TW202205018A - Method of manufacturing hollow structure and method of manufacturing hollow package capable of stably manufacturing a hollow structure with enhanced strength in which deformation of a top plate part by a curing operation is suppressed - Google Patents

Method of manufacturing hollow structure and method of manufacturing hollow package capable of stably manufacturing a hollow structure with enhanced strength in which deformation of a top plate part by a curing operation is suppressed Download PDF

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TW202205018A
TW202205018A TW110114459A TW110114459A TW202205018A TW 202205018 A TW202205018 A TW 202205018A TW 110114459 A TW110114459 A TW 110114459A TW 110114459 A TW110114459 A TW 110114459A TW 202205018 A TW202205018 A TW 202205018A
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hollow structure
photosensitive resin
film
preferable
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TW110114459A
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Chinese (zh)
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今井洋文
近藤崇弘
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日商東京應化工業股份有限公司
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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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

An object of this invention is to provide a manufacturing method that suppresses deformation of a top plate part resulting from a curing operation and stably produces a hollow structure of which the strength is further enhanced. The solution is a method for manufacturing a hollow structure (100), comprising the following steps: a step of arranging a photosensitive resist film (80) comprising a negative photosensitive resin film (30); a step of exposing the arranged photosensitive resin film (30); a step of subjecting the exposed photosensitive resin film (30) to heat treatment; a step of developing the heat-treated photosensitive resin films (30A and 30B) to form a negative pattern (30A); and a step of performing further heat treatment to cure the negative pattern (30A) so as to obtain a hollow structure (100) having a top plate part formed of a cured body (40) of the photosensitive resin film. The heat treatment performed after the development is performed by an operation of heating at a temperature below 150 DEG C for 10 minutes, followed by further heating at a temperature higher than 150 DEG C, or an operation of heating at a temperature higher than 100 DEG C after irradiation with ultraviolet ray.

Description

中空構造體的製造方法，及中空封裝體的製造方法Manufacturing method of hollow structure, and manufacturing method of hollow package

本發明係關於中空構造體的製造方法、及中空封裝體的製造方法。The present invention relates to a method for producing a hollow structure and a method for producing a hollow package.

近年來，表面聲波(SAW，surface acoustic wave)過濾器等微型電子裝置的開發不斷進展。密封有此種電子裝置的封裝體具有用於確保表面聲波的傳播、電子裝置的可動構件的可動性的中空構造。 為了形成前述中空構造，可使用感光性樹脂組成物，可藉由在將形成有電極的配線基板上保持中空的狀態下進行模具成型，來製造封裝體。 例如，專利文獻1中，揭示了一種中空封裝體的製造方法，其具有下述步驟：以覆蓋在基板上形成的微機電系統(Micro Electro Mechanical Systems，MEMS)的方式形成空腔確保部，從而製作中空構造體的步驟；與藉由傳遞成型，用密封層將中空構造體整體密封的步驟。 前述空腔確保部按照以下方式形成。 向MEMS的周圍塗布感光性樹脂組成物後，隔著光罩進行曝光，進行曝光後烘烤(PEB)、顯影，製作側壁。 接下來，將從基礎膜、感光性樹脂組成物層與覆蓋膜依次積層而成的乾式膜阻劑剝離覆蓋膜而得到的產物層合在前述側壁的上方，形成頂板部，再次隔著光罩進行曝光，進行PEB、顯影，將不要的部分除去，由此，形成空腔確保部。 [先前技術文獻] [專利文獻] 專利文獻1：國際公開第2009/151050號In recent years, the development of microelectronic devices such as surface acoustic wave (SAW) filters has progressed. The package in which such an electronic device is sealed has a hollow structure for ensuring the propagation of the surface acoustic wave and the movability of the movable member of the electronic device. In order to form the above-mentioned hollow structure, a photosensitive resin composition can be used, and a package can be manufactured by mold-molding in a state in which the wiring board on which the electrodes are formed is kept hollow. For example, Patent Document 1 discloses a method of manufacturing a hollow package including a step of forming a cavity securing portion so as to cover a Micro Electro Mechanical Systems (MEMS) formed on a substrate, thereby The step of making a hollow structure; and the step of sealing the hollow structure as a whole with a sealing layer by transfer molding. The aforementioned cavity securing portion is formed as follows. After applying the photosensitive resin composition to the periphery of the MEMS, exposure is performed through a photomask, and post-exposure bake (PEB) and development are performed to produce sidewalls. Next, a product obtained by peeling off the cover film from the dry film resist in which the base film, the photosensitive resin composition layer, and the cover film are laminated in this order is laminated on the upper side of the side wall to form a top plate portion, and the photomask is again interposed therebetween. Exposure is performed, PEB and development are performed, and unnecessary portions are removed, thereby forming a cavity securing portion. [Prior Art Literature] [Patent Literature] Patent Document 1: International Publication No. 2009/151050

[發明所欲解決之課題] 製作中空構造體時，通常，為了提高感光性樹脂組成物層的硬化膜強度，針對顯影後的前述空腔確保部，例如進一步進行於200℃以上的高溫的加熱處理(硬化操作)。 然而，在製作專利文獻1中記載的中空構造體的方法中，存在下述此種問題：形成空腔確保部時，由於前述硬化操作，導致膜狀的頂板部容易變形。 另外，隨著微型電子裝置的開發的進展，現狀是，要求元件的高度進一步降低。與之相伴，在前述封裝體中，需要在確保在配線基板上形成的電極附近的空間的同時，謀求中空構造的小型化。 然而，如上所述地謀求中空構造的小型化時，對於將以往的負型感光性樹脂組成物或感光性阻劑膜硬化而得到的硬化膜而言，強度不足，例如相對於在模具成型時被施加的高壓力，可能變得難以維持中空構造。 本發明是鑒於上述情況而作出的，課題在於提供能抑制因硬化操作而導致的頂板部的變形、並且能穩定地製造強度被進一步提高的中空構造體的中空構造體的製造方法、及中空封裝體的製造方法。 [用以解決課題之手段] 為了解決上述的課題，本發明採用以下的構成。 即，本發明的第1方式為中空構造體的製造方法，其是由凹部、與封堵該凹部的開口面的頂板部形成的中空構造體的製造方法，其特徵在於，具有下述步驟：步驟(0)，準備在表面具有凹部的基板與感光性阻劑膜，該感光性阻劑膜具有：含有含環氧基的樹脂(A)及因曝光而產生酸的光起始劑(I)的負型感光性樹脂膜；步驟(i)，按照前述感光性阻劑膜的感光性樹脂膜表面封堵前述基板中的前述凹部的開口面的方式，配置前述感光性阻劑膜；步驟(ii)，在前述步驟(i)後，將前述感光性樹脂膜曝光；步驟(iii)，對前述步驟(ii)後的前述感光性樹脂膜進行加熱處理；步驟(iv)，在前述步驟(iii)後，將前述感光性樹脂膜顯影，形成負型圖型；與步驟(v)，針對前述步驟(iv)後的前述負型圖型，進一步進行加熱處理，由此使其硬化，得到前述頂板部由前述感光性樹脂膜的硬化體形成的中空構造體，藉由於150℃以下的溫度加熱10分鐘以上後、進一步於高於150℃的溫度進行加熱的操作(x)、或照射紫外線後、於100℃以上的溫度進行加熱的操作(y)，進行前述步驟(v)中的加熱處理。 本發明的第2方式是中空封裝體的製造方法，其特徵在於，具有下述步驟：藉由密封材料將利用前述第1方式涉及的製造方法製造的中空構造體密封從而得到中空封裝體的步驟。 [發明效果] 根據本發明，可提供能抑制因硬化操作而導致的頂板部的變形、並且能穩定地製造強度被進一步提高的中空構造體的中空構造體的製造方法、及中空封裝體的製造方法。[The problem to be solved by the invention] When producing a hollow structure, in order to increase the cured film strength of the photosensitive resin composition layer, generally, the cavity securing portion after development is further subjected to heat treatment (hardening operation) at a high temperature of 200° C. or higher, for example. However, in the method of producing the hollow structure described in Patent Document 1, there is a problem that the film-like top plate portion is easily deformed by the aforementioned curing operation when forming the cavity securing portion. In addition, with the progress of development of microelectronic devices, the current situation is that the height of elements is required to be further reduced. Along with this, in the package described above, it is necessary to reduce the size of the hollow structure while securing the space near the electrodes formed on the wiring board. However, in order to reduce the size of the hollow structure as described above, the cured film obtained by curing the conventional negative-type photosensitive resin composition or photosensitive resist film has insufficient strength, for example, when molding a mold. The high pressure applied may make it difficult to maintain the hollow structure. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a hollow structure and a hollow package that can stably produce a hollow structure whose strength is further improved while suppressing deformation of a top plate portion due to a hardening operation. body manufacturing method. [means to solve the problem] In order to solve the above-mentioned problems, the present invention adopts the following configuration. That is, the first aspect of the present invention is a method of manufacturing a hollow structure, which is a method of manufacturing a hollow structure formed by a recessed portion and a top plate portion that blocks an opening surface of the recessed portion, characterized by comprising the following steps: Step (0), prepare the substrate and photosensitive resist film with recessed part on the surface, and this photosensitive resist film has: contain epoxy group-containing resin (A) and photoinitiator (I) which generates acid due to exposure ) negative photosensitive resin film; step (i), in accordance with the photosensitive resin film surface of the photosensitive resist film to block the opening surface of the aforementioned recess in the substrate, configure the aforementioned photosensitive resist film; step (ii), after the aforementioned step (i), exposing the photosensitive resin film; step (iii), heating the aforementioned photosensitive resin film after the aforementioned step (ii); step (iv), after the aforementioned step After (iii), the photosensitive resin film is developed to form a negative pattern; and in step (v), the negative pattern after the step (iv) is further subjected to heat treatment, thereby hardening, After obtaining the hollow structure in which the top plate portion is formed from the cured body of the photosensitive resin film, after being heated at a temperature of 150° C. or lower for 10 minutes or more, the operation (x) of further heating at a temperature higher than 150° C., or by irradiation After ultraviolet rays, the operation (y) of heating at a temperature of 100° C. or higher is performed, and the heat treatment in the above-mentioned step (v) is performed. A second aspect of the present invention is a method for producing a hollow package, comprising a step of sealing the hollow structure manufactured by the manufacturing method according to the first aspect with a sealing material to obtain a hollow package. . [Inventive effect] ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a hollow structure which can suppress deformation|transformation of the top-plate part by hardening operation, and can manufacture the hollow structure with the further improved intensity|strength stably, and the manufacturing method of a hollow package can be provided.

本說明書及申請專利範圍中，所謂「脂肪族」，是相對於芳香族的相對的概念，定義為表示不具有芳香族性的基、不具有芳香族性的化合物等的概念。 對於「烷基」而言，只要沒有特別說明，包含直鏈狀、支鏈狀及環狀的1價飽和烴基。烷氧基中的烷基也同樣。 對於「伸烷基」而言，只要沒有特別說明，包含直鏈狀、支鏈狀及環狀的2價飽和烴基。 「鹵化烷基」是烷基的氫原子的一部分或全部被鹵素原子取代而得到的基，作為該鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子。 「氟化烷基」是指烷基的氫原子的一部分或全部被氟原子取代而得到的基。 所謂「構成單位」，是指構成高分子化合物(樹脂、聚合物、共聚物)的單體單元(單體單元)。 記載為「可以具有取代基的」的情況下，包含用1價基取代氫原子(-H)的情況、與用2價基取代亞甲基(-CH2 -)的情況這兩者。 「曝光」是包含放射線的照射整體的概念。 (中空構造體的製造方法) 本發明的第1方式涉及的製造方法是由凹部、與封堵該凹部的開口面的頂板部形成的中空構造體的製造方法，具有下述的步驟(0)及步驟(i)～(v)。進而，第1方式涉及的製造方法中，藉由於150℃以下的溫度加熱10分鐘以上後，進一步在高於150℃的溫度進行加熱的操作(x)，或照射紫外線後，於100℃以上的溫度進行加熱的操作(y)，進行前述步驟(v)中的加熱處理。 步驟(0)：準備在表面具有凹部的基板，與具有含有含環氧基的樹脂(A)及因曝光而產生酸的光起始劑(I)的負型感光性樹脂膜的感光性阻劑膜的步驟 步驟(i)：以前述感光性阻劑膜的感光性樹脂膜表面封堵前述基板中的前述凹部的開口面的方式，配置前述感光性阻劑膜的步驟 步驟(ii)：在前述步驟(i)後，將前述感光性樹脂膜曝光的步驟 步驟(iii)：對前述步驟(ii)後的前述感光性樹脂膜進行加熱處理的步驟 步驟(iv)：在前述步驟(iii)後，將前述感光性樹脂膜顯影，形成負型圖型的步驟 步驟(v)：針對前述步驟(iv)後的前述負型圖型，進一步進行加熱處理，由此，使其硬化，得到前述頂板部由前述感光性樹脂膜的硬化體形成的中空構造體的步驟 藉由本方式涉及的製造方法製造的中空構造體由凹部、與封堵該凹部的開口面的頂板部形成。該中空構造體可合適地用於可在SAW過濾器、MEMS、各種感測器等中利用的中空封裝體。 [步驟(0)] 本方式中的步驟(0)中，準備在表面具有凹部的基板，與具有含有含環氧基的樹脂(A)及因曝光而產生酸的光起始劑(I)的負型感光性樹脂膜的感光性阻劑膜。 《關於在表面具有凹部的基板》 作為在表面具有凹部的基板，可舉出在基板上形成有圖型的構造體、高低差基板等。需要說明的是，該凹部可由有機材料構成，也可由無機材料構成。 此種在表面具有凹部的基板例如可藉由具有下述步驟的方法來製造：使用負型感光性樹脂組成物，在支撐體上形成感光性樹脂膜的步驟(以下，稱為「膜形成步驟」)；將前述感光性樹脂膜曝光的步驟(以下，稱為「曝光步驟」)；用含有有機溶劑的顯影液將前述曝光後的感光性樹脂膜顯影，形成成為凹部的側壁的負型圖型的步驟(以下，稱為「顯影步驟」)。此種製造在表面具有凹部的基板的方法可按照以下方式進行。 膜形成步驟： 首先，利用旋塗法、輥塗法、絲網印刷法等已知的方法，將負型感光性樹脂組成物塗布在支撐體上，進行烘烤(塗布後烘烤(PAB))處理，例如在50～150℃的溫度條件下實施2～60分鐘，形成感光性樹脂膜。 需要說明的是，該膜形成步驟也可藉由將使用負型感光性樹脂組成物預先製作的感光性樹脂組成物層配置在支撐體上來進行。 作為支撐體，沒有特別限制，可使用現有已知的支撐體，例如，可舉出電子零件用的基板、在其上形成了規定的配線圖型的電子零件用的基板等。 作為電子零件用的基板，更具體而言，可舉出矽、氮化矽、鈦、鉭、鉭酸鋰(LiTaO3 )、鈮、鈮酸鋰(LiNbO3 )、鈀、鈦鎢、銅、鉻、鐵、鋁等金屬製的基板、玻璃基板等。 作為配線圖型的材料，例如可使用銅、鋁、鎳、金等。 由負型感光性樹脂組成物形成的感光性樹脂膜的膜厚沒有特別限制，優選為10～100μm左右。 曝光步驟： 接下來，針對形成的感光性樹脂膜，使用已知的曝光裝置，進行隔著形成了規定的圖型的遮罩(遮罩圖型)的曝光、或利用不隔著遮罩圖型的基於電子束的直接照射的繪圖等進行的選擇性的曝光後，根據需要，例如在80～150℃的溫度條件下，實施40～1200秒、優選40～1000秒、更優選60～900秒烘烤(曝光後烘烤(PEB))處理。 用於曝光的波長沒有特別限制，選擇性地照射(曝光)放射線、例如波長為300～500nm的紫外線、i線(波長365nm)或可見光線。作為該等放射線的線源，可使用低壓汞燈、高壓汞燈、超高壓汞燈、金屬鹵化物燈、氬氣雷射等。 此處所謂放射線，是指紫外線、可見光線、遠紫外線、X射線、電子束等。放射線照射量根據組成物中的各成分的種類、摻合量、塗膜的膜厚等的不同而不同，例如在使用超高壓汞燈的情況下，為100～2000 mJ/cm2 。 感光性樹脂膜的曝光方法可以是在空氣、氮氣等非活性氣體中進行的通常的曝光(乾式曝光)，也可以是液浸曝光(Liquid Immersion Lithography)。 顯影步驟： 接下來，用含有有機溶劑的顯影液(有機系顯影液)將前述曝光後的感光性樹脂膜顯影。顯影之後，優選進行潤洗處理。根據需要，可進行烘烤處理(後烘烤)。 作為有機系顯影液所含有的有機溶劑，可從已知的有機溶劑中適當選擇。具體而言，可舉出酮系溶劑、酯系溶劑、醇系溶劑、腈系溶劑、醯胺系溶劑、醚系溶劑等極性溶劑、烴系溶劑等。 作為酮系溶劑，可舉出例如1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、4-庚酮、1-己酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙醯丙酮、丙酮基丙酮、紫羅酮、二丙酮基醇、乙醯甲醇、苯乙酮、甲基萘基酮、異佛爾酮、碳酸丙烯酯、γ-丁內酯、甲基戊基酮(2-庚酮)等。該等中，作為酮系溶劑，優選甲基戊基酮(2-庚酮)。 作為酯系溶劑，可舉出例如乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯、乙酸異戊酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、丙二醇單甲基醚乙酸酯(PGMEA)、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單苯基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單丙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單苯基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯、乙酸2-甲氧基丁酯、乙酸3-甲氧基丁酯、乙酸4-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、乙酸3-乙基-3-甲氧基丁酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙酸2-乙氧基丁酯、乙酸4-乙氧基丁酯、乙酸4-丙氧基丁酯、乙酸2-甲氧基戊酯、乙酸3-甲氧基戊酯、乙酸4-甲氧基戊酯、乙酸2-甲基-3-甲氧基戊酯、乙酸3-甲基-3-甲氧基戊酯、乙酸3-甲基-4-甲氧基戊酯、乙酸4-甲基-4-甲氧基戊酯、丙二醇二乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸丙酯等。該等中，作為酯系溶劑，優選乙酸丁酯或PGMEA。 作為腈系溶劑，可舉出例如乙腈、丙腈、戊腈、丁腈等。 根據需要，可在有機系顯影液中摻合已知的添加劑。作為該添加劑，可舉出例如界面活性劑。作為界面活性劑，沒有特別限制，例如可使用離子性、非離子性的氟系及/或矽系界面活性劑等。 作為界面活性劑，優選非離子性的界面活性劑，更優選非離子性的氟系界面活性劑，或非離子性的矽系界面活性劑。 摻合界面活性劑的情況下，相對於有機系顯影液的總量而言，其摻合量通常為0.001～5質量%，優選為0.005～2質量%，更優選為0.01～0.5質量%。 顯影處理可利用已知的顯影方法實施，可舉出例如將支撐體在顯影液中浸漬一定時間的方法(浸漬法)、藉由表面張力將顯影液堆積在支撐體表面上並靜置一定時間的方法(旋覆浸沒式(puddle)顯影法)、將顯影液噴霧至支撐體表面的方法(噴霧法)、一邊使顯影液排出噴嘴以一定速度在以一定速度旋轉的支撐體上掃描、一邊持續排出顯影液的方法(動態分配(dynamic dispense)法)等。 使用了潤洗液的潤洗處理(洗淨處理)可利用已知的潤洗方法實施。作為該潤洗處理的方法，可舉出例如向以一定速度旋轉的支撐體上持續排出潤洗液的方法(旋轉塗布法)、將支撐體在潤洗液中浸漬一定時間的方法(浸漬法)、將潤洗液噴霧至支撐體表面的方法(噴霧法)等。 潤洗處理優選使用含有有機溶劑的潤洗液。 藉由上述的膜形成步驟、曝光步驟及顯影步驟，能製造在表面具有凹部的基板(在基板上形成了圖型的構造體、高低差基板)。 側壁的厚度(相對於支撐體而言的水準方向的尺寸)及高度(相對於支撐體而言的垂直方向的尺寸)可基於根據被收容在凹部的電子裝置的種類而確定的中空部的大小適當設定。 《關於感光性阻劑膜》 本方式中的感光性阻劑膜具有含有含環氧基的樹脂(A)(以下，稱為「(A)成分」。)及因曝光而產生酸的光起始劑(I)(以下，稱為「(I)成分」)的負型感光性樹脂膜。 在後文中對構成所述感光性阻劑膜的成分進行詳細說明。 使用所述感光性阻劑膜，形成感光性樹脂膜，針對該感光性樹脂膜，選擇性地進行曝光時，在該感光性樹脂膜的曝光部，由(I)成分產生酸，藉由該酸的作用，(A)成分中的環氧基進行開環聚合，該(A)成分在含有有機溶劑的顯影液中的溶解性減少，另一方面，在該感光性樹脂膜的未曝光部，該(A)成分在含有有機溶劑的顯影液中的溶解性不發生變化，因此，在該感光性樹脂膜的曝光部與未曝光部之間，產生在含有有機溶劑的顯影液中的溶解性的差異。即，該感光性樹脂膜為負型。因此，若用含有有機溶劑的顯影液將該感光性樹脂膜顯影，則可將未曝光部溶解除去，可形成負型圖型。 此處，感光性阻劑膜所具有的負型感光性樹脂膜典型地由B階段(B-Stage)狀(半硬化狀態)的樹脂材料構成。 作為感光性阻劑膜，可舉出由感光性樹脂膜積層於基材膜而成的積層膜形成的感光性阻劑膜。 所述感光性阻劑膜可藉由以下方式來製造：將(A)成分及(I)成分溶解於溶劑中而成的負型感光性樹脂組成物塗布於基材膜上，使其乾燥，從而形成感光性樹脂膜。 對於負型感光性樹脂組成物向基材膜上的塗布而言，使用基於塗敷器(applicator)、刮刀塗布機(blade coater)、唇式塗布機(lip coater)、逗號塗布機(comma coater)、膜塗機(film coater)等的適當的方法進行即可。 感光性樹脂膜的厚度優選為100μm以下，更優選為5～50μm。 作為基材膜，可使用已知的基材膜，例如可使用熱塑性樹脂膜等。作為該熱塑性樹脂，可舉出例如聚對苯二甲酸乙二醇酯等聚酯。基材膜的厚度優選為2～150μm。 本方式的中空構造體的製造方法中，使用上述步驟(0)中準備的在表面具有凹部的基板、與感光性阻劑膜，進行步驟(i)～步驟(v)。 作為中空構造體的製造方法，分別可舉出例如以下所示的第1實施方式，及第2實施方式。 以下，參照附圖，對中空構造體的製造方法的各實施方式進行說明。 ＜第1實施方式＞ 步驟(0)中，作為感光性阻劑膜，準備由感光性樹脂膜積層於基材膜而成的積層膜形成的感光性阻劑膜的情況下，依次進行步驟(i)、步驟(ii)、步驟(iii)、步驟(iv)、步驟(v)的方式。 此外，藉由於150℃以下的溫度加熱10分鐘以上後、進一步在高於150℃的溫度進行加熱的操作(x)進行前述步驟(v)中的加熱處理的方式。 圖1為說明第1實施方式涉及的中空構造體的製造方法的示意圖。 圖1中，由基板10與在基板10上形成的側壁20，構成了在表面具有凹部15的基板。作為感光性阻劑膜，使用了由感光性樹脂膜30積層於基材膜50而成的積層膜80形成的感光性阻劑膜。 本實施方式中，側壁20由感光性樹脂材料形成。形成側壁20的感光性樹脂材料可以為與構成頂板部的感光性樹脂膜相同的材料，也可以為不同的材料。 [步驟(i)] 步驟(i)中，以感光性阻劑膜(積層膜80)的感光性樹脂膜30表面封堵基板10中的凹部15的開口面的方式，配置積層膜80。 圖1中，積層膜80以隔著側壁20與基板10相對的方式配置。而且，形成了由基板10、側壁20、與感光性樹脂膜30圍成的中空的密閉空間。 [步驟(D)] 步驟(D)中，在步驟(i)之後，從積層膜80中的感光性樹脂膜30剝離基材膜50。 [步驟(ii)] 步驟(ii)中，將感光性樹脂膜30曝光。 例如，針對感光性樹脂膜30，使用已知的曝光裝置，進行隔著形成有規定的圖型的光罩60的選擇性的曝光。 用於曝光的波長沒有特別限制，選擇性地照射(曝光)放射線、例如波長為300～500nm的紫外線、i線(波長365nm)或可見光線。作為該等放射線的線源，可使用低壓汞燈、高壓汞燈、超高壓汞燈、金屬鹵化物燈、氬氣雷射等。 [步驟(iii)] 步驟(iii)中，對曝光後的感光性樹脂膜30進行加熱處理，所謂的曝光後烘烤(PEB)處理。 PEB處理例如在80～150℃的溫度條件下進行40～600秒、優選60～300秒。 藉由步驟(iii)中的加熱處理，曝光後的感光性樹脂膜30成為(A)成分中的環氧基進行了開環聚合的曝光部30A，與無變化的未曝光部30B。 [步驟(iv)] 步驟(iv)中，將PEB處理後的感光性樹脂膜30顯影，形成負型圖型。 此處的顯影可按照與上述的[步驟(0)]中的顯影步驟同樣的方式進行。顯影後，優選進行潤洗處理。 藉由步驟(iv)中的顯影，可將未曝光部30B溶解除去，作為負型圖型，成為頂板部的曝光部30A殘留而形成圖像。 [步驟(v)] 步驟(v)中，針對顯影後的負型圖型(曝光部30A)，進一步進行加熱處理(硬化操作)，由此使其硬化，得到頂板部由感光性樹脂膜30的硬化體40形成的中空構造體100。圖1中，對於硬化體40而言，形成側壁20的感光性樹脂材料與感光性樹脂膜30分別進行硬化而進行一體化。 步驟(v)中的加熱處理藉由於150℃以下的溫度加熱10分鐘以上(第1加熱)後、進一步在高於150℃的溫度進行加熱(第2加熱)的操作(x)進行。 關於操作(x)： 操作(x)為進行第1加熱後、進一步進行第2加熱的操作。 第1加熱為於150℃以下的溫度加熱10分鐘以上的步驟。 第1加熱中的溫度、其持續時間優選為50℃以上且150℃以下，更優選為50℃以上且125℃以下，優選為30分鐘以上且120分鐘以下，更優選為60分鐘以上且90分鐘以下。 第1加熱中的加熱操作可藉由一步驟進行，也可藉由兩步驟以上進行。例如，藉由兩步驟進行第1加熱的情況下，優選可舉出藉由下述方式進行第1加熱中的加熱操作的方案：於50℃以上且90℃以下的溫度加熱30分鐘以上且90分鐘以下後，進而在高於90℃且為150℃以下的溫度加熱10分鐘以上且60分鐘以下。 第2加熱為在高於150℃的溫度加熱的步驟。 第2加熱中的溫度、其持續時間優選為高於150℃且為250℃以下，更優選為160℃以上且220℃以下，優選為30分鐘以上且120分鐘以下，更優選為60分鐘以上且90分鐘以下。 第2加熱中的加熱操作可藉由一步驟進行，也可藉由兩步驟以上進行。例如，藉由兩步驟進行第2加熱的情況下，優選可舉出藉由下述方式進行第2加熱中的加熱操作的方案：在高於150℃且為180℃以下的溫度加熱10分鐘以上且60分鐘以下後，進而在高於180℃且為220℃以下的溫度加熱30分鐘以上且90分鐘以下。 第1實施方式涉及的中空構造體的製造方法中，作為上述操作(x)，從能抑制頂板部的變形、並且容易進一步提高強度方面考慮，優選進行下述操作：於50℃以上且125℃以下的溫度加熱10分鐘以上後，進一步於160℃以上的溫度加熱30分鐘以上的操作。 另外，對於上述操作(x)而言，優選藉由兩步驟以上進行第1加熱，而且藉由兩步驟以上進行第2加熱。進而，從生產率(時間週期(time cycle)等)方面考慮，對於上述操作(x)而言，更優選的是，第1加熱藉由兩步驟進行，而且，第2加熱也藉由兩步驟進行。 上文中說明的第1實施方式涉及的中空構造體的製造方法中，藉由於150℃以下的溫度加熱10分鐘以上後、進一步在高於150℃的溫度進行加熱的操作(x)，進行在步驟(v)中的加熱處理(硬化操作)。 藉由如上所述地在從低於150℃的低溫側向高於150℃的高溫側提高溫度的同時，對顯影後的負型圖型(曝光部30A)進行加熱，從而在硬化操作時，與以往相比，不僅能抑制中空內的空氣的膨脹，降低內壓，而且能使硬化充分進行。因此，藉由第1實施方式，能抑制因硬化操作而導致的頂板部的變形，並且能穩定地製造強度被進一步提高的中空構造體。 ＜第2實施方式＞ 步驟(0)中，作為感光性阻劑膜，準備由感光性樹脂膜積層於基材膜而成的積層膜形成的感光性阻劑膜的情況下，依次進行步驟(i)、步驟(ii)、步驟(iii)、步驟(iv)、步驟(v’)的方式。 此外，藉由照射紫外線後、於100℃以上的溫度進行加熱的操作(y)進行前述步驟(v’)中的加熱處理的方式。 針對第2實施方式中的步驟(i)、步驟(ii)、步驟(iii)及步驟(iv)的說明與針對上述的第1實施方式中的步驟(i)、步驟(ii)、步驟(iii)及步驟(iv)的說明同樣。 [步驟(v’)] 步驟(v’)中，針對顯影後的負型圖型(曝光部)，進一步進行加熱處理(硬化操作)，由此使其硬化，得到頂板部由感光性樹脂膜的硬化體形成的中空構造體。 步驟(v’)中的加熱處理藉由照射紫外線後，於100℃以上的溫度進行加熱的操作(y)進行。 關於操作(y)： 操作(y)為照射紫外線後，進行加熱的操作。 紫外線的照射例如優選以1000～10000 mJ/cm2 的照射量進行。 操作(y)中的加熱為於100℃以上的溫度的加熱。 操作(y)中的加熱的溫度，其持續時間優選為100℃以上且200℃以下，更優選為150℃以上且180℃以下，優選為15分鐘以上且120分鐘以下，更優選為30分鐘以上且90分鐘以下。 操作(y)中的加熱操作可藉由一步驟進行，也可藉由兩步驟以上進行。 第2實施方式涉及的中空構造體的製造方法中，作為上述操作(y)，從能抑制頂板部的變形、並且容易進一步提高強度方面考慮，優選進行下述操作：照射1000～10000mJ/cm2 紫外線後，於160℃以上的溫度加熱30分鐘以上。 上文中說明的第2實施方式涉及的中空構造體的製造方法中，藉由照射紫外線後、於100℃以上的溫度進行加熱的操作(y)，進行在步驟(v)中的加熱處理(硬化操作)。 藉由如上所述針對顯影後的負型圖型(曝光部)、照射紫外線後進行加熱，可將硬化操作的加熱溫度設置為較低值。由此，與以往相比，能抑制中空內的空氣的膨脹，能降低內壓。此外，能使顯影後的負型圖型(曝光部)的硬化充分進行。因此，藉由第2實施方式，能抑制因硬化操作而導致的頂板部的變形、並且能穩定地製造強度被進一步提高的中空構造體。 ＜其他實施方式＞ 對於上述的實施方式涉及的中空構造體的製造方法，作為感光性阻劑膜，對準備由感光性樹脂膜積層於基材膜而成的積層膜形成的感光性阻劑膜的情況進行了說明，但不限於此，例如，也可以是準備由感光性樹脂膜形成的單層的感光性阻劑膜、或由在基材膜上依次積層感光性樹脂膜與覆蓋膜而成的積層體形成的感光性阻劑膜的情況。 作為覆蓋膜，可使用已知的覆蓋膜，例如可使用聚乙烯膜、聚丙烯膜等。作為覆蓋膜，優選與感光性樹脂膜的黏接力小於基材膜的膜。 覆蓋膜的厚度優選為2～150μm，更優選為2～100μm，進一步優選為5～50μm。 基材膜與覆蓋膜可以為相同的膜材料，也可以為不同的膜材料。 在使用時，例如，可一邊剝離覆蓋膜，一邊作為感光性樹脂膜/基材膜的積層膜使用。 另外，上述的實施方式涉及的中空構造體的製造方法中，例示了在前述步驟(i)與前述步驟(ii)之間進行構成感光性阻劑膜的基材膜的剝離操作的情況，但不限於此，也可以是在前述步驟(ii)與前述步驟(iii)之間、或前述步驟(iii)與前述步驟(iv)之間進行構成感光性阻劑膜的基材膜的剝離操作的情況。 《關於構成感光性阻劑膜的成分》 本方式中的感光性阻劑膜具有：含有含環氧基的樹脂(A)及因曝光而產生酸的光起始劑(I)的負型感光性樹脂膜。 ・含環氧基的樹脂(A)： 含環氧基的樹脂((A)成分)沒有特別限制，為在1分子中具有對於藉由曝光而形成圖型而言充分的環氧基的樹脂即可。 作為(A)成分，可舉出例如酚醛(Novolac)型環氧樹脂(Anv)、雙酚A型環氧樹脂(Abp)、雙酚F型環氧樹脂、脂肪族環氧樹脂、丙烯酸樹脂(Aac)。 ・・酚醛型環氧樹脂(Anv) 作為酚醛型環氧樹脂(Anv)，可以合適地舉出下述通式(A1)表示的樹脂(A1)(以下，也稱為「(A1)成分」)。

Figure 02_image001
[式中，Rp1 及Rp2 各自獨立地為氫原子或碳原子數為1～5的烷基。複數個Rp1 相互可以相同也可以不同。複數個Rp2 相互可以相同也可以不同。n1 為1～5的整數。REP 為含環氧基的基。複數個REP 相互可以相同也可以不同。] 前述式(A1)中，Rp1 、Rp2 的碳原子數為1～5的烷基例如為碳原子數為1～5的直鏈狀、支鏈狀、或環狀的烷基。作為直鏈狀或支鏈狀的烷基，可舉出甲基、乙基、丙基、異丙基、正丁基、異丁基、叔丁基、戊基、異戊基、新戊基等，作為環狀的烷基，可舉出環丁基、環戊基等。 其中，作為Rp1 、Rp2 ，優選氫原子或者直鏈狀或支鏈狀的烷基，更優選氫原子或者直鏈狀的烷基，特別優選氫原子或者甲基。 式(A1)中，複數個Rp1 相互可以相同也可以不同。複數個Rp2 相互可以相同也可以不同。 式(A1)中，n1 為1～5的整數，優選為2或3，更優選為2。 式(A1)中，REP 為含環氧基的基。 作為REP 的含環氧基的基，沒有特別限制，可舉出僅由環氧基形成的基；僅由脂環式環氧基形成的基；具有環氧基或脂環式環氧基、與2價連結基的基。 所謂脂環式環氧基，是具有作為三員環醚的氧雜環丙烷構造的脂環式基，具體而言，是具有脂環式基與氧雜環丙烷構造的基。 作為成為脂環式環氧基的基本骨架的脂環式基，可以為單環，也可以為多環。作為單環的脂環式基，可舉出環丙基、環丁基、環戊基、環己基、環庚基、環辛基等。另外，作為多環的脂環式基，可舉出降冰片基、異冰片基、三環壬基、三環癸基、四環十二烷基等。另外，該等脂環式基的氫原子可以被烷基、烷氧基、羥基等取代。 具有環氧基或脂環式環氧基、與2價連結基的基的情況下，優選環氧基或脂環式環氧基隔著鍵結於式中的氧原子(-O-)的2價連結基進行鍵結。 此處，作為2價連結基，沒有特別限制，可舉出可以具有取代基的2價烴基、包含雜原子的2價連結基等作為優選的例子。 關於可以具有取代基的2價烴基： 所述2價烴基可以為脂肪族烴基，也可以為芳香族烴基。 2價烴基中的脂肪族烴基可以為飽和，也可以為不飽和，通常優選為飽和。 作為該脂肪族烴基，更具體而言，可舉出直鏈狀或支鏈狀的脂肪族烴基、或在構造中包含環的脂肪族烴基等。 前述直鏈狀的脂肪族烴基的碳原子數優選為1～10，更優選為1～6，進一步優選為1~4，最優選為1～3。作為直鏈狀的脂肪族烴基，優選直鏈狀的伸烷基，具體而言，可舉出亞甲基[-CH2 -]、伸乙基[-(CH2 )2 -]、三亞甲基 [-(CH2 )3 -]、四亞甲基[-(CH2 )4 -]、五亞甲基[-(CH2 )5 -]等。 前述支鏈狀的脂肪族烴基的碳原子數優選為2～10，更優選為2～6，進一步優選為2～4，最優選為2或3。作為支鏈狀的脂肪族烴基，優選支鏈狀的伸烷基，具體而言，可舉出-CH(CH3 )-、-CH(CH2 CH3 )-、-C(CH3 )2 -、 -C(CH3 )(CH2 CH3 )-、-C(CH3 )(CH2 CH2 CH3 )-、-C(CH2 CH3 )2 -等烷基亞甲基；-CH(CH3 )CH2 -、-CH(CH3 )CH(CH3 )-、 -C(CH3 )2 CH2 -、-CH(CH2 CH3 )CH2 -、-C(CH2 CH3 )2 -CH2 -等烷基伸乙基；-CH(CH3 )CH2 CH2 -、-CH2 CH(CH3 )CH2 -等烷基三亞甲基；-CH(CH3 )CH2 CH2 CH2 -、-CH2 CH(CH3 )CH2 CH2 -等烷基四亞甲基等烷基伸烷基等。作為烷基伸烷基中的烷基，優選碳原子數為1～5的直鏈狀的烷基。 作為前述在構造中包含環的脂肪族烴基，可舉出脂環式烴基(從脂肪族烴環中除去2個氫原子而成的基)、脂環式烴基鍵結於直鏈狀或支鏈狀的脂肪族烴基的末端而成的基、脂環式烴基存在於直鏈狀或支鏈狀的脂肪族烴基的中間的基等。作為前述直鏈狀或支鏈狀的脂肪族烴基，可舉出與前述同樣的例子。 前述脂環式烴基的碳原子數優選為3～20，更優選為3～12。 前述脂環式烴基可以為多環式基，也可以為單環式基。作為單環式的脂環式烴基，優選從單環烷中除去2個氫原子而成的基。作為該單環烷，優選碳原子數為3～6的單環烷，具體而言，可舉出環戊烷、環己烷等。 作為多環式的脂環式烴基，優選從多環烷中除去2個氫原子而成的基，作為該多環烷，優選碳原子數為7～12的多環烷，具體而言，可舉出金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷等。 2價烴基中的芳香族烴基為具有至少1個芳香環的烴基。該芳香環沒有特別限制，只要是具有(4n+2)個π電子的環狀共軛系統即可，可以為單環式，也可以為多環式。芳香環的碳原子數優選為5～30，更優選為5～20，進一步優選為6～15，特別優選為6～12。作為芳香環，具體而言，可舉出苯、萘、蒽、菲等芳香族烴環；構成前述芳香族烴環的碳原子的一部分被雜原子取代而成的芳香族雜環等。作為芳香族雜環中的雜原子，可舉出氧原子、硫原子、氮原子等。作為芳香族雜環，具體而言，可舉出吡啶環、噻吩環等。 作為芳香族烴基，具體而言，可舉出從前述芳香族烴環或芳香族雜環中除去除去2個氫原子而成的基(伸芳基或伸雜芳基)；從包含2個以上芳香環的芳香族化合物(例如聯苯、茀等)中除去2個氫原子而成的基；從前述芳香族烴環或芳香族雜環中除去1個氫原子而成的基(芳基或雜芳基)的1個氫原子被伸烷基取代而成的基(例如，從苄基、苯乙基、1-萘基甲基、2-萘基甲基、1-萘基乙基、2-萘基乙基等芳基烷基中的芳基中進一步除去1個氫原子而成的基)等。鍵結於前述芳基或雜芳基的伸烷基的碳原子數優選為1～4，更優選為1～2，特別優選為1。 2價烴基可以具有取代基。 作為2價烴基的、直鏈狀或支鏈狀的脂肪族烴基可以具有取代基，也可不具有取代基。作為該取代基，可舉出氟原子、被氟原子取代的碳原子數為1～5的氟化烷基、羰基等。 作為2價烴基的、在構造中包含環的脂肪族烴基中的脂環式烴基可以具有取代基，也可不具有取代基。作為該取代基，可舉出烷基、烷氧基、鹵素原子、鹵化烷基、羥基、羰基等。 關於作為前述取代基的烷基，優選碳原子數為1～5的烷基，最優選為甲基、乙基、丙基、正丁基、叔丁基。 關於作為前述取代基的烷氧基，優選碳原子數為1～5的烷氧基，優選甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、叔丁氧基，最優選為甲氧基、乙氧基。 關於作為前述取代基的鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子等，優選氟原子。 關於作為前述取代基的鹵化烷基，可舉出前述烷基的氫原子的一部分或全部被前述鹵素原子取代而成的基。 對於脂環式烴基而言，構成其環構造的碳原子的一部分可以被包含雜原子的取代基取代。作為該包含雜原子的取代基，優選-O-、-C(=O)-O-、-S-、-S(=O)2 -、-S(=O)2 -O-。 對於作為2價烴基的、芳香族烴基而言，該芳香族烴基所具有的氫原子可以被取代基取代。例如，鍵結於該芳香族烴基中的芳香環的氫原子可以被取代基取代。作為該取代基，可舉出例如烷基、烷氧基、鹵素原子、鹵化烷基、羥基等。 關於作為前述取代基的烷基，優選碳原子數為1～5的烷基，最優選為甲基、乙基、丙基、正丁基、叔丁基。 關於作為前述取代基的烷氧基、鹵素原子及鹵化烷基，可舉出作為取代前述脂環式烴基所具有的氫原子的取代基而例舉的例子。 關於包含雜原子的2價連結基： 所謂包含雜原子的2價連結基中的雜原子，是碳原子及氫原子以外的原子，可舉出例如氧原子、氮原子、硫原子、鹵素原子等。 包含雜原子的2價連結基中，作為優選作為該連結基的例子，可舉出-O-、-C(=O)-O-、-C(=O)-、-O-C(=O)-O-；-C(=O)-NH-、-NH-、-NH-C(=O)-O-、-NH-C(=NH)-(H可以被烷基、醯基等取代基取代。)；-S-、-S(=O)2 -、 -S(=O)2 -O-、通式-Y21 -O-Y22 -、-Y21 -O-、-Y21 -C(=O)-O-、-C(=O)-O-Y21 、-[Y21 -C(=O)-O]m” -Y22 -或-Y21 -O-C(=O)-Y22 -表示的基[式中，Y21 及Y22 各自獨立地為可以具有取代基的2價烴基，O為氧原子，m”為0～3的整數。]等。 前述包含雜原子的2價連結基為-C(=O)-NH-、-NH-、 -NH-C(=O)-O-、-NH-C(=NH)-時，其H可以被烷基、醯基等取代基取代。該取代基(烷基、醯基等)的碳原子數優選為1～10，進一步優選為1～8，特別優選為1～5。 式-Y21 -O-Y22 -、-Y21 -O-、-Y21 -C(=O)-O-、-C(=O)-O-Y21 -、-[Y21 -C(=O)-O]m” -Y22 -或-Y21 -O-C(=O)-Y22 -中，Y21 及Y22 各自獨立地為可以具有取代基的2價烴基。作為該2價烴基，可舉出與作為上述的2價連結基的說明中列舉的「可以具有取代基的2價烴基」同樣的例子。 作為Y21 ，優選直鏈狀的脂肪族烴基，更優選直鏈狀的伸烷基，進一步優選碳原子數為1～5的直鏈狀的伸烷基，特別優選亞甲基或伸乙基。 作為Y22 ，優選直鏈狀或支鏈狀的脂肪族烴基，更優選亞甲基、伸乙基或烷基亞甲基。該烷基亞甲基中的烷基優選為碳原子數為1～5的直鏈狀的烷基，更優選為碳原子數為1～3的直鏈狀的烷基，最優選為甲基。 式-[Y21 -C(=O)-O]m” -Y22 -表示的基中，m”為0～3的整數，優選為0～2的整數，更優選為0或1，特別優選為1。即，作為式-[Y21 -C(=O)-O]m” -Y22 -表示的基，特別優選式 -Y21 -C(=O)-O-Y22 -表示的基。其中，優選式-(CH2 )a’ -C(=O)-O-(CH2 )b’ -表示的基。該式中，a’為1～10的整數，優選為1～8的整數，更優選為1～5的整數，進一步優選為1或2，最優選為1。b’為1～10的整數，優選為1～8的整數，更優選為1～5的整數，進一步優選為1或2，最優選為1。 其中，作為REP 中的含環氧基的基，優選環氧丙基。 另外，作為酚醛型環氧樹脂(Anv)，還優選可舉出具有下述通式(anv1)表示的構成單位的樹脂。
Figure 02_image003
[式中，REP 為含環氧基的基，Ra22 、Ra23 各自獨立地為氫原子、碳原子數為1～5的烷基或鹵素原子。] 式(anv1)中，Ra22 、Ra23 的碳原子數為1～5的烷基與前述式(A1)中的Rp1 、Rp2 的碳原子數為1～5的烷基同樣。Ra22 、Ra23 的鹵素原子優選為氯原子或溴原子。 式(anv1)中，REP 與前述式(A1)中的REP 同樣，優選為環氧丙基。 以下，展示出前述式(anv1)表示的構成單位的具體例。
Figure 02_image005
酚醛型環氧樹脂(Anv)可以為僅由前述構成單位(anv1)形成的樹脂，也可以為具有構成單位(anv1)與其他構成單位的樹脂。作為該其他構成單位，可舉出例如由下述通式(anv2)～(anv3)分別表示的構成單位。
Figure 02_image007
[式中，Ra24 為可以具有取代基的烴基。Ra25 ～Ra26 、Ra28 ～Ra30 各自獨立地為氫原子、碳原子數為1～5的烷基或鹵素原子。Ra27 為含環氧基的基或可以具有取代基的烴基。] 式(anv2)中，Ra24 為可以具有取代基的烴基。作為可以具有取代基的烴基，可舉出直鏈狀或支鏈狀的烷基、或環狀的烴基。 該直鏈狀的烷基的碳原子數優選為1～5，更優選為1～4，進一步優選為1或2。具體而言，可舉出甲基、乙基、正丙基、正丁基、正戊基等。該等中，優選甲基、乙基或正丁基，更優選甲基或乙基。 該支鏈狀的烷基的碳原子數優選為3～10，更優選為3～5。具體而言，可舉出異丙基、異丁基、叔丁基、異戊基、新戊基、1,1-二乙基丙基、2,2-二甲基丁基等，優選為異丙基。 Ra24 成為環狀的烴基時，該烴基可以為脂肪族烴基，也可以為芳香族烴基，另外，可以為多環式基，也可以為單環式基。 關於作為單環式基的脂肪族烴基，優選從單環烷中除去1個氫原子而成的基。作為該單環烷，優選碳原子數為3～6的單環烷，具體而言，可舉出環戊烷、環己烷等。 關於作為多環式基的脂肪族烴基，優選從多環烷中除去1個氫原子而成的基，作為該多環烷，優選碳原子數為7～12的多環烷，具體而言，可舉出金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷等。 Ra24 的環狀的烴基成為芳香族烴基時，該芳香族烴基為具有至少1個芳香環的烴基。 該芳香環沒有特別限制，只要是具有4n+2個π電子的環狀共軛系統即可，可以為單環式，也可以為多環式。芳香環的碳原子數優選為5～30，更優選為5～20，進一步優選為6～15，特別優選為6～12。作為芳香環，具體而言，可舉出苯、萘、蒽、菲等芳香族烴環；構成前述芳香族烴環的碳原子的一部分被雜原子取代而成的芳香族雜環等。作為芳香族雜環中的雜原子，可舉出氧原子、硫原子、氮原子等。作為芳香族雜環，具體而言，可舉出吡啶環、噻吩環等。 作為Ra24 中的芳香族烴基，具體而言，可舉出從前述芳香族烴環或芳香族雜環中除去1個氫原子而成的基(芳基或雜芳基)；從包含2個以上芳香環的芳香族化合物(例如聯苯、茀等)中除去1個氫原子而成的基；前述芳香族烴環或芳香族雜環的1個氫原子被伸烷基取代而成的基(例如，苄基、苯乙基、1-萘基甲基、2-萘基甲基、1-萘基乙基、2-萘基乙基等芳基烷基等)等。鍵結於前述芳香族烴環或芳香族雜環的伸烷基的碳原子數優選為1～4，更優選為1～2，特別優選為1。 式(anv2)、(anv3)中，Ra25 ～Ra26 、Ra28 ～Ra30 各自獨立地為氫原子、碳原子數為1～5的烷基或鹵素原子，碳原子數為1～5的烷基、鹵素原子分別與前述Ra22 、Ra23 同樣。 式(anv3)中，Ra27 為含環氧基的基或可以具有取代基的烴基。Ra27 的含環氧基的基與前述式(A1)中的REP 同樣，Ra27 的可以具有取代基的烴基與Ra24 同樣。 以下，展示出由前述式(anv2)～(anv3)分別表示的構成單位的具體例。
Figure 02_image009
酚醛型環氧樹脂(Anv)不僅具有構成單位(anv1)還具有其他構成單位時，樹脂(Anv)中的各構成單位的比例沒有特別限制，相對於構成樹脂(Anv)的全部構成單位的合計而言，具有環氧基的構成單位的合計優選為10～90莫耳%，更優選為20～80莫耳%，進一步優選為30～70莫耳%。 ・・雙酚A型環氧樹脂(Abp) 作為雙酚A型環氧樹脂(Abp)，可舉出下述通式(abp1)表示的構造的環氧樹脂。
Figure 02_image011
[式中，REP 為含環氧基的基，Ra31 、Ra32 各自獨立地為氫原子或碳原子數為1～5的烷基，na31 為1～50的整數。] 式(abp1)中，Ra31 、Ra32 的碳原子數為1～5的烷基與前述式(A1)中的Rp1 、Rp2 的碳原子數為1～5的烷基同樣。其中，作為Ra31 、Ra32 ，優選氫原子或甲基。 REP 與前述式(A1)中的REP 同樣，優選為環氧丙基。 ・・脂肪族環氧樹脂、丙烯酸樹脂(Aac) 作為脂肪族環氧樹脂、丙烯酸樹脂(Aac)，可舉出例如具有由下述通式(a1-1)～(a1-2)分別表示的含有環氧基的單元的樹脂。
Figure 02_image013
[式中，R為氫原子、碳原子數為1～5的烷基或碳原子數為1～5的鹵化烷基。Va41 為可以具有取代基的2價烴基。na41 為0～2的整數。Ra41 、Ra42 為含環氧基的基。na42 為0或1。Wa41 為(na43 +1)價脂肪族烴基。na43 為1～3的整數。] 前述式(a1-1)中，R為氫原子、碳原子數為1～5的烷基或碳原子數為1～5的鹵化烷基。 R的碳原子數為1～5的烷基優選為直鏈狀或支鏈狀，具體而言，可舉出甲基、乙基、丙基、異丙基、正丁基、異丁基、叔丁基、戊基、異戊基、新戊基等。 R的碳原子數為1～5的鹵化烷基為前述碳原子數為1～5的烷基的氫原子的一部分或全部被鹵素原子取代而成的基。作為該鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子等，特別優選氟原子。 作為R，優選氫原子、碳原子數為1～5的烷基或碳原子數為1～5的氟化烷基，從工業上入手的容易性考慮，最優選氫原子或甲基。 前述式(a1-1)中，Va41 為可以具有取代基的2價烴基，可舉出與前述式(A1)中的REP 中說明的可以具有取代基的2價烴基同樣的基。 上述中，Va41 的烴基優選為脂肪族烴基，更優選為直鏈狀或支鏈狀的脂肪族烴基，進一步優選為直鏈狀的脂肪族烴基，特別優選為直鏈狀的伸烷基。 式(a1-1)中，na41 為0～2的整數，優選為0或1。 式(a1-1)、(a1-2)中，Ra41 、Ra42 為含環氧基的基，與前述式(A1)中的REP 同樣。 式(a1-2)中，Wa41 中的(na43 +1)價脂肪族烴基是指不具有芳香族性的烴基，可以為飽和，也可以為不飽和，通常優選為飽和。作為前述脂肪族烴基，可舉出直鏈狀或支鏈狀的脂肪族烴基、在構造中包含環的脂肪族烴基、或將直鏈狀或支鏈狀的脂肪族烴基與在構造中包含環的脂肪族烴基組合而成的基。 式(a1-2)中，na43 為1～3的整數，優選為1或2。 以下，展示出前述式(a1-1)或(a1-2)表示的構成單位的具體例。
Figure 02_image015
Figure 02_image017
Figure 02_image019
Figure 02_image021
上述式中，Rα 表示氫原子、甲基或三氟甲基。 Ra51 表示碳原子數為1～8的2價烴基。Ra52 表示碳原子數為1～20的2價烴基。Ra53 表示氫原子或甲基。na51 為0～10的整數。 Ra51 、Ra52 、Ra53 分別可以相同也可以不同。 此外，對於丙烯酸樹脂(Aac)而言，出於適度地控制物理、化學特性的目的，可具有由其他聚合性化合物衍生的構成單位。作為此種聚合性化合物，可舉出已知的自由基聚合性化合物、陰離子聚合性化合物。作為此種聚合性化合物，可舉出例如丙烯酸、甲基丙烯酸、巴豆酸等單羧酸類；馬來酸、富馬酸、衣康酸等二羧酸類；琥珀酸2-甲基丙烯醯基氧基乙酯、馬來酸2-甲基丙烯醯基氧基乙酯、鄰苯二甲酸2-甲基丙烯醯基氧基乙酯、六氫鄰苯二甲酸2-甲基丙烯醯基氧基乙酯等具有羧基及酯鍵的甲基丙烯酸衍生物類；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸烷基酯類；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等(甲基)丙烯酸羥基烷基酯類；(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸芳基酯類；馬來酸二乙酯、富馬酸二丁酯等二羧酸二酯類；苯乙烯、α-甲基苯乙烯、氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯、羥基苯乙烯、α-甲基羥基苯乙烯、α-乙基羥基苯乙烯等含乙烯基的芳香族化合物類；乙酸乙烯酯等含乙烯基的脂肪族化合物類；丁二烯、異戊二烯等共軛二烯烴類；丙烯腈、甲基丙烯腈等含腈基的聚合性化合物類；氯乙烯、偏二氯乙烯等含氯的聚合性化合物；丙烯醯胺、甲基丙烯醯胺等含醯胺鍵的聚合性化合物類；等等。 脂肪族環氧樹脂、丙烯酸樹脂(Aac)具有其他構成單位時，該樹脂中的含有環氧基的單元的含有比率優選為5～40莫耳%，更優選為10～30莫耳%，最優選為15～25莫耳%。 另外，作為脂肪族環氧樹脂，還可優選舉出包含下述通式(m1)表示的部分構造的化合物(以下，也稱為「(m1)成分」)。
Figure 02_image023
[式中，n2 為1～4的整數。*表示化學鍵。] 式(m1)中，n2 為1～4的整數，優選為1～3的整數，更優選為2。 作為(m1)成分，可舉出隔著2價連結基或單鍵、鍵結有複數個上述通式(m1)表示的部分構造的化合物。其中，優選隔著2價連結基、鍵結有複數個上述通式(m1)表示的部分構造的化合物。 作為此處的2價連結基，沒有特別限制，可舉出可以具有取代基的2價烴基、包含雜原子的2價連結基等作為優選的例子。關於可以具有取代基的2價烴基、包含雜原子的2價連結基，與上述式(A1)中的REP (含環氧基的基)中說明的可以具有取代基的2價烴基、包含雜原子的2價連結基同樣，其中，優選包含雜原子的2價連結基，更優選-Y21 -C(=O)-O-表示的基、-C(=O)-O-Y21 -表示的基。作為Y21 ，優選直鏈狀的脂肪族烴基，更優選直鏈狀的伸烷基，進一步優選碳原子數為1～5的直鏈狀的伸烷基，特別優選亞甲基或伸乙基。 此外，作為脂肪族環氧樹脂，還可優選舉出下述通式(m2)表示的化合物(以下，也稱為「(m2)成分」)。
Figure 02_image025
[式中，REP 為含環氧基的基。複數個REP 相互可以相同也可以不同。] 式(m2)中，REP 為含環氧基的基，與前述式(A1)中的REP 同樣。 作為(A)成分，可以單獨使用1種，也可並用2種以上。 (A)成分優選包含選自由酚醛型環氧樹脂(Anv)、雙酚A型環氧樹脂(Abp)、雙酚F型環氧樹脂、脂肪族環氧樹脂、及丙烯酸樹脂(Aac)所成群的至少1種樹脂。 該等中，(A)成分更優選包含選自由酚醛型環氧樹脂(Anv)、雙酚A型樹脂(Abp)、脂肪族環氧樹脂、及丙烯酸樹脂(Aac)所成群的至少1種樹脂。 其中，對於(A)成分而言，進一步優選包含選自由酚醛型環氧樹脂(Anv)、脂肪族環氧樹脂、及丙烯酸樹脂(Aac)所成群的至少1種樹脂，特別優選至少包含酚醛型環氧樹脂(Anv)。酚醛型環氧樹脂(Anv)中，優選使用(A1)成分。 另外，(A)成分特別優選包含選自由酚醛型環氧樹脂(Anv)、脂肪族環氧樹脂、及丙烯酸樹脂(Aac)所成群的2種以上樹脂。 作為(A)成分，並用2種以上的情況下，從在製成感光性阻劑膜時、膜特性(層合性等)及強度提高方面考慮，(A)成分優選包含酚醛型環氧樹脂(Anv)與脂肪族環氧樹脂的組合。 作為所述組合，具體而言，可舉出(A1)成分、與選自由(m1)成分及(m2)成分所成群的至少1種(以下，稱為「(m)成分」)的組合。其中，最優選(A1)成分與(m1)成分與(m2)成分的組合。 同時具有(m1)成分與(m2)成分的情況下，(m1)成分與(m2)成分的比率以(m1)成分/(m2)成分表示的質量比計，優選為2/8～8/2，更優選為3/7～7/3，進一步優選為4/6～6/4。上述質量比為前述的優選範圍內時，製成感光性阻劑膜時，膜特性(層合性等)及強度進一步提高。 尤其是，(A)成分含有(A1)成分、(m1)成分與(m2)成分，(m1)成分與(m2)成分的合計含量在(A1)成分、(m1)成分與(m2)成分的合計含量中所占的比例從硬化膜的強度與柔軟性的均衡性方面考慮優選為15質量%以上，更優選為20質量%以上，進一步優選為25質量%以上，特別優選大於25質量%，最優選大於25質量%且為30質量%以下。 (A)成分的按照聚苯乙烯換算的質均分子量優選為100～300000，更優選為200～200000，進一步優選為300～200000。藉由成為此種質均分子量，與支撐體的剝離變得不易發生，能充分提高形成的硬化膜的強度。 另外，(A)成分的分散度優選為1.05以上。藉由成為此種分散度，從而在圖型形成中，微影特性進一步提高。 此處所謂分散度，是指將質均分子量除以數均分子量而得到的值。 作為(A)成分的市售品，例如，作為酚醛型環氧樹脂(Anv)，可舉出JER-152、JER-154、JER-157S70、JER-157S65(以上為Mitsubishi Chemical Corporation製)、EPICLON N-740、EPICLON N-740、EPICLON N-770、EPICLON N-775、EPICLON N-660、EPICLON N-665、EPICLON N-670、EPICLON N-673、EPICLON N-680、EPICLON N-690、EPICLON N-695、EPICLON HP5000(以上為DIC股份有限公司製)、EOCN-1020(以上為日本化藥股份有限公司製)等。 作為雙酚A型環氧樹脂(Abp)，可舉出JER-827、JER-828、JER-834、JER-1001、JER-1002、JER-1003、JER-1055、JER-1007、JER-1009、JER-1010(以上為Mitsubishi Chemical Corporation製)、EPICLON860、EPICLON1050、EPICLON1051、EPICLON1055(以上為DIC股份有限公司製)等。 作為雙酚F型環氧樹脂，可舉出JER-806、JER-807、JER-4004、JER-4005、JER-4007、JER-4010(以上為Mitsubishi Chemical Corporation製)、EPICLON830、EPICLON835(以上為DIC股份有限公司製)、LCE-21、RE-602S(以上為日本化藥股份有限公司製)等。 作為脂肪族環氧樹脂，可舉出ADEKA RESIN EP-4080S、ADEKA RESIN EP-4085S、ADEKA RESIN EP-4088S(以上為股份有限公司ADEKA製)、Celloxide 2021P、Celloxide 2081、Celloxide 2083、Celloxide 2085、Celloxide 8000、Celloxide 8010、EHPE-3150、EPOLEAD PB 3600、EPOLEAD PB 4700(以上為Daicel Corporation製)、Denacol  EX-211L、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L(以上為Nagase ChemteX Corporation製)、TEPIC-VL(日產化學工業股份有限公司製)等。 實施方式的感光性樹脂膜中的(A)成分的含量根據想要形成的感光性樹脂膜的膜厚等調整即可。 ・因曝光而產生酸的光起始劑(I) 光起始劑((I)成分)是接受紫外線、遠紫外線、KrF、ArF等準分子雷射、X射線、電子束等之類的活性能量射線的照射、產生陽離子、該陽離子可成為聚合起始劑的化合物。 本實施方式的感光性樹脂膜中的(I)成分沒有特別限制，可舉出例如下述通式(I1)表示的化合物(以下，稱為「(I1)成分」)、下述通式(I2-1)或(I2-2)表示的化合物(以下，稱為「(I2)成分」)、下述通式(I3-1)或(I3-2)表示的化合物(以下，稱為「(I3)成分」)。 上述中，對於(I1)成分及(I2)成分而言，均藉由曝光而產生較強的酸，因此，使用含有(I)成分的感光性樹脂組成物形成圖型的情況下，能得到充分的敏感度，能形成良好的圖型。 ・・(I1)成分 (I1)成分為下述通式(I1)表示的化合物。
Figure 02_image027
[式中，Rb01 ～Rb04 各自獨立地為可以具有取代基的芳基、或氟原子。q為1以上的整數，Qq+ 各自獨立地為q價有機陽離子。] ・・・陰離子部 前述式(I1)中，Rb01 ～Rb04 各自獨立地為可以具有取代基的芳基、或氟原子。 Rb01 ～Rb04 中的芳基的碳原子數優選為5～30，更優選為5～20，進一步優選為6～15，特別優選為6～12。具體而言，可舉出萘基、苯基、蒽基等，從容易入手方面考慮，優選苯基。 Rb01 ～Rb04 中的芳基可以具有取代基。作為該取代基，沒有特別限制，優選鹵素原子、羥基、烷基(優選直鏈狀或支鏈狀的烷基，碳原子數優選為1～5)、鹵化烷基，更優選鹵素原子或碳原子數為1～5的鹵化烷基，特別優選氟原子或碳原子數為1～5的氟化烷基。藉由使芳基具有氟原子，從而陰離子部的極性提高，是優選的。 其中，作為式(I1)的Rb01 ～Rb04 ，分別優選經氟化的苯基，特別優選全氟苯基。 作為式(I1)表示的化合物的陰離子部的優選的具體例，可舉出四(五氟苯基)硼酸鹽([B(C6 F5 )4 ]- )；四[(三氟甲基)苯基]硼酸鹽([B(C6 H4 CF3 )4 ]- )；二氟雙(五氟苯基)硼酸鹽([(C6 F5 )2 BF2 ]- )；三氟(五氟苯基)硼酸鹽([(C6 F5 )BF3 ]- )；四(二氟苯基)硼酸鹽([B(C6 H3 F2 )4 ]- )等。 其中，特別優選四(五氟苯基)硼酸鹽([B(C6 F5 )4 ]- )。 ・・・陽離子部 式(I1)中，q為1以上的整數，Qq+ 各自獨立地為q價有機陽離子。 作為該Qq+ ，可優選舉出鋶陽離子、錪陽離子，特別優選由下述的通式(ca-1)～(ca-5)分別表示的有機陽離子。
Figure 02_image029
[式中，R201 ～R207 、及R211 ～R212 各自獨立地表示可以具有取代基的芳基、雜芳基、烷基或烯基。R201 ～R203 、R206 ～R207 、R211 ～R212 可以相互鍵結，與式中的硫原子一起形成環。R208 ～R209 各自獨立地表示氫原子或碳原子數為1～5的烷基。R210 為可以具有取代基的芳基、可以具有取代基的烷基、可以具有取代基的烯基、或可以具有取代基的含SO2 -的環式基。L201 表示-C(=O)-或-C(=O)-O-。Y201 各自獨立地表示伸芳基、伸烷基或伸烯基。x為1或2。W201 表示(x+1)價連結基。] 作為R201 ～R207 、及R211 ～R212 中的芳基，可舉出碳原子數為6～20的未取代的芳基，優選苯基、萘基。 作為R201 ～R207 、及R211 ～R212 中的雜芳基，可舉出構成前述芳基的碳原子的一部分被雜原子取代而成的基。作為雜原子，可舉出氧原子、硫原子、氮原子等。作為該雜芳基，可舉出從9H-噻噸除去1個氫原子而成的基；作為取代雜芳基，可舉出從9H-噻噸-9-酮除去1個氫原子而成的基等。 作為R201 ～R207 、及R211 ～R212 中的烷基，優選為碳原子數為1～30的鏈狀或環狀的烷基。 作為R201 ～R207 、及R211 ～R212 中的烯基，優選碳原子數為2～10。 作為R201 ～R207 、及R210 ～R212 可以具有的取代基，可舉出例如烷基、鹵素原子、鹵化烷基、羰基、氰基、氨基、氧代基(=O)、芳基、由下述式(ca-r-1)～(ca-r-10)分別表示的基。
Figure 02_image031
[式中，R’201 各自獨立地為氫原子、可以具有取代基的環式基、可以具有取代基的鏈狀的烷基、或可以具有取代基的鏈狀的烯基。] 前述的式(ca-r-1)～(ca-r-10)中，R’201 各自獨立地為氫原子、可以具有取代基的環式基、可以具有取代基的鏈狀的烷基、或可以具有取代基的鏈狀的烯基。 可以具有取代基的環式基： 該環式基優選為環狀的烴基，該環狀的烴基可以為芳香族烴基，也可以為環狀的脂肪族烴基。脂肪族烴基是指不具有芳香族性的烴基。另外，脂肪族烴基可以為飽和，也可以為不飽和，通常優選為飽和。 R’201 中的芳香族烴基為具有芳香環的烴基。該芳香族烴基的碳原子數優選為3～30，更優選為5～30，進一步優選為5～20，特別優選為6～15，最優選為6～10。但是，該碳原子數不包含取代基中的碳原子數。 作為R’201 中的芳香族烴基所具有的芳香環，具體而言，可舉出苯、茀、萘、蒽、菲、聯苯、或構成該等芳香環的碳原子的一部分被雜原子取代而成的芳香族雜環、或構成該等芳香環或芳香族雜環的氫原子的一部分被氧代基等取代而得到的環。作為芳香族雜環中的雜原子，可舉出氧原子、硫原子、氮原子等。 作為R’201 中的芳香族烴基，具體而言，可舉出從前述芳香環除去1個氫原子而成的基(芳基：例如，苯基、萘基、蒽基等)、前述芳香環的1個氫原子被伸烷基取代而成的基(例如，苄基、苯乙基、1-萘基甲基、2-萘基甲基、1-萘基乙基、2-萘基乙基等芳基烷基等)、從構成前述芳香環的氫原子的一部分被氧代基等取代而得到的環(例如蒽醌等)中除去1個氫原子而成的基、從芳香族雜環(例如9H-噻噸、9H-噻噸-9-酮等)除去1個氫原子而成的基等。前述伸烷基(芳基烷基中的烷基鏈)的碳原子數優選為1～4，更優選為1～2，特別優選為1。 關於R’201 中的環狀的脂肪族烴基，可舉出在構造中包含環的脂肪族烴基。 作為該在構造中包含環的脂肪族烴基，可舉出脂環式烴基(從脂肪族烴環中除去1個氫原子而成的基)、脂環式烴基鍵結於直鏈狀或支鏈狀的脂肪族烴基的末端而成的基、脂環式烴基存在於直鏈狀或支鏈狀的脂肪族烴基的中間的基等。 前述脂環式烴基的碳原子數優選為3～20，更優選為3～12。 前述脂環式烴基可以為多環式基，也可以為單環式基。作為單環式的脂環式烴基，優選從單環烷中除去1個以上氫原子而成的基。作為該單環烷，優選碳原子數為3～6的單環烷，具體而言，可舉出環戊烷、環己烷等。作為多環式的脂環式烴基，優選從多環烷中除去1個以上氫原子而得到的基，作為該多環烷，優選碳原子數為7～30的多環烷。其中，作為該多環烷，更優選金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷等具有交聯環系的多環式骨架的多環烷；具有具備類固醇骨架的環式基等稠環系的多環式骨架的多環烷。 其中，作為R’201 中的環狀的脂肪族烴基，優選從單環烷或多環烷中除去1個以上氫原子而成的基，更優選從多環烷中除去1個氫原子而成的基，特別優選金剛烷基、降冰片基，最優選金剛烷基。 可以鍵結於脂環式烴基的、直鏈狀或支鏈狀的脂肪族烴基的碳原子數優選為1～10，更優選為1～6，進一步優選為1~4，最優選為1～3。 作為直鏈狀的脂肪族烴基，優選直鏈狀的伸烷基，具體而言，可舉出亞甲基[-CH2 -]、伸乙基[-(CH2 )2 -]、三亞甲基[-(CH2 )3 -]、四亞甲基[-(CH2 )4 -]、五亞甲基[-(CH2 )5 -]等。 作為支鏈狀的脂肪族烴基，優選支鏈狀的伸烷基，具體而言，可舉出-CH(CH3 )-、-CH(CH2 CH3 )-、-C(CH3 )2 -、 -C(CH3 )(CH2 CH3 )-、-C(CH3 )(CH2 CH2 CH3 )-、-C(CH2 CH3 )2 -等烷基亞甲基；-CH(CH3 )CH2 -、-CH(CH3 )CH(CH3 )-、 -C(CH3 )2 CH2 -、-CH(CH2 CH3 )CH2 -、-C(CH2 CH3 )2 -CH2 -等烷基伸乙基；-CH(CH3 )CH2 CH2 -、-CH2 CH(CH3 )CH2 -等烷基三亞甲基；-CH(CH3 )CH2 CH2 CH2 -、-CH2 CH(CH3 )CH2 CH2 -等烷基四亞甲基等烷基伸烷基等。作為烷基伸烷基中的烷基，優選碳原子數為1～5的直鏈狀的烷基。 可以具有取代基的鏈狀的烷基： 作為R’201 的鏈狀的烷基，可以為直鏈狀或支鏈狀中的任意烷基。 作為直鏈狀的烷基，碳原子數優選為1～20，更優選為1～15，最優選為1～10。具體而言，可舉出例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、異十三烷基、十四烷基、十五烷基、十六烷基、異十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基等。 作為支鏈狀的烷基，碳原子數優選為3～20，更優選為3～15，最優選為3～10。具體而言，可舉出例如1-甲基乙基、1-甲基丙基、2-甲基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丁基、2-乙基丁基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基等。 可以具有取代基的鏈狀的烯基： 作為R’201 的鏈狀的烯基，可以為直鏈狀或支鏈狀中的任意烯基，碳原子數優選為2～10，更優選為2～5，進一步優選為2～4，特別優選為3。作為直鏈狀的烯基，可舉出例如乙烯基、丙烯基(烯丙基)、丁烯基等。作為支鏈狀的烯基，可舉出例如1-甲基乙烯基、2-甲基乙烯基、1-甲基丙烯基、2-甲基丙烯基等。 作為鏈狀的烯基，上述中，優選直鏈狀的烯基，更優選乙烯基、丙烯基，特別優選乙烯基。 作為R’201 的環式基、鏈狀的烷基或烯基中的取代基，可舉出例如烷氧基、鹵素原子、鹵化烷基、羥基、羰基、硝基、氨基、氧代基(oxo)、上述R’201 中的環式基、烷基羰基、噻吩基羰基等。 其中，R’201 優選為可以具有取代基的環式基、可以具有取代基的鏈狀的烷基。 R201 ～R203 、R206 ～R207 、R211 ～R212 相互鍵結、與式中的硫原子一起形成環時，可以隔著硫原子、氧原子、氮原子等雜原子、羰基、-SO-、-SO2 -、-SO3 -、-COO-、 -CONH-或-N(RN )-(該RN 為碳原子數為1～5的烷基。)等官能基鍵結。作為形成的環，在其環骨架中包含式中的硫原子的1個環包含硫原子在內優選為三～十員環，特別優選為五～七員環。作為形成的環的具體例，可舉出例如噻吩環、噻唑環、苯並噻吩環、噻蒽環、苯並噻吩環、二苯並噻吩環、9H-噻噸環、噻噸酮環、噻蒽環、吩噁噻環、四氫噻吩鎓環、四氫噻喃環等。 前述式(ca-3)中，R208 ～R209 各自獨立地表示氫原子或碳原子數為1～5的烷基，優選氫原子或碳原子數為1～3的烷基，成為烷基時，可以相互鍵結而形成環。 前述式(ca-3)中，R210 為可以具有取代基的芳基、可以具有取代基的烷基、可以具有取代基的烯基、或可以具有取代基的含SO2 -的環式基。 作為R210 中的芳基，可舉出碳原子數為6～20的未取代的芳基，優選苯基、萘基。 作為R210 中的烷基，優選為碳原子數為1～30的鏈狀或環狀的烷基。 作為R210 中的烯基，優選碳原子數為2～10。 前述的式(ca-4)、式(ca-5)中，Y201 各自獨立地表示伸芳基、伸烷基或伸烯基。 關於Y201 中的伸芳基，可舉出從作為R’201 中的芳香族烴基而例舉的芳基中除去1個氫原子而成的基。 關於Y201 中的伸烷基、伸烯基，可舉出從作為R’201 中的鏈狀的烷基、鏈狀的烯基而例舉的基中除去1個氫原子而成的基。 前述的式(ca-4)、式(ca-5)中，x為1或2。 W201 為(x+1)價、即2價或3價連結基。 作為W201 中的2價連結基，優選可以具有取代基的2價烴基，優選與上述式(A1)中的REP 中例舉的可以具有取代基的2價烴基同樣的基。W201 中的2價連結基可以為直鏈狀、支鏈狀、環狀中的任何，優選為環狀。其中，優選在伸芳基的兩端組合2個羰基而成的基、或僅由伸芳基形成的基。作為伸芳基，可舉出伸苯基、伸萘基等，特別優選伸苯基。 作為W201 中的3價連結基，可舉出從前述W201 中的2價連結基中除去1個氫原子而成的基、在前述2價連結基上進一步鍵結前述2價連結基而成的基等。作為W201 中的3價連結基，優選在伸芳基上鍵結2個羰基而成的基。 作為前述式(ca-1)表示的優選的陽離子，具體而言，可舉出由下述式(ca-1-1)～(ca-1-24)分別表示的陽離子。
Figure 02_image033
Figure 02_image035
[式中，R”201 為氫原子或取代基。作為該取代基，與作為前述R201 ～R207 、及R210 ～R212 可以具有的取代基而列舉的例子同樣。] 另外，作為前述式(ca-1)表示的陽離子，還優選由下述通式(ca-1-25)～(ca-1-35)分別表示的陽離子。
Figure 02_image037
Figure 02_image039
[式中，R’211 為烷基。Rhal 為氫原子或鹵素原子。] 另外，作為前述式(ca-1)表示的陽離子，還優選由下述化(ca-1-36)～(ca-1-47)分別表示的陽離子。
Figure 02_image041
作為前述式(ca-2)表示的優選的陽離子，具體而言，可舉出二苯基錪陽離子、雙(4-叔丁基苯基)錪陽離子等。 作為前述式(ca-3)表示的優選的陽離子，具體而言，可舉出由下述式(ca-3-1)～(ca-3-6)分別表示的陽離子。
Figure 02_image043
作為前述式(ca-4)表示的優選的陽離子，具體而言，可舉出由下述式(ca-4-1)～(ca-4-2)分別表示的陽離子。
Figure 02_image045
另外，作為前述式(ca-5)表示的陽離子，還優選由下述通式(ca-5-1)～(ca-5-3)分別表示的陽離子。
Figure 02_image047
[式中，R’212 為烷基或氫原子。R’211 為烷基。] 上述中，陽離子部[(Qq+ )1/q ]優選通式(ca-1)表示的陽離子，更優選由式(ca-1-1)～(ca-1-47)分別表示的陽離子，進一步優選由式(ca-1-25)、(ca-1-29)、(ca-1-35)、(ca-1-47)分別表示的陽離子。 ・・(I2)成分 (I2)成分為下述通式(I2-1)或(I2-2)表示的化合物。
Figure 02_image049
[式中，Rb05 為可以具有取代基的氟化烷基、或氟原子。複數個Rb05 相互可以相同也可以不同。q為1以上的整數，Qq+ 為q價有機陽離子。]
Figure 02_image051
[式中，Rb06 為可以具有取代基的氟化烷基、或氟原子。複數個Rb06 相互可以相同也可以不同。q為1以上的整數，Qq+ 為q價有機陽離子。] ・・・陰離子部 前述式(I2-1)中，Rb05 為可以具有取代基的氟化烷基、或氟原子。複數個Rb05 相互可以相同也可以不同。 Rb05 中的氟化烷基的碳原子數優選為1～10，更優選為1～8，進一步優選為1～5。具體而言，可舉出碳原子數為1～5的烷基中，氫原子的一部分或全部被氟原子取代而得到的基。 其中，作為Rb05 ，優選氟原子或碳原子數為1～5的氟化烷基，更優選氟原子或碳原子數為1～5的全氟烷基，進一步優選氟原子、三氟甲基或五氟乙基。 式(I2-1)表示的化合物的陰離子部優選由下述通式(b0-2a)表示。
Figure 02_image053
[式中，Rbf05 為可以具有取代基的氟化烷基。nb1 為1～5的整數。] 式(b0-2a)中，作為Rbf05 中的可以具有取代基的氟化烷基，與前述Rb05 中列舉的、可以具有取代基的氟化烷基同樣。 式(b0-2a)中，nb1 優選為1～4的整數，更優選為2～4的整數，最優選為3。 前述式(I2-2)中，Rb06 為可以具有取代基的氟化烷基、或氟原子。複數個Rb06 相互可以相同也可以不同。 Rb06 中的氟化烷基的碳原子數優選為1～10，更優選為1～8，進一步優選為1～5。具體而言，可舉出碳原子數為1～5的烷基中，氫原子的一部分或全部被氟原子取代而得到的基。 其中，作為Rb06 ，優選氟原子或碳原子數為1～5的氟化烷基，更優選氟原子或碳原子數為1～5的全氟烷基，進一步優選氟原子。 ・・・陽離子部 式(I2-1)及式(I2-2)中，q為1以上的整數，Qq+ 各自獨立地為q價有機陽離子。 作為該Qq+ ，可舉出與上述式(I1)同樣的例子，其中，優選通式(ca-1)表示的陽離子，更優選由式(ca-1-1)～(ca-1-47)分別表示的陽離子，進一步優選由式(ca-1-25)、(ca-1-29)、(ca-1-35)、(ca-1-47)分別表示的陽離子。 ・・(I3)成分 (I3)成分為下述通式(I3-1)或(I3-2)表示的化合物。
Figure 02_image055
[式中，Rb11 ～Rb12 為可以具有鹵素原子以外的取代基的環式基、可以具有鹵素原子以外的取代基的鏈狀的烷基、或可以具有鹵素原子以外的取代基的鏈狀的烯基。m為1以上的整數，Mm+ 各自獨立地為m價有機陽離子。] {(I3-1)成分} ・・・陰離子部 式(I3-1)中，Rb12 為可以具有鹵素原子以外的取代基的環式基、可以具有鹵素原子以外的取代基的鏈狀的烷基、或可以具有鹵素原子以外的取代基的鏈狀的烯基，可舉出上述的R’201 的說明中的環式基、鏈狀的烷基、鏈狀的烯基中、不具有取代基的基或具有鹵素原子以外的取代基的基。 作為Rb12 ，優選為可以具有鹵素原子以外的取代基的鏈狀的烷基、或可以具有鹵素原子以外的取代基的脂肪族環式基。作為鏈狀的烷基，優選為碳原子數為1～10，更優選為3～10。作為脂肪族環式基，更優選為從金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷等中除去1個以上氫原子而成的基(可以具有鹵素原子以外的取代基)；從樟腦等中除去1個以上氫原子而成的基。 Rb12 的烴基可具有鹵素原子以外的取代基，作為該取代基，可舉出與前述式(I3-2)的Rb11 中的烴基(芳香族烴基、脂肪族環式基、鏈狀的烷基)可以具有的鹵素原子以外的取代基同樣的取代基。 此處所謂「可以具有鹵素原子以外的取代基」，不僅將具有僅由鹵素原子形成的取代基的情況排除，而且將具有包含鹵素原子(即使為1個)的取代基的情況(例如，取代基為氟化烷基的情況等)排除。 以下，展示出(I3-1)成分的陰離子部的優選的具體例。
Figure 02_image057
・・・陽離子部 式(I3-1)中，Mm+ 為m價有機陽離子。 作為Mm+ 的有機陽離子，可優選舉出與由上述通式(ca-1)～(ca-5)分別表示的陽離子同樣的例子，該等中，更優選上述通式(ca-1)表示的陽離子。其中，從解析度、粗糙特性提高方面考慮，特別優選上述通式(ca-1)中的R201 、R202 、R203 中的至少1個為可以具有取代基的碳原子數為16以上的有機基(芳基、雜芳基、烷基或烯基)的鋶陽離子。 作為前述的有機基可以具有的取代基，與上述同樣，可舉出由烷基、鹵素原子、鹵化烷基、羰基、氰基、氨基、氧代基(=O)、芳基、上述式(ca-r-1)～(ca-r-10)分別表示的基。 前述的有機基(芳基、雜芳基、烷基或烯基)中的碳原子數優選為16～25，更優選為16～20，特別優選為16～18，作為所述Mm+ 的有機陽離子，優選可舉出例如由上述式(ca-1-25)、(ca-1-26)、(ca-1-28)～(ca-1-36)、(ca-1-38)、(ca-1-46)、(ca-1-47)分別表示的陽離子。 {(I3-2)成分} ・・・陰離子部 式(I3-2)中，Rb11 為可以具有鹵素原子以外的取代基的環式基、可以具有鹵素原子以外的取代基的鏈狀的烷基、或可以具有鹵素原子以外的取代基的鏈狀的烯基，可舉出上述的R’201 的說明中的環式基、鏈狀的烷基、鏈狀的烯基中、不具有取代基的基或具有鹵素原子以外的取代基的基。 該等中，作為Rb11 ，優選可以具有鹵素原子以外的取代基的芳香族烴基、可以具有鹵素原子以外的取代基的脂肪族環式基、或可以具有鹵素原子以外的取代基的鏈狀的烷基。作為該等基可以具有的取代基，可舉出羥基、氧代基、烷基、芳基、含內酯的環式基、醚鍵、酯鍵、或它們的組合。 包含醚鍵、酯鍵作為取代基時，可以存在伸烷基，作為這種情況下的取代基，優選由下述通式(y-al-1)～(y-al-7)分別表示的連結基。
Figure 02_image059
[式中，V’101 為單鍵或碳原子數為1～5的伸烷基，V’102 為碳原子數為1～30的2價飽和烴基。] V’102 中的2價飽和烴基優選為碳原子數為1～30的伸烷基，更優選為碳原子數為1～10的伸烷基，進一步優選為碳原子數為1～5的伸烷基。 作為V’101 及V’102 中的伸烷基，可以為直鏈狀的伸烷基，也可以為支鏈狀的伸烷基，優選直鏈狀的伸烷基。 作為V’101 及V’102 中的伸烷基，具體而言，可舉出亞甲基[-CH2 -]；-CH(CH3 )-、-CH(CH2 CH3 )-、-C(CH3 )2 -、  -C(CH3 )(CH2 CH3 )-、-C(CH3 )(CH2 CH2 CH3 )-、-C(CH2 CH3 )2 -等烷基亞甲基；伸乙基[-CH2 CH2 -]；-CH(CH3 )CH2 -、    -CH(CH3 )CH(CH3 )-、-C(CH3 )2 CH2 -、-CH(CH2 CH3 )CH2 -等烷基伸乙基；三亞甲基(亞正丙基)[-CH2 CH2 CH2 -]； -CH(CH3 )CH2 CH2 -、-CH2 CH(CH3 )CH2 -等烷基三亞甲基；四亞甲基[-CH2 CH2 CH2 CH2 -]；-CH(CH3 )CH2 CH2 CH2 -、 -CH2 CH(CH3 )CH2 CH2 -等烷基四亞甲基；五亞甲基 [-CH2 CH2 CH2 CH2 CH2 -]等。 另外，V’101 或V’102 中的前述伸烷基中的一部分亞甲基可以被碳原子數為5～10的2價脂肪族環式基取代。該脂肪族環式基優選為從R’201 的環狀的脂肪族烴基(單環式的脂環式烴基、多環式的脂環式烴基)中進一步除去1個氫原子而成的2價基，更優選亞環己基、1,5-亞金剛烷基或2,6-亞金剛烷基。 作為前述芳香族烴基，更優選苯基或萘基。 作為前述脂肪族環式基，更優選為從金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷等多環烷中除去1個以上氫原子而成的基。 作為前述鏈狀的烷基，優選碳原子數為1～10，具體而言，可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀的烷基；1-甲基乙基、1-甲基丙基、2-甲基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丁基、2-乙基丁基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基等支鏈狀的烷基。 作為Rb11 ，優選可以具有鹵素原子以外的取代基的環式基。 以下，展示出(I3-2)成分的陰離子部的優選的具體例。
Figure 02_image061
・・・陽離子部 式(I3-2)中，Mm+ 為m價有機陽離子，與前述式(I3-1)中的Mm+ 同樣。 另外，從樹脂膜的高彈性化、及無殘渣、容易形成微細構造方面考慮，(I)成分優選為因曝光而產生pKa(酸解離常數)為-5以下的酸的光起始劑。藉由使用產生更優選pKa為-6以下、進一步優選pKa為-8以下的酸的光起始劑，可得到相對於曝光的高敏感度。(I)成分產生的酸的pKa的下限值優選為-15以上。藉由使用產生上述優選的pKa的酸的光起始劑，將會容易實現高敏感度化。 此處所謂「pKa(酸解離常數)」，是指作為表示物件物質的酸強度的指標而通常使用的指標。需要說明的是，本說明書中的pKa為25℃的溫度條件下的值。另外，pKa值可利用已知的方法進行測定而求出。另外，也可使用利用了「ACD/Labs」(商品名，Advanced Chemistry Development公司製)等已知的軟體的計算值。 以下舉出優選的(I)成分的具體例。
Figure 02_image063
Figure 02_image065
Figure 02_image067
作為(I)成分，可以單獨使用1種，也可並用2種以上。 (I)成分優選包含選自由(I1)成分、(I2)成分及(I3)成分所成群的2種以上。 其中，關於(I)成分，更優選組合使用(I1)成分與(I2)成分。或者，關於(I)成分，更優選組合使用選自由(I1)成分及(I2)成分所成群的1種以上、與(I3)成分。 關於(I)成分的含量，相對於(A)成分100質量份而言，優選為0.5～6.0質量份，更優選為1.0～5.0質量份，進一步優選為1.0～3.0質量份。 (I)成分的含量為前述的優選範圍的下限值以上時，能得到充分的敏感度，圖型的微影特性進一步提高。此外，能進一步提高硬化膜的強度。另一方面，為前述的優選範圍的上限值以下時，能適度地控制敏感度，將會容易得到良好的形狀的圖型。 ・其他成分 對於本實施方式的感光性樹脂膜而言，除了前述的(A)成分及(I)成分以外，根據需要可含有其他成分。 根據期望，可向實施方式的感光性樹脂膜中適當添加而含有具有混合性的添加劑、例如金屬氧化物、增感劑成分、矽烷耦合劑、溶劑、用於改良膜的性能的附加的樹脂、溶解抑制劑、鹼性化合物、塑化劑、穩定劑、著色劑、防暈影劑等。 ・・金屬氧化物 對於本實施方式的感光性樹脂膜而言，藉由不僅具有(A)成分及(I)成分、還同時具有金屬氧化物(以下，也稱為「(M)成分」)，從而能得到提高了強度的硬化膜。另外，可形成良好的形狀且高解析度的圖型。 作為(M)成分，可舉出例如矽(金屬矽)、鈦、鋯、鉿等金屬的氧化物。該等中，優選矽的氧化物，其中，更優選使用二氧化矽，特別優選以二氧化矽填料的形式使用。 另外，(M)成分的形狀優選為粒子狀。 作為所述粒子狀的(M)成分，優選由體積平均粒徑為5～40nm的粒子組形成的(M)成分，更優選由體積平均粒徑為5～30nm的粒子組形成的(M)成分，進一步優選由體積平均粒徑為10～20nm的粒子組形成的(M)成分。 (M)成分的體積平均粒徑為前述的優選範圍的下限值以上時，將會容易提高硬化膜的強度。另一方面，為前述的優選範圍的上限值以下時，在圖型的形成中，將不易產生殘渣，將容易形成更高解析度的圖型。 (M)成分的粒徑根據曝光光源適當選擇即可。通常，對於具有相對於光的波長而言為1/10以下的粒徑的粒子而言，可以基本不考慮光散射的影響。因此，例如，藉由利用i線(365nm)的微影法形成微細構造的情況下，作為(M)成分，優選使用1次粒徑(體積平均值)10～20nm的粒子組(特別優選二氧化矽粒子群)。 作為(M)成分，可以單獨使用1種，也可並用2種以上。 關於(M)成分的含量，相對於(A)成分100質量份而言，優選為10～30質量份，更優選為15～25質量份。 (M)成分的含量為前述的優選範圍的下限值以上時，能進一步提高硬化膜的強度。另一方面，為前述的優選範圍的上限值以下時，將會容易維持感光性樹脂組成物的流動性。 本實施方式的感光性樹脂膜含有(M)成分的情況下，關於(I)成分的含量，相對於(A)成分與(M)成分的總量100質量份而言，優選為1～5質量份，更優選為1.1～4質量份，進一步優選為1.5～3質量份。 (I)成分的含量為前述的優選範圍內時，能進一步提高硬化膜的強度，將會容易形成良好的形狀且高解析度的圖型。 本實施方式的感光性樹脂膜中，(A)成分的含量在前述的(A)成分、(I)成分與(M)成分的合計含量中所占的比例優選為35～90質量%，更優選為40～85質量%，進一步優選為45～80質量%。 所述(A)成分的含量為前述的優選範圍內時，不僅能進一步提高硬化膜的強度，而且製成感光性阻劑膜時的膜特性(層合性等)進一步提高。 ・・增感劑成分 實施方式的感光性樹脂膜可以進一步含有增感劑成分。 作為增感劑成分，沒有特別限制，只要是可吸收基於曝光的能量，將該能量傳遞至其他物質的物質即可。 作為增感劑成分，具體而言，可使用二苯甲酮、p,p’-四甲基二氨基二苯甲酮等二苯甲酮系光增感劑、哢唑系光增感劑、苯乙酮系光增感劑、1,5-二羥基萘等萘系光增感劑、苯酚系光增感劑、9-乙氧基蒽等蒽系光增感劑、雙乙醯、曙紅、玫瑰紅、芘、吩噻嗪、蒽酮等已知的光增感劑。 增感劑成分可以單獨使用1種，也可並用2種以上。 向實施方式的感光性樹脂膜中添加增感劑成分時，關於增感劑成分的含量，相對於(A)成分100質量份而言，優選為0.1～15質量份，更優選為0.3～10質量份，進一步優選為0.5～5質量份。 增感劑成分的含量為前述的優選範圍時，能進一步提高敏感度及解析度。 ・・矽烷耦合劑 對於實施方式的感光性樹脂膜而言，為了提高與支撐體的黏接性，可以進一步含有黏接助劑。作為該黏接助劑，優選矽烷耦合劑。 作為矽烷耦合劑，可舉出例如具有羧基、甲基丙烯醯基、異氰酸酯基、環氧基等反應性取代基的矽烷耦合劑。作為具體例，可舉出三甲氧基甲矽烷基苯甲酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等。 矽烷耦合劑可以單獨使用1種，也可並用2種以上。 向實施方式的感光性樹脂膜中添加矽烷耦合劑時，關於矽烷耦合劑的含量，相對於(A)成分100質量份而言，優選為2.5～20質量份，更優選為3～15質量份，進一步優選為3～10質量份。 矽烷耦合劑的含量為前述的優選範圍時，能進一步提高硬化膜的強度。此外，能進一步增強硬化膜與支撐體的黏接性。 《溶劑》 實施方式的感光性樹脂膜可藉由將感光性材料溶解或分散於溶劑(以下，稱為「(S)成分」)中來製造。 作為(S)成分，可舉出例如γ-丁內酯等內酯類；丙酮、甲基乙基酮(MEK)、環己酮、甲基正戊基酮、甲基異戊基酮、2-庚酮等酮類；乙二醇、二乙二醇、丙二醇、二丙二醇等多元醇類；乙二醇單乙酸酯、二乙二醇單乙酸酯、丙二醇單乙酸酯、或二丙二醇單乙酸酯等具有酯鍵的化合物、前述多元醇類或前述具有酯鍵的化合物的單甲基醚、單乙基醚、單丙基醚、單丁基醚等單烷基醚或單苯基醚等具有醚鍵的化合物等多元醇類的衍生物[該等中，優選乙酸甲氧基丁酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單甲基醚(PGME)]；二氧雜環己烷此種環式醚類、乳酸甲酯、乳酸乙酯(EL)、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等酯類；苯甲醚、乙基苄基醚、甲苯基甲基醚、二苯基醚、二苄基醚、苯乙醚、丁基苯基醚、乙基苯、二乙基苯、戊基苯、異丙基苯、甲苯、二甲苯、傘花烴、均三甲苯等芳香族系有機溶劑、二甲基亞碸(DMSO)等。 (S)成分可以單獨使用1種，也可以以2種以上的混合溶劑的形式使用。 (S)成分的使用量沒有特別限制，可以以可塗布於基板等的濃度，根據塗布膜厚適當設定。 關於感光性樹脂組成物中的(S)成分的含量，相對於感光性樹脂組成物的總量(100質量%)而言，優選為1～25質量%，更優選為5～20質量%。 (中空封裝體的製造方法) 本發明的第2方式涉及的製造方法為具有利用密封材料將利用上述的第1方式涉及的製造方法製造的中空構造體密封從而得到中空封裝體的步驟的、中空封裝體的製造方法。 作為密封材料，例如可使用樹脂組成物。密封材料中可使用的樹脂沒有特別限制，只要是能使中空構造體進行密封及絕緣中的至少一方的樹脂即可，可舉出例如環氧系樹脂或聚矽氧烷系樹脂等。 對於密封材料而言，除了樹脂以外還可以包含填料等其他成分。 利用密封材料將中空構造體密封的方法沒有特別限制，以覆蓋中空構造體的方式，將經加熱熔融的密封材料向中空構造體上供給，進行壓縮成型，由此，製作在中空構造體上設置有密封材料層的中空封裝體。 前述密封材料層具有保護中空構造體內的MEMS、配線部位等免受外部環境影響的功能。 利用本方式涉及的製造方法製造的中空封裝體具備利用上述的第1方式涉及的製造方法製造的中空構造體100，因此，在密封時、或導體圖型與引線框(lead frame)的一併連接時，或基於切割(dicing)等的基板的分割等時，可抑制中空構造體變形等不良情況的發生。因此，能可靠地保持中空構造體內部的空間，可提供可靠性高的微型裝置。 實施例 以下，藉由實施例進一步詳細地說明本發明，但本發明不受該等例子的限制。各製造例的說明中的「份」表示質量份。 ＜負型感光性樹脂組成物的調製＞ (調製例1～4) 將表1所示的各成分混合，將其溶解，使用PTFE過濾器(孔徑為1μm，PALL公司製)進行過濾，分別調製各例的負型感光性樹脂組成物(固態成分約為84～86質量%的MEK溶液)。
Figure 02_image069
表1中，各縮寫分別具有以下的含義。[ ]內的數值為各成分的摻合量(質量份；按照固態成分換算)。 (A)-1：下述化學式(A11)表示的含環氧基的樹脂。商品名「JER-157S70」，Mitsubishi Chemical Corporation製。
Figure 02_image071
(A)-2：下述化學式(m1-1)表示的化合物。商品名「Celloxide 8000」，Daicel Corporation製。 (A)-3：下述化學式(m2-1)表示的化合物。商品名「TEPIC-VL」，日產化學股份有限公司製。
Figure 02_image073
(I)-1：下述化學式(I1-4)表示的光起始劑。商品名「Irgacure290」，BASF公司製。 (I)-3：下述化學式(I1-1)表示的光起始劑。商品名「CPI-310B」，San-Apro Ltd.製。 (I)-4：下述化學式(I1-3)表示的光起始劑。商品名「CPI-410B」，San-Apro Ltd.製。 (I)-5：下述化學式(I2-1-2)表示的光起始劑。商品名「CPI-410S」，San-Apro Ltd.製。
Figure 02_image075
(I)-2：下述化學式(I3-1-1)表示的光起始劑。商品名「HS-1CS」，San-Apro Ltd.製。
Figure 02_image077
(C)-1：二氧化矽填料。商品名「MEK-EC-2130Y」，日產化學股份有限公司製。1次粒徑φ=15nm(體積平均值)。二氧化矽成分濃度31質量%的甲基乙基酮分散液。 (D)-1：增感劑。α萘酚。 (E)-1：矽烷耦合劑。商品名「Shin-Etsu Silicone(注冊商標)OFS6040SILANE」，信越化學工業股份有限公司製。 (E)-2：矽烷耦合劑。商品名「Shin-Etsu Silicone(注冊商標)X-12-967C」，信越化學工業股份有限公司製。 (S)-1：溶劑。甲基乙基酮。 ＜中空構造體的製造方法＞ 作為基材膜，使用了聚矽氧烷系表面脫模處理PET膜(商品名「A53」，帝人股份有限公司製)。 (實施例1) 步驟(0)： 使用塗敷器，將調製例1的負型感光性樹脂組成物塗布於前述基材膜上，在烘箱中進行溫度60℃、5分鐘的加熱後，進行70℃、10分鐘的烘烤處理(PAB)，由此，形成膜厚為30μm的感光性樹脂膜，得到感光性阻劑膜(1)。 另外，準備在表面具有凹部的高低差基板。 步驟(i)： 以前述感光性阻劑膜(1)的感光性樹脂膜表面封堵前述高低差基板中的前述凹部的開口面的方式，配置前述感光性阻劑膜(1)。 在前述步驟(i)後，進行從前述感光性阻劑膜(1)的感光性樹脂膜剝離前述基材膜的操作。 步驟(ii)： 接下來，使用Canon PLA-501 ghi線 對準曝光機(aligner)，對前述感光性樹脂膜進行300mJ/cm2 (換算為i線)曝光。 步驟(iii)： 針對前述步驟(ii)中的曝光後的感光性樹脂膜，用加熱板進行溫度90℃、5分鐘的加熱處理。 步驟(iv)： 針對前述步驟(iii)中的加熱處理後的感光性樹脂膜，使用丙二醇單甲基醚乙酸酯作為顯影液，於23℃進行旋覆浸沒顯影，由此，形成成為頂板部的負型圖型。 步驟(v)： 針對前述步驟(iv)後的前述負型圖型，進一步在烘箱中進行下述分步硬化(Step cure)條件的加熱處理，由此，使其硬化，得到頂板部由感光性樹脂膜的硬化體形成的中空構造體(中空構造部分的高度方向截面為長方形：縱(高度)200μm×橫500μm)。 分步硬化條件的加熱處理： 在烘箱中，於溫度60℃，進行60分鐘的加熱處理，然後，在烘箱中，於溫度100℃，進行30分鐘的加熱處理，然後，進而在烘箱中，於溫度160℃，進行30分鐘的加熱處理，然後，在烘箱中，於溫度200℃，進行60分鐘的加熱處理。 (實施例2) 前述步驟(v)中，針對前述步驟(iv)後的前述負型圖型，照射1000mJ/cm2 紫外線後，在烘箱中，於溫度160℃，進行60分鐘的加熱處理，除此之外，與實施例1同樣地操作，得到中空構造體。 (實施例3) 前述步驟(v)中，將針對前述步驟(iv)後的前述負型圖型的紫外線的照射量變更為5000mJ/cm2 ，除此之外，與實施例2同樣地操作，得到中空構造體。 (實施例4) 前述步驟(v)中，將針對前述步驟(iv)後的前述負型圖型的紫外線的照射量變更為10000mJ/cm2 ，除此之外，與實施例2同樣地操作，得到中空構造體。 (實施例5) 將調製例1的負型感光性樹脂組成物變更為調製例2的負型感光性樹脂組成物，除此之外，與實施例1同樣地操作，得到中空構造體。 (實施例6) 將調製例1的負型感光性樹脂組成物變更為調製例3的負型感光性樹脂組成物，除此之外，與實施例1同樣地操作，得到中空構造體。 (實施例7) 將調製例1的負型感光性樹脂組成物變更為調製例4的負型感光性樹脂組成物，除此之外，與實施例1同樣地操作，得到中空構造體。 (實施例8) 將調製例1的負型感光性樹脂組成物變更為調製例2的負型感光性樹脂組成物，除此之外，與實施例2同樣地操作，得到中空構造體。 (實施例9) 將調製例1的負型感光性樹脂組成物變更為調製例3的負型感光性樹脂組成物，除此之外，與實施例2同樣地操作，得到中空構造體。 (實施例10) 將調製例1的負型感光性樹脂組成物變更為調製例4的負型感光性樹脂組成物，除此之外，與實施例2同樣地操作，得到中空構造體。 (比較例1) 前述步驟(v)中，針對前述步驟(iv)後的前述負型圖型，進一步在烘箱中於200℃進行60分鐘的加熱處理，除此之外，與實施例1同樣地操作，得到中空構造體。 (比較例2) 前述步驟(v)中，針對前述步驟(iv)後的前述負型圖型，進一步在烘箱中於160℃進行60分鐘的加熱處理，除此之外，與實施例1同樣地操作，得到中空構造體。 (比較例3) 前述步驟(v)中，針對前述步驟(iv)後的前述負型圖型，進一步在烘箱中於160℃進行60分鐘的加熱處理，除此之外，與實施例5同樣地操作，得到中空構造體。 (比較例4) 前述步驟(v)中，針對前述步驟(iv)後的前述負型圖型，進一步在烘箱中於160℃進行60分鐘的加熱處理，除此之外，與實施例6同樣地操作，得到中空構造體。 (比較例5) 前述步驟(v)中，針對前述步驟(iv)後的前述負型圖型，進一步在烘箱中於160℃進行60分鐘的加熱處理，除此之外，與實施例7同樣地操作，得到中空構造體。 ＜評價＞ 對得到的各例的中空構造體中的頂板部的變形及強度進行評價。 對於所述評價而言，分別按照以下方式，對頂板部鼓起、構成頂板部的硬化膜的拉伸彈性模量E*進行評價。 [頂板部鼓起] 將剛製造後的中空構造體沿高度方向切斷，使用Dektak表面高低差計，測定中空構造部分的高度方向的變形(頂板部鼓起)的程度。 而且，按照下述的評價基準，將該結果作為「頂板部鼓起(μm)」，展示於表2～4。()內的數值表示頂板部的鼓起最大的部位的變形量(μm)。 評價基準 ○：中空構造部分的高度方向的變形為5μm以下。 ×：中空構造部分的高度方向的變形超過5μm。 [硬化膜的拉伸彈性模量E*的測定] 按照以下方式，測定構成步驟(v)中得到的中空構造體的頂板部的硬化膜的拉伸彈性模量E*。 將硬化膜從矽晶圓剝離，藉由以下的評價裝置及測定條件，測定175℃時的硬化膜的拉伸彈性模量E*。將該結果作為「拉伸彈性模量E*(GPa)」，展示於表2～4。 ・評價裝置：Reogel E-4000(UBM公司製) ・測定條件：拉伸模式，頻率為1.0Hz，夾頭間距離為10mm 該拉伸彈性模量E*越高，表示硬化膜的強度越高。 [表2]    實施例1 實施例2 實施例3 實施例4 負型感光性樹脂組成物 調製例1 調製例1 調製例1 調製例1 步驟(v)中 的操作 - 紫外線照射 1000 mJ/cm2 紫外線照射 5000 mJ/cm2 紫外線照射 10000 mJ/cm2 加熱處理 分步硬化 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 頂板部鼓起 (μm) ○(4) ○(2) ○(2) ○(1.5) 拉伸彈性模量E*(GPa) 2.1 2.1 2.1 2.1 [表3]    實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 負型感光性 樹脂組成物 調製例2 調製例3 調製例4 調製例2 調製例3 調製例4 步驟(v)中 的操作 - - - 紫外線 照射 1000 mJ/cm2 紫外線 照射 1000 mJ/cm2 紫外線 照射 1000 mJ/cm2 加熱處理 分步硬化 加熱處理 分步硬化 加熱處理 分步硬化 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 頂板部鼓起 (μm) ○(3) ○(2) ○(2) ○(2) ○(1) ○(1) 拉伸彈性 模量E* (GPa) 1.0 1.1 1.1 1.0 1.1 1.1 [表4]    比較例1 比較例2 比較例3 比較例4 比較例5 負型感光性樹脂組成物 調製例1 調製例1 調製例2 調製例3 調製例4 步驟(v)中 的操作 - - - - - 加熱處理 200℃ 60分鐘 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 加熱處理 160℃ 60分鐘 頂板部鼓起 (μm) ×(12) ×(8) ×(7) ○(5) ○(5) 拉伸彈性 模量E* (GPa) 2.1 1.3 0.6 0.7 0.7 根據表2及4所示的結果，藉由負型感光性樹脂組成物同樣的實施例1～4與比較例1～2的對比可知，對於實施例1～4的中空構造體而言，因其製造時的硬化操作而導致的頂板部鼓起均被抑制為低水準。進而可知，實施例1～4的中空構造體具有充分的強度。 另一方面，確認到比較例1的中空構造體雖然具有充分的強度，但因其製造時的硬化操作而導致的頂板部鼓起大。對於比較例2的中空構造體而言，分別確認到因其製造時的硬化操作而導致的頂板部鼓起大，而且，與實施例1～4的中空構造體相比，強度差。 根據表3及4所示的結果，藉由負型感光性樹脂組成物同樣的實施例5、8與比較例3的對比可知，對於實施例5、8的中空構造體而言，因其製造時的硬化操作而導致的頂板部鼓起均被抑制為低水準。另一方面，對於比較例3的中空構造體而言，確認到因其製造時的硬化操作而導致的頂板部鼓起大。 另外，對於實施例5、8的中空構造體而言，均確認到與比較例3的中空構造體相比強度高。 根據表3及4所示的結果，藉由負型感光性樹脂組成物同樣的實施例6、9與比較例4的對比可知，對於實施例6、9及比較例4的中空構造體而言，因其製造時的硬化操作而導致的頂板部鼓起均被抑制為低水準。藉由兩者的對比可知，實施例6、9的中空構造體與比較例4的中空構造體相比，因其製造時的硬化操作而導致的頂板部鼓起被進一步抑制為低水準。 另外可知，對於實施例6、9的中空構造體而言，均與比較例4的中空構造體相比強度高。 根據表3及4所示的結果，藉由負型感光性樹脂組成物同樣的實施例7、10與比較例5的對比可知，對於實施例7、10及比較例5的中空構造體而言，因其製造時的硬化操作而導致的頂板部鼓起均被抑制為低水準。藉由兩者的對比可知，實施例7、10的中空構造體與比較例5的中空構造體相比，因其製造時的硬化操作而導致的頂板部鼓起被進一步抑制為低水準。 另外可知，對於實施例7、10的中空構造體而言，均與比較例5的中空構造體相比強度高。 因此確認到，藉由應用本發明，能抑制因硬化操作而導致的頂板部的變形、並且能穩定地製造強度被進一步提高的中空構造體。In the present specification and the scope of the patent application, "aliphatic" is a relative concept with respect to aromatic, and is defined as a concept indicating a group without aromaticity, a compound without aromaticity, or the like. The "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. The "alkylene" includes linear, branched and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The "halogenated alkyl group" is a group obtained by substituting a part or all of hydrogen atoms of an alkyl group with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "fluorinated alkyl group" refers to a group obtained by substituting a part or all of the hydrogen atoms of an alkyl group with a fluorine atom. "Constituent unit" refers to a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer). When it is described as "which may have a substituent", it includes the case of substituting a hydrogen atom (-H) with a monovalent group, and the case of substituting a methylene group (-CH) with a divalent group.2 -) in the case of both. "Exposure" is a concept including the entire irradiation of radiation. (Manufacturing method of hollow structure) The manufacturing method according to the first aspect of the present invention is a method for manufacturing a hollow structure formed of a recess and a top plate portion that closes an opening surface of the recess, and includes the following steps (0) and steps (i) to (v) ). Furthermore, in the production method according to the first aspect, after heating at a temperature of 150° C. or lower for 10 minutes or more, the operation (x) of further heating at a temperature higher than 150° C. The operation (y) of heating is performed at the temperature, and the heat treatment in the aforementioned step (v) is performed. Step (0): Prepare a substrate having a concave portion on the surface, and a photoresist with a negative photosensitive resin film containing an epoxy group-containing resin (A) and a photoinitiator (I) that generates acid by exposure The steps of the film Step (i): the step of arranging the photosensitive resist film so that the photosensitive resin film surface of the photosensitive resist film blocks the opening surface of the concave portion in the substrate Step (ii): after the aforementioned step (i), the step of exposing the aforementioned photosensitive resin film Step (iii): the step of heat-treating the photosensitive resin film after the step (ii) Step (iv): after the aforementioned step (iii), developing the aforementioned photosensitive resin film to form a negative pattern Step (v): The negative pattern after the above step (iv) is further subjected to heat treatment to be cured to obtain a hollow structure in which the top plate portion is formed of the cured body of the photosensitive resin film. step The hollow structure manufactured by the manufacturing method which concerns on this aspect is formed of the recessed part and the top plate part which blocks the opening surface of this recessed part. This hollow structure can be suitably used for a hollow package that can be utilized in SAW filters, MEMS, various sensors, and the like. [step (0)] In the step (0) in this aspect, a substrate having a recessed portion on the surface, and a negative photosensitive resin having an epoxy group-containing resin (A) and a photoinitiator (I) that generates acid by exposure are prepared Photoresist film for film. "About a substrate having a concave portion on the surface" As a board|substrate which has a recessed part on the surface, the structure which formed the pattern on a board|substrate, a level|step difference board|substrate, etc. are mentioned. In addition, this recessed part may be comprised from an organic material, and may be comprised from an inorganic material. Such a substrate having recesses on the surface can be produced, for example, by a method having a step of forming a photosensitive resin film on a support using a negative photosensitive resin composition (hereinafter, referred to as "film forming step"). "); the step of exposing the photosensitive resin film (hereinafter, referred to as "exposure step"); the photosensitive resin film after the exposure is developed with a developing solution containing an organic solvent to form a negative image of the side wall of the concave portion type step (hereinafter, referred to as "development step"). The method of manufacturing the board|substrate which has such a recessed part on the surface can be performed as follows. Film formation steps: First, the negative photosensitive resin composition is coated on the support by known methods such as spin coating, roll coating, screen printing, etc., and is subjected to baking (post-coating bake (PAB)) treatment, for example It implements for 2 to 60 minutes under the temperature condition of 50-150 degreeC, and forms a photosensitive resin film. In addition, this film formation process can also be performed by arrange|positioning the photosensitive resin composition layer produced in advance using a negative photosensitive resin composition on a support body. The support is not particularly limited, and a conventionally known support can be used, and examples thereof include a substrate for electronic components, a substrate for electronic components on which a predetermined wiring pattern is formed, and the like. As a substrate for electronic components, more specifically, silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3 ), niobium, lithium niobate (LiNbO3 ), palladium, titanium tungsten, copper, chromium, iron, aluminum and other metal substrates, glass substrates, etc. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used. The film thickness of the photosensitive resin film formed from the negative photosensitive resin composition is not particularly limited, but is preferably about 10 to 100 μm. Exposure steps: Next, the formed photosensitive resin film is exposed through a mask (mask pattern) having a predetermined pattern formed thereon using a known exposure apparatus, or by using a After selective exposure such as drawing by direct irradiation of electron beams, if necessary, for example, under temperature conditions of 80 to 150° C., baking is performed for 40 to 1200 seconds, preferably 40 to 1000 seconds, more preferably 60 to 900 seconds (Post-Exposure Bake (PEB)) treatment. The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, i-rays (wavelength of 365 nm), or visible rays are selectively irradiated (exposed). As the radiation source of these radiations, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used. Here, radiation refers to ultraviolet rays, visible rays, extreme ultraviolet rays, X-rays, electron beams, and the like. The amount of radiation exposure varies depending on the type of each component in the composition, the blending amount, the film thickness of the coating film, etc., but for example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ/cm2 . The exposure method of the photosensitive resin film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be liquid immersion exposure (Liquid Immersion Lithography). Development steps: Next, the photosensitive resin film after the above-mentioned exposure is developed with a developer (organic developer) containing an organic solvent. After development, rinse treatment is preferably performed. If necessary, baking treatment (post-baking) can be performed. The organic solvent contained in the organic developer can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, hydrocarbon-based solvents, and the like can be mentioned. Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl ketone. ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetone, acetone acetone, ionone, diacetone alcohol, acetone methanol, Acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, as the ketone-based solvent, methyl amyl ketone (2-heptanone) is preferable. Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, and propylene glycol. Monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl Ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether ethyl Acetate, Diethylene Glycol Monobutyl Ether Acetate, Diethylene Glycol Monoethyl Ether Acetate, 2-Methoxybutyl Acetate, 3-Methoxybutyl Acetate, 4-Methoxy Acetate butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxyacetate Amyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methyl acetate Oxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactic acid Propyl, Ethyl Carbonate, Propyl Carbonate, Butyl Carbonate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Butyl Pyruvate, Methyl Acetate, Ethyl Acetate, Methyl Propionate ester, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate acid ethyl ester, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Among these, as the ester solvent, butyl acetate or PGMEA is preferable. As a nitrile-type solvent, acetonitrile, propionitrile, valeronitrile, butyronitrile, etc. are mentioned, for example. If necessary, known additives may be blended with the organic developer. As this additive, a surfactant is mentioned, for example. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or silicon-based surfactant can be used. As the surfactant, a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable. When a surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass relative to the total amount of the organic developer. The development treatment can be carried out by a known development method, for example, a method of immersing the support in a developing solution for a certain period of time (dipping method), depositing the developing solution on the surface of the support by surface tension, and allowing it to stand for a certain period of time. method (puddle development method), method of spraying the developer onto the surface of the support (spray method), while scanning the developer discharge nozzle at a constant speed on the support rotating at a constant speed, while A method of continuously discharging the developer (dynamic dispense method) and the like. The rinsing treatment (washing treatment) using the rinsing solution can be carried out by a known rinsing method. As a method of this rinsing treatment, for example, a method of continuously discharging a rinsing liquid onto a support rotating at a constant speed (spin coating method), and a method of immersing the support in the rinsing liquid for a certain period of time (dipping method) ), the method of spraying the rinse solution on the surface of the support (spray method), etc. The rinse treatment preferably uses a rinse solution containing an organic solvent. Through the above-mentioned film formation step, exposure step, and development step, a substrate having a concave portion on the surface (a structure having a pattern formed on the substrate, a step substrate) can be produced. The thickness of the side wall (dimension in the horizontal direction relative to the support body) and height (dimension in the vertical direction relative to the support body) can be based on the size of the hollow portion determined according to the type of electronic device housed in the recessed portion appropriate settings. 《About photoresist film》 The photoresist film in this aspect has epoxy group-containing resin (A) (hereinafter, referred to as "component (A)".) and a photoinitiator (I) (hereinafter, referred to as "component (A)") that generates acid by exposure A negative photosensitive resin film called "(I) component"). The components constituting the photosensitive resist film will be described in detail later. When a photosensitive resin film is formed using the photosensitive resist film, and the photosensitive resin film is selectively exposed to light, an acid is generated from the component (I) in the exposed portion of the photosensitive resin film, and the Due to the action of an acid, the epoxy group in the component (A) undergoes ring-opening polymerization, and the solubility of the component (A) in a developing solution containing an organic solvent decreases. On the other hand, in the unexposed part of the photosensitive resin film Since the solubility of the component (A) in the developing solution containing the organic solvent does not change, the dissolution in the developing solution containing the organic solvent occurs between the exposed part and the unexposed part of the photosensitive resin film. gender differences. That is, this photosensitive resin film is a negative type. Therefore, when the photosensitive resin film is developed with a developing solution containing an organic solvent, the unexposed part can be dissolved and removed, and a negative pattern can be formed. Here, the negative photosensitive resin film which the photosensitive resist film has is comprised typically from the resin material of a B-stage (B-Stage) shape (semi-cured state). As a photosensitive resist film, the photosensitive resist film formed from the laminated film which laminated|stacked the photosensitive resin film on the base film is mentioned. The photosensitive resist film can be produced by applying the negative photosensitive resin composition obtained by dissolving the (A) component and the (I) component in a solvent on a base film and drying it, Thus, a photosensitive resin film is formed. For the coating of the negative photosensitive resin composition on the base film, an applicator, a blade coater, a lip coater, and a comma coater are used. ), a film coater or the like by an appropriate method. The thickness of the photosensitive resin film is preferably 100 μm or less, and more preferably 5 to 50 μm. As the base film, a known base film can be used, for example, a thermoplastic resin film or the like can be used. As this thermoplastic resin, polyester, such as polyethylene terephthalate, is mentioned, for example. The thickness of the base film is preferably 2 to 150 μm. In the manufacturing method of the hollow structure of this form, using the board|substrate which has a recessed part on the surface prepared in the said process (0), and a photosensitive resist film, process (i) - process (v) are performed. As a manufacturing method of a hollow structure, the 1st Embodiment shown below, and a 2nd Embodiment, respectively, are mentioned, for example. Hereinafter, each embodiment of the manufacturing method of a hollow structure is demonstrated, referring drawings. <First Embodiment> In step (0), when preparing a photoresist film formed of a laminated film in which a photosensitive resin film is laminated on a base film as the photosensitive resist film, step (i) and step (ii) are performed in this order. ), step (iii), step (iv), step (v). Moreover, after heating for 10 minutes or more at a temperature of 150°C or lower, the heat treatment in the aforementioned step (v) is performed by operation (x) of further heating at a temperature higher than 150°C. FIG. 1 is a schematic diagram illustrating a method of manufacturing the hollow structure according to the first embodiment. In FIG. 1, the board|substrate which has the recessed part 15 on the surface is comprised by the board|substrate 10 and the side wall 20 formed in the board|substrate 10. As the photosensitive resist film, a photosensitive resist film formed of a laminate film 80 in which the photosensitive resin film 30 was laminated on the base film 50 was used. In this embodiment, the side wall 20 is formed of a photosensitive resin material. The photosensitive resin material which forms the side wall 20 may be the same material as the photosensitive resin film which comprises the top plate part, and a different material may be sufficient as it. [Step (i)] In step (i), the build-up film 80 is arranged so that the surface of the photosensitive resin film 30 of the photosensitive resist film (the build-up film 80 ) blocks the opening surface of the concave portion 15 in the substrate 10 . In FIG. 1 , the build-up film 80 is arranged so as to face the substrate 10 with the side wall 20 interposed therebetween. Furthermore, a hollow airtight space surrounded by the substrate 10 , the side walls 20 , and the photosensitive resin film 30 is formed. [Step (D)] In step (D), after step (i), the base film 50 is peeled off from the photosensitive resin film 30 in the laminate film 80 . [Step (ii)] In step (ii), the photosensitive resin film 30 is exposed to light. For example, the photosensitive resin film 30 is selectively exposed through a photomask 60 on which a predetermined pattern is formed using a known exposure apparatus. The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet rays having a wavelength of 300 to 500 nm, i-rays (wavelength of 365 nm), or visible rays are selectively irradiated (exposed). As the radiation source of these radiations, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used. [Step (iii)] In step (iii), the photosensitive resin film 30 after exposure is subjected to heat treatment, so-called post-exposure bake (PEB) treatment. The PEB treatment is performed, for example, at a temperature of 80 to 150° C. for 40 to 600 seconds, preferably 60 to 300 seconds. By the heat treatment in step (iii), the photosensitive resin film 30 after exposure becomes the exposed part 30A in which the epoxy group in (A) component undergoes ring-opening polymerization, and the unexposed part 30B which does not change. [Step (iv)] In step (iv), the PEB-treated photosensitive resin film 30 is developed to form a negative pattern. The development here can be performed in the same manner as the development step in the above-mentioned [Step (0)]. After development, rinse treatment is preferably performed. By the development in step (iv), the unexposed portion 30B can be dissolved and removed, and the exposed portion 30A serving as the top plate portion can be left as a negative pattern to form an image. [Step (v)] In step (v), heat treatment (hardening operation) is further performed on the developed negative pattern (exposure portion 30A), thereby being hardened, and a top plate portion formed of the hardened body 40 of the photosensitive resin film 30 is obtained. The hollow structure 100 . In FIG. 1, in the cured body 40, the photosensitive resin material and the photosensitive resin film 30 which form the side wall 20 are each hardened and integrated. The heat treatment in step (v) is performed by operation (x) of heating at a temperature of 150° C. or lower for 10 minutes or more (first heating), and further heating at a temperature higher than 150° C. (second heating). Regarding operation (x): The operation (x) is an operation of further performing the second heating after the first heating. The first heating is a step of heating at a temperature of 150° C. or lower for 10 minutes or more. The temperature during the first heating and the duration thereof are preferably 50°C or higher and 150°C or lower, more preferably 50°C or higher and 125°C or lower, preferably 30 minutes or more and 120 minutes or less, and more preferably 60 minutes or more and 90 minutes the following. The heating operation in the first heating may be performed in one step, or may be performed in two or more steps. For example, in the case of performing the first heating in two steps, preferably, the heating operation in the first heating is performed by heating at a temperature of 50° C. or higher and 90° C. or lower for 30 minutes or more and 90° C. After minutes or less, it is further heated at a temperature higher than 90° C. and 150° C. or lower for 10 minutes or more and 60 minutes or less. The second heating is a step of heating at a temperature higher than 150°C. The temperature during the second heating and the duration thereof are preferably higher than 150°C and 250°C or lower, more preferably 160°C or higher and 220°C or lower, preferably 30 minutes or higher and 120 minutes or lower, more preferably 60 minutes or longer and under 90 minutes. The heating operation in the second heating may be performed in one step, or may be performed in two or more steps. For example, when the second heating is performed in two steps, preferably, the heating operation in the second heating is performed by heating at a temperature higher than 150° C. and 180° C. or lower for 10 minutes or more. And after 60 minutes or less, it further heats for 30 minutes or more and 90 minutes or less at the temperature higher than 180 degreeC and 220 degrees C or less. In the method for producing the hollow structure according to the first embodiment, as the operation (x), it is preferable to perform the following operation at 50° C. or higher and 125° C. from the viewpoint that deformation of the top plate portion can be suppressed and the strength can be further easily improved. After heating at the following temperature for 10 minutes or more, an operation of further heating at a temperature of 160° C. or more for 30 minutes or more. Moreover, in the said operation (x), it is preferable to perform a 1st heating by two or more steps, and to perform a 2nd heating by two or more steps. Furthermore, from the viewpoint of productivity (time cycle, etc.), in the above-mentioned operation (x), it is more preferable that the first heating is performed in two steps, and the second heating is also performed in two steps. . In the manufacturing method of the hollow structure according to the first embodiment described above, after heating at a temperature of 150° C. or lower for 10 minutes or more, and further heating at a temperature higher than 150° C., the operation (x) is performed in the step. Heat treatment (hardening operation) in (v). By heating the negative pattern (exposure portion 30A) after development while increasing the temperature from the low temperature side lower than 150° C. to the high temperature side higher than 150° C. as described above, during the hardening operation, Compared with the prior art, the expansion of the air in the hollow can be suppressed and the internal pressure can be reduced, and the hardening can be sufficiently advanced. Therefore, according to the first embodiment, the deformation of the top plate portion due to the hardening operation can be suppressed, and the hollow structure with further improved strength can be stably produced. <Second Embodiment> In step (0), when preparing a photoresist film formed of a laminated film in which a photosensitive resin film is laminated on a base film as the photosensitive resist film, step (i) and step (ii) are performed in this order. ), step (iii), step (iv), step (v'). Further, the heat treatment in the above-mentioned step (v') is performed by the operation (y) of heating at a temperature of 100°C or higher after irradiation with ultraviolet rays. The description of step (i), step (ii), step (iii) and step (iv) in the second embodiment is the same as that of step (i), step (ii), step ( iii) and the description of step (iv) are the same. [step (v')] In step (v'), heat treatment (hardening operation) is further performed on the negative pattern (exposure portion) after development, thereby being hardened to obtain a hollow structure in which the top plate portion is formed of the hardened body of the photosensitive resin film body. The heat treatment in the step (v') is performed by the operation (y) of heating at a temperature of 100°C or higher after irradiation with ultraviolet rays. Regarding operation (y): The operation (y) is an operation of heating after irradiation with ultraviolet rays. The irradiation of ultraviolet rays is preferably 1,000 to 10,000 mJ/cm, for example.2 dose of irradiation. The heating in operation (y) is heating at a temperature of 100°C or higher. The temperature of the heating in operation (y) is preferably 100°C or more and 200°C or less, more preferably 150°C or more and 180°C or less, preferably 15 minutes or more and 120 minutes or less, and more preferably 30 minutes or more. and less than 90 minutes. The heating operation in the operation (y) may be performed by one step, or may be performed by two or more steps. In the method for producing a hollow structure according to the second embodiment, as the operation (y), it is preferable to perform the following operation: irradiating at 1000 to 10000 mJ/cm, from the viewpoint that deformation of the top plate portion can be suppressed and the strength can be further easily improved.2 After ultraviolet rays, it is heated at a temperature of 160° C. or more for 30 minutes or more. In the manufacturing method of the hollow structure according to the second embodiment described above, the heat treatment (hardening) in the step (v) is performed by the operation (y) of heating at a temperature of 100° C. or higher after irradiation with ultraviolet rays. operate). The heating temperature of the hardening operation can be set to a low value by heating after irradiating ultraviolet rays with respect to the negative pattern (exposed part) after development as described above. Thereby, the expansion of the air in the hollow can be suppressed compared with the past, and the internal pressure can be reduced. Moreover, hardening of the negative pattern (exposed part) after image development can fully progress. Therefore, according to 2nd Embodiment, the deformation|transformation of the top-plate part by a hardening operation can be suppressed, and the hollow structure whose intensity|strength is further improved can be manufactured stably. <Other Embodiments> The method for producing the hollow structure according to the above-described embodiment has been described with reference to a case where a photosensitive resist film formed of a laminate film in which a photosensitive resin film is laminated on a base film is prepared as a photosensitive resist film. However, it is not limited to this. For example, a single-layer photosensitive resist film formed of a photosensitive resin film may be prepared, or a laminate formed by laminating a photosensitive resin film and a cover film in this order on a base film may be formed. the case of the photoresist film. As the cover film, a known cover film can be used, and for example, a polyethylene film, a polypropylene film, or the like can be used. As a coverlay film, the film whose adhesive force with a photosensitive resin film is smaller than a base film is preferable. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and further preferably 5 to 50 μm. The base film and the cover film may be the same film material or different film materials. In use, for example, it can be used as a laminated film of a photosensitive resin film/base film while peeling off the cover film. In addition, in the manufacturing method of the hollow structure according to the above-mentioned embodiment, the case where the peeling operation of the base film constituting the photosensitive resist film is performed between the above-mentioned step (i) and the above-mentioned step (ii) is exemplified, but Not limited to this, the peeling operation of the base film constituting the photosensitive resist film may be performed between the aforementioned step (ii) and the aforementioned step (iii), or between the aforementioned step (iii) and the aforementioned step (iv). Case. "About the components constituting the photoresist film" The photosensitive resist film in this form has the negative photosensitive resin film containing the photoinitiator (I) which produces|generates acid by an epoxy group containing resin (A) and exposure. ・Epoxy group-containing resin (A): The epoxy group-containing resin (component (A)) is not particularly limited, and may be a resin having sufficient epoxy groups in one molecule to form a pattern by exposure. (A) component, for example, novolac (Novolac) type epoxy resin (Anv), bisphenol A type epoxy resin (Abp), bisphenol F type epoxy resin, aliphatic epoxy resin, acrylic resin ( Aac). ・・Novolac epoxy resin (Anv) As a novolak-type epoxy resin (Anv), resin (A1) (henceforth, also called "(A1) component") represented by following general formula (A1) is mentioned suitably.
Figure 02_image001
[where, Rp1 and Rp2 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. multiple Rp1 They may be the same or different from each other. multiple Rp2 They may be the same or different from each other. n1 is an integer from 1 to 5. REP is an epoxy-containing group. multiple REP They may be the same or different from each other. ] In the aforementioned formula (A1), Rp1 , Rp2 The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl etc., as a cyclic alkyl group, a cyclobutyl group, a cyclopentyl group, etc. are mentioned. where, as Rp1 , Rp2 , a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable. In formula (A1), a plurality of Rp1 They may be the same or different from each other. multiple Rp2 They may be the same or different from each other. In formula (A1), n1 It is an integer of 1-5, Preferably it is 2 or 3, More preferably, it is 2. In formula (A1), REP is an epoxy-containing group. as REP The epoxy group-containing group of the The base of the valence linking base. The alicyclic epoxy group is an alicyclic group having an oxirane structure as a three-membered cyclic ether, and specifically, a group having an alicyclic group and an oxirane structure. The alicyclic group serving as the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned. In addition, the hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, the epoxy group or the alicyclic epoxy group is preferably bonded to the oxygen atom (-O-) in the formula through A divalent linking group is bonded. Here, the divalent linking group is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like are mentioned as preferable examples. Regarding the divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, but is usually preferably saturated. As the aliphatic hydrocarbon group, more specifically, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group including a ring in the structure, and the like can be mentioned. The number of carbon atoms of the linear aliphatic hydrocarbon group is preferably 1-10, more preferably 1-6, still more preferably 1-4, and most preferably 1-3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and a methylene group [—CH2 -], ethyl extension [-(CH2 )2 -], trimethylene [-(CH2 )3 -], tetramethylene [-(CH2 )4 -], pentamethylene [-(CH2 )5 -]Wait. The number of carbon atoms of the branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and most preferably 2 or 3. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH(CH) is exemplified.3 )-, -CH(CH2 CH3 )-, -C(CH3 )2 -, -C(CH3 )(CH2 CH3 )-, -C(CH3 )(CH2 CH2 CH3 )-, -C(CH2 CH3 )2 -isoalkylmethylene; -CH(CH3 )CH2 -, -CH(CH3 )CH(CH3 )-, -C(CH3 )2 CH2 -, -CH(CH2 CH3 )CH2 -, -C(CH2 CH3 )2 -CH2 -Isoalkyl ethylidene; -CH(CH3 )CH2 CH2 -, -CH2 CH(CH3 )CH2 -Isoalkyl trimethylene; -CH(CH3 )CH2 CH2 CH2 -, -CH2 CH(CH3 )CH2 CH2 - Alkyl tetramethylene, etc. alkylene alkylene, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms. Examples of the aliphatic hydrocarbon group including a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group bonded to a linear or branched chain A group formed at the end of an aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group exists in the middle of a linear or branched aliphatic hydrocarbon group, and the like. As the linear or branched aliphatic hydrocarbon group, the same examples as described above can be given. 3-20 are preferable and, as for the carbon number of the said alicyclic hydrocarbon group, 3-12 are more preferable. The aforementioned alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferable, and specific examples thereof include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from the polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. are mentioned. The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. 5-30 are preferable, as for the carbon number of an aromatic ring, 5-20 are more preferable, 6-15 are still more preferable, and 6-12 are especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, and the like. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. As an aromatic heterocyclic ring, a pyridine ring, a thiophene ring, etc. are mentioned specifically,. Specific examples of the aromatic hydrocarbon group include groups obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl-extended aryl group or heteroaryl-extended aryl group); A group obtained by removing two hydrogen atoms from an aromatic compound of an aromatic ring (for example, biphenyl, fluoride, etc.); a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl or Heteroaryl) in which one hydrogen atom is substituted with an alkylene group (for example, from benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl and other arylalkyl groups in the aryl group in which one hydrogen atom was further removed) and the like. The number of carbon atoms of the alkylene group bonded to the aforementioned aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as a divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, and the like. The alicyclic hydrocarbon group in the aliphatic hydrocarbon group including a ring in the structure as a divalent hydrocarbon group may or may not have a substituent. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc. are mentioned. As for the alkyl group as the aforementioned substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, a n-butyl group, and a tert-butyl group are most preferable. Regarding the alkoxy group as the aforementioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group are preferable. group, most preferably methoxy and ethoxy. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned as the halogen atom which is the said substituent, and a fluorine atom is preferable. As a halogenated alkyl group as the said substituent, the group in which a part or all of the hydrogen atoms of the said alkyl group was substituted by the said halogen atom is mentioned. In the case of the alicyclic hydrocarbon group, a part of the carbon atoms constituting the ring structure thereof may be substituted with a heteroatom-containing substituent. As the substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) are preferable2 -, -S(=O)2 -O-. In the aromatic hydrocarbon group which is a divalent hydrocarbon group, the hydrogen atom which the aromatic hydrocarbon group has may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, etc. are mentioned, for example. As for the alkyl group as the aforementioned substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, a n-butyl group, and a tert-butyl group are most preferable. As for the alkoxy group, the halogen atom, and the halogenated alkyl group which are the said substituent, the example exemplified as the substituent which replaces the hydrogen atom which the said alicyclic hydrocarbon group has is mentioned. Regarding divalent linking groups containing heteroatoms: The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and the like. Among the divalent linking groups containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O) -O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)-(H can be substituted by alkyl, acyl, etc. base substitution.); -S-, -S(=O)2 -, -S(=O)2 -O-, general formula -Ytwenty one -O-Ytwenty two -, -Ytwenty one -O-, -Ytwenty one -C(=O)-O-, -C(=O)-O-Ytwenty one , -[Ytwenty one -C(=O)-O]m” -Ytwenty two -or-Ytwenty one -O-C(=O)-Ytwenty two - represents the base [where, ytwenty one and Ytwenty two Each independently is a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m" is an integer of 0 to 3.] and the like. When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)-, its H can be Substituted by substituents such as alkyl and acyl. 1-10 are preferable, 1-8 are more preferable, and 1-5 are especially preferable. formula-Ytwenty one -O-Ytwenty two -, -Ytwenty one -O-, -Ytwenty one -C(=O)-O-, -C(=O)-O-Ytwenty one -, -[Ytwenty one -C(=O)-O]m” -Ytwenty two -or-Ytwenty one -O-C(=O)-Ytwenty two - Medium, Ytwenty one and Ytwenty two Each independently is a divalent hydrocarbon group which may have a substituent. As this divalent hydrocarbon group, the same example as the "divalent hydrocarbon group which may have a substituent" exemplified in the description of the above-mentioned divalent linking group can be given. as Ytwenty one , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is still more preferable, and a methylene group or an ethyl group is particularly preferable. as Ytwenty two , preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylidene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group . formula-[Ytwenty one -C(=O)-O]m” -Ytwenty two In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as the formula -[Ytwenty one -C(=O)-O]m” -Ytwenty two -represented radicals, particularly preferably the formula -Ytwenty one -C(=O)-O-Ytwenty two - represents the base. Among them, the preferred formula -(CH2 )a' -C(=O)-O-(CH2 )b' - represents the base. In this formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. where, as REP The epoxy-containing group in is preferably glycidyl. Moreover, as a novolak-type epoxy resin (Anv), the resin which has a structural unit represented by following general formula (anv1) is also mentioned preferably.
Figure 02_image003
[where, REP is an epoxy-containing group, Ra22 , Ra23 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. ] In formula (anv1), Ra22 , Ra23 The alkyl group having 1 to 5 carbon atoms and R in the aforementioned formula (A1)p1 , Rp2 The same is true for alkyl groups having 1 to 5 carbon atoms. Ra22 , Ra23 The halogen atom is preferably a chlorine atom or a bromine atom. In formula (anv1), REP with R in the aforementioned formula (A1)EP Likewise, glycidyl is preferred. Hereinafter, the specific example of the structural unit represented by the said formula (anv1) is shown.
Figure 02_image005
The novolak-type epoxy resin (Anv) may be a resin formed of only the aforementioned structural unit (anv1), or may be a resin having the structural unit (anv1) and other structural units. As this other structural unit, the structural unit each represented by the following general formula (anv2) - (anv3) is mentioned, for example.
Figure 02_image007
[where, Ra24 is a hydrocarbon group which may have a substituent. Ra25 ~Ra26 , Ra28 ~Ra30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. Ra27 It is an epoxy group-containing group or a hydrocarbon group which may have a substituent. ] In formula (anv2), Ra24 is a hydrocarbon group which may have a substituent. As a hydrocarbon group which may have a substituent, a linear or branched alkyl group, or a cyclic hydrocarbon group is mentioned. The number of carbon atoms of the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 or 2. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. are mentioned. Among these, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is more preferred. The number of carbon atoms of the branched alkyl group is preferably 3-10, and more preferably 3-5. Specifically, isopropyl group, isobutyl group, tert-butyl group, isoamyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc. are mentioned, and preferred are Isopropyl. Ra24 In the case of a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The aliphatic hydrocarbon group which is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferable, and specific examples thereof include cyclopentane, cyclohexane, and the like. The aliphatic hydrocarbon group as the polycyclic group is preferably a group obtained by removing one hydrogen atom from the polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically, Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. are mentioned. Ra24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited, as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be a monocyclic or polycyclic. 5-30 are preferable, as for the carbon number of an aromatic ring, 5-20 are more preferable, 6-15 are still more preferable, and 6-12 are especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, and the like. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. As an aromatic heterocyclic ring, a pyridine ring, a thiophene ring, etc. are mentioned specifically,. as Ra24 Specifically, the aromatic hydrocarbon group in the group includes a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring; A group in which one hydrogen atom is removed from the aromatic compounds (such as biphenyl, fluoride, etc.); a group in which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkyl group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl and other arylalkyl groups, etc.) and the like. The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. In formulas (anv2) and (anv3), Ra25 ~Ra26 , Ra28 ~Ra30 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and an alkyl group having 1 to 5 carbon atoms and a halogen atom are respectively the same as the aforementioned Ra22 , Ra23 same. In formula (anv3), Ra27 It is an epoxy group-containing group or a hydrocarbon group which may have a substituent. Ra27 The epoxy group-containing group and R in the aforementioned formula (A1)EP Likewise, Ra27 The hydrocarbon group that may have substituents is related to Ra24 same. Hereinafter, specific examples of the constituent units represented by the aforementioned formulae (anv2) to (anv3) will be shown.
Figure 02_image009
When the novolac epoxy resin (Anv) has not only the structural unit (anv1) but also other structural units, the ratio of each structural unit in the resin (Anv) is not particularly limited, and it is relative to the total of all the structural units constituting the resin (Anv) Specifically, the total of the constituent units having an epoxy group is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %. ・・Bisphenol A epoxy resin (Abp) As a bisphenol A type epoxy resin (Abp), the epoxy resin of the structure represented by following general formula (abp1) is mentioned.
Figure 02_image011
[where, REP is an epoxy-containing group, Ra31 , Ra32 each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, na31 is an integer from 1 to 50. ] In formula (abp1), Ra31 , Ra32 The alkyl group having 1 to 5 carbon atoms and R in the aforementioned formula (A1)p1 , Rp2 The same is true for alkyl groups having 1 to 5 carbon atoms. where, as Ra31 , Ra32 , preferably a hydrogen atom or a methyl group. REP with R in the aforementioned formula (A1)EP Likewise, glycidyl is preferred. ・・Aliphatic epoxy resin, acrylic resin (Aac) As an aliphatic epoxy resin and an acrylic resin (Aac), the resin which has an epoxy group-containing unit each represented by the following general formula (a1-1) - (a1-2) is mentioned, for example.
Figure 02_image013
[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va41 It is a divalent hydrocarbon group which may have a substituent. na41 is an integer from 0 to 2. Ra41 , Ra42 is an epoxy-containing group. na42 is 0 or 1. Wa41 for (na43 +1) Valence aliphatic hydrocarbon group. na43 is an integer of 1 to 3. ] In the aforementioned formula (a1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms in R is preferably linear or branched, and specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which a part or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable. As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable in view of ease of industrial availability. In the aforementioned formula (a1-1), Va41 As a divalent hydrocarbon group which may have a substituent, R in the above-mentioned formula (A1) can be exemplifiedEP The same group as the divalent hydrocarbon group which may have a substituent described in. Among the above, Va41 The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, further preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group. In formula (a1-1), na41 is an integer of 0 to 2, preferably 0 or 1. In formula (a1-1), (a1-2), Ra41 , Ra42 is an epoxy group-containing group, which is the same as R in the aforementioned formula (A1)EP same. In formula (a1-2), Wa41 in (na43 The +1)-valent aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in its structure, or a linear or branched aliphatic hydrocarbon group having a ring in its structure. A base composed of aliphatic hydrocarbon groups. In formula (a1-2), na43 is an integer of 1 to 3, preferably 1 or 2. Below, the specific example of the structural unit represented by the said formula (a1-1) or (a1-2) is shown.
Figure 02_image015
Figure 02_image017
Figure 02_image019
Figure 02_image021
In the above formula, Ralpha Represents a hydrogen atom, a methyl group or a trifluoromethyl group. Ra51 Represents a divalent hydrocarbon group having 1 to 8 carbon atoms. Ra52 Represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Ra53 Represents a hydrogen atom or a methyl group. na51 is an integer from 0 to 10. Ra51 , Ra52 , Ra53 They may be the same or different. In addition, the acrylic resin (Aac) may have a structural unit derived from another polymerizable compound for the purpose of appropriately controlling physical and chemical properties. As such a polymerizable compound, a known radical polymerizable compound and an anion polymerizable compound are mentioned. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxy succinate. Ethyl ethyl ester, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxy hexahydrophthalate Methacrylic acid derivatives with carboxyl and ester bonds such as ethyl ester; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; (Meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; (meth)acrylate, benzyl (meth)acrylate, etc. ( Meth) acrylic acid aryl esters; diethyl maleate, dibutyl fumarate and other dicarboxylic acid diesters; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, Vinyl toluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl-containing aromatic compounds; vinyl acetate and other vinyl-containing aliphatic compounds; butadiene, Conjugated dienes such as isoprene; nitrile-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; acrylamide, methacrylic acid Polymeric compounds containing amide bonds such as amide; and so on. When the aliphatic epoxy resin or acrylic resin (Aac) has other structural units, the content ratio of the epoxy group-containing unit in the resin is preferably 5 to 40 mol %, more preferably 10 to 30 mol %, and most preferably 5 to 40 mol %. Preferably it is 15-25 mol%. Moreover, as aliphatic epoxy resin, the compound (henceforth, also called "(m1) component") containing the partial structure represented by following general formula (m1) is also mentioned suitably.
Figure 02_image023
[where, n2 is an integer of 1 to 4. * denotes chemical bond. ] In formula (m1), n2 It is an integer of 1-4, Preferably it is an integer of 1-3, More preferably, it is 2. As the component (m1), a compound having a partial structure represented by the above-mentioned general formula (m1) is exemplified through a divalent linking group or a single bond. Among them, a compound in which a plurality of partial structures represented by the above-mentioned general formula (m1) are bonded via a divalent linking group is preferable. Although it does not specifically limit as a divalent linking group here, The divalent hydrocarbon group which may have a substituent, the divalent linking group containing a hetero atom, etc. are mentioned as a preferable example. The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as R in the above formula (A1).EP The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom described in (Epoxy group-containing group) are the same. Among them, the divalent linking group containing a heteroatom is preferable, and -Y is more preferable.twenty one The base represented by -C(=O)-O-, -C(=O)-O-Ytwenty one - represents the base. as Ytwenty one , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is still more preferable, and a methylene group or an ethyl group is particularly preferable. Moreover, as an aliphatic epoxy resin, the compound (henceforth, also called "(m2) component") represented by following general formula (m2) is also mentioned suitably.
Figure 02_image025
[where, REP is an epoxy-containing group. multiple REP They may be the same or different from each other. ] In formula (m2), REP is an epoxy group-containing group, which is the same as R in the aforementioned formula (A1)EP same. As (A) component, 1 type may be used individually, and 2 or more types may be used together. The component (A) preferably contains a component selected from the group consisting of a novolac type epoxy resin (Anv), a bisphenol A type epoxy resin (Abp), a bisphenol F type epoxy resin, an aliphatic epoxy resin, and an acrylic resin (Aac). At least one resin of the group. Among these, it is more preferable that the component (A) contains at least one selected from the group consisting of a novolac-type epoxy resin (Anv), a bisphenol A-type resin (Abp), an aliphatic epoxy resin, and an acrylic resin (Aac). resin. Among them, the component (A) preferably contains at least one resin selected from the group consisting of novolac epoxy resin (Anv), aliphatic epoxy resin, and acrylic resin (Aac), and particularly preferably contains at least novolak Type epoxy resin (Anv). Among the novolak-type epoxy resins (Anv), the component (A1) is preferably used. Moreover, it is especially preferable that (A) component contains 2 or more types of resins chosen from the group consisting of a novolac epoxy resin (Anv), an aliphatic epoxy resin, and an acrylic resin (Aac). When two or more types are used in combination as the component (A), it is preferable that the component (A) contains a novolak-type epoxy resin from the viewpoint of improvement in film properties (lamination properties, etc.) and strength when used as a photoresist film. (Anv) in combination with aliphatic epoxy resins. Specific examples of the combination include a combination of (A1) component and at least one selected from the group consisting of (m1) component and (m2) component (hereinafter, referred to as "(m) component"). . Among these, the combination of (A1) component, (m1) component, and (m2) component is most preferable. When the (m1) component and the (m2) component are present at the same time, the ratio of the (m1) component to the (m2) component is preferably 2/8 to 8/in the mass ratio represented by the (m1) component/(m2) component 2, more preferably 3/7 to 7/3, still more preferably 4/6 to 6/4. When the said mass ratio is in the said preferable range, when it becomes a photosensitive resist film, film characteristics (lamination property etc.) and intensity|strength are further improved. In particular, (A) component contains (A1) component, (m1) component and (m2) component, and the total content of (m1) component and (m2) component is in (A1) component, (m1) component and (m2) component The ratio of the total content of the cured film is preferably 15 mass % or more, more preferably 20 mass % or more, still more preferably 25 mass % or more, particularly preferably more than 25 mass % , most preferably more than 25 mass % and 30 mass % or less. The mass average molecular weight of the component (A) in terms of polystyrene is preferably 100 to 300,000, more preferably 200 to 200,000, and still more preferably 300 to 200,000. By setting it as such a mass average molecular weight, it becomes difficult to generate|occur|produce peeling with a support body, and the intensity|strength of the cured film formed can fully be improved. Moreover, it is preferable that the dispersion degree of (A) component is 1.05 or more. By having such a degree of dispersion, the lithography characteristics are further improved in pattern formation. Here, the dispersity refers to a value obtained by dividing the mass average molecular weight by the number average molecular weight. As a commercial item of (A) component, for example, as a novolac epoxy resin (Anv), JER-152, JER-154, JER-157S70, JER-157S65 (the above are made by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (the above are manufactured by DIC Co., Ltd.), EOCN-1020 (the above are manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of bisphenol A-type epoxy resins (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, and JER-1009 , JER-1010 (the above are manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (the above are manufactured by DIC Corporation) and the like. Examples of bisphenol F-type epoxy resins include JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (the above are manufactured by Mitsubishi Chemical Corporation), EPICLON830, and EPICLON835 (the above are DIC Co., Ltd.), LCE-21, RE-602S (the above are manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of aliphatic epoxy resins include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (the above are manufactured by ADEKA Co., Ltd.), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 8000, Celloxide 8010, EHPE-3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (made by Daicel Corporation above), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above) Nagase ChemteX Corporation), TEPIC-VL (Nissan Chemical Industry Co., Ltd.), etc. What is necessary is just to adjust content of (A) component in the photosensitive resin film of embodiment according to the film thickness etc. of the photosensitive resin film to be formed. ・Photoinitiator (I) that generates acid due to exposure The photoinitiator (component (I)) is irradiated with active energy rays such as ultraviolet rays, extreme ultraviolet rays, KrF, ArF and other excimer lasers, X-rays, electron beams, etc., to generate cations, and the cations can become polymerization initiators. starter compound. The (I) component in the photosensitive resin film of the present embodiment is not particularly limited, and examples thereof include a compound represented by the following general formula (I1) (hereinafter referred to as "(I1) component"), the following general formula ( A compound represented by I2-1) or (I2-2) (hereinafter, referred to as "(I2) component"), a compound represented by the following general formula (I3-1) or (I3-2) (hereinafter, referred to as "" (I3) Ingredient"). In the above, both the (I1) component and the (I2) component generate a strong acid by exposure. Therefore, when a pattern is formed using the photosensitive resin composition containing the (I) component, it is possible to obtain Sufficient sensitivity to form a good pattern. ・・(I1) Ingredients The component (I1) is a compound represented by the following general formula (I1).
Figure 02_image027
[where, Rb01 ~Rb04 Each independently is an aryl group which may have a substituent, or a fluorine atom. q is an integer greater than 1, Qq+ Each independently is a q-valent organic cation. ] ・・・Anion Department In the aforementioned formula (I1), Rb01 ~Rb04 Each independently is an aryl group which may have a substituent, or a fluorine atom. Rb01 ~Rb04 The number of carbon atoms in the aryl group is preferably 5-30, more preferably 5-20, still more preferably 6-15, particularly preferably 6-12. Specifically, a naphthyl group, a phenyl group, an anthracenyl group, etc. are mentioned, and a phenyl group is preferable in view of easy availability. Rb01 ~Rb04 The aryl group in may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, and the number of carbon atoms is preferably 1 to 5), a halogenated alkyl group, and more preferably a halogen atom or carbon The halogenated alkyl group having 1 to 5 atoms is particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When an aryl group has a fluorine atom, the polarity of an anion part improves, and it is preferable. wherein, as R of formula (I1)b01 ~Rb04 , respectively, fluorinated phenyl groups are preferred, and perfluorophenyl groups are particularly preferred. Preferable specific examples of the anion moiety of the compound represented by the formula (I1) include tetrakis(pentafluorophenyl)borate ([B(C)6 F5 )4 ]- ); Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6 H4 CF3 )4 ]- ); difluorobis(pentafluorophenyl)borate ([(C6 F5 )2 BF2 ]- ); trifluoro(pentafluorophenyl)borate ([(C6 F5 )BF3 ]- ); Tetrakis(difluorophenyl)borate ([B(C6 H3 F2 )4 ]- )Wait. Among them, tetrakis(pentafluorophenyl)borate ([B(C)6 F5 )4 ]- ). ・・・Cation Department In formula (I1), q is an integer of 1 or more, and Qq+ Each independently is a q-valent organic cation. as the Qq+ Among them, pericynium cations and iodonium cations are preferable, and organic cations represented by the following general formulae (ca-1) to (ca-5) are particularly preferable.
Figure 02_image029
[where, R201 ~R207 , and R211 ~R212 Each independently represents an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent. R201 ~R203 , R206 ~R207 , R211 ~R212 They can be bonded to each other to form a ring together with the sulfur atom in the formula. R208 ~R209 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted SO-containing group2 - the cyclic base. L201 Represents -C(=O)- or -C(=O)-O-. Y201 Each independently represents an arylidene group, an alkylene group or an alkenylene group. x is 1 or 2. W201 Represents a (x+1) valent linking group. ] as R201 ~R207 , and R211 ~R212 Among the aryl groups, unsubstituted aryl groups having 6 to 20 carbon atoms are exemplified, and phenyl and naphthyl are preferred. as R201 ~R207 , and R211 ~R212 Among the heteroaryl groups, a group in which a part of carbon atoms constituting the aforementioned aryl group is substituted by a hetero atom is exemplified. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Examples of the heteroaryl group include those obtained by removing one hydrogen atom from 9H-thioxanthene, and examples of the substituted heteroaryl group include those obtained by removing one hydrogen atom from 9H-thioxanthene-9-one. Base et al. as R201 ~R207 , and R211 ~R212 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. as R201 ~R207 , and R211 ~R212 In the alkenyl group, the number of carbon atoms is preferably 2-10. as R201 ~R207 , and R210 ~R212 Possible substituents include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, a group represented by the following formula (ca-r-1) to (ca-r-10), respectively.
Figure 02_image031
[where, R'201 Each independently is a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group. ] In the aforementioned formulas (ca-r-1) to (ca-r-10), R'201 Each independently is a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group. Cyclic radicals that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferably saturated. R’201 The aromatic hydrocarbon group in is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably 3-30, more preferably 5-30, still more preferably 5-20, particularly preferably 6-15, and most preferably 6-10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. as R'201 Specifically, the aromatic ring possessed by the aromatic hydrocarbon group in the aromatic ring includes benzene, fluorine, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic ring formed by substituting a part of carbon atoms constituting these aromatic rings with heteroatoms. A heterocyclic ring, or a ring in which a part of the hydrogen atoms constituting the aromatic ring or the aromatic heterocyclic ring is substituted with an oxo group or the like. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. as R'201 Specifically, the aromatic hydrocarbon group in the group includes a group obtained by removing one hydrogen atom from the above-mentioned aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, an anthracenyl group, etc.), and one hydrogen atom of the above-mentioned aromatic ring. Groups in which atoms are substituted with alkylene groups (for example, aryl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. alkyl, etc.), a group obtained by removing one hydrogen atom from a ring in which a part of the hydrogen atoms constituting the above-mentioned aromatic ring is substituted with an oxo group or the like (for example, anthraquinone, etc.), a group obtained by removing one hydrogen atom from an aromatic heterocyclic ring (for example, 9H -thioxanthene, 9H-thioxanthene-9-one, etc.) a group obtained by removing one hydrogen atom, etc. The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. About R'201 Among the cyclic aliphatic hydrocarbon groups, there may be mentioned aliphatic hydrocarbon groups including a ring in the structure. Examples of the aliphatic hydrocarbon group including a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group bonded to a straight or branched chain. A group formed at the end of an aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group exists in the middle of a linear or branched aliphatic hydrocarbon group, and the like. 3-20 are preferable and, as for the carbon number of the said alicyclic hydrocarbon group, 3-12 are more preferable. The aforementioned alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. As the monocycloalkane, a monocycloalkane having 3 to 6 carbon atoms is preferable, and specific examples thereof include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 30 carbon atoms. Among them, as the polycycloalkane, polycycloalkanes having a polycyclic skeleton having a cross-linked ring system, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, are more preferable; A polycyclic alkane of a polycyclic skeleton of a polycyclic skeleton of a condensed ring system such as a cyclic group of the skeleton. where, as R'201 The cyclic aliphatic hydrocarbon group in is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and particularly preferably diamond Alkyl, norbornyl, most preferably adamantyl. The number of carbon atoms of the linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 1. 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and a methylene group [—CH2 -], ethyl extension [-(CH2 )2 -], trimethylene [-(CH2 )3 -], tetramethylene [-(CH2 )4 -], pentamethylene [-(CH2 )5 -]Wait. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH(CH3 )-, -CH(CH2 CH3 )-, -C(CH3 )2 -, -C(CH3 )(CH2 CH3 )-, -C(CH3 )(CH2 CH2 CH3 )-, -C(CH2 CH3 )2 -isoalkylmethylene; -CH(CH3 )CH2 -, -CH(CH3 )CH(CH3 )-, -C(CH3 )2 CH2 -, -CH(CH2 CH3 )CH2 -, -C(CH2 CH3 )2 -CH2 -Isoalkyl ethylidene; -CH(CH3 )CH2 CH2 -, -CH2 CH(CH3 )CH2 -Isoalkyl trimethylene; -CH(CH3 )CH2 CH2 CH2 -, -CH2 CH(CH3 )CH2 CH2 - Alkyl tetramethylene, etc. alkylene alkylene, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms. Chained alkyl groups that may have substituents: as R'201 The chain alkyl group can be any alkyl group in straight chain or branched chain. As a linear alkyl group, 1-20 are preferable, 1-15 are more preferable, and 1-10 are the most preferable. Specifically, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl can be mentioned. base, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, di- Undecyl, behenyl, etc. As a branched alkyl group, 3-20 are preferable, 3-15 are more preferable, and 3-10 are the most preferable. Specifically, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc. Chain-like alkenyl which may have substituents: as R'201 The chain alkenyl group can be any straight chain or branched alkenyl group, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. As a linear alkenyl group, a vinyl group, a propenyl group (allyl group), a butenyl group, etc. are mentioned, for example. As a branched alkenyl group, a 1-methylvinyl group, a 2-methylvinyl group, a 1-methacryl group, a 2-methacryl group, etc. are mentioned, for example. Among the above-mentioned chain alkenyl groups, linear alkenyl groups are preferable, vinyl groups and propenyl groups are more preferable, and vinyl groups are particularly preferable. as R'201 The substituents in the cyclic group, chain alkyl group or alkenyl group include, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R'201 Cyclic group, alkylcarbonyl group, thienylcarbonyl group, etc. Among them, R'201 Preferably it is a cyclic group which may have a substituent, and a chain alkyl group which may have a substituent. R201 ~R203 , R206 ~R207 , R211 ~R212 When they are bonded to each other and form a ring together with the sulfur atom in the formula, heteroatoms such as sulfur atom, oxygen atom, nitrogen atom, carbonyl group, -SO-, -SO may be interposed between them.2 -, -SO3 -, -COO-, -CONH- or -N(RN )-(The RN is an alkyl group having 1 to 5 carbon atoms. ) and other functional groups. The ring to be formed is preferably a three- to ten-membered ring, particularly preferably a five- to seven-membered ring, including the sulfur atom in one ring including the sulfur atom in the formula in the ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, and a thioxanthene ring. Anthracene ring, phenoxthiane ring, tetrahydrothiophenium ring, tetrahydrothiopyran ring, etc. In the aforementioned formula (ca-3), R208 ~R209 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In the aforementioned formula (ca-3), R210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted SO-containing group2 - the cyclic base. as R210 Among the aryl groups, unsubstituted aryl groups having 6 to 20 carbon atoms are exemplified, and phenyl and naphthyl are preferred. as R210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. as R210 In the alkenyl group, the number of carbon atoms is preferably 2-10. In the aforementioned formula (ca-4) and formula (ca-5), Y201 Each independently represents an arylidene group, an alkylene group or an alkenylene group. About Y201 The extended aryl group in , can be enumerated from as R'201 A group obtained by removing one hydrogen atom from the aromatic hydrocarbon group exemplified in the aryl group. About Y201 Among the alkylene groups and alkenylene groups, as R'201 A group obtained by removing one hydrogen atom from the group exemplified in the chain alkyl group and the chain alkenyl group. In the aforementioned formula (ca-4) and formula (ca-5), x is 1 or 2. W201 It is a (x+1) valent, that is, a bivalent or trivalent linking base. as W201 The divalent linking group in the above is preferably a divalent hydrocarbon group which may have a substituent, and is preferably the same as R in the above formula (A1).EP The same groups as the divalent hydrocarbon group which may have a substituent exemplified in . W201 The divalent linking group in may be any of linear, branched, and cyclic, and is preferably cyclic. Among them, a group formed by combining two carbonyl groups at both ends of an aryl-extended group, or a group consisting of only an aryl-extended group is preferable. As the arylidene group, a phenylene group, a naphthylene group, etc. are mentioned, and a phenylene group is particularly preferable. as W201 The trivalent linking group in the above-mentioned W201 Among the divalent linking groups in the above, a group obtained by removing one hydrogen atom, a group obtained by further bonding the aforementioned divalent linking group to the aforementioned divalent linking group, and the like. as W201 Among the trivalent linking groups, a group in which two carbonyl groups are bonded to an aryl group is preferable. As a preferable cation represented by the said formula (ca-1), the cation represented by the following formula (ca-1-1) - (ca-1-24) is mentioned specifically,.
Figure 02_image033
Figure 02_image035
[where, R"201 is a hydrogen atom or a substituent. As the substituent, with the aforementioned R201 ~R207 , and R210 ~R212 Examples of the substituent which may be possessed are the same. ] Moreover, as a cation represented by the said formula (ca-1), the cation represented by the following general formula (ca-1-25) - (ca-1-35) is also preferable.
Figure 02_image037
Figure 02_image039
[where, R'211 is an alkyl group. Rhal is a hydrogen atom or a halogen atom. ] Moreover, as a cation represented by the said formula (ca-1), the cation represented by the following (ca-1-36) - (ca-1-47) is also preferable.
Figure 02_image041
As a preferable cation represented by the said formula (ca-2), a diphenyl iodonium cation, a bis (4-tert-butylphenyl) iodonium cation, etc. are mentioned specifically,. As a preferable cation represented by the said formula (ca-3), the cation represented by the following formula (ca-3-1) - (ca-3-6) is mentioned specifically,.
Figure 02_image043
As a preferable cation represented by the said formula (ca-4), the cation represented by following formula (ca-4-1) - (ca-4-2) is mentioned specifically,.
Figure 02_image045
Moreover, as a cation represented by the said formula (ca-5), the cation represented by the following general formula (ca-5-1) - (ca-5-3) is also preferable.
Figure 02_image047
[where, R'212 is an alkyl group or a hydrogen atom. R’211 is an alkyl group. ] In the above, the cation part [(Qq+ )1/q ] is preferably a cation represented by the general formula (ca-1), more preferably a cation represented by the formulae (ca-1-1) to (ca-1-47), and further preferably a cation represented by the formula (ca-1-25), ( ca-1-29), (ca-1-35), and (ca-1-47) cations, respectively. ・・(I2) Ingredient The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2).
Figure 02_image049
[where, Rb05 It is an optionally substituted fluorinated alkyl group, or a fluorine atom. multiple Rb05 They may be the same or different from each other. q is an integer greater than 1, Qq+ is a q-valent organic cation. ]
Figure 02_image051
[where, Rb06 It is an optionally substituted fluorinated alkyl group, or a fluorine atom. multiple Rb06 They may be the same or different from each other. q is an integer greater than 1, Qq+ is a q-valent organic cation. ] ・・・Anion Department In the aforementioned formula (I2-1), Rb05 It is an optionally substituted fluorinated alkyl group, or a fluorine atom. multiple Rb05 They may be the same or different from each other. Rb05 The number of carbon atoms of the fluorinated alkyl group in is preferably 1-10, more preferably 1-8, still more preferably 1-5. Specifically, among the alkyl groups having 1 to 5 carbon atoms, a part or all of hydrogen atoms are substituted with fluorine atoms. where, as Rb05 , preferably a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group with 1 to 5 carbon atoms, still more preferably a fluorine atom, trifluoromethyl or pentafluoroethyl . The anion moiety of the compound represented by the formula (I2-1) is preferably represented by the following general formula (b0-2a).
Figure 02_image053
[where, Rbf05 is an optionally substituted fluorinated alkyl group. nb1 is an integer from 1 to 5. ] In formula (b0-2a), as Rbf05 The optionally substituted fluorinated alkyl group in theb05 The fluorinated alkyl groups which may have a substituent listed in the above are the same. In formula (b0-2a), nb1 The integer of 1-4 is preferable, the integer of 2-4 is more preferable, and 3 is the most preferable. In the aforementioned formula (I2-2), Rb06 It is an optionally substituted fluorinated alkyl group, or a fluorine atom. multiple Rb06 They may be the same or different from each other. Rb06 The number of carbon atoms of the fluorinated alkyl group in is preferably 1-10, more preferably 1-8, still more preferably 1-5. Specifically, among the alkyl groups having 1 to 5 carbon atoms, a part or all of hydrogen atoms are substituted with fluorine atoms. where, as Rb06 Among them, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a fluorine atom is still more preferable. ・・・Cation Department In formula (I2-1) and formula (I2-2), q is an integer of 1 or more, and Qq+ Each independently is a q-valent organic cation. as the Qq+ , the same examples as those of the above formula (I1) can be cited, among them, the cations represented by the general formula (ca-1) are preferable, and the cations represented by the formulas (ca-1-1) to (ca-1-47) are more preferable. The cations are more preferably cations represented by formulae (ca-1-25), (ca-1-29), (ca-1-35), and (ca-1-47), respectively. ・・(I3) Ingredient The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).
Figure 02_image055
[where, Rb11 ~Rb12 It is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, Mm+ Each independently is an m-valent organic cation. ] {(I3-1) Component} ・・・Anion Department In formula (I3-1), Rb12 A cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, the above-mentioned R'201 Among the cyclic groups, chain alkyl groups, chain alkenyl groups, unsubstituted groups or groups having substituents other than halogen atoms in the description of . as Rb12 , preferably a chain-like alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom. As a chain-shaped alkyl group, it is preferable that carbon number is 1-10, and it is more preferable that it is 3-10. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (may have other than a halogen atom) Substituents); a group formed by removing one or more hydrogen atoms from camphor, etc. Rb12 The hydrocarbon group may have a substituent other than a halogen atom, and as the substituent, R with the aforementioned formula (I3-2) can be exemplifiedb11 The hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the group is the same as the substituent other than the halogen atom which may have. Here, the term "may have a substituent other than a halogen atom" not only excludes the case of having a substituent consisting of only a halogen atom, but also excludes the case of having a substituent containing a halogen atom (even if it is one) (for example, substituted The case where the group is a fluorinated alkyl group, etc.) is excluded. Hereinafter, preferable specific examples of the anion part of the component (I3-1) are shown.
Figure 02_image057
・・・Cation Department In formula (I3-1), Mm+ is an m-valent organic cation. as Mm+ As the organic cation, the same examples as the cations represented by the above general formulae (ca-1) to (ca-5) can be preferably used, and among these, the cation represented by the above general formula (ca-1) is more preferred. Among them, R in the above-mentioned general formula (ca-1) is particularly preferable from the viewpoint of improving the resolution and roughness characteristics.201 , R202 , R203 At least one of them is a periconium cation of an optionally substituted organic group (aryl, heteroaryl, alkyl, or alkenyl) having 16 or more carbon atoms. As a substituent which the above-mentioned organic group may have, in the same manner as described above, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (=O), an aryl group, the above-mentioned formula ( The groups represented by ca-r-1) to (ca-r-10), respectively. The number of carbon atoms in the aforementioned organic group (aryl, heteroaryl, alkyl or alkenyl) is preferably 16-25, more preferably 16-20, particularly preferably 16-18, as the Mm+ The organic cations of the ), (ca-1-46), and (ca-1-47) cations, respectively. {(I3-2) Component} ・・・Anion Department In formula (I3-2), Rb11 A cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, the above-mentioned R'201 Among the cyclic groups, chain alkyl groups, chain alkenyl groups, unsubstituted groups or groups having substituents other than halogen atoms in the description of . Among these, as Rb11 Preferably, an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, an alkylene group may be present, and the substituent in this case is preferably represented by the following general formulae (y-al-1) to (y-al-7), respectively link base.
Figure 02_image059
[where, V'101 is a single bond or an alkylene group with 1 to 5 carbon atoms, V'102 It is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ] V’102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 5 carbon atoms. as V'101 and V’102 The alkylene group in can be a straight-chain alkylene group or a branched-chain alkylene group, preferably a straight-chain alkylene group. as V'101 and V’102 Among the alkylene groups, specifically, methylene [-CH2 -]; -CH(CH3 )-, -CH(CH2 CH3 )-, -C(CH3 )2 -, -C(CH3 )(CH2 CH3 )-, -C(CH3 )(CH2 CH2 CH3 )-, -C(CH2 CH3 )2 -isoalkylmethylene; ethylidene [-CH2 CH2 -]; -CH(CH3 )CH2 -, -CH(CH3 )CH(CH3 )-, -C(CH3 )2 CH2 -, -CH(CH2 CH3 )CH2 -Isoalkyl ethylidene; Trimethylene(n-propylidene)[-CH2 CH2 CH2 -]; -CH(CH3 )CH2 CH2 -, -CH2 CH(CH3 )CH2 -isoalkyl trimethylene; tetramethylene [-CH2 CH2 CH2 CH2 -]; -CH(CH3 )CH2 CH2 CH2 -, -CH2 CH(CH3 )CH2 CH2 -Isoalkyl tetramethylene; pentamethylene [-CH2 CH2 CH2 CH2 CH2 -]Wait. In addition, V'101 or V'102 A part of the methylene groups in the aforementioned alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably from R'201 A divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group), more preferably cyclohexylene, 1,5- Adamantylene or 2,6-adamantylene. As the aforementioned aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The chain-like alkyl group preferably has 1 to 10 carbon atoms, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Linear alkyl groups such as decyl; 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl Alkyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl and other branched alkyl groups . as Rb11 , preferably a cyclic group which may have a substituent other than a halogen atom. Hereinafter, the preferable specific example of the anion part of (I3-2) component is shown.
Figure 02_image061
・・・Cation Department In formula (I3-2), Mm+ is an m-valent organic cation, which is the same as M in the aforementioned formula (I3-1)m+ same. In addition, the component (I) is preferably a photoinitiator that generates an acid having a pKa (acid dissociation constant) of -5 or less upon exposure from the viewpoints of high elasticity of the resin film, no residue, and easy formation of a fine structure. High sensitivity to exposure can be obtained by using a photoinitiator that generates an acid having a more preferable pKa of -6 or less, and still more preferably a pKa of -8 or less. The lower limit value of the pKa of the acid generated by the component (I) is preferably -15 or more. High sensitivity will be easily achieved by using a photoinitiator that produces an acid with the above-mentioned preferred pKa. Here, the "pKa (acid dissociation constant)" refers to an index generally used as an index representing the acid strength of an object substance. In addition, pKa in this specification is the value under the temperature condition of 25 degreeC. In addition, the pKa value can be obtained by measuring by a known method. In addition, it is also possible to use "ACD/Labs" (trade name, Advanced Chemistry Calculation value of known software such as Development Corporation). Specific examples of preferable (I) component are given below.
Figure 02_image063
Figure 02_image065
Figure 02_image067
As the component (I), one type may be used alone, or two or more types may be used in combination. The (I) component preferably contains two or more types selected from the group consisting of the (I1) component, the (I2) component, and the (I3) component. Among them, as for the component (I), it is more preferable to use the component (I1) and the component (I2) in combination. Alternatively, as for the component (I), it is more preferable to use one or more components selected from the group consisting of the component (I1) and the component (I2) and the component (I3) in combination. About content of (I) component, 0.5-6.0 mass parts is preferable with respect to 100 mass parts of (A) components, 1.0-5.0 mass parts is more preferable, 1.0-3.0 mass parts is still more preferable. When the content of the component (I) is at least the lower limit value of the aforementioned preferable range, sufficient sensitivity can be obtained, and the lithography characteristics of the pattern can be further improved. Moreover, the intensity|strength of a cured film can be improved further. On the other hand, when it is below the upper limit of the above-mentioned preferable range, the sensitivity can be appropriately controlled, and a pattern with a favorable shape can be easily obtained. ・Other ingredients In addition to the above-mentioned (A) component and (I) component, the photosensitive resin film of this embodiment can contain other components as needed. The photosensitive resin film of the embodiment may be appropriately added to the photosensitive resin film of the embodiment to contain mixed additives such as metal oxides, sensitizer components, silane coupling agents, solvents, additional resins for improving film performance, Dissolution inhibitors, alkaline compounds, plasticizers, stabilizers, colorants, anti-vignetting agents, etc. ··Metal oxide The photosensitive resin film of the present embodiment can be improved by having not only the (A) component and the (I) component, but also a metal oxide (hereinafter, also referred to as "(M) component") at the same time. Hardened film with increased strength. In addition, a good shape and high-resolution pattern can be formed. As the (M) component, for example, oxides of metals such as silicon (metal silicon), titanium, zirconium, and hafnium are mentioned. Among these, oxides of silicon are preferred, and among them, silica is more preferably used, and it is particularly preferably used as a silica filler. Moreover, it is preferable that the shape of (M) component is a particle form. The particulate (M) component is preferably the component (M) composed of a group of particles having a volume average particle diameter of 5 to 40 nm, and more preferably (M) composed of a group of particles having a volume average particle diameter of 5 to 30 nm The component is more preferably the component (M) formed from a group of particles having a volume average particle diameter of 10 to 20 nm. (M) When the volume average particle diameter of a component is more than the lower limit of the said preferable range, it will become easy to improve the intensity|strength of a cured film. On the other hand, when it is equal to or less than the upper limit of the above-mentioned preferable range, residues are less likely to be generated during pattern formation, and higher-resolution patterns can be easily formed. The particle diameter of the component (M) may be appropriately selected according to the exposure light source. In general, for particles having a particle diameter of 1/10 or less of the wavelength of light, the influence of light scattering can hardly be considered. Therefore, for example, in the case of forming a fine structure by lithography using i-line (365 nm), as the component (M), it is preferable to use a particle group having a primary particle size (volume average) of 10 to 20 nm (especially preferably two silica particles). As the (M) component, one type may be used alone, or two or more types may be used in combination. About content of (M) component, 10-30 mass parts is preferable with respect to 100 mass parts of (A) components, and 15-25 mass parts is more preferable. When content of (M)component is more than the lower limit of the said preferable range, the intensity|strength of a cured film can be improved more. On the other hand, when it is below the upper limit of the said preferable range, the fluidity|liquidity of a photosensitive resin composition will be easily maintained. When the photosensitive resin film of this embodiment contains the (M) component, the content of the (I) component is preferably 1 to 5 with respect to 100 parts by mass of the total amount of the (A) component and the (M) component. The mass part is more preferably 1.1 to 4 parts by mass, still more preferably 1.5 to 3 parts by mass. (I) When content of a component is in the said preferable range, the intensity|strength of a cured film can be improved further, and it becomes easy to form a favorable shape and a high-resolution pattern. In the photosensitive resin film of the present embodiment, the ratio of the content of the component (A) to the total content of the component (A), the component (I), and the component (M) described above is preferably 35 to 90% by mass, and more Preferably it is 40-85 mass %, More preferably, it is 45-80 mass %. When content of the said (A) component exists in the said preferable range, not only the intensity|strength of a cured film can be improved further, but the film characteristics (lamination property etc.) at the time of making a photosensitive resist film can be improved further. ・・Sensitizer ingredient The photosensitive resin film of embodiment may further contain a sensitizer component. The sensitizer component is not particularly limited as long as it can absorb energy by exposure and transmit the energy to other substances. As the sensitizer component, specifically, benzophenone-based photosensitizers such as benzophenone, p,p'-tetramethyldiaminobenzophenone, oxazole-based photosensitizers, Acetophenone-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, diacetyl, Known photosensitizers such as red, rose bengal, pyrene, phenothiazine, anthrone, etc. A sensitizer component may be used individually by 1 type, and may use 2 or more types together. When the sensitizer component is added to the photosensitive resin film of the embodiment, the content of the sensitizer component is preferably 0.1 to 15 parts by mass, and more preferably 0.3 to 10 parts by mass relative to 100 parts by mass of the (A) component. The mass part is more preferably 0.5 to 5 mass parts. When content of a sensitizer component is the said preferable range, sensitivity and resolution can be improved more. ・・Silane coupling agent The photosensitive resin film of the embodiment may further contain an adhesive adjuvant in order to improve the adhesiveness with the support. As the adhesion aid, a silane coupling agent is preferable. As a silane coupling agent, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, is mentioned, for example. Specific examples include trimethoxysilyl benzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-ring Oxypropoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together. When adding a silane coupling agent to the photosensitive resin film of the embodiment, the content of the silane coupling agent is preferably 2.5 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the component (A). , more preferably 3 to 10 parts by mass. When content of a silane coupling agent is the said preferable range, the intensity|strength of a cured film can be improved further. In addition, the adhesiveness between the cured film and the support can be further enhanced. "Solvent" The photosensitive resin film of embodiment can be manufactured by dissolving or dispersing a photosensitive material in a solvent (henceforth "(S) component"). Examples of the component (S) include lactones such as γ-butyrolactone; acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, 2 - Ketones such as heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or diethylene glycol monoacetate Compounds having ester bonds, such as propylene glycol monoacetate, monoalkyl ethers such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and the like of the aforementioned polyols or the aforementioned compounds having ester bonds; Derivatives of polyhydric alcohols such as compounds having ether bonds such as phenyl ether [Among these, methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME) are preferred] ; Cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxy Methyl propionate, ethyl ethoxypropionate and other esters; anisole, ethylbenzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether , Aromatic organic solvents such as ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, cymene, mesitylene, dimethylsulfoxide (DMSO), etc. (S) component may be used individually by 1 type, and may be used as a mixed solvent of 2 or more types. The usage-amount of (S) component is not specifically limited, It can be set suitably according to the thickness of a coating film at the density|concentration which can apply|coat to a board|substrate etc.. About content of (S) component in the photosensitive resin composition, 1-25 mass % is preferable with respect to the total amount (100 mass %) of the photosensitive resin composition, and 5-20 mass % is more preferable. (Manufacturing method of hollow package) A manufacturing method according to a second aspect of the present invention is a method for manufacturing a hollow package including a step of sealing the hollow structure manufactured by the manufacturing method according to the first aspect described above with a sealing material to obtain a hollow package. As the sealing material, for example, a resin composition can be used. The resin that can be used for the sealing material is not particularly limited, as long as it is a resin that can seal and insulate the hollow structure, and examples thereof include epoxy-based resins, polysiloxane-based resins, and the like. In addition to resin, other components, such as a filler, may be contained in a sealing material. The method of sealing the hollow structure with the sealing material is not particularly limited, but the heat-melted sealing material is supplied to the hollow structure so as to cover the hollow structure, and then compression molding is performed to produce the set on the hollow structure. A hollow package with a sealing material layer. The aforementioned sealing material layer has a function of protecting the MEMS, the wiring portion, and the like in the hollow structure from the influence of the external environment. The hollow package manufactured by the manufacturing method according to the present aspect includes the hollow structure 100 manufactured by the manufacturing method according to the first aspect described above, and therefore, at the time of sealing, or when the conductor pattern and the lead frame are integrated When connecting or dividing the substrate by dicing or the like, it is possible to suppress the occurrence of inconveniences such as deformation of the hollow structure. Therefore, the space inside the hollow structure can be reliably maintained, and a highly reliable micro device can be provided. Example Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples. "Parts" in the description of each production example means parts by mass. <Preparation of negative photosensitive resin composition> (Preparation Examples 1 to 4) The components shown in Table 1 were mixed, dissolved, and filtered using a PTFE filter (pore size: 1 μm, manufactured by PALL Corporation) to prepare negative photosensitive resin compositions (solid content of about 84 to 86) for each example. mass % MEK solution).
Figure 02_image069
In Table 1, each abbreviation has the following meaning, respectively. The numerical value in [ ] is the compounding quantity (mass part; based on solid content conversion) of each component. (A)-1: An epoxy group-containing resin represented by the following chemical formula (A11). Trade name "JER-157S70", manufactured by Mitsubishi Chemical Corporation.
Figure 02_image071
(A)-2: a compound represented by the following chemical formula (m1-1). Trade name "Celloxide 8000", manufactured by Daicel Corporation. (A)-3: a compound represented by the following chemical formula (m2-1). Trade name "TEPIC-VL", manufactured by Nissan Chemical Co., Ltd.
Figure 02_image073
(I)-1: A photoinitiator represented by the following chemical formula (I1-4). Brand name "Irgacure290", manufactured by BASF Corporation. (I)-3: A photoinitiator represented by the following chemical formula (I1-1). Trade name "CPI-310B", manufactured by San-Apro Ltd. (I)-4: A photoinitiator represented by the following chemical formula (I1-3). Trade name "CPI-410B", manufactured by San-Apro Ltd. (I)-5: A photoinitiator represented by the following chemical formula (I2-1-2). Trade name "CPI-410S", manufactured by San-Apro Ltd.
Figure 02_image075
(I)-2: A photoinitiator represented by the following chemical formula (I3-1-1). Trade name "HS-1CS", manufactured by San-Apro Ltd.
Figure 02_image077
(C)-1: silica filler. Trade name "MEK-EC-2130Y", manufactured by Nissan Chemical Co., Ltd. Primary particle size φ=15 nm (volume average). A methyl ethyl ketone dispersion having a silica component concentration of 31% by mass. (D)-1: Sensitizer. Alpha Naphthol. (E)-1: Silane coupling agent. Trade name "Shin-Etsu Silicone (registered trademark) OFS6040SILANE", manufactured by Shin-Etsu Chemical Co., Ltd. (E)-2: Silane coupling agent. Trade name "Shin-Etsu Silicone (registered trademark) X-12-967C", manufactured by Shin-Etsu Chemical Co., Ltd. (S)-1: Solvent. methyl ethyl ketone. <Manufacturing method of hollow structure> As the base film, a polysiloxane-based surface-release-treated PET film (trade name "A53", manufactured by Teijin Co., Ltd.) was used. (Example 1) Step (0): Using an applicator, the negative photosensitive resin composition of Preparation Example 1 was applied on the aforementioned base film, heated in an oven at a temperature of 60° C. for 5 minutes, and then baked at 70° C. for 10 minutes ( PAB), the photosensitive resin film with a film thickness of 30 micrometers was formed by this, and the photosensitive resist film (1) was obtained. In addition, a level difference substrate having a concave portion on the surface is prepared. Step (i): The said photosensitive resist film (1) is arrange|positioned so that the surface of the photosensitive resin film of the said photosensitive resist film (1) may block the opening surface of the said recessed part in the said height difference board|substrate. After the said step (i), the operation of peeling the said base film from the photosensitive resin film of the said photosensitive resist film (1) is performed. Step (ii): Next, using a Canon PLA-501 ghi line aligner, the aforementioned photosensitive resin film was subjected to 300 mJ/cm2 (Converted to i-line) exposure. Step (iii): About the photosensitive resin film after the exposure in the said process (ii), the heat processing of temperature 90 degreeC and 5 minutes was performed with the hotplate. Step (iv): The photosensitive resin film after the heat treatment in the aforementioned step (iii) was subjected to spin-over immersion development at 23° C. using propylene glycol monomethyl ether acetate as a developer, thereby forming a negative image of the top plate portion. type. Step (v): The negative pattern after the above-mentioned step (iv) is further subjected to heat treatment under the following step curing conditions in an oven, thereby curing it and obtaining curing of the top plate portion by the photosensitive resin film The hollow structure formed by the body (the cross section in the height direction of the hollow structure portion is a rectangle: 200 μm in length (height)×500 μm in width). Heat treatment for step-hardening conditions: In an oven, heat treatment was performed at a temperature of 60° C. for 60 minutes, then, a heat treatment was performed at a temperature of 100° C. for 30 minutes in an oven, and further, a heat treatment was performed at a temperature of 160° C. for 30 minutes in an oven. After heat treatment, heat treatment was performed in an oven at a temperature of 200° C. for 60 minutes. (Example 2) In the aforementioned step (v), for the aforementioned negative pattern after the aforementioned step (iv), irradiate 1000 mJ/cm2 After the ultraviolet rays, the hollow structure was obtained in the same manner as in Example 1, except that heat treatment was performed at a temperature of 160° C. for 60 minutes in an oven. (Example 3) In the aforementioned step (v), the irradiation amount of the ultraviolet rays for the aforementioned negative pattern after the aforementioned step (iv) was changed to 5000 mJ/cm2 , except that, it carried out similarly to Example 2, and obtained the hollow structure. (Example 4) In the aforementioned step (v), the irradiation amount of ultraviolet rays for the aforementioned negative pattern after the aforementioned step (iv) was changed to 10000 mJ/cm2 , except that, it carried out similarly to Example 2, and obtained the hollow structure. (Example 5) Except having changed the negative photosensitive resin composition of Preparation Example 1 to the negative type photosensitive resin composition of Preparation Example 2, it carried out similarly to Example 1, and obtained the hollow structure. (Example 6) Except having changed the negative photosensitive resin composition of Preparation Example 1 to the negative type photosensitive resin composition of Preparation Example 3, it carried out similarly to Example 1, and obtained the hollow structure. (Example 7) Except having changed the negative photosensitive resin composition of Preparation Example 1 to the negative type photosensitive resin composition of Preparation Example 4, it carried out similarly to Example 1, and obtained the hollow structure. (Example 8) Except having changed the negative photosensitive resin composition of Preparation Example 1 to the negative type photosensitive resin composition of Preparation Example 2, it carried out similarly to Example 2, and obtained the hollow structure. (Example 9) Except having changed the negative photosensitive resin composition of Preparation Example 1 to the negative type photosensitive resin composition of Preparation Example 3, it carried out similarly to Example 2, and obtained the hollow structure. (Example 10) Except having changed the negative photosensitive resin composition of Preparation Example 1 to the negative type photosensitive resin composition of Preparation Example 4, it carried out similarly to Example 2, and obtained the hollow structure. (Comparative Example 1) In the above-mentioned step (v), the above-mentioned negative pattern after the above-mentioned step (iv) was further heat-treated in an oven at 200° C. for 60 minutes, except that it was carried out in the same manner as in Example 1 to obtain a hollow Construct. (Comparative Example 2) In the above-mentioned step (v), the above-mentioned negative pattern after the above-mentioned step (iv) was further heated in an oven at 160° C. for 60 minutes, except that it was carried out in the same manner as in Example 1 to obtain a hollow Construct. (Comparative Example 3) In the above-mentioned step (v), the above-mentioned negative pattern after the above-mentioned step (iv) was further heat-treated in an oven at 160° C. for 60 minutes, except that it was carried out in the same manner as in Example 5 to obtain a hollow Construct. (Comparative Example 4) In the above-mentioned step (v), the above-mentioned negative pattern after the above-mentioned step (iv) was further heat-treated in an oven at 160° C. for 60 minutes, except that it was carried out in the same manner as in Example 6 to obtain a hollow Construct. (Comparative Example 5) In the above-mentioned step (v), the above-mentioned negative pattern after the above-mentioned step (iv) was further heated in an oven at 160° C. for 60 minutes, except that it was carried out in the same manner as in Example 7 to obtain a hollow Construct. ＜Evaluation＞ The deformation and strength of the top plate portion of the hollow structures obtained in the respective examples were evaluated. The said evaluation evaluated the tensile elastic modulus E* of the cured film which swelled the top-plate part and comprises the top-plate part as follows, respectively. [top plate part bulges] The hollow structure body immediately after manufacture was cut|disconnected in the height direction, and the degree of deformation|transformation of the height direction of a hollow structure part (the top plate part swelling) was measured using a Dektak surface height difference meter. In addition, according to the following evaluation criteria, this result is shown in Tables 2-4 as "top plate part swelling (micrometer)". The numerical value in ( ) represents the deformation amount (μm) of the portion of the top plate portion where the bulge is the largest. Evaluation benchmark ○: The deformation in the height direction of the hollow structure portion is 5 μm or less. ×: The deformation in the height direction of the hollow structure portion exceeds 5 μm. [Measurement of Tensile Elastic Modulus E* of Cured Film] The tensile elastic modulus E* of the cured film constituting the top plate portion of the hollow structure obtained in the step (v) was measured as follows. The cured film was peeled off from the silicon wafer, and the tensile elastic modulus E* of the cured film at 175° C. was measured by the following evaluation apparatus and measurement conditions. This result is shown in Tables 2-4 as "tensile elastic modulus E* (GPa)". ・Evaluation device: Reogel E-4000 (manufactured by UBM) ・Measurement conditions: Tensile mode, frequency 1.0 Hz, distance between chucks 10 mm The higher the tensile elastic modulus E*, the higher the strength of the cured film. [Table 2] Example 1 Example 2 Example 3 Example 4 Negative photosensitive resin composition Modulation Example 1 Modulation Example 1 Modulation Example 1 Modulation Example 1 Operation in step (v) - UV exposure 1000 mJ/cm 2 UV exposure 5000 mJ/cm 2 UV irradiation 10000 mJ/cm 2 Heat treatment step hardening Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Top plate bulge (μm) ○(4) ○(2) ○(2) ○(1.5) Tensile elastic modulus E*(GPa) 2.1 2.1 2.1 2.1 [table 3] Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Negative photosensitive resin composition Modulation example 2 Preparation example 3 Preparation example 4 Modulation example 2 Preparation example 3 Preparation example 4 Operation in step (v) - - - UV exposure 1000 mJ/cm 2 UV exposure 1000 mJ/cm 2 UV exposure 1000 mJ/cm 2 Heat treatment step hardening Heat treatment step hardening Heat treatment step hardening Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Top plate bulge (μm) ○(3) ○(2) ○(2) ○(2) ○(1) ○(1) Tensile elastic modulus E* (GPa) 1.0 1.1 1.1 1.0 1.1 1.1 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Negative photosensitive resin composition Modulation Example 1 Modulation Example 1 Modulation example 2 Preparation example 3 Preparation example 4 Operation in step (v) - - - - - Heat treatment at 200°C for 60 minutes Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Heat treatment at 160°C for 60 minutes Top plate bulge (μm) ×(12) ×(8) ×(7) ○(5) ○(5) Tensile elastic modulus E* (GPa) 2.1 1.3 0.6 0.7 0.7 From the results shown in Tables 2 and 4, it can be seen from the comparison of Examples 1 to 4 with Comparative Examples 1 to 2 that have the same negative photosensitive resin composition, the hollow structures of Examples 1 to 4 are The bulging of the top plate portion due to the hardening operation at the time of manufacture was suppressed to a low level. Furthermore, it was found that the hollow structures of Examples 1 to 4 had sufficient strength. On the other hand, although the hollow structure of Comparative Example 1 had sufficient strength, it was confirmed that the top plate portion swelled greatly due to the hardening operation at the time of manufacture. In the hollow structure of Comparative Example 2, it was confirmed that the top plate portion bulged greatly due to the hardening operation at the time of manufacture, and the strength was inferior to that of the hollow structures of Examples 1 to 4. From the results shown in Tables 3 and 4, it can be seen from the comparison of Examples 5 and 8 with the same negative photosensitive resin composition and Comparative Example 3 that the hollow structures of Examples 5 and 8 were produced by The bulging of the top plate portion due to the hardening operation at the time was suppressed to a low level. On the other hand, in the hollow structure of Comparative Example 3, it was confirmed that the top plate portion swelled greatly due to the hardening operation at the time of manufacture. In addition, the strength of the hollow structures of Examples 5 and 8 was confirmed to be higher than that of the hollow structure of Comparative Example 3. From the results shown in Tables 3 and 4, it can be seen from the comparison of Examples 6 and 9 with the same negative photosensitive resin composition and Comparative Example 4 that the hollow structures of Examples 6 and 9 and Comparative Example 4 , the bulging of the top plate portion caused by the hardening operation at the time of manufacture is suppressed to a low level. As can be seen from the comparison of the two, the hollow structures of Examples 6 and 9 are further suppressed to a lower level than the hollow structure of Comparative Example 4, due to the hardening operation at the time of manufacture. In addition, it was found that the hollow structures of Examples 6 and 9 had higher strengths than the hollow structures of Comparative Example 4. From the results shown in Tables 3 and 4, it can be seen from the comparison of Examples 7 and 10 with the same negative photosensitive resin composition and Comparative Example 5 that the hollow structures of Examples 7 and 10 and Comparative Example 5 , the bulging of the top plate portion caused by the hardening operation at the time of manufacture is suppressed to a low level. As can be seen from the comparison of the two, the hollow structures of Examples 7 and 10 are further suppressed to a lower level than the hollow structure of Comparative Example 5 in that the bulging of the top plate portion due to the hardening operation at the time of manufacture. In addition, it was found that the hollow structures of Examples 7 and 10 had higher strengths than the hollow structures of Comparative Example 5. Therefore, it was confirmed that, by applying the present invention, the deformation of the top plate portion due to the hardening operation can be suppressed, and the hollow structure whose strength is further improved can be stably produced.

10:基板 20:側壁 30:感光性樹脂膜 40:硬化體 50:基材膜 60:光罩 80:積層膜 100:中空構造體10: Substrate 20: Sidewall 30: Photosensitive resin film 40: Hardened body 50: substrate film 60: Photomask 80: Laminated film 100: Hollow Construct

[圖1]為說明第1實施方式涉及的中空構造體的製造方法的示意圖。1 is a schematic diagram illustrating a method of manufacturing the hollow structure according to the first embodiment.

10:基板10: Substrate

15:凹部15: Recess

20:側壁20: Sidewall

30:感光性樹脂膜30: Photosensitive resin film

30A:曝光部30A: Exposure Department

30B:未曝光部30B: Unexposed part

40:硬化體40: Hardened body

50:基材膜50: substrate film

60:光罩60: Photomask

80:積層膜80: Laminated film

100:中空構造體100: Hollow Construct

Claims (6)

一種中空構造體的製造方法，其是由凹部，與封堵該凹部的開口面的頂板部形成的中空構造體的製造方法，且具有下述步驟： 步驟(0)，準備在表面具有凹部的基板與感光性阻劑膜，該感光性阻劑膜具有：含有含環氧基的樹脂(A)及因曝光而產生酸的光起始劑(I)的負型感光性樹脂膜； 步驟(i)，以前述感光性阻劑膜的感光性樹脂膜表面封堵前述基板中的前述凹部的開口面的方式，配置前述感光性阻劑膜； 步驟(ii)，在前述步驟(i)後，將前述感光性樹脂膜曝光； 步驟(iii)，對所述步驟(ii)後的前述感光性樹脂膜進行加熱處理； 步驟(iv)，在所述步驟(iii)後，將前述感光性樹脂膜顯影，形成負型圖型；與 步驟(v)，針對前述步驟(iv)後的前述負型圖型，進一步進行加熱處理，藉此使其硬化，得到前述頂板部係由前述感光性樹脂膜的硬化體形成的中空構造體； 藉由於150℃以下的溫度加熱10分鐘以上後，進一步在高於150℃的溫度進行加熱的操作(x)，或照射紫外線後，於100℃以上的溫度進行加熱的操作(y)，來進行前述步驟(v)中的加熱處理。A method of manufacturing a hollow structure comprising a hollow structure formed by a recess and a top plate portion that blocks an opening surface of the recess, and comprising the following steps: Step (0), prepare the substrate and photosensitive resist film with recessed part on the surface, and this photosensitive resist film has: contain epoxy group-containing resin (A) and photoinitiator (I) which generates acid due to exposure ) negative photosensitive resin film; Step (i), disposing the photosensitive resist film so that the surface of the photosensitive resin film of the photosensitive resist film blocks the opening surface of the concave portion in the substrate; Step (ii), after the aforementioned step (i), exposing the aforementioned photosensitive resin film; Step (iii), heat-treating the photosensitive resin film after the step (ii); step (iv), after the step (iii), developing the aforementioned photosensitive resin film to form a negative pattern; and step (v), further heat-treating the negative pattern after the step (iv), thereby making it hardened, to obtain a hollow structure in which the top plate portion is formed of the hardened body of the photosensitive resin film; It is carried out by the operation (x) of heating at a temperature higher than 150°C after heating at a temperature of 150°C or lower for 10 minutes or more, or by the operation (y) of heating at a temperature of 100°C or higher after irradiating ultraviolet rays The heat treatment in the aforementioned step (v). 如請求項1之中空構造體的製造方法，其中，作為前述操作(x)，進行下述操作：於50℃以上且125℃以下的溫度加熱10分鐘以上後，進一步於160℃以上的溫度加熱30分鐘以上。The method for producing a hollow structure according to claim 1, wherein, as the operation (x), the following operation is performed: after heating at a temperature of 50° C. or higher and 125° C. or lower for 10 minutes or longer, further heating at a temperature of 160° C. or higher more than 30 minutes. 如請求項1之中空構造體的製造方法，其中，作為前述操作(y)，進行下述操作：照射1000～10000 mJ/cm2 紫外線後，於160℃以上的溫度加熱30分鐘以上。The method for producing a hollow structure according to claim 1, wherein, as the operation (y), an operation of irradiating with 1000 to 10000 mJ/cm 2 of ultraviolet rays is performed, followed by heating at a temperature of 160° C. or higher for 30 minutes or more. 如請求項1～3中任一項之中空構造體的製造方法，其中，前述含環氧基的樹脂(A)包含下述通式(A1)表示的樹脂(A1)；
Figure 03_image001
式中，Rp1 及Rp2 各自獨立地為氫原子或碳原子數為1～5的烷基；複數個Rp1 相互可以相同也可以不同；複數個Rp2 相互可以相同也可以不同；n1 為1～5的整數；REP 為含環氧基的基；複數個REP 相互可以相同也可以不同。The method for producing a hollow structure according to any one of claims 1 to 3, wherein the epoxy group-containing resin (A) includes a resin (A1) represented by the following general formula (A1);
Figure 03_image001
In the formula, R p1 and R p2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; a plurality of R p1 may be the same or different from each other; a plurality of R p2 may be the same or different from each other; n 1 is an integer of 1 to 5; R EP is an epoxy group-containing group; and plural R EPs may be the same or different from each other. 如請求項1～4中任一項之中空構造體的製造方法，其中，前述光起始劑(I)包含選自由下述通式(I1)表示的化合物、及下述通式(I2)表示的化合物所成群的1種以上，
Figure 03_image003
式中，Rb01 ～Rb04 各自獨立地為可以具有取代基的芳基、或氟原子；Rb05 為可以具有取代基的氟化烷基、或氟原子；複數個Rb05 相互可以相同也可以不同；q為1以上的整數，Qq+ 各自獨立地為q價有機陽離子。The method for producing a hollow structure according to any one of claims 1 to 4, wherein the photoinitiator (I) contains a compound selected from the group consisting of a compound represented by the following general formula (I1) and the following general formula (I2) 1 or more of the compounds represented by the group,
Figure 03_image003
In the formula, R b01 to R b04 are each independently an aryl group or a fluorine atom that may have a substituent; R b05 is a fluorinated alkyl group that may have a substituent, or a fluorine atom; a plurality of R b05 may be the same as each other. different; q is an integer of 1 or more, and Q q+ are each independently a q-valent organic cation. 一種中空封裝體的製造方法，其係具有下述步驟：藉由密封材料將藉由如請求項1～5中任一項之製造方法所製造的中空構造體密封從而得到中空封裝體的步驟。A method of manufacturing a hollow package, comprising the step of sealing the hollow structure manufactured by the manufacturing method according to any one of claims 1 to 5 with a sealing material to obtain a hollow package.
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