TWI564664B - Positive photosensitive resin composition, forming method of harden film, harden film, liquid crystal display device and organic electroluminescence - Google Patents

Positive photosensitive resin composition, forming method of harden film, harden film, liquid crystal display device and organic electroluminescence Download PDF

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TWI564664B
TWI564664B TW101140649A TW101140649A TWI564664B TW I564664 B TWI564664 B TW I564664B TW 101140649 A TW101140649 A TW 101140649A TW 101140649 A TW101140649 A TW 101140649A TW I564664 B TWI564664 B TW I564664B
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resin composition
photosensitive resin
acid
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TW201319750A (en
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米澤裕之
川島敬史
山健太
疋田政憲
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富士軟片股份有限公司
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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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

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  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)

Description

正型感光性樹脂組成物、硬化膜的形成方法、硬化膜、液晶顯示裝置及有機電致發光顯示裝置 Positive photosensitive resin composition, method for forming cured film, cured film, liquid crystal display device, and organic electroluminescence display device

本發明關於一種正型感光性樹脂組成物、硬化膜的形成方法、硬化膜、液晶顯示裝置及有機電致發光(Electroluminescence，EL)顯示裝置。更詳細而言，本發明關於一種適合於形成液晶顯示裝置、有機EL顯示裝置、積體電路元件、固體攝像元件等電子零件的平坦化膜、保護膜或層間絕緣膜的正型感光性樹脂組成物、及使用其的硬化膜的形成方法。 The present invention relates to a positive photosensitive resin composition, a method for forming a cured film, a cured film, a liquid crystal display device, and an organic electroluminescence (EL) display device. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming a planarizing film, a protective film or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit device, or a solid-state image sensor. And a method of forming a cured film using the same.

在薄膜電晶體(以下，記作“TFT(Thin Film Transistor)”)型液晶顯示元件或磁頭元件、集成電路元件、固體攝像元件等電子零件中，通常為了使配置成層狀的配線之間絕緣而設置有層間絕緣膜。作為形成層間絕緣膜的材料，優選用以獲得所需的圖案形狀的步驟數少且具有充分的平坦性的材料，因此廣泛使用感光性樹脂組成物。 In an electronic component such as a thin film transistor (hereinafter referred to as a "TFT (Thin Film Transistor)" type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state imaging element, it is common to insulate wirings arranged in layers. An interlayer insulating film is provided. As a material for forming the interlayer insulating film, a material having a small number of steps for obtaining a desired pattern shape and having sufficient flatness is preferable, and thus a photosensitive resin composition is widely used.

所述電子零件之中，例如TFT型液晶顯示元件經過在所述層間絕緣膜上形成透明電極膜(氧化銦錫(Indium Tin Oxide，ITO))，進而在透明電極膜上形成包含鉬(Mo)或鈦(Ti)等金屬的配線，然後形成液晶配向膜的步驟來製造，因此層間絕緣膜在透明電極膜的形成步驟中暴露在高溫條件下，或者暴露在用於形成電極的圖案的抗蝕劑的剝離液(主要為單乙醇胺(Monoethanolamine，MEA))、或形成液晶配向膜時所使用的N-甲基吡咯烷酮(N-Methylpyrrolidone，NMP)中，因此需要對於它們的充分的耐受性。另外，層間絕緣膜有時也會被實施乾蝕刻步驟，因此也需要對於乾蝕刻的充分的耐受 性。 Among the electronic components, for example, a TFT-type liquid crystal display device is formed with a transparent electrode film (Indium Tin Oxide (ITO)) on the interlayer insulating film, and further includes molybdenum (Mo) formed on the transparent electrode film. Or a wiring of a metal such as titanium (Ti), and then a step of forming a liquid crystal alignment film, so that the interlayer insulating film is exposed to a high temperature condition in the formation step of the transparent electrode film, or is exposed to a resist for forming a pattern of the electrode. The stripping solution of the agent (mainly monoethanolamine (MEA)) or N-methylpyrrolidone (NMP) used in forming a liquid crystal alignment film requires sufficient tolerance to them. In addition, the interlayer insulating film is sometimes subjected to a dry etching step, and thus sufficient resistance to dry etching is also required. Sex.

另外，在日本專利特開2009-258722號公報中提出有如下的正型感光性樹脂組成物，其包括：含有藉由解離性基解離而產生羧基的特定的丙烯酸系構成單元、不溶於鹼或難溶於鹼、且當酸解離性基解離時成為鹼可溶性的樹脂；具有從含有環氧基的自由基聚合性單體衍生出的構成單元的樹脂；分子內具有2個以上的環氧基的化合物(但是，具有包含含有環氧基的自由基聚合性化合物的構成單元的所述樹脂除外)；藉由波長為300 nm以上的光化射線的照射而產生酸的化合物。 In addition, Japanese Laid-Open Patent Publication No. 2009-258722 proposes a positive photosensitive resin composition comprising: a specific acrylic structural unit containing a carboxyl group generated by dissociation of a dissociable group, insoluble in alkali or a resin which is insoluble in alkali and which becomes alkali-soluble when the acid dissociable group dissociates; a resin having a constituent unit derived from a radical polymerizable monomer containing an epoxy group; and having two or more epoxy groups in the molecule The compound (except for the resin having a constituent unit containing a radical polymerizable compound containing an epoxy group); a compound which generates an acid by irradiation with an actinic ray having a wavelength of 300 nm or more.

另外，在國際公開第2009/136647號手冊中，提出有一種含有鹼可溶性樹脂(A)、感光劑(B)、特定的矽化合物(C)的正型感光性樹脂組成物。 Further, in the International Publication No. 2009/136647, a positive photosensitive resin composition containing an alkali-soluble resin (A), a photosensitive agent (B), and a specific ruthenium compound (C) has been proposed.

但是，日本專利特開2009-258722號公報及國際公開第2009/136647號手冊中所提出的感光性樹脂組成物對於形成層間絕緣膜後所使用的抗蝕劑的剝離液(主要為單乙醇胺(MEA))、或者尤其對於作為溶劑的NMP(N-甲基吡咯烷酮)的耐受性不高，進而對於乾蝕刻的耐受性不高，因此容易產生液晶顯示裝置的顯示不良，而要求改善。 However, the photosensitive resin composition proposed in the Japanese Patent Laid-Open Publication No. 2009-258722 and the International Publication No. 2009/136647 is a stripping liquid (mainly monoethanolamine) of a resist used after forming an interlayer insulating film. MEA)) or, in particular, NMP (N-methylpyrrolidone) as a solvent is not highly resistant, and further resistant to dry etching is not high, so that display failure of a liquid crystal display device is likely to occur, and improvement is required.

本發明是鑒於如上所述的情況而完成的發明，其解決以下的課題。 The present invention has been made in view of the above circumstances, and solves the following problems.

即，本發明欲解決的課題在於提供一種可獲得對於抗蝕劑剝離液或NMP的耐受性高、且耐乾蝕刻性優異、在顯示裝置中也不易產生顯示不良的硬化膜的正型感光性樹脂組成物，使所述感光性樹脂組成物硬化而獲得的硬化膜及其形成方法，以及具備所述硬化膜的有機EL顯示裝置及液晶顯示裝置。 In other words, the object of the present invention is to provide a positive photosensitive film which is excellent in resistance to a resist stripping liquid or NMP and which is excellent in dry etching resistance and which is less likely to cause display defects in a display device. A resin composition, a cured film obtained by curing the photosensitive resin composition, a method for forming the same, and an organic EL display device and a liquid crystal display device including the cured film.

在所述狀況下，本申請案發明者進行了努力研究，結果發現藉由使用具有特定的結構的矽化合物，可解決所述課題。其原因在於：在具有交聯性基的化學增幅型抗蝕劑中，烷氧基矽烷基化合物作為與交聯性基或經脫保護的酸基進行鍵結的硬化劑而有效地發揮功能。具體而言，藉由下述手段<1>或手段<16>，更優選下述手段<2>~手段<16>來解決所述課題。 Under the circumstances, the inventors of the present application conducted diligent research and found that the problem can be solved by using a ruthenium compound having a specific structure. The reason for this is that in the chemically amplified resist having a crosslinkable group, the alkoxyfluorenyl compound functions as a curing agent bonded to a crosslinkable group or a deprotected acid group. Specifically, the above means <1> or means <16> is more preferable, and the following means <2> to means <16> are more preferable to solve the above problem.

<1>一種正型感光性樹脂組成物，其特徵在於：包括(成分A)含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分，(1)具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物，(2)具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物；(成分C)光酸產生劑；以及(成分D)溶劑；進而包括(成分X)1分子內具有2個以上由式(X1)所表示的水解性矽烷基及/或矽烷醇基的矽化合物。 <1> A positive-type photosensitive resin composition comprising (a component A) a polymer component containing a polymer satisfying at least one of the following (1) and (2) below, (1) having ( A1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, and (2) having (a1) an acid group-containing group protected by an acid-decomposable group. a polymer of a constituent unit of a group; and a polymer having (a2) a constituent unit containing a crosslinkable group; (Component C) a photoacid generator; and (Component D) a solvent; and further comprising (Component X) 1 intramolecular An anthracene compound having two or more hydrolyzable alkylene groups and/or stanol groups represented by the formula (X1).

(式中，RX1~RX3的至少1個表示選自由烷氧基、巰基、鹵素原子、醯胺基、乙醯氧基、氨基、烯丙氧基、及異丙烯氧基所組成的組群中的水解性基，或羥基。剩餘的RX1~RX3分 別獨立地表示氫原子、鹵素原子、或一價的有機取代基) (wherein at least one of R X1 to R X3 represents a group selected from the group consisting of an alkoxy group, a fluorenyl group, a halogen atom, a decylamino group, an ethoxy group, an amino group, an allyloxy group, and an isopropenyloxy group. a hydrolyzable group in the group, or a hydroxyl group. The remaining R X1 to R X3 independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent)

<2>根據<1>所述的正型感光性樹脂組成物，其特徵在於：所述構成單元(X1)之中，RX1~RX3中的至少2個為烷氧基。 <2> The positive photosensitive resin composition according to <1>, wherein at least two of R X1 to R X3 among the structural units (X1) are alkoxy groups.

<3>根據<1>或<2>所述的正型感光性樹脂組成物，其特徵在於：相對於樹脂組成物的除溶劑以外的成分的合計，所述成分X的含量為0.1 wt%(重量百分比)以上。 (3) The positive photosensitive resin composition according to <1>, wherein the content of the component X is 0.1 wt% based on the total of components other than the solvent of the resin composition. (% by weight) or more.

<4>根據<1>至<3>中任一項所述的正型感光性樹脂組成物，其特徵在於：所述構成單元(a1)為具有羧基由縮醛或縮酮保護的殘基的構成單元。 The positive photosensitive resin composition according to any one of <1>, wherein the structural unit (a1) is a residue having a carboxyl group protected by an acetal or a ketal. The constituent unit.

<5>根據<1>至<4>中任一項所述的正型感光性樹脂組成物，其特徵在於：所述構成單元(a1)為由式(a1-1)所表示的構成單元。 The positive photosensitive resin composition according to any one of the above aspects, wherein the structural unit (a1) is a constituent unit represented by the formula (a1-1). .

(式中，R1及R2分別表示氫原子、烷基或芳基，至少R1及R2的任一個為烷基或芳基，R3表示烷基或芳基，R1或R2與R3可連結而形成環狀醚，R4表示氫原子或甲基，X表示單鍵或亞芳基) (wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, and R 1 or R 2 R 3 may be bonded to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

<6>根據<1>至<5>中任一項所述的正型感光性樹脂組成物，其特徵在於：所述構成單元(X1)的RX1~RX3中的至少2個為甲氧基或乙氧基。 The positive photosensitive resin composition according to any one of the above aspects, wherein at least two of R X1 to R X3 of the structural unit (X1) are a Oxy or ethoxy.

<7>根據<1>至<6>中任一項所述的正型感光性樹 脂組成物，其特徵在於：所述構成單元(a2)為具有選自環氧基、氧雜環丁基中的至少1種的構成單元。 <7> The positive photosensitive tree according to any one of <1> to <6> In the lipid composition, the structural unit (a2) is a constituent unit having at least one selected from the group consisting of an epoxy group and an oxetanyl group.

<8>根據<1>至<7>中任一項所述的正型感光性樹脂組成物，其特徵在於：成分A的含量WA與成分B的含量WB的重量比率為WA/WB=98/2~20/80。 The positive photosensitive resin composition according to any one of <1> to <7> wherein the weight ratio of the content W A of the component A to the content W B of the component B is W A / W B = 98/2~20/80.

<9>根據<1>至<8>中任一項所述的正型感光性樹脂組成物，其特徵在於：成分C為具有由式(c0)所表示的肟磺酸酯殘基的至少1個的肟磺酸酯化合物。 The positive photosensitive resin composition according to any one of the above aspects, wherein the component C is at least having an oxime sulfonate residue represented by the formula (c0). One oxime sulfonate compound.

<10>一種硬化膜的形成方法，其特徵在於包括：(1)將根據<1>至<9>中任一項所述的正型感光性樹脂組成物塗布在基板上的步驟；(2)從所塗布的感光性樹脂組成物中去除溶劑的步驟；(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟；(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟；以及(5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 <10> A method of forming a cured film, comprising: (1) a step of applying a positive photosensitive resin composition according to any one of <1> to <9> on a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition with actinic rays; and (4) using an aqueous developing solution for exposure to light. a step of developing the resin composition; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

<11>根據<10>所述的硬化膜的形成方法，其特徵在於：在所述顯影步驟後、所述後烘烤步驟前，包括對經顯影的感光性樹脂組成物進行全面曝光的步驟。 <11> The method for forming a cured film according to <10>, comprising the step of performing full exposure of the developed photosensitive resin composition after the developing step and before the post-baking step .

<12>根據<10>或<11>所述的硬化膜的形成方法， 其特徵在於：更包括(6)對具有進行熱硬化而獲得的硬化膜的基板進行乾蝕刻的步驟。 <12> The method for forming a cured film according to <10> or <11>, It is characterized by further comprising (6) a step of dry etching a substrate having a cured film obtained by thermal curing.

<13>一種硬化膜，其特徵在於：藉由根據<10>至<12>中任一項所述的硬化膜的形成方法來形成。 <13> A cured film which is formed by the method of forming a cured film according to any one of <10> to <12>.

<14>根據<13>所述的硬化膜，其特徵在於：其為層間絕緣膜。 <14> The cured film according to <13>, which is characterized in that it is an interlayer insulating film.

<15>一種有機EL顯示裝置或液晶顯示裝置，其特徵在於：包括根據<13>或<14>所述的硬化膜。 <15> An organic EL display device or a liquid crystal display device comprising the cured film according to <13> or <14>.

<16>一種正型感光性樹脂組成物的耐化學品性提升劑，其特徵在於：包括1分子內具有2個以上由式(X1)所表示的水解性矽烷基及/或矽烷醇基的矽化合物。 <16> A chemical resistance improving agent of a positive photosensitive resin composition, which comprises two or more hydrolyzable alkylene groups and/or stanol groups represented by the formula (X1) in one molecule.矽 compound.

(式中，RX1~RX3的至少1個表示選自由烷氧基、巰基、鹵素原子、醯胺基、乙醯氧基、氨基、烯丙氧基、及異丙烯氧基所組成的組群中的水解性基，或羥基。剩餘的RX1~RX3分別獨立地表示氫原子、鹵素原子、或一價的有機取代基) (wherein at least one of R X1 to R X3 represents a group selected from the group consisting of an alkoxy group, a fluorenyl group, a halogen atom, a decylamino group, an ethoxy group, an amino group, an allyloxy group, and an isopropenyloxy group. a hydrolyzable group in the group, or a hydroxyl group. The remaining R X1 to R X3 independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent)

根據本發明，可提供一種可獲得對於MEA或NMP的耐受性高、且耐乾蝕刻性優異、在顯示裝置中也不易產生顯示不良的硬化膜的正型感光性樹脂組成物，使所述感光性樹脂組成物硬化而獲得的硬化膜及其形成方法，以及具備所述硬化膜的有機EL顯示裝置及液晶顯示裝置。 According to the present invention, it is possible to provide a positive photosensitive resin composition which is excellent in resistance to MEA or NMP and which is excellent in dry etching resistance and which is less likely to cause display defects in a display device. A cured film obtained by curing a resin composition, a method for forming the same, and an organic EL display device and a liquid crystal display device including the cured film.

以下，對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.

再者，說明書中，“下限~上限”的記載表示“下限以上、上限以下”，“上限~下限”的記載表示“上限以下、下限以上”。即，表示包含上限及下限的數值範圍。 In the specification, the description of "lower limit to upper limit" means "above the lower limit and the upper limit", and the description of "the upper limit to the lower limit" means "the upper limit is equal to or lower than the lower limit". That is, the numerical range including the upper limit and the lower limit is indicated.

另外，將“(成分C)光酸產生劑等”也簡稱為“成分C”等，將“(a1)含有酸基由酸分解性基保護的殘基的構成單元”等也簡稱為“構成單元(a1)”等。 In addition, "(component C) photoacid generator or the like" is also simply referred to as "component C" or the like, and "(a1) a constituent unit of a residue having an acid group-protected group by an acid-decomposable group" or the like is also simply referred to as "constituting" Unit (a1)" and so on.

另外，在表示“丙烯酸酯”、“甲基丙烯酸酯”兩者或任一者的情況下，有時記載為“(甲基)丙烯酸酯”，在表示“丙烯酸”、“甲基丙烯酸”兩者或任一者的情況下，有時記載為“(甲基)丙烯酸”。 In addition, when either or both of "acrylate" and "methacrylate" are shown, it may be described as "(meth)acrylate" and "acrylic" and "methacrylic". In the case of either or both, it may be described as "(meth)acrylic acid".

(正型感光性樹脂組成物) (Positive photosensitive resin composition)

本發明的正型感光性樹脂組成物(以下，也簡稱為“感光性樹脂組成物”)的特徵在於：包括(成分A)含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分，(1)具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物，(2)具備具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物、及(a2)含有交聯性基的構成單元的共聚物；(成分C)光酸產生劑；(成分D)溶劑；以及(X成分)1分子內具有2個以上由式(X1)所表示的水解性矽烷基及/或矽烷醇基的矽化合物。 The positive photosensitive resin composition of the present invention (hereinafter also referred to simply as "photosensitive resin composition") is characterized by including (component A) containing at least one of the following (1) and (2) below. The polymer component of the polymer (1) has (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, and (2) having (a1) a polymer having a structural unit of a group in which an acid group is protected by an acid-decomposable group, and a polymer having (a2) a structural unit containing a crosslinkable group, and (a2) a structural unit containing a crosslinkable group Copolymer; (Component C) photoacid generator; (Component D) solvent; and (X component) having two or more hydrolyzable alkylene groups and/or stanol groups represented by formula (X1) in one molecule矽 compound.

進而，本發明的感光性樹脂組成物優選含有如下的共聚 物，該共聚物不具有含有酸基由酸分解性基保護的殘基的構成單元，且至少具有含有酸基的構成單元與含有交聯性基的構成單元。 Further, the photosensitive resin composition of the present invention preferably contains the following copolymerization The copolymer does not have a constituent unit containing a residue in which an acid group is protected by an acid-decomposable group, and has at least a constituent unit containing an acid group and a constituent unit containing a crosslinkable group.

本發明的感光性樹脂組成物藉由含有特定的樹脂(成分A)、光酸產生劑、及特定的矽化合物，而可形成如下的硬化膜，該硬化膜對於剝離液，特別是含有單乙醇胺的剝離液或NMP的耐受性高，與透明電極膜或金屬的密接性也良好，另外，耐乾蝕刻性優異，在顯示裝置中也不易產生顯示不良。 The photosensitive resin composition of the present invention can form a cured film containing a specific resin (component A), a photoacid generator, and a specific ruthenium compound, and the cured film contains a monoethanolamine for a stripping liquid. The peeling liquid or NMP is highly resistant, and has good adhesion to a transparent electrode film or a metal, and is excellent in dry etching resistance, and is also less likely to cause display failure in a display device.

另外，本發明的感光性樹脂組成物優選化學增幅型的正型感光性樹脂組成物(化學增幅正型感光性樹脂組成物)。 Further, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

進而，本發明的感光性樹脂組成物可適宜用作乾蝕刻抗蝕劑用正型感光性樹脂組成物。 Further, the photosensitive resin composition of the present invention can be suitably used as a positive photosensitive resin composition for dry etching resist.

再者，在本說明書中的基(原子團)的表述中，未記載經取代及未經取代的表述包括不具有取代基者，並且也包括具有取代基者。例如，“烷基”不僅包括不具有取代基的烷基(未經取代的烷基)，也包括具有取代基的烷基(經取代的烷基)。 Further, in the expression of the group (atomic group) in the present specification, the description that the substituted or unsubstituted is not described includes those having no substituent, and also includes a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

另外，導入本發明中使用的成分A等共聚物所含有的構成單元的方法可以是聚合法，也可以是高分子反應法。聚合法中，在預先合成含有規定的官能基的單體後，使這些單體共聚。高分子反應法中，在進行聚合反應後，利用所獲得的共聚物的構成單元中所含有的反應性基將所需的官能基導入至構成單元中。此處，作為官能基，可例示：用以保護羧基或酚性羥基等酸基，同時在強酸的存在下分解而使這些酸基遊離的保護基；環氧基或氧雜環丁基等交聯性基；以及如酚性羥基或羧基般的鹼可溶性基(酸基)等。 Further, the method of introducing the constituent unit contained in the copolymer such as the component A used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, after a monomer having a predetermined functional group is synthesized in advance, these monomers are copolymerized. In the polymer reaction method, after the polymerization reaction, the desired functional group is introduced into the constituent unit by the reactive group contained in the constituent unit of the obtained copolymer. Here, examples of the functional group include a protecting group for protecting an acid group such as a carboxyl group or a phenolic hydroxyl group, and decomposing in the presence of a strong acid to free these acid groups; and an epoxy group or an oxetanyl group. A linking group; and an alkali-soluble group (acid group) such as a phenolic hydroxyl group or a carboxyl group.

<(A)聚合物成分> <(A) Polymer component>

本發明的組成物包含如下聚合物的至少一種作為聚合物成分：(1)具有(a1)含有酸基由酸分解性基保護的殘基的構成單元、及(a2)含有交聯性基的構成單元的聚合物，以及(2)具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物。進而，也可以含有這些聚合物以外的聚合物。本發明中的(A)聚合物成分(以下，有時稱為“(A)成分”)只要未特別說明，則是指除所述(1)及/或(2)以外，也包含視需要而添加的其他聚合物的聚合物成分。 The composition of the present invention contains at least one of the following polymers as a polymer component: (1) a constituent unit having (a1) a residue having an acid group protected by an acid-decomposable group, and (a2) a crosslinkable group-containing group. The polymer constituting the unit, and (2) a polymer having (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, and a polymer having (a2) a structural unit containing a crosslinkable group. Further, a polymer other than these polymers may be contained. The polymer component (A) (hereinafter sometimes referred to as "(A) component)" in the present invention means that, in addition to the above (1) and/or (2), it is included as needed. And the polymer component of other polymers added.

(A)成分優選加成聚合型的樹脂，更優選含有源自(甲基)丙烯酸及/或其酯的構成單元的聚合物。再者，也可以具有源自(甲基)丙烯酸及/或其酯的構成單元以外的構成單元，例如源自苯乙烯的構成單元、或源自乙烯基化合物的構成單元等。 The component (A) is preferably an addition polymerization type resin, and more preferably a polymer containing a constituent unit derived from (meth)acrylic acid and/or an ester thereof. Further, it may have a constituent unit other than the constituent unit derived from (meth)acrylic acid and/or an ester thereof, for example, a constituent unit derived from styrene or a constituent unit derived from a vinyl compound.

再者，將“源自(甲基)丙烯酸及/或其酯的構成單元”也稱為“丙烯酸系構成單元”。另外，“(甲基)丙烯酸”是指“甲基丙烯酸及/或丙烯酸”。 In addition, the "constitutive unit derived from (meth)acrylic acid and/or its ester" is also referred to as "acrylic constituent unit". Further, "(meth)acrylic acid" means "methacrylic acid and/or acrylic acid".

<<構成單元(a1)>> <<constitution unit (a1)>>

成分A至少具有(a1)含有酸基由酸分解性基保護的基的構成單元。藉由(A)成分具有構成單元(a1)，可製成感光度極高的感光性樹脂組成物。 Component A has at least (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group. By having the constituent unit (a1) as the component (A), a photosensitive resin composition having extremely high sensitivity can be obtained.

本發明中的“酸基由酸分解性基保護的基”可使用作為酸基及酸分解性基所公知的基，並無特別限定。作為具體的酸基，可優選列舉羧基、及酚性羥基。另外，作為酸分解性基，可使用比較容易藉由酸而分解的基(例如由後述的式(A1)所表示的基的酯結構、四氫吡喃酯基、或四氫呋喃酯基等縮醛系官能基)、或比較難以藉由酸而分解的基(例如叔丁酯基等 三級烷基、碳酸叔丁酯基等碳酸三級烷基酯基)。 In the present invention, the "acid group which is protected by an acid-decomposable group" can be used as a group known as an acid group or an acid-decomposable group, and is not particularly limited. As a specific acid group, a carboxyl group and a phenolic hydroxyl group are preferable. In addition, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure represented by the formula (A1) to be described later, an acetal such as a tetrahydropyranyl ester group or a tetrahydrofuran ester group can be used. a functional group) or a group which is relatively difficult to decompose by an acid (for example, a tert-butyl ester group, etc.) A tertiary alkyl carbonate group such as a tertiary alkyl group or a tert-butyl carbonate group.

(a1)含有酸基由酸分解性基保護的基的構成單元優選含有由酸分解性基保護的保護羧基的構成單元、或含有由酸分解性基保護的保護酚性羥基的構成單元。 (a1) The structural unit containing a group in which an acid group is protected by an acid-decomposable group preferably contains a structural unit protecting a carboxyl group protected by an acid-decomposable group or a constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group.

以下，依次對含有由酸分解性基保護的保護羧基的構成單元(a1-1)、及含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)分別進行說明。 Hereinafter, the constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group and the constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group will be sequentially described.

<<<(a1-1)含有由酸分解性基保護的保護羧基的構成單元>>> <<<(a1-1) A constituent unit containing a protected carboxyl group protected by an acid-decomposable group>>>

所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)，是含有羧基的構成單元的羧基具有以下將詳細說明的由酸分解性基保護的保護羧基的構成單元。 The structural unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is a structural unit in which a carboxyl group of a structural unit containing a carboxyl group has a protective carboxyl group protected by an acid-decomposable group, which will be described in detail below.

作為可用於所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的所述含有羧基的構成單元，可無特別限制地使用公知的構成單元。例如可列舉：源自不飽和單羧酸、不飽和二羧酸、不飽和三羧酸等分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)，或同時具有乙烯性不飽和基與源自酸酐的結構的構成單元(a1-1-2)。 As the structural unit containing a carboxyl group which can be used for the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group, a known structural unit can be used without particular limitation. For example, a constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid, or both A constituent unit (a1-1-2) having an ethylenically unsaturated group and an acid anhydride-derived structure.

以下，依次對可用作所述含有羧基的構成單元的(a1-1-1)源自分子中具有至少1個羧基的不飽和羧酸等的構成單元、及(a1-1-2)同時具有乙烯性不飽和基與源自酸酐的結構的構成單元分別進行說明。 In the following, (a1-1-1) which can be used as the structural unit containing a carboxyl group, is derived from a constituent unit of an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) The constituent units having an ethylenically unsaturated group and an acid anhydride-derived structure will be separately described.

<<<<(a1-1-1)源自分子中具有至少1個羧基的不飽和羧酸等的構成單元>>>> <<<<(a1-1-1) is derived from a constituent unit of an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>>

作為所述源自分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)，可使用如以下所列舉的不飽和羧酸作為 本發明中所使用的不飽和羧酸。即，作為不飽和單羧酸，例如可列舉：丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸等。另外，作為不飽和二羧酸，例如可列舉：順丁烯二酸、反丁烯二酸、衣康酸、檸康酸、中康酸等。另外，用於獲得含有羧基的構成單元的不飽和多元羧酸也可以是其酸酐。具體而言，可列舉順丁烯二酸酐、衣康酸酐、檸康酸酐等。另外，不飽和多元羧酸也可以是多元羧酸的單(2-甲基丙烯醯氧基烷基)酯，例如可列舉：丁二酸單(2-丙烯醯氧基乙基)酯、丁二酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯等。進而，不飽和多元羧酸也可以是其兩末端二羧基聚合物的單(甲基)丙烯酸酯，例如可列舉ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。另外，作為不飽和羧酸，也可以使用丙烯酸-2-羧基乙酯、甲基丙烯酸-2-羧基乙酯、順丁烯二酸單烷基酯、反丁烯二酸單烷基酯、4-羧基苯乙烯等。 As the constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, an unsaturated carboxylic acid as exemplified below can be used. The unsaturated carboxylic acid used in the present invention. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(methyl)acryloxyethyl succinic acid, and 2-(A). Base) acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalate, and the like. Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Further, the unsaturated polycarboxylic acid used to obtain a structural unit containing a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and butyl. Di(2-methylpropenyloxyethyl) diester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate ) esters, etc. Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 may be used. - Carboxystyrene and the like.

其中，就顯影性的觀點而言，為了形成所述源自分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)，優選使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、或不飽和多元羧酸的酐等，更優選使用丙烯酸、甲基丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸。 In view of the developability, in order to form the constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, and 2- are preferably used. (methyl) propylene oxiranyl ethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalic acid, As the anhydride of the unsaturated polycarboxylic acid or the like, acrylic acid, methacrylic acid or 2-(meth)acryloxyethyl hexahydrophthalic acid is more preferably used.

所述源自分子中具有至少1個羧基的不飽和羧酸等的構成單元(a1-1-1)可單獨包含1種，也可以包含2種以上。 The constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.

<<<<(a1-1-2)同時具有乙烯性不飽和基與源自酸酐 的結構的構成單元>>>> <<<<(a1-1-2) has both ethylenically unsaturated groups and anhydrides Composition of the structure >>>>

同時具有乙烯性不飽和基與源自酸酐的結構的構成單元(a1-1-2)優選源自使含有乙烯性不飽和基的構成單元中所存在的羥基與酸酐進行反應而獲得的單體的單元。 The constituent unit (a1-1-2) having both an ethylenically unsaturated group and an acid anhydride-derived structure is preferably derived from a monomer obtained by reacting a hydroxyl group present in a constituent unit containing an ethylenically unsaturated group with an acid anhydride. Unit.

作為所述酸酐，可使用公知的酸酐，具體而言，可列舉：順丁烯二酸酐、丁二酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、氯菌酸酐等二元酸酐；偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四羧酸酐、聯苯四羧酸酐等酸酐。這些酸酐之中，就顯影性的觀點而言，優選鄰苯二甲酸酐、四氫鄰苯二甲酸酐、或丁二酸酐。 As the acid anhydride, a known acid anhydride can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroortylene. A dibasic acid anhydride such as dicarboxylic anhydride or chloric anhydride; an acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

就顯影性的觀點而言，所述酸酐對於羥基的反應率優選10莫耳%~100莫耳%，更優選30莫耳%~100莫耳%。 From the viewpoint of developability, the reaction rate of the acid anhydride to the hydroxyl group is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%.

<<<<可用於構成單元(a1-1)的酸分解性基>>>> <<<< can be used to form the acid-decomposable group of unit (a1-1) >>>>

作為可用於所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的所述酸分解性基，可使用所述酸分解性基。 The acid-decomposable group which can be used for the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group can be used.

這些酸分解性基之中，就感光性樹脂組成物的基本物性，特別是感光度或圖案形狀、接觸孔的形成性、感光性樹脂組成物的保存穩定性的觀點而言，優選羧基為由縮醛的形式保護的保護羧基。進而，酸分解性基之中，就感光度的觀點而言，更優選羧基為由以下述通式(a1-10)所表示的縮醛的形式保護的保護羧基。再者，當羧基為由以下述通式(a1-10)所表示的縮醛的形式保護的保護羧基時，保護羧基的整體變成-(C=O)-O-CR101R102(OR103)的結構。 Among these acid-decomposable groups, from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition, it is preferred that the carboxyl group be composed of Protected carboxyl groups in the form of acetal protection. Further, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected by an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. Further, when the carboxyl group is a protected carboxyl group protected by an acetal represented by the following formula (a1-10), the entire protective carboxyl group becomes -(C=O)-O-CR 101 R 102 (OR 103 )Structure.

通式(a1-10) General formula (a1-10)

(式(a1-10)中，R101及R102分別獨立地表示氫原子或烷基，其中，排除R101與R102均為氫原子的情況。R103表示烷基。R101或R102與R103可連結而形成環狀醚。) (In the formula (a1-10), R 101 and R 102 each independently represent a hydrogen atom or an alkyl group, wherein R 101 and R 102 are each a hydrogen atom. R 103 represents an alkyl group. R 101 or R 102 It can be linked to R 103 to form a cyclic ether.)

所述通式(a1-10)中，R101~R103分別獨立地表示氫原子或烷基，所述烷基可為直鏈狀、支鏈狀、環狀的任一種。此處，不存在R101及R102兩者表示氫原子的情況，R101及R102的至少一個表示烷基。 In the above formula (a1-10), R 101 to R 103 each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, there is no case where both R 101 and R 102 represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.

所述通式(a1-10)中，當R101、R102及R103表示烷基時，所述烷基可為直鏈狀、支鏈狀或環狀的任一種。 In the above formula (a1-10), when R 101 , R 102 and R 103 represent an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic group.

作為所述直鏈狀或支鏈狀的烷基，優選碳數為1~12，更優選碳數為1~6，進而更優選碳數為1~4。具體而言，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、新戊基、正己基、2,3-二甲基-2-丁基(thexyl)、正庚基、正辛基、2-乙基己基、正壬基、正癸基等。 The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, and 2, 3-xyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

作為所述環狀烷基，優選碳數為3~12，更優選碳數為4~8，進而更優選碳數為4~6。作為所述環狀烷基，例如可列舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異冰片基等。 The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

所述烷基也可以具有取代基，作為取代基，可例示鹵素原子、芳基、烷氧基。當具有鹵素原子作為取代基時，R101、R102、R103成為鹵代烷基，當具有芳基作為取代基時，R101、R102、R103成為芳烷基。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a halogen atom is used as a substituent, R 101 , R 102 and R 103 are a halogenated alkyl group, and when an aryl group is used as a substituent, R 101 , R 102 and R 103 are an aralkyl group.

作為所述鹵素原子，可例示氟原子、氯原子、溴原子、碘 原子，這些鹵素原子之中，優選氟原子或氯原子。 As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and iodine can be exemplified. Among the atoms, among these halogen atoms, a fluorine atom or a chlorine atom is preferred.

另外，作為所述芳基，優選碳數為6~20的芳基，更優選碳數為6~12的芳基，具體而言，可例示苯基、α-甲基苯基、萘基等，作為由芳基取代的烷基整體，即芳烷基，可例示苄基、α-甲基苄基、苯乙基、萘基甲基等。 Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, a naphthyl group, and the like. As the whole alkyl group substituted with an aryl group, that is, an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, a naphthylmethyl group or the like can be exemplified.

作為所述烷氧基，優選碳數為1~6的烷氧基，更優選碳數為1~4的烷氧基，進而更優選甲氧基或乙氧基。 The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group.

另外，當所述烷基為環狀的烷基時，所述環狀的烷基可具有碳數為1~10的直鏈狀或支鏈狀的烷基作為取代基，當烷基為直鏈狀或支鏈狀的烷基時，可具有碳數為3~12的環狀的烷基作為取代基。 Further, when the alkyl group is a cyclic alkyl group, the cyclic alkyl group may have a linear or branched alkyl group having a carbon number of 1 to 10 as a substituent, and when the alkyl group is straight In the case of a chain or branched alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms may be used as a substituent.

這些取代基也可以由所述取代基進一步取代。 These substituents may also be further substituted by the substituents.

所述通式(a1-10)中，當R101、R102及R103表示芳基時，所述芳基優選碳數為6~12，更優選碳數為6~10。所述芳基可具有取代基，作為所述取代基，可優選例示碳數為1~6的烷基。作為芳基，例如可例示苯基、甲苯基、異丙苯基、1-萘基等。 In the above formula (a1-10), when R 101 , R 102 and R 103 represent an aryl group, the aryl group preferably has a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a cumyl group, a 1-naphthyl group and the like.

另外，R101、R102及R103可相互鍵結，並與它們所鍵結的碳原子一同形成環。作為R101與R102、R101與R103或R102與R103鍵結時的環結構，例如可列舉：環丁基、環戊基、環己基、環庚基、四氫呋喃基、金剛烷基及四氫吡喃基等。 Further, R 101 , R 102 and R 103 may be bonded to each other and form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded to each other include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And tetrahydropyranyl and the like.

再者，所述通式(a1-10)中，優選R101及R102的任一個為氫原子或甲基。 Further, in the above formula (a1-10), it is preferred that any of R 101 and R 102 is a hydrogen atom or a methyl group.

用於形成含有由所述通式(a1-10)所表示的保護羧基的構成單元的自由基聚合性單體可使用市售的自由基聚合性單體，也可以使用藉由公知的方法所合成的自由基聚合性單體。 例如，可藉由日本專利特開2011-221494號公報的段落號0037~段落號0040中所記載的合成方法等來合成。 A commercially available radical polymerizable monomer may be used as the radical polymerizable monomer for forming a constituent unit containing a protective carboxyl group represented by the above formula (a1-10), or a known method may be used. Synthetic free radical polymerizable monomer. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494.

所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的第一優選的形態為由下述通式所表示的構成單元。 The first preferred embodiment of the structural unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is a constituent unit represented by the following formula.

(式中，R1及R2分別表示氫原子、烷基或芳基，至少R1及R2的任一個為烷基或芳基，R3表示烷基或芳基，R1或R2與R3可連結而形成環狀醚，R4表示氫原子或甲基，X表示單鍵或亞芳基) (wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, and R 1 or R 2 R 3 may be bonded to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

當R1及R2為烷基時，優選碳數為1~10的烷基。當R1及R2為芳基時，優選苯基。R1及R2分別優選氫原子或碳數為1~4的烷基。 When R 1 and R 2 are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 1 and R 2 are an aryl group, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R3表示烷基或芳基，優選碳數為1~10的烷基，更優選碳數為1~6的烷基。 R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X表示單鍵或亞芳基，優選單鍵。 X represents a single bond or an arylene group, preferably a single bond.

所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的第二優選的形態為下述通式的結構單元。 The second preferred embodiment of the structural unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is a structural unit of the following formula.

(式中，R121表示氫原子或碳數為1~4的烷基，L1表示羰基或亞苯基，R122~R128分別獨立地表示氫原子或碳數為1~4的烷基。) (wherein R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; .)

R121優選氫原子或甲基。 R 121 is preferably a hydrogen atom or a methyl group.

L1優選羰基。 L 1 is preferably a carbonyl group.

R122~R128優選氫原子。 R 122 to R 128 are preferably a hydrogen atom.

作為所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的優選的具體例，可例示下述的構成單元。再者，R表示氫原子或甲基。 As a preferable specific example of the structural unit (a1-1) containing the protective carboxyl group protected by the acid-decomposable group, the following structural unit can be exemplified. Further, R represents a hydrogen atom or a methyl group.

<<<(a1-2)含有由酸分解性基保護的保護酚性羥基的構成單元>>> <<<(a1-2) A constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group>>>

所述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)是含有酚性羥基的構成單元具有以下將詳細說明的由酸分解性基保護的保護酚性羥基的構成單元。 The constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group is a constituent unit containing a phenolic hydroxyl group and has a constituent unit for protecting a phenolic hydroxyl group protected by an acid-decomposable group, which will be described in detail below. .

<<<<(a1-2-1)含有酚性羥基的構成單元>>>> <<<<(a1-2-1) constitutive unit containing phenolic hydroxyl group>>>>

作為所述含有酚性羥基的構成單元，可列舉羥基苯乙烯系構成單元或酚醛清漆系的樹脂中的構成單元，這些構成單元之中，就感光度的觀點而言，優選源自羥基苯乙烯、或α-甲基羥基苯乙烯的構成單元。另外，作為含有酚性羥基的構成單元，就感光度的觀點而言，由下述通式(a1-20)所表示的構成單元也優選。 Examples of the constituent unit containing the phenolic hydroxyl group include a constituent unit in a hydroxystyrene-based constituent unit or a novolak-based resin. Among these constituent units, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene. Or a constituent unit of α-methylhydroxystyrene. In addition, as a constituent unit containing a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.

(通式(a1-20)中，R220表示氫原子或甲基，R221表示單鍵或二價的連結基，R222表示鹵素原子或碳數為1~5的直鏈或支鏈狀的烷基，a表示1~5的整數，b表示0~4的整數，a+b為5以下。再者，當存在2個以上的R222時，這些R222相互可不同，也可以相同。) (In the formula (a1-20), R 220 represents a hydrogen atom or a methyl group, R 221 represents a single bond or a divalent linking group, and R 222 represents a halogen atom or a straight or branched chain having a carbon number of 1 to 5. The alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a+b is 5 or less. Further, when two or more R 222 are present, these R 222 may be different from each other or may be the same. .)

所述通式(a1-20)中，R220表示氫原子或甲基，優選甲基。 In the above formula (a1-20), R 220 represents a hydrogen atom or a methyl group, preferably a methyl group.

另外，R221表示單鍵或二價的連結基。當R221為單鍵時，可提升感光度，進而可提升硬化膜的透明性，因此優選。作為R221的二價的連結基，可例示亞烷基，作為R221為亞烷基的具體例，可列舉：亞甲基、亞乙基、亞丙基、異亞丙基、正亞丁基、異亞丁基、叔亞丁基、亞戊基、異亞戊基、新亞戊基、亞己基等。其中，R221優選單鍵、亞甲基、亞乙基。另外，所述 二價的連結基可具有取代基，作為取代基，可列舉鹵素原子、羥基、烷氧基等。另外，a表示1~5的整數，但就本發明的效果的觀點、或容易製造這一觀點而言，優選a為1或2，更優選a為1。 Further, R 221 represents a single bond or a divalent linking group. When R 221 is a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. R 221 is a divalent linking group, may be exemplified alkylene groups, R 221 is an alkylene group as specific examples include: methylene, ethylidene, propylidene, isopropylidene, n-butylene , isobutylene, tert-butylene, pentylene, isopentylene, neopentylene, hexylene, and the like. Among them, R 221 is preferably a single bond, a methylene group or an ethylene group. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like. Further, a represents an integer of 1 to 5. However, from the viewpoint of the effects of the present invention or the ease of production, a is preferably 1 or 2, and more preferably a is 1.

另外，當將與R221進行鍵結的碳原子作為基準(1位)時，苯環中的羥基的鍵結位置優選鍵結在4位上。 Further, when a carbon atom bonded to R 221 is used as a reference (1 position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position.

R222為鹵素原子或者碳數為1~5的直鏈或支鏈狀的烷基。具體而言，可列舉：氟原子、氯原子、溴原子、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。其中，就容易製造這一觀點而言，優選氯原子、溴原子、甲基或乙基。 R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Base. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable from the viewpoint of easy production.

另外，b表示0或1~4的整數。 In addition, b represents an integer of 0 or 1 to 4.

<<<<可用於構成單元(a1-2)的酸分解性基>>>> <<<< can be used to form the acid-decomposable group of unit (a1-2) >>>>

作為可用於所述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的所述酸分解性基，與可用於所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)的所述酸分解性基同樣地，可使用公知的酸分解性基，並無特別限定。酸分解性基之中，就感光性樹脂組成物的基本物性，特別是感光度或圖案形狀、感光性樹脂組成物的保存穩定性、接觸孔的形成性的觀點而言，優選含有由縮醛保護的保護酚性羥基的構成單元。進而，酸分解性基之中，就感光度的觀點而言，更優選酚性羥基為由以所述通式(a1-10)所表示的縮醛的形式保護的保護酚性羥基。再者，當酚性羥基為由以所述通式(a1-10)所表示的縮醛的形式保護的保護酚性羥基時，保護酚性羥基的整體變成-Ar-O-CR101R102(OR103)的結構。再者，Ar表示亞芳基。 The acid-decomposable group which can be used for the structural unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group, and a composition which can be used for the protective carboxyl group which is protected by an acid-decomposable group Similarly to the acid-decomposable group of the unit (a1-1), a known acid-decomposable group can be used, and it is not particularly limited. Among the acid-decomposable groups, it is preferable to contain an acetal from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores. A protective unit that protects the phenolic hydroxyl group. Further, among the acid-decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a protective phenolic hydroxyl group protected by the acetal represented by the above formula (a1-10). Further, when the phenolic hydroxyl group is a protective phenolic hydroxyl group protected by the form of the acetal represented by the above formula (a1-10), the entirety of the protective phenolic hydroxyl group becomes -Ar-O-CR 101 R 102 The structure of (OR 103 ). Further, Ar represents an arylene group.

酚性羥基的縮醛酯結構的優選例可例示R101=R102=R103= 甲基、或R101=R102=甲基且R103=苄基的組合。 A preferred example of the acetal ester structure of the phenolic hydroxyl group is exemplified by a combination of R 101 = R 102 = R 103 = methyl group, or R 101 = R 102 = methyl group and R 103 = benzyl group.

另外，作為用於形成含有酚性羥基由縮醛的形式保護的保護酚性羥基的構成單元的自由基聚合性單體，例如可列舉日本專利特開2011-215590號公報的段落號0042中所記載的自由基聚合性單體等。 In addition, as a radically polymerizable monomer which forms a structural unit which protects a phenolic hydroxyl group which has a phenolic hydroxyl group and is protected by the acetal, it is set, for example, in the paragraph 0042 of Unexamined-Japanese-Patent No. 2011-215590. A radical polymerizable monomer or the like described.

這些自由基聚合性單體之中，就透明性的觀點而言，優選甲基丙烯酸4-羥基苯酯的1-烷氧基烷基保護體、甲基丙烯酸4-羥基苯酯的四氫吡喃基保護體。 Among these radically polymerizable monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a tetrahydropyridyl 4-hydroxyphenyl methacrylate is preferable. Cycloprotector.

作為酚性羥基的縮醛保護基的具體例，可列舉1-烷氧基烷基，例如可列舉1-乙氧基乙基、1-甲氧基乙基、1-正丁氧基乙基、1-異丁氧基乙基、1-(2-氯乙氧基)乙基、1-(2-乙基己氧基)乙基、1-正丙氧基乙基、1-環己氧基乙基、1-(2-環己基乙氧基)乙基、1-苄氧基乙基等，這些基可單獨使用、或將2種以上組合使用。 Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl group, 1-methoxyethyl group, and 1-n-butoxyethyl group. , 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyl An oxyethyl group, a 1-(2-cyclohexylethoxy)ethyl group, a 1-benzyloxyethyl group, etc. may be used alone or in combination of two or more.

用於形成所述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的自由基聚合性單體可使用市售的自由基聚合性單體，也可以使用藉由公知的方法所合成的自由基聚合性單體。例如，可藉由在酸觸媒的存在下使含有酚性羥基的化合物與乙烯基醚進行反應來合成。所述合成也可以事先使含有酚性羥基的單體與其他單體進行共聚，然後在酸觸媒的存在下與乙烯基醚進行反應。 A radically polymerizable monomer for forming the structural unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group may be a commercially available radical polymerizable monomer, or may be used. The free radical polymerizable monomer synthesized by the method. For example, it can be synthesized by reacting a compound containing a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The synthesis may also be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with another monomer and then reacting with a vinyl ether in the presence of an acid catalyst.

作為所述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)的優選的具體例，可例示下述的構成單元，但本發明並不限定於這些構成單元。 A preferred specific example of the structural unit (a1-2) containing the protective phenolic hydroxyl group protected by the acid-decomposable group is exemplified by the following constituent units, but the present invention is not limited to these constituent units.

<<<構成單元(a1)的優選的形態>>> <<<Preferred form of constituent unit (a1)>>>

當含有所述構成單元(a1)的聚合物實質上不含構成單元(a2)時，構成單元(a1)在含有該構成單元(a1)的聚合物中，優選20莫耳%~100莫耳%，更優選30莫耳%~90莫耳%。 When the polymer containing the constituent unit (a1) contains substantially no constituent unit (a2), the constituent unit (a1) is preferably 20 mol% to 100 mol in the polymer containing the constituent unit (a1). %, more preferably 30% by mole to 90% by mole.

當含有所述構成單元(a1)的聚合物含有下述構成單元(a2)時，就感光度的觀點而言，構成單元(a1)在含有該構 成單元(a1)與構成單元(a2)的聚合物中，優選3莫耳%~70莫耳%，更優選10莫耳%~60莫耳%。另外，尤其在可用於所述構成單元(a1)的所述酸分解性基具有羧基由縮醛的形式保護的保護羧基的構成單元的情況下，優選20莫耳%~50莫耳%。 When the polymer containing the structural unit (a1) contains the following structural unit (a2), the constituent unit (a1) contains the structure in terms of sensitivity. In the polymer of the unit (a1) and the constituent unit (a2), it is preferably 3 mol% to 70 mol%, more preferably 10 mol% to 60 mol%. Further, in particular, in the case where the acid-decomposable group which can be used in the structural unit (a1) has a constituent unit for protecting a carboxyl group in which a carboxyl group is protected by an acetal form, it is preferably 20 mol% to 50 mol%.

與所述含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)相比，所述含有由酸分解性基保護的保護羧基的構成單元(a1-1)具有顯影快的特徵。因此，在欲快速顯影的情況下，優選含有由酸分解性基保護的保護羧基的構成單元(a1-1)。相反地，在欲使顯影變慢的情況下，優選使用含有由酸分解性基保護的保護酚性羥基的構成單元(a1-2)。 The constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group has a faster development than the constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group. feature. Therefore, in the case of rapid development, a constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group is preferable. Conversely, in the case where the development is to be slowed down, it is preferred to use a constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group.

<<(a2)含有交聯性基的構成單元>> <<(a2) Component unit containing a crosslinkable group>>

(A)成分具有含有交聯性基的構成單元(a2)。所述交聯性基只要是藉由加熱處理而產生硬化反應的基，則並無特別限定。作為優選的含有交聯性基的構成單元的形態，可列舉含有選自由環氧基、氧雜環丁基、由-NH-CH2-O-R(R為碳數為1~20的烷基)所表示的基、及乙烯性不飽和基所組成的組群中的至少1個的構成單元，優選選自環氧基、氧雜環丁基、及由-NH-CH2-O-R(R為碳數為1~20的烷基)所表示的基中的至少1種。其中，本發明的感光性樹脂組成物優選所述(A)成分包含含有環氧基及氧雜環丁基中的至少1個的構成單元。更詳細而言，可列舉以下者。 The component (A) has a structural unit (a2) containing a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which generates a curing reaction by heat treatment. The form of the preferable structural unit containing a crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms). The constituent unit of at least one of the group represented by the group and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH 2 -OR (R is At least one of the groups represented by the alkyl group having 1 to 20 carbon atoms. In the photosensitive resin composition of the present invention, the component (A) preferably contains at least one of an epoxy group and an oxetanyl group. More specifically, the following are mentioned.

<<<(a2-1)具有環氧基及/或氧雜環丁基的構成單元>>> <<<(a2-1) constituent unit having an epoxy group and/or an oxetanyl group>>>

所述(A)聚合物優選含有具有環氧基及/或氧雜環丁基的構成單元(構成單元(a2-1))。所述3員環的環狀醚基也被稱 為環氧基，4員環的環狀醚基也被稱為氧雜環丁基。 The (A) polymer preferably contains a constituent unit (constituting unit (a2-1)) having an epoxy group and/or an oxetanyl group. The cyclic ether group of the 3-membered ring is also called The cyclic ether group of the 4-membered ring is also an oxetanyl group.

所述具有環氧基及/或氧雜環丁基的構成單元(a2-1)只要1個構成單元中具有至少1個環氧基或氧雜環丁基即可，可具有1個以上的環氧基及1個以上的氧雜環丁基、2個以上的環氧基、或2個以上的氧雜環丁基，並無特別限定，但優選具有合計為1個~3個的環氧基及/或氧雜環丁基，更優選具有合計為1個或2個的環氧基及/或氧雜環丁基，進而更優選具有1個環氧基或氧雜環丁基。 The constituent unit (a2-1) having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more members. The epoxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, but preferably have a total of one to three rings. The oxy group and/or oxetanyl group are more preferably one or two epoxy groups and/or oxetanyl groups in total, and more preferably one epoxy group or oxetanyl group.

作為用於形成具有環氧基的構成單元的自由基聚合性單體的具體例，例如可列舉丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧基丁酯、甲基丙烯酸-3,4-環氧基丁酯、丙烯酸-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧環己基甲酯、α-乙基丙烯酸-3,4-環氧環己基甲酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、日本專利第4168443號公報的段落號0031~段落號0035中所記載的含有脂環式環氧基骨架的化合物等，這些內容被編入至本申請案說明書中。 Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-positive propylene. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Cyclohexyl methyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinylbenzyl glycidyl ether, m-vinyl benzyl The glycidyl ether, the p-vinylbenzyl glycidyl ether, the alicyclic epoxy group-containing compound described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,184,443, etc., are incorporated herein. In the application note.

作為用於形成具有氧雜環丁基的構成單元的自由基聚合性單體的具體例，例如可列舉日本專利特開2001-330953號公報的段落號0011~段落號0016中所記載的具有氧雜環丁基的(甲基)丙烯酸酯等，這些內容被編入至本申請案說明書中。 Specific examples of the radical polymerizable monomer for forming a structural unit having an oxetanyl group include oxygen having the oxygen described in paragraph No. 0011 to paragraph 0016 of JP-A-2001-330953. Heterocyclic butyl (meth) acrylates and the like are incorporated in the specification of the present application.

作為用於形成所述具有環氧基及/或氧雜環丁基的構成單元(a2-1)的自由基聚合性單體的具體例，優選含有甲基丙烯酸酯結構的單體、含有丙烯酸酯結構的單體。 Specific examples of the radical polymerizable monomer for forming the structural unit (a2-1) having an epoxy group and/or an oxetanyl group are preferably a monomer having a methacrylate structure and containing acrylic acid. A monomer of an ester structure.

這些之中，優選的單體是甲基丙烯酸縮水甘油酯、丙烯酸 3,4-環氧環己基甲酯、甲基丙烯酸3,4-環氧環己基甲酯、丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、及甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯。這些構成單元可單獨使用1種、或將2種以上組合使用。 Among these, the preferred monomers are glycidyl methacrylate, acrylic acid. 3,4-epoxycyclohexylmethyl ester, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetan-3-yl)methyl acrylate, and methacrylic acid (3) -Ethyloxetane-3-yl)methyl ester. These constituent units may be used alone or in combination of two or more.

作為所述具有環氧基及/或氧雜環丁基的構成單元(a2-1)的優選的具體例，可例示下述的構成單元。再者，R表示氫原子或甲基。 Preferred specific examples of the structural unit (a2-1) having an epoxy group and/or an oxetanyl group include the following constituent units. Further, R represents a hydrogen atom or a methyl group.

<<<(a2-2)具有乙烯性不飽和基的構成單元>>> <<<(a2-2) constituent unit having an ethylenically unsaturated group>>>

作為所述含有交聯性基的構成單元(a2)的1種，可列舉具有乙烯性不飽和基的構成單元(a2-2)(以下，也稱為“構成單元(a2-2)”)。作為所述具有乙烯性不飽和基的構成單元(a2-2)，優選側鏈上具有乙烯性不飽和基的構成單元，更優選末端具有乙烯性不飽和基、且具有碳數為3~16的側鏈的構成單元，進而更優選具有由下述通式(a2-2-1)所表示的側鏈的構成單元。 One type of the structural unit (a2) containing the crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter, also referred to as "structural unit (a2-2)"). . The constituent unit (a2-2) having an ethylenically unsaturated group is preferably a constituent unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal, and having a carbon number of 3 to 16 Further, the constituent unit of the side chain is more preferably a constituent unit having a side chain represented by the following general formula (a2-2-1).

(通式(a2-2-1)中，R301表示碳數為1~13的二價的連結基，R302表示氫原子或甲基，*表示與含有交聯性基的構成單元(a2)的主鏈連結的部位。) (In the formula (a2-2-1), R 301 represents a divalent linking group having a carbon number of 1 to 13, R 302 represents a hydrogen atom or a methyl group, and * represents a constituent unit having a crosslinkable group (a2). ) The main link of the link.)

R301為碳數為1~13的二價的連結基，包含烯基、亞芳基或將它們組合而成的基，也可以含有酯鍵、醚鍵、醯胺鍵、聚氨酯鍵等鍵。另外，二價的連結基可在任意的位置上具有羥基、羧基等取代基。作為R301的具體例，可列舉下述的二價的連結基。 R 301 is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, an arylene group or a combination thereof, and may contain a bond such as an ester bond, an ether bond, a guanamine bond or a urethane bond. Further, the divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at any position. Specific examples of R 301 include the following divalent linking groups.

由所述通式(a2-2-1)所表示的側鏈之中，優選包含由所述R301所表示的二價的連結基的脂肪族的側鏈。 Among the side chains represented by the above formula (a2-2-1), an aliphatic side chain containing a divalent linking group represented by the above R 301 is preferable.

關於其他(a2-2)具有乙烯性不飽和基的構成單元，可參考日本專利特開2011-215580號公報的段落號0072~段落號0090的記載，這些內容被編入至本申請案說明書中。 For the other (a2-2) constituent unit having an ethylenically unsaturated group, the description of Paragraph No. 0072 to Paragraph No. 0090 of JP-A-2011-215580 can be referred to in the specification of the present application.

<<<(a2-3)具有由-NH-CH2-O-R(R為碳數為1~20的烷基)所表示的基的構成單元>>> <<<(a2-3) A constituent unit having a group represented by -NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms) >>>

本發明中所使用的聚合物也優選具有由-NH-CH2-O-R(R為碳數為1~20的烷基)所表示的基的構成單元。藉由具有構 成單元(a2-3)，可利用緩和的加熱處理產生硬化反應，而可獲得各種特性優異的硬化膜。此處，R優選碳數為1~9的烷基，更優選碳數為1~4的烷基。另外，烷基可為直鏈、分支或環狀的烷基的任一種，但優選直鏈或分支的烷基。構成單元(a2)更優選具有由下述通式(a2-30)所表示的基的構成單元。 The polymer used in the present invention is also preferably a constituent unit having a group represented by -NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), a hardening reaction can be generated by a gentle heat treatment, and a cured film excellent in various properties can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, but a linear or branched alkyl group is preferred. The constituent unit (a2) more preferably has a constituent unit represented by the following formula (a2-30).

(通式(a2-30)中，R1表示氫原子或甲基，R2表示碳數為1~20的烷基。) (In the formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 20 carbon atoms.)

R2優選碳數為1~9的烷基，更優選碳數為1~4的烷基。另外，烷基可為直鏈、分支或環狀的烷基的任一種，但優選直鏈或分支的烷基。 R 2 is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, but a linear or branched alkyl group is preferred.

作為R2的具體例，可列舉：甲基、乙基、正丁基、異丁基、環己基、及正己基。其中，優選異丁基、正丁基、甲基。 Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and an n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<<構成單元(a2)的優選的形態>>> <<<Preferred form of constituent unit (a2)>>>

當含有所述構成單元(a2)的聚合物實質上不含構成單元(a1)時，構成單元(a2)在含有該構成單元(a2)的聚合物中，優選5莫耳%~90莫耳%，更優選20莫耳%~80莫耳%。 When the polymer containing the constituent unit (a2) contains substantially no constituent unit (a1), the constituent unit (a2) is preferably 5 mol% to 90 mol in the polymer containing the constituent unit (a2). %, more preferably 20% by mole to 80% by mole.

當含有所述構成單元(a2)的聚合物含有所述構成單元(a1)時，就耐化學品性的觀點而言，構成單元(a2)在含有該構成單元(a1)與構成單元(a2)的聚合物中，優選3莫耳 %~70莫耳%，更優選10莫耳%~60莫耳%。 When the polymer containing the constituent unit (a2) contains the constituent unit (a1), the constituent unit (a2) contains the constituent unit (a1) and the constituent unit (a2) from the viewpoint of chemical resistance. Of the polymer, preferably 3 moles %~70% by mole, more preferably 10% by mole to 60% by mole.

進而，在本發明中，不論何種形態，在(A)成分的所有構成單元中，優選含有3莫耳%~70莫耳%的構成單元(a2)，更優選含有10莫耳%~60莫耳%的構成單元(a2)。 Further, in the present invention, in all the constituent units of the component (A), it is preferable to contain 3 mol% to 70 mol% of the constituent unit (a2), and more preferably 10 mol% to 60. Mol% of the constituent unit (a2).

若為所述數值的範圍內，則由感光性樹脂組成物所獲得的硬化膜的透明性及耐化學品性變得良好。 When it is in the range of the numerical value, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition become favorable.

<<(a3)其他構成單元>> <<(a3) Other constituent units>>

在本發明中，(A)成分除所述構成單元(a1)及/或構成單元(a2)以外，也可以具有它們以外的其他構成單元(a3)。所述聚合物成分(1)及/或聚合物成分(2)可含有這些構成單元。另外，除所述聚合物成分(1)或聚合物成分(2)以外，也可以含有實質上不含(a1)及(a2)而具有其他構成單元(a3)的聚合物成分。當除所述聚合物成分(1)或聚合物成分(2)以外，含有實質上不含(a1)及(a2)而具有其他構成單元(a3)的聚合物成分時，該聚合物成分的調配量在所有聚合物成分中，優選60質量%以下，更優選40質量%以下，進而更優選20質量%以下。 In the present invention, the component (A) may have other constituent units (a3) other than the constituent unit (a1) and/or the constituent unit (a2). The polymer component (1) and/or the polymer component (2) may contain these constituent units. Further, in addition to the polymer component (1) or the polymer component (2), a polymer component having substantially no (a1) and (a2) and having another constituent unit (a3) may be contained. When a polymer component having substantially no (a1) and (a2) and having another constituent unit (a3) is contained in addition to the polymer component (1) or the polymer component (2), the polymer component is The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less based on all the polymer components.

作為成為其他構成單元(a3)的單體，並無特別限制，例如可列舉：苯乙烯類、(甲基)丙烯酸烷基酯、(甲基)丙烯酸環狀烷基酯、(甲基)丙烯酸芳基酯、不飽和二羧酸二酯、雙環不飽和化合物類、順丁烯二醯亞胺化合物類、不飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、不飽和二羧酸、不飽和二羧酸酐、其他不飽和化合物。另外，如後述般，也可以具有含有酸基的構成單元。成為其他構成單元(a3)的單體可單獨使用、或將2種以上組合使用。 The monomer to be used as the other constituent unit (a3) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and (meth)acrylic acid. Aryl ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated two Carboxylic acid, unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as will be described later, a constituent unit containing an acid group may be provided. The monomers which are other constituent units (a3) may be used singly or in combination of two or more kinds.

以下，列舉本發明的聚合物成分的優選的實施形態，但本 發明並不限定於這些實施形態。 Hereinafter, preferred embodiments of the polymer component of the present invention are listed, but The invention is not limited to these embodiments.

(第1實施形態) (First embodiment)

聚合物成分(1)進而具有1種或2種以上的其他構成單元(a3)的形態。 The polymer component (1) further has one or two or more types of other constituent units (a3).

(第2實施形態) (Second embodiment)

聚合物成分(2)的具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物進而具有1種或2種以上的其他構成單元(a3)的形態。 In the polymer component (2), the polymer having (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group further has one or two or more kinds of other constituent units (a3).

(第3實施形態) (Third embodiment)

聚合物成分(2)的具有(a2)含有交聯性基的構成單元的聚合物進而具有1種或2種以上的其他構成單元(a3)的形態。 The polymer of the polymer component (2) having (a2) a structural unit containing a crosslinkable group further has one or two or more types of other constituent units (a3).

(第4實施形態) (Fourth embodiment)

在所述第1實施形態~第3實施形態的任一實施形態中，包含至少含有酸基的構成單元作為其他構成單元(a3)的形態。 In any of the first to third embodiments, the constituent unit containing at least an acid group is included as another constituent unit (a3).

(第5實施形態) (Fifth Embodiment)

除所述聚合物成分(1)或聚合物成分(2)以外，進而具有實質上不含(a1)及(a2)而含有其他構成單元(a3)的聚合物的形態。 In addition to the polymer component (1) or the polymer component (2), it further has a form of a polymer containing substantially no (a1) and (a2) and containing another structural unit (a3).

(第6實施形態) (Sixth embodiment)

至少含有聚合物成分(2)的形態。 At least the form of the polymer component (2) is contained.

(第7實施形態) (Seventh embodiment)

包含所述第1實施形態~第6的實施形態的2種以上的組合的形態。 The form of the combination of two or more types of the first to sixth embodiments is included.

(第8實施形態) (Eighth embodiment)

除所述聚合物成分(1)或聚合物成分(2)以外，包含具 有至少含有酸基的構成單元作為其他構成單元(a3)的聚合物的形態。 In addition to the polymer component (1) or the polymer component (2), There is a form in which a constituent unit containing at least an acid group is a polymer of another constituent unit (a3).

(第9實施形態) (Ninth Embodiment)

除所述聚合物成分(1)或聚合物成分(2)以外，包含具有至少含有酸基的構成單元、及含有交聯性基的構成單元作為其他構成單元(a3)的共聚物的形態。 In addition to the polymer component (1) or the polymer component (2), a form of a copolymer having a structural unit containing at least an acid group and a structural unit containing a crosslinkable group as another constituent unit (a3) is contained.

(第10實施形態) (Tenth embodiment)

在所述實施形態8或實施形態9中，酸基為含有羧基及/或酚性羥基的構成單元的形態。 In the eighth embodiment or the ninth embodiment, the acid group is a form of a constituent unit containing a carboxyl group and/or a phenolic hydroxyl group.

具體而言，構成單元(a3)可列舉利用苯乙烯、叔丁氧基苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、氯苯乙烯、乙烯基苯甲酸甲酯、乙烯基苯甲酸乙酯、4-羥基苯甲酸(3-甲基丙烯醯氧基丙基)酯、(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異冰片酯、丙烯腈、乙二醇單乙醯乙酸酯單(甲基)丙烯酸酯等的構成單元。除此以外，可列舉日本專利特開2004-264623號公報的段落號0021~段落號0024中所記載的化合物。 Specifically, the constituent unit (a3) may be exemplified by styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, methoxystyrene. , ethoxystyrene, chlorostyrene, methyl benzoate, ethyl vinyl benzoate, 4-hydroxypropenyl propyl methacrylate, (meth)acrylic acid, Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid A constituent unit of 2-hydroxypropyl ester, benzyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetate mono(meth)acrylate, or the like. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.

另外，作為其他構成單元(a3)，就電特性的觀點而言，優選苯乙烯類、具有脂肪族環式骨架的基。具體而言，可列舉：苯乙烯、叔丁氧基苯乙烯、甲基苯乙烯、羥基苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苄酯等。 In addition, as the other structural unit (a3), a styrene type or a group having an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ester, isobornyl (meth)acrylate, benzyl (meth)acrylate, and the like.

進而，作為其他構成單元(a3)，就密接性的觀點而言， 優選(甲基)丙烯酸烷基酯。具體而言，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)丙烯酸正丁酯等，更優選(甲基)丙烯酸甲酯。構成聚合物(A)的構成單元中，所述構成單元(a3)的含有率優選60莫耳%以下，更優選50莫耳%以下，進而更優選40莫耳%以下。作為下限值，可為0莫耳%，但例如可設為1莫耳%以上，進而可設為5莫耳%以上。若為所述數值的範圍內，則由感光性樹脂組成物所獲得的硬化膜的各種特性變得良好。 Further, as another constituent unit (a3), from the viewpoint of adhesion, Preference is given to alkyl (meth)acrylates. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. In the constituent unit constituting the polymer (A), the content of the constituent unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The lower limit value may be 0 mol%, but may be, for example, 1 mol% or more, and may be 5 mol% or more. When it is within the range of the numerical value, various properties of the cured film obtained from the photosensitive resin composition are good.

作為其他構成單元(a3)，優選含有酸基。藉由含有酸基，容易溶解在鹼性的顯影液中，本發明的效果得以更有效地發揮。本發明中的酸基是指pKa小於7的質子解離性基。通常，使用可形成酸基的單體作為含有酸基的構成單元，而將酸基導入至聚合物中。藉由在聚合物中包含此種含有酸基的構成單元，而存在容易溶解在鹼性的顯影液中的傾向。 The other constituent unit (a3) preferably contains an acid group. The effect of the present invention can be more effectively exhibited by containing an acid group and easily dissolving in an alkaline developing solution. The acid group in the present invention means a proton dissociative group having a pKa of less than 7. Usually, a monomer capable of forming an acid group is used as a constituent unit containing an acid group, and an acid group is introduced into the polymer. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution.

作為本發明中所使用的酸基，可例示源自羧酸基的酸基、源自磺醯胺基的酸基、源自膦酸基的酸基、源自磺酸基的酸基、源自酚性羥基的酸基、磺醯胺基、磺醯基醯亞胺基等，優選源自羧酸基的酸基及/或源自酚性羥基的酸基。 The acid group used in the present invention may, for example, be an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, or a source. The acid group derived from a phenolic hydroxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, or the like is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group.

作為用於形成含有羧基的構成單元的自由基聚合性單體，例如可列舉丙烯酸、甲基丙烯酸、巴豆酸等單羧酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、衣康酸等二羧酸等不飽和羧酸作為優選的自由基聚合性單體。 Examples of the radical polymerizable monomer for forming a structural unit containing a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, and the like. An unsaturated carboxylic acid such as a dicarboxylic acid such as a benic acid or itaconic acid is preferred as the radical polymerizable monomer.

另外，作為用於形成含有羧酸酐殘基的構成單元的自由基聚合性單體，例如可列舉順丁烯二酸酐、衣康酸酐等作為優選的自由基聚合性單體。 In addition, examples of the radical polymerizable monomer for forming a constituent unit containing a carboxylic anhydride residue include maleic anhydride, itaconic anhydride, and the like as a preferred radical polymerizable monomer.

作為用於形成含有酚性羥基的構成單元的自由基聚合性 單體，例如可列舉對羥基苯乙烯、α-甲基-對羥基苯乙烯等羥基苯乙烯類，日本專利特開2008-40183號公報的段落0011~段落0016中所記載的化合物，日本專利第2888454號公報的段落0007~段落0010中所記載的4-羥基苯甲酸衍生物類，4-羥基苯甲酸與甲基丙烯酸縮水甘油酯的加成反應物，4-羥基苯甲酸與丙烯酸縮水甘油酯的加成反應物等作為優選的自由基聚合性單體。 As a radical polymerizable property for forming a constituent unit containing a phenolic hydroxyl group Examples of the monomer include a hydroxystyrene such as p-hydroxystyrene or α-methyl-p-hydroxystyrene, and a compound described in paragraphs 0011 to 0016 of JP-A-2008-40183, Japanese Patent No. 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of 2888454, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and glycidyl acrylate The addition reaction or the like is preferred as the radical polymerizable monomer.

這些自由基聚合性單體之中，優選甲基丙烯酸、丙烯酸、日本專利特開2008-40183號公報的段落0011~段落0016中所記載的化合物、日本專利第2888454號公報的段落0007~段落0010中所記載的4-羥基苯甲酸衍生物類、4-羥基苯甲酸與甲基丙烯酸縮水甘油酯的加成反應物、4-羥基苯甲酸與丙烯酸縮水甘油酯的加成反應物，更優選日本專利特開2008-40183號公報的段落0011~段落0016中所記載的化合物、日本專利第2888454號公報的段落0007~段落0010中所記載的4-羥基苯甲酸衍生物類、4-羥基苯甲酸與甲基丙烯酸縮水甘油酯的加成反應物、4-羥基苯甲酸與丙烯酸縮水甘油酯的加成反應物，更優選源自選自由丙烯酸、甲基丙烯酸、對羥基苯乙烯、及α-甲基-對羥基苯乙烯所組成的組群中的至少1種的構成單元，進而更優選源自丙烯酸或甲基丙烯酸的構成單元，特優選源自甲基丙烯酸的構成單元。這些構成單元可單獨使用1種、或將2種以上組合使用。 Among these radically polymerizable monomers, methacrylic acid, acrylic acid, a compound described in paragraphs 0011 to 0016 of JP-A-2008-40183, and paragraph 0007 to paragraph 0010 of Japanese Patent No. 2888454 are preferable. The addition reaction product of the 4-hydroxybenzoic acid derivative, the addition reaction of 4-hydroxybenzoic acid and glycidyl methacrylate, and the addition reaction of 4-hydroxybenzoic acid and glycidyl acrylate, more preferably Japan The compound described in paragraphs 0011 to 0016 of JP-A-2008-40183, and the 4-hydroxybenzoic acid derivative and 4-hydroxybenzoic acid described in paragraph 0007 to paragraph 0010 of Japanese Patent No. 2888454 An addition reaction with glycidyl methacrylate, an addition reaction of 4-hydroxybenzoic acid with glycidyl acrylate, more preferably derived from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene, and α-A The constituent unit of at least one of the group consisting of hydroxy-p-hydroxystyrene is more preferably a constituent unit derived from acrylic acid or methacrylic acid, and particularly preferably a composition derived from methacrylic acid. Yuan. These constituent units may be used alone or in combination of two or more.

作為構成單元(b1)的優選的具體例，可例示下述的構成單元。 As a preferable specific example of the structural unit (b1), the following structural unit can be exemplified.

含有酸基的構成單元優選所有聚合物成分的構成單元的1莫耳%~80莫耳%，更優選1莫耳%~50莫耳%，進而更優選5莫耳%~40莫耳%，尤其優選5莫耳%~30莫耳%，特優選5莫耳%~20莫耳%。 The constituent unit containing an acid group is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, still more preferably from 5 mol% to 40 mol%, of the constituent units of all the polymer components. It is particularly preferably 5 mol% to 30 mol%, particularly preferably 5 mol% to 20 mol%.

在本發明中，作為除所述聚合物成分(1)或聚合物成分(2)以外，實質上不含(a1)及(a2)而具有其他構成單元(a3)的聚合物，優選側鏈上具有羧基的樹脂。例如可列舉如日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本專利特公昭58-12577號、日本專利特公昭54-25957號、日本專 利特開昭59-53836號、日本專利特開昭59-71048號的各公報中所記載般的甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物等、以及側鏈上具有羧基的酸性纖維素衍生物、在具有羥基的聚合物中加成酸酐而成者等，進而也可以列舉側鏈上具有(甲基)丙烯醯基的高分子聚合物作為優選的聚合物。 In the present invention, as the polymer having the other constituent unit (a3), which does not substantially contain (a1) and (a2), in addition to the polymer component (1) or the polymer component (2), a side chain is preferred. A resin having a carboxyl group. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Special Publication No. Sho 58-12577, Japanese Patent Special Publication No. 54-25957, and Japanese Patent No. A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid, as described in each of the publications of Japanese Patent Laid-Open Publication No. SHO 59-71048 a diacid copolymer, a partially esterified maleic acid copolymer, or the like, an acidic cellulose derivative having a carboxyl group in a side chain, an acid anhydride added to a polymer having a hydroxyl group, and the like. A high molecular polymer having a (meth) acrylonitrile group in the chain is preferred as the polymer.

例如可列舉：(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸2-羥基乙酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、日本專利特開平7-140654號公報中所記載的(甲基)丙烯酸2-羥基丙酯/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯大分子單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。 For example, benzyl (meth)acrylate / (meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic copolymer, Japanese patent 2-Hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxy acrylate, as described in Kaiping No. 7-140654 Propyl propyl ester / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / A methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

除此以外，也可以使用日本專利特開平7-207211號公報、日本專利特開平8-259876號公報、日本專利特開平10-300922號公報、日本專利特開平11-140144號公報、日本專利特開平11-174224號公報、日本專利特開2000-56118號公報、日本專利特開2003-233179號公報、日本專利特開2009-52020號公報等中所記載的公知的高分子化合物，這些內容被編入至本申請案說明書中。 In addition, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, Japanese Patent Application Laid-Open No. Hei 11-140144, and Japanese Patent No. A known polymer compound described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. It is incorporated into the specification of this application.

這些聚合物可僅含有1種，也可以含有2種以上。 These polymers may be contained alone or in combination of two or more.

作為這些聚合物，也可以使用市售的SMA 1000P、SMA 2000P、SMA 3000P、SMA 1440F、SMA 17352P、SMA 2625P、SMA 3840F(以上，沙多瑪(Sartomer)公司製造)，ARUFON UC-3000、ARUFON UC-3510、ARUFON UC-3900、ARUFON UC-3910、ARUFON UC-3920、ARUFON UC-3080(以上，東亞合成(股份)製造)，Joncryl 690、Joncryl 678、Joncryl 67、Joncryl 586(以上，巴斯夫(BASF)製造)等。 As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, Sartomer), ARUFON can also be used. UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF).

當使用苯乙烯或α-甲基苯乙烯等苯乙烯類作為其他構成單元(a3)時，優選進而具有由下述式(b3-1)所表示的構成單元。R4優選氫原子。 When styrene such as styrene or α-methylstyrene is used as the other structural unit (a3), it is preferable to further have a structural unit represented by the following formula (b3-1). R 4 is preferably a hydrogen atom.

(式中，R4表示氫原子或甲基。) (wherein R 4 represents a hydrogen atom or a methyl group.)

另外，作為構成單元(b3)的例子，可優選列舉源自選自由(甲基)丙烯酸酯類、苯乙烯類、及N取代順丁烯二醯亞胺所組成的組群中的至少1種的構成單元，可更優選列舉源自選自由(甲基)丙烯酸酯類、及苯乙烯類所組成的組群中的至少1種的構成單元。 In addition, as an example of the structural unit (b3), at least one selected from the group consisting of (meth) acrylates, styrenes, and N-substituted maleimide is preferable. More preferably, the constituent unit derived from at least one selected from the group consisting of (meth) acrylates and styrenes.

其中，作為用於形成構成單元(b3)的自由基聚合性單體，可優選例示如(甲基)丙烯酸二環戊酯、(甲基)丙烯酸環己酯、丙烯酸環己酯般的具有脂環結構的(甲基)丙烯酸酯類，(甲基)丙烯酸甲酯，(甲基)丙烯酸2-羥基乙酯，苯乙烯，可更優選例示(甲基)丙烯酸甲酯、(甲基)丙烯酸2-羥基乙酯、苯乙烯，可進而優選例示(甲基)丙烯酸甲酯，可特優選例示甲基丙烯酸甲酯。 In addition, as the radical polymerizable monomer for forming the structural unit (b3), a lipid such as dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate or cyclohexyl acrylate can be preferably exemplified. The (meth) acrylate of the ring structure, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene, more preferably exemplified by methyl (meth) acrylate or (meth) acrylate Further, 2-hydroxyethyl acrylate and styrene are more preferably exemplified by methyl (meth) acrylate, and methyl methacrylate is particularly preferably exemplified.

<<(A)聚合物的分子量>> <<(A) Molecular Weight of Polymer>>

(A)聚合物的分子量以聚苯乙烯換算重量平均分子量計，優選1,000~200,000，更優選2,000~50,000的範圍。若為所述數值的範圍內，則各種特性良好。數量平均分子量與重量平均分子量的比(分散度)優選1.0~5.0，更優選1.5~3.5。 The molecular weight of the (A) polymer is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the range of the numerical value, various characteristics are good. The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<<(A)聚合物的製造方法>> <<(A) Method for producing polymer>>

另外，關於(A)成分的合成法，也已知有各種方法，若列舉一例，則可藉由利用自由基聚合起始劑，使至少含有用於形成由所述(a1)及所述(a3)所表示的構成單元的自由基聚合性單體的自由基聚合性單體混合物在有機溶劑中進行聚合來合成。另外，也可以藉由所謂的高分子反應來合成。 Further, various methods are also known for the synthesis method of the component (A), and if an example is used, at least the content of the (a1) and the (a1) can be formed by using a radical polymerization initiator. A3) The radically polymerizable monomer mixture of the radical polymerizable monomer of the constituent unit represented by the polymerization is synthesized by polymerization in an organic solvent. Alternatively, it may be synthesized by a so-called polymer reaction.

相對於總固體成分100質量份，本發明的感光性樹脂組成物優選以50質量份~99.9質量份的比例含有(A)成分，更優選以70質量份~98質量份的比例含有(A)成分。 The photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 parts by mass to 99.9 parts by mass, more preferably 70 parts by mass to 98 parts by mass, based on 100 parts by mass of the total solid content (A). ingredient.

<成分(X)> <ingredient (X)>

本發明中所使用的矽化合物的特徵在於：1分子內具有2個以上由下式(X1)所表示的水解性矽烷基及/或矽烷醇基。 The hydrazine compound used in the present invention is characterized in that it has two or more hydrolyzable alkylene groups and/or stanol groups represented by the following formula (X1) in one molecule.

(式中，RX1~RX3的至少1個表示選自由烷氧基、巰基、鹵素原子、醯胺基、乙醯氧基、氨基、烯丙氧基、及異丙烯氧基所組成的組群中的水解性基，或羥基。剩餘的RX1~RX3分別獨立地表示氫原子、鹵素原子、或一價的有機取代基。) (wherein at least one of R X1 to R X3 represents a group selected from the group consisting of an alkoxy group, a fluorenyl group, a halogen atom, a decylamino group, an ethoxy group, an amino group, an allyloxy group, and an isopropenyloxy group. a hydrolyzable group in the group, or a hydroxyl group. The remaining R X1 to R X3 independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent.

式(X1)中，RX1~RX3的至少1個表示選自由烷氧基、巰基、鹵素原子、醯胺基、乙醯氧基、氨基、烯丙氧基、及異丙烯氧基所組成的組群中的水解性基，或羥基。剩餘的RX1~RX3分別獨立地表示氫原子、鹵素原子、或一價的有機取代基(例如烷基、芳基、烯基、炔基、芳烷基)。 In the formula (X1), at least one of R X1 to R X3 is selected from the group consisting of an alkoxy group, a decyl group, a halogen atom, a decylamino group, an ethoxy group, an amino group, an allyloxy group, and an isopropenyloxy group. a hydrolyzable group in the group, or a hydroxyl group. The remaining R X1 to R X3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or an aralkyl group).

式(X1)中，作為鍵結在矽原子上的水解性基，尤其優選烷氧基、鹵素原子，更優選烷氧基。 In the formula (X1), as the hydrolyzable group bonded to the ruthenium atom, an alkoxy group or a halogen atom is particularly preferable, and an alkoxy group is more preferable.

作為烷氧基，就沖洗性與耐刷性的觀點而言，優選碳數為1~30的烷氧基，更優選碳數為1~15的烷氧基，進而優選碳數為1~5的烷氧基，進而更優選碳數為1~3的烷氧基，特優選甲氧基或乙氧基。 The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and more preferably 1 to 5 carbon atoms, from the viewpoint of rinsing property and printing durability. The alkoxy group is more preferably an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

另外，作為鹵素原子，可列舉F原子、Cl原子、Br原子、I原子，就合成的容易性及穩定性的的觀點而言，可優選列舉Cl原子及Br原子，可更優選列舉Cl原子。 In addition, as a halogen atom, a F atom, a Cl atom, a Br atom, and an I atom are mentioned, and a point which is easy to synthesize and stability, and a Cl atom and a Br atom are preferable, and a Cl atom is more preferable.

成分X具有2個以上由式(X1)所表示的基。即，可優選使用分子內具有2個以上鍵結有水解性基的矽原子的化合物。成分A中所含有的鍵結有水解性基的矽原子的數量優選2~6，更優選2~4，進而更優選2或3。 Component X has two or more groups represented by formula (X1). That is, a compound having two or more ruthenium atoms having a hydrolyzable group bonded thereto in the molecule can be preferably used. The number of the ruthenium atoms having a hydrolyzable group bonded to the component A is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3.

藉由具有2種以上的構成成分(X1)，在硬化膜內部作為交聯劑發揮功能，可提升硬化膜對於剝離液或溶劑的耐受性。 By having two or more kinds of constituent components (X1), it functions as a crosslinking agent inside the cured film, and the resistance of the cured film to the peeling liquid or the solvent can be improved.

所述水解性基能夠以1個~4個的範圍鍵結在1個矽原子上，式(X1)中的水解性基的總個數優選2個或3個範圍，特優選鍵結有3個水解性基。當2個以上的水解性基鍵結在矽原子上時，這些水解性基相互可相同，也可以不同。 The hydrolyzable group may be bonded to one germanium atom in a range of from 1 to 4, and the total number of hydrolyzable groups in the formula (X1) is preferably two or three, and particularly preferably 3 Hydrolyzable groups. When two or more hydrolyzable groups are bonded to a ruthenium atom, these hydrolyzable groups may be the same as or different from each other.

作為所述水解性基而優選的烷氧基例如可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、叔丁氧基、苯氧基、苄 氧基等。可以將多個所述各烷氧基組合使用，也可以將多個不同的烷氧基組合使用。 Preferable examples of the alkoxy group as the hydrolyzable group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, a phenoxy group, and a benzyl group. Oxyl and the like. A plurality of the above alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.

作為烷氧基所鍵結的烷氧基矽烷基，例如可列舉：三甲氧基矽烷基、三乙氧基矽烷基、三異丙氧基矽烷基、三苯氧基矽烷基等三烷氧基矽烷基；二甲氧基甲基矽烷基、二乙氧基甲基矽烷基等二烷氧基單烷基矽烷基；甲氧基二甲基矽烷基、乙氧基二甲基矽烷基等單烷氧基二烷基矽烷基。 Examples of the alkoxyalkylene group to which the alkoxy group is bonded include a trialkoxy group such as a trimethoxysulfanyl group, a triethoxydecylalkyl group, a triisopropoxydecylalkyl group or a triphenoxyfluorenyl group. a decyl group; a dialkoxy monoalkyl decyl group such as a dimethoxymethyl decyl group or a diethoxymethyl fluorenyl group; a methoxy dimethyl fluorenyl group, an ethoxy dimethyl decyl group, etc. Alkoxydialkylalkylene.

成分X也可以含有硫原子、酯鍵、聚氨酯鍵、醚鍵、脲鍵、或亞氨基。其中，就交聯性的觀點而言，成分X優選含有硫原子，另外，就鹼顯影性的觀點而言，優選含有容易藉由鹼水而分解的酯鍵、聚氨酯鍵或醚鍵(特別是氧基亞烷基中所含有的醚鍵)。含有硫原子的成分X有時作為硫化劑發揮功能，而促進硬化膜的反應(交聯)。另外，本發明中的成分X優選不具有乙烯性不飽和鍵的化合物。成分X優選僅具有水解性矽烷基及/或矽烷醇基作為聚合性基。 Component X may also contain a sulfur atom, an ester bond, a urethane bond, an ether bond, a urea bond, or an imino group. In view of the crosslinkability, the component X preferably contains a sulfur atom, and from the viewpoint of alkali developability, it preferably contains an ester bond, a urethane bond or an ether bond which is easily decomposed by alkali water (especially An ether bond contained in an oxyalkylene group). The component X containing a sulfur atom sometimes functions as a vulcanizing agent, and promotes a reaction (crosslinking) of the cured film. Further, the component X in the present invention is preferably a compound having no ethylenically unsaturated bond. Component X preferably has only a hydrolyzable alkylene group and/or a stanol group as a polymerizable group.

本發明中的成分X可列舉多個由所述式(X1)所表示的基經由二價的連結基而鍵結的化合物，作為此種二價的連結基，就效果的觀點而言，優選具有硫基(-S-)、亞氨基(-N(R)-)、或聚氨酯鍵(-OCON(R)-或N(R)COO-)的連結基。再者，R表示氫原子或取代基。作為R中的取代基，可例示：烷基、芳基、烯基、炔基、或芳烷基。 The component X in the present invention is a compound in which a plurality of groups represented by the above formula (X1) are bonded via a divalent linking group, and as such a divalent linking group, from the viewpoint of the effect, it is preferred. A linking group having a thio group (-S-), an imino group (-N(R)-), or a urethane bond (-OCON(R)- or N(R)COO-). Further, R represents a hydrogen atom or a substituent. The substituent in R may, for example, be an alkyl group, an aryl group, an alkenyl group, an alkynyl group or an aralkyl group.

作為成分X的合成方法，並無特別限制，可藉由公知的方法來合成。作為一例，表示包含具有所述特定結構的連結基的成分X的代表性的合成方法。 The synthesis method of the component X is not particularly limited, and it can be synthesized by a known method. As an example, a representative synthesis method including the component X having the linking group of the specific structure is shown.

<具有硫基作為連結基、且具有水解性矽烷基及/或矽烷醇基的化合物的合成法> <Synthesis of a compound having a sulfur group as a linking group and having a hydrolyzable alkylene group and/or a stanol group>

具有硫基作為連結基的成分X(以下，適宜稱為“含硫基連結基的成分X”)的合成法並無特別限定，具體而言，例如可例示：具有鹵化烴基的成分X與硫化鹼的反應、具有巰基的成分X與鹵化烴的反應、具有巰基的成分X與具有鹵化烴基的成分X的反應、具有鹵化烴基的成分X與硫醇類的反應、具有乙烯性不飽和鍵的成分X與硫醇類的反應、具有乙烯性不飽和鍵的成分X與具有巰基的成分X的反應、具有乙烯性不飽和鍵的化合物與具有巰基的成分X的反應、酮類與具有巰基的成分X的反應、重氮鹽與具有巰基的成分X的反應、具有巰基的成分X與環氧乙烷類的反應、具有巰基的成分X與具有環氧乙烷基的成分X的反應、以及硫醇類與具有環氧乙烷基的成分X的反應、具有巰基的成分X與氮丙啶(aziridinc)類的反應等合成方法。 The method for synthesizing the component X having a sulfur group as a linking group (hereinafter referred to as "the component X of the sulfur-containing linking group" as appropriate) is not particularly limited, and specific examples thereof include a component X having a halogenated hydrocarbon group and sulfurization. Reaction of a base, reaction of a component X having a mercapto group with a halogenated hydrocarbon, reaction of a component X having a mercapto group with a component X having a halogenated hydrocarbon group, reaction of a component X having a halogenated hydrocarbon group with a mercaptan, and having an ethylenically unsaturated bond Reaction of component X with a thiol, reaction of a component X having an ethylenically unsaturated bond with a component X having a mercapto group, reaction of a compound having an ethylenically unsaturated bond with a component X having a mercapto group, ketones and a group having a mercapto group a reaction of component X, a reaction of a diazonium salt with a component X having a mercapto group, a reaction of a component X having a mercapto group with an oxirane, a reaction of a component X having a mercapto group with a component X having an oxiranyl group, and A synthetic method such as a reaction of a thiol with a component X having an oxirane group, a reaction of a component X having a mercapto group with an aziridin.

<具有亞氨基作為連結基、且具有水解性矽烷基及/或矽烷醇基的化合物的合成法> <Synthesis of a compound having an imino group as a linking group and having a hydrolyzable alkylene group and/or a stanol group>

具有亞氨基作為連結基的成分X(以下，適宜稱為“含亞氨基連結基的成分X”)的合成法並無特別限定，例如可例示：具有氨基的成分X與鹵化烴的反應、具有氨基的成分X與具有鹵化烴基的成分X的反應、具有鹵化烴基的成分X與胺類的反應、具有氨基的成分X與環氧乙烷類的反應、具有氨基的成分X與具有環氧乙烷基的成分X的反應、胺類與具有環氧乙烷基的成分X的反應、具有氨基的成分X與氮丙啶類的反應、具有乙烯性不飽和鍵的成分X與胺類的反應、具有乙烯性不飽和鍵的成分X與具有氨基的成分X的反應、具有乙烯性不飽和鍵的化合物與具有氨基的成分X的反應、具有乙炔性不飽和鍵的化合物與具有氨基的成分X的反應、具有亞 胺性不飽和鍵的成分X與有機鹼金屬化合物的反應、具有亞胺性不飽和鍵的成分X與有機鹼土金屬化合物的反應、以及羰基化合物與具有氨基的成分X的反應等合成方法。 The synthesis method of the component X having an imino group as a linking group (hereinafter referred to as "component X containing an imino group-containing group" is not particularly limited), and for example, a reaction of a component X having an amino group with a halogenated hydrocarbon can be exemplified. Reaction of a component X of an amino group with a component X having a halogenated hydrocarbon group, a reaction of a component X having a halogenated hydrocarbon group with an amine, a reaction of a component X having an amino group with an oxirane, a component X having an amino group, and having an epoxy group B Reaction of component X of an alkyl group, reaction of an amine with a component X having an oxirane group, reaction of a component X having an amino group with an aziridine, reaction of a component X having an ethylenically unsaturated bond with an amine Reaction of a component X having an ethylenic unsaturated bond with a component X having an amino group, a reaction of a compound having an ethylenically unsaturated bond with a component X having an amino group, a compound having an acetylene unsaturated bond, and a component having an amino group X Reaction, with sub A method of synthesizing a reaction of a component X of an amine unsaturated bond with an organic alkali metal compound, a reaction of a component X having an imidative unsaturated bond with an organic alkaline earth metal compound, and a reaction of a carbonyl compound with a component X having an amino group.

<具有聚氨酯鍵(亞脲基)作為連結基、且具有水解性矽烷基及/或矽烷醇基的化合物的合成法> <Synthesis of a compound having a urethane bond (urelm group) as a linking group and having a hydrolyzable alkylene group and/or a stanol group>

具有亞脲基作為連結基的成分X(以下，適宜稱為“含亞脲基連結基的成分X”)的合成法並無特別限定，具體而言，例如可例示：具有氨基的成分X與異氰酸酯類的反應、具有氨基的成分X與具有異氰酸酯的成分X的反應、以及胺類與具有異氰酸酯的成分X的反應等合成方法。 The synthesis method of the component X having a ureylene group as a linking group (hereinafter referred to as "the component X containing a ureylene group-containing linking group" is not particularly limited), and specific examples thereof include a component X having an amino group and A synthesis method such as a reaction of an isocyanate, a reaction of a component X having an amino group with a component X having an isocyanate, and a reaction of an amine with a component X having an isocyanate.

作為成分X的具體例，可列舉：1,2-雙(三乙氧基矽烷基)乙烷、1,4-雙(三甲氧基矽烷基)丁烷、1-甲基二甲氧基矽烷基-4-三甲氧基矽烷基丁烷、1,4-雙(甲基二甲氧基矽烷基)丁烷、1,5-雙(三甲氧基矽烷基)戊烷、1,4-雙(三甲氧基矽烷基)戊烷、1-甲基二甲氧基矽烷基-5-三甲氧基矽烷基戊烷、1,5-雙(甲基二甲氧基矽烷基)戊烷、1,6-雙(三甲氧基矽烷基)己烷、1,4-雙(三甲氧基矽烷基)己烷、1,5-雙(三甲氧基矽烷基)己烷、2,5-雙(三甲氧基矽烷基)己烷、1,6-雙(甲基二甲氧基矽烷基)己烷、1,7-雙(三甲氧基矽烷基)庚烷、2,5-雙(三甲氧基矽烷基)庚烷、2,6-雙(三甲氧基矽烷基)庚烷、1,8-雙(三甲氧基矽烷基)辛烷、2,5-雙(三甲氧基矽烷基)辛烷、2,7-雙(三甲氧基矽烷基)辛烷、1,9-雙(三甲氧基矽烷基)壬烷、2,7-雙(三甲氧基矽烷基)壬烷、1,10-雙(三甲氧基矽烷基)癸烷、3,8-雙(三甲氧基矽烷基)癸烷、乙烯基三氯矽烷、1,3-雙(三氯矽烷)丙烷、1,3-雙(三溴矽烷)丙烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮 水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、對苯乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、N-(β-氨基乙基)-γ-氨基丙基甲基二甲氧基矽烷、N-(β-氨基乙基)-γ-氨基丙基三甲氧基矽烷、N-(β-氨基乙基)-γ-氨基丙基三乙氧基矽烷、γ-氨基丙基三甲氧基矽烷、γ-氨基丙基三乙氧基矽烷、N-苯基-γ-氨基丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、二甲氧基-3-巰基丙基甲基矽烷、2-(2-氨基乙硫基乙基)二乙氧基甲基矽烷、3-(2-乙醯氧基乙硫基丙基)二甲氧基甲基矽烷、2-(2-氨基乙硫基乙基)三乙氧基矽烷、二甲氧基甲基-3-(3-苯氧基丙硫基丙基)矽烷、雙(三乙氧基矽烷基丙基)二硫化物、雙(三乙氧基矽烷基丙基)四硫化物、1,4-雙(三乙氧基矽烷基)苯、雙(三乙氧基矽烷基)乙烷、1,6-雙(三甲氧基矽烷基)己烷、1,8-雙(三乙氧基矽烷基)辛烷、1,2-雙(三甲氧基矽烷基)癸烷、雙(三乙氧基矽烷基丙基)胺、雙(三甲氧基矽烷基丙基)脲、γ-氯丙基三甲氧基矽烷、(甲基)丙烯酸γ-三乙氧基矽烷基丙酯、γ-脲基丙基三乙氧基矽烷、三甲基矽烷醇、二苯基矽烷二醇、三苯基矽烷醇等。 Specific examples of the component X include 1,2-bis(triethoxydecyl)ethane, 1,4-bis(trimethoxydecyl)butane, and 1-methyldimethoxydecane. Base-4-trimethoxydecylalkylbutane, 1,4-bis(methyldimethoxydecyl)butane, 1,5-bis(trimethoxydecyl)pentane, 1,4-double (trimethoxydecyl)pentane, 1-methyldimethoxydecyl-5-trimethoxydecylpentane, 1,5-bis(methyldimethoxydecyl)pentane, 1 ,6-bis(trimethoxydecyl)hexane, 1,4-bis(trimethoxydecyl)hexane, 1,5-bis(trimethoxydecyl)hexane, 2,5-double ( Trimethoxydecyl)hexane, 1,6-bis(methyldimethoxydecyl)hexane, 1,7-bis(trimethoxydecyl)heptane, 2,5-bis(trimethoxy) Base alkyl)heptane, 2,6-bis(trimethoxydecyl)heptane, 1,8-bis(trimethoxydecyl)octane, 2,5-bis(trimethoxydecyl)octyl Alkane, 2,7-bis(trimethoxydecyl)octane, 1,9-bis(trimethoxydecyl)decane, 2,7-bis(trimethoxydecyl)decane, 1,10 - bis(trimethoxydecyl)decane, 3,8-bis(trimethoxydecyl)decane Vinyl trichloromethane, 1,3-bis(trichlorodecane)propane, 1,3-bis(tribromodecan)propane, vinyltrimethoxydecane, vinyltriethoxydecane, β-(3, 4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-shrinkage Glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, p-styryl Trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl triethyl Oxydecane, γ-acryloxypropyltrimethoxydecane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxydecane, N-(β-aminoethyl)- γ-Aminopropyltrimethoxydecane, N-(β-aminoethyl)-γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxy Decane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, dimethoxy -3-mercaptopropylmethyldecane, 2-(2-aminoethylthioethyl)diethoxymethyldecane, 3-(2-acetoxyethylthiopropyl)dimethoxymethyl Baseline, 2-(2-aminoethylthioethyl)triethoxydecane, dimethyl Methyl-3-(3-phenoxypropylthiopropyl)decane, bis(triethoxydecylpropyl)disulfide, bis(triethoxydecylpropyl)tetrasulfide, 1,4-bis(triethoxydecyl)benzene, bis(triethoxydecyl)ethane, 1,6-bis(trimethoxydecyl)hexane, 1,8-bis (triethyl) Oxyalkylene)octane, 1,2-bis(trimethoxydecyl)decane, bis(triethoxydecylpropyl)amine, bis(trimethoxydecylpropyl)urea, γ- Chloropropyltrimethoxydecane, γ-triethoxydecyl propyl (meth)acrylate, γ-ureidopropyltriethoxydecane, trimethylstanol, diphenyldecanediol, three Phenyl stanol and the like.

除此以外，也可以列舉以下所示的化合物作為優選者，但本發明不受這些化合物限制。 In addition, the compounds shown below are also preferable, but the present invention is not limited by these compounds.

所述各式中，R、及R1分別表示選自以下的結構中的部分結構。當分子內存在多個R、及R1時，這些R、及R1相互可相同，也可以不同，在合成適應性方面，優選相同。 In the above formulae, R and R 1 each represent a partial structure selected from the following structures. When a plurality of R and R 1 are present in the molecule, these R and R 1 may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

成分X也可以适宜合成来获得，但就成本方面而言，优选使用市售品。作為成分X，例如由信越化學工業(股份)、東麗道康寧(Toray Dow Corning)(股份)、邁圖高新材料(Momentive Performance Materials)(股份)、智索(Chisso) (股份)等所銷售的矽烷製品、矽烷偶聯劑等市售品相當於成分X，因此可根據目的而適宜選擇這些市售品來用於本發明的樹脂組成物。 The component X can also be obtained by suitable synthesis, but in terms of cost, it is preferred to use a commercially available product. As ingredient X, for example, Shin-Etsu Chemical Industries (shares), Toray Dow Corning (shares), Momentive Performance Materials (shares), Chisso Commercial products such as a decane product or a decane coupling agent sold by the company are equivalent to the component X. Therefore, these commercially available products can be appropriately selected and used for the resin composition of the present invention depending on the purpose.

作為本發明中的成分X，可使用利用1種具有水解性矽烷基及/或矽烷醇基的化合物所獲得的部分水解縮合物、或利用2種以上具有水解性矽烷基及/或矽烷醇基的化合物所獲得的部分共水解縮合物。以下，有時將這些化合物稱為“部分(共)水解縮合物”。 As the component X in the present invention, a partially hydrolyzed condensate obtained by using one compound having a hydrolyzable alkylene group and/or a stanol group, or a hydrolyzable decyl group and/or a stanol group may be used. Partially cohydrolyzed condensate obtained from the compound. Hereinafter, these compounds are sometimes referred to as "partial (co)hydrolyzed condensates".

作為部分(共)水解縮合物前驅物的矽烷化合物之中，就通用性、成本方面、膜的相容性的觀點而言，優選具有選自甲基及苯基中的取代基作為矽上的取代基的矽烷化合物，具體而言，可例示甲基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷作為優選的前驅物。 Among the decane compounds which are partial (co)hydrolyzed condensate precursors, it is preferred to have a substituent selected from a methyl group and a phenyl group as a ruthenium from the viewpoint of versatility, cost, and compatibility of the film. The decane compound of the substituent, specifically, methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, dimethyldimethoxydecane can be exemplified. Dimethyldiethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane are preferred precursors.

在此情況下，作為部分(共)水解縮合物，可適宜使用作為如上所述的矽烷化合物的2聚體(使水1莫耳作用於矽烷化合物2莫耳來使醇2莫耳脫離，而變成二矽氧烷單元者)~100聚體，優選2聚體~50聚體，更優選2聚體~30聚體者，也可以使用將2種以上的矽烷化合物作為原料的部分共水解縮合物。 In this case, as the partial (co)hydrolyzed condensate, a dimer which is a decane compound as described above can be suitably used (water 1 is allowed to act on the decane compound 2 to desorb the alcohol 2 molar, and It is a dimer of a dioxane unit, preferably a dimer to a 50-mer, more preferably a dimer to a 30-mer, or a partial co-hydrolysis condensation using two or more kinds of decane compounds as a raw material. Things.

再者，此種部分(共)水解縮合物也可以使用作為矽酮烷氧基寡聚物所銷售者(例如，由信越化學工業(股份)等銷售)，另外，也可以使用根據常規方法，藉由使水解性矽烷化合物與未滿當量的水解水進行反應後，將醇、鹽酸等副產物去除所製造者。在製造時，作為成為前驅物的原料的水解性矽烷化合 物，例如當使用如上所述的烷氧基矽烷類或醯氧基矽烷類時，只要使鹽酸、硫酸等酸，氫氧化鈉、氫氧化鉀等鹼金屬或鹼土金屬的氫氧化物，三乙胺等鹼性有機物質等作為反應觸媒進行部分水解縮合即可，當從氯矽烷類直接製造時，只要使副產的鹽酸作為觸媒與水及醇進行反應即可。 Further, such a partial (co)hydrolyzed condensate may also be used as a seller of an anthrone alkoxy oligomer (for example, sold by Shin-Etsu Chemical Co., Ltd.), or may be used according to a conventional method. By reacting the hydrolyzable decane compound with less than equivalent amount of hydrolyzed water, by-products such as alcohol and hydrochloric acid are removed. Hydrolyzable decane compound as a raw material for the precursor at the time of manufacture For example, when an alkoxy decane or a decyloxy decane as described above is used, an acid such as hydrochloric acid or sulfuric acid, or an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or potassium hydroxide may be used. The alkaline organic substance such as an amine may be partially hydrolyzed and condensed as a reaction catalyst, and when it is directly produced from a chlorosilane, the by-produced hydrochloric acid may be used as a catalyst to react with water and an alcohol.

就硬化性、粘結性、耐熱著色穩定性、及透明性與粘結強度的平衡更優異，耐濕熱粘結性優異這一觀點而言，更優選雙(三烷氧基矽烷基)烷烴，進而優選選自由雙-(3-三甲氧基矽烷基丙基)胺、1,2-雙(三乙氧基矽烷基)乙烷、1,6-雙(三甲氧基矽烷基)己烷、1,7-雙(三甲氧基矽烷基)庚烷、1,8-雙(三甲氧基矽烷基)辛烷、1,9-雙(三甲氧基矽烷基)壬烷及1,10-雙(三甲氧基矽烷基)癸烷所組成的組群中的至少1種，進而更優選1,6-雙(三甲氧基矽烷基)己烷、雙-(3-三甲氧基矽烷基丙基)胺。 The bis(trialkoxyalkylalkyl)alkane is more preferable from the viewpoint of excellent balance between curability, adhesion, heat-resistant coloring stability, transparency, and bond strength, and excellent wet heat adhesion resistance. Further preferably selected from the group consisting of bis-(3-trimethoxydecylpropyl)amine, 1,2-bis(triethoxydecyl)ethane, 1,6-bis(trimethoxydecyl)hexane, 1,7-bis(trimethoxydecyl)heptane, 1,8-bis(trimethoxydecyl)octane, 1,9-bis(trimethoxydecyl)decane and 1,10-double At least one of the groups consisting of (trimethoxydecyl) decane, and more preferably 1,6-bis(trimethoxydecyl)hexane, bis-(3-trimethoxydecylpropyl) )amine.

本發明中所使用的X成分特優選由式(X2)所表示的矽化合物。 The X component used in the present invention is particularly preferably an anthracene compound represented by the formula (X2).

Ro-(X)a(X2) R o -(X) a (X2)

(式中，X表示由所述式(X1)所表示的基，a表示2以上的整數。Ro表示a價的連結基。) (wherein, X represents a group represented by the formula (X1), and a represents an integer of 2 or more. Ro represents a linking group of a valence.)

式(X2)中的X的含義與由所述式(X1)所表示的基相同，優選的範圍也相同。 The meaning of X in the formula (X2) is the same as the group represented by the formula (X1), and the preferred range is also the same.

式(X2)中，a優選2~4，更優選2或3。 In the formula (X2), a is preferably 2 to 4, more preferably 2 or 3.

由式(X2)所表示的化合物更優選由下述式(X3)所表示的化合物。 The compound represented by the formula (X2) is more preferably a compound represented by the following formula (X3).

Roo-[(CH2)n-(X)]a(X3) Roo-[(CH 2 ) n -(X)] a (X3)

(式中，X表示所述式(X1)，a表示2以上的整數。n表示1~5的整數。Roo表示單鍵或a價的連結基。) (wherein, X represents the formula (X1), a represents an integer of 2 or more. n represents an integer of 1 to 5. Roo represents a single bond or a bond of a valence.)

式(X3)中的X的含義與由所述式(X1)所表示的基相同，優選的範圍也相同。 The meaning of X in the formula (X3) is the same as the group represented by the formula (X1), and the preferred range is also the same.

式(X3)中，a優選2~4，更優選2或3，特優選2。 In the formula (X3), a is preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2.

式(X3)中，Roo優選單鍵、以及-CR2-(R為氫原子或碳數為1~3的烷基)、-S-、-CO-、-O-、亞苯基、 In the formula (X3), Roo is preferably a single bond, and -CR 2 - (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), -S-, -CO-, -O-, phenylene group,

及包含這些基的2個以上的組合的基。 And a group comprising two or more combinations of these groups.

式(X3)中，Roo更優選單鍵、以及-CR2-(R為氫原子或碳數為1~3的烷基)、-S-、-CO-、-O-及包含這些基的組合的基，進而更優選單鍵、以及-CH2-、-S-、及包含這些基的組合的基。 In the formula (X3), Roo is more preferably a single bond, and -CR 2 - (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), -S-, -CO-, -O-, and a group containing the same. The group to be combined is more preferably a single bond, and -CH 2 -, -S-, and a group containing a combination of these groups.

式(X3)中，n優選1~3的整數，更優選1或2。 In the formula (X3), n is preferably an integer of 1 to 3, more preferably 1 or 2.

本發明中所使用的矽化合物的分子量優選100~1500，更優選250~1100。 The molecular weight of the ruthenium compound used in the present invention is preferably from 100 to 1,500, more preferably from 250 to 1,100.

本發明中，特優選採用式(S-1)~式(S-17)中所記載的矽化合物。 In the present invention, the ruthenium compound described in the formula (S-1) to the formula (S-17) is particularly preferably used.

成分X可分別單獨使用、或將2種以上組合使用。 The component X may be used alone or in combination of two or more.

在本發明中，就硬化性、粘結性、耐熱著色穩定性、及透明性與粘結強度的平衡這一觀點而言，相對於樹脂組成物的除溶劑以外的成分的合計，成分X的量優選0.1 wt%以上，更優選0.5 wt%以上。上限值並無特別規定，但優選10 wt%以下，更優選5 wt%以下。 In the present invention, from the viewpoint of the balance between the curability, the adhesion, the heat-resistant coloring stability, and the transparency and the bond strength, the total of the components other than the solvent of the resin composition, the component X The amount is preferably 0.1% by weight or more, more preferably 0.5% by weight or more. The upper limit is not particularly limited, but is preferably 10% by weight or less, and more preferably 5% by weight or less.

(成分C)光酸產生劑 (Component C) Photoacid generator

本發明的感光性樹脂組成物含有(成分C)光酸產生劑。 The photosensitive resin composition of the present invention contains (Component C) a photoacid generator.

作為成分C，優選感應波長為300 nm以上，優選波長為300 nm~450 nm的光化射線而產生酸的化合物，但不受其化學結構限制。另外，關於不直接感應波長為300 nm以上的光 化射線的光酸產生劑，若為藉由與增感劑並用來感應波長為300 nm以上的光化射線而產生酸的化合物，則也可以與增感劑組合後優選使用。 As the component C, a compound which induces an acid by an actinic ray having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, is preferable, but is not limited by its chemical structure. In addition, it does not directly sense light with a wavelength of 300 nm or more. The photo-acid generator of the ray is preferably used in combination with a sensitizer if it is used in combination with a sensitizer to induce an actinic ray having a wavelength of 300 nm or more.

作為成分C，優選產生pKa為4以下的酸的光酸產生劑，更優選產生pKa為3以下的酸的光酸產生劑。 As the component C, a photoacid generator which produces an acid having a pKa of 4 or less is preferable, and a photoacid generator which produces an acid having a pKa of 3 or less is more preferable.

作為光酸產生劑的例子，可列舉：三氯甲基-均三嗪類、鋶鹽或錪鹽、四級銨鹽類、重氮甲烷化合物、醯亞胺磺酸酯化合物、及肟磺酸酯化合物等。這些光酸產生劑之中，就感光度高的觀點而言，優選使用肟磺酸酯化合物。這些光酸產生劑可單獨使用1種、或將2種以上組合使用。作為這些光酸產生劑的具體例，可列舉日本專利特開2004-264623號公報的段落0029~段落0032中所記載的光酸產生劑，可優選使用4,7-二-正丁氧基-1-萘基四氫噻吩鎓三氟甲磺酸酯等。 Examples of the photoacid generator include trichloromethyl-s-triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, sulfhydryl sulfonate compounds, and sulfonic acid. Ester compound and the like. Among these photoacid generators, an oxime sulfonate compound is preferably used from the viewpoint of high sensitivity. These photoacid generators may be used alone or in combination of two or more. Specific examples of the photo-acid generator include the photoacid generator described in paragraphs 0029 to 0032 of JP-A-2004-264623, and 4,7-di-n-butoxy group can be preferably used. 1-naphthyltetrahydrothiophene trifluoromethanesulfonate and the like.

本發明的感光性樹脂組成物優選含有具有由下述式(c0)所表示的肟磺酸酯殘基的至少1個的肟磺酸酯化合物作為(成分C)光酸產生劑。再者，波狀線部分表示與其他化學結構的鍵結位置。 The photosensitive resin composition of the present invention preferably contains at least one oxime sulfonate compound having an oxime sulfonate residue represented by the following formula (c0) as a (component C) photoacid generator. Furthermore, the wavy line portion indicates the bonding position with other chemical structures.

具有由所述式(c0)所表示的肟磺酸酯殘基的至少1個的肟磺酸酯化合物優選由下述式(c1)所表示的化合物。 The at least one oxime sulfonate compound having the oxime sulfonate residue represented by the above formula (c0) is preferably a compound represented by the following formula (c1).

(式(c1)中，R5及R6分別獨立地表示一價的有機基，R5及R6可連結而形成環，R7表示烷基、或芳基。) (In the formula (c1), R 5 and R 6 each independently represent a monovalent organic group, R 5 and R 6 may be bonded to form a ring, and R 7 represents an alkyl group or an aryl group.)

式(c1)中，R5表示碳原子數為1~6的烷基、碳原子數為1~4的鹵化烷基、苯基、聯苯基、萘基、2-呋喃基、2-噻吩基、碳原子數為1~4的烷氧基或氰基。當R5為苯基、聯苯基、萘基或蒽基時，這些基可由選自由鹵素原子、羥基、碳原子數為1~4的烷基、碳原子數為1~4的烷氧基及硝基所組成的組群中的取代基取代。 In the formula (c1), R 5 represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group or a 2-thiophene group. An alkoxy group or a cyano group having 1 to 4 carbon atoms. When R 5 is a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, these groups may be selected from a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. And a substituent in the group consisting of a nitro group is substituted.

式(c1)中，R6表示碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基、碳原子數為1~5的鹵化烷氧基、可由W取代的苯基、可由W取代的萘基或可由W取代的蒽基、二烷基氨基、嗎啉基、或氰基。R6與R5可相互鍵結而形成5員環或6員環，所述5員環或6員環能夠與可具有1個或2個任意的取代基的苯環鍵結。 In the formula (c1), R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 to 1 carbon atom. a halogenated alkoxy group of 5, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group, a dialkylamino group, a morpholinyl group or a cyano group which may be substituted by W. R 6 and R 5 may be bonded to each other to form a 5-membered or 6-membered ring which is capable of bonding to a benzene ring which may have 1 or 2 arbitrary substituents.

式(c1)中，R7表示碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基、碳原子數為1~5的鹵化烷氧基、可由W取代的苯基、可由W取代的萘基或可由W取代的蒽基。烷基也可以是環狀烷基。W表示鹵素原子、氰基、硝基、碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基或碳原子數為1~5的鹵化烷氧基。 In the formula (c1), R 7 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 to 1 carbon atom. a halogenated alkoxy group of 5, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W. The alkyl group may also be a cyclic alkyl group. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a carbon atom number. 1 to 5 halogenated alkoxy groups.

由R5所表示的碳原子數為1~6的烷基可為直鏈烷基或支 鏈烷基，例如可列舉：甲基、乙基、丙基、異丙基、正丁基、仲丁基、叔丁基、正戊基、異戊基、正己基、或2-乙基丁基。 The alkyl group having 1 to 6 carbon atoms represented by R 5 may be a linear alkyl group or a branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a secondary group. Butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, or 2-ethylbutyl.

作為由R5所表示的碳原子數為1~4的鹵化烷基，例如可列舉：氯甲基、三氯甲基、三氟甲基、或2-溴丙基。 Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R 5 include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

作為由R5所表示的碳原子數為1~4的烷氧基，可列舉甲氧基或乙氧基。 The alkoxy group having 1 to 4 carbon atoms represented by R 5 may, for example, be a methoxy group or an ethoxy group.

當R5表示苯基、聯苯基、萘基或蒽基時，這些基可由選自由鹵素原子(例如氯原子、溴原子、碘原子等)、羥基、碳原子數為1~4的烷基(例如甲基、乙基、丙基、異丙基、正丁基、仲丁基、叔丁基)、碳原子數為1~4的烷氧基(例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基)及硝基所組成的組群中的取代基取代。 When R 5 represents a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, these groups may be selected from an alkyl group selected from a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, and a carbon number of 1 to 4. (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl), alkoxy having 1 to 4 carbon atoms (e.g., methoxy, ethoxy, positive) Substituents in the group consisting of propoxy, isopropoxy, n-butoxy) and nitro are substituted.

作為由R6所表示的碳原子數為1~10的烷基的具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、正己基、正庚基、正辛基、正壬基、正癸基等。 Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R 6 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like.

作為由R6所表示的碳原子數為1~10的烷氧基的具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、正戊氧基、正辛氧基、正癸氧基等。 Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R 6 include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and a n-pentyl group. An oxy group, a n-octyloxy group, a n-decyloxy group or the like.

作為由R6所表示的碳原子數為1~5的鹵化烷基的具體例，可列舉：三氟甲基、五氟乙基、全氟-正丙基、全氟-正丁基、全氟-正戊基等。 Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R 6 include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, and a whole. Fluorine-n-pentyl and the like.

作為由R6所表示的碳原子數為1~5的鹵化烷氧基的具體例，可列舉：三氟甲氧基、五氟乙氧基、全氟-正丙氧基、全氟-正丁氧基、全氟-正戊氧基等。 Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R 6 include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, and a perfluoro-positive group. Butoxy, perfluoro-n-pentyloxy and the like.

作為由R6所表示的可由W取代的苯基的具體例，可列 舉：鄰甲苯基、間甲苯基、對甲苯基、鄰乙基苯基、間乙基苯基、對乙基苯基、對(正丙基)苯基、對(異丙基)苯基、對(正丁基)苯基、對(異丁基)苯基、對(仲丁基)苯基、對(叔丁基)苯基、對(正戊基)苯基、對(異戊基)苯基、對(叔戊基)苯基、鄰甲氧基苯基、間甲氧基苯基、對甲氧基苯基、鄰乙氧基苯基、間乙氧基苯基、對乙氧基苯基、對(正丙氧基)苯基、對(異丙氧基)苯基、對(正丁氧基)苯基、對(異丁氧基)苯基、對(仲丁氧基)苯基、對(叔丁氧基)苯基、對(正戊氧基)苯基、對(異戊氧基)苯基、對(叔戊氧基)苯基、對氯苯基、對溴苯基、對氟苯基、2,4-二氯苯基、2,4-二溴苯基、2,4-二氟苯基、2,4,6-二氯苯基、2,4,6-三溴苯基、2,4,6-三氟苯基、五氯苯基、五溴苯基、五氟苯基、對聯苯基等。 Specific examples of the phenyl group which may be substituted by W represented by R 6 include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, P-(n-propyl)phenyl, p-(isopropyl)phenyl, p-(n-butyl)phenyl, p-(isobutyl)phenyl, p-(sec-butyl)phenyl, p-tert-butyl Phenyl, p-(n-pentyl)phenyl, p-(isopentyl)phenyl, p-(tert-amyl)phenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxybenzene , o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p-(n-propoxy)phenyl, p-(isopropoxy)phenyl, p-(n-butoxy) Phenyl, p-(isobutoxy)phenyl, p-(sec-butoxy)phenyl, p-(tert-butoxy)phenyl, p-(n-pentyloxy)phenyl, p-(isopentyloxy) Phenyl, p-(tert-pentyloxy)phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4- Difluorophenyl, 2,4,6-dichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-trifluorophenyl, pentachlorophenyl, pentabromophenyl, pentafluoro Phenyl, p-biphenyl, and the like.

作為由R6所表示的可由W取代的萘基的具體例，可列舉：2-甲基-1-萘基、3-甲基-1-萘基、4-甲基-1-萘基、5-甲基-1-萘基、6-甲基-1-萘基、7-甲基-1-萘基、8-甲基-1-萘基、1-甲基-2-萘基、3-甲基-2-萘基、4-甲基-2-萘基、5-甲基-2-萘基、6-甲基-2-萘基、7-甲基-2-萘基、8-甲基-2-萘基等。 Specific examples of the naphthyl group which may be substituted by W represented by R 6 include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, and 4-methyl-1-naphthyl group. 5-methyl-1-naphthyl, 6-methyl-1-naphthyl, 7-methyl-1-naphthyl, 8-methyl-1-naphthyl, 1-methyl-2-naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthyl, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl-2-naphthyl and the like.

作為由R6所表示的可由W取代的蒽基的具體例，可列舉：2-甲基-1-蒽基、3-甲基-1-蒽基、4-甲基-1-蒽基、5-甲基-1-蒽基、6-甲基-1-蒽基、7-甲基-1-蒽基、8-甲基-1-蒽基、9-甲基-1-蒽基、10-甲基-1-蒽基、1-甲基-2-蒽基、3-甲基-2-蒽基、4-甲基-2-蒽基、5-甲基-2-蒽基、6-甲基-2-蒽基、7-甲基-2-蒽基、8-甲基-2-蒽基、9-甲基-2-蒽基、10-甲基-2-蒽基等。 Specific examples of the fluorenyl group which may be substituted by W represented by R 6 include 2-methyl-1-indenyl group, 3-methyl-1-indenyl group, and 4-methyl-1-indenyl group. 5-methyl-1-indenyl, 6-methyl-1-indenyl, 7-methyl-1-indenyl, 8-methyl-1-indenyl, 9-methyl-1-indenyl, 10-methyl-1-indenyl, 1-methyl-2-indenyl, 3-methyl-2-indenyl, 4-methyl-2-indenyl, 5-methyl-2-indenyl, 6-methyl-2-indenyl, 7-methyl-2-indenyl, 8-methyl-2-indenyl, 9-methyl-2-indenyl, 10-methyl-2-indenyl, etc. .

作為由R6所表示的二烷基氨基，可列舉：二甲氨基、二乙氨基、二丙氨基、二丁氨基、二苯氨基等。 Examples of the dialkylamino group represented by R 6 include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

作為由R7所表示的碳原子數為1~10的烷基的具體例， 可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、正己基、正庚基、正辛基、正壬基、正癸基等。 Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R 7 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl and the like.

作為由R7所表示的碳原子數為1~10的烷氧基的具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、正戊氧基、正辛氧基、正癸氧基等。 Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R 7 include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and a n-pentyl group. An oxy group, a n-octyloxy group, a n-decyloxy group or the like.

作為由R7所表示的碳原子數為1~5的鹵化烷基的具體例，可列舉：三氟甲基、五氟乙基、全氟-正丙基、全氟-正丁基、全氟-正戊基等。 Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R 7 include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, and a whole. Fluorine-n-pentyl and the like.

作為由R7所表示的碳原子數為1~5的鹵化烷氧基的具體例，可列舉：三氟甲氧基、五氟乙氧基、全氟-正丙氧基、全氟-正丁氧基、全氟-正戊氧基等。 Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R 7 include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, and a perfluoro-positive group. Butoxy, perfluoro-n-pentyloxy and the like.

作為由R7所表示的可由W取代的苯基的具體例，可列舉：鄰甲苯基、間甲苯基、對甲苯基、鄰乙基苯基、間乙基苯基、對乙基苯基、對(正丙基)苯基、對(異丙基)苯基、對(正丁基)苯基、對(異丁基)苯基、對(仲丁基)苯基、對(叔丁基)苯基、對(正戊基)苯基、對(異戊基)苯基、對(叔戊基)苯基、鄰甲氧基苯基、間甲氧基苯基、對甲氧基苯基、鄰乙氧基苯基、間乙氧基苯基、對乙氧基苯基、對(正丙氧基)苯基、對(異丙氧基)苯基、對(正丁氧基)苯基、對(異丁氧基)苯基、對(仲丁氧基)苯基、對(叔丁氧基)苯基、對(正戊氧基)苯基、對(異戊氧基)苯基、對(叔戊氧基)苯基、對氯苯基、對溴苯基、對氟苯基、2,4-二氯苯基、2,4-二溴苯基、2,4-二氟苯基、2,4,6-二氯苯基、2,4,6-三溴苯基、2,4,6-三氟苯基、五氯苯基、五溴苯基、五氟苯基、對聯苯基等。 Specific examples of the phenyl group which may be substituted by W represented by R 7 include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, P-(n-propyl)phenyl, p-(isopropyl)phenyl, p-(n-butyl)phenyl, p-(isobutyl)phenyl, p-(sec-butyl)phenyl, p-tert-butyl Phenyl, p-(n-pentyl)phenyl, p-(isopentyl)phenyl, p-(tert-amyl)phenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxybenzene , o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p-(n-propoxy)phenyl, p-(isopropoxy)phenyl, p-(n-butoxy) Phenyl, p-(isobutoxy)phenyl, p-(sec-butoxy)phenyl, p-(tert-butoxy)phenyl, p-(n-pentyloxy)phenyl, p-(isopentyloxy) Phenyl, p-(tert-pentyloxy)phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4- Difluorophenyl, 2,4,6-dichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-trifluorophenyl, pentachlorophenyl, pentabromophenyl, pentafluoro Phenyl, p-biphenyl, and the like.

作為由R7所表示的可由W取代的萘基的具體例，可列舉： 2-甲基-1-萘基、3-甲基-1-萘基、4-甲基-1-萘基、5-甲基-1-萘基、6-甲基-1-萘基、7-甲基-1-萘基、8-甲基-1-萘基、1-甲基-2-萘基、3-甲基-2-萘基、4-甲基-2-萘基、5-甲基-2-萘基、6-甲基-2-萘基、7-甲基-2-萘基、8-甲基-2-萘基等。 Specific examples of the naphthyl group which may be substituted by W represented by R 7 include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, and 4-methyl-1-naphthyl group. 5-methyl-1-naphthyl, 6-methyl-1-naphthyl, 7-methyl-1-naphthyl, 8-methyl-1-naphthyl, 1-methyl-2-naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthyl, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl-2-naphthyl and the like.

作為由R7所表示的可由W取代的蒽基的具體例，可列舉：2-甲基-1-蒽基、3-甲基-1-蒽基、4-甲基-1-蒽基、5-甲基-1-蒽基、6-甲基-1-蒽基、7-甲基-1-蒽基、8-甲基-1-蒽基、9-甲基-1-蒽基、10-甲基-1-蒽基、1-甲基-2-蒽基、3-甲基-2-蒽基、4-甲基-2-蒽基、5-甲基-2-蒽基、6-甲基-2-蒽基、7-甲基-2-蒽基、8-甲基-2-蒽基、9-甲基-2-蒽基、10-甲基-2-蒽基等。 Specific examples of the fluorenyl group which may be substituted by W represented by R 7 include 2-methyl-1-indenyl group, 3-methyl-1-indenyl group, and 4-methyl-1-indenyl group. 5-methyl-1-indenyl, 6-methyl-1-indenyl, 7-methyl-1-indenyl, 8-methyl-1-indenyl, 9-methyl-1-indenyl, 10-methyl-1-indenyl, 1-methyl-2-indenyl, 3-methyl-2-indenyl, 4-methyl-2-indenyl, 5-methyl-2-indenyl, 6-methyl-2-indenyl, 7-methyl-2-indenyl, 8-methyl-2-indenyl, 9-methyl-2-indenyl, 10-methyl-2-indenyl, etc. .

作為由W所表示的碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基、及碳原子數為1~5的鹵化烷氧基的具體例，可列舉與作為由R6或R7所表示的碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基、及碳原子數為1~5的鹵化烷氧基的具體例所列舉的基相同的基。 The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the carbon number of 1 to 5 represented by W Specific examples of the halogenated alkoxy group include an alkyl group having 1 to 10 carbon atoms represented by R 6 or R 7 , an alkoxy group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. The group having the same group as the specific examples of the halogenated alkyl group of 5 and the halogenated alkoxy group having 1 to 5 carbon atoms.

R6與R5可相互鍵結而形成5員環或6員環。 R 6 and R 5 may be bonded to each other to form a 5-membered ring or a 6-membered ring.

當R6與R5相互鍵結而形成5員環或6員環時，作為該5員環或6員環，可列舉碳環式基及雜環式環基，例如可為環戊烷、環己烷、環庚烷、吡咯、呋喃、噻吩、咪唑、惡唑、噻唑、吡喃、吡啶、吡嗪、嗎啉、呱啶或呱嗪環。所述5員環或6員環也可以與可具有任意的取代基的苯環鍵結，作為其例，可列舉：四氫萘、二氫蒽、茚、色滿(chromane)、芴、二苯並呱喃(xanthene)或噻噸環系。所述5員環或6員環也可以含有羰基，作為其例，可列舉環已二烯酮、萘酮及蒽酮環系。 When R 6 and R 5 are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or the 6-membered ring include a carbocyclic group and a heterocyclic ring group, and for example, may be cyclopentane. Cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, acridine or pyridazine ring. The 5-membered ring or the 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent, and examples thereof include tetrahydronaphthalene, dihydroanthracene, anthracene, chromane, anthracene, and bis. Xanthene or thioxan ring system. The 5-membered ring or the 6-membered ring may contain a carbonyl group, and examples thereof include a cyclohexadienone, a naphthone, and an anthrone ring system.

由所述式(c1)所表示的化合物的合適的形態之一為由下 述式(c1-1)所表示的化合物。由式(c1-1)所表示的化合物是式(c1)中的R6與R5鍵結而形成5員環的化合物。 One of the suitable forms of the compound represented by the formula (c1) is a compound represented by the following formula (c1-1). The compound represented by the formula (c1-1) is a compound in which R 6 and R 5 in the formula (c1) are bonded to each other to form a 5-membered ring.

(式(c1-1)中，R7的含義與式(c1)中的R7相同，X表示烷基、烷氧基或鹵素原子，t表示0~3的整數，當t為2或3時，多個X可相同，也可不同。) (In the formula (C1-1), the same meaning as R in the formula (c1) 7 of the R 7, X represents an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0 to 3, when t is 2 or 3 When multiple Xs are the same or different.)

作為由X所表示的烷基，優選碳原子數為1~4的直鏈狀烷基或支鏈狀烷基。 The alkyl group represented by X is preferably a linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms.

作為由X所表示的烷氧基，優選碳原子數為1~4的直鏈狀烷氧基或支鏈狀烷氧基。 The alkoxy group represented by X is preferably a linear alkoxy group or a branched alkoxy group having 1 to 4 carbon atoms.

作為由X所表示的鹵素原子，優選氯原子或氟原子。 As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferred.

作為t，優選0或1。 As t, 0 or 1 is preferred.

式(c1-1)中，特優選t為1，X為甲基，X的取代位置為鄰位，R7為碳原子數為1~10的直鏈狀烷基、7,7-二甲基-2-氧代降冰片基甲基、或對甲苯甲醯基的化合物。 In the formula (c1-1), t is preferably 1, X is a methyl group, the substitution position of X is an ortho position, and R 7 is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethylene. A compound of the group -2-oxo norbornylmethyl or p-tolylmethyl.

作為由式(c1-1)所表示的肟磺酸酯化合物的具體例，可列舉下述化合物(i)、化合物(ii)、化合物(iii)、化合物(iv)等，這些化合物可單獨使用1種，也可以並用2種以上。化合物(i)~化合物(iv)可作為市售品而獲得。 Specific examples of the oxime sulfonate compound represented by the formula (c1-1) include the following compounds (i), (ii), (iii), and (iv), which can be used alone. One type may be used in combination of two or more types. The compound (i) to the compound (iv) can be obtained as a commercial product.

另外，也可以與其他種類的光酸產生劑進行組合來使用。 Further, it may be used in combination with other types of photoacid generators.

由式(c1)所表示的化合物的優選的形態之一為如下的化合物：R5表示碳原子數為1~4的烷基、三氟甲基、苯基、氯苯基、二氯苯基、甲氧基苯基、4-聯苯基、萘基或蒽基；R6表示氰基；R7表示碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基、碳原子數為1~5的鹵化烷氧基、可由W取代的苯基、可由W取代的萘基或可由W取代的蒽基，W表示鹵素原子、氰基、硝基、碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基或碳原子數為1~5的鹵化烷氧基。 One of the preferable forms of the compound represented by the formula (c1) is a compound wherein R 5 represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group or a dichlorophenyl group. , methoxyphenyl, 4-biphenylyl, naphthyl or anthracenyl; R 6 represents a cyano group; R 7 represents an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W, and W represents a halogen. Atom, cyano group, nitro group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, halogenated alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms Halogenated alkoxy groups.

作為由式(c1)所表示的化合物，也優選由下述式(c1-2)所表示的化合物。 The compound represented by the formula (c1) is also preferably a compound represented by the following formula (c1-2).

式(c1-2)中，R8表示鹵素原子、羥基、碳原子數為1~4的烷基、碳原子數為1~4的烷氧基或硝基，L表示0~5的整數。R7表示碳原子數為1~10的烷基、碳原子數為1~10 的烷氧基、碳原子數為1~5的鹵化烷基、碳原子數為1~5的鹵化烷氧基、可由W取代的苯基、可由W取代的萘基或可由W取代的蒽基，W表示鹵素原子、氰基、硝基、碳原子數為1~10的烷基、碳原子數為1~10的烷氧基、碳原子數為1~5的鹵化烷基或碳原子數為1~5的鹵化烷氧基。 In the formula (c1-2), R 8 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and L represents an integer of 0 to 5. R 7 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W, and W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1~ An alkoxy group of 10, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

作為式(c1-2)中的R7，優選甲基、乙基、正丙基、正丁基、正辛基、三氟甲基、五氟乙基、全氟-正丙基、全氟-正丁基、對甲苯基、4-氯苯基或五氟苯基，特優選甲基、乙基、正丙基、正丁基或對甲苯基。 As R 7 in the formula (c1-2), methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro is preferable. - n-Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably methyl, ethyl, n-propyl, n-butyl or p-tolyl.

作為由R8所表示的鹵素原子，優選氟原子、氯原子或溴原子。 The halogen atom represented by R 8 is preferably a fluorine atom, a chlorine atom or a bromine atom.

作為由R8所表示的碳原子數為1~4的烷基，優選甲基或乙基。 The alkyl group having 1 to 4 carbon atoms represented by R 8 is preferably a methyl group or an ethyl group.

作為由R8所表示的碳原子數為1~4的烷氧基，優選甲氧基或乙氧基。 The alkoxy group having 1 to 4 carbon atoms represented by R 8 is preferably a methoxy group or an ethoxy group.

作為L，優選0~2，特優選0~1。 L is preferably 0 to 2, and particularly preferably 0 to 1.

由式(c1)所表示的化合物之中，包含在由式(c1-2)所表示的化合物中的化合物的優選的形態為如下的形態：式(c1)中，R5表示苯基或4-甲氧基苯基，R6表示氰基，R7表示甲基、乙基、正丙基、正丁基或4-甲苯基。 Among the compounds represented by the formula (c1), a preferred form of the compound contained in the compound represented by the formula (c1-2) is a form in which, in the formula (c1), R 5 represents a phenyl group or 4 -Methoxyphenyl, R 6 represents a cyano group, and R 7 represents a methyl group, an ethyl group, a n-propyl group, an n-butyl group or a 4-tolyl group.

以下，表示由式(c1)所表示的化合物之中，包含在由式(c1-2)所表示的化合物中的化合物的特優選的例子，但本發明並不限定於這些例子。 In the following, a particularly preferable example of the compound included in the compound represented by the formula (c1-2) among the compounds represented by the formula (c1) is shown, but the present invention is not limited to these examples.

α-(甲基磺醯氧基亞氨基)苄基氰(R5=苯基，R6=氰基，R7=甲基) Α-(methylsulfonyloxyimino)benzyl cyanide (R 5 =phenyl, R 6 = cyano, R 7 =methyl)

α-(乙基磺醯氧基亞氨基)苄基氰(R5=苯基，R6=氰基，R7= 乙基) Α-(ethylsulfonyloxyimino)benzyl cyanide (R 5 =phenyl, R 6 = cyano, R 7 = ethyl)

α-(正丙基磺醯氧基亞氨基)苄基氰(R5=苯基，R6=氰基，R7=正丙基) Α-(n-propylsulfonyloxyimino)benzyl cyanide (R 5 =phenyl, R 6 = cyano, R 7 = n-propyl)

α-(正丁基磺醯氧基亞氨基)苄基氰(R5=苯基，R6=氰基，R7=正丁基) Α-(n-butylsulfonyloxyimino)benzyl cyanide (R 5 =phenyl, R 6 = cyano, R 7 = n-butyl)

α-(4-甲苯磺醯氧基亞氨基)苄基氰(R5=苯基，R6=氰基，R7=4-甲苯基) Α-(4-Toluenesulfonyloxyimino)benzyl cyanide (R 5 =phenyl, R 6 = cyano, R 7 = 4-tolyl)

α-[(甲基磺醯氧基亞氨基)-4-甲氧基苯基]乙腈(R5=4-甲氧基苯基，R6=氰基，R7=甲基) --[(Methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 5 = 4-methoxyphenyl, R 6 = cyano, R 7 = methyl)

α-[(乙基磺醯氧基亞氨基)-4-甲氧基苯基]乙腈(R5=4-甲氧基苯基，R6=氰基，R7=乙基) --[(ethylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 5 = 4-methoxyphenyl, R 6 = cyano, R 7 = ethyl)

α-[(正丙基磺醯氧基亞氨基)-4-甲氧基苯基]乙腈(R5=4-甲氧基苯基，R6=氰基，R7=正丙基) --[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 5 = 4-methoxyphenyl, R 6 = cyano, R 7 = n-propyl)

α-[(正丁基磺醯氧基亞氨基)-4-甲氧基苯基]乙腈(R5=4-甲氧基苯基，R6=氰基，R7=正丁基) --[(n-butylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 5 = 4-methoxyphenyl, R 6 = cyano, R 7 = n-butyl)

α-[(4-甲苯磺醯氧基亞氨基)-4-甲氧基苯基]乙腈(R5=4-甲氧基苯基，R6=氰基，R7=4-甲苯基) --[(4-Toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R 5 = 4-methoxyphenyl, R 6 = cyano, R 7 = 4-tolyl)

另外，作為具有至少1個由所述式(c0)所表示的肟磺酸酯殘基的化合物，優選由下述式(OS-3)、式(OS-4)、或式(OS-5)所表示的肟磺酸酯化合物。 Further, as the compound having at least one oxime sulfonate residue represented by the above formula (c0), it is preferably represented by the following formula (OS-3), formula (OS-4), or formula (OS-5). The oxime sulfonate compound represented.

(式(OS-3)~式(OS-5)中，R1表示烷基、芳基、或雜 芳基，存在多個的R2分別獨立地表示氫原子、烷基、芳基、或鹵素原子，存在多個的R6分別獨立地表示鹵素原子、烷基、烷氧基、磺酸基、氨基磺醯基、或烷氧基磺醯基，X表示O或S，n表示1或2，m表示0~6的整數。) (In the formula (OS-3) to (OS-5), R 1 represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, a plurality of R 6 respectively independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X represents O or S, and n represents 1 or 2, m represents an integer from 0 to 6.)

所述式(OS-3)~式(OS-5)中，由R1所表示的烷基、芳基或雜芳基可具有取代基。 In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group represented by R 1 may have a substituent.

所述式(OS-3)~式(OS-5)中，作為由R1所表示的烷基，優選可具有取代基的總碳數為1~30的烷基。 In the above formula (OS-3) to formula (OS-5), the alkyl group represented by R 1 is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

另外，所述式(OS-3)~式(OS-5)中，作為由R1所表示的芳基，優選可具有取代基的總碳數為6~30的芳基。 Further, in the above formula (OS-3) to formula (OS-5), as the aryl group represented by R 1 , an aryl group having a total carbon number of 6 to 30 which may have a substituent is preferable.

另外，所述式(OS-3)~式(OS-5)中，作為由R1所表示的雜芳基，優選可具有取代基的總碳數為4~30的雜芳基，只要是至少1個雜芳香環即可，例如雜芳香環與苯環也可以進行縮環。 Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group represented by R 1 is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent, as long as it is At least one heteroaromatic ring may be used. For example, a heteroaromatic ring and a benzene ring may also be condensed.

作為由R1所表示的烷基、芳基或雜芳基可具有的取代基，可列舉：鹵素原子、烷氧基、芳氧基、烷硫基、芳硫基、烷氧基羰基、芳氧基羰基、氨基羰基。 Examples of the substituent which the alkyl group, the aryl group or the heteroaryl group represented by R 1 may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aromatic group. Oxycarbonyl group, aminocarbonyl group.

所述式(OS-3)~式(OS-5)中，R2優選氫原子、烷基、或芳基，更優選氫原子或烷基。 In the above formula (OS-3) to formula (OS-5), R 2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

所述式(OS-3)~式(OS-5)中，優選在化合物中存在2個以上的R2中的1個或2個為烷基、芳基或鹵素原子，更優選1個R2為烷基、芳基或鹵素原子，特優選1個R2為烷基、且剩餘的R2為氫原子。 In the above formula (OS-3) to formula (OS-5), it is preferred that one or two of two or more R 2 in the compound are an alkyl group, an aryl group or a halogen atom, and more preferably one R. 2 is an alkyl group, an aryl group or a halogen atom, and particularly preferably one R 2 is an alkyl group, and the remaining R 2 is a hydrogen atom.

所述式(OS-3)~式(OS-5)中，由R2所表示的烷基或芳基可具有取代基。 In the above formula (OS-3) to formula (OS-5), the alkyl group or the aryl group represented by R 2 may have a substituent.

作為由R2所表示的烷基或芳基可具有的取代基，可例示 與所述R1中的烷基或芳基可具有的取代基相同的基。 The substituent which the alkyl group or the aryl group represented by R 2 may have is the same as the substituent which the alkyl group or the aryl group in R 1 may have.

所述式(OS-3)~式(OS-5)中，作為由R2所表示的烷基，優選可具有取代基的總碳數為1~12的烷基，更優選可具有取代基的總碳數為1~6的烷基。 In the above formula (OS-3) to formula (OS-5), the alkyl group represented by R 2 is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably may have a substituent. The total carbon number is 1 to 6 alkyl groups.

作為由R2所表示的烷基，優選甲基、乙基、正丙基、正丁基、正己基，更優選甲基。 The alkyl group represented by R 2 is preferably a methyl group, an ethyl group, a n-propyl group, a n-butyl group or a n-hexyl group, and more preferably a methyl group.

所述式(OS-3)~式(OS-5)中，作為由R2所表示的芳基，優選可具有取代基的總碳數為6~30的芳基。 In the above formula (OS-3) to formula (OS-5), as the aryl group represented by R 2 , an aryl group having a total carbon number of 6 to 30 which may have a substituent is preferable.

作為由R2所表示的芳基，優選苯基、對甲基苯基、鄰氯苯基、對氯苯基、鄰甲氧基苯基、對苯氧基苯基。 The aryl group represented by R 2 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group or a p-phenoxyphenyl group.

所述式(OS-3)~式(OS-5)中，X表示O或S，優選O。 In the formula (OS-3) to formula (OS-5), X represents O or S, preferably O.

所述式(OS-3)~式(OS-5)中，含有X作為環員的環為5員環或6員環。 In the above formula (OS-3) to formula (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.

所述式(OS-3)~式(OS-5)中，n表示1或2，當X為O時，n優選1，另外，當X為S時，n優選2。 In the formula (OS-3) to formula (OS-5), n represents 1 or 2. When X is 0, n is preferably 1, and when X is S, n is preferably 2.

所述式(OS-3)~式(OS-5)中，由R6所表示的烷基及烷氧基可具有取代基。 In the above formula (OS-3) to formula (OS-5), the alkyl group and the alkoxy group represented by R 6 may have a substituent.

所述式(OS-3)~式(OS-5)中，作由為R6所表示的烷基，優選可具有取代基的總碳數為1~30的烷基。 In the above formula (OS-3) to formula (OS-5), the alkyl group represented by R 6 is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

作為由R6所表示的烷氧基，優選甲氧基、乙氧基、丁氧基、己氧基、苯氧基乙氧基、三氯甲氧基、或乙氧基乙氧基。 As the alkoxy group represented by R 6 , a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a phenoxyethoxy group, a trichloromethoxy group, or an ethoxyethoxy group is preferable.

作為R6中的氨基磺醯基，可列舉：甲氨基磺醯基、二甲氨基磺醯基、苯氨基磺醯基、甲基苯氨基磺醯基、氨基磺醯基。 Examples of the aminosulfonyl group in R 6 include a methylaminosulfonyl group, a dimethylsulfamoyl group, a phenylaminosulfonyl group, a methylphenylsulfonyl group, and an aminosulfonyl group.

作為由R6所表示的烷氧基磺醯基，可列舉：甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、丁氧基磺醯基。 Examples of the alkoxysulfonyl group represented by R 6 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, and a butoxysulfonyl group.

作為由R6所表示的烷基或烷氧基可具有的取代基，可列 舉：鹵素原子、烷氧基、芳氧基、烷硫基、芳硫基、烷氧基羰基、芳氧基羰基、氨基羰基。 Examples of the substituent which the alkyl group or the alkoxy group represented by R 6 may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , aminocarbonyl.

另外，所述式(OS-3)~式(OS-5)中，m表示0~6的整數，優選0~2的整數，更優選0或1，特優選0。 Further, in the above formula (OS-3) to formula (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

另外，由所述式(OS-3)所表示的化合物特優選由下述式(OS-6)、式(OS-10)或式(OS-11)所表示的化合物，由所述式(OS-4)所表示的化合物特優選由下述式(OS-7)所表示的化合物，由所述式(OS-5)所表示的化合物特優選由下述式(OS-8)或式(OS-9)所表示的化合物。 Further, the compound represented by the above formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), formula (OS-10) or formula (OS-11), from which The compound represented by OS-4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the above formula (OS-5) is particularly preferably represented by the following formula (OS-8) or formula Compound represented by (OS-9).

式(OS-6)~式(OS-11)中，R1表示烷基、芳基或雜芳基，R7表示氫原子或溴原子，R8表示氫原子、碳數為1~8的烷基、鹵素原子、氯甲基、溴甲基、溴乙基、甲氧基甲基、苯基或氯苯基，R9表示氫原子、鹵素原子、甲基或甲氧基，R10表示氫原子或甲基。 In the formula (OS-6)~(OS-11), R 1 represents an alkyl group, an aryl group or a heteroaryl group, R 7 represents a hydrogen atom or a bromine atom, and R 8 represents a hydrogen atom and has a carbon number of 1-8. An alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and R 9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R 10 represents A hydrogen atom or a methyl group.

所述式(OS-6)~式(OS-11)中的R1的含義與所述式(OS-3)~式(OS-5)中的R1相同，優選的形態也相同。 The same as in (OS-6) ~ formula (OS-11) R 1 in the formula the meanings as in the formula - (OS-5) R of the formula (OS-3) 1, a preferred embodiment is also the same.

所述式(OS-6)中的R7表示氫原子或溴原子，優選氫原子。 R 7 in the formula (OS-6) represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

所述式(OS-6)~式(OS-11)中的R8表示氫原子、碳數為1~8的烷基、鹵素原子、氯甲基、溴甲基、溴乙基、甲氧基甲基、苯基或氯苯基，優選碳數為1~8的烷基、鹵素原子或苯基，更優選碳數為1~8的烷基，進而更優選碳數為1~6的烷基，特優選甲基。 R 8 in the formula (OS-6) to formula (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxy group. The methyl group, the phenyl group or the chlorophenyl group is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms. An alkyl group is particularly preferably a methyl group.

所述式(OS-8)及式(OS-9)中的R9表示氫原子、鹵素原子、甲基或甲氧基，優選氫原子。 R 9 in the formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and preferably a hydrogen atom.

所述式(OS-8)~式(OS-11)中的R10表示氫原子或甲基，優選氫原子。 R 10 in the formula (OS-8) to formula (OS-11) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

另外，在所述肟磺酸酯化合物中，關於肟的立體結構(E、Z)，可以是任一者，也可以是混合物。 Further, in the oxime sulfonate compound, the steric structure (E, Z) of ruthenium may be either a mixture or a mixture.

作為由所述式(OS-3)~式(OS-5)所表示的肟磺酸酯化合物的具體例，可列舉下述例示化合物，但本發明並不限定於這些例示化合物。 Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to formula (OS-5) include the following exemplified compounds, but the present invention is not limited to these exemplified compounds.

作為具有至少1個由所述式(c0)所表示的肟磺酸酯殘基的肟磺酸酯化合物的合適的其他形態，也可以列舉日本專利特開2011-209719號公報的段落0117~段落0129中所記載者。 As another suitable form of the oxime sulfonate compound having at least one oxime sulfonate residue represented by the above formula (c0), paragraph 0117 to paragraph of JP-A-2011-209719 The person recorded in 0129.

本發明的感光性樹脂組成物優選不含1,2-醌二疊氮化合物作為感應光化射線的(成分C)光酸產生劑。其原因在於：1,2-醌二疊氮化合物雖然藉由逐步型光化學反應而生成羧基，但其量子產率為1以下，感光度比肟磺酸酯化合物低。 The photosensitive resin composition of the present invention preferably does not contain a 1,2-quinonediazide compound as a (component C) photoacid generator for inducing actinic rays. The reason for this is that the 1,2-quinonediazide compound generates a carboxyl group by a stepwise photochemical reaction, but its quantum yield is 1 or less, and the sensitivity is lower than that of the sulfonate compound.

相對於此，推測肟磺酸酯化合物由於感應光化射線而生成的酸作為觸媒對經保護的酸性基的脫保護發揮作用，因此藉由1個光量子的作用而生成的酸有助於多個脫保護反應，量子產率超過1，例如變成如10的幾乘方般的大的值，作為所謂的化學增幅的結果，可獲得高感光度。 On the other hand, it is presumed that the acid generated by the inducing actinic ray of the oxime sulfonate compound acts as a catalyst to deprotect the protected acidic group. Therefore, the acid generated by the action of one photon contributes to more For each deprotection reaction, the quantum yield exceeds 1, for example, a large value such as several powers of 10, and as a result of the so-called chemical amplification, high sensitivity can be obtained.

相對於成分A及成分B的總含量100重量份，本發明的感光性樹脂組成物中的(成分C)光酸產生劑的含量優選0.1重量份~10重量份，更優選0.5重量份~10重量份。 The content of the (component C) photoacid generator in the photosensitive resin composition of the present invention is preferably 0.1 part by weight to 10 parts by weight, more preferably 0.5 part by weight to 10 parts by weight based on 100 parts by weight of the total content of the component A and the component B. Parts by weight.

(成分D)溶劑 (ingredient D) solvent

本發明的感光性樹脂組成物優選含有(成分D)溶劑。本發明的感光性樹脂組成物優選作為使本發明的各成分溶解在(成分D)溶劑中而成的溶液來製備。 The photosensitive resin composition of the present invention preferably contains (Component D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving each component of the present invention in a solvent (Component D).

作為本發明的感光性樹脂組成物中所使用的溶劑，可使用公知的溶劑，可例示：乙二醇單烷基醚類、乙二醇二烷基醚類、乙二醇單烷基醚醋酸酯類、丙二醇單烷基醚類、丙二醇二烷基醚類、丙二醇單烷基醚醋酸酯類、二乙二醇二烷基醚類、二乙二醇單烷基醚醋酸酯類、二丙二醇單烷基醚類、二丙二醇二烷基醚類、二丙二醇單烷基醚醋酸酯類、酯類、酮類、醯胺類、 內酯類等。作為本發明的感光性樹脂組成物中所使用的溶劑，例如可列舉日本專利特開2009-258722號公報的段落0074中所記載的溶劑。 As the solvent to be used in the photosensitive resin composition of the present invention, a known solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetate. Esters, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol Monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, Lactones and the like. The solvent to be used in the photosensitive resin composition of the present invention is, for example, a solvent described in paragraph 0074 of JP-A-2009-258722.

所述溶劑之中，特優選二乙二醇乙基甲醚、及/或丙二醇單甲醚醋酸酯。 Among the solvents, diethylene glycol ethyl methyl ether and/or propylene glycol monomethyl ether acetate are particularly preferred.

這些溶劑可單獨使用1種、或將2種以上混合使用。可用於本發明的溶劑優選單獨使用1種、或並用2種，更優選並用2種，進而更優選並用丙二醇單烷基醚醋酸酯類與二乙二醇二烷基醚類。 These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two or more. More preferably, two kinds are used in combination, and further, propylene glycol monoalkyl ether acetate and diethylene glycol dialkyl ether are more preferably used in combination.

相對於成分A 100重量份，本發明的感光性樹脂組成物中的成分D的含量優選50重量份~3,000重量份，更優選100重量份~2,000重量份，進而更優選150重量份~1,500重量份。 The content of the component D in the photosensitive resin composition of the present invention is preferably 50 parts by weight to 3,000 parts by weight, more preferably 100 parts by weight to 2,000 parts by weight, still more preferably 150 parts by weight to 1,500 parts by weight, based on 100 parts by weight of the component A. Share.

相對於成分A及成分B的總含量100重量份，本發明的感光性樹脂組成物中的(成分D)溶劑的含量優選50重量份~3,000重量份，更優選100重量份~2,000重量份，進而更優選150重量份~1,500重量份。 The content of the (Component D) solvent in the photosensitive resin composition of the present invention is preferably 50 parts by weight to 3,000 parts by weight, more preferably 100 parts by weight to 2,000 parts by weight, based on 100 parts by weight of the total content of the component A and the component B. Further, it is more preferably 150 parts by weight to 1,500 parts by weight.

<其他成分> <Other ingredients>

本發明的感光性樹脂組成物可含有其他成分。 The photosensitive resin composition of the present invention may contain other components.

作為其他成分，就感光度的觀點而言，本發明的感光性樹脂組成物優選含有光敏劑，就液體保存穩定性的觀點而言，優選含有鹼性化合物，就膜物性的觀點而言，優選含有交聯劑，就基板密接性的觀點而言，優選含有密接改良劑，另外，就塗布性的觀點而言，優選含有界面活性劑。 In the viewpoint of sensitivity, the photosensitive resin composition of the present invention preferably contains a photosensitizer, and it is preferable to contain a basic compound from the viewpoint of liquid storage stability, and it is preferable from the viewpoint of film properties. The crosslinking agent is preferably contained in the viewpoint of coating properties, and it is preferable to contain a surfactant, from the viewpoint of coating properties.

以下，對本發明的感光性樹脂組成物中可含有的其他成分進行說明。 Hereinafter, other components which can be contained in the photosensitive resin composition of the present invention will be described.

[光敏劑] [Photosensitizer]

本發明的感光性樹脂組成物優選含有光敏劑。 The photosensitive resin composition of the present invention preferably contains a photosensitizer.

藉由含有光敏劑，對於提升曝光靈敏度有效，在曝光光源為g射線、h射線混合線的情況下特別有效。 It is effective for improving the exposure sensitivity by containing a photosensitizer, and is particularly effective in the case where the exposure light source is a g-ray or an h-ray mixing line.

作為光敏劑，優選蒽衍生物、吖啶酮衍生物、硫雜蒽酮衍生物、香豆素衍生物、基質苯乙烯基衍生物、二苯乙烯基苯衍生物。 As the photosensitizer, an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a matrix styryl derivative, and a distyrylbenzene derivative are preferable.

作為蒽衍生物，優選蒽、9,10-二丁氧基蒽、9,10-二氯蒽、2-乙基-9,10-二甲氧基蒽、9-羥甲基蒽、9-溴蒽、9-氯蒽、9,10-二溴蒽、2-乙基蒽、9,10-二甲氧基蒽。 As the anthracene derivative, ruthenium, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9- are preferable. Bromide, 9-chloropurine, 9,10-dibromofluorene, 2-ethylhydrazine, 9,10-dimethoxyfluorene.

作為吖啶酮衍生物，優選吖啶酮、N-丁基-2-氯吖啶酮、N-甲基吖啶酮、2-甲氧基吖啶酮、N-乙基-2-甲氧基吖啶酮。 As the acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, N-ethyl-2-methoxy Acridinone.

作為硫雜蒽酮衍生物，優選硫雜蒽酮、二乙基硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮、2-氯硫雜蒽酮。 As the thioxanthone derivative, thioxanthone, diethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, or 2-chlorothiazinone is preferable.

作為香豆素衍生物，優選香豆素-1、香豆素-6H、香豆素-110、香豆素-102。 As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110, and coumarin-102 are preferable.

作為基質苯乙烯基衍生物，可列舉2-(4-二甲氨基苯乙烯基)苯並惡唑、2-(4-二甲氨基苯乙烯基)苯並噻唑、2-(4-二甲氨基苯乙烯基)萘噻唑。 As the matrix styryl derivative, 2-(4-dimethylaminostyryl)benzoxazole, 2-(4-dimethylaminostyryl)benzothiazole, 2-(4-dimethyl) Aminostyryl)naphthazole.

作為二苯乙烯基苯衍生物，可列舉二苯乙烯基苯、二(4-甲氧基苯乙烯基)苯、二(3,4,5-三甲氧基苯乙烯基)苯。 Examples of the distyrylbenzene derivative include distyrylbenzene, bis(4-methoxystyryl)benzene, and bis(3,4,5-trimethoxystyryl)benzene.

這些光敏劑之中，優選蒽衍生物，更優選9,10-二烷氧基蒽(烷氧基的碳數為1~6)。 Among these photosensitizers, an anthracene derivative is preferred, and a 9,10-dialkyloxyfluorene (the alkoxy group has a carbon number of 1 to 6) is more preferred.

作為光敏劑的具體例，可列舉下述者。再者，在下述中，Me表示甲基，Et表示乙基，Bu表示丁基。 Specific examples of the photosensitizer include the following. Further, in the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

相對於成分A及成分B的總含量100重量份，本發明的感光性樹脂組成物中的光敏劑的含量優選0.1重量份~10重量份，更優選0.5重量份~10重量份。若光敏劑的含量為0.1重量份以上，則容易獲得所期望的感光度，另外，若光敏劑的含量10重量份以下，則容易確保塗膜的透明性。 The content of the photosensitizer in the photosensitive resin composition of the present invention is preferably 0.1 part by weight to 10 parts by weight, more preferably 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the total content of the component A and the component B. When the content of the photosensitizer is 0.1 part by weight or more, the desired sensitivity is easily obtained, and when the content of the photosensitizer is 10 parts by weight or less, the transparency of the coating film is easily secured.

[鹼性化合物] [alkaline compound]

就液體保存穩定性的觀點而言，本發明的感光性樹脂組成物優選含有鹼性化合物。 The photosensitive resin composition of the present invention preferably contains a basic compound from the viewpoint of liquid storage stability.

作為鹼性化合物，可從化學增幅抗蝕劑中所使用的鹼性化合物中任意地選擇來使用。例如可列舉：脂肪族胺、芳香族胺、雜環式胺、氫氧化四級銨、及羧酸的四級銨鹽等。 As the basic compound, it can be arbitrarily selected from the basic compounds used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, and a quaternary ammonium salt of a carboxylic acid can be mentioned.

作為脂肪族胺，例如可列舉：三甲胺、二乙胺、三乙胺、二-正丙胺、三-正丙胺、二-正戊胺、三-正戊胺、二乙醇胺、三乙醇胺、二環己胺、二環己基甲胺等。 Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and bicyclol. Hexylamine, dicyclohexylmethylamine, and the like.

作為芳香族胺，例如可列舉：苯胺、苄基胺、N,N-二甲基苯胺、二苯基胺等。 Examples of the aromatic amine include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.

作為雜環式胺，例如可列舉：吡啶、2-甲基吡啶、4-甲基吡啶、2-乙基吡啶、4-乙基吡啶、2-苯基吡啶、4-苯基吡啶、N-甲基-4-苯基吡啶、4-二甲氨基吡啶、咪唑、苯並咪唑、4-甲基咪唑、2-苯基苯並咪唑、2,4,5-三苯基咪唑、煙鹼、煙鹼 酸、煙鹼醯胺、喹啉、8-羥基喹啉、吡嗪、吡唑、噠嗪、嘌呤、吡咯烷、呱啶、呱嗪、嗎啉、4-甲基嗎啉、N-環己基-N'-[2-(4-嗎啉基)乙基]硫脲、1,5-二氮雙環[4.3.0]-5-壬烯、1,8-二氮雙環[5.3.0]-7-十一烯等。 Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N- Methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Nicotine Acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, indole, pyrrolidine, acridine, pyridazine, morpholine, 4-methylmorpholine, N-cyclohexyl -N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0] -7-undecene and the like.

作為氫氧化四級銨，例如可列舉：氫氧化四甲基銨、氫氧化四乙基銨、四-正丁基氫氧化銨、氫氧化四-正己基銨等。 Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

作為羧酸的四級銨鹽，例如可列舉：醋酸四甲基銨、苯甲酸四甲基銨、醋酸四-正丁基銨、苯甲酸四-正丁基銨等。 Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

可用於本發明的鹼性化合物可單獨使用1種，也可以並用2種以上，優選並用2種以上，更優選並用2種，進而更優選並用2種雜環式胺。 The basic compound which can be used in the present invention may be used singly or in combination of two or more kinds, and it is preferred to use two or more kinds in combination, and it is more preferred to use two kinds in combination, and it is more preferred to use two kinds of heterocyclic amines in combination.

相對於成分A及成分B的總含量100重量份，本發明的感光性樹脂組成物中的鹼性化合物的含量優選0.001重量份~1重量份，更優選0.002重量份~0.2重量份。 The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 part by weight to 1 part by weight, more preferably 0.002 part by weight to 0.2 part by weight, based on 100 parts by weight of the total content of the component A and the component B.

[交聯劑] [crosslinking agent]

視需要，本發明的感光性樹脂組成物優選含有交聯劑。藉由添加交聯劑，可使由本發明的感光性樹脂組成物所獲得的硬化膜變成更牢固的膜。 The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can be made into a stronger film by adding a crosslinking agent.

作為交聯劑，例如可添加以下所述的分子內具有2個以上的環氧基或氧雜環丁基的化合物、含有烷氧基甲基的交聯劑、或具有至少1個乙烯性不飽和雙鍵的化合物。 As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, a crosslinking agent containing an alkoxymethyl group, or at least one ethylenic group may be added. A compound that saturates a double bond.

這些交聯劑之中，優選分子內具有2個以上的環氧基或氧雜環丁基的化合物，特優選環氧樹脂。 Among these crosslinking agents, a compound having two or more epoxy groups or oxetanyl groups in the molecule is preferable, and an epoxy resin is particularly preferable.

相對於感光性樹脂組成物的總固體成分，本發明的感光性樹脂組成物中的交聯劑的添加量優選0.05重量份~50重量份，更優選0.5重量份~44重量份，進而更優選3重量份~40 重量份。藉由在該範圍內進行添加，可獲得機械強度及耐溶劑性優異的硬化膜。 The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably 0.05 parts by weight to 50 parts by weight, more preferably 0.5 parts by weight to 44 parts by weight, even more preferably, based on the total solid content of the photosensitive resin composition. 3 parts by weight ~40 Parts by weight. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.

-分子內具有2個以上的環氧基或氧雜環丁基的化合物- a compound having two or more epoxy groups or oxetanyl groups in the molecule -

作為分子內具有2個以上的環氧基的化合物的具體例，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、脂肪族環氧樹脂等。 Specific examples of the compound having two or more epoxy groups in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type ring. Oxygen resin, aliphatic epoxy resin, and the like.

這些化合物可作為市售品而獲得，可列舉JER150S65或JER1031S(均為三菱化學(股份)製造)等日本專利特開2009-258722號公報的段落0051~段落0053中所記載者。這些化合物可單獨使用1種、或將2種以上組合使用。 These compounds are available as a commercial product, and those described in paragraphs 0051 to 0053 of JP-A-2009-258722, such as JER150S65 or JER1031S (all manufactured by Mitsubishi Chemical Corporation). These compounds may be used alone or in combination of two or more.

這些化合物之中，可優選列舉環氧樹脂，可更優選列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、及苯酚酚醛清漆型環氧樹脂，可特優選列舉雙酚A型環氧樹脂。 Among these compounds, an epoxy resin is preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenol novolak type epoxy resin are more preferable, and a bisphenol A type ring is especially preferable. Oxygen resin.

作為分子內具有2個以上的氧雜環丁基的化合物的具體例，可使用ARON OXETANE OXT-121、OXT-221、OX-SQ、PNOX(以上，東亞合成(股份)製造)。 Specific examples of the compound having two or more oxetanyl groups in the molecule include ARON OXETANE OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.).

另外，含有氧雜環丁基的化合物優選單獨使用、或與含有環氧基的化合物混合後使用。 Further, the oxetanyl group-containing compound is preferably used singly or in combination with an epoxy group-containing compound.

當將成分A及成分B的總含量設為100重量份時，這些化合物之中，分子內具有2個以上的環氧基或氧雜環丁基的化合物朝本發明的感光性樹脂組成物中的添加量優選1重量份~50重量份，更優選3重量份~30重量份。 When the total content of the component A and the component B is 100 parts by weight, among these compounds, a compound having two or more epoxy groups or oxetanyl groups in the molecule is used in the photosensitive resin composition of the invention. The amount of addition is preferably from 1 part by weight to 50 parts by weight, more preferably from 3 parts by weight to 30 parts by weight.

-含有烷氧基甲基的交聯劑、或具有至少1個乙烯性不飽和雙鍵的化合物- a crosslinking agent containing an alkoxymethyl group or a compound having at least one ethylenically unsaturated double bond -

作為含有烷氧基甲基的交聯劑，優選烷氧基甲基化三聚氰胺、烷氧基甲基化苯代三聚氰胺、烷氧基甲基化甘脲及烷氧基 甲基化脲等。另外，作為具有至少1個乙烯性不飽和雙鍵的化合物，可優選使用單官能(甲基)丙烯酸酯、二官能(甲基)丙烯酸酯、三官能以上的(甲基)丙烯酸酯等(甲基)丙烯酸酯化合物。 As the crosslinking group containing an alkoxymethyl group, alkoxymethylated melamine, alkoxymethylated benzene melamine, alkoxymethylated glycoluril, and alkoxy group are preferable. Methylated urea and the like. Further, as the compound having at least one ethylenically unsaturated double bond, a monofunctional (meth) acrylate, a difunctional (meth) acrylate, a trifunctional or higher (meth) acrylate, or the like can be preferably used (A Base) acrylate compound.

作為含有烷氧基甲基的交聯劑、或具有至少1個乙烯性不飽和雙鍵的化合物的具體例，可列舉日本專利特開2011-170305號公報的段落0093~段落0100中所記載者，添加量或組合的優選的範圍也相同。 Specific examples of the crosslinking agent containing an alkoxymethyl group or a compound having at least one ethylenically unsaturated double bond include those described in paragraphs 0093 to 0100 of JP-A-2011-170305. The preferred range of addition amount or combination is also the same.

[密接改良劑] [Close Connection Improver]

就基板密接性的觀點而言，本發明的感光性樹脂組成物優選含有密接改良劑。 The photosensitive resin composition of the present invention preferably contains a adhesion improving agent from the viewpoint of substrate adhesion.

可用於本發明的感光性樹脂組成物的密接改良劑是提升成為基板的無機物，例如矽、氧化矽、氮化矽等矽化合物，鉬、鈦、氧化銦錫、金、銅、鋁等金屬與絕緣膜的密接性的化合物。具體而言，可列舉矽烷偶聯劑、硫醇系化合物等。作為本發明中所使用的密接改良劑的矽烷偶聯劑是以界面的改質為目標者，並無特別限定，可使用公知的矽烷偶聯劑。 The adhesion improving agent which can be used for the photosensitive resin composition of the present invention is an inorganic substance which is promoted to be a substrate, for example, a cerium compound such as cerium, cerium oxide or cerium nitride, or a metal such as molybdenum, titanium, indium tin oxide, gold, copper or aluminum. A compound of an insulating film. Specific examples thereof include a decane coupling agent, a thiol compound, and the like. The decane coupling agent which is an adhesion improving agent used in the present invention is not particularly limited as long as it is intended to modify the interface, and a known decane coupling agent can be used.

這些密接改良劑之中，可優選例示矽烷偶聯劑。但是，本發明的矽烷偶聯劑是指1分子中具有1個水解性矽烷基或矽烷醇基的化合物，本發明的矽烷偶聯劑中不含相當於成分X的矽化合物。 Among these adhesion improving agents, a decane coupling agent is preferably exemplified. However, the decane coupling agent of the present invention refers to a compound having one hydrolyzable alkylene group or stanol group in one molecule, and the hydrazine coupling agent of the present invention does not contain a quinone compound corresponding to the component X.

作為優選的矽烷偶聯劑，例如可列舉：γ-氨基丙基三甲氧基矽烷、γ-氨基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三烷氧基矽烷、γ-縮水甘油氧基丙基烷基二烷氧基矽烷、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧基丙基烷基二烷氧基矽烷、γ-氯丙基三烷氧基矽烷、γ-巰基丙基三烷氧基矽烷、β-(3,4-環氧環己基)乙基三烷氧基矽烷、乙烯基三烷氧基矽烷。 Preferred examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-shrinkage. Glyceroxypropylalkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloride Propyltrialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane.

這些矽烷偶聯劑之中，更優選γ-縮水甘油氧基丙基三烷氧基矽烷、及γ-甲基丙烯醯氧基丙基三烷氧基矽烷，進而更優選γ-縮水甘油氧基丙基三烷氧基矽烷。 Among these decane coupling agents, γ-glycidoxypropyl trialkoxy decane and γ-methacryloxypropyl trialkoxy decane are more preferable, and γ-glycidyloxy group is more preferable. Propyl trialkoxy decane.

這些密接改良劑可單獨使用1種、或將2種以上組合使用。這些密接改良劑對於與基板的密接性的提升有效，並且對於與基板的圓錐角的調整也有效。 These adhesion improving agents may be used alone or in combination of two or more. These adhesion improvers are effective for improving the adhesion to the substrate, and are also effective for adjusting the taper angle with the substrate.

相對於成分A及成分B的總含量100重量份，本發明的感光性樹脂組成物中的密接改良劑的含量優選0.1重量份~20重量份，更優選0.5重量份~10重量份。 The content of the adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 part by weight to 20 parts by weight, more preferably 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the total content of the component A and the component B.

[界面活性劑] [Surfactant]

就塗布性的觀點而言，本發明的感光性樹脂組成物優選含有界面活性劑。 From the viewpoint of coatability, the photosensitive resin composition of the present invention preferably contains a surfactant.

作為界面活性劑，可使用陰離子系、陽離子系、非離子系、或兩性的任一種，但優選的界面活性劑為非離子系界面活性劑。 As the surfactant, any of anionic, cationic, nonionic or amphoteric may be used, but a preferred surfactant is a nonionic surfactant.

作為非離子系界面活性劑的例子，可列舉：聚氧乙烯高級烷基醚類、聚氧乙烯高級烷基苯醚類、聚氧乙烯二醇的高級脂肪酸二酯類、氟系、矽酮系界面活性劑。 Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene diol, fluorine-based and fluorenone-based compounds. Surfactant.

本發明的感光性樹脂組成物更優選含有氟系界面活性劑、及/或矽酮系界面活性劑作為界面活性劑。 More preferably, the photosensitive resin composition of the present invention contains a fluorine-based surfactant and/or an anthrone-based surfactant as a surfactant.

作為所述氟系界面活性劑、矽酮系界面活性劑，例如可列舉日本專利特開昭62-36663號、日本專利特開昭61-226746號、日本專利特開昭61-226745號、日本專利特開昭62-170950號、日本專利特開昭63-34540號、日本專利特開平7-230165號、日本專利特開平8-62834號、日本專利特開平9-54432號、日本專利特開平9-5988號、日本專利特開2001-330953號各 公報中記載的界面活性劑，也可以使用市售的界面活性劑。 Examples of the fluorine-based surfactant and the anthrone-based surfactant include Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japan. Japanese Patent Laid-Open No. Sho 62-170950, Japanese Patent Laid-Open No. Sho 63-34540, Japanese Patent Laid-Open No. Hei 7-230165, Japanese Patent Laid-Open No. Hei 8-62834, Japanese Patent Laid-Open No. Hei 9-54432, Japanese Patent Laid-Open 9-5988, Japanese Patent Special Open 2001-330953 Commercially available surfactants can also be used as the surfactant described in the publication.

作為可使用的市售的界面活性劑，例如可列舉：Eftop EF301、EF303(以上，新秋田化成(股份)製造)，Fluorad FC430、431(以上，住友3M(Sumitomo 3M)(股份)製造)，Megafac F171、F173、F176、F189、R08(以上，迪愛生(DIC)(股份)製造)，Surflon S-382、SC101、102、103、104、105、106(以上，旭硝子(股份)製造)，PolyFox系列(歐諾法(OMNOVA)公司製造)等氟系界面活性劑或矽酮系界面活性劑。另外，聚矽氧烷聚合物KP-341(信越化學工業(股份)製造)也可以用作矽酮系界面活性劑。 Examples of commercially available surfactants that can be used include Eftop EF301 and EF303 (above, New Akita Chemicals Co., Ltd.), and Fluorad FC430 and 431 (above, Sumitomo 3M (manufactured by Sumitomo 3M)). Megafac F171, F173, F176, F189, R08 (above, manufactured by Di Aisheng (DIC) (share)), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.) A fluorine-based surfactant such as a PolyFox series (manufactured by OMNOVA) or an anthrone-based surfactant. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as an anthrone-based surfactant.

另外，作為界面活性劑，可列舉如下的共聚物作為優選例，該共聚物含有由下述式(1)所表示的構成單元A及構成單元B，且將四氫呋喃(Tetrahydrofuran，THF)作為溶劑時的由凝膠滲透色譜法所測定的聚苯乙烯換算的重量平均分子量(Mw)為1,000以上、10,000以下。 In addition, as a surfactant, a copolymer containing a structural unit A and a structural unit B represented by the following formula (1) and having tetrahydrofuran (THF) as a solvent is exemplified. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000 or more and 10,000 or less.

(式(1)中，R1及R3分別獨立地表示氫原子或甲基，R2表示碳數為1以上、4以下的直鏈亞烷基，R4表示氫原子或碳數為1以上、4以下的烷基，L表示碳數為3以上、6以下的亞烷基，p及q為表示聚合比的重量百分率，p表示10 wt%以上、80 wt%以下的數值，q表示20 wt%以上、90 wt%以下的 數值，r表示1以上、18以下的整數，n表示1以上、10以下的整數。) (In the formula (1), R 1 and R 3 each independently represent a hydrogen atom or a methyl group, R 2 represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R 4 represents a hydrogen atom or a carbon number of 1 In the above alkyl group, 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are weight percentages indicating a polymerization ratio, and p is a numerical value of 10% by weight or more and 80% by weight or less, and q is a value. A numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

所述L優選由下述式(2)所表示的分支亞烷基。式(2)中的R5表示碳數為1以上、4以下的烷基，就相容性與對於被塗布面的潤濕性的觀點而言，優選碳數為1以上、3以下的烷基，更優選碳數為2或3的烷基。 The L is preferably a branched alkylene group represented by the following formula (2). R 5 in the formula (2) is an alkyl group having 1 or more and 4 or less carbon atoms, and from the viewpoint of compatibility and wettability to a surface to be coated, an alkane having 1 or more and 3 or less carbon atoms is preferable. The base is more preferably an alkyl group having 2 or 3 carbon atoms.

所述共聚物的重量平均分子量(Mw)更優選1,500以上、5,000以下。 The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

這些界面活性劑可單獨使用1種、或將2種以上混合使用。 These surfactants may be used alone or in combination of two or more.

相對於成分A及成分B的總含量100重量份，本發明的感光性樹脂組成物中的界面活性劑的添加量優選10重量份以下，更優選0.01重量份~10重量份，進而更優選0.01重量份~1重量份。 The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 parts by weight to 10 parts by weight, even more preferably 0.01, based on 100 parts by weight of the total content of the component A and the component B. Parts by weight to 1 part by weight.

<其他> <Other>

視需要，可向本發明的感光性樹脂組成物中添加塑化劑、熱自由基產生劑、熱酸產生劑、酸增殖劑、顯影促進劑、抗氧化劑等其他成分。關於這些成分，例如可使用日本專利特開2009-98616號公報、日本專利特開2009-244801號公報中所記載的成分，其他公知的成分。另外，也可以將“高分子添加劑的新進展(日刊工業新聞社(股份))”中所記載的各種紫外線吸收劑、或金屬鈍化劑等添加至本發明的感光性樹脂組成物中。 A component such as a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, a development accelerator, or an antioxidant may be added to the photosensitive resin composition of the present invention as needed. For the components, for example, the components described in JP-A-2009-98616, JP-A-2009-244801, and other known components can be used. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikkei Industrial News Co., Ltd.)" may be added to the photosensitive resin composition of the present invention.

(硬化膜的形成方法) (Method of forming a cured film)

其次，對本發明的硬化膜的形成方法進行說明。 Next, a method of forming the cured film of the present invention will be described.

本發明的硬化膜的形成方法除使用本發明的正型感光性樹脂組成物以外，並無特別限制，但優選包括以下的(1)~(5)的步驟。 The method for forming the cured film of the present invention is not particularly limited, except that the positive photosensitive resin composition of the present invention is used. However, the following steps (1) to (5) are preferably included.

(1)將本發明的正型感光性樹脂組成物塗布在基板上的步驟 (1) Step of coating the positive photosensitive resin composition of the present invention on a substrate

(2)從所塗布的感光性樹脂組成物中去除溶劑的步驟 (2) Step of removing a solvent from the applied photosensitive resin composition

(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟 (3) a step of exposing the photosensitive resin composition from which the solvent has been removed by using actinic rays

(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟 (4) a step of developing the exposed photosensitive resin composition using an aqueous developing solution

(5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟 (5) Post-baking step of thermally curing the developed photosensitive resin composition

在本發明的硬化膜的形成方法中，也可以在所述曝光步驟中的曝光後，不進行加熱處理，而進行所述(4)的顯影步驟。 In the method for forming a cured film of the present invention, the development step of the above (4) may be carried out without performing heat treatment after exposure in the exposure step.

另外，也可以在所述後烘烤步驟前，進而包括對經顯影的感光性樹脂組成物進行全面曝光的步驟。 Further, before the post-baking step, a step of comprehensively exposing the developed photosensitive resin composition may be further included.

另外，本發明的硬化膜的形成方法優選進而包括(6)對具有進行熱硬化而獲得的硬化膜的基板進行乾蝕刻的乾蝕刻步驟。 Further, the method for forming a cured film of the present invention preferably further comprises (6) a dry etching step of dry etching a substrate having a cured film obtained by thermal curing.

以下依次對各步驟進行說明。 Each step will be described in order below.

在(1)的塗布步驟中，優選將本發明的正型感光性樹脂組成物塗布在基板上而製成含有溶劑的濕潤膜。 In the coating step of (1), the positive photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.

在(2)的溶劑去除步驟中，優選藉由減壓(真空)及/或加熱而從所塗布的所述膜中去除溶劑，從而在基板上形成乾燥塗膜。 In the solvent removal step of (2), it is preferred to remove the solvent from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate.

在(3)的曝光步驟中，優選對所獲得的塗膜照射波長為300 nm以上、450 nm以下的光化射線。在該步驟中，特定酸產生劑分解並產生酸。成分A中所含有的構成單元(a1)中的酸分解性基因所產生的酸的觸媒作用而分解，從而生成酸基。 In the exposure step of (3), it is preferred that the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, the specific acid generator decomposes and produces an acid. The acid generated by the acid-decomposable gene in the structural unit (a1) contained in the component A is decomposed by an action of an acid to form an acid group.

在生成有酸觸媒的區域中，為了加快所述分解反應，視需要也可以進行曝光後加熱處理：曝光後烘烤(Post Exposure Bake)(以下，也稱為“PEB”)。藉由PEB，可促進來自酸分解性基的酸基的生成。 In the region where the acid catalyst is formed, in order to accelerate the decomposition reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed as needed. The formation of an acid group derived from an acid-decomposable group can be promoted by PEB.

特定樹脂中的構成單元(a1)中的酸分解性基由於酸分解的活化能低，容易因由曝光所產生的源自光酸產生劑的酸而分解，並產生酸基，因此不一定必須進行PEB。因此，優選在曝光步驟後，不進行加熱處理而進行所述顯影步驟。更詳細而言，優選在(3)的曝光步驟後不進行PEB，且在(4)的顯影步驟中進行顯影，由此形成正像。 The acid-decomposable group in the structural unit (a1) in the specific resin is low in activation energy due to acid decomposition, and is easily decomposed by an acid derived from a photo-acid generator generated by exposure, and an acid group is generated, so that it is not necessarily necessary. PEB. Therefore, it is preferred that the development step be performed without performing a heat treatment after the exposure step. More specifically, it is preferable that PEB is not performed after the exposure step of (3), and development is performed in the development step of (4), thereby forming a positive image.

再者，也可以在比較低的溫度下進行PEB，由此不產生交聯反應，而促進酸分解性基的分解。進行PEB時的溫度優選30℃以上、130℃以下，更優選40℃以上、110℃以下，特優選50℃以上、90℃以下。 Further, it is also possible to carry out PEB at a relatively low temperature, thereby preventing decomposition of the acid-decomposable group without causing a crosslinking reaction. The temperature at the time of PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 90° C. or lower.

在(4)的顯影步驟中，優選使用鹼性顯影液對具有遊離的酸基的成分A及具有酸基的成分B進行顯影。將包含具有容易溶解在鹼性顯影液中的酸基的感光性樹脂組成物的曝光部區域去除，由此可形成正像。 In the developing step of (4), it is preferred to develop the component A having a free acid group and the component B having an acid group using an alkaline developing solution. The exposed portion region containing the photosensitive resin composition having an acid group which is easily dissolved in the alkaline developing solution is removed, whereby a positive image can be formed.

在(5)的後烘烤步驟中，可藉由對所獲得的正像進行加熱，例如使構成單元(b1)中的酸基、及對構成單元(a1)中的酸分解性基進行熱分解而生成的酸基與構成單元(a2)及構成單元(b2)中的交聯性基進行交聯，而形成硬化膜。該加熱 優選加熱至150℃以上的高溫，更優選加熱至180℃~250℃，特優選加熱至200℃~250℃。可根據加熱時間、加熱溫度等而適宜設定，但優選設為10分鐘~90分鐘的範圍內。 In the post-baking step of (5), by heating the obtained positive image, for example, the acid group in the constituent unit (b1) and the acid-decomposable group in the constituent unit (a1) are heated. The acid group formed by decomposition is crosslinked with the crosslinkable group in the structural unit (a2) and the structural unit (b2) to form a cured film. The heating It is preferably heated to a high temperature of 150 ° C or higher, more preferably to 180 ° C to 250 ° C, and particularly preferably heated to 200 ° C to 250 ° C. The temperature can be appropriately set depending on the heating time, the heating temperature, etc., but it is preferably in the range of 10 minutes to 90 minutes.

由本發明的感光性樹脂組成物所獲得的硬化膜可適宜用作乾蝕刻抗蝕劑。 The cured film obtained from the photosensitive resin composition of the present invention can be suitably used as a dry etching resist.

當將藉由(5)的後烘烤步驟進行熱硬化而獲得的硬化膜用作乾蝕刻抗蝕劑時，可進行灰化、電漿蝕刻、臭氧蝕刻等乾蝕刻處理作為蝕刻處理。 When the cured film obtained by thermally hardening the post-baking step of (5) is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, or ozone etching may be performed as an etching treatment.

(6)的乾蝕刻步驟中，可例示使基板暴露在反應氣體中來實施蝕刻的反應性氣體蝕刻處理、或利用電漿使反應氣體離子化．自由基化後實施蝕刻的反應性離子蝕刻(Reactive Ion Etching，RIE)等公知的乾蝕刻處理。所述氣體種類或蝕刻方法只要根據進行乾蝕刻的材料、所期望的速度或精度等而適宜選擇即可。另外，作為進行乾蝕刻的裝置，可使用公知的裝置。 In the dry etching step of (6), a reactive gas etching treatment for exposing the substrate to the reaction gas to perform etching, or ionizing the reaction gas with plasma may be exemplified. A known dry etching treatment such as reactive ion etching (RIE) which performs etching after radicalization. The gas type or etching method may be appropriately selected depending on the material to be dry-etched, the desired speed, accuracy, and the like. Further, as a device for performing dry etching, a known device can be used.

進而，在後烘烤步驟前，優選包括對經顯影的感光性樹脂組成物進行全面曝光的步驟，若加入對經顯影的感光性樹脂組成物的圖案全面照射光化射線，優選紫外線的步驟，則可藉由因光化射線的照射而產生的酸來促進交聯反應。 Further, before the post-baking step, it is preferable to include a step of performing total exposure of the developed photosensitive resin composition, and if a pattern of irradiating the actinic composition of the developed photosensitive resin composition is irradiated, ultraviolet rays are preferably added, The crosslinking reaction can be promoted by an acid generated by irradiation of actinic rays.

其次，對使用本發明的感光性樹脂組成物的硬化膜的形成方法進行具體說明。 Next, a method of forming a cured film using the photosensitive resin composition of the present invention will be specifically described.

[感光性樹脂組成物的製備方法] [Method for Preparing Photosensitive Resin Composition]

在特定樹脂及酸產生劑的必需成分中，視需要以規定的比例且以任意的方法混合溶劑，然後進行攪拌溶解來製備感光性樹脂組成物。例如，也可以在事先使特定樹脂或酸產生劑分別溶解在溶劑中而製成溶液後，將它們以規定的比例混合來製備感光性樹脂組成物。如以上般製備的感光性樹脂組成物的溶液 也可以在使用孔徑為0.1 μm的過濾器等進行過濾後，供於使用。 In the essential component of the specific resin and the acid generator, a solvent is mixed at a predetermined ratio and optionally in an arbitrary manner, and then stirred and dissolved to prepare a photosensitive resin composition. For example, a specific resin or an acid generator may be dissolved in a solvent to prepare a solution, and then they may be mixed in a predetermined ratio to prepare a photosensitive resin composition. a solution of a photosensitive resin composition prepared as above It can also be used after being filtered using a filter having a pore size of 0.1 μm or the like.

<塗布步驟及溶劑去除步驟> <Coating step and solvent removal step>

將感光性樹脂組成物塗布在規定的基板上，藉由減壓及/或加熱(預烤)來去除溶劑，由此可形成所期望的乾燥塗膜。作為所述基板，例如在液晶顯示裝置的製造中，可例示設置偏光板，進而視需要設置黑色矩陣層、彩色濾光片層，進而設置透明導電電路層而成的玻璃板等。朝基板上的塗布方法並無特別限定，但優選塗布，例如可使用狹縫塗布法、噴霧法、輥塗法、旋轉塗布法等方法。其中，就適合於大型基板這一觀點而言，優選狹縫塗布法。此處所謂大型基板，是指各邊為1 m以上的大小的基板。 The photosensitive resin composition is applied onto a predetermined substrate, and the solvent is removed by pressure reduction and/or heating (prebaking), whereby a desired dried coating film can be formed. In the production of the liquid crystal display device, for example, a polarizing plate is provided, and a black matrix layer, a color filter layer, and a transparent conductive circuit layer are provided as needed. The coating method on the substrate is not particularly limited, but is preferably applied, and for example, a method such as a slit coating method, a spray method, a roll coating method, or a spin coating method can be used. Among them, a slit coating method is preferred from the viewpoint of being suitable for a large substrate. Here, the large-sized substrate refers to a substrate having a size of 1 m or more on each side.

另外，(2)溶劑去除步驟的加熱條件為在未曝光部中的成分A中的構成單元(a1)中，酸分解性基分解，且不使成分A在鹼性顯影液中溶解的範圍，也根據各成分的種類或調配比而不同，但優選在70℃~120℃下加熱30秒~300秒左右。 In addition, (2) the heating condition of the solvent removal step is a range in which the acid-decomposable group is decomposed in the constituent unit (a1) in the component A in the unexposed portion, and the component A is not dissolved in the alkaline developing solution. It is also different depending on the type of each component or the mixing ratio, but it is preferably heated at 70 ° C to 120 ° C for about 30 seconds to 300 seconds.

<曝光步驟> <Exposure step>

在(3)曝光步驟中，對設置有感光性樹脂組成物的乾燥塗膜的基板照射規定的圖案的光化射線。曝光可經由遮罩而進行，也可以直接描繪規定的圖案。可優選使用具有300 nm以上、450 nm以下的波長的光化射線。在曝光步驟後，視需要也可以進行PEB。 In the (3) exposure step, the substrate on which the dried coating film of the photosensitive resin composition is provided is irradiated with actinic rays of a predetermined pattern. The exposure can be performed via a mask, or a predetermined pattern can be directly drawn. An actinic ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure step, PEB can also be performed as needed.

在利用光化射線的曝光中，可使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、雷射產生裝置、發光二極管(Light Emitting Diode，LED)光源等。 In the exposure using actinic rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a laser generating device, a light emitting diode (LED) light source, or the like can be used.

當使用水銀燈時，可優選使用具有g射線(436 nm)、i 射線(365 nm)、h射線(405 nm)等的波長的光化射線。水銀燈與雷射相比，就適合於大面積的曝光這一觀點而言優選。 When using a mercury lamp, it is preferable to use g-ray (436 nm), i Actinic rays of wavelengths such as rays (365 nm) and h rays (405 nm). Mercury lamps are preferred from the viewpoint of being suitable for large-area exposure as compared with lasers.

當使用雷射時，若為固體釔鋁石榴石(Yttrium Aluminium Garnet，YAG)雷射，則可適宜使用343 nm、355 nm，若為准分子雷射，則可適宜使用351 nm(XeF)，進而若為半導體雷射，則可適宜使用375 nm、405 nm。其中，就穩定性、成本等的觀點而言，更優選355 nm、405 nm。可對塗膜照射1次雷射、或分成多次來照射。另外，關於能量密度、脈衝寬度、雷射頻率、曝光裝置、及濾光片的具體例或優選的範圍，可列舉日本專利特開2011-186398號公報的段落0098~段落0100中所記載者。 When using a laser, if it is a solid Yttrium Aluminium Garnet (YAG) laser, it can be suitably used at 343 nm and 355 nm. If it is an excimer laser, it can be suitably used at 351 nm (XeF). Further, in the case of a semiconductor laser, 375 nm and 405 nm can be suitably used. Among them, from the viewpoints of stability, cost, and the like, 355 nm and 405 nm are more preferable. The coating film may be irradiated with one laser or divided into multiple times. Further, as a specific example or a preferred range of the energy density, the pulse width, the laser frequency, the exposure device, and the filter, those described in paragraphs 0098 to 0100 of JP-A-2011-186398 can be cited.

<顯影步驟> <Development step>

在(4)顯影步驟中，使用鹼性顯影液將曝光部區域去除而形成圖像圖案。作為用於顯影液的鹼性化合物，例如可使用：氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物類；碳酸鈉、碳酸鉀等鹼金屬碳酸鹽類；重碳酸鈉、重碳酸鉀等鹼金屬重碳酸鹽類；氫氧化四甲基銨、氫氧化四乙基銨、氫氧化膽鹼等氫氧化銨類；矽酸鈉、偏矽酸鈉等的水溶液。另外，也可以將向所述鹼類的水溶液中添加適當量甲醇或乙醇等水溶性有機溶劑或界面活性劑而成的水溶液用作顯影液。 In the (4) developing step, the exposed portion region is removed using an alkaline developing solution to form an image pattern. Examples of the basic compound used in the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate and heavy An alkali metal bicarbonate such as potassium carbonate; an ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; or an aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the base may be used as the developer.

只要可進行顯影，則顯影液的pH並無特別限制，但優選10.0~14.0。 The pH of the developer is not particularly limited as long as development is possible, but it is preferably from 10.0 to 14.0.

顯影時間優選30秒~180秒，另外，顯影的方法可為水坑式(puddle)顯影法、浸漬法、噴淋法等的任一種。顯影後，可進行10秒~90秒的流水清洗，而形成所期望的圖案。 The development time is preferably 30 seconds to 180 seconds, and the development method may be any one of a puddle development method, a dipping method, and a shower method. After development, a running water wash can be performed for 10 seconds to 90 seconds to form a desired pattern.

<後烘烤步驟(交聯步驟)> <Post-baking step (cross-linking step)>

使用加熱板或烘箱等加熱裝置，在規定的溫度，例如180℃~250℃下，以規定的時間，例如若在加熱板上則為5分鐘~60分鐘，若為烘箱則為30分鐘~90分鐘，對與藉由顯影而獲得的未曝光區域相對應的圖案進行加熱處理，由此使特定樹脂中的酸分解性基分解，而產生羧基及/或酚性羥基，然後與特定樹脂中的環氧基及/或氧雜環丁基即交聯性基進行反應，而進行交聯，由此可形成耐熱性、硬度等優異的保護膜或層間絕緣膜。另外，當進行加熱處理時，也可以在氮氣環境下進行，由此提升透明性。 Use a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C for a predetermined period of time, for example, 5 minutes to 60 minutes on a hot plate, or 30 minutes to 90 minutes for an oven. In a minute, the pattern corresponding to the unexposed area obtained by development is subjected to heat treatment, whereby the acid-decomposable group in the specific resin is decomposed to generate a carboxyl group and/or a phenolic hydroxyl group, and then in a specific resin. The epoxy group and/or the oxetanyl group, that is, the crosslinkable group, is reacted and crosslinked, whereby a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. Further, when the heat treatment is performed, it can also be carried out under a nitrogen atmosphere, thereby improving transparency.

再者，優選在加熱處理之前，利用光化射線對形成有圖案的基板進行再曝光後，進行後烘烤(再曝光/後烘烤)，由此從存在於未曝光部分中的酸產生劑(B)產生酸，並使其作為促進交聯的觸媒發揮功能。 Further, it is preferred to re-expose the patterned substrate with actinic rays before the heat treatment, and then perform post-baking (re-exposure/post-baking), thereby taking the acid generator present in the unexposed portion. (B) Producing an acid and functioning as a catalyst for promoting crosslinking.

即，本發明中的硬化膜的形成方法優選在顯影步驟與後烘烤步驟之間，包括利用光化射線進行再曝光的步驟。 That is, the method of forming the cured film in the present invention preferably includes a step of performing re-exposure with actinic rays between the developing step and the post-baking step.

再曝光步驟中的曝光只要利用與所述曝光步驟相同的方法來進行即可，在所述再曝光步驟中，優選對基板的由本發明的感光性樹脂組成物而形成有膜之側進行全面曝光。再曝光步驟的優選的曝光量為100 mJ/cm2~1,000 mJ/cm2。 The exposure in the re-exposure step may be carried out by the same method as the exposure step, and in the re-exposure step, it is preferable to perform overall exposure on the side of the substrate on which the photosensitive resin composition of the present invention is formed. . The preferred exposure amount of the re-exposure step is from 100 mJ/cm 2 to 1,000 mJ/cm 2 .

<乾蝕刻步驟> <dry etching step>

本發明中的乾蝕刻步驟是對具有在所述後烘烤步驟中，進行熱硬化而獲得的硬化膜的基板進行乾蝕刻的步驟。由本發明的感光性樹脂組成物所獲得的硬化膜由於耐乾蝕刻性優異，因此即便暴露在乾蝕刻條件下，膜減少量也少。 The dry etching step in the present invention is a step of dry etching a substrate having a cured film obtained by thermally hardening in the post-baking step. Since the cured film obtained from the photosensitive resin composition of the present invention is excellent in dry etching resistance, the amount of film reduction is small even when exposed to dry etching conditions.

作為可用於本發明的被乾蝕刻材料，包括矽、二氧化矽、氮化矽、氧化鋁、玻璃、玻璃-陶瓷、砷化鎵、磷化銦、銅、 鋁、鎳、鐵、鋼、銅-矽合金、銦-錫氧化物被覆玻璃；含有金屬、半導體、及絕緣材料的圖案化區域的任意的基板等，但並不限定於這些材料。 As the dry etching material usable in the present invention, including cerium, cerium oxide, cerium nitride, aluminum oxide, glass, glass-ceramic, gallium arsenide, indium phosphide, copper, Aluminum, nickel, iron, steel, copper-bismuth alloy, indium-tin oxide coated glass, and any substrate or the like containing a patterned region of a metal, a semiconductor, or an insulating material, but is not limited thereto.

作為電漿的產生方法，並無特別限制，減壓電漿法、大氣電漿法的任一種均可進行塗布。 The method for producing the plasma is not particularly limited, and any of the reduced pressure plasma method and the atmospheric plasma method can be applied.

另外，在電漿蝕刻中，例如可優選使用選自氦氣、氫氣、氪氣、氙氣中的惰性氣體，O2，CF4，C2F4，N2，CO2，SF6，CHF3，至少含有O、N、F或Cl的反應性氣體。 Further, in the plasma etching, for example, an inert gas selected from the group consisting of helium, hydrogen, helium, and neon, O 2 , CF 4 , C 2 F 4 , N 2 , CO 2 , SF 6 , CHF 3 may be preferably used. a reactive gas containing at least O, N, F or Cl.

在乾蝕刻步驟中，例如當基底為SiNx或SiO2等矽系的層時，優選使用O2與CF4、SiF6等氟系的反應氣體。 In the dry etching step, for example, when the substrate is a lanthanoid layer such as SiN x or SiO 2 , a fluorine-based reaction gas such as O 2 , CF 4 or SiF 6 is preferably used.

另外，乾蝕刻步驟中的基板與所述塗布步驟中的基板可以是相同的基板，也可以是不同的基板。例如，也可以將所述塗布步驟中的基板作為臨時的基板，在其他基板上對該硬化膜進行轉印等，直至所述乾蝕刻步驟之前為止。 In addition, the substrate in the dry etching step and the substrate in the coating step may be the same substrate or different substrates. For example, the substrate in the coating step may be used as a temporary substrate, and the cured film may be transferred or the like on another substrate until the dry etching step.

另外，將本發明的感光性樹脂組成物硬化而獲得的硬化膜也適宜用作乾蝕刻或濕蝕刻等蝕刻處理時的犧牲層，當在蝕刻處理後將所述硬化膜剝離時，可進行利用灰化等已知的乾式電漿製程、或鹼性化學品處理等已知的濕式製程的剝離。本發明的硬化膜由於經過烘烤步驟而硬化，因此特優選利用乾式電漿製程的剝離。 In addition, the cured film obtained by curing the photosensitive resin composition of the present invention is also suitably used as a sacrificial layer in an etching treatment such as dry etching or wet etching, and can be used when the cured film is peeled off after the etching treatment. Peeling of known wet processes such as ashing, or known wet processes such as alkaline chemical treatment. Since the cured film of the present invention is hardened by the baking step, it is particularly preferable to use the peeling of the dry plasma process.

即便在用作作為蝕刻用抗蝕劑的平面抗蝕劑的情況下，也適宜使用氧電漿處理，但也可以藉由利用藥液的加熱處理來將抗蝕劑剝離去除。 Even when it is used as a planar resist as a resist for etching, an oxygen plasma treatment is preferably used, but the resist may be peeled off by heat treatment using a chemical liquid.

將本發明的感光性樹脂組成物硬化而獲得的硬化膜可特別適宜地用作乾蝕刻抗蝕劑。 The cured film obtained by curing the photosensitive resin composition of the present invention can be suitably used as a dry etching resist.

本發明的硬化膜是將本發明的感光性樹脂組成物硬化而 獲得的硬化膜，可適宜地用作層間絕緣膜。另外，本發明的硬化膜優選藉由本發明的硬化膜的形成方法所獲得的硬化膜。 The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The obtained cured film can be suitably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

藉由本發明的感光性樹脂組成物，可獲得具有高感光度、顯影時的殘渣的產生得到抑制、且具有平滑性優異的表面的硬化膜，該硬化膜作為層間絕緣膜有用。另外，使用本發明的感光性樹脂組成物而成的層間絕緣膜具有高透明性，可形成形狀良好的圖案形狀，另外，其表面的平滑性也優異，因此在有機EL顯示裝置或液晶顯示裝置的用途中有用。 According to the photosensitive resin composition of the present invention, a cured film having high sensitivity and suppressing generation of residue during development and having excellent smoothness can be obtained, and the cured film is useful as an interlayer insulating film. In addition, the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency, can form a shape having a good shape, and is excellent in surface smoothness, and therefore is used in an organic EL display device or a liquid crystal display device. Useful for the purpose.

作為可塗布本發明的感光性樹脂組成物的有機EL顯示裝置或液晶顯示裝置，除將使用本發明的感光性樹脂組成物所形成的硬化膜用作平坦化膜或保護膜、層間絕緣膜以外，並無特別限制，可列舉採用各種構造的公知的各種有機EL顯示裝置或液晶顯示裝置。 In the organic EL display device or the liquid crystal display device to which the photosensitive resin composition of the present invention is applied, a cured film formed using the photosensitive resin composition of the present invention is used as a planarizing film, a protective film, or an interlayer insulating film. There is no particular limitation, and various known organic EL display devices or liquid crystal display devices having various structures can be cited.

例如，作為本發明的有機EL顯示裝置及液晶顯示裝置所具備的TFT(Thin-Film Transistor)的具體例，可列舉：非晶矽-TFT、低溫多晶矽-TFT、氧化物半導體TFT等。本發明的硬化膜由於電特性優異，因此可與這些TFT組合後優選使用。 For example, examples of the TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

另外，作為本發明的液晶顯示裝置可採用的液晶顯示裝置的方式，可列舉：扭轉向列(Twisted Nematic，TN)方式、垂直配向(Vertical Alignment，VA)方式、共面切換(In-Plane Switching，IPS)方式、邊緣場切換(Fringe Field Switching，FFS)方式、光學補償彎曲(Optically Compensated Bend，OCB)方式等。 Further, examples of the liquid crystal display device which can be used in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and a coplanar switching (In-Plane Switching). , IPS) mode, Fringe Field Switching (FFS) mode, Optically Compensated Bend (OCB) mode, etc.

另外，作為本發明的液晶顯示裝置可採用的液晶配向膜的具體的配向方式，可列舉摩擦配向法、光配向法等。另外，也可以藉由日本專利特開2003-149647或日本專利特開 2011-257734中所記載的聚合物穩定配向(Polymer Sustained Alignment，PSA)技術而得到聚合物配向支持。 In addition, as a specific alignment method of the liquid crystal alignment film which can be used for the liquid crystal display device of the present invention, a rubbing alignment method, a photoalignment method, and the like can be given. In addition, it can also be opened by Japanese Patent Laid-Open No. 2003-149647 or Japanese Patent Laid-Open The Polymer Disstained Alignment (PSA) technique described in 2011-257734 provides polymer alignment support.

另外，本發明的感光性樹脂組成物及本發明的硬化膜並不限定於所述用途，可用於各種用途。例如，除平坦化膜或保護膜、層間絕緣膜以外，也可適宜地用於用以將液晶顯示裝置中的液晶層的厚度保持為固定的墊片、或固體攝像元件中設置在彩色濾光片上的微透鏡、蝕刻用抗蝕劑，特優選乾蝕刻用抗蝕劑等。 Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the planarization film or the protective film or the interlayer insulating film, it may be suitably used for a spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device to be fixed, or for color filter provided in the solid-state imaging device. The on-chip microlens and the etching resist are preferably a dry etching resist or the like.

圖1表示使用本發明的感光性樹脂組成物的有機EL顯示裝置的一例的構成概念圖。表示底部發光型的有機EL顯示裝置中的基板的示意剖面圖，且具有平坦化膜4。 FIG. 1 is a conceptual view showing an example of an organic EL display device using the photosensitive resin composition of the present invention. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and having a planarization film 4.

在玻璃基板6上形成底柵型的TFT1，並在覆蓋該TFT1的狀態下形成包含Si3N4的絕緣膜3。在絕緣膜3上形成此處省略了圖示的接觸孔後，經由該接觸孔而在絕緣膜3上形成連接於TFT1的配線2(高度為1.0 μm)。配線2是用以將TFT1間、或將其後的步驟中形成的有機EL元件與TFT1加以連接的線。 A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si 3 N 4 is formed in a state of covering the TFT 1. After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.

進而，為了使由配線2的形成所產生的凹凸平坦化，在埋入由配線2所產生的凹凸的狀態下，在絕緣膜3上形成平坦化膜4。 Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness generated by the wiring 2 is buried.

在平坦化膜4上形成底部發光型的有機EL元件。即，使包含ITO的第一電極5經由接觸孔7連接於配線2而形成在平坦化膜4上。第一電極5相當於有機EL元件的陽極。 A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. The first electrode 5 corresponds to the anode of the organic EL element.

形成覆蓋第一電極5的周緣的形狀的絕緣膜8，藉由設置該絕緣膜8，可防止第一電極5與其後的步驟中所形成的第二電極之間的短路。 The insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

進而，雖然圖1中未圖示，但經由所期望的圖案遮罩而依次進行蒸鍍來設置電洞傳輸層、有機發光層、電子傳輸層，繼而，在基板上方的整個面上形成包含Al的第二電極，然後藉由使用密封用玻璃板與紫外線硬化型環氧樹脂進行貼合來密封，而獲得在各有機EL元件上連接用以對其進行驅動的TFT1而成的主動矩陣型的有機EL顯示裝置。 Further, although not shown in FIG. 1, the hole transport layer, the organic light-emitting layer, and the electron transport layer are provided by sequentially performing vapor deposition through a desired pattern mask, and then Al is formed on the entire upper surface of the substrate. The second electrode is then sealed by bonding with a glass plate for sealing and an ultraviolet curable epoxy resin to obtain an active matrix type in which TFTs 1 for driving the organic EL elements are connected to each other. Organic EL display device.

圖2是表示主動矩陣方式的液晶顯示裝置10的一例的概念剖面圖。該彩色液晶顯示裝置10為背面具有背光單元12的液晶面板，液晶面板配置有與配置在貼附有偏光膜的2片玻璃基板14、玻璃基板15之間的所有像素相對應的TFT16的元件。在形成於玻璃基板上的各元件中，藉由形成在硬化膜17中的接觸孔18而佈線有形成像素電極的ITO透明電極19。在ITO透明電極19上設置有液晶20的層、及配置有黑色矩陣的RGB彩色濾光片22。 FIG. 2 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is provided with an element of the TFT 16 corresponding to all the pixels disposed between the two glass substrates 14 and the glass substrate 15 to which the polarizing film is attached. Among the elements formed on the glass substrate, the ITO transparent electrode 19 forming the pixel electrode is wired by the contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and an RGB color filter 22 in which a black matrix is disposed are provided on the ITO transparent electrode 19.

實例 Instance

其次，藉由實例來更具體地說明本發明。但是，本發明並不由這些實例限定。再者，只要事先無特別說明，則“份”、“%”為重量基準。 Next, the present invention will be more specifically described by way of examples. However, the invention is not limited by these examples. In addition, unless otherwise indicated, "part" and "%" are the weight basis.

<合成例1> <Synthesis Example 1>

向具備冷卻管、攪拌機的燒瓶中添加二乙二醇乙基甲醚150重量份，並在氮氣環境下升溫至90℃。將作為單體成分的甲基丙烯酸1-乙氧基乙酯41.3重量份、甲基丙烯酸3-乙基-3-氧雜環丁基甲酯31.0重量份、甲基丙烯酸5.6重量份、甲基丙烯酸2-乙基己酯17.0重量份，及作為聚合起始劑的二甲基-2,2'-偶氮雙(2-甲基丙酸酯)(和光純藥製造)10.0重量份溶解並歷時2小時滴加在該溶液中。滴加結束後攪拌2小時。進而向該 溶液中添加二甲基-2,2'-偶氮雙(2-甲基丙酸酯)2.5重量份，進而攪拌2小時後使反應結束。由此獲得共聚物A-1。重量平均分子量為11,000。 150 parts by weight of diethylene glycol ethyl methyl ether was added to a flask equipped with a cooling tube and a stirrer, and the temperature was raised to 90 ° C under a nitrogen atmosphere. 41.3 parts by weight of 1-ethoxyethyl methacrylate as a monomer component, 31.0 parts by weight of 3-ethyl-3-oxetanyl methacrylate, 5.6 parts by weight of methacrylic acid, and methacrylic acid 2 17.0 parts by weight of ethylhexyl ester, and 10.0 parts by weight of dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were dissolved and lasted for 2 An hour is added dropwise to the solution. After the completion of the dropwise addition, the mixture was stirred for 2 hours. Further to 2.5 parts by weight of dimethyl-2,2'-azobis(2-methylpropionate) was added to the solution, and the mixture was further stirred for 2 hours to complete the reaction. Thus, copolymer A-1 was obtained. The weight average molecular weight was 11,000.

<合成例2~合成例38> <Synthesis Example 2 to Synthesis Example 38>

除變更所使用的單體及其量以外，以與合成例1相同的方式分別合成下述表中所示的共聚物A-2~共聚物A-15、共聚物B-1~共聚物B-16、及共聚物b-1~共聚物b-5。所合成的各共聚物的組成比(莫耳%)及重量平均分子量(Mw)如下述表中所示。 The copolymer A-2 to copolymer A-15 and copolymer B-1 to copolymer B shown in the following tables were synthesized in the same manner as in Synthesis Example 1, except that the monomers used and the amounts thereof were changed. -16, and copolymer b-1 to copolymer b-5. The composition ratio (% by mole) and the weight average molecular weight (Mw) of each of the synthesized copolymers are shown in the following table.

表1及表2中的略號如下所述。 The abbreviations in Tables 1 and 2 are as follows.

MAEVE：甲基丙烯酸1-乙氧基乙酯 MAEVE: 1-ethoxyethyl methacrylate

MATHF：甲基丙烯酸四氫-2H-呋喃-2-基酯 MATHF: tetrahydro-2H-furan-2-yl methacrylate

MACHOE：甲基丙烯酸1-(環己氧基)乙酯 MACHOE: 1-(cyclohexyloxy)ethyl methacrylate

MATHP：甲基丙烯酸四氫-2H-吡喃-2-基酯 MATHP: tetrahydro-2H-pyran-2-yl methacrylate

PHSEVE：對羥基苯乙烯的1-乙氧基乙基保護體 PHSEVE: 1-Ethoxyethyl Protector of p-Hydroxystyrene

OXE-30：甲基丙烯酸3-乙基-3-氧雜環丁基甲酯(大阪有機化學工業(股份)製造) OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (Manufactured by Osaka Organic Chemical Industry Co., Ltd.)

GMA：甲基丙烯酸縮水甘油酯 GMA: glycidyl methacrylate

NBMA：正丁氧基甲基丙烯醯胺 NBMA: n-butoxymethyl acrylamide

VBGE：對乙烯基苄基縮水甘油醚 VBGE: p-vinylbenzyl glycidyl ether

MAA：甲基丙烯酸 MAA: Methacrylic acid

PHS：對羥基苯乙烯 PHS: p-hydroxystyrene

HEMA：甲基丙烯酸2-乙基己酯 HEMA: 2-ethylhexyl methacrylate

THFFMA：甲基丙烯酸四氫糠酯 THFFMA: tetrahydrofurfuryl methacrylate

St：苯乙烯 St: Styrene

α-MeSt：α-甲基苯乙烯 α-MeSt: α-methylstyrene

MMA：甲基丙烯酸甲酯 MMA: Methyl methacrylate

DCPM：甲基丙烯酸(三環[5.2.1.02,6]癸烷-8-基)酯 DCPM: methacrylic acid (tricyclo[5.2.1.0 2,6 ]decane-8-yl) ester

(實例1~實例143及比較例1~比較例34) (Example 1 to Example 143 and Comparative Example 1 to Comparative Example 34)

以固體成分濃度變成27 wt%的方式，使下述表中所記載的量(固體成分)溶解在二乙二醇甲基乙基醚：丙二醇單甲醚醋酸酯=1：1(重量比)的混合溶劑中後，利用孔徑為0.2 μm的薄膜過濾器進行過濾而分別製成各感光性樹脂組成物。 The amount (solid content) described in the following table was dissolved in diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1:1 (weight ratio) so that the solid content concentration became 27 wt%. After the mixed solvent, the film was filtered through a membrane filter having a pore size of 0.2 μm to prepare each photosensitive resin composition.

所述表中，各種添加劑的略號如下所述。 In the table, the abbreviations of the various additives are as follows.

C-1：下述結構的化合物(合成品) C-1: a compound of the following structure (synthetic)

C-2：下述結構的化合物(合成品) C-2: a compound of the following structure (synthetic)

C-3：下述結構的化合物(合成品) C-3: a compound of the following structure (synthetic)

C-4：CGI-1397(BASF公司製造) C-4: CGI-1397 (manufactured by BASF Corporation)

C-5：下述結構的化合物(根據日本專利特表2002-528451號公報的段落0108中所記載的方法合成) C-5: a compound of the following structure (synthesized according to the method described in paragraph 0108 of JP-A-2002-528451)

C-6：PAI-1001(綠化學(Midori Kagaku)(股份)製造) C-6: PAI-1001 (Midori Kagaku (share) manufacturing)

C-7：4,7-二-正丁氧基-1-萘基四氫噻吩鎓三氟甲磺酸酯 C-7: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate

<C-1的合成> <Synthesis of C-1>

向2-萘酚(10 g)、氯苯(30 mL)的懸浮溶液中添加氯化鋁(10.6 g)、2-氯丙醯氯(10.1 g)，將混合液加熱至40℃後反應2小時。在冰浴冷卻下，向反應液中滴加4N HCl水溶液(60 mL)，然後添加醋酸乙酯(50 mL)來進行分液。向有機層中添加碳酸鉀(19.2 g)，在40℃下反應1小 時後，添加2N HCl水溶液(60 mL)來進行分液，將有機層濃縮後，利用二異丙醚(10 mL)對結晶進行再打漿(reslurry)，然後進行過濾、乾燥而獲得酮化合物(6.5 g)。 Add aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and heat the mixture to 40 ° C. hour. Under ice cooling, a 4N aqueous HCl solution (60 mL) was added dropwise to the mixture, and ethyl acetate (50 mL) was added to carry out liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, and the reaction was carried out at 40 ° C for 1 hour. After that, a 2N aqueous HCl solution (60 mL) was added to carry out liquid separation, and the organic layer was concentrated, and the crystals were re-slurryed with diisopropyl ether (10 mL), followed by filtration and drying to obtain a ketone compound ( 6.5 g).

向所獲得的酮化合物(3.0 g)、甲醇(18 mL)的懸浮溶液中添加醋酸(7.3 g)、50 wt%羥基胺水溶液(8.0 g)，並加熱回流10小時。放置冷卻後，添加水(50 mL)，對所析出的結晶進行過濾，利用冷甲醇進行清洗後，加以乾燥而獲得肟化合物(2.4 g)。 To a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), acetic acid (7.3 g), 50 wt% aqueous hydroxyamine (8.0 g) was added, and heated under reflux for 10 hours. After standing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g).

使所獲得的肟化合物(1.8 g)溶解在丙酮(20 mL)中，在冰浴冷卻下添加三乙胺(1.5 g)、對甲苯磺醯氯(2.4 g)，升溫至室溫後反應1小時。向反應液中添加水(50 mL)，對所析出的結晶進行過濾後，利用甲醇(20 mL)進行再打漿，然後進行過濾、乾燥而獲得C-1(2.3 g)。 The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the mixture was warmed to room temperature and then reacted. hour. Water (50 mL) was added to the reaction mixture, and the precipitated crystals were filtered, and then re-pulped with methanol (20 mL), then filtered and dried to give C-1 (2.3 g).

再者，C-1的1H-NMR光譜(300 MHz，CDCl3)為δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6(dd,1H),7.4(dd,1H),7.3(d,2H),7.1(d,1H),5.6(q,1H),2.4(s,3H),1.7(d,3H)。 Furthermore, the 1 H-NMR spectrum of C-1 (300 MHz, CDCl 3 ) is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

<C-2的合成> <Synthesis of C-2>

使2-萘酚(20 g)溶解在N,N-二甲基乙醯胺(150 mL)中，添加碳酸鉀(28.7 g)、2-溴辛酸乙酯(52.2 g)後在100℃下反應2小時。向反應液中添加水(300 mL)、醋酸乙酯(200 mL)來進行分液，將有機層濃縮後，添加48 wt%氫氧化鈉水溶液(23 g)、乙醇(50 mL)、水(50 mL)，並反應2小時。將反應液倒出至1N HCl水溶液(500 mL) 中，對所析出的結晶進行過濾、水洗而獲得羧酸粗產物後，添加多磷酸30 g並在170℃下反應30分鐘。將反應液倒出至水(300 mL)中，添加醋酸乙酯(300 mL)來進行分液，將有機層濃縮後藉由矽膠柱色譜法來進行精製，而獲得酮化合物(10 g)。 2-naphthol (20 g) was dissolved in N,N-dimethylacetamide (150 mL), and potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) were added at 100 ° C. Reaction for 2 hours. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction mixture for liquid separation, and the organic layer was concentrated, then 48 wt% aqueous sodium hydroxide (23 g), ethanol (50 mL), and water ( 50 mL) and react for 2 hours. The reaction solution was poured into 1N aqueous HCl (500 mL) Then, the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid product, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C for 30 minutes. The reaction liquid was poured into water (300 mL), and ethyl acetate (300 mL) was added to carry out liquid separation. The organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

向所獲得的酮化合物(10.0 g)、甲醇(100 mL)的懸浮溶液中添加醋酸鈉(30.6 g)、鹽酸羥基胺(25.9g)、硫酸鎂(4.5 g)，並加熱回流24小時。放置冷卻後，添加水(150 mL)、醋酸乙酯(150 mL)來進行分液，利用水80 mL對有機層進行4次分液，加以濃縮後藉由矽膠柱色譜法來進行精製，而獲得肟化合物(5.8 g)。 Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the obtained ketone compound (10.0 g) and methanol (100 mL), and heated under reflux for 24 hours. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated, and purified by silica gel column chromatography. A hydrazine compound (5.8 g) was obtained.

與C-1同樣地，對所獲得的肟(3.1 g)進行磺酸酯化，而獲得C-2(3.2 g)。 The obtained hydrazine (3.1 g) was subjected to sulfonation in the same manner as in C-1 to obtain C-2 (3.2 g).

再者，C-2的1H-NMR光譜(300 MHz，CDCl3)為δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6(dd,1H),7.5(dd,1H),7.3(d,2H),7.1(d,1H),5.6(dd,1H),2.4(s,3H),2.2(ddt,1H),1.9(ddt,1H),1.4~1.2(m,8H),0.8(t,3H)。 Furthermore, the 1 H-NMR spectrum of C-2 (300 MHz, CDCl 3 ) is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4~1.2 (m, 8H), 0.8 (t, 3H).

<C-3的合成> <Synthesis of C-3>

除使用苯磺醯氯來代替C-1中的對甲苯磺醯氯以外，以與C-1相同的方式合成C-3。 C-3 was synthesized in the same manner as C-1 except that benzenesulfonium chloride was used instead of p-toluenesulfonyl chloride in C-1.

再者，C-3的1H-NMR光譜(300 MHz，CDCl3)為δ=8.3(d,1H),8.1(d,2H),7.9(d,1H),7.8(d,1H),7.7-7.5(m,4H),7.4(dd,1H),7.1(d.1H),5.6(q,1H),1.7(d,3H)。 Furthermore, the 1 H-NMR spectrum of C-3 (300 MHz, CDCl 3 ) is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (d, 3H).

D-1：DBA(9,10-二丁氧基蒽，川崎化成工業(股份) 製造) D-1: DBA (9,10-dibutoxy oxime, Kawasaki Chemical Industry Co., Ltd.) Manufacturing)

E-1：1,5-二氮雙環[4,3,0]-5-壬烯(東京化成工業(股份)製造) E-1:1,5-diazabicyclo[4,3,0]-5-pinene (manufactured by Tokyo Chemical Industry Co., Ltd.)

E-2：下述結構的化合物 E-2: a compound of the following structure

S-1：下述化合物(製造商：信越化學工業(股份)，型號：KBE-3026) S-1: The following compounds (manufacturer: Shin-Etsu Chemical Co., Ltd., model: KBE-3026)

S-6：下述化合物(製造商：東麗道康寧(股份)，型號：Z6920) S-6: The following compounds (manufacturer: Toray Dow Corning (share), model: Z6920)

S-7：下述化合物(製造商：信越化學工業(股份)，型號：KBE-846) S-7: The following compounds (manufacturer: Shin-Etsu Chemical Co., Ltd., model: KBE-846)

S-8：下述化合物(製造商：信越化學工業(股份)，型號：KBM-9659) S-8: The following compounds (manufacturer: Shin-Etsu Chemical Co., Ltd., model: KBM-9659)

F-1：JER150S65(三菱化學(股份)製造) F-1: JER150S65 (Mitsubishi Chemical (stock) manufacturing)

F-2：JER1031S(三菱化學(股份)製造) F-2: JER1031S (Mitsubishi Chemical (stock) manufacturing)

G-1：3-縮水甘油氧基丙基三甲氧基矽烷(KBM-403，信越化學工業(股份)製造) G-1: 3-glycidoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

H-1：下述結構的化合物 H-1: a compound of the following structure

<耐化學品性(耐剝離液性)的評價> <Evaluation of chemical resistance (peeling resistance)>

將各感光性樹脂組成物狹縫塗布在玻璃基板(Corning1737，0.7 mm厚(康寧(Corning)公司製造))上後，在加熱板上以90℃/120秒進行加熱，由此去除溶劑，而形成膜厚為4.0 μm的感光性樹脂組成物層。 Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then heated on a hot plate at 90 ° C / 120 seconds to remove the solvent. A photosensitive resin composition layer having a film thickness of 4.0 μm was formed.

利用佳能(Canon)(股份)製造的PLA-501F曝光機(超高壓水銀燈)，以累計照射量達到300 mJ/cm2(能量強度：20 mW/cm2，i射線)的方式對所獲得的感光性樹脂組成物層進行曝光，其後，利用烘箱在230℃下對該基板進行1小時加熱而獲得硬化膜。 A PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon (share) was used to obtain a total irradiation amount of 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray). The photosensitive resin composition layer was exposed, and thereafter, the substrate was heated at 230 ° C for 1 hour in an oven to obtain a cured film.

在60℃下，使該硬化膜在單乙醇胺中浸漬5分鐘，撈起該膜並拭去表面的液體後，立即測定膜厚。對浸漬前的膜厚與浸漬後的膜厚進行比較，並以百分率來表述增加的比例。將結果示於下述表中。數值越小，硬化膜的耐剝離液性越良好，優選A或B。 The cured film was immersed in monoethanolamine at 60 ° C for 5 minutes, and after picking up the film and wiping off the liquid on the surface, the film thickness was measured immediately. The film thickness before immersion was compared with the film thickness after immersion, and the increased ratio was expressed in percentage. The results are shown in the following table. The smaller the value, the better the peeling resistance of the cured film, and A or B is preferable.

膨潤率(%)=浸漬後的膜厚(μm)/浸漬前的膜厚(μm)×100 Swelling rate (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100

A：100%以上、未滿102% A: 100% or more, less than 102%

B：102%以上、未滿105% B: 102% or more, less than 105%

C：105%以上、未滿110% C: 105% or more and less than 110%

D：110%以上、未滿115% D: 110% or more, less than 115%

E：115%以上 E: 115% or more

<耐化學品性(耐NMP性)的評價> <Evaluation of chemical resistance (NMP resistance)>

將各感光性樹脂組成物狹縫塗布在玻璃基板(Corning1737，0.7 mm厚(康寧公司製造))上後，在加熱板上以90℃/120秒進行加熱，由此去除溶劑，而形成膜厚為4.0 μm的感光性樹脂組成物層。 Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then heated on a hot plate at 90 ° C / 120 seconds to remove the solvent to form a film thickness. It is a photosensitive resin composition layer of 4.0 μm.

利用佳能(股份)製造的PLA-501F曝光機(超高壓水銀燈)，以累計照射量達到300 mJ/cm2(能量強度：20 mW/cm2，i射線)的方式對所獲得的感光性樹脂組成物層進行曝光，其後，利用烘箱在230℃下對該基板進行1小時加熱而獲得硬化膜。 Using the PLA-501F exposure machine (Ultra High Pressure Mercury Lamp) manufactured by Canon (share), the obtained photosensitive resin was obtained in such a manner that the cumulative irradiation amount reached 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray). The composition layer was exposed, and thereafter, the substrate was heated at 230 ° C for 1 hour in an oven to obtain a cured film.

在80℃下，使該硬化膜在NMP中浸漬10分鐘，撈起該膜並拭去表面的液體後，立即測定膜厚。對浸漬前的膜厚與浸漬後的膜厚進行比較，並以百分率來表述增加的比例。將結果示於下述表中。數值越小，硬化膜的耐NMP性越良好，優選A或B。 The cured film was immersed in NMP at 80 ° C for 10 minutes, and after picking up the film and wiping off the liquid on the surface, the film thickness was measured immediately. The film thickness before immersion was compared with the film thickness after immersion, and the increased ratio was expressed in percentage. The results are shown in the following table. The smaller the value, the better the NMP resistance of the cured film, and A or B is preferable.

膨潤率(%)=浸漬後的膜厚(μm)/浸漬前的膜厚(μm)×100 Swelling rate (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100

A：100%以上、未滿102% A: 100% or more, less than 102%

B：102%以上、未滿105% B: 102% or more, less than 105%

C：105%以上、未滿110% C: 105% or more and less than 110%

D：110%以上、未滿115% D: 110% or more, less than 115%

E：115%以上 E: 115% or more

<耐乾蝕刻性> <dry etching resistance>

將各感光性樹脂組成物狹縫塗布在玻璃基板(Corning1737，0.7 mm厚(康寧公司製造))上後，在加熱板上以90℃/120秒進行加熱，由此去除溶劑，而形成膜厚為4.0 μm的感光性樹脂組成物層。 Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then heated on a hot plate at 90 ° C / 120 seconds to remove the solvent to form a film thickness. It is a photosensitive resin composition layer of 4.0 μm.

利用佳能(股份)製造的PLA-501F曝光機(超高壓水銀燈)，以累計照射量達到300 mJ/cm2(能量強度：20 mW/cm2，i射線)的方式對所獲得的感光性樹脂組成物層進行曝光，其後，利用烘箱在230℃下對該基板進行1小時加熱而獲得硬化膜。使用乾蝕刻裝置“CDE-80N(芝浦機電(Shibaura Mechatronics)(股份)製造)”，利用CF4(50 ml/min)、O2(10 ml/min)作為蝕刻氣體，以輸出功率為400 mW，蝕刻時間為90秒的條件對該硬化膜進行乾蝕刻。根據其膜減少量而算出蝕刻速度。數值越小，耐乾蝕刻性越高，優選A或B。 Using the PLA-501F exposure machine (Ultra High Pressure Mercury Lamp) manufactured by Canon (share), the obtained photosensitive resin was obtained in such a manner that the cumulative irradiation amount reached 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray). The composition layer was exposed, and thereafter, the substrate was heated at 230 ° C for 1 hour in an oven to obtain a cured film. Using a dry etching device "CDE-80N (Shibaura Mechatronics (manufactured by Shibaura Mechatronics)"), using CF 4 (50 ml/min), O 2 (10 ml/min) as an etching gas, with an output power of 400 mW The cured film was dry etched under conditions of an etching time of 90 seconds. The etching rate was calculated from the amount of film reduction. The smaller the value, the higher the dry etching resistance, and A or B is preferable.

A：30 Å/秒以上、未滿35 Å/秒 A: 30 Å/sec or more, less than 35 Å/sec

B：35 Å/秒以上、未滿40 Å/秒 B: 35 Å/sec or more, less than 40 Å/sec

C：40 Å/秒以上、未滿45 Å/秒 C: 40 Å/sec or more, less than 45 Å/sec

<實例144> <Example 144>

在日本專利第3321003號公報的圖1中所記載的主動矩陣型液晶顯示裝置中，如以下般形成硬化膜17作為層間絕緣膜，而獲得實例144的液晶顯示裝置。即，使用實例1的感光性樹脂組成物，形成硬化膜17作為層間絕緣膜。 In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3,321,003, a cured film 17 is formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 144 is obtained. That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film.

即，作為提升日本專利第3321003號公報的第58段的基板與層間絕緣膜17的潤濕性的前處理，使基板在六甲基二矽氮烷(Hexamethyldisilazane，HMDS)蒸氣下暴露30秒，其後，旋塗實例1的感光性樹脂組成物，然後在90℃下在加熱板上預烤2分鐘來使溶劑揮發，而形成膜厚為3 μm的感光性樹脂組成物層。繼而，使用佳能(股份)製造的MPA 5500CF(高壓水銀燈)，以達到40 mJ/cm2(能量強度：20 mW/cm2，i射線)的方式，經由10 μmφ的孔圖的遮罩對所獲得的感光性樹脂組成物層進行曝光。然後，利用鹼性顯影液(0.4%的氫氧化四甲基銨水溶液)對曝光後的感光性樹脂組成物層進行23℃/60秒顯影後，利用超純水沖洗20秒。繼而，使用超高壓水銀燈，以累計照射量達到300 mJ/cm2(能量強度：20 mW/cm2，i射線)的方式進行全面曝光，其後，利用烘箱在230℃下對該基板進行30分鐘加熱而獲得硬化膜。 In other words, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in the 58th paragraph of Japanese Patent No. 3321003, the substrate is exposed to Hexamethyldisilazane (HMDS) vapor for 30 seconds. Thereafter, the photosensitive resin composition of Example 1 was spin-coated, and then prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, MPA 5500CF (high-pressure mercury lamp) manufactured by Canon (share) was used to reach a mask of 10 μmφ through a hole pattern of 40 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray). The obtained photosensitive resin composition layer was exposed. Then, the exposed photosensitive resin composition layer was developed at 23 ° C / 60 seconds using an alkaline developing solution (0.4% aqueous solution of tetramethylammonium hydroxide), and then rinsed with ultrapure water for 20 seconds. Then, using an ultrahigh pressure mercury lamp, total exposure was performed in such a manner that the cumulative irradiation amount reached 300 mJ/cm 2 (energy intensity: 20 mW/cm 2 , i-ray), and thereafter, the substrate was subjected to 30° at 230° C. in an oven. The hardened film was obtained by heating in minutes.

塗布所述感光性樹脂組成物時的塗布性良好，在曝光、顯影、煆燒後所獲得的硬化膜中，未看到皺褶或裂痕的產生。 The coating property at the time of applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and calcination.

對所獲得的液晶顯示裝置施加驅動電壓的結果，可知 其為顯現良好的顯示特性、且可靠性高的液晶顯示裝置。 As a result of applying a driving voltage to the obtained liquid crystal display device, it is known This is a liquid crystal display device which exhibits good display characteristics and is highly reliable.

<實例145> <Example 145>

與實例144相比僅變更以下的製程，而獲得相同的液晶顯示裝置。即，即便在省略作為基板的前處理的六甲基二矽氮烷(HMDS)處理，塗布實例52的感光性樹脂組成物的情況下，所獲得的硬化膜也是無圖案的缺失或剝落的良好的狀態。另外，與實例144同樣地，液晶顯示裝置的性能也良好。可認為其原因在於本發明的組成物與基板的密接性優異。就提升生產性的觀點而言，也優選省略所述基板的前處理的步驟。 The same process was changed as in the example 144, and the same liquid crystal display device was obtained. That is, even in the case of omitting the pretreated hexamethyldioxane (HMDS) treatment as the substrate and applying the photosensitive resin composition of Example 52, the obtained cured film is also excellent in pattern-free missing or peeling. status. Further, similarly to the example 144, the performance of the liquid crystal display device was also good. This is considered to be because the composition of the present invention is excellent in adhesion to the substrate. It is also preferable to omit the step of pre-processing of the substrate from the viewpoint of improving productivity.

<實例146> <Example 146>

與實例144相比僅變更以下的製程，而獲得相同的液晶顯示裝置。即，即便將鹼性顯影液從0.4%的氫氧化四甲基銨水溶液變更成2.38%的氫氧化四甲基銨水溶液，所獲得的硬化膜也是無圖案的缺失或剝落的良好的狀態。另外，與實例144同樣地，液晶顯示裝置的性能也良好。可認為其原因在於本發明的組成物與基板的密接性優異。 The same process was changed as in the example 144, and the same liquid crystal display device was obtained. That is, even if the alkaline developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 2.38% aqueous solution of tetramethylammonium hydroxide, the obtained cured film was in a state in which no pattern was missing or peeled off. Further, similarly to the example 144, the performance of the liquid crystal display device was also good. This is considered to be because the composition of the present invention is excellent in adhesion to the substrate.

<實例147> <Example 147>

與實例144相比僅變更以下的製程，而獲得相同的液晶顯示裝置。即，即便將鹼性顯影液從0.4%的氫氧化四甲基銨水溶液變更成0.04%的KOH水溶液，所獲得的硬化膜也是無圖案的缺失或剝落的良好的狀態。另外，與實例144同樣地，液晶顯示裝置的性能也良好。可認為其原因在於本發明的組成物與基板的密接性優異。 The same process was changed as in the example 144, and the same liquid crystal display device was obtained. That is, even if the alkaline developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 0.04% aqueous KOH solution, the obtained cured film was in a good state in which no pattern was missing or peeled off. Further, similarly to the example 144, the performance of the liquid crystal display device was also good. This is considered to be because the composition of the present invention is excellent in adhesion to the substrate.

<實例148> <Example 148>

與實例144相比僅變更以下的製程，而獲得相同的液晶顯示裝置。即，省略顯影．沖洗後的全面曝光的步驟，利用烘箱在230℃下加熱30分鐘而獲得硬化膜。與實例144同樣地，所獲得的液晶顯示裝置的性能良好。可認為其原因在於本發明的組成物的耐化學品性優異。就提升生產性的觀點而言，也優選省略全面曝光的步驟。 The same process was changed as in the example 144, and the same liquid crystal display device was obtained. That is, the development is omitted. The step of full exposure after rinsing was carried out by heating at 230 ° C for 30 minutes in an oven to obtain a cured film. As in the example 144, the performance of the obtained liquid crystal display device was good. The reason for this is considered to be that the composition of the present invention is excellent in chemical resistance. It is also preferable to omit the step of full exposure from the viewpoint of improving productivity.

<實例149> <Example 149>

與實例144相比僅變更以下的製程，而獲得相同的液晶顯示裝置。即，在全面曝光的步驟與利用烘箱的230℃/30分鐘加熱步驟之間，追加在100℃下在加熱板上加熱3分鐘的步驟。與實例144同樣地，所獲得的液晶顯示裝置的性能良好。就使孔圖的形狀齊整這一觀點而言，也優選追加本步驟。 The same process was changed as in the example 144, and the same liquid crystal display device was obtained. That is, a step of heating on a hot plate at 100 ° C for 3 minutes was added between the step of full exposure and the 230 ° C / 30 minute heating step using an oven. As in the example 144, the performance of the obtained liquid crystal display device was good. It is also preferable to add this step from the viewpoint of making the shape of the hole pattern uniform.

<實例150> <Example 150>

與實例144相比僅變更以下的製程，而獲得相同的液晶顯示裝置。即，在顯影．沖洗的步驟與全面曝光的步驟之間，追加在100℃下在加熱板上加熱3分鐘的步驟。與實例144同樣地，所獲得的液晶顯示裝置的性能良好。就使孔圖的形狀齊整這一觀點而言，也優選追加本步驟。 The same process was changed as in the example 144, and the same liquid crystal display device was obtained. That is, in development. Between the step of rinsing and the step of full exposure, a step of heating on a hot plate at 100 ° C for 3 minutes is additionally added. As in the example 144, the performance of the obtained liquid crystal display device was good. It is also preferable to add this step from the viewpoint of making the shape of the hole pattern uniform.

<實例151> <Example 151>

藉由以下的方法來製作使用薄膜電晶體(TFT)的有機EL顯示裝置(參照圖1)。 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).

在玻璃基板6上形成底柵型的TFT1，並在覆蓋該 TFT1的狀態下形成包含Si3N4的絕緣膜3。繼而，在該絕緣膜3上形成此處省略了圖示的接觸孔後，經由該接觸孔而在絕緣膜3上形成連接於TFT1的配線2(高度為1.0 μm)。該配線2是用以將TFT1間、或將其後的步驟中形成的有機EL元件與TFT1加以連接的線。 A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si 3 N 4 is formed in a state of covering the TFT 1. Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. This wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.

進而，為了使由配線2的形成所產生的凹凸平坦化，在埋入由配線2所產生的凹凸的狀態下，朝絕緣膜3上形成平坦化膜4。朝絕緣膜3上的平坦化膜4的形成是將實例1的感光性樹脂組成物旋塗在基板上，在加熱板上進行預烤(90℃×2分鐘)後，使用高壓水銀燈從遮罩上照射45 mJ/cm2(能量強度為20 mW/cm2)的i射線(365 nm)，然後利用鹼性水溶液(0.4%的TMAH水溶液)進行顯影而形成圖案，以累計照射量達到300 mJ/cm2(能量強度：20 mW/cm2，i射線)的方式，使用超高壓水銀燈進行全面曝光，然後在230℃下進行60分鐘的加熱處理。塗布該感光性樹脂組成物時的塗布性良好，在曝光、顯影、煆燒後所獲得的硬化膜中，未看到皺褶或裂痕的產生。進而，配線2的平均階差為500 nm，所製作的平坦化膜4的膜厚為2,000 nm。 Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness generated by the wiring 2 is buried. The formation of the planarization film 4 on the insulating film 3 was performed by spin coating the photosensitive resin composition of Example 1 on a substrate, pre-baking on a hot plate (90 ° C × 2 minutes), and using a high-pressure mercury lamp from the mask. I-ray (365 nm) was irradiated with 45 mJ/cm 2 (energy intensity of 20 mW/cm 2 ), and then developed with an alkaline aqueous solution (0.4% aqueous TMAH solution) to form a pattern with a cumulative irradiation amount of 300 mJ. /cm 2 (energy intensity: 20 mW/cm 2 , i-ray) was subjected to full exposure using an ultrahigh pressure mercury lamp, followed by heat treatment at 230 ° C for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and calcination. Further, the average step of the wiring 2 was 500 nm, and the thickness of the flattening film 4 produced was 2,000 nm.

繼而，在所獲得的平坦化膜4上形成底部發光型的有機EL元件。首先，使包含ITO的第一電極5經由接觸孔7連接於配線2而形成在平坦化膜4上。其後，塗布抗蝕劑，並進行預烤，經由所期望的圖案的遮罩進行曝光，然後進行顯影。將該抗蝕劑圖案作為遮罩，藉由使用ITO蝕 刻劑的濕蝕刻來進行圖案加工。其後，使用抗蝕劑剝離液(單乙醇胺與二甲基亞碸(Dimethyl sulfoxide，DMSO)的混合液)將該抗蝕劑圖案剝離。以所述方式獲得的第一電極5相當於有機EL元件的陽極。 Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 containing ITO is connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Thereafter, the resist is applied, pre-baked, exposed through a mask of a desired pattern, and then developed. Using the resist pattern as a mask by using ITO etch The wet etching of the engraving agent is used for pattern processing. Thereafter, the resist pattern was peeled off using a resist stripper (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

繼而，形成覆蓋第一電極5的周緣的形狀的絕緣膜8。將實例3的感光性樹脂組成物用於絕緣膜，以與所述相同的方法形成絕緣膜8。藉由設置該絕緣膜，可防止第一電極5與其後的步驟中所形成的第二電極之間的短路。 Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The photosensitive resin composition of Example 3 was used for an insulating film, and the insulating film 8 was formed in the same manner as described above. By providing the insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

進而，在真空蒸鍍裝置內，經由所期望的圖案遮罩而依次進行蒸鍍來設置電洞傳輸層、有機發光層、電子傳輸層。繼而，在基板上方的整個面上形成包含Al的第二電極。從蒸鍍機中取出所獲得的所述基板，藉由使用密封用玻璃板與紫外線硬化型環氧樹脂進行貼合來密封。 Further, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially performing vapor deposition through a desired pattern mask. Then, a second electrode containing Al is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine and sealed by bonding with a glass plate for sealing and an ultraviolet curable epoxy resin.

如以上般，獲得在各有機EL元件上連接用以對其進行驅動的TFT1而成的主動矩陣型的有機EL顯示裝置。經由驅動電路而施加電壓的結果，可知其為顯現良好的顯示特性、且可靠性高的液晶顯示裝置。 As described above, an active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. As a result of applying a voltage via the driving circuit, it is understood that the liquid crystal display device exhibits excellent display characteristics and high reliability.

<實例152> <Example 152>

在實例144中，將實例1的感光性樹脂組成物替換成實例16的感光性樹脂組成物，除此以外，同樣地製作液晶顯示裝置。可知其為顯現良好的顯示特性、且可靠性高的液晶顯示裝置。 In the example 144, a liquid crystal display device was produced in the same manner except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 16. It is known that it is a liquid crystal display device which exhibits good display characteristics and is highly reliable.

<實例153> <Example 153>

在實例144中，將實例1的感光性樹脂組成物替換成 實例31的感光性樹脂組成物，除此以外，同樣地製作液晶顯示裝置。可知其為顯現良好的顯示特性、且可靠性高的液晶顯示裝置。 In Example 144, the photosensitive resin composition of Example 1 was replaced with A liquid crystal display device was produced in the same manner as in the photosensitive resin composition of Example 31. It is known that it is a liquid crystal display device which exhibits good display characteristics and is highly reliable.

<實例154> <Example 154>

在實例144中，將實例1的感光性樹脂組成物替換成實例132的感光性樹脂組成物，除此以外，同樣地製作有機EL裝置。可知其為顯現良好的顯示特性、且可靠性高的有機EL顯示裝置。 In the example 144, an organic EL device was produced in the same manner except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 132. It is known that it is an organic EL display device which exhibits good display characteristics and is highly reliable.

<實例155> <Example 155>

在實例151中，將實例1的感光性樹脂組成物替換成實例16的感光性樹脂組成物，除此以外，同樣地製作有機EL裝置。可知其為顯現良好的顯示特性、且可靠性高的有機EL顯示裝置。 In the example 151, an organic EL device was produced in the same manner except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 16. It is known that it is an organic EL display device which exhibits good display characteristics and is highly reliable.

<實例156> <Example 156>

在實例151中，將實例1的感光性樹脂組成物替換成實例31的感光性樹脂組成物，除此以外，同樣地製作有機EL裝置。可知其為顯現良好的顯示特性、且可靠性高的有機EL顯示裝置。 In the example 151, an organic EL device was produced in the same manner except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 31. It is known that it is an organic EL display device which exhibits good display characteristics and is highly reliable.

<實例157> <Example 157>

在實例151中，將實例1的感光性樹脂組成物替換成實例133的感光性樹脂組成物，除此以外，同樣地製作有機EL裝置。可知其為顯現良好的顯示特性、且可靠性高的有機EL顯示裝置。 In the example 151, an organic EL device was produced in the same manner except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 133. It is known that it is an organic EL display device which exhibits good display characteristics and is highly reliable.

1‧‧‧TFT(薄膜電晶體) 1‧‧‧TFT (thin film transistor)

2‧‧‧配線 2‧‧‧Wiring

3‧‧‧絕緣膜 3‧‧‧Insulation film

4‧‧‧平坦化膜 4‧‧‧Flat film

5‧‧‧第一電極 5‧‧‧First electrode

6‧‧‧玻璃基板 6‧‧‧ glass substrate

7‧‧‧接觸孔 7‧‧‧Contact hole

8‧‧‧絕緣膜 8‧‧‧Insulation film

10‧‧‧液晶顯示裝置 10‧‧‧Liquid crystal display device

12‧‧‧背光單元 12‧‧‧Backlight unit

14、15‧‧‧玻璃基板 14, 15‧‧‧ glass substrate

16‧‧‧TFT 16‧‧‧TFT

17‧‧‧硬化膜 17‧‧‧ hardened film

18‧‧‧接觸孔 18‧‧‧Contact hole

19‧‧‧ITO透明電極 19‧‧‧ITO transparent electrode

20‧‧‧液晶 20‧‧‧LCD

22‧‧‧彩色濾光片 22‧‧‧Color filters

圖1表示有機EL顯示裝置的一例的構成概念圖。表示底部發光型的有機EL顯示裝置中的基板的示意剖面圖，且具有平坦化膜4。 FIG. 1 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and having a planarization film 4.

圖2表示液晶顯示裝置的一例的構成概念圖。表示液晶顯示裝置中的主動矩陣基板的示意剖面圖，且具有作為層間絕緣膜的硬化膜17。 FIG. 2 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, and having a cured film 17 as an interlayer insulating film.

1‧‧‧TFT(薄膜電晶體) 1‧‧‧TFT (thin film transistor)

2‧‧‧配線 2‧‧‧Wiring

3‧‧‧絕緣膜 3‧‧‧Insulation film

4‧‧‧平坦化膜 4‧‧‧Flat film

5‧‧‧第一電極 5‧‧‧First electrode

6‧‧‧玻璃基板 6‧‧‧ glass substrate

7‧‧‧接觸孔 7‧‧‧Contact hole

8‧‧‧絕緣膜 8‧‧‧Insulation film

Claims (20)

一種正型感光性樹脂組成物，其特徵在於包括：成分A：含有滿足下述(1)及下述(2)的至少一個的聚合物的聚合物成分，(1)具有(a1)含有酸基由酸分解性基保護的基的構成單元、及(a2)含有交聯性基的構成單元的聚合物，(2)具有(a1)含有酸基由酸分解性基保護的基的構成單元的聚合物、及具有(a2)含有交聯性基的構成單元的聚合物；成分C：光酸產生劑；以及成分D：溶劑；進而包括成分X：1分子內具有2個以上由式(X1)所表示的水解性矽烷基及/或矽烷醇基的矽化合物； 式中，RX1~RX3的至少1個表示選自由烷氧基、巰基、鹵素原子、醯胺基、乙醯氧基、氨基、烯丙氧基、及異丙烯氧基所組成的組群中的水解性基，或羥基；剩餘的RX1~RX3分別獨立地表示氫原子、鹵素原子、或一價的有機取代基。 A positive photosensitive resin composition comprising: component A: a polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) having (a1) an acid a constituent unit of a group protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, and (2) a constituent unit having a group (a1) having an acid group-protected group protected by an acid-decomposable group a polymer, and a polymer having (a2) a structural unit containing a crosslinkable group; a component C: a photoacid generator; and a component D: a solvent; further comprising a component X: 1 having two or more formulas in the molecule ( a hydrolyzable alkylene group and/or a stanol-based oxime compound represented by X1); In the formula, at least one of R X1 to R X3 represents a group selected from the group consisting of an alkoxy group, a fluorenyl group, a halogen atom, a decylamino group, an ethoxy group, an amino group, an allyloxy group, and an isopropenyloxy group. the hydrolyzable group or a hydroxyl group; the remaining R X1 ~ R X3 each independently represents an organic hydrogen atom, a halogen atom, or a monovalent substituent. 如申請專利範圍第1項所述的正型感光性樹脂組成 物，其中：所述構成單元(X1)之中，RX1~RX3中的至少2個為烷氧基。 The positive photosensitive resin composition according to the first aspect of the invention, wherein at least two of R X1 to R X3 among the structural units (X1) are alkoxy groups. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：相對於樹脂組成物的除溶劑以外的成分的合計，所述成分X的含量為0.1wt%以上。 The positive photosensitive resin composition according to the first or second aspect of the invention, wherein the content of the component X is 0.1% by weight or more based on the total of the components other than the solvent of the resin composition. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述構成單元(a1)為具有羧基由縮醛或縮酮保護的殘基的構成單元。 The positive photosensitive resin composition according to claim 1 or 2, wherein the structural unit (a1) is a constituent unit having a residue in which a carboxyl group is protected by an acetal or a ketal. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述構成單元(a1)為由式(a1-1)所表示的構成單元， 式中，R1及R2分別表示氫原子、烷基或芳基，至少R1及R2的任一個為烷基或芳基，R3表示烷基或芳基，R1或R2與R3可連結而形成環狀醚，R4表示氫原子或甲基，X表示單鍵或亞芳基。 The positive photosensitive resin composition according to the first or second aspect of the invention, wherein the constituent unit (a1) is a constituent unit represented by the formula (a1-1), In the formula, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group, R 3 represents an alkyl group or an aryl group, and R 1 or R 2 is R 3 may be bonded to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述構成單元(X1)的RX1~RX3中的至少2個為甲氧基或乙氧基。 The positive photosensitive resin composition according to claim 1 or 2, wherein at least two of R X1 to R X3 of the structural unit (X1) are a methoxy group or an ethoxy group. . 如申請專利範圍第1項或第2項所述的正型感光性 樹脂組成物，其中：所述構成單元(a2)為具有選自環氧基、氧雜環丁基中的至少1種的構成單元。 Positive sensitivity as described in item 1 or 2 of the patent application scope In the resin composition, the structural unit (a2) is a constituent unit having at least one selected from the group consisting of an epoxy group and an oxetanyl group. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：成分A的含量WA與成分B的含量WB的重量比率為WA/WB=98/2~20/80。 The positive photosensitive resin composition according to claim 1 or 2, wherein the weight ratio of the content W A of the component A to the content W B of the component B is W A /W B =98/2 ~20/80. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：成分C為由具有式(c0)所表示的肟磺酸酯殘基的至少1個的肟磺酸酯化合物， The positive photosensitive resin composition according to claim 1 or 2, wherein the component C is at least one sulfonium sulfonic acid having an oxime sulfonate residue represented by the formula (c0). Ester compound, 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述構成單元(X1)之中，RX1~RX3中的至少2個為烷氧基，且相對於樹脂組成物的除溶劑以外的成分的合計，所述成分X的含量為0.1wt%以上。 The positive photosensitive resin composition according to the first or second aspect of the invention, wherein at least two of R X1 to R X3 among the structural units (X1) are alkoxy groups, and The content of the component X is 0.1% by weight or more based on the total of the components other than the solvent of the resin composition. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述構成單元(X1)之中，RX1~RX3中的至少2個為烷氧基，且所述構成單元(X1)的RX1~RX3中的至少2個為甲氧基或乙氧基。 The positive photosensitive resin composition according to the first or second aspect of the invention, wherein at least two of R X1 to R X3 among the structural units (X1) are alkoxy groups, and At least two of R X1 to R X3 of the structural unit (X1) are a methoxy group or an ethoxy group. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述構成單元(X1)之中，RX1~RX3中的至少2個為烷氧基，相對於樹脂組成物的除溶劑以外的成分的合計，所述成分X的含量為0.1wt%以上，且所 述構成單元(X1)的RX1~RX3中的至少2個為甲氧基或乙氧基。 The positive photosensitive resin composition according to claim 1 or 2, wherein at least two of R X1 to R X3 in the structural unit (X1) are alkoxy groups, and In the total of the components other than the solvent of the resin composition, the content of the component X is 0.1% by weight or more, and at least two of R X1 to R X3 of the structural unit (X1) are methoxy or B. Oxygen. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述光酸產生劑為產生pKa為3以下的酸的光酸產生劑。 The positive photosensitive resin composition according to the first or second aspect of the invention, wherein the photoacid generator is a photoacid generator which produces an acid having a pKa of 3 or less. 如申請專利範圍第1項或第2項所述的正型感光性樹脂組成物，其中：所述成分A包含含有源自(甲基)丙烯酸酯及/或其酯的構成單元的聚合物。 The positive photosensitive resin composition according to the first or second aspect of the invention, wherein the component A contains a polymer containing a constituent unit derived from (meth) acrylate and/or an ester thereof. 一種硬化膜的形成方法，其特徵在於包括：(1)將如申請專利範圍第1項所述的正型感光性樹脂組成物塗布在基板上的步驟；(2)從所塗布的感光性樹脂組成物中去除溶劑的步驟；(3)利用光化射線對去除了溶劑的感光性樹脂組成物進行曝光的步驟；(4)利用水性顯影液對經曝光的感光性樹脂組成物進行顯影的步驟；以及(5)對經顯影的感光性樹脂組成物進行熱硬化的後烘烤步驟。 A method for forming a cured film, comprising: (1) a step of applying a positive photosensitive resin composition according to claim 1 of the patent application to a substrate; (2) applying a photosensitive resin from the coating a step of removing the solvent in the composition; (3) a step of exposing the solvent-removed photosensitive resin composition with actinic rays; and (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution And (5) a post-baking step of thermally curing the developed photosensitive resin composition. 如申請專利範圍第15項所述的硬化膜的形成方法，其中：在所述顯影步驟後、所述後烘烤步驟前，包括對經顯影的感光性樹脂組成物進行全面曝光的步驟。 The method of forming a cured film according to claim 15, wherein the step of performing the full exposure of the developed photosensitive resin composition is performed after the developing step and before the post-baking step. 如申請專利範圍第15項或第16項所述的硬化膜的形成方法，其中：更包括(6)對具有進行熱硬化而獲得的硬化膜的基板進行乾蝕刻的步驟。 The method for forming a cured film according to claim 15 or claim 16, further comprising the step of (6) dry etching the substrate having the cured film obtained by thermal curing. 一種硬化膜，其特徵在於：藉由如申請專利範圍第15項所述的硬化膜的形成方法來形成。 A cured film which is formed by a method of forming a cured film according to claim 15 of the patent application. 如申請專利範圍第18項所述的硬化膜，其中：其為層間絕緣膜。 The cured film according to claim 18, wherein: it is an interlayer insulating film. 一種有機電致發光顯示裝置或液晶顯示裝置，其特徵在於：包括如申請專利範圍第18項所述的硬化膜。 An organic electroluminescence display device or a liquid crystal display device comprising the cured film according to claim 18 of the patent application.
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