TW201133144A - Negative photo sensitive resin composition, interlayer insulating film and forming method thereof - Google Patents

Negative photo sensitive resin composition, interlayer insulating film and forming method thereof Download PDF

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TW201133144A
TW201133144A TW100106488A TW100106488A TW201133144A TW 201133144 A TW201133144 A TW 201133144A TW 100106488 A TW100106488 A TW 100106488A TW 100106488 A TW100106488 A TW 100106488A TW 201133144 A TW201133144 A TW 201133144A
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group
carbon atoms
resin composition
negative
film
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TW100106488A
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TWI413861B (en
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Takehiro Fukuyama
Katsuyuki Masuda
Tomohiro Hirata
Yuuji Kobayashi
Katsuhiko Yasu
Satoshi Ninomiya
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Hitachi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F277/00—Macromolecular compounds obtained by polymerising monomers on to polymers of carbocyclic or heterocyclic monomers as defined respectively in group C08F32/00 or in group C08F34/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Chemical & Material Sciences (AREA)
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  • General Physics & Mathematics (AREA)
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  • Polymers & Plastics (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

A negative photo sensitive resin composition includes: (A) cycloolefin resin including repeating unit represented by the following formula (1): (wherein R1, R2, R3 and R4 are independently substituent selected from hydrogen atom, C1-15 alkyl group, C2-20 alkenyl group, C5-15 cycloalkyl group, C6-20 aryl group or C1-20 alkoxy group, or hydrolysis silyl sroup, C2-20 alkoxycarbonyl group, C4-20 trialkylsiloxycarbonyl group, C2-20 alkylcarbonyloxy group, C3-20 alkenylcarbonyloxy group and oxetanyl group, which can be bonded to each other directly or by oxygen atom, nitrogen atom, or sulfur atom, (B) multifunctional acryl monomer and (C) photo-polymerize initiator.

Description

201133144 …v * * r** 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種負片型感光性樹脂組成物、層間 絕緣膜及其形成方法。 【先前技術】 薄膜電晶體（thinfilmtransist〇r，以下記作「TFT」） 型液晶顯示元件、磁頭元件、積體電路元件及固體攝像管 元件等電子零件巾’通常為了使配置為層狀的配線之間絕 緣而汉置有層間絕緣膜（參照專利文獻丨）。作為上述層間 絕緣膜的材料，較佳為用簡得必需圖案形狀的步驟數 v而且具有充分的平坦十生的材料，因此廣泛使用負片型 感光性樹脂組成物（參照專利文獻2 )。 [先前技術文獻] [專利文獻] 專利文獻1 :日本專利特開2000-10089號公報 專利文獻2 :日本專利第3650985號公報 絕緣中，TFT型液晶顯示元件是經過在層間 、、邑、.彖膜上軸相電_，_於 條件的充分耐性 而製造。此時，該層間絕緣膜由於= …°· .·、·/中暴露於南溫條件下，故需要對該高溫 古t:t’TFT型液晶顯示元件中，於大晝面化、 二5元::=、及高速響應化等多種技術動向下， 件的結構魏之複雜化。因此，關於所使用的 201133144 d於低介電常數、高透光率（>8()%，λ=侧励〕 要求與絲任何時候相比均更高陳能，並且於 =曰曰顯不轉的結構上亦有可厚膜化至5—左右等特殊 要本。 但是，先前的層間絕緣膜形成時通常使用的負片型感 先性樹脂組成物巾，同時達成輕化與高透光率化及高解 析度極其ϋ難’故強烈要翔發出可形成兼具上述特性的 層間絕緣膜的負片型感光性樹脂組成物。 【發明内容】 本發明是赛於上述情況而成，目的在於提供一種可形 成即便厚麻，解析度、透雜、耐錄、耐熱變色性及 耐溶劑性等諸乡紐亦充分優異的層瞧賴的負片型感 光性樹脂組成物。另外，本發明的目的在於提供一種由上 述負片型感光性樹脂組成物所形成的層間絕緣膜及其形成 方法。 本發明提供一種負片型感光性樹脂組成物，其包含： 包含下述通式（1)所表示的重複單元的（Α)環狀烯烴樹 脂、（Β)多官能性丙烯酸單體、及（c)光聚合起始劑。 式（1)中R1、^、以及“分別獨立地表示選自氫原子、 碳數1〜15的烷基、碳數2〜2〇的烯基、碳數5〜15的環 烧基、碳數6〜20的芳基或碳數丨〜如的烷氧基，或者水 解性矽烷基、碳數2〜20的烷氧基羰基、碳數4〜20的三 烧基碎烧氧基羰基、碳數2〜2〇的烷基羰氧基、碳數3〜 20的烯基幾氧基及氧雜環丁基中的取代基，可直接或者經 Θ 6 201133144 由氧原子、氮原子或硫原子而相互連結。 [化1][Technical Field] The present invention relates to a negative-type photosensitive resin composition, an interlayer insulating film, and a method of forming the same. [Prior Art] A thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, and an electronic component tape such as a solid-state image sensor element are generally arranged in a layered wiring. An interlayer insulating film is interposed between the two (see Patent Document 丨). As the material of the above-mentioned interlayer insulating film, it is preferable to use a negative-type photosensitive resin composition (see Patent Document 2) because the number of steps v of the necessary pattern shape is sufficient and the material is sufficiently flat. [Prior Art Document] [Patent Document 1] Patent Document 1: Japanese Patent Laid-Open Publication No. 2000-10089 (Patent Document 2): Japanese Patent No. 3650985, in which the TFT-type liquid crystal display element is passed through the interlayer, 邑, 彖. The on-axis phase of the film is made _, _ under conditions of sufficient tolerance. At this time, since the interlayer insulating film is exposed to the south temperature condition in the case of = ... ° · ····, it is required to be used in the high temperature ancient t:t' TFT type liquid crystal display element. Yuan::=, and high-speed response and other technologies are moving downwards, and the structure of the pieces is complicated. Therefore, regarding the use of 201133144 d, the low dielectric constant, high light transmittance (> 8 ()%, λ = side excitation) are required to be higher than that of the wire at any time, and The non-rotating structure also has a special film which can be thickened to about 5 to about. However, the negative interlayer type resin composition towel which is usually used in the formation of the interlayer insulating film at the same time achieves lightening and high light transmission at the same time. It is extremely difficult to increase the rate and high resolution. Therefore, it is strongly desired to form a negative-type photosensitive resin composition capable of forming an interlayer insulating film having the above characteristics. [Invention] The present invention is made in the above-described manner, and the object is to Provided is a negative-type photosensitive resin composition which can form a layer which is excellent even in a wide range of properties such as a high-density, a resolution, a pass-through, a recording resistance, a heat-resistant discoloration property, and a solvent resistance. Moreover, the object of the present invention An interlayer insulating film formed of the above-described negative-type photosensitive resin composition and a method for forming the same are provided. The present invention provides a negative-type photosensitive resin composition comprising: a weight represented by the following general formula (1) a unitary (Α) cyclic olefin resin, a (Β) polyfunctional acrylic monomer, and (c) a photopolymerization initiator. In the formula (1), R1, ^, and "each independently represent a hydrogen atom, An alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 2 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having a carbon number of 丨~, or hydrolyzed a mercaptoalkyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a trialkyl group of a calcined oxycarbonyl group having 4 to 20 carbon atoms, an alkylcarbonyloxy group having 2 to 2 carbon atoms, and an alkene having 3 to 20 carbon atoms The substituents in the benzyloxy group and the oxetanyl group may be bonded to each other directly or via an oxygen atom, a nitrogen atom or a sulfur atom via 2011 6 201133144.

R2炉 具備上述構成的負片型感光性樹脂組成物可形成即便 厚f化，解析度、透明性、耐熱性、耐熱變色性及耐溶劑 性等諸多特性亦充分優異的層間絕緣膜。 一 （A)裱狀烯烴樹脂較佳為包含由上述通式（〗）所表 示且R、R、r1R4為氫原子的結構單元。 另外’⑷環狀稀烴樹脂較佳為包含由上述通式⑴ ΐ R1、R2、R3及R4中的任一者為碳數2〜20的 烧基羰氧基的結構單元。 PUS t月提供種負片型感光性樹脂組成物，其用於層 二鮮/㈣成方法’該形成方法包括對由該負片型感光 =的日ίΓΓ斤形成的膜的至少一部分照射波長400 -以下的紫外線的步驟。 含^外驗片型感光性樹脂組成物較佳為更包 本發明提供一種由上述負片型感光性樹脂組成物所形 201133144 / UT /^,ΙΑ 成的層間絕緣膜。 本發明提供一種層間絕緣膜的形成方法，其包括以下 步驟.對由上述負片型感光性樹脂組成物所形成的膜的至 少:部分照射光；將照射光後的上述膜進行顯影；以及將 顯影後的上述膜煅燒而形成層間絕緣膜。 [發明的效果] 依據本發明，可提供一種可形成即便厚膜化，解析度、 透明性、耐熱性、耐熱變色性及耐溶劑性等諸多特性亦充 分優異的層間絕緣膜的負片型感光性樹脂組成物。 【實施方式】 以下’對本發明的較佳實施形態進行詳細說明。 本實施形態的負片型感光性樹脂組成物包含（Α)環 狀烯烴樹脂、（Β)多官能性丙烯酸單體、及（C)光聚合 起始劑。以下對各成分進行詳細說明。 -(Α)環狀稀烴樹脂_ 本實施形態的（Α)環狀烯烴樹脂是具有由下述通式 (1)所表示的重複單元的聚合物。 [化2]In the R2 furnace, the negative-type photosensitive resin composition having the above-described configuration can be formed into an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when the thickness is increased. The (A) olefin-like olefin resin preferably contains a structural unit represented by the above formula (I) and wherein R, R and r1R4 are a hydrogen atom. Further, the '(4) cyclic dilute hydrocarbon resin is preferably a structural unit containing a carbonyloxy group having 2 to 20 carbon atoms, which is one of the above formula (1) ΐ R1, R2, R3 and R4. PUS t month provides a negative-type photosensitive resin composition for use in a layer two-color/(four) forming method. The forming method includes irradiating at least a portion of a film formed of the negative-type photosensitive photosensitive film to a wavelength of 400 - or less. The steps of UV. The photosensitive resin composition containing the external test sheet is preferably further provided. The present invention provides an interlayer insulating film formed of the above-mentioned negative-type photosensitive resin composition in the form of 201133144 / UT / ^. The present invention provides a method of forming an interlayer insulating film, comprising the steps of: irradiating at least a portion of a film formed of the negative-type photosensitive resin composition; developing the film after irradiation; and developing The latter film is fired to form an interlayer insulating film. [Effects of the Invention] According to the present invention, it is possible to provide a negative-type photosensitive film of an interlayer insulating film which is excellent in various properties such as resolution, transparency, heat resistance, heat-resistant discoloration property, and solvent resistance even when thickened. Resin composition. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail. The negative-type photosensitive resin composition of the present embodiment contains a (?) cyclic olefin resin, a (?) polyfunctional acrylic monomer, and (C) a photopolymerization initiator. Each component will be described in detail below. - (Α) cyclic dilute hydrocarbon resin _ The cyclic olefin resin of the present embodiment is a polymer having a repeating unit represented by the following general formula (1). [Chemical 2]

201133144 Λ. Μ» 上述R1、R2、R3及r4分別獨立地表示選自氫原子、 石反數1〜15的烧基、碳數2〜20的稀基、碳數$〜15的環 烧基、奴數6〜20的芳基或碳數1〜2〇的烧氧基，或者水 解性矽烷基、碳數2〜20的烷氧基羰基、碳數4〜2〇的三 烷基矽烷氧基羰基、碳數2〜20的烷基羰氧基、碳數3〜 20的烯基羰氧基及氧雜環丁基中的取代基，可直接或者經 由氧原子、氮原子或硫原子而相互連結。 更佳為R1、R2、R3及R4分別獨立地為選自氫原子、 碳數1〜15的烷基、碳數2〜2〇的烯基、碳數6〜15的芳 基、或者碳數6〜20的烷氧基以及碳數2〜2〇的烷基羰氧 基中的取代基。藉由設為上述構成，獲得於各種溶劑中的 溶解性提高的效果。 其中，水解性矽烷基具體可列舉三曱氧基矽烷基、甲 基二曱氧基矽烷基。 石反數2〜20的烧基幾氧基具體可列舉：曱g旨、第三丁 酯、2^基己酯、节酯、環戊醋、環己醋及烯丙酯。該些 烧基幾氧基中，就财熱性方面而言，特佳為使用甲醋 酯等。 本實施形態中使用的（A)環狀烯烴樹脂較佳為以環 狀烯烴中的式（1)的結構單元的總量為基準，包含！莫耳 =分比（mol%)以上的由上述通式（丨）所表示且Rl、R2、 R3及R4為氫原子的結構單元，更佳為包含1()mGl%以上。 於該比例為1 mol%以上的情況，存在所得負片型感 脂組成物的耐熱性提高的傾向。另外，上述比例較佳為6〇 201133144 mol%以下，更佳為50mol%以下。於上述比例為6〇m〇1% 以下的情況，存在於用以製備負片型感光性樹脂組成物的 溶劑中的可溶性提高的傾向。 本實施形態中使用的（A)環狀烯烴樹脂較佳為以環 狀浠烴中的式（1 )的結構單元的總量為基準，包含i m〇1〇/〇 以上的由上述通式（1)所表示且尺^“〜以及^中的任 一者為碳數2〜20的烷基羰氧基的結構單元，更佳為包含 10 mol%以上。於該比例為} m〇1%以上的情況存在獲得 於用以製備負片型感光性樹脂組成物的溶劑中的可溶性提 咼的效果的傾向。上述比例較佳為6〇 m〇1%以下，更佳為 50 mol%以下。於上述比例為6〇 m〇1%以下的情況存在獲 得所得負片型感紐細旨組成物的耐熱性提高的效果的傾 上述（A)環狀稀煙樹脂可藉由將下述通式（2)所表 示的單體於溶劑中’在金屬觸媒的存在下進行加成共聚合 而製造。201133144 Λ. Μ» The above R1, R2, R3 and r4 each independently represent a halogen group selected from a hydrogen atom, a stone inverse number of 1 to 15, a carbon number of 2 to 20, and a cycloalkyl group having a carbon number of from 1,500 to 15 An aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or a trialkyldecaneoxy group having 4 to 2 carbon atoms. a carbonyl group, an alkylcarbonyloxy group having 2 to 20 carbon atoms, an alkenylcarbonyloxy group having 3 to 20 carbon atoms, and a substituent in the oxetanyl group may be directly or via an oxygen atom, a nitrogen atom or a sulfur atom. Connected to each other. More preferably, R1, R2, R3 and R4 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 2 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a carbon number. a substituent in an alkoxy group of 6 to 20 and an alkylcarbonyloxy group having 2 to 2 carbon atoms. According to the above configuration, the effect of improving the solubility in various solvents is obtained. Specific examples of the hydrolyzable alkylene group include a tridecyloxyalkylene group and a methyldimethoxyoxyalkylene group. Specific examples of the pyridyloxy group having a reciprocal number of 2 to 20 include hydrazine, tributyl acrylate, hexyl hexyl acrylate, decyl ester, cyclopentaacetic acid, cyclohexanoic acid, and allyl ester. Among these alkyloxy groups, it is particularly preferable to use methyl acetate or the like in terms of fuel economy. The (A) cyclic olefin resin used in the present embodiment is preferably contained in the total amount of the structural unit of the formula (1) in the cyclic olefin; Mohr = fraction (mol%) or more of the structural unit represented by the above formula (丨) and R1, R2, R3 and R4 are a hydrogen atom, and more preferably 1 () mGl% or more. When the ratio is 1 mol% or more, the heat resistance of the obtained negative-type photosensitive composition tends to be improved. Further, the above ratio is preferably 6 〇 201133144 mol% or less, more preferably 50 mol% or less. In the case where the above ratio is 6 〇 m 〇 1% or less, the solubility in the solvent for preparing the negative-type photosensitive resin composition tends to be improved. The (A) cyclic olefin resin used in the present embodiment preferably contains the above formula (including im〇1〇/〇 or more) based on the total amount of the structural unit of the formula (1) in the cyclic anthracene hydrocarbon. 1) The structural unit represented by the alkylcarbonyloxy group having a carbon number of 2 to 20, and more preferably 10 mol% or more, in which the ratio is "m〇1%". In the above case, there is a tendency to obtain an effect of improving the solubility in a solvent for preparing a negative-type photosensitive resin composition. The above ratio is preferably 6 〇m 〇 1% or less, more preferably 50 mol % or less. When the ratio is 6 〇m 〇 1% or less, the effect of obtaining the effect of improving the heat resistance of the obtained negative-type sensation composition may be obtained by the following formula (2). The monomer represented by the above is produced by addition copolymerization in the presence of a metal catalyst in a solvent.

(A)環狀稀烴樹脂的製造時使用的溶劑例如可列 舉.戍烧（pentane )、己燒（hexane )及庚院（heptane ) 201133144 等脂肪族烴’環己烧（cyclohexane )等脂環族煙，笨 (benzene)、曱苯（toluene)及二甲苯（Xyiene)等芳香族 烴，二氯曱烷（dichloromethane)、氣仿（chl〇r〇f〇rm)及 氣本（chlorobenzene )等鹵化經’硝基甲燒（nitromethane)、 硝基苯（nitrobenzene )及乙腈（acetonitrile )等含氮系煙， 以及二乙醚（diethyl ether)、二噁烷（dioxane)及四氫咳 喃（tetrahydrofuran)等醚類。該些溶劑可單獨使用1種， 或者將2種以上混合使用。 (A)環狀烯烴樹脂的聚合時使用的觸媒（e)較佳為 於選自元素週期表第8族元素、第9族元素及第1〇族元素 中的一種過渡金屬上至少配位有環戊二稀基 (cyclopentadienyl)系配位子的錯合物。具體例可列舉鐵 (Fe )、钻（Co )、錄（Ni)、釕（Ru )、錢（Rh )、把（Pd )、 及鉑（Pt)。該些金屬中，就提高觸媒的聚合活性的觀點而 吕較佳的元素為姑、鎳、把、及翻，特佳為使用飽。 (Α)環狀烯烴樹脂的聚合時使用的助觸媒（ρ)較佳 為促進形成觸媒（Ε)的錯合物的配位子的解離的助觸媒。 例如可列舉將以下所例示的非配位性陰離子與陽離子組合 而成的離子性化合物。 非配位性陰離子例如可列舉：四（苯基）硼酸鹽 (tetra(phenyl)borate)、四（說苯基)硼酸鹽、四（二氟苯基) 硼酸鹽、四（三氟苯基)硼酸鹽、四（四氟苯基)硼酸鹽、四（五 氟苯基)硼酸鹽、四（四氟甲基苯基)硼酸鹽、四（曱苯基)硼 酸鹽（tetra(tolyl)borate )、四（二曱笨基）硼酸鹽 11 201133144 / V/-f t tetra(Xylyl)b〇rate)、（三苯基，五氟苯基)删酸鹽、[三(五氟苯 基），苯基]硼酸鹽及十三氫化_7,8_二碳代十一硼酸鹽 (tridecahydride-7,8-dicarbaundecaborate)。 上述陽離子可列舉：碳鑌（carb〇niurn)陽離子、氧鏽 (oxonium )陽離子、錄（amm〇njum )陽離子、鎸 (phosphonium)知離子、環庚三稀基（CyCi〇heptyitrienyi) 1%離子及具有過渡金屬的二茂鐵（ferr〇ceniuin)陽離子等。 碳鏽陽離子的具體例可列舉三苯基碳鑌陽離子及三取 代苯基碳鑌陽離子等三取代碳鑌陽離子。三取代苯基碳鑌 陽離子的具體例可列舉三（曱基苯基)碳鏽陽離子及三（二 曱基苯基)碳鏽陽離子。 銨陽離子的具體例可列舉：三甲基銨（trimethyl ammonium)陽離子、三乙基銨陽離子、三丙基銨陽離子、 三丁基銨陽離子及三（正丁基）銨陽離子等三烷基銨陽離 子 ’ N，N-二乙基苯銨（N，N-diethyl anilinium)陽離子及 N，N-2,4,6-五曱基苯銨陽離子等N，N_二烷基苯銨陽離子， 以及二(異丙基)銨陽離子及二環己基銨陽離子等二烷基銨 陽離子。 鱗陽離子的具體例可列舉：三苯基鳞 (triphenylphosphonium)陽離子、三（曱基苯基)鱗陽離子 及二(一曱基本基)鱗離子等三芳基鱗陽離子。 上述離子性化合物例如為三苯甲基四（五氟苯基)硼酸 鹽（trityl tetra(pentafluorophenyl)borate)、三苯基碳鑌四（氟 苯基）爛酸鹽 （triphenylcarbonium 6 201133144 j t u-r /pii. tetra(fluorophenyl)borate )、N,N-二曱基苯銨四（五氟苯基) 棚酸鹽 （ N，N-dimethylanilinium tetra(pentafluorophenyl)borate)及 1，1，_二曱基二茂鐵四（五 氣本基）石朋酸鹽（1 ,Γ-dimethylferrocenium tetra(pentafluorophenyl)borate ) ° 本實施形態中，觸媒（E)與助觸媒（F)的比例由於 根據各種條件而有所不同，故無法一概而定，但通常較佳 為以觸媒E/助觸媒F (莫耳比）計為1/0.1〜1/1〇〇〇〇，更 佳為1/0.5〜1/5000，進而更佳為1/1〜1/2000。 本實施形態的（A)環狀烯烴樹脂的聚苯乙烯換算重 量平均分子量（以下稱為「Mw」）較佳為2χ103至2χ105 , 更佳為2χ104至1.8><105。若Mw小於2><103，則所得被膜 存在耐熱性及表面硬度下降的傾向。另一方面，若Mw超 過2xl〇5，則存在顯影性、於感光性樹脂組成物製備用溶 劑中的溶解性下降的傾向。 -(B)多官能性丙烯酸單體_ 本實施形態的（B)多官能性丙烯酸單體是使用二官 能以上的多官能（甲基）丙烯酸酯。具體可列舉：二季戊四 醇六丙烯酸酯（dipentaerythritol hexaacrylate)、二季戊四 醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇 五甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四曱基 =_旨、季戊四醇三丙稀酸、季戊四醇三曱基丙稀酸 ^季戊四醇二丙烯酸酯、季戊四醇二甲基丙烯酸酯、四 1甲基丙燒四丙稀酸酯（tetramethyl〇lpr〇pane(A) The solvent used in the production of the cyclic dilute hydrocarbon resin may, for example, be an alicyclic hydrocarbon such as pentane, hexane or heptane 201133144, such as an aliphatic hydrocarbon such as cyclohexane. Aromatic hydrocarbons such as benzene, toluene and xyiene, dichloromethane, chl〇r〇f〇rm and chlorobenzene Halogenated nitrogen-containing cigarettes such as nitromethane, nitrobenzene, and acetonitrile, and diethyl ether, dioxane, and tetrahydrofuran Ethers. These solvents may be used alone or in combination of two or more. The catalyst (e) used in the polymerization of the cyclic olefin resin (A) is preferably at least coordinated to a transition metal selected from the group consisting of a Group 8 element, a Group 9 element, and a Group 1 element of the periodic table. There is a complex of a cyclopentadienyl ligand. Specific examples thereof include iron (Fe), drill (Co), nickel (Ru), ruthenium (Rh), palladium (Pd), and platinum (Pt). Among these metals, in terms of improving the polymerization activity of the catalyst, the preferred elements are agglomerates, nickels, handles, and turns, and particularly preferably used. The promoter (ρ) used in the polymerization of the cyclic olefin resin is preferably a promoter which promotes the dissociation of the ligand of the complex of the catalyst (Ε). For example, an ionic compound obtained by combining a non-coordinating anion exemplified below with a cation can be mentioned. Examples of the non-coordinating anion include tetra(phenyl)borate, tetrakis(phenyl)borate, tetrakis(difluorophenyl)borate, and tetrakis(trifluorophenyl). Borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate , tetra (diphenyl) borate 11 201133144 / V / - ft tetra (Xylyl) b〇rate), (triphenyl, pentafluorophenyl) decadate, [tris(pentafluorophenyl), benzene Boronate and tridecahydride-7,8-dicarbaundecaborate. Examples of the above cation include a carb〇niurn cation, an oxonium cation, an amm〇njum cation, a phosphonium ion, a CyCi〇heptyitrienyi 1% ion, and A ferrocene cation having a transition metal or the like. Specific examples of the carbon rust cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation and a trisubstituted phenylcarbonium cation. Specific examples of the trisubstituted phenylcarbenium cation include a tris(nonylphenyl)carbon rust cation and a tris(didecylphenyl)carbon rust cation. Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation, and tri(n-butyl) ammonium cation. 'N,N-diethyl anilinium cation and N,N-dialkylanilinium cation such as N,N-2,4,6-pentamethylanilinium cation, and a dialkylammonium cation such as an (isopropyl)ammonium cation or a dicyclohexylammonium cation. Specific examples of the scaly cation include triarylphosphonium cations, tris(nonylphenyl) squamenes, and triaryl sulfonium cations such as bis(indenyl) scaly ions. The above ionic compound is, for example, trityl tetra(pentafluorophenyl)borate, triphenylcarbonate tetrakis(fluorophenyl) rotate (triphenylcarbonium 6 201133144 jt ur /pii . Tetra (fluorophenyl)borate ), N,N-dimethylanilinium tetra(pentafluorophenyl)borate and 1,1,-didecyldiphenyl In the present embodiment, the ratio of the catalyst (E) to the promoter (F) is different depending on various conditions. The difference is not uniform, but it is usually preferably 1/0.1 to 1/1 〇〇〇〇, more preferably 1/0.5 〜1, based on the catalyst E/catalyst F (mole ratio). /5000, and further preferably 1/1 to 1/2000. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the (A) cyclic olefin resin of the present embodiment is preferably 2χ103 to 2χ105, more preferably 2χ104 to 1.8><105. When Mw is less than 2 < 103, the obtained film tends to have heat resistance and surface hardness. On the other hand, when Mw exceeds 2xl〇5, the developability and the solubility in the solvent for preparing a photosensitive resin composition tend to be lowered. - (B) Polyfunctional acrylic monomer (B) The polyfunctional acrylic monomer of the present embodiment is a polyfunctional (meth)acrylate having a difunctional or higher content. Specific examples thereof include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetradecyl group, and pentaerythritol. Tripropylene acid, pentaerythritol tridecyl acrylic acid, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethyl hydrazine tetrapropyl acrylate (tetramethyl 〇 lpr〇pane)

201133144 j / wr I tetraacrylate)、四經曱基丙烧四曱基丙稀酸S旨、四經曱基 曱烷四丙烯酸酯、四羥曱基甲烷四曱基丙烯酸酯、三羥曱 基丙烷三丙烯酸酯、三羥曱基丙烷三曱基丙烯酸酯、1，3,5-三丙烯醯基六氫-均三。秦（l，3,5-triacryloyl hexahydro-s-triazine )、1，3,5-三曱基丙稀醯基六氫-均三 嗓、三（經基乙基丙婦醯基）三聚異氰酸酯 (tris(hydroxyethylacryloyl)isocyanurate )、三（羥基乙基曱 基丙烯醯基)三聚異氰酸酯、三丙烯醯基縮曱醛（triacryloyl formal)、三曱基丙烯醯基縮甲醛、1，6-己二醇丙烯酸酯 (l，6-hexanediol acrylate)、1，6_ 己二醇曱基丙稀酸酯、新 戊二醇二丙烯酸g旨（neopentyl glycol diacrylate)、新戊二 醇二曱基丙稀酸醋、乙二醇二丙烯酸自旨（ethylene glycol diacrylate)、乙二醇二甲基丙烯酸酯、2-羥基丙二醇二丙烯 酸S旨（2-hydroxy propanediol diacrylate)、2-羥基丙二醇二 曱基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二曱基丙 烯酸酯、異丙二醇二丙烯酸酯、異丙二醇二曱基丙烯酸酯、 三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、N，N，-雙（丙烯醯基)半胱胺酸（N，N'-bis(acryloyl)cysteine)、Ν,Ν'-雙（曱基丙烯醯基）半胱胺酸、硫代雙乙醇二丙烯酸酯 (thiodiglycol diacrylate)、硫代雙乙醇二曱基丙烯酸酯、 雙盼A二丙烯酸醋（bisphenol A diacrylate )、雙酴A二曱 基丙烯酸酯、雙酚F二丙烯酸酯、雙酚F二曱基丙烯酸酯、 雙酚S二丙烯酸酯、雙酚S二甲基丙烯酸酯、雙苯氧基乙 醇荈二丙烯酸g旨（bisphenoxy ethanol fluorene diacrylate)、201133144 j / wr I tetraacrylate), tetrapyridyl propyl sulfonate tetradecyl acrylate S, tetrapyridyl decane tetraacrylate, tetrahydro hydroxy methane tetradecyl acrylate, trishydroxy propyl propane Acrylate, trihydroxymercaptopropane tridecyl acrylate, 1,3,5-tripropylene decyl hexahydro-all. Qin (l,3,5-triacryloyl hexahydro-s-triazine), 1,3,5-trimercaptopropylphosphonium hexahydro--tris-trimethylene, tris(transethyl acetophenone) trimeric isocyanate (tris(hydroxyethylacryloyl)isocyanurate ), tris(hydroxyethylmercaptopropenyl)trimeric isocyanate, triacryloyl formal, tridecyl propylene fluorenyl formal, 1,6-hexane 1,6-hexanediol acrylate, 1,6-hexanediol mercapto acrylate, neopentyl glycol diacrylate, neopentyl glycol dimercapto acrylate Ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxy propanediol diacrylate, 2-hydroxypropanediol dimercapto acrylate, Ethylene glycol diacrylate, diethylene glycol dimercapto acrylate, isopropyl glycol diacrylate, isopropyl glycol dimercapto acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N ,N,-bis(acryloyl)cysteine (N,N'-bis(acrylo) Yl)cysteine), hydrazine, Ν'-bis(mercaptopropenyl)cysteine, thiodiglycol diacrylate, thiodiethanol dimercapto acrylate, bicanti A diacrylate Bisphenol A diacrylate, biguanide A dimercapto acrylate, bisphenol F diacrylate, bisphenol F dimercapto acrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, diphenyl Bisphenoxy ethanol fluorene diacrylate

201133144 -；/ \JT / piA 雙苯氧基乙醇第二甲基丙婦酸酯、二烯丙醚雙紛A (diallyletherbisphenolA)、鄰二烯丙基雙酚 a、順丁烯二 酸二烯丙酯（diallyl maleate )及偏苯三曱酸三烯丙酯 (triallyl trimellitate )。藉由使用二官能以上的多官能（曱基) 丙烯酸酯，而獲得機械強度增加的效果。 上述多官能性丙烯酸單體可作為市售品而容易獲取， 例如可列舉：Kyarad T-1420、Kyarad DPHA、Kyarad DPHA-2C ' Kyarad D-310 ' Kyarad D-330 > Kyarad DPCA-20、Kyarad DPCA-30、Kyarad DPCA-60、Kyarad DPCA-120、Kyarad DN-0075、Kyarad DN-2475、Kyarad R-526、Kyarad NPGDA、Kyarad PEG400DA、Kyarad MANDA、Kyarad R_ 167、Kyarad HX-220、Kyarad HX620、 Kyarad R-551、Kyarad R-712、Kyarad R-604、Kyarad R-684、Kyarad GPO-303、Kyarad TMPTA、Kyarad THE-330、Kyarad TPA-320、Kyarad TPA-330、Kyarad PET-30、Kyarad RP-1040 (以上由日本化藥（股）製造）； Aronix M-210、Aronix M-240、Aronix M-6200、Aronix M-305'Aronix M-309'Aronix M-400'Aronix M-402'Aronix M-405、Aronix M-450、Aronix M-7100、Aronix M-8030、 Aronix M-8060、Aronix M-1310、Aronix M-1600、Aronix M-l960、Aronix M-8100、Aronix M-8530、Aronix M-8560、 Aronix M-9050 (以上由東亞合成（股）製造）；Viscoat 295、 Viscoat 300、Viscoat 360、Viscoat GPT、Viscoat 3PA、Viscoat 400、Viscoat 260、Viscoat 312 及 Viscoat 335HP (以上由 15 201133144 j /υι /ριι ΐ造)。另外’該些多官能性丙稀 酉夂早體了早獨使用！種，或者將2種以上 該些多，丙轉體中，就於顯影液= 容解性 二：ί而1 :#ί佳為二季戊四醇六丙烯酸酯、二季戊四 醇八甲基丙稀酸自旨、二季戊四醇五丙烯_旨、二季戊四 五甲基丙稀義、季戊四醇四丙烯咖、季戊四醇 丙烯咖、季戊四醇三丙烯_、季細醇三曱基丙婦ς 醋、季戊四醇二丙烯_旨及季細醇二？基丙稀酸醋。 _ (C)光聚合起始劑- 本實施形態的（C)光聚合起始劑可列舉感光性自由 基聚合起始劑。該感光性自由基聚合起始劑例如可列舉： 苯偶醯（benzil)及雙乙醯（diacetyl)等 α•二酮（a diket〇ne ) 類，安息香（benzoin)等醇酮（acyloin)類，安息香甲驗 (benzoin methylether )、安息香乙醚及安息香異丙醚等醇 酮醚（acyloin ether)類’噻吨酮（thioxanth〇ne)、2,4_二 乙基噻吨酮、噻吨酮-4-磺酸，二苯甲酮（benzophen〇ne)、 4,4'-雙（二曱基胺基)二苯曱酮及4,4，-雙(二乙基胺基)二苯 甲酉同等一本甲酮類’苯乙嗣（acetophenone)、對二甲基胺 基苯乙嗣（p-dimethylamino acetophenone)、α,α，-二甲氧基 乙醯氧基二苯甲酮（a，a'-dimethoxy acetoxy benzophenone)、2,2'-二甲氧基-2·苯基苯乙酮、對曱氧基苯 乙酮、2-甲基（4-(甲基硫基）苯基）-2-嗎啉基-1-丙酮 (2-methyl(4-(methylthio)phenyl)-2-morpholino-1 -propanon e)及2-节基-2-二曱基胺基-1-(4-嗎啉基苯基)-丁-1-酮等苯 201133144 / u-τ / pil 乙酮類，蒽i昆(anthraquinone )及1，4-萘酉昆 (l，4-naphthoquinone)等醌（quinone)類，苯甲醯甲基氣 (phenacyl chloride)、三漠曱基苯基石風（tribromomethyl phenyl sulfone ) 及三（三氯曱基）-均三嗪 (tris(trichloromethyl)-s-triazine)等卤化物，2,4,6-三曱基 苯曱酿基二苯基氧化膦（2,4,6-trimethyl benzoyl diphenyl phosphine oxide)、雙(2,6-二曱氧基苯曱醯基)-2,4,4-三甲基 -戊基氧化膦及雙(2,4,6-三曱基苯曱醯基）苯基氧化膦等醯 基氧化膦、及過氧化二第三丁基（di-t-butyl peroxide)等 過氧化物等。藉由使用感光性自由基聚合起始劑，獲得負 片型感光性樹脂組成物對光的感度提高的效果。 作為該些感光性自由基聚合起始劑的市售品，例如可 列舉：Irgacure-184、Irgacure-369、Irgacure-500、 Irgacure-651、Irgacure-907、Irgacure，1700、Irgacure-819、 Irgacure-124、Irgacure-1000、Irgacure-2959、Irgacure-149、 Irgacure-1800 、Irgacure-1850 、Irgacure-OXE-Ol 、 Darocur-1173、Darocur-1116、Darocur-2959、Darocur-1664、 Darocur-4043 (以上由 Ciba Specialty Chemicals 公司製 造)；Kayacure-DETX、Kayacure-MBP、Kayacure-DMBI、 Kayacure-EPA、Kayacure-OA (以上由日本化藥（股）製 造）；Lucirintpo(BASF Co.LTD 製造）；Vicure-10、Vicure_55 (以上由 STAUFFER Co.LTD 製造）；Trigonal PI (AKZO Co.LTD 製造）；Sandoray 1000 ( SANDOZ Co.LTD 製造）； DEAP ( APJOHN Co.LTD 製造）；Quantacure-PDO、 17 201133144201133144 -; / \JT / piA diphenoxyethanol second methyl acetoacetate, diallyl ether A (diallyletherbisphenol A), o-diallyl bisphenol a, maleic acid diene Diallyl maleate and triallyl trimellitate. The effect of increasing the mechanical strength is obtained by using a difunctional or higher polyfunctional (fluorenyl) acrylate. The above polyfunctional acrylic monomer can be easily obtained as a commercially available product, and examples thereof include Kyarad T-1420, Kyarad DPHA, Kyarad DPHA-2C 'Kyarad D-310 'Kyarad D-330 > Kyarad DPCA-20, Kyarad DPCA-30, Kyarad DPCA-60, Kyarad DPCA-120, Kyarad DN-0075, Kyarad DN-2475, Kyarad R-526, Kyarad NPGDA, Kyarad PEG400DA, Kyarad MANDA, Kyarad R_167, Kyarad HX-220, Kyarad HX620, Kyarad R-551, Kyarad R-712, Kyarad R-604, Kyarad R-684, Kyarad GPO-303, Kyarad TMPTA, Kyarad THE-330, Kyarad TPA-320, Kyarad TPA-330, Kyarad PET-30, Kyarad RP -1040 (above manufactured by Nippon Kayaku Co., Ltd.); Aronix M-210, Aronix M-240, Aronix M-6200, Aronix M-305'Aronix M-309'Aronix M-400'Aronix M-402'Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-1310, Aronix M-1600, Aronix M-l960, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050 (above manufactured by East Asia Synthetic Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA Viscoat 400, Viscoat 260, Viscoat 312, and Viscoat 335HP (of more than 15 201133144 j / υι / ριι ΐ Shuzo). In addition, these polyfunctional propylene amps have been used early! Species, or more than two or more, in the propane, in the developer = capacitive two: ί and 1: #ί佳 is dipentaerythritol hexaacrylate, dipentaerythritol octamethyl propylene acid , dipentaerythritol pentapropene _, dipentaerythritol tetrapentamethyl propylene, pentaerythritol tetra propylene coffee, pentaerythritol propylene coffee, pentaerythritol tripropylene _, quaternary alcohol triterpene propylene glycol vinegar, pentaerythritol dipropylene _ Fine alcohol II? Acrylic acid vinegar. (C) Photopolymerization initiator - The (C) photopolymerization initiator of the embodiment may be a photosensitive radical polymerization initiator. Examples of the photosensitive radical polymerization initiator include α-dione (a diket〇ne) such as benzil and diacetyl, and acyloin such as benzoin. , benzoin methylether, benzoin ether and benzoin ether, acyloin ether, thioxanthene, 2,4-diethylthioxanthone, thioxanthone 4-sulfonic acid, benzophenone, 4,4'-bis(didecylamino)benzophenone and 4,4,-bis(diethylamino)benzhydrazide An equivalent of ketones 'acetophenone, p-dimethylamino acetophenone, α,α,-dimethoxyacetoxybenzophenone (a, A'-dimethoxy acetoxy benzophenone), 2,2'-dimethoxy-2-phenylphenone, p-methoxyacetophenone, 2-methyl(4-(methylthio)phenyl) 2-methyl(4-(methylthio)phenyl)-2-morpholino-1 -propanon e) and 2-pyryl-2-didecylamino-1-(4) -morpholinylphenyl)-butan-1-one and other benzene 201133144 / u-τ / pil ethyl ketone, 蒽i Kun (anthraquinon e) and 1,4-naphthoquinone and other quinones, phenacyl chloride, tribromomethyl phenyl sulfone and three Halides such as tris(trichloromethyl)-s-triazine, 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide (2,4,6-trimethyl benzoyl) Diphenyl phosphine oxide), bis(2,6-dimethoxyphenylphenyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimercaptobenzoquinone) a sulfhydrylphosphine oxide such as phenylphosphine oxide or a peroxide such as di-t-butyl peroxide. By using a photosensitive radical polymerization initiator, the effect of improving the sensitivity of the negative-type photosensitive resin composition is obtained. Examples of the commercially available ones of the photosensitive radical polymerization initiators include Irgacure-184, Irgacure-369, Irgacure-500, Irgacure-651, Irgacure-907, Irgacure, 1700, Irgacure-819, Irgacure- 124, Irgacure-1000, Irgacure-2959, Irgacure-149, Irgacure-1800, Irgacure-1850, Irgacure-OXE-Ol, Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (above Ciba Specialty Chemicals, Inc.; Kayacure-DETX, Kayacure-MBP, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd.); Lucirintpo (manufactured by BASF Co. LTD); Vicure-10 , Vicure_55 (above manufactured by STAUFFER Co. LTD); Trigonal PI (manufactured by AKZO Co. LTD); Sandoray 1000 (manufactured by SANDOZ Co. LTD); DEAP (manufactured by APJOHN Co. LTD); Quantacure-PDO, 17 201133144

Quantacure-ITX 及 Quantacure-EPD (以上由 WARDBLEKINSOP Co.LTD製造）。另外，藉由將該些感 光性自由基聚合起始劑與感光增感劑併用，亦可獲得由氧 引起的失活少的高感度的負片型感光性樹脂組成物。 上述感光性自由基聚合起始劑中，就於感光性樹脂組 成物製備液中的溶解性、曝光後的透明性而言，特佳為α，α，_ 二曱氧基乙醯氧基二苯曱酮、2-甲基(4-(甲基硫基)苯基)_2_ 嗎啉基-1-丙酮及2-甲基(4-(甲基硫基)苯基)_2_嗎啉基小丙 -(D)鹼可溶性樹脂_ 其中，尤佳肩 顯影的樹脂。 尤佳為可溶於有機溶劑中且可利用弱鹼 本實施形態的鹼可溶性樹脂是線狀有機高分子聚合 物’可自分子（較佳為㈣烯_絲物、苯乙烯系共聚 物為主鏈的分子）巾具有至少^促紐可紐的基團（例 如竣基'雜基及俩基等）祕可溶性翻旨㈣當選擇。 水溶液進行 製造驗可溶性樹脂時，Quantacure-ITX and Quantacure-EPD (above manufactured by WARDBLEKINSOP Co. LTD). In addition, by using these photosensitive radical polymerization initiators together with a photosensitizing agent, it is possible to obtain a high-sensitivity negative-plate type photosensitive resin composition which is less deactivated by oxygen. Among the above-mentioned photosensitive radical polymerization initiators, in terms of solubility in the photosensitive resin composition preparation liquid and transparency after exposure, it is particularly preferable that α,α,_dimethoxyethoxyethoxy group II Phenyl ketone, 2-methyl(4-(methylthio)phenyl)_2_morpholinyl-1-propanone and 2-methyl(4-(methylthio)phenyl)_2_morpholinyl Small propylene-(D) alkali-soluble resin _ Among them, a resin which is particularly excellent for shoulder development. It is particularly preferable that the alkali-soluble resin which is soluble in an organic solvent and which can utilize a weak base is a linear organic high molecular polymer, which is a self-molecule (preferably a (tetra) ene-filament, a styrene-based copolymer. The molecular chain of the chain has at least a group that promotes the nucleus (for example, a thiol-hetero group and a two-group, etc.). When an aqueous solution is used to make a soluble resin,

201133144 本專利特公昭54-25957缺 α . ^ 及曰太直刹蛀叫 儿、日本專利特開昭59-53830號 專利特開昭59_71〇48號 烯酸共聚物、丙稀酸共聚物、報中5己載的尹基丙 AU „15 -Τ- LJC 衣康I共聚物、丁稀酸丑聚 物、順丁烯二酸共聚物、部分醋化順丁婦讀 j 側鏈具有幾酸的酸性纖維素衍生物及具美^吏 ^成有酸酐的高分子聚合物等，進而亦可列工舉^彳鏈“ j 的高分子聚合物作為較佳聚合物。-物中’特佳為包含（甲基巧烯酸1^旨《甲美） ==及(甲基)丙稀酸怖(甲基)丙烯酸/其他單:) 己二；除此以外，亦可列舉使甲基丙烯酸2-羥基 ;=合而成的聚合物等作為有用的聚合物。該聚合； 可以任意的量混合使用。 除^述以外’可列舉：日本專利特開平71條54號公 =中_的（甲基)丙烯酸2_經基丙醋/聚笨乙稀巨單體/甲 基丙婦酸./甲基丙烯酸共聚物、丙騎2•經基 基丙醋/聚曱基丙稀酸甲醋巨單體/甲基丙缔酸付/甲 烯酸共聚物、曱基丙烯酸2_經基乙s旨/聚苯乙烯巨單 基丙烯酸甲g旨/甲基㈣酸共聚物及甲基丙稀酸2_經基乙 醋/聚苯乙烯巨單體/曱基丙稀酸节g旨/甲基丙烯酸共聚物 等。 〆、 關於（D)鹼可溶性樹脂的具體結構單元，特佳為（曱 基）丙烯酸與可與其共聚合的其他單體的共聚物。可與上述 (曱基)丙烯酸共聚合的其他單體可列舉（曱基)丙稀^烷基 酯、（曱基)丙烯酸芳酯及乙烯基化合物等。其中，烷基及 19 201133144 芳基的氫原子亦可由取代基取代。 上述（甲基）丙烯酸烷基酯及（甲基）丙烯酸芳基酯的具 體例可列舉：（甲基）丙烯酸甲酯、（甲基)丙烯酸乙酯、（甲 基)丙烯酸丙酯、（甲基)丙烯酸丁酯、（甲基)丙烯酸異丁醋、 (甲基）丙烯酸戊酯、（曱基）丙烯酸己酯、（曱基）丙埽酸辛 酉曰、（甲基）丙稀酸苯g旨、丙烯酸苄醋、丙稀酸曱苯醋、丙 稀酸蔡s旨及丙稀酸環己@旨。 另外，上述乙烯基化合物例如可列舉：苯乙烯、 基苯乙烯、乙烯基甲苯、曱基丙烯酸縮水甘油酯、丙稀腈、 乙酸乙埽醋、Ν-乙烯基η比π各u定酮（N-vinyl pyrrolidone)、 甲基丙稀酸四氫糠醋（tetrahydrofurfuryl methacrylate)、聚 苯乙烯巨單體、聚甲基丙烯酸曱酯巨單體、CH2=CR5R6〔其 中’ R5表示氫原子或碳數1〜5的烷基，R6表示碳數6〜 10的芳香族烴環〕及ch2=c(r5)(coor7)〔其中，R5表示 氫原子或碳數1〜5的烷基，R7表示碳數i〜8的烷基或碳 數6〜12的芳烷基>該些可共聚合的其他單體可單獨使用 1種’或者將2種以上組合使用。 較佳的可共聚合的其他單體是選自ch2=cr5r6、 CH2=C(R5)(COOR7)、（曱基）丙烯酸苯酯、（曱基)丙烯酸节 酯及苯乙烯中的至少1種，特佳為CH2=CR5R6及/或 ch2=c(r5)(coor7)〇 -負片型感光性樹脂組成物的製備_ 本貫施形態的負片型感光性樹脂組成物是藉由將上述 (A)環狀烯烴樹脂、（B)多官能性丙烯酸單體及（c) β 20 201133144 J I WT / 光聚合起始劑的各成分混合而製備。上述負片型感光性樹 脂組成物適宜溶解於適當的溶劑中而以溶液狀態使用。例 如可藉由將（A)環狀烯烴樹脂、（B)多官能性丙烯酸單 體、（C)光聚合起始劑、及視需要的其他調配劑以預定比 例混合，而製備溶液狀態的負片型感光性樹脂組成物。 本實施形態的負片型感光性樹脂組成物是以相對於 (A)環狀烯烴樹脂1〇重量份，較佳為1〇重量份〜 重量份、更佳為40重量份〜120重量份的比例含有（B) 多官能性丙烯酸單體。於（B)多官能性丙烯酸單體小於 1〇重量份的情況，存在無法獲得充分的感光性的傾向。另 一方面，於超過150重量份的情況，存在斷裂強度下降的 傾向。另外’以較佳為1重量份〜40重量份、更佳為3重 量份〜35重量份的比例含有（C)光聚合起始劑。於（c) 光聚合起始劑小於1重量份的情況，存在無法獲得耐熱 性、表面硬度及耐藥品性的傾向。另一方面，於超過^ 重量份的情況’存在透明性下降的傾向。 本貫施形態的負片型感光性樹脂組成物的製備時使用 的溶劑是使用溶解（A)環狀烯烴樹脂、（B)多官能性丙 稀酸單體及（C)光聚合起始劑的各成分且不與各成分反 應的溶劑。具體可列舉：甲醇及乙醇等醇類，四氫呋喃等 醚類，乙二醇單甲醚及乙二醇單乙醚等二醇醚類，甲基溶 纖劑乙酸酯及乙基溶纖劑乙酸酯等乙二醇烷基醚乙 類，一乙二醇單甲鱗、二乙二醇單乙醚、二乙二醇二甲_、 二乙二醇乙基曱醚及二乙二醇二乙醚等二乙二醇類，丙二 21 201133144 J / \J-T I yil. 醇曱謎、丙二醇乙_ _ 00 Λ 皱、丙二醇丙醚及丙二醇丁醚等丙二醇 早烧基醚類’丙二醇甲鱗乙_旨、丙二醇乙醚乙酸醋、丙 一醇丙&乙^日及丙二醇丁峻乙酸醋等丙二醇炫基趟乙酸 Sa類丙—醇曱、丙二醇乙_丙酸醋、丙二醇丙 醚，IS日及丙—醇丁㈣酸自旨等丙二賴基醚乙酸醋類， 甲苯及一曱苯等芳麵煙類，甲基乙基酮、環己酮及4-經 基-4-曱基·2·細等_，以及乙酸甲醋、乙酸乙酯、乙酸 丙酉a ,乙I丁 S曰' 2-羥基丙酸乙酯、2_羥基_2_曱基丙酸曱 酉曰2罗工基2曱基丙駿乙醋、經基乙酸曱酉旨、經基乙酸乙 醋、經基乙酸丁酉旨、乳酸曱酉旨、乳酸乙醋、乳酸丙酯、乳 酸丁酉曰、3-經基丙酸曱g旨、3·經基丙酸乙g旨、3_經基丙酸 丙醋、3-經基丙酸甲画旨、3·丁氧基丙酸乙醋、3_丁氧基丙 酸丙酯及3-丁氧基丙酸丁酯等酯類。 該些溶劑中，就溶解性、與各成分的反應性及塗膜的 形成容易度而言’較佳為使用丙二醇烷基醚乙酸酯類、丙 一醉烧基謎乙酸醋類及芳香族煙類。201133144 This patent special public Zhao 54-25957 lacks α. ^ and 曰太直刹蛀叫儿, Japanese Patent Laid-Open No. 59-53830 Patent Special Open 59_71〇48 olefinic acid copolymer, acrylic copolymer, reported Yinji AU „15 -Τ- LJC Yikang I copolymer, butyric acid oligosaccharide, maleic acid copolymer, partially acetated cis-butyl read j side chain with several acids An acidic cellulose derivative and a polymer having an acid anhydride, and the like, may further comprise a polymer having a chain of "j" as a preferred polymer. -In the case of 'excellent' (including methyl methacrylate 1^, "Kami") == and (meth) acrylic acid (meth) acrylate / other single:) hexane; in addition, A polymer obtained by combining 2-hydroxyl methacrylate; = can be used as a useful polymer. The polymerization; can be used in any amount. In addition to the description, it can be exemplified: Japanese Patent Unexamined 71, No. 54, No. = Medium, (M)acrylic acid, 2, propyl acetonide, polystyrene, methacrylic acid, methyl ketone Acrylic copolymer, propylene riding 2 • propyl propyl vinegar / poly methacrylic acid methyl acetonate macro monomer / methyl propyl hydroxy acid / methacrylic acid copolymer, methacrylic acid 2 _ base s s / Polystyrene macromonoacrylic acid methyl ketone / methyl (tetra) acid copolymer and methyl acrylate acid 2 - ethyl acetoacetate / polystyrene macromonomer / mercapto acrylate acid / g methacrylic acid copolymerization Things and so on. With respect to the specific structural unit of the (D) alkali-soluble resin, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is particularly preferred. Examples of the other monomer copolymerizable with the above (fluorenyl)acrylic acid include (fluorenyl) propylene oxide, aryl (meth) acrylate, and vinyl compound. Among them, the hydrogen atom of the alkyl group and the 19 201133144 aryl group may also be substituted by a substituent. Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Butyl acrylate, isobutyl methacrylate, amyl (meth)acrylate, hexyl (decyl) acrylate, octyl phthalate, phenyl g (meth) acrylate The purpose is to use benzyl acrylate, acetoacetate, acrylic acid, and acrylic acid. Further, examples of the vinyl compound include styrene, styrene styrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, ethyl acetate vinegar, and fluorene-vinyl η ratio π each sulfonate (N). -vinyl pyrrolidone), tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH2=CR5R6 [where 'R5 represents a hydrogen atom or a carbon number of 1 ～5 alkyl, R6 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and ch2=c(r5)(coor7) (wherein R5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R7 represents a carbon number; An alkyl group of 1 to 8 or an aralkyl group having 6 to 12 carbon atoms. The other monomers which can be copolymerized may be used singly or in combination of two or more. Preferred copolymerizable other monomers are at least one selected from the group consisting of ch2=cr5r6, CH2=C(R5)(COOR7), (mercapto)acrylic acid phenyl ester, (mercapto)acrylic acid ester, and styrene. , particularly preferably CH2=CR5R6 and/or ch2=c(r5)(coor7) 〇-negative type photosensitive resin composition preparation_ The negative-type photosensitive resin composition of the present embodiment is obtained by the above (A The cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (c) each component of β 20 201133144 JI WT / photopolymerization initiator are mixed and prepared. The above negative-type photosensitive resin composition is suitably dissolved in a suitable solvent and used in a solution state. For example, a negative film in a solution state can be prepared by mixing (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, (C) a photopolymerization initiator, and optionally other formulation agents in a predetermined ratio. A photosensitive resin composition. The negative-type photosensitive resin composition of the present embodiment is preferably used in an amount of 1 part by weight to 1 part by weight, more preferably 40 parts by weight to 120 parts by weight, based on 1 part by weight of the (A) cyclic olefin resin. Contains (B) a polyfunctional acrylic monomer. When the (B) polyfunctional acrylic monomer is less than 1 part by weight, sufficient photosensitivity may not be obtained. On the other hand, in the case of more than 150 parts by weight, there is a tendency that the breaking strength is lowered. Further, (C) a photopolymerization initiator is contained in a ratio of preferably 1 part by weight to 40 parts by weight, more preferably 3 parts by weight to 35 parts by weight. When (c) the photopolymerization initiator is less than 1 part by weight, heat resistance, surface hardness, and chemical resistance may not be obtained. On the other hand, in the case of exceeding ^ parts by weight, the transparency tends to decrease. The solvent used in the preparation of the negative-type photosensitive resin composition of the present embodiment is a solution of (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. A solvent which does not react with each component. Specific examples thereof include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl cellosolve acetate and ethyl cellosolve acetate. Ethylene glycol alkyl ethers such as esters, monoethylene glycol monomethyl scale, diethylene glycol monoethyl ether, diethylene glycol dimethyl ketone, diethylene glycol ethyl oxime ether, diethylene glycol diethyl ether, etc. Diethylene glycol, C2 21 201133144 J / \JT I yil. Alcohol, propylene glycol B _ _ 00 Λ wrinkle, propylene glycol propyl ether and propylene glycol butyl ether and other propylene glycol early alkyl ether 'propylene glycol A scale B , propylene glycol ethyl ether acetate vinegar, propanol propyl & ethane day and propylene glycol succinic acid vinegar and other propylene glycol succinic hydrazine acetic acid Sa propylene glycol propylene glycol, propylene glycol propylene glycol propylene glycol, propylene glycol propyl ether, IS day and C - Alcohol butyl (tetra) acid from the purpose of propylene glycol acetate, toluene and monoterpene benzene and other aromatic tobacco, methyl ethyl ketone, cyclohexanone and 4-pyridyl-4-mercapto 2 · fine Etc., as well as methyl acetate, ethyl acetate, acetonitrile acetate, ethyl butyl sulfonate, ethyl 2-hydroxyl-hydrazide propionate 2 Base B , by acetaminophen, transacetic acid ethyl acetate, butyl acetate, lactic acid, lactic acid ethyl acetate, propyl lactate, butyl lactate, 3-pyridyl propionate g, 3 ·乙基丙酸, 3_ propyl propyl vinegar, 3- propyl propionic acid 甲, 3 · butoxy propionic acid vinegar, 3 - butoxy propionate propyl and 3-butoxy Esters such as butyl propionate. Among these solvents, in terms of solubility, reactivity with each component, and ease of formation of a coating film, it is preferred to use propylene glycol alkyl ether acetate, propylene glycol, acetic acid vinegar, and aromatic tobacco. class.

進而亦可將高沸點溶劑與上述溶劑併用。可併用的高 沸點溶劑例如可列舉：N-曱基曱醯胺（N-methyl formamide )、N，N-二曱基曱醯胺(Ν,Ν-dimethyl formamide)、N-曱基甲醯苯胺（N-methyl formanilide)、N-甲基乙醯胺（N-methyl acetamide )、N，N-二曱基乙醢胺 (Ν,Ν-dimethyl acetamide )、N-曱基0比》各口定 _( N-methyl pyrrolidone )、二甲基亞颯（dimethyl sulfoxide )、苄基乙趟、 二己鱗、丙g同基丙酮（acetonyl acetone )、異佛爾酿I 22 201133144 •j / \j~r / pix (isophorone )、己酸（caproic acid )、辛酸（caprylic acid )、 1-辛醇（1-octanol)、l-壬醇（l-nonanol)、苄醇（benzyl alcohol)、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二 酸二乙S旨、γ-丁内醋（γ-butyrolactone)、碳酸乙二醋、碳 酸丙二酯及苯基溶纖劑乙酸酯。本實施形態的負片型感光 性樹脂組成物可於不損及本發明目的的範圍内，視需要含 有上述以外的其他成分。 以上述方式製備的負片型感光性樹脂組成物可使用孔 徑0.2 μιη〜0.5 μιη左右的微孔過濾器等進行過濾後，供於 使用。 -層間絕緣膜的形成方法_ 本實施形態的層間絕緣膜的形成方法至少包括下述步 驟。（1)將上述負片型感光性樹脂組成物的膜形成於基板 的步驟；（2)對上述膜的至少一部分照射光（以下存在 「曝光」的情況）的步驟；（3)將曝光後的上述膜進行顯 影的步驟；以及4)將顯影後的上述膜煅燒（以下存在「烘 烤」的情況）而形成層間絕緣膜的步驟。Further, a high boiling point solvent may be used in combination with the above solvent. Examples of the high-boiling solvent which can be used in combination include N-methyl formamide, N,N-dimethylformamide, and N-mercaptoformamide. (N-methyl formanilide), N-methyl acetamide, N,N-dimethyl acetamide (N-methyl acetamide), N-mercapto 0 ratio _( N-methyl pyrrolidone ), dimethyl sulfoxide, benzyl acetamidine, dihexin scale, acetonyl acetone, isophora I 22 201133144 •j / \j~ r / pix (isophorone), caproic acid, caprylic acid, 1-octanol, l-nonanol, benzyl alcohol, benzyl acetate , ethyl benzoate, diethyl oxalate, diethyl succinic acid, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate . The negative-type photosensitive resin composition of the present embodiment may contain other components than those described above, without departing from the object of the present invention. The negative-type photosensitive resin composition prepared in the above manner can be used by filtration using a micropore filter having a pore diameter of about 0.2 μm to about 0.5 μm. - Method of Forming Interlayer Insulating Film - The method of forming the interlayer insulating film of the present embodiment includes at least the following steps. (1) a step of forming a film of the negative-type photosensitive resin composition on a substrate; (2) a step of irradiating at least a part of the film with light (hereinafter, "exposure" is present); (3) after exposing a step of developing the film; and 4) a step of forming the interlayer insulating film by firing the developed film (hereinafter, "baking").

/、中，本貫施形態所謂的「光」，是指包括紫外線、遠 ，、夕線X射線、電子束、分子束、γ射 光及質子料的光。 U 以下，對該些步驟進行詳細說明。 -(1)步驟- 23 201133144 去除溶劑’形成負片型感光性樹脂組成物的膜。 可使用的基板的種類可列舉玻璃基板、矽晶圓以及於 該些基板的表面形成有各種金屬的基板等。組成物溶液的 膜形成方法並無特別限定，較佳為藉由塗佈的方法。塗佈 方法可採用喷射法、輥塗法、旋轉塗佈法、狹縫式模塗法、 棒塗法及喷墨法等適當的方法。 預烘烤的條件根據負片型感光性樹脂組成物的構成成 分的種類及使用比例等而有所不同，例如可設為60艺〜 130 C下30秒〜15分鐘。所形成的上述膜的膜厚較佳為以 預烘烤後的值計為5 μηι〜20 μιη。 -(2)步驟- 於（2)步驟中，對所形成的上述膜的至少一部分進行 曝光。於此情況，當僅對上述膜的一部分進行曝光時，通 常是經由具有預定形狀的圖案的光罩而進行曝光。 曝光時使用的光例如可列舉：i線（波長365 nm)等 务外線、KrF準分子雷射及Arj7準分子雷射等遠紫外線、 同步加速器光等X射線、以及電子束等荷電粒子束。該些 光中，較佳為紫外線，更佳為波長4〇〇 nm以下的紫外線， 進而更佳為包含i線的紫外線。曝光量較佳為設為5〇J/m2 〜10000 J/m2左右。 -(3 )步驟- 於（3)步驟中’藉由將曝光後的上述膜進行顯影，去 除未曝光部而形成預定形狀的圖案。 顯影時使用的顯影液較佳為：氫氧化鈉、氫氧化鉀、/, medium, and the form of "light" refers to light including ultraviolet rays, far rays, ray X rays, electron beams, molecular beams, gamma rays, and protons. U These steps are described in detail below. - (1) Step - 23 201133144 Removal of solvent 'A film forming a negative-type photosensitive resin composition. Examples of the type of the substrate that can be used include a glass substrate, a tantalum wafer, and a substrate on which various metals are formed on the surfaces of the substrates. The film formation method of the composition solution is not particularly limited, and a method of coating is preferred. The coating method may be an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an ink jet method. The pre-baking conditions vary depending on the type of the constituent component of the negative-type photosensitive resin composition, the ratio of use, and the like, and can be, for example, 60 to 130 C for 30 seconds to 15 minutes. The film thickness of the film formed is preferably 5 μηη to 20 μηη based on the value after prebaking. - (2) Step - In the step (2), at least a part of the formed film is exposed. In this case, when only a part of the above film is exposed, exposure is usually performed via a photomask having a pattern of a predetermined shape. Examples of the light used for the exposure include an external beam such as an i-line (wavelength 365 nm), a far-ultraviolet light such as a KrF excimer laser or an Arj7 excimer laser, an X-ray such as a synchrotron light, and a charged particle beam such as an electron beam. Among these light rays, ultraviolet rays are preferable, and ultraviolet rays having a wavelength of 4 〇〇 nm or less are more preferable, and ultraviolet rays containing i-lines are more preferable. The exposure amount is preferably set to about 5 〇 J/m 2 to 10000 J/m 2 . - (3) Step - In the step (3), a pattern of a predetermined shape is formed by developing the exposed film to remove the unexposed portion. The developing solution used for development is preferably sodium hydroxide or potassium hydroxide.

24 201133144 •J / νττ / 碳酸納、石夕酸納、偏石夕酸納、氨、乙胺、正丙胺、二乙胺、 二乙基胺基乙醇、二正丙胺、三乙胺、曱基二乙胺、二曱 基乙醇胺、三乙醇胺、四曱基氫氧化銨、四乙基氫氧化銨、 吡咯（pyrrole)、哌啶（piperidine )、1,8-二氮雜雙環[5,4,0]-7-H 烯（l，8-diazabicyclo[5,4,0]-7-undecene)及 1，5-二lu雜 雙環[4,3,0]-5-壬烯（l，5-diazabicyclo[4,3,0]-5-nonene)等驗 性化合物的水溶液。上述鹼性化合物的水溶液中可適量添 加曱醇及乙醇等水溶性有機溶劑、以及界面活性劑。 另外’本實施形態中，於負片型感光性樹脂組成物不 含填充材料或顏料等不溶性成分的情況，亦可使用溶解構 成成分的各種有機溶劑作為顯影液。 顯影方法可採用液池法、浸潰法、搖動浸潰法及喷淋 法等適當方法。 顯影時間根據負片型感光性樹脂組成物的調配組成而 有所不同，例如可設為30秒〜300秒。此外，自先前以來 ^於形成層間魏朗貞#㈣光性樹餘成物由於若顯 景=夺間自最佳條件超出2〇秒以上，則所形成的圖案產生剝 落等不良情況，故必需嚴格控制顯影時間，但於本發明的 負片^感光1±奶旨組成物的情況，即便自最佳顯影時間的 ΐ出時間為3 G秒以上，亦可形成良好的圖案，製品良率提 尚。 -(4)步驟-然二 25 201133144 / V-r I yii 膜硬化而形成層間絕緣膜。後曝光時使用的光例如可列 舉：1線（波長365 nm)等紫外線、KrF準分子雷射及ArF 準分子雷射等遠紫外線、同步加速器光等x射線、以及電 子束專何電粒子束。 該些光中’較佳為紫外線，更佳為波長4〇〇 nm以下 的紫外線，進而更佳為包含i線的紫外線。後曝光的曝光 量較佳為設為50 J/m2〜10000 j/m2。烘烤條件根據負片型 感光性樹脂組成物的構成成分的種類及使用比例、所需圖 案形狀、以及所使用的加熱裝置等而有所不同，但於加熱 板的情況，例如為15〇它〜240〇C下10分鐘〜3〇分鐘，於 烘箱的情況，例如為150¾〜240°C下30分鐘〜90分鐘。 另外火、烤時，亦可採用進行2次以上加熱處理的階段烘 烤法等。 如上所述’可將作為目標的層間絕緣_成於基板 上。所得的層間絕緣膜即便厚膜化，解析度、透明性、财 熱性、耐熱變色性及耐溶舰等諸多特性亦優異，例如可 用於包含TFT型液晶顯示元件的各種液晶顯示元 ^、磁頭元件、雜電路元件及固爾像元件等電子零件 等。另外，本實施轉的層間_膜的形成方法，可 以率簡便地形成具有優異特性的層間 [貫例] 明』：i示實t對本發明進行更具體的說明，但本發 明並不限疋於該些實例。 (實例1 )24 201133144 • J / νττ / sodium carbonate, sodium sulphate, sodium sulphate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, sulfhydryl Diethylamine, decylethanolamine, triethanolamine, tetradecylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperididine, 1,8-diazabicyclo[5,4, 0]-7-H-ene (l,8-diazabicyclo[5,4,0]-7-undecene) and 1,5-dilubicyclo[4,3,0]-5-pinene (l,5) -diazabicyclo[4,3,0]-5-nonene) An aqueous solution of an isocratic compound. A water-soluble organic solvent such as decyl alcohol or ethanol or a surfactant may be added to the aqueous solution of the basic compound in an appropriate amount. In the present embodiment, when the negative-type photosensitive resin composition does not contain an insoluble component such as a filler or a pigment, various organic solvents which dissolve the constituent components may be used as the developer. The developing method may be a suitable method such as a liquid pool method, a dipping method, a shaking dipping method, or a spray method. The development time varies depending on the compounding composition of the negative-type photosensitive resin composition, and can be, for example, 30 seconds to 300 seconds. In addition, since the beginning of the formation of the interlayer Weilang 贞 # (4) optical tree residuals, if the appearance of the scene = the interval between the best conditions beyond 2 sec seconds, the resulting pattern is sparse and other problems, it must be strictly controlled Although the development time is, in the case of the negative film 1 photosensitive composition of the present invention, even if the extraction time from the optimum development time is 3 G seconds or more, a favorable pattern can be formed, and the product yield is improved. - (4) Step - Ran 25 201133144 / V-r I yii The film is hardened to form an interlayer insulating film. Examples of the light used for the post-exposure include ultraviolet rays such as 1 line (wavelength 365 nm), extreme ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, x-rays such as synchrotron light, and electron beam beams. . Among these lights, 'preferably ultraviolet rays, more preferably ultraviolet rays having a wavelength of 4 〇〇 nm or less, and more preferably ultraviolet rays containing i-lines. The exposure amount of the post exposure is preferably set to 50 J/m2 to 10000 j/m2. The baking conditions vary depending on the type and use ratio of the constituent components of the negative-type photosensitive resin composition, the desired pattern shape, and the heating device to be used, but in the case of a hot plate, for example, it is 15 〜 Under 240 〇C for 10 minutes ~ 3 〇 minutes, in the case of the oven, for example, 1503⁄4~240 °C for 30 minutes ~ 90 minutes. In the case of fire or baking, a stage baking method in which heat treatment is performed twice or more may be employed. As described above, the target interlayer insulation can be formed on the substrate. The obtained interlayer insulating film is excellent in various properties such as resolution, transparency, heat recovery, heat discoloration resistance, and solvent resistance, and can be used for various liquid crystal display elements and magnetic head elements including a TFT type liquid crystal display element, for example. Electronic components such as miscellaneous circuit components and solid image components. Further, in the method of forming the interlayer film which is transferred in the present embodiment, it is possible to form an interlayer having excellent characteristics at a simple rate. The present invention will be more specifically described. However, the present invention is not limited to the present invention. These examples. (Example 1)

S 26 201133144 / U-T I pix -負片型感光性樹脂組成物的製備- 將作為（B )多官能性丙烯酸單體的Aronix M-305 (東 亞合成（股）製造，商品名）10 g溶解於曱苯364 g中， 接著向所得的溶液中添加使R1、R2及R4為氫原子且R3為 曱酯基的單體與尺1、R2、R3及R4為氫原子的單體以i : i (莫耳比）進行共聚合而成的（A)環狀烯烴樹脂1 g，及 作為（C)光聚合起始劑的2-甲基-1-(4-曱基硫基苯基)_2_ 嗎琳基丙-1-酮（Ciba Specialty Chemicals公司製造，商品 名：IRGACURE-907 ) 0.6 g，然後利用孔徑0.5 μηι的薄膜 過濾器進行過濾’製備整體的固體成分濃度為3〇重量百分 比（wt〇/〇)的溶液狀態的負片型感光性樹脂組成物（S1)。 -層間絕緣膜的形成- 使用台式塗佈機將負片型感光性樹脂組成物（s _ i )塗 佈於玻璃基板上後，於8〇°C的防爆乾燥機内預烘烤1〇分 鐘，形成塗膜。接著，對該塗膜，經由具有預定形狀的圖 案的光罩，將波長365 nm的紫外線以累計曝光量成為1〇〇 mJ/cm2的方式進行曝光。然後，使用2 3 8 wt%的四甲基氫 氧化銨水溶液，於25。(：下浸潰顯影5分鐘後，以純水清洗 1分鐘，藉此去除不需要的部分，獲得圖案狀薄膜。 接著’將所得的圖案狀薄膜於2〇〇t：的烘箱中烘烤3〇 分鐘’使其硬化’藉此獲得具有特定圖案形狀的膜厚5〇 μιη 的層間絕緣膜。 -評價_ 接著，以下述要領進行評價。將評價結果與層間絕緣 27 201133144 膜的膜厚一併（以下同樣）示於表1中。 -解析度的評價- 對於所得的層間絕緣膜，使用直徑50 μιη的遮罩圖案 來評價解析度。將5G μΓΠ見方的孔圖案可解析的情況評價 為良好（Α)’將50 μιηΐ方的孔圖案無法解析的情況評價 為不良（Β)。 -透明性的評價- 對所得的層間絕緣膜的連續膜部分，使用雙光束分光 光度計U-29GG ((股）日立製作所製造，商品名）來測定 波長働nm Τ的穿透率進行評價。當該穿透率超過9〇% 時，可以說透明性良好（Α)。 -耐熱性的評價- 的縣中加熱6〇分鐘， 使用（股）Mitutoy。製造的數位式量錶來測定加熱前後的 膜厚的變化率（％)〔=(加熱前的膜厚·加熱後的 xlOO/加熱前的膜厚〕，進行評價。當該變化㈣汎以内 時，可以說耐熱性良好（A)。 -耐熱變色性的評價- 對250 C的供箱進行氮氣沖洗，將所得的層間絕緣膜 於該烘箱中加熱6G分鐘’然後對相絕緣_連續膜部 分，使用雙光束分光光度計U-2900 (商品名，（股）曰立 製作所製造）來測定波長_ nm下的穿透率。根據加熱 前後的穿透率㈣化率（％)〔=(加熱前的穿透率-加敎 後的穿透率）xlOO/加熱前的穿透率〕進行評價。當該變化S 26 201133144 / UT I pix - Preparation of a negative-type photosensitive resin composition - 10 g of Aronix M-305 (manufactured by Toagosei Co., Ltd., trade name) as a (B) polyfunctional acrylic monomer was dissolved in 曱In 364 g of benzene, a monomer having R1, R2 and R4 as a hydrogen atom and R3 is an oxime ester group and a monomer having a hydrogen atom of 1, 2, R2, R3 and R4 are added to the obtained solution as i: i ( 1 g of (A) cyclic olefin resin obtained by copolymerization, and 2-methyl-1-(4-mercaptothiophenyl)_2_ as (C) photopolymerization initiator Linski propan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE-907) 0.6 g, and then filtered using a membrane filter having a pore size of 0.5 μm to prepare a whole solid concentration of 3 〇 by weight (wt〇 Negative-type photosensitive resin composition (S1) in a solution state. - Formation of interlayer insulating film - The negative-type photosensitive resin composition (s _ i ) was applied onto a glass substrate using a table coater, and then pre-baked in an explosion-proof dryer at 8 ° C for 1 minute to form Coating film. Then, the coating film was exposed to ultraviolet light having a wavelength of 365 nm so that the cumulative exposure amount became 1 〇〇 mJ/cm 2 via a mask having a pattern having a predetermined shape. Then, 2 3 8 wt% of an aqueous solution of tetramethylammonium hydroxide was used at 25. (: After 5 minutes of immersion development, it was washed with pure water for 1 minute, thereby removing unnecessary portions, and obtaining a patterned film. Then 'the resulting patterned film was baked in an oven of 2 〇〇t: 3 〇 minutes 'hardened' to obtain an interlayer insulating film having a film thickness of 5 μm in a specific pattern shape. - Evaluation _ Next, evaluation was performed in the following manner. The evaluation result was combined with the film thickness of the interlayer insulating 27 201133144 film. (The same applies hereinafter.) - Evaluation of the resolution - The obtained interlayer insulating film was evaluated for the resolution using a mask pattern having a diameter of 50 μm. The case where the hole pattern of 5 G μ square was analyzed was evaluated as good. (Α) 'The case where the hole pattern of 50 μm ΐ square could not be analyzed was evaluated as defective (Β). - Evaluation of transparency - For the continuous film portion of the obtained interlayer insulating film, a double beam spectrophotometer U-29GG (( The product is manufactured by Hitachi, Ltd., and the transmittance is measured at a wavelength of 働nm Τ. When the transmittance exceeds 9〇%, it can be said that the transparency is good (Α). - Evaluation of heat resistance - County China and Canada The rate of change (%) of the film thickness before and after heating was measured by using a digital scale manufactured by Mitutoy (6). [= film thickness before heating, x100 after heating, film thickness before heating] When the change (4) is within the range, it can be said that the heat resistance is good (A). - Evaluation of heat-resistant discoloration - Nitrogen flushing of the 250 C supply tank, and the resulting interlayer insulating film is heated in the oven by 6G In the minute, then the phase-insulation_continuous film portion was measured using a two-beam spectrophotometer U-2900 (trade name, manufactured by Sigma) to determine the transmittance at wavelength _ nm. (4) The rate (%) [= (penetration before heating - penetration after twisting) x lOO / transmittance before heating] is evaluated. When the change

S 28 201133144 «·/ / V/ Τ / ρΛΙ 率為5%以内時，可以說耐熱變色性良好（A)。 -耐溶劑性的評價- 將形成有層間絕緣膜的玻璃基板於50°C的N-曱基。比 咯啶酮中浸潰15分鐘，使用（股）Mitutoyo製造的數位式 量錶來測定浸潰前後的層間絕緣膜的膜厚的變化率（％) 〔=(浸潰後的膜厚-浸潰前的膜厚）xlOO/浸潰前的膜 厚〕，進行評價。當該變化率為士 10%以内時，可以說耐溶 劑性良好（A )。 (實例2) 於實例1中，除了代替10 g的Aronix M-305而使用 10 g的Aronix M-402 (東亞合成（股）製造，商品名）以 外，以與實例1相同之方式製備溶液狀態的負片型感光性 樹脂組成物（S-2)，獲得具有預定圖案形狀的膜厚40 μιη 的層間絕緣膜。將評價結果示於表1中。 29 201133144 [表i]S 28 201133144 «· / / V / Τ / ρ ΛΙ When the rate is less than 5%, it can be said that heat discoloration is good (A). - Evaluation of Solvent Resistance - The glass substrate on which the interlayer insulating film was formed was N-fluorenyl at 50 °C. The ratio of the film thickness of the interlayer insulating film before and after the immersion was measured by using a digital scale manufactured by Mitutoyo (%) in a ratio of 15 minutes (in). The film thickness before the collapse) x lOO / film thickness before the impregnation] was evaluated. When the rate of change is within 10%, it can be said that the solvent resistance is good (A). (Example 2) In Example 1, a solution state was prepared in the same manner as in Example 1 except that 10 g of Aronix M-402 (manufactured by East Asia Synthetic Co., trade name) was used instead of 10 g of Aronix M-305. The negative-type photosensitive resin composition (S-2) obtained an interlayer insulating film having a film thickness of 40 μm in a predetermined pattern shape. The evaluation results are shown in Table 1. 29 201133144 [Table i]

膜化=實=任：絕緣膜均可確認，即便厚 亦優異。 耐熱性、耐熱變色性及耐溶劑性 【圖式簡單說明】 〇 【主要元件符號說明】 無。Film formation = real = any: The insulating film can be confirmed, and it is excellent even if it is thick. Heat resistance, heat discoloration resistance and solvent resistance [Simple description of the drawing] 〇 [Explanation of main component symbols] None.

Claims (1)

201133144 七、申請專利範圍： 1· -種負片型感光性樹脂組成物，包含：（Α)環狀稀 煙樹脂，其包含下述通式⑴所表示的重複單元： [化1]201133144 VII. Patent application scope: 1. A negative-type photosensitive resin composition comprising: (Α) a cyclic smoky resin comprising a repeating unit represented by the following formula (1): [Chemical Formula 1] (式中r1、r2、r3及R4分別獨立地表示選自氫原子、 碳數1〜15的烷基、碳數2〜2〇的烯基、碳數5〜15的環 烷基、碳數6〜20的芳基或碳數1〜20的烷氧基，或者水 解性矽烷基、碳數2〜2〇的烷氧基羰基、碳數4〜2〇的三 烷基矽烷氧基羰基、碳數2〜2〇的烷基羰氧基、碳數3〜 2〇的烯基基及氧雜環丁基巾的取代基，可直接或者經 由氧原子、氮原子或硫原子而相互連結）； (B) 多官能性丙烯酸單體；以及 (C) 光聚合起始劑。 2. 如申請專利範圍第丨項所述之負片型感絲樹脂組 成物，其中上述（A)環㈣烴樹脂包含由上述通式⑴ 所表示，且“、^以及R4為氫原子的結構單元。 3. 如申請專利範圍第！項或第2項所述之負片型感光 31 201133144 f f f A A 性樹脂組成物’其中上述（A)環狀烯烴樹脂包含由上述 通式（1 )所表示’且R1、R2、R3及R4中的任—者為碳數 2〜20的烷基羰氧基的結構單元。 4. 如申請專利範圍第1項至第3項中任一項所述之負 片型感光性樹脂組成物，其用於層間絕緣膜的形成方法， 該形成方法包括對由該負片型感光性樹脂組成物所形成的 膜的至少一部分照射波長4 〇 〇 nm以下的紫外線的步驟。 5. 如申請專利範圍第！項至第4項中任一項所述之負 片型感光性樹脂組成物，其中更包含（D)鹼可溶性樹脂。 6. —種層間絕緣膜，其是由如申請專利範圍第^項至 第5項中任一項所述之負片型感光性樹脂組成物而形成。 7· —種層間絕緣膜的形成方法，其包括以下步驟： 對由如申請專利範圍第丨項至第5項中任一項所述之 負片型感光性樹脂組成物所形成的膜的至少一部分照射 光； ° ’’、、 將照射光後的上述膜進行顯影；以及 將顯影後的上述膜般燒而形成層間絕緣膜。(wherein r1, r2, r3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 2 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, and a carbon number; An aryl group of 6 to 20 or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 2 carbon atoms, a trialkyldecyloxycarbonyl group having 4 to 2 carbon atoms, The alkylcarbonyloxy group having 2 to 2 carbon atoms, the alkenyl group having 3 to 2 carbon atoms, and the substituent of the oxetanyl ring may be bonded to each other directly or via an oxygen atom, a nitrogen atom or a sulfur atom. (B) a polyfunctional acrylic monomer; and (C) a photopolymerization initiator. 2. The negative-type photosensitive resin composition according to the above aspect of the invention, wherein the (A) ring (tetra) hydrocarbon resin comprises a structural unit represented by the above formula (1), and wherein "," and R4 are a hydrogen atom; 3. The negative-type photosensitive material 31 201133144 fff AA resin composition as described in claim 2 or 2, wherein the above (A) cyclic olefin resin comprises the above formula (1) and Any one of R1, R2, R3 and R4 is a structural unit of an alkylcarbonyloxy group having 2 to 20 carbon atoms. 4. The negative film type according to any one of claims 1 to 3. A photosensitive resin composition for forming an interlayer insulating film, which comprises the step of irradiating at least a part of a film formed of the negative-type photosensitive resin composition with ultraviolet rays having a wavelength of 4 〇〇 nm or less. The negative-type photosensitive resin composition according to any one of the items of the present invention, which further comprises (D) an alkali-soluble resin. 6. An interlayer insulating film which is applied by Any of the patent scopes from item ^ to item 5 The negative-type photosensitive resin composition is formed. The method for forming an interlayer insulating film, comprising the following steps: The negative film according to any one of the above claims At least a part of the film formed of the photosensitive resin composition is irradiated with light; °', the film after the irradiation of light is developed; and the film after development is baked to form an interlayer insulating film. 32 201133144 四、 指定代表囷： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明： 五、 本案若有化學式時，請揭示最能顯示發明特徵 的化學式：32 201133144 IV. Designation of representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R2 R3 式中R1、R2、R3及R4分別獨立地表示選自氫原子、 碳數1〜15的烷基、碳數2〜2〇的烯基、碳數5〜15的環 烷基、碳數6〜20的芳基或碳數丨〜⑽的烷氧基，或者水 解性矽烷基、碳數2〜20的烷氧基羰基、碳數4〜2〇的三 烷基矽烷氧基羰基、碳數2〜20的烷基羰氧基、碳數3〜 2〇的烯基羰氧基及氧雜環丁基中的取代基，可直接或者經 由氧原子、氮原子或硫原子而相互連結。 β 4R2 R3 wherein R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 2 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, and carbon. An aryl group having 6 to 20 carbon atoms or an alkoxy group having a carbon number of 丨~(10), or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a trialkyldecyloxycarbonyl group having 4 to 2 carbon atoms, The alkylcarbonyloxy group having 2 to 20 carbon atoms, the alkenylcarbonyloxy group having 3 to 2 carbon atoms, and the substituent in the oxetanyl group may be linked to each other directly or via an oxygen atom, a nitrogen atom or a sulfur atom. . β 4
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