TWI827824B - Positive photosensitive resin composition, cured film manufacturing method, cured film, optical element and electronic material - Google Patents

Positive photosensitive resin composition, cured film manufacturing method, cured film, optical element and electronic material Download PDF

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TWI827824B
TWI827824B TW109110209A TW109110209A TWI827824B TW I827824 B TWI827824 B TW I827824B TW 109110209 A TW109110209 A TW 109110209A TW 109110209 A TW109110209 A TW 109110209A TW I827824 B TWI827824 B TW I827824B
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photosensitive resin
resin composition
positive photosensitive
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polysiloxane
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TW202040275A (en
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今西世志美
日比野利保
諏訪充史
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日商東麗股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/075—Silicon-containing compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Abstract

本發明的目的在於提供一種圖案加工性優異且能夠於低溫下硬化、其硬化膜的耐化學品性優異的正型感光性樹脂組成物。本發明為一種正型感光性樹脂組成物，其特徵在於含有：具有通式(1)及通式(2)所表示的結構的聚矽氧烷(A1)、萘醌二疊氮化合物(B)以及於200nm~360nm具有極大吸收波長的光自由基產生劑(C1)及/或光酸產生劑(C1')。另外，本發明的另一態樣的感光性樹脂組成物為如下的正型感光性樹脂組成物，其特徵在於：含有於重複單元中具有含有不飽和雙鍵的有機基的聚矽氧烷(A2)、萘醌二疊氮化合物(B)、以及光自由基產生劑(C2)及/或光酸產生劑(C2')，光自由基產生劑(C2)及/或光酸產生劑(C2')於200nm~360nm下的吸光係數的最大值為於360nm~450nm下的吸光係數的最大值的2倍以上。 An object of the present invention is to provide a positive photosensitive resin composition that is excellent in pattern processability, can be cured at low temperature, and has excellent chemical resistance of its cured film. The present invention is a positive photosensitive resin composition, which is characterized by containing: polysiloxane (A1) having a structure represented by general formula (1) and general formula (2), naphthoquinonediazide compound (B ) and a photoradical generator (C1) and/or a photoacid generator (C1') that has a maximum absorption wavelength between 200nm and 360nm. In addition, a photosensitive resin composition according to another aspect of the present invention is a positive photosensitive resin composition characterized by containing a polysiloxane having an organic group containing an unsaturated double bond in a repeating unit ( A2), naphthoquinonediazide compound (B), and photoradical generator (C2) and/or photoacid generator (C2'), photoradical generator (C2) and/or photoacid generator ( C2') The maximum value of the absorption coefficient at 200nm~360nm is more than 2 times the maximum value of the absorption coefficient at 360nm~450nm.

Description

正型感光性樹脂組成物、硬化膜的製造方法、 硬化膜、光學元件以及電子材料 Positive photosensitive resin composition and method for manufacturing cured film, Hardened film, optical components and electronic materials

本發明是有關於一種圖案加工性優異、能夠於低溫下硬化且其硬化膜的耐化學品性優異的正型感光性樹脂組成物，其硬化膜以及具備其的光學元件。 The present invention relates to a positive photosensitive resin composition that has excellent pattern processability, can be cured at low temperature, and has excellent chemical resistance of its cured film, its cured film, and an optical element provided with the same.

近年來，隨著使用液晶顯示器件等的資訊終端機的急速的製品開發，不斷推進電子電路、顯示器、感測器等先前於使用玻璃或金屬等無機材料的部位使用有機材料的製品的開發。伴隨於此，需要能夠於有機材料的耐熱溫度以下進行成形、加工的保護膜、平坦化膜、絕緣膜材料，以不使器件的構成材料熱劣化。特別是，有機電致發光(electroluminescence，EL)發光材料的耐熱溫度被認為是100℃以下，要求能夠於低於100℃的低溫條件下硬化、硬度、耐化學品性優異、且能夠進行圖案加工的感光性透明材料，但此種材料的例子少。 In recent years, with the rapid development of products using information terminals such as liquid crystal display devices, the development of products using organic materials in parts that previously used inorganic materials such as glass or metal has been promoted, such as electronic circuits, displays, and sensors. Accordingly, there is a need for protective films, planarizing films, and insulating film materials that can be formed and processed below the heat-resistant temperature of organic materials so as to prevent thermal degradation of the constituent materials of the device. In particular, the heat-resistant temperature of organic electroluminescence (EL) light-emitting materials is considered to be 100°C or lower, and they are required to be able to be cured at low temperatures below 100°C, have excellent hardness and chemical resistance, and be capable of pattern processing Photosensitive transparent materials, but there are few examples of such materials.

作為用於保護膜等的感光性透明材料，於專利文獻1~專利文獻3中記載有含有矽氧烷聚合物與醌二疊氮化合物的光可溶化型的正型感光材料。該些材料達成可形成尺寸為5μm以下的圖案的高解析度。而且，藉由在200℃~230℃下進行熱處理而硬化，其結果顯示出耐溶劑性（耐化學品性）。另外，於專利文獻4及專利文獻5中記載有含有鹼可溶性聚合物、聚合起始劑、及其他添加劑的光硬化型的負型感光材料。專利文獻4中所記載的材料達成解析度10 μm，藉由在120℃下進行加熱而硬化，顯示出耐化學品性。另外，專利文獻5中所記載的材料進而於低溫即100℃下亦會硬化，顯示出耐化學品性。 [現有技術文獻] [專利文獻]As photosensitive transparent materials used for protective films and the like, Patent Documents 1 to 3 describe photo-solubilizable positive-type photosensitive materials containing a siloxane polymer and a quinonediazide compound. These materials achieve high resolution that can form patterns with dimensions of 5 μm or less. Furthermore, it is hardened by heat treatment at 200°C to 230°C, and the result shows solvent resistance (chemical resistance). In addition, Patent Document 4 and Patent Document 5 describe a photocurable negative photosensitive material containing an alkali-soluble polymer, a polymerization initiator, and other additives. The material described in Patent Document 4 achieves a resolution of 10 μm, is cured by heating at 120° C., and exhibits chemical resistance. In addition, the material described in Patent Document 5 further hardens at a low temperature, that is, 100° C., and exhibits chemical resistance. [Prior art documents] [Patent Document]

[專利文獻1]日本專利特開2006-293337號公報 [專利文獻2]日本專利特開2009-223293號公報 [專利文獻3]日本專利特開2017-173741號公報 [專利文獻4]日本專利特開2015-18226號公報 [專利文獻5]日本專利特開2018-91940號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2006-293337 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-223293 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-173741 [Patent Document 4] Japanese Patent Application Publication No. 2015-18226 [Patent Document 5] Japanese Patent Application Publication No. 2018-91940

[發明所欲解決之課題] 於專利文獻1～專利文獻4所記載的材料中，於對此種感光材料而言為低溫的100℃以下進行加熱的情況下，存在硬化不充分、耐化學品性降低的課題。另外，專利文獻5所記載的材料存在解析度為50 μm以上的課題。[Problem to be solved by the invention] Among the materials described in Patent Documents 1 to 4, when heating is performed at 100° C. or lower, which is a low temperature for such photosensitive materials, there is a problem that the curing is insufficient and the chemical resistance is reduced. In addition, the material described in Patent Document 5 has a problem of a resolution of 50 μm or more.

根據以上的背景，要求一種例如能夠於被認為是有機EL發光材料的耐熱溫度的100℃以下這一低溫下硬化、耐化學品性、圖案加工性優異的感光性透明材料。本發明的目的在於提供達成該些內容的感光性樹脂組成物。 [解決課題之手段]Based on the above background, there is a demand for a photosensitive transparent material that can be cured at a low temperature of 100° C. or lower, which is considered to be the heat-resistant temperature of organic EL light-emitting materials, and has excellent chemical resistance and pattern processability. An object of the present invention is to provide a photosensitive resin composition that achieves these contents. [Means to solve the problem]

為了解決所述課題，本發明揭示以下的感光性樹脂組成物。 （1）一種正型感光性樹脂組成物，其特徵在於含有：具有下述通式（1）及通式（2）所表示的結構的聚矽氧烷（A1）、萘醌二疊氮化合物（B）、以及於200 nm～360 nm具有極大吸收波長的光自由基產生劑（C1）及/或光酸產生劑（C1'）。In order to solve the said problem, this invention discloses the following photosensitive resin composition. (1) A positive photosensitive resin composition characterized by containing: polysiloxane (A1) having a structure represented by the following general formula (1) and general formula (2), and a naphthoquinonediazide compound (B), and a photoradical generator (C1) and/or a photoacid generator (C1') that has a maximum absorption wavelength between 200 nm and 360 nm.

[化1] [Chemical 1]

（R1 為氫原子或甲基，R2 及R3 為單鍵或者經取代或未經取代的碳數1～8的烴基。星號直接鍵結於矽原子。） （2）一種正型感光性樹脂組成物，其特徵在於：含有於重複單元中具有含有不飽和雙鍵的有機基的聚矽氧烷（A2）、萘醌二疊氮化合物（B）、以及光自由基產生劑（C2）及/或光酸產生劑（C2'），光自由基產生劑（C2）及/或光酸產生劑（C2'）於200 nm～360 nm下的吸光係數的最大值為於360 nm～450 nm下的吸光係數的最大值的2倍以上。(R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are a single bond or a substituted or unsubstituted hydrocarbon group with 1 to 8 carbon atoms. The asterisk is directly bonded to the silicon atom.) (2) A positive-type photosensitive A resin composition characterized by containing polysiloxane (A2) having an organic group containing an unsaturated double bond in a repeating unit, a naphthoquinonediazide compound (B), and a photoradical generator (C2 ) and/or photoacid generator (C2'), the maximum value of the absorption coefficient of photoradical generator (C2) and/or photoacid generator (C2') at 200 nm ~ 360 nm is at 360 nm ~ More than 2 times the maximum value of the absorption coefficient at 450 nm.

作為該些感光性樹脂組成物的較佳態樣而揭示有以下的感光性樹脂組成物。 （3）如所述任一項所述的正型感光性樹脂組成物，其中所述光自由基產生劑（C1）或光酸產生劑（C1'）、或者所述光自由基產生劑（C2）或光酸產生劑（C2'）於200 nm～360 nm下的吸光係數的最大值為於360 nm～450 nm下的吸光係數的最大值的4倍以上。 （4）如所述任一項所述的正型感光性樹脂組成物，其中所述光自由基產生劑（C1）或光酸產生劑（C1'）、或者所述光自由基產生劑（C2）或光酸產生劑（C2'）於300 nm～360 nm下的吸光係數的最大值為3000 mL/g·cm以上。 （5）如所述任一項所述的正型感光性樹脂組成物，其中所述光自由基產生劑（C1）或光酸產生劑（C1'）、或者所述光自由基產生劑（C2）或光酸產生劑（C2'）於360 nm～450 nm下的吸光係數的最大值未滿500 mL/g·cm。 （6）如所述任一項所述的正型感光性樹脂組成物，其中所述聚矽氧烷（A1）或所述聚矽氧烷（A2）進而具有下述通式（3）所表示的結構。The following photosensitive resin compositions are disclosed as preferred aspects of these photosensitive resin compositions. (3) The positive photosensitive resin composition according to any one of the above, wherein the photoradical generator (C1) or the photoacid generator (C1'), or the photoradical generator ( The maximum value of the absorption coefficient of C2) or the photoacid generator (C2') at 200 nm to 360 nm is more than 4 times the maximum value of the absorption coefficient at 360 nm to 450 nm. (4) The positive photosensitive resin composition according to any one of the above, wherein the photoradical generator (C1) or the photoacid generator (C1'), or the photoradical generator ( The maximum value of the absorption coefficient of C2) or photoacid generator (C2') at 300 nm to 360 nm is more than 3000 mL/g·cm. (5) The positive photosensitive resin composition according to any one of the above, wherein the photoradical generator (C1) or the photoacid generator (C1'), or the photoradical generator ( The maximum value of the absorption coefficient of C2) or photoacid generator (C2') at 360 nm to 450 nm is less than 500 mL/g·cm. (6) The positive photosensitive resin composition according to any one of the above, wherein the polysiloxane (A1) or the polysiloxane (A2) further has the following general formula (3): represented structure.

[化2] [Chemicalization 2]

（R4 為單鍵或者經取代或未經取代的二價的碳數1～6的烴基，可具有取代基。） （7）如所述任一項所述的正型感光性樹脂組成物，其中所述聚矽氧烷（A1）或所述聚矽氧烷（A2）具有含有羧基或羧酸酐基的有機基。 （8）如所述任一項所述的正型感光性樹脂組成物，其中相對於所述聚矽氧烷（A1）或所述聚矽氧烷（A2）中的矽原子的總量，所述通式（1）及通式（2）所表示的結構的總量為30 mol%～60 mоl%。 （9）如所述任一項所述的正型感光性樹脂組成物，進而含有具有酸酐基的化合物（D）。 （10）如所述任一項所述的正型感光性樹脂組成物，進而含有具有兩個以上不飽和雙鍵的多官能單體（E）。 （11）如所述任一項所述的正型感光性樹脂組成物，其中所述光自由基產生劑（C1）或光酸產生劑（C1'）或者所述光自由基產生劑（C2）或光酸產生劑（C2'）於300 nm～360 nm具有極大吸收波長。(R 4 is a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent.) (7) The positive photosensitive resin composition according to any one of the above , wherein the polysiloxane (A1) or the polysiloxane (A2) has an organic group containing a carboxyl group or a carboxylic acid anhydride group. (8) The positive photosensitive resin composition according to any one of the above, wherein relative to the total amount of silicon atoms in the polysiloxane (A1) or the polysiloxane (A2), The total amount of the structures represented by the general formula (1) and the general formula (2) is 30 mol% to 60 mol%. (9) The positive photosensitive resin composition according to any one of the above, further containing the compound (D) having an acid anhydride group. (10) The positive photosensitive resin composition according to any one of the above, further containing a polyfunctional monomer (E) having two or more unsaturated double bonds. (11) The positive photosensitive resin composition according to any one of the above, wherein the photoradical generator (C1) or the photoacid generator (C1') or the photoradical generator (C2 ) or photoacid generator (C2') has a maximum absorption wavelength between 300 nm and 360 nm.

而且，作為本發明的感光性樹脂組成物的利用方法及利用本發明的感光性樹脂組成物者，存在以下。 （12）一種硬化膜的製造方法，依序進行以下的步驟： （i）將如（1）至（11）中任一項所述的正型感光性樹脂組成物塗佈於基板上而形成塗膜的步驟； （ii）以365 nm、405 nm、436 nm中任一種光的曝光量為合計10 mJ/m2 以上、且波長未滿350 nm的光的曝光量為合計1 mJ/m2 以下的方式對該塗膜進行圖案曝光後，利用顯影液進行顯影，藉此去除塗膜的曝光部分的步驟； （iii）於所述顯影後，以所述光自由基產生劑（C1）及/或光酸產生劑（C1'）、或者所述光自由基產生劑（C2）及/或光酸產生劑（C2'）於波長200 nm～350 nm下的曝光量為合計10 mJ/m2 以上的方式對殘留的塗膜進行曝光的步驟；以及 （iv）對所述曝光後的塗膜進行加熱的步驟。 （13）一種硬化膜，為如所述任一項所述的正型感光性樹脂組成物的硬化膜。 （14）一種光學元件或電子材料，包括所述硬化膜。 （15）一種光學元件或電子材料，包括選自由包含所述硬化膜的光波導、平坦化膜、保護膜、及層間絕緣膜所組成的群組中的至少一種。 [發明的效果]Furthermore, there are the following methods of utilizing the photosensitive resin composition of the present invention and those utilizing the photosensitive resin composition of the present invention. (12) A method for manufacturing a cured film, the following steps are performed in sequence: (i) Coating the positive photosensitive resin composition as described in any one of (1) to (11) on a substrate to form Steps of coating film; (ii) The exposure amount of any light of 365 nm, 405 nm, and 436 nm is a total of 10 mJ/m 2 or more, and the exposure amount of light with a wavelength less than 350 nm is a total of 1 mJ/m 2. After pattern-exposing the coating film in the following manner, developing with a developer to remove the exposed portion of the coating film; (iii) After the development, using the photoradical generator (C1) and/or the photoacid generator (C1'), or the photoradical generator (C2) and/or the photoacid generator (C2'), the exposure amount at a wavelength of 200 nm to 350 nm is a total of 10 mJ/ The step of exposing the remaining coating film in a manner of m 2 or more; and (iv) the step of heating the exposed coating film. (13) A cured film of the positive photosensitive resin composition according to any one of the above. (14) An optical element or electronic material including the cured film. (15) An optical element or electronic material including at least one selected from the group consisting of an optical waveguide including the cured film, a planarizing film, a protective film, and an interlayer insulating film. [Effects of the invention]

本發明的感光性樹脂組成物的圖案加工性優異，能夠於低溫條件下進行硬化，其硬化膜的耐化學品性優異。The photosensitive resin composition of the present invention has excellent pattern processability, can be cured under low-temperature conditions, and its cured film has excellent chemical resistance.

本發明的感光性樹脂組成物為如下的正型感光性樹脂組成物，其特徵在於含有：具有通式（1）及通式（2）所表示的結構的聚矽氧烷（A1）、萘醌二疊氮化合物（B）以及於200 nm～360 nm具有極大吸收波長的光自由基產生劑（C1）及/或光酸產生劑（C1'）。The photosensitive resin composition of the present invention is a positive photosensitive resin composition characterized by containing polysiloxane (A1) having a structure represented by general formula (1) and general formula (2), naphthalene Quinonediazide compound (B) and a photoradical generator (C1) and/or a photoacid generator (C1') having a maximum absorption wavelength between 200 nm and 360 nm.

[化3] [Chemical 3]

（R1 為氫原子或甲基，R2 及R3 為單鍵或者經取代或未經取代的碳數1～8的烴基，可分別具有取代基。作為所述取代基，可列舉：甲基、乙基、羥基等。） 另外，本發明的另一態樣的感光性樹脂組成物為如下的正型感光性樹脂組成物，其特徵在於：含有於重複單元中具有含有不飽和雙鍵的有機基的聚矽氧烷（A2）、萘醌二疊氮化合物（B）、以及光自由基產生劑（C2）及/或光酸產生劑（C2'），光自由基產生劑（C2）及/或光酸產生劑（C2'）於200 nm～360 nm下的吸光係數的最大值為於360 nm～450 nm下的吸光係數的最大值的2倍以上。 ＜聚矽氧烷（A1）及聚矽氧烷（A2）＞ 本發明中所使用的聚矽氧烷（A1）具有所述通式（1）及通式（2）所表示的結構。藉由聚矽氧烷具有共聚性高的所述通式（1）及通式（2）所表示的結構，利用熱硬化時的熱聚合，可賦予高耐熱性、耐化學品性。進而視需要，所需的耐熱性、耐化學品性可藉由更低溫度下的硬化來實現。(R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are a single bond or a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, and each may have a substituent. Examples of the substituent include: group, ethyl group, hydroxyl group, etc.) In addition, the photosensitive resin composition according to another aspect of the present invention is the following positive photosensitive resin composition, characterized in that the repeating unit contains an unsaturated double bond. Organic polysiloxane (A2), naphthoquinone diazide compound (B), and photoradical generator (C2) and/or photoacid generator (C2'), photoradical generator (C2 ) and/or the maximum value of the absorption coefficient of the photoacid generator (C2') at 200 nm to 360 nm is more than twice the maximum value of the absorption coefficient at 360 nm to 450 nm. <Polysiloxane (A1) and polysiloxane (A2)> The polysiloxane (A1) used in the present invention has a structure represented by the general formula (1) and the general formula (2). Since polysiloxane has a structure represented by the general formula (1) and general formula (2) with high copolymerizability, high heat resistance and chemical resistance can be provided by thermal polymerization during thermal curing. If necessary, the required heat resistance and chemical resistance can be achieved by hardening at a lower temperature.

作為所述聚矽氧烷（A1）的例子，可列舉可藉由使含有苯乙烯基的烷氧基矽烷化合物與含有(甲基)丙烯酸基的烷氧基矽烷化合物進行水解及縮合而獲得的聚矽氧烷。Examples of the polysiloxane (A1) include those obtained by hydrolyzing and condensing a styrene group-containing alkoxysilane compound and a (meth)acrylic acid group-containing alkoxysilane compound. Polysiloxane.

另外，作為所述聚矽氧烷（A2）的例子，可列舉可藉由使含有苯乙烯基的烷氧基矽烷化合物或含有(甲基)丙烯酸基的烷氧基矽烷化合物進行水解及縮合而獲得的聚矽氧烷。於聚矽氧烷（A2）中，亦較佳為如聚矽氧烷（A1）般具有通式（1）及通式（2）兩者的結構。Examples of the polysiloxane (A2) include hydrolysis and condensation of an alkoxysilane compound containing a styrene group or an alkoxysilane compound containing a (meth)acrylic acid group. Polysiloxane obtained. In polysiloxane (A2), a structure having both general formula (1) and general formula (2) like polysiloxane (A1) is also preferred.

作為該些原料的烷氧基矽烷化合物由於市售，故容易獲取。作為具有苯乙烯基的烷氧基矽烷化合物的例子，可列舉：苯乙烯基三甲氧基矽烷、苯乙烯基三乙氧基矽烷、苯乙烯基三(甲氧基乙氧基)矽烷、苯乙烯基三(丙氧基)矽烷、苯乙烯基三(丁氧基)矽烷、苯乙烯基甲基二甲氧基矽烷、苯乙烯基乙基二甲氧基矽烷、苯乙烯基甲基二乙氧基矽烷、苯乙烯基甲基二(甲氧基乙氧基)矽烷等。作為含有(甲基)丙烯酸基的烷氧基矽烷化合物的例子，可列舉：γ-丙烯醯基丙基三甲氧基矽烷、γ-丙烯醯基丙基三乙氧基矽烷、γ-甲基丙烯醯基丙基三甲氧基矽烷、γ-甲基丙烯醯基丙基三乙氧基矽烷、γ-甲基丙烯醯基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯基丙基甲基二乙氧基矽烷、γ-丙烯醯基丙基甲基二甲氧基矽烷、γ-丙烯醯基丙基甲基二乙氧基矽烷等。The alkoxysilane compounds used as these raw materials are commercially available and are therefore easily available. Examples of the alkoxysilane compound having a styryl group include styryltrimethoxysilane, styryltriethoxysilane, styryltris(methoxyethoxy)silane, styrene Tris(propoxy)silane, styryltris(butoxy)silane, styrylmethyldimethoxysilane, styrylethyldimethoxysilane, styrylmethyldiethoxysilane Silane, styrylmethylbis(methoxyethoxy)silane, etc. Examples of the alkoxysilane compound containing a (meth)acrylic acid group include γ-acrylylpropyltrimethoxysilane, γ-acrylylpropyltriethoxysilane, and γ-methacrylamide acylpropyltrimethoxysilane, γ-methacrylylpropyltriethoxysilane, γ-methacrylylpropylmethyldimethoxysilane, γ-methacrylylpropyl Methyl diethoxysilane, γ-acrylylpropylmethyldimethoxysilane, γ-acrylylpropylmethyldimethoxysilane, etc.

聚矽氧烷（A1）中所含的通式（1）及通式（2）所表示的結構所佔的比例並無特別限制，相對於聚矽氧烷中的矽原子的總量，所述通式（1）及通式（2）所表示的結構直接鍵結的矽原子較佳為20 mol%～80 mol%，更佳為相對於聚矽氧烷中的矽原子的總量，所述通式（1）及通式（2）所表示的結構的總量為30 mol%～60 mol%。進而佳為相對於通式（2）所表示的結構的總量，通式（1）所表示的結構的總量以莫耳（mol）比計為1.0～3.0。The proportion of the structure represented by the general formula (1) and the general formula (2) contained in the polysiloxane (A1) is not particularly limited, and the ratio is relative to the total amount of silicon atoms in the polysiloxane. The silicon atoms directly bonded to the structure represented by the general formula (1) and the general formula (2) are preferably 20 mol% to 80 mol%, and more preferably relative to the total amount of silicon atoms in the polysiloxane, The total amount of the structures represented by the general formula (1) and the general formula (2) is 30 mol% to 60 mol%. Furthermore, it is preferable that the total amount of the structures represented by the general formula (1) is 1.0 to 3.0 in molar (mol) ratio relative to the total amount of the structures represented by the general formula (2).

聚矽氧烷（A2）中所含的不飽和雙鍵較佳為具有自由基聚合性。而且，相對於聚矽氧烷中的矽原子的總量，聚矽氧烷（A2）中所含的含有不飽和雙鍵的有機基所鍵結的矽原子較佳為20 mol%～80 mol%，更佳為30 mol%～60 mol%。於聚矽氧烷（A2）中具有通式（1）及通式（2）的結構兩者時，較佳為相對於通式（2）所表示的結構的總量，通式（1）所表示的結構的總量以莫耳比計為1.0～3.0。It is preferable that the unsaturated double bond contained in polysiloxane (A2) has radical polymerizability. Furthermore, the silicon atoms to which the organic groups containing unsaturated double bonds contained in the polysiloxane (A2) are bonded are preferably 20 mol % to 80 mol relative to the total amount of silicon atoms in the polysiloxane. %, more preferably 30 mol% ~ 60 mol%. When the polysiloxane (A2) has both the structures of the general formula (1) and the general formula (2), it is preferable that the general formula (1) is based on the total amount of the structures represented by the general formula (2). The total amount of the represented structure is 1.0 to 3.0 in molar ratio.

以下，對聚矽氧烷（A1）及聚矽氧烷（A2）共同進行說明。以上說明了通式（1）及通式（2）所鍵結的矽的比例、以及具有不飽和雙鍵的有機基所鍵結的矽的較佳比例。Hereinafter, polysiloxane (A1) and polysiloxane (A2) will be described together. The above describes the preferred ratio of silicon bonded to the general formula (1) and general formula (2) and the silicon bonded to the organic group having an unsaturated double bond.

其餘的20 mоl%～60 mоl%、更佳為40 mоl%～70 mоl%可列舉將後述的烷氧基矽烷化合物用作原料時可導入的結構，作為具體的例子，可列舉：甲基、乙基、丙氧基、乙醯氧基、甲氧基、乙氧基、苯基、乙烯基直接鍵結於矽原子的結構、或者後述的通式（3）所表示的結構、後述的通式（4）～通式（6）的R5 ～R7 、R9 ～R11 、R13 ～R15 中的一個以上連結於氧原子的結構等。The remaining 20 mоl% to 60 mоl%, more preferably 40 mоl% to 70 mоl% include structures that can be introduced when an alkoxysilane compound described below is used as a raw material. Specific examples include: methyl, A structure in which an ethyl group, a propoxy group, an acetyloxy group, a methoxy group, an ethoxy group, a phenyl group, or a vinyl group is directly bonded to a silicon atom, or a structure represented by the general formula (3) described below, or a structure represented by the general formula (3) described below. A structure in which at least one of R 5 to R 7 , R 9 to R 11 , and R 13 to R 15 of formula (4) to general formula (6) is connected to an oxygen atom, etc.

具有通式（1）所表示的結構例如苯乙烯基等的聚矽氧烷藉由狄爾斯-阿爾德（Diels-Alder）反應，於圖案加工時容易產生殘渣。為了抑制殘渣的產生，理想的是進而含有通式（3）所表示的結構。Polysiloxanes having a structure represented by the general formula (1), such as styrene groups, etc., easily generate residues during pattern processing through the Diels-Alder reaction. In order to suppress the generation of residues, it is desirable to further contain a structure represented by general formula (3).

[化4] [Chemical 4]

（R4 為單鍵或者經取代或未經取代的碳數1～6的飽和烴基，可具有取代基。作為所述取代基，可列舉：甲基、乙基、羥基等。星號直接鍵結於矽原子。） 作為具有該通式（3）的聚矽氧烷的原料的烷氧基矽烷化合物由於市售，故容易獲取。作為此種烷氧基矽烷化合物的例子，可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基正丙氧基矽烷、乙烯基三-1-丙氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基甲基二乙氧基矽烷、乙烯基甲基二正丙氧基矽烷、乙烯基甲基二-1-丙氧基矽烷、乙烯基甲基二乙醯氧基矽烷、乙烯基乙基二甲氧基矽烷、乙烯基乙基二乙氧基矽烷、乙烯基乙基二正丙氧基矽烷、乙烯基乙基二-1-丙氧基矽烷、乙烯基乙基二乙醯氧基矽烷、乙烯基苯基二甲氧基矽烷、乙烯基苯基二乙氧基矽烷、乙烯基苯基正丙氧基矽烷、乙烯基苯基-1-丙氧基矽烷、乙烯基苯基二乙醯氧基矽烷等。(R 4 is a single bond or a substituted or unsubstituted saturated hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent. Examples of the substituent include: methyl, ethyl, hydroxyl, etc. The asterisk is directly bonded (in silicon atoms.) The alkoxysilane compound, which is a raw material of the polysiloxane having the general formula (3), is commercially available and is therefore easily available. Examples of such alkoxysilane compounds include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl n-propoxysilane, vinyl tri-1-propoxysilane, vinyl Triethyloxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldi-1-propoxysilane , vinyl methyl diethyloxysilane, vinyl ethyl dimethoxysilane, vinyl ethyl diethoxysilane, vinyl ethyl di-n-propoxysilane, vinyl ethyl di-1 -Propoxysilane, vinylethyl diethyloxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, vinylphenyl n-propoxysilane, vinylbenzene -1-propoxysilane, vinylphenyl diethyloxysilane, etc.

通式（1）、通式（2）及通式（3）所表示的結構例如苯乙烯基及(甲基)丙烯酸基及乙烯基有助於耐熱性、耐化學品性，另一方面，由於疏水性高，故於基板的外周部潤濕擴展差，有良率降低之虞。為了均勻地塗佈至基板的外周部而提高良率，理想的是向聚矽氧烷中導入親水性基。另外，藉由在聚矽氧烷中具有親水性基，可提高於作為顯影液的鹼性溶液中的溶解性，抑制顯影後的殘留，即便於室溫下長期保管後亦可將曝光中的感度、解析度保持得高。作為該親水性基，更佳為具有羧基或羧酸酐基的有機基。Structures represented by general formula (1), general formula (2) and general formula (3) such as styrene group, (meth)acrylic group and vinyl group contribute to heat resistance and chemical resistance. On the other hand, Due to its high hydrophobicity, the wetting and spreading on the outer peripheral part of the substrate is poor, and the yield may be reduced. In order to uniformly coat the outer peripheral portion of the substrate and improve the yield, it is desirable to introduce a hydrophilic group into the polysiloxane. In addition, by having a hydrophilic group in polysiloxane, the solubility in an alkaline solution used as a developer can be improved, and residues after development can be suppressed. Even after long-term storage at room temperature, exposed parts can be removed. Sensitivity and resolution remain high. The hydrophilic group is more preferably an organic group having a carboxyl group or a carboxylic acid anhydride group.

作為含有具有該羧基或羧酸酐基的有機基的聚矽氧烷的原料的烷氧基矽烷化合物由於市售，故容易獲取。作為此種烷氧基矽烷化合物的例子，可列舉下述通式（4）～通式（6）的任一者所表示的有機矽烷化合物。可使用該些中的兩種以上。Alkoxysilane compounds, which are raw materials for polysiloxane containing an organic group having a carboxyl group or a carboxylic anhydride group, are commercially available and are therefore easily available. Examples of such alkoxysilane compounds include organosilane compounds represented by any one of the following general formulas (4) to (6). Two or more of these may be used.

[化5] [Chemistry 5]

（通式（4）～通式（6）中，R5 ～R7 、R9 ～R11 及R13 ～R15 表示碳數1～6的烷基、碳數1～6的烷氧基、苯基、苯氧基或碳數2～6的烷基羰氧基。再者，R5 ～R7 、R9 ～R11 及R13 ～R15 中至少一者設為碳數1～6的烷氧基。R8 、R12 及R16 表示單鍵、或碳數1～10的鏈狀脂肪族烴基、碳數3～16的環狀脂肪族烴基、碳數2～6的烷基羰氧基、羰基、醚基、酯基、醯胺基、芳香族基、或者具有該些基的任一者的二價基。該些基亦可經取代。h及k表示0～3的整數。作為R8 、R12 及R16 的具體例，可列舉：-C2 H4 -、-C3 H6 -、-C4 H8 -、-O-、-C3 H6 OCH2 CH(OH)CH2 O2 C-、-CO-、-CO2 -、-CONH-、以下所列舉的有機基等。） 作為通式（4）所表示的烷氧基矽烷化合物的具體例，可列舉：[3-(三甲氧基矽烷基)丙基]琥珀酸酐、[3-(三乙氧基矽烷基)丙基]琥珀酸酐、3-三苯氧基矽烷基丙基琥珀酸酐等。作為通式（5）所表示的有機矽烷化合物的具體例，可列舉3-三甲氧基矽烷基丙基環己基二羧酸酐等。作為通式（6）所表示的烷氧基矽烷化合物的具體例，可列舉3-三甲氧基矽烷基丙基鄰苯二甲酸酐等。(In the general formula (4) to the general formula (6), R 5 to R 7 , R 9 to R 11 and R 13 to R 15 represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. , phenyl, phenoxy group or alkylcarbonyloxy group having 2 to 6 carbon atoms. Furthermore, at least one of R 5 to R 7 , R 9 to R 11 and R 13 to R 15 is set to have a carbon number of 1 to 6 6 alkoxy group. R 8 , R 12 and R 16 represent a single bond, or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, or an alkane having 2 to 6 carbon atoms. A carbonyloxy group, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group, or a divalent group having any one of these groups. These groups may also be substituted. h and k represent 0 to 3 an integer. Specific examples of R 8 , R 12 and R 16 include: -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -, -O-, -C 3 H 6 OCH 2 CH(OH)CH 2 O 2 C-, -CO-, -CO 2 -, -CONH-, organic groups listed below, etc.) Specific examples of the alkoxysilane compound represented by the general formula (4) Examples include: [3-(trimethoxysilyl)propyl]succinic anhydride, [3-(triethoxysilyl)propyl]succinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride wait. Specific examples of the organosilane compound represented by general formula (5) include 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride and the like. Specific examples of the alkoxysilane compound represented by general formula (6) include 3-trimethoxysilylpropylphthalic anhydride and the like.

進而，除所述烷氧基矽烷化合物以外，亦可將其他烷氧基矽烷化合物作為原料。關於該些烷氧基矽烷化合物，作為三官能烷氧基矽烷化合物，例如可列舉：甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丙氧基矽烷、甲基三異丙氧基矽烷、甲基三丁氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、己基三甲氧基矽烷、十八烷基三甲氧基矽烷、十八烷基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基三異丙氧基矽烷、3-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-(N,N-二縮水甘油基)胺基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、β-氰基乙基三乙氧基矽烷、三氟甲基三甲氧基矽烷、三氟甲基三乙氧基矽烷、三氟丙基三甲氧基矽烷、三氟丙基三乙氧基矽烷、全氟丙基乙基三甲氧基矽烷、全氟丙基乙基三乙氧基矽烷、全氟戊基乙基三甲氧基矽烷、全氟戊基乙基三乙氧基矽烷、十三氟辛基三甲氧基矽烷、十三氟辛基三乙氧基矽烷、十三氟辛基三丙氧基矽烷、十三氟辛基三異丙氧基矽烷、十七氟癸基三甲氧基矽烷、十七氟癸基三乙氧基矽烷等。Furthermore, in addition to the alkoxysilane compound described above, other alkoxysilane compounds may be used as raw materials. Regarding these alkoxysilane compounds, examples of trifunctional alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltriisopropyl Oxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethyl Oxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl base)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethyl Oxysilane, trifluoropropyltriethoxysilane, perfluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane, perfluoropentylethyltrimethoxysilane, perfluorinated silane Pentylethyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropyl Oxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, etc.

作為二官能烷氧基矽烷化合物，例如可列舉：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、甲基苯基二甲氧基矽烷、甲基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、γ-甲基丙烯酸氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯酸氧基丙基甲基二乙氧基矽烷、三氟丙基甲基二甲氧基矽烷、三氟丙基甲基二乙氧基矽烷、三氟丙基乙基二甲氧基矽烷、三氟丙基乙基二乙氧基矽烷、三氟丙基乙烯基二甲氧基矽烷、三氟丙基乙烯基二乙氧基矽烷、十七氟癸基甲基二甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基甲基二乙氧基矽烷、環己基甲基二甲氧基矽烷、十八烷基甲基二甲氧基矽烷等。Examples of the difunctional alkoxysilane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methoxysilane. phenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropyl methyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, γ- Methacrylateoxypropylmethyldimethoxysilane, γ-methacrylateoxypropylmethyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyl Diethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane Oxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane silane, octadecylmethyldimethoxysilane, etc.

作為三官能性烷氧基矽烷化合物，例如就所獲得的塗膜的耐化學品性的觀點而言，該些中較佳為甲基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、及苯基三乙氧基矽烷。As the trifunctional alkoxysilane compound, for example, from the viewpoint of the chemical resistance of the coating film obtained, preferred are methyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Trimethoxysilane, and phenyltriethoxysilane.

作為二官能性烷氧基矽烷化合物，為了對所獲得的塗膜賦予可撓性，該些中可較佳地使用二甲基二烷氧基矽烷。 除該些化合物以外，作為四官能性烷氧基矽烷化合物，例如可列舉四甲氧基矽烷、四乙氧基矽烷等。As the bifunctional alkoxysilane compound, in order to impart flexibility to the obtained coating film, dimethyl dialkoxysilane can be preferably used among these. In addition to these compounds, examples of tetrafunctional alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane, and the like.

該些烷氧基矽烷化合物可單獨使用，亦可將兩種以上組合而使用。These alkoxysilane compounds may be used alone or in combination of two or more.

本發明的感光性樹脂組成物中所使用的聚矽氧烷（A1）或聚矽氧烷（A2）可藉由將烷氧基矽烷化合物水解後，使該水解物於溶媒的存在下或於無溶媒下進行縮合反應而獲得。The polysiloxane (A1) or polysiloxane (A2) used in the photosensitive resin composition of the present invention can be obtained by hydrolyzing an alkoxysilane compound and then making the hydrolyzate in the presence of a solvent or in the presence of a solvent. Obtained by condensation reaction without solvent.

關於水解中的各種條件，可藉由考慮反應規模、反應容器的大小、形狀等來設定例如酸（鹼）濃度、反應溫度、反應時間等，來獲得適於目標用途的物性。Regarding various conditions in hydrolysis, physical properties suitable for the intended use can be obtained by setting, for example, acid (alkali) concentration, reaction temperature, reaction time, etc., by considering the reaction scale, the size, shape of the reaction vessel, etc.

作為用於水解反應的觸媒，可列舉酸觸媒與鹼觸媒。作為酸觸媒，可列舉：鹽酸、乙酸、甲酸、硝酸、草酸、鹽酸、硫酸、磷酸、多磷酸、多元羧酸或其酐、以及離子交換樹脂等。作為鹼觸媒，可列舉：單乙醇胺、二乙醇胺、三乙醇胺、二異丙基胺、三丙基胺、二丁基胺、二異丁基胺、三異丁基胺、二異戊基胺、二氮雜雙環十一碳烯、二環己基胺、二環己基甲基胺、三戊基胺、三異戊基胺、三己基胺、三庚基胺、三辛基胺等。作為觸媒的較佳的含量，相對於水解反應時所使用的所有烷氧基矽烷化合物100重量份，較佳為0.05重量份以上，更佳為0.1重量份以上，且較佳為10重量份以下，更佳為5重量份以下。此處，所謂所有烷氧基矽烷化合物量是指包含烷氧基矽烷化合物、其水解物及其縮合物全部的量，設為以下相同。藉由將觸媒的量設為0.05重量份以上，水解順暢地進行，且藉由設為10重量份以下，容易控制水解反應。Catalysts used for the hydrolysis reaction include acid catalysts and alkali catalysts. Examples of the acid catalyst include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid or its anhydride, and ion exchange resin. Examples of the alkali catalyst include monoethanolamine, diethanolamine, triethanolamine, diisopropylamine, tripropylamine, dibutylamine, diisobutylamine, triisobutylamine, and diisoamylamine. , diazabicycloundecene, dicyclohexylamine, dicyclohexylmethylamine, tripentylamine, triisopentylamine, trihexylamine, triheptylamine, trioctylamine, etc. The preferred content of the catalyst is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and more preferably 10 parts by weight based on 100 parts by weight of all alkoxysilane compounds used in the hydrolysis reaction. or less, more preferably 5 parts by weight or less. Here, the total amount of the alkoxysilane compound refers to the amount including all the alkoxysilane compounds, hydrolysates and condensates thereof, and is the same as below. By setting the amount of the catalyst to 0.05 parts by weight or more, hydrolysis proceeds smoothly, and by setting the amount of the catalyst to 10 parts by weight or less, the hydrolysis reaction is easily controlled.

用於水解反應的溶媒並無特別限定，考慮感光性樹脂組成物的穩定性、潤濕性、揮發性等而適宜選擇。溶媒不僅可使用一種亦可使用兩種以上。作為溶媒的具體例，例如可列舉：甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、第三丁醇、戊醇、4-甲基-2-戊醇、3-甲基-2-丁醇、3-甲基-3-甲氧基-1-丁醇、二丙酮醇等醇類；乙二醇、丙二醇等二醇類；乙二醇單甲醚、乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、丙二醇單第三丁醚、乙二醇二甲醚、乙二醇二***、乙二醇二丁醚、二***等醚類；甲基乙基酮、乙醯丙酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、二異丁基酮、環戊酮、2-庚酮等酮類；二甲基甲醯胺、二甲基乙醯胺等醯胺類；乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、乳酸甲酯、乳酸乙酯、乳酸丁酯等乙酸酯類；甲苯、二甲苯、己烷、環己烷等芳香族或脂肪族烴；以及γ-丁內酯、N-甲基-2-吡咯啶酮、二甲基亞碸等。The solvent used for the hydrolysis reaction is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the photosensitive resin composition. Not only one type of solvent may be used, but two or more types of solvents may be used. Specific examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, 4-methyl-2-pentanol, and 3-methyl -Alcohols such as 2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monotertiary butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether and other ethers; ketones such as methyl ethyl ketone, acetoacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone, etc. ; Dimethylformamide, dimethylacetamide and other amide compounds; Ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether ethyl Acid esters, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate and other acetate esters; toluene, xylene, hexane, Aromatic or aliphatic hydrocarbons such as cyclohexane; as well as γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl styrene, etc.

該些中，就硬化膜的透過率、耐龜裂性、聚合穩定性等觀點而言，可較佳地使用二丙酮醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、丙二醇單第三丁醚、γ-丁內酯等。Among these, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, and the like can be preferably used from the viewpoints of the transmittance, crack resistance, and polymerization stability of the cured film. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-tert-butyl ether, γ-butyrolactone, etc.

亦較佳為於水解反應結束後進而添加溶媒，藉此調整為作為感光性樹脂組成物而適當的濃度。另外，亦可於水解後藉由加熱及/或減壓下將生成醇等的總量或一部分餾出、去除，然後添加較佳的溶媒。It is also preferable to add a solvent after the completion of the hydrolysis reaction to adjust the concentration to an appropriate concentration for the photosensitive resin composition. In addition, after hydrolysis, the total amount or a part of the alcohol etc. produced can also be distilled off and removed by heating and/or under reduced pressure, and then a better solvent can be added.

相對於所有烷氧基矽烷化合物100質量份，水解反應時所使用的溶媒的量較佳為50質量份以上，更佳為80質量份以上，且較佳為500質量份以下，更佳為200質量份以下。藉由將溶媒的量設為50質量份以上，可抑制凝膠的生成。另外，藉由設為500質量份以下，水解反應迅速進行。另外，作為用於水解反應中的水，較佳為離子交換水。水的量可任意選擇，較佳為相對於烷氧基矽烷化合物1莫耳而以1.0莫耳～4.0莫耳的範圍使用。The amount of the solvent used in the hydrolysis reaction is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and preferably 500 parts by mass or less, more preferably 200 parts by mass, relative to 100 parts by mass of all alkoxysilane compounds. parts by mass or less. By setting the amount of the solvent to 50 parts by mass or more, the formation of gel can be suppressed. In addition, by setting the content to 500 parts by mass or less, the hydrolysis reaction proceeds quickly. In addition, as the water used in the hydrolysis reaction, ion-exchange water is preferred. The amount of water can be selected arbitrarily, but it is preferably used in the range of 1.0 mol to 4.0 mol relative to 1 mol of the alkoxysilane compound.

另外，就組成物的儲存穩定性的觀點而言，較佳為水解、部分縮合後的聚矽氧烷溶液中不包含所述觸媒，可視需要進行觸媒的去除。去除方法並無特別限制，就操作的簡便度與去除性的方面而言，較佳為水清洗及/或離子交換樹脂的處理。所謂水清洗是以適當的疏水性溶劑將聚矽氧烷溶液稀釋後，以水清洗數次，利用蒸發器等將所獲得的有機層濃縮的方法。所謂利用離子交換樹脂的處理是使聚矽氧烷溶液與適當的離子交換樹脂接觸的方法。In addition, from the viewpoint of storage stability of the composition, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain the catalyst, and the catalyst can be removed if necessary. The removal method is not particularly limited, but in terms of ease of operation and removability, water cleaning and/or ion exchange resin treatment are preferred. The so-called water washing is a method of diluting the polysiloxane solution with an appropriate hydrophobic solvent, washing it several times with water, and concentrating the obtained organic layer using an evaporator or the like. The treatment using an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

本發明的感光性樹脂組成物中所使用的聚矽氧烷（A1）或聚矽氧烷（A2）的重量平均分子量（Mw）並無特別限制，以利用凝膠滲透層析（Gel Permeation Chromatography，GPC）所測定的聚苯乙烯換算計，較佳為1,000以上，更佳為2,000以上。另外，較佳為100,000以下，進而佳為50,000以下。藉由將Mw設為所述範圍，可獲得良好的塗佈特性，形成圖案時於顯影液中的溶解性亦變良好。The weight average molecular weight (Mw) of the polysiloxane (A1) or polysiloxane (A2) used in the photosensitive resin composition of the present invention is not particularly limited. Gel Permeation Chromatography , GPC), the polystyrene conversion meter is preferably 1,000 or more, more preferably 2,000 or more. In addition, the price is preferably 100,000 or less, and more preferably 50,000 or less. By setting Mw in the above range, good coating characteristics can be obtained, and the solubility in a developer becomes good when forming a pattern.

本發明的感光性樹脂組成物中，聚矽氧烷（A1）或聚矽氧烷（A2）的含量並無特別限制，可根據所需的膜厚或用途而任意選擇，相對於本發明的感光性樹脂組成物的固體成分100質量份，一般而言為10質量份～80質量份。In the photosensitive resin composition of the present invention, the content of polysiloxane (A1) or polysiloxane (A2) is not particularly limited and can be arbitrarily selected according to the required film thickness or use. The solid content of the photosensitive resin composition is generally 10 to 80 parts by mass per 100 parts by mass.

＜萘醌二疊氮化合物（B）＞ 本發明的感光性樹脂組成物含有萘醌二疊氮化合物（B）。藉由使用萘醌二疊氮化合物，顯示出曝光部被顯影液去除的正型的感光性。作為萘醌二疊氮化合物，較佳為萘醌二疊氮的磺酸以酯鍵結於具有酚性羥基的化合物而成的化合物。<Naphthoquinonediazide compound (B)> The photosensitive resin composition of the present invention contains a naphthoquinonediazide compound (B). By using a naphthoquinonediazide compound, positive-type photosensitivity is achieved in which the exposed portion is removed by the developer. As the naphthoquinonediazide compound, a compound in which sulfonic acid of naphthoquinonediazide is bonded with a compound having a phenolic hydroxyl group through an ester is preferred.

所使用的萘醌二疊氮化合物並無特別限制，較佳為萘醌二疊氮的磺酸以酯鍵結於具有酚性羥基的化合物而成的化合物。作為此處所使用的具有酚性羥基的化合物，例如可列舉：Bis-Z、BisOC-Z、BisOPP-Z、BisP-CP、Bis26X-Z、BisOTBP-Z、BisOCHP-Z、BisOCR-CP、BisP-MZ、BisP-EZ、Bis26X-CP、BisP-PZ、BisP-IPZ、BisCR-IPZ、BisOCP-IPZ、BisOIPP-CP、Bis26X-IPZ、BisOTBP-CP、TekP-4HBPA（Tetrakis P-DO-BPA）、TrisP-HAP、TrisP-PA、BisOFP-Z、BisRS-2P、BisPG-26X、BisRS-3P、BisOC-OCHP、BisPC-OCHP、Bis25X-OCHP、Bis26X-OCHP、BisOCHP-OC、Bis236T-OCHP、亞甲基三-FR-CR、BisRS-26X、BisRS-OCHP（以上為商品名，本州化學工業（股）製造）、BIR-OC、BIP-PC、BIR-PC、BIR-PTBP、BIR-PCHP、BIP-BIOC-F、4PC、BIR-BIPC-F、TEP-BIP-A（以上為商品名，旭有機材工業（股）製造）、4,4'-磺醯基二苯酚（和光純藥（股）製造）、BPFL（商品名，JFE化學（股）製造）。The naphthoquinonediazide compound used is not particularly limited, but a compound in which sulfonic acid of naphthoquinonediazide is bonded with a compound having a phenolic hydroxyl group through an ester is preferred. Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP- MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylene Bissan-FR-CR, BisRS-26X, BisRS-OCHP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP -BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), 4,4'-sulfonyldiphenol (Wako Pure Chemical Industries, Ltd. ), BPFL (trade name, manufactured by JFE Chemical Co., Ltd.).

該些中，作為較佳的具有酚性羥基的化合物，例如可列舉：Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、亞甲基三-FR-CR、BisRS-26X、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F等。該些中，作為特佳的具有酚性羥基的化合物，例如為Bis-Z、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisRS-2P、BisRS-3P、BIR-PC、BIR-PTBP、BIR-BIPC-F、4,4'-磺醯基二苯酚、BPFL。可例示利用酯鍵將1,2-萘醌二疊氮-4-磺酸、2,1-萘醌二疊氮-4-磺酸、1,2-萘醌二疊氮-5-磺酸、2,1-萘醌二疊氮-5-磺酸等4-（或5-）萘醌二疊氮磺酸導入至該些具有酚性羥基的化合物而成者作為較佳者。亦可使用其以外的化合物。萘醌二疊氮化合物的分子量較佳為300～1500，進而佳為350～1200。藉由將分子量設為300以上，可獲得未曝光部的溶解抑制效果。另外，藉由將分子量設為1500以下，可獲得無浮渣等的良好的凹凸圖案。Among these, preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ. , BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F etc. Among these, particularly preferred compounds having a phenolic hydroxyl group include Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, and BIR. -BIPC-F, 4,4'-sulfonyldiphenol, BPFL. For example, 1,2-naphthoquinonediazide-4-sulfonic acid, 2,1-naphthoquinonediazide-4-sulfonic acid, and 1,2-naphthoquinonediazide-5-sulfonic acid can be exemplified by using an ester bond. , 2,1-naphthoquinonediazide-5-sulfonic acid and other 4-(or 5-)naphthoquinonediazide-sulfonic acid are preferably introduced into these compounds having phenolic hydroxyl groups. Compounds other than these may also be used. The molecular weight of the naphthoquinonediazide compound is preferably 300 to 1,500, more preferably 350 to 1,200. By setting the molecular weight to 300 or more, the effect of inhibiting dissolution of unexposed parts can be obtained. In addition, by setting the molecular weight to 1,500 or less, a good uneven pattern without scum or the like can be obtained.

該些萘醌二疊氮化合物可單獨使用，亦可將兩種以上組合而使用。These naphthoquinonediazide compounds may be used alone or in combination of two or more.

相對於本發明的感光性樹脂組成物的固體成分100質量份，該些化合物的含量為1質量份～50質量份，更佳為2質量份～10質量份。藉由設為1質量份以上，可以實用的感度進行圖案形成。另外，藉由設為50質量份以下，可獲得透過率或圖案解析性優異的感光性樹脂組成物。The content of these compounds is 1 to 50 parts by mass, more preferably 2 to 10 parts by mass relative to 100 parts by mass of the solid content of the photosensitive resin composition of the present invention. By setting the content to 1 part by mass or more, pattern formation can be performed with practical sensitivity. In addition, by setting the content to 50 parts by mass or less, a photosensitive resin composition excellent in transmittance and pattern resolution can be obtained.

於添加萘醌二疊氮化合物的情況下，未反應的感光劑殘留於未曝光部，有時於加熱硬化後產生膜的著色。為了獲得透明的硬化膜，較佳為對顯影後的膜的整個面照射紫外線而將萘醌二疊氮化合物分解，之後進行加熱硬化。When a naphthoquinonediazide compound is added, unreacted photosensitive agent remains in an unexposed part, which may cause coloring of the film after heat curing. In order to obtain a transparent cured film, it is preferable to irradiate the entire surface of the developed film with ultraviolet rays to decompose the naphthoquinonediazide compound, and then heat and cure the film.

＜光自由基產生劑（C1或C2）、及光酸產生劑（C1'或C2'）＞ 本發明的感光性樹脂組成物含有光自由基產生劑（C1或C2）、及/或光酸產生劑（C1'或C2'）。所謂光自由基產生劑是可藉由可見光線、紫外線、遠紫外線、電子束、X射線等放射線的曝光而產生自由基的化合物，所述自由基為可引發苯乙烯基、(甲基)丙烯酸基或乙烯基的加成聚合的活性種。另外，所謂光酸產生劑是可藉由所述放射線的曝光而釋放酸的化合物。認為所產生的活性種或酸有助於聚矽氧烷及後述的具有酸酐基的化合物的加成反應或縮聚等交聯反應。＜Photoradical generator (C1 or C2), and photoacid generator (C1' or C2')＞ The photosensitive resin composition of the present invention contains a photoradical generator (C1 or C2) and/or a photoacid generator (C1' or C2'). The so-called photoradical generator is a compound that can generate free radicals by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, Active species for addition polymerization of base or vinyl groups. In addition, the so-called photoacid generator is a compound that can release acid upon exposure to the radiation. It is considered that the generated active species or acid contributes to cross-linking reactions such as addition reaction or polycondensation of polysiloxane and a compound having an acid anhydride group described below.

該些化合物較佳為並非藉由顯影步驟之前的曝光，而是藉由顯影步驟之後的曝光而分解來產生活性種或酸，理想的是對於顯影步驟之前的曝光時的波長而言吸收少。萘醌二疊氮化合物（B）於g射線（436 nm）、h射線（405 nm）、i射線（365 nm）區域具有吸收。因此，可利用該些光源進行圖案曝光，加以顯影而進行圖案的形成，進而利用亦包含波長更短的光在內的光源進行曝光，使圖案硬化。本發明中可使用的光自由基產生劑（C1）及光酸產生劑（C1'）於波長200 nm與360 nm之間具有吸收的極大值。更佳為進而於300 nm與360 nm之間具有吸收的極大值。如果於200 nm與360 nm之間無極大吸收波長的極大值，於超過360 nm的波長存在極大值的情況下，於處於顯影步驟之前的圖案曝光時硬化過剩進行，有圖案加工性降低之虞。It is preferable that these compounds are decomposed not by exposure before the development step but by exposure after the development step to generate active species or acids. It is desirable that they absorb little at the wavelength at the time of exposure before the development step. Naphthoquinonediazide compound (B) has absorption in the g-ray (436 nm), h-ray (405 nm), and i-ray (365 nm) regions. Therefore, these light sources can be used to perform pattern exposure and development to form the pattern, and further, a light source including light with a shorter wavelength can be used to perform exposure to harden the pattern. The photoradical generator (C1) and photoacid generator (C1') that can be used in the present invention have absorption maximum values between wavelengths of 200 nm and 360 nm. More preferably, it has an absorption maximum value between 300 nm and 360 nm. If there is no maximum value of the maximum absorption wavelength between 200 nm and 360 nm, and there is a maximum value at a wavelength exceeding 360 nm, hardening may proceed excessively during the pattern exposure before the development step, and the pattern processability may be reduced. .

另外，為了兼顧耐化學品性的提高與高解析度，於本發明中可使用的光自由基產生劑（C2）及光酸產生劑（C2'）中，較佳為200 nm～360 nm下的吸光係數的最大值為360 nm～450 nm下的吸光係數的最大值的2倍以上，進而佳為200 nm～360 nm下的吸光係數的最大值為360 nm～450 nm下的吸光係數的最大值的4倍以上。該要求於可於第一發明中使用的光自由基產生劑（C1）及光酸產生劑（C1'）亦相同。In addition, in order to achieve both improvement in chemical resistance and high resolution, among the photoradical generator (C2) and photoacid generator (C2') that can be used in the present invention, the wavelength between 200 nm and 360 nm is preferred. The maximum value of the absorption coefficient is more than twice the maximum value of the absorption coefficient at 360 nm to 450 nm, and more preferably, the maximum value of the absorption coefficient at 200 nm to 360 nm is the maximum value of the absorption coefficient at 360 nm to 450 nm. More than 4 times the maximum value. This requirement is also the same for the photoradical generator (C1) and the photoacid generator (C1') that can be used in the first invention.

該波長200 nm～360 nm下的吸光係數的最大值與360 nm～450 nm下的吸光係數的最大值的關係中，最大值是各範圍中的吸光係數的極大值與成為各範圍的端部的波長下的吸光係數中大的一者。於不存在極大值的情況下，是成為各範圍的端部的波長下的吸光係數中大的一者。In the relationship between the maximum value of the absorption coefficient at a wavelength of 200 nm to 360 nm and the maximum value of the absorption coefficient at a wavelength of 360 nm to 450 nm, the maximum value is the sum of the maximum value of the absorption coefficient in each range and the end of each range. The larger one of the absorption coefficients at the wavelength. When there is no maximum value, the absorption coefficient at the wavelength at the end of each range is the larger one.

再者，即便於在超過360 nm的波長無極大值的情況下、或者於200 nm～360 nm下的吸光係數的最大值與360 nm～450 nm下的吸光係數的最大值滿足所述比率的情況下，於360 nm～450 nm下的吸光係數過大時，亦有圖案加工性降低之虞，因此360 nm～450 nm下的吸光係數的最大值較佳為未滿500 mL/g·cm。另外，即便於在300 nm～360 nm之間具有吸收的極大值的情況下、或者於200 nm～360 nm下的吸光係數的最大值與360 nm～450 nm下的吸光係數的最大值滿足所述比率的情況下，於300 nm～360 nm下的吸光係數的最大值未滿3000 mL/g·cm時，亦有耐化學品性惡化之虞，因此300 nm～360 nm下的吸光係數的最大值較佳為3000 mL/g·cm以上。Furthermore, even if there is no maximum value at a wavelength exceeding 360 nm, or the maximum value of the absorption coefficient at 200 nm to 360 nm and the maximum value of the absorption coefficient at 360 nm to 450 nm satisfy the above ratio. In this case, if the absorbance coefficient at 360 nm to 450 nm is too large, the pattern processability may be reduced. Therefore, the maximum value of the absorbance coefficient at 360 nm to 450 nm is preferably less than 500 mL/g·cm. In addition, even when there is a maximum value of absorption between 300 nm and 360 nm, or the maximum value of the absorption coefficient between 200 nm and 360 nm and the maximum value of the absorption coefficient between 360 nm and 450 nm satisfy the requirements. In the case of the above ratio, if the maximum value of the absorbance coefficient at 300 nm to 360 nm is less than 3000 mL/g·cm, there is a risk of deterioration in chemical resistance, so the absorbance coefficient at 300 nm to 360 nm is The maximum value is preferably 3000 mL/g·cm or more.

關於滿足所述的化合物的例子，作為光自由基產生劑的例子，可列舉：NCI-930、N-1919、NCI-831（商品名，艾迪科（ADEKA）（股）製造）、豔佳固（Irgacure）127、豔佳固（Irgacure）184、豔佳固（Irgacure）500、豔佳固（Irgacure）651、豔佳固（Irgacure）MBF、豔佳固（Irgacure）754、豔佳固（Irgacure）907、達羅固（Darocure）1173（商品名，日本巴斯夫（BASF Japan）（股）製造）等，作為光酸產生劑的例子，可列舉：SP-082、SP-606、SP-171（商品名，艾迪科（ADEKA）（股）製造）、PAG169、CGI725等，但並不限定於該些。該些中，特佳為使用二苯甲酮系光自由基產生劑，作為此種化合物的例子，可列舉：苯基乙醛酸甲酯、氧基苯基乙酸2-[2-羥基-乙氧基]-乙酯、氧基苯基乙酸2-[2-氧代-2-苯基-乙醯氧基-乙氧基]-乙酯等。Examples of compounds that satisfy the above requirements include, for example, photoradical generators: NCI-930, N-1919, NCI-831 (trade name, manufactured by ADEKA Co., Ltd.), Yanjia Irgacure 127, Irgacure 184, Irgacure 500, Irgacure 651, Irgacure MBF, Irgacure 754, Irgacure ( Irgacure) 907, Darocure 1173 (trade name, manufactured by BASF Japan Co., Ltd.), etc. Examples of photoacid generators include: SP-082, SP-606, SP-171 (trade name, manufactured by ADEKA Co., Ltd.), PAG169, CGI725, etc., but are not limited to these. Among these, benzophenone-based photoradical generators are particularly preferably used. Examples of such compounds include: methyl phenylglyoxylate, oxyphenylacetic acid 2-[2-hydroxy-ethyl Oxy]-ethyl ester, oxyphenylacetic acid 2-[2-oxo-2-phenyl-acetyloxy-ethoxy]-ethyl ester, etc.

該些化合物可單獨使用，亦可將兩種以上組合而使用。These compounds may be used alone or in combination of two or more.

相對於本發明的感光性樹脂組成物的固體成分100質量份，光自由基產生劑及光酸產生劑的含量較佳為0.01質量份以上，更佳為0.1質量份以上，進而佳為0.5質量份以上。另外，較佳為20質量份以下，更佳為10質量份以下，進而佳為5質量份以下。藉由設為所述範圍，可促進硬化而期待耐化學品性的提高，且可防止過剩的硬化。The content of the photoradical generator and the photoacid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass, based on 100 parts by mass of the solid content of the photosensitive resin composition of the present invention. More than one serving. In addition, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it within the above range, hardening can be accelerated, improvement in chemical resistance is expected, and excessive hardening can be prevented.

＜具有酸酐基的化合物（D）＞ 本發明的感光性樹脂組成物可進而包含具有酸酐基的化合物。該化合物藉由比較低溫下的加熱而水解，並釋放酸，因此促進聚矽氧烷的縮合反應，有助於提高所獲得的硬化膜的耐化學品性。另外，藉由比較低溫下的加熱，可與聚矽氧烷中的官能基或添加劑反應而形成交聯結構，因此有助於提高硬化膜的耐化學品性。<Compound (D) having an acid anhydride group> The photosensitive resin composition of the present invention may further contain a compound having an acid anhydride group. This compound is hydrolyzed by heating at a relatively low temperature and releases acid, thereby promoting the condensation reaction of polysiloxane and helping to improve the chemical resistance of the obtained cured film. In addition, heating at a relatively low temperature can react with functional groups or additives in polysiloxane to form a cross-linked structure, thus helping to improve the chemical resistance of the cured film.

作為具有酸酐基的化合物的例子，可列舉：琥珀酸酐、辛基琥珀酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、納迪克酸酐、甲基納迪克酸酐、馬來酸酐、順式-1,2-環己烷二羧酸酐、順式-1,2-環己烯二羧酸酐、5-降冰片烯-2,3-二羧酸酐、1,2,4,5-環己烷四羧酸二酐、雙環[2,2,2]辛-7-烯-2,3,5,6-四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、均苯四甲酸酐、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐、雙環[3.3.0]辛烷-2,4,6,8-四羧酸二酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、1,2,3,4-丁烷四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐等，但並不限定於該些。該些中，就溶解性（顯影性）或耐化學品性的觀點而言，特佳為琥珀酸酐、鄰苯二甲酸酐、順式-1,2-環己烯二羧酸酐、5-降冰片烯-2,3-二羧酸酐等。Examples of compounds having an acid anhydride group include succinic anhydride, octylsuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, cis-1,2-cyclohexene Dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2 ,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxylic-1,2,3,4 -Tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-di Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc., but It is not limited to these. Among these, from the viewpoint of solubility (developerability) or chemical resistance, particularly preferred ones are succinic anhydride, phthalic anhydride, cis-1,2-cyclohexenedicarboxylic anhydride, and 5-decanoic acid anhydride. Bornene-2,3-dicarboxylic anhydride, etc.

該些化合物可單獨使用，亦可將兩種以上組合而使用。These compounds may be used alone or in combination of two or more.

相對於本發明的感光性樹脂組成物的固體成分100質量份，具有酸酐基的化合物的含量較佳為0.01質量份以上，更佳為0.1質量份以上，進而佳為0.5質量份以上。另外，較佳為20質量份以下，更佳為10質量份以下，進而佳為5質量份以下。藉由設為所述範圍內，可促進硬化而期待耐化學品性的提高，且防止保存穩定性的降低。The content of the compound having an acid anhydride group is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more relative to 100 parts by mass of the solid content of the photosensitive resin composition of the present invention. In addition, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it within the above range, hardening can be accelerated, improvement in chemical resistance can be expected, and reduction in storage stability can be prevented.

＜具有兩個以上不飽和雙鍵的多官能單體（E）＞ 本發明的感光性樹脂組成物除具有不飽和雙鍵的聚矽氧烷以外，亦可含有具有兩個以上不飽和雙鍵的多官能單體（E）。該化合物藉由曝光或所述光自由基產生劑，單體彼此及與聚矽氧烷中的官能基發生反應而促進硬化。此種化合物並無特別限定，但若考慮自由基聚合性的容易度，則較佳為具有(甲基)丙烯酸基的多官能單體。作為此種化合物的例子，例如可列舉：二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、三羥甲基丙烷二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、二羥甲基-三環癸烷二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三季戊四醇七丙烯酸酯、三季戊四醇八丙烯酸酯、四季戊四醇九丙烯酸酯、四季戊四醇十丙烯酸酯、五季戊四醇十一丙烯酸酯、五季戊四醇十二丙烯酸酯、三季戊四醇七甲基丙烯酸酯、三季戊四醇八甲基丙烯酸酯、四季戊四醇九甲基丙烯酸酯、四季戊四醇十甲基丙烯酸酯、五季戊四醇十一甲基丙烯酸酯、五季戊四醇十二甲基丙烯酸酯、二羥甲基-三環癸烷二甲基丙烯酸酯等，但並不限定於該些。<Polyfunctional monomer (E) having two or more unsaturated double bonds> The photosensitive resin composition of the present invention may contain, in addition to the polysiloxane having an unsaturated double bond, a polyfunctional monomer (E) having two or more unsaturated double bonds. This compound promotes hardening by reaction of the monomers with each other and with the functional groups in the polysiloxane through exposure or the photoradical generator. Such a compound is not particularly limited, but in consideration of ease of radical polymerization, a polyfunctional monomer having a (meth)acrylic acid group is preferred. Examples of such compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. Methacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate Methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1, 4-Butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dihydroxy Methyl-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate Acrylate, tripentaerythritol octaacrylate, pentaerythritol nonacrylate, pentaerythritol tenacrylate, pentaerythritol undecyl acrylate, pentaerythritol dodecacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate , Pentaerythritol nona methacrylate, Pentaerythritol ten methacrylate, Pentaerythritol undeca methacrylate, Pentaerythritol dodeca methacrylate, dimethylol-tricyclodecane dimethacrylate, etc. , but are not limited to these.

該些化合物可單獨使用，亦可將兩種以上組合而使用。These compounds may be used alone or in combination of two or more.

相對於本發明的感光性樹脂組成物的固體成分100質量份，該些化合物的含量較佳為3質量份以上，且較佳為30質量份以下。The content of these compounds is preferably 3 parts by mass or more and preferably 30 parts by mass or less relative to 100 parts by mass of the solid content of the photosensitive resin composition of the present invention.

＜其他成分＞ 本發明的感光性樹脂組成物可含有溶劑。本發明的感光性樹脂組成物可較佳地使用大氣壓下的沸點為250℃以下的溶劑，亦可使用該些中的兩種以上。另外，若於使本發明的感光性樹脂組成物加熱硬化而成的硬化膜中殘存溶劑，則耐化學品性或與基板的密接性會隨時間經過而受到損害，故大氣壓下的沸點為150℃以下的溶劑較佳為感光性樹脂組成物中的溶劑整體的50質量份以上。＜Other ingredients＞ The photosensitive resin composition of the present invention may contain a solvent. The photosensitive resin composition of the present invention can preferably use a solvent whose boiling point under atmospheric pressure is 250° C. or lower, and two or more of these solvents can be used. In addition, if a solvent remains in the cured film obtained by heating and curing the photosensitive resin composition of the present invention, the chemical resistance or the adhesiveness with the substrate will be impaired with the passage of time. Therefore, the boiling point at atmospheric pressure is 150 The solvent with a temperature of ℃ or lower is preferably 50 parts by mass or more of the total solvent in the photosensitive resin composition.

作為大氣壓下的沸點為150℃以下的溶劑，例如可列舉：乙醇、異丙醇、1-丙醇、1-丁醇、2-丁醇、異戊醇、乙二醇單甲醚、乙二醇二甲醚、乙二醇單***、乙酸甲氧基甲酯、丙二醇單甲醚、丙二醇單***、丙二醇單甲醚乙酸酯、丙二醇單丙醚、乙二醇單甲醚乙酸酯、1-甲氧基丙基-2-乙酸酯、丙酮醇、乙醯丙酮、甲基異丁基酮、甲基乙基酮、甲基丙基酮、乳酸甲酯、甲苯、環戊酮、環己烷、正庚烷、苯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丁酯、乙酸丁酯、乙酸異戊酯、乙酸戊酯、3-羥基-3-甲基-2-丁酮、4-羥基-3-甲基-2-丁酮、5-羥基-2-戊酮。Examples of solvents having a boiling point of 150° C. or less under atmospheric pressure include ethanol, isopropyl alcohol, 1-propanol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, and ethylene glycol. Glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-Methoxypropyl-2-acetate, acetol, acetoacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, Cyclohexane, n-heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, amyl acetate, 3-hydroxy-3-methyl-2 -Butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone.

作為大氣壓下的沸點為150℃～250℃的溶劑，例如可列舉：乙二醇二***、乙二醇單正丁醚、乙二醇單第三丁醚、丙二醇單正丁醚、丙二醇單第三丁醚、乙酸2-乙氧基乙酯、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、乙酸3-甲氧基-3-甲基丁酯、乙酸3-甲氧基丁酯、3-乙氧基丙酸乙酯、丙二醇單甲醚丙酸酯、二丙二醇甲醚、二異丁基酮、二丙酮醇、乳酸乙酯、乳酸丁酯、二甲基甲醯胺、二甲基乙醯胺、γ-丁內酯、γ-戊內酯、δ-戊內酯、碳酸伸丙酯、N-甲基吡咯啶酮、環己酮、環庚酮、二乙二醇單丁醚、乙二醇二丁醚。Examples of solvents having a boiling point of 150°C to 250°C under atmospheric pressure include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, and propylene glycol mono-butyl ether. Tributyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate , 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate , dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propyl carbonate, N-methylpyrrolidone, cyclohexanone, Cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether.

該些溶劑可含有兩種以上。另外，溶劑的含量並無特別限制，可根據塗佈方法等使用任意的量。例如於藉由旋轉塗佈進行膜形成的情況下，一般而言設為本發明的感光性樹脂組成物整體的50質量份以上且95質量份以下。These solvents may contain two or more types. In addition, the content of the solvent is not particularly limited, and any amount can be used depending on the coating method and the like. For example, when forming a film by spin coating, it is generally made into 50 mass parts or more and 95 mass parts or less based on the whole photosensitive resin composition of this invention.

為了提高塗佈時的流動性或膜厚的均勻性，本發明的感光性樹脂組成物可含有各種界面活性劑。界面活性劑的種類並無特別限制，例如可使用氟系界面活性劑、矽酮系界面活性劑、聚環氧烷系界面活性劑、聚(甲基)丙烯酸酯系界面活性劑等。該些中，就流動性或膜厚均勻性的觀點而言，可特佳地使用氟系界面活性劑。In order to improve the fluidity during coating or the uniformity of film thickness, the photosensitive resin composition of the present invention may contain various surfactants. The type of surfactant is not particularly limited, and for example, fluorine-based surfactants, silicone-based surfactants, polyalkylene oxide-based surfactants, poly(meth)acrylate-based surfactants, and the like can be used. Among these, a fluorine-based surfactant can be used particularly preferably from the viewpoint of fluidity or film thickness uniformity.

相對於感光性樹脂組成物中所含的聚矽氧烷100質量份，界面活性劑的含量通常為0.001質量份～10質量份。該些可使用一種或同時使用兩種以上。The content of the surfactant is usually 0.001 to 10 parts by mass relative to 100 parts by mass of polysiloxane contained in the photosensitive resin composition. These may be used alone or two or more may be used simultaneously.

進而，例如出於抑制預烘烤時的熱聚合的目的，本發明的感光性樹脂組成物亦可含有聚合抑制劑。關於本發明的感光性樹脂組成物中的聚合抑制劑含量，相對於感光性樹脂組成物整體，較佳為0.000005質量份～0.2質量份，更佳為0.00005質量份～0.1質量份。另外，相對於有機溶媒以外的所有成分，較佳為0.0001質量份～0.5質量份，更佳為0.001質量份～0.2質量份。進而，本發明的感光性樹脂組成物視需要可含有黏度調整劑、穩定化劑、著色劑、增感劑、紫外線吸收劑等。Furthermore, the photosensitive resin composition of the present invention may contain a polymerization inhibitor for the purpose of suppressing thermal polymerization during prebaking, for example. The content of the polymerization inhibitor in the photosensitive resin composition of the present invention is preferably 0.000005 to 0.2 parts by mass, and more preferably 0.00005 to 0.1 parts by mass relative to the entire photosensitive resin composition. In addition, the content is preferably 0.0001 to 0.5 parts by mass, and more preferably 0.001 to 0.2 parts by mass relative to all components except the organic solvent. Furthermore, the photosensitive resin composition of this invention may contain a viscosity adjuster, a stabilizer, a coloring agent, a sensitizer, an ultraviolet absorber, etc. as needed.

＜硬化膜的形成方法＞ 舉例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說明。利用微凹版塗佈、旋轉塗佈、浸漬塗佈、幕流塗佈、輥塗佈、噴霧塗佈、狹縫塗佈等公知的方法，將本發明的感光性樹脂組成物塗佈於基底基板上，並利用加熱板、烘箱等加熱裝置進行預烘烤。預烘烤是於50℃～130℃的範圍內進行30秒鐘～30分鐘，預烘烤後的膜厚較佳為設為0.1 μm～15 μm。＜How to form cured film＞ The formation method of the cured film using the photosensitive resin composition of this invention is demonstrated using an example. The photosensitive resin composition of the present invention is applied to the base substrate using known methods such as microgravure coating, spin coating, dip coating, curtain coating, roll coating, spray coating, and slit coating. and use heating devices such as heating plates and ovens for pre-baking. Prebaking is performed in the range of 50°C to 130°C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably set to 0.1 μm to 15 μm.

預烘烤後，使用步進機、鏡面投影式光罩對準曝光機（Mirror Projection mask Aligner，MPA）、平行光式光罩對準曝光機（Parallel Light mask Aligner，PLA）等曝光機進行曝光。以曝光量10 J/m2 ～4000 J/m2 左右，介隔所需的遮罩或者不介隔遮罩來照射該光。曝光光源並無限制，可使用i射線、g射線、h射線等紫外線、或KrF（波長248 nm）雷射、ArF（波長193 nm）雷射等，就圖案加工性的觀點而言，理想的是利用g射線（436 nm）、h射線（405 nm）、i射線（365 nm）或者該些的混合光源進行。After pre-baking, use a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA) and other exposure machines for exposure. . The light is irradiated with an exposure amount of approximately 10 J/m 2 to 4000 J/m 2 with or without a required mask. There are no restrictions on the exposure light source. Ultraviolet rays such as i-rays, g-rays, and h-rays, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, etc. can be used. From the perspective of pattern processability, the ideal It is carried out using g-rays (436 nm), h-rays (405 nm), i-rays (365 nm) or a mixed light source of these.

其次，可藉由顯影而使曝光部溶解，從而獲得正型圖案。作為顯影方法，較佳為利用噴淋、浸漬、覆液等方法於顯影液中浸漬5秒鐘～10分鐘。作為顯影液，可使用公知的鹼性顯影液。作為具體例，可列舉包含鹼金屬的氫氧化物、碳酸鹽、磷酸鹽、矽酸鹽、硼酸鹽等無機鹼、2-二乙基胺基乙醇、單乙醇胺、二乙醇胺等胺類、氫氧化四甲基銨、膽鹼等四級銨鹽中的一種或兩種以上的水溶液等。於顯影後較佳為以水進行淋洗，繼而亦可於50℃～130℃的範圍內進行乾燥烘烤。Secondly, the exposed portion can be dissolved by development to obtain a positive pattern. As a developing method, it is preferable to immerse in the developer for 5 seconds to 10 minutes by spraying, immersing, liquid coating, etc. As the developer, a well-known alkaline developer can be used. Specific examples include hydroxides containing alkali metals, inorganic bases such as carbonates, phosphates, silicates, and borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, and hydroxides. One or more aqueous solutions of quaternary ammonium salts such as tetramethylammonium and choline. After development, it is best to rinse with water, and then dry and bake in the range of 50°C to 130°C.

之後，利用包含波長360 nm以下的光的光源對該膜進行全面曝光，並利用加熱板、烘箱等加熱裝置於60℃～200℃的範圍內加熱15分鐘～3小時左右。 [實施例]Thereafter, the film is fully exposed using a light source containing light with a wavelength of 360 nm or less, and heated in the range of 60°C to 200°C for about 15 minutes to 3 hours using heating devices such as a hot plate and an oven. [Example]

以下，列舉實施例對本發明加以更具體說明，但本發明並不限定於該些實施例。合成例、實施例及比較例中使用的化合物中的使用簡稱者示於以下。Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples. The abbreviations of the compounds used in the synthesis examples, examples and comparative examples are shown below.

＜烷氧基矽烷化合物＞ MeTMS：甲基三甲氧基矽烷 PhTMS：苯基三甲氧基矽烷 StTMS：苯乙烯基三甲氧基矽烷 AcTMS：丙烯酸3-(三甲氧基矽烷基)丙酯 SucTMS：[3-(三甲氧基矽烷基)丙基]琥珀酸酐 VnTMS：乙烯基三甲氧基矽烷。<Alkoxysilane compound> MeTMS: Methyltrimethoxysilane PhTMS: phenyltrimethoxysilane StTMS: styryltrimethoxysilane AcTMS: 3-(trimethoxysilyl)propyl acrylate SucTMS: [3-(trimethoxysilyl)propyl]succinic anhydride VnTMS: Vinyltrimethoxysilane.

＜溶媒及添加劑＞ PGMEA：丙二醇單甲醚乙酸酯 DAA：二丙酮醇 TMAH：氫氧化四甲基銨 IPA：異丙醇。＜Solution and additives＞ PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol TMAH: tetramethylammonium hydroxide IPA: isopropyl alcohol.

＜固體成分濃度的測定＞ 聚矽氧烷溶液的固體成分濃度是藉由以下方法來求出。秤取1.0 g的聚矽氧烷溶液至鋁杯中，使用加熱板於250℃下加熱30分鐘而使液體成分蒸發。對加熱後殘留於鋁杯中的固體成分進行秤量，求出聚矽氧烷溶液的固體成分濃度。<Measurement of solid content concentration> The solid content concentration of the polysiloxane solution is determined by the following method. Weigh 1.0 g of the polysiloxane solution into an aluminum cup, and heat it at 250°C for 30 minutes using a hot plate to evaporate the liquid component. The solid content remaining in the aluminum cup after heating was weighed to determine the solid content concentration of the polysiloxane solution.

＜苯乙烯基及丙烯酸基的存在比例的測定＞ 進行29 Si-核磁共振（Nuclear Magnetic Resonance，NMR）的測定，根據矽原子整體的積分值與各個官能基直接鍵結的矽原子的積分值計算目標官能基的存在比例。將作為試樣的聚矽氧烷溶液注入至直徑10 mm的「鐵氟龍（Teflon）」（註冊商標）製造的NMR樣品管中，用於測定。以下示出29 Si-NMR的測定條件。<Measurement of the proportion of styrene groups and acrylic groups> 29 Si-Nuclear Magnetic Resonance (NMR) is measured and calculated based on the integral value of the entire silicon atom and the integral value of the silicon atom directly bonded to each functional group. The proportion of target functional groups present. The polysiloxane solution as a sample was poured into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm, and used for measurement. The measurement conditions of 29 Si-NMR are shown below.

裝置：日本電子公司製造的JNM GX-270，測定法：閘控去偶（gated decoupling）法 測定核頻率：53.6693 MHz（29 Si核），光譜寬：20000 Hz 脈衝寬：12 μsec（45°脈衝），脈衝重覆時間：30.0 sec 溶媒：丙酮-d6，標準物質：四甲基矽烷 測定溫度：室溫，試樣轉速：0.0 Hz。Device: JNM GX-270 manufactured by JEOL, measurement method: gated decoupling method, nuclear frequency: 53.6693 MHz ( 29 Si core), spectral width: 20000 Hz, pulse width: 12 μsec (45° pulse ), pulse repetition time: 30.0 sec, solvent: acetone-d6, standard material: tetramethylsilane, measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

＜光自由基產生劑及光酸產生劑的極大吸收波長及吸光係數的測定＞ 對於各光自由基產生劑及光酸產生劑，於10 mL容量瓶中秤取0.03 g，加入乙腈至標線為止來製備溶液。進而利用0.5 mL移液管將該溶液移至10 mL容量瓶中，加入乙腈至標線為止，將以上操作進行兩次，並稀釋400倍。利用紫外-可見分光光度計「UV-260」（島津製作所（股）製造），使用1 cm見方的石英槽，對波長200 nm～800 nm測定各稀釋液的UV光譜。再者，作為本底測定，僅利用乙腈進行測定，並自各溶液的吸光度減去乙腈的吸光度，藉此求出光自由基產生劑及光酸產生劑的吸光度。進而藉由各吸光度除以濃度（g/mL）來算出吸光係數（mL/g·cm）。<Measurement of maximum absorption wavelength and absorption coefficient of photoradical generators and photoacid generators> For each photoradical generator and photoacid generator, weigh 0.03 g in a 10 mL volumetric flask, and add acetonitrile up to the mark to prepare a solution. Then use a 0.5 mL pipette to move the solution into a 10 mL volumetric flask, add acetonitrile up to the mark, repeat the above operation twice, and dilute 400 times. Using an ultraviolet-visible spectrophotometer "UV-260" (manufactured by Shimadzu Corporation), a 1 cm square quartz cell was used to measure the UV spectrum of each dilution solution at a wavelength of 200 nm to 800 nm. In addition, as a background measurement, only acetonitrile was used for measurement, and the absorbance of acetonitrile was subtracted from the absorbance of each solution to determine the absorbance of the photoradical generator and the photoacid generator. Furthermore, the absorbance coefficient (mL/g·cm) was calculated by dividing each absorbance by the concentration (g/mL).

＜實施例中使用的聚合物的合成＞ 合成例1      P-1的合成 於500 mL的三口燒瓶中投入26.74 g（0.20 mol）的MeTMS、58.71 g（0.26 mol）的StTMS、46.00 g（0.20 mol）的AcTMS、129.44 g的DAA，一面於室溫下攪拌，一面花費30分鐘添加水35.34 g與磷酸0.58 g的混合液。之後，將燒瓶浸漬於70℃的油浴中並攪拌1小時後，花費30分鐘將油浴昇溫至110℃為止。昇溫開始1小時後，溶液的內溫達到100℃，然後加熱攪拌1小時（內溫為100℃～110℃）。以固體成分濃度成為40%的方式向殘留於燒瓶內的聚矽氧烷的DAA溶液中追加DAA，將其設為P-1的DAA溶液。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為40 mol%、30 mol%。<Synthesis of the polymer used in the examples> Synthesis Example 1 Synthesis of P-1 Into a 500 mL three-necked flask, 26.74 g (0.20 mol) of MeTMS, 58.71 g (0.26 mol) of StTMS, 46.00 g (0.20 mol) were put ) of AcTMS and 129.44 g of DAA, while stirring at room temperature, add a mixture of 35.34 g of water and 0.58 g of phosphoric acid over 30 minutes. Thereafter, the flask was immersed in a 70°C oil bath and stirred for 1 hour, and then the oil bath was heated up to 110°C over 30 minutes. One hour after the temperature rise starts, the internal temperature of the solution reaches 100°C, and then the solution is heated and stirred for 1 hour (the internal temperature is 100°C to 110°C). DAA was added to the DAA solution of polysiloxane remaining in the flask so that the solid content concentration became 40%, and this was set as the DAA solution of P-1. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 40 mol% and 30 mol% respectively.

合成例2   P-2的合成 以與合成例1相同的順序投入71.30 g（0.52 mol）的MeTMS、14.68 g（0.065 mol）的StTMS、15.33 g（0.065 mol）的AcTMS、84.24 g的DAA，並添加水35.34 g與磷酸0.50 g的混合液，從而合成P-2。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為10 mol%、10 mol%。Synthesis Example 2 Synthesis of P-2 In the same order as Synthesis Example 1, 71.30 g (0.52 mol) of MeTMS, 14.68 g (0.065 mol) of StTMS, 15.33 g (0.065 mol) of AcTMS, and 84.24 g of DAA were added, and A mixture of 35.34 g of water and 0.50 g of phosphoric acid was added to synthesize P-2. The molar amounts of the styrene group and the acrylic acid group relative to the silicon atoms measured by 29 Si-NMR were 10 mol% and 10 mol% respectively.

合成例3   P-3的合成 以與合成例1相同的順序投入49.02 g（0.36 mol）的MeTMS、44.03 g（0.20 mol）的StTMS、23.00 g（0.10 mol）的AcTMS、106.35 g的DAA，並添加水35.34 g與磷酸0.58 g的混合液，從而合成P-3。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為30 mol%、15 mol%。Synthesis Example 3 Synthesis of P-3 In the same order as Synthesis Example 1, 49.02 g (0.36 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 23.00 g (0.10 mol) of AcTMS, and 106.35 g of DAA were added, and A mixture of 35.34 g of water and 0.58 g of phosphoric acid was added to synthesize P-3. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 30 mol% and 15 mol% respectively.

合成例4   P-4的合成 以與合成例1相同的順序投入49.02 g（0.36 mol）的MeTMS、44.03 g（0.20 mol）的StTMS、15.33 g（0.065 mol）的AcTMS、98.24 g的DAA，並添加水33.57 g與磷酸0.54 g的混合液，從而合成P-4。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為30 mol%、10 mol%。 合成例5      P-5的合成 以與合成例1相同的順序投入62.39 g（0.45 mol）的MeTMS、29.36 g（0.13 mol）的StTMS、15.33 g（0.065 mol）的AcTMS、92.89 g的DAA，並添加水35.34 g與磷酸0.54 g的混合液，從而合成P-5。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為20 mol%、10 mol%。 合成例6      P-6的合成 以與合成例1相同的順序投入53.48 g（0.39 mol）的MeTMS、29.36 g（0.13 mol）的StTMS、30.67 g（0.13 mol）的AcTMS、102.52 g的DAA，並添加水35.34 g與磷酸0.57 g的混合液，從而合成P-6。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為20 mol%、20 mol%。Synthesis Example 4 Synthesis of P-4 In the same order as Synthesis Example 1, 49.02 g (0.36 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 15.33 g (0.065 mol) of AcTMS, and 98.24 g of DAA were added, and A mixture of 33.57 g of water and 0.54 g of phosphoric acid was added to synthesize P-4. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 30 mol% and 10 mol% respectively. Synthesis Example 5 Synthesis of P-5 In the same order as Synthesis Example 1, 62.39 g (0.45 mol) of MeTMS, 29.36 g (0.13 mol) of StTMS, 15.33 g (0.065 mol) of AcTMS, and 92.89 g of DAA were added, and A mixture of 35.34 g of water and 0.54 g of phosphoric acid was added to synthesize P-5. The molar amounts of styrene group and acrylic acid group relative to silicon atoms measured by 29 Si-NMR were 20 mol% and 10 mol% respectively. Synthesis Example 6 Synthesis of P-6 In the same order as Synthesis Example 1, 53.48 g (0.39 mol) of MeTMS, 29.36 g (0.13 mol) of StTMS, 30.67 g (0.13 mol) of AcTMS, and 102.52 g of DAA were added, and A mixture of 35.34 g of water and 0.57 g of phosphoric acid was added to synthesize P-6. The molar amounts of styrene group and acrylic acid group relative to silicon atoms measured by 29 Si-NMR were 20 mol% and 20 mol% respectively.

合成例7   P-7的合成 以與合成例1相同的順序投入35.65 g（0.26 mol）的MeTMS、58.71 g（0.26 mol）的StTMS、30.67 g（0.13 mol）的AcTMS、122.27 g的DAA，並添加水35.34 g與磷酸0.63 g的混合液，從而合成P-7。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為40 mol%、20 mol%。Synthesis Example 7 Synthesis of P-7 In the same order as Synthesis Example 1, 35.65 g (0.26 mol) of MeTMS, 58.71 g (0.26 mol) of StTMS, 30.67 g (0.13 mol) of AcTMS, and 122.27 g of DAA were added, and A mixture of 35.34 g of water and 0.63 g of phosphoric acid was added to synthesize P-7. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 40 mol% and 20 mol% respectively.

合成例8   P-8的合成 以與合成例1相同的順序投入44.57 g（0.33 mol）的MeTMS、44.03 g（0.20 mol）的StTMS、23.00 g（0.10 mol）的AcTMS、4.85 g（0.03 mol）的VnTMS、106.94 g的DAA，並添加水35.34 g與磷酸0.58 g的混合液，從而合成P-8。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為30 mol%、15 mol%。Synthesis Example 8 Synthesis of P-8 In the same order as Synthesis Example 1, 44.57 g (0.33 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 23.00 g (0.10 mol) of AcTMS, and 4.85 g (0.03 mol) were added. VnTMS, 106.94 g of DAA, and a mixture of 35.34 g of water and 0.58 g of phosphoric acid were added to synthesize P-8. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 30 mol% and 15 mol% respectively.

合成例9   P-9的合成 以與合成例1相同的順序投入40.11 g（0.29 mol）的MeTMS、44.03 g（0.20 mol）的StTMS、23.00 g（0.10 mol）的AcTMS、4.85 g（0.03 mol）的VnTMS、8.58 g（0.03 mol）的SucTMS、114.02 g的DAA，並添加水35.93 g與磷酸0.56 g的混合液，從而合成P-9。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為30 mol%、15 mol%。Synthesis Example 9 Synthesis of P-9 In the same order as Synthesis Example 1, 40.11 g (0.29 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 23.00 g (0.10 mol) of AcTMS, and 4.85 g (0.03 mol) were added. VnTMS, 8.58 g (0.03 mol) SucTMS, 114.02 g DAA, and a mixture of 35.93 g water and 0.56 g phosphoric acid was added to synthesize P-9. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 30 mol% and 15 mol% respectively.

合成例10      P-10的合成 以與合成例1相同的順序投入44.57 g（0.33 mol）的MeTMS、44.03 g（0.20 mol）的StTMS、23.00 g（0.10 mol）的AcTMS、8.58 g（0.03 mol）的SucTMS、113.43 g的DAA，並添加水35.93 g與磷酸0.56 g的混合液，從而合成P-10。利用29 Si-NMR所測定的苯乙烯基、丙烯酸基相對於矽原子的莫耳量分別為30 mol%、15 mol%。Synthesis Example 10 Synthesis of P-10 In the same order as Synthesis Example 1, 44.57 g (0.33 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 23.00 g (0.10 mol) of AcTMS, and 8.58 g (0.03 mol) were added. SucTMS, 113.43 g of DAA, and a mixture of 35.93 g of water and 0.56 g of phosphoric acid were added to synthesize P-10. The molar amounts of styrene groups and acrylic groups relative to silicon atoms measured by 29 Si-NMR were 30 mol% and 15 mol% respectively.

＜比較例的聚合物合成＞ 合成例11    R-1的合成 於500 mL的三口燒瓶中投入49.02 g（0.36 mol）的MeTMS、38.93 g（0.20 mol）的PhTMS、23.00 g（0.10 mol）的AcTMS、98.70 g的DAA，一面於室溫下攪拌，一面花費30分鐘添加水35.34 g與磷酸0.56 g的混合液。之後，將燒瓶浸漬於70℃的油浴中並攪拌1小時後，花費30分鐘將油浴昇溫至110℃為止。昇溫開始1小時後，溶液的內溫達到100℃，然後加熱攪拌1小時（內溫為100℃～110℃）。以固體成分濃度成為40%的方式向殘留於燒瓶內的聚矽氧烷的DAA溶液中追加DAA，將其設為R-1的DAA溶液。利用29 Si-NMR所測定的丙烯酸基的莫耳量為15 mol%。<Polymer synthesis of comparative examples> Synthesis Example 11 Synthesis of R-1 Into a 500 mL three-necked flask, 49.02 g (0.36 mol) of MeTMS, 38.93 g (0.20 mol) of PhTMS, and 23.00 g (0.10 mol) of AcTMS were put , 98.70 g of DAA, while stirring at room temperature, add a mixture of 35.34 g of water and 0.56 g of phosphoric acid over 30 minutes. Thereafter, the flask was immersed in a 70°C oil bath and stirred for 1 hour, and then the oil bath was heated up to 110°C over 30 minutes. One hour after the temperature rise starts, the internal temperature of the solution reaches 100°C, and then the solution is heated and stirred for 1 hour (the internal temperature is 100°C to 110°C). DAA was added to the DAA solution of polysiloxane remaining in the flask so that the solid content concentration became 40%, and this was set as the DAA solution of R-1. The molar amount of acrylic group measured by 29 Si-NMR was 15 mol%.

合成例12      R-2的合成 以與合成例11相同的順序投入49.02 g（0.36 mol）的MeTMS、69.00 g（0.29 mol）的AcTMS、109.30 g的DAA，並添加水35.34 g與磷酸0.59 g的混合液，從而合成R-2。利用29 Si-NMR所測定的丙烯酸基的莫耳量為45 mol%。Synthesis Example 12 Synthesis of R-2 In the same order as Synthesis Example 11, 49.02 g (0.36 mol) of MeTMS, 69.00 g (0.29 mol) of AcTMS, and 109.30 g of DAA were added, and 35.34 g of water and 0.59 g of phosphoric acid were added. mixture to synthesize R-2. The molar amount of acrylic groups measured by 29 Si-NMR was 45 mol%.

合成例13      R-3的合成 以與合成例11相同的順序投入62.39 g（0.46 mol）的MeTMS、38.93 g（0.20 mol）的PhTMS、84.25 g的DAA，並添加水35.34 g與磷酸0.51 g的混合液，從而合成R-3。Synthesis Example 13 Synthesis of R-3 In the same order as Synthesis Example 11, 62.39 g (0.46 mol) of MeTMS, 38.93 g (0.20 mol) of PhTMS, and 84.25 g of DAA were added, and a mixture of 35.34 g of water and 0.51 g of phosphoric acid was added to synthesize R-3. .

合成例14      R-4的合成 以與合成例11相同的順序投入62.39 g（0.46 mol）的MeTMS、44.03 g（0.20 mol）的StTMS、91.91 g的DAA，並添加水35.34 g與磷酸0.53 g的混合液，從而合成R-4。利用29 Si-NMR所測定的苯乙烯基的莫耳量為30 mol%。Synthesis Example 14 Synthesis of R-4 In the same order as Synthesis Example 11, 62.39 g (0.46 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, and 91.91 g of DAA were added, and 35.34 g of water and 0.53 g of phosphoric acid were added. mixture to synthesize R-4. The molar amount of the styrene group measured by 29 Si-NMR was 30 mol%.

合成例15      R-5的合成 以與合成例11相同的順序投入49.02 g（0.36 mol）的MeTMS、66.05 g（0.29 mol）的StTMS、104.88 g的DAA，並添加水35.34 g與磷酸0.58 g的混合液，從而合成R-5。利用29 Si-NMR所測定的苯乙烯基的莫耳量為45 mol%。Synthesis Example 15 Synthesis of R-5 In the same order as Synthesis Example 11, 49.02 g (0.36 mol) of MeTMS, 66.05 g (0.29 mol) of StTMS, and 104.88 g of DAA were added, and 35.34 g of water and 0.58 g of phosphoric acid were added. mixture to synthesize R-5. The molar amount of the styrene group measured by 29 Si-NMR was 45 mol%.

合成例16      R-6的合成 以與合成例11相同的順序投入44.57 g（0.33 mol）的MeTMS、66.05 g（0.29 mol）的StTMS、4.85 g（0.03 mol）的VnTMS、105.47 g的DAA，並添加水35.34 g與磷酸0.58 g的混合液，從而合成R-6。利用29 Si-NMR所測定的苯乙烯基的莫耳量為45 mol%。 將合成例1～合成例16的組成匯總示於表1。Synthesis Example 16 Synthesis of R-6 In the same order as Synthesis Example 11, 44.57 g (0.33 mol) of MeTMS, 66.05 g (0.29 mol) of StTMS, 4.85 g (0.03 mol) of VnTMS, and 105.47 g of DAA were added, and A mixture of 35.34 g of water and 0.58 g of phosphoric acid was added to synthesize R-6. The molar amount of the styrene group measured by 29 Si-NMR was 45 mol%. The compositions of Synthesis Examples 1 to 16 are summarized in Table 1.

[表1] [表1] No. （A） 作為原料的烷氧基矽烷 成分a 投入量（mol%） 成分b 投入量（mol%） 成分c 投入量（mol%） 成分d 投入量（mol%） 成分e 投入量（mol%） 成分f 投入量（mol%） 合成例1 P-1 StTMS 40 AcTMS 30 MeTMS 30 --- --- --- --- --- --- 合成例2 P-2 StTMS 10 AcTMS 10 MeTMS 80 --- --- --- --- --- --- 合成例3 P-3 StTMS 30 AcTMS 15 MeTMS 55 --- --- --- --- --- --- 合成例4 P-4 StTMS 30 AcTMS 10 MeTMS 60 合成例5 P-5 StTMS 20 AcTMS 10 MeTMS 70 --- --- --- --- --- --- 合成例6 P-6 StTMS 20 AcTMS 20 MeTMS 60 --- --- --- --- --- --- 合成例7 P-7 StTMS 40 AcTMS 20 MeTMS 40 --- --- --- --- --- --- 合成例8 P-8 StTMS 30 AcTMS 15 MeTMS 50 VnTMS 5 --- --- --- --- 合成例9 P-9 StTMS 30 AcTMS 15 MeTMS 45 VnTMS 5 SucTMS 5 --- --- 合成例10 P-10 StTMS 30 AcTMS 15 MeTMS 50 --- --- SucTMS 5 --- --- 合成例11 R-1 --- --- AcTMS 15 MeTMS 55 --- --- --- --- PhTMS 30 合成例12 R-2 --- --- AcTMS 45 MeTMS 55 --- --- --- --- --- --- 合成例13 R-3 --- --- --- --- MeTMS 70 --- --- --- --- PhTMS 30 合成例14 R-4 StTMS 30 --- --- MeTMS 70 --- --- --- --- --- --- 合成例15 R-5 StTMS 45 --- --- MeTMS 55 --- --- --- --- --- --- 合成例16 R-6 StTMS 45 --- --- MeTMS 50 VnTMS 5 --- --- --- --- [Table 1] [Table 1] No. (A) Alkoxysilane as raw material Ingredients a Input amount (mol%) Component b Input amount (mol%) Ingredients c Input amount (mol%) Ingredient d Input amount (mol%) Ingredient e Input amount (mol%) Ingredients f Input amount (mol%) Synthesis example 1 P-1 TMs 40 AcTMS 30 MeTMS 30 --- --- --- --- --- --- Synthesis example 2 P-2 TMs 10 AcTMS 10 MeTMS 80 --- --- --- --- --- --- Synthesis example 3 P-3 TMs 30 AcTMS 15 MeTMS 55 --- --- --- --- --- --- Synthesis example 4 P-4 TMs 30 AcTMS 10 MeTMS 60 Synthesis example 5 P-5 TMs 20 AcTMS 10 MeTMS 70 --- --- --- --- --- --- Synthesis example 6 P-6 TMs 20 AcTMS 20 MeTMS 60 --- --- --- --- --- --- Synthesis Example 7 P-7 TMs 40 AcTMS 20 MeTMS 40 --- --- --- --- --- --- Synthesis example 8 P-8 TMs 30 AcTMS 15 MeTMS 50 wxya 5 --- --- --- --- Synthesis example 9 P-9 TMs 30 AcTMS 15 MeTMS 45 wxya 5 SucTMS 5 --- --- Synthesis example 10 P-10 TMs 30 AcTMS 15 MeTMS 50 --- --- SucTMS 5 --- --- Synthesis Example 11 R-1 --- --- AcTMS 15 MeTMS 55 --- --- --- --- PhTMS 30 Synthesis example 12 R-2 --- --- AcTMS 45 MeTMS 55 --- --- --- --- --- --- Synthesis example 13 R-3 --- --- --- --- MeTMS 70 --- --- --- --- PhTMS 30 Synthesis Example 14 R-4 TMs 30 --- --- MeTMS 70 --- --- --- --- --- --- Synthesis Example 15 R-5 TMs 45 --- --- MeTMS 55 --- --- --- --- --- --- Synthesis Example 16 R-6 TMs 45 --- --- MeTMS 50 wxya 5 --- --- --- ---

＜感光性樹脂組成物的製作＞ 實施例1 將6.90 g的作為聚矽氧烷（A）的P-1的DAA溶液（40%）、0.23 g的作為萘醌二疊氮化合物（B）的STP-528（商品名，安智電子材料（AZ Electronic Materials）（股））、0.15 g的作為光自由基產生劑（C）的NCI-831（商品名，日本巴斯夫（BASF Japan）（股））、1.28 g及1.39 g的作為溶媒的PGMEA及DAA於黃色燈下混合，振盪攪拌後，利用直徑0.2 μm的過濾器進行過濾而獲得感光性樹脂組成物。將組成示於表2。＜Preparation of photosensitive resin composition＞ Example 1 6.90 g of the DAA solution (40%) of P-1 as the polysiloxane (A) and 0.23 g of STP-528 (trade name, Anzhi Electronic Materials (B) as the naphthoquinone diazide compound (B) AZ Electronic Materials (Co., Ltd.), 0.15 g of NCI-831 (trade name, BASF Japan (Co., Ltd.)) as a photoradical generator (C), 1.28 g and 1.39 g of PGMEA as a solvent and DAA under a yellow light, oscillated and stirred, and then filtered through a filter with a diameter of 0.2 μm to obtain a photosensitive resin composition. The composition is shown in Table 2.

實施例2～實施例25、比較例1～比較例8 以與實施例1相同的順序並依據表2所示的組成來製作感光性樹脂組成物。Example 2 to Example 25, Comparative Example 1 to Comparative Example 8 A photosensitive resin composition was produced in the same procedure as Example 1 and based on the composition shown in Table 2.

表2所示的化合物的編號示出以下者。 B-1：STP-528  安智電子材料（AZ Electronic Materials）（股）製造 C-1：NCI-831   艾迪科（ADEKA）（股）製造 C-2：達羅固（Darocur）1173     日本巴斯夫（BASF Japan）（股）製造 C-3：豔佳固（Irgacure）819  日本巴斯夫（BASF Japan）（股）製造 C-4：豔佳固（Irgacure）907  日本巴斯夫（BASF Japan）（股）製造 C-5：豔佳固（Irgacure）754  日本巴斯夫（BASF Japan）（股）製造 C-6：SP-606     艾迪科（ADEKA）（股）製造 C-7：SP-082     艾迪科（ADEKA）（股）製造 C-8：SP-056     艾迪科（ADEKA）（股）製造 C-9：豔佳固（Irgacure）OXE02  日本巴斯夫（BASF Japan）（股）製造 D-1：馬來酸酐 富士膠片和光純藥（股）製造 D-2：琥珀酸酐 富士膠片和光純藥（股）製造 E-1：二季戊四醇六丙烯酸酯（DPHA） 日本化藥（股）製造 PGMEA：丙二醇單甲醚乙酸酯 DAA：二丙酮醇。The numbers of the compounds shown in Table 2 are as follows. B-1: STP-528 Manufactured by AZ Electronic Materials (Co., Ltd.) C-1: NCI-831 Manufactured by ADEKA (Co., Ltd.) C-2: Darocur 1173 Manufactured by BASF Japan (Co., Ltd.) C-3: Irgacure 819 manufactured by BASF Japan (Co., Ltd.) C-4: Irgacure 907 manufactured by BASF Japan (Co., Ltd.) C-5: Irgacure 754 manufactured by BASF Japan (Co., Ltd.) C-6: SP-606 Made by ADEKA (Co., Ltd.) C-7: SP-082 Made by ADEKA (Co., Ltd.) C-8: SP-056 Made by ADEKA (Co., Ltd.) C-9: Irgacure OXE02 Manufactured by BASF Japan (Co., Ltd.) D-1: Maleic anhydride Manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd. D-2: Succinic anhydride Manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd. E-1: Dipentaerythritol hexaacrylate (DPHA) Manufactured by Nippon Kayaku Co., Ltd. PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol.

再者，NCI-831的極大吸收波長為276 nm、370 nm，達羅固（Darocure）-1173的極大吸收波長為247 nm、273 nm，豔佳固（Irgacure）-819的極大吸收波長為203 nm、291 nm、368 nm、390 nm，豔佳固（Irgacure）-907的極大吸收波長為228 nm、302 nm，豔佳固（Irgacure）-754的極大吸收波長為253 nm、336 nm，SP-606的極大吸收波長為231 nm、344 nm，SP-082的極大吸收波長為228 nm、337 nm，SP-056的極大吸收波長為231 nm、266 nm、274 nm。另外，將各光自由基產生劑及光酸產生劑於200 nm～360 nm下的吸光係數的最大值、於300 nm～360 nm下的吸光係數的最大值、於360 nm～450 nm下的吸光係數的最大值示於表3。Furthermore, the maximum absorption wavelength of NCI-831 is 276 nm and 370 nm, the maximum absorption wavelength of Darocure-1173 is 247 nm and 273 nm, and the maximum absorption wavelength of Irgacure-819 is 203 nm. nm, 291 nm, 368 nm, 390 nm, the maximum absorption wavelength of Irgacure-907 is 228 nm, 302 nm, the maximum absorption wavelength of Irgacure-754 is 253 nm, 336 nm, SP The maximum absorption wavelengths of -606 are 231 nm and 344 nm, the maximum absorption wavelengths of SP-082 are 228 nm and 337 nm, and the maximum absorption wavelengths of SP-056 are 231 nm, 266 nm, and 274 nm. In addition, the maximum value of the absorption coefficient of each photoradical generator and the photoacid generator at 200 nm to 360 nm, the maximum value of the absorption coefficient at 300 nm to 360 nm, and the maximum value of the absorption coefficient at 360 nm to 450 nm were calculated. The maximum value of the absorbance coefficient is shown in Table 3.

[表2A] [表2A] No. （I）感光性樹脂組成物 感光性樹脂組成物的名稱 聚矽氧烷（A） 比率（質量%） 萘醌二疊氮化合物（B） 比率（質量%） 光自由基產生劑/光酸產生劑（C1,C1',C2,C2'） 比率（質量%） 酸酐化合物（D） 比率（質量%） 多官能單體（E） 比率（質量%） 溶劑 比率（質量%） 實施例1 組成物1 P-1 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例2 組成物2 P-2 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例3 組成物3 P-3 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例4 組成物4 P-4 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例5 組成物5 P-5 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例6 組成物6 P-6 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例7 組成物7 P-7 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例8 組成物8 P-3 27.6 B-1 2.25 C-2 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例9 組成物9 P-3 27.6 B-1 2.25 C-3 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例10 組成物10 P-3 27.6 B-1 2.25 C-4 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例11 組成物11 P-3 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例12 組成物12 P-3 27.6 B-1 2.25 C-6 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例13 組成物13 P-3 27.6 B-1 2.25 C-7 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例14 組成物14 P-3 27.6 B-1 2.25 C-8 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例15 組成物15 P-8 27.6 B-1 2.25 C-8 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例16 組成物16 P-8 27 B-1 2.25 C-8 0.15 D-1 0.6 --- --- PGMEA/DAA 56/14 [Table 2A] [Table 2A] No. (I) Photosensitive resin composition Name of photosensitive resin composition Polysiloxane (A) Ratio (mass %) Naphthoquinone diazide compound (B) Ratio (mass %) Photoradical generator/photoacid generator (C1, C1', C2, C2') Ratio (mass %) Acid anhydride compound (D) Ratio (mass %) Multifunctional monomer (E) Ratio (mass %) Solvent Ratio (mass %) Example 1 Composition 1 P-1 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 2 Composition 2 P-2 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 3 Composition 3 P-3 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 4 Composition 4 P-4 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 5 Composition 5 P-5 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 6 Composition 6 P-6 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 7 Composition 7 P-7 27.6 B-1 2.25 C-1 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 8 Composition 8 P-3 27.6 B-1 2.25 C-2 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 9 Composition 9 P-3 27.6 B-1 2.25 C-3 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 10 Composition 10 P-3 27.6 B-1 2.25 C-4 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 11 Composition 11 P-3 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 12 Composition 12 P-3 27.6 B-1 2.25 C-6 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 13 Composition 13 P-3 27.6 B-1 2.25 C-7 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 14 Composition 14 P-3 27.6 B-1 2.25 C-8 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 15 Composition 15 P-8 27.6 B-1 2.25 C-8 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 16 Composition 16 P-8 27 B-1 2.25 C-8 0.15 D-1 0.6 --- --- PGMEA/DAA 56/14

[表2B] [表2B] No. （I）感光性樹脂組成物 感光性樹脂組成物的名稱 聚矽氧烷（A） 比率（質量%） 萘醌二疊氮化合物（B） 比率（質量%） 光自由基產生劑/光酸產生劑（C1,C1',C2,C2'） 比率（質量%） 酸酐化合物（D） 比率（質量%） 多官能單體（E） 比率（質量%） 溶劑 比率（質量%） 實施例17 組成物17 P-9 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例18 組成物18 P-9 27 B-1 2.25 C-5 0.15 D-2 0.6 --- --- PGMEA/DAA 56/14 實施例19 組成物19 P-9 26.7 B-1 2.25 C-5 0.15 D-1 0.6 E-1 0.3 PGMEA/DAA 56/14 實施例20 組成物20 P-9 27.3 B-1 2.25 C-5 0.15 --- --- E-1 0.3 PGMEA/DAA 56/14 實施例21 組成物21 P-10 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 實施例22 組成物22 P-10 27 B-1 2.25 C-8 0.15 D-1 0.6 --- --- PGMEA/DAA 56/14 實施例23 組成物23 P-10 26.7 B-1 2.25 C-8 0.15 D-1 0.6 E-1 0.3 PGMEA/DAA 56/14 實施例24 組成物24 P-3 27 B-1 2.25 C-8 0.15 D-2 0.6 --- --- PGMEA/DAA 56/14 實施例25 組成物25 P-3 26.7 B-1 2.25 C-5 0.15 D-1 0.6 E-1 0.3 PGMEA/DAA 56/14 比較例1 組成物26 R-1 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 比較例2 組成物27 R-2 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 比較例3 組成物28 R-3 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 比較例4 組成物29 R-4 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 比較例5 組成物30 R-5 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 比較例6 組成物31 R-6 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 比較例7 組成物32 P-2 27.75 B-1 2.25 --- --- --- --- --- --- PGMEA/DAA 56/14 比較例8 組成物33 P-2 39 --- --- C-7 0.8 --- --- --- --- PGMEA/DAA 56/14 [Table 2B] [Table 2B] No. (I) Photosensitive resin composition Name of photosensitive resin composition Polysiloxane (A) Ratio (mass %) Naphthoquinone diazide compound (B) Ratio (mass %) Photoradical generator/photoacid generator (C1, C1', C2, C2') Ratio (mass %) Acid anhydride compound (D) Ratio (mass %) Multifunctional monomer (E) Ratio (mass %) Solvent Ratio (mass %) Example 17 Composition 17 P-9 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 18 Composition 18 P-9 27 B-1 2.25 C-5 0.15 D-2 0.6 --- --- PGMEA/DAA 56/14 Example 19 Composition 19 P-9 26.7 B-1 2.25 C-5 0.15 D-1 0.6 E-1 0.3 PGMEA/DAA 56/14 Example 20 Composition 20 P-9 27.3 B-1 2.25 C-5 0.15 --- --- E-1 0.3 PGMEA/DAA 56/14 Example 21 Composition 21 P-10 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Example 22 Composition 22 P-10 27 B-1 2.25 C-8 0.15 D-1 0.6 --- --- PGMEA/DAA 56/14 Example 23 Composition 23 P-10 26.7 B-1 2.25 C-8 0.15 D-1 0.6 E-1 0.3 PGMEA/DAA 56/14 Example 24 Composition 24 P-3 27 B-1 2.25 C-8 0.15 D-2 0.6 --- --- PGMEA/DAA 56/14 Example 25 Composition 25 P-3 26.7 B-1 2.25 C-5 0.15 D-1 0.6 E-1 0.3 PGMEA/DAA 56/14 Comparative example 1 Composition 26 R-1 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Comparative example 2 Composition 27 R-2 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Comparative example 3 Composition 28 R-3 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Comparative example 4 Composition 29 R-4 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Comparative example 5 Composition 30 R-5 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Comparative example 6 Composition 31 R-6 27.6 B-1 2.25 C-5 0.15 --- --- --- --- PGMEA/DAA 56/14 Comparative example 7 Composition 32 P-2 27.75 B-1 2.25 --- --- --- --- --- --- PGMEA/DAA 56/14 Comparative example 8 Composition 33 P-2 39 --- --- C-7 0.8 --- --- --- --- PGMEA/DAA 56/14

[表3] [table 3]

＜硬化膜的形成及評價＞ 使用所製作的感光性樹脂組成物，並利用以下的方法來製成硬化膜。另外，利用以下的方法進行硬化膜的評價。將評價結果示於表4。＜Formation and evaluation of cured film＞ Using the produced photosensitive resin composition, a cured film was produced by the following method. In addition, the cured film was evaluated by the following method. The evaluation results are shown in Table 4.

（1）硬化膜的形成 使用旋塗機（東京電子（Tokyo Electron）（股）製造，型號名克托馬（Clean Track Mark）7）以成為目標膜厚的轉速，將感光性樹脂組成物塗佈於4吋矽晶圓基板上。於塗佈後，使用加熱板SCW-636（大日本網屏（Dainippon Screen）製造（股）製造）於80℃下對基板預烘烤3分鐘。使用自動顯影裝置AD-2000（瀧澤產業（股）製造）以2.38 wt%氫氧化四甲基銨水溶液ELM-D（三菱瓦斯化學（股）製造）對其進行90秒鐘覆液顯影，繼而以水淋洗30秒鐘。使用平行光式光罩對準曝光機PLA-501F（佳能（Canon）（股）製造）對所製作的膜的整個面進行曝光後，最後使用烘箱IHPS-222（塔巴依愛斯佩克（TABAI Espec）（股）製造）於大氣下、80℃下固化120分鐘，從而獲得約1.5 μm的硬化膜。(1) Formation of hardened film The photosensitive resin composition was coated on a 4-inch silicon wafer using a spin coater (manufactured by Tokyo Electron Co., Ltd., model name: Clean Track Mark 7) at a rotation speed to achieve the target film thickness. on the substrate. After coating, the substrate was pre-baked at 80° C. for 3 minutes using a heating plate SCW-636 (manufactured by Dainippon Screen Manufacturing Co., Ltd.). The automatic developing device AD-2000 (manufactured by Takizawa Sangyo Co., Ltd.) was used to perform liquid development for 90 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and then Rinse with water for 30 seconds. After exposing the entire surface of the produced film using a parallel light type mask alignment exposure machine PLA-501F (manufactured by Canon Co., Ltd.), the oven IHPS-222 (Tabai Espec) was finally used. TABAI Espec Co., Ltd.) is cured in the atmosphere at 80°C for 120 minutes to obtain a cured film of approximately 1.5 μm.

（2）耐化學品性的評價 使用蘭達艾斯（Lambda Ace）STM-602（大日本網屏（Dainippon Screen）（股）製造）對利用所述（1）記載的方法所獲得的各硬化膜的膜厚（T1）進行測定。繼而，將該帶有硬化膜的基板於IPA、PGME、或NMP中且於23℃下浸漬1分鐘。測定於各溶劑中浸漬後的膜厚（T2），根據下述式來算出浸漬前後的膜厚變化率，並如以下般判定。另外，於浸漬後以目視確認、評價有無部分剝離。 膜厚變化率（%）=（T2/T1）×100 A：98%以上 B：50%以上且未滿98% C：未滿50%。(2) Evaluation of chemical resistance The film thickness (T1) of each cured film obtained by the method described in (1) was measured using Lambda Ace STM-602 (manufactured by Dainippon Screen Co., Ltd.) . Next, the substrate with the cured film was immersed in IPA, PGME, or NMP at 23° C. for 1 minute. The film thickness (T2) after immersion in each solvent was measured, and the film thickness change rate before and after immersion was calculated according to the following formula, and judged as follows. In addition, after immersion, the presence or absence of partial peeling was visually confirmed and evaluated. Film thickness change rate (%) = (T2/T1) × 100 A: More than 98% B: More than 50% and less than 98% C: Less than 50%.

（3）圖案加工性（解析度）的評價 使用旋塗機（東京電子（Tokyo Electron）（股）製造，型號名克托馬（Clean Track Mark）7）以成為目標膜厚的轉速，將感光性樹脂組成物塗佈於4吋矽晶圓基板上。於塗佈後，使用加熱板SCW-636（大日本網屏（Dainippon Screen）製造（股）製造）於80℃下對基板預烘烤3分鐘。使用i射線步進式曝光機進行圖案曝光。使用自動顯影裝置AD-2000（瀧澤產業（股）製造）以2.38 wt%氫氧化四甲基銨水溶液ELM-D（三菱瓦斯化學（股）製造）進行90秒鐘覆液顯影，繼而以水淋洗30秒鐘，從而獲得包含感光性樹脂組成物的圖案。該圖案形成為正型。使用平行光式光罩對準曝光機PLA-501F（佳能（Canon）（股）製造）對所製作的膜的整個面進行曝光後，最後使用烘箱IHPS-222（塔巴依愛斯佩克（TABAI Espec）（股）製造）於大氣下、80℃下固化120分鐘，從而獲得約1.5 μm的硬化膜。對於各硬化膜，將以1對1的寬度形成40 μm的L/S圖案的曝光量中的顯影後的最小圖案尺寸x作為解析度，並如以下般判定。 A：x＜10 μm B：10 μm≦x＜30 μm C：30 μm≦x 另外，如以下般判定顯微鏡觀察中有無殘渣。 ·關於最小圖案尺寸x或30 μm中小的一者的圖案 A：於顯微鏡觀察中無殘渣。 B：於顯微鏡觀察中有殘渣。 ·關於最小圖案尺寸x或10 μm中小的一者的圖案（其中僅於解析度判定A或B的情況下評價） A：於顯微鏡觀察中無殘渣。 B：於顯微鏡觀察中有殘渣。(3) Evaluation of pattern processability (resolution) The photosensitive resin composition was coated on a 4-inch silicon wafer using a spin coater (manufactured by Tokyo Electron Co., Ltd., model name: Clean Track Mark 7) at a rotation speed to achieve the target film thickness. on the substrate. After coating, the substrate was pre-baked at 80° C. for 3 minutes using a heating plate SCW-636 (manufactured by Dainippon Screen Manufacturing Co., Ltd.). Use i-ray stepper exposure machine for pattern exposure. An automatic developing device AD-2000 (manufactured by Takizawa Sangyo Co., Ltd.) was used to perform liquid development for 90 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.), followed by water rinsing Wash for 30 seconds to obtain a pattern including the photosensitive resin composition. The pattern is formed into a positive shape. After exposing the entire surface of the produced film using a parallel light type mask alignment exposure machine PLA-501F (manufactured by Canon Co., Ltd.), the oven IHPS-222 (Tabai Espec) was finally used. TABAI Espec Co., Ltd.) is cured in the atmosphere at 80°C for 120 minutes to obtain a cured film of approximately 1.5 μm. For each cured film, the minimum pattern size x after development in the exposure amount to form an L/S pattern with a width of 1 to 1 of 40 μm was used as the resolution, and it was determined as follows. A：x＜10 μm B: 10 μm≦x＜30 μm C: 30 μm≦x In addition, the presence or absence of residues in the microscopic observation was determined as follows. ·Patterns with minimum pattern size x or 30 μm, whichever is smaller A: There is no residue in microscopic observation. B: There are residues in microscopic observation. ・Patterns regarding the smaller of the minimum pattern size x or 10 μm (evaluated only in the case of resolution judgment A or B) A: There is no residue in microscopic observation. B: There are residues in microscopic observation.

根據實施例與比較例的對比，可知本發明的感光性樹脂組成物的低溫硬化性及圖案加工性優異。且可知，其硬化膜的耐化學品性優異。Comparison between Examples and Comparative Examples shows that the photosensitive resin composition of the present invention has excellent low-temperature curability and pattern processability. Furthermore, it was found that the cured film has excellent chemical resistance.

[表4A] [表4A] No. 感光性樹脂組成物 耐化學品性 顯影後解析度 殘渣 IPA PGME NMP x μm或30 μm x μm或10 μm 膜厚變化率 剝離 膜厚變化率 剝離 膜厚變化率 剝離 實施例1 組成物1 A 有 A 有 A 有 C B --- 實施例2 組成物2 A 有 B 有 C 有 B A B 實施例3 組成物3 A 有 B 有 B 有 B B B 實施例4 組成物4 A 有 B 有 B 有 B B B 實施例5 組成物5 A 有 B 有 B 有 B B B 實施例6 組成物6 A 有 B 有 B 有 B B B 實施例7 組成物7 A 有 B 有 B 有 B B B 實施例8 組成物8 A 有 B 有 B 有 A B B 實施例9 組成物9 A 有 A 有 B 有 B B B 實施例10 組成物10 A 無 A 有 B 有 B B B 實施例11 組成物11 A 無 A 有 B 有 A B B 實施例12 組成物12 A 有 B 有 B 有 B B B 實施例13 組成物13 A 無 A 有 B 有 B B B 實施例14 組成物14 A 無 A 有 B 有 A B B 實施例15 組成物15 A 無 A 有 B 有 A A B 實施例16 組成物16 A 無 A 無 B 有 A A B [Table 4A] [Table 4A] No. Photosensitive resin composition chemical resistance Resolution after development residue IPA PGME NMP x μm or 30 μm x μm or 10 μm Film thickness change rate peel off Film thickness change rate peel off Film thickness change rate peel off Example 1 Composition 1 A have A have A have C B --- Example 2 Composition 2 A have B have C have B A B Example 3 Composition 3 A have B have B have B B B Example 4 Composition 4 A have B have B have B B B Example 5 Composition 5 A have B have B have B B B Example 6 Composition 6 A have B have B have B B B Example 7 Composition 7 A have B have B have B B B Example 8 Composition 8 A have B have B have A B B Example 9 Composition 9 A have A have B have B B B Example 10 Composition 10 A without A have B have B B B Example 11 Composition 11 A without A have B have A B B Example 12 Composition 12 A have B have B have B B B Example 13 Composition 13 A without A have B have B B B Example 14 Composition 14 A without A have B have A B B Example 15 Composition 15 A without A have B have A A B Example 16 Composition 16 A without A without B have A A B

[表4B] [表4B] No. 感光性樹脂組成物 耐化學品性 顯影後解析度 殘渣 IPA PGME NMP x μm或30 μm x μm或10 μm 膜厚變化率 剝離 膜厚變化率 剝離 膜厚變化率 剝離 實施例17 組成物17 A 無 A 有 B 有 A A A 實施例18 組成物18 A 無 A 無 A 有 A A A 實施例19 組成物19 A 無 A 無 A 無 B A A 實施例20 組成物20 A 無 A 有 A 有 A A A 實施例21 組成物21 A 無 A 有 B 有 A A B 實施例22 組成物22 A 無 A 無 A 有 A A B 實施例23 組成物23 A 無 A 無 A 無 B A B 實施例24 組成物24 A 無 A 無 B 有 A B B 實施例25 組成物25 A 無 A 無 A 無 B B B 比較例1 組成物26 C 有 C 有 C 有 B B B 比較例2 組成物27 B 有 C 有 C 有 C B --- 比較例3 組成物28 C 有 C 有 C 有 B B B 比較例4 組成物29 C 有 C 有 C 有 B B B 比較例5 組成物30 B 有 C 有 C 有 C B --- 比較例6 組成物31 B 有 C 有 C 有 B B B 比較例7 組成物32 B 有 C 有 C 有 B B B 比較例8 組成物33 A 無 A 有 B 有 C B --- [產業上之可利用性][Table 4B] [Table 4B] No. Photosensitive resin composition chemical resistance Resolution after development residue IPA PGME NMP x μm or 30 μm x μm or 10 μm Film thickness change rate peel off Film thickness change rate peel off Film thickness change rate peel off Example 17 Composition 17 A without A have B have A A A Example 18 Composition 18 A without A without A have A A A Example 19 Composition 19 A without A without A without B A A Example 20 Composition 20 A without A have A have A A A Example 21 Composition 21 A without A have B have A A B Example 22 Composition 22 A without A without A have A A B Example 23 Composition 23 A without A without A without B A B Example 24 Composition 24 A without A without B have A B B Example 25 Composition 25 A without A without A without B B B Comparative example 1 Composition 26 C have C have C have B B B Comparative example 2 Composition 27 B have C have C have C B --- Comparative example 3 Composition 28 C have C have C have B B B Comparative example 4 Composition 29 C have C have C have B B B Comparative example 5 Composition 30 B have C have C have C B --- Comparative example 6 Composition 31 B have C have C have B B B Comparative example 7 Composition 32 B have C have C have B B B Comparative example 8 Composition 33 A without A have B have C B --- [Industrial availability]

由本發明的感光性樹脂組成物形成的硬化膜可用於各種電子零件、其中為固體攝像器件、抗反射膜、抗反射板、光學膜、顯示器等光學元件等。作為具體的使用例，可列舉：形成於固體攝像器件等中的光波導、微透鏡、平坦化材、液晶顯示器或彩色濾光片的保護膜、有機EL器件或液晶顯示器件等的層間絕緣膜等。The cured film formed from the photosensitive resin composition of the present invention can be used for various electronic components, including solid-state imaging devices, anti-reflective films, anti-reflective plates, optical films, optical components such as displays, and the like. Specific examples of use include optical waveguides, microlenses, planarizing materials formed in solid-state imaging devices, etc., protective films for liquid crystal displays or color filters, and interlayer insulating films for organic EL devices, liquid crystal display devices, etc. wait.

無without

無without

Claims (15)

一種正型感光性樹脂組成物，其特徵在於，含有：具有下述通式(1)及通式(2)所表示的結構的聚矽氧烷(A1)、萘醌二疊氮化合物(B)、以及於200nm~360nm具有極大吸收波長的光自由基產生劑(C1)及/或光酸產生劑(C1')，其中相對於所述聚矽氧烷(A1)中的矽原子的總量，所述通式(1)及通式(2)所表示的結構的總量為30mol%~60mol%，
Figure 109110209-A0305-02-0049-1
 R1為氫原子或甲基，R2及R3為單鍵或者經取代或未經取代的碳數1~8的烴基；星號直接鍵結於矽原子。 A positive photosensitive resin composition characterized by containing polysiloxane (A1) having a structure represented by the following general formula (1) and general formula (2), and a naphthoquinonediazide compound (B ), and a photoradical generator (C1) and/or a photoacid generator (C1') with a maximum absorption wavelength of 200nm~360nm, wherein relative to the total number of silicon atoms in the polysiloxane (A1) The total amount of the structures represented by the general formula (1) and the general formula (2) is 30mol%~60mol%,
Figure 109110209-A0305-02-0049-1
 R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are a single bond or a substituted or unsubstituted hydrocarbon group with 1 to 8 carbon atoms; the asterisk is directly bonded to the silicon atom. 如請求項1所述的正型感光性樹脂組成物，其中所述光自由基產生劑(C1)或光酸產生劑(C1')於200nm~360nm下的吸光係數的最大值為於360nm~450nm下的吸光係數的最大值的4倍以上。 The positive photosensitive resin composition as described in claim 1, wherein the maximum value of the light absorption coefficient of the photoradical generator (C1) or photoacid generator (C1') at 200nm~360nm is at 360nm~ More than 4 times the maximum value of the absorption coefficient at 450nm. 如請求項1所述的正型感光性樹脂組成物，其中所述光自由基產生劑(C1)或光酸產生劑(C1')於300nm~360nm下的吸光係數的最大值為3000mL/g．cm以上。 The positive photosensitive resin composition according to claim 1, wherein the maximum value of the light absorption coefficient of the photoradical generator (C1) or photoacid generator (C1') at 300nm~360nm is 3000mL/g ． cm or above. 如請求項1所述的正型感光性樹脂組成物，其中所述光自由基產生劑(C1)或光酸產生劑(C1')於360nm~450nm 下的吸光係數的最大值未滿500mL/g．cm。 The positive photosensitive resin composition as described in claim 1, wherein the photoradical generator (C1) or photoacid generator (C1') is between 360nm and 450nm. The maximum value of the absorbance coefficient is less than 500mL/g. cm. 如請求項1至請求項4中任一項所述的正型感光性樹脂組成物，其中所述聚矽氧烷(A1)進而具有下述通式(3)所表示的結構，
Figure 109110209-A0305-02-0050-2
 R4為單鍵或者經取代或未經取代的二價的碳數1~6的烴基，可具有取代基。 The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the polysiloxane (A1) further has a structure represented by the following general formula (3),
Figure 109110209-A0305-02-0050-2
 R 4 is a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent. 如請求項1至請求項4中任一項所述的正型感光性樹脂組成物，其中所述聚矽氧烷(A1)具有有機基，所述有機基含有羧基或羧酸酐基。 The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the polysiloxane (A1) has an organic group, and the organic group contains a carboxyl group or a carboxylic acid anhydride group. 如請求項1至請求項4中任一項所述的正型感光性樹脂組成物，進而含有具有酸酐基的化合物(D)。 The positive photosensitive resin composition according to any one of claims 1 to 4, further containing a compound (D) having an acid anhydride group. 如請求項1至請求項4中任一項所述的正型感光性樹脂組成物，進而含有具有兩個以上不飽和雙鍵的多官能單體(E)。 The positive photosensitive resin composition according to any one of claims 1 to 4, further containing a polyfunctional monomer (E) having two or more unsaturated double bonds. 如請求項1至請求項4中任一項所述的正型感光性樹脂組成物，其中所述光自由基產生劑(C1)或光酸產生劑(C1')於300nm~360nm具有極大吸收波長。 The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the photoradical generator (C1) or photoacid generator (C1') has a maximum absorption at 300nm~360nm wavelength. 一種硬化膜的製造方法，依序進行以下的步驟：(i)將如請求項1至請求項9中任一項所述的正型感光性樹 脂組成物塗佈於基板上而形成塗膜的步驟；(ii)以365nm、405nm、436nm中任一種光的曝光量為合計10mJ/m2以上、且波長未滿350nm的光的曝光量為合計1mJ/m2以下的方式對所述塗膜進行圖案曝光後，利用顯影液進行顯影，藉此去除塗膜的曝光部分的步驟；(iii)於所述顯影後，以所述光自由基產生劑(C1)及/或光酸產生劑(C1')於波長200nm~350nm下的曝光量為合計10mJ/m2以上的方式對殘留的塗膜進行曝光的步驟；以及(iv)對所述曝光後的塗膜進行加熱的步驟。 A method for manufacturing a cured film, the following steps are performed in sequence: (i) applying the positive photosensitive resin composition as described in any one of claims 1 to 9 on a substrate to form a coating film Step; (ii) Treat the coating film in such a way that the exposure amount of any light of 365nm, 405nm, and 436nm is a total of 10mJ/ m2 or more, and the exposure amount of light with a wavelength less than 350nm is a total of 1mJ/ m2 or less. After pattern exposure, use a developer to develop, thereby removing the exposed portion of the coating film; (iii) After the development, use the photo radical generator (C1) and/or the photo acid generator ( C1') the step of exposing the remaining coating film at a wavelength of 200 nm to 350 nm such that the total exposure dose is 10 mJ/m 2 or more; and (iv) the step of heating the exposed coating film. 一種硬化膜，為如請求項1至請求項9中任一項所述的正型感光性樹脂組成物的硬化膜。 A cured film is a cured film of the positive photosensitive resin composition according to any one of claims 1 to 9. 一種光學元件，包括如請求項11所述的硬化膜。 An optical element including the cured film according to claim 11. 一種電子材料，包括如請求項11所述的硬化膜。 An electronic material including the cured film according to claim 11. 一種光學元件，包括選自由包含如請求項11所述的硬化膜的光波導、平坦化膜、保護膜、及層間絕緣膜所組成的群組中的至少一種。 An optical element including at least one selected from the group consisting of an optical waveguide including the cured film according to claim 11, a planarizing film, a protective film, and an interlayer insulating film. 一種電子材料，包括選自由包含如請求項11所述的硬化膜的光波導、平坦化膜、保護膜、及層間絕緣膜所組成的群組中的至少一種。 An electronic material including at least one selected from the group consisting of an optical waveguide including the cured film according to claim 11, a planarizing film, a protective film, and an interlayer insulating film.
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