TW202024672A - Negative-type photosensitive resin composition - Google Patents

Negative-type photosensitive resin composition Download PDF

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TW202024672A
TW202024672A TW108128458A TW108128458A TW202024672A TW 202024672 A TW202024672 A TW 202024672A TW 108128458 A TW108128458 A TW 108128458A TW 108128458 A TW108128458 A TW 108128458A TW 202024672 A TW202024672 A TW 202024672A
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resin composition
photosensitive resin
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TWI815946B (en
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鈴木朋哉
安達勲
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日商日產化學股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

To provide a novel negative-working photosensitive resin composition. A negative-working photosensitive resin composition comprising a component (A), a component (B) in an amount of 80 to 90% by mass relative to 100% by mass of the component (A), a component (C) in an amount of 3 to 20% by mass relative to 100% by mass, i.e., the whole amount, of the component (B), and a solvent: (A): an alkali soluble polymer; (B): at least two crosskinkable compounds each having at least two polymerizable groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an allyl group and a vinyl group per molecule; and (C): at least one photopolymerization initiator.

Description

負型感光性樹脂組成物Negative photosensitive resin composition

本發明係關於一種含有鹼可溶性聚合物、至少2種交聯性化合物、至少1種光聚合起始劑及溶劑的負型感光性樹脂組成物者。特別為有關使用於微鏡形成的負型感光性樹脂組成物者。The present invention relates to a negative photosensitive resin composition containing an alkali-soluble polymer, at least two crosslinkable compounds, at least one photopolymerization initiator, and a solvent. Especially for the negative photosensitive resin composition used for micromirror formation.

自過去，對於CCD/CMOS圖像傳感器等電子裝置上欲提高集光效率而設有微鏡。作為CCD/CMOS圖像傳感器用微鏡的製作方法之1，已知有回蝕(Etch back)方法(專利文獻1及專利文獻2)。即，在於彩色過濾器上所形成的微鏡用樹脂層上形成阻劑圖型，藉由熱處理，將該阻劑圖型進行回流後形成透鏡圖型。將該阻劑圖型進行回流所形成的透鏡圖型作為蝕刻光罩，將下層的微鏡用樹脂層進行回蝕，藉由將透鏡圖型形狀於微鏡用樹脂層進行轉印而製作出微鏡。如此微鏡的耐藥品性、高透明性等各種特性被要求著。Since the past, electronic devices such as CCD/CMOS image sensors have been equipped with micromirrors to improve the light collection efficiency. As one of the manufacturing methods of the micromirror for CCD/CMOS image sensors, an etch back method is known (Patent Document 1 and Patent Document 2). That is, a resist pattern is formed on the resin layer for micromirrors formed on the color filter, and the resist pattern is reflowed by heat treatment to form a lens pattern. The lens pattern formed by reflowing the resist pattern is used as an etching mask, and the lower resin layer for micromirrors is etched back, and the lens pattern shape is transferred to the resin layer for micromirrors to produce Micro mirror. Various properties such as chemical resistance and high transparency of the micromirror are required.

又，僅在CCD/CMOS圖像傳感器、液晶顯示及有機EL顯示等電子裝置元件上的任意處使膜進行圖型形成時，要求其光刻性。對於如此感光性材料，要求以低曝光量形成圖型(感度特性)，及可抑制鹼顯像後的殘渣產生。In addition, photolithography is required only when the film is patterned at any place on electronic device elements such as CCD/CMOS image sensors, liquid crystal displays, and organic EL displays. For such photosensitive materials, it is required to form patterns (sensitivity characteristics) with a low exposure amount, and to suppress the generation of residues after alkali development.

然而，已有含有馬來醯亞胺系共聚物的微鏡形成用感光性樹脂組成物(專利文獻3)、含有三嗪骨架的正型阻劑組成物(專利文獻4)被提案。但這些專利文獻因為了要滿足上述諸特性，特別滿足耐溶劑性，必須要在超過100℃，例如在140℃至260℃的高溫下加熱，在100℃以下的低溫加熱下未能滿足前述特性。 [先前技術文獻] [專利文獻]However, a photosensitive resin composition for forming a micromirror containing a maleimide copolymer (Patent Document 3), and a positive resist composition containing a triazine skeleton (Patent Document 4) have been proposed. However, these patent documents must meet the above characteristics, especially solvent resistance, and must be heated at a high temperature exceeding 100°C, such as 140°C to 260°C, and fail to meet the aforementioned characteristics under low temperature heating below 100°C. . [Prior Technical Literature] [Patent Literature]

[專利文獻1] 日本特開平1-10666號公報 [專利文獻2] 日本特開平6-112459號公報 [專利文獻3] 日本專利第5867735號公報 [專利文獻4] 日本專利第5673963號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 1-10666 [Patent Document 2] Japanese Patent Laid-Open No. 6-112459 [Patent Document 3] Japanese Patent No. 5867735 [Patent Document 4] Japanese Patent No. 5673963

[發明所解決的問題][Problem Solved by Invention]

本發明係以前述情事為基礎者，該所要解決的課題為提供一種在100℃的烘烤溫度下所得的膜可顯著改善高透明性、耐溶劑性、感度特性及未曝光部的殘渣之負型感光性樹脂組成物。 [解決課題的手段]The present invention is based on the foregoing situation. The problem to be solved is to provide a film obtained at a baking temperature of 100°C that can significantly improve high transparency, solvent resistance, sensitivity characteristics, and negative effects of unexposed residues. Type photosensitive resin composition. [Means to solve the problem]

本發明者們，欲解決前述課題而進行詳細檢討結果而完成本發明。即，本發明為一種含有下述(A)成分，對於該(A)成分100質量%而言為80質量%至90質量%的下述(B)成分、對於該(B)成分的總量100質量%而言為3質量%至20質量%的下述(C)成分，及溶劑之負型感光性樹脂組成物。 (A)：鹼可溶性聚合物 (B)：於1分子中具有2個以上選自由丙烯醯基氧基、甲基丙烯醯基氧基、烯丙基及乙烯基所成群的聚合性基之至少2種的交聯性化合物 (C)：至少1種的光聚合起始劑The inventors of the present invention conducted detailed examination results to solve the aforementioned problems and completed the present invention. That is, the present invention is a component containing the following (A) component, 80% to 90% by mass relative to 100% by mass of the (A) component, and the total amount of the following (B) component 100% by mass is a negative photosensitive resin composition of the following (C) component of 3% to 20% by mass and a solvent. (A): Alkali-soluble polymer (B): A crosslinkable compound having at least two polymerizable groups selected from the group consisting of acryloxy, methacryloxy, allyl and vinyl groups in one molecule (C): At least one photopolymerization initiator

前述至少2種的交聯性化合物，例如含有：作為前述聚合性基，於1分子中具有2個丙烯醯基氧基或甲基丙烯醯基氧基的交聯性化合物，及作為前述聚合性基，於1分子中具有3個以上的丙烯醯基氧基或甲基丙烯醯基氧基的交聯性化合物。The aforementioned at least two types of crosslinkable compounds include, for example, as the aforementioned polymerizable group, a crosslinkable compound having two acryloxy groups or methacryloxy groups in one molecule, and as the aforementioned polymerizable group A group is a crosslinkable compound having 3 or more acryloxy groups or methacryloxy groups in one molecule.

前述鹼可溶性聚合物，例如具有選自由下述式(1a)、式(1b)、式(1c)、式(1d)及式(1e)所成群的結構單位。

Figure 02_image001
(式中，R1 表示氫原子或甲基，A表示-O-基或-NH-基，X表示單鍵、碳原子數1至3的伸烷基，或含有碳原子數1至3的伸烷氧基之二價的連結基，Z1 表示羥基苯基或羧基苯基，Z2 表示羥基苯基、羧基苯基或羧基，Z3 表示氫原子、羥基苯基或羧基苯基)。 前述二價的連結基，例表示前述碳原子數1至3的伸烷氧基，或2個以上的該碳原子數1至3的伸烷氧基經鍵結的基。The aforementioned alkali-soluble polymer has, for example, a structural unit selected from the group consisting of the following formula (1a), formula (1b), formula (1c), formula (1d), and formula (1e).
Figure 02_image001
(In the formula, R 1 represents a hydrogen atom or a methyl group, A represents an -O- group or a -NH- group, and X represents a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylene group containing 1 to 3 carbon atoms The divalent linking group of the alkoxy group, Z 1 represents a hydroxyphenyl group or a carboxyphenyl group, Z 2 represents a hydroxyphenyl group, a carboxyphenyl group or a carboxy group, and Z 3 represents a hydrogen atom, a hydroxyphenyl group or a carboxyphenyl group). The aforementioned divalent linking group includes, for example, the aforementioned alkoxy group having 1 to 3 carbon atoms, or a group in which two or more alkoxy groups having 1 to 3 carbon atoms are bonded.

前述鹼可溶性聚合物，例如為進一步具有與前述結構單位相異的選自由下述式(2a)、式(2b)及式(2c)所成群的結構單位之共聚物。

Figure 02_image003
(式中，R1 表示氫原子或甲基，A表示-O-基或-NH-基，X表示單鍵、碳原子數1至3的伸烷基，或含有碳原子數1至3的伸烷氧基之二價的連結基，Z4 表示碳原子數1至3的直鏈狀之有機基，或碳原子數3至14的分支鏈狀或者環狀之有機基)。The aforementioned alkali-soluble polymer is, for example, a copolymer further having a structural unit different from the aforementioned structural unit selected from the group consisting of the following formula (2a), formula (2b) and formula (2c).
Figure 02_image003
(In the formula, R 1 represents a hydrogen atom or a methyl group, A represents an -O- group or a -NH- group, and X represents a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylene group containing 1 to 3 carbon atoms The divalent linking group of alkoxy, Z 4 represents a linear organic group having 1 to 3 carbon atoms, or a branched or cyclic organic group having 3 to 14 carbon atoms).

前述二價的連結基，例如表示由前述碳原子數1至3的伸烷氧基，或該碳原子數1至3的伸烷氧基以2個以上進行鍵結的基。前述有機基可具有至少1個之氮原子、氧原子等雜原子，亦可於2個碳原子之間或於碳原子與雜原子之間具有雙鍵或參鍵。作為前述環狀的有機基，例如可舉出芳香族烴基、脂環式烴基、交聯環烴基、雜環基。The aforementioned divalent linking group means, for example, a group in which the aforementioned alkoxy group having 1 to 3 carbon atoms or the aforementioned alkoxy group having 1 to 3 carbon atoms are bonded by two or more. The aforementioned organic group may have at least one nitrogen atom, oxygen atom and other heteroatoms, and may also have a double bond or a parametric bond between two carbon atoms or between a carbon atom and a heteroatom. Examples of the aforementioned cyclic organic group include an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, and a heterocyclic group.

本發明之負型感光性樹脂組成物，例如使用於微鏡形成上。The negative photosensitive resin composition of the present invention is used, for example, for forming a micromirror.

本發明又為一種微鏡的製造方法，其為具有：將前述負型感光性樹脂組成物塗布於基板上，並經預烘烤後形成樹脂膜之步驟、通過光罩而使前述樹脂膜進行曝光的步驟、將前述曝光後的樹脂膜使用鹼性顯像液使其顯像的步驟，及使前述顯像後的樹脂膜之全面進行曝光的步驟。The present invention is also a method for manufacturing a micromirror, which includes the steps of coating the negative photosensitive resin composition on a substrate, and forming a resin film after pre-baking, and forming the resin film through a photomask. The step of exposing, the step of developing the above-mentioned exposed resin film with an alkaline developer, and the step of exposing the entire surface of the above-mentioned developed resin film.

於將前述顯像後的樹脂膜之全面進行曝光的步驟之後或該步驟之前，可進一步具有使該樹脂膜進行後烘烤的步驟。 [發明之效果]After or before the step of exposing the entire surface of the developed resin film, there may be a step of post-baking the resin film. [Effects of Invention]

本發明之負型感光性樹脂組成物為，藉由使鹼可溶性聚合物、至少2種交聯性化合物，及至少1種光聚合起始劑之添加量最適化，可得使用該組成物在100℃的烘烤溫度下所得之膜具有高透明，且高感度下未曝光部的殘渣為少，對於溶劑耐性亦優良者。因此，本發明之負型感光性樹脂組成物可作為形成微鏡的材料而適用。The negative photosensitive resin composition of the present invention can be obtained by optimizing the addition amount of an alkali-soluble polymer, at least two crosslinking compounds, and at least one photopolymerization initiator. The film obtained at a baking temperature of 100°C is highly transparent, has less residue in the unexposed area at high sensitivity, and has excellent solvent resistance. Therefore, the negative photosensitive resin composition of the present invention can be suitably used as a material for forming micromirrors.

[實施發明的型態][Type of Implementation of Invention]

本發明的負型感光性樹脂組成物為含有(A)成分、對於該(A)成分100質量%而言為80質量%至90質量%的(B)成分、對於該(B)成分的總量100質量%而言為3質量%至20質量%的(C)成分，及溶劑。以下詳細說明本發明之各成分。由本發明之負型感光性樹脂組成物中除去溶劑的固體成分，通常為1質量%至50質量%。對於本說明書，將除去溶劑的本發明之負型感光性樹脂組成物之成分定義為固體成分。The negative photosensitive resin composition of the present invention contains (A) component, 80% by mass to 90% by mass relative to 100% by mass of the (A) component (B) component, and the total of the (B) component The amount of 100% by mass is 3% by mass to 20% by mass of the component (C) and the solvent. The components of the present invention are explained in detail below. The solid content removed from the solvent in the negative photosensitive resin composition of the present invention is usually 1% by mass to 50% by mass. In this specification, the component of the negative photosensitive resin composition of the present invention from which the solvent is removed is defined as a solid component.

＜(A)成分＞ 於本發明之負型感光性樹脂組成物中之(A)成分為鹼可溶性聚合物。該聚合物為含有以下原料單體的聚合物，該原料單體為含有具有鹼可溶性基之單體及任意的其他單體者。(A)成分的鹼可溶性聚合物僅具有鹼可溶性基即可，對於構成該聚合物的高分子之主鏈的骨架及側鏈之種類等並無特別限定。前述鹼可溶性聚合物之重量平均分子量，例如為1000至50000，較佳為3000至40000。且，重量平均分子量藉由凝膠滲透層析法(GPC)，使用作為標準試料的聚苯乙烯而得到的值。＜(A) Ingredient＞ The (A) component in the negative photosensitive resin composition of the present invention is an alkali-soluble polymer. This polymer is a polymer containing the following raw material monomers, and the raw material monomers are those containing a monomer having an alkali-soluble group and any other monomers. (A) The alkali-soluble polymer of the component only needs to have an alkali-soluble group, and there are no particular limitations on the types of the backbone and side chains of the main chain of the polymer constituting the polymer. The weight average molecular weight of the aforementioned alkali-soluble polymer is, for example, 1,000 to 50,000, preferably 3,000 to 40,000. In addition, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

作為前述具有鹼可溶性基的單體，例如可舉出具有羧基的單體、具有酚性羥基的單體、具有酸酐基的單體、具有馬來醯亞胺基的單體。As the monomer having an alkali-soluble group, for example, a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, a monomer having an acid anhydride group, and a monomer having a maleimide group.

作為具有前述羧基的單體，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、單-(2-(丙烯醯氧基)乙基)鄰苯二甲酸酯、單-(2-(甲基丙烯醯氧)乙基)鄰苯二甲酸酯、N-(羧基苯基)馬來醯亞胺、N-(羧基苯基)甲基丙烯醯胺、N-(羧基苯基)丙烯醯胺、4-乙烯基安息香酸。As the monomer having the aforementioned carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, mono-(2-(methyl) (Acrylonyloxy) ethyl) phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide , 4-vinylbenzoic acid.

作為前述具有酚性羥基的單體，例如可舉出羥基苯乙烯、N-(羥基苯基)丙烯醯胺、N-(羥基苯基)甲基丙烯醯胺、N-(羥基苯基)馬來醯亞胺。Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)acrylamide. Leimine.

作為前述具有酸酐基的單體，例如可舉出馬來酸酐、衣康酸酐。Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.

作為前述具有馬來醯亞胺基的單體，例如可舉出前述N-(羧基苯基)馬來醯亞胺及N-(羥基苯基)馬來醯亞胺、馬來醯亞胺。Examples of the monomer having a maleimide group include the aforementioned N-(carboxyphenyl)maleimide, N-(hydroxyphenyl)maleimide, and maleimide.

前述具有鹼可溶性基的單體之中，亦以含有選自由丙烯酸、甲基丙烯酸、馬來酸酐及馬來醯亞胺所成群的至少1種之單體的聚合物為佳。Among the aforementioned monomers having an alkali-soluble group, a polymer containing at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, and maleimide is also preferred.

又，(A)成分的鹼可溶性聚合物可為前述具有鹼可溶性基的單體與其他單體之共聚物。該共聚物並未限定於由2種單體所得之共聚物，亦可由3種單體所得的三元共聚物(Terpolymer)。作為前述其他單體之具體例子，例如可舉出丙烯酸酯化合物、甲基丙烯酸酯化合物、N-取代馬來醯亞胺化合物、丙烯腈化合物、丙烯醯胺化合物、甲基丙烯醯胺化合物、苯乙烯化合物及乙烯基化合物。以下可舉出前述其他單體之具體例子，但並未限定於此等。In addition, the alkali-soluble polymer of the component (A) may be a copolymer of the aforementioned monomer having an alkali-soluble group and other monomers. The copolymer is not limited to a copolymer obtained from two types of monomers, and may also be a terpolymer (Terpolymer) obtained from three types of monomers. Specific examples of the aforementioned other monomers include, for example, acrylate compounds, methacrylate compounds, N-substituted maleimide compounds, acrylonitrile compounds, acrylamide compounds, methacrylamide compounds, benzene Vinyl compounds and vinyl compounds. Specific examples of the aforementioned other monomers can be given below, but they are not limited to these.

作為前述丙烯酸酯化合物，例如可舉出甲基丙烯酸酯、乙基丙烯酸酯、異丙基丙烯酸酯、苯甲基丙烯酸酯、萘丙烯酸酯、蒽基丙烯酸酯、蒽基甲基丙烯酸酯、苯基丙烯酸酯、苯氧基乙基丙烯酸酯、2,2,2-三氟乙基丙烯酸酯、tert-丁基丙烯酸酯、環己基丙烯酸酯、異冰片基丙烯酸酯、2-甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、2-乙氧基乙基丙烯酸酯、四氫糠基丙烯酸酯、3-甲氧基丁基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、2-丙基-2-金剛烷基丙烯酸酯、8-甲基-8-三環癸基丙烯酸酯、2-羥基乙基丙烯酸酯、2-羥基丙基丙烯酸酯、4-羥基丁基丙烯酸酯、2,3-二羥基丙基丙烯酸酯、二乙二醇單丙烯酸酯、己內酯2-(丙烯醯氧基)乙基酯、聚(乙二醇)乙基醚丙烯酸酯、5-丙烯醯氧基-6-羥基降冰片烯-2-羧酸-6-內酯、丙烯醯氧基乙基異氰酸酯、8-乙基-8-三環癸基丙烯酸酯、縮水甘油基丙烯酸酯。Examples of the aforementioned acrylate compounds include methacrylate, ethacrylate, isopropyl acrylate, benzyl methacrylate, naphthalene acrylate, anthracenyl acrylate, anthryl methacrylate, and phenyl methacrylate. Acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate Esters, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate Ester, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl Acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, 5 -Acrylicoxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, acryloxyethyl isocyanate, 8-ethyl-8-tricyclodecyl acrylate, glycidyl acrylate .

作為前述甲基丙烯酸酯化合物，例如可舉出甲基丙烯酸甲酯、乙基甲基丙烯酸酯、異丙基甲基丙烯酸酯、苯甲基丙烯酸甲酯、萘甲基丙烯酸酯、蒽基甲基丙烯酸酯、蒽基甲基丙烯酸甲酯、苯基甲基丙烯酸酯、苯氧基乙基甲基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、tert-丁基甲基丙烯酸酯、環己基甲基丙烯酸酯、異冰片基甲基丙烯酸酯、2-甲氧基乙基甲基丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、2-乙氧基乙基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、3-甲氧基丁基甲基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、γ-丁內酯甲基丙烯酸酯、2-丙基-2-金剛烷基甲基丙烯酸酯、8-甲基-8-三環癸基甲基丙烯酸酯、2-羥基乙基甲基丙烯酸酯、2-羥基丙基甲基丙烯酸酯、4-羥基丁基甲基丙烯酸酯、2,3-二羥基丙基甲基丙烯酸酯、二乙二醇單甲基丙烯酸酯、己內酯2-(甲基丙烯醯氧)乙基酯、聚(乙二醇)乙基醚甲基丙烯酸酯、5-甲基丙烯醯氧-6-羥基降冰片烯-2-羧酸-6-內酯、甲基丙烯醯氧乙基異氰酸酯、8-乙基-8-三環癸基甲基丙烯酸酯、縮水甘油基甲基丙烯酸酯。As the aforementioned methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methyl benzyl methacrylate, naphthalene methacrylate, anthrylmethyl Acrylate, anthryl methyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, Cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate , Tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl- 2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutylmethacrylate Base acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloxy) ethyl ester, poly(ethylene glycol) ethylene Base ether methacrylate, 5-methacryloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, methacryloxyethyl isocyanate, 8-ethyl-8-tricyclic Decyl methacrylate, glycidyl methacrylate.

作為前述乙烯基化合物，例如可舉出甲基乙烯基醚、苯甲基乙烯基醚、乙烯基萘、乙烯基蒽、乙烯基聯苯基、乙烯基咔唑、2-羥基乙基乙烯基醚、苯基乙烯基醚、丙基乙烯基醚。Examples of the aforementioned vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, and 2-hydroxyethyl vinyl ether. , Phenyl vinyl ether, propyl vinyl ether.

作為前述苯乙烯化合物，例如可舉出苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯。Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

作為前述N-取代馬來醯亞胺化合物，例如可舉出N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺。As the aforementioned N-substituted maleimide compound, for example, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide can be cited.

作為前述丙烯腈化合物，例如可舉出丙烯腈。As said acrylonitrile compound, acrylonitrile is mentioned, for example.

且，作為具有鹼可溶性基的單體與其他單體之裝入比，以具有鹼可溶性基的單體/其他單體=5至50質量%/50至95質量%者為佳。對於其他單體的具有鹼可溶性基的單體之裝入比若過少時，未曝光部會不溶解於顯像液中而容易成為殘膜或殘渣之原因。又，對於其他單體的具有鹼可溶性基的單體之裝入比若過多時，曝光部之硬化性會不足，而有無法形成圖型之可能性。In addition, as a charging ratio of the monomer having an alkali-soluble group to other monomers, the monomer having an alkali-soluble group/other monomer=5 to 50% by mass/50 to 95% by mass is preferred. If the loading ratio of the monomer having an alkali-soluble group to other monomers is too small, the unexposed part will not dissolve in the developing solution and will easily cause film or residue. In addition, if the loading ratio of the monomer having an alkali-soluble group to other monomers is too large, the curability of the exposed part will be insufficient, and there is a possibility that the pattern cannot be formed.

得到(A)成分的鹼可溶性聚合物之方法並無特別限定，但一般為藉由將含有上述具有鹼可溶性基的單體之原料單體，在聚合溶劑中，通常50℃至110℃之溫度下使其進行聚合反應而得。The method for obtaining the alkali-soluble polymer of component (A) is not particularly limited, but it is generally performed by mixing the raw material monomer containing the above-mentioned alkali-soluble group-containing monomer in a polymerization solvent, usually at a temperature of 50°C to 110°C It is obtained by polymerization reaction.

藉由前述方法所得的鹼可溶性聚合物具有選自由前述式(1a)、式(1b)、式(1c)、式(1d)及式(1e)所成群的結構單位。該鹼可溶性聚合物可進一步具有與前述結構單位相異的選自由前述式(2a)、式(2b)及式(2c)所成群的結構單位。The alkali-soluble polymer obtained by the aforementioned method has a structural unit selected from the group consisting of the aforementioned formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e). The alkali-soluble polymer may further have a structural unit different from the aforementioned structural unit selected from the group of the aforementioned formula (2a), formula (2b) and formula (2c).

於本發明之負型感光性樹脂組成物中之(A)成分的含有量，依據該組成物之固體成分中的含有量，通常為48質量%至55質量%。The content of the component (A) in the negative photosensitive resin composition of the present invention is usually 48% by mass to 55% by mass, depending on the solid content of the composition.

＜(B)成分＞ 於本發明之負型感光性樹脂組成物中之(B)成分為，於1分子中具有2個以上選自由丙烯醯基氧基、甲基丙烯醯基氧基、烯丙基及乙烯基所成群的聚合性基之至少2種的交聯性化合物。作為(B)成分，以於1分子中具有2個該聚合性基之交聯性化合物，與於1分子中具有3個以上的該聚合性基之交聯性化合物的組合者為佳。該聚合性基存在於交聯性化合物之分子末端。＜(B) Ingredient＞ The component (B) in the negative photosensitive resin composition of the present invention has two or more selected from the group consisting of acryloxy group, methacryloxy group, allyl group and vinyl group in one molecule. A group of at least two types of crosslinkable compounds of polymerizable groups. As the (B) component, a combination of a crosslinkable compound having two such polymerizable groups in one molecule and a crosslinkable compound having three or more such polymerizable groups in one molecule is preferable. The polymerizable group exists at the molecular end of the crosslinkable compound.

(B)成分之交聯性化合物，由與本發明之負型感光性樹脂組成物的其他成分之相溶性良好，且對於顯影性未有影響的觀點來看，以重量平均分子量200至1,000之化合物為佳。(B) The cross-linking compound of the component has good compatibility with the other components of the negative photosensitive resin composition of the present invention and has no effect on developability. The weight average molecular weight is between 200 and 1,000. The compound is preferred.

作為前述交聯性化合物，例如可舉出二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇二甲基丙烯酸酯、四羥甲基丙烷四丙烯酸酯、四羥甲基丙烷四甲基丙烯酸酯、四羥甲基甲烷四丙烯酸酯、四羥甲基甲烷四甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、1,3,5-三丙烯醯基六氫-S-三嗪、1,3,5-三甲基丙烯醯基六氫-S-三嗪、參(羥基乙基丙烯醯基)異氰脲酸酯、參(羥基乙基甲基丙烯醯基)異氰脲酸酯、三丙烯醯基甲醛、三甲基丙烯醯基甲醛、1,6-己二醇丙烯酸酯、1,6-己二醇甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、乙烷二醇二丙烯酸酯、乙烷二醇二甲基丙烯酸酯、2-羥基丙烷二醇二丙烯酸酯、2-羥基丙烷二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、異丙二醇二丙烯酸酯、異丙二醇二甲基丙烯酸酯、三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、N,N’-雙(丙烯醯基)半胱胺酸、N,N’-雙(甲基丙烯醯基)半胱胺酸、硫代二甘醇二丙烯酸酯、硫代二甘醇二甲基丙烯酸酯、雙酚A二丙烯酸酯、雙酚A二甲基丙烯酸酯、雙酚F二丙烯酸酯、雙酚F二甲基丙烯酸酯、雙酚S二丙烯酸酯、雙酚S二甲基丙烯酸酯、雙苯氧基乙醇芴二丙烯酸酯、雙苯氧基乙醇芴二甲基丙烯酸酯、二烯丙基醚雙酚A、o,o’-二烯丙基雙酚A、馬來酸二烯丙基、三烯丙基偏苯三酸酯。Examples of the crosslinkable compound include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate. , Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane Tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropenylhexahydro-S- Triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, ginseng (hydroxyethyl acrylate) isocyanurate, ginseng (hydroxyethyl methacrylate) isocyanurate Cyanurate, triacrylic formaldehyde, trimethacrylic formaldehyde, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, new Pentylene glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, two Ethylene glycol diacrylate, diethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N ,N'-bis(acryloyl)cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethyl Acrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate , Bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, diallyl ether bisphenol A, o,o'-diallyl bisphenol A, maleic diene Propyl, triallyl trimellitate.

前述交聯性化合物，可作為販售品而容易入手，例如可舉出KAYARAD(註冊商標)T-1420、同DPHA、同DPHA-2C、同D-310、同D-330、同DPCA-20、同DPCA-30、同DPCA-60、同DPCA-120、同DN-0075、同DN-2475、同R-526、同NPGDA、同PEG400DA、同MANDA、同R-167、同HX-220、同HX620、同R-551、同R-712、同R-604、同R-684、同GPO-303、同TMPTA、同THE-330、同TPA-320、同TPA-330、同PET-30、同RP-1040(以上為日本化藥(股)製)；Aronix(註冊商標)M-210、同M-208、同M-211B、同M-215、同M-220、同M-225、同M-270、同M-240、同M-6100、同M-6250、同M-6500、同M-6200、同M-309、同M-310、同M-321、同M-350、同M-360、同M-313、同M-315、同M-306、同M-303、同M-452、同M-408、同M-403、同M-400、同M-402、同M-405、同M-406、同M-450、同M-460、同M-510、同M-520、同M-1100、同M-1200、同M-6100、同M-6200、同M-6250、同M-6500、同M-7100、同M8030、同M8060、同M8100、同M8530、同M-8560、同M9050(以上為東亞合成(股)製)；Biscote295、同300、同360、同GPT、同3PA、同400、同260、同312、同335HP、同700(以上為大阪有機化學工業(股)製)；A-200、A-400、A-600、A-1000、AB1206PE、ABE-300、A-BPE-10、A-BPE-20、A-BPE-30、A-BPE-4、A-BPEF、A-BPP-3、A-DCP、A-DOD-N、A-HD-N、A-NOD-N、APG-100、APG-200、APG-400、APG-700、A-PTMG-65、A-9300、A-9300-1CL、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、AD-TMP、ATM-35E、A-TMMT、A-9550、A-DPH、TMPT、9PG、701A、1206PE、NPG、NOD-N、HD-N、DOD-N、DCP、BPE-1300N、BPE-900、BPE-200、BPE-100、BPE-80N、23G、14G、9G、4G、3G、2G、1G(以上為新中村化學工業(股)製)；Light esterEG、同2EG、同3EG、同4EG、同9EG、同14EG、同1.4BG、同NP、同1.6HX、同1.9ND、同G-101P、同G-201P、同DCP-M、同BP-2EMK、同BP-4EM、同BP-6EM、同TMP、light丙烯酸酯3EG-A、同4EG-A、同9EG-A、同14EG-A、同PTMGA-250、同NP-A、同MPD-A、同1.6HX-A、同1.9ND-A、同MOD-A、同DCP-A、同BP-4PA、同BA-134、同BP-10EA、同HPP-A、同G-201P、同TMP-A、同TMP-3EO-A、同TMP-6EO-3A、同PE-3A、同PE-4A、同DPE-6A、環氧酯40EM、同70PA、同200PA、同80MFA、同3002M、同3002A、同3000MK、同3000A、同EX-0205、AH-600、AT-600、UA-306H、UA-306T、UA-306I、UA-510H、UF-8001G、DAUA-167(共榮公司化學(股)製)；EBECRYL(註冊商標)TPGDA、同145、同150、同PEG400DA、同11、同HPNDA、同PETIA、同PETRA、同TMPTA、同TMPEOTA、同OTA480、同DPHA、同180、同40、同140、同204、同205、同210、同215、同220、同6202、同230、同244、同245、同264、同265、同270、同280/15IB、同284、同285、同294/25HD、同1259、同KRM8200、同4820、同4858、同5129、同8210、同8301、同8307、同8402、同8405、同8411、同8804、同8807、同9260、同9270、同KRM7735、同KRM8296、同KRM8452、同8311、同8701、同9227EA、同80、同436、同438、同446、同450、同505、同524、同525、同770、同800、同810、同811、同812、同1830、同846、同851、同852、同853、同1870、同884、同885、同600、同605、同645、同648、同860、同1606、同3500、同3608、同3700、同3701、同3702、同3703、同3708、同6040(大賽璐･Ornex(股)製)；SR212、SR213、SR230、SR238F、SR259、SR268、SR272、SR306H、SR344、SR349、SR508、CD560、CD561、CD564、SR601、SR602、SR610、SR833S、SR9003、CD9043、SR9045、SR9209、SR205、SR206、SR209、SR210、SR214、SR231、SR239、SR248、SR252、SR297、SR348、SR480、CD540、CD541、CD542、SR603、SR644、SR9036、SR351S、SR368、SR415、SR444、SR454、SR492、SR499、CD501、SR502、SR9020、CD9021、SR9035、SR350、SR295、SR355、SR399、SR494、SR9041(Sartomer公司製)。The aforementioned cross-linking compounds can be easily obtained as sold products, for example, KAYARAD (registered trademark) T-1420, the same as DPHA, the same as DPHA-2C, the same as D-310, the same as D-330, and the same as DPCA-20 , Same DPCA-30, same DPCA-60, same DPCA-120, same DN-0075, same DN-2475, same R-526, same NPGDA, same PEG400DA, same MANDA, same R-167, same HX-220, Same as HX620, same R-551, same R-712, same R-604, same R-684, same GPO-303, same TMPTA, same THE-330, same TPA-320, same TPA-330, same PET-30 , Same as RP-1040 (the above are manufactured by Nippon Kayaku Co., Ltd.); Aronix (registered trademark) M-210, same as M-208, same as M-211B, same as M-215, same as M-220, same as M-225 , Same M-270, Same M-240, Same M-6100, Same M-6250, Same M-6500, Same M-6200, Same M-309, Same M-310, Same M-321, Same M-350 , Same as M-360, Same as M-313, Same as M-315, Same as M-306, Same as M-303, Same as M-452, Same as M-408, Same as M-403, Same as M-400, Same as M-402 , Same M-405, Same M-406, Same M-450, Same M-460, Same M-510, Same M-520, Same M-1100, Same M-1200, Same M-6100, Same M-6200 , Same as M-6250, Same as M-6500, Same as M-7100, Same as M8030, Same as M8060, Same as M8100, Same as M8530, Same as M-8560, Same as M9050 (Above are manufactured by East Asia Synthetic (Stock)); Biscote295, Same as 300 , The same 360, the same GPT, the same 3PA, the same 400, the same 260, the same 312, the same 335HP, the same 700 (the above are manufactured by Osaka Organic Chemical Industry Co., Ltd.); A-200, A-400, A-600, A -1000, AB1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD -N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-9300, A-9300-1CL, A-GLY -9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A -DPH, TMPT, 9PG, 701A, 1206 PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (The above is manufactured by Shinnakamura Chemical Industry Co., Ltd.); Light esterEG, same 2EG, same 3EG, same 4EG, same 9EG, same 14EG, same 1.4BG, same NP, same 1.6HX, same 1.9ND, same G- 101P, same G-201P, same DCP-M, same BP-2EMK, same BP-4EM, same BP-6EM, same TMP, light acrylate 3EG-A, same 4EG-A, same 9EG-A, same 14EG- A. Same PTMGA-250, same NP-A, same MPD-A, same 1.6HX-A, same 1.9ND-A, same MOD-A, same DCP-A, same BP-4PA, same BA-134, same BP-10EA, same HPP-A, same G-201P, same TMP-A, same TMP-3EO-A, same TMP-6EO-3A, same PE-3A, same PE-4A, same DPE-6A, epoxy Ester 40EM, same 70PA, same 200PA, same 80MFA, same 3002M, same 3002A, same 3000MK, same 3000A, same EX-0205, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA -510H, UF-8001G, DAUA-167 (made by Gongrong Chemical Co., Ltd.); EBECRYL (registered trademark) TPGDA, the same 145, the same 150, the same PEG400DA, the same 11, the same HPNDA, the same PETIA, the same PETRA, the same TMPTA, same TMPEOTA, same OTA480, same DPHA, same 180, same 40, same 140, same 204, same 205, same 210, same 215, same 220, same 6202, same 230, same 244, same 245, same 264, Same 265, same 270, same 280/15IB, same 284, same 285, same 294/25HD, same 1259, same KRM8200, same 4820, same 4858, same 5129, same 8210, same 8301, same 8307, same 8402 8405, same 8411, same 8804, same 8807, same 9260, same 9270, same KRM7735, same KRM8296, same KRM8452, same 8311, same 8701, same 9227EA, same 80, same 436, same 438, same 446, same 450, Same 505, same 524, same 525, same 770, same 800, same 810, same 811, same 812, same 1830, same 846, same 851, same 852, same 853, same 1870, same 884, same 885, same 600, same 605, same 645, same 648, same 860, same 1606, same 3500, same 3608, same 3700, same 3701, same 3702, same 3703, same 3708, same 6040 (Daicel･Ornex (share) system) ; SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, CD9043, SR9045, SR9209, SR205, SR206, SR209 , SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020 , CD9021, SR9035, SR350, SR295, SR355, SR399, SR494, SR9041 (manufactured by Sartomer).

(B)成分之交聯性化合物可組合2種以上而使用。作為2種以上之組合，以於1分子中具有2個聚合性基之交聯性化合物及於1分子中具有3個以上聚合性基之交聯性化合物者為佳。作為該於1分子中具有3個以上聚合性基之交聯性化合物，亦可為聚合性基之數為相異的2種以上的交聯性化合物之組合。又，作為該聚合性基，以丙烯醯基氧基或甲基丙烯醯基氧基為佳。(B) The crosslinkable compound of a component can be used in combination of 2 or more types. As a combination of two or more types, a crosslinkable compound having two polymerizable groups in one molecule and a crosslinkable compound having three or more polymerizable groups in one molecule are preferred. As the crosslinkable compound having three or more polymerizable groups in one molecule, it may be a combination of two or more types of crosslinkable compounds having different polymerizable groups. In addition, as the polymerizable group, an acryloxy group or a methacryloxy group is preferable.

本發明之負型感光性樹脂組成物中之(B)成分的含有量，對於(A)成分100質量%而言為80質量%至90質量%。The content of the component (B) in the negative photosensitive resin composition of the present invention is 80% by mass to 90% by mass relative to 100% by mass of the component (A).

＜(C)成分＞ 於本發明之負型感光性樹脂組成物中之(C)成分為至少1種的光聚合起始劑。(C)成分之光聚合起始劑若為於使用於光硬化時的光源上具有吸收者即可，並無特別限定。＜(C) Ingredient＞ The (C) component in the negative photosensitive resin composition of the present invention is at least one photopolymerization initiator. The photopolymerization initiator of the component (C) is not particularly limited as long as it has an absorber for the light source used during photocuring.

作為前述光聚合起始劑，例如可舉出tert-丁基過氧基-iso-丁酸酯、2,5-二甲基-2,5-雙(苯甲醯基二氧基)己烷、1,4-雙[α-(tert-丁基二氧基)-iso-丙氧基]苯、二-tert-丁基過氧化物、2,5-二甲基-2,5-雙(tert-丁基二氧基)己烯過氧化氫、α-(iso-丙基苯基)-iso-丙基過氧化氫、tert-丁基過氧化氫、1,1-雙(tert-丁基二氧基)-3,3,5-三甲基環己烷、丁基-4,4-雙(tert-丁基二氧基)戊酸酯、環己酮過氧化物、2,2’,5,5’-四(tert-丁基過氧羰基)二苯甲酮、3,3’,4,4’-四(tert-丁基過氧羰基)二苯甲酮、3,3’,4,4’-四(tert-戊基過氧羰基)二苯甲酮、3,3’,4,4’-四(tert-己基過氧羰基)二苯甲酮、3,3’-雙(tert-丁基過氧羰基)-4,4’-二羧基二苯甲酮、tert-丁基過氧基苯甲酸酯、二-tert-丁基二過氧基間苯二甲酸酯等的有機過氧化物；9,10-蒽醌、1-氯蒽醌、2-氯蒽醌、八甲基蒽醌、1,2-苯並蒽醌等的醌類；安息香甲基、安息香乙基醚、α-甲基安息香、α-苯基安息香等的安息香衍生物；2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-[4-{4-(2-羥基-2-甲基-丙醯基)苯甲基}-苯基]-2-甲基-丙烷-1-酮、苯基乙醛酸甲基酯、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉代丙烷-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉代苯基)-1-丁酮、2-二甲基胺基-2-(4-甲基-苯甲基)-1-(4-嗎啉-4-基-苯基)-丁烷-1-酮等的烷基苯乙酮系化合物；雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、2,4,6-三甲基苯甲醯基-二苯基-膦氧化物等的醯膦氧化物系化合物；2-(O-苯甲醯肟)-1-[4-(苯基硫基)苯基]-1,2-辛烷二酮、1-(O-乙醯肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮等的肟酯系化合物。Examples of the aforementioned photopolymerization initiator include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis(benzyldioxy)hexane , 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert- Butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2, 2',5,5'-tetra(tert-butylperoxycarbonyl) benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) benzophenone, 3, 3',4,4'-tetra(tert-pentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3 '-Bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate Organic peroxides such as formate esters; Quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, etc.; Benzoin A Benzoin derivatives such as benzoin ethyl ether, α-methyl benzoin, α-phenyl benzoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propane-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl -Propane-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzene Methyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1 -(4-morpholin-4-yl-phenyl)-butan-1-one and other alkyl acetophenone compounds; bis(2,4,6-trimethylbenzyl)-phenyl Phosphine oxide compounds such as phosphine oxide, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide; 2-(O-benzyl oxime)-1-[4- (Phenylthio)phenyl)-1,2-octanedione, 1-(O-acetoxime)-1-[9-ethyl-6-(2-methylbenzyl)- 9H-carbazol-3-yl] ethyl ketone and other oxime ester compounds.

前述光聚合起始劑可作為販售品而入手，例如可舉出OMNIRAD(註冊商標)651、同184、同500、同2959、同127、同754、同907、同369、同379、同379EG、同819、同819DW、同1700、同1870、同784、同1173、同MBF、同4265、同TPO(以上為IGM Resins公司製)[舊IRGACURE(註冊商標)651、同184、同500、同2959、同127、同754、同907、同369、同379、同379EG、同819、同819DW、同1700、同1870、同784、同1173、同MBF、同4265、同TPO(以上為BASFJapan(股)製)]、IRGACURE(註冊商標)1800、同OXE01、同OXE02 (以上為BASFJapan(股)製)、KAYACURE(註冊商標) DETX、同MBP、同DMBI、同EPA、同OA(以上為日本化藥(股)製)、VICURE-10、同55(以上為STAUFFER Co.LTD製)、ESACURE(註冊商標)KIP150、同TZT、同1001、同KTO46、同KB1、同KL200、同KS300、同EB3、三嗪-PMS、三嗪A、三嗪B(以上為DKSHJapan(股)製)、ADEKA OPTOMERN-1717、同N-1414、同N-1606((股)ADEKA製)。The aforementioned photopolymerization initiator can be sold as a commercial product, for example, OMNIRAD (registered trademark) 651, the same 184, the same 500, the same 2959, the same 127, the same 754, the same 907, the same 369, the same 379, the same 379EG, the same 819, the same 819DW, the same 1700, the same 1870, the same 784, the same 1173, the same MBF, the same 4265, the same TPO (the above are made by IGM Resins) (old IRGACURE (registered trademark) 651, the same 184, the same 500 , Same 2959, same 127, same 754, same 907, same 369, same 379, same 379EG, same 819, same 819DW, same 1700, same 1870, same 784, same 1173, same MBF, same 4265, same TPO (above BASFJapan (stock) system)), IRGACURE (registered trademark) 1800, the same OXE01, the same OXE02 (the above are BASFJapan (share) system), KAYACURE (registered trademark) DETX, the same MBP, the same DMBI, the same EPA, the same OA ( The above is Nippon Kayaku Co., Ltd.), VICURE-10, the same 55 (the above is the STAUFFER Co.LTD system), ESACURE (registered trademark) KIP150, the same TZT, the same 1001, the same KTO46, the same KB1, the same KL200, the same KS300, same as EB3, triazine-PMS, triazine A, triazine B (the above are manufactured by DKSH Japan (stock)), ADEKA OPTOMERN-1717, the same as N-1414, and the same as N-1606 (manufactured by ADEKA).

(C)成分的光聚合起始劑可單獨使用1種或組合2種以上而使用。(C) The photopolymerization initiator of component can be used individually by 1 type or in combination of 2 or more types.

本發明之負型感光性樹脂組成物中之(C)成分的含有量，對於(B)成分之總量100質量%而言為3質量%至20質量%。The content of the component (C) in the negative photosensitive resin composition of the present invention is 3% by mass to 20% by mass relative to 100% by mass of the total amount of the component (B).

＜溶劑＞ 本發明之負型感光性樹脂組成物為含有溶劑。作為該溶劑，僅可溶解前述(A)成分、(B)成分及(C)成分者即可，並無特別限定。＜Solvent＞ The negative photosensitive resin composition of the present invention contains a solvent. As the solvent, only those that can dissolve the aforementioned (A) component, (B) component, and (C) component are not particularly limited.

作為前述溶劑，例如可舉出乙二醇單甲基醚、乙二醇單乙基醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、丙二醇單丁基醚、丙二醇單丁基醚乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙基、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、2-庚酮、γ-丁內酯。Examples of the aforementioned solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, Toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl glycolate Ester, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Methyl propionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone.

前述溶劑之中，亦由塗膜之塗平性的提高之觀點來看，以丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、2-庚酮、乳酸乙酯、乳酸丁酯及環己酮為佳。Among the aforementioned solvents, from the viewpoint of improving the smoothness of the coating film, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate and cyclic Hexanone is preferred.

前述溶劑可單獨使用1種或組合2種以上而使用。The aforementioned solvents can be used alone or in combination of two or more kinds.

＜界面活性劑＞ 本發明之負型感光性樹脂組成物以提高塗布性作為目的，可含有界面活性劑。作為該界面活性劑，例如可舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯十六烷基醚、聚氧乙烯油基醚等的聚氧乙烯烷基醚類、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等的聚氧乙烯烷基芳基醚類、聚氧乙烯･聚氧伸丙基嵌段共聚物類、山梨糖醇單月桂酸酯、山梨糖醇單棕櫚酸酯、山梨糖醇單硬脂酸酯、山梨糖醇單油酸酯、山梨糖醇三油酸酯、山梨糖醇三硬脂酸酯等的山梨糖醇脂肪酸酯類、聚氧乙烯山梨糖醇單月桂酸酯、聚氧乙烯山梨糖醇單棕櫚酸酯、聚氧乙烯山梨糖醇單硬脂酸酯、聚氧乙烯山梨糖醇三油酸酯、聚氧乙烯山梨糖醇三硬脂酸酯等的聚氧乙烯山梨糖醇脂肪酸酯類等的非離子系界面活性劑、EFTOP(註冊商標)EF301、同EF303、同EF352(以上為MITSUBISHI MATERIAL電子化成(股)製)、Megafac(註冊商標)F-171、同F-173、同R-30、同R-40、同R-40-LM(以上為DIC(股)製)、FLUORADFC430、同FC431(以上為3MJapan(股)製)、Asahi Guard(註冊商標)AG710、Surflon(註冊商標)S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106 (AGC(股)製)、FTX-206D、FTX-212D、FTX-218、FTX-220D、FTX-230D、FTX-240D、FTX-212P、FTX-220P、FTX-228P、FTX-240G等Footagent系列((股)Neos製)等的氟系界面活性劑、有機矽氧烷聚合物KP341(信越化學工業(股)製)。＜Surface active agent＞ The negative photosensitive resin composition of the present invention has the purpose of improving coatability, and may contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. Polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether, polyoxyethylene and polyoxypropylene block copolymers, sorbitol monolauric acid Sorbitol fatty acid esters such as sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate Class, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitol tristearate, EFTOP (registered trademark) EF301, the same as EF303, and the same EF352 (the above are MITSUBISHI MATERIAL Electronic Chemicals (stock) System), Megafac (registered trademark) F-171, same as F-173, same as R-30, same as R-40, same as R-40-LM (above is DIC (share) system), FLUORADFC430, same as FC431 (above is 3MJapan (share) system), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, same SC101, same SC102, same SC103, same SC104, same SC105, same SC106 (AGC (share) system), FTX -206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G and other Footagent series ((share) Neos system), etc. Fluorine-based surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

前述界面活性劑可單獨使用1種或組合2種以上而使用。又，前述界面活性劑被使用時，於本發明之負型感光性樹脂組成物中之該含有量為依據該組成物之固體成分中的含有量時為3質量%以下，例如為0.0001質量%至3質量%，以0.001質量%至1質量%為佳，較佳為0.01質量%至0.5質量%。The aforementioned surfactants can be used alone or in combination of two or more kinds. In addition, when the aforementioned surfactant is used, the content in the negative photosensitive resin composition of the present invention is 3% by mass or less, for example, 0.0001% by mass, depending on the content in the solid content of the composition. To 3% by mass, preferably 0.001% to 1% by mass, and more preferably 0.01% to 0.5% by mass.

＜其他添加劑＞ 本發明之負型感光性樹脂組成物在不損害本發明之效果下，視必要可將硬化助劑、紫外線吸收劑、增感劑、可塑劑、抗氧化劑、密著助劑或多價酚、多元羧酸等溶解促進劑作為其他添加劑而含有。＜Other additives＞ In the negative photosensitive resin composition of the present invention, without impairing the effects of the present invention, if necessary, curing aids, ultraviolet absorbers, sensitizers, plasticizers, antioxidants, adhesion aids or polyvalent phenols, Dissolution accelerators such as polycarboxylic acids are contained as other additives.

＜組成物之調製方法＞ 本發明之負型感光性樹脂組成物的調製方法並無特別限定，例如可舉出將(A)成分的鹼可溶性聚合物溶解於前述溶劑中，於所得之溶液中，將(B)成分之交聯性化合物及(C)成分之光聚合起始劑以所定比例進行混合，成為均勻溶液之方法。進一步可舉出於該調製方法之適當階段，視必要進一步添加前述其他添加劑而進行混合之方法。＜Preparation method of composition＞ The method for preparing the negative photosensitive resin composition of the present invention is not particularly limited. For example, the alkali-soluble polymer of component (A) is dissolved in the aforementioned solvent, and in the resulting solution, the component (B) The cross-linking compound and the photopolymerization initiator of the component (C) are mixed in a predetermined ratio to form a uniform solution. Furthermore, the method of mixing by adding the aforementioned other additives as necessary at an appropriate stage of the preparation method can be cited.

＜負型感光性樹脂組成物之使用＞ 於基板［例如以氧化矽膜包覆的矽等半導體基板、以氮化矽膜或氧化氮化矽膜包覆的矽等半導體基板、氮化矽基板、石英基板、玻璃基板(含有無鹼玻璃、低鹼玻璃、結晶化玻璃)、以銦錫氧化物(ITO)膜所形成的玻璃基板］上，藉由旋塗器、塗佈機等適當塗布方法，塗布本發明之負型感光性樹脂組成物，其後，使用加熱板等加熱手段藉由預烘烤而形成塗膜。＜Use of negative photosensitive resin composition＞ On substrates (e.g., semiconductor substrates such as silicon coated with silicon oxide film, semiconductor substrates such as silicon coated with silicon nitride film or silicon oxide nitride film, silicon nitride substrate, quartz substrate, glass substrate (including alkali-free glass) , Low-alkali glass, crystallized glass), on a glass substrate formed with indium tin oxide (ITO) film], apply the negative photosensitive resin of the present invention by appropriate coating methods such as spin coater and coater The composition is then pre-baked using heating means such as a hot plate to form a coating film.

作為前述預烘烤條件，適宜地選自烘烤溫度80℃至150℃、烘烤時間0.3至60分鐘之中，以烘烤溫度80℃至100℃，烘烤時間0.5至5分鐘為佳。As the aforementioned pre-baking conditions, a baking temperature of 80°C to 150°C and a baking time of 0.3 to 60 minutes are suitably selected, and a baking temperature of 80°C to 100°C and a baking time of 0.5 to 5 minutes are preferred.

又，作為由本發明之負型感光性樹脂組成物所形成的膜之膜厚，例如為0.005μm至20μm，較佳為0.01μm至15μm。In addition, the film thickness of the film formed from the negative photosensitive resin composition of the present invention is, for example, 0.005 μm to 20 μm, preferably 0.01 μm to 15 μm.

其次於所得之前述膜上，欲形成所定圖型而通過光罩(Reticle)進行曝光。曝光為，例如可使用g線、i線、KrF準分子激光。曝光後，視必要進行曝光後加熱(Post Exposure Bake)。作為曝光後加熱之條件，可適宜地選自加熱溫度80℃至100℃、加熱時間0.3至60分鐘之中。然後以鹼性顯像液進行顯像。Secondly, on the obtained film, to form a predetermined pattern, it is exposed through a photomask (Reticle). For exposure, for example, g-line, i-line, or KrF excimer laser can be used. After exposure, post-exposure heating (Post Exposure Bake) is performed as necessary. As the conditions for heating after exposure, the heating temperature can be suitably selected from 80°C to 100°C and the heating time from 0.3 to 60 minutes. Then develop with an alkaline developer.

作為前述鹼性顯像液，例如可舉出氫氧化鉀、氫氧化鈉等的鹼金屬氫氧化物之水溶液、氫氧化四甲基銨、氫氧化四乙基銨、科林等的氫氧化四級銨之水溶液、乙醇胺、丙基胺、乙二胺等的胺水溶液等的鹼性水溶液。這些顯像液中可進一步添加界面活性劑。As the aforementioned alkaline developing solution, for example, aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide such as Colin Alkaline aqueous solutions such as aqueous solutions of grade ammonium, aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Surfactants can be further added to these developing solutions.

作為顯像之條件，可適宜地選自顯像溫度5℃至50℃、顯像時間10秒至300秒。由本發明之負型感光性樹脂組成物所形成的膜為，使用氫氧化四甲基銨水溶液，在室溫下可容易地進行顯像。顯像後，使用作為輕洗(rinse)液，例如超純水進行適宜的輕洗。As the conditions for the development, it can be suitably selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. The film formed from the negative photosensitive resin composition of the present invention uses a tetramethylammonium hydroxide aqueous solution and can be easily developed at room temperature. After development, use as a rinse solution, such as ultrapure water, for appropriate rinse.

其後，例如使用g線、i線或KrF準分子激光，將顯像後的膜進行全面曝光。進一步於全面曝光之前或後，可使用對顯像後之膜的加熱板等加熱手段進行後烘烤。作為後烘烤條件，例如可適宜地選自烘烤溫度80℃至100℃、烘烤時間0.5分至60分鐘之中。 [實施例]After that, for example, g-line, i-line, or KrF excimer laser is used to expose the entire developed film. Further, before or after the full exposure, a heating means such as a heating plate for developing the film can be used for post-baking. As the post-baking conditions, for example, a baking temperature of 80°C to 100°C and a baking time of 0.5 minutes to 60 minutes can be appropriately selected. [Example]

以下舉出合成例及實施例而更詳細說明本發明，但本發明並未限定於下述實施例。Hereinafter, synthesis examples and examples are given to explain the present invention in more detail, but the present invention is not limited to the following examples.

[重量平均分子量之測定] 裝置：日本分光(股)製GPC系統 管柱：Shodex[註冊商標]GPC KF-804L及GPC KF-803L 管柱烤箱：40℃ 流量：1ml/分 溶離液：四氫呋喃 標準資料：聚苯乙烯[Determination of weight average molecular weight] Installation: GPC system manufactured by JASCO Corporation Column: Shodex [registered trademark] GPC KF-804L and GPC KF-803L Column oven: 40℃ Flow rate: 1ml/min Eluent: Tetrahydrofuran Standard material: Polystyrene

[合成例1] 將甲基丙烯酸60g、甲基丙烯酸甲基240g，及2,2’-偶氮二異丁腈7.6g溶解於丙二醇單甲基醚132g後，將該溶液經3小時滴入於保持在70℃的放有丙二醇單甲基醚440g之燒瓶中。滴入終了後，藉由進行18小時反應後，得到具有下述式(1b-1)所示結構單位及下述式(2a-1)所示結構單位之鹼可溶性聚合物(共聚物)的溶液(固體成分濃度35質量%)。所得之共聚物的重量平均分子量Mw為35,000(聚苯乙烯換算)。

Figure 02_image005
[Synthesis Example 1] After dissolving 60 g of methacrylic acid, 240 g of methyl methacrylate, and 7.6 g of 2,2'-azobisisobutyronitrile in 132 g of propylene glycol monomethyl ether, the solution was dropped over 3 hours Put it in a flask holding 440 g of propylene glycol monomethyl ether kept at 70°C. After the dropping was completed, the reaction was carried out for 18 hours to obtain an alkali-soluble polymer (copolymer) having a structural unit represented by the following formula (1b-1) and a structural unit represented by the following formula (2a-1) Solution (35% by mass solid content). The weight average molecular weight Mw of the obtained copolymer was 35,000 (in terms of polystyrene).
Figure 02_image005

[合成例2] 將甲基丙烯酸61g、甲基丙烯酸甲基122g、苯乙烯122g及2,2’-偶氮二異丁腈7.6g溶解於丙二醇單甲基醚134g後，將該溶液經3小時滴入於保持在70℃之放有丙二醇單甲基醚446g之燒瓶中。滴入終了後，藉由進行18小時反應，得到具有下述式(1b-1)所示結構單位、下述式(2a-1)所示結構單位及下述式(2b-1)所示結構單位之鹼可溶性聚合物(三元共聚物)之溶液(固體成分濃度35質量%)。所得之共聚物的重量平均分子量Mw為35,000(聚苯乙烯換算)。

Figure 02_image007
[Synthesis Example 2] After dissolving 61 g of methacrylic acid, 122 g of methyl methacrylate, 122 g of styrene and 7.6 g of 2,2'-azobisisobutyronitrile in 134 g of propylene glycol monomethyl ether, the solution was passed through 3 It was dropped into a flask containing 446 g of propylene glycol monomethyl ether kept at 70°C for an hour. After the completion of the dropping, the reaction was carried out for 18 hours to obtain the structural unit represented by the following formula (1b-1), the structural unit represented by the following formula (2a-1), and the following formula (2b-1) Alkali-soluble polymer (terpolymer) solution of structural unit (solid content 35% by mass). The weight average molecular weight Mw of the obtained copolymer was 35,000 (in terms of polystyrene).
Figure 02_image007

[實施例1] 將在合成例1所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)19.7g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)3.4g及ABE-300(新中村化學工業(股)製)2.1g、作為(C)成分之光聚合起始劑的IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.21g及OMNIRAD(註冊商標)184(IGM Resins公司製)[舊 IRGACURE(註冊商標)184(BASFJapan(股)製)]0.62g以及作為界面活性劑的DFX-18(Neos(股)製)0.0040g，溶解於丙二醇單甲基醚5.6g及丙二醇單甲基醚乙酸酯18.4g作成溶液。此後，使用孔徑1μm之聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。[Example 1] 19.7 g of the alkali-soluble polymer solution (solid content 35 mass%) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a cross-linking compound of component (B) Manufacturing) 3.4 g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 2.1 g, IRGACURE (registered trademark) OXE01 (manufactured by BASF Japan Co., Ltd.) 0.21 g and OMNIRAD as the photopolymerization initiator of component (C) (Registered trademark) 184 (manufactured by IGM Resins) (old IRGACURE (registered trademark) 184 (manufactured by BASF Japan Co., Ltd.)] 0.62 g and DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant 0.0040 g, dissolved in 5.6 g of propylene glycol monomethyl ether and propylene glycol monomethyl ether 18.4 g of acetate was made into a solution. After that, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition.

[實施例2] 將在合成例1所得之(A)成分的鹼可溶性聚合物的溶液(固體成分濃度35質量%)19.6g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)4.1g及ABE-300(新中村化學工業(股)製)2.1g、作為(C)成分的光聚合起始劑之 IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.21g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0040g，溶解於丙二醇單甲基醚5.6g及丙二醇單甲基醚乙酸酯18.4g中成為溶液。其後，使用孔徑1μm之聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。[Example 2] 19.6 g of the alkali-soluble polymer solution (solid content 35 mass%) of (A) component obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of (B) component Preparation) 4.1 g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 2.1 g, as a photopolymerization initiator of component (C) 0.21 g of IRGACURE (registered trademark) OXE01 (manufactured by BASF Japan) and 0.0040 g of DFX-18 (manufactured by Neos) as a surfactant, dissolved in 5.6 g of propylene glycol monomethyl ether and propylene glycol monomethyl ether Acetate became a solution in 18.4 g. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition.

[實施例3] 將在合成例1所得的(A)成分之鹼可溶性聚合物的溶液(固體成分濃度35質量%)18.8g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)3.9g及ABE-300(新中村化學工業(股)製)2.0g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.20g及OMNIRAD(註冊商標)184(IGM Resins公司製)[舊 IRGACURE(註冊商標)184(BASFJapan(股)製)]0.59g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0040g，溶解於丙二醇單甲基醚6.2g及丙二醇單甲基醚乙酸酯18.4g而作成溶液。其後，使用孔徑1μm之聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。[Example 3] 18.8 g of the alkali-soluble polymer solution (solid content 35 mass%) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a cross-linking compound of component (B) Manufactured) 3.9g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 2.0g, IRGACURE (registered trademark) OXE01 (made by BASF Japan Co., Ltd.) 0.20g and OMNIRAD as a photopolymerization initiator of component (C) (Registered trademark) 184 (manufactured by IGM Resins) (old IRGACURE (registered trademark) 184 (made by BASF Japan (stock))] 0.59g, and DFX-18 (made by Neos (stock)) as a surfactant 0.0040g, dissolved in 6.2g of propylene glycol monomethyl ether and propylene glycol monomethyl 18.4 g of ether acetate was made into a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition.

[實施例4] 將在合成例2所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)23.7g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)5.0g及ABE-300(新中村化學工業(股)製)2.5g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.25g及OMNIRAD(註冊商標)184(IGM Resins公司製)[舊 IRGACURE(註冊商標)184(BASFJapan(股)製)]0.75g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0050g，溶解於丙二醇單甲基醚1.2g及丙二醇單甲基醚乙酸酯16.6g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。[Example 4] 23.7 g of the alkali-soluble polymer solution (solid content 35% by mass) of component (A) obtained in Synthesis Example 2 and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) Made) 5.0g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 2.5g, IRGACURE (registered trademark) OXE01 (made by BASF Japan Co., Ltd.) 0.25g and OMNIRAD as the photopolymerization initiator of component (C) (Registered trademark) 184 (manufactured by IGM Resins) (old IRGACURE (registered trademark) 184 (made by BASF Japan (stock))] 0.75g, and DFX-18 (made by Neos (stock)) as a surfactant 0.0050g, dissolved in 1.2g of propylene glycol monomethyl ether and propylene glycol monomethyl 16.6 g of ether acetate was made into a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition.

[比較例1] 將在合成例1所得的(A)成分之鹼可溶性聚合物的溶液(固體成分濃度35質量%)20.8g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)2.9g及ABE-300(新中村化學工業(股)製)2.2g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.22g及OMNIRAD(註冊商標)184(IGM Resins公司製)[舊 IRGACURE(註冊商標)184(BASFJapan(股)製)]0.65g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0040g，溶解於丙二醇單甲基醚4.9g及丙二醇單甲基醚乙酸酯18.4g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例之負型感光性樹脂組成物中(B)成分的含有量在本發明之範圍外。[Comparative Example 1] 20.8 g of the alkali-soluble polymer solution (solid content 35% by mass) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) (Product) 2.9 g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 2.2 g, IRGACURE (registered trademark) OXE01 (manufactured by BASF Japan Co., Ltd.) 0.22 g and OMNIRAD as the photopolymerization initiator of component (C) (Registered trademark) 184 (manufactured by IGM Resins) (old IRGACURE (registered trademark) 184 (made by BASF Japan)] 0.65g, and DFX-18 (made by Neos (stock)) as a surfactant 0.0040g, dissolved in 4.9 g of propylene glycol monomethyl ether and propylene glycol monomethyl 18.4 g of ether acetate was made into a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of this comparative example is outside the scope of the present invention.

[比較例2] 將在合成例1所得的(A)成分之鹼可溶性聚合物的溶液(固體成分濃度35質量%)15.6g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)3.3g及ABE-300(新中村化學工業(股)製)3.3g、作為(C)成分的光聚合起始劑之 IRGACURE(註冊商標)OXE01(BASFJapan(股)製)1.3g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0040g，溶解於丙二醇單甲基醚8.3g及丙二醇單甲基醚乙酸酯18.5g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例的負型感光性樹脂組成物中(B)成分的含有量在本發明之範圍外。[Comparative Example 2] 15.6 g of the alkali-soluble polymer solution (solid content 35 mass%) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) Co., Ltd.) 3.3g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 3.3g, as the photopolymerization initiator of component (C) 1.3 g of IRGACURE (registered trademark) OXE01 (made by BASF Japan), and 0.0040 g of DFX-18 (made by Neos) as a surfactant, dissolved in 8.3 g of propylene glycol monomethyl ether and propylene glycol monomethyl ether Acetate 18.5g was made into a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of this comparative example is outside the scope of the present invention.

[比較例3] 將在合成例1所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)24.5g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)4.3g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.13g，及作為界面活性劑的DFX-18(Neos(股)製) 0.0039g，溶解於丙二醇單甲基醚2.6g及丙二醇單甲基醚乙酸酯18.5g後作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例的負型感光性樹脂組成物中(B)成分的含有量為本發明之範圍外，且該(B)成分未含有於1分子中具有2個聚合性基之交聯性化合物。[Comparative Example 3] 24.5 g of the alkali-soluble polymer solution (solid content 35% by mass) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) (Product) 4.3g, IRGACURE (registered trademark) OXE01 (made by BASF Japan Co., Ltd.) as a photopolymerization initiator of component (C) 0.13 g, and DFX-18 (made by Neos Co., Ltd.) as a surfactant 0.0039 g, dissolved in 2.6 g of propylene glycol monomethyl ether and 18.5 g of propylene glycol monomethyl ether acetate to make a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of this comparative example is outside the scope of the present invention, and the component (B) does not contain a crosslinkable compound having two polymerizable groups in one molecule.

[比較例4] 將在合成例1所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)23.2g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)4.1g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.8g，及作為界面活性劑的DFX-18(Neos(股)製) 0.0039g，溶解於丙二醇單甲基醚3.4g及丙二醇單甲基醚乙酸酯18.5g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例的負型感光性樹脂組成物中(B)成分的含有量為本發明之範圍外，且該(B)成分未含有於1分子中具有2個聚合性基之交聯性化合物。[Comparative Example 4] 23.2 g of the alkali-soluble polymer solution (solid content 35 mass%) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) (Product) 4.1 g, IRGACURE (registered trademark) OXE01 (produced by BASF Japan Co., Ltd.) as a photopolymerization initiator of component (C) 0.8 g, and DFX-18 (produced by Neos Co., Ltd.) as a surfactant 0.0039 g, dissolved in 3.4 g of propylene glycol monomethyl ether and 18.5 g of propylene glycol monomethyl ether acetate to prepare a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of this comparative example is outside the scope of the present invention, and the component (B) does not contain a crosslinkable compound having two polymerizable groups in one molecule.

[比較例5] 將在合成例1所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)19.5g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)4.1g及ABE-300(新中村化學工業(股)製)2.0g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.061g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0039g，溶解於丙二醇單甲基醚5.9g及丙二醇單甲基醚乙酸酯18.5g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例的負型感光性樹脂組成物為，(C)成分的含有量在本發明之範圍外。[Comparative Example 5] 19.5 g of the alkali-soluble polymer solution (solid content 35% by mass) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) Made) 4.1 g and 2.0 g of ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.), IRGACURE (registered trademark) OXE01 (made by BASF Japan Co., Ltd.) 0.061 g as the photopolymerization initiator of component (C), and 0.0039 g of DFX-18 (manufactured by Neos Corporation) as a surfactant was dissolved in 5.9 g of propylene glycol monomethyl ether and 18.5 g of propylene glycol monomethyl ether acetate to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. In the negative photosensitive resin composition of this comparative example, the content of the component (C) is outside the scope of the present invention.

[比較例6] 將在合成例1所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)17.1g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)3.6g及ABE-300(新中村化學工業(股)製)1.8g、作為(C)成分的光聚合起始劑之 IRGACURE(註冊商標)OXE01(BASFJapan(股)製)1.6g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0039g，溶解於丙二醇單甲基醚7.4g及丙二醇單甲基醚乙酸酯18.5g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例的負型感光性樹脂組成物為，(C)成分的含有量在本發明之範圍外。[Comparative Example 6] 17.1 g of the alkali-soluble polymer solution (solid content 35% by mass) of component (A) obtained in Synthesis Example 1, and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) (Product) 3.6g and ABE-300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 1.8g, as a photopolymerization initiator of component (C) IRGACURE (registered trademark) OXE01 (made by BASF Japan) 1.6g, and DFX-18 (made by Neos (stock)) as a surfactant 0.0039g, dissolved in 7.4g of propylene glycol monomethyl ether and propylene glycol monomethyl ether Acetate 18.5g was made into a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. In the negative photosensitive resin composition of this comparative example, the content of the component (C) is outside the scope of the present invention.

[比較例7] 將在合成例2所得之(A)成分的鹼可溶性聚合物之溶液(固體成分濃度35質量%)24.9g、作為(B)成分的交聯性化合物之PET-30(日本化藥(股)製)5.3g、作為(C)成分的光聚合起始劑之IRGACURE(註冊商標)OXE01(BASFJapan(股)製)0.26g及OMNIRAD(註冊商標)184(IGM Resins公司製) [舊IRGACURE(註冊商標)184(BASFJapan(股)製)]0.78g，以及作為界面活性劑的DFX-18(Neos(股)製)0.0045g，溶解於丙二醇單甲基醚1.3g及丙二醇單甲基醚乙酸酯17.5g而作成溶液。其後，使用孔徑1μm的聚乙烯製微濾器進行過濾後調製出負型感光性樹脂組成物。本比較例的負型感光性樹脂組成物中(B)成分的含有量為本發明之範圍外，且該(B)成分未含有於1分子中具有2個聚合性基之交聯性化合物。[Comparative Example 7] 24.9 g of the alkali-soluble polymer solution (solid content 35% by mass) of component (A) obtained in Synthesis Example 2 and PET-30 (Nippon Kayaku Co., Ltd.) as a crosslinkable compound of component (B) IRGACURE (registered trademark) OXE01 (manufactured by BASF Japan (stock)) 0.26 g and OMNIRAD (registered trademark) 184 (manufactured by IGM Resins) as the photopolymerization initiator of the component (C) (former IRGACURE (registered) Trademark) 184 (manufactured by BASF Japan Co., Ltd.)] 0.78 g, and 0.0045 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant, dissolved in 1.3 g of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetic acid 17.5 g of ester was made into a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore diameter of 1 μm to prepare a negative photosensitive resin composition. The content of the component (B) in the negative photosensitive resin composition of this comparative example is outside the scope of the present invention, and the component (B) does not contain a crosslinkable compound having two polymerizable groups in one molecule.

[透過率測定] 將在實施例1至實施例4及比較例1至比較例7所調製的各負型感光性樹脂組成物，於石英基板上使用旋轉塗布機進行塗布，對於加熱板上以100℃進行90秒的預烘烤後，形成如表1所示膜厚的樹脂膜。其次，藉由紫外線照射裝置PLA-501(F)(Canon(股)製)，將於365nm中之照射量為1000mJ/cm2 的紫外線對前述樹脂膜全面進行照射。此後，將前述樹脂膜對於加熱板上以100℃進行5分鐘後烘烤。進一步藉由分批式UV照射裝置(高壓水銀燈2kW×1燈)(Eye graphics(股)製)，將在365nm中之曝光量為1000mJ/cm2 的紫外線對前述樹脂膜全面進行照射後，於前述石英基板上形成硬化膜。前述預烘烤及後烘烤皆於大氣中實施。對於此等硬化膜，使用紫外線可視分光光度計UV-2550((股)島津製作所製)，在波長400nm至800nm的範圍下以2nm之間隔單位變化波長而測定透過率。在波長400nm至800nm之範圍所測定的最低透過率之值如表2所示。該數值越接近100%時，表示越可得到透明的膜。[Transmittance measurement] Each negative photosensitive resin composition prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 7 was coated on a quartz substrate using a spin coater. After pre-baking at 100°C for 90 seconds, a resin film having the film thickness shown in Table 1 was formed. Next, with the ultraviolet irradiation device PLA-501 (F) (manufactured by Canon Co., Ltd.), the entire surface of the resin film is irradiated with ultraviolet rays with an irradiation amount of 1000 mJ/cm 2 at 365 nm. After that, the aforementioned resin film was post-baked on the hot plate at 100°C for 5 minutes. Furthermore, a batch-type UV irradiation device (high-pressure mercury lamp 2kW×1 lamp) (manufactured by Eye Graphics (stock)) was used to irradiate the resin film with ultraviolet rays with an exposure amount of 1000 mJ/cm 2 at 365 nm. A cured film is formed on the aforementioned quartz substrate. The aforementioned pre-baking and post-baking are implemented in the atmosphere. For these cured films, an ultraviolet visible spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) was used, and the transmittance was measured by changing the wavelength in units of 2 nm intervals in a wavelength range of 400 nm to 800 nm. The lowest transmittance values measured in the wavelength range of 400nm to 800nm are shown in Table 2. The closer the value is to 100%, the more transparent film can be obtained.

[耐溶劑性試驗] 將在實施例1至實施例4及比較例1至比較例7所調製的各負型感光性樹脂組成物，於矽晶圓上使用旋轉塗布機進行塗布，對於加熱板上以100℃進行90秒預烘烤後，形成如表1所示膜厚的樹脂膜。其次，藉由紫外線照射裝置PLA-501(F)(Canon(股)製)，將於365nm中之照射量為1000mJ/cm2 的紫外線對前述樹脂膜全面進行照射。其後，將前述樹脂膜，作為鹼性顯像液使用表1所示濃度的氫氧化四甲基銨(TMAH)水溶液進行60秒顯像，以超純水進行20秒輕洗(rinse)並乾燥。其結果，在比較例3及比較例5所調製的負型感光性樹脂組成物所形成的樹脂膜，由前述矽晶圓上除去。且，將殘留的樹脂膜對於加熱板上以100℃進行5分鐘後烘烤。最後，藉由分批式UV照射裝置(高壓水銀燈2kW×1燈)(Eye graphics(股)製)，將在365nm中之曝光量為1000mJ/cm2 的紫外線對前述樹脂膜全面進行照射後，於前述矽晶圓上形成硬化膜。前述預烘烤及後烘烤皆在大氣中實施。對於此等硬化膜，對各丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、乳酸乙酯、3-甲氧基丙酸甲酯，及2.38質量%濃度之氫氧化四甲基銨(TMAH)水溶液，在23℃之溫度條件下進行含浸2分鐘之試驗。對於浸漬前後測定前述硬化膜之膜厚變化。使用於浸漬試驗的上述溶劑中即使任一種對於浸漬前之該硬化膜的膜厚，若顯示10%以上的膜厚增減時評估為“×”，若為未達10%且5%以上之膜厚增減時評估為“△”，對於所有溶劑的膜厚增減皆未達5%者則評估為“○”，無法測定者則以“-”表示，藉此評估耐溶劑性。評估結果如表2所示。[Solvent resistance test] The negative photosensitive resin composition prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 7 was coated on a silicon wafer using a spin coater. After pre-baking at 100°C for 90 seconds, a resin film with the film thickness shown in Table 1 was formed. Next, with the ultraviolet irradiation device PLA-501 (F) (manufactured by Canon Co., Ltd.), the entire surface of the resin film is irradiated with ultraviolet rays with an irradiation amount of 1000 mJ/cm 2 at 365 nm. After that, the aforementioned resin film was developed as an alkaline developing solution using a tetramethylammonium hydroxide (TMAH) aqueous solution of the concentration shown in Table 1 for 60 seconds, followed by a 20-second rinse with ultrapure water. dry. As a result, the resin film formed from the negative photosensitive resin composition prepared in Comparative Example 3 and Comparative Example 5 was removed from the silicon wafer. In addition, the remaining resin film was post-baked on the hot plate at 100°C for 5 minutes. Finally, a batch-type UV irradiation device (high-pressure mercury lamp 2kW×1 lamp) (manufactured by Eye Graphics) was used to irradiate the entire resin film with ultraviolet rays with an exposure amount of 1000mJ/cm 2 at 365nm. A cured film is formed on the aforementioned silicon wafer. The aforementioned pre-baking and post-baking are implemented in the atmosphere. For these cured films, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl 3-methoxypropionate, and 2.38% by mass of tetramethylammonium hydroxide ( The TMAH) aqueous solution was impregnated for 2 minutes at a temperature of 23°C. The thickness change of the aforementioned cured film was measured before and after immersion. For any of the above solvents used in the immersion test, the film thickness of the cured film before immersion is evaluated as "×" if it shows a film thickness increase or decrease of 10% or more, and if it is less than 10% and 5% or more The film thickness increase or decrease is evaluated as "△", the film thickness increase or decrease of all solvents is less than 5% is evaluated as "○", and those that cannot be measured are evaluated as "-" to evaluate the solvent resistance. The evaluation results are shown in Table 2.

[殘膜率、感度及殘渣評估] 將在實施例1至實施例4及比較例1至比較例7所調製的各負型感光性樹脂組成物，於矽晶圓上使用旋轉塗布機進行塗布，對於加熱板上以100℃進行90秒預烘烤後，形成如表1所示的膜厚之樹脂膜。前述預烘烤於大氣中實施。使用光干涉式膜厚測定裝置Lambda AceVM-2110( SCREENSemiconductor Solutions(股)製)，測定此等樹脂膜之膜厚。其此，藉由i線StepperNSR-2205i12D(NA=0.63) ((股)Nikon製)，隔著二元光罩將前述樹脂膜進行曝光。其後，將前述樹脂膜，使用作為鹼性顯像液之如表1所示的濃度之氫氧化四甲基銨(TMAH)水溶液進行60秒顯像，以超純水進行20秒輕洗(rinse)並乾燥。其結果自由在實施例1至實施例4、比較例1、比較例2、比較例4、比較例6及比較例7所調製的負型感光性樹脂組成物而形成的樹脂膜，7mm×7mm之矩形圖型形成於前述矽晶圓上。另一方面，自由在比較例3及比較例5所調製的負型感光性樹脂組成物所形成的樹脂膜，未形成前述矩形圖型。對於前述矽晶圓上之形成物，以與前述樹脂膜之膜厚測定的同樣方法測定膜厚。比較預烘烤直後之樹脂膜的膜厚，評估殘膜率(%)。其結果如表2所示。殘膜率係由式(顯像後膜厚/預烘烤後膜厚)×100而計算出，該數值越接近100%，表示前述樹脂膜之曝光部越不容易溶解於顯像液故較佳。[Residual film rate, sensitivity and residue evaluation] Each negative photosensitive resin composition prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 7 was coated on a silicon wafer using a spin coater, and 90°C was applied to a hot plate at 100°C. After the second pre-baking, a resin film with the film thickness shown in Table 1 was formed. The aforementioned pre-baking is carried out in the atmosphere. Use the optical interference type film thickness measuring device Lambda AceVM-2110 ( SCREENSemiconductor Solutions (Co., Ltd.), to measure the thickness of these resin films. Here, the above-mentioned resin film was exposed through a binary mask through the i-line StepperNSR-2205i12D (NA=0.63) (manufactured by Nikon). After that, the aforementioned resin film was developed for 60 seconds using an alkaline developer solution with a concentration of tetramethylammonium hydroxide (TMAH) as shown in Table 1 for 60 seconds, and lightly washed with ultrapure water for 20 seconds ( rinse) and dry. The result is a resin film formed from the negative photosensitive resin composition prepared in Example 1 to Example 4, Comparative Example 1, Comparative Example 2, Comparative Example 4, Comparative Example 6, and Comparative Example 7, 7mm×7mm The rectangular pattern is formed on the aforementioned silicon wafer. On the other hand, the resin film formed from the negative photosensitive resin composition prepared in Comparative Example 3 and Comparative Example 5 did not form the aforementioned rectangular pattern. For the formation on the aforementioned silicon wafer, the film thickness was measured in the same way as the aforementioned measurement of the thickness of the resin film. Compare the film thickness of the resin film straight after pre-baking, and evaluate the residual film rate (%). The results are shown in Table 2. The residual film rate is calculated from the formula (film thickness after development/film thickness after pre-baking)×100. The closer the value is to 100%, the less likely the exposed part of the resin film is to dissolve in the developing solution, so it is more good.

且，評估殘膜率成為最大時的最低曝光量。其結果如表2所示。即使曝光量為800mJ/cm2 以上，殘膜率並未能成為最大時，或無法形成7mm×7mm之矩形圖型時，記載為測定不能之“-”。最低曝光量越小，表示前述樹脂膜顯示越高感度。In addition, the minimum exposure amount at which the residual film rate becomes the maximum was evaluated. The results are shown in Table 2. Even if the exposure amount is 800 mJ/cm 2 or more, when the residual film rate is not maximized, or when a rectangular pattern of 7 mm×7 mm cannot be formed, it is described as "-" which cannot be measured. The smaller the minimum exposure, the higher the sensitivity of the aforementioned resin film.

且使用光干涉式膜厚測定裝置Lambda AceVM-2110((股)SCREENSemiconductor Solutions製)，測定前述樹脂膜之未曝光部的膜厚。前述膜厚越薄，表示殘渣越少。該膜厚若為10nm以上時則評估為“×”，若未達10nm且5nm以上時評估為“△”，未達5nm時評估為“○”，對殘渣進行評估。評估結果如表2所示。And use the optical interference type film thickness measuring device Lambda AceVM-2110 (manufactured by SCREENS Semiconductor Solutions), measured the film thickness of the unexposed part of the resin film. The thinner the aforementioned film thickness, the less residue. If the film thickness is 10 nm or more, it is evaluated as "x", if it is less than 10 nm and 5 nm or more, it is evaluated as "△", if it is less than 5 nm, it is evaluated as "○", and the residue is evaluated. The evaluation results are shown in Table 2.

Figure 02_image009
Figure 02_image011
Figure 02_image009
Figure 02_image011

Claims (7)

一種負型感光性樹脂組成物，其特徵為含有下述(A)成分、(B)成分、(C)成分，及溶劑者；對於該(A)成分100質量%而言為80質量%至90質量%的下述(B)成分，對於該(B)成分之總量100質量%而言為3質量%至20質量%的下述(C)成分； (A)：鹼可溶性聚合物 (B)：於1分子中具有2個以上選自由丙烯醯基氧基、甲基丙烯醯基氧基、烯丙基及乙烯基所成群的聚合性基之至少2種的交聯性化合物 (C)：至少1種的光聚合起始劑。A negative photosensitive resin composition characterized by containing the following (A) component, (B) component, (C) component, and solvent; for 100% by mass of the (A) component, it is 80% by mass to 90% by mass of the following (B) component is 3% to 20% by mass of the following (C) component with respect to 100% by mass of the total amount of the (B) component; (A): Alkali-soluble polymer (B): A crosslinkable compound having at least two polymerizable groups selected from the group consisting of acryloxy, methacryloxy, allyl and vinyl groups in one molecule (C): At least one photopolymerization initiator. 如請求項1之負型感光性樹脂組成物，其中前述至少2種的交聯性化合物為含有：於1分子中具有2個作為前述聚合性基的丙烯醯基氧基或甲基丙烯醯基氧基之交聯性化合物，及於1分子中具有3個以上作為前述聚合性基的丙烯醯基氧基或甲基丙烯醯基氧基之交聯性化合物。The negative photosensitive resin composition of claim 1, wherein the aforementioned at least two types of crosslinkable compounds contain: acryloxy or methacryloxy groups having two polymerizable groups in one molecule A crosslinkable compound of an oxy group, and a crosslinkable compound of an acryloxy group or a methacryloxy group having 3 or more of the aforementioned polymerizable groups in one molecule. 如請求項1或2之負型感光性樹脂組成物，其中前述鹼可溶性聚合物為具有：選自由下述式(1a)、式(1b)、式(1c)、式(1d)及式(1e)所成群的結構單位；
Figure 03_image001
(式中，R1 表示氫原子或甲基，A表示-O-基或-NH-基，X表示單鍵、碳原子數1至3的伸烷基，或含有碳原子數1至3的伸烷氧基的二價之連結基，Z1 表示羥基苯基或羧基苯基，Z2 表示羥基苯基、羧基苯基或羧基，Z3 表示氫原子、羥基苯基或羧基苯基)。The negative photosensitive resin composition of claim 1 or 2, wherein the alkali-soluble polymer has: selected from the following formula (1a), formula (1b), formula (1c), formula (1d) and formula ( 1e) The group of structural units;
Figure 03_image001
(In the formula, R 1 represents a hydrogen atom or a methyl group, A represents an -O- group or a -NH- group, and X represents a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylene group containing 1 to 3 carbon atoms The divalent linking group of the alkoxy group, Z 1 represents a hydroxyphenyl group or a carboxyphenyl group, Z 2 represents a hydroxyphenyl group, a carboxyphenyl group or a carboxy group, and Z 3 represents a hydrogen atom, a hydroxyphenyl group or a carboxyphenyl group). 如請求項3之負型感光性樹脂組成物，其中前述鹼可溶性聚合物為進一步具有與前述結構單位相異的選自由下述式(2a)、式(2b)及式(2c)所成群的結構單位之共聚物；
Figure 03_image003
(式中，R1 、A及X與請求項3所記載的定義相同，Z4 表示碳原子數1至3之直鏈狀的有機基，或具有碳原子數3至14的分支鏈狀或者環狀的有機基)。The negative photosensitive resin composition of claim 3, wherein the alkali-soluble polymer further has a different structural unit from the group selected from the following formula (2a), formula (2b) and formula (2c) The structure unit of the copolymer;
Figure 03_image003
(In the formula, R 1 , A and X have the same definitions as described in claim 3, and Z 4 represents a linear organic group with 1 to 3 carbon atoms, or a branched chain with 3 to 14 carbon atoms, or Cyclic organic group). 如請求項1至4中任一項之負型感光性樹脂組成物，其為使用於微鏡形成。The negative photosensitive resin composition according to any one of claims 1 to 4, which is used for the formation of micromirrors. 一種微鏡之製作方法，其特徵為具有： 將請求項5之負型感光性樹脂組成物塗布於基板上，經預烘烤後形成樹脂膜的步驟、通過光罩使前述樹脂膜進行曝光的步驟、將前述曝光後的樹脂膜使用鹼性顯像液進行顯像的步驟，及使前述顯像後的樹脂膜之全面進行曝光的步驟。A method for manufacturing a micromirror, which is characterized by: The step of applying the negative photosensitive resin composition of claim 5 on a substrate and forming a resin film after pre-baking, the step of exposing the resin film through a photomask, and the use of an alkaline resin film after the exposure The step of developing the developing solution and the step of exposing the entire surface of the developed resin film. 如請求項6之製作方法，於將前述顯像後的樹脂膜之全面進行曝光的步驟之後或該步驟之前，進一步具有使該樹脂膜進行後烘烤的步驟。According to the manufacturing method of claim 6, after the step of exposing the entire surface of the developed resin film or before the step, there is a step of post-baking the resin film.
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