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TWI578103B - A radiation-sensitive resin composition, an insulating film, and a display device - Google Patents

A radiation-sensitive resin composition, an insulating film, and a display device Download PDF

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Publication number
TWI578103B
TWI578103B TW103104275A TW103104275A TWI578103B TW I578103 B TWI578103 B TW I578103B TW 103104275 A TW103104275 A TW 103104275A TW 103104275 A TW103104275 A TW 103104275A TW I578103 B TWI578103 B TW I578103B
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group
substituent
carbon atoms
resin composition
sensitive resin
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TW103104275A
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TW201432377A (en
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Akira Katano
Yasuhide Ohuchi
Kazuya Someya
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Tokyo Ohka Kogyo Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)

Description

感放射線性樹脂組成物、絕緣膜、及顯示裝置 Radiation-sensitive linear resin composition, insulating film, and display device

本發明關於一種感放射線性樹脂組成物、使用該感放射線性樹脂組成物而形成的絕緣膜、及具備該絕緣膜之顯示裝置。 The present invention relates to a radiation sensitive resin composition, an insulating film formed using the radiation sensitive resin composition, and a display device including the insulating film.

於如液晶顯示裝置之顯示裝置中，如絕緣膜或間隔件之材料，需要使由如背光源這樣的光源所發出的光高效地透過。因此，使用利用曝光而提供透明的硬化膜之感放射線性樹脂組成物(感光性樹脂組成物)，以形成絕緣膜或間隔件的圖案。藉由將此種感放射線性樹脂組成物選擇性地曝光，可形成透明的硬化膜的圖案。 In a display device such as a liquid crystal display device, such as an insulating film or a spacer, it is necessary to efficiently transmit light emitted from a light source such as a backlight. Therefore, a radiation-sensitive resin composition (photosensitive resin composition) which provides a transparent cured film by exposure is used to form a pattern of an insulating film or a spacer. By selectively exposing such a radiation sensitive resin composition, a pattern of a transparent cured film can be formed.

作為可形成透明的硬化膜之感放射線性樹脂組成物(感光性樹脂組成物)，提出一種例如包含樹脂、聚合性化合物、特定結構的聚合引發劑及溶劑之組成物(專利文獻1)。具體而言，於專利文獻1的實施例中，揭示出一種感放射線性樹脂組成物，其包含甲基丙烯酸與具有脂環式環氧基之丙烯酸酯的共聚物、二季戊四醇六丙烯酸酯、由下式所表示之聚合引發劑、及由3-甲氧基-1-丁醇、丙二醇單甲醚乙酸酯、3-乙氧基丙酸乙酯及3-甲氧基乙酸丁酯所構成之混合溶劑。 As a radiation-sensitive resin composition (photosensitive resin composition) which can form a transparent cured film, for example, a composition containing a resin, a polymerizable compound, a polymerization initiator having a specific structure, and a solvent is proposed (Patent Document 1). Specifically, in the embodiment of Patent Document 1, a radiation sensitive resin composition comprising a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, and the like is disclosed. a polymerization initiator represented by the following formula, and a composition consisting of 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxyacetic acid butyl ester a mixed solvent.

[先前技術文獻] [Previous Technical Literature] (專利文獻) (Patent Literature)

專利文獻1：日本特開2012-58728號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-58728

然而，使用專利文獻1所記載的感放射線性樹脂組成物而形成的硬化膜，其透明性並不充分。又，在將專利文獻1所記載的感放射性樹脂組成物的塗膜曝光之後，利用如氫氧化四甲銨的水溶液之鹼性顯影液將塗膜顯影時，應殘留的曝光部會過度溶解，難以形成所需形狀的圖案。 However, the cured film formed by using the radiation sensitive resin composition described in Patent Document 1 is not sufficiently transparent. In addition, after the coating film of the radiation-sensitive resin composition described in Patent Document 1 is exposed, and the coating film is developed by an alkaline developing solution such as an aqueous solution of tetramethylammonium hydroxide, the exposed exposed portion is excessively dissolved. It is difficult to form a pattern of a desired shape.

本發明是鑒於上述問題而完成，其目的在於提供一種感放射線性樹脂組成物、使用該感放射線性樹脂組成物而形成的絕緣膜及具備該絕緣膜之顯示裝置，其中，該感放射線性樹脂組成物提供透明性優異的硬化膜，並於曝光後的顯 影時抑制曝光部的過度溶解。 The present invention has been made in view of the above problems, and an object thereof is to provide a radiation sensitive resin composition, an insulating film formed using the radiation sensitive resin composition, and a display device including the same, wherein the radiation sensitive resin The composition provides a cured film excellent in transparency and is exposed after exposure The film is suppressed from excessive dissolution of the exposed portion.

本發明人發現，藉由向感放射性樹脂組成物中，調配(A)鹼可溶性樹脂、(B)光聚合性化合物及(C)光聚合引發劑，可解決上述問題，從而完成本發明；其中，該(A)鹼可溶性樹脂是由包含(a1)來自於不飽和羧酸之單元、與(a2)來自於不飽和化合物之單元之共聚物所構成，該不飽和化合物含有不具有環氧基之脂環式骨架；該(C)光聚合引發劑包含特定結構的肟酯化合物。 The present inventors have found that the above problems can be solved by blending (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator into a radiation-sensitive resin composition, thereby completing the present invention; The (A) alkali-soluble resin is composed of a copolymer comprising (a1) a unit derived from an unsaturated carboxylic acid and (a2) a unit derived from an unsaturated compound, which contains no epoxy group. An alicyclic skeleton; the (C) photopolymerization initiator contains an oxime ester compound of a specific structure.

本發明的第一態樣是一種感放射線性樹脂組成物，其包含(A)鹼可溶性樹脂、(B)光聚合性化合物及(C)光聚合引發劑；前述(A)鹼可溶性樹脂，包含(a1)來自於不飽和羧酸之單元、與(a2)來自於不飽和化合物之單元，該不飽和化合物含有不具有環氧基之脂環式骨架；前述(C)光聚合引發劑，包含由下述式(1)所表示之肟酯化合物， A first aspect of the present invention is a radiation sensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator; and the above (A) an alkali-soluble resin, comprising (a1) a unit derived from an unsaturated carboxylic acid, and (a2) a unit derived from an unsaturated compound containing an alicyclic skeleton having no epoxy group; and the above (C) photopolymerization initiator, comprising An oxime ester compound represented by the following formula (1),

(R1為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，m為0~4的整數，p為0或1，R2為亦可具有取代基之苯基或亦可具有取代基之咔唑基，R3為 氫原子或碳數1~6的烷基)。 (R 1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R 2 is The phenyl group which may have a substituent or the carbazolyl group which may have a substituent, and R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

本發明的第二態樣，是一種絕緣膜，其使用第一態樣的感放射線性樹脂組成物而形成。 A second aspect of the present invention is an insulating film formed using the first aspect of the radiation sensitive resin composition.

本發明的第三態樣，是一種顯示裝置，其具備第二態樣的絕緣膜。 A third aspect of the invention is a display device comprising a second aspect of an insulating film.

根據本發明，可提供一種感放射線性樹脂組成物、使用該感放射線性樹脂組成物而形成的絕緣膜及具備該絕緣膜之顯示裝置，其中，該感放射線性樹脂組成物提供透明性優異的硬化膜，並於曝光後的顯影時抑制曝光部的過度溶解。 According to the present invention, it is possible to provide a radiation sensitive resin composition, an insulating film formed using the radiation sensitive resin composition, and a display device including the same, wherein the radiation sensitive resin composition provides excellent transparency The film is cured and excessive dissolution of the exposed portion is suppressed at the time of development after exposure.

《感放射線性樹脂組成物》 Radiation-sensitive resin composition

本發明的感放射線性樹脂組成物，含有：(A)鹼可溶性樹脂，其包含特定的單元；(B)光聚合性化合物；及，(C)光聚合引發劑，其包含特定結構的肟酯化合物。以下，說明感放射線性樹脂組成物中所含有的各成分。 The radiation sensitive resin composition of the present invention comprises: (A) an alkali-soluble resin comprising a specific unit; (B) a photopolymerizable compound; and (C) a photopolymerization initiator comprising a decyl ester having a specific structure Compound. Hereinafter, each component contained in the radiation sensitive resin composition will be described.

<(A)鹼可溶性樹脂> <(A) alkali soluble resin>

(A)鹼可溶性樹脂，是指利用樹脂濃度20質量%的樹脂溶液(溶劑：丙二醇單甲醚乙酸酯)，於基板上形成膜厚1μm的樹脂膜，當在23℃浸漬於2.38質量%的氫氧化四甲銨(Tetramethylammonium Hydroxide，TMAH)水溶液中1分鐘時，膜厚溶解0.01μm以上者。 (A) the alkali-soluble resin is a resin solution having a resin thickness of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a resin film having a thickness of 1 μm is formed on the substrate, and is immersed at 2.38 mass% at 23 ° C. When the aqueous solution of tetramethylammonium hydroxide (TMAH) was used for 1 minute, the film thickness was 0.01 μm or more.

作為(A)鹼可溶性樹脂，使用包含以下單元之共聚物：(a1)來自於不飽和羧酸之單元(以下，亦記為(a1)單元)、與(a2)來自於不飽和化合物之單元(以下，亦記為(a2)單元)，該不飽和化合物含有不具有環氧基之脂環式骨架。藉由使用包含(a1)單元與(a2)單元之(A)鹼可溶性樹脂，易於獲得以下感放射線性樹脂組成物：提供透明性優異的硬化膜，並於曝光後的顯影時抑制曝光部的過度溶解。 As the (A) alkali-soluble resin, a copolymer comprising the following units: (a1) a unit derived from an unsaturated carboxylic acid (hereinafter also referred to as a unit (a1)), and (a2) a unit derived from an unsaturated compound. (Hereinafter, it is also referred to as a unit (a2)), and the unsaturated compound contains an alicyclic skeleton having no epoxy group. By using the (A) alkali-soluble resin containing the unit (a1) and the unit (a2), it is easy to obtain the following radiation-sensitive resin composition: a cured film excellent in transparency is provided, and the exposed portion is suppressed at the time of development after exposure Overly dissolved.

作為(A)成分而使用之樹脂，若為包含(a1)單元與(a2)單元之樹脂，則並無特別限定，可自以往各種感放射線性樹脂組成物中所使用的鹼可溶性樹脂適當選擇並使用。 The resin to be used as the component (A) is not particularly limited as long as it is a resin containing the unit (a1) and the unit (a2), and can be appropriately selected from alkali-soluble resins used in conventional radiation-sensitive resin compositions. And use.

作為生成(a1)單元之不飽和羧酸，可列舉：(甲基)丙烯酸、巴豆酸等單羧酸；馬來酸、富馬酸、檸康酸、中康酸及伊康酸等二羧酸；及，該等二羧酸的酐等。其中，自共聚反應性、所獲得之樹脂的鹼溶性及取得的容易性等方面來看，較佳為(甲基)丙烯酸和馬來酸酐。(A)鹼可溶性樹脂亦可包含組合2種以上的由該等不飽和羧酸所衍生的(a1)單元。 Examples of the unsaturated carboxylic acid which forms the unit (a1) include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. An acid; and an anhydride of the dicarboxylic acid. Among them, (meth)acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, and ease of availability. (A) The alkali-soluble resin may further comprise a combination of two or more types of (a1) units derived from the unsaturated carboxylic acids.

(a2)單元，若為來自於不飽和化合物之單元(該不飽和化合物含有不具有環氧基之脂環式骨架)，則並無特別限定。脂環式骨架可為單環亦可為多環。作為含有脂環式骨架之不飽和化合物中所包含之單環的脂環式基團，可列舉環戊基、環己基等。又，作為多環的脂環式基團，可列舉金剛烷基、降莰基、異莰基、三環壬基、三環癸基及四環十二烷基等。(A)鹼可溶性樹脂亦可包含組合2種以上的(a2)單元。 The unit (a2) is not particularly limited as long as it is a unit derived from an unsaturated compound (the unsaturated compound contains an alicyclic skeleton having no epoxy group). The alicyclic skeleton may be a single ring or a polycyclic ring. Examples of the alicyclic group of the monocyclic ring contained in the unsaturated compound containing an alicyclic skeleton include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, and a tetracyclododecyl group. (A) The alkali-soluble resin may further contain two or more types of (a2) units.

作為提供(a2)單元之不飽和化合物(該不飽和化合物 含有不具有環氧基之脂環式基團)，可列舉例如由下述式(a2-1)~(a2-7)所表示之化合物。於該等中，自易於獲得顯影性良好的感放射線性樹脂組成物之方面來看，較佳為由下述式(a2-3)~(a2-8)所表示之化合物，更佳為由下述式(a2-3)或(a2-4)所表示之化合物。 As an unsaturated compound providing the (a2) unit (the unsaturated compound) Examples of the alicyclic group having no epoxy group include compounds represented by the following formulas (a2-1) to (a2-7). In the above, from the viewpoint of easily obtaining a radiation-sensitive resin composition having good developability, a compound represented by the following formulas (a2-3) to (a2-8) is preferred, and more preferably A compound represented by the following formula (a2-3) or (a2-4).

上述式中，Ra1表示氫原子或甲基，Ra2表示單鍵或碳數1~6的2價的脂肪族飽和烴基，Ra3表示氫原子或碳數1~5的烷基。作為Ra2，較佳為單鍵、直連狀或支鏈狀的亞烷基(伸烷基)，例如為亞甲基、亞乙基、亞丙基、四亞甲基、乙基亞乙基(ethyl ethylene group)、五亞甲基、六亞甲基。作為Ra3，較佳為甲基、乙基。 In the above formula, R a1 represents a hydrogen atom or a methyl group, R a2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R a3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R a2 , a single bond, a straight-chain or a branched alkylene group (alkylene group) is preferable, and examples thereof include a methylene group, an ethylene group, a propylene group, a tetramethylene group, and an ethylylene group. (ethyl ethylene group), pentamethylene, hexamethylene. R a3 is preferably a methyl group or an ethyl group.

又，較佳為，(A)鹼可溶性樹脂不僅包含(a1)單元和(a2)單元，亦包含(a3)來自於含有脂環式環氧基之不飽和化合物之單元(以下，亦記為(a3)單元)。於(A)鹼可溶性樹脂包含(a3)單元之情況下，當將使用感放射線性樹脂組成物而形成的塗佈膜曝光後，進行後烘乾時，易於抑制塗佈膜的過度的形狀變化。 Further, it is preferable that the (A) alkali-soluble resin contains not only the unit (a1) and the unit (a2), but also (a3) a unit derived from an unsaturated compound containing an alicyclic epoxy group (hereinafter also referred to as (a3) unit). In the case where the (A) alkali-soluble resin contains the unit (a3), when the coating film formed using the radiation-sensitive resin composition is exposed, it is easy to suppress excessive shape change of the coating film when post-baking is performed. .

於(a3)單元中，構成脂環式環氧基之脂環式基團， 可為單環亦可為多環。作為單環的脂環式基團，可列舉環戊基、環己基等。又，作為多環的脂環式基團，可列舉降莰基、異莰基、三環壬基、三環癸基及四環十二烷基等。(A)鹼可溶性樹脂亦可將(a3)單元組合2種以上來包含。 In the unit (a3), an alicyclic group constituting an alicyclic epoxy group, It can be a single ring or a multiple ring. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, and a tetracyclododecyl group. (A) The alkali-soluble resin may be contained in combination of two or more types of (a3) units.

作為提供(a3)單元之不飽和化合物(該不飽和化合物含有脂環式環氧基)的具體例，可列舉例如由下述式(a3-1)~(a3-16)所表示之化合物。其中，為了使感放射性樹脂組成物的顯影性為適當的程度，較佳為由下述式(a3-1)~(a3-6)所表示之化合物，更佳為由下述式(a3-1)~(a3-4)所表示之化合物。 Specific examples of the unsaturated compound (the unsaturated compound containing an alicyclic epoxy group) which provides the unit (a3) include compounds represented by the following formulas (a3-1) to (a3-16). In order to make the developability of the radiation-sensitive resin composition suitable, the compound represented by the following formulas (a3-1) to (a3-6) is preferable, and more preferably, it is represented by the following formula (a3- 1) The compound represented by ~(a3-4).

上述式中，Ra4表示氫原子或甲基，Ra5表示碳數1~6的2價的脂肪族飽和烴基，Ra6表示碳數1~10的2價的烴基，n表示0~10的整數。作為Ra5，較佳為直連狀或支鏈狀的亞烷基，例如為亞甲基、亞乙基、亞丙基、四亞甲基、乙基亞乙基、五亞甲基及六亞甲基。作為R13，較佳為例如亞甲基、亞乙基、亞丙基、四亞甲基、乙基亞乙基、五亞甲基、六亞甲基、亞苯基、亞環己基及-CH2-Ph-CH2-(Ph表示亞苯基)。 In the above formula, R a4 represents a hydrogen atom or a methyl group, R a5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R a6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 to 10; Integer. R a5 is preferably a straight-chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene and six Methylene. R 13 is preferably, for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene and CH 2 -Ph-CH 2 - (Ph represents a phenylene group).

(A)鹼可溶性樹脂亦可包含上述(a1)單元、(a2)單元及(a3)單元以外之單元。作為提供上述單元以外之單元之化合物，可列舉(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、烯丙化合 物、乙烯醚類、乙烯酯類、苯乙烯類及含有不具有脂環式基團之環氧基之不飽和化合物等。該等化合物可單獨使用，或組合2種以上使用。 (A) The alkali-soluble resin may further contain units other than the above (a1) unit, (a2) unit, and (a3) unit. Examples of the compound which provides a unit other than the above unit include (meth) acrylates, (meth) acrylamides, and allylates. And vinyl ethers, vinyl esters, styrenes, and unsaturated compounds containing an epoxy group having no alicyclic group. These compounds may be used singly or in combination of two or more.

作為(甲基)丙烯酸酯類，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸戊酯及(甲基)丙烯酸三級辛酯等直連狀或支鏈狀的(甲基)丙烯酸烷基酯；(甲基)丙烯酸氯乙酯、2,2-二甲基羥基(甲基)丙烯酸丙酯、(甲基)丙烯酸2-羥乙酯、三羥甲基丙烷單(甲基)丙烯酸酯、(甲基)丙烯酸苄酯及(甲基)丙烯酸糠酯等。 Examples of the (meth) acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and (meth)acrylic acid. Straight or branched alkyl (meth)acrylate such as octyl ester; chloroethyl (meth)acrylate, propyl 2,2-dimethylhydroxy(meth)acrylate, (methyl) 2-hydroxyethyl acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, and decyl (meth)acrylate.

作為(甲基)丙烯醯胺類，可列舉：(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N-芳基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺、N,N-芳基(甲基)丙烯醯胺、N-甲基-N-苯基(甲基)丙烯醯胺及N-羥乙基-N-甲基(甲基)丙烯醯胺等。 Examples of the (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, and N, N-di. Alkyl (meth) acrylamide, N,N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N- Base (meth) acrylamide and the like.

作為烯丙化合物，可列舉：乙酸烯丙酯、己酸烯丙酯、辛酸烯丙酯、月桂酸烯丙酯、棕櫚酸烯丙酯、硬脂酸烯丙酯、苯甲酸烯丙酯、乙醯乙酸烯丙酯及乳酸烯丙酯等烯丙酯類；及，烯丙氧基乙醇等。 Examples of the allylic compound include allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, and B. Allyl esters such as allyl acetate and allyl lactate; and allyloxyethanol.

作為乙烯醚類，可列舉：己基乙烯醚、辛基乙烯醚、癸基乙烯醚、乙基己基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙烯醚、氯乙基乙烯醚、1-甲基-2,2-二甲基丙基乙烯醚、2-乙基丁基乙烯醚、羥乙基乙烯醚、二乙二醇乙烯醚、二甲基氨乙基乙烯醚、二乙基氨乙基乙烯醚、丁基氨乙基乙烯醚、苄基乙烯醚、四氫化糠基乙烯醚等烷基乙烯醚；及，乙烯基苯基醚、乙烯基甲苯基醚、乙烯基氯苯醚、乙烯基-2,4-二氯 苯醚、乙烯基萘基醚、乙烯基蒽醚等乙烯基芳基醚等。 Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, and chloroethyl vinyl ether. 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethyl Alkyl vinyl ethers such as hydroxyethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; and, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorobenzene Ether, vinyl-2,4-dichloro A vinyl aryl ether such as phenyl ether, vinyl naphthyl ether or vinyl anthracene.

作為乙烯酯類，可列舉：丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、二乙基乙酸乙烯酯、戊酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、甲氧基乙酸乙烯酯、丁氧基乙酸乙烯酯、乙烯基乙酸苯酯、乙醯乙酸乙烯酯、乳酸乙烯酯、乙烯基-β-丁酸苯酯、苯甲酸乙烯酯、水楊酸乙烯酯、氯苯甲酸乙烯酯、四氯苯甲酸乙烯酯及萘甲酸乙烯酯等。 Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, and dichloro Vinyl acetate, methoxyvinyl acetate, butoxy vinyl acetate, phenyl vinyl acetate, ethylene glycol acetate, vinyl lactate, phenyl-β-butyric acid phenyl ester, vinyl benzoate, water Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthalate.

作為苯乙烯類，可列舉：苯乙烯；甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯及乙醯氧基甲基苯乙烯等烷基苯乙烯；甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯及二甲氧基苯乙烯等烷氧基苯乙烯；及，氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、4-氟-3-三氟甲基苯乙烯等鹵代苯乙烯等。 Examples of the styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, and butylstyrene. An alkane such as hexyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, and ethoxymethyl styrene Styrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; and, chlorostyrene, dichlorostyrene, trichlorobenzene Ethylene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro Halogenated styrene such as -3-trifluoromethylstyrene.

作為含有不具有脂環式基團之環氧基之不飽和化合物，可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯及(甲基)丙烯酸6,7-環氧庚酯等(甲基)丙烯酸環氧烷基酯類；α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯及α-乙基丙烯酸6,7-環氧庚酯等α-烷基丙烯酸環氧 烷基酯類等。於該等中，較佳為(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯及(甲基)丙烯酸6,7-環氧庚酯。 Examples of the unsaturated compound containing an epoxy group having no alicyclic group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and (meth)acrylic acid 3. Epoxyalkyl (meth)acrylates such as 4-epoxybutyl acrylate and 6,7-epoxyheptyl (meth)acrylate; glycidyl α-ethyl acrylate, glycidol α-n-propyl acrylate Alpha-alkyl acrylate epoxy such as ester, α-n-butyl acrylate glycidyl ester and α-ethyl acrylate 6,7-epoxyheptyl ester Alkyl esters and the like. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate are preferred.

上述(a1)單元、上述(a2)單元及上述(a3)單元於(A)鹼可溶性樹脂也就是共聚物中所佔之比例，於不妨礙本發明的目的之範圍內並無特別限定。上述(a1)單元於(A)鹼可溶性樹脂也就是共聚物中所佔之比例，較佳為5~25質量%，更佳為8~16質量%。上述(a2)單元於(A)鹼可溶性樹脂也就是共聚物中所佔之比例，較佳為10~50質量%，更佳為11~30質量%。上述(a3)單元於(A)鹼可溶性樹脂也就是共聚物中所佔之比例，較佳為10~70質量%，更佳為15~50質量%。 The ratio of the above-mentioned (a1) unit, the above-mentioned (a2) unit, and the above-mentioned (a3) unit to the (A) alkali-soluble resin, that is, the copolymer, is not particularly limited as long as the object of the present invention is not impaired. The proportion of the above (a1) unit in the (A) alkali-soluble resin, that is, the copolymer, is preferably 5 to 25% by mass, more preferably 8 to 16% by mass. The proportion of the above (a2) unit in the (A) alkali-soluble resin, that is, the copolymer, is preferably from 10 to 50% by mass, more preferably from 11 to 30% by mass. The proportion of the above (a3) unit in the (A) alkali-soluble resin, that is, the copolymer, is preferably from 10 to 70% by mass, more preferably from 15 to 50% by mass.

(A)鹼可溶性樹脂的質量平均分子量(Mw：利用凝膠滲透層析法(Gel Permeation Chromatography，GPC)的苯乙烯換算所獲得之測定值；於本說明書中相同。)，較佳為2000~200000，更佳為2000~18000，尤其較佳為3000~15000。藉由使用質量平均分子量處於上述範圍內之(A)鹼可溶性樹脂，易於使感放射線性樹脂組成物的曝光後的顯影性尤其優異。 (A) Mass average molecular weight of the alkali-soluble resin (Mw: measured value obtained by styrene conversion by Gel Permeation Chromatography (GPC); the same in the present specification), preferably 2000~ 200000, more preferably 2000~18000, especially preferably 3000~15000. By using the (A) alkali-soluble resin having a mass average molecular weight within the above range, the developability after exposure of the radiation-sensitive resin composition is particularly excellent.

(A)鹼可溶性樹脂可利用公知的自由基聚合法來製造。也就是說，可藉由在將提供以上所說明的單元之單體與公知的自由基聚合引發劑溶解於聚合溶劑後，進行加熱攪拌來製造。 (A) The alkali-soluble resin can be produced by a known radical polymerization method. In other words, it can be produced by dissolving a monomer which supplies the unit described above and a known radical polymerization initiator in a polymerization solvent, followed by heating and stirring.

<(B)光聚合性化合物> <(B) Photopolymerizable Compound>

作為感放射線性樹脂組成物中所含有的(B)光聚合性化合物(以下，亦記為(B)成分)，可較佳為使用具有乙烯性不飽 和基團之化合物。於此具有乙烯性不飽和基團之化合物中，存在單官能化合物與多官能化合物。 The (B) photopolymerizable compound (hereinafter also referred to as component (B)) contained in the radiation sensitive resin composition is preferably used to have an ethylenic unsaturated state. And compounds of the group. Among the compounds having an ethylenically unsaturated group, a monofunctional compound and a polyfunctional compound are present.

作為單官能化合物，可列舉：(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、(甲基)丙烯酸、富馬酸、馬來酸、馬來酸酐、伊康酸、伊康酸酐、檸康酸、檸康酸酐、巴豆酸、2-丙烯醯胺-2-甲基丙烷磺酸、三級丁基丙烯醯胺磺酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、2-苯氧基-(甲基)丙烯酸2-羥丙酯、2-(甲基)丙烯醯氧基-2-羥基丙基鄰苯二甲酸酯、單(甲基)丙烯酸甘油酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸二甲胺基酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯及鄰苯二甲酸衍生物的半(甲基)丙烯酸酯等。該等單官能單體可單獨使用，或組合2種以上使用。 Examples of the monofunctional compound include (meth)acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (meth) propylene. Indoleamine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propenylamine 2-methylpropanesulfonic acid, tertiary butyl propylene sulfonamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-(meth) acrylate Ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-benzene 2-hydroxypropyl (meth)acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, (methyl) Tetrahydrofurfuryl acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, (A) ) 2,2,2-trifluoroethyl acrylate, ethyl (meth) acrylate half (meth) acrylate ester and 2,2,3,3-tetrafluoro-phthalic acid derivatives. These monofunctional monomers may be used singly or in combination of two or more.

另一方面，作為多官能單體，可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二(甲基)丙烯酸甘油酯、季戊四醇三丙烯酸酯、季戊 四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇二(甲基)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(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、三丙烯酸甘油酯、聚縮水甘油醚聚(甲基)丙烯酸甘油酯、氨酯(甲基)丙烯酸酯(也就是，甲苯二異氰酸酯)、三甲基六亞甲基二異氰酸酯和六亞甲基二異氰酸酯等與(甲基)丙烯酸2-羥乙酯的反應物、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多元醇與N-羥甲基(甲基)丙烯醯胺的縮合物、三丙烯醯基縮甲醛(Triacrylformal)、2,4,6-三氧代六氫-1,3,5-三嗪-1,3,5-三乙醇三丙烯酸酯、及2,4,6-三氧代六氫-1,3,5-三嗪-1,3,5-三乙醇二丙烯酸酯等。該等多官能單體可單獨使用，或組合2種以上使用。 On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(a) Acrylate, trimethylolpropane tri(meth)acrylate, di(meth)acrylate, pentaerythritol triacrylate, penta Tetraol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol five (a) Acrylate, dipentaerythritol hexa(meth) acrylate, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(A) Acetyleneoxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di(methyl) Acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl di(meth)acrylate, glyceryl triacrylate, polyglycidyl ether poly(meth)acrylic acid Reaction of glycerol ester, urethane (meth) acrylate (ie, toluene diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate , methylene bis(meth) acrylamide, (meth) acrylamide, methylene ether, polyol and N-methylol (meth) propylene Amine condensate, Triacrylformal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol triacrylate, and 2 , 4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol diacrylate, and the like. These polyfunctional monomers may be used singly or in combination of two or more.

於該等具有乙烯性不飽和基團之化合物中，自可獲得提供強度、與對基板的密接性優異的硬化物之感放射線性樹脂組成物之方面來看，較佳為3官能以上的多官能單體。 Among these compounds having an ethylenically unsaturated group, it is preferably a trifunctional or higher compound from the viewpoint of obtaining a radiation-sensitive resin composition having a strength and a cured product excellent in adhesion to a substrate. Functional monomer.

(B)成分的含量，相對於感放射線性樹脂組成物的固體成分，較佳為5~60質量%，更佳為10~50質量%。藉由使感放射線性樹脂組成物中的(B)成分的含量為上述範圍，存在易於使感放射線性樹脂組成物的敏感度、顯影性及解析度 保持平衡之趨勢。 The content of the component (B) is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass based on the solid content of the radiation sensitive resin composition. When the content of the component (B) in the radiation-sensitive resin composition is in the above range, sensitivity, developability, and resolution of the radiation-sensitive resin composition are likely to be easily obtained. Maintain a trend of balance.

<(C)光聚合性化合物> <(C) Photopolymerizable Compound>

感放射線性樹脂組成物，含有下述結構的肟酯化合物作為(C)光聚合引發劑(以下，亦記為(C)成分)。藉由使用由下述式(1)所表示之結構的肟酯化合物來作為光聚合引發劑，可獲得可形成透明性優異的硬化膜之感放射線性樹脂組成物。 The radiation sensitive resin composition contains an oxime ester compound having the following structure as (C) a photopolymerization initiator (hereinafter also referred to as a component (C)). By using an oxime ester compound having a structure represented by the following formula (1) as a photopolymerization initiator, a radiation-sensitive resin composition capable of forming a cured film having excellent transparency can be obtained.

(R1為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，m為0~4的整數，p為0或1，R2為亦可具有取代基之苯基或亦可具有取代基之咔唑基，R3為氫原子或碳數1~6的烷基)。 (R 1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R 2 is The phenyl group which may have a substituent or the carbazolyl group which may have a substituent, and R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

上述式(1)中，當R1為1價的有機基團時，R1於不妨礙本發明的目的之範圍內，並無特別限定，可自各種有機基團適當選擇。作為R1為有機基團時之適合的例子，可列舉：烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、飽和脂肪族醯氧基、亦可具有取代基之苯基、亦可具有取代基之苯氧基、亦可具有取代基之苯甲醯基、亦可具有取代基之苯氧基羰基、亦可具有取代基之苯甲醯氧基、亦可具有取代基之苯基烷基、亦可具有取代基之萘基、亦可具有取代基之萘氧基、亦可具有取代基之萘甲醯基、亦可具有取 代基之萘氧基羰基、亦可具有取代基之萘甲醯氧基、亦可具有取代基之萘基烷基、亦可具有取代基之雜環基、被1價或2價的有機基團所取代之胺基、嗎啉-1-基及呱嗪-1-基等。當m為2~4的整數時，R1可相同亦可不同。又，取代基的碳數中，不包含取代基進一步具有之取代基的碳數。 In the above formula (1), when R 1 is a monovalent organic group, R 1 is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from various organic groups. Examples of suitable examples when R 1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyl group, and a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzamethylene oxide which may have a substituent a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl fluorenyl group which may have a substituent, and a naphthalene which may have a substituent An oxycarbonyl group, a naphthylmethoxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and a monovalent or divalent organic group Amino, morpholin-1-yl and pyridazin-1-yl and the like. When m is an integer of 2 to 4, R 1 may be the same or different. Further, the carbon number of the substituent does not include the carbon number of the substituent further possessed by the substituent.

當R1為烷基時，其碳數較佳為1~20，更佳為1~6。又，當R1為烷基時，可為直連，亦可為支鏈。作為R1為烷基時之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、異戊基、二級戊基、三級戊基、正己基、正庚基、正辛基、異辛基、二級辛基、三級辛基、正壬基、異壬基、正癸基及異癸基等。又，當R1為烷基時，烷基亦可於碳鏈中包含醚鍵(-O-)。作為碳鏈中具有醚鍵之烷基的例子，可列舉甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基及甲氧基丙基等。 When R 1 is an alkyl group, the carbon number thereof is preferably from 1 to 20, more preferably from 1 to 6. Further, when R 1 is an alkyl group, it may be a direct bond or a branched chain. Specific examples of the case where R 1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tert-butyl group, n-pentyl group, and the like. Isoamyl, secondary pentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, n-decyl, isodecyl, n-decyl And isoindyl groups, etc. Further, when R 1 is an alkyl group, the alkyl group may further contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propoxyethoxy group. Base ethyl and methoxypropyl and the like.

當R1為烷氧基時，其碳數較佳為1~20，更佳為1~6。又，當R1為烷氧基時，可為直連，亦可為支鏈。作為R1為烷氧基時之具體例，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、二級丁氧基、三級丁氧基、正戊氧基、異戊氧基、二級戊氧基、三級戊氧基、正己氧基、正庚氧基、正辛氧基、異辛氧基、二級辛氧基、三級辛氧基、正壬氧基、異壬氧基、正癸氧基及異癸氧基等。又，當R1為烷氧基時，烷氧基亦可於碳鏈中包含醚鍵(-O-)。作為碳鏈中具有醚鍵之烷氧基的例子，可列舉甲氧基乙氧 基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙氧基乙氧基乙氧基及甲氧基丙氧基等。 When R 1 is an alkoxy group, the carbon number thereof is preferably from 1 to 20, more preferably from 1 to 6. Further, when R 1 is an alkoxy group, it may be a direct bond or a branched chain. Specific examples of the case where R 1 is an alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a secondary butoxy group, and the like. Butoxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, secondary octyloxy Base, tertiary octyloxy, n-decyloxy, isodecyloxy, n-decyloxy and isodecyloxy. Further, when R 1 is an alkoxy group, the alkoxy group may further contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Propoxyethoxyethoxy and methoxypropoxy and the like.

當R1為環烷基或環烷氧基時，其碳數較佳為3~10，更佳為3~6。作為R1為環烷基時之具體例，可列舉環丙基、環丁基、環戊基、環己基、環庚基及環辛基等。作為R1為環烷氧基時之具體例，可列舉環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基及環辛氧基等。 When R 1 is a cycloalkyl group or a cycloalkoxy group, the carbon number thereof is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R 1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the case where R 1 is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

當R1為飽和脂肪族醯基或飽和脂肪族醯氧基時，其碳數較佳為2~20，更佳為2~7。作為R1為飽和脂肪族醯基時之具體例，可列舉乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一醯基、正十二醯基、正十三醯基、正十四醯基、正十五醯基及正十六醯基等。作為R1為飽和脂肪族醯氧基時之具體例，可列舉乙醯氧基、丙醯氧基、正丁醯氧基、2-甲基丙醯氧基、正戊醯氧基、2,2-二甲基丙醯氧基、正己醯氧基、正庚醯氧基、正辛醯氧基、正壬醯氧基、正癸醯氧基、正十一醯氧基、正十二醯氧基、正十三醯氧基、正十四醯氧基、正十五醯氧基及正十六醯氧基。 When R 1 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the carbon number thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R 1 is a saturated aliphatic fluorenyl group include an ethyl group, a propyl group, a n-butyl group, a 2-methyl propyl group, a n-pentyl group, and a 2,2-dimethyl propyl group. , 正己醯基,正庚醯基,正辛醯基,正壬醯基,正癸醯基,正十一醯基,正十二醯基,正十三醯基,正十四醯基,正十五醯基和正六醯基等. Specific examples of the case where R 1 is a saturated aliphatic oxime group include an ethoxycarbonyl group, a propenyloxy group, a n-butenyloxy group, a 2-methylpropoxy group, a n-pentamoxy group, and 2, 2-dimethylpropenyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-decyloxy, n-dodecyl Oxyl, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy and n-hexadecyloxy.

當R1為烷氧羰基時，其碳數較佳為2~20，更佳為2~7。作為R1為烷氧羰基時之具體例，可列舉：甲氧基羰基、乙氧基羰基、正丙氧基羰基、異丙氧基羰基、正丁氧基羰基、異丁氧基羰基、二級丁氧基羰基、三級丁氧基羰基、正戊氧基羰基、異戊氧基羰基、二級戊氧基羰基、三級戊氧基羰基、正己氧基羰基、正庚氧基羰基、正辛氧基羰基、異辛氧基羰 基、二級辛氧基羰基、三級辛氧基羰基、正壬氧基羰基、異壬氧基羰基、正癸氧基羰基及異癸氧基羰基等。 When R 1 is an alkoxycarbonyl group, the carbon number thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R 1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, and the like. Butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, secondary pentyloxycarbonyl, tertiary pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-Octyloxycarbonyl, isooctyloxycarbonyl, secondary octyloxycarbonyl, tertiary octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, n-decyloxycarbonyl and isodecyloxycarbonyl .

當R1為苯基烷基時，其碳數較佳為7~20，更佳為7~10。又，當R1為萘基烷基時，其碳數較佳為11~20，更佳為11~14。作為R1為苯基烷基時之具體例，可列舉苄基、2-苯乙基、3-苯丙基及4-苯丁基。作為R1為萘基烷基時之具體例，可列舉α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基及2-(β-萘基)乙基。當R1為苯基烷基或萘基烷基時，R1亦可於苯基或萘基上進一步具有取代基。 When R 1 is a phenylalkyl group, the carbon number thereof is preferably from 7 to 20, more preferably from 7 to 10. Further, when R 1 is a naphthylalkyl group, the carbon number thereof is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R 1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R 1 is a naphthylalkyl group include α-naphthylmethyl group, β -naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. . When R 1 is a phenylalkyl group or a naphthylalkyl group, R 1 may further have a substituent on the phenyl group or a naphthyl group.

當R1為雜環基時，雜環基為包含1以上的N、S、O之5員或6員的單環、或相關單環彼此或相關單環與苯環縮合之雜環基。當雜環基為縮合環時，環數最多為3。作為相關之構成雜環基之雜環，可列舉：呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑琳桐、三唑、吡啶、吡嗪、嘧啶、噠嗪、苯并呋喃、苯并噻吩、吲跺、異吲跺、吲嗪、苯并咪唑、苯并三唑、苯并噁唑、苯并噻唑、咔唑、嘌呤、奎林、異奎林、喹唑啉、酞嗪、1,2-二氮萘及奎喏林等。當R1為雜環基時，雜環基亦可進一步具有取代基。 When R 1 is a heterocyclic group, the heterocyclic group is a monocyclic ring containing 5 or 6 members of N, S, O or a heterocyclic group in which a related monocyclic ring or a related monocyclic ring is condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is at most 3. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazolin, triazole, pyridine, pyrazine. , pyrimidine, pyridazine, benzofuran, benzothiophene, anthracene, isoindole, pyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinine, Isoquine, quinazoline, pyridazine, 1,2-diazaphthalene, and quinoidin. When R 1 is a heterocyclic group, the heterocyclic group may further have a substituent.

當R1為被1價或2價的有機基團所取代之胺基時，有機基團的適合的例子，可列舉：碳數1~20的烷基、碳數3~10的環烷基、碳數2~20的飽和脂肪族醯基、亦可具有取代基之苯基、亦可具有取代基之苯甲醯基、亦可具有取代基之碳數7~20的苯基烷基、亦可具有取代基之萘基、亦可具有取代基之萘甲醯基、亦可具有取代基之碳數11~20的萘基 烷基及雜環基等。該等適合的有機基團的具體例與R1相同。作為被1價或2價的有機基團所取代之氨基的具體例，可列舉：甲胺基、乙胺基、二乙胺基、正丙胺基、二正丙胺基、異丙胺基、正丁胺基、二正丁胺基、正戊胺基、正己胺基、正庚胺基、正辛胺基、正壬胺基、正癸胺基、苯胺基、萘胺基、乙醯胺基、丙醯胺基、正丁醯胺基、正戊醯胺基、正己醯胺基、正庚醯胺基、正辛醯胺基、正癸醯胺基、苯甲醯胺基、α-萘醯胺基及β-萘醯胺基等。 When R 1 is an amine group substituted with a monovalent or divalent organic group, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzyl group which may have a substituent, a phenylalkyl group having a substituent of 7 to 20 carbon atoms, Further, it may have a naphthyl group having a substituent, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having a substituent of 11 to 20 carbon atoms, a heterocyclic group, and the like. Specific examples of such suitable organic groups are the same as R 1 . Specific examples of the amino group substituted with a monovalent or divalent organic group include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamine group, and a n-butyl group. Amino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-nonylamino, anilino, naphthylamino, ethenyl Propylamine, n-butylammonium, n-pentamethyleneamine, n-hexylamine, n-heptylamino, n-octylamine, n-nonylamine, benzamidine, alpha-naphthoquinone Amine group and β -naphthylamine group and the like.

作為R1中所包含之苯基、萘基及雜環基進一步具有取代基時之取代基，可列舉：碳數1~6的烷基、碳數1~6的烷氧基、碳數2~7的飽和脂肪族醯基、碳數2~7的烷氧羰基、碳數2~7的飽和脂肪族醯氧基、具有碳數1~6的烷基之單烷基胺基、具有碳數1~6的烷基之二烷基胺基、嗎啉-1-基、呱嗪-1-基、鹵素、硝基及氰基等。當R1中所包含之苯基、萘基及雜環基進一步具有取代基時，該取代基的數量，於不妨礙本發明的目的之範圍內，並無限定，但較佳為1~4。當R1中所包含之苯基、萘基及雜環基具有複數個取代基時，複數個取代基，可相同亦可不同。 Examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in R 1 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of 2 a saturated aliphatic fluorenyl group of ~7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic decyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, having carbon A dialkylamino group, a morpholin-1-yl group, a pyridazin-1-yl group, a halogen, a nitro group, a cyano group or the like of an alkyl group having 1 to 6 carbon atoms. When the phenyl group, the naphthyl group and the heterocyclic group contained in R 1 further have a substituent, the number of the substituent is not limited insofar as it does not hinder the object of the present invention, but is preferably 1 to 4 . When the phenyl group, the naphthyl group and the heterocyclic group contained in R 1 have a plurality of substituents, the plurality of substituents may be the same or different.

於R1中，自化學上穩定、立體的障礙較少而容易合成肟酯化合物、及相對於溶劑之溶解性較高等方面來看，較佳為選自由硝基、碳數1~6的烷基、碳數1~6的烷氧基及碳數2~7的飽和脂肪族醯基所組成之群組中的基團，更佳為硝基或碳數1~6的烷基，尤其較佳為硝基或甲基。 In R 1 , it is preferably selected from the group consisting of a nitro group and a carbon number of 1 to 6 from the viewpoints of chemically stable, three-dimensional obstacles, easy synthesis of an oxime ester compound, and high solubility with respect to a solvent. a group in the group consisting of an alkoxy group having 1 to 6 carbon atoms and a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl group having 1 to 6 carbon atoms, especially Good is nitro or methyl.

R1鍵結於苯基之位置，關於R1鍵結之苯基，當以苯 基與肟酯化合物的主骨架的原子鍵結的位置為1位、以甲基的位置為2位時，較佳為4位或5位，更加為5位。又，m較佳為0~3的整數，更佳為0~2的整數，尤其較佳為0或1。 R 1 is bonded to the position of the phenyl group, and when the phenyl group bonded to the R 1 is bonded to the position of the atom of the main skeleton of the phenyl group and the oxime ester compound, and the position of the methyl group is 2 positions, It is preferably 4 or 5 bits, and more preferably 5 bits. Further, m is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R2為亦可具有取代基之苯基或亦可具有取代基之咔唑基。又，當R2為亦可具有取代基之咔唑基時，咔唑基上的氮原子，亦可被碳數1~6的烷基所取代。 R 2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. Further, when R 2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

於R2中，苯基或咔唑基具有之取代基，於不妨礙本發明的目的之範圍內，並無特別限定。作為苯基或咔唑基亦可於碳原子上具有之適合的取代基的例子，可列舉：碳數1~20的烷基、碳數1~20的烷氧基、碳數3~10的環烷基、碳數3~10的環烷氧基、碳數2~20的飽和脂肪族醯基、碳數2~20的烷氧羰基、碳數2~20的飽和脂肪族醯氧基、亦可具有取代基之苯基、亦可具有取代基之苯氧基、亦可具有取代基之苯硫基、亦可具有取代基之苯甲醯基、亦可具有取代基之苯氧基羰基、亦可具有取代基之苯甲醯氧基、亦可具有取代基之碳數7~20的苯基烷基、亦可具有取代基之萘基、亦可具有取代基之萘氧基、亦可具有取代基之萘甲醯基、亦可具有取代基之萘氧基羰基、亦可具有取代基之萘甲醯氧基、亦可具有取代基之碳數11~20的萘基烷基、亦可具有取代基之雜環基、亦可具有取代基之雜環羰基、胺基、被1價或2價的有機基團所取代之胺基、嗎啉-1-基及呱嗪-1-基、鹵素、硝基及氰基等。 The substituent of the phenyl group or the carbazolyl group in R 2 is not particularly limited as long as it does not impair the object of the present invention. Examples of the phenyl or carbazolyl group which may have a suitable substituent on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 3 to 10. a cycloalkyl group, a cycloalkyloxy group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzamyl group which may have a substituent, and a phenoxycarbonyl group which may have a substituent a benzyl methoxy group having a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, and a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent of 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group, an amine group substituted with a monovalent or divalent organic group, morpholin-1-yl and pyridazine-1 - base, halogen, A cyano group, and the like.

當R2為咔唑基時，作為咔唑基亦可於氮原子上具有之適合的取代基的例子，可列舉：碳數1~20的烷基、碳數3 ~10的環烷基、碳數2~20的飽和脂肪族醯基、碳數2~20的烷氧羰基、亦可具有取代基之苯基、亦可具有取代基之苯甲醯基、亦可具有取代基之苯氧基羰基、亦可具有取代基之碳數7~20的苯基烷基、亦可具有取代基之萘基、亦可具有取代基之萘甲醯基、亦可具有取代基之萘氧基羰基、亦可具有取代基之碳數11~20的萘基烷基、亦可具有取代基之雜環基及亦可具有取代基之雜環羰基等。於該等取代基中，較佳為碳數1~20的烷基，更佳為碳數1~6的烷基，尤其較佳為乙基。 When R 2 is a carbazolyl group, examples of a suitable substituent which may be a carbazolyl group on a nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, and a phenoxy group which may have a substituent a carbonyl group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, and a naphthyloxycarbonyl group which may have a substituent Further, it may have a naphthylalkyl group having 11 to 20 carbon atoms as a substituent, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

於苯基或咔唑基亦可具有之取代基的具體例中，關於烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧羰基、飽和脂肪族醯氧基、亦可具有取代基之苯基烷基、亦可具有取代基之萘基烷基、亦可具有取代基之雜環基及被1價或2價的有機基團所取代之胺基，與R1相同。 In a specific example of a substituent which the phenyl group or the carbazolyl group may have, regarding an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic oxime a phenylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with a monovalent or divalent organic group, Same as R 1 .

於R2中，作為苯基或咔唑基具有之取代基中所包含之苯基、萘基及雜環基進一步具有取代基時之取代基的例子，可列舉：碳數1~6的烷基；碳數1~6的烷氧基；碳數2~7的飽和脂肪族醯基；碳數2~7的烷氧羰基；碳數2~7的飽和脂肪族醯氧基；苯基；萘基；苯甲醯基；萘甲醯基；苯甲醯基，其被選自由碳數1~6的烷基、嗎啉-1-基、呱嗪-1-基及苯基所組成之群組中的基團所取代；單烷基胺基，其具有碳數1~6的烷基；二烷基胺基，其具有碳數1~6的烷基；嗎啉-1-基；呱嗪-1-基；鹵素；硝基；及，氰基。當苯基或咔唑基具有之取代基中所包含之苯基、萘基及雜環基進一步具 有取代基時，其取代基的數量，於不妨礙本發明的目的之範圍內，並無限定，但較佳為1~4。當苯基、萘基及雜環基具有複數個取代基時，複數個取代基，可相同亦可不同。 In the case of R 2 , examples of the substituent when the phenyl group, the naphthyl group and the heterocyclic group which are contained in the substituent of the phenyl group or the carbazolyl group further have a substituent include an alkane having 1 to 6 carbon atoms. Alkoxy group having 1 to 6 carbon atoms; saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms; phenyl group; Naphthyl; benzhydryl; naphthylmethyl; benzylidene, which is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a pyridazin-1-yl group, and a phenyl group. Substituted by a group in the group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; Pyridazin-1-yl; halogen; nitro; and, cyano. When the phenyl group, the naphthyl group and the heterocyclic group which are contained in the substituent of the phenyl or carbazolyl group further have a substituent, the number of the substituents is not limited insofar as it does not impair the object of the present invention. , but preferably 1~4. When the phenyl group, the naphthyl group and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

於R2中，自感放射線性樹脂組成物的敏感度優異之方面來看，較佳為由下述式(2)或(3)所表示之基團，更佳為由下述式(2)所表示之基團，於由下述式(2)所表示之基團中，尤其較佳為A為S之基團。 In the case of R 2 , the sensitivity of the self-inductive radiation-linear resin composition is preferably a group represented by the following formula (2) or (3), and more preferably a formula (2) In the group represented by the following formula (2), a group represented by the following formula (2) is particularly preferably a group in which A is S.

(R4為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，A為S或O，n為0~4的整數)。 (R 4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, and A is S or O, and n is an integer of 0 to 4).

(R5和R6分別為1價的有機基團)。 (R 5 and R 6 are each a monovalent organic group).

當式(2)中的R4為有機基團時，於不妨礙本發明的目的之範圍內，可自各種有機基團選擇。於式(2)中，作為R4為有機基團時之適合的例子，可列舉：碳數1~6的烷基；碳數1~6的烷氧基；碳數2~7的飽和脂肪族醯基；碳數2~7的烷氧羰基；碳數2~7的飽和脂肪族醯氧基；苯基；萘基； 苯甲醯基；萘甲醯基；苯甲醯基，其被選自由碳數1~6的烷基基、嗎啉-1-基、呱嗪-1-基及苯基所組成之群組中的基團所取代；單烷基胺基，其具有碳數1~6的烷基；二烷基胺基，其具有碳數1~6的烷基；嗎啉-1-基；呱嗪-1-基；鹵素；硝基；及，氰基。 When R 4 in the formula (2) is an organic group, it can be selected from various organic groups within the range not inhibiting the object of the present invention. In the formula (2), examples of suitable examples when R 4 is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated fat having 2 to 7 carbon atoms. Alkyl fluorenyl group; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzamidine group; naphthylmethyl fluorenyl group; Substituting a group in a group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a pyridazin-1-yl group, and a phenyl group; a monoalkylamino group having a carbon number An alkyl group of 1 to 6; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a pyridazin-1-yl group; a halogen; a nitro group; and a cyano group.

於R4中，較佳為：苯甲醯基；萘甲醯基；苯甲醯基，其被選自由碳數1~6的烷基、嗎啉-1-基、呱嗪-1-基及苯基所組成之群組中的基團所取代；及，硝基；更佳為：苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(呱嗪-1-基)苯基羰基；及，4-(苯基)苯基羰基。 In R 4 , preferred is: benzylidene group; naphthylmethyl group; benzhydryl group selected from alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, pyridazin-1-yl group And a group in the group consisting of phenyl groups; and, a nitro group; more preferably: benzamyl; naphthylmethyl group; 2-methylphenylcarbonyl; 4-(pyridazine-1- Phenylcarbonyl; and, 4-(phenyl)phenylcarbonyl.

又，於式(2)中，n較佳為0~3的整數，更佳為0~2的整數，尤其較佳為0或1。當n為1時，R4鍵結之位置，相對於R4鍵結之苯基與硫原子鍵結之原子鍵結，較佳為對位。 Further, in the formula (2), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n is 1, R 4 knot key position with respect to R 4 are bonded to the phenyl group bonded to a sulfur atom bonded to the atom, preferably a para position.

式(3)中的R5，於不妨礙本發明的目的之範圍內，可自各種有機基團選擇。作為R5的適合的例子，可列舉：碳數1~20的烷基、碳數3~10的環烷基、碳數2~20的飽和脂肪族醯基、碳數2~20的烷氧羰基、亦可具有取代基之苯基、亦可具有取代基之苯甲醯基、亦可具有取代基之苯氧基羰基、亦可具有取代基之碳數7~20的苯基烷基、亦可具有取代基之萘基、亦可具有取代基之萘甲醯基、亦可具有取代基之萘氧基羰基、亦可具有取代基之碳數11~20的萘基烷基、亦可具有取代基之雜環基及亦可具有取代基之雜環羰基等。 R 5 in the formula (3) can be selected from various organic groups within a range not inhibiting the object of the present invention. Suitable examples of R 5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and an alkoxy group having 2 to 20 carbon atoms. a carbonyl group, a phenyl group which may have a substituent, a benzylidene group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent of 7 to 20 carbon atoms, Further, a naphthyl group having a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having a substituent of 11 to 20 carbon atoms, or A heterocyclic group having a substituent and a heterocyclic carbonyl group which may have a substituent.

於R5中，較佳為碳數1~20的烷基，更佳為碳數1~6的烷基，尤其較佳為乙基。 In R 5 , an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

式(3)中的R6，於不妨礙本發明的目的之範圍內，並無特別限定，可自各種有機基團選擇。作為R6的適合的基團的具體例，可列舉碳數1~20的烷基、亦可具有取代基之苯基、亦可具有取代基之基及亦可具有取代基之雜環基。作為R6，於該等基團中，更佳為亦可具有取代基之苯基，尤其較佳為2-甲基苯基。 R 6 in the formula (3) is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of a suitable group of R 6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a group which may have a substituent, and a heterocyclic group which may have a substituent. As R 6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

作為R4、R5或R6中所包含之苯基、萘基及雜環基進一步具有取代基時之取代基，可列舉：碳數1~6的烷基、碳數1~6的烷氧基、碳數2~7的飽和脂肪族醯基、碳數2~7的烷氧羰基、碳數2~7的飽和脂肪族醯氧基、具有碳數1~6的烷基之單烷基胺基、具有碳數1~6的烷基之二烷基胺基、嗎啉-1-基、呱嗪-1-基、鹵素、硝基及氰基等。當R4、R5或R6中所包含之苯基、萘基及雜環基進一步具有取代基時，其取代基的數量，於不妨礙本發明的目的之範圍內，並無限定，但較佳為1~4。當R4、R5或R6中所包含之苯基、萘基及雜環基具有複數個取代基時，複數個取代基，可相同亦可不同。 Examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclic group contained in R 4 , R 5 or R 6 further have a substituent include an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. An oxy group, a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic decyloxy group having 2 to 7 carbon atoms, and a monoalkyl group having an alkyl group having 1 to 6 carbon atoms An amino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a pyridazin-1-yl group, a halogen, a nitro group, a cyano group or the like. When the phenyl group, the naphthyl group and the heterocyclic group contained in R 4 , R 5 or R 6 further have a substituent, the number of the substituents is not limited insofar as it does not impair the object of the present invention, but It is preferably 1 to 4. When the phenyl group, the naphthyl group and the heterocyclic group contained in R 4 , R 5 or R 6 have a plurality of substituents, the plurality of substituents may be the same or different.

式(1)中的R3，為氫原子或碳數1~6的烷基。作為R3，較佳為甲基或乙基，更佳為甲基。當R3為甲基時，由式(1)所表示之化合物所構成之光聚合引發劑，敏感度尤其優異。 R 3 in the formula (1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R 3 , a methyl group or an ethyl group is preferred, and a methyl group is more preferred. When R 3 is a methyl group, the photopolymerization initiator composed of the compound represented by the formula (1) is particularly excellent in sensitivity.

由式(1)所表示之肟酯化合物，當p為0時，可依照例如下述方案1來合成。具體而言，可使用由下述式(1-2)所表示之鹵代烴化合物，將由下述式(1-1)所表示之芳香族化合物利用夫裡德耳-誇夫特(Friedel-Crafts)反應進行醯化，獲得 由下述式(1-3)所表示之酮化合物，將所得之酮化合物(1-3)利用羥胺進行肟化，獲得由下述式(1-4)所表示之肟類化合物，繼而，使式(1-4)的肟類化合物與由下述式(1-5)所表示之酸酐((R3CO)2O)、或由下述式(1-6)所表示之酸鹵化物(R3COHal、Hal為鹵素)反應，獲得由下述式(1-7)所表示之肟酯化合物。再者，於下述式(1-2)中，Hal為鹵素，於下述式(1-1)、(1-2)、(1-3)、(1-4)及(1-7)中，R1、R2、R3及m與式(1)相同。 The oxime ester compound represented by the formula (1), when p is 0, can be synthesized, for example, according to the following scheme 1. Specifically, a halogenated hydrocarbon compound represented by the following formula (1-2) can be used, and an aromatic compound represented by the following formula (1-1) can be used by Friedel-Furite (Friedel- The reaction is carried out to obtain a ketone compound represented by the following formula (1-3), and the obtained ketone compound (1-3) is deuterated by hydroxylamine to obtain a formula (1-4): An anthracene compound represented by the compound of the formula (1-4), an acid anhydride represented by the following formula (1-5) ((R 3 CO) 2 O), or the following formula (1) -6) The acid halide (R 3 COHal, Hal is a halogen) is reacted to obtain an oxime ester compound represented by the following formula (1-7). Further, in the following formula (1-2), Hal is a halogen, and is represented by the following formulas (1-1), (1-2), (1-3), (1-4), and (1-7). In the formula, R 1 , R 2 , R 3 and m are the same as in the formula (1).

<方案1> <Scheme 1>

由式(1)所表示之肟酯化合物，當p為1時，可依照例如下述方案2來合成。具體而言，可對由下述式(2-1)所表示之酮化合物，於鹽酸的存在下使由下述式(2-2)所表示之亞硝酸酯(RONO、R為碳數1~6的烷基)反應，獲得由下述式(2-3)所表示之酮肟化合物，繼而，使由下述式(2-3)所表示之酮肟化合物與由下述式(2-4)所表示之酸酐((R3CO)2O)、或由下述式(2-5)所表示之酸鹵化物(R3COHal、Hal為鹵素)反應，獲得由下述式(2-6)所表示之肟酯化合物。再者，於下述式(2-1)、(2-3)、(2-4)、(2-5)及(2-6)中，R1、R2、R3及m與式(1)相同。 The oxime ester compound represented by the formula (1), when p is 1, can be synthesized, for example, according to the following scheme 2. Specifically, the nitrite compound represented by the following formula (2-1) can be made to have a nitrite represented by the following formula (2-2) in the presence of hydrochloric acid (RONO, R is a carbon number of 1) a ketone oxime compound represented by the following formula (2-3), and then a ketoxime compound represented by the following formula (2-3) and a formula (2) -4) An acid anhydride ((R 3 CO) 2 O) or an acid halide (R 3 COHal, Hal is a halogen) represented by the following formula (2-5), which is obtained by the following formula ( 2-6) The oxime ester compound represented. Further, in the following formulae (2-1), (2-3), (2-4), (2-5) and (2-6), R 1 , R 2 , R 3 and m have the formula (1) Same.

<方案2> <Scheme 2>

又，由式(1)所表示之肟酯化合物，當p為1，R1為甲基，相對於鍵結於R1鍵結之苯環之甲基，R1鍵結於對位時，例如亦可藉由用與方案1相同的方法，將由下述式(2-7)所表示之化合物進行肟化和醯化來合成。再者，於下述式(2-7)中，R2與式(1)相同。 Further, the oxime ester compound represented by the formula (1), when p is 1, and R 1 is a methyl group, when R 1 is bonded to the para position with respect to the methyl group bonded to the benzene ring bonded to R 1 , For example, the compound represented by the following formula (2-7) can be synthesized by deuteration and deuteration by the same method as in the first embodiment. Further, in the following formula (2-7), R 2 is the same as the formula (1).

作為由式(1)所表示之肟酯化合物中特別適合的化合物，可列舉下述式的化合物。 The compound which is especially suitable among the oxime ester compound represented by Formula (1) is a compound of the following formula.

感放射線性樹脂組成物，於不妨礙本發明的目的之範圍內，亦可根據需要包含除由式(1)所表示之肟酯化合物以外之其他光聚合引發劑。作為其他光聚合引發劑的具體例，可列舉：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、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、雙(4-二甲胺基苯基)酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、乙酮，1-[9-乙基-6-(2-甲基苯甲醯)-9H-咔唑-3-基]，1-(鄰乙 醯肟)、2,4,6-三甲基苯甲醯二苯基氧化膦、4-苯甲醯-4'-甲基二甲硫醚、4-二甲胺基苯甲酸、4-二甲胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸丁酯、4-二甲胺基苯甲酸2-乙基己酯、4-二甲胺基苯甲酸2-異戊酯、苄基-β-甲氧基乙基縮醛、苄基二甲基縮酮、1-苯基-1,2-丙二酮-2-(鄰乙氧羰基)肟、鄰苯甲醯苯甲酸甲酯、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、1-氯-4-丙氧基噻噸酮、噻噸、2-氯噻噸、2,4-二乙基噻噸、2-甲基噻噸、2-異丙基噻噸、2-乙基恩菎、八甲基恩菎、1,2-苯并恩菎、2,3-二苯基恩菎、偶氮雙異丁腈、過氧化苯甲醯、過氧化異丙基苯、2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二苯基咪唑二聚體、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚體、2-(鄰氟苯基)-4,5-二苯基咪唑二聚體、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚體、2-(對甲氧基苯基)-4,5-二苯基咪唑二量體、2,4,5-三芳基咪唑二量體、二苯甲酮、2-氯二苯甲酮、4,4’-雙二甲胺基二苯甲酮(也就是，米其勒酮)、4,4’-雙二乙胺基二苯甲酮(也就是，乙基米其勒酮)、4,4’-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苄基、苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻正丁醚、苯偶姻異丁醚、苯偶姻丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對三級丁基苯乙酮、對二甲胺基苯乙酮、對三級丁基三氯苯乙酮、對三級丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、二苯并環庚酮、戊基-4-二 甲胺基苯甲酸酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三嗪、2,4,6-三(三氯甲基)-s-三嗪、2-甲基-4,6-雙(三氯甲基)-s-三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-s-三嗪及2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-s-三嗪等。其中，自敏感度的方面來看，尤其較佳為使用肟系的光聚合引發劑。該等光聚合引發劑，可單獨使用，或組合2種以上使用。 The radiation-sensitive resin composition may contain a photopolymerization initiator other than the oxime ester compound represented by the formula (1) as needed, within the range not obstructing the object of the present invention. Specific examples of the other photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl). Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, Bis(4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-indole Zin-3-yl], 1-(o-B 醯肟), 2,4,6-trimethylbenzimidium diphenylphosphine oxide, 4-benzylformamidine-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-di Methyl methyl benzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylamine 2-isoamyl benzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)肟, methyl phthalic acid benzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxy Thioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylnene, octamethyl enamine 1,2-Benzene, 2,3-diphenylene, azobisisobutyronitrile, benzamidine peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercapto Benzooxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxy Phenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-di Phenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2- Chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., miconesone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Miclotone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzene Affinity diethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylene Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tertiary butyl trichloride Acetophenone, p-tert-butyl butyl dichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthene Ketone, dibenzocycloheptanone, pentyl-4-di Methylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3 - bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis (three Chloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[ 2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl) Vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloro) Methyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl) -4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2, 4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4- Methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine and 2,4 - bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine or the like. Among them, from the viewpoint of sensitivity, it is particularly preferable to use a lanthanide photopolymerization initiator. These photopolymerization initiators may be used singly or in combination of two or more.

當感放射線性樹脂組成物包含除由式(1)所表示之肟酯化合物以外之其他光聚合引發劑時，其他光聚合性化合物的含量，於不妨礙本發明的目的之範圍內，並無特別限定。此時，其他光聚合引發劑的含量，典型地為相對於感放射線性樹脂組成物中所包含之光聚合引發劑的總量，較佳為50質量%以下，更佳為30質量%以下，尤其較佳為10質量%以下。 When the radiation sensitive resin composition contains a photopolymerization initiator other than the oxime ester compound represented by the formula (1), the content of the other photopolymerizable compound is not within the range not impairing the object of the present invention. Specially limited. In this case, the content of the other photopolymerization initiator is preferably 50% by mass or less, and more preferably 30% by mass or less based on the total amount of the photopolymerization initiator contained in the radiation sensitive resin composition. It is especially preferably 10% by mass or less.

(C)成分也就是光聚合引發劑的含量，相對於感放射線性樹脂組成物的固體成分的合計100質量份，較佳為0.1~ 50質量份，更佳為0.5~10質量份。藉由以上述範圍內的量使用(C)成分，可利用放射線使感放射性樹脂組成物充分地硬化，而獲得提供透明性優異的硬化膜之感放射性樹脂組成物。 The content of the component (C), that is, the photopolymerization initiator, is preferably 0.1 part by mass based on 100 parts by mass of the total solid content of the radiation sensitive resin composition. 50 parts by mass, more preferably 0.5 to 10 parts by mass. By using the component (C) in an amount within the above range, the radiation-sensitive resin composition can be sufficiently cured by radiation to obtain a radiation-sensitive resin composition which provides a cured film having excellent transparency.

<(S)溶劑> <(S) Solvent>

本發明的感放射線性樹脂組成物，較佳為包含(S)有機溶劑(以下，亦稱為「(S)成分」)，以改善塗佈性和調整黏度。 The radiation sensitive resin composition of the present invention preferably contains (S) an organic solvent (hereinafter also referred to as "(S) component") to improve coatability and adjust viscosity.

作為有機溶劑，具體而言，可列舉：乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚及三丙二醇單乙醚等(聚)烯烴二醇單烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯(Propylene glycol monomethyl ether acetate，PGMEA)及丙二醇單乙醚乙酸酯等(聚)烯烴二醇單烷基醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚及四氫呋喃等其他醚類；甲基乙基酮、環已酮、2-庚酮及3-庚酮等酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等乳酸烷基酯類；2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基乙酸丁酯、3-甲基-3-甲氧基乙酸丁酯、3-甲基-3-甲氧基丁 基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、酪酸乙酯、酪酸正丙酯、酪酸異丙酯、酪酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯及2-氧代丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；及，N-甲基吡咯啶酮、N,N-二甲基甲醯胺及N,N-二甲基乙醯胺等醯胺類等。其中，較佳為烯烴二醇單烷基醚類、烯烴二醇單烷基醚乙酸酯類、上述之其他醚類、乳酸烷基酯類及上述之其他酯類；更佳為烯烴二醇單烷基醚乙酸酯類、上述之其他醚類及上述之其他酯類。該等溶劑，可單獨使用，或組合2種以上使用。 Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethyl ether. Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single positive Propylene ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether (poly) olefin Alcohol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate (poly) olefin diol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl Other ethers such as ether, diethylene glycol diethyl ether and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-glycol Ketones; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3 -ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyl Methyl ester, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, 3-methyl-3-methoxybutyl Propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid N-propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate and ethyl 2-oxobutanoate Other esters; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide Wait. Among them, preferred are olefin diol monoalkyl ethers, olefin diol monoalkyl ether acetates, the above other ethers, alkyl lactates, and other esters mentioned above; more preferably olefin diols Alkyl ether acetates, other ethers mentioned above, and other esters mentioned above. These solvents may be used singly or in combination of two or more.

感放射線性樹脂組成物中的(S)成分的含量，並無特別限定，以可將感放射線性樹脂組成物塗佈於基板等之範圍內的量，並根據塗佈膜厚適當設定。感放射線性樹脂組成物的黏度，較佳為0.9~500cp，更佳為1~50cp，進一步較佳為1~30cp。又，感放射線性樹脂組成物的固體成分濃度，較佳為1~80質量%，更佳為5~50質量%。 The content of the (S) component in the radiation-sensitive resin composition is not particularly limited, and the radiation-sensitive resin composition can be applied in an amount within the range of the substrate or the like, and is appropriately set depending on the coating film thickness. The viscosity of the radiation sensitive resin composition is preferably from 0.9 to 500 cp, more preferably from 1 to 50 cp, still more preferably from 1 to 30 cp. Further, the solid content concentration of the radiation sensitive resin composition is preferably from 1 to 80% by mass, more preferably from 5 to 50% by mass.

<其他成分> <Other ingredients>

可根據需要使本發明的感放射線性樹脂組成物中含有表面活性劑、密接性提高劑、熱聚合抑制劑、及消泡劑等添加劑。任一種添加劑，均可使用以往公知的添加劑。作為表面活性劑，可列舉陰離子系、陽離子系及非離子系等的化合物；作為密接性提高劑，可列舉以往公知的矽烷偶合劑(Silane coupling agent)；作為熱聚合抑制劑，可列舉氫醌、氫醌單乙醚 等；作為消泡劑，可列舉矽酮系、氟系化合物等。 The radiation sensitive resin composition of the present invention may contain an additive such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as needed. As the additive, a conventionally known additive can be used. Examples of the surfactant include a compound such as an anionic system, a cationic system, and a nonionic system. Examples of the adhesion improving agent include a conventionally known silane coupling agent; and examples of the thermal polymerization inhibitor include hydroquinone. Hydroquinone monoethyl ether The antifoaming agent may, for example, be an anthrone or a fluorine compound.

<感放射線性樹脂組成物的製備方法> <Preparation method of radiation sensitive resin composition>

本發明的感放射線性樹脂組成物，可使用電磁攪拌器將上述各成分攪拌、混合溶解，並根據需要用0.2μm膜片過濾器等過濾器進行過濾來製備。 The radiation sensitive resin composition of the present invention can be prepared by stirring, mixing, and dissolving the above components using a magnetic stirrer, and filtering them with a filter such as a 0.2 μm membrane filter as needed.

《絕緣膜》 "Insulation film"

本發明的絕緣膜，除使用上述的感放射線性樹脂組成物以外，與使用感放射線性樹脂組成物而形成的以往的絕緣膜相同。以下，僅說明絕緣膜的形成方法。 The insulating film of the present invention is the same as the conventional insulating film formed using the radiation sensitive resin composition except that the above-described radiation sensitive resin composition is used. Hereinafter, only the method of forming the insulating film will be described.

使用上述的感放射線性樹脂組成物形成絕緣膜之方法，並無特別限制，可自以往所採用之方法適當選擇。作為適合的絕緣膜的形成方法，可列舉包含以下步驟之方法：塗佈步驟，其將上述的感放射線性樹脂組成物塗佈於基板上，形成感放射線性樹脂層；曝光步驟，其將感放射線性樹脂層按照特定的絕緣膜的圖案進行曝光；及，顯影步驟，其將經曝光之感放射線性樹脂層顯影，形成絕緣膜的圖案。 The method of forming the insulating film using the radiation sensitive resin composition described above is not particularly limited, and can be appropriately selected from conventional methods. As a method of forming a suitable insulating film, a method comprising the steps of applying the above-described radiation sensitive resin composition onto a substrate to form a radiation sensitive resin layer, and an exposure step, which is a feeling, may be mentioned. The radiation-sensitive resin layer is exposed in a pattern of a specific insulating film; and, in a developing step, the exposed photosensitive resin layer is developed to form a pattern of the insulating film.

首先，於塗佈步驟中，使用輥式塗佈機、逆轉塗佈機、棒式塗佈機等接觸轉印型塗佈裝置或旋轉器(旋轉式塗佈裝置)、幕塗流動塗料器(curtain flow coater)等非接觸型塗佈裝置，將本發明的感放射線性樹脂組成物塗佈於應形成絕緣膜之基板上，並根據需要利用乾燥去掉溶劑，形成感放射線性樹脂層。 First, in the coating step, a contact transfer type coating device or a rotator (rotary coating device) or a curtain coating flow coater is used using a roll coater, a reverse coater, a bar coater or the like ( In a non-contact type coating device such as a curtain flow coater, the radiation sensitive resin composition of the present invention is applied onto a substrate on which an insulating film is to be formed, and if necessary, the solvent is removed by drying to form a radiation sensitive resin layer.

繼而，將表面形成有感放射線性樹脂層之基板提供至曝光步驟中。於曝光步驟中，經由負像遮片(negative mask)，向感放射線性樹脂層上照射ArF準分子激光、KrF準分子激光、F2準分子激光、極紫外線(extreme ultraviolet，EUV)、真空紫外線(vacuum ultraviolet rays，VUV)、電子束、X線及軟X線等放射線，將感放射線性樹脂層按照特定的絕緣膜的圖案部分曝光。曝光量根據感放射線性樹脂組成物的組成而不同，但例如10~600mJ/cm2左右為較佳。 Then, the substrate on which the surface is formed with the radiation sensitive resin layer is supplied to the exposure step. In the exposure step, the radiation-sensitive resin layer is irradiated with an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, an extreme ultraviolet (EUV), a vacuum ultraviolet light (via a negative mask). Radiation rays such as vacuum ultraviolet rays (VUV), electron beams, X-rays, and soft X-rays expose the radiation-sensitive resin layer to a pattern portion of a specific insulating film. The amount of exposure varies depending on the composition of the radiation sensitive resin composition, but is preferably, for example, about 10 to 600 mJ/cm 2 .

前述的感放射線性樹脂組成物，難以於曝光後，相對於鹼性顯影液而過度地溶解。因此，藉由使用前述的感放射線性樹脂組成物，易於形成以曝光部為凸部、以未曝光部為凹部之圖案來作為良好形狀的圖案。 The above-mentioned radiation sensitive resin composition is difficult to be excessively dissolved with respect to the alkaline developer after exposure. Therefore, by using the above-described radiation sensitive resin composition, it is easy to form a pattern in which the exposed portion is a convex portion and the unexposed portion is a concave portion as a good shape.

於顯影步驟中，藉由將曝光後的感放射線性樹脂層用顯影液進行顯影，來形成特定圖案的絕緣膜。顯影方法並無特別限定，可使用浸漬法、噴塗等。作為顯影液的具體例，可列舉：單乙醇胺、二乙醇胺及三乙醇胺等有機系的顯影液；或，氫氧化鈉、氫氧化鉀、碳酸鈉、阿摩尼亞及季銨鹽等的水溶液。 In the developing step, an insulating film having a specific pattern is formed by developing the exposed radiation-sensitive resin layer with a developing solution. The development method is not particularly limited, and a dipping method, spray coating, or the like can be used. Specific examples of the developer include organic developing solutions such as monoethanolamine, diethanolamine, and triethanolamine; or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium, and quaternary ammonium salts.

之後，根據需要，對顯影後的絕緣膜的圖案施加後烘乾，來加熱硬化。後烘乾的溫度較佳為150~270℃。 Thereafter, if necessary, the pattern of the developed insulating film is applied and then dried to be heat-hardened. The post-baking temperature is preferably from 150 to 270 °C.

使用前述的感放射線性樹脂組成物而形成的絕緣膜，由於透明性優異，因此，可適合用作內嵌式觸控面板方式的液晶顯示裝置、超高孔徑(Ultra High Aperture，UHA)面板等需要透明性優異的絕緣膜之顯示裝置用的絕緣膜。 The insulating film formed by using the radiation sensitive resin composition described above is excellent in transparency, and thus can be suitably used as a liquid crystal display device of an in-cell touch panel type, an ultra high aperture (UHA) panel, or the like. An insulating film for a display device of an insulating film having excellent transparency is required.

[實施例] [Examples]

以下，利用實施例進一步詳細地說明本發明，但本 發明並非被該等實施例所限定。 Hereinafter, the present invention will be described in further detail by way of examples, but The invention is not limited by the embodiments.

[實施例1~實施例24和比較例1~比較例5] [Example 1 to Example 24 and Comparative Example 1 to Comparative Example 5]

將由表1中記載的單元所構成之鹼可溶性樹脂15質量份、光聚合性化合物7質量份、光聚合引發劑0.5質量份、表面調整劑(BYK-310，聚酯改性聚二甲基矽氧烷，BYK Japan KK製造)0.5質量份、丙二醇單甲醚乙酸酯15質量份及二乙二醇單甲醚35質量份混合，使成為均勻的溶液，來製備實施例1~實施例24和比較例1~比較例5的感放射線性樹脂組成物。 15 parts by mass of an alkali-soluble resin composed of the units described in Table 1, 7 parts by mass of a photopolymerizable compound, 0.5 parts by mass of a photopolymerization initiator, and a surface conditioner (BYK-310, polyester-modified polydimethyl hydrazine) Oxygenane, manufactured by BYK Japan KK) 0.5 parts by mass, 15 parts by mass of propylene glycol monomethyl ether acetate, and 35 parts by mass of diethylene glycol monomethyl ether were mixed to form a uniform solution to prepare Examples 1 to 24. And the radiation sensitive resin composition of Comparative Example 1 to Comparative Example 5.

表2中記載的構成鹼可溶性樹脂之單元I~Ⅶ為由下式所表示之單元。 The units I to VII constituting the alkali-soluble resin described in Table 2 are units represented by the following formula.

作為光聚合性化合物，使用2,4,6-三氧代六氫-1,3,5-三嗪-1,3,5-三乙醇三丙烯酸酯和2,4,6-三氧代六氫-1,3,5-三嗪 -1,3,5-三乙醇二丙烯酸酯的混合物也就是M315(東亞合成股份有限公司(Toagosei Co.,Ltd.)製造)。 As the photopolymerizable compound, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol triacrylate and 2,4,6-trioxo-6 are used. Hydrogen-1,3,5-triazine A mixture of -1,3,5-triethanol diacrylate is also M315 (manufactured by Toagosei Co., Ltd.).

作為光聚合引發劑，使用由下式所表示之化合物。 As the photopolymerization initiator, a compound represented by the following formula is used.

關於實施例1~實施例24和比較例1~比較例5中獲得之感放射線性樹脂組成物，依照以下的方法，進行殘膜率、耐熱性及分離解析度的評價與斷點(break point，BP)的測定。評價結果記於表1。 With respect to the radiation sensitive resin compositions obtained in Examples 1 to 24 and Comparative Examples 1 to 5, evaluation of residual film ratio, heat resistance and separation resolution, and break point were performed according to the following methods. , BP) determination. The evaluation results are shown in Table 1.

(殘膜率評價) (residual film rate evaluation)

將上述各實施例和比較例中製備之感放射線性樹脂組成物用旋轉器(Mikasa spinner IH-360S，Mikasa Corporation製造)旋塗於玻璃基板上後，以100℃使塗膜乾燥120秒，形成感光放射線性樹脂層。繼而，利用曝光裝置(MPA600FA，佳能股份有限公司(CANON INC)製造)，以曝光量100mJ/cm2，將感放射線性樹脂層曝光。繼而，將氫氧化四甲銨的濃度2.38質量%的水溶液用作顯影液，在23℃進行60秒水坑式顯影(Puddle Development)，形成圖案。顯影後，將圖案以230℃後烘乾20分鐘。後烘乾後的圖案的膜厚為6μm。使用觸針式表面形狀測定器(Dektak 3st，愛發科股份有限公司(ULVAC,Inc.)製造)測定圖案的膜厚。測定後烘乾後的膜厚/顯影前的膜厚，求得殘膜率。依照以下的標準判定殘膜率得當與否。 The radiation sensitive resin composition prepared in each of the above Examples and Comparative Examples was spin-coated on a glass substrate by a spinner (Mikasa spinner IH-360S, manufactured by Mikasa Corporation), and then dried at 100 ° C for 120 seconds to form a film. Photosensitive linear resin layer. Then, the radiation sensitive resin layer was exposed by an exposure apparatus (MPA600FA, manufactured by CANON INC) at an exposure amount of 100 mJ/cm 2 . Then, an aqueous solution having a concentration of tetramethylammonium hydroxide of 2.38 mass% was used as a developing solution, and puddle development was performed at 23 ° C for 60 seconds to form a pattern. After development, the pattern was dried at 230 ° C for 20 minutes. The film thickness of the post-baking pattern was 6 μm. The film thickness of the pattern was measured using a stylus type surface shape measuring instrument (Dektak 3st, manufactured by ULVAC, Inc.). The film thickness after drying and the film thickness before development were measured, and the residual film ratio was determined. Determine whether the residual film rate is appropriate or not according to the following criteria.

○：80%以上。 ○: 80% or more.

×：不足80%。 ×: Less than 80%.

(耐熱性評價) (heat resistance evaluation)

用與殘膜率評價相同的方法，形成顯影後的形狀的錐角為50°以上且90°以下、後烘乾後的膜厚為6μm之圖案。根據後烘乾後的圖案的剖面照片，於基板表面與圖案的表面所成之角中，測定銳角也就是錐角(°)。基於錐角的測定結果，並依照以下的標準判定耐熱性。 In the same manner as the evaluation of the residual film ratio, a pattern having a taper angle of 50° or more and 90° or less after development and a film thickness of 6 μm after post-baking was formed. According to the cross-sectional photograph of the pattern after the post-baking, the acute angle, that is, the taper angle (°), is measured at an angle formed between the surface of the substrate and the surface of the pattern. The heat resistance was determined based on the measurement results of the taper angle in accordance with the following criteria.

○：錐角為30~70°。 ○: The taper angle is 30 to 70°.

×：錐角不足30°，或超過70°。 ×: The taper angle is less than 30° or exceeds 70°.

(分離解析度) (separation resolution)

用與殘膜率評價相同的方法，進行曝光和顯影，形成具有孔徑10μm的孔之孔圖案。後烘乾處理後，觀察孔的底部是否到達基板。基於孔的觀察結果，並依照以下的標準判定分離解析度。 Exposure and development were carried out in the same manner as in the evaluation of the residual film rate to form a hole pattern having pores having a pore diameter of 10 μm. After the post-baking treatment, it is observed whether the bottom of the hole reaches the substrate. Based on the observation results of the holes, the separation resolution was determined according to the following criteria.

○：孔的底部到達基板。 ○: The bottom of the hole reaches the substrate.

×：孔的底部未到達基板。 ×: The bottom of the hole did not reach the substrate.

(斷點的測定) (Measurement of breakpoints)

將上述各實施例和比較例中製備之感放射線性樹脂組成物用旋轉器(Mikasa spinner IH-360S，Mikasa Corporation製造)旋塗於Si基板後，以100℃使塗膜乾燥120秒，形成感光放射線性樹脂層。繼而，利用曝光裝置(MPA600FA，佳能股份有限公司製造)，以曝光量100mJ/cm2，將感放射線性樹脂層曝光。繼而，將氫氧化四甲銨的濃度2.38質量%的水溶液用作顯影液，在23℃進行60秒水坑式顯影，測定自顯影 液接觸基板之時間至光阻膜消失之時間，作為斷點。 The radiation-sensitive resin composition prepared in each of the above Examples and Comparative Examples was spin-coated on a Si substrate by a spinner (Mikasa spinner IH-360S, manufactured by Mikasa Corporation), and then dried at 100 ° C for 120 seconds to form a photosensitive film. A linear resin layer. Then, the radiation sensitive resin layer was exposed by an exposure apparatus (MPA600FA, manufactured by Canon Inc.) at an exposure amount of 100 mJ/cm 2 . Then, an aqueous solution having a concentration of tetramethylammonium hydroxide of 2.38 mass% was used as a developing solution, and puddle development was performed at 23 ° C for 60 seconds, and the time from when the developer contacted the substrate to when the photoresist film disappeared was measured as a breakpoint. .

根據實施例1~實施例24和比較例1~比較例5得知，若為包含(A)鹼可溶性樹脂、(B)光聚合性化合物及(C)光聚合引發劑之感放射線樹脂組成物，則於曝光後的顯影時，曝光部不會過度溶解，其中，該(A)鹼可溶性樹脂是由包含(a1)來自於不飽和羧酸之單元(單元I)與(a2)來自於含有不具有環氧基之脂環式骨架之不飽和化合物之單元(單元Ⅱ)之共聚物所構成，該(C)光聚合引發劑包含由上述式(1)所表示之結構的肟酯化合物。 According to Example 1 to Example 24 and Comparative Example 1 to Comparative Example 5, the radiation-sensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator was obtained. , the exposed portion is not excessively dissolved during development after exposure, wherein the (A) alkali-soluble resin is derived from a unit containing the (a1) unsaturated carboxylic acid (unit I) and (a2) A copolymer of a unit (unit II) having no epoxy group-containing alicyclic skeleton, and the (C) photopolymerization initiator contains an oxime ester compound having a structure represented by the above formula (1).

(透明性評價) (transparency evaluation)

使用實施例11的感放射線性樹脂組成物、與比較例6和比較例7的感放射線性樹脂組成物，評價使用感放射線性樹 脂組成物而獲得之絕緣膜的透明性，其中，比較例6和比較例7的感放射線性樹脂組成物，除光聚合引發劑的種類以外，與實施例11的感光性組成物為相同的組成。 The radiation sensitive linear resin composition of Example 11 and the radiation sensitive resin composition of Comparative Example 6 and Comparative Example 7 were used to evaluate the use of a radiation sensitive linear tree. The transparency of the insulating film obtained by the lipid composition was the same as that of the photosensitive composition of Example 11 except that the radiation-sensitive resin composition of Comparative Example 6 and Comparative Example 7 was the same as the type of the photopolymerization initiator. composition.

於比較例6中，使用由下式所表示之光聚合引發劑。 In Comparative Example 6, a photopolymerization initiator represented by the following formula was used.

於比較例7中，使用由下式所表示之光聚合引發劑。 In Comparative Example 7, a photopolymerization initiator represented by the following formula was used.

使用各實施例和比較例的感放射線性樹脂組成物，除曝光時選擇性進行曝光以外，與前述的殘膜率的評價方法同樣地形成經後烘乾之感放射線性樹脂組成物的硬化膜。硬化膜的膜厚為6μm。使用MCPD-3000(大塚電子(股)(Otsuka Electronics Co.,Ltd.)製造)測定所形成之硬化膜於波長400nm中的240度透過率後，實施例11的感放射線性樹脂組成物的硬化膜的透過率為88.8%，比較例6的感放射線性樹脂組成物的硬化膜的透過率為76.2%，比較例7的感放射線性樹脂組成物的硬化膜的透過率為76.1%。 Using the radiation sensitive resin composition of each of the examples and the comparative examples, a cured film of the post-baked radiation-sensitive resin composition was formed in the same manner as the above-described method for evaluating the residual film ratio, except that the exposure was selectively performed during the exposure. . The film thickness of the cured film was 6 μm. Hardening of the radiation sensitive resin composition of Example 11 after measuring the transmittance of the cured film formed at a wavelength of 400 nm using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) The transmittance of the film was 88.8%, the transmittance of the cured film of the radiation sensitive resin composition of Comparative Example 6 was 76.2%, and the transmittance of the cured film of the radiation sensitive resin composition of Comparative Example 7 was 76.1%.

根據以上的結果得知，相較於包含式(1)所不包含之化合物作為光聚合引發劑之感放射線性樹脂組成物，前述包含由式(1)所表示之化合物作為光聚合引發劑之感放射線性樹脂組成物提供透明性顯著優異的絕緣膜。 According to the above results, the above-mentioned compound containing the compound represented by the formula (1) is contained as a photopolymerization initiator as compared with the radiation-sensitive resin composition containing the compound not contained in the formula (1) as a photopolymerization initiator. The radiation sensitive linear resin composition provides an insulating film which is remarkably excellent in transparency.

Claims (6)

一種感放射線性樹脂組成物，其包含(A)鹼可溶性樹脂、(B)光聚合性化合物及(C)光聚合引發劑；前述(A)鹼可溶性樹脂，包含(a1)來自於不飽和羧酸之單元、與(a2)來自於不飽和化合物之單元，該不飽和化合物含有不具有環氧基之脂環式骨架；前述(C)光聚合引發劑，包含由下述式(1)所表示之肟酯化合物： R1為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，m為0~4的整數，p為0或1，R2為亦可具有取代基之苯基或亦可具有取代基之咔唑基，R3為氫原子或碳數1~6的烷基，其中，前述咔唑基亦可具有的取代基是選自下述的基團：碳數1~20的烷基、碳數1~20的烷氧基、碳數3~10的環烷基、碳數3~10的環烷氧基、碳數2~20的飽和脂肪族醯基、碳數2~20的烷氧羰基、碳數2~20的飽和脂肪族醯氧基、亦可具有取代基之苯基、亦可具有取代基之苯氧基、亦可具有 取代基之苯硫基、亦可具有取代基之苯甲醯基、亦可具有取代基之苯氧基羰基、亦可具有取代基之苯甲醯氧基、亦可具有取代基之碳數7~20的苯基烷基、亦可具有取代基之萘基、亦可具有取代基之萘氧基、亦可具有取代基之萘甲醯基、亦可具有取代基之萘氧基羰基、亦可具有取代基之萘甲醯氧基、亦可具有取代基之碳數11~20的萘基烷基、亦可具有取代基之雜環基、亦可具有取代基之雜環羰基、胺基、被1價或2價的有機基團所取代之胺基、嗎啉-1-基及呱嗪-1-基、鹵素、及氰基；前述肟酯化合物不包含下述化合物： A radiation sensitive linear resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator; and the above (A) an alkali-soluble resin comprising (a1) derived from an unsaturated carboxylic acid a unit of an acid, and (a2) a unit derived from an unsaturated compound containing an alicyclic skeleton having no epoxy group; and the above (C) photopolymerization initiator comprising the following formula (1); Deuterated ester compound: R 1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R 2 is also a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, and R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the substituent of the above oxazolyl group may be selected from the group consisting of the following The group is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, and a carbon number of 2 to 20 a saturated aliphatic fluorenyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic decyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, or a phenylthio group having a substituent, a benzylidene group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzamidineoxy group which may have a substituent, and a carbon number which may have a substituent a phenylalkyl group of 7 to 20, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl fluorenyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxy group having a substituent, Further, it may have a naphthylalkyl group having 11 to 20 carbon atoms of a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group, or a monovalent or divalent organic group. Substituted amine group, morpholin-1-yl and pyridazin-1-yl, halogen, and cyano; the aforementioned oxime ester compound does not contain the following compounds: 如請求項1所述之感放射線性樹脂組成物，其中，前述R2是由下式(2)所表示之基團： R4為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，A為S或O，n為0~4的整數；或R2為由下式(3)所表示之基團： R5和R6分別為1價的有機基團。 The radiation sensitive resin composition according to claim 1, wherein the aforementioned R 2 is a group represented by the following formula (2): R 4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, A is S or O, and n is an integer of 0 to 4; or R 2 is a group represented by the following formula (3): R 5 and R 6 are each a monovalent organic group. 一種感放射線性樹脂組成物，其包含(A)鹼可溶性樹脂、(B)光聚合性化合物及(C)光聚合引發劑；前述(A)鹼可溶性樹脂，包含(a1)來自於不飽和羧酸之單元、與(a2)來自於不飽和化合物之單元，該不飽和化合物含有不具有環氧基之脂環式骨架；前述(C)光聚合引發劑，包含由下述式(1)所表示之肟酯化合物： R1為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，m為0~4的整數，p為0或1，R2是由下式(2)所表示之基團： R4為選自由1價的有機基團、胺基、鹵素、硝基及氰基所組成之群組中的基團，A為S或O，n為0~4的整數；或R2為由下式(3)所表示之基團， R5和R6分別為1價的有機基團，R3為氫原子或碳數1~6的烷基。 A radiation sensitive linear resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator; and the above (A) an alkali-soluble resin comprising (a1) derived from an unsaturated carboxylic acid a unit of an acid, and (a2) a unit derived from an unsaturated compound containing an alicyclic skeleton having no epoxy group; and the above (C) photopolymerization initiator comprising the following formula (1); Deuterated ester compound: R 1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R 2 is The group represented by the following formula (2): R 4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, A is S or O, and n is an integer of 0 to 4; or R 2 is a group represented by the following formula (3), R 5 and R 6 are each a monovalent organic group, and R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 如請求項1~3中任一項所述之感放射線性樹脂組成物，其中，前述(A)鹼可溶性樹脂，進一步包含(a3)來自於含有脂環式環氧基之不飽和化合物之單元。 The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the (A) alkali-soluble resin further comprises (a3) a unit derived from an unsaturated compound containing an alicyclic epoxy group. . 一種絕緣膜，其使用如請求項1~4中任一項所述之感放射線性樹脂組成物而形成。 An insulating film formed using the radiation sensitive resin composition according to any one of claims 1 to 4. 一種顯示裝置，其具備如請求項5所述之絕緣膜。 A display device comprising the insulating film according to claim 5.
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