200813633 九、發明說明 【發明所屬之技術領域】 本發明係關於可形成高解析性、高長寬比的圖型，而 且高感度及液保存安定性優異的感光性樹脂組成物、其層 合物、其硬化物及使用該組成物之圖型的形成方法。 【先前技術】 可光微影加工之光阻，最近被廣泛地使用於半導體或 MEMS (微機電系統）用途，如此的用途，此光微影加工 係在基板上藉由圖型化曝光而進行，接著用顯影液進行顯 影，選擇性地去除曝光區域或非曝光區域而逹成。可光微 影加工之光阻（光致抗蝕劑）有正型或負型，經由曝光而 溶解於顯影液者爲正型，不溶者爲負型。尖端的電封裝用 途（electropackage application)要求高長寬比，另一方 面MEMS用途則要求均勻的旋轉塗佈膜的形成能及於100 // m以上的厚膜維持直線的形狀，而且高長寬比及可光微 影之光阻。其中，長寬比係藉由光阻膜厚/圖型線寬表 示，爲表示光微影的性能的重要特性。 以二萘醌-酚醛清漆反應爲基礎之先前技術的正型光 阻，不適用於要求50//m以上的厚膜之用途，厚膜化時有 極限，這是因爲一般被使用於光阻曝光的近紫外區域波長 ( 3 5 0〜450nm)之二萘醌型（DNQ)光反應物具有比較高 的光吸收，DNQ型光阻又因爲顯影液中曝光區域與非曝光 區域之特有的溶解性不同，故側壁形狀不是直線形反而呈 -6- 200813633 現傾斜形狀。藉由光吸收可使照射在薄膜的頂部至底部的 照射強度漸減，但若是此光吸收太高，則光阻的底部與頂 部比較下顯得曝光不足，故側壁形狀會呈現傾斜形狀或歪 斜形狀。 負型的化學增強型之可厚膜光微影加工的組成物，已 知在3 5 0〜45 Onm波長範圍具有非常低的光吸收，此光阻的 組成由多官能雙酚 A酚醛清漆環氧樹脂（Res〇luti〇n Performance Product 製 EP ON S U- 8 樹月旨）、如 Dow Chemical製CYRACURE UVI_6 974之光致陽離子聚合起始 劑（此光致陽離子聚合起始劑爲由芳香族六氟銻酸銃的丙 烯碳酸酯溶液所成）所成，此光阻組成物係藉由旋轉塗佈 或淋幕式塗佈於各種的基板上，接著經由烘烤使溶劑揮 發，形成100//m或此數値以上的厚度的固體光阻層，再 使用接觸式曝光、接近式曝光、投射式曝光等之各種曝光 方法，隔著光罩照射近紫外光而進行光微影加工，接著， 浸漬於顯影液中，使非曝光區域溶解，而在基板上形成高 解析的光罩的負影像。 EP ON SU-8樹脂，係在厚膜且高長寬比的光微影加工 中具有優異的特徵之低分子量環氧低聚物，此優異的特徵 係（1)高環氧官能基數、（“）高支鏈度、（：^) 3 5 0〜 4 5 Onm的高穿透率、（iv )形成固形物所必須的低分子 量；高環氧官能基數及高支鏈度係在強酸觸媒下引起充分 的交聯，高穿透率性係穿透厚膜而均勻被光照射，具有形 成1 00 // m以上的厚膜且長寬比1 0以上的圖型之光阻性 200813633 通。選擇具有高環氧官能基數與高支鏈度之樹 欲形成具有直線的側壁及具有高長寬比之結構 要項目；選擇低分子量樹脂，係可用最小塗佈 板上形成厚膜光阻固形物層。 以锍鹽或碘鑰鹽爲基礎的光致陽離子聚合 熟知，揭示具有適當的吸光度之有用的光致陽 始劑，含有羰基-P-苯撐硫醚（專利文獻1、2 可添加如2-烷基-9,10-二甲氧基蒽或其他的蒽 石或吡咯基（pyrryl )化合物之增感劑，亦可 陽離子聚合起始劑（專利文獻3 )。 以適合旋轉塗佈之如上述揭示的化合物爲 光阻，由 MICRO CHEM公司所販售，特別是 用於MEMS裝置零件。例如由MICRO CHEM 的「SU-8系列」，爲了形成 30〜100 μ m β 1 000〜3 000rpm旋轉塗佈，接著曝光•顯影後， // m以上的膜厚且長寬比1 〇以上的圖型。 亦揭示關於塗佈於如聚酯薄膜的基材上之 用途（專利文獻4 )。 揭示適合作爲防焊劑（s ο 1 d e r m a s k )使用 陽離子聚合性難燃劑的組成物（專利文獻5、 爲由含有10〜80重量％之雙酚A與表氯醇的縮 物所成，由含有20〜90重量％的雙酚 A酚醛 脂、35〜50重量％的環氧化四溴雙酚A、0.1〜15 致陽離子聚合起始劑之組成而成。 脂，係對於 物而言爲重 階段數在基 起始劑爲人 離子聚合起 )，而且亦 、萘、綠柱 導入於光致 基礎之負型 在商業上使 公司所提供 f的膜而以 可形成1 〇 0 乾膜光阻的 之可感光的 6、7 )，此 合物之混合 清漆環氧樹 重量％的光 -8- 200813633 亦揭示以含羥基之添加物、光致陽離子聚合起始劑及 官能基數1 .5以上的環氧樹脂爲基礎之光聚合性化合物， 已有報告提出含羥基之添加物，增加可撓性或降低1 00 // m厚以上的厚膜之應力（專利文獻8 )。 專利文獻9中，揭示在可EB硬化的用途中使用硬質 環氧樹脂系製作之方法，其中主要的改善重點，係經照射 硬化的環氧樹脂的易碎性，大多數的構造物或耗材用的樹 脂（環氧樹脂），爲了承受多年的嚴格使用，一定要具有 充分的強度與耐衝擊性，其中揭示包括SU-8樹脂之廣泛 的強韌材料，關於增加的強度，於專利文獻9中權利要求 之發明的有效性，係藉由破壞韌性與彎曲彈性率表示，此 強韌材料係由各種的熱塑性塑膠、含羥基之熱塑性塑膠低 聚物、含環氧之熱塑性塑膠低聚物、反應性柔軟性、彈性 體、橡膠及此等的混合物所成。惟，專利文獻9所記載的 組成物，係適用於以非圖型EB照射而被影像化的膜之組 成物，被用UV、X射線、EB照射進行圖型化曝光時，此 等的組成物的特性不能作爲感光用途的參考。 提議許多關於含環氧之光阻組成物（專利文獻1 〇 )， 其中，例如揭示調製適用於旋轉塗佈法之光阻組成物之必 要性，要求流變學的特性，再加上此處的組成物對於如通 過膜厚後光分解光起始劑之曝光照射必須具有充分的穿透 率。此外，此光阻組成物爲了承受各種的用途，必須具有 耐焊性或耐油墨性或強度不會明顯的劣化或密著性不會降 低之適當的物理的、化學的特性。如果此光阻組成物被使 -9 - 200813633 用於如鈾刻用光阻之其他用途時，則要求其他的特性， 惟，如此之滿足所有的各種要件之特定的環氧樹脂目前不 存在’已揭示許多不同的組合或各種的環氧樹脂的混合 物’著名的專利皆記載著關於光硬化組成物用的各種樹 脂、光起始劑，其中多半爲適合作爲永久膜用途之可感光 的光阻，惟，此等皆未揭示我們試圖完成的最適合於 MEM S用途的組成，實際上可塑劑、軟化劑、強韌劑的例 子大部份會使微影性能降低。 〔專利文獻1〕美國專利第5 502083號說明書 〔專利文獻2〕美國專利第6 3 6 8 7 6 9號說明書 〔專利文獻3〕美國專利第5 1 02772號說明書 〔專利文獻4〕美國專利第4882245號說明書 〔專利文獻5〕美國專利第5026624號說明書 〔專利文獻6〕美國專利第52780 1 0號說明書 〔專利文獻7〕美國專利第53 04457號說明書 〔專利文獻8〕美國專利第425 6828號說明書 〔專利文獻9〕美國專利第57262 1 6號說明書 〔專利文獻10〕美國專利第5264325號說明書 【發明內容】 〔發明所欲解決之課題〕 使用酚醛清漆型環氧樹脂等之多官能環氧樹脂之先前 技術的感光性樹脂組成物，因爲所含有的光致陽離子聚合 起始劑的感度低，需要大量的起始劑，故會有無法於短時 -10- 200813633 間內將光罩圖型忠實重現於樹脂圖型之問題點，此外，含 有SbF6_之光致陽離子聚合起始劑較屬於高感度，但會有 因其毒性的問題而使用用途受到限制之問題。 本發明係鑑於上述先前技術的事情所完成之發明，其 課題係提供可形成高解析性、高長寬比的圖型，而且高感 度及毒性少之感光性樹脂組成物。 〔用以解決課題之手段〕 本發明者等爲了解決上述課題，關於感光性樹脂組成 物之高感度化、高解析度化，重複精心硏究、實驗及檢討 的結果’發現組合特定的多官能環氧樹脂與特定的光致陽 離子聚合起始劑調製感光性樹脂組成物，若使用此感光性 樹脂組成物形成樹脂圖型，可形成高感度且長寬比高的樹 脂圖型。亦即，本發明的構成如下述。 (1 ) 一種感光性樹脂組成物，其係含有參（五氟乙 基）二氣憐酸鏡之光致陽離子聚合起始劑（A)、與下述 式（1 )所表示的特定結構的多官能環氧樹脂（B )所成。 200813633[Technical Field] The present invention relates to a photosensitive resin composition which is excellent in high sensitivity and liquid storage stability, a laminate thereof, and a pattern thereof which can form a high resolution and a high aspect ratio. A cured product and a method of forming a pattern using the composition. [Prior Art] Photoresistive photo-resistance has recently been widely used in semiconductor or MEMS (Micro-Electro-Mechanical Systems) applications for such lithography processes by patterning exposure on a substrate. Then, development is carried out with a developing solution to selectively remove the exposed or non-exposed areas. The photoresist (photoresist) which can be photolithographically processed has a positive or negative type, and is positively dissolved in the developing solution by exposure, and negative in insoluble. The advanced electropackage application requires a high aspect ratio. On the other hand, MEMS applications require uniform spin coating film formation and a thick film of 100 // m or more to maintain a straight shape, and a high aspect ratio and illuminance. Light resistance of lithography. Among them, the aspect ratio is represented by the thickness of the photoresist film/line width, and is an important characteristic indicating the performance of photolithography. The prior art positive photoresist based on the naphthoquinone-novolac reaction is not suitable for applications requiring thick films of 50//m or more, and has a limit when thick filming, because it is generally used for photoresist The exposure of the near-ultraviolet region wavelength (350~450nm) of the dinaphthoquinone type (DNQ) photoreactant has a relatively high light absorption, and the DNQ type photoresist is dissolved by the specific exposed and non-exposed areas in the developer. The difference in nature is such that the shape of the side wall is not linear but instead is -6-200813633. The light intensity can be gradually reduced by the light absorption at the top to the bottom of the film, but if the light absorption is too high, the bottom of the photoresist appears to be underexposed in comparison with the top portion, so that the side wall shape may have an inclined shape or a skewed shape. Negative chemically enhanced thick film photolithographic composition, known to have very low light absorption in the 35 to 45 Onm wavelength range, consisting of a polyfunctional bisphenol A novolac ring Oxygen resin (EP ON S U-8, manufactured by Res〇luti〇n Performance Product), photocationic polymerization initiator such as CYRACURE UVI_6 974 manufactured by Dow Chemical (the photocationic polymerization initiator is aromatic) A propylene carbonate solution of bismuth hexafluoroantimonate is formed by spin coating or shower coating on various substrates, followed by baking to evaporate the solvent to form 100/ /m or a solid photoresist layer having a thickness of several or more, and then using various exposure methods such as contact exposure, proximity exposure, and projection exposure, and performing photolithography on the near-ultraviolet light through the photomask, and then Immersed in the developer to dissolve the non-exposed areas, and a negative image of the high-resolution mask is formed on the substrate. EP ON SU-8 resin is a low molecular weight epoxy oligomer with excellent characteristics in thick film and high aspect ratio photolithography. This excellent feature is (1) high epoxy functional group, (") High branching degree, (:^) 3 5 0~ 4 5 high penetration of Onm, (iv) low molecular weight necessary for formation of solids; high epoxy functional group and high branching degree cause sufficient crosslinking under strong acid catalyst The high-permeability system penetrates the thick film and is uniformly illuminated by light. It has a resistive pattern of 200813633 which forms a thick film of 10000 m or more and has an aspect ratio of 10 or more. The selection has a high ring. The tree of oxygen functional group and high branching degree is intended to form a side wall having a straight line and a structure having a high aspect ratio; selecting a low molecular weight resin can form a thick film photoresist solid layer on a minimum coated plate. Salt-based photocationic polymerization is well known, revealing useful photoinitiators with suitable absorbance, containing carbonyl-P-phenylene sulfide (Patent Documents 1, 2 can be added as 2-alkyl-9, 10 - Dimethoxy oxime or other vermiculite or pyrrolylation The sensitizer of the substance may also be a cationic polymerization initiator (Patent Document 3). The compound as disclosed above suitable for spin coating is a photoresist, which is sold by MICRO CHEM, in particular for MEMS device parts. For example, in the "SU-8 series" of MICRO CHEM, in order to form a spin coating of 30 to 100 μm β 1 000 to 3 000 rpm, and then after exposure and development, a film thickness of // m or more and an aspect ratio of 1 〇 or more The use of the coating on a substrate such as a polyester film is disclosed (Patent Document 4). A composition suitable for use as a solder resist (s ο 1 dermask) using a cationically polymerizable flame retardant is disclosed (Patent Document 5) It is made of a condensation product containing 10 to 80% by weight of bisphenol A and epichlorohydrin, and contains 20 to 90% by weight of bisphenol A phenolic acid and 35 to 50% by weight of epoxidized tetrabromobisphenol A. And 0.1~15 is a composition of a cationic polymerization initiator. The fat is a heavy stage for the substance, and the base initiator is a human ion polymerization), and the naphthalene and the green column are introduced into the photo-based basis. The negative type is commercially available to the company to provide the film of f The photosensitive varnish of the dry film varnish is sensitized to light, 6, 7), and the mixed varnish of the composite epoxide weight % of light -8-200813633 also reveals the addition of hydroxyl-containing additives, photocationic polymerization. A photopolymerizable compound based on an epoxy resin based on an epoxy resin having a functional group of 1.5 or more. It has been reported that a hydroxyl group-containing additive increases flexibility or reduces the stress of a thick film of 100 Å or more thick (patent Literature 8). Patent Document 9 discloses a method of producing a hard epoxy resin in an EB-curable application, in which the main improvement point is the friability of the epoxy resin which is hardened by irradiation, and most of the structures or consumables are used. Resin (epoxy resin), in order to withstand years of strict use, must have sufficient strength and impact resistance, which reveals a wide range of tough materials including SU-8 resin, regarding the increased strength, in Patent Document 9 The effectiveness of the invention of the claims is expressed by the fracture toughness and the flexural modulus, which are composed of various thermoplastic plastics, hydroxyl-containing thermoplastic oligomers, epoxy-containing thermoplastic oligomers, and reactions. Sexual softness, elastomer, rubber and a mixture of these. However, the composition described in Patent Document 9 is applied to a composition of a film that is imaged by non-pattern EB irradiation, and is patterned by UV, X-ray, or EB irradiation. The properties of the substance cannot be used as a reference for sensitized use. Many proposals have been made for an epoxy-containing photoresist composition (Patent Document 1), which, for example, discloses the necessity of modulating a photoresist composition suitable for spin coating, and requires rheological properties, plus here. The composition must have sufficient transmittance for exposure to light such as a photodegradation photoinitiator after film thickness. Further, in order to withstand various applications, the photoresist composition must have appropriate physical and chemical properties such as resistance to soldering or ink resistance, deterioration of strength, or deterioration of adhesion. If this photoresist composition is used for other purposes such as uranium engraving photoresist, other characteristics are required, but the specific epoxy resin that satisfies all the various requirements is not present. Many different combinations or mixtures of various epoxy resins have been disclosed. The well-known patents describe various resins and photoinitiators for photohardenable compositions, most of which are photosensitive photoresists suitable for permanent film applications. However, none of these reveals the composition that we are trying to accomplish that is most suitable for MEM S use. In fact, most examples of plasticizers, softeners, and tougheners can degrade lithography performance. [Patent Document 1] U.S. Patent No. 5,502,083 [Patent Document 2] U.S. Patent No. 6 3 6 7 7 9 (Patent Document 3) U.S. Patent No. 5 1 02772 (Patent Document 4) U.S. Patent No. U.S. Patent No. 4,026, 245, U.S. Patent No. 5,026, 624, U.S. Patent No. 5, 026, 00, U.S. Patent Application Serial No. [Patent Document 9] U.S. Patent No. 57,262,166, [Patent Document 10], U.S. Patent No. 5,264,325, the disclosure of the present invention, the disclosure of the present invention, and the use of a polyfunctional epoxy such as a novolac type epoxy resin. The photosensitive resin composition of the prior art of the resin, because the photo-cationic polymerization initiator contained therein has low sensitivity and requires a large amount of an initiator, there is a possibility that the photomask cannot be obtained in a short period of time -10 200813633. The type faithfully reproduces the problem of the resin pattern. In addition, the photo-cationic polymerization initiator containing SbF6_ is relatively high-sensitivity, but there may be The problem of toxicity is limited by the use of the problem. The present invention has been made in view of the above-described problems of the prior art, and it is an object of the invention to provide a photosensitive resin composition which can form a pattern having high resolution and a high aspect ratio and which has high sensitivity and low toxicity. [Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention have repeated the results of careful investigation, experimentation, and review regarding the high sensitivity and high resolution of the photosensitive resin composition. The epoxy resin and a specific photocationic polymerization initiator prepare a photosensitive resin composition, and when the photosensitive resin composition is used to form a resin pattern, a resin pattern having high sensitivity and a high aspect ratio can be formed. That is, the constitution of the present invention is as follows. (1) A photosensitive resin composition containing a photo-cationic polymerization initiator (A) of ginseng (pentafluoroethyl) dioxic acid mirror and a specific structure represented by the following formula (1) Made of a multifunctional epoxy resin (B). 200813633
(2 )如上述（1 )所記載之感光性樹脂組成物，其中 光致陽離子聚合起始劑（A)爲下述式（2)所表示之化合 物。(2) The photosensitive resin composition according to the above (1), wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (2).
(2) (3 )如上述（1 )或（2 )所記載之感光性樹脂組成 物，其係含有反應性環氧單體（C )。 -12- 200813633 (4 )如上述（1 )至（3 )中任一項所記載之感光性 樹脂組成物，其中於含有溶劑（D )之感光性樹脂組成物 中，其固體成份濃度爲5〜95重量％。 (5 ) —種感光性樹脂組成物層合物，其係用基材挾 入上述（1 )至（4 )中任一項所記載之感光性樹脂組成 物。 (6 ) —種硬化物，其係含有上述（1 )至（4 )中任 一項所記載之感光性樹脂組成物所成。 (7 ) —種圖型形成方法，其係包含將於所望的支撐 體上塗佈上述（1 )至（4 )中任一項所記載之感光性樹脂 組成物所得到的感光性樹脂組成物層，乾燥後，依所定的 圖型曝光，曝光後烘烤，顯影樹脂組成物層，加熱處理所 得到的樹脂圖型後，得到所定形狀的硬化樹脂圖型之步驟 所成。 (8 ) —種圖型形成方法，其係包含將從上述（5 )所 記載的層合物去除基材後殘留的感光性樹脂組成物層，貼 合於上述所望的支撐體上後層合，將此感光性樹脂組成物 層依所定的圖型曝光，曝光後烘烤，顯影樹脂組成物層， 加熱處理所得到的樹脂圖型後，得到所定形狀的硬化樹脂 圖型之步驟所成。 (9 ) 一種感光性樹脂組成物，其係含有參（五氟乙 基）三氟磷酸鏡之光致陽離子聚合起始劑（A)、與下述 式（3 )所表示的特定結構的多官能環氧樹脂（b )所成。 -13- 200813633(2) The photosensitive resin composition according to the above (1) or (2), which contains a reactive epoxy monomer (C). The photosensitive resin composition according to any one of the above (1) to (3), wherein the photosensitive resin composition containing the solvent (D) has a solid concentration of 5 ~95% by weight. (5) A photosensitive resin composition laminate comprising the photosensitive resin composition according to any one of the above (1) to (4). (6) A cured product comprising the photosensitive resin composition according to any one of the above (1) to (4). (7) A pattern forming method comprising the photosensitive resin composition obtained by applying the photosensitive resin composition according to any one of the above (1) to (4) to a desired support. After drying, the layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape. (8) A pattern forming method comprising a photosensitive resin composition layer remaining after removing a substrate from the laminate according to (5), bonded to the desired support, and laminated The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern having a predetermined shape. (9) A photosensitive resin composition comprising a photocationic polymerization initiator (A) having a quinone (pentafluoroethyl)trifluorophosphate mirror and a specific structure represented by the following formula (3) Made of functional epoxy resin (b). -13- 200813633
(1 0 )如上述（9 )所記載之感光性樹脂組成物，其 中光致陽離子聚合起始劑（A)爲下述式（4)所表示之化 合物。 [化4](10) The photosensitive resin composition according to the above (9), wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (4). [Chemical 4]
-14- (2) 200813633 (1 1 )如上述（9 )或（1 0 )所記載之感光性樹脂組 成物，其係含有反應性環氧單體（C )。 (1 2 )如上述（9 )至（1 1 )中任一項所記載之感光 性樹脂組成物，其中於含有溶劑（D )之感光性樹脂組成 物中，其固體成份濃度爲5〜95重量％。 (1 3 ) —種感光性樹脂組成物層合物，其係用基材挾 入上述（1 )至（1 2 )中任一項所記載之感光性樹脂組成 物。 (I4) 一種硬化物，其係含有上述（1)至（12)中 任一項所記載之感光性樹脂組成物所成。 (1 5 ) —種圖型形成方法，其係包含將於所望的支撐 體上塗佈上述（9 )至（1 2 )中任一項所記載之感光性樹 脂組成物所得到的感光性樹脂組成物層，乾燥後，依所定 的圖型曝光，曝光後烘烤，顯影樹脂組成物層，加熱處理 所得到的樹脂圖型後’得到所定形狀的硬化樹脂圖型之步 驟所成。 (1 6 ) —種圖型形成方法，其係包含將從上述（丨3 ) 所記載的層合物去除基材後殘留的感光性樹脂組成物層， 貼合於上述所望的支撐體上後層合，將此感光性樹脂組成 物層依所定的圖型曝光，曝光後烘烤，顯影樹脂組成物 層，加熱處理所得到的樹脂圖型後，得到所定形狀的硬化 樹脂圖型之步驟所成。 〔發明之效果〕 -15- 200813633 本發明的感光性樹脂組成物，適用於具有高長寬比的 外形之樹脂圖型的形成，特別是適用於微細尺寸的電子裝 置等中之尺寸安定性高的樹脂成形。 〔實施發明之最佳形態〕 以下說明關於本發明的實施形態。 本發明的感光性樹脂組成物，其特徵係含有毓的參 (五氟乙基）三氟磷酸鹽離子的鹽之光致陽離子聚合起始 劑（A )、與特定結構的多官能環氧樹脂（B )，可形成高 感度且高長寬比的樹脂圖型，而且形成上述樹脂圖型的能 力不會劣化，可賦予可長時間發揮之特性。此等的組合有 各種可能，但特別是上述式（3 )所表示的特定構造的多 官能環氧樹脂（例如日本化藥（股）製 NC63 00 )與上述 式（2 )所表示的化合物之光致陽離子聚合起始劑之組合 最佳。 本發明之光致陽離子聚合起始劑，係受到紫外線、遠 紫外線、KrF、ArF等之準分子雷射、X射線、及電子束 等之放射線的照射後產生陽離子，而此陽離子可變成聚合 起始劑之化合物。 該光致陽離子聚合起始劑（A)爲參（五氟乙基）三 氟磷酸锍。 該光致陽離子聚合起始劑的锍，可列舉三苯基毓、 三-P-甲苯基銃、三-甲苯基毓、參（4 -甲氧基苯基） 锍、1-萘基二苯基銃、2 -萘基二苯基锍、參（4 -氟苯基） -16- 200813633 毓、三-1_萘基锍、三-2-萘基毓、參（4-羥基苯基）毓、 4-(苯基硫）苯基二苯基毓、4- (p-甲苯基硫）苯基二-P-甲苯基鏡、4- (4-甲氧基苯基硫）苯基雙（4-甲氧基苯 基）毓、4-(苯基硫）苯基雙（4-氟苯基）毓、4-(苯基 硫）苯基雙（4-甲氧基苯基）毓、4-(苯基硫）苯基二-P-甲苯基锍、雙[4-(二苯基琉基）苯基]硫醚、雙[4-(雙[4-(2-羥基乙氧基）苯基]琉基）苯基]硫醚、雙（4-[雙（4-氟苯基）琉基]苯基）硫醚、雙（4-[雙（4-甲基苯基）琉 基]苯基）硫醚、雙（4-[雙（4-甲氧基苯基）琉基]苯基） 硫醚、4- (4-苯甲醯-4-氯苯基硫）苯基雙（4-氟苯基） 锍、4- ( 4-苯甲醯-4-氯苯基硫）苯基二苯基毓、4- ( 4-苯 甲醯苯基硫）苯基雙（4-氟苯基）锍、4-(4-苯甲醯苯基 硫）苯基二苯基锍、4-異丙基-4-氧代-10-硫雜-9，10-二氫 恩-2-基一^-p -甲苯基鏡、7 -異丙基-9-氧代-10 -硫雑-9,10 - ___. 氫蒽-2-基二-苯基锍、2-[(二-P-甲苯基）琉基]噻噸酮、 2-[(二苯基）琉基]噻噸酮、4-[4- ( 4-tert-丁基苯甲醯） 苯基硫]苯基二-P -甲苯基锍、4-[4- ( 4-tert-丁基苯甲醯） 苯基硫]苯基二苯基毓、4-[4-(苯甲醯苯基硫）]苯基二-P-甲苯基毓、4-[4-(苯甲醯苯基硫）]苯基二苯基毓、5-(4-甲氧基苯基）硫雜 anthrenium、5-苯基硫雜 anthrenium、5-甲苯基硫雜 anthrenium、5- ( 4-乙氧基苯 基）硫雜&1^11^11丨\1111、5-(2,4,6-三甲基苯基）硫雜 anthrenium等之三芳基鏑；二苯基苯醯甲基鏡、二苯基4-硝基苯醯甲基毓、二苯基苄基毓、二苯基甲基毓等之二芳 -17- 200813633 基銃；苯基甲基苄基毓、4-羥基苯基甲基苄基毓、4-甲氧 基苯基甲基苄基毓、4-乙醯羰基氧化苯基甲基苄基毓、2-萘基甲基苄基毓、2-萘基甲基（1-乙氧基羰基）乙基毓、 苯基甲基苯醯甲基锍、4-羥基苯基甲基苯醯甲基毓、4-甲 氧基苯基甲基苯醯甲基銃、4-乙醯羰基氧化苯基甲基苯醯 甲基毓、2-萘基甲基苯醯甲基銃、2-萘基十八烷基苯醯甲 基毓、9-蒽基甲基苯醯甲基毓等之單芳基毓；二甲基苯醯 甲基銃、苯醯甲基四氫噻吩鑰、二甲基苄基锍、苄基四氫 噻吩鑰、十八烷基甲基苯醯甲基毓等之三烷基毓等。此等 記載於以下文獻。 關於三芳基銃，可列舉美國專利第423 1 95 1號、美國 專利第4256828號、特開平7-61964號、特開平8-165290 號、特開平7-10914號、特開平7-25922號、特開平 8- 27208號、特開平8-27209號、特開平8- 1 65290號、特 開平8-3 0 1 99 1號、特開平9- 1 432 1 2號、特開平9-2788 1 3 號、特開平1 0-7680號、特開平10_287643號、特開平 1 0-245 3 78 號、特開平 8 - 1 5 75 1 0 號、特開平 1 0-204083 號、特開平8-245566號、特開平8- 1 5 745 1號、特開平 7-3 24069號、特開平9-26820 5號、特開平9-27 893 5號、 特開200 1 _2 8 8205號、特開平1 1-801 18號、特開平 1 0- 1 82825 號、特開平 1 0-3 3 0 3 5 3 號、特開平 1 0- 1 52495 號、特開平5 -23 92 1 3號、特開平7-3 3 3 83 4號、特開平 9- 1 253 7號、特開平8-32 5259號、特開平8- 1 60606號、 特開20 00- 1 8 607 1號（美國專利第63 68769號）等；關於 -18- 200813633 二芳基鏡，可列舉特開平7-3 005 04號、特開昭64-45 3 5 7 號、特開昭64-294 1 9號等；關於單芳基毓，可列舉特開 平6-345726號、特開平8-325225號、特開平9-118663號 (美國專利第6093 753號）、特開平2- 1 968 1 2號、特開 平2-1 470號、特開平2- 1 968 1 2號、特開平3 -23 7 1 07號、 特開平3-17101號、特開平6-228086號、特開平 1 0- 1 52469 號、特開平 7-3 00505 號、特開 2003 -277353 號、特開2003 -2773 52號等；關於三烷基鏡，可列舉特開 平 4-308563號、特開平 5_140210號、特開平 5-140209 號、特開平5 -23 0 1 8 9號、特開平6-27 1 532號、特開昭 58-37003 號、特開平 2-178303 號、特開平 10-338688 號、特開平9-3 2 8 5 0 6號、特開平1 1 -22 8 5 3 4號、特開平 8-27 1 02號、特開平7 -3 3 3 8 3 4號、特開平5-222 1 67號、 特開平1卜2 1 3 07號、特開平1 1 -3 5 6 1 3號、美國專利第 6 0 3 1 0 1 4 號等。 特別是上述光致陽離子聚合起始劑的銃，以三苯基 锍、4-(苯基硫）苯基二苯基毓較佳，下述式（2 )所表 示的4-(苯基硫）苯基二苯基锍最佳。 -19- 200813633 [化5]The photosensitive resin composition as described in (9) or (10) above contains the reactive epoxy monomer (C). (1) The photosensitive resin composition according to any one of the above (9) to (1), wherein the solid content of the photosensitive resin composition containing the solvent (D) is 5 to 95. weight%. (1) A photosensitive resin composition laminate according to any one of the above (1) to (1), wherein the photosensitive resin composition is used as the substrate. (I4) A cured product comprising the photosensitive resin composition according to any one of the above (1) to (12). (1) A method for forming a pattern comprising a photosensitive resin obtained by applying the photosensitive resin composition according to any one of the above (9) to (1) to a desired support. After the composition layer is dried, it is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a hardened resin pattern of a predetermined shape. (1) A method for forming a pattern comprising a photosensitive resin composition layer remaining after removing a substrate from the laminate described in the above (丨3), and bonding the layer to the desired support Laminating, exposing the photosensitive resin composition layer to a predetermined pattern, baking after exposure, developing a resin composition layer, and heat-treating the obtained resin pattern to obtain a hardened resin pattern of a predetermined shape to make. [Effects of the Invention] -15-200813633 The photosensitive resin composition of the present invention is suitable for the formation of a resin pattern having a high aspect ratio, and is particularly suitable for a resin having a high dimensional stability in a micro-sized electronic device or the like. Forming. [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described. The photosensitive resin composition of the present invention is characterized in that it contains a photo-cationic polymerization initiator (A) of a salt of cerium (pentafluoroethyl)trifluorophosphate ion of cerium, and a polyfunctional epoxy resin having a specific structure (B), a resin pattern having a high sensitivity and a high aspect ratio can be formed, and the ability to form the above resin pattern is not deteriorated, and the characteristics which can be exhibited for a long period of time can be imparted. There are various possibilities for such a combination, and in particular, a polyfunctional epoxy resin having a specific structure represented by the above formula (3) (for example, NC63 00 manufactured by Nippon Kayaku Co., Ltd.) and a compound represented by the above formula (2) The combination of photocationic polymerization initiators is optimal. The photocationic cationic polymerization initiator of the present invention is subjected to irradiation with radiation of excimer laser, X-ray, electron beam or the like of ultraviolet rays, far ultraviolet rays, KrF, ArF or the like to generate cations, and the cation can be polymerized. The compound of the starting agent. The photocationic polymerization initiator (A) is ruthenium (pentafluoroethyl)trifluorophosphate. The ruthenium of the photocationic polymerization initiator may, for example, be triphenylsulfonium, tri-P-methylphenylphosphonium, trimethylphenylphosphonium, stilbene (4-methoxyphenyl)phosphonium or 1-naphthyldiphenylbenzene. Base, 2-naphthyldiphenylfluorene, ginseng (4-fluorophenyl)-16-200813633 毓, tri-1_naphthyl anthracene, tri-2-naphthyl anthracene, ginseng (4-hydroxyphenyl)毓, 4-(phenylthio)phenyldiphenylphosphonium, 4-(p-tolylthio)phenyldi-P-tolyl mirror, 4-(4-methoxyphenylthio)phenyl double (4-methoxyphenyl)anthracene, 4-(phenylthio)phenylbis(4-fluorophenyl)anthracene, 4-(phenylthio)phenylbis(4-methoxyphenyl)anthracene , 4-(phenylthio)phenyldi-P-tolylhydrazine, bis[4-(diphenylfluorenyl)phenyl] sulfide, bis[4-(bis[4-(2-hydroxyethoxy) Phenyl]fluorenyl)phenyl] sulfide, bis(4-[bis(4-fluorophenyl)indenyl]phenyl) sulfide, bis(4-[bis(4-methylphenyl)) Mercapto]phenyl)thioether, bis(4-[bis(4-methoxyphenyl)indenyl]phenyl) sulfide, 4-(4-benzoguanidine-4-chlorophenylthio)benzene Bis(4-fluorophenyl)anthracene, 4-(4-benzothymol-4-chlorophenylsulfanyl)phenyldiphenylphosphonium, 4-(4- Methyl phenyl thio) phenyl bis(4-fluorophenyl) fluorene, 4-(4-benzylidene phenyl phenyl) phenyl diphenyl fluorene, 4-isopropyl-4-oxo-10- Thio-9,10-dihydro-2-yl-^-p-tolyl mirror, 7-isopropyl-9-oxo-10-thioindole-9,10 - ___. hydroquinone-2- Bis-phenylindole, 2-[(di-P-methylphenyl)indolyl]thioxanthone, 2-[(diphenyl)indenyl]thioxanthone, 4-[4-(4-tert- Butylbenzhydrazide) phenylsulfonyl]phenyldi-P-tolylhydrazine, 4-[4-(4-tert-butylbenzylidene)phenylthio]phenyldiphenylphosphonium, 4-[ 4-(benzimidylthio)]phenyldi-P-tolylhydrazine, 4-[4-(benzylidenephenylthio)]phenyldiphenylanthracene, 5-(4-methoxyl) Phenyl)thia anthrenium, 5-phenylthiaanthenium, 5-tolylthiaanthenium, 5-(4-ethoxyphenyl)thiane &1^11^11丨\1111, 5-(( Triaryl hydrazine of 2,4,6-trimethylphenyl)thiaanthrenium; diphenylphenylhydrazine methyl mirror, diphenyl 4-nitrophenylhydrazine methylhydrazine, diphenylbenzylhydrazine, Diphenylmethylhydrazine, etc., diaryl-17- 200813633 base; phenylmethylbenzyl hydrazine, 4-hydroxyphenylmethylbenzyl hydrazine, 4-methoxybenzene Methylbenzyl hydrazine, 4-ethyl hydrazine carbonyl phenyl methyl benzyl hydrazine, 2-naphthylmethyl benzyl hydrazine, 2-naphthylmethyl (1-ethoxycarbonyl) ethyl hydrazine, phenyl Methyl benzoquinone methyl hydrazine, 4-hydroxyphenyl methyl phenyl hydrazine methyl hydrazine, 4-methoxyphenyl methyl phenyl hydrazine methyl hydrazine, 4-ethyl hydrazine carbonyl phenyl phenyl hydrazine methyl Monoaryl hydrazine such as fluorene, 2-naphthylmethylphenylhydrazine methyl hydrazine, 2-naphthyl octadecyl phenyl hydrazine methyl hydrazine, 9-fluorenylmethyl phenyl hydrazine methyl hydrazine; dimethylbenzene A trialkylsulfonium such as hydrazine methyl hydrazine, benzoquinone methyltetrahydrothiophene key, dimethylbenzyl hydrazine, benzyl tetrahydrothiophene key, octadecylmethyl phenyl hydrazine methyl hydrazine or the like. These are described in the following documents. Examples of the triaryl sulfonium include U.S. Patent No. 4,231,951, U.S. Patent No. 4,256,828, U.S. Patent No. 4-6,1964, JP-A No. 8-165290, JP-A No. 7-10914, and JP-A No. 7-25922. Special Kaiping No. 8-27208, Special Kaiping No. 8-27209, Special Kaiping No. 8-1 65290, Special Kaiping No. 8-3 0 1 99 No., Special Kaiping 9- 1 432 1 2, Special Kaiping 9-2788 1 3 No., No. 1 0-7680, Special Kaiping 10_287643, Special Kaiping 1 0-245 3 78, Special Kaiping 8 - 1 5 75 1 0, Special Kaiping 1 0-204083, Special Kaiping 8-245566 , special Kaiping 8 - 1 5 745 1 , special Kaiping 7-3 24069, special Kaiping 9-26820 5, special Kaiping 9-27 893 5, special opening 200 1 _2 8 8205, special Kaiping 1 1- 801 18, special Kaiping 1 0- 1 82825, special Kaiping 1 0-3 3 0 3 5 3, special Kaiping 1 0- 1 52495, special Kaiping 5 -23 92 1 3, special Kaiping 7-3 3 3 83 4, special Kaiping 9- 1 253 7 , special Kaiping 8-32 5259, special Kaiping 8-1 60606, special opening 20 00- 1 8 607 1 (US Patent No. 63 68769), etc. ;About -18- 200813633 Diaryl mirror, can be listed as special Kaiping 7-3 005 04, special Kai-zhao 64-45 3 5 7 , special-opening 64-294 1 9 and so on; for the mono-aryl oxime, it can be cited in JP-A-6-345726, JP-A-8-325225, and JP-A 9-118663 ( US Patent No. 6093 753), Special Kaiping 2- 1 968 1 2, Special Kaiping 2-1 470, Special Kaiping 2- 1 968 1 2, Special Kaiping 3 -23 7 1 07, Special Kaiping 3- No. 17101, Special Kaiping No. 6-228086, Special Kaiping No. 1 0- 1 52469, Special Kaiping No. 7-3 00505, Special Open 2003-277353, Special Open 2003 - 2773 52, etc.; Listed by Kaikaiping No. 4-308563, Special Kaiping No. 5_140210, Special Kaiping No. 5-140209, Special Kaiping No. 5-23 0 1 8 9 , Special Kaiping 6-27 1 532, Special Kaikai No. 58-37003, Special Kaiping 2-178303, Special Kaiping 10-338688, Special Kaiping 9-3 2 8 5 0 6 , Special Kaiping 1 1 -22 8 5 3 4, Special Kaiping 8-27 1 02, Special Kaiping 7 -3 3 3 8 3 4, Special Kaiping 5-222 1 67, Special Kaiping 1 Bu 2 1 3 07, Special Kaiping 1 1 -3 5 6 1 3, US Patent No. 6 0 3 1 0 1 4, etc. . In particular, the oxime of the photocationic polymerization initiator is preferably triphenylphosphonium or 4-(phenylthio)phenyldiphenylphosphonium, 4-(phenylsulfate) represented by the following formula (2). Phenyldiphenylphosphonium is most preferred. -19- 200813633 [化5]
2 本發明中之具有上述特定結構之多官能環氧樹脂 (B )，只要是用於形成厚膜的圖型之一分子中含有充分 的環氧基之多官能環氧樹脂即可，可爲任何環氧樹脂，此 等具有上述特定結構之多官能環氧樹脂的環氧當量爲15〇〜 4 0 〇較佳，小於此範圍，由硬化收縮大而易發生硬化物的 翹曲或裂縫之觀點而言較不佳’另一方面，大於此範圍 時，因爲交聯密度變小、硬化膜的強度或耐藥品性、耐熱 性、耐裂縫性差而較不佳。符合上述範圍的多官能環氧樹 脂，以上述特定結構的多官能環氧樹脂（例如NC 6 3 〇〇曰 本化藥（股）製）爲特別佳。 具有上述特定結構之多官能環氧樹脂（B ) ’以下述 式（3 )表不。 -20- 200813633(2) The polyfunctional epoxy resin (B) having the above specific structure in the present invention may be a polyfunctional epoxy resin having a sufficient epoxy group in one of the patterns for forming a thick film, and may be Any epoxy resin, such a polyfunctional epoxy resin having the above specific structure has an epoxy equivalent of 15 〇 to 40 〇, preferably less than this range, and is hard to be warped or cracked by hardening. On the other hand, when it is larger than this range, the crosslinking density is small, the strength of the cured film or the chemical resistance, heat resistance, and crack resistance are poor. The polyfunctional epoxy resin having the above-mentioned range is particularly preferably a polyfunctional epoxy resin having a specific structure as described above (for example, NC 6 3 〇〇曰). The polyfunctional epoxy resin (B)' having the above specific structure is represented by the following formula (3). -20- 200813633
多官能環氧樹脂的軟化點低時，圖型化時易發生光罩 黏著，而且，作爲乾膜光阻使用時，因爲於常溫中軟化而 較不佳，另一方面，多官能環氧樹脂的軟化點高時，將乾 膜光阻層壓於基板時不易軟化，與基板的貼合性變差，故 較不佳。基於上述理由，多官能環氧樹脂的較佳軟化點爲 40〜120。(：，更佳爲 50〜100°C。 上述光致陽離子聚合起始劑（A )於該感光性樹脂組 成物中的含量太高’具有上述特定結構之多官能環氧樹脂 (B )於上述感光性樹脂組成物中的含量太低時’該樹脂 組成物的顯影困難，而且硬化後的膜變脆’故較不佳。相 反的，上述光致陽離子聚合起始劑（A )於該感光性樹脂 組成物中的含量太低’具有上述特定結構之多官能環氧樹 -21 - 200813633 脂（B )於上述感光性樹脂組成物中的含量太高時，塗佈 於基板上時該樹脂組成物之藉由放射線曝光的硬化時間變 長而較不佳。考量上述問題之下，光致陽離子聚合起始劑 (A)與具有上述特定結構之多官能環氧樹脂（B)的使用 比例以 0.1 : 99.9〜15 : 85爲佳，較佳爲 0 · 5 : 9 9 · 5〜1 0 ·· 90 ° 本發明的感光性樹脂組成物，爲了更加改良圖型的性 能，可添加具有混合性之反應性環氧單體（C )，反應性 環氧單體，可使用縮水甘油醚化合物，可列舉例如二乙二 醇二縮水甘油醚、己二醇二縮水甘油醚、二羥甲基丙烷二 縮水甘油醚、聚丙二醇二縮水甘油醚（旭電化工業（股） 製，ED5 0 6 )、三羥甲基丙烷三縮水甘油醚（旭電化工業 (股）製，ED5 05 )、季戊四醇四縮水甘油醚等；此等可 單獨使用或混合2種以上使用。反應性環氧單體（C )成 份’其目的係被使用於改善光阻的反應性或硬化膜的物 性’反應性環氧單體成份以液狀較多，該成份爲液狀時， 若摻合多於20重量。/。，則溶劑去除後的皮膜上易發生沾黏 而引起光罩黏著等，而較不適當，由此觀點而言，摻合反 應丨生環氧單體成份時，其摻合比例係（A)成份、（B)成 份及（C )成份的合計，以光阻的固體成份而言，相對於 此固體成份以1〜1〇重量％爲佳，特別是以2〜7重量％較適 合。 _彳氐本發明的感光性樹脂組成物的黏度，可使用提升 塗膜性之溶劑（D )，溶劑係可使用一般所使用的有機溶 -22- 200813633 劑且可溶解各成份者皆可使用，如此的有機溶劑可列舉丙 酮、甲基乙基酮、環己酮等之酮類，甲苯、二甲苯、四甲 基苯等之芳香族烴類，二丙二醇二甲基醚、二丙二醇二乙 基醚等之二醇醚類，乙酸乙酯、乙酸丁酯、丁基溶纖劑乙 酸酯、卡必醇乙酸酯、丙二醇單甲基醚乙酸酯、r-丁內 酯等之酯類，甲醇、乙醇、溶纖劑、甲基溶纖劑等之醇 類，辛烷、癸烷等之脂肪族烴、石油醚、石腦油、氫化石 腦油、溶劑石腦油等之石油系溶劑等之有機溶劑類等。 此等溶劑可單獨使用或組合2種以上使用，溶劑成份 的添加目的係調整塗佈於基材時的膜厚或塗佈性，爲了保 持適當的主成份的溶解性、成份的揮發性、組成物的液黏 度，相對於感光性樹脂組成物而言以5重量％〜95重量％較 佳，特別佳爲10重量％〜90重量％。 本發明的感光性樹脂組成物，爲了更提升組成物對於 基板的密著性之目的，亦可使用具有混合性之密著性賦予 劑，密著性賦予劑可使用矽烷偶合劑、鈦偶合劑等之偶合 劑，較佳者爲矽烷偶合劑。 上述矽烷偶合劑，可列舉3 -氯丙基三甲氧基矽烷、乙 稀基二氯砂院、乙嫌基二乙氧基砍院、乙燃基二甲氧基砂 烷、乙烯基•參（2-甲氧基乙氧基）矽烷、3-甲基丙烯氧 基丙基三甲氧基矽烷、2-(3,4-環氧環己基）乙基三甲氧 基矽烷、3 -環氧丙氧基丙基三甲氧基矽烷、3 -锍基丙基三 甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2·(胺基乙 基）-3-胺基丙基三甲氧基矽烷、3-醯脲丙基三乙氧基矽烷 -23- 200813633 等。此等密著性賦予劑，可單獨使用或組合2種以上使 用’密著性賦予劑因爲主成份爲未反應性，故除了於基材 界面作用的成份以外，在硬化後以殘存成份存在，所以， 大量使用則會產生物性降低等之壞影響，依基材的不同， 由即使少量亦可發揮效果之觀點而言，在不產生壞影響的 範圍內使用較爲適當，其使用比例係相對於感光性樹脂組 成物而言1 5重量％以下爲佳，特別佳爲1 0重量％以下。 本發明的感光性樹脂組成物中，亦可再使用目的爲吸 收紫外線而將所吸收的光能量供予光致陽離子聚合起始劑 之增感劑，作爲增感劑，較佳爲例如9位與1 0位上具有 烷氧基之蒽化合物（9,10-二烷氧基蒽衍生物），烷氧基可 列舉例如甲氧基、乙氧基、丙氧基等之C1〜C4的烷氧基。 9,10-二烷氧基蒽衍生物，亦可再具有取代基，取代基可列 舉例如氟原子、氯原子、溴原子、碘原子等之鹵素原子， 甲基、乙基、丙基等之C1〜C4的烷基或磺酸烷基酯基、羧 酸烷基酯基等。磺酸烷基酯基或羧酸烷基酯之烷基，可列 舉例如甲基、乙基、丙基等之C 1〜C4之烷基，此等的取代 基的取代位置爲2位較佳。 9，10-二烷氧基蒽衍生物，可列舉例如9，10-二甲氧基 蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二甲氧基· 2-乙基蒽、9，10-二乙氧基-2-乙基蒽、9，10-二丙氧基-2_乙 基蒽、9,10·二甲氧基-2-氯蒽、9,10-二甲氧基蒽-2-磺酸甲 基酯、9,10-二乙氧基蒽-2-磺酸甲基酯、9,10-二甲氧基蒽-2-羧酸甲基酯等；此等可單獨使用或混合2種以上使用。 -24- 200813633 增感劑成份’因爲少量即可發揮效果，故其使用比例係相 對於光致陽離子聚合起始劑（A )而言3重量％以下爲 佳，特別佳爲1重量％以下。 本發明中，必須降低因爲來自光致陽離子起始聚合劑 (A )的離子所產生的壞影響時，亦可添加參甲氧基銘、 參乙氧基鋁、參異丙氧基鋁、異丙氧基二乙氧基鋁、參丁 氧基銘等之院氧基銘，參苯氧基銘、參對甲基苯氧基銘等 之苯氧基鋁，參乙醯氧基鋁、參硬脂酸鋁、參丁酸鋁、參 丙酸鋁、參乙醯丙酮鋁、參三氟乙醯丙酮鋁、參乙基乙醯 乙酸鋁、二乙醯丙酮二（三甲基乙醯）甲酸鋁、二異丙氧 基（乙基乙醯乙酸）鋁等之有機鋁化合物等之離子捕捉 劑；此等成份可單獨使用或組合2種以上使用，此外，其 摻合量係可爲相對於固體成份而言1 0重量％以下。 而且本發明中必要時，可使用熱塑性樹脂、著色劑、 增黏劑、消泡劑、塗平劑等之各種添加劑。熱塑性樹脂可 列舉例如聚醚礪、聚苯乙烯、聚碳酸酯等；著色劑可列舉 例如酞菁藍、酞菁綠、碘綠、結晶紫、氧化鈦、碳黑、萘 黑等。增黏劑可列舉例如Orben、潘通、蒙脫石等；消泡 劑可列舉例如聚矽氧烷系、氟系及高分子系等之消泡劑。 使用此等添加劑等，其使用量係在本發明的感光性樹脂組 成物中，例如各自爲0.1〜30重量％左右爲大槪的簡單標 準，可依其使用目的而適當增減。 此外，本發明中，可使用硫酸鋇、鈦酸鋇、氧化砂、 無定形二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化 -25- 200813633 鋁、氫氧化鋁、雲母粉等之無機塡充劑，其摻合比例可爲 組成物中的0〜60重量％。 本發明的感光性樹脂組成物，較佳爲依下述表1的比 例添加，必要時亦可添加上述密著性賦予劑、增感劑、離 子捕捉劑、熱塑性樹脂、著色劑、增黏劑、消泡劑、塗平 劑及無機塡充劑。以一般的方法混合，亦可僅攪拌，必要 時亦可使用溶解器、均化器、3輥機等之分散機進行分 散、混合，混合後可再用、網狀篩、膜濾器等過濾。 [表1] 重量份 光致陽離子聚合起始劑(A) 0.1 〜15 本發明之多官能環氧樹脂(B) 85-99.9 反應性環氧單體(C) 1〜10 溶劑(D) 5.8 〜2090 本發明的感光性樹脂組成物，較佳爲以液狀使用，使 用本發明的感光性樹脂組成物時，例如可使用旋轉塗佈機 等以0.1〜1 00 0 // m的厚度塗佈於矽晶圓、玻璃等基板上， 以60〜130°C熱處理5〜60分鐘左右，去除溶劑而形成感光 性樹脂組成物層後，載置具有所定圖型的光罩後照射紫外 線，以50〜130°C進行1〜50分鐘左右的加熱處理後，將未 曝光部份用顯影液以室溫〜50°C顯影1〜180分鐘左右後形 成圖型，接著以130〜200°C加熱處理，得到符合諸特性之 永久保護膜。顯影液可使用例如r - 丁內酯、三乙二醇二 甲基醚、丙二醇單甲基醚乙酸酯等之有機溶劑、或上述有 -26- 200813633 機溶劑與水的混合液，顯影亦可使用攪拌型、噴 淋型等之顯影裝置，必要時亦可進行超音波照射 本發明的感光性樹脂組成物，係使用滾軸塗 縫式塗佈機（d i e c 〇 at e r )、刮刀塗佈機、棒塗佈 凹版印刷塗佈機等塗佈該組成物於基礎薄膜上後 在45〜100 °C的乾燥爐進行乾燥，藉由去除所定量 又必要時藉由層合外層膜作爲乾膜光阻。此時， 上的光阻的厚度調製爲2〜100/zm，基礎薄膜及 可使用例如聚酯、聚丙烯、聚乙烯、TAC、聚醯 薄膜，此等薄膜必要時可使用藉由矽系離型處理 系離型處理劑被離型處理的薄膜。使用此乾膜光 藉由手動式滾軸、層壓機等剝離外層膜，以40 °C 壓力0·05〜2MPa轉印於基板，可進行與上述相同 曝光後烘烤、顯影、加熱處理。 將上述的感光性樹脂組成物以薄膜供給，可 於支撐體、及乾燥的步驟，可更簡便地進行圖型？ 藉由上述方法所得到的本發明的樹脂組成 物，例如作爲永久光阻膜利用於噴射記錄噴頭等 零件。 【實施方式】 [實施例] 以下說明本發明的實施例，此等實施例僅爲 明本發明之例子，並非限定本發明。 霧型、噴 〇 佈機、狹 機、照相 ，用設定 的溶劑， 基礎薄膜 外層膜， 亞胺等之 劑或非矽 阻，例如 〜100〇C、 的曝光、 省略塗佈 杉成。 物的硬化 MEMS 用 適當地說 -27- 200813633 實施例1〜3、比較例1 (感光性樹脂組成物） 依照表2所記載的摻合量（單位爲重量份），將多官 能環氧樹脂、光致陽離子聚合起始劑、及其他的成份，於 附有攪拌機的燒瓶中以60 °C攪拌混合1小時，得到感光性 樹脂組成物。 (感光性樹脂組成物的圖型化） 將此感光性樹脂組成物用旋轉塗佈機塗佈於矽晶圓上 後乾燥，而得到具有80 // m的膜厚之感光性樹脂組成物 層，將此感光性樹脂組成物層藉由加熱板以65 t進行5分 鐘及95 °C進行20分鐘之預烘烤，然後，使用i線曝光裝 置（光罩對準裝置：USHIO電機公司製）進行圖型曝光 (軟式接觸，i線），藉由加熱板以95 °C進行6分鐘的曝 光後烘烤（PEB )，接著使用丙二醇單甲基醚乙酸酯，藉 由浸漬法以23 °C進行7分鐘的顯影處理’於基板上得到硬 化樹脂圖型。 (感光性樹脂組成物的評估） 顯影後藉由必要曝光量進行下述評估’結果列示於下 述表2。 最適曝光量：使光罩轉印精密度爲最佳之曝光量 長寬比··膜厚/所形成的光阻圖型中所密著之最細的 -28- 200813633 圖型寬 [表2] 摻合成份 實施例 比較例 1 2 3 1 光致陽離子聚合起始劑 A 4.6 4.6 2.8 G 9.2 本發明之多官能環氧樹脂 B 100 100 100 100 反應性環氧單體 C 4 4 4 溶劑 D 30 30 30 30 塗平劑 E 0.06 0.06 0.06 0.06 矽烷偶合劑 F 2 2 2 最適曝光量(mJ/cm2) 350 350 500 550 長寬比 9.1 9.1 5.5 5.4 註解z (A) :光致陽離子聚合起始劑 (商品名：CPI-210S san-apro (股）製） (B) :本發明之多官能環氧樹脂 〇 (商品名：NC63 00曰本化藥（股）製） (C) :反應性環氧單體 (商品名：ED 5 06旭電化工業（股）製） (D ):溶劑環戊酮 (E ):塗平劑 (商品名：MEGAFAC F-470 大日本油墨化學工業 (股）製） (F ):矽烷偶合劑 (商品名：S-510CHISSO (股）製） (G ):光致陽離子聚合起始劑 -29- 200813633 (商品名：UVI-6974 Dow Chemical公司製5 0 %碳酸丙 烯溶液） 如表2所示，實施例1〜3皆爲好的結果。 實施例4 (感光性樹脂組成物） 混合1 〇〇重量份的本發明之多官能樹脂（商品名 NC63 00日本化藥（股）製）、4.6重量份的光致聚合起 始劑（商品名 CPI-210S san-apro (股）製）、4重量份 的反應性環氧單體（商品名 ED5 06旭電化工業（股） 製）、及3 0重量份的甲基乙基酮，得到感光性樹脂組成 物。 (感光性樹脂組成物的圖型化） 將此感光性樹脂組成物均勻地塗佈於6 0 // m的聚丙烯 (PP)薄膜（基礎薄膜，東麗（股）製）上，藉由溫風對 流乾燥機以65 °C進行10分鐘及80 °C進行15分鐘乾燥 後，於感光性樹脂組成物層上層合膜厚60 // m的PP薄膜 (外層膜，東麗（股）製），形成40 // m的膜厚的感光性 樹脂組成物層合物。 剝離此感光性樹脂組成物層合物的外層膜，以滾軸溫 度7〇°C、氣體壓力〇.2MPa、速度0.5m/min層合於矽晶圓 上，剝離基礎薄膜，再重複此操作而得到8 0 # m的感光性 樹脂組成物層。於此感光性樹脂組成物層上，使用i線曝 -30- 200813633 光裝置（光罩對準裝置：us HIO電機公司製）進行圖型曝 光（軟式接觸，i線），然後，藉由加熱板以95t進行6 分鐘的PEB，接著使用丙二醇單甲基醚乙酸酯，藉由浸漬 法以2 3 °C進行7分鐘的顯影處理，於基板上得到硬化樹脂 圖型。得到最適曝光量3 5 0mJ/cm2、長寬比9.1之優良的 結果。 由實施例1〜4與比較例1結果的比較，可清楚的知道 藉由特定結構的多官能環氧樹脂與特定的光致陽離子聚合 起始劑的組合，可得到其他組合所無法得到的高感度且高 長寬比的外形的樹脂圖型。 〔產業上的可利用性〕 如上述，本發明該相關的感光性樹脂組成物，適合形 成具有高長寬比的外形之樹脂圖型，特別是適合於微細尺 寸的電子裝置等之尺寸安定性高的樹脂成形。 -31 -When the softening point of the polyfunctional epoxy resin is low, the mask is likely to adhere when patterning, and when used as a dry film photoresist, it is less preferred to soften at room temperature, and on the other hand, a multifunctional epoxy resin. When the softening point is high, when the dry film photoresist is laminated on the substrate, it is hard to soften, and the adhesion to the substrate is deteriorated, which is not preferable. For the above reasons, the polyfunctional epoxy resin preferably has a softening point of 40 to 120. (:, more preferably 50 to 100 ° C. The photocationic polymerization initiator (A) is too high in the photosensitive resin composition. The polyfunctional epoxy resin (B) having the above specific structure is When the content in the photosensitive resin composition is too low, the development of the resin composition is difficult, and the cured film becomes brittle, which is less preferable. Conversely, the photocationic polymerization initiator (A) is The content of the photosensitive resin composition is too low. 'The polyfunctional epoxy tree having the above specific structure - 200813633 The fat (B) is too high when the content of the photosensitive resin composition is applied to the substrate. The curing time of the resin composition by radiation exposure becomes longer and less. Considering the above problems, the use of the photocationic polymerization initiator (A) and the polyfunctional epoxy resin (B) having the above specific structure is used. The ratio is preferably 0.1:99.9 to 15:85, preferably 0 · 5 : 9 9 · 5 to 1 0 ·· 90 ° The photosensitive resin composition of the present invention may be added in order to further improve the performance of the pattern. Mixed reactive epoxy monomer (C), As the epoxy monomer, a glycidyl ether compound can be used, and examples thereof include diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, and polypropylene glycol diglycidyl ether. (Asahi Chemical Industry Co., Ltd., ED5 0 6 ), trimethylolpropane triglycidyl ether (made by Asahi Kasei Co., Ltd., ED5 05), pentaerythritol tetraglycidyl ether, etc.; these can be used alone or mixed Two or more types are used. The reactive epoxy monomer (C) component is used for improving the reactivity of the photoresist or the physical properties of the cured film. The reactive epoxy monomer component is more in liquid form. In the case of liquid, if the blending is more than 20% by weight, the film after removal of the solvent is liable to stick to the viscous mask, and is less suitable. From this point of view, the blending reaction twin ring In the case of an oxygen monomer component, the blending ratio is a total of (A) component, (B) component, and (C) component, and the solid component of the photoresist is 1 to 1% by weight relative to the solid component. Good, especially suitable for 2~7 wt%. _彳氐本发For the viscosity of the photosensitive resin composition, a solvent (D) for improving the coating property can be used, and the solvent can be used by using the organic solvent -22-200813633 which is generally used, and the components can be dissolved. Such an organic solvent can be used. Examples thereof include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; Alcohol ethers, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, r-butyrolactone and other esters, methanol, ethanol, dissolved An organic solvent such as an alcohol such as a fiber or a methyl cellosolve; an aliphatic hydrocarbon such as octane or decane, petroleum petroleum, naphtha, hydrogenated naphtha or solvent naphtha; Wait. These solvents may be used singly or in combination of two or more. The purpose of the solvent component is to adjust the film thickness or coatability when applied to a substrate, in order to maintain proper solubility of the main component, volatility of the component, and composition. The liquid viscosity of the material is preferably from 5% by weight to 95% by weight, particularly preferably from 10% by weight to 90% by weight, based on the photosensitive resin composition. In the photosensitive resin composition of the present invention, in order to further improve the adhesion of the composition to the substrate, a miscibility imparting agent having a miscibility may be used, and a decane coupling agent or a titanium coupling agent may be used as the adhesion imparting agent. The coupling agent is preferably a decane coupling agent. The above decane coupling agent may, for example, be 3-chloropropyltrimethoxydecane, ethylene dichlorosilane, Ethylene diethoxy chopping, Ethyl dimethoxy sulane, Vinyl ginseng ( 2-methoxyethoxy)decane, 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxy Propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2·(Aminoethyl)-3-aminopropyltrimethoxy Baseline, 3-ureidopropyltriethoxydecane-23-200813633, and the like. These adhesion imparting agents may be used singly or in combination of two or more kinds. The adhesiveness imparting agent is used because the main component is unreactive, and therefore, in addition to the component acting on the interface of the substrate, the residual component exists after hardening. Therefore, if it is used in a large amount, it will cause a bad influence such as a decrease in physical properties. Depending on the substrate, it is appropriate to use it in a range that does not cause adverse effects from the viewpoint of exerting a small amount of effect, and the ratio of use is relatively The photosensitive resin composition is preferably 15% by weight or less, particularly preferably 10% by weight or less. In the photosensitive resin composition of the present invention, a sensitizer which absorbs ultraviolet light and supplies the absorbed light energy to the photocationic polymerization initiator may be further used as the sensitizer, preferably, for example, 9-position. And a fluorene compound having alkoxy group at the 10 position (9,10-dialkyloxyanthracene derivative), and the alkoxy group may, for example, be a C1 to C4 alkane such as a methoxy group, an ethoxy group or a propoxy group. Oxygen. The 9,10-dialkoxyfluorene derivative may further have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a methyl group, an ethyl group, a propyl group or the like. An alkyl group or a sulfonic acid alkyl ester group or a carboxylic acid alkyl ester group of C1 to C4. The alkyl group of the alkyl sulfonate group or the alkyl carboxylate may, for example, be a C 1 to C 4 alkyl group such as a methyl group, an ethyl group or a propyl group, and the substitution position of these substituents is preferably 2 positions. . The 9,10-dialkoxypurine derivative may, for example, be 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Methoxy 2-ethyl hydrazine, 9,10-diethoxy-2-ethyl hydrazine, 9,10-dipropoxy-2-ethyl hydrazine, 9,10-dimethoxy-2 -chloropurine, 9,10-dimethoxyindole-2-sulfonic acid methyl ester, 9,10-diethoxyindole-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene- 2-carboxylic acid methyl ester or the like; these may be used singly or in combination of two or more. -24- 200813633 The sensitizer component is effective in a small amount, and therefore the use ratio is preferably 3% by weight or less, particularly preferably 1% by weight or less, based on the photocationic polymerization initiator (A). In the present invention, it is necessary to reduce the adverse effects due to ions derived from the photocationic cationic starting polymerization agent (A), and it is also possible to add methoxymethoxy, ethoxylated aluminum, paraisopropoxide, and the like. Propyloxydiethoxyaluminum, hexyleneoxy, etc., oxyalkyl, phenoxy, phenoxymethyl, phenoxymethyl, phenoxy Aluminum stearate, aluminum arsenate, aluminum propionate, aluminum acetonide, aluminum hexafluoroacetate, aluminum acetoacetate, diethyl acetonide acetonate An ion scavenger such as an organoaluminum compound such as aluminum or diisopropoxy (ethyl acetoacetate) aluminum; these components may be used singly or in combination of two or more kinds, and the blending amount thereof may be relative to The solid content is 10% by weight or less. Further, in the case of the present invention, various additives such as a thermoplastic resin, a colorant, a tackifier, an antifoaming agent, and a leveling agent can be used. Examples of the thermoplastic resin include polyether oxime, polystyrene, and polycarbonate; and examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, and the like. Examples of the tackifier include Orben, Pantone, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as polysiloxanes, fluorines, and polymers. The amount of the additive to be used in the photosensitive resin composition of the present invention is, for example, about 0.1 to 30% by weight, which is a simple standard for large sputum, and can be appropriately increased or decreased depending on the purpose of use. Further, in the present invention, inorganic salts such as barium sulfate, barium titanate, oxidized sand, amorphous ceria, talc, clay, magnesium carbonate, calcium carbonate, oxidized -25-200813633 aluminum, aluminum hydroxide, mica powder, etc. may be used. The chelating agent may be incorporated in an amount of from 0 to 60% by weight of the composition. The photosensitive resin composition of the present invention is preferably added in the proportions shown in Table 1 below, and if necessary, the above-mentioned adhesion imparting agent, sensitizer, ion trapping agent, thermoplastic resin, coloring agent, and tackifier may be added. , defoamer, coating agent and inorganic chelating agent. The mixture may be mixed in a usual manner, or may be stirred only, and if necessary, it may be dispersed, mixed by a dispersing machine such as a dissolver, a homogenizer or a 3-roller, and may be reused after filtration, a mesh sieve, a membrane filter or the like. [Table 1] Parts by weight photo-cationic polymerization initiator (A) 0.1 to 15 Polyfunctional epoxy resin (B) of the present invention 85-99.9 Reactive epoxy monomer (C) 1 to 10 Solvent (D) 5.8 ～2090 The photosensitive resin composition of the present invention is preferably used in the form of a liquid, and when the photosensitive resin composition of the present invention is used, it can be coated, for example, by a spin coater or the like at a thickness of 0.1 to 100 μm. It is placed on a substrate such as a wafer or a glass, and heat-treated at 60 to 130 ° C for about 5 to 60 minutes to remove a solvent to form a photosensitive resin composition layer. Then, a mask having a predetermined pattern is placed and irradiated with ultraviolet rays. After heating at 50 to 130 ° C for about 1 to 50 minutes, the unexposed portion is developed with a developer at room temperature to 50 ° C for about 1 to 180 minutes to form a pattern, followed by heating at 130 to 200 ° C. The treatment results in a permanent protective film that meets the characteristics. The developing solution may be an organic solvent such as r-butyrolactone, triethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate, or a mixture of the above-mentioned solvent of -26-200813633 and water, and developed. A developing device such as a stirring type or a shower type can be used, and if necessary, the photosensitive resin composition of the present invention can be ultrasonically irradiated, and a roller coating machine (diec 〇at er ) or doctor blade coating can be used. Coating the composition on a base film by a machine, a bar coating gravure coater, etc., and drying it in a drying oven at 45 to 100 ° C, by removing the amount and, if necessary, by laminating the outer film as a dry film. Light resistance. At this time, the thickness of the upper photoresist is adjusted to 2 to 100/zm, and the base film and the like, for example, polyester, polypropylene, polyethylene, TAC, and polyfluorene film can be used, and these films can be used by using a ruthenium The type of treatment is a film in which the release treatment agent is subjected to release treatment. By using this dry film light, the outer layer film is peeled off by a manual roller, a laminator or the like, and transferred to the substrate at a pressure of 0. 05 to 2 MPa at 40 ° C, and the same post-exposure baking, development, and heat treatment as described above can be performed. The above-mentioned photosensitive resin composition is supplied as a film, and the support can be dried and the drying step can be carried out more easily. The resin composition of the present invention obtained by the above method is used, for example, as a permanent photoresist film for ejecting a recording head or the like. [Embodiment] [Embodiment] The embodiments of the present invention are described below, and the embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Mist type, spray cloth machine, slit machine, photographing, using a set solvent, base film outer film, imine or the like or non-resistance, for example, ~100〇C, exposure, omitting coating. The hardened MEMS of the material is appropriately used. -27-200813633 Examples 1 to 3, Comparative Example 1 (Photosensitive resin composition) According to the blending amount (unit: parts by weight) described in Table 2, a polyfunctional epoxy resin is used. The photo-cationic polymerization initiator and other components were stirred and mixed at 60 ° C for 1 hour in a flask equipped with a stirrer to obtain a photosensitive resin composition. (Picture of the photosensitive resin composition) The photosensitive resin composition was applied onto a tantalum wafer by a spin coater and dried to obtain a photosensitive resin composition layer having a film thickness of 80 // m. The photosensitive resin composition layer was prebaked by a heating plate at 65 t for 5 minutes and at 95 ° C for 20 minutes, and then an i-line exposure apparatus (mask aligning device: manufactured by USHIO Electric Co., Ltd.) was used. Pattern exposure (soft contact, i-line), post-exposure bake (PEB) at 95 °C for 6 minutes, followed by propylene glycol monomethyl ether acetate, by dipping at 23 ° C was subjected to development treatment for 7 minutes to obtain a hardened resin pattern on the substrate. (Evaluation of photosensitive resin composition) The following evaluation was carried out by the necessary exposure amount after development. The results are shown in Table 2 below. Optimum exposure: make the reticle transfer precision the best exposure amount aspect ratio · · film thickness / the thinnest of the formed photoresist pattern -28- 200813633 pattern width [Table 2 Doped Composition Example Comparative Example 1 2 3 1 Photocationic Polymerization Initiator A 4.6 4.6 2.8 G 9.2 Multifunctional Epoxy Resin B 100 100 100 100 100 Reactive Epoxy Monomer C 4 4 4 Solvent D 30 30 30 30 Leveling agent E 0.06 0.06 0.06 0.06 decane coupling agent F 2 2 2 Optimum exposure (mJ/cm2) 350 350 500 550 Aspect ratio 9.1 9.1 5.5 5.4 Note z (A): photocationic polymerization initiation (product name: CPI-210S san-apro (manufactured by the company)) (B): The polyfunctional epoxy resin of the present invention (trade name: NC63 00 曰 化 化 化) (C): Reactivity Epoxy monomer (trade name: ED 5 06 Asahi Chemical Co., Ltd.) (D): Solvent cyclopentanone (E): coating agent (trade name: MEGAFAC F-470 Dainippon Ink Chemical Industry Co., Ltd.) (F): decane coupling agent (trade name: S-510CHISSO (manufactured by the company)) (G): photocationic polymerization initiator -29- 200813633 (trade name: UVI-6974 Dow C As shown in Table 2, all of Examples 1 to 3 were good results. Example 4 (Photosensitive Resin Composition) The polyfunctional resin of the present invention (trade name: NC63 00, manufactured by Nippon Chemical Co., Ltd.) and 4.6 parts by weight of a photopolymerization initiator (trade name) were mixed in an amount of 1 part by weight. CPI-210S san-apro (manufactured by San-apro Co., Ltd.), 4 parts by weight of reactive epoxy monomer (trade name: ED5 06 Asahi Chemical Co., Ltd.), and 30 parts by weight of methyl ethyl ketone, which are photosensitive Resin composition. (Picture of the photosensitive resin composition) The photosensitive resin composition was uniformly applied to a 60 (μm) polypropylene (PP) film (base film, manufactured by Toray Industries Co., Ltd.). After drying in a warm air convection dryer at 65 ° C for 10 minutes and at 80 ° C for 15 minutes, a PP film having a film thickness of 60 // m was laminated on the photosensitive resin composition layer (outer film, manufactured by Toray Industries, Inc.) ), a photosensitive resin composition laminate having a film thickness of 40 // m was formed. The outer layer film of the photosensitive resin composition laminate was peeled off, laminated on a ruthenium wafer at a roller temperature of 7 〇 ° C, a gas pressure of 2 2 MPa, and a speed of 0.5 m / min, and the base film was peeled off, and this operation was repeated. Thus, a photosensitive resin composition layer of 80 #m was obtained. On the photosensitive resin composition layer, pattern exposure (soft contact, i line) was performed using an i-ray exposure -30-200813633 optical device (mask aligning device: manufactured by Us HIO Motor Co., Ltd.), and then, by heating The plate was subjected to PEB at 95 t for 6 minutes, and then propylene glycol monomethyl ether acetate was used, and development treatment was carried out at 23 ° C for 7 minutes by a dipping method to obtain a hardened resin pattern on the substrate. An excellent result of an optimum exposure amount of 305 mJ/cm2 and an aspect ratio of 9.1 was obtained. From the comparison of the results of Examples 1 to 4 and Comparative Example 1, it is clear that a combination of a polyfunctional epoxy resin having a specific structure and a specific photocationic polymerization initiator can provide a high which cannot be obtained by other combinations. A resin pattern with a shape of sensitivity and a high aspect ratio. [Industrial Applicability] As described above, the photosensitive resin composition according to the present invention is suitable for forming a resin pattern having an outer shape having a high aspect ratio, and is particularly suitable for a high dimensional stability of an electronic device having a fine size. Resin molding. -31 -