to solve the above problems, and as a result, found that a binder polymer is mainly composed of a photopolymerizable monomer. Photopolymerization 101106904 6 201245870 The photosensitive resin composition of the initiator contains a monomer having an amine group as a photopolymerizable grass component, and The benzotriazole derivative having a carboxyl group as a release component exhibits high resolution and high adhesion, and the base of the cured photoresist after development is extremely small, and the peeling property is also good, and the above-mentioned purpose is achieved by the town.遂Complete the invention. That is, the present invention relates to a photosensitive resin composition characterized by comprising: (A) a binder polymer, (B) an amine group-containing photopolymerizable monomer, and (C) a photopolymerization initiator; And (D) a stupid and three (10) creature. Furthermore, the present invention relates to a photoresist film comprising: a photosensitive resin composition layer composed of the photosensitive resin composition of the present invention, and a support layer 0. Further, the present invention relates to a photoresist pattern. A forming method comprising the step of exposing and developing the layer of the resin composition on the substrate by the use of the remainder (4) of the present invention. Further, the present invention relates to a method for forming a conductor pattern, which comprises the steps of forming a photoresist pattern by forming a photosensitive property on a circuit for forming a substrate by exposure, development, and forming a photoresist pattern; The above-described circuit shape and substrate of the above-mentioned 総(4) are subjected to a step of coating and then peeling off the photoresist pattern. The invention includes the following aspects. The composition, the teacher's sign contains: (4) bonding agent. () an amine-based and photopolymerizable monomer, (c) a photopolymerization initiator, and 101106904 201245870 (D) a regenerative benzotrident derivative. [2] The photosensitive resin composition according to [1], wherein (b) the photopolymerizable unsaturated compound represented by the following general formula (I) having an amine group and a photopolymerizable single system; [Chemical 1]
(其中’式中的心係Η或CH3。R2及R3係表示分別獨立之 從氫原子、烷基、烷氧基及齒基所構成群組中選擇的基，亦 可由Rz與R3相互鍵結形成含N的環β χ係表示碳數丨〜1〇 之伸烷基、或依(C2H4〇)m 4(c3H6〇)n所示且m、η分別為 1〜10之整數的聚氧化伸烷基，聚氧化伸烷基係無規聚合或 嵌段聚合。） [3] 如[1]或[2]所記载的感光性樹脂組成⑯，其巾，⑻具胺 基且可光聚合之單體係相對於(Α)黏結劑聚合物1〇〇重量 份，含有0.01〜30重量份。 [4] 如[1]〜[3]中任一項所記載的感光性樹脂組成物，其 中’（D)具羧基之笨并三唑衍生物係相對於黏結劑聚合物 100重量份’含有〇.〇1〜2重量份。 [5] 如[1]〜[4]中任一項所記載的感光性樹脂組成物，其 101106904 8 201245870 中，（A)黏結劑聚合物係具有羧基，且酸值為 100〜300mgKOH/g。 [6] -種光阻薄膜，係含有由⑴〜附任―項所記載的感 光性樹脂組成物構成的感光性難組成物層、與支撑層。 [7] 種光阻圖案之形成方法，係使用间所記载的光阻薄 膜’在基材上形成感光性樹脂組成物層，經曝光，再施行顯 影。 [8] -種導體圖案之形成方法，係、包括有：使謂所記載 的光阻薄膜’在電路形成用基板上形成感光性樹脂組成物 層，經曝光’再施行顯影，而形成光阻圖案；以及對已形成 上述光阻㈣的上述f路形成用基板騎關或鍍覆，再將 上述光阻圖案予以剝離。 (發明效果） 本發明的感光性樹脂組成物及光阻薄膜係具有解像性與 密接性均良好，且顯影後的硬化光阻之底腳極小，剝離性亦 良好的效果。所以，藉由使用本發明光阻薄膜的光阻圖案之 升y成方法及導體圖案之形成方法，可獲得降低光阻圖案的剝 離不良與導體圖案(佈線)剝落之效果。 【實施方式】 以下’針對本發明進行具體說明。 另外，本說明書中’（甲基）丙烯基係指丙烯基或其所對應 的曱基丙烯基；（曱基）丙烯酸酯係指丙烯酸酯或其所對應的 101106904 9 201245870 曱基丙烯酸酯；（甲基）丙烯醯基係指丙烯醯基或其所對應的 曱基丙稀醢基。 〔感光性樹脂組成物〕 本發明的感光性樹脂組成物係包含有：（A)黏結劑聚合 物、（B)具胺基且可光聚合之單體、（c)光聚合起始劑、及①) 具缓基之本并三哇衍生物。 (A)黏結劑聚合物可舉例如丙烯酸系聚合體、苯乙烯系聚 合體、％氧系聚合體、醯胺系聚合體、醯胺環氧系聚合體、 醇酸系聚合體、盼系聚合體等，可單獨使用該等聚合體中之 1種、或組合使用2種以上。該等聚合體之中較佳係含 之聚合物》 & 含幾基之聚合物可舉例示如丙稀酸系聚合體、聚自旨系聚合 體、聚酿胺系聚合體、環氧系聚合體等，其中，較佳係使: :(甲，W稀酸S旨與乙烯性不飽和_、及視需要的其他可 共聚合單體進行共聚合而構成的丙烯酸系聚合體。 以上述（曱基）丙烯酸酯為基礎的構成單元之含有量[(甲美 丙稀酸酸相對於所使用的總聚合性單體之比例]: =:生曾解像度及剝離崎 量份。質1份、更j含有2。〜6G質量份、特佳含有I%質 101106904 201245870 例），係從解像性、密接性、 ± 仰制底腳發生、及剝離性的觀 乂佳為3有12〜50質量份、更佳含有15〜4〇質量 份、、特佳含有18〜3G質量份^職補補的含有量 過/貝丨驗反紐差’有顯影時間、剝離時間變長的傾向； 反之，若過多，則有顯影液耐性降低、密接性降低的傾向。 再者，以其他可共聚合單體為基礎的構成單元之含有量 (其他可共聚合單體相對於所使用的總聚合性單體之比 例）’較佳為含有10〜80質量份、更佳含有2〇〜7〇質量份、 特佳含有30〜60質量份。 該等含缓基之聚合物可單獨使用、或組合使用2種以上。 當組合使用2種以上的情況’含竣基之聚合物可舉例如：2 種以上之㈣同的絲合成分所構_含縣之聚合物、2 種以上之不同重量平均分子量的含敎基之聚合物、2種以上 之不同分散度的含羧基之聚合物等。 以下，針對該丙烯酸系聚合體進行說明。惟，本發明所使 用的丙烯酸系聚合體並不侷限於以下。 作為上述（曱基）丙烯酸醋可舉例如：（甲基)丙稀酸甲酉旨、 (曱基）丙烯酸乙酯、（曱基）丙烯酸丙醋、（曱基）丙烯酸丁酯、 (曱基）丙婦酸己酯、（曱基）丙烯酸2_乙基己酯、（曱基）丙烯 酸環己醋等烧基瘦數1〜20、較佳1〜1〇的脂肪族（曱基）丙婦 酸酯；（曱基）丙烯酸节酯等芳族（甲基）丙烯酸酯；（曱基）丙 烯酸二乙基胺基乙酯、（曱基）丙烯酸二曱基胺基乙酯等含胺 101106904 11 201245870 基之（曱基）丙烯酸醋；（曱基）内缔酸經乙醋 經丙醋等含經基之（曱基)丙歸動 土）兩烯酸 醋、（曱基)丙稀酸四氫糠醋等，該等可單獨’、’:二敗乙 用2種以上。 或組合使 上述乙稀性不飽和叛酸最好使用例如：丙鱗、甲 酸、巴豆酸等單麟，亦可使用例如：順了烯二^、2 = 二酸、衣康酸等二麟、或該等的去水物、W，該等可? 獨使用、或組合使用2種以上。其中，特佳係丙歸酸甲= 丙烯酸。 土 作為上述其他可共聚合的單體，可舉例如：（曱基 胺、（曱基）丙烯酸-2,2,3,3-四氟丙醋、丙烯醯胺、二丙嗣丙 烤醯胺、笨乙稀、α·曱基笨乙歸、乙稀基萘、乙縣環己燒、 乙烯基甲苯、醋酸乙烯酯、烷基乙烯醚、（曱基）丙烯腈等， 該等可單獨使用、或組合使用2種以上。 關於該丙烯酸系聚合體.，係從解像性、密接性、底腳發生 抑制、及剝離性的觀點而言，重量平均分子量較佳為〇,5萬 〜20萬、更佳1萬〜10萬’酸值較佳為1〇〇〜3〇〇mgKOH/g、 更佳 120〜250mgKOH/g、特佳 140〜190mgKOH/g。另外，重 量平均分子量(Mw)係使用GPC(凝膠滲透色層分析儀）裝 置’針對乾燥聚合物的THF(四氫呋喃）溶解液依照聚苯乙烯 基準進行測定的值。 101106904 12 201245870 該酸值係為中和聚合物lg所需要之K〇H(氫氧化鉀）的重 量，例如係藉由對使溶解於曱醇等醇類、或丙酮、曱乙酮等 酮類、或料的混合溶射之聚合物，進行巾和滴定而測得。 若該重量平均分子量過小，則有硬化後的感光性樹脂組成 物變脆的傾向，反之若過A，财解像性、光阻剝離性降低 的傾向。又，若上述酸值過小，則有抑制解像性、光阻剝離 性降低的效果趨弱之傾向，反之若過大，則有抑制硬化光阻 之細線密接性降低的效果趨弱之傾向。 上述丙烯酸系聚合體的玻璃轉移溫度（Tg) t堡為 3〇〜150°C範圍、更佳60〜12(rc範圍。若玻璃轉移溫度過低， 則感光性樹脂組成物容易流動，當作為光阻薄膜並形成捲筒 狀時有引起邊緣熔接的傾向，反之，若玻璃轉移溫度過高， 則當使用作為光阻薄膜時’有對基材表面之凹凸的追蹤性降 低之傾向。 該玻璃轉移溫度(Tg)係可利用DSC(Differential Scanning Calorimetry，微分掃描熱量計）進行測定，或當黏結劑聚合 物的共聚合單體之均聚物之玻璃轉移溫度為已知的情‘況，可 使用Fox公式計算出。本發明係採用依F〇x公式計算出者。 [數1](wherein the cardinic system or CH3 in the formula: R2 and R3 are groups independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and a dentate group, and may also be bonded to each other by Rz and R3. Forming a ring-containing β-containing system containing N represents an alkylene group having a carbon number of 丨1 to 1 Å, or a polyoxyalkylene group represented by (C2H4〇)m 4(c3H6〇)n and m and η are each an integer of 1 to 10, respectively. The alkyl group, the polyoxyalkylene group is a random polymerization or a block polymerization. [3] The photosensitive resin composition as described in [1] or [2], the towel, (8) having an amine group and photopolymerizable The single system contains 0.01 to 30 parts by weight based on 1 part by weight of the (Α) binder polymer. [4] The photosensitive resin composition according to any one of [1] to [3], wherein '(D) a benzoic triazole derivative having a carboxyl group is contained in 100 parts by weight of the binder polymer' 〇.〇 1 to 2 parts by weight. [5] The photosensitive resin composition according to any one of [1] to [4] wherein, in the 101106904 8 201245870, the (A) binder polymer has a carboxyl group and has an acid value of 100 to 300 mgKOH/g. . [6] A photoresist film comprising a photosensitive hard-to-treat layer composed of the photosensitive resin composition described in (1) to (attachment), and a support layer. [7] A method of forming a photoresist pattern by forming a photosensitive resin composition layer on a substrate using a photoresist film described in the above, and performing exposure after exposure. [8] A method of forming a conductive pattern, comprising: forming a photosensitive resin composition layer on a circuit forming substrate by forming a photoresist film as described above, and performing development by exposure to form a photoresist a pattern; and the above-described f-channel forming substrate on which the photoresist (4) has been formed is caught or plated, and the photoresist pattern is peeled off. (Effect of the Invention) The photosensitive resin composition and the photoresist film of the present invention have excellent resolution and adhesion, and have an effect that the foot of the cured photoresist after development is extremely small and the peeling property is also good. Therefore, by using the method of forming the photoresist pattern of the photoresist film of the present invention and the method of forming the conductor pattern, the effect of reducing the peeling failure of the photoresist pattern and the peeling of the conductor pattern (wiring) can be obtained. [Embodiment] Hereinafter, the present invention will be specifically described. In the present specification, '(meth)acrylyl means propylene or its corresponding mercaptopropenyl; (mercapto) acrylate means acrylate or its corresponding 101106904 9 201245870 decyl acrylate; The methyl) acrylonitrile group means an acryl fluorenyl group or a corresponding fluorenyl fluorenyl group thereof. [Photosensitive Resin Composition] The photosensitive resin composition of the present invention comprises: (A) a binder polymer, (B) an amine group-containing photopolymerizable monomer, and (c) a photopolymerization initiator; And 1) a slow-based base and a three-wow derivative. (A) The binder polymer may, for example, be an acrylic polymer, a styrene polymer, a % oxygen polymer, a guanamine polymer, a guanamine epoxy polymer, an alkyd polymer, or a polymerization. One type of these polymers may be used alone or two or more types may be used in combination. The polymer which is preferably contained in the above polymers can be exemplified by an acrylic acid polymer, a polyglycol polymer, a polyamine polymer, and an epoxy resin. The polymer or the like is preferably an acrylic polymer composed of: (A, W, dilute acid S, and ethylenic unsaturation, and optionally other copolymerizable monomers). The content of the (mercapto) acrylate-based constituent unit [(the ratio of the metformin acid to the total polymerizable monomer used): =: the resolution of the raw material and the amount of the stripping amount. , j further contains 2 to 6G mass parts, and particularly contains I% quality 101106904 201245870 case), which is based on resolution, adhesion, ± raised foot, and peelability. 50 parts by mass, more preferably 15 to 4 parts by mass, and particularly preferably 18 to 3G parts by mass, and the content of the material is over/there is a tendency to develop and the peeling time becomes longer; On the other hand, if it is too much, the developer resistance may be lowered and the adhesion may be lowered. Further, other copolymerizable monomers may be used. The content of the basic constituent unit (the ratio of the other copolymerizable monomer to the total polymerizable monomer used) is preferably from 10 to 80 parts by mass, more preferably from 2 to 7 parts by mass, particularly It is preferable to contain 30 to 60 parts by mass. These slow-group-containing polymers may be used singly or in combination of two or more. When two or more types are used in combination, the thiol-containing polymer may be, for example, two or more kinds. (4) The composition of the same silk composition: a polymer containing a county, a polymer containing two or more kinds of fluorenyl groups having different weight average molecular weights, a polymer having two or more different degrees of dispersion, and the like. The acrylic polymer to be used in the present invention is not limited to the following. The (meth)acrylic acid vinegar may, for example, be a (meth)acrylic acid methyl group or a Ethyl acrylate, (mercapto) acrylic propylene vinegar, (butyl) butyl acrylate, (mercapto) hexyl hexanoate, (meth)acrylic acid 2-ethylhexyl acrylate, (fluorenyl) acrylate Fat such as vinegar and soaked fat 1~20, preferably 1~1〇 Group (mercapto) propionate; aromatic (meth) acrylate such as (fluorenyl) acrylate; diethylaminoethyl (meth) acrylate, dimethyl fluorenyl (mercapto) acrylate Ethyl ester and other amines 101106904 11 201245870 based on (mercapto) acrylic vinegar; (mercapto) internal acid via ethyl vinegar via propyl vinegar, etc. containing sulfonic acid (mercapto) propionate soil) oleic acid vinegar, (曱Base) tetrahydroanthracene vinegar, etc., which can be used alone or in combination with two or more types. Or a combination of the above-mentioned ethylenic unsaturated tauic acid is preferably used, for example, a single lining such as acrylonitrile, formic acid or crotonic acid, and may also be used, for example, bis- ene, 2 = diacid, itaconic acid, etc. Or such dehydrated materials, W, these may be used alone or in combination of two or more. Among them, the special best is AMD = acrylic. As the other copolymerizable monomer, the soil may, for example, be: (decylamine, (mercapto)acrylic acid-2,2,3,3-tetrafluoropropane vinegar, acrylamide, dipropylene acetonide , stupid ethylene, α·曱基笨乙归, ethylene naphthalene, Yixian cyclohexanone, vinyl toluene, vinyl acetate, alkyl vinyl ether, (fluorenyl) acrylonitrile, etc., can be used alone In the case of the acrylic polymer, the weight average molecular weight is preferably 〇, 50,000 to 20 from the viewpoints of resolution, adhesion, inhibition of the foot, and peelability. 10,000, more preferably 10,000 to 100,000' acid value is preferably 1 〇〇 to 3 〇〇 mgKOH / g, more preferably 120 to 250 mg KOH / g, particularly preferably 140 to 190 mg KOH / g. In addition, weight average molecular weight (Mw) The value measured by a GPC (Gel Penetration Chromatography Analyzer) apparatus 'THF (tetrahydrofuran) solution for a dry polymer according to a polystyrene standard. 101106904 12 201245870 The acid value is required to neutralize the polymer lg. The weight of K〇H (potassium hydroxide) is, for example, dissolved in an alcohol such as decyl alcohol, or acetone or hydrazine. A polymer such as a ketone or a mixture of ketones or a mixture of materials is measured by a towel and titration. If the weight average molecular weight is too small, the photosensitive resin composition after curing tends to become brittle, and vice versa. When the acid value is too small, the effect of suppressing the resolution and the peeling resistance is weakened, and if it is too large, the curing resist is suppressed. The effect of lowering the adhesion of the fine line is weaker. The glass transition temperature (Tg) of the above acrylic polymer is in the range of 3 〇 to 150 ° C, more preferably 60 to 12 (rc range. If the glass transition temperature is too low, Then, the photosensitive resin composition easily flows, and when it is formed into a roll shape as a photoresist film, there is a tendency to cause edge fusion. Conversely, if the glass transition temperature is too high, when used as a photoresist film, there is a surface to the substrate. The tendency of the tracking property to be lowered is reduced. The glass transition temperature (Tg) can be measured by DSC (Differential Scanning Calorimetry), or when the copolymer polymer is copolymerized. The glass transition temperature of the homopolymer is known, and can be calculated using the Fox formula. The present invention is calculated using the F〇x formula. [Number 1]
Fox 公式 + = ! + 1 ·Fox formula + = ! + 1 ·
Tg Ta Tb (Tg係表示共聚合體的玻璃轉移溫度。Wa、wb、. · ·係表 101106904 ^ 201245870 不a成分、b成分、· · ·的重量分率。Ta、Tb、· · ·係表 丁 a成刀、b成分、···的均聚物之玻璃轉移溫度。） (B)具胺基且可光聚合之單體可舉例如：N，N-二曱基（曱基) 醯胺、N，N-二乙基（甲基）丙烯醯胺、二曱胺基丙基（曱基） 丙婦醜胺、二乙胺基丙基（甲基)丙稀醯胺、正丙基（曱基）丙 稀酿胺、異丙基（曱基)丙婦醯胺、N-(甲基)丙烯醯基味琳等， 此外尚可舉例如從下述一般式(I)所示群組中選擇至少一種 之可光聚合的残和化合物n從減少底腳之效果的觀 2而。’較佳係使用下述一般式⑴所示之可光聚合的不飽和 化合物。 [化2] ( Ύ^Ν)/Χ\Ν〆仏⑴ R3 (其中，式中的4系Η或CH3。M R3係表示分別獨立之 ，氫原子、烧基、絲基及•基所構成群組巾選擇的基，亦 可由1與r3相互鍵結形成含N的環。X係表示碳數㈣ 之伸燒基、或依(阳也或咖仇所示且m、n分別為 1〜10之整數㈣氧化狀基，聚氧化伸縣係無規聚合或 嵌段聚合。） 上述-般式(I)中，式中的Ri係H或CH3。R2及R3係表 101106904 201245870 示分別獨立之從氫原？、貌基、炫氧基及齒基所構成群組中 選擇的基，亦可由R2與R3相互鍵結形成含1^的環❶烷基及 燒氧基的碳數通常係1〜10、較佳1〜6。X係表示碳數卜忉、 較佳1〜6之伸烷基、或依所示且m、n 分別為1~1〇之整數的聚氧化伸烷基。聚氧化伸烷基可為無 規聚合、亦可為嵌段聚合。） 上述一般式（I)所示化合物具體可舉例如：（曱基）丙烯酸 N，N-二曱基胺基曱酯、（曱基）丙稀酸n，N-二曱基胺基乙酯、 (曱基）丙烯酸Ν，Ν·二曱基胺基丙酯、（甲基）丙烯酸N，N_二曱 基胺基丁酯、（甲基）丙烯酸N，N-二甲基胺基戊酯、（曱基）丙 烯酸N，N-二甲基胺基己酯、（曱基）丙烯酸N，N_二曱基胺基 庚酯、（曱基）丙烯酸N，N-二曱基胺基辛酯、（曱基）丙烯酸 N，N-二曱基胺基壬酯、（甲基）丙烯酸n，N-二曱基胺基癸酯、 (曱基）丙烯酸-N，N-二乙基胺基曱酯、（曱基）丙烯酸n，N-二乙 基胺基乙酯、（曱基）丙烯酸_n,n-二乙基胺基丙酯、（曱基） 丙烯酸Ν，Ν·二乙基胺基丁酯、（曱基）丙烯酸_Ν，Ν:乙基胺 基戊酯、（曱基）丙烯酸Ν，Ν-二乙基胺基己酯、（甲基）丙烯酸 -Ν，Ν-二乙基胺基庚酯、（曱基）丙烯酸ν，Ν-二乙基胺基辛 酯、（曱基）丙烯酸-Ν，Ν-二乙基胺基壬酯、（曱基）丙烯酸Ν，Ν-二乙基胺基癸酯等（曱基）丙烯酸二烷基胺基烷基酯；（曱基) 丙烯酸Ν-正丙基胺基乙酯、（甲基）丙烯酸Ν-異丙基胺基乙 酯、（甲基）丙烯酸Ν-第三丁基胺基乙酯、（曱基）丙烯酸Ν-101106904 15 201245870 正丁基胺基乙醋等（甲基）丙烯酸單烷基胺基烷基酯；N，N_二 甲基胺基聚乙二醇（甲基）丙烯酸酯、N，N-二乙基胺基聚乙二 醇（曱基）丙烯酸酯、N，N_二曱基胺基聚丙二醇（曱基）丙烯酸 酯、N，N-二乙基胺基聚丙二醇（曱基）丙烯酸酯等二烷基胺基 聚驗（曱基）丙稀酸酯；（甲基）丙烯酸咪啉基乙酯等環狀（曱基) 丙烯酸胺基燒基酿。纟中，較佳係使用（甲基）丙稀酸二院基 胺基烧基醋、更佳係（曱基）丙稀酸二乙基胺基烧基醋。 另外，從取得容易度的觀點而言，最佳係上述一般式中， R!為ch3、r2與r3均為C2h5、χ為C2H5的化合物，亦即 甲基丙稀酸N，N-二乙基胺基乙醋[例如共榮社化學(股)製、 商品名：LIGHT ESTER DE]。 此處’硬化光阻的底腳發生推測係硬化較弱的半硬化光阻 之酸性基其中-部分與顯影液產生反應而未被除去，在顯影 後的乾燥時，半硬化光阻移往光阻下部而再附著所致。⑻ 可光聚合的單體之胺基’係在感光性樹脂組成物中與⑷黏 結劑聚合物中義絲產生巾和反應，而覆蓋(A)黏結劑聚 合物的酸絲，賊升耐顯驗性，並減少半硬化光阻的再 附著、亦即可使底腳變小。又，因為⑻的單體具有可光聚 合的構造’所以亦可期待硬化度提升、密接性提升。因此， 作為⑻的單體係若具有胺基且能光聚合的構造，則可期待 同樣的效果。 另外’使用於光阻薄膜用途的感光性樹脂組成物中，使用 101106904 16 201245870 (B)具胺基且可光聚合之單體作為可光聚合的單體成分的情 形，係因考慮到有對鍍浴、蝕刻液等酸性溶液造成污染等不 良情況的顧慮，而習知均未採行。但是，本發明中，特別大 膽使用具有胺基的單體，意外地發現並未出現不良情況，可 達成本發明目的。 本發明中，上述(B)具胺基且可光聚合之單體的含有量， 係相對於(A)黏結劑聚合物1〇〇重量份，較佳為〇.〇1〜30重 量份、更佳0.1〜25重量份、特佳〇.5〜20重量份、最佳1〜15 重量份。若該含有量過少，則有減少底腳的效果不足的傾 向’反之若過多，則有解像性降低的傾向。 (B)具胺基且可光聚合之單體亦可與下述所示之可光聚合 的單體一同使用。例如作為具有1個聚合性不飽和基的單 體可舉例如·（曱基）丙稀酸2-經乙g旨、（曱基）丙稀酸2·經 丙酯、（甲基）丙烯酸2-羥丁酯、（曱基）丙烯酸2-苯氧基-2-羥丙酯、2-(曱基）丙烯醯氧基-2-羥丙基酞酸酯、（曱基）丙烯 黾3-氣-2-羥丙酯、甘油單（曱基）丙烯酸酯、2_(甲基）丙烯醯 氣基乙基酸性磷酸酯、酞酸衍生物的半（甲基）丙烯酸酯等， 該等可單獨使用、或組合使用2種以上。 又作為具有2個^^合性不餘和基的單體，可舉例如：乙 一醇二（甲基）丙烯酸酯、二乙二醇二（曱基）丙烯酸酯、四乙 〜醇二（甲基）丙烯酸酯、聚乙二醇二（曱基）丙烯酸酯、丙二 醇二（甲基）丙烯酸酯、聚丙二醇二（曱基）丙蝉酸酯、聚乙二 101106904 17 201245870 醇•聚丙二醇二（甲基）丙烯酸酯、丁二醇二（曱基）丙烯酸酯、 新戊二醇二（甲基）丙烯酸酯+氧化伸乙基之雙酚入型二（曱 基）丙烯酸酯+氧化伸丙基之雙酚A型二（甲基）丙烯酸酯、 含氧化伸乙基•氧化伸丙基之雙酚A型二（曱基）丙烯酸酯、 1,6-己二醇二（曱基）丙烯酸酯、甘油二（甲基）丙烯酸酯、季戊 四醇二（曱基）丙烯酸酯、乙二醇二環氧丙基醚二（曱基）丙烯 酸酯、二乙二醇二環氧丙基醚二（甲基）丙烯酸酯、酞酸二環 氧丙酯二（曱基）丙烯酸酯、羥基三曱基乙酸改質新戊二醇二 (甲基）丙稀酸醋等，該等可單獨使用、或組合使用2種以上。 其中’特佳係使用含氧化伸乙基之雙酚A型二（曱基）丙烯酸 酯、聚乙二醇•聚丙二醇二（曱基）丙烯酸酯。 再者，作為具有3個以上聚合性不飽和基的單體，可舉例 如.二羥曱基丙烷三（曱基）丙烯酸酯、季戊四醇三（曱基）丙 烯酸酯、二季戊四醇五（曱基）丙烯酸酯、三（曱基）丙烯醯氧 基乙氧基三羥曱基丙烷、甘油聚環氧丙基醚聚（曱基）丙烯酸 醋等’該等可單獨使用、或組合使用2種以上。 再者’亦可舉例如胺基甲酸乙酯（曱基）丙烯酸酯。作為胺 基甲酸乙S旨（甲基）丙烯酸酯可舉例如：由六亞曱基二異氰酸 醋、二異氰酸曱苯酯等二異氰酸酯，與例如丙烯酸2_經乙 酯、丙烯酸2-羥丙酯、寡聚丙二醇單甲基丙烯酸酯等之一 分子中具有經基與（曱基）丙烯基的含羥基之（甲基）丙婦酸 醋’以及視需要的多元醇進行反應而獲得的化合物。該等可 101106904 201245870 單獨使用、亦可併用2種以上。 本發明中，關於⑻具胺基且可絲合之單體、及 外之可光聚合之單義合計量，係相躲(彻結劑聚 酬重量份’較佳為H)，重量份、更佳3。〜_重量口严、 再更佳5G〜12G重量份、最佳6(M⑻重量份。若該含' 過少’則有硬化不足的傾向，反之若過多，則有容 ^ 流的傾仓。 v (c)光聚合起始劑可舉例如：（C1)六絲雙w街生物、 (C2)烧基胺基二苯基_生物、N_絲甘赠衍生物、。丫。定 衍生物、二胺基蒽醌等蒽醌衍生物；忱况^，抑_四芳某聯= 胺衍生物、三醋酸核黃素、二苯基酮、节基二甲基:縮醇本 噻噸酮衍生物、烷基胺基苯曱酸烷基酯、三畊衍生物、香豆 素6等香豆素魅物；三苯基膦、三曱苯基膦、三(二甲笨 基)膦、三聯苯基膦、三萘基膦、三蒽基膦、三菲基膦等二 芳基膦(triaryl phosphine)等，該等可單獨使用、或組合使用 2種以上。 (ci)六芳基雙咪唑衍生物可舉例如：2,2,_雙(2，夂二氣苯 基)_4,4’，5,5'-肆(3_甲氧基苯基）雙咪唑、2,2，-雙(2,3_二氣苯 基)·4,4'，5,5’-肆(4_甲氧基苯基）雙咪唑、2,2'-雙(2,4_二氣苯 基)-4,4’，5,5’_肆(3-甲氧基苯基)苯基雙咪唑、2,2，_雙(2,5-二氯 苯基)-4,4’，5,5，-肆(3-曱氧基苯基)雙咪唑、2,2，·雙(2,6_二氣笨 基)-4,4’，5,5'-肆(3-甲氧基苯基）雙咪唑、2,2·，4,4·_肆(2·氯苯 101106904 19 201245870 基）-5,雙（3-曱氧基苯基）雙味唾、2,2|·雙（2_氣苯 基)-4,4，，5,5’-四苯基雙輕、2,2，，4,4,_肆(2_氣苯基)_5,5，_雙^ 甲氧基苯基)雙咪。坐、2,2，，4,4’-肆(2_氣苯基)_5,5,_雙(2,3_二甲 氧基苯基)雙咪嗤、2,2，，4,4，-肆(2_氣苯基)_5,5，.雙(3,4二甲氧 基苯基)雙咪唾、2,2，·雙(2_氣苯基)_4,4，，5,5，·肆&甲氧基苯基) 雙味唾、2,2，_雙(2-氣苯基)_4,4，，5,5，·肆(3,4_二曱氧基苯基)雙 味嗤、2,2’-雙(2-氯苯基)-4,4，，5,5，-肆(3,4,5_三甲氧基苯基)雙 咪唾、2,2’-雙(2-氯苯基)-4,5-雙(3·甲氧基苯基)_4，，5,二笨夷 ㈣唾、 二苯基雙㈣、2,2’·雙（2•氣苯基)邻，4二甲氧基苯 基)-4，，5,5，-三苯基雙味吐等’其中，較佳係2,2，，4,4，_肆⑺氣 苯基)-5,5’-雙(3_曱氧基苯基）雙咪唾、2,2|，4,4|_肆(2·氣苯 基）5,5 -雙（2,3- 一甲氧基苯基）雙咪唑、2,2，_雙氣苯 基)斗(3,4·二甲氧基苯基)·4，，5,5·-三苯基雙咪4、2,2，-雙(2· 氣苯基)-4,4’，5,5’_四苯基雙咪如該村單獨使用、或組合 使用2種以上。 (c2)烧胺基二笨基酮衍生物可舉例如：μ·雙(二乙基胺基 苯基酉同、3,3，-二甲基甲氧基二苯基g同、 胺基)二苯基轉，其中較佳係4,4，雙(二乙基胺基)二 酮，該等可單獨使用、或組合使用2種以上。 土 本發明的感絲樹脂組成物係從高感度化的觀點而言，作 為光聚合起始劑(C)，較佳係至少含有(C1)六芳基雙味唾衍 101106904 20 201245870 生物、更佳係含有（ci)六芳基雙咪σ坐衍生物及其他的光聚合 起始劑、特佳係含有（C1)六芳基雙咪唑衍生物及(C2)烷基胺 基二苯基嗣衍生物。 (C )光聚合起始劑的含有量係相對於(A)黏結劑聚合物1 〇 〇 重量份，較佳為1〜20重量份、更佳2〜16重量份、特佳3〜12 重ϊ：份。若(C)光聚合起始劑的含有量過少，則有無法獲得 必要的感度、解像性、及密接性之傾向；反之若過多，則有 在感光性樹脂組成物中生成不溶物質的傾向。 在併用（C1)六芳基雙咪唑衍生物及其他的光聚合起始劑 之情況，例如併用（ci)六芳基雙咪唑衍生物及(C2)烷基胺基 一苯基酮衍生物的情況，係相對於(A)黏結劑聚合物1〇〇重 量份，（C1)六芳基雙咪唾衍生物較倖為丨〜16重量份、更佳 2 13重量伤特佳3〜1〇重量份，（C2)烧胺基二苯基酮衍生 物較佳為G.G1〜4重量份、更佳G.G2〜3重量份、特佳0.06〜2 重量份。 (D)具叛基之笨并三唾衍生物適合使用例如：4缓基苯并 三唾、5_減苯并三唾、HU·二誠乙基）苯并三峻、 1-(2'，3，-二缓基丙基）苯并三唾、1·((雙(2-乙基己基)胺基）甲 基)-1Η-笨并三唾紐，料可單獨使用、或組合使用2種 以上。另外’從取得容易度的觀點而言，更佳係、4·叛基笨 并三唑、5-羧基笨并三唑。 已知苯并一坐仿生物係與銅金屬的親和性良好，一般認為 101106904 21 201245870 在銅基材上積層了光阻薄膜之後，苯并三唑衍生物會配位於 銅基材上。具鼓基之苯并三嗤衍生物係由於剝離時的強驗水 溶液與該羧基產生中和反應’所以推測可輕易地將光阻從銅 基材的界面上剝離。 (D)具羧基之苯并三唑衍生物的含有量係相對於(A)黏結 劑聚合物100重量份，較佳為0.01〜2重量份、更佳0 044 6 重量份、特佳0.08〜1重量份。若(D)具羧基之苯并三唑衍生 物的含有量過少，則有剝離性降低的傾向，反之若過多，則 有密接性降低、底腳亦變大的傾向。 再者，本發明中，從兼顧底腳減輕及剝離性的觀點而言， 重要的疋併用上述(B)成分與上述(D)成分，上述(b)成分與 上述(D)成分的重量比率(B)/(D)，較佳係}以上且5〇〇以下 的範圍。特佳係重量比率(B)/(D)3以上且20〇以下的範圍、 更佳係重量比率（B)/(D)為5以上且50以下的範圍。若該此 率過低，則雖可輕易地剝離，但卻有底腳變大的傾向，反之 若過高，則雖能抑制底腳發生，但有剝離趨於困難的傾向« 本發明的感紐樹脂組成物中，除了上述(a)〜(D)化合物 之外，車乂佳係更進〜步含有染料’該染料可舉例如:結晶紫 孔雀綠、孔雀綠色幾、煙綠、鑽石綠、專利藍、甲基紫(CHD olet)，、隹夕利亞、維多利亞純藍、油溶藍、驗性藍扣 薔薇笨胺、副品紅、乙烯紫等著色染料；參⑷二曱基胺基 甲基苯基）曱峨色隱性結晶紫]、參⑷二甲基胺基-2-甲J 101106904 22 201245870 苯基）曱烷[無色隱性孔雀綠]、螢光黃母體染料(fluoran dye) 等無色隱性染料等等。 再者’本發明的感光性樹脂組成物中，亦可含有齒化合 物。_化合物可舉例如：演戊烧(amyl bromide)、、;臭異戊烧、 〉臭化異丁烯、溴化乙烯、二苯基溴化曱烷(diphenyl methyl br〇mide)、溴曱苯（benzyl bromide)、二溴曱烷（methylene bronude)、三溴甲基苯砜、四溴化碳、參(2,3_二溴丙基)磷酸 知、二氯乙醯胺、碘戊烷、碘異丁烷、三氯_2,2_雙（對 氣笨基）乙烷、氣化三讲化合物等。 再者，本發明的感光性樹脂組成物中，視需要亦可含有可 塑劑等添加劑。此種添加劑可舉例如：聚乙二醇、聚丙二醇、 i氧化伸丙基聚氧乙烯醚、聚氧化伸乙基單曱醚、聚氧化伸 丙基單曱醚、聚氧化伸乙基聚氧化伸丙基單曱醚、聚氧化伸 乙基單乙醚、聚氧化伸丙基單乙醚、聚氧化伸乙基聚氧化伸 丙基單乙醚等二醇·酯類；二乙基酞酸酯等酞酸酯類；鄰曱 笨磺酸醯胺、對甲苯磺酸醯胺、擰檬酸三丁酯、檸檬酸三乙 鲳、乙醯基檸檬酸三乙酯、乙醯基擰檬酸三正丙酯、乙醯基 檸檬酸三正丁酯等。 為了提升本發明感光性樹脂組成物的熱安定性、保存安定 性，亦可使感光性樹脂組成物含有自由基聚合終止劑。自由 基聚合終止劑可舉例如：對曱氧基酚、氫醌、五倍子酚、萘 胺 '第三丁基兒茶酚、氯化亞銅、2,6_二第三丁基對曱酚、 101106904 23 201245870 U·亞曱基”6•第三丁基盼）、2,2|亞曱基雙⑷乙基 -6-第三丁基紛）、亞确基苯基經胺紹鹽、及二苯基亞硝胺等。 本發明的感光性樹脂組成物係視需要，亦可溶解於甲醇、 乙醇、丙酮、甲乙_、甲基赛路蘇、乙基賽路蘇1苯、、 Ν，Ν-二曱基曱醯胺、丙二醇單f叫溶劑或該等的混合溶劑 中，形成固形份30〜60重量％左右的溶液。可將該溶液使用 作為後述光阻薄膜之用於形成感紐樹脂組成物層的塗佈 液。另。外，將該塗佈液塗佈於電路形成用基板等基板上使 其乾燥亦可形成感光性樹脂組成物層，但從作業效率等觀 點而言’較佳係用於形成後述絲薄膜之感光性樹脂組成物 層。 再者本發明的感光性樹脂組成物中，亦可適當含有密接 性賦予劑、抗氧化劑、熱聚合終止劑、表面張力改質劑、安 定劑、鏈轉移劑、消泡劑、難燃劑等添加劑，在含有的情況， 。亥3有量係相對於(A)〜(D)成分的固形份總量質量份’ 較佳係分別含有f量份、更佳含有㈣〜15質量 份、特佳含有0.03〜1〇質量份。該等可單獨使用、或組合使 用2種以上。 〔光阻薄膜〕 本發明的光阻薄膜係含有：由感光性樹脂組成物構成的感 光性樹脂組成物層、與支撐層。此處所使用的支撐層，最好 為能使從曝光光源所放射出之光穿透的透明者。 101106904 24 201245870 作為此種支㈣可舉例如：聚對苯二曱酸乙二㈣膜'聚 乙烯醇薄膜、聚氯乙烯薄膜、氯己烯共聚合體薄膜、聚偏二 氣乙烯薄膜、偏二氣乙烯共聚合薄膜、聚曱基丙烯酸甲醋共 聚合體薄膜、聚苯乙烯薄膜、聚丙烯腈薄膜、苯乙埽共聚合 體薄膜、聚醯胺薄膜、纖維素衍生物薄膜等，其中較佳係聚 對苯一m乙二g旨薄膜^該等薄膜視需要亦可使用經延伸 者。 支稽層的霧值較佳係在5以下。支揮層的厚度係越薄者， 在影像形成性與經濟性方面越有利，但因為必需維持強度， 所以較佳係使用1G〜3Gpm者。光阻_的感光性樹脂組成 物層厚度，係依照用途而有所不同，較佳係5〜刚师、更 佳7〜6〇μΐη、特佳10〜50μιη。若感光性樹脂組成物層過薄， 則有膜強度過低的傾向；反之若過厚，則有密接性、感度、 解像性降低的傾向。 本心月的光阻薄膜係視需要，亦可在感光性樹脂組成物層 之與支撲層側為相反側的表面上設置保護層。光阻薄膜所使 用之保護層的4要特性之-，係使料可輕易地從感光性樹 脂組成物層上剝離，所以關於與感光性樹脂組成物層間之密 接力，係要求保護層充分小於支撐層。保護層較佳係可使用 例如聚乙烯薄膜、聚丙烯薄膜。保護層的膜厚較佳係 * < ♦ 10〜ΙΟΟμιη、更佳 1〇〜5〇μιη。 本發明的.光阻薄膜係將含有本發明感光性樹脂組成物的 101106904 25 201245870 塗佈液，塗佈於支撐層的單面上，經乾燥，更進一步視需要， 在該塗佈面上覆蓋保護層便可製得。更具體而言，係在支撐 層的單面上，利用輥塗法、棒塗法等均勻塗佈含有本發明感 光性樹脂組成物的塗錢，再於5G〜12(rc、或依序提高溫 度的烤箱中進行乾燥而形成感光性樹脂組成物層，接著，於 該層的上面加壓積層保護層便可製得。 〔光阻圖案之形成方法〕 針對使用本發明的光阻薄膜，在基材上形成光阻圖案的各 步驟進行說明。 使用了本發明光阻薄膜的光阻圖案係經由包括有積層步 驟、曝光步驟、及顯影步驟的步驟便可形成q述例示具體 方法之一例。 作為被加工基材，在印刷佈線板製造目的時可舉例如銅结 積層板，又，在凹凸基材製造目的時，可舉例如：玻璃基材 (例如電漿顯示面板用基材、表面電解顯示器基材)、已形成 有貫通孔㈣晶圓及料基材等。所謂「電_示面板用基 材」m在玻璃基材上形成電極之後，再形成介電質層，接 著塗佈隔㈣玻璃糊’並對㈣用玻翻部分施行喷砂加 工’而形成隔壁的基材。 首先，使用層壓機施行積層步驟。在光阻薄膜具有保護層 的隋況’係在剝離保護層之後，利用層壓機將感光性樹脂組 成物層施行加熱壓接而積層於被加工基材表面上 。此時，感 101106904 26 201245870 光性樹脂組成物層可僅積層於基材表面的單面上，亦可積層 於雙面上。此時的加熱溫度一般係40〜160°C。 其次，使用曝光機施行曝光步驟。視需要剝離支撐層，再 經由光罩利用活性光施行曝光。曝光量係依照光源照度與曝 光時間而決定，亦可使用光量計進行測定。 再者，曝光步驟亦可使用直接描繪曝光方法。直接描繪曝 光方法係在未使用光罩的情況下，於基材上直接描繪並施行 曝光的方式。光源可使用例如波長350〜410nm的半導體雷 射、超高壓水銀燈。描繪圖案係利用電腦進行控制，此時的 曝光量係依照光源照度與基板移動速度而決定。 其次，視需要在剝離除去支撐層之後施行顯影。因為本發 明的感光性樹脂組成物屬於稀鹼顯影型，因而顯影時，係使 用含有碳酸鈉、碳酸鉀、氫氧化四曱銨等鹼化合物〇1〜5重 量％的驗性水溶液實施。上述驗性水溶液的pH較佳係設為 範圍而其/jnL度係配合感光性樹脂組成物層的顯影性 進行調節。藉由此顯影，感光性樹脂組成物層中的未曝光部 (除了所需圖案影像外的區域)被除去，而形成光阻圖案。另 外，上述鹼性水溶液中’亦可混入界面活性劑、消泡劑、及 用於促進顯影的少量有機溶劑等。 依照^述步驟可獲得光阻_，依航亦可更進—步施行 =〇, 3〇〇C的加熱步驟、或―硬化步驟。藉由實施該等步 ，可更進一步提升耐藥性。 101106904 27 201245870 〔導體圖案之形成方法〕 本發明導體圖案之形成方法，係使用銅箔積層板或可撓性 基板專電路形成用基板作為基板’經施行上述光阻圖案形成 之後，再經由以下步驟而實施。首先，在藉顯影而露出的基 板面上，使用鍛覆法、或触刻法等已知方法形成導體圖案。 作為施行鍍覆時的鍍覆方法’可舉例如：硫酸鋼鍍覆、焦 磷酸鍍銅等鍍銅；高分佈鍍焊等鍍焊；瓦特浴(硫酸鎳-氣化 鎳)鍍覆；胺磺酸鎳等鍍鎳；硬鍍金、軟鍍金等鍍金等等。 施行鍍覆時，較佳係使用脫脂劑、軟蝕刻劑等鍍覆前處理劑 施行前處理。又，蝕刻通常係使用氣化銅_鹽酸水溶液、三 氯化鐵-鹽酸水溶液等酸性蝕刻液，依照常法 使用氨系祕刻液。 待鍍覆或蝕刻結束後，使用由含有氫氧化鈉、 鹼化合物G.1〜1G重量％左右濃度的鹼水溶液所出化金 離液、或Μ重歸溶液的有機胺系剝 = 乙醇胺為主成分者），施行光阻圖案的剝離除去。糸上」 另外，當使用光阻圖案在貫通孔内填充錢 亦可在未去除光聞案之情況下，於級、障况& 膜。於鍍覆的情況，係接著施行快轴刻。㈣以上積層導 可形成印刷佈線板等電路基㈣導體圖^ 上的步舉 [實施例;j 惟本發明 以下’列舉實施㈣對本發明進行更具體說明， 101106904 28 201245870 以下實施例。另外 在不逾越其主旨的前提下，並不揭限於 以下「％」、「份」均係指重量基準。 1)評價用樣品之製作 實施例及比較例的光阻薄膜係依如下述進行製作。將表^ 所示之感光性樹脂組成物的歸姆成固形份量Μ重量 % ’經充分搜拌、混合，再於作於支樓薄膜的厚Μ吨聚對 苯二甲酸乙二酯(PET)薄耻，使用赫器依乾燥後的塗佈 膜厚成為25μπι方式施行塗佈。於6〇°c、90〇c的烤箱分別施 行乾燥2分鐘，再從該感光性樹脂組成物層的上方被覆厚度 21 μπι t乙烯薄膜’獲得光阻薄膜。針對所獲得之光阻薄膜， 如下述評價以下的項目。 [表1] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 比較例 1 比較例 2 比較例 3 比較例 4 P-1 250 250 250 250 250 250 一 250 250 250 — P-2 — 一 — — — — 250 一 — — 250 M-1 10 20 10 10 10 — 10 一 10 — — M-2 一 — — — — 10 — 一 — 一 一 M-3 63 53 63 63 63 63 63 73 63 73 63 M-4 10 10 10 10 10 10 10 10 10 10 10 J-1 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 Ί-2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 D-1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 卜0.4 0.4 D-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 T-1 0.3 0.3 0.6 — — 0.3 0.3 — 一 0.3 一 T-2 一 — — 0.3 — — — — — — 一 T-3 — 一 一 — 0.3 — — — — — 一 T-4 — — 一 — — — 一 一 0.3 一 一 F-1 7 7 7 7 7 7 7 7 7 7 7 表中的數值係表示重量份。 29 101106904 201245870 表1中的符號係表示如下。 〔（A)黏結劑聚合物〕 • P-1 :使甲基丙烯酸/曱基丙烯酸曱酯/苯乙烯（重量比 22/38/40)進行聚合而獲得，重量平均分子量42,000的40% 曱乙酮溶液。固形份酸值= 143.4mgKOH/g。玻璃轉移溫度 =113.9°C。 • P-2 :使曱基丙烯酸/甲基丙烯酸曱酯/苯乙烯（重量比 28/32/40)進行聚合而獲得，重量平均分子量34,000的40% 曱乙酮溶液。固形份酸值=182.5mgKOH/g。玻璃轉移溫度 =118.1〇C 0 〔可光聚合的單體〕 • M-1 :曱基丙烯酸N，N-二乙基胺基乙酯 CH2=CH(CH3)COOC2H5N(C2H5)2〔共榮社化學公司製、商品 名：LIGHT ESTER DE〕 • M-2 :曱基丙烯酸N-第三丁基胺基乙酯 CH2=CH(CH3)COOC2H5NH(t-C4H9) •M-3 :在雙酚A的二侧分別加成了平均5莫耳之氧化伸 乙基的含氧化伸乙基之雙酚A型二曱基丙烯酸酯〔新中村 化學工業公司製、商品名：BPE-500〕 • M-4 :九乙二醇二曱基丙烯酸酯〔新中村化學工業公司 製、商品名：9G〕 〔光聚合起始劑〕 101106904 30 201245870 1 . 2,2-雙(2-氯苯基)-4,4’，5,5'-四笨基雙咪口坐 • 1-2 : 4,4’-雙（二乙基胺基)二苯基酮 〔染料〕 • D-1 :孔雀綠 • D-2 :無色隱性結晶紫 〔苯并三唑衍生物〕 • T-1 : 4-羧基苯并三唑 • T-2 : 1-(1’，2’·二羧基乙基）苯并三唑 • T-3 · 1-((雙(2·乙基己基)胺基）甲基)_1H_苯并三唑羧酸 • T-4 :苯并三哇 〔溶劑〕 • F·1 :曱乙酮 2)評價方法 將上述光阻薄膜的聚乙烯薄膜予以剝離後，依感光性樹脂 組成物層面接觸到銅箔基板上的方式，依層壓輥溫度 i〇〇°c、該輥壓〇.3MPa、積層速度丨2m/min施行積層。然 後’使用依使光穿透量呈階段性減少方式製成的負片 (Stouffer 21級曝光尺），利用具有超高壓水銀燈的平行曝光 機(0RC製作所公司製、商品名：EXM-1201)，對Stouffer 21 級曝光尺(Stouffer 21 step tablet)整面施行均勻曝光。曝光 後’經15分鐘後剝離pet薄膜，在27。(：下，將0.7%碳酸 納水溶液依中斷點（breakpoint)(未曝光部分呈完全溶解的時 101106904 31 201245870 間)之2倍顯影時間進行喷灑，將未曝光部a予以溶解除去 而獲付硬化光阻影像。利用各曝光量與顯影後的殘留級數， 調查StC>Uffer 21級曝光尺經顯影後的殘存步進級數成為6 級時的曝光量(mj/cm2)。 〔解像性〕 曝光時的玻璃鉻光罩(chromium mask)係使用曝光部與未 曝光部之線寬為1 ·· 1比率的線圖案光罩，依曝光尺級數成 為6級的曝光里施行曝光，並顯影^將硬化光阻圖案形成正 常時的最小光罩線寬(㈣設為解像性的值。 〔密接性〕 、作為曝光時的光罩薄難使用單獨只有曝料的線圖案 遮罩，依曝光尺級數成為6級的曝光量施行曝光，並顯影。 將硬化光阻圖案正常形成時的最小遮罩線寬㈣設為密接 性的值。 〔顯影後的硬化光阻之底腳〕 對基板上所積層的光阻_，透過絡玻璃遮罩依曝光尺級 數成為6級的曝光量施行曝光，並㈣。針對所獲得之光阻 圖案的線寬/線距=10/10_、線之底腳，依下述賦予等級。底 腳尾跡（skirt trailing)係利用SEM(日本電子公司製、商品 名：JSM-6390)，測定硬化光阻圖案的底部的底腳邊寬度。 ◎:在硬化光阻圖案的底部發現一以下的底腳尾跡。 〇：在硬化光阻圖案的底部發現超過一且3卿以下的 1〇1106904 201245870 底腳尾跡。 X :在硬化光阻圖案的底部發現超過3μπι的底腳尾跡。 〔剝離性〕 對基板上所積層的光阻薄膜，依曝光尺級數成為6級的曝 光量’對4cmx4cm正方形圖案施行曝光。依最小顯影時間 的2倍顯影時間施行顯影後，施行硫酸銅鍍覆。再利用 50°C、3重量％的苛性鈉水溶液施行喷霧，並測定硬化光阻 的剝離時間，針對硬化光阻的剝離性如下述賦予等級。 光阻剝離時間為50秒以下。 〇：光阻剝離時間超過50秒且為60秒以下。 x :光阻剝離時間超過60秒。 3)評價結果 實施例及比較例的評價結果係如表2所示。 [表2] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 比較例 1 比較例 2 比較例 3 比較例 4 解像性 9 9 9 9 9 9 9 11 11 11 11 密接性 6 6 6 7 6 6 7 9 8 9 9 底腳 ◎ ◎ 〇 ◎ ◎ ◎ 〇 X 〇 X X 剝離性 ◎ ◎ ◎ ◎. 〇 ◎ ◎ X X 〇 〇 如表2所示，實施例1〜7的感光性樹脂組成物係解像性、 密接性均優異。再者，因為硬化光阻的底腳較小，故在後續 步驟的蝕刻與鍍覆時不易造成障礙。又，因為剝離性亦良 好，所以可確保安定的生產性。 另一方面，比較例1〜4的感光性樹脂組成物係解像性、密 101106904 33 201245870 接性均較差。又，比較例1、3、4的感光性樹脂組成物係因 為硬化光阻的底腳較大，故在後續步驟的蝕刻與鍍覆時有造 成障礙的可能性。又，比較例1、2的感光性樹脂組成物係 因為剝離性亦差，因而難以獲得安定的產能。 以上雖針對本發明參照詳細内容及特定之實施態樣進行 了說明，惟在不脫逸本發明精神與範疇的前提下，可進行各 種變更與修正，此係熟習此技術者可輕易思及。 本申睛案係以2011年3月3日所提出申請的日本專利申 請案（特願2011-046373)為基礎，參照其内容並引入於本案 中。 (產業上之可利用性） 本务明的感光性樹脂組成物及光阻薄膜係具有解像性及 密接ί·生均良好、且顯影後的硬化総之底腳極小、剝離性亦 = 所以’本發明的感光性樹脂組成物及光阻薄膜 可適用在印刷佈線板、引線框架、半導體封裝等的製造、金 屬的精密加工尊領诚Φ 寻貝域中’可有效利用作為蝕刻光阻、鍍覆光 阻專光阻材料。 【圖式簡單說明】 光【’係田使用習知光阻薄膜，在基板(銅薄膜)上形成硬化 生而1、形成鍍覆(銅佈線）時，因底腳(硬化光阻底腳部）發 丨t成Μ題的7剖視。A_影後’ B係鍍覆後，（ 你刹離後的剖視圖。 101106904 34 201245870 【主要元件符號說明】 1 硬化光阻 2 基板(銅薄膜） 3 底腳 4 鍍覆(銅佈線） 101106904 35Tg Ta Tb (Tg is the glass transition temperature of the copolymer. Wa, wb, . . . ) is a weight fraction of a component, b component, · · · · Ta, Tb, · · · The glass transition temperature of the homopolymer of the b-forming agent, the b component, and the .... (B) The monomer having an amine group and photopolymerizable may, for example, be N,N-diindenyl (fluorenyl) fluorene Amine, N,N-diethyl(meth)acrylamide, dimethylaminopropyl (decyl) propyl guanamine, diethylaminopropyl (meth) acrylamide, n-propyl (mercapto) acrylamide, isopropyl (indenyl) propyl sulfonamide, N-(methyl) propylene sulfhydryl, etc., and further, for example, a group represented by the following general formula (I) At least one of the photopolymerizable residues and the compound n are selected from the group to reduce the effect of the foot. The photopolymerizable unsaturated compound represented by the following general formula (1) is preferably used. (化2Ν)/Χ\Ν〆仏(1) R3 (wherein the 4 series Η or CH3 in the formula. M R3 series means independent, hydrogen atom, alkyl group, silk group and base group The group selected by the group towel may also be bonded to each other by a bond between 1 and r3 to form a ring containing N. The X system represents the carbon number (4) of the extended base, or (Yang or Qiqiu and m and n are respectively 1~) An integer of 10 (4) oxidized group, polyoxidative extension is a random polymerization or block polymerization.) In the above general formula (I), Ri is H or CH3 in the formula. R2 and R3 are shown in Table 101106904 201245870, respectively. The group selected from the group consisting of hydrogenogen, phenotypic, methoxy, and dentate may also be bonded to each other by R2 and R3 to form a cycloalkyl group and alkoxy group. 1 to 10, preferably 1 to 6. X represents a carbon number dip, preferably an alkylene group of 1 to 6, or a polyoxyalkylene group which is an integer of 1 to 1 Å, respectively, and m and n are respectively The polyoxyalkylene group may be a random polymerization or a block polymerization.) The compound represented by the above general formula (I) is specifically, for example, N,N-didecylamino decyl (meth) acrylate. (曱基)acrylic acid n,N-dimercapto Ethyl ester, bismuth (mercapto) acrylate, ruthenium dimercaptopropyl propyl ester, N,N-didecylaminobutyl (meth) acrylate, N,N-dimethyl (meth) acrylate Amidopentyl ester, N,N-dimethylaminohexyl (meth)acrylate, N,N-didecylaminoheptyl (decyl)acrylate, N,N-difluorene (fluorenyl)acrylate Aminooctyl octyl ester, N,N-didecylamino decyl (meth) acrylate, n,N-didecylamino decyl (meth) acrylate, (mercapto) acrylate - N, N- Diethylamino decyl ester, n,N-diethylaminoethyl (meth) acrylate, _n, n-diethylaminopropyl (mercapto) acrylate, fluorenyl (decyl) acrylate, Ν·Diethylaminobutyl butyl ester, (mercapto)acrylic acid Ν, hydrazine: ethyl amido pentyl ester, fluorenyl (mercapto) acrylate, hydrazine-diethylaminohexyl acrylate, (meth)acrylic acid Ν,Ν-diethylaminoheptyl heptyl ester, (fluorenyl)acrylic acid ν, Ν-diethylaminooctyl octyl ester, (fluorenyl)acrylic acid-hydrazine, hydrazine-diethylamino decyl ester, (fluorenyl) Ν(Ν-diethylamino decyl acrylate) (曱) Ν-n-propylaminoethyl acrylate, hydrazine-isopropylaminoethyl (meth) acrylate, hydrazine-tert-butylaminoethyl (meth) acrylate, (fluorenyl) Acrylic acid-101106904 15 201245870 monoalkylaminoalkyl (meth)acrylate such as n-butylaminoethyl vinegar; N,N-dimethylamino polyethylene glycol (meth) acrylate, N , N-diethylamino polyethylene glycol (fluorenyl) acrylate, N,N-didecylaminopolypropylene glycol (mercapto) acrylate, N,N-diethylaminopolypropylene glycol (曱A dialkylamine-based poly(fluorenyl) acrylate such as acrylate; a cyclic (fluorenyl) acrylate-based amide group such as metholinylethyl (meth)acrylate. Among the oximes, it is preferred to use (meth)acrylic acid di-enylamino propyl vinegar, and more preferably (mercapto) acrylic acid diethylamino ketone vinegar. Further, from the viewpoint of ease of availability, in the above general formula, R! is a compound in which c3, r2 and r3 are both C2h5 and χ is C2H5, that is, methacrylic acid N,N-diethyl Aminoethyl vinegar [for example, manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ESTER DE]. Here, the 'hardened photoresist' foot is presumably hardened by the weakly hardened semi-hardened photoresist. The - part is reacted with the developer without being removed. During the drying after development, the semi-hardened photoresist is moved to the light. Block the lower part and reattach it. (8) The amine group of the photopolymerizable monomer is formed in the photosensitive resin composition and (4) the binder polymer generates a towel and reacts, and covers the acid filament of the (A) binder polymer. Verifyability and reduce the re-adhesion of the semi-hardened photoresist can also make the foot smaller. Further, since the monomer of (8) has a structure capable of photopolymerization, it is expected that the degree of hardening is improved and the adhesion is improved. Therefore, the same effect can be expected as a single system of (8) having an amine group and photopolymerizable structure. In addition, in the case of a photosensitive resin composition used for a photoresist film, 101106904 16 201245870 (B) an amine-based and photopolymerizable monomer as a photopolymerizable monomer component is used, since it is considered Acidic solutions such as plating baths and etching solutions cause contamination and other problems, and are not known. However, in the present invention, a monomer having an amine group is particularly daringly used, and it has been unexpectedly found that no problem has occurred, and the object of the present invention can be attained. In the present invention, the content of the (B) amino group-containing photopolymerizable monomer is preferably from 1 to 30 parts by weight based on 1 part by weight of the (A) binder polymer. More preferably, it is 0.1 to 25 parts by weight, particularly preferably 5 to 20 parts by weight, and most preferably 1 to 15 parts by weight. If the content is too small, there is a tendency to reduce the effect of insufficient footing. On the other hand, if the content is too large, the resolution tends to be lowered. (B) The amine group-containing and photopolymerizable monomer can also be used together with the photopolymerizable monomer shown below. For example, as a monomer having one polymerizable unsaturated group, for example, (mercapto)acrylic acid 2- to ethyl ketone, (mercapto)acrylic acid 2·propyl ester, (meth)acrylic acid 2 - hydroxybutyl ester, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(indenyl) propylene oxy-2-hydroxypropyl phthalate, (mercapto) propylene hydrazine 3- Gaso-2-hydroxypropyl ester, glycerol mono(decyl) acrylate, 2-(meth) propylene sulfonyl ethyl acid phosphate, decanoic acid derivative semi-(meth) acrylate, etc., etc. Use two types or more in combination or in combination. Further, examples of the monomer having two compounds and a group include, for example, ethylene glycol di(meth)acrylate, diethylene glycol bis(indenyl)acrylate, and tetraethylene glycol-2 (A). Acrylate, polyethylene glycol bis(indenyl) acrylate, propylene glycol di(meth) acrylate, polypropylene glycol bis(indenyl) propionate, polyethylene 2101106904 17 201245870 alcohol • polypropylene glycol II Methyl) acrylate, butanediol bis(indenyl) acrylate, neopentyl glycol di(meth) acrylate + ethoxylated ethyl bisphenol into bis(indenyl) acrylate + oxidized propyl group Bisphenol A type di(meth) acrylate, bisphenol A type bis(indenyl) acrylate containing oxidized exoethyl oxidized propyl group, 1,6-hexanediol bis(indenyl) acrylate , glycerol di(meth) acrylate, pentaerythritol di(decyl) acrylate, ethylene glycol diepoxypropyl ether bis(indenyl) acrylate, diethylene glycol diepoxypropyl ether bis (methyl Acrylate, diglycidyl phthalate di(indenyl) acrylate, hydroxytrimercaptoacetic acid modified neopentyl Glycol di (meth) acrylic acid vinegar, these may be used alone or in combination of two or more thereof. Among them, "extra" is a bisphenol A type bis(indenyl) acrylate containing an ethoxylated ethyl group, and polyethylene glycol/polypropylene glycol bis(indenyl) acrylate. Further, examples of the monomer having three or more polymerizable unsaturated groups include dihydroxymercaptopropane tri(indenyl)acrylate, pentaerythritol tri(indenyl)acrylate, and dipentaerythritol penta(indenyl). Acrylate, tris(fluorenyl) propylene methoxy ethoxy trihydroxy hydrazine propane, glycerol polyepoxy propyl ether poly(indenyl) acrylate vinegar, etc. may be used alone or in combination of two or more. Further, for example, ethyl urethane (mercapto) acrylate can also be mentioned. Examples of the (meth) acrylate of the amino carboxylic acid ethane group include diisocyanates such as hexamethylene diisocyanate and phenyl phenyl diisocyanate, and, for example, 2 - ethyl acrylate and acrylic acid 2 - a hydroxypropyl ester, an oligopropylene glycol monomethacrylate or the like having a hydroxyl group-containing (meth) acetoacetate in a molecule of a (fluorenyl) propylene group, and optionally a polyol The compound obtained. These may be used alone or in combination of two or more. In the present invention, with respect to (8) a monomer having an amine group and a splicable monomer, and a photopolymerizable unity of the photopolymerization, the phase is hidden (preferably, the weight of the component is preferably H), parts by weight, Better 3. ~ _ weight, more preferably 5G ~ 12G parts by weight, best 6 (M (8) parts by weight. If the number is too small, there is a tendency to be insufficiently hardened, and if too much, there is a dumping of the flow. (c) The photopolymerization initiator may, for example, be (C1) a six-wire double-w street organism, (C2) an alkylaminodiphenyl-organism, a N-silane derivative, or a derivative. Anthracene derivative such as diamine hydrazine; 忱 ^ ^, _ _ tetra aryl = amine derivative, riboflavin triacetate, diphenyl ketone, benzyl dimethyl: ketal thioxanthone derivative , acetamide alkyl phthalate, tricotylation derivative, coumarin 6 and other coumarin charm; triphenylphosphine, triterpene phenylphosphine, tris(dimethylphenyl)phosphine, triple a triaryl phosphine such as phenylphosphine, trinaphthylphosphine, tridecylphosphine or triphenanthrylphosphine, etc., which may be used alone or in combination of two or more. (ci) Hexaarylbisimidazole The derivative may, for example, be 2,2,_bis(2,nonanediphenyl)_4,4',5,5'-fluorene (3-methoxyphenyl)bisimidazole, 2,2,-double (2,3_diphenyl)-4,4',5,5'-indole (4-methoxyphenyl)bisimidazole, 2,2'-bis (2,4_2 Phenyl)-4,4',5,5'-肆(3-methoxyphenyl)phenylbisimidazole, 2,2,_bis(2,5-dichlorophenyl)-4,4 ',5,5,-肆(3-decyloxyphenyl)biimidazole, 2,2,·bis(2,6-dioxyl)-4,4',5,5'-肆(3 -Methoxyphenyl)biimidazole, 2,2·,4,4·_肆(2·chlorobenzene 101106904 19 201245870 base)-5, bis(3-decyloxyphenyl) double taste saliva, 2, 2|·Bis(2-hydrophenyl)-4,4,5,5'-tetraphenylbis, 2,2,,4,4,_肆(2_gasphenyl)_5,5, _ bis ^ methoxy phenyl) double microphone. Sit, 2,2,,4,4'-肆(2_gasphenyl)_5,5,_bis(2,3-dimethoxyphenyl) bismuth, 2,2,,4,4 ,-肆(2_气phenyl)_5,5,.bis(3,4-dimethoxyphenyl) bis-pyrene, 2,2,·bis(2-hydrophenyl)_4,4,,5 ,5,·肆&methoxyphenyl) double-salt saliva, 2,2,_bis(2-phenylphenyl)_4,4,5,5,·肆(3,4-didecyloxy Phenyl) bismuth, 2,2'-bis(2-chlorophenyl)-4,4,5,5,-indole (3,4,5-trimethoxyphenyl) bis-pyrene, 2 , 2'-bis(2-chlorophenyl)-4,5-bis(3.methoxyphenyl)_4,,5, di-pupid (tetra) saliva, diphenylbis(tetra), 2,2'·double (2•Phenylphenyl) o-, 4-dimethoxyphenyl)-4,,5,5,-triphenyl double-sweet, etc. Among them, preferably 2, 2, 4, 4, _ 肆(7) gas phenyl)-5,5'-bis(3-hydroxyphenyl) bis-pyrene, 2,2|, 4,4|_肆(2·gas phenyl) 5,5-double (2 , 3-methoxyphenyl)biimidazole, 2,2,_bis-phenylphenyl) bucket (3,4·dimethoxyphenyl)·4,5,5·-triphenylbicarbazole 4, 2, 2, - bis(2·gasphenyl)-4,4',5,5'-tetraphenyl bis-imide is used alone or in combination of two or more kinds in the village. (c2) The aromatized diphenyl ketone derivative may, for example, be: μ·bis(diethylaminophenyl hydrazino, 3,3,-dimethyl methoxy diphenyl g, and an amine group) The diphenyl group is preferably a 4,4 or bis(diethylamino)dione, and these may be used alone or in combination of two or more. From the viewpoint of high sensitivity, the photosensitive resin composition of the present invention is preferably a photopolymerization initiator (C), and preferably contains at least (C1) hexaaryl bisphenol saliva 101106904 20 201245870 The best contains (ci) hexaaryl bis- sigma derivatives and other photopolymerization initiators, especially contains (C1) hexaarylbisimidazole derivatives and (C2) alkylaminodiphenyl hydrazine derivatives Things. (C) The content of the photopolymerization initiator is preferably 1 to 20 parts by weight, more preferably 2 to 16 parts by weight, particularly preferably 3 to 12 parts by weight based on 1 part by weight of the (A) binder polymer. ϊ: share. When the content of the (C) photopolymerization initiator is too small, the necessary sensitivity, resolution, and adhesion tend not to be obtained, and if it is too large, there is a tendency to form an insoluble matter in the photosensitive resin composition. . In the case of using (C1) a hexaarylbisimidazole derivative together with other photopolymerization initiators, for example, (ci) a hexaarylbisimidazole derivative and a (C2)alkylaminomonophenyl ketone derivative are used in combination. In the case, relative to (A) the binder polymer, 1 part by weight, (C1) hexaaryl bis-sodium derivative is more preferably 丨 16 parts by weight, more preferably 2 13 weights, particularly good 3 to 1 〇 The (C2) amphoteric diphenyl ketone derivative is preferably G.G1 to 4 parts by weight, more preferably G.G2 to 3 parts by weight, particularly preferably 0.06 to 2 parts by weight. (D) Stupid and tris-salt derivatives suitable for use, for example: 4 sulfobenzotris, 5 减 benzotris, HU· bis succinyl) benzotris, 1-(2' , 3,-disylpropyl)benzotrisole, 1 ((bis(2-ethylhexyl)amino)methyl)-1Η-stupid and trisporin, which may be used alone or in combination 2 or more types. Further, from the viewpoint of easiness of availability, it is more preferable, and it is a triazole and a 5-carboxy-p-triazole. It is known that the affinity of the benzo-like bio-system with copper metal is good. It is generally believed that 101106904 21 201245870 after the photoresist film is laminated on the copper substrate, the benzotriazole derivative is disposed on the copper substrate. Since the benzotriazine derivative having a drum base is neutralized by the strong aqueous solution at the time of peeling and the carboxyl group, it is presumed that the photoresist can be easily peeled off from the interface of the copper substrate. The content of the (D) carboxyl group-containing benzotriazole derivative is preferably 0.01 to 2 parts by weight, more preferably 0,044 parts by weight, particularly preferably 0.08 to 100 parts by weight of the (A) binder polymer. 1 part by weight. When the content of the benzotriazole derivative having a carboxyl group (D) is too small, the peeling property tends to be lowered, and if it is too large, the adhesion is lowered and the foot tends to be large. Further, in the present invention, from the viewpoint of achieving both the reduction of the foot and the peeling property, the weight ratio of the component (B) to the component (D) and the component (b) and the component (D) is preferably used in combination. (B)/(D) is preferably in the range of more than 5 Å. The weight ratio (B)/(D) is preferably 3 or more and 20 Å or less, and more preferably the weight ratio (B)/(D) is 5 or more and 50 or less. If the rate is too low, the peeling tends to be easy, but the foot tends to be large. On the other hand, if the height is too high, the occurrence of the foot can be suppressed, but the peeling tends to be difficult. In the neo-resin composition, in addition to the above-mentioned (a) to (D) compounds, the ruthenium-based system further contains a dye. The dye may be, for example, crystal violet malachite green, peacock green, smoke green, diamond green. , patent blue, methyl violet (CHD olet), 隹 利亚 、, Victoria pure blue, oil soluble blue, blue blue 验 笨 笨 笨 、 、 、 、 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Methylphenyl) leuco-recessive crystal violet], ginseng (4) dimethylamino-2-methyl J 101106904 22 201245870 phenyl) decane [colorless recessive malachite green], fluorescent yellow mother dye (fluoran dye) ) such as colorless recessive dyes and so on. Further, the photosensitive resin composition of the present invention may further contain a tooth compound. The compound may be, for example, amyl bromide, odorous acesulfame, odorized isobutylene, ethylene bromide, diphenyl methyl br〇mide, benzyl bromide. Bromide), methylene bronude, tribromomethylphenylsulfone, carbon tetrabromide, bis(2,3-dibromopropyl)phosphoric acid, dichloroacetamidine, iodopentane, iodine Butane, trichloro-2, 2_bis (p-stupyl) ethane, gasification of three compounds, and the like. Further, the photosensitive resin composition of the present invention may contain an additive such as a plasticizer as needed. Such additives may, for example, be polyethylene glycol, polypropylene glycol, oxidized propyl ethoxylate, polyoxylated ethyl monodecyl ether, polyoxylated propyl monodecyl ether, polyoxylated ethylene polyoxylate a diol/ester such as propyl monodecyl ether, polyoxyalkylene monoethyl ether, polyoxypropylene propyl monoethyl ether, polyoxy-extension ethyl polyoxy-extension monoethyl ether; diethyl phthalate etc. Acid esters; o-nonyl sulfonate decylamine, p-toluene sulfonate decylamine, tributyl citrate, triacetic acid citrate, triethyl citrate triethyl citrate, acetaminophen citrate tri-n-propyl Ester, tri-n-butyl citrate and the like. In order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, the photosensitive resin composition may contain a radical polymerization terminator. The radical polymerization terminator may, for example, be p-nonyloxyphenol, hydroquinone, gallic phenol, naphthylamine 't-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-nonylphenol, 101106904 23 201245870 U·Alkenylene “6•Terti-butyl”, 2,2|-indenyl bis(4)ethyl-6-t-butyl), argene phenyl via amine salt, and Diphenyl nitrosamine, etc. The photosensitive resin composition of the present invention may be dissolved in methanol, ethanol, acetone, methyl ethyl ketone, methyl sedum, ethyl sirosu 1 benzene, hydrazine, if necessary. A solution of about 30 to 60% by weight of a solid content is formed in a solvent of the hydrazine-dimercaptosamine, propylene glycol, or a mixed solvent of the above, and the solution can be used as a photosensitive film to be formed later. The coating liquid of the resin composition layer is applied to a substrate such as a circuit for forming a substrate, and dried to form a photosensitive resin composition layer, but from the viewpoint of work efficiency and the like. It is preferably used to form a photosensitive resin composition layer of the silk film described later. Further, in the photosensitive resin composition of the present invention, When an additive such as an adhesion imparting agent, an antioxidant, a thermal polymerization terminator, a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, or a flame retardant is contained, in the case of inclusion, The total mass fraction of the solid content of the components (A) to (D) is preferably contained in an amount of f, more preferably (four) to 15 parts by mass, particularly preferably 0.03 to 1 part by mass. These may be used alone. Two or more types are used in combination. [Photoresist film] The photoresist film of the present invention contains a photosensitive resin composition layer composed of a photosensitive resin composition and a support layer. 101106904 24 201245870 As such a branch (4), for example, a polyethylene terephthalate film (polyvinyl alcohol film), a polyvinyl alcohol film, a polyvinyl chloride film, Chlorhexene copolymer film, polyvinylidene gas film, partial ethylene ethylene copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, poly Indole film, The film of the vitamin derivative, etc., wherein the film is preferably a poly(p-phenylene terephthalate) film, and the film may be extended if necessary. The haze value of the support layer is preferably below 5. The thinner the thickness is, the more advantageous it is in terms of image formation and economy. However, since it is necessary to maintain strength, it is preferable to use 1 G to 3 Gpm. The thickness of the photosensitive resin composition layer of the photoresist is according to the use. The difference is preferably 5 to just division, more preferably 7 to 6 〇μΐη, and particularly preferably 10 to 50 μm. If the photosensitive resin composition layer is too thin, the film strength tends to be too low; if it is too thick, There is a tendency for the adhesion, the sensitivity, and the resolution to be lowered. The photoresist film of the present invention may be provided with a protective layer on the surface opposite to the side of the photosensitive layer of the photosensitive resin composition layer as needed. The characteristics of the protective layer used in the photoresist film are such that the material can be easily peeled off from the photosensitive resin composition layer, so that the adhesion to the photosensitive resin composition layer is required to be sufficiently smaller than the protective layer. Support layer. The protective layer is preferably made of, for example, a polyethylene film or a polypropylene film. The film thickness of the protective layer is preferably * < ♦ 10~ΙΟΟμιη, better 1〇~5〇μιη. In the photoresist film of the present invention, a coating liquid containing 101106904 25 201245870 of the photosensitive resin composition of the present invention is applied onto one surface of a support layer, dried, and further covered as needed on the coated surface. A protective layer can be made. More specifically, the coating material containing the photosensitive resin composition of the present invention is uniformly applied to one surface of the support layer by a roll coating method, a bar coating method, or the like, and further increased in 5G to 12 (rc, or sequentially). The photosensitive resin composition layer is dried in a temperature oven, and then a protective layer is laminated on the upper surface of the layer. [Method of Forming Photoresist Pattern] For the use of the photoresist film of the present invention, The steps of forming the photoresist pattern on the substrate will be described. The photoresist pattern using the photoresist film of the present invention can be formed as an example of a specific method of exemplification by a step including a lamination step, an exposure step, and a development step. As a substrate to be processed, for example, a copper-clad laminate can be used for the purpose of manufacturing a printed wiring board, and in the case of the production of the uneven substrate, for example, a glass substrate (for example, a substrate for a plasma display panel, surface electrolysis) A display substrate), a through-hole (four) wafer, a material substrate, and the like are formed. The "electrical-display panel substrate" m forms an electrode on the glass substrate, and then a dielectric layer is formed, followed by coating. (4) Glass paste 'and (4) sandblasting the glass transition portion to form a partition substrate. First, a lamination step is performed using a laminator. After the photoresist film has a protective layer, it is after peeling off the protective layer. The photosensitive resin composition layer is laminated by heat and pressure bonding on the surface of the substrate to be processed by a laminator. At this time, the photosensitive resin composition layer can be laminated only on one surface of the surface of the substrate. It can also be laminated on both sides. The heating temperature at this time is generally 40 to 160 ° C. Next, an exposure step is performed using an exposure machine. The support layer is peeled off as needed, and exposure is performed by active light through a photomask. The illuminance of the light source and the exposure time are determined, and the measurement can also be performed using a light meter. Further, the exposure step can also use a direct drawing exposure method. The direct drawing exposure method is directly drawn on the substrate without using a photomask. The method of performing exposure can be performed by using, for example, a semiconductor laser or an ultra-high pressure mercury lamp having a wavelength of 350 to 410 nm. The drawing pattern is controlled by a computer. The amount of exposure is determined according to the illuminance of the light source and the moving speed of the substrate. Secondly, development is performed after peeling off the support layer as needed. Since the photosensitive resin composition of the present invention belongs to a dilute alkali developing type, it is used to develop sodium carbonate. An aqueous solution of 5% to 5% by weight of an alkali compound such as potassium carbonate or tetraammonium hydroxide is used. The pH of the above-mentioned aqueous solution is preferably set to a range, and the /jnL degree is blended with the photosensitive resin composition layer. The developability is adjusted. By the development, the unexposed portion (the region other than the desired pattern image) in the photosensitive resin composition layer is removed to form a photoresist pattern. Incorporating a surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development, etc. The photoresist can be obtained according to the steps described, and the heating step of the step 〇, 3〇〇C can be further performed. Or "hardening step. By implementing these steps, drug resistance can be further improved. 101106904 27 201245870 [Method of Forming Conductor Pattern] The method for forming a conductor pattern of the present invention is to form a substrate using a copper foil laminate or a flexible substrate-specific circuit as a substrate, and then perform the following steps. And implementation. First, a conductor pattern is formed on a surface of a substrate exposed by development using a known method such as a forging method or a lithography method. The plating method at the time of performing plating may be, for example, copper plating such as sulfuric acid steel plating or copper pyrophosphate plating; plating welding such as high-distribution welding; Watt bath (nickel sulfate-vaporized nickel) plating; Nickel plating such as nickel acid; hard gold plating, soft gold plating, etc. When plating is applied, it is preferred to carry out pretreatment by using a pre-coating agent such as a degreasing agent or a soft etchant. Further, the etching is usually carried out using an acidic etching solution such as a vaporized copper-hydrochloric acid aqueous solution or a ferric chloride-hydrochloric acid aqueous solution, and an ammonia-based secret engraving liquid is used in accordance with a usual method. After the plating or etching is completed, the organic amine stripping solution or the ethanolamine is used to extract the gold chaotropic solution or the bismuth reductive solution from an aqueous alkali solution containing sodium hydroxide and an alkali compound G.1 to 1 G% by weight. Ingredients), stripping of the photoresist pattern is performed. In addition, when the light is filled in the through hole by using the photoresist pattern, it is also possible to remove the light in the case of the film, the barrier, and the film. In the case of plating, a fast axis engraving is then performed. (4) The above laminated layer can form a circuit board (such as a printed wiring board). (Examples of the present invention) The following embodiments are described in more detail. In addition, the following "%" and "parts" refer to the weight basis without exceeding the subject matter. 1) Preparation of sample for evaluation The photoresist films of the examples and the comparative examples were produced as follows. The amount of the photosensitive resin composition shown in Table ^ is determined to be in the form of a solid amount, Μ% by weight, 'completely mixed, mixed, and then used in a thick film of polyethylene terephthalate (PET). It is thin and shameful, and coating is carried out by using a coating film having a thickness of 25 μm. The oven was dried in an oven at 6 ° C and 90 ° C for 2 minutes, and a photoresist film was coated with a thickness of 21 μm from the top of the photosensitive resin composition layer. With respect to the obtained photoresist film, the following items were evaluated as follows. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 P-1 250 250 250 250 250 250 One 250 250 250 — P-2 — 一 — — — — 250 — — 250 M-1 10 20 10 10 10 — 10 —10 — — M-2 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 63 63 63 73 63 73 63 M-4 10 10 10 10 10 10 10 10 10 10 10 J-1 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 Ί-2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 D -1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Bu 0.4 0.4 D-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 T-1 0.3 0.3 0.6 — — 0.3 0.3 — A 0.3 A T-2 A — — 0.3 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — The numerical values are in parts by weight. 29 101106904 201245870 The symbols in Table 1 are expressed as follows. [(A) binder polymer] • P-1: obtained by polymerizing methacrylic acid/mercapto methacrylate/styrene (weight ratio 22/38/40), 40% by weight average molecular weight 42,000 Ketone solution. Solid acid value = 143.4 mg KOH / g. Glass transfer temperature = 113.9 °C. • P-2: A 40% methyl ethyl ketone solution having a weight average molecular weight of 34,000 obtained by polymerizing methacrylic acid/imyl methacrylate/styrene (weight ratio 28/32/40). Solid acid value = 182.5 mg KOH / g. Glass transition temperature = 118.1 〇C 0 [photopolymerizable monomer] • M-1 : N,N-diethylaminoethyl hydrazide CH2=CH(CH3)COOC2H5N(C2H5)2[Chengrongshe Chemical company, trade name: LIGHT ESTER DE] • M-2: N-tert-butylaminoethyl methacrylate CH2=CH(CH3)COOC2H5NH(t-C4H9) •M-3: in bisphenol A Two sides of the oxidized ethyl group-containing bisphenol A type dimercapto acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: BPE-500) were added to each of the two sides. 4: Nine-glycol dimercapto acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: 9G) [Photopolymerization initiator] 101106904 30 201245870 1. 2,2-bis(2-chlorophenyl)-4 , 4', 5, 5'-four stupid double sip sit • 1-2 : 4,4'-bis(diethylamino)diphenyl ketone [dye] • D-1 : malachite green • D -2 : colorless recessive crystal violet [benzotriazole derivative] • T-1 : 4-carboxybenzotriazole • T-2 : 1-(1',2'.dicarboxyethyl)benzotriene Azole • T-3 · 1-((bis(2·ethylhexyl)amino)methyl)_1H_benzotriazolecarboxylic acid • T-4: benzotrizole [Solvent] • F·1 : Ethyl Ketone 2) Evaluation Method After peeling off the polyethylene film of the above-mentioned photoresist film, depending on the temperature of the laminating roll according to the level of the photosensitive resin composition layer contacting the copper foil substrate积°c, the roll pressure 〇3MPa, and the laminating speed 丨2m/min were applied. Then, a negative film (Stouffer 21-level exposure ruler) which is produced in a stepwise manner in which the amount of light penetration is reduced is used, and a parallel exposure machine (manufactured by ORC Co., Ltd., trade name: EXM-1201) having an ultrahigh pressure mercury lamp is used. Stouffer 21-level exposure scale (Stouffer 21 step tablet) is applied evenly across the entire surface. After exposure, the pet film was peeled off after 15 minutes at 27. (:, the 0.7% sodium carbonate aqueous solution was sprayed twice according to the breakpoint (between the unexposed portions being completely dissolved, 101106904 31 201245870), and the unexposed portion a was dissolved and removed to be paid. Hardened resist image. Using the exposure amount and the number of residual steps after development, the exposure amount (mj/cm2) of the StC>Uffer 21-stage exposure scale after the development of the remaining step number is 6 (mj/cm2). The glass chrome mask used for exposure is a line pattern mask having a line width of 1 ··1 ratio between the exposed portion and the unexposed portion, and exposure is performed in an exposure level of 6 steps. And developing the minimum mask line width when the hardened resist pattern is formed normally ((4) is set as the resolution value. [Adhesiveness], as a thin mask when exposed, it is difficult to use a separate line pattern mask. Exposure is performed according to the exposure amount of the exposure scale level of 6 and developed. The minimum mask line width (4) when the cured photoresist pattern is normally formed is set to the value of the adhesion. [The base of the cured photoresist after development 〕 through the layer of photoresist on the substrate _, through The glass mask is exposed to an exposure amount of 6 steps according to the number of exposure steps, and (4). The line width/line distance of the obtained photoresist pattern is 10/10_, and the foot of the line is given a rating as follows. In the skirt trailing, the bottom edge width of the bottom of the cured resist pattern was measured by SEM (manufactured by JEOL Ltd., trade name: JSM-6390). ◎: One or less of the bottom of the cured photoresist pattern was found. Foot trails. 〇: 1〇1106904 201245870 foot trails of more than one and less than 3 qing are found at the bottom of the hardened resist pattern. X: A foot trail of more than 3 μm is found at the bottom of the hardened resist pattern. The photoresist film laminated on the substrate was exposed to a 4 cm x 4 cm square pattern according to the exposure amount of the order of the exposure level. The development was carried out by developing at twice the development time of the minimum development time, and then copper sulfate plating was performed. Spraying was carried out at 50 ° C and a 3% by weight aqueous solution of caustic soda, and the peeling time of the cured photoresist was measured, and the peeling property against the cured photoresist was graded as follows. The photoresist peeling time was 50 seconds or less. The time is over 50 seconds and is 60 seconds or less. x : The photoresist peeling time exceeds 60 seconds. 3) Evaluation results The evaluation results of the examples and comparative examples are shown in Table 2. [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Resolution 9 9 9 9 9 9 9 11 11 11 11 Adhesion 6 6 6 7 6 6 7 9 8 9 9 脚 ◎ ◎ 〇 〇 〇 XX detachability ◎ ◎ ◎ ◎ 〇 ◎ ◎ XX As shown in Table 2, the photosensitive resin compositions of Examples 1 to 7 are resolution. Excellent adhesion. Furthermore, since the footprint of the hardened photoresist is small, it is less likely to cause an obstacle in etching and plating in subsequent steps. Moreover, since the peelability is also good, stable productivity can be ensured. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 4 were inferior in resolution and density of 101106904 33 201245870. Further, in the photosensitive resin compositions of Comparative Examples 1, 3, and 4, since the feet of the cured photoresist were large, there was a possibility of causing an obstacle in etching and plating in the subsequent step. Further, in the photosensitive resin compositions of Comparative Examples 1 and 2, since the peeling property was also inferior, it was difficult to obtain a stable productivity. The present invention has been described with reference to the details and specific embodiments thereof, and various modifications and changes can be made without departing from the spirit and scope of the invention. This application is based on the Japanese patent application filed on March 3, 2011 (Japanese Patent Application No. 2011-046373), and its contents are incorporated in the present case. (Industrial Applicability) The photosensitive resin composition and the photoresist film of the present invention have excellent resolution and adhesion, good adhesion, and a small amount of hardened crucible after development, and also have good peelability. The photosensitive resin composition and the photoresist film of the present invention can be suitably used for the production of a printed wiring board, a lead frame, a semiconductor package, etc., and the precision processing of a metal can be effectively utilized as an etching photoresist. Plated photoresist photoresist. [Simple description of the diagram] Light ['The use of the conventional photoresist film in the field, the hardening of the substrate (copper film), and the formation of plating (copper wiring), due to the foot (hardened photoresist foot)丨t into a 7-section of the title. After the B-plating, the cross-sectional view of the B-series is applied. 101106904 34 201245870 [Description of main components] 1 Hardened photoresist 2 Substrate (copper film) 3 Foot 4 Plating (copper wiring) 101106904 35