200813626 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、高長寬比的圖型之感 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1〇〇 μιη 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 μιη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 0〜45 0 nm)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現 -4- 200813626 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350〜45 0 nm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iution Performance Product 製 EPON SU-8樹脂）、如 Dow Chemical 製 CYRACURE UVI-6974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毓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1 00 μιη 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。 EPON 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、（2)高支鏈度、（3)350〜450 nm的高 穿透率、（4)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 μιη以上 的厚膜且長寬比10以上的圖型之光阻性能。選擇具有高環 -5- 200813626 氧官能基數與高支鏈度之樹脂，係對於欲形成具有直線的 側壁及具有高長寬比之結構物而言爲重要項目；選擇低分 子量樹脂，係可用最小塗佈階段數在基板上形成厚膜光阻 固形物層。 以锍鹽或碘鑰鹽爲基礎的光致陽離子聚合起始劑爲人 熟知，揭示具有適當的吸光度之有用的光致陽離子聚合起 始劑，含有羰基-P-苯撐硫醚（專利文獻1、2)，而且亦可添 加如2-烷基-9,10-二甲氧基蒽或其他的蒽、萘、綠柱石或 吡咯基（pyrryl)化合物之增感劑，亦可導入於光致陽離子 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基礎之負型 光阻，由MICRO CHEM公司所販售，特別是在商業上使 用於MEMS裝置零件。例如由MICRO CHEM公司所提供 的「SU_8系列」，爲了形成30〜100 μιη厚的膜而以 1 000〜3 000 rpm旋轉塗佈，接著曝光•顯影後，可形成 1〇〇 μπι以上的膜厚且長寬比10以上的圖型。 亦揭示關於塗佈於如聚酯薄膜的基材上之乾膜光阻的 用途（專利文獻4)。 揭示適合作爲防焊劑（soldermask)使用之可感光的陽 離子聚合性難燃劑的組成物（專利文獻5、6、7)，此爲由 含有10〜80重量％之雙酚A與表氯醇的縮合物之混合物所 成，由含有20〜90重量％的雙酚 A酚醛清漆環氧樹脂、 35〜50重量％的環氧化四溴雙酚 A、0.1〜15重量％的光致陽 離子聚合起始劑之組成而成。 -6- 200813626 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 μιη 厚以上的厚膜之應力（專利文獻8)。 專利文獻9中，揭示在可ΕΒ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ΕΒ照射而被影像化的膜之組成 物，被用UV、X射線、ΕΒ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10)，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用 200813626 於如飩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 〇 關於含環氧之光阻組成物，已揭示許多不同的組合或 各種的環氧樹脂的混合物’者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MEMS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]USP 5,502,083 [專利文獻 2]USP 6,3 68,769 [專利文獻 3]USP 5，1 02,772 [專利文獻 4]USP 4,882,245 [專利文獻 5]USP 5,026,624 [專利文獻 6]USP 5,278,0 1 0 [專利文獻 7]USP 5,3 04,45 7 [專利文獻 8]USP 4,25 6,828 [專利文獻 9]USP 5,726,2 1 6 [專利文獻 l〇]USP 5,264,3 2 5 【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 -8- 200813626 起始劑的感度低，需要大量的起始劑，故會有無法於短時 間內將光罩圖型忠實重現於樹脂圖型之問題點，此外，含 有SbF^之先4(^離子聚合起始劑較屬於局感度，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）三 氟磷酸毓之光致陽離子聚合起始劑（A)、與主鏈結構上具 有脂環結構且環氧基爲3個以上之多官能環氧化合物（B)所 成。 (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（1)所表示之化合物（A-1) ° 200813626 【化1】[Technical Field] The present invention relates to a photosensitive resin composition capable of forming a high resolution, high aspect ratio pattern, a laminate thereof, a cured product thereof, and a pattern using the same The method of formation. [Prior Art] Photoresistive photo-resistance has recently been widely used in semiconductor or MEMS (Micro-Electro-Mechanical Systems) applications. Such lithography is performed on a substrate by pattern exposure. Then, development is carried out with a developing solution to selectively remove the exposed or non-exposed areas. The photo-resistance (photoresist) processed by photolithography has a positive or negative type, and is dissolved in the developing solution by exposure to a positive type, and insoluble is a negative type. The advanced electropackage application requires a high aspect ratio. On the other hand, the MEMS application requires uniform formation of a spin coating film and a thick film of 1 〇〇μη 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 a thick film of 50 μm or more, and there is a limit in thick film formation because it is generally used for photoresist exposure. The dinaphthoquinone type (DNQ) photoreactant in the near-ultraviolet region (3 5 0~45 0 nm) has a relatively high light absorption, and the DNQ type photoresist is dissolved by the specific exposed area and non-exposed area in the developing solution. The difference in nature is such that the shape of the side wall is not linear but instead presents a slanted shape of -4-200813626. 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, 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 350 to 45 nm wavelength range, consisting of polyfunctional bisphenol A novolac epoxy Resin (EPON SU-8 resin manufactured by Res〇Iution Performance Product), photocationic polymerization initiator such as CYRACURE UVI-6974 manufactured by Dow Chemical (this photocationic polymerization initiator is yttrium aromatic hexafluoroantimonate) Prepared by a propylene carbonate solution, the photoresist composition is applied to various substrates by spin coating or curtain coating, and then the solvent is volatilized by baking to form 100 μm or more. a solid photoresist layer having a thickness of a plurality of exposure methods, such as contact exposure, proximity exposure, and projection exposure, which is subjected to photolithography by irradiating a near-ultraviolet light through a photomask, and then immersed in a developing solution. The non-exposed areas are dissolved to form a negative image of the highly resolved mask on the substrate. EPON 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 and (2) high branch chain. Degree, (3) high transmittance of 350~450 nm, (4) low molecular weight necessary for solid form formation; high epoxy functional group and high branching degree cause sufficient cross-linking under high acid catalyst, high penetration The rate system penetrates the thick film and is uniformly irradiated with light, and has a photoresist pattern of a thick film having a thickness of 100 μm or more and an aspect ratio of 10 or more. Selecting a resin having a high ring-5-200813626 oxygen functional group and a high degree of branching is an important item for forming a side wall having a straight line and a structure having a high aspect ratio; selecting a low molecular weight resin, the number of minimum coating stages available A thick film photoresist layer is formed on the substrate. A photocationic polymerization initiator based on a phosphonium salt or an iodine salt is well known, and a useful photocationic polymerization initiator having a suitable absorbance is disclosed, which contains a carbonyl-P-phenylene sulfide (Patent Document 1) And 2), and may also add a sensitizer such as 2-alkyl-9,10-dimethoxyanthracene or other anthracene, naphthalene, beryl or pyrryl compound, or may be introduced into the photo-induced Cationic polymerization initiator (Patent Document 3). Negative photoresists based on compounds suitable for spin coating, such as those disclosed above, are sold by MICRO CHEM Corporation, particularly commercially for use in MEMS device parts. For example, the "SU_8 series" supplied by MICRO CHEM Co., Ltd. can be spin-coated at a temperature of 1 000 to 3 000 rpm in order to form a film having a thickness of 30 to 100 μm, and then a film thickness of 1 μm or more can be formed after exposure and development. And the aspect ratio of 10 or more. The use of a dry film photoresist coated on a substrate such as a polyester film is also disclosed (Patent Document 4). A composition of a photosensitive cationically polymerizable flame retardant suitable for use as a solder mask (Patent Documents 5, 6, and 7) is disclosed, which is composed of 10 to 80% by weight of bisphenol A and epichlorohydrin. a mixture of condensates, starting from 20 to 90% by weight of bisphenol A novolac epoxy resin, 35 to 50% by weight of epoxidized tetrabromobisphenol A, 0.1 to 15% by weight of photocationic polymerization The composition of the agent. -6- 200813626 Also disclosed is a photopolymerizable compound based on an epoxy group-containing additive, a photocationic polymerization initiator, and an epoxy resin having a functional group number of 1.5 or more, and a hydroxyl group-containing additive has been reported to be added. Flexibility or stress reduction of a thick film of 100 Å or more thick (Patent Document 8). Patent Document 9 discloses a method of using a hard epoxy resin for use in a hardenable application, in which the main improvement 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. The tough material is composed of various thermoplastic plastics, hydroxyl-containing thermoplastic plastic 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 irradiation with a non-pattern, and is patterned by exposure to UV, X-ray, or xenon. 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 10) in which, for example, the necessity of modulating a photoresist composition suitable for a spin coating method is required, and rheological properties are required, plus here. The composition must have sufficient transmittance for exposure irradiation such as photodegradation of the photoinitiator after passing through the film thickness. Further, in order to withstand various uses, 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 in other applications such as the use of photoresists in 200813626, other characteristics are required, but the specific epoxy resin that satisfies all the various requirements is currently not present. The photoresist composition, which has been disclosed in many different combinations or mixtures of various epoxy resins, has been described in various patents relating to photohardenable compositions, photoinitiators, most of which are suitable as permanent films. Photosensitive photoresist for use. However, none of these reveals the composition that we are trying to accomplish that is most suitable for MEMS applications. In fact, most examples of plasticizers, softeners, and tougheners can degrade lithography performance. [Patent Document 1] USP 5,502,083 [Patent Document 2] USP 6,3 68,769 [Patent Document 3] USP 5,1 02,772 [Patent Document 4] USP 4,882,245 [Patent Document 5] USP 5,026,624 [Patent Document 6] USP 5,278,0 10 [Patent Document 7] USP 5, 3 04, 45 7 [Patent Document 8] USP 4, 25 6, 828 [Patent Document 9] USP 5,726, 2 1 6 [Patent Document 10] USP 5,264, 3 2 5 [Invention [Problems to be Solved by the Invention] A photosensitive resin composition of the prior art using a polyfunctional epoxy resin such as a novolac type epoxy resin, because of the photocationic polymerization of the initiator - 8 - 201113626 The sensitivity is low, a large amount of initiator is required, so there is a problem that the mask pattern cannot be faithfully reproduced in the resin pattern in a short time, and the first 4 (Sion polymerization initiator) containing SbF^ is compared. The present invention is based on the above-mentioned prior art, and the object of the present invention is to provide a pattern capable of forming a high resolution and a high aspect ratio. It is also a photosensitive resin composition with high sensitivity and low toxicity. In order to solve the problem, the inventors of the present invention have found that the photosensitive resin composition is highly sensitive and high-resolution, and the results of careful investigation, experimentation, and review are repeated, and it is found that a specific polyfunctional epoxy is combined. The resin and a specific photo-cationic 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. The composition is as follows. (1) A photosensitive resin composition comprising a photo-cationic polymerization initiator (A) containing ruthenium (pentafluoroethyl)trifluorophosphonate and having an alicyclic structure on a main chain structure Further, the epoxy group is a photosensitive resin composition as described in the above (1), wherein the photocationic polymerization initiator (A) is as follows. The compound represented by the formula (1) (A-1) ° 200813626 [Chemical 1]
(3 ) $Π丄述（1)或（2)所記載之感光性樹脂組成 含有反應性環氧單體（C)。 (4) 如上述（1)至（3)中任一項所記載之感光性 物，其中於含有溶劑（D)之感光性樹脂組成物中 成份濃度爲5〜95重量％。 (5) 如上述（1)至（4)中任一項所記載之感光性 物，其中多官能環氧化合物（B)的主鏈結構，爲 結構的伸烷基鏈。 (6) —種感光性樹脂組成物層合物，其係用 上述（1)至（5)中任一項所記載之感光性樹脂組成牛 (7) —種硬化物，其係含有上述（1)至（5)中任 載之感光性樹脂組成物所成。 (8) —種圖型形成方法，其係包含將於所望 上塗佈上述（1)至（5)中任一項所記載之感光性樹 所得到的感光性樹脂組成物層，乾燥後，依所定 光，曝光後烘烤，顯影樹脂組成物層，加熱處理 樹脂圖型後，得到所定形狀的硬化樹脂圖型之步 -10- 钧，其係 樹脂組成 ，其固體 樹脂組成 具有支鏈 基材挾入 7] ° 一項所記 的支撐體 脂組成物 的圖型曝 所得到的 驟所成。 200813626 (9)一種圖型形成方法，其係包含將從上述（6)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。 [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，其特徵係含有锍的參（ 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)、與主鏈結構上具有脂環結構且環氧基爲3個以上之多 官能環氧化合物（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，但例如XD-1 000(日本化藥股份有限公司製）等之主鏈結構上具有脂環 結構且環氧基爲3個以上之多官能環氧化合物，或艾伯里 GT3 00、艾伯里 GT400、Ε Η P E 3 1 5 0 (D AIC E L 化學工業股 份有限公司製）等之主鏈結構上具有脂肪族結構與支鏈結 構之伸烷基鏈且環氧基爲3個以上之多官能環氧化合物與 上述式（1)所示的化合物之光致陽離子聚合起始劑的組合 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 -11 - 200813626 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)爲毓與參（五氟乙基）三 氟磷酸鹽離子之鹽。 該光致陽離子聚合起始劑的毓，可列舉三苯基銃、 三-P-甲苯基毓、三甲苯基銃、參（4-甲氧基苯基）鏡、1-萘基二苯基锍、2·萘基二苯基锍、參（4-氟苯基）锍、三-1-萘基锍、三-2-萘基毓、參（4-羥基苯基）銃、4-(苯基硫）苯 基二苯基毓、4_(?_甲苯基硫）苯基二-P-甲苯基毓、4-(4-甲 氧基苯基硫）苯基雙（4-甲氧基苯基）鏡、4-(苯基硫）苯基雙 (4-氟苯基）鏡、4-(苯基硫）苯基雙（4_甲氧基苯基）鏡、4-( 苯基硫）苯基二-P-甲苯基鏡、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）毓、4-(4-苯甲醯苯基硫）苯基二苯基锍、4-異 丙基-4-氧代-10-硫雜-9，10-二氫蒽-2-基二-P-甲苯基毓、7-異丙基-9-氧代-10·硫雜-9，10-二氫蒽-2-基二-苯基毓、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 -12- 200813626 二苯基鏡、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 anthr enium、5 - (2，4，6 -二甲基苯基）硫雜 anthrenium等之三芳基鍊，一本基苯醯甲基Μ、一苯基4-硝基苯醯甲基毓、二苯基苄基銃、二苯基甲基銃等之二芳 基毓；苯基甲基苄基锍、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锍、2-萘基甲基苄基鏡、2 -萘基甲基（1-乙氧基羰基）乙基毓、苯 基甲基苯醯甲基毓、4 -羥基苯基甲基苯醯甲基毓、4 -甲氧 基苯基甲基苯醯甲基锍、4 -乙醯鑛基氧化苯基甲基苯醯甲 基鏡、2 -萘基甲基苯醯甲基銃、2_萘基十八院基苯醯甲基 銃、9 -恵基甲基苯醯甲基蔬等之卓方基鏡’ 一甲基本酿甲 基锍、苯醯甲基四氫噻吩錙、二甲基节基銃、节基四氫嚷 吩鑰、十八烷基甲基苯醯甲基鏡等之三院基鏡等。此等記 載於以下文獻。 關於三芳基毓，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8-165290號、特開平8-301991號、特開平9-143212號、特開平9-278813號、特開 平10-7680號、特開平10-287643號、特開平10-245378號 、特開平8· 1 5 75 1 0號、特開平1 0-204083號、特開平8-2455 66號、特開平8- 1 5 745 1號、特開平7-324069號、特開 平 9-268205號、特開平 9-278935號、特開 2001-288205 號 -13- 200813626 、特開平11-80118號、特開平10-182825號、特開平l〇-330353號、特開平10-152495號、特開平5-239213號、特 開平7-333834號、特開平9-12537號、特開平8-325259號 、特開平8- 1 60606號、特開2000- 1 8607 1號（美國專利第 6368769號）等；關於二芳基毓，可列舉特開平7-300504號 、特開昭64-45 3 57號、特開昭64-294 1 9號等；關於單芳基 锍，可列舉特開平6 - 3 4 5 7 2 6號、特開平8 - 3 2 5 2 2 5號、特開 平9-118663號（美國專利第6093753號）、特開平2-196812號 、特開平2-1470號、特開平2-196812號、特開平3-237107 號、特開平3-171〇1號、特開平6-22 8 086號、特開平1〇_ 1 52469 號、特開平 7-3 00 5 05 號、特開 2003 -2773 5 3 號、特 開2003 -2773 52號等；關於三烷基锍，可列舉特開平4-3 08 5 63號、特開平5- 1 402 1 0號、特開平5- 1 40209號、特開 平5-23 0 1 89號、特開平6-27 1 5 3 2號、特開昭5 8 -3 7003號、 特開平2- 1 783 03號、特開平10-3 3 868 8號、特開平9-328506號、特開平11-228534號、特開平8-27102號、特開 平7-3 33 834號、特開平5-222 1 67號、特開平1 1 -2 1 3 07號、 特開平H-3 56 1 3號、美國專利第603 1 0 14號等。 特別是上述光致陽離子聚合起始劑的锍，以三苯基毓 、4 _(苯基硫）苯基二苯基锍較佳，下述式（1)所表示的4-( 苯基硫）苯基二苯基毓（A-1)最佳。 -14- 200813626 【化2】(3) The photosensitive resin composition described in (1) or (2) contains a reactive epoxy monomer (C). (4) The photosensitive material according to any one of the above (1) to (3) wherein the concentration of the component in the photosensitive resin composition containing the solvent (D) is 5 to 95% by weight. (5) The photosensitive material according to any one of the above (1) to (4) wherein the main chain structure of the polyfunctional epoxy compound (B) is a structural alkyl chain. (6) A photosensitive resin composition laminate comprising the photosensitive resin according to any one of the above (1) to (5), which comprises a bovine (7) type cured product, which comprises the above ( 1) A photosensitive resin composition as contained in (5). (8) A pattern forming method comprising the photosensitive resin composition layer obtained by applying the photosensitive tree according to any one of the above (1) to (5), and drying, According to the predetermined light, after exposure and baking, the resin composition layer is developed, and the resin pattern is heated to obtain a hardened resin pattern of the shape of the step -10 钧, which is a resin composition, and the solid resin composition has a branched group. Material intrusion 7] ° A note of the pattern of exposure of the body fat composition recorded. (1) A method of forming a pattern comprising a photosensitive resin composition layer remaining after removing a substrate from the laminate according to the above (6), and laminating the layer on the desired support, and laminating 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. 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 has an alicyclic structure with a main chain structure. Further, the epoxy group is composed of three or more polyfunctional epoxy compounds (B), and a resin pattern having high sensitivity and 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 combinations, but for example, XD-1 000 (manufactured by Nippon Kayaku Co., Ltd.) has an alicyclic structure and an epoxy group having three or more polyfunctional epoxy compounds, or Burley GT3 00, Ebury GT400, Ε Η PE 3 1 5 0 (D AIC EL Chemical Industry Co., Ltd.), etc. The main chain structure has an alkyl chain and an epoxy chain with an aliphatic structure and a branched structure. The combination of three or more polyfunctional epoxy compounds and a photocationic polymerization initiator of the compound represented by the above formula (1) is most preferable. The photocationic cationic polymerization initiator of the present invention is subjected to irradiation with radiation of ultraviolet, far ultraviolet rays, KrF, ArF or the like excimer laser, X-ray, and electron beam-11 - 200813626, etc., and the cation is generated. A compound which can be converted into a polymerization initiator. The photocationic polymerization initiator (A) is a salt of cerium and hexafluoroethyltrifluorophosphate ion. Examples of the ruthenium of the photocationic polymerization initiator include triphenylsulfonium, tris-P-tolylhydrazine, trimethylphenylphosphonium, stilbene (4-methoxyphenyl) mirror, and 1-naphthyldiphenyl.锍, 2·naphthyldiphenyl hydrazine, ginseng (4-fluorophenyl) fluorene, tri-1-naphthyl fluorene, tri-2-naphthyl fluorene, ginseng (4-hydroxyphenyl) fluorene, 4-( Phenylthio)phenyldiphenylphosphonium, 4-(?-tolylthio)phenyldi-P-tolylhydrazine, 4-(4-methoxyphenylsulfanyl)phenylbis(4-methoxy Phenyl) mirror, 4-(phenylthio)phenylbis(4-fluorophenyl) mirror, 4-(phenylthio)phenylbis(4-methoxyphenyl) mirror, 4-(phenyl Thio)phenyl di-P-tolyl mirror, bis[4-(diphenylfluorenyl)phenyl] sulfide, bis[4-(bis[4-(2-hydroxyethoxy)phenyl]anthracene Phenyl] thioether, bis(4-[bis(4-fluorophenyl)indenyl]phenyl) sulfide, bis(4-[bis(4-methylphenyl)indenyl]phenyl) Thioether, bis(4-[bis(4-methoxyphenyl)indenyl]phenyl) sulfide, 4-(4-benzoguanidine-4-chlorophenylthio)phenyl bis(4-fluoro Phenyl)anthracene, 4-(4-benzhydrazin-4-chlorophenylsulfanyl)phenyldiphenylphosphonium, 4-(4-benzylidenephenylthio)phenyl (4-fluorophenyl)anthracene, 4-(4-benzylidenephenylthio)phenyldiphenylphosphonium, 4-isopropyl-4-oxo-10-thia-9,10-dihydro Indole-2-yldi-P-tolylhydrazine, 7-isopropyl-9-oxo-10.thia-9,10-dihydroindol-2-yldiphenylene, 2-[( bis-P-tolyl)indenyl]thioxanthone, 2-[(diphenyl)indenyl]thioxanthone, 4-[4-(4-tert-butylbenzylidene)phenylthio]benzene Di-P-tolylhydrazine, 4-[4-(4-tert-butylbenzylidene)phenylthio]phenyldiphenylanthracene, 4-[4-(benzhydrylphenylthio)] Phenyl di-P-tolyl fluorene, 4-[4-(benzylidene phenyl thio) phenyl-12- 200813626 diphenyl mirror, 5-(4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthenium, 5-tolylthia anthrenium, 5-(4-ethoxyphenyl)thia anthenium, 5-(2,4,6-dimethylphenyl)thiaanthenium a triaryl aryl group, a bisphenyl hydrazine, a phenyl 4-nitrophenyl hydrazine methyl hydrazine, a diphenyl benzyl hydrazine, a diphenylmethyl hydrazine or the like; a phenyl group; Methylbenzyl hydrazine, 4-hydroxyphenylmethylbenzyl hydrazine, 4-methoxyphenylmethylbenzyl hydrazine, 4-ethyl hydrazine carbonyl oxidation Methylbenzyl hydrazine, 2-naphthylmethylbenzyl mirror, 2-naphthylmethyl(1-ethoxycarbonyl)ethyl hydrazine, phenylmethylphenylhydrazine methyl hydrazine, 4-hydroxyphenyl Methyl phenyl hydrazine methyl hydrazine, 4-methoxyphenyl methyl phenyl hydrazine methyl hydrazine, 4 - acetaminophen oxyphenyl phenyl hydrazine methyl mirror, 2-naphthylmethyl phenyl hydrazine methyl铳, 2_naphthyl 18-yard phenyl hydrazine methyl hydrazine, 9-mercaptomethyl phenyl hydrazine methyl vegetable, etc. 'One-methyl ketone methyl hydrazine, phenyl hydrazine methyl tetrahydro thiophene hydrazine , dimethyl sulfhydryl hydrazine, a quaternary tetrahydroquinone key, an octadecylmethyl benzoquinone methyl mirror, etc. These are listed in the following documents. As for the triaryl sulfonium, there are exemplified by U.S. Patent No. 4,231,951, U.S. Patent No. 4,256,828, U.S. Patent No. 4-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922, No. 8-27208, special Kaiping 8-27209, special Kaiping 8-165290, special Kaiping 8-301991, special Kaiping 9-143212, special Kaiping 9-278813, special Kaiping 10-7680, special Kaiping 10 -287643, special Kaiping 10-245378, special Kaiping 8·1 5 75 1 0, special Kaiping 1 0-204083, special Kaiping 8-2455 66, special Kaiping 8 - 1 5 745 1 , special Kaiping 7-324069, special Kaiping 9-268205, special Kaiping 9-278935, special opening 2001-288205-13-200813626, special Kaiping 11-80118, special Kaiping 10-182825, special Kaiping l〇-330353 No., No. 10-152495, Special Kaiping No. 5-239213, Special Kaiping No. 7-333834, Special Kaiping No. 9-12537, Special Kaiping No. 8-325259, Special Kaiping No. 8- 1 60606, Special Opening 2000-1 8607 No. 1 (U.S. Patent No. 6,368,769), etc.; as for the diaryl sulfonium, JP-A-7-300504, JP-A-64-45 3 57, JP-A-64-294 1-9, etc.; The basics can be cited in JP-A-6- 3 4 5 7 2 6 , JP-A-8- 3 2 5 2 2 5, JP-A 9-118663 (US Pat. No. 6,093,537), and JP-A-2-196812. Special Kaiping 2-1470, Special Kaiping 2-196812, Special Kaiping 3-237107, Special Kaiping 3-171〇1, Special Kaiping 6-22 8 086, Special Kaiping 1〇_ 1 52469, Special Kaiping 7-3 00 5 05, special open 2003 - 2773 5 3, special open 2003 - 2773 52, etc.; for trialkyl hydrazine, special open flat 4-3 08 5 63, special open flat 5 - 1 402 No. 10, Special Kaiping No. 5 - 1 40209, Special Kaiping No. 5-23 0 1 89, Special Kaiping 6-27 1 5 3 No. 2, Special Kaikai No. 5 8 -3 7003, Special Kaiping 2- 1 783 03 No., special Kaiping 10-3 3 868 8 , special Kaiping 9-328506, special Kaiping 11-228534, special Kaiping 8-27102, special Kaiping 7-3 33 834, special Kaiping 5-222 1 67 , Special Kaiping 1 1 - 2 1 3 07, Special Kai Hing H-3 56 1 3, US Patent No. 6031 0 14 and so on. In particular, the oxime of the photocationic polymerization initiator is preferably triphenylphosphonium or 4-phenylsulfonylphenyldiphenylphosphonium, 4-(phenylthio) represented by the following formula (1). Phenyldiphenylphosphonium (A-1) is the best. -14- 200813626 【化2】
本發明中之主鏈結構上具有脂環結構且環氧基爲3個 以上之多官能環氧化合物（B)，只要是用於形成厚膜的圖 型之一分子中含有充分的多官能環氧樹脂即可，可爲任何 環氧樹脂。此等多官能環氧樹脂的環氧當量爲150〜400較 佳，小於此範圍則硬化收縮大，另一方面，大於此範圍時 ，因爲交聯密度變小而較不佳。符合上述範圍的 XD_ 1 0 00(日本化藥股份有限公司製）等之主鏈結構上具有脂環 結構且環氧基爲3個以上之多官能環氧化合物，或艾伯里 GT3 00、艾伯里 GT400 > EHPE3 1 5 0(D AICEL 化學工業股 份有限公司製）等之主鏈結構上具有脂肪族結構與支鏈結 構之伸烷基鏈且環氧基爲3個以上之多官能環氧化合物等 爲特別佳。 上述主鏈結構上具有脂環結構且環氧基爲3個以上之 多官能環氧化合物的軟化點低時，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，主鏈結構上具有脂環結構且環氧基爲3 個以上之多官能環氧化合物的軟化點高時，將乾膜光阻層 -15- 200813626 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4 0〜1 2 0 °C ，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，主鏈結構上具有脂環結構且環氧基爲3 個以上之多官能環氧化合物（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，主鏈結構上 具有脂環結構且環氧基爲3個以上之多官能環氧化合物（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 主鏈結構上具有脂環結構且環氧基爲3個以上之多官能環 氧化合物（B)的使用比例以0.1 : 99.9〜15 : 85爲佳，較佳爲 0.5 ： 99.5〜10: 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 06)、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 -16- 200813626 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，摻合反應性環氧單體成份 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1〜10重量％ 爲佳，特別是以2〜7重量％較適合。 降低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、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％〜9 5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 -17- 200813626 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 烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽 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5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（9，1 0 -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、 -18- 200813626 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C1〜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。 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，亦可添加參甲氧基鋁、參 乙氧基鋁、參異丙氧基鋁、異丙氧基二乙氧基鋁、參丁氧 基鋁等之烷氧基鋁，參苯氧基鋁、參對甲基苯氧基鋁等之 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 〇重量％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 -19- 200813626 列舉例如聚醚颯、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。增黏劑可列舉例如〇rben、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，例如各自爲〇 · 1〜3 0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、氧化矽、 無定形二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁 、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0〜6 0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 主鏈結構上具有脂環結構且環氧基 85 〜99.9 爲3個以上之多官能環氧化合物 反應性環氧單體(C) 1〜10 溶劑(D) 5.8 〜2090 -20 - 200813626 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0.1〜1 000 // 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〜5 0°C顯影1〜180分鐘左右後形成圖型 ，接著以130〜2 0 0 °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7 - 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、或上述有機溶劑 與水的混合液，顯影亦可使用攪拌型、噴霧型、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，係使用滾軸塗佈機、狹 縫式塗佈機（die coater)、刮刀塗佈機、棒塗佈機、照相凹 版印刷塗佈機等塗佈該組成物於基礎薄膜上後，用設定在 4 5〜10 0 °C的乾燥爐進行乾燥，藉由去除所定量的溶劑，又 必要時藉由層合外層膜作爲乾膜光阻。此時，基礎薄膜上 的光阻的厚度調製爲2〜100 μιη，基礎薄膜及外層膜，可使 用例如聚酯、聚丙烯、聚乙烯、TAC、聚醯亞胺等之薄膜 ，此等薄膜必要時可使用藉由矽系離型處理劑或非矽系離 型處理劑被離型處理的薄膜。使用此乾膜光阻，例如藉由 手動式滾軸、層壓機等剝離外層膜，以4(TC〜100 °C、壓力 0.0 5〜2 MPa轉印於基板，可進行與前一段落相同的曝光 、曝光後烘烤、顯影、加熱處理。 -21 - 200813626 將上述的感光性樹脂組成物以薄膜供給，可省略塗佈 於支撐體、及乾燥的步驟，可更簡便地進行圖型形成。 藉由上述方法所得到的本發明的樹脂組成物的硬化物 ，例如作爲永久光阻膜利用於噴射記錄噴頭等MEMS用 零件。 【實施方式】 [實施例] 以下說明本發明的實施例，此等實施例僅爲適當地說 明本發明之例子，並非限定本發明。 (實施例1〜4、比較例1〜3) (感光性樹脂組成物） 依照下述表中所記載的摻合量（單位爲重量份），將多 官能環氧樹脂、光致陽離子聚合起始劑、及其他的成份而 得到感光性樹脂組成物。 (感光性樹脂組成物的圖型化） (實施例1〜3、及比較例1〜3) 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8 0 // 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 °C進行5分鐘 及95 °C進行15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 -22- 200813626 觸，i線），藉由加熱板以9 5 °C進 (PEB)，接著使用丙二醇單甲基醚 23t進行6分鐘的顯影處理，於基 (感光性樹脂組成物的評估） 顯影後藉由必要曝光量進行下 述表2。 最適曝光量：使光罩轉印精密 長寬比：膜厚/所形成的光阻 圖型寬 行6分鐘的曝光後烘烤 乙酸酯，藉由浸漬法以 板上得到硬化樹脂圖型 述評估，結果列示於下 度爲最佳之曝光量 圖型中所密著之最細的 -23- 200813626 【cn¥ 比較例 m 100 (N ON 寸 0.06 CN 270 卜 (N 100 <N 〇\ 寸 0.06 (Ν 250 卜 r-H 100 (N 〇\ 寸 0.06 CN 300 卜 寸 100 (N 寸 0.06 (Ν 200 寸 m 100 寸 寸 0.06 (Ν 110 寸 U (N 100 VO 寸 寸 0.06 (Ν 100 寸 r-H 100 Ό 寸 寸 0.06 CN 120 寸 摻合成份 EHPE3150 GT300 GT400 CPI-210S UVI-6974 ED506 Ρη 〇 ΜΕΚ F-470 S-510 最適曝光量(mJ/cm2) 長寬比 τ—Η 1 Β-2 m 1 PQ < Ο U 1 Q (Ν 1 Q 多官能環氧樹脂 光致陽離子起始劑 反應性環氧單體 溶劑 塗平劑 偶合劑 -24- 200813626 註解： (A-l):光致陽離子聚合起始劑（商品名CPI-210S san-apro(股）製） (B-1):脂環式多官能環氧化合物（商品名ehpE3150 DAICEL化學工業公司製） (B-2)· fl曰環式多官能環氧化合物（商品名GT3〇〇 DAICEL化學工業公司製） (B-3):脂環式多官能環氧化合物（商品名GT4〇〇 DAICEL化學工業公司製） (C):反應性環氧單體（商品名ED506旭電化工業（股）製）In the present invention, the main chain structure has an alicyclic structure and the epoxy group is three or more polyfunctional epoxy compounds (B), as long as one of the patterns for forming a thick film contains a sufficient polyfunctional ring. It can be an oxy resin and can be any epoxy resin. The epoxy equivalent of these polyfunctional epoxy resins is preferably from 150 to 400. When the amount is less than this range, the hardening shrinkage is large. On the other hand, when the ratio is larger than this range, the crosslinking density is small and it is not preferable. XD_100 (manufactured by Nippon Kayaku Co., Ltd.) which meets the above-mentioned range, has an alicyclic structure and an epoxy group of three or more polyfunctional epoxy compounds, or Aberdeen GT3 00, Ai Bury GT400 > EHPE3 1 50 (manufactured by D AICEL Chemical Industry Co., Ltd.), etc. The main chain structure has an aliphatic chain structure and a branched structure, and the epoxy group has three or more polyfunctional rings. Oxygen compounds and the like are particularly preferred. When the softening point of the polyfunctional epoxy compound having an alicyclic structure and the epoxy group is three or more is low, the mask is likely to adhere when patterning, and when used as a dry film photoresist, Softening at room temperature is less preferred. On the other hand, when the softening structure of the polyfunctional epoxy compound having an alicyclic structure and an epoxy group of 3 or more is high, the dry film photoresist layer -15- 200813626 It is not easy to soften when pressed against the substrate, and the adhesion to the substrate is deteriorated, so it is not preferable. For the above reasons, the polyfunctional epoxy resin preferably has a softening point of from 40 to 1 20 ° C, more preferably from 50 to 100 ° C. The photocationic polymerization initiator (A) is too high in the photosensitive resin composition, and has an alicyclic structure and an epoxy group having 3 or more polyfunctional epoxy compounds (B). When the content of the photosensitive resin composition is too low, development of the resin composition is difficult, and the film after curing becomes brittle, which is not preferable. On the other hand, the photocationic polymerization initiator (A) is too low in the photosensitive resin composition, and has an alicyclic structure on the main chain structure and an epoxy group of three or more polyfunctional epoxy compounds ( B) When the content in the photosensitive resin composition is too high, the hardening time of the resin composition by radiation exposure becomes long when applied to a substrate, which is less preferable. Considering the above problems, the photocationic polymerization initiator (A) and the polyfunctional epoxy compound (B) having an alicyclic structure and having an epoxy group of three or more are used in a ratio of 0.1:99.9. 〜15: 85 is preferred, preferably 0.5: 99.5~10: 90. In the photosensitive resin composition of the present invention, in order to further improve the performance of the pattern, a reactive epoxy monomer (C) having a miscibility may be added, and a reactive epoxy monomer may be used. For example, a glycidyl ether compound may be used. Diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (made by Asahi Kasei Co., Ltd., ED5 06), trimethylol Propane triglycidyl ether (ED5 05, manufactured by Asahi Kasei Co., Ltd.), pentaerythritol tetraglycidyl ether, etc.; these may be used alone or in combination of two or more. The reactive epoxy monomer (C) component is used for improving the reactivity of the photoresist or the physical properties of the cured film by the use of -16,136,426, and the reactive epoxy monomer component is more liquid, and the component is liquid. In the case of blending, if the blending is more than 20% by weight, the film after solvent removal tends to be sticky and causes the mask to adhere, etc., and is less suitable. From this point of view, the reactive epoxy monomer component is blended. When the blending ratio is the total of the (A) component, the (B) component, and the (C) component, the solid content of the photoresist is preferably from 1 to 10% by weight based on the solid component, particularly 2 to 7 wt% is more suitable. When the viscosity of the photosensitive resin composition of the present invention is lowered, a solvent (D) which improves the coating property can be used, and a solvent can be used by using an organic solvent which is generally used and which can dissolve each component. Such an organic solvent can be exemplified. a ketone such as acetone, methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a glycol ether such as dipropylene glycol dimethyl ether or dipropylene glycol diethyl ether; Ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, butyrolactone, etc., methanol, ethanol, cellosolve, A An alcohol such as a cellosolve or an organic solvent such as an aliphatic hydrocarbon such as octane or decane, a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha. 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 9% by weight, particularly preferably from 10% by weight to 90% by weight, based on the photosensitive resin composition. In order to further improve the adhesion of the composition to the substrate, the photosensitive resin composition of the present invention may be used in the form of a mixed adhesiveness -17-200813626, and the adhesion imparting agent may be a decane coupling agent. A coupling agent such as a titanium coupling agent is preferably a decane coupling agent. The above decane coupling agent may, for example, be 3-chloropropyltrimethoxydecane, vinyltrichlorodecane, vinyltriethoxydecane, vinyltrimethoxydecane or vinyl•glycol (2-methoxyethoxyl). Base) decane, 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-mercaptopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-quinoneurea Propyltriethoxydecane, and the like. These adhesion imparting agents may be used singly or in combination of two or more. Since the main component is unreactive, the adhesion imparting agent exists as a residual component after hardening, in addition to the component acting on the interface of the substrate. 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 can be used in a range that does not cause a bad influence 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 5% 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 an anthracene compound having an alkoxy group at the 10 position (9,10-dialkyloxyanthracene derivative), and the alkoxy group may, for example, be a C1 to C4 group such as a methoxy group, an ethoxy group or a propoxy group. Alkoxy. 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. C1-C4 alkyl or sulfonic acid alkyl ester group, -18-200813626 alkyl carboxylate group, and the like. The alkyl group of the alkyl sulfonate group or the alkyl carboxylate may, for example, be a C1 to C4 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. 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 caused by ions derived from the photocationic cationic starting polymerization agent (A), and it is also possible to add methoxy aluminum, ethoxylated aluminum, and isopropoxy aluminum. Aluminum alkoxide such as propoxydiethoxyaluminum or butylaluminum hydride; phenoxy aluminum such as phenoxy aluminum or para-methylphenoxy aluminum; 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 ethyl acetonitrile) 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 1% 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. The thermoplastic resin may be exemplified by, for example, polyether oxime, polystyrene, polycarbonate, etc.; and the coloring agent may, for example, be phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, or the like. . Examples of the tackifier include 〇rben, pantone, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as polyoxyalkylene-based, fluorine-based, and polymeric. The amount of the additive used in the photosensitive resin composition of the present invention is, for example, a simple standard of about 1 to 30% by weight, which is a large standard, and can be appropriately increased or decreased depending on the purpose of use. Further, in the present invention, an inorganic chelating agent such as barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide or mica powder may be used. The blending ratio may be 0 to 60% by weight in 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 and mixed using a disperser such as a dissolver, a homogenizer or a 3-roller, and after mixing, it may be reused, filtered by a mesh sieve, a membrane filter or the like. [Table 1] parts by weight photo-cationic polymerization initiator (A) 0.1 to 15 main chain structure having an alicyclic structure and epoxy group 85 to 99.9 being three or more polyfunctional epoxy compound reactive epoxy monomers (C) 1 to 10 Solvent (D) 5.8 to 2090 -20 - 200813626 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, for example, a spin coating can be used. The cloth machine or the like is applied to a substrate such as a ruthenium wafer or a glass at a thickness of 0.1 to 1 000 // m, 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. After placing a mask having a predetermined pattern, irradiating ultraviolet rays, performing heat treatment at 50 to 130 ° C for about 1 to 50 minutes, and then developing the unexposed portion with a developer at room temperature to 50 ° C for 1 to 180 A pattern is formed after about a minute, and then heat-treated at 130 to 200 ° C to obtain a permanent protective film conforming to various characteristics. As the developer, an organic solvent such as 7-butyrolactone, triethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate, or a mixture of the above organic solvent and water can be used, and a development type can also be used. A developing device such as a spray type or a shower type may be subjected to ultrasonic irradiation if necessary. The photosensitive resin composition of the present invention is coated with a roller coater, a die coater, a knife coater, a bar coater, a gravure coater, or the like. After drying on the base film, it was dried in a drying oven set at 45 to 10 ° C, by removing the amount of solvent, and if necessary, by laminating the outer layer film as a dry film photoresist. At this time, the thickness of the photoresist on the base film is adjusted to 2 to 100 μm, and the base film and the outer layer film may be films such as polyester, polypropylene, polyethylene, TAC, polyimine, etc., and such films are necessary. A film which is subjected to release treatment by an oxime release treatment agent or a non-oxime release treatment agent can be used. By using this dry film photoresist, for example, by peeling the outer layer film by a manual roller, a laminator or the like, the substrate is transferred to the substrate at 4 (TC to 100 ° C, pressure 0.0 5 to 2 MPa), and the same as in the previous paragraph can be performed. Exposure, post-exposure baking, development, and heat treatment. -21 - 200813626 The above-mentioned photosensitive resin composition is supplied as a film, and the step of applying to the support and drying can be omitted, and pattern formation can be performed more easily. The cured product of the resin composition of the present invention obtained by the above method is used as a permanent photoresist film for a MEMS component such as a jet recording head. [Embodiment] [Embodiment] Hereinafter, an embodiment of the present invention will be described. The examples are merely illustrative of the present invention and are not intended to limit the present invention. (Examples 1 to 4, Comparative Examples 1 to 3) (Photosensitive resin composition) According to the blending amount described in the following table ( A photosensitive resin composition is obtained by using a polyfunctional epoxy resin, a photocationic polymerization initiator, and other components in a unit of weight. (Illustration of a photosensitive resin composition) (Examples 1 to 3) And comparison Examples 1 to 3) 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 μm, and this photosensitive property was obtained. The resin composition layer was prebaked by a hot plate at 65 ° C for 5 minutes and at 95 ° C for 15 minutes, and then subjected to pattern exposure using an i-line exposure apparatus (mask alignment device: manufactured by USHIO Electric Co., Ltd.). (Soft type -22-200813626 touch, i line), by heating plate at 95 ° C (PEB), followed by propylene glycol monomethyl ether 23t for 6 minutes development treatment, based on (photosensitive resin composition Evaluation After development, the following exposure is carried out by the necessary exposure amount. Table 2: Optimal exposure: Transfer the mask to a precise aspect ratio: film thickness / formed photoresist pattern, wide line for 6 minutes, post-exposure B The acid ester is evaluated by the impregnation method on the plate to obtain the hardened resin pattern, and the results are listed as the thinnest in the lower exposure mode. -23-200813626 [cn¥ Comparative Example m 100 (N ON inch 0.06 CN 270 卜 (N 100 <N 〇\ inch 0.06 (Ν 250 卜rH 100 (N 〇 \ inch 0.06 CN 300 卜 inch 100 (N inch 0.06 (Ν 200 inch m 100 inch inch 0.06 (Ν 110 inch U (N 100 VO inch inch 0.06 (Ν 100 inch rH 100 Ό inch inch 0.06 CN 120 inch blended composition EHPE3150 GT300 GT400 CPI-210S UVI-6974 ED506 Ρη 〇ΜΕΚ F-470 S-510 Optimum exposure (mJ/cm2) Aspect ratio τ—Η 1 Β-2 m 1 PQ < Ο U 1 Q (Ν 1 Q Functional epoxy resin photocationic starter reactive epoxy monomer solvent coating agent coupling agent-24- 200813626 Notes: (Al): photocationic polymerization initiator (trade name CPI-210S san-apro) (B-1): alicyclic polyfunctional epoxy compound (trade name: ehpE3150 DAICEL Chemical Industry Co., Ltd.) (B-2) · fl曰 cyclic polyfunctional epoxy compound (trade name GT3〇〇DAICEL chemistry) (B-3): alicyclic polyfunctional epoxy compound (trade name: GT4〇〇DAICEL Chemical Industry Co., Ltd.) (C): Reactive epoxy monomer (trade name: ED506 Asahi Chemical Industry Co., Ltd.) system)
(D-1):溶劑環戊酮 (D-2):溶劑 MEK (E) :氟系塗平劑（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-5 1 0 CHISSO(股）製） (G) :光致陽離子聚合起始劑（商品名UVI-6974 Dow Chemical公司製50%碳酸丙烯溶液） 實施例1〜4如表2所示皆爲好的結果。 (實施例4) (感光性樹脂組成物） 混合混合100重量份的脂環式多官能環氧樹脂（商品名 EHPE3 150，DAICEL化學工業公司製）、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 -25- 200813626 的反應性環氧單體（商品名ED506旭電化工業（股）製）、 及40重量份的MEK，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 μ m的聚丙嫌 (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1〇分鐘及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 μιη的PP薄膜（外層膜，東麗 (股）製），形成40 μηι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70°C、氣體壓力〇·2 MPa、速度0.5 m/min層合於矽晶圓 上，剝離基礎薄膜，再重複1次此操作而得到80 μιη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），然後，藉由加熱板以95 °C進行4分 鐘的PEB，接著使用PGMEA，藉由浸漬法以23°C進行4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120 mJ/cm2、長寬比7.4優良的結果。 由實施例1〜5結果，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] -26- 200813626 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。 -27-(D-1): Solvent cyclopentanone (D-2): Solvent MEK (E): Fluorine-based leveling agent (trade name: MEGAFAC F-470, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (F): decane Mixture (trade name: S-5 1 0 CHISSO Co., Ltd.) (G): photocationic polymerization initiator (trade name: UVI-6974 50% propylene carbonate solution manufactured by Dow Chemical Co., Ltd.) Examples 1 to 4 are shown in Table 2. Both are good results. (Example 4) (Photosensitive resin composition) 100 parts by weight of an alicyclic polyfunctional epoxy resin (trade name: EHPE3 150, manufactured by DAICEL Chemical Industry Co., Ltd.) and 4.6 parts by weight of a photopolymerization initiator were mixed and mixed ( The product name is CPI-210S san-apro (manufactured by the company), and 4 parts by weight of the reactive epoxy monomer (trade name: ED506 Asahi Chemical Co., Ltd.) and 40 parts by weight of MEK are obtained. Resin composition. (Picture of the photosensitive resin composition) This photosensitive resin composition was uniformly applied to a 60 μm polypropylene (PP) film (base film, manufactured by Toray Industries Co., Ltd.) by means of temperature. The air convection dryer was dried at 65 ° C for 1 minute and at 80 ° C for 15 minutes, and then a PP film (outer film, manufactured by Toray Industries, Inc.) having a film thickness of 60 μm was laminated on the photosensitive resin composition layer. A photosensitive resin composition laminate having a film thickness of 40 μm was formed. The outer layer film of the photosensitive resin composition laminate was peeled off, laminated on a ruthenium wafer at a roll temperature of 70 ° C, a gas pressure of 2 2 MPa, and a speed of 0.5 m / min, and the base film was peeled off and repeated once more. In this operation, a photosensitive resin composition layer of 80 μm was obtained. On the photosensitive resin composition layer, pattern exposure (soft contact, i line) was performed using an i-ray exposure apparatus (mask alignment apparatus: manufactured by USHIO Electric Co., Ltd.), and then, at 95 ° C by a heating plate 4 minutes of PEB, followed by PGMEA, developed by a dipping method at 23 ° C for 4 minutes to obtain a hardened resin pattern on the substrate. The results were as follows: an optimum exposure amount of 120 mJ/cm2 and an aspect ratio of 7.4. From the results of Examples 1 to 5, it is clear that a combination of a polyfunctional epoxy resin having a specific structure and a specific photo-cationic polymerization initiator can provide a high-sensitivity and high aspect ratio shape which cannot be obtained by other combinations. Resin pattern. [Industrial Applicability] -26-200813626 As described above, the photosensitive resin composition according to the present invention is suitable for forming a resin pattern having a high aspect ratio outer shape, particularly a size suitable for a micro-sized electronic device or the like. Resin molding with high stability. -27-