TW201013311A - A photosensitive resin composition for cavity packaging, a cured product thereof, and a laminated body and a micro device using the resin composition - Google Patents
A photosensitive resin composition for cavity packaging, a cured product thereof, and a laminated body and a micro device using the resin composition Download PDFInfo
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- TW201013311A TW201013311A TW98119256A TW98119256A TW201013311A TW 201013311 A TW201013311 A TW 201013311A TW 98119256 A TW98119256 A TW 98119256A TW 98119256 A TW98119256 A TW 98119256A TW 201013311 A TW201013311 A TW 201013311A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
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- Spectroscopy & Molecular Physics (AREA)
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Abstract
Description
201013311 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種感光性樹脂組合物。更詳細而言，本 發明係關於一種半導體、MEMS用感光性材料，尤其是適 合於具有MEMS等微細機械結構之微裝置之中空封裝的中 空封裝用感光性樹脂組合物。 本案係基於2008年6月10日於日本提出申請之日本專利 特願2008-15 1273號並主張其優先權，其内容在此引用。 【先前技術】 近年來，於微裝置之領域中期待：藉由在具有半導體晶 片等之半導體裝置中進一步組入具有微細機械結構之加速 度計或表面聲波（SAW，Surface Acoustic Wave)遽波器、 角速度計、壓電薄膜共振器（FBAR，Film Bulk Acoustic-wave Resonator，薄膜塊體聲波共振器）、微開關、微可變 電容等各種微電子機械系統（Micro-electro-mechanical Systems，以下稱為「MEMS」），而應對更廣泛之用途； 或者藉由與半導體晶片組合，而可進行更精密之控制等。 上述各種MEMS與可嵌設於樹脂中之半導體晶片不同， 為使機械結構自身進行驅動等而發揮功能，大多情況下於 該結構之周圍必須具有一定空間（空腔）。又，由於此種機 械結構非常微細，故有時於切割等後步驟製程時會被破 壞，而無法充分發揮功能。因此，必須藉由以具有一定空 腔之方式用保護材料進行包圍的中空封裝，以晶圓水準來 保護機械結構部不受外部環境之影響。先前，此種中空封 140909.doc 201013311 裝係採用藉由陽極接合、共晶接合、擴散接合等方法於設 有機械結構之基板上接合具有凹凸之基板的中空封裝。然 而’該等方法一般需要在非常高之溫度下進行作業，故存 在處理耗費時間而生產性差之問題。 非專利文獻1中提出有如下方法：使用某種感光性樹脂 组合物來進行光微影，而獲得中空封裝。使用感光性樹脂 組合物之方法一般無需高溫製程，可簡便且產量佳地獲得 Φ 中二封裝，故可將生產成本抑制得較低，而且微細加工相 對較為容易，故具有可使元件小型化、薄化之優點。 [專利文獻1]曰本專利特公表2007-522531號公報 [非專利文獻 l]The third Asia-pacific c〇nference 〇f transducers and Micr〇_Nan〇 Techn〇1〇gy (Apc〇T2〇〇幻預稿 集293頁 【發明内容】 [發明所欲解決之問題] ❹然而，僅使用感光性樹脂組合物之硬化物，會使元件於 使用裒境中之可罪性缺之，而必須實施用以對設有中空封 裝之元件賦予可靠性之2次加工。作為用以對元件賦予可 靠性之方法，已提出有各種方法，其中，利用轉移模塑法 之密封係作為低成本且具可靠性之密封方法而為市場所認 知。然而’於藉由該轉移模塑法來將設有使用例如專利文 獻1記載之感光性樹脂組合物的中空封裝之元件進行密封 時’存在轉移模塑時之溫度下的中空封裝之強度不足、中 空封裝之形成空間無法充分保持之情形。此時，搭載於中 140909.doc 201013311 二封裝中之MEMS無法正常動作，而導致微装置之可靠性 下降、或不良品所致之製造成本上升。又，若欲保持中空 封裝之形成空間，則存在對空腔之形狀或尺寸施以較大之 限制、從而微裝置之性能明顯下降之問題。因此，期待一 種對高溫下之處理之耐受性優異、即便於轉移模塑法中亦 可充分保持空間的中空封裝用感光性樹脂組合物。再者， 本發明之意圖在於提供一種用以設置包圍MEMS之中空部 (空腔）之感光性樹脂組合物，為方便起見，本發明中將該 樹脂組合物稱作「中空封裝用感光性樹脂組合物」。 [解決問題之技術手段] 為解決上述問題，本發明者等人反覆潛心研究，結果發 現，藉由選擇特定之環氧樹脂，可獲得於進行轉移模塑之 咼溫範圍内亦表現出高強度、具有作為MEMS封裝用材料 之充分強度的感光性樹脂組合物，進而，藉由添加液狀環 氧樹脂，可獲得易於操作形成積層體（乾膜光阻）而不會伴 有硬化物之強度下降之感光性樹脂組合物，從而完成了本 發明。 即’本發明係關於： () 種中^封裝用感光性樹脂組合物，其係含有以下 述式（1)所表示之三笨酚曱烷型環氧樹脂（A)與陽離子光聚 合起始劑（B)而形成者： 140909.doc 201013311 [化1]201013311 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive material for semiconductors and MEMS, and more particularly to a photosensitive resin composition for hollow packaging which is suitable for a hollow package having a micro device having a fine mechanical structure such as MEMS. The present application is based on Japanese Patent Application No. 2008-15 1273, filed on Jan. 10, 2008, in [Prior Art] In recent years, in the field of micro devices, it is expected to further incorporate an accelerometer or a surface acoustic wave (SAW) chopper having a fine mechanical structure in a semiconductor device having a semiconductor wafer or the like. Various micro-electro-mechanical systems (hereinafter referred to as angular velocity meters, piezoelectric thin film resonators (FBAR, Film Bulk Acoustic-wave Resonator), micro-switches, micro-variable capacitors, etc. "MEMS") for a wider range of applications; or by combining with semiconductor wafers for more sophisticated control. Unlike the semiconductor wafer which can be embedded in the resin, the above-described various MEMS function to drive the mechanical structure itself, and in many cases, it is necessary to have a certain space (cavity) around the structure. Further, since the mechanical structure is extremely fine, it may be damaged during the post-cutting process, and the function may not be fully utilized. Therefore, it is necessary to protect the mechanical structure portion from the external environment by wafer level by means of a hollow package surrounded by a protective material in a cavity. Previously, such a hollow seal 140909.doc 201013311 was a hollow package in which a substrate having irregularities was bonded to a substrate having a mechanical structure by anodic bonding, eutectic bonding, diffusion bonding or the like. However, these methods generally require work at very high temperatures, so there is a problem that the processing is time consuming and the productivity is poor. Non-Patent Document 1 proposes a method of performing photolithography using a certain photosensitive resin composition to obtain a hollow package. The method of using the photosensitive resin composition generally does not require a high-temperature process, and the Φ medium-two package can be obtained simply and with good yield, so that the production cost can be suppressed low, and the micro-machining is relatively easy, so that the component can be miniaturized. The advantages of thinning. [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-522531 [Non-Patent Document 1] The third Asia-pacific c〇nference 〇f transducers and Micr〇_Nan〇Techn〇1〇gy (Apc〇T2 〇〇幻Preface 293 pages [Summary of the Invention] [Problems to be Solved by the Invention] However, the use of only a cured product of a photosensitive resin composition may make the component inconvenient in the use environment, and must be implemented. The secondary processing for imparting reliability to a component provided with a hollow package has been proposed as a method for imparting reliability to a component, and a sealing system using a transfer molding method is low-cost and reliable. The sealing method is known to the market. However, when the element having a hollow package using, for example, the photosensitive resin composition described in Patent Document 1 is sealed by the transfer molding method, there is a case where transfer molding is present. The strength of the hollow package at the temperature is insufficient, and the space for forming the hollow package cannot be sufficiently maintained. At this time, the MEMS mounted in the package of 140909.doc 201013311 cannot operate normally, resulting in micro The reliability of the device is lowered, or the manufacturing cost due to defective products is increased. Moreover, if the space for forming the hollow package is to be maintained, there is a limitation on the shape or size of the cavity, so that the performance of the micro device is significantly degraded. In view of the above, it is desired to provide a photosensitive resin composition for a hollow package which is excellent in resistance to a treatment at a high temperature and which can sufficiently maintain a space even in a transfer molding method. Further, the present invention is intended to provide a photosensitive resin composition. In the present invention, the photosensitive resin composition for providing a hollow portion (cavity) surrounding the MEMS is referred to as a "photosensitive resin composition for hollow encapsulation" in the present invention. [Technical Problem Solving] Means for solving the above problems, the present inventors have repeatedly studied and researched, and found that by selecting a specific epoxy resin, it is possible to exhibit high strength in the temperature range of transfer molding, and to have a MEMS package. By using a photosensitive resin composition having a sufficient strength of the material, and further adding a liquid epoxy resin, it is possible to easily form a laminate (dry film). The present invention has been completed in a photosensitive resin composition which is not accompanied by a decrease in the strength of a cured product. That is, the present invention relates to: (a) a photosensitive resin composition for encapsulation, which contains the following The trisphenol phenol type epoxy resin (A) represented by the formula (1) and the cationic photopolymerization initiator (B) are formed by: 140909.doc 201013311 [Chemical 1]
(式（1)中，R分別獨立表示f周 虱原子、碳數為1〜6之烷基、烯 丙基或苯基；m為R之個數，八s丨主_ W數分別表不1〜3之整數；又，η 為平均值，〇SnSl〇); ()如上it項⑴之巾空封裝用感光性樹脂組合物，其係 進而含有！分子中具有2個以上之環氧基之環氧樹腊（c)而 形成者； (3)如上述項（2)之中空封裝用感光性樹脂組合物，其中 瘳 W子中具有2個以上之環氧基之環氧樹脂（C)係選自以下 述式（2)所表示之環氧樹脂（C-1)、以下述式（3)所表示之環 氧樹月旨（C-2)及以下述式⑷所表*之環氧樹脂（c十所組 I40909.doc 201013311 [化2](In the formula (1), R independently represents a f-circumferential atom, an alkyl group having a carbon number of 1 to 6, an allyl group or a phenyl group; m is the number of R, and the number of the eight s 丨 main _ W respectively indicates An integer of 1 to 3; η is an average value, 〇SnSl〇); () The photosensitive resin composition for the empty package of the item (1) above, which further contains! A photosensitive resin composition for hollow encapsulation of the above item (2), wherein the yttrium has two or more of the above-mentioned (2) epoxy resin waxes (c). The epoxy group-containing epoxy resin (C) is selected from the epoxy resin (C-1) represented by the following formula (2) and the epoxy resin (C-2) represented by the following formula (3). And epoxy resin represented by the following formula (4) (c group of I40909.doc 201013311 [Chemical 2]
(式（2)中，k為平均值，OS kg 10); [化3](in equation (2), k is the average value, OS kg 10); [Chemical 3]
⑶ (式（3)中，R及m表示與上述項（1)之式（1)中者相同之意 義；又，p為平均值，OSpS 10); [化4](3) (In the formula (3), R and m represent the same meanings as in the formula (1) of the above item (1); further, p is an average value, OSpS 10); [Chemical 4]
140909.doc 201013311 /4)如上述項⑴至(3)申任一項之中空封裝用感光性樹 脂組合物，其係進而含有反應性環氧單體（D)而形成者； (5)如上述項（4)之中空封裝用感光性樹赌組合物，其中 反應性環氧單體（D)為雙酚A二縮水甘油趟； 、 广如上述項⑴至(5)中任一項之中空封裝用感光性樹 月曰組合物，其係進而含有無機填充劑（F)而形成者； 二）-種硬化物，其係、使如上述項⑴至⑹中任一項之 ❹中空封裝用感光性樹脂組合物硬化而獲得者； ⑻一種微裝置，其係、具備下述部分而形成者：基板； 微^子機械系統’其係形成於該基板上；空腔確保部，其 係含有如上述項⑺之硬化物而形成者，且以於上述微電子 Ί充之周圍確保空間之方式而包覆上述微電子機械系 、-、及孩、封層，其係含有樹脂而形成者，且以包覆上述空 腔確保部之方式而設置； ()種中空封裝用感光性樹脂組合物之積層體，其係 基材夾持有如上述項⑴至⑻中任一項之中空封裝用感 光性樹脂組合物者。 [發明之效果] ^發月之中空封裝用感光性樹脂組合物之硬化物具有於 $溫軏圍内亦表現出高強度之特徵’藉由使用該樹脂組合 即便於藉由轉移模塑法來密封中空封裝時，亦可充分 1呆持由中空封裝形成之空間（空腔）。尤其，本發明之中空 封裝用感光性樹脂組合物於製造具有空腔iMEMs元件之 方面較為有用。 14〇909.d〇c 201013311 【實施方式】 以下’就本發明之實施形態加以詳細說明。 本發明之以式（1)所表示之三苯酚甲烷型環氧樹脂（A)係 其本身公知之環氧樹脂： [化5]The photosensitive resin composition for hollow encapsulation according to any one of the above items (1) to (3), which further comprises a reactive epoxy monomer (D) and is formed; (5) The photosensitive tree gambling composition for hollow encapsulation according to the above item (4), wherein the reactive epoxy monomer (D) is bisphenol A diglycidyl hydrazine; and as in any one of the above items (1) to (5) a photosensitive dendrimer composition for hollow encapsulation, which further comprises an inorganic filler (F); and a hardened material, which is a hollow encapsulation according to any one of the above items (1) to (6) A device obtained by curing with a photosensitive resin composition; (8) A micro device comprising: a substrate; a micro mechanical system formed on the substrate; and a cavity securing portion The cured product of the above item (7) is formed, and the microelectromechanical system, the -, the child, and the sealing layer are coated so as to ensure a space around the microelectron filling. And provided in such a manner as to cover the cavity securing portion; () a sense of hollow package The laminate of the photosensitive resin composition is a photosensitive resin composition for hollow package according to any one of the above items (1) to (8). [Effects of the Invention] The cured product of the photosensitive resin composition for hollow encapsulation has a characteristic of exhibiting high strength in the temperature range by using the resin combination even by transfer molding. When the hollow package is sealed, the space (cavity) formed by the hollow package can be sufficiently held. In particular, the photosensitive resin composition for hollow encapsulation of the present invention is useful for producing a device having a cavity iMEMs. 14〇909.d〇c 201013311 [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. The trisphenol methane type epoxy resin (A) represented by the formula (1) of the present invention is an epoxy resin known per se: [Chemical 5]
(式（1)中，R分別獨立表示氫原子、碳數為之烷基、烯 丙基或苯基；爪為尺之個數，分別表示^之整數；n為平 均值，0各ng 1〇);該三苯酚曱烷型環氧樹脂（A)例如可藉 由如下方式而製造：使用常法，利用表氣醇等表函醇將視 需要於氮氣環境下使齡類與經基苯甲_反應所得之紛衍 生物加以縮水甘油化。 ‘處所謂以式（1)所表示之三苯酚甲烷型環氧 係指將以式（1)所矣(In the formula (1), R independently represents a hydrogen atom, an alkyl group having an alkyl group, an allyl group or a phenyl group; the number of the claws is a ruler, and each represents an integer of ^; n is an average value, and each ng 1 is 0.三); the trisphenol decane type epoxy resin (A) can be produced, for example, by using a conventional method, using an epitheliol such as epigas alcohol to make the age class and the benzene group in a nitrogen atmosphere as needed. The derivative obtained by the reaction was glycidylated. ‘The trisphenol methane type epoxy represented by formula (1) means that it will be treated by formula (1).
…，真肌π «ν W巧？ ——AmTqwπ亦包含於本發 再者，此處所謂 樹脂（A)」，係指將」 環氧樹脂， (1)所表示之 明之技術範圍内。 作為式（1)之R的碳數為1〜6之烷基，例 基、乙甚、石|、丁 里 句叭之κ的硬數马1〜6之燒基， 乙基、丙基、丁基及環己基等。作 ，例如可列舉：甲 作為R,較好的是氫 140909.doc 201013311 原子或甲基’最好的是氫原子。 該等三苯酚甲烷型環氧樹脂（A)亦可自市場上獲取。例 如可獲取.EPPN-501H(商品名，日本化藥股份有限公司 製造，環氧當量為162〜172 g/eq.，軟化點為51〜57。〇、 EPPN-501HY(商品名’日本化藥股份有限公司製造，環氧 田量為 163 175 g/eq·，軟化點為 57〜63°C )、EPPN-502H(商 如名，日本化藥股份有限公司製造，環氧當量為 φ g/eq·’軟化點為60〜72°C)、EPPN-503(商品名，日本化藥 股份有限公司製造，環氧當量為m〜削g/eq，軟化點為 80〜l〇〇°C )等。 本發明中所使用之三苯酚f烷型環氧樹脂（A)之環氧當 量較好的是400以下。當大於4〇〇時，交聯密度變低，並可 見硬化膜之強度或耐化學藥品性、耐熱性、耐龜裂性下降 之傾向。又，當該環氧樹脂之軟化點過低時，圖案化時容 易發生遮罩黏附現象，進而，於形成積層體（乾膜光阻）而 〇 使用時亦存在常溫下容易軟化之傾向。另一方面，當該環 氧樹脂之軟化點過高時，將積層體（乾膜光阻）層壓於基板 上時不易軟化，而可見與基板之貼合性變差之傾向。出於 上述原因，三苯酚甲烷型環氧樹脂（A)之較好的 〜H)〇t，更好的是60〜9η：β 點為 、於本發明中’所謂陽離子光聚合起始劑⑻，係指藉由 活性能量線之照射而產生陽離子種之化學種。作為本發明 中所使用之陽離子光聚合起始劑，只要係具有使上述三苯 酚甲烧型環氧樹脂（A)硬化之充分性能者，則並無特別限 140909.doc 201013311 定。作為可使用之陽離子光聚合起始劑（B)，例如可列舉 芳香族錤錯鹽或芳香族銃錯鹽。其中，作為芳香族錤錯鹽 之具體例，可列舉：二苯基錤四（五氟苯基）硼酸鹽、二苯 基錤六氟磷酸鹽、二苯基錤六氟銻酸鹽、二（4-壬基苯基） 錤六氟磷酸鹽、曱苯基異丙苯基錤四（五氟苯基）硼酸鹽（商 品名：Rhodorsil Photoinitiator 2074，Rhodia公司製造）、 二（4-第三丁基）錤三（三氟甲磺醯基）甲烷化物（商品名： CGI BBIC C1，汽巴精化（Ciba Specialty Chemicals)公司製 造）等。 又，作為芳香族銃錯鹽之具體例，可較好地使用：4-硫 代苯基二苯基銃六氟銻酸鹽（商品名：CPI-101A，San-Apro股份有限公司製造）、硫代苯基二苯基銕三（五氟乙基） 三氟磷酸鹽（商品名：CPI-210S，San-Apro股份有限公司製 造）、4-{4-(2-氣苯曱醯基）苯硫基}苯基雙（4-氟苯基）锍六 氟銻酸鹽（商品名：SP-172，旭電化工業股份有限公司製 造）、含有4-硫代苯基二苯基锍六氟銻酸鹽之芳香族銃六氟 録酸鹽之混合物（商品名：UVI-6976，Dow Chemical公司 製造）及三苯基銃三（三氟甲磺醯基）甲烷化物（商品名：CGI TPS Cl，汽巴精化公司製造）、三[4-(4-乙醯基苯基對胺苯 磺基）苯基]銃三[(三氟甲基）磺醯基]甲烷化物（商品名： GSID26-1，汽巴精化公司製造）、（2-(4-甲氧基萘-1-基）-2-側氧基乙基）二甲基銕四（五氟苯基）硼酸鹽（商品名： TAG382，東洋油墨製造股份有限公司製造）等。 以上陽離子光聚合起始劑中，本發明中就熱穩定性優異 140909.doc -12- 201013311 之方面而言，較好的是芳香族銃錯鹽，芳香族銃錯鹽中更 好的疋非銻系之硫代苯基二苯基銃三（五氟乙基）三氟磷酸 ^ 一本基銃二（二氟f續酿基）甲燒化物、[2-(4-曱氧基 萘1基）-2-側氧基乙基]二甲基銃四（五氟苯基）硼酸鹽、三 [4-(4-乙醯基苯基對胺苯磺基）苯基]銃三[(三氟曱基）磺醯 基]甲烷化物等。 對於β亥等陽離子光聚合起始劑（B)，可於本發明之中空 φ 封裝用感光性樹脂組合物中單獨使用1種或併用2種以上。 田中二封裝用感光性樹脂組合物中之陽離子光聚合起始劑 之含里過少時，會難以獲得充分之硬化速度，反之，過多 %並不經濟。就該等方面而言，本發明之中空封裝用感光 性樹脂組合物中的陽離子光聚合起始劑（Β)之含量為，於 環氧樹脂之總量（含有後述環氧樹脂（C)及/或反應性環氧單 體（D)時則包含該等）中較好的是〇〇1〜15質量％，更好的是 1〜1〇質量％。 ❹ 本毛月之中空封裝用感光性樹脂組合物中，可進而含有 子中具有2個以上之環氧基之環氧樹脂（C)。作為環氧 樹月曰（C) ’只要i分子中具有2個以上之環氧基則並無特別 限制，較好的是硬化物於高溫範圍内亦表現出高強度之芳 香族系多官能縮水甘油醚。作為可使用之芳香族系多官能 縮水甘油喊’可列舉：雙盼麵駿清漆型環氧樹脂、苯齡 ㈣清漆型環氧樹脂、曱⑽酸清漆型環氧樹脂 、苯齡芳 、元基至環氧樹脂、二環戊二烯型環氧樹脂、萘酚曱酚共縮 聚型環氧樹脂等’尤其好的是以下述式⑺至⑷所表示之 140909.doc -13 · 201013311 多官能環氧樹脂（C-1)至（C-3): [化6]..., true muscle π «ν W巧? - AmTqwπ is also included in the present invention. Here, the term "resin (A)" refers to the technical range indicated by the epoxy resin (1). The alkyl group having a carbon number of 1 to 6 as the R of the formula (1), an alkyl group of 1 to 6 of the κ of the benzyl group, the ethyl group, the stone, and the κ of the Dingli period, an ethyl group, a propyl group, Butyl and cyclohexyl groups. For example, a is preferable, and R is preferably hydrogen. 140909.doc 201013311 The atom or the methyl group is preferably a hydrogen atom. These trisphenol methane type epoxy resins (A) are also commercially available. For example, EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 162 to 172 g/eq., softening point of 51 to 57. 〇, EPPN-501HY (trade name 'Nippon Chemicals') is available. Made by the company, the amount of epoxy is 163 175 g / eq ·, softening point is 57 ~ 63 ° C), EPPN-502H (as the name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is φ g / Eq·'softening point is 60 to 72 ° C), EPPN-503 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is m~cut g/eq, softening point is 80~l〇〇°C) The epoxy equivalent of the trisphenol f-type epoxy resin (A) used in the present invention is preferably 400 or less. When it is more than 4 Å, the crosslinking density becomes low, and the strength of the cured film or Chemical resistance, heat resistance, and crack resistance tend to decrease. When the softening point of the epoxy resin is too low, mask adhesion tends to occur during patterning, and further, a laminate (dry film light) is formed. Resistance) and when used, there is a tendency to soften at room temperature. On the other hand, when the softening point of the epoxy resin is too high, When the laminate (dry film photoresist) is laminated on the substrate, it is not easy to soften, and the adhesion to the substrate tends to be deteriorated. For the above reasons, the trisphenol methane type epoxy resin (A) is preferable. H) 〇t, more preferably 60 to 9 η: The β point is, in the present invention, the term "the so-called cationic photopolymerization initiator (8)" refers to a chemical species which generates a cationic species by irradiation with an active energy ray. The cationic photopolymerization initiator used in the present invention is not particularly limited as long as it has sufficient properties to cure the above-mentioned benzenephenol-based epoxy resin (A). The cationic photopolymerization initiator (B) which can be used may, for example, be an aromatic sulfonium salt or an aromatic sulfonium salt. Specific examples of the aromatic sulfonium salt include diphenyl sulfonium tetrakis(pentafluorophenyl) borate, diphenyl sulfonium hexafluorophosphate, diphenyl sulfonium hexafluoroantimonate, and 4-nonylphenyl) sulfonium hexafluorophosphate, fluorenylphenyl isopropyl phenyl sulfonium tetrakis(pentafluorophenyl) borate (trade name: Rhodorsil Photoinitiator 2074, manufactured by Rhodia), two (4-third butyl)錤) tris(trifluoromethanesulfonyl) methanide (trade name: CGI BBIC C1, manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like. Further, as a specific example of the aromatic sulfonium salt, 4-thiophenyldiphenylphosphonium hexafluoroantimonate (trade name: CPI-101A, manufactured by San-Apro Co., Ltd.) can be preferably used. Thiophenyldiphenylphosphonium tris(pentafluoroethyl)trifluorophosphate (trade name: CPI-210S, manufactured by San-Apro Co., Ltd.), 4-{4-(2-benzophenanthryl) Phenylthio}phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate (trade name: SP-172, manufactured by Asahi Kasei Kogyo Co., Ltd.), containing 4-thiophenyldiphenylphosphonium hexafluoride A mixture of an aromatic hexafluoroantimonate of citrate (trade name: UVI-6976, manufactured by Dow Chemical Co., Ltd.) and triphenylsulfonium tris(trifluoromethanesulfonyl) methanide (trade name: CGI TPS Cl) , manufactured by Ciba Specialty Chemicals Co., Ltd., tris[4-(4-ethylmercaptophenyl p-aminophenylsulfonyl)phenyl]indole tris[(trifluoromethyl)sulfonyl] methanide (trade name: GSID26) -1, manufactured by Ciba Specialty Chemicals Co., Ltd., (2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylammonium tetrakis(pentafluorophenyl)borate First Name: TAG382, Toyo Ink Manufacturing Co., Ltd. Limited) and the like. Among the above cationic photopolymerization initiators, in the present invention, in terms of excellent thermal stability, 140909.doc -12 to 201013311, it is preferred that the aromatic sulfonium salt and the aromatic sulfonium salt are better. Thiophenyl phenyl diphenyl sulfonium tris(pentafluoroethyl)trifluorophosphate 一 本 铳 ( 二 二 二 二 二 、 、 、 、 Benzyl-2-ethyloxyethyl]dimethylammonium tetrakis(pentafluorophenyl)borate, tris[4-(4-ethylmercaptophenyl-p-aminophenylsulfonyl)phenyl]indole[ Trifluoromethylsulfonyl]methane and the like. In the photosensitive resin composition for hollow φ encapsulation of the present invention, one type of the cationic photopolymerization initiator (B) can be used alone or in combination of two or more. When the content of the cationic photopolymerization initiator in the photosensitive resin composition for the middle of the package is too small, it is difficult to obtain a sufficient curing rate, and on the contrary, too much % is not economical. In this regard, the content of the cationic photopolymerization initiator (Β) in the photosensitive resin composition for hollow encapsulation of the present invention is the total amount of the epoxy resin (containing the epoxy resin (C) described later and The preferred one of the reactive epoxy monomers (D) is preferably from 1 to 15% by mass, more preferably from 1 to 1% by mass. The photosensitive resin composition for hollow encapsulation of the present invention may further contain an epoxy resin (C) having two or more epoxy groups in the sub-group. The epoxy tree cerium (C) ' is not particularly limited as long as it has two or more epoxy groups in the i molecule, and it is preferred that the cured product exhibits high strength aromatic polyfunctional shrinkage in a high temperature range. Glycerol ether. As an aromatic polyfunctional glycidol that can be used, it can be exemplified: Shuangpan noodles varnish type epoxy resin, benzene age (four) varnish type epoxy resin, bismuth (10) acid varnish type epoxy resin, benzoin, yuan base The epoxy resin, the dicyclopentadiene type epoxy resin, the naphthol phenolic copolycondensation type epoxy resin, etc. are particularly preferably 140909.doc -13 · 201013311 polyfunctional ring represented by the following formulas (7) to (4) Oxygen resin (C-1) to (C-3): [Chem. 6]
(式（2)中，k為平均值，OSkS 10); 作為以式（2)所表示之環氧樹脂（C-1)之具體例，可自市 場上獲取jERl 57(商品名，日本環氧樹脂（Japan Epoxy Resins)股份有限公司製造，環氧當量為1 80〜250 g/eq.，軟 化點為 80~90°C)、EPON SU-8(商品名，Resolution Performance Products公司製造，環氧當量為195〜230 g/eq.，軟化點為 80〜90〇C )等； [化7](In the formula (2), k is an average value, OSkS 10); As a specific example of the epoxy resin (C-1) represented by the formula (2), jERl 57 (trade name, Japanese ring) can be obtained from the market. Oxygen resin (Japan Epoxy Resins) Co., Ltd., epoxy equivalent of 180 ~ 250 g / eq., softening point of 80 ~ 90 ° C), EPON SU-8 (trade name, manufactured by Resolution Performance Products, ring The oxygen equivalent is 195~230 g/eq., the softening point is 80~90〇C); [Chem. 7]
(式（3)中，R分別獨立表示氫原子、碳數為1〜6之烷基、烯 140909.doc -14- 201013311 丙基或本基，πι為R之個數 均值，0 ^ P S 1 〇；); 表示1〜3以下 之整數；p為平 作為式（3)之R的碳數為 例如可列舉：甲 基乙基、丙基、丁基及環己基等， 使^ , 土寸权好的是氫原子或甲 基，更好的是f基；作為式之最 、取野的組合，可列舉R為(In the formula (3), R independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkene 140909.doc -14-201013311 propyl group or a benzyl group, and πι is a number average of R, 0 ^ PS 1 〇;); represents an integer of 1 to 3 or less; p is a flat carbon number of R of the formula (3), for example, methyl ethyl, propyl, butyl, cyclohexyl, etc. The right weight is a hydrogen atom or a methyl group, and more preferably an f group; as a combination of the formula and the wild type, R is
甲基、m為卜且R之取代位置相對於縮水甘油基為鄰位的 鄰甲齡㈣清漆型環氧樹脂；作為以式（3)所表示之環氧樹 脂（C-2)之具體例，可自市場上獲取eocn」啊商品名， 曰本化藥股份有限公司製造，環氧當量為19〇〜2i〇岁叫.， 軟化點為55〜85°C)、E〇CN-4400H(商品名，日本化藥股份有 限公司製造’環氧當量為185〜2〇〇 g/eq.，軟化點為 55〜64 C )、EOCN-102S(商品名，日本化藥股份有限公司製 造’環氧當量為205〜225 g/eq.，軟化點為55〜80°C )、EOCN- 103S(商品名，日本化藥股份有限公司製造，環氧當量為 210~230 g/eq.，軟化點為 80~90°C)、EOCN-104S(商品名， 曰本化藥股份有限公司製造，環氧當量為210〜230 g/eq.，軟 化點為90~95°C)、EPPN-201(商品名，日本化藥股份有限公 司製造，環氧當量為180〜200 g/eq_，軟化點為65〜78°C)等； [化8]A methyl group, m is a phthalocyanine type epoxy resin in which the substitution position of R is ortho to the glycidyl group, and a specific example of the epoxy resin (C-2) represented by the formula (3) , can be obtained from the market eocn" ah brand name, manufactured by Sakamoto Chemical Co., Ltd., epoxy equivalent is 19 〇 ~ 2i 〇 years old, softening point is 55 ~ 85 ° C), E 〇 CN-4400H ( The product name, Nippon Kayaku Co., Ltd. manufactures 'epoxy equivalent weight 185~2〇〇g/eq., softening point is 55~64 C), EOCN-102S (trade name, manufactured by Nippon Kayaku Co., Ltd.) Oxygen equivalent is 205~225 g/eq., softening point is 55~80 °C), EOCN-103S (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is 210~230 g/eq., softening point) 80~90°C), EOCN-104S (trade name, manufactured by Sakamoto Chemical Co., Ltd., epoxy equivalent 210~230 g/eq., softening point 90~95°C), EPPN-201 ( Trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is 180~200 g/eq_, softening point is 65~78 °C); [Chem. 8]
(4) 140909.doc • 15· 201013311 作為以式（4)所表示之環氧樹脂（C3)之具體例，可自市 場上獲取NC-6000(商品名，曰本化藥股份有限公司製造， 環氧當量為205〜2I5 g/eq•，軟化點為55〜65。〇、nc_ 6麵(商品$ ’日本化藥股份有限公司製造，環氧當量為 230〜235 g/eq.，軟化點為7〇〜at )等。 本發明之中空封裝用感光性樹脂組合物中，可任意地選 擇使用1種或2種以上的丨分子中具有2個以上之環氧基之環 氧樹脂（C)，較好的是使用1種或2種以上的以上述式至 (4)所表示之環氧樹脂（C-1)至（C-3)。 本發明之中空封裝用感光性樹脂組合物中的丨分子中具 有2個以上之環氧基之環氧樹脂（c)(以下有時亦簡稱為「C 成分」）的調配比例為，相對於三苯酚甲烷型環氧樹脂 (A)(以下有時亦簡稱為r A成分」）、後述反應性環氧單體 (D)及C成分之總量，通常為〇〜95質量％，較好的是5〇〜95 質量m量超過95質量％，則A成分之調配比例變得過 少，硬化物於高溫範圍内表現不出高強度。又，若含量少 於5 0質量/〇，則有感光性樹脂組合物之感度下降之虞，為 獲得於高溫範圍内亦表現出高強度之硬化物而必須進行長 時間之光照射，並不經濟。 本發明之中空封裝用感光性樹脂組合物中，為了進—步 使形成積層體（乾膜光阻）時之柔軟性提昇而易於操作，亦 可添加反應性.環氧單體（D)(以下有時亦簡稱為「^成 分」）。此處所謂反應性環氧單體，係指於常溫下為液體 或軟化點為40°C以下之環氧樹脂。作為反應性環氧單體 140909.doc -16 - 201013311 (D)，可使用與A成分、B成分、C成分具有混和性的縮水 甘油醚化合物，作為其具體例，可列舉：二乙二醇二縮水 甘油醚、己二醇二縮水甘油醚、二幾甲基丙烧二縮水甘油 醚、聚丙二醇二縮水甘油醚（商品名：ED506 ’ Adeka股份 有限公司製造）、三經甲基丙烧三縮水甘油醚（商品名： ED505 ’ Adeka股份有限公司製造）、三羥曱基丙烷三縮水(4) 140909.doc • 15· 201013311 As a specific example of the epoxy resin (C3) represented by the formula (4), NC-6000 (trade name, manufactured by Sakamoto Chemical Co., Ltd.) can be obtained from the market. The epoxy equivalent is 205~2I5 g/eq•, and the softening point is 55~65. 〇, nc_ 6 side (product $ 'made by Nippon Kayaku Co., Ltd., epoxy equivalent is 230~235 g/eq., softening point In the photosensitive resin composition for hollow encapsulation of the present invention, an epoxy resin having two or more epoxy groups in one or more kinds of anthracene molecules can be arbitrarily selected and used (C) It is preferred to use one or two or more kinds of the epoxy resins (C-1) to (C-3) represented by the above formulas (4). The photosensitive resin composition for hollow encapsulation of the present invention The blending ratio of the epoxy resin (c) having two or more epoxy groups in the ruthenium molecule (hereinafter sometimes referred to as "C component") is relative to the trisphenol methane type epoxy resin (A) ( Hereinafter, the total amount of the reactive epoxy monomer (D) and the component C to be described later may be simply referred to as "r A component"), and is usually 〇95% by mass, preferably 5〇~ When the amount of the mass m is more than 95% by mass, the proportion of the component A is too small, and the cured product does not exhibit high strength in a high temperature range. Further, if the content is less than 50% by mass, the photosensitive resin composition is present. In the photosensitive resin composition for hollow encapsulation of the present invention, it is not economical to obtain a cured product having a high strength and exhibits a high-strength hardened material in a high temperature range. The flexibility in forming a laminate (dry film photoresist) is improved and easy to handle, and a reactive epoxy resin (D) (hereinafter sometimes referred to simply as "component") may be added. Epoxy monomer refers to an epoxy resin which is liquid at room temperature or has a softening point of 40 ° C or less. As a reactive epoxy monomer 140909.doc -16 - 201013311 (D), it can be used with A component, B The component and the component C have a glycidyl ether compound having a miscibility. Specific examples thereof include diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethicone diglycidyl ether, and poly Propylene glycol diglycidyl ether (trade name) : ED506 ’ manufactured by Adeka Co., Ltd.), trimethyl methacrylate triglycidyl ether (trade name: ED505 ‘Adeka Co., Ltd.), trishydroxypropyl propane tricondensate
甘油醚（商品名：EX321L，長瀨化成（Nagase ChemteX)股 份有限公司製造，低氯型）、季戊四醇四縮水甘油謎、雙 酚A二縮水甘油醚、雙酚ρ二縮水甘油醚等。該等之中，尤 其就可獲得於高溫範圍内亦表現出高強度之硬化物的方面 而言’較好的是雙酚A二縮水甘油醚。該等可單獨使用或 混合使用2種以上。於本發明之中空封裝用感光性樹脂組 成中，若D成分之調配比例過少，則不足以改善積層體（乾 膜光阻）之柔軟性，若過多則乾燥後之皮膜會發黏，容易 引起遮罩黏附現象等而不佳。出於上述原因，D成分之添 加畺相對於A成分、C成分及D成分之總量較好的是2〇質量 〇/〇以下’尤其好的是5質量。/〇〜1 5質量％。 為使本發明之中空封裝用感光性樹脂組合物之黏度下 降、使塗膜性提高，可使用溶劑（E)<5作為溶劑，可使用 油墨、塗料等通常應用之有機溶劑，相對於上述各成分具 有充分之溶解力者全部可使用。作為此種有機溶劑，可列 舉：丙綱、乙基甲基_、環己酮及環戊酮等綱類，曱苯、 二甲苯及四甲基苯等芳香族烴類，二丙二醇二曱醚及二丙 二醇二***等二醇醚類，乙酸乙酯 乙酸丁酯、丁基溶纖 140909.doc 201013311 :丨，酸s曰卡必醇乙酸酯、丙二醇單甲醚乙酸酯及丁内 西曰等西曰類甲醇、乙醇、溶纖劑及甲基溶纖劑等酵類，辛 烷及癸燒等脂肪族煙，石油趟、石油腦、氣化石油腦及溶 劑石油腦等石油系溶劑等。 該等冷劑可單獨使用或混合使用2種以上。溶劑成分係 以對塗布於基材上時之膜厚或塗布性進行調整為目的而添 力者為適田地保持上述各成分之溶解性或揮發性、樹脂 組合物整體之液黏度等，中空封裳用感光性樹脂組合物中 之溶劑之含量較好的是95質量％以下，尤其好的是ι〇〜9〇 質量％。 本發明之中空封裝用感光性樹脂組合物中，為使樹脂組 2物對基板之密著性進—步提昇，亦可使用具有混和性之 密著性賦予劑。作為密著性賦予劑，可使用矽烷偶合劑、 鈦偶合劑等偶合劑，作為較好者，可列舉矽烷偶合劑。 作為可使用之矽烷偶合劑之具體例，可列舉：3_氯丙基 一甲氧基矽烷、乙烯基三氣矽烷、乙烯基三乙氧基矽烷、 乙婦基三甲氧基矽烷、乙烯基三（2_甲氧基乙氧基）矽烷、 3-甲基丙烯醯氧基丙基三甲氧基矽烷、2_(3,4_環氧環己基） 乙基二甲氧基矽烷、3_縮水甘油氧基丙基三甲氧基矽烷、 3-巯基丙基三f氧基矽烷、3·胺基丙基三乙氧基矽烷、Ν_ 2_(胺基乙基）-3-胺基丙基三甲氧基矽烷、3_脲基丙基三乙 氧基石夕烧等。該等密著姓賦予劑可單獨使用或組合使用2 種以上。 當過剩使用密著性賦予劑時，可能會使本發明之中空封 140909.doc -18- 201013311 裝用環氧樹脂組合物之硬化物的交聯密度下降，或由於未 反應而仍殘存於硬化物中導致硬化物之物性值下降。對於 後著I生賦予劑，就視基材不同即便量較少亦發揮效果之方 面而言，較合適的是於不產生不良影響之範圍内使用，其 使用比例於本發明之中空封裝用環氧樹脂組合物中較好的 是15質量％以下，尤其好的是5質量。/〇以下。 於本發明之中空封裝用感光性樹脂組合物中亦可使用 ❹發揮如下作用之增感劑：吸收紫外線，並將所吸收之光能 量提供給陽離子光聚合起始劑。作為可使用之増感劑之 例，例如可列舉9位及10位上具有烷氧基之蒽化合物（9,1〇_ 二烷氧基蒽衍生物）、9-氧硫咄蠖類等。作為9，1〇_二烷氧 基蒽衍生物之烧氧基，例如可列舉：甲氧基、乙氧基、丙 氧基、丁氧基等C1〜C4之烷氧基^ 9，1〇_二烷氧基蒽衍生物 亦可於9位及1 〇位以外之部位進而具有取代基。作為進而 可具有之取代基，例如可列舉：氟原子、氣原子、溴原 ❹子、碘原子等鹵素原子，甲基、乙基、丙基等(：卜以之烷 基或磺酸烷基酯基、羧酸烷基酯基等。作為磺酸烷基酯基 或叛酸烧基S旨中之烧基，例如可列舉甲基、乙基、丙某等 C1〜C4之烷基。該等取代基之取代位置較好的是2位。 作為9，10-二烷氧基蒽衍生物之具體例，例如可列舉·· 9,10-二甲氧基蒽、9，10-二乙氧基蒽、9,1 〇_二丙氧基蒽、 9,10 -一丁乳基蒽、9,10-二甲氧基_2_乙基蒽、9,1〇_二乙氧 基-2-乙基恩、9，10-二丙氧基_2_乙基蒽、9，1〇_二甲氧基_2-氣蒽、9,10-二甲氧基蒽-2-磺酸甲酯、9,10-二乙氧基蒽_2_ 140909.doc .19· 201013311 磺酸甲酯、9,10-二甲氧基蒽_2_甲酸甲酯等。尤其好的是 使用9,1 0-—甲氧基-2-乙基蒽、9,1 〇-二丁氧基蒽。 作為9-乳硫p山p星類之具體例，可列舉：2,4_二甲基_9_氧 硫星、2,4-二乙基_9_氧硫ρ山p星、2-氯-9-氧硫咄p星、2,4- 二異丙基-9-氧硫P山噬等，較好的是2,4二乙基_9_氧硫 口山畦（商品名：Kayacure DETX-S，日本化藥股份有限公司 製造）、2-異丙基-9-氧硫咄P星，尤其好的是2,4_二乙基_9_ 氧硫！I山嗤。 該等增感劑可單獨使用或混合使用2種以上，為使增感 _ 劑成分以少量而發揮效果’其使用比例相對於陽離子光聚 合起始劑（B)較好的是100質量％以下，尤其好的是2〇質量 %以下。 對於本發明之中空封裝用感光性樹脂組合物而言，當必 須減少由源自陽離子光聚合起始劑（B)之離子所引起之不 良影響時，亦可添加離子捕捉劑。作為離子捕捉劑之具體 例，可列舉：三曱氧基鋁、三乙氧基鋁、三異丙氧基鋁、 異丙氧基二乙氧基鋁及三丁氧基鋁等烷氧基鋁，三苯氧基 _ 銘及一對甲基苯氧基結等苯氧基|呂’三乙醯氧基紹，三硬 月曰酸紹二丁酸铭、三丙酸铭、三乙酿丙酮銘、三（三說 乙酿丙_)紹、二乙基乙酿乙酸IS、二乙醢丙酮-2,2,6,6-四 甲基-3,5-庚二酮鋁及二異丙氧基（乙基乙醯乙酸）鋁等有機 銘化合物等’該等成分可單獨使用或組合使用2種以上。 又’其調配量相對於A成分、B成分、C成分及D成分之總 質量為10質量％以下。 140909.doc -20· 201013311 本發明之中空封裝用感光性樹脂組合物中，視需要可使 用熱塑性樹脂、著色劑、增稠劑、消泡劑、句化劑等各種 添加劑。作為熱塑性樹脂，例如可列舉聚㈣、聚苯乙稀 及聚碳酸酯等。作為著色劑，例如可列舉酞菁藍、酞菁 綠、填綠、結晶紫、氧化鈦、碳黑及萘黑等。作為增稠 劑’例如可列舉0RBEN、BENT0N及蒙脫石等。作為消泡 劑，例如可列舉㈣系、氟系及高分子系等之消泡劑。關 ❹於該等添加劑等之使用量，於本發明之中空封裝用感光性 樹脂組合物中例如各含有0.1〜30質量％左右係大體上之標 準’但根據使用目的可適當增減。 本發明之中空封裝用感光性樹脂組合物中，例如可使用 硫酸鋇、㈣鋇、氧切、m氧切（am〇rph〇us 心)、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化 鋁、雲母粉等無機填充劑（F)，其使用量於本發明之中空 封裝用感光性樹脂組合物中為6〇質量％以下。若無機填充 ❹齊J之粒徑過大，則有光之透射性下降而表現不出充分之微 影性能之虞。因此，無機填充劑之平均粒徑較好的是直徑 為5 μηι以下’更好的是直徑為1 μιη以下。 本發明之中空封裝用感光性樹脂組合物可僅藉由視需要 ^上述必須成分中添加上述任意成分並加以混合、攪拌而 製備，視需要亦可使用分散攪拌機、均質機、三輥研磨機 等分散機加以分散、混合。又，亦可於混合後進一步使用 篩網、薄膜過濾器等進行過濾。 本發明之中空封裝用感光性樹脂組合物較好的是以液狀 140909.doc -21 · 201013311 而使用。以下，對使用本發明之中空封裝用感光性樹脂組 合物時之塗布法、硬化法加以概略說明。 例如’於矽、鋁、銅等之金屬基板，鈕酸鋰、玻璃、氧 化矽、氮化矽等之陶瓷基板，聚醯亞胺、聚對苯二甲酸乙 二酯等之基板上，使用旋塗機等以〇〗〜〗〇〇〇 μιη之厚度塗 布本發明之中空封裝用感光性樹脂組合物，藉由 60〜130°C、5〜60分鐘左右之熱處理將溶劑去除，而形成感 光性樹脂組合物層。繼而，在設置於基板上之感光性樹脂 組合物層上載置具有既定圖案之遮罩並照射紫外線，進行 50〜130C、1〜50分鐘左右之加熱處理（pEB，p〇st以”⑽代 Bake，曝光後烘烤）後，使用顯影液以室溫 分鐘左右之條件對未曝光部進行顯影而形成圖案。進而， 對所得圖案實施13〇〜20(TC、10〜360分鐘左右之加熱處 理，藉此可獲得滿足各種特性之本發明之中空封裝用感光 性樹脂組合物之硬化物。作為顯影液，例如可使用丫·丁内 酯、三乙二醇二甲醚、丙二醇單曱醚乙酸酯等有機溶劑， 或上述有機溶劑與水之混合液等。顯影時可使用 喷霧式、喷淋式等之顯影裝置，視需要料進行超音波昭 射。 ’、 使用輥塗機、模塗機、刀片塗布機、棒塗機、凹版塗布 機等’將本發明之中空封裝用感光性樹脂組合物塗布於基 膜上之後，使用設定於45〜10(rc之乾燥爐將既定量之溶劑 去除’進而視需要積層t蓋膜等，#此可形成積層體（乾 膜光阻）。此時，基膜上之光阻厚度係調整為2〜ι〇〇 I40909.doc -22- 201013311 基膜及覆蓋膜例如可使用聚酿、聚丙烯、聚乙烯、 TAC(Triacetyl Cellulose，三乙酿纖維素）、聚醯亞胺等之 膜。對於該賴’視需要亦可藉切㈣脫模處理劑或非Glycerol ether (trade name: EX321L, manufactured by Nagase ChemteX Co., Ltd., low chlorine type), pentaerythritol tetraglycidol mystery, bisphenol A diglycidyl ether, bisphenol ρ diglycidyl ether, and the like. Among these, bisphenol A diglycidyl ether is preferred because it can be obtained in a high temperature range and exhibits a high strength cured product. These may be used alone or in combination of two or more. In the photosensitive resin composition for hollow package of the present invention, if the blending ratio of the D component is too small, the flexibility of the laminate (dry film photoresist) is not improved, and if it is too large, the film after drying becomes sticky, which is likely to cause The mask sticking phenomenon is not good. For the above reasons, the addition of the component D to the total amount of the component A, the component C, and the component D is preferably 2 〇 mass 〇 / 〇 or less, and particularly preferably 5 mass. /〇~1 5 mass%. In order to reduce the viscosity of the photosensitive resin composition for hollow encapsulation of the present invention and to improve the coating property, a solvent (E) < 5 can be used as a solvent, and an organic solvent which is usually used, such as an ink or a paint, can be used. All components having sufficient solvency can be used. Examples of such an organic solvent include an anthracene such as a propyl group, an ethylmethyl group, a cyclohexanone, and a cyclopentanone; an aromatic hydrocarbon such as toluene, xylene, and tetramethylbenzene; and dipropylene glycol dioxime ether. And glycol ethers such as dipropylene glycol diethyl ether, ethyl acetate butyl acetate, butyl cellulosic 140909.doc 201013311: hydrazine, acid s-carbitol acetate, propylene glycol monomethyl ether acetate and butene Nicotinamide methanol, ethanol, cellosolve and methyl cellosolve and other enzymes, octane and simmering aliphatic smoke, petroleum sputum, petroleum brain, gasified petroleum brain and solvent petroleum brain and other petroleum solvents. These refrigerants may be used alone or in combination of two or more. In order to adjust the film thickness or the coating property when applied to a substrate, the solvent component is added to the field to maintain the solubility or volatility of the above components, the liquid viscosity of the entire resin composition, and the like. The content of the solvent in the photosensitive resin composition for hairdressing is preferably 95% by mass or less, and particularly preferably 1% by mass to 9% by mass. In the photosensitive resin composition for a hollow package of the present invention, in order to further improve the adhesion of the resin group to the substrate, an adhesiveness imparting agent having a miscibility can be used. As the adhesion imparting agent, a coupling agent such as a decane coupling agent or a titanium coupling agent can be used, and a decane coupling agent is preferable. Specific examples of the decane coupling agent which can be used include 3-chloropropyl monomethoxy decane, vinyl trioxane, vinyl triethoxy decane, ethenyl trimethoxy decane, and vinyl trisole. (2-methoxyethoxy)decane, 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyldimethoxydecane, 3-glycidyl Oxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxypropane, 3·aminopropyltriethoxydecane, Ν-2-((aminoethyl)-3-aminopropyltrimethoxy Decane, 3-ureidopropyltriethoxy zebra, etc. These secret name-imparting agents may be used alone or in combination of two or more. When the adhesion imparting agent is excessively used, the crosslinking density of the cured product of the epoxy resin composition of the hollow seal of the present invention may be lowered, or may remain in the hardening due to unreacted reaction. The substance causes a decrease in the physical property value of the hardened substance. It is preferable to use it in the range which does not produce an adverse effect, and it is used in the aspect of the hollow-packing ring of The oxygen resin composition is preferably 15% by mass or less, particularly preferably 5 parts by mass. /〇The following. In the photosensitive resin composition for hollow encapsulation of the present invention, a sensitizer which functions to absorb ultraviolet rays and supply the absorbed light energy to the cationic photopolymerization initiator can also be used. Examples of the sensitizing agent which can be used include an anthracene compound having an alkoxy group at the 9-position and the 10-position (9,1 〇-dialkoxyfluorene derivative), and 9-oxothione. Examples of the alkoxy group of the quinone-dialkyloxy fluorene derivative include a C1-C4 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The diazoxy anthracene derivative may further have a substituent at a position other than the 9-position and the 1-position. Examples of the substituent which may be further included, for example, a halogen atom such as a fluorine atom, a gas atom, a bromine pronator or an iodine atom, a methyl group, an ethyl group, a propyl group or the like (: an alkyl group or a sulfonic acid alkyl group) An ester group, a carboxylic acid alkyl ester group, etc. Examples of the alkyl group of the sulfonic acid alkyl ester group or the tick acid group S include, for example, a C1 to C4 alkyl group such as a methyl group, an ethyl group or a C. group. The substitution position of the substituent is preferably 2. Specific examples of the 9,10-dialkoxyfluorene derivative include, for example, 9,10-dimethoxyanthracene, 9,10-diethyl Oxime, 9,1 〇-dipropoxy fluorene, 9,10-butyryl hydrazine, 9,10-dimethoxy-2-ethyl hydrazine, 9,1 hydrazine-diethoxy- 2-ethylen, 9,10-dipropoxy-2-ethyl hydrazine, 9,1 fluorene dimethoxy-2-gas, 9,10-dimethoxyindole-2-sulfonic acid Methyl ester, 9,10-diethoxy hydrazine_2_140909.doc .19· 201013311 methyl sulfonate, methyl 9,10-dimethoxyindole-2-carboxylate, etc. It is especially preferred to use 9, 1 0--methoxy-2-ethyl fluorene, 9,1 fluorene-dibutoxy fluorene. Specific examples of the 9-lactose p mountain p star include 2,4 dimethyl _ 9_oxysulfide 2,4-diethyl_9_oxysulfur p-p-star, 2-chloro-9-oxopurine p-star, 2,4-diisopropyl-9-oxo-sulfur P, and the like It is 2,4 diethyl _9_ oxysulfonate yam (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.), 2-isopropyl-9-oxopurine P star, especially good It is 2,4_diethyl_9_ oxysulfide! I. Hawthorn. These sensitizers can be used alone or in combination of two or more, in order to make the sensitizer ingredient act in a small amount. The cationic photopolymerization initiator (B) is preferably 100% by mass or less, particularly preferably 2% by mass or less. For the photosensitive resin composition for hollow encapsulation of the present invention, when it is necessary to reduce the cation-derived When the photopolymerization initiator (B) is adversely affected by ions, an ion scavenger may be added. Specific examples of the ion scavenger include trisethoxy aluminum, triethoxy aluminum, and triisopropyl. Alkoxy aluminum such as oxyaluminum, isopropoxydiethoxyaluminum and tributoxyaluminum, phenoxy group such as triphenyloxy _ _ and a pair of methyl phenoxy cations| 吕'三乙醯Oxydipine, tri-hard niacin Dibutyric acid Ming, Sanpropionic acid Ming, Sanyi brewing acetone Ming, three (three said B brewing _) Shao, diethyl ethyl acetate acetic acid, diethyl acetonide-2,2,6,6-four For example, these components may be used singly or in combination of two or more kinds of organic compounds such as bis- 3,5-heptanedione aluminum and diisopropoxy (ethyl ethanoacetic acid) aluminum. The total mass of the A component, the B component, the C component, and the D component is 10% by mass or less. 140909.doc -20·201013311 The photosensitive resin composition for hollow encapsulation of the present invention may optionally contain a thermoplastic resin or a coloring agent. Various additives such as thickeners, defoamers, and syntactic agents. Examples of the thermoplastic resin include poly(tetra), polystyrene, and polycarbonate. Examples of the coloring agent include phthalocyanine blue, phthalocyanine green, green-filled, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of the thickeners include 0RBEN, BENT0N, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as (iv), fluorine, and polymer. In the photosensitive resin composition for hollow encapsulation of the present invention, for example, each of the photosensitive resin compositions for hollow encapsulation is contained in an amount of about 0.1 to 30% by mass, which is a standard of the above, but may be appropriately increased or decreased depending on the purpose of use. In the photosensitive resin composition for hollow encapsulation of the present invention, for example, barium sulfate, (tetra) sulfonium, oxygen chopping, m-oxygen (am〇rph〇us heart), talc, clay, magnesium carbonate, calcium carbonate, alumina, or the like can be used. An inorganic filler (F) such as aluminum hydroxide or mica powder is used in an amount of 6% by mass or less based on the photosensitive resin composition for hollow encapsulation of the present invention. If the particle size of the inorganic filler J is too large, the light transmittance is lowered and the sufficient lithographic performance is not exhibited. Therefore, the average particle diameter of the inorganic filler is preferably 5 μηι or less in diameter, and more preferably 1 μηη or less in diameter. The photosensitive resin composition for hollow encapsulation of the present invention can be prepared by adding the above-mentioned optional components to the above-mentioned essential components, mixing and stirring, and if necessary, a dispersing mixer, a homogenizer, a three-roll mill, or the like can be used. The disperser is dispersed and mixed. Further, it may be further filtered using a sieve, a membrane filter or the like after mixing. The photosensitive resin composition for hollow encapsulation of the present invention is preferably used in the form of liquid 140909.doc - 21 · 201013311. Hereinafter, the coating method and the curing method in the case of using the photosensitive resin composition for hollow encapsulation of the present invention will be briefly described. For example, a metal substrate such as ruthenium, aluminum or copper, a ceramic substrate such as lithium nitrite, glass, ruthenium oxide or tantalum nitride, or a substrate such as polyimide or polyethylene terephthalate. The photosensitive resin composition for hollow encapsulation of the present invention is applied to the photosensitive resin composition for hollow encapsulation of the present invention by a coating machine or the like, and the solvent is removed by heat treatment at 60 to 130 ° C for 5 to 60 minutes to form a photosensitive property. A layer of the resin composition. Then, a mask having a predetermined pattern is placed on the photosensitive resin composition layer provided on the substrate, and ultraviolet rays are irradiated thereto, and heat treatment is performed at 50 to 130 C for about 1 to 50 minutes (pEB, p〇st to "10" for Bake. After the post-exposure bake, the unexposed portion was developed using a developing solution at a temperature of about room temperature for a pattern. Further, the obtained pattern was subjected to a heat treatment of 13 Torr to 20 (TC, about 10 to 360 minutes, Thereby, a cured product of the photosensitive resin composition for hollow encapsulation of the present invention which satisfies various characteristics can be obtained. As the developer, for example, yttrium butyrolactone, triethylene glycol dimethyl ether, propylene glycol monoterpene ether acetate can be used. An organic solvent such as an ester or a mixture of the above organic solvent and water, etc. A developing device such as a spray type or a shower type can be used for development, and ultrasonic irradiation can be performed as needed. ', using a roll coater, die coating 'Applicator, blade coater, bar coater, gravure coater, etc.' After applying the photosensitive resin composition for hollow package of the present invention to a base film, it is used in a drying oven set at 45 to 10 (rc) Remove the agent' and then build a layer of t-film or the like as needed. #This can form a laminate (dry film photoresist). At this time, the thickness of the photoresist on the base film is adjusted to 2~ι〇〇I40909.doc -22- 201013311 For the base film and the cover film, for example, a film of polystyrene, polypropylene, polyethylene, TAC (Triacetyl Cellulose, triethylcellulose), polyimine, or the like can be used. Treatment agent or non
石夕_系脫模處理劑等實施脫模處理。使用該積層體時，例 如藉由手動輥、貼合機等以溫度為4〇〜1〇〇r、壓力為 〇.〇5〜2 MPa之條件將剝離了覆蓋膜之積層體轉印於基板 上，而獲得感光性樹脂組合物層（樹脂層），對於該感光性 樹脂組合物層（樹脂層）’與上述以液狀來使用本發明之中 空封裝用感光性樹脂組合物的情形同樣地實施曝光、曝光 後烘烤、顯影、加熱處理即可。 若將本發明之Μ封制感光性樹社合物製成積層體 而使用，則可省略於基板上之塗布、及乾燥之步驟，從而 可更簡便地使用本發明之巾空封裝用感光性樹脂组合物來 形成圖案。 藉由組合上述液狀及/或積層體狀之本發明之中空封枣 用感光性樹脂組合物，並使用光微影之方法，可製備具有 疋空間（空腔）之樹脂硬化物之結構體。 本發明之中空封裝用感光性樹脂組合物可於在具有機械 結構之元件等之周圍具有一定空間（空腔）的狀態下穩定^ 保持基板、配線、元件等，故可較好地用於製作以阻斷氣 體或液體自外部環境侵入為目的之中空封裝。尤其是，本 發明之中空封裝用感光性樹脂組合物可最好地用於製作元 件為MEMS元件之情形之封裝。 繼而，參照圖1〜圖2，就使用本發明之中空封裝用感光 I40909.doc -23- 201013311 性樹脂組合物的微裝置之構成及製造方法加以說明。 圖1係表示微裝置之一例之剖面圖。微裝置1係具備下述 部分而構成：基板2、形成於基板2上之MEMS3、用以確 保設置於MEMS3周圍之空腔C(空間、中空部）之空腔確保 部4、及以包覆上述部分之方式而設置之密封層6等。 設置於導線架5上之基板2係由矽等所形成，於其一方之 面上藉由姓刻等而形成有由金屬薄膜等所構成之導體圖案 7。MEMS3與導體圖案7電性連接，而形成於基板2上。導 體圖案7經由金屬線8而與導線架5連接，可將微裝置i組入參 至其他機器中。 空腔確保部4係由側壁4A與頂棚4B構成之大致箱狀之結 構物，上述側壁4A係以包圍配置於基板2上之MEM”之周 圍的方式而配置，上述頂棚4B係設置於侧壁4A之上方。 刪S3之水平方向之周圍及上方係由空腔確保部*所覆 盍，藉此用於MEMS3驅動之空間即空腔c形成於細趣之 Φ J便用本發明之封裝 作為形成空腔確保部4之材料 感光性樹脂組合物之硬化物。 密封層6係以覆蓋基板 成，具有伴蠖美卜側之方式藉由轉移成形而形 啕保濩基板2上2MEMS3或導 連接部位等不成 圖案7與金屬線8之 丨等不受外部環境影響之功能。 作為密封層6之材料，可採用與 封所用者相同之材 干蜍體日曰片尊之密 環氧密封劑通二=列舉各種環氧密封劑。該等 3被乳樹脂、紛硬化劑、硬化促進劑、 140909.doc -24- 201013311 =充料，亦可含有阻燃劑、脫模劑、著色劑、偶合劑。 、中’就於低麼下可成型纟對空腔c之損傷較少之方面而 s，較好的是使用低黏度環氧樹脂之高流動性者。 略’就以上述方式構成之微裝置1之製造方法加以概Shi Xi _ is a mold release treatment agent and the like to perform mold release treatment. When the laminated body is used, the laminated body from which the cover film is peeled off is transferred onto the substrate by, for example, a manual roll or a laminator at a temperature of 4 Torr to 1 Torr and a pressure of 〇. 5 to 2 MPa. In the same manner as in the case of using the photosensitive resin composition layer (resin layer) of the present invention, the photosensitive resin composition layer (resin layer) is used in the same manner as the above-described photosensitive resin composition for hollow package of the present invention. It is sufficient to carry out exposure, post-exposure baking, development, and heat treatment. When the enamel-sealed photosensitive tree composition of the present invention is used as a laminate, the steps of coating and drying on the substrate can be omitted, and the photosensitivity for the empty package of the present invention can be more easily used. The resin composition is patterned to form. A structure in which a resin cured product having a crucible space (cavity) can be prepared by combining the above-mentioned photosensitive resin composition for hollow jelly of the present invention in a liquid and/or laminated form and using a method of photolithography . The photosensitive resin composition for hollow encapsulation of the present invention can be used for production by stably holding a substrate, a wiring, a component, and the like in a state in which a space (cavity) is provided around a device having a mechanical structure or the like. A hollow package for the purpose of blocking the intrusion of gas or liquid from the external environment. In particular, the photosensitive resin composition for hollow encapsulation of the present invention can be preferably used for packaging in the case where the element is a MEMS element. Next, a configuration and a manufacturing method of a microdevice using the photosensitive resin composition for hollow encapsulation of the present invention, I40909.doc -23-201013311, will be described with reference to Figs. 1 to 2 . Fig. 1 is a cross-sectional view showing an example of a micro device. The microdevice 1 includes a substrate 2, a MEMS 3 formed on the substrate 2, a cavity securing portion 4 for securing a cavity C (space, hollow portion) provided around the MEMS 3, and a cladding The sealing layer 6 or the like provided in the above manner. The substrate 2 provided on the lead frame 5 is formed of tantalum or the like, and a conductor pattern 7 made of a metal thin film or the like is formed on one surface thereof by a surname or the like. The MEMS 3 is electrically connected to the conductor pattern 7 and formed on the substrate 2. The conductor pattern 7 is connected to the lead frame 5 via a metal wire 8, and the micro device i can be incorporated into other machines. The cavity securing portion 4 is a substantially box-shaped structure composed of a side wall 4A and a ceiling 4B, and the side wall 4A is disposed so as to surround the MEM" disposed on the substrate 2, and the ceiling 4B is provided on the side wall. Above the 4A. The circumference and the top of the horizontal direction of the S3 are covered by the cavity securing portion*, whereby the space for the MEMS3 drive, that is, the cavity c is formed in a fine Φ J, and the package of the present invention is used as the package. The cured material of the material photosensitive resin composition of the cavity securing portion 4 is formed. The sealing layer 6 is formed by covering the substrate, and is formed by transfer molding to form the 2 MEMS 3 or the conductive connection on the substrate 2 by means of transfer molding. The position and the like are not affected by the external environment such as the pattern 7 and the metal wire 8. As the material of the sealing layer 6, the same material as the sealing material can be used as the sealing material. = List various epoxy sealants. These 3 are latex resin, hardener, hardening accelerator, 140909.doc -24- 201013311 = charge, can also contain flame retardant, mold release agent, colorant, coupler , 中中's can be formed under low temperature The less damage aspect of the cavity c and s, preferably by using a high fluidity low viscosity epoxy. Slightly 'on the method for manufacturing a micro device constituting the above-described manner shall be
—以下係於單Ha日圓上形成複數個微裝置叉之基板2的 藉由所謂晶圓水準封裝來製造微裝置1之例。該方法具有 無需組裝步驟之設備、M聰於分割時得 點 但製造方法並不限定於此。 該製造方法係包含以下3個步驟：於基板2上形成 则咖之步驟（第1步驟）、以覆蓋MEMS3之方式形成空腔 確保部4之步驟（第2步驟）、及藉由轉移成形以密封層6將整 體密封之步驟（第3步驟）。 於第1步驟中，於基板上形_EMS。 基板係藉由在石夕晶圓之表面上設置複數個凹部而形成， 其後，藉由組合㈣電路製作技誠犧牲層㈣技術而製 作裝置之表面微加Trc „ . (Surface Micromachining)、或主要利 用濕式钱刻或深如y 飞深挖乾式蝕刻等對S〇I(Silicon On- The following is an example in which the microdevice 1 is manufactured by a so-called wafer level packing by forming a substrate 2 of a plurality of micro device forks on a single Ha yen. This method has a device that does not require an assembly step, and M has a point in the division, but the manufacturing method is not limited thereto. The manufacturing method includes the following steps: a step of forming a coffee on the substrate 2 (first step), a step of forming the cavity securing portion 4 to cover the MEMS 3 (second step), and a transfer molding The step of sealing the entire sealing layer 6 (third step). In the first step, _EMS is formed on the substrate. The substrate is formed by providing a plurality of recesses on the surface of the Shi Xi wafer, and then the surface of the device is micro-added by the combination of the (four) circuit fabrication technique (Surface Micromachining), or Mainly use wet money engraving or as deep as y fly deep dig dry etching, etc. S〇I (Silicon On
Insulator，絕緩 jb μ 帝.χ ' s上覆矽）晶圓或基板自身進行加工而製作 裝置之體型微加工、> 或者兩者之組合來形成MEMS及導體 圖案。 再者’導體圖幸φ M張T，連接MEMS及金屬線之處以外的部 分亦可藉由Si〇2岑— 土 4 biN之類的無機絕緣膜或者聚醯亞胺、 聚苯并呤唑、笨并環 开展丁烯、環氧樹脂等加以保護。又，導 140909.doc •25· 201013311 趙圖案7亦可經由藉由深挖乾式蝕刻或喷砂而製作之貫通 孔自基板之背面（與形成有MEMS之面相反側之面）而安 裝。 於第2步驟中，於MEMS之周圍形成空腔確保部。（參照 圖2) 首先，於MEMS3之周圍塗布本發明之中空封裴用感光 性樹脂組合物，然後經由光罩進行曝光、PEB、顯影，形 成側壁4A。側壁4A之厚度（圖2(a)中之4A之左右方向之尺 寸）及高度（圖2(a)中之4A之上下方向之尺寸），可根據視 MEMS3之各部尺寸或驅動態樣而決定的必要空腔之大小 而適當設定。 其次’如圖2(b)所示，於側壁4A之上方，將中空封裝用 感光性樹脂組合物之積層體之覆蓋膜剝離後進行層壓，而 形成頂棚4B。再次經由光罩進行曝光、pEB、顯影，去除 多餘之部分後，如圖2(c)所示，製作出保持空腔c之空腔 確保部4。 又，亦可代替該方法，而如非專利文獻〗所記載般，藉 由光微影於基材上積層結構體之後藉由轉印而形成空腔確 保部4,或者藉由壓印等方法而轉印預先形成有凹凸之感 光性樹脂層後，藉由光微影形成空腔確保部。 又，亦可預先用犧牲層材料密封厘£河8後，利用嘴塗 機、棒塗機、旋塗機等來塗布液狀之中空封裝用感光性樹 脂組合物後加以乾燥，或者將中空封装用感光性樹脂組合 物之積層體之覆蓋膜剝離後於真空中進行層壓，藉此以覆 140909.doc -26 - 201013311 蓋犧牲層之方式形成中空封裝用感光性樹脂组合物層，繼 而藉由光微影同時製作空腔確保部4之一部分與去除犧牲 1之孔’自所製作之孔中去除犧牲層，進而塗布或層壓中 空封裝用感光性樹脂組合物，藉由光微影而形成空腔確保 部。 再者，於圖2(a)、圖2(b)及圖2(c)中，2表示基板（石夕晶 e 圓）’ 3表不MEMS，7表示導體圖案，直至仏步驟為止之 各步驟係於基板（矽晶圓）上進行。 ;第3步驟中，藉由切割等將形成有空腔確保部之基板 ’將各基板配置於導線架中央，經由金屬線將導體圖 案與導線架-攬連接之後，進行轉移成形。硬化結束後， 將多餘部分去除，而製作出如圖1所示之微裝置。 據本實鈀形態之微裝置’因利用於高溫下亦表現出高 強度之本發明之令空封裝用感光性樹脂組合物之硬化物來 形成空腔確保部，故藉由轉移成形來形成密封層時、或導 =圖案與導線架之-攬連接時、或藉由切割等切開基板等 :產：抑制空腔確保部4發生變形、或被壓壞等不良狀況 因此’可確實地保持空腔確保部内部之空腔，從 而可提供可靠性高之微裝置。 腔從 月Μ且^腔確保部之形成係藉由使用中空封襄用感光性樹 二:物之光微影步驟來進行。因此，無須為了確保空腔 生接合石夕或玻璃等材料等來形成空财保部，可 產性佳且低成本地提供可靠性高之微裝置。 以上’就本發明之-實施形態進行了說明，但本發明之 140909.doc -27· 201013311 技術範圍並不限定於上述實施形態，可於不偏離本發明主 旨之範圍内施加各種變更。 例如，上述實施形態中，就空腔確保部係由侧壁與頂棚 構成之例進行了說明，但空腔確保部之構成並不限定於 此。 作為一例，亦可於空腔内之不阻礙MEMS驅動之位置設 置支撐頂棚之柱狀結構，而以由側壁及柱狀結構支撐頂棚 之方式來構成空腔確保部。x，亦可於側壁或頂棚之表面 設置氧化膜而提高剛性。 進而’亦可藉由_等挖人基板之—部分㈣成凹狀之 空腔，於該s腔内形成μεμ·，在空腔之上方配置積層 體狀之空腔確保部材料而形成空腔。此時，空腔確保部係 由以基板之-部分形成之側壁、與由確保部材料構成之頂 棚所形成。 又，上述實施形態中，就空腔確保部為大致箱狀之例進 行了說明，取而代之，亦可藉由使側壁形成為圓形而使空 腔確保部形成為大致圓筒狀。進而，亦可使用轉印等使空 腔碟保部形成為圓頂狀之形狀，而進一步提高财壓性。即 便為該等般之構成’亦可良好地確保用於MEMS驅動之空 腔。 本發月之中工封裝用感光性樹脂組合物因強度（尤其是 冋Γ下之強度）極為優異，故具有如τ特徵：於設置具有 中工構之7G件之⑨封層時，即便於採用轉移模塑法的情 況下’亦可充分保持空間。因此，藉由使用本發明之中空 140909.doc 201013311 封裳用S光性樹脂組合物’於製造具有中空結構之mems 元件、半導體元件等元件時，可獲得廉價'良率佳、且可 靠性高之中空封裝。 [實施例] 以下，藉由實施例對本發明加以更詳細說明，但該等實 施例僅係用以較好地說明本發明之例示，絲毫未限定本發 明。再者，以下，將本發明之中空封裴用感光性樹脂組合 物簡稱為感光性樹脂組合物。又，「份」係指質量份。 實施例1〜7及比較例 (感光性樹脂組合物及樹脂組合物（比較用）之製備以及使用 該等之積層體之製作） 依據表1所6己載之調配1 (单位為份），將三苯盼甲烧型 環氧樹脂（Α)、陽離子光聚合起始劑（β)、1分子中具有2個 以上之環氧基之環氧樹脂（C)、反應性環氧單體（D)及其他 成分於附有攪拌機之燒瓶中在8(TC下攪拌1小時，分別獲 φ 得本發明之感光性樹脂組合物及比較用之樹脂組合物。將 該等感光性樹脂組合物及樹脂組合物（比較用）均勻地塗布 於膜厚為50 μηι之聚對苯二甲酸乙二酯（PET，p〇lyethylene * terePhthalate)膜（基膜，Toray股份有限公司製造）上，利用 - 溫風對流乾燥機於95 °C下乾燥5分鐘以及於11〇。〇下乾燥5 分鐘之後’於露出面上層壓38 μηι之經脫模處理之PET膜 (覆盡膜’二愛化學聚醋膜（Mitsubishi Chemical Polyester Film)股份有限公司製造），_而分別獲得50 μηι厚之感光性樹 月旨組合物及樹脂組合物（比較用）之積層體（乾膜光阻）。 140909.doc -29· 201013311 (感光性樹脂組合物及樹脂組合物（比較用）之積層體之圖案 化） 將上述所得之各積層體之覆蓋膜剝離，以70°C之輥溫 度、0.2 MPa之氣壓、0.5 m/min之速度層壓於石夕晶圓上， 而獲得5 0 μπι之感光性樹脂組合物及樹脂組合物（比較用） 之樹脂層。使用光罩對準曝光機（ΜΑ-20，Mikasa股份有限 公司製造）以25 0〜1000 mJ/cm2之曝光量對該等樹脂層進行 圖案曝光（軟接觸，超高壓水銀燈）。其後藉由加熱板於 95°C下進行6分鐘曝光後烘烤（PEB)，使用丙二醇單甲醚乙 酸 S旨（PGMEA，Propylene Glycol Methyl Ether Acetate)， 藉由浸潰法於23°C下進行6分鐘顯影處理，而於基板上獲 得已硬化之樹脂圖案。 (曝光量之評價） 上述積層體之圖案化時，使用線與間隙為50 μπι之光罩 進行曝光，藉由顯影處理而獲得無殘渣而密著於基板之樹 脂圖案，並且藉由 DSC(Differential Scanning Calorimeter， 示差掃描熱析儀）之分析來確認觀測不到由環氧基反應引 起之發熱的最小曝光量。結果示於表1。 (解析性之評價） 上述圖案曝光中，對使用線與間隙為50 μπι之光罩是否 無殘渣地解析、是否密著於基板進行評價。結果示於表 1 ° 評價基準 〇：無殘潰，且亦密著於基板 140909.doc -30- 201013311 χ:有殘渣、及自基板剝離之現象中出現任一方，或兩 方均出現 (強度之評價） 將上述所得之各積層體各準備2片，將各自之覆蓋膜剝 離’以70°C之輥溫度、〇.2 MPa之氣壓、0.5 m/min之速度 進行貼合而分別形成1〇〇 μηι厚之積層膜。將各積層膜之積 層體之一方的基膜剝離，使用超高壓水銀燈曝光裂置 (Ushio電機公司製造）以2000 mJ/cm2之曝光量進行曝光。 ® 曝光後使用加熱板於951下進行10分鐘PEB，將積層膜切 斷成5 mm寬後，將另一方之基膜剝離，進而使用烘箱於 200°C下進行30分鐘熱處理。使用所得之硬化物之膜，利 用動態黏彈性測定裝置（DMS6100，精工精密（Seik〇 Instruments)股份有限公司製造）測定i8〇〇c之儲存彈性模 數，作為熱時強度之指標。結果示於表i。 (環氧模造物之製備） 參 使用捏合機將EOCN-1020-62(商品名，日本化藥股份有 限公司製造，鄰甲酚酚醛清漆型環氧樹脂）36 8份、(商 品名，明和化成股份有限公司製造，苯酚酚醛清漆樹 脂）19_6份、三苯基膦0.624份、Kyki〇s MSR-2212(商品 名，龍森股份有限公司製造，填料）34〇份、巴西棕櫚蠟i 號（商品名，Cerarica Noda股份有限公司製造，蠟）12份及 KBM-303(商品名，信越化學工業股份有限公司製造，矽 烷偶合劑）1.35份混合至均勻後，使用壓製機成型為片狀。 (模塑耐性之評價） 140909.doc •31- 201013311 將上述所得之各感光性樹脂組合物及樹脂組合物（比較 用）之積層體各準備2片，將各自之覆蓋膜剝離，以7〇。(：之 親溫度、0.2 MPa之氣壓、0.5 m/min之速度進行貼合，而 形成100 μιη厚之感光性樹脂組合物或樹脂組合物（比較用） 之積層膜。將該等積層膜之一方之基膜剝離，於具有深度 為50 μηι且一邊為1〇〇、300及500 μιη之四方空腔的矽晶圓 之基板上，以45。(：之輥溫度、0.2 MPa之氣壓、0.5 m/min 之速度進行層壓。使用光罩對準曝光機（MA-20，Mikasa股 份有限公司製造），以250〜1000 mJ/cm2之曝光量進行圖案 曝光（軟接觸’超高壓水銀燈其後藉由加熱板於65〇CT 進行1分鐘PEB、於95°C下進行6分鐘PEB，進而使用烘箱 於200°C下進行30分鐘熱處理，然後切斷基板而獲得空腔 之頂棚部由感光性樹脂組合物或樹脂組合物之各積層膜之 硬化物構成的試驗片。將試驗片固定於聚醯亞胺膜上並使 用轉移模塑用模具，使用上述環氧模造物於成型溫度為 180°C、成型壓力為8 MPa之條件下進行轉移模塑成型。藉 由切割將空腔部切斷，利用顯微鏡來確認頂棚部之積層膜 硬化物是否由於轉移模塑時之壓力發生變形而與基板接 觸’並依照下述基準進行評價。結果示於表1。 評價基準 〇：一邊為500 μηι之四方空腔之頂棚部未與基板接觸。 △: 一邊為300 μηι之四方空腔之頂棚部未與基板接觸， 但一邊為500 μηι之四方空腔之頂棚部與基板接觸。 X: —邊為100 μιη之四方空腔之頂棚部未與基板接觸， 140909.doc -32- 201013311 但一邊為300 μιη之四方空腔之頂棚部與基板接觸。 [表1]Insulator, which is used to form MEMS and conductor patterns, is made by processing the wafer or the substrate itself to produce a wafer or a substrate itself. Furthermore, the conductor pattern is φ M sheets T, and the portion other than the MEMS and the metal line may be connected by an inorganic insulating film such as Si〇2岑-土 4 biN or polybenzazole or polybenzoxazole. , stupid and ring to carry out the protection of butene, epoxy resin and so on. Further, the guide pattern may be mounted on the back surface of the substrate (the surface opposite to the surface on which the MEMS surface is formed) through a through hole made by deep etch etching or sand blasting. In the second step, a cavity securing portion is formed around the MEMS. (Refer to Fig. 2) First, the photosensitive resin composition for a hollow package of the present invention is applied around the MEMS 3, and then exposed, PEB, and developed through a photomask to form the side wall 4A. The thickness of the side wall 4A (the size of the left and right direction of 4A in Fig. 2(a)) and the height (the size of the upper and lower directions of 4A in Fig. 2(a)) can be determined according to the size or driving state of each part of the MEMS 3 The size of the necessary cavity is appropriately set. Then, as shown in Fig. 2 (b), the cover film of the laminate of the photosensitive resin composition for hollow encapsulation is peeled off and laminated on the side wall 4A to form a ceiling 4B. After exposing, pEB, and developing through the mask again, the excess portion is removed, and as shown in Fig. 2(c), the cavity securing portion 4 for holding the cavity c is formed. Further, instead of the method, as described in the non-patent document, the cavity securing portion 4 may be formed by transfer after the laminated structure is formed by photolithography on the substrate, or by imprinting or the like. After the photosensitive resin layer in which the unevenness is formed in advance is transferred, the cavity securing portion is formed by photolithography. Further, the liquid resin can be applied to the photosensitive resin composition for hollow encapsulation by a nozzle coater, a bar coater, a spin coater or the like, and then dried, or a hollow package can be used. After the cover film of the laminate of the photosensitive resin composition is peeled off and laminated in a vacuum, a photosensitive resin composition layer for hollow encapsulation is formed by covering a sacrificial layer with a coating of 140909.doc -26 - 201013311, and then borrows Simultaneously, one portion of the cavity securing portion 4 and the hole for removing the sacrificial layer 1 are simultaneously removed by photolithography to remove the sacrificial layer from the prepared hole, and then the photosensitive resin composition for hollow encapsulation is coated or laminated by photolithography. A cavity securing portion is formed. 2(a), 2(b), and 2(c), 2 indicates that the substrate (Shi***g method to obtain a cured resin pattern on a substrate. (Evaluation of Exposure) Patterning of the above laminated body , using lines and gaps of 5 The mask of 0 μπι was exposed, and a resin pattern having no residue adhered to the substrate was obtained by development treatment, and it was confirmed by DSC (Differential Scanning Calorimeter) analysis that epoxy was not observed. The minimum exposure amount of the heat generated by the radical reaction is shown in Table 1. (Evaluation of the analytical property) In the above-mentioned pattern exposure, whether or not the mask having a line and a gap of 50 μm is analyzed without any residue, and whether it is adhered to the substrate Evaluation. The results are shown in Table 1 ° Evaluation criteria 无: no residue, and also adhered to the substrate 140909.doc -30- 201013311 χ: either one of the residue and the phenomenon of peeling off from the substrate, or both sides appear (strength Evaluation) Each of the laminates obtained above was prepared in two pieces, and the respective cover films were peeled off and bonded at a roll temperature of 70 ° C, a gas pressure of 2 2 MPa, and a speed of 0.5 m / min to form 1 each. 〇〇μηι thick laminated film. The base film of one of the laminates of each of the laminated films was peeled off, and exposed by an ultrahigh pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.) at an exposure amount of 2000 mJ/cm 2 . ® After exposure, a PEB was applied at 951 for 10 minutes using a hot plate. After the laminated film was cut into a width of 5 mm, the other base film was peeled off, and further heat-treated at 200 ° C for 30 minutes using an oven. Using the obtained cured film, the storage elastic modulus of i8〇〇c was measured by a dynamic viscoelasticity measuring apparatus (DMS6100, manufactured by Seik〇 Instruments Co., Ltd.) as an index of thermal strength. The results are shown in Table i. (Preparation of epoxy molding) XYCN-1020-62 (trade name, manufactured by Nippon Kayaku Co., Ltd., o-cresol novolac type epoxy resin) was used in a kneading machine, 36 parts, (trade name, Minghe Chemical) Manufactured by the company, phenol novolak resin) 19_6 parts, 0.624 parts of triphenylphosphine, Kyki〇s MSR-2212 (trade name, manufactured by Longsen Co., Ltd.), 34 parts, carnauba wax i (commodity) 12 parts, manufactured by Cerarica Noda Co., Ltd., wax), and 1.35 parts of KBM-303 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent) were mixed and homogenized, and then molded into a sheet shape using a press. (Evaluation of Molding Resistance) 140909.doc • 31-201013311 Two sheets of each of the photosensitive resin composition and the resin composition (comparative) obtained above were prepared, and the respective cover films were peeled off to 7 〇. . (: a temperature of 0.2 MPa, a pressure of 0.5 m/min, and a laminated film of a 100 μm thick photosensitive resin composition or a resin composition (comparative). The base film of one of the layers is peeled off on a substrate of a tantalum wafer having a depth of 50 μm and a square cavity of 1 〇〇, 300, and 500 μm on one side, at 45. (: roll temperature, pressure of 0.2 MPa, 0.5 Lamination at a speed of m/min. Using a photomask alignment machine (MA-20, manufactured by Mikasa Co., Ltd.), pattern exposure was performed at an exposure of 250 to 1000 mJ/cm2 (soft contact 'Ultra high pressure mercury lamp followed by The PEB was heated at 65 〇 CT for 1 minute, and PEB at 95 ° C for 6 minutes, and then heat-treated at 200 ° C for 30 minutes using an oven, and then the substrate was cut to obtain a ceiling portion of the cavity. a test piece comprising a cured product of each laminated film of a resin composition or a resin composition. The test piece is fixed on a polyimide film and a mold for transfer molding is used, and the above epoxy molding is used at a molding temperature of 180°. C, the molding pressure is 8 MPa The transfer molding was carried out, and the cavity portion was cut by cutting, and it was confirmed by a microscope whether or not the cured film of the laminated portion in the ceiling portion was deformed by the pressure at the time of transfer molding, and was contacted with the substrate, and evaluated according to the following criteria. The results are shown in Table 1. Evaluation criteria: The ceiling portion of the square cavity of 500 μηι was not in contact with the substrate. △: The ceiling portion of the square cavity of 300 μηι was not in contact with the substrate, but the side was 500 μηι The ceiling portion of the square cavity is in contact with the substrate. X: The ceiling portion of the square cavity having a side of 100 μm is not in contact with the substrate, 140909.doc -32- 201013311 but the ceiling portion and the substrate of the square cavity of 300 μm Contact. [Table 1]
調配成分 實施例 比較例 1 2 3 4 5 6 7 1 環氧樹脂 A 100 50 20 20 20 20 20 C-1 50 80 75 65 53.5 C-2 80 C-3 80 C-4 25 C-5 15 陽離子光聚合起始劑 B 8 8 8 8 8 8 8 8 反應性環氧單體 D-1 5 15 D-2 5 溶剤 E 40 40 40 40 40 40 40 40 勻化制 F 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 偶合劑 G 2 2 2 2 2 2 2 2 曝光量〇nJ/cm2J 3000 3000 1000 1000 1000 1000 1000 250 解析性 〇 〇 〇 〇 〇 〇 〇 〇 儲存彈性模數(GPa) 1.7 2.6 2.0 2.4 2.5 2.0 1.8 0.5 模塑耐性 △ 〇 〇 〇 〇 Δ Δ XFormulation Composition Example Comparative Example 1 2 3 4 5 6 7 1 Epoxy Resin A 100 50 20 20 20 20 20 C-1 50 80 75 65 53.5 C-2 80 C-3 80 C-4 25 C-5 15 Cation Photopolymerization initiator B 8 8 8 8 8 8 8 8 Reactive epoxy monomer D-1 5 15 D-2 5 Solvent E 40 40 40 40 40 40 40 40 Homogenization F 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Coupler G 2 2 2 2 2 2 2 2 Exposure 〇nJ/cm2J 3000 3000 1000 1000 1000 1000 1000 250 Analytical 〇〇〇〇〇〇〇〇 Storage Elastic Modulus (GPa) 1.7 2.6 2.0 2.4 2.5 2.0 1.8 0.5 Molding resistance △ 〇〇〇〇Δ Δ X
再者’表1中之Α〜G分別表示下述物質。 A :上述式（1)中之η約為1.3的三苯酚甲烷型環氧樹脂（商品名： • ΕΡΡΝ_502Η，日本化藥股份有限公司製造） Β :陽離子光聚合起始劑（商品名：uvi-6976，Dow Chemical公 司製造） C-1 :上述式（2)中之k約為2的1分子中具有2個以上之環氧基之 環氧樹月日（商品名：EPON SU_8，Resolution Performance Products製造） C-2 :上述式（3)中之p約為6的1分子中具有2個以上之環氧基之 環氧樹脂（商品名：e〇cn_103S，日本化藥股份有限公司製造） 140909.doc -33- 201013311 C-3 :以上述式（4)所表示之1分子中具有2個以上之環氧基之環 氧樹脂（商品名：NC-6300H，日本化藥股份有限公司製造） C-4 :專利文獻1記載之環氧樹脂（商品名：NC_300〇H，日本化 藥股份有限公司製造） C-5 :專利文獻1記載之環氧樹脂（商品名：NER-7604，日本化 藥股份有限公司製造） D-1 :反應性環氧單體（商品名：jER828，日本環氧樹脂股份有 限公司製造） D-2 :反應性環氧單體（商品名：EX-321L，長瀨化成股份有限 公司製造） E:溶劑環戊酮 F :氟系勻化劑（商品名Megaface F-470，DIC股份有限公司 製造） G :矽烷偶合劑（商品名：S-510，Chisso股份有限公司製造） 如表1所示，明確可知，本發明之感光性樹脂組合物與 比較例1之樹脂組合物相比，熱時（18 0 °C )之強度較高’並 表現出較高之模塑耐性。 實施例8 依照上述式（1)中之η約為1.3的三苯酚甲烷型環氧樹脂 (商品名：ΕΡΡΝ-502Η，日本化藥股份有限公司製造）2〇 份、陽離子光聚合起始劑（商品名：GSID26-1 ’汽巴精化 公司製造）0.5份、上述式（2)中之k約為2的1分子中具有2個 以上之環氧基之環氧樹脂（商品名：EPON SU-8，Resolution Performance Products製造）65份、反應性環乳單體（商品名： 140909.doc • 34- 201013311 jER828，曰本環氧樹脂股份有限公司製造）15份、作為溶 劑之環戊酮4〇份、氟系勻化劑（商品名：Megaface F-470， DIC股份有限公司製造）0.05份、矽烷偶合劑（商品名：S-510， Chisso股份有限公司製造）2份之調配量，進行與上述實施 例1相同之操作而獲得感光性樹脂組合物之積層體。對所 得積層體進行與實施例1相同之評價，結果曝光量為1000 mJ/cm2、解析性為〇，儲存彈性模數為2.3 GPa，模塑耐 性為〇。 零 實施例9 使用DISPERMAT SL-C-12(英弘精機股份有限公司製 造），使上述式（2)中之k約為2的1分子中具有2個以上之環 氧基之環氧樹脂（商品名：EPON SU-8，Resolution Performance Products製造）65份、丙二醇單曱醚60份、 NanoTek Alumina SPC(C.I. Kasei股份有限公司製造；球狀 氧化鋁，平均粒徑為50 nm)30份分散4小時。於分散液中 A 添加上述式（1)中之η約為1.3的三苯酚曱烷型環氧樹脂（商 品名：ΕΡΡΝ-502Η，日本化藥股份有限公司製造）20份、 陽離子光聚合起始劑（商品名：GSID26-1，汽巴精化公司 製造）0.5份、反應性環氧單體（商品名：jER828，曰本環氧 樹脂股份有限公司製造）15份、氟系勻化劑（商品名： Megaface F-470，DIC股份有限公司製造）0.05份、矽烷偶 合劑（商品名：S-510，Chisso股份有限公司製造）2份，進 行與上述實施例1相同之操作而獲得感光性樹脂組合物之 積層體。對所得積層體進行與實施例1相同之評價，結果 140909.doc -35- 201013311 解析性為〇、儲存彈性模數為 2.8 曝光量為1000 mj/cm2、 GPa、模塑耐性為〇。 [產業上之可利用性] 本發明之中空封裝用感光性樹脂組合物係可藉由光_ 來製作中空結似於轉移模塑法中亦可充分保持空間之中/ 空封裝用感光性樹脂組合物。於藉由使用本發明之中*封 裝用感光性樹脂組合物來製造MEMS元件及半導體等元件 時，可進行廉價、良率佳、且可靠性高之中空封裝。兀件 【圖式簡單說明】 ° 面 圖1係表示作為本發明之一實施形態的微裝置之剖 圖；及 ° 圖2(a)〜（c)係表示該微裝置之製造方法中 τ〜成空腔確保 部之順序之概略圖。 【主要元件符號說明】 1 微裝置 2 基板 3 微電子機械系統（MEMS) 4 空腔確保部（4Α側壁、4Β頂棚、c空腔） 5 導線架 6 密封層 7 導體圖案 8 金屬線 140909.doc -36-Further, Α to G in Table 1 indicate the following substances, respectively. A: a trisphenol methane type epoxy resin having a η of about 1.3 in the above formula (1) (trade name: • ΕΡΡΝ_502Η, manufactured by Nippon Kayaku Co., Ltd.) Β : cationic photopolymerization initiator (trade name: uvi- 6976, manufactured by Dow Chemical Co., Ltd.) C-1: Epoxy tree having two or more epoxy groups in one molecule of k in the above formula (2) of about 2 (trade name: EPON SU_8, Resolution Performance Products (manufacturing) C-2: an epoxy resin having two or more epoxy groups in one molecule of p in the above formula (3) (trade name: e〇cn_103S, manufactured by Nippon Kayaku Co., Ltd.) 140909 .doc -33-201013311 C-3: Epoxy resin having two or more epoxy groups in one molecule represented by the above formula (4) (trade name: NC-6300H, manufactured by Nippon Kayaku Co., Ltd.) C-4: Epoxy resin (trade name: NC_300〇H, manufactured by Nippon Kayaku Co., Ltd.) C-5: Epoxy resin described in Patent Document 1 (trade name: NER-7604, Japan) Pharmacopoeia Co., Ltd.) D-1 : Reactive epoxy monomer (trade name: jER828, Japan Epoxy Resin Co., Ltd.) D-2 : Reactive epoxy monomer (trade name: EX-321L, manufactured by Nagase Chemical Co., Ltd.) E: Solvent cyclopentanone F: Fluorine homogenizing agent (trade name) "Megaface F-470, manufactured by DIC Co., Ltd.) G: decane coupling agent (trade name: S-510, manufactured by Chisso Co., Ltd.) As shown in Table 1, it is clear that the photosensitive resin composition of the present invention and a comparative example Compared with the resin composition of 1, the strength at the time of heat (18 ° C) is higher 'and exhibits higher molding resistance. Example 8 According to the above formula (1), a trisphenol methane type epoxy resin (trade name: ΕΡΡΝ-502Η, manufactured by Nippon Kayaku Co., Ltd.) having a η of about 1.3 was used as a cationic photopolymerization initiator ( Trade name: GSID26-1 - Manufactured by Ciba Specialty Chemicals Co., Ltd., 0.5 parts, and epoxy resin having two or more epoxy groups in one molecule of k in the above formula (2) (trade name: EPON SU) -8, manufactured by Resolution Performance Products, 65 parts, reactive ring-milk monomer (trade name: 140909.doc • 34-201013311 jER828, manufactured by Sakamoto Epoxy Co., Ltd.) 15 parts, cyclopentanone as solvent 4 5%, a fluorine-based homogenizing agent (trade name: Megaface F-470, manufactured by DIC Co., Ltd.), and a blending amount of 2 parts of a decane coupling agent (trade name: S-510, manufactured by Chisso Co., Ltd.) A laminate of the photosensitive resin composition was obtained in the same manner as in the above Example 1. The obtained laminate was evaluated in the same manner as in Example 1. As a result, the exposure amount was 1000 mJ/cm2, the analytical property was 〇, the storage elastic modulus was 2.3 GPa, and the molding resistance was 〇. Example 9 Epoxy resin having two or more epoxy groups in one molecule of k in the above formula (2), which is about 2 in the above formula (2), using DISPERMAT SL-C-12 (manufactured by Hideo Seiki Co., Ltd.) Name: EPON SU-8, manufactured by Resolution Performance Products) 65 parts, 60 parts of propylene glycol monoterpene ether, NanoTek Alumina SPC (manufactured by CI Kasei Co., Ltd.; spherical alumina, average particle diameter of 50 nm) 30 parts dispersed for 4 hours . In the dispersion A, a trisphenol decane type epoxy resin (trade name: ΕΡΡΝ-502Η, manufactured by Nippon Kayaku Co., Ltd.) having a η of about 1.3 in the above formula (1) was added, and cationic photopolymerization was started. 0.5 parts of a reagent (trade name: GSID26-1, manufactured by Ciba Specialty Chemicals Co., Ltd.), reactive epoxy monomer (trade name: jER828, manufactured by Sakamoto Epoxy Co., Ltd.), 15 parts, fluorine-based homogenizing agent ( Product name: Megaface F-470, manufactured by DIC Co., Ltd., 0.05 part, decane coupling agent (trade name: S-510, manufactured by Chisso Co., Ltd.), 2 parts, and the same operation as in the above Example 1 was carried out to obtain photosensitivity. A laminate of a resin composition. The obtained laminate was subjected to the same evaluation as in Example 1. The result was 140909.doc -35 - 201013311. The analytical property was 〇, the storage elastic modulus was 2.8, the exposure amount was 1000 mj/cm2, GPa, and the molding resistance was 〇. [Industrial Applicability] The photosensitive resin composition for hollow encapsulation of the present invention can be made by using a light ray to form a hollow smear like a transfer molding method. combination. When a device such as a MEMS device or a semiconductor is produced by using the photosensitive resin composition for sealing in the present invention, a hollow package which is inexpensive, has a good yield, and has high reliability can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a micro device as an embodiment of the present invention; and FIG. 2(a) to (c) are diagrams showing a manufacturing method of the micro device. A schematic view of the sequence of the cavity securing portions. [Main component symbol description] 1 Micro device 2 Substrate 3 Microelectromechanical system (MEMS) 4 Cavity securing part (4 Α side wall, 4 Β ceiling, c cavity) 5 Lead frame 6 Sealing layer 7 Conductor pattern 8 Metal wire 140909.doc -36-
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| CN110931433A (en) * | 2019-10-22 | 2020-03-27 | 深圳市汇芯通信技术有限公司 | Integrated device manufacturing method and related product |
| CN111146235A (en) * | 2019-11-21 | 2020-05-12 | 深圳市汇芯通信技术有限公司 | Integrated module of filter and power amplifier, manufacturing method thereof and electronic device |
| TWI764921B (en) * | 2016-08-31 | 2022-05-21 | 日商東京應化工業股份有限公司 | Negative photosensitive resin composition, photosensitive resist film, pattern formation method, curing film and producing method for curing film |
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| JP5691987B2 (en) * | 2010-10-13 | 2015-04-01 | 信越化学工業株式会社 | Photocurable resin composition, dry film thereof, pattern forming method, and film for protecting electric / electronic parts |
| CN110058490A (en) * | 2011-08-10 | 2019-07-26 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist |
| JP5967824B2 (en) * | 2012-10-26 | 2016-08-10 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP5901070B2 (en) * | 2012-10-26 | 2016-04-06 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP5939965B2 (en) * | 2012-11-22 | 2016-06-29 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP6021180B2 (en) * | 2012-11-22 | 2016-11-09 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP6066413B2 (en) * | 2012-11-22 | 2017-01-25 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP6049075B2 (en) * | 2012-11-22 | 2016-12-21 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP5939963B2 (en) * | 2012-11-22 | 2016-06-29 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP5939964B2 (en) * | 2012-11-22 | 2016-06-29 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP6066414B2 (en) * | 2012-11-22 | 2017-01-25 | 日本化薬株式会社 | Photosensitive resin composition, resist laminate and cured product thereof |
| JP2013178526A (en) * | 2013-04-01 | 2013-09-09 | Hitachi Chemical Co Ltd | Hollow structure and method for producing the same |
| KR101709689B1 (en) | 2013-12-19 | 2017-02-23 | 주식회사 엘지화학 | Dicing film adhesion layer composition and dicing film |
| WO2015093794A1 (en) * | 2013-12-19 | 2015-06-25 | 주식회사 엘지화학 | Composition for forming dicing film adhesive layer, and dicing film |
| JP6376551B2 (en) * | 2014-02-20 | 2018-08-22 | 日東電工株式会社 | Liquid photosensitive resin composition for forming optical waveguide core, optical waveguide using the same, and flexible printed wiring board |
| EP3156845B1 (en) * | 2014-06-13 | 2019-05-08 | Nippon Kayaku Kabushiki Kaisha | Photosensitive resin composition, resist laminate, cured product of photosensitive resin composition, and cured product of resist laminate |
| CN107222181A (en) * | 2016-12-29 | 2017-09-29 | 杭州左蓝微电子技术有限公司 | FBAR based on SOI Substrate and preparation method thereof |
| CN107231138A (en) * | 2016-12-29 | 2017-10-03 | 杭州左蓝微电子技术有限公司 | FBAR with supporting construction and preparation method thereof |
| US20220185946A1 (en) * | 2019-03-27 | 2022-06-16 | Adeka Corporation | Curable resin composition |
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| JPS63262893A (en) * | 1987-04-21 | 1988-10-31 | 日本化薬株式会社 | Method of forming solder resist pattern |
| US20050260522A1 (en) * | 2004-02-13 | 2005-11-24 | William Weber | Permanent resist composition, cured product thereof, and use thereof |
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| TWI764921B (en) * | 2016-08-31 | 2022-05-21 | 日商東京應化工業股份有限公司 | Negative photosensitive resin composition, photosensitive resist film, pattern formation method, curing film and producing method for curing film |
| CN110931433A (en) * | 2019-10-22 | 2020-03-27 | 深圳市汇芯通信技术有限公司 | Integrated device manufacturing method and related product |
| CN111146235A (en) * | 2019-11-21 | 2020-05-12 | 深圳市汇芯通信技术有限公司 | Integrated module of filter and power amplifier, manufacturing method thereof and electronic device |
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