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TW201300952A - Radiation sensitive resin composition, cured film for display device, fabricating method of cured film for display device and display device - Google Patents

Radiation sensitive resin composition, cured film for display device, fabricating method of cured film for display device and display device Download PDF

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Publication number
TW201300952A
TW201300952A TW101123355A TW101123355A TW201300952A TW 201300952 A TW201300952 A TW 201300952A TW 101123355 A TW101123355 A TW 101123355A TW 101123355 A TW101123355 A TW 101123355A TW 201300952 A TW201300952 A TW 201300952A
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group
compound
resin composition
mass
radiation
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TW101123355A
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Tsuyoshi Nakagawa
Kouji Nishikawa
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Jsr Corp
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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
    • 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
    • C08F220/22—Esters containing halogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • 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

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)

Abstract

The object of this invention is to provide a radiation sensitive resin composition having a sufficient resolution and photosensitivity, and a cured film for display device excellent in compression property, transmission, light-resistance, voltage holding ratio, develope-resistance, heat-resistance and chemical-resistance. This invention is a radiation sensitive resin composition that includes: [A] an alkali soluable resin, [B] a polymerizable compound with an ethylene unsufficient bond, [C] a photo-polymerization initiator represented in the following formula (1), [D] at least a compound selected from the group consisted of a compound containing hindered phenol, a compound containing hindered amine, a compound containing phosphate and a compound containing thioether, and a content of [C] the photo-polymerization initiator is 0.1 parts by mass to 5 parts by mass based on 100 parts by mass of [A] an alkali soluable resin.

Description

感放射線性樹脂組成物、顯示元件用硬化膜、顯示元件用硬化膜的形成方法及顯示元件 Radiation-sensitive linear resin composition, cured film for display element, method for forming cured film for display element, and display element

本發明關於一種感放射線性樹脂組成物、顯示元件用硬化膜、顯示元件用硬化膜的形成方法及顯示元件。 The present invention relates to a radiation sensitive resin composition, a cured film for a display element, a method of forming a cured film for a display element, and a display element.

在薄膜晶體管型液晶顯示元件等電子零件中，通常為了使配置成層狀的配線之間絕緣而設置有層間絕緣膜。例如，薄膜晶體管型液晶顯示元件經過如下步驟來製造：在層間絕緣膜上形成透明電極膜，進而在透明電極膜上形成液晶配向膜。因此，在透明電極膜的形成步驟中，層間絕緣膜暴露在高溫條件下、或暴露在用於形成電極的圖案的抗蝕劑的剝離液中，因此需要針對它們的充分的耐熱性及耐溶劑性。 In an electronic component such as a thin film transistor type liquid crystal display device, an interlayer insulating film is usually provided in order to insulate between wirings arranged in a layer. For example, a thin film transistor type liquid crystal display element is manufactured by forming a transparent electrode film on an interlayer insulating film, and further forming a liquid crystal alignment film on the transparent electrode film. Therefore, in the step of forming the transparent electrode film, the interlayer insulating film is exposed to a high temperature condition or to a stripping liquid of a resist for forming a pattern of electrodes, and thus sufficient heat resistance and solvent resistance are required for them. Sex.

就圖案化性能的觀點而言，先前的液晶顯示元件用的層間絕緣膜使用利用了萘醌二疊氮等酸產生劑的正型感放射線性樹脂組成物(參照日本專利特開2001-354822號公報)。近年來，負型感放射線性樹脂組成物的高感光度、所獲得的硬化膜的高光線透過率等性能受到矚目，且正不斷應用負型感放射線性樹脂組成物(參照日本專利特開2000-162769號公報)。 From the viewpoint of the patterning performance, the interlayer insulating film for the liquid crystal display element of the prior art uses a positive-type radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide (refer to Japanese Patent Laid-Open No. 2001-354822). Bulletin). In recent years, the high sensitivity of the negative-type radiation-sensitive resin composition and the high light transmittance of the obtained cured film have been attracting attention, and the negative-type radiation-sensitive resin composition is being continuously applied (refer to Japanese Patent Laid-Open No. 2000). -162769).

另一方面，液晶顯示元件中所使用的構件之中，間隔片、保護膜、彩色濾光片用著色圖案等也大多使用負型感放射線性樹脂組成物來形成(參照日本專利特開平6-43643號公報)。近年來，對液晶顯示元件要求進一步的大畫面化、高亮度化、薄型化等，就步驟時間的縮短及削減成本的觀點而言，需要負型感放射線性樹脂組成物的高感光度化及高解析度化。 On the other hand, among the members used in the liquid crystal display device, a spacer, a protective film, a coloring pattern for a color filter, and the like are often formed using a negative-type radiation-sensitive resin composition (refer to Japanese Patent Laid-Open No. 6-- Bulletin No. 43643). In recent years, in order to reduce the step time and reduce the cost, the liquid crystal display device is required to have a larger screen size, higher brightness, and a smaller thickness, and the high sensitivity of the negative-type radiation-sensitive resin composition is required. High resolution.

作為針對所述步驟時間的縮短的對策，已對包含肟酯系光聚合起始劑的感放射線性樹脂組成物的技術進行了研究(參照 日本專利特開2005-227525號公報)。但是，該光聚合起始劑多為在可見區域中具有極大吸收的化合物，且光聚合起始劑本身略帶紅色的情況多。若使用此種先前的光聚合起始劑來形成硬化膜，則硬化膜也同樣地略呈紅色，光線透過率下降，因此根據液晶裝置而存在無法應用的情況。 As a countermeasure against shortening of the step time, a technique of a radiation sensitive resin composition containing an oxime ester photopolymerization initiator has been studied (refer to Japanese Patent Laid-Open Publication No. 2005-227525). However, the photopolymerization initiator is mostly a compound having a large absorption in the visible region, and the photopolymerization initiator itself is slightly reddish. When such a conventional photopolymerization initiator is used to form a cured film, the cured film is also slightly red in color, and the light transmittance is lowered. Therefore, it may not be applied depending on the liquid crystal device.

由於此種狀況，因此期望開發一種具有充分的解析度及感光度的感放射線性樹脂組成物，以及壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。 Due to such a situation, it is desired to develop a radiation-sensitive resin composition having sufficient resolution and sensitivity, and excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance, and solvent resistance. The display element is a cured film.

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

[專利文獻1]日本專利特開2001-354822號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-354822

[專利文獻2]日本專利特開2000-162769號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-162769

[專利文獻3]日本專利特開平6-43643號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 6-43643

[專利文獻4]日本專利特開2005-227525號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-227525

本發明是基於如上所述的情況而完成的發明，其目的在於提供一種具有充分的解析度及感光度的感放射線性樹脂組成物，以及壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a radiation sensitive resin composition having sufficient resolution and sensitivity, and compression properties, transmittance, light resistance, voltage holding ratio, and resistance. A cured film for display elements excellent in developability, heat resistance and solvent resistance.

為了解決所述課題而完成的發明是一種感放射線性樹脂組成物，其特徵在於包含：[A]鹼可溶性樹脂；[B]具有乙烯性不飽和鍵的聚合性化合物(以下，也稱為“[B]聚合性化合物”)；[C]由下述式(1)所表示的光聚合起始劑(以下，也稱為“[C] 光聚合起始劑”)；以及[D]選自由含有受阻酚結構的化合物、含有受阻胺結構的化合物、含有亞磷酸酯結構的化合物及含有硫醚結構的化合物所組成的組群中的至少1種化合物(以下，也稱為“[D]化合物”)；且相對於[A]鹼可溶性樹脂100質量份，[C]光聚合起始劑的含量為0.1質量份以上、5質量份以下。 The invention completed to solve the above problems is a radiation sensitive resin composition comprising: [A] an alkali-soluble resin; [B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter, also referred to as " [B] polymerizable compound "); [C] a photopolymerization initiator represented by the following formula (1) (hereinafter, also referred to as "[C] a photopolymerization initiator "); and [D] at least one selected from the group consisting of a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing a phosphite structure, and a compound having a thioether structure. 1 compound (hereinafter, also referred to as "[D] compound"); and the content of the [C] photopolymerization initiator is 0.1 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. .

(式(1)中，R1及R4分別獨立為碳數為1~12的烷基、碳數為4~20的脂環式烴基或苯基。其中，所述苯基所具有的氫原子的一部分或全部可由碳數為1~12的烷基或碳數為1~12的烷氧基取代。 (In the formula (1), R 1 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a phenyl group, wherein the hydrogen of the phenyl group A part or all of the atom may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

R2為亞甲基或碳數為2~20的伸烷基。 R 2 is a methylene group or an alkylene group having 2 to 20 carbon atoms.

R3為碳數為4~20的脂環式烴基、苯基或萘基。 R 3 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms, a phenyl group or a naphthyl group.

R5為苯基、甲苯基、二甲苯基、萘基、蒽基、菲基、9-芴基、2-呋喃基或2-噻吩基。其中，這些基所具有的氫原子的一部分或全部可由碳數為1~12的烷基或碳數為1~12的烷氧基取代)。 R 5 is phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, 9-fluorenyl, 2-furyl or 2-thienyl. Here, a part or all of the hydrogen atoms of these groups may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

該感放射線性樹脂組成物含有[A]鹼可溶性樹脂、[B]聚合性化合物、所述特定量的[C]光聚合起始劑、及[D]化合物。該感放射線性樹脂組成物藉由利用了感放射線性的曝光．顯影而可容易地形成微細且精巧的圖案，而且具有充分的解析度及感光度。另外，該感放射線性樹脂組成物含有特定量的具有所述特定結構的[C]光聚合起始劑，由此可形成壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。進而，該感放射線性樹脂組成物含有[D]化合物，由此該感放射線性樹脂組成物可形成提高了耐光性及耐熱性的顯示元件用硬化膜。 The radiation sensitive resin composition contains [A] an alkali-soluble resin, [B] a polymerizable compound, the above-mentioned specific amount of [C] photopolymerization initiator, and [D] compound. The radiation-sensitive linear resin composition utilizes a radiation-sensitive exposure. It is developed to easily form a fine and delicate pattern, and has sufficient resolution and sensitivity. Further, the radiation sensitive resin composition contains a specific amount of the [C] photopolymerization initiator having the specific structure, whereby compression properties, transmittance, light resistance, voltage retention, development resistance, and heat resistance can be formed. A cured film for display elements excellent in properties and solvent resistance. Further, the radiation sensitive linear resin composition contains the [D] compound, whereby the radiation sensitive linear resin composition can form a cured film for display elements having improved light resistance and heat resistance.

[A]鹼可溶性樹脂優選包含：(a1)選自由源自不飽和羧酸的結構單元、及源自不飽和羧酸酐的結構單元所組成的組群中的至少1種結構單元(以下，也稱為“(a1)結構單元”)；以及(a2)由下述式(2)所表示的結構單元(以下，也稱為“(a2)結構單元”)。 The [A] alkali-soluble resin preferably contains at least one structural unit selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic anhydride (hereinafter, also It is referred to as "(a1) structural unit"); and (a2) is a structural unit represented by the following formula (2) (hereinafter also referred to as "(a2) structural unit").

(式(2)中，R6為碳數為1~12的烷基、環己基、環戊基、苯基、甲苯基、二甲苯基、萘基或苄基)。 (In the formula (2), R 6 is an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a cyclopentyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a benzyl group).

藉由[A]鹼可溶性樹脂含有(a1)結構單元，而使對於鹼性水溶液的溶解性最佳化，並且可獲得放射線性感光度優異的感 放射線性樹脂組成物。另外，藉由[A]鹼可溶性樹脂含有(a1)結構單元與(a2)結構單元，可提升所獲得的顯示元件用硬化膜的耐熱性。進而，由於與[C]光聚合起始劑的相容性提升，因此[C]光聚合起始劑均勻地分散，可提升顯示元件用硬化膜形成時的感光度。 By using the [A] alkali-soluble resin containing the structural unit (a1), the solubility in the alkaline aqueous solution is optimized, and a feeling of excellent linear sensitivity is obtained. A linear resin composition. In addition, the [A] alkali-soluble resin contains (a1) structural unit and (a2) structural unit, and the heat resistance of the obtained cured film for display elements can be improved. Further, since the compatibility with the [C] photopolymerization initiator is improved, the [C] photopolymerization initiator is uniformly dispersed, and the sensitivity at the time of formation of the cured film for a display element can be improved.

[A]鹼可溶性樹脂優選包含：(a1)結構單元；以及(a3)由下述式(3)所表示的結構單元(以下，也稱為“(a3)結構單元”)。 The [A] alkali-soluble resin preferably contains: (a1) a structural unit; and (a3) a structural unit represented by the following formula (3) (hereinafter also referred to as "(a3) structural unit").

(式(3)中，R7及R8為氫原子或甲基。R9為由所述式(4-1)或式(4-2)所表示的基。n為1~6的整數。 (In the formula (3), R 7 and R 8 are a hydrogen atom or a methyl group. R 9 is a group represented by the formula (4-1) or the formula (4-2). n is an integer of 1 to 6 .

式(4-1)中，R10為氫原子或甲基。式(4-1)及式(4-2)中，＊表示與所述式(3)中的氧原子鍵結的部位)。 In the formula (4-1), R 10 is a hydrogen atom or a methyl group. In the formulae (4-1) and (4-2), * represents a moiety bonded to the oxygen atom in the formula (3).

藉由[A]鹼可溶性樹脂含有(a1)結構單元與(a3)結構單元，可進一步提升所獲得的顯示元件用硬化膜的硬化性等。 When the [A] alkali-soluble resin contains the (a1) structural unit and the (a3) structural unit, the hardenability and the like of the obtained cured film for a display element can be further enhanced.

[A]鹼可溶性樹脂優選包含：(a1)結構單元；以及 (a4)源自含有環氧基的不飽和化合物的結構單元(以下，也稱為“(a4)結構單元”)。 [A] the alkali-soluble resin preferably comprises: (a1) a structural unit; (a4) A structural unit derived from an epoxy group-containing unsaturated compound (hereinafter also referred to as "(a4) structural unit").

藉由[A]鹼可溶性樹脂含有(a1)結構單元與(a4)結構單元，可進一步提升所獲得的顯示元件用硬化膜的硬化性等。 When the [A] alkali-soluble resin contains the (a1) structural unit and the (a4) structural unit, the hardenability and the like of the obtained cured film for display elements can be further enhanced.

優選[B]聚合性化合物為二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物。藉由將[B]聚合性化合物設為所述特定化合物，可使該感放射線性樹脂組成物的感光度及所形成的顯示元件用硬化膜的耐熱性等以高水準並存。 Preferably, the [B] polymerizable compound is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. By using the [B] polymerizable compound as the specific compound, the sensitivity of the radiation sensitive resin composition and the heat resistance of the formed cured film for a display element can be made to a high level.

所述式(1)中，優選R1為甲基或苯基，R2為亞甲基或伸乙基，R3為環戊基或環己基，R4為碳數為1~6的烷基或苯基，R5為甲苯基或萘基。 In the formula (1), R 1 is preferably a methyl group or a phenyl group, R 2 is a methylene group or an ethyl group, R 3 is a cyclopentyl group or a cyclohexyl group, and R 4 is an alkane having a carbon number of 1 to 6. Or phenyl, R 5 is a tolyl or naphthyl group.

藉由將[C]光聚合起始劑設為所述特定化合物，可提升[C]光聚合起始劑對於感放射線性樹脂組成物的溶解性。 By setting the [C] photopolymerization initiator as the specific compound, the solubility of the [C] photopolymerization initiator for the radiation sensitive resin composition can be improved.

優選[D]化合物為所述含有受阻酚結構的化合物，且相對於[A]鹼可溶性樹脂100質量份，該[D]化合物的含量為0.01質量份以上、10質量份以下。藉由[D]化合物為所述特定的化合物，且該感放射線性樹脂組成物含有特定量的該特定的化合物，可進一步提高所形成的顯示元件用硬化膜的耐光性及耐熱性。 The compound [D] is preferably a compound having a hindered phenol structure, and the content of the [D] compound is 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the [D] compound is the specific compound and the radiation sensitive resin composition contains a specific amount of the specific compound, the light resistance and heat resistance of the formed cured film for display elements can be further improved.

優選該感放射線性樹脂組成物進一步含有[E]著色劑。藉由該感放射線性樹脂組成物進一步含有[E]著色劑，可形成例如作為彩色濾光片用著色圖案等的顯示元件用硬化膜。 Preferably, the radiation sensitive resin composition further contains [E] a colorant. By further containing the [E] coloring agent, the radiation-sensitive resin composition can form, for example, a cured film for a display element such as a coloring pattern for a color filter.

優選該感放射線性樹脂組成物用於形成顯示元件用硬化膜。另外，本發明中適宜包含由該感放射線性樹脂組成物所形 成的顯示元件用硬化膜、及具備該顯示元件用硬化膜的顯示元件。 Preferably, the radiation sensitive resin composition is used to form a cured film for a display element. Further, in the present invention, it is preferable to comprise a composition of the radiation-sensitive resin composition A cured film for a display element and a display element including the cured film for the display element.

本發明的顯示元件用硬化膜的形成方法包括如下步驟：(1)使用該感放射線性樹脂組成物，在基板上形成塗膜；(2)對所述塗膜的至少一部分照射放射線；(3)對照射了所述放射線的塗膜進行顯影；以及(4)對經所述顯影的塗膜進行加熱。 The method for forming a cured film for a display element of the present invention comprises the steps of: (1) forming a coating film on a substrate using the radiation sensitive resin composition; (2) irradiating at least a portion of the coating film with radiation; (3) Developing a coating film irradiated with the radiation; and (4) heating the developed coating film.

根據本發明的形成方法，可形成壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。 According to the formation method of the present invention, a cured film for a display element which is excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance and solvent resistance can be formed.

再者，本說明書中所述的“感放射線性樹脂組成物”的“放射線”是包含可見光線、紫外線、遠紫外線、X射線、荷電粒子束等的概念。 In addition, the "radiation" of the "radiation-sensitive linear resin composition" described in the present specification is a concept including visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

(發明的效果) (Effect of the invention)

如以上所說明般，本發明的感放射線性樹脂組成物可容易地形成微細且精巧的圖案，並具有充分的解析度及感光度。另外，該感放射線性樹脂組成物可形成壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。因此，該感放射線性樹脂組成物適合於顯示元件用彩色濾光片，陣列用層間絕緣膜，固體攝像元件的色分解用彩色濾光片，有機電致發光(Electroluminescence，EL)顯示元件用彩色濾光片，電子紙等柔性顯示器用彩色濾光片，觸控面板用保護膜，金屬配線或金屬凸塊的形成、基板的加工等中所使用的光加工用抗蝕劑等。 As described above, the radiation sensitive resin composition of the present invention can easily form a fine and delicate pattern and has sufficient resolution and sensitivity. Further, the radiation sensitive resin composition can form a cured film for a display element which is excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance, and solvent resistance. Therefore, the radiation sensitive resin composition is suitable for color filters for display elements, interlayer insulating films for arrays, color filters for color separation of solid-state imaging devices, and color for organic electroluminescence (EL) display elements. A color filter for a flexible display such as a color filter, a protective film for a touch panel, a metal wiring or a metal bump, a substrate for processing, or the like.

<感放射線性樹脂組成物> <Inductive Radiation 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、[B]聚合性化合物、[C]光聚合起始劑、及[D]化合物。另外，該感放射線性樹脂組成物可含有[E]著色劑作為適宜成分。進而，只要無損本發明的效果，則該感放射線性樹脂組成物也可以含有其他任意成分。以下，對各成分進行詳述。 The radiation sensitive resin composition of the present invention contains [A] an alkali-soluble resin, [B] a polymerizable compound, [C] a photopolymerization initiator, and a [D] compound. Further, the radiation sensitive resin composition may contain an [E] colorant as a suitable component. Further, the radiation sensitive resin composition may contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A]鹼可溶性樹脂> <[A] alkali soluble resin>

[A]鹼可溶性樹脂只要是具有鹼解離性的樹脂，則並無特別限定，但優選含有(a1)結構單元及(a2)結構單元的樹脂。另外，[A]鹼可溶性樹脂為含有(a1)結構單元及(a3)結構單元的樹脂也優選，[A]鹼可溶性樹脂為含有(a1)結構單元及(a4)結構單元的樹脂也優選。再者，只要無損本發明的效果，則[A]鹼可溶性樹脂也可以含有(a1)結構單元~(a4)結構單元以外的其他結構單元。 The alkali-soluble resin is not particularly limited as long as it is an alkali dissociable resin, but a resin containing the (a1) structural unit and the (a2) structural unit is preferred. Further, the [A] alkali-soluble resin is preferably a resin containing the (a1) structural unit and the (a3) structural unit, and the [A] alkali-soluble resin is also preferably a resin containing the (a1) structural unit and the (a4) structural unit. Further, the [A] alkali-soluble resin may contain other structural units other than the structural unit to the structural unit (a4), as long as the effects of the present invention are not impaired.

[A]鹼可溶性樹脂可藉由在溶劑中、且在聚合起始劑的存在下，對提供各結構單元的化合物進行自由基聚合來合成。以下，對提供各結構單元的化合物進行詳述。再者，所述各化合物也可以並用2種以上。 [A] The alkali-soluble resin can be synthesized by radical polymerization of a compound which provides each structural unit in a solvent and in the presence of a polymerization initiator. Hereinafter, the compounds providing the respective structural units will be described in detail. Further, the above compounds may be used in combination of two or more kinds.

[(a1)結構單元] [(a1) structural unit]

(a1)結構單元為選自由源自不飽和羧酸的結構單元、及源自不飽和羧酸酐的結構單元所組成的組群中的至少1種結構單元。作為提供(a1)結構單元的化合物，例如可列舉：不飽和一元羧酸、不飽和二羧酸、不飽和二羧酸的酐、多元羧酸的單[(甲基)丙烯醯氧基烷基]酯、兩末端具有羧基與羥基的聚合物的單(甲基)丙烯酸酯、具有羧基的不飽和多環式化合物及其酐等。 (a1) The structural unit is at least one structural unit selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic anhydride. Examples of the compound which provides the structural unit of (a1) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid, and a mono[(meth)acryloxyalkyl group of a polyvalent carboxylic acid. An ester, a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, an unsaturated polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

作為不飽和一元羧酸，例如可列舉：丙烯酸、甲基丙烯酸、 巴豆酸等。作為不飽和二羧酸，例如可列舉：順丁烯二酸、反丁烯二酸、檸康酸、中康酸、衣康酸等。作為不飽和二羧酸的酐，例如可列舉作為所述二羧酸所例示的化合物的酐等。作為多元羧酸的單[(甲基)丙烯醯氧基烷基]酯，例如可列舉：丁二酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等。作為兩末端具有羧基與羥基的聚合物的單(甲基)丙烯酸酯，例如可列舉ω-羧基聚己內酯單(甲基)丙烯酸酯等。作為具有羧基的不飽和多環式化合物及其酐，例如可列舉：5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯酐等。 Examples of the unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Crotonic acid, etc. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like. Examples of the anhydride of the unsaturated dicarboxylic acid include an anhydride such as the compound exemplified as the dicarboxylic acid. Examples of the mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid include succinic acid mono [2-(methyl) propylene oxyethyl ester], phthalic acid mono [ 2-(Methyl) propylene methoxyethyl] ester or the like. Examples of the mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals include ω-carboxypolycaprolactone mono(meth)acrylate. Examples of the unsaturated polycyclic compound having a carboxyl group and an anhydride thereof include 5-carboxybicyclo[2.2.1]hept-2-ene and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene. 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. .

它們之中，優選一元羧酸、二羧酸的酐，就共聚反應性、對於鹼性水溶液的溶解性及獲得的容易性而言，更優選(甲基)丙烯酸、順丁烯二酸酐。 Among them, an anhydride of a monocarboxylic acid or a dicarboxylic acid is preferable, and (meth)acrylic acid and maleic anhydride are more preferable in terms of copolymerization reactivity, solubility in an aqueous alkaline solution, and ease of availability.

作為[A]鹼可溶性樹脂中的(a1)結構單元的含有比例，相對於所有結構單元，優選5莫耳%~30莫耳%，更優選10莫耳%~25莫耳%。藉由將(a1)結構單元的含有比例設為5莫耳%~30莫耳%，而使[A]鹼可溶性樹脂對於鹼性水溶液的溶解性最佳化，並且可獲得放射線性感光度優異的感放射線性樹脂組成物。 The content ratio of the (a1) structural unit in the [A] alkali-soluble resin is preferably 5 mol% to 30 mol%, and more preferably 10 mol% to 25 mol%, based on all structural units. By setting the content ratio of the (a1) structural unit to 5 mol% to 30 mol%, the solubility of the [A] alkali-soluble resin to the alkaline aqueous solution is optimized, and excellent radiation sensitivity is obtained. A radiation sensitive resin composition.

[(a2)結構單元] [(a2) structural unit]

(a2)結構單元為由所述式(2)所表示的結構單元。藉由[A]鹼可溶性樹脂含有(a2)結構單元，可提升所獲得的顯示元件用硬化膜的耐熱性。另外，由於與[C]光聚合起始劑的相容性提升，因此[C]光聚合起始劑均勻地分散，可提升顯示元 件用硬化膜形成時的感光度。 (a2) The structural unit is a structural unit represented by the above formula (2). By the (A) alkali-soluble resin containing the (a2) structural unit, the heat resistance of the obtained cured film for display elements can be improved. In addition, since the compatibility with the [C] photopolymerization initiator is improved, the [C] photopolymerization initiator is uniformly dispersed, and the display element can be improved. Sensitivity when forming a cured film.

所述式(2)中，R6為碳數為1~12的烷基、環己基、環戊基、苯基、甲苯基、二甲苯基、萘基或苄基。 In the formula (2), R 6 is an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a cyclopentyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a benzyl group.

作為由所述R6所表示的碳數為1~12的烷基，例如可列舉：甲基、乙基、丙基、丁基、戊基、己基等。 Examples of the alkyl group having 1 to 12 carbon atoms represented by the above R 6 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

作為提供(a2)結構單元的化合物，例如可列舉：N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-甲苯基順丁烯二醯亞胺、N-萘基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺等。 Examples of the compound which provides the structural unit of (a2) include N-phenyl maleimide, N-cyclohexyl maleimide, N-tolyl maleimide, and N-tolyl maleimide. N-naphthyl maleimide, N-ethyl maleimide, N-hexyl maleimide, N-benzyl maleimide, and the like.

它們之中，就與[C]光聚合起始劑的相容性提升的觀點而言，優選N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺。 Among them, N-phenyl maleimide and N-cyclohexylmethyleneimine are preferred from the viewpoint of improving compatibility with the [C] photopolymerization initiator.

作為[A]鹼可溶性樹脂中的(a2)結構單元的含有比例，相對於所有結構單元，優選5莫耳%~30莫耳%，更優選10莫耳%~25莫耳%。藉由將(a2)結構單元的含有比例設為5莫耳%~30莫耳%，可提升所獲得的顯示元件用硬化膜的耐熱性，進而，與[C]光聚合起始劑的相容性提升。 The content ratio of the (a2) structural unit in the [A] alkali-soluble resin is preferably 5 mol% to 30 mol%, and more preferably 10 mol% to 25 mol%, based on all structural units. By setting the content ratio of the (a2) structural unit to 5 mol% to 30 mol%, the heat resistance of the obtained cured film for display elements can be improved, and further, the phase of the [C] photopolymerization initiator can be improved. Increased capacity.

[(a3)結構單元] [(a3) structural unit]

(a3)結構單元為由所述式(3)所表示的結構單元。所述式(3)中，R7及R8為氫原子或甲基。R9為由所述式(4-1)或式(4-2)所表示的基。n為1~6的整數。式(4-1)中，R10為氫原子或甲基。式(4-1)及式(4-2)中，＊表示與所述式(3)中的氧原子鍵結的部位。 (a3) The structural unit is a structural unit represented by the above formula (3). In the formula (3), R 7 and R 8 are a hydrogen atom or a methyl group. R 9 is a group represented by the formula (4-1) or the formula (4-2). n is an integer from 1 to 6. In the formula (4-1), R 10 is a hydrogen atom or a methyl group. In the formulae (4-1) and (4-2), * represents a moiety bonded to the oxygen atom in the formula (3).

(a3)結構單元可藉由(a1)結構單元中的羧基與後述的(a4)結構單元中的環氧基進行反應，並形成酯鍵而獲得。若列舉具體例來詳述，則例如當使具有(a1)結構單元的共聚物與提供(a4)結構單元的甲基丙烯酸縮水甘油酯、甲基丙烯酸2-甲基 縮水甘油酯等化合物進行反應時，所述式(3)中的R9變成由所述式(4-1)所表示的基。另一方面，當使甲基丙烯酸3,4-環氧環己基甲酯等化合物作為提供(a4)結構單元的化合物進行反應時，所述式(3)中的R9變成由所述式(4-2)所表示的基。 The (a3) structural unit can be obtained by reacting a carboxyl group in the structural unit (a1) with an epoxy group in the (a4) structural unit described later, and forming an ester bond. As will be described in detail by way of specific examples, for example, when a copolymer having the structural unit (a1) is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate which provides the (a4) structural unit. At the time, R 9 in the formula (3) becomes a group represented by the formula (4-1). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted as a compound which provides a structural unit of (a4), R 9 in the formula (3) becomes the formula ( 4-2) The base represented.

作為[A]鹼可溶性樹脂中的(a3)結構單元的含有比例，相對於所有結構單元，優選5莫耳%~60莫耳%，更優選10莫耳%~50莫耳%。藉由將(a3)結構單元的含有比例設為5莫耳%~60莫耳%，可形成具有優異的硬化性等的顯示元件用硬化膜。 The content ratio of the (a3) structural unit in the [A] alkali-soluble resin is preferably 5 mol% to 60 mol%, and more preferably 10 mol% to 50 mol%, based on all structural units. By setting the content ratio of the (a3) structural unit to 5 mol% to 60 mol%, it is possible to form a cured film for display elements having excellent curability and the like.

[(a4)結構單元] [(a4) structural unit]

(a4)結構單元為源自含有環氧基的不飽和化合物的結構單元。作為環氧基，可列舉環氧乙烷基(1,2-環氧基結構)及氧雜環丁基(1,3-環氧基結構)。 (a4) The structural unit is a structural unit derived from an unsaturated compound containing an epoxy group. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

作為具有環氧乙烷基的不飽和化合物，例如可列舉：丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧基丁酯、甲基丙烯酸-3,4-環氧基丁酯、丙烯酸-6,7-環氧基庚酯、甲基丙烯酸-6,7-環氧基庚酯、α-乙基丙烯酸-6,7-環氧基庚酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、甲基丙烯酸3,4-環氧環己酯等。 Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α-positive. Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid-6 , 7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidol Ether, 3,4-epoxycyclohexyl methacrylate, and the like.

作為具有氧雜環丁基的不飽和化合物，例如可列舉：3-(丙烯醯氧基甲基)氧雜環丁烷、3-(丙烯醯氧基甲基)-2-甲基氧雜環丁烷、3-(丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯氧基甲 基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-苯基氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2-二氟氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(2-丙烯醯氧基乙基)氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-乙基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-3-乙基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-三氟甲基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-五氟乙基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2-苯基氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2,2-二氟氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(2-丙烯醯氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的丙烯酸酯； 3-(甲基丙烯醯氧基甲基)氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-苯基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2-二氟氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-乙基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-3-乙基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-三氟甲基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-五氟乙基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2-苯基氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2,2-二氟氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(2-甲基丙烯醯氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的甲基丙烯酸酯等。 Examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-2-methyloxycyclohexane. Butane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-( Acryloxy 2-pentafluoroethyl oxetane, 3-(acryloxymethyl)-2-phenyl oxetane, 3-(acryloxymethyl)-2,2 -difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)-2,2,4 , 4-tetrafluorooxetane, 3-(2-propenyloxyethyl)oxetane, 3-(2-propenyloxyethyl)-2-ethyloxetane Alkane, 3-(2-propenyloxyethyl)-3-ethyloxetane, 3-(2-propenyloxyethyl)-2-trifluoromethyloxetane, 3-(2-propenyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-propenyloxyethyl)-2-phenyloxetane, 3- (2-propenyloxyethyl)-2,2-difluorooxetane, 3-(2-propenyloxyethyl)-2,2,4-trifluorooxetane, An acrylate such as 3-(2-propenyloxyethyl)-2,2,4,4-tetrafluorooxetane; 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxyloxy) Methyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl) --2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)- 2,2-Difluorooxetane, 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl) -2,2,4,4-tetrafluorooxetane, 3-(2-methylpropenyloxyethyl)oxetane, 3-(2-methylpropenyloxy) 2-ethyl-2-oxetane, 3-(2-methylpropenyloxyethyl)-3-ethyloxetane, 3-(2-methylpropenyloxy-4- 2-trifluoromethyloxetane, 3-(2-methylpropenyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methylpropene醯oxyethyl)-2-phenyloxetane, 3-(2-methylpropenyloxyethyl)-2,2-difluorooxetane, 3-(2-A Acryloxyethyl)-2,2, A methacrylate such as 4-trifluorooxetane or 3-(2-methylpropenyloxyethyl)-2,2,4,4-tetrafluorooxetane or the like.

它們之中，就共聚反應性及提升顯示元件用硬化膜的耐溶 劑性的觀點而言，優選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-6,7-環氧基庚酯、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、甲基丙烯酸3,4-環氧環己酯。 Among them, copolymerization reactivity and improvement of the curing resistance of the cured film for display elements From the viewpoint of the agent properties, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, and Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate.

作為[A]鹼可溶性樹脂中的(a4)結構單元的含有比例，相對於所有結構單元，優選5莫耳%~60莫耳%，更優選10莫耳%~50莫耳%。藉由將(a4)結構單元的含有比例設為5莫耳%~60莫耳%，可形成具有優異的硬化性等的顯示元件用硬化膜。 The content ratio of the (a4) structural unit in the [A] alkali-soluble resin is preferably 5 mol% to 60 mol%, more preferably 10 mol% to 50 mol%, based on all structural units. By setting the content ratio of the (a4) structural unit to 5 mol% to 60 mol%, it is possible to form a cured film for display elements having excellent curability and the like.

再者，作為[A]鹼可溶性樹脂，也可以將含有(a1)結構單元及(a3)結構單元的樹脂、與含有(a1)結構單元及(a4)結構單元的樹脂混合。 Further, as the [A] alkali-soluble resin, a resin containing the (a1) structural unit and the (a3) structural unit may be mixed with a resin containing the (a1) structural unit and the (a4) structural unit.

[其他結構單元] [Other structural units]

作為提供(a1)結構單元~(a4)結構單元以外的其他結構單元的化合物，該其他結構單元是[A]鹼可溶性樹脂可在無損本發明的效果的範圍內含有的結構單元，例如可列舉：具有羥基的(甲基)丙烯酸酯、(甲基)丙烯酸鏈狀烷基酯、(甲基)丙烯酸環狀烷基酯、(甲基)丙烯酸芳基酯、不飽和芳香族化合物、共軛二烯、含有四氫呋喃骨架等的不飽和化合物。 The compound which is a structural unit other than the structural unit of the (a1) structural unit to the (a4) structural unit, and the other structural unit is a structural unit which the [A] alkali-soluble resin can contain in the range which does not impair the effect of this invention, for example. : (meth) acrylate having a hydroxyl group, a chain alkyl (meth) acrylate, a cyclic alkyl (meth) acrylate, an aryl (meth) acrylate, an unsaturated aromatic compound, conjugate A diene, an unsaturated compound containing a tetrahydrofuran skeleton or the like.

作為具有羥基的(甲基)丙烯酸酯，例如可列舉：丙烯酸2-羥基乙酯、丙烯酸3-羥基丙酯、丙烯酸4-羥基丁酯、丙烯酸5-羥基戊酯、丙烯酸6-羥基己酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸3-羥基丙酯、甲基丙烯酸4-羥基丁酯、甲基丙烯酸5-羥基戊酯、甲基丙烯酸6-羥基己酯等。 Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate. 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

作為(甲基)丙烯酸鏈狀烷基酯，例如可列舉：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸第二 丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異癸酯、甲基丙烯酸正月桂酯、甲基丙烯酸十三烷基酯、甲基丙烯酸正硬脂基酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸第二丁酯、丙烯酸第三丁酯、丙烯酸2-乙基己酯、丙烯酸異癸酯、丙烯酸正月桂酯、丙烯酸十三烷基酯、丙烯酸正硬脂基酯等。 Examples of the (meth)acrylic chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and methacrylic acid. Butyl ester, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate Base ester, methyl acrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate A base ester, a n-stearyl acrylate or the like.

作為(甲基)丙烯酸環狀烷基酯，例如可列舉：甲基丙烯酸環己酯、甲基丙烯酸2-甲基環己酯、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基氧基乙酯、甲基丙烯酸異冰片酯、丙烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、丙烯酸三環[5.2.1.02,6]癸烷-8-基氧基乙酯、丙烯酸異冰片酯等。 Examples of the (meth)acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo [meth] acrylate [5.2.1.0 2,6 ] decane- 8-yl ester, tricyclo [5.0.1.02 2,6 ]decane-8-yloxyethyl ester, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, Tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate, tricyclo[5.2.1.0 2,6 ]decane-8-yloxyethyl acrylate, isobornyl acrylate, and the like.

作為(甲基)丙烯酸芳基酯，例如可列舉：甲基丙烯酸苯酯、甲基丙烯酸苄酯、丙烯酸苯酯、丙烯酸苄酯等。 Examples of the aryl (meth)acrylate include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

作為不飽和芳香族化合物，例如可列舉：苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯等。 Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

作為共軛二烯，例如可列舉：1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of the conjugated diene include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

作為含有四氫呋喃骨架的不飽和化合物，例如可列舉：(甲基)丙烯酸四氫糠酯、2-甲基丙烯醯氧基-丙酸四氫糠酯、3-(甲基)丙烯醯氧基四氫呋喃-2-酮等。 Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth)acrylate, 2-methylpropenyloxy-tetrahydrofurfuryl propionate, and 3-(methyl)acryloxytetrahydrofuran. 2-ketone and the like.

作為用以合成[A]鹼可溶性樹脂的聚合反應中所使用的溶劑，例如可列舉：醇、二醇醚、乙二醇烷基醚乙酸酯、二乙二醇單烷基醚、二乙二醇二烷基醚、二丙二醇二烷基醚、丙二醇單烷基醚、丙二醇烷基醚乙酸酯、丙二醇單烷基醚丙酸酯、酮、 酯等。 Examples of the solvent used in the polymerization reaction for synthesizing the [A] alkali-soluble resin include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, and diethyl ether. Diol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, Ester and the like.

作為用以合成[A]鹼可溶性樹脂的聚合反應中所使用的聚合起始劑，可使用通常作為自由基聚合起始劑而為人所知者。作為自由基聚合起始劑，例如可列舉：2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物。 As the polymerization initiator used in the polymerization for synthesizing the [A] alkali-soluble resin, those generally known as radical polymerization initiators can be used. As the radical polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'- An azo compound such as azobis-(4-methoxy-2,4-dimethylvaleronitrile).

在用以製造[A]鹼可溶性樹脂的聚合反應中，為了調整分子量，可使用分子量調整劑。作為分子量調整劑，例如可列舉：氯仿、四溴化碳等鹵化烴類；正己基硫醇、正辛基硫醇、正十二烷基硫醇、第三十二烷基硫醇、硫代乙醇酸等硫醇類；一硫化二甲基黃原酸酯、二硫化二異丙基黃原酸酯等黃原酸類；異松油烯、α-甲基苯乙烯二聚物等。 In the polymerization reaction for producing the [A] alkali-soluble resin, a molecular weight modifier may be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tridodecyl mercaptan, and thio Mercaptans such as glycolic acid; xanthogens such as dimethyl xanthogenate monosulfide and diisopropyl xanthate disulfide; terpinene, α-methylstyrene dimer, and the like.

作為[A]鹼可溶性樹脂的重量平均分子量(Mw)，優選1,000~30,000，更優選5,000~20,000。藉由將[A]鹼可溶性樹脂的Mw設為所述特定範圍，可提高該感放射線性樹脂組成物的感光度及顯影性。再者，本說明書中的聚合物的Mw及數量平均分子量(Mn)是藉由利用下述條件的凝膠滲透色譜法(Gel Permeation Chromatography，GPC)來測定。 The weight average molecular weight (Mw) of the [A] alkali-soluble resin is preferably 1,000 to 30,000, more preferably 5,000 to 20,000. By setting the Mw of the [A] alkali-soluble resin to the above specific range, the sensitivity and developability of the radiation sensitive resin composition can be improved. Further, the Mw and the number average molecular weight (Mn) of the polymer in the present specification are measured by gel permeation chromatography (GPC) under the following conditions.

裝置：GPC-101(昭和電工公司) Device: GPC-101 (Showa Denko Co., Ltd.)

管柱：將GPC-KF-801、GPC-KF-802、GPC-KF-803及GPC-KF-804結合 Pipe column: combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

流動相：四氫呋喃 Mobile phase: tetrahydrofuran

管柱溫度：40℃ Column temperature: 40 ° C

流速：1.0mL/min Flow rate: 1.0mL/min

試樣濃度：1.0質量% Sample concentration: 1.0% by mass

試樣注入量：100 μL Sample injection amount: 100 μL

檢測器：示差折射儀 Detector: differential refractometer

標準物質：單分散聚苯乙烯 Reference material: monodisperse polystyrene

<[B]聚合性化合物> <[B] polymerizable compound>

作為該感放射線性樹脂組成物中所含有的[B]聚合性化合物，只要是具有乙烯性不飽和鍵的聚合性化合物，則並無特別限定，例如除ω-羧基聚己內酯單(甲基)丙烯酸酯、乙二醇(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、雙苯氧基乙醇芴二(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯、甲基丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、(甲基)丙烯酸2-(2'-乙烯氧基乙氧基)乙酯、三羥甲基丙烷三(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、三(2-(甲基)丙烯醯氧基乙基)磷酸酯、環氧乙烷改質二季戊四醇六丙烯酸酯、丁二酸改質季戊四醇三丙烯酸酯等以外，可列舉使具有直鏈伸烷基及脂環式結構、且具有2個以上的異氰酸酯基的化合物與分子內具有1個以上的羥基、且具有3個~5個(甲基)丙烯醯氧基的化合物進行反應而獲得的(甲基)丙烯酸聚氨酯化合物等。 The [B] polymerizable compound contained in the radiation-sensitive resin composition is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond, for example, ω-carboxypolycaprolactone alone (A) Acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, tetraethylene glycol (Meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, dimethylol tricyclic fluorene Alkenyl di(meth)acrylate, 2-hydroxy-3-(methyl)propenyl propyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (meth)acrylate, Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , tris(2-(meth)acryloxyethyl)phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, etc. In addition, a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanate groups may have one or more hydroxyl groups in the molecule and have three to five (meth) acrylonitrile groups. A (meth)acrylic urethane compound obtained by reacting a compound of an oxy group or the like.

優選[B]聚合性化合物為二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物。藉由將[B]聚合性化合物設為所述特定化合物，可使該感放射線性樹脂組成物的感光度及所形成的顯示元件用硬化膜的耐熱性等以高水準並存。 Preferably, the [B] polymerizable compound is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. By using the [B] polymerizable compound as the specific compound, the sensitivity of the radiation sensitive resin composition and the heat resistance of the formed cured film for a display element can be made to a high level.

作為[B]聚合性化合物的市售品，例如可列舉：Aronix M-400、Aronix M-402、Aronix M-405、Aronix M-450、Aronix M-1310、Aronix M-1600、Aronix M-1960、Aronix M-7100、Aronix M-8030、Aronix M-8060、Aronix M-8100、Aronix M-8530、Aronix M-8560、Aronix M-9050、Aronix TO-756、Aronix TO-1450、Aronix TO-1382(以上，東亞合成公司)；KAYARAD DPHA、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120、KAYARAD MAX-3510(以上，日本化藥公司)；Viscoat 295、Viscoat 300、Viscoat 360、Viscoat GPT、Viscoat 3PA、Viscoat 400、Viscoat 802(以上，大阪有機化學工業公司)；作為丙烯酸聚氨酯系化合物的New Frontier R-1150(第一工業制藥公司)；KAYARAD DPHA-40H、UX-5000(以上，日本化藥公司)；UN-9000H(根上工業公司)；Aronix M-5300、Aronix M-5600、Aronix M-5700、M-210、Aronix M-220、Aronix M-240、Aronix M-270、Aronix M-6200、Aronix M-305、Aronix M-309、Aronix M-310、Aronix M-315(以上，東亞合成公司)；KAYARAD HDDA、KAYARAD HX-220、KAYARAD HX-620、KAYARAD R-526、KAYARAD R-167、KAYARAD R-604、KAYARAD R-684、KAYARAD R-551、KAYARAD R-712、UX-2201、UX-2301、UX-3204、UX-3301、UX-4101、UX-6101、UX-7101、UX-8101、UX-0937、MU-2100、MU-4001(以上，日本化藥公司)；Artrejin UN-9000PEP 、 Artrejin UN-92OOA 、 Artrejin UN-7600、Artrejin UN-333、Artrejin UN-1003、Artrejin UN-1255、Artrejin UN-6060PTM、Artrejin UN-6060P(以上，根上工業公司)；SH-500B Viscoat 260、Viscoat 312、Viscoat 335HP(以上，大阪有機化學工業公司)等。 As a commercial item of the [B] polymerizable compound, for example, Aronix M-400, Aronix M-402, Aronix M-405, Aronix can be cited. M-450, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, Aronix TO-756, Aronix TO-1450, Aronix TO-1382 (above, East Asia Synthetic Company); KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above, Nippon Kayaku Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400, Viscoat 802 (above, Osaka Organic Chemical Industry Co., Ltd.); New Frontier as an acrylic polyurethane compound R-1150 (First Industrial Pharmaceutical Company); KAYARAD DPHA-40H, UX-5000 (above, Nippon Kayaku Co., Ltd.); UN-9000H (Keed Industrial Co., Ltd.); Aronix M-5300, Aronix M-5600, Aronix M -5700, M-210, Aronix M-220, Aronix M-240, Aronix M-270, Aronix M-6200, Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315 (above, East Asia Synthetic company); KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-167, KAYARAD R-604 KAYARAD R-684, KAYARAD R-551, KAYARAD R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937 , MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.); Artrejin UN-9000PEP, Artrejin UN-92OOA, Artrejin UN-7600, Artrejin UN-333, Artrejin UN-1003, Artrejin UN-1255, Artrejin UN-6060PTM, Artrejin UN-6060P (above, Roots Industrial Company); SH-500B Viscoat 260, Viscoat 312, Viscoat 335HP (above, Osaka Organic Chemical Industry Co., Ltd., etc.

[B]聚合性化合物可單獨使用、或將2種以上混合使用。作為該感放射線性樹脂組成物中的[B]聚合性化合物的含量，相對於[A]鹼可溶性樹脂100質量份，優選10質量份~700質量份，更優選20質量份~600質量份。藉由將[B]聚合性化合物的含量設為所述特定範圍，即便在低曝光量下，該感放射線性樹脂組成物也可以形成具有充分的耐熱性、耐溶劑性、電壓保持率的顯示元件用硬化膜。 [B] The polymerizable compound may be used singly or in combination of two or more. The content of the [B] polymerizable compound in the radiation-sensitive resin composition is preferably 10 parts by mass to 700 parts by mass, more preferably 20 parts by mass to 600 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content of the [B] polymerizable compound to the specific range, the radiation sensitive resin composition can form a display having sufficient heat resistance, solvent resistance, and voltage holding ratio even at a low exposure amount. A cured film for components.

<[C]光聚合起始劑> <[C] Photopolymerization initiator>

[C]光聚合起始劑為由所述式(1)所表示的光聚合起始劑，相對於[A]鹼可溶性樹脂100質量份，該感放射線性樹脂組成物中的[C]光聚合起始劑的含量為0.1質量份以上、5質量份以下。藉由該感放射線性樹脂組成物含有特定量的具有所述特定結構的[C]光聚合起始劑，可形成壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。 [C] The photopolymerization initiator is a photopolymerization initiator represented by the above formula (1), and [C] light in the radiation-sensitive resin composition is 100 parts by mass relative to the [A] alkali-soluble resin. The content of the polymerization initiator is 0.1 part by mass or more and 5 parts by mass or less. The radiation-sensitive resin composition contains a specific amount of the [C] photopolymerization initiator having the specific structure, and can form compression properties, transmittance, light resistance, voltage retention, development resistance, heat resistance, and A cured film for display elements excellent in solvent resistance.

所述式(1)中，R1及R4分別獨立為碳數為1~12的烷基、碳數為4~20的脂環式烴基或苯基。其中，上述苯基所具有的氫原子的一部分或全部可由碳數為1~12的烷基或碳數為1~12的烷氧基取代。R2為亞甲基或碳數為2~20的伸烷基。R3為碳數為4~20的脂環式烴基、苯基或萘基。R5為苯基、甲苯基、二甲苯基、萘基、蒽基、菲基、9-芴基、2-呋喃基或2-噻 吩基。其中，這些基所具有的氫原子的一部分或全部可由碳數為1~12的烷基或碳數為1~12的烷氧基取代。 In the formula (1), R 1 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a phenyl group. Here, a part or all of the hydrogen atoms of the phenyl group may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. R 2 is a methylene group or an alkylene group having 2 to 20 carbon atoms. R 3 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms, a phenyl group or a naphthyl group. R 5 is phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, 9-fluorenyl, 2-furyl or 2-thienyl. Here, a part or all of the hydrogen atoms of these groups may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

作為由所述R1及R4所表示的碳數為1~12的烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、正己基等。 Examples of the alkyl group having 1 to 12 carbon atoms represented by the above R 1 and R 4 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a third group. Butyl, n-pentyl, n-hexyl and the like.

作為由所述R1及R4所表示的碳數為4~20的脂環式烴基，例如可列舉：環戊基、環己基、環庚基、環辛基、冰片基、降冰片基、金剛烷基等。 Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by the above R 1 and R 4 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a borneyl group, and a norbornyl group. Adamantyl and the like.

作為所述取代基即碳數為1~12的烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、正己基等。作為所述取代基即碳數為1~12的烷氧基，例如可列舉：甲氧基、乙氧基、丙氧基等。 Examples of the alkyl group having 1 to 12 carbon atoms as the substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and n-pentyl group. , Zhengjiji and so on. Examples of the alkoxy group having 1 to 12 carbon atoms as the substituent include a methoxy group, an ethoxy group, a propoxy group and the like.

作為由所述R2所表示的碳數為2~20的伸烷基，例如可列舉：伸乙基、伸丙基、伸丁基、伸戊基、伸己基等。 Examples of the alkylene group having 2 to 20 carbon atoms represented by the above R 2 include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

作為由所述R3所表示的碳數為4~20的脂環式烴基，例如可列舉：環戊基、環己基、環庚基、環辛基、冰片基、降冰片基、金剛烷基等。 Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by the above R 3 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a borneol group, a norbornyl group, and an adamantyl group. Wait.

所述式(1)中，優選R1為甲基或苯基，R2為亞甲基或伸乙基，R3為環戊基或環己基，R4為碳數為1~6的烷基或苯基，R5為甲苯基或萘基。藉由將[C]光聚合起始劑設為所述特定化合物，可提升[C]光聚合起始劑對於感放射線性樹脂組成物的溶解性。 In the formula (1), R 1 is preferably a methyl group or a phenyl group, R 2 is a methylene group or an ethyl group, R 3 is a cyclopentyl group or a cyclohexyl group, and R 4 is an alkane having a carbon number of 1 to 6. Or phenyl, R 5 is a tolyl or naphthyl group. By setting the [C] photopolymerization initiator as the specific compound, the solubility of the [C] photopolymerization initiator for the radiation sensitive resin composition can be improved.

作為[C]光聚合起始劑，例如可列舉由下述式(C-1)~下述式(C-10)所表示的化合物等。 Examples of the [C] photopolymerization initiator include compounds represented by the following formula (C-1) to the following formula (C-10).

[化4] [Chemical 4]

[化5] [Chemical 5]

相對於[A]鹼可溶性樹脂100質量份，[C]光聚合起始劑的含量為0.1質量份以上、5質量份以下，優選1質量份以上、5 質量份以下。藉由將[C]光聚合起始劑的含量設為所述特定範圍，可進一步提升該感放射線性組成物的感光度及所獲得的顯示元件用硬化膜的透過率。 The content of the [C] photopolymerization initiator is 0.1 parts by mass or more and 5 parts by mass or less, preferably 1 part by mass or more, based on 100 parts by mass of the [A] alkali-soluble resin. Below the mass. By setting the content of the [C] photopolymerization initiator to the specific range, the sensitivity of the radiation sensitive composition and the transmittance of the obtained cured film for a display element can be further improved.

<[C']光聚合起始劑> <[C'] Photopolymerization initiator>

該感放射線性樹脂組成物可含有一種[C]光聚合起始劑以外的[C']光聚合起始劑、或含有2種以上[C]光聚合起始劑以外的[C']光聚合起始劑。 The radiation sensitive linear resin composition may contain a [C'] photopolymerization initiator other than the [C] photopolymerization initiator or [C'] light other than two or more [C] photopolymerization initiators. Polymerization initiator.

作為[C']光聚合起始劑，例如可列舉：硫雜蒽酮(thioxanthone)系化合物、苯乙酮系化合物、聯咪唑系化合物、三嗪系化合物、O-醯基肟系化合物、鎓鹽系化合物、安息香系化合物、二苯甲酮系化合物、α-二酮系化合物、多核醌系化合物、二偶氮系化合物、醯亞胺磺酸鹽系化合物等。它們之中，作為[C']光聚合起始劑，優選含有選自由硫雜蒽酮系化合物、苯乙酮系化合物、聯咪唑系化合物、三嗪系化合物及O-醯基肟系化合物所組成的組群中的至少1種。 Examples of the [C'] photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-mercapto quinone compound, and hydrazine. A salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polynuclear oxime compound, a diazo compound, a quinone sulfonate compound, or the like. Among them, the [C'] photopolymerization initiator preferably contains a compound selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-fluorenyl compound. At least one of the group consisting of.

作為硫雜蒽酮系化合物，例如可列舉：硫雜蒽酮、2-氯硫雜蒽酮、2-甲基硫雜蒽酮、2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二氯硫雜蒽酮、2,4-二甲基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮等。 Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothiazinone, 2-methylthiaxanthone, 2-isopropylthioxanthone, and 4-isopropylsulfuric acid. Xanthone, 2,4-dichlorothiazepinone, 2,4-dimethylthiaxanone, 2,4-diethylthiaxanone, 2,4-diisopropylthiazepine Ketones, etc.

作為苯乙酮系化合物，例如可列舉：2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲氨基-1-(4-嗎啉基苯基)丁烷-1-酮、2-(4-甲基苄基)-2-(二甲氨基)-1-(4-嗎啉基苯基)丁烷-1-酮等。 Examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl) Butane-1-one and the like.

作為聯咪唑系化合物，例如可列舉：2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯 基)-4,4',5,5'-四苯基-1,2'-聯咪唑等。再者，當使用聯咪唑系化合物作為光聚合起始劑時，就可改良感光度的觀點而言，優選並用供氫體。所謂供氫體，是指可對藉由曝光而從聯咪唑系化合物中產生的自由基提供氫原子的化合物。作為供氫體，例如可列舉：2-巰基苯並噻唑、2-巰基苯並惡唑等硫醇系供氫體；4,4'-雙(二甲氨基)二苯甲酮、4,4'-雙(二乙氨基)二苯甲酮等胺系供氫體。在本發明中，供氫體可單獨使用、或將2種以上混合使用，但就可進一步改良感光度的觀點而言，優選將1種以上的硫醇系供氫體與1種以上的胺系供氫體組合使用。 Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'. - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichloro benzene Base 4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like. Further, when a biimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The hydrogen donor is a compound which can supply a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include a mercaptan hydrogen donor such as 2-mercaptobenzothiazole or 2-mercaptobenzoxazole; 4,4′-bis(dimethylamino)benzophenone, 4,4 An amine-based hydrogen donor such as '-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. However, from the viewpoint of further improving the sensitivity, it is preferred to use one or more kinds of thiol-based hydrogen donors and one or more amines. A hydrogen donor is used in combination.

作為三嗪系化合物，例如可列舉：2,4,6-三(三氯甲基)-均三嗪、2-甲基-4,6-雙(三氯甲基)-均三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三嗪、2-[2-(4-二乙氨基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-均三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-均三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三嗪、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-均三嗪等。 Examples of the triazine-based compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, and 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(trichloromethyl)-s-triazine, 2-(4-methoxy Phenyl)-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 or the like.

作為O-醯基肟系化合物，例如可列舉：1,2-辛二酮-1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)、乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜環戊烷基)甲氧基苯甲醯基}-9H-哢唑-3-基]-1-(O-乙醯基肟)等。 Examples of the O-indenyl lanthanide compound include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine), ethyl ketone- 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidoxime), ethyl ketone-1-[9- Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1-(O-ethylindenyl), ethyl ketone-1- [9-Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzylidene}-9H-carbazole -3-yl]-1-(O-ethylindenyl) and the like.

作為[C']光聚合起始劑的含量，相對於[A]鹼可溶性樹脂100質量份，優選0.01質量份~60質量份，更優選1質量份~55質量份。藉由將[C']光聚合起始劑的含量設為所述特定範 圍，可充分地獲得由曝光所引起的硬化，並可適當地確保與基板的密接性。 The content of the [C'] photopolymerization initiator is preferably 0.01 parts by mass to 60 parts by mass, more preferably 1 part by mass to 55 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content of the [C'] photopolymerization initiator to the specific range The curing caused by the exposure can be sufficiently obtained, and the adhesion to the substrate can be appropriately ensured.

<[D]化合物> <[D] compound>

[D]化合物為選自由含有受阻酚結構的化合物、含有受阻胺結構的化合物、含有亞磷酸酯結構的化合物及含有硫醚結構的化合物所組成的組群中的至少1種化合物。藉由該感放射線性樹脂組成物含有[D]化合物，可形成提高了耐光性及耐熱性的顯示元件用硬化膜。推測其原因如下：[D]化合物捕捉曝光時、加熱時等所產生的自由基，或將因氧化而生成的過氧化物分解，由此可抑制[A]鹼可溶性樹脂的分子裂解。再者，由於[D]化合物為含有所述結構的化合物，因此即便該感放射線性樹脂組成物含有該[D]化合物，也維持對於放射線的高感光度、且所獲得的顯示元件用硬化膜等的透過率及電壓保持率的下降少。 The compound [D] is at least one compound selected from the group consisting of a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing a phosphite structure, and a compound having a thioether structure. When the radiation sensitive linear resin composition contains the [D] compound, a cured film for a display element having improved light resistance and heat resistance can be formed. The reason is presumed to be as follows: [D] The compound can capture the radical generated during exposure, heating, or the like, or decompose the peroxide formed by oxidation, thereby suppressing molecular cleavage of the [A] alkali-soluble resin. In addition, since the [D] compound is a compound containing the above-described structure, even if the radiation sensitive resin composition contains the [D] compound, the high sensitivity to radiation and the obtained cured film for display elements are obtained. The decrease in transmittance and voltage retention rate is small.

作為含有受阻酚結構的化合物，例如可列舉：季戊四醇四[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、硫代二伸乙基雙[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、十八烷基-3-(3,5-二-第三丁基-4-羥苯基)丙酸酯、三(3,5-二-第三丁基-4-羥基苄基)異氰脲酸酯、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯、N,N'-己烷-1,6-二基雙[3-(3,5-二-第三丁基-4-羥苯基丙醯胺)、3,3',3",5,5',5"-六-第三丁基-a,a',a"-(均三甲苯-2,4,6-三基)三-對甲酚、4,6-雙(辛硫基甲基)-鄰甲酚、4,6-雙(十二烷硫基甲基)-鄰甲酚、伸乙基雙(羥乙基)雙[3-(5-第三丁基-4-羥基-間甲苯基)丙酸酯]、六亞甲基雙[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、1,3,5-三[(4-第三丁基-3-羥基-2,6-二甲苯基)甲基]-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、2,6-二-第三丁基-4-(4,6-雙(辛硫 基)-1,3,5-三嗪-2-基胺)苯酚、2,5-二-第三丁基對苯二酚等。它們之中，作為含有受阻酚結構的化合物，優選季戊四醇四[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]2,5-二-第三丁基對苯二酚、三(3,5-二-第三丁基-4-羥基苄基)異氰脲酸酯、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯。 Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and thiodiethylidene bis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Ester, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di -T-butyl-4-hydroxybenzyl)benzene, N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropane Guanamine), 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl) -p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethyl bis(hydroxyethyl) Bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 1,3,5-tris[(4-t-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione, 2,6-di-t-butyl-4-(4,6-bis(octyl sulphide) Base-1,3,5-triazin-2-ylamine)phenol, 2,5-di-t-butyl hydroquinone, and the like. Among them, as a compound having a hindered phenol structure, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] 2,5-di-t-butyl group is preferred. Hydroquinone, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl)benzene.

作為含有受阻酚結構的化合物的市售品，例如可列舉：Adekastab AO-20、Adekastab AO-30、Adekastab AO-40、Adekastab AO-50、Adekastab AO-60、Adekastab AO-70、Adekastab AO-80、Adekastab AO-330(以上，艾迪科(ADEKA)公司)，sumilizer GM、sumilizer GS、sumilizer MDP-S、sumilizer BBM-S、sumilizer WX-R、sumilizer GA-80(以上，住友化學公司)，IRGANOX 1010、IRGANOX 1035、IRGANOX 1076、IRGANOX 1098、IRGANOX 1135、IRGANOX 1330、IRGANOX 1726、IRGANOX 1425WL、IRGANOX 1520L、IRGANOX 245、IRGANOX 259、IRGANOX 3114、IRGANOX 565、IRGAMOD 295(以上，汽巴日本(Ciba Japan)公司)，Yoshinox BHT、Yoshinox BB、Yoshinox 2246G、Yoshinox 425、Yoshinox 250、Yoshinox 930、Yoshinox SS、Yoshinox TT、Yoshinox 917、Yoshinox 314(以上，愛彼埃(API)公司)等。 As a commercial item of the compound containing a hindered phenol structure, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80 are mentioned, for example. , Adekastab AO-330 (above, ADEKA), sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 (above, Sumitomo Chemical Co., Ltd.), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD 295 (above, Ciba Japan (Ciba Japan) )), Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 (above, Abbie (API)).

作為含有受阻胺結構的化合物，例如可列舉：雙(2,2,6,6-四甲基-4-呱啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-呱啶基)丁二酸酯、雙(1,2,2,6,6-五甲基-4-呱啶基)癸二酸酯、雙(N-辛氧基-2,2,6,6-四甲基-4-呱啶基)癸二酸酯、雙(N-苄氧基-2,2,6,6-四甲基-4-呱啶基)癸二酸酯、雙(N-環己氧基-2,2,6,6-四甲基-4-呱啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-呱啶基)2-(3,5-二-第三丁基-4-羥基苄基)-2-丁基丙二酸酯、雙(1-丙烯醯基-2,2,6,6-四甲 基-4-呱啶基)2,2-雙(3,5-二-第三丁基-4-羥基苄基)-2-丁基丙二酸酯、雙(1,2,2,6,6-五甲基-4-呱啶基)癸二酸酯、2,2,6,6-四甲基-4-呱啶基甲基丙烯酸酯、4-[3-(3,5-二-第三丁基-4-羥苯基)丙醯氧基]-1-[2-(3-(3,5-二-第三丁基-4-羥苯基)丙醯氧基)乙基]-2,2,6,6-四甲基呱啶、2-甲基-2-(2,2,6,6-四甲基-4-呱啶基)氨基-N-(2,2,6,6-四甲基-4-呱啶基)丙醯胺、四(2,2,6,6-四甲基-4-呱啶基)1,2,3,4-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-呱啶基)1,2,3,4-丁烷四羧酸酯等化合物；N,N',N",N'''-四-[4,6-雙-[丁基-(N-甲基-2,2,6,6-四甲基呱啶-4-基)氨基]-三嗪-2-基]-4,7-二氮癸烷-1,10-二胺、二丁胺、1,3,5-三嗪．N,N'-雙(2,2,6,6-四甲基-4-呱啶基)-1,6-己二胺及N-(2,2,6,6-四甲基-4-呱啶基)丁胺的聚縮合物，二丁胺、1,3,5-三嗪及N,N'-雙(2,2,6,6-四甲基-4-呱啶基)丁胺的聚縮合物，聚[{(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-呱啶基)亞氨基}六亞甲基{(2,2,6,6-四甲基-4-呱啶基)亞氨基}]、1,6-己二胺-N,N'-雙(2,2,6,6-四甲基-4-呱啶基)及嗎啉-2,4,6-三氯-1,3,5-三嗪的聚縮合物，聚[(6-嗎啉基-均三嗪-2,4-二基)[(2,2,6,6-四甲基-4-呱啶基)亞氨基]-六亞甲基[(2,2,6,6-四甲基-4-呱啶基)亞氨基]]等經由三嗪骨架而鍵結有多個呱啶環的高分子量受阻胺光穩定劑(Hindered Amine Light Stabilizer，HALS)；丁二酸二甲酯與4-羥基-2,2,6,6-四甲基-1-呱啶乙醇的聚合物，1,2,3,4-丁烷四羧酸、1,2,2,6,6-五甲基-4-呱啶醇及3,9-雙(2-羥基-1,1-二甲基乙基)-2,4,8,10-四氧雜螺[5,5]十一烷的混合酯化物等的經由酯鍵而鍵結有呱啶環化合物等的聚合物等。它們之中，作為含有受阻胺結構的化合物，優選雙(2,2,6,6-四甲基-4-呱啶基)癸二酸酯。 Examples of the compound having a hindered amine structure include bis(2,2,6,6-tetramethyl-4-acridinyl)sebacate and bis(2,2,6,6-tetramethyl group). 4--4-acridinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-acridinyl)sebacate, bis(N-octyloxy-2,2 ,6,6-tetramethyl-4-acridinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-acridinyl) sebacate , bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-acridinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4 -acridinyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-propenylfluorenyl-2,2,6,6 -Four 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis (1,2,2,6) ,6-pentamethyl-4-acridinyl) sebacate, 2,2,6,6-tetramethyl-4-acridinyl methacrylate, 4-[3-(3,5- Di-t-butyl-4-hydroxyphenyl)propanoxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy) Ethyl]-2,2,6,6-tetramethylacridine, 2-methyl-2-(2,2,6,6-tetramethyl-4-acridinyl)amino-N-(2 , 2,6,6-tetramethyl-4-acridinyl)propanamide, tetrakis(2,2,6,6-tetramethyl-4-acridinyl) 1,2,3,4-butyl a compound such as an alkyltetracarboxylate or a tetrakis(1,2,2,6,6-pentamethyl-4-acridinyl) 1,2,3,4-butanetetracarboxylate; N,N', N",N'''-tetra-[4,6-bis-[butyl-(N-methyl-2,2,6,6-tetramethylacridin-4-yl)amino]-triazine -2-yl]-4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine. N,N'-bis(2,2,6,6- Polycondensate of tetramethyl-4-acridinyl)-1,6-hexanediamine and N-(2,2,6,6-tetramethyl-4-acridinyl)butylamine, dibutylamine Polycondensate of 1,3,5-triazine and N,N'-bis(2,2,6,6-tetramethyl-4-acridinyl)butylamine, poly[{(1,1, 3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4 -Acridine)imino}hexamethylene {(2,2,6,6-tetramethyl-4-acridinyl)imino}], 1,6-hexanediamine-N,N'- Poly(condensate of bis(2,2,6,6-tetramethyl-4-acridinyl) and morpholine-2,4,6-trichloro-1,3,5-triazine, poly[(6) -morpholinyl-s-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-acridinyl)imino]-hexamethylene[2,2, Hindered Amine Light Stabilizer (HALS), which is bonded to a plurality of acridine rings via a triazine skeleton, such as 6,6-tetramethyl-4-acridinyl)imino] a polymer of dimethyl diacid and 4-hydroxy-2,2,6,6-tetramethyl-1-acridine ethanol, 1,2,3,4-butanetetracarboxylic acid, 1,2,2 6,6-pentamethyl-4-acridinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 a polymer such as an acridine ring compound or the like which is bonded via an ester bond, such as a mixed esterified product of undecane, etc. Among them, as a compound having a hindered amine structure, bis(2,2,6, 6-Tetramethyl-4-acridinyl) sebacate.

作為含有受阻胺結構的化合物的市售品，例如可列舉：Adekastab LA-52、Adekastab LA57、Adekastab LA-62、Adekastab LA-67、Adekastab LA-63P、Adekastab LA-68LD、Adekastab LA-77、Adekastab LA-82、Adekastab LA-87(以上，艾迪科公司)，sumilizer 9A(住友化學公司)，CHIMASSORB 119FL、CHIMASSORB 2020FDL、CHIMASSORB 944FDL、TINUVIN 622LD、TINUVIN 144、TINUVIN 765、TINUVIN 770DF(汽巴日本公司)等。 As a commercial item of the compound containing a hindered amine structure, Adekastab LA-52, Adekastab LA57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab are mentioned, for example. LA-82, Adekastab LA-87 (above, Adico), sumilizer 9A (Sumitomo Chemical Company), CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD, TINUVIN 144, TINUVIN 765, TINUVIN 770DF (Ciba Japan )Wait.

作為含有亞磷酸酯結構的化合物，例如可列舉：三(壬基苯基)亞磷酸酯、三(對第三辛基苯基)亞磷酸酯、三[2,4,6-三(α-苯基乙基)]亞磷酸酯、三(對2-丁烯基苯基)亞磷酸酯、亞磷酸雙(對壬基苯基)環己酯、三(2,4-二-第三丁基苯基)亞磷酸酯、二(2,4-二-第三丁基苯基)季戊四醇二亞磷酸酯、2,2'-亞甲基雙(4,6-二-第三丁基-1-苯氧基)(2-乙基己氧基)磷、二硬脂基季戊四醇二亞磷酸酯、亞磷酸4,4'-異亞丙基-二苯酚烷基酯、四-十三烷基-4,4'-亞丁基-雙(3-甲基-6-第三丁基苯酚)二亞磷酸酯、亞磷酸四(2,4-二-第三丁基苯基)-4,4'-亞聯苯酯、2,6-二-第三丁基-4-甲基苯基．苯基．季戊四醇二亞磷酸酯、2,6-第三丁基-4-甲基苯基．苯基．季戊四醇二亞磷酸酯、2,6-二-第三丁基-4-乙基苯基．硬脂基．季戊四醇二亞磷酸酯、二(2,6-第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、2,6-二-第三戊基-4-甲基苯基．苯基．季戊四醇二亞磷酸酯等。它們之中，作為含有亞磷酸酯結構的化合物，優選2,2'-亞甲基雙(4,6-二-第三丁基-1-苯氧基)(2-乙基己氧基)磷、二硬脂基季戊四醇二亞磷酸酯。 Examples of the compound having a phosphite structure include tris(nonylphenyl)phosphite, tris(p-t-octylphenyl)phosphite, and tris[2,4,6-tri(α-). Phenylethyl)]phosphite, tris(p-butenylphenyl)phosphite, bis(p-nonylphenyl)cyclohexyl phosphite, tris(2,4-di-third) Phenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butyl- 1-phenoxy)(2-ethylhexyloxy)phosphorus, distearyl pentaerythritol diphosphite, 4,4'-isopropylidene-diphenol alkyl phosphite, tetra-tridecane 4-,4'-butylene-bis(3-methyl-6-tert-butylphenol) diphosphite, tetrakis(2,4-di-t-butylphenyl)-4, 4'-biphenylene ester, 2,6-di-tert-butyl-4-methylphenyl. Phenyl. Pentaerythritol diphosphite, 2,6-tert-butyl-4-methylphenyl. Phenyl. Pentaerythritol diphosphite, 2,6-di-t-butyl-4-ethylphenyl. Stearyl. Pentaerythritol diphosphite, bis(2,6-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,6-di-third amyl-4-methylphenyl. Phenyl. Pentaerythritol diphosphite, and the like. Among them, as a compound having a phosphite structure, 2,2'-methylenebis(4,6-di-t-butyl-1-phenoxy)(2-ethylhexyloxy) is preferred. Phosphorus, distearyl pentaerythritol diphosphite.

作為含有亞磷酸酯結構的化合物的市售品，例如可列舉：Adekastab PEP-4C、Adekastab PEP-8、Adekastab PEP-8W、 Adekastab PEP-24G、Adekastab PEP-36、Adekastab HP-10、Adekastab 2112、Adekastab 260、Adekastab 522A、Adekastab 1178、Adekastab 1500、Adekastab C、Adekastab 135A、Adekastab 3010、Adekastab TPP(以上，艾迪科公司)，IRGAFOS168(汽巴日本公司)等。 As a commercial item of the compound containing a phosphite structure, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, etc. are mentioned, for example. Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP (above, Edike) IRGAFOS168 (Ciba Japan) and so on.

作為含有硫醚結構的化合物，例如可列舉：硫代二丙酸二月桂酯、硫代二丙酸二-十三烷基酯、硫代二丙酸二肉豆蔻酯、硫代二丙酸二硬脂基酯、季戊四醇四(硫代丙酸3-月桂酯)、季戊四醇四(硫代丙酸3-十八烷基酯)、季戊四醇四(硫代丙酸3-肉豆蔻酯)、季戊四醇四(硫代丙酸3-硬脂基酯)等。它們之中，作為含有硫醚結構的化合物，優選季戊四醇四(硫代丙酸3-月桂酯)。 Examples of the compound having a thioether structure include dilauryl thiodipropionate, di-tridecyl thiodipropionate, dimyristyl thiodipropionate, and thiodipropionic acid. Stearyl ester, pentaerythritol tetra (3-lauryl thiopropionate), pentaerythritol tetra (3-octadecyl thiopropionate), pentaerythritol tetra (thiopropionate 3-myristyl ester), pentaerythritol IV (3-stearyl thiopropionate) and the like. Among them, as the compound having a thioether structure, pentaerythritol tetra(3-lauryl thiopropionate) is preferable.

作為含有硫醚結構的化合物的市售品，例如可列舉：Adekastab AO-412S、Adekastab AO-503(以上，艾迪科公司)，sumilizer TPL-R、sumilizer TPM、sumilizer TPS、sumilizer TP-D、sumilizer MB(以上，住友化學公司)，IRGANOXPS800FD、IRGANOXPS802FD(汽巴日本公司)，DLTP、DSTP、DMTP、DTTP(以上，愛彼埃公司)等。 As a commercial item of the compound containing a thioether structure, Adekastab AO-412S, Adekastab AO-503 (above, Adico Corporation), sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D, Sumilizer MB (above, Sumitomo Chemical Co., Ltd.), IRGANOXPS800FD, IRGANOXPS802FD (Ciba Japan), DLTP, DSTP, DMTP, DTTP (above, Aude Pride).

[D]化合物可單獨使用、或將2種以上混合使用。作為該感放射線性樹脂組成物中的[D]化合物的含量，相對於[A]聚合物100質量份，優選0.01質量份以上、10質量份以下，更優選0.1質量份以上、5質量份以下。藉由將[D]化合物的含量設為所述範圍，可有效地提高由該感放射線性樹脂組成物所形成的顯示元件用硬化膜的耐光性及耐熱性。 The compound [D] may be used singly or in combination of two or more. The content of the [D] compound in the radiation-sensitive resin composition is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the [A] polymer. . By setting the content of the [D] compound to the above range, the light resistance and heat resistance of the cured film for a display element formed of the radiation sensitive resin composition can be effectively improved.

優選[D]化合物為所述含有受阻酚結構的化合物，且相對於[A]鹼可溶性樹脂100質量份，該[D]化合物的含量為0.01質量 份以上、10質量份以下。藉由[D]化合物為所述化合物，且該感放射線性樹脂組成物含有所述特定量的該化合物，可進一步提高所形成的顯示元件用硬化膜的耐光性及耐熱性。 Preferably, the [D] compound is the compound having a hindered phenol structure, and the content of the [D] compound is 0.01 mass based on 100 parts by mass of the [A] alkali-soluble resin. More than 10 parts by weight. When the [D] compound is the compound and the radiation sensitive resin composition contains the specific amount of the compound, the light resistance and heat resistance of the cured film for a display element can be further improved.

<[E]著色劑> <[E] colorant>

優選該感放射線性樹脂組成物進一步含有[E]著色劑。藉由該感放射線性樹脂組成物進一步含有[E]著色劑，可形成例如作為彩色濾光片用著色圖案等的顯示元件用硬化膜。 Preferably, the radiation sensitive resin composition further contains [E] a colorant. By further containing the [E] coloring agent, the radiation-sensitive resin composition can form, for example, a cured film for a display element such as a coloring pattern for a color filter.

作為[E]著色劑，只要具有著色性，則並無特別限定，可根據彩色濾光片的用途來適宜選擇色彩或材質。作為著色劑，可使用例如顏料、染料及天然色素的任一種，但由於對彩色濾光片要求高色純度、亮度、對比度等，因此優選顏料、染料。在本發明中，著色劑可單獨使用、或將2種以上混合使用。 The coloring agent [E] is not particularly limited as long as it has coloring properties, and a color or a material can be appropriately selected depending on the use of the color filter. As the coloring agent, for example, any of a pigment, a dye, and a natural coloring matter can be used. However, since a color filter is required to have high color purity, brightness, contrast, and the like, a pigment or a dye is preferable. In the present invention, the coloring agents may be used singly or in combination of two or more.

作為顏料，可為有機顏料、無機顏料的任一種，作為有機顏料，例如可列舉在染料索引(Colour Index)(C.I.；The Society of Dyers and Colourists(英國染色與印染工作者協會)公司發行)中被分類為顏料的化合物。具體而言，可列舉被賦予了如下所述的染料索引(C.I.)名的顏料。 The pigment may be any of an organic pigment and an inorganic pigment, and examples of the organic pigment include, for example, a Colour Index (CI; The Society of Dyers and Colourists). A compound classified as a pigment. Specifically, a pigment to which a dye index (C.I.) name as described below is given can be cited.

可列舉：C.I.顏料黃12、C.I.顏料黃13、C.I.顏料黃14、C.I.顏料黃17、C.I.顏料黃20、C.I.顏料黃24、C.I.顏料黃31、C.I.顏料黃55、C.I.顏料黃83、C.I.顏料黃93、C.I.顏料黃109、C.I.顏料黃110、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃153、C.I.顏料黃154、C.I.顏料黃155、C.I.顏料黃166、C.I.顏料黃168、C.I.顏料黃180、C.I.顏料黃211；C.I.顏料橙5、C.I.顏料橙13、C.I.顏料橙14、C.I.顏料橙24、C.I.顏料橙34、C.I.顏料橙36、C.I.顏料橙38、C.I.顏料橙40、C.I.顏料橙43、C.I.顏料橙46、C.I.顏料橙49、C.I.顏料橙 61、C.I.顏料橙64、C.I.顏料橙68、C.I.顏料橙70、C.I.顏料橙71、C.I.顏料橙72、C.I.顏料橙73、C.I.顏料橙74；C.I.顏料紅1、C.I.顏料紅2、C.I.顏料紅5、C.I.顏料紅17、C.I.顏料紅31、C.I.顏料紅32、C.I.顏料紅41、C.I.顏料紅122、C.I.顏料紅123、C.I.顏料紅144、C.I.顏料紅149、C.I.顏料紅166、C.I.顏料紅168、C.I.顏料紅170、C.I.顏料紅171、C.I.顏料紅175、C.I.顏料紅176、C.I.顏料紅177、C.I.顏料紅178、C.I.顏料紅179、C.I.顏料紅180、C.I.顏料紅185、C.I.顏料紅187、C.I.顏料紅202、C.I.顏料紅206、C.I.顏料紅207、C.I.顏料紅209、C.I.顏料紅214、C.I.顏料紅220、C.I.顏料紅221、C.I.顏料紅224、C.I.顏料紅242、C.I.顏料紅243、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料紅262、C.I.顏料紅264、C.I.顏料紅272；C.I.顏料紫1、C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫29、C.I.顏料紫32、C.I.顏料紫36、C.I.顏料紫38；C.I.顏料藍15、C.I.顏料藍15：3、C.I.顏料藍15：4、C.I.顏料藍15：6、C.I.顏料藍60、C.I.顏料藍80；C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠58；C.I.顏料棕23、C.I.顏料棕25；C.I.顏料黑1、C.I.顏料黑7等。 Can be cited as: CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38; CI Pigment Blue 15, CI Pigment Blue 1 5:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, CI Pigment Blue 80; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7, and the like.

另外，作為所述無機顏料，例如可列舉：氧化鈦、硫酸鋇、碳酸鈣、氧化鋅、硫酸鉛、黃色鉛、鋅黃、三氧化二鐵(紅色氧化鐵(III))、鎘紅、群青、普魯士藍、氧化鉻綠、鈷綠、棕土、鈦黑、合成鐵黑、碳黑等。 Further, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, ferric oxide (red iron oxide (III)), cadmium red, and ultramarine blue. , Prussian blue, chrome oxide green, cobalt green, brown earth, titanium black, synthetic iron black, carbon black and so on.

在本發明中，也可以藉由再結晶法、再沉澱法、溶劑清洗法、昇華法、真空加熱法或這些方法的組合對顏料加以精製後 使用。另外，視需要，也可以利用樹脂對顏料的粒子表面進行改質後使用。作為對顏料的粒子表面進行改質的樹脂，例如可列舉日本專利特開2001-108817號公報中所記載的載色基樹脂、或市售的各種顏料分散用的樹脂等。作為碳黑表面的樹脂包覆方法，例如可採用日本專利特開平9-71733號公報、日本專利特開平9-95625號公報、日本專利特開平9-124969號公報等中所記載的方法。另外，有機顏料優選藉由所謂的軟磨(Soft Milling)，將一次粒子微細化後使用。作為軟磨的方法，例如可列舉日本專利特開平08-179111號公報中所揭示的方法等。 In the present invention, the pigment may be refined by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination of these methods. use. Further, if necessary, the surface of the particles of the pigment may be modified by a resin and used. For example, the chromophore resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments can be used as the resin for modifying the surface of the pigment particles. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-H09-95625, JP-A-H09-124969, and the like can be used. Further, the organic pigment is preferably used after the primary particles are refined by so-called soft milling. As a method of the soft grinding, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111, and the like can be cited.

作為染料，只要可溶於有機溶劑，則可使用公知的染料，例如可列舉：油溶性染料、酸性染料或其衍生物、直接染料、媒染料等。具體而言，可列舉被賦予了如下所述的染料索引(C.I.)名的染料。 As the dye, a known dye can be used as long as it is soluble in an organic solvent, and examples thereof include an oil-soluble dye, an acid dye or a derivative thereof, a direct dye, a mordant dye, and the like. Specifically, a dye to which a dye index (C.I.) name as described below is given can be cited.

可列舉：C.I.溶劑黃4、C.I.溶劑黃14、C.I.溶劑黃15、C.I.溶劑黃23、C.I.溶劑黃24、C.I.溶劑黃38、C.I.溶劑黃62、C.I.溶劑黃63、C.I.溶劑黃68、C.I.溶劑黃82、C.I.溶劑黃88、C.I.溶劑黃94、C.I.溶劑黃98、C.I.溶劑黃99、C.I.溶劑黃162、C.I.溶劑黃179；C.I.溶劑紅45、C.I.溶劑紅49、C.I.溶劑紅125、C.I.溶劑紅130；C.I.溶劑橙2、C.I.溶劑橙7、C.I.溶劑橙11、C.I.溶劑橙15、C.I.溶劑橙26、C.I.溶劑橙56；C.I.溶劑藍35、C.I.溶劑藍37、C.I.溶劑藍59、C.I.溶劑藍67；C.I.酸性黃1、C.I.酸性黃3、C.I.酸性黃7、C.I.酸性黃9、 C.I.酸性黃11、C.I.酸性黃17、C.I.酸性黃23、C.I.酸性黃25、C.I.酸性黃29、C.I.酸性黃34、C.I.酸性黃36、C.I.酸性黃38、C.I.酸性黃40、C.I.酸性黃42、C.I.酸性黃54、C.I.酸性黃65、C.I.酸性黃72、C.I.酸性黃73、C.I.酸性黃76；C.I.酸性紅91、C.I.酸性紅92、C.I.酸性紅97、C.I.酸性紅114、C.I.酸性紅138、C.I.酸性紅151；C.I.酸性橙51、C.I.酸性橙63；C.I.酸性藍80、C.I.酸性藍83、C.I.酸性藍90；C.I.酸性綠9、C.I.酸性綠16、C.I.酸性綠25、C.I.酸性綠27等。 For example, CI Solvent Yellow 4, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 23, CI Solvent Yellow 24, CI Solvent Yellow 38, CI Solvent Yellow 62, CI Solvent Yellow 63, CI Solvent Yellow 68, CI Solvent Yellow 82, CI Solvent Yellow 88, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 99, CI Solvent Yellow 162, CI Solvent Yellow 179; CI Solvent Red 45, CI Solvent Red 49, CI Solvent Red 125, CI Solvent Red 130; CI Solvent Orange 2, CI Solvent Orange 7, CI Solvent Orange 11, CI Solvent Orange 15, CI Solvent Orange 26, CI Solvent Orange 56; CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59, CI Solvent Blue 67; CI acid yellow 1, CI acid yellow 3, CI acid yellow 7, CI acid yellow 9, CI Acid Yellow 11, CI Acid Yellow 17, CI Acid Yellow 23, CI Acid Yellow 25, CI Acid Yellow 29, CI Acid Yellow 34, CI Acid Yellow 36, CI Acid Yellow 38, CI Acid Yellow 40, CI Acid Yellow 42, CI Acid Yellow 54, CI Acid Yellow 65, CI Acid Yellow 72, CI Acid Yellow 73, CI Acid Yellow 76; CI Acid Red 91, CI Acid Red 92, CI Acid Red 97, CI Acid Red 114, CI Acid Red 138, CI Acid Red 151; CI Acid Orange 51, CI Acid Orange 63; CI Acid Blue 80, CI Acid Blue 83, CI Acid Blue 90; CI Acid Green 9, CI Acid Green 16, CI Acid Green 25, CI Acid Green 27, etc. .

藉由使用染料作為[E]著色劑，可實現僅使用顏料無法達成的高亮度化或高對比度化。但是，若在先前的感放射線性樹脂組成物中使用染料作為[E]著色劑，則存在鹼顯影性、像素的耐熱性、耐溶劑性等顯著惡化的情況。根據該感放射線性樹脂組成物，即便在使用染料作為[E]著色劑的情況下，也可以獲得鹼顯影性良好的感放射線性樹脂組成物。 By using a dye as the [E] coloring agent, it is possible to achieve high brightness or high contrast which cannot be achieved by using only a pigment. However, when a dye is used as the [E] coloring agent in the conventional radiation-sensitive resin composition, the alkali developability, the heat resistance of the pixel, the solvent resistance, and the like may be remarkably deteriorated. According to the radiation sensitive resin composition, even when a dye is used as the [E] coloring agent, a radiation sensitive resin composition having good alkali developability can be obtained.

作為[E]著色劑的含量，就形成亮度高且色純度優異的像素、或遮光性優異的黑色矩陣的觀點而言，相對於感放射線性樹脂組成物的總固體成分為5質量%~70質量%，優選5質量%~60質量%。 The content of the [E] colorant is 5% by mass to 70% of the total solid content of the radiation-sensitive resin composition from the viewpoint of forming a pixel having high luminance and excellent color purity or a black matrix having excellent light-shielding properties. % by mass, preferably 5% by mass to 60% by mass.

<其他任意成分> <Other optional ingredients>

除[A]鹼可溶性樹脂、[B]聚合性化合物、[C]光聚合起始劑、[D]化合物、及[E]著色劑以外，該感放射線性樹脂組成物也可以在無損本發明的效果的範圍內，視需要含有[F]黏結助劑、[G]界面活性劑、[H]環氧化合物、保存穩定劑等其他任意成分。這些其他任意成分可單獨使用，也可以將2種以上混合 使用。以下，對各成分進行詳述。 The radiation sensitive linear resin composition may be used in addition to the [A] alkali-soluble resin, the [B] polymerizable compound, the [C] photopolymerization initiator, the [D] compound, and the [E] colorant. Within the range of the effect, other optional components such as [F] adhesion aid, [G] surfactant, [H] epoxy compound, storage stabilizer, etc. may be contained. These other optional components may be used alone or in combination of two or more. use. Hereinafter, each component will be described in detail.

[[F]黏結助劑] [[F]bonding aid]

[F]黏結助劑可用於使所獲得的硬化膜與基板的黏結性提升。作為[F]黏結助劑，優選具有羧基、甲基丙烯醯基、乙烯基、異氰酸酯基、環氧乙烷基等反應性官能基的官能性矽烷偶聯劑，例如可列舉：三甲氧基甲矽烷基苯甲酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等。 [F] A bonding aid can be used to improve the adhesion of the obtained cured film to the substrate. The [F] adhesion promoter is preferably a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an oxirane group, and examples thereof include trimethoxy group. a nonyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanatopropyl triethoxy decane, Γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

作為[F]黏結助劑的含量，相對於[A]鹼可溶性樹脂100質量份，優選20質量份以下，更優選15質量份以下。若[F]黏結助劑的含量超過20質量份，則存在容易產生顯影殘留的傾向。 The content of the [F] adhesion aid is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the content of the [F] adhesion aid exceeds 20 parts by mass, there is a tendency that development residue tends to occur.

[[G]界面活性劑] [[G] surfactant]

[G]界面活性劑可用於使該感放射線性樹脂組成物的塗膜形成性進一步提升。作為[G]界面活性劑，例如可列舉氟系界面活性劑、矽酮系界面活性劑等。 The [G] surfactant can be used to further improve the coating film formability of the radiation sensitive resin composition. Examples of the [G] surfactant include fluorine-based surfactants and anthrone-based surfactants.

作為氟系界面活性劑，優選末端、主鏈及側鏈的至少任一個部位上具有氟烷基及/或氟伸烷基的化合物。作為氟系界面活性劑的市售品，例如可列舉：Ftergent FT-100、Ftergent FT-110、Ftergent FT-140A、Ftergent FT-150、Ftergent FT-250、Ftergent FT-251、Ftergent FT-300、Ftergent FT-310、Ftergent FT-400S、Ftergent FTX-218、Ftergent FTX-251(以上，雷歐時(Neos)公司)等。 The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group in at least one of a terminal, a main chain and a side chain. Examples of commercially available fluorine-based surfactants include Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Ftergent FT-250, Ftergent FT-251, and Ftergent FT-300. Ftergent FT-310, Ftergent FT-400S, Ftergent FTX-218, Ftergent FTX-251 (above, Neos).

作為矽酮系界面活性劑的市售品，例如可列舉：Toray Silicone DC3PA、Toray Silicone DC7PA、Toray Silicone SH11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH-190、Toray Silicone SH-193、Toray Silicone SZ-6032、Toray Silicone SF-8428、Toray Silicone DC-57、Toray Silicone DC-190(以上，東麗道康寧矽酮(Dow Corning Toray Silicone)公司)等。 As a commercial item of an anthrone-type surfactant, for example, Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190 (above, Dow Corning Toray Silicone).

作為[G]界面活性劑的含量，相對於[A]鹼可溶性樹脂100質量份，優選1.0質量份以下，更優選0.7質量份以下。若[G]界面活性劑的含量超過1.0質量份，則容易產生膜不均。 The content of the [G] surfactant is preferably 1.0 part by mass or less, and more preferably 0.7 part by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the content of the [G] surfactant is more than 1.0 part by mass, film unevenness is likely to occur.

[[H]環氧化合物] [[H]epoxy compound]

該感放射線性樹脂組成物可含有[H]環氧化合物。作為[H]環氧化合物，例如可列舉1分子內具有2個以上的3,4-環氧環己基的化合物等。 The radiation sensitive resin composition may contain a [H] epoxy compound. Examples of the [H] epoxy compound include a compound having two or more 3,4-epoxycyclohexyl groups in one molecule.

作為1分子內具有2個以上的3,4-環氧環己基的化合物，例如可列舉：3,4-環氧環己基甲基-3',4'-環氧環己烷羧酸酯、2-(3,4-環氧環己基-5,5-螺-3,4-環氧基)環己烷-間二惡烷、雙(3,4-環氧環己基甲基)己二酸酯、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、3,4-環氧基-6-甲基環己基-3',4'-環氧基-6'-甲基環己烷羧酸酯、亞甲基雙(3,4-環氧環己烷)、二環戊二烯二環氧化物、乙二醇的二(3,4-環氧環己基甲基)醚、伸乙基雙(3,4-環氧環己烷羧酸酯)、內酯改質3,4-環氧環己基甲基-3',4'-環氧環己烷羧酸酯等。 Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate. 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)hexane Acid ester, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy Benzyl-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4- Epoxycyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3', 4'-ring Oxycyclohexane carboxylate and the like.

作為其他[H]環氧化合物，例如可列舉：雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚、氫化雙酚A二縮水甘油醚、氫化雙酚F二縮水甘油醚、氫化雙酚AD二縮水甘油醚、溴化雙酚A二縮水甘油醚、 溴化雙酚F二縮水甘油醚、溴化雙酚S二縮水甘油醚等雙酚化合物的二縮水甘油醚；1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚等多元醇的聚縮水甘油醚；藉由在乙二醇、丙二醇、甘油等脂肪族多元醇中加成1種或2種以上的環氧烷而獲得的聚醚多元醇的聚縮水甘油醚；苯酚酚醛清漆型環氧樹脂；甲酚酚醛清漆型環氧樹脂；多酚型環氧樹脂；環狀脂肪族環氧樹脂；脂肪族長鏈二元酸的二縮水甘油酯；高級脂肪酸的縮水甘油酯；環氧化大豆油、環氧化亞麻子油等。 Examples of the other [H] epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F. Diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ether of bisphenol compound such as brominated bisphenol F diglycidyl ether or brominated bisphenol S diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol condensed water a polyglycidyl ether of a polyhydric alcohol such as glyceryl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; a polyglycidyl ether of a polyether polyol obtained by adding one or more kinds of alkylene oxides to an aliphatic polyol such as propylene glycol or glycerin; a phenol novolac type epoxy resin; and a cresol novolak type epoxy resin Polyphenol type epoxy resin; cyclic aliphatic epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid; glycidyl ester of higher fatty acid; epoxidized soybean oil, epoxidized linseed oil, and the like.

作為[H]環氧化合物的市售品，例如可列舉：作為雙酚A型環氧樹脂的Epikote 604、Epikote 1001、Epikote 1002、Epikote 1003、Epikote 1004、Epikote 1007、Epikote 1009、Epikote 1010、Epikote 828(以上，日本環氧樹脂(Japan Epoxy Resins)公司)等；作為雙酚F型環氧樹脂的Epikote 807(日本環氧樹脂公司)等；作為苯酚酚醛清漆型環氧樹脂的Epikote 152、Epikote 154、Epikote 157S65(以上，日本環氧樹脂公司)，EPPN 201、EPPN 202(以上，日本化藥公司)等；作為甲酚酚醛清漆型環氧樹脂的EOCN 102、EOCN 103S、EOCN 104S、EOCN 1020、EOCN 1025、EOCN 1027(以 上，日本化藥公司)，Epikote 180S75(日本環氧樹脂公司)等；作為多酚型環氧樹脂的Epikote 1032H60、Epikote XY-4000(以上，日本環氧樹脂公司)等；作為環狀脂肪族環氧樹脂的CY-175、CY-177、CY-179，Araldite CY-182、Araldite CY-192、Araldite CY-184(以上，汽巴精化公司)，ERL-4234、4299、4221、4206(以上，優西西(U.C.C)公司)，Shodyne 509(昭和電工公司)，Epiclon 200、Epiclon 400(以上，大日本油墨公司)，Epikote 871、Epikote 872(以上，日本環氧樹脂公司)，ED-5661、ED-5662(以上，賽拉尼斯塗裝(Celanese coating)公司)等；作為脂肪族聚縮水甘油醚的Epolight 100ME(共榮社化學公司)、Epiol TMP(日本油脂公司)等。 As a commercial item of the [H] epoxy compound, for example, Epikote 604, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote which are bisphenol A type epoxy resins are mentioned. 828 (above, Japan Epoxy Resins Co., Ltd.); Epikote 807 (Japan Epoxy Resin Co., Ltd.) as a bisphenol F-type epoxy resin; Epikote 152, Epikote as a phenol novolac type epoxy resin; 154, Epikote 157S65 (above, Japan Epoxy Co., Ltd.), EPPN 201, EPPN 202 (above, Nippon Kayaku Co., etc.); EOCN 102, EOCN 103S, EOCN 104S, EOCN 1020 as cresol novolac type epoxy resin , EOCN 1025, EOCN 1027 (to , Nippon Chemical Co., Ltd., Epikote 180S75 (Japan Epoxy Co., Ltd.), etc.; Epikote 1032H60, Epikote XY-4000 (above, Japan Epoxy Co., Ltd.) as a polyphenol epoxy resin; Epoxy resin CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 ( Above, UCC), Shadyne 509 (Showa Denko), Epiclon 200, Epiclon 400 (above, Dainippon Ink), Epikote 871, Epikote 872 (above, Nippon Epoxy Co., Ltd.), ED-5661 ED-5662 (above, Celanese Coating Co., Ltd.), Epolight 100ME (Kyoeisha Chemical Co., Ltd.), Epiol TMP (Nippon Oil & Fats Co., Ltd.), etc., which are aliphatic polyglycidyl ethers.

它們之中，優選雙酚A型環氧樹脂、苯酚酚醛清漆型環氧樹脂。 Among them, a bisphenol A type epoxy resin and a phenol novolak type epoxy resin are preferable.

作為[H]環氧化合物的含量，相對於[A]鹼可溶性樹脂100質量份，優選50質量份以下，更優選30質量份以下。若[H]環氧化合物的使用量超過50質量份，則存在該感放射線性樹脂組成物的保存穩定性下降的傾向。 The content of the [H] epoxy compound is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the amount of the [H] epoxy compound used exceeds 50 parts by mass, the storage stability of the radiation sensitive resin composition tends to decrease.

[保存穩定劑] [storage stabilizer]

作為保存穩定劑，例如可列舉硫、醌類、對苯二酚類、聚氧化合物、胺、硝基-亞硝基化合物等，更具體而言，可列舉4-甲氧基苯酚、N-亞硝基-N-苯基羥基胺鋁等。 Examples of the storage stabilizer include sulfur, anthraquinone, hydroquinone, a polyoxygen compound, an amine, and a nitro-nitroso compound. More specifically, 4-methoxyphenol and N- are mentioned. Nitroso-N-phenylhydroxylamine aluminum and the like.

作為保存穩定劑的含量，相對於[A]鹼可溶性樹脂100質量份，優選3.0質量份以下，更優選1.0質量份以下。若保存穩定劑的含量超過3.0質量份，則存在該感放射線性樹脂組成物的感光度下降且圖案形狀劣化的情況。 The content of the storage stabilizer is preferably 3.0 parts by mass or less, and more preferably 1.0 part by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the content of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity of the radiation-sensitive resin composition may be lowered and the pattern shape may be deteriorated.

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

該感放射線性樹脂組成物是藉由將[A]鹼可溶性樹脂、[B]聚合性化合物、[C]光聚合起始劑及[D]化合物、視需要的[E]著色劑及其他任意成分以規定的比例混合來製備。該感放射線性樹脂組成物優選溶解在適當的溶劑中而以溶液狀態來使用。 The radiation sensitive resin composition is obtained by using [A] alkali-soluble resin, [B] polymerizable compound, [C] photopolymerization initiator, and [D] compound, optionally [E] colorant, and the like. The ingredients are prepared by mixing in a prescribed ratio. The radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state.

作為該感放射線性樹脂組成物的製備中所使用的溶劑，可使用使[A]鹼可溶性樹脂、[B]聚合性化合物、[C]光聚合起始劑、[D]化合物、[E]著色劑及其他任意成分均勻地溶解或分散，且不與各成分進行反應的溶劑。 As the solvent used in the preparation of the radiation sensitive resin composition, [A] alkali-soluble resin, [B] polymerizable compound, [C] photopolymerization initiator, [D] compound, [E] can be used. A solvent in which a coloring agent and other optional components are uniformly dissolved or dispersed, and does not react with each component.

作為溶劑，例如就各成分的溶解性、與各成分的反應性、塗膜形成的容易性等的觀點而言，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、三丙二醇單乙醚等(聚)烷二醇單烷基醚類；乙酸乙二醇單甲醚、乙酸乙二醇單乙醚、乙酸乙二醇單-正丙醚、乙酸乙二醇單-正丁醚、乙酸二乙二醇單甲醚、乙酸二乙二醇單乙醚、乙酸二乙二醇單-正丙醚、乙酸二乙二醇單-正丁醚、乙酸丙二醇單甲醚、乙酸丙二醇單乙醚、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯等乙酸(聚)烷二醇單烷基醚類；二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚、四氫呋喃等其他醚類； 甲基乙基酮、環己酮、2-庚酮、3-庚酮、二丙酮醇(4-羥基-4-甲基戊烷-2-酮)、4-羥基-4-甲基己烷-2-酮等酮類；丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯等二乙酸酯類；乳酸甲酯、乳酸乙酯等乳酸烷基酯類；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、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙酸正丁酯、丙酸3-甲基-3-甲氧基丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、羥基乙酸乙酯、乙氧基乙酸乙酯、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、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、2-羥基-2-甲基丙酸乙酯、2-羥基-3-甲基丁酸甲酯、2-氧代丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類等。 Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol alone, from the viewpoints of solubility of each component, reactivity with each component, and ease of formation of a coating film. - n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, three Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether, ethylene glycol single Ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy acetate And butyl acetate (poly) alkylene glycol monoalkyl ether; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane Ketones such as 2-ketone; diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate; methyl lactate, ethyl lactate Ethyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate Ester, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-hydroxy-2-methylpropionate Other esters such as methyl 2-hydroxy-3-methylbutanoate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidine An amide such as a ketone, N,N-dimethylformamide or N,N-dimethylacetamide.

這些溶劑之中，優選丙二醇單甲醚、丙二醇單乙醚、乙酸乙二醇單甲醚、乙酸丙二醇單甲醚、乙酸丙二醇單乙醚、乙酸3-甲氧基丁酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、環己酮、2-庚酮、3-庚酮、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯、乳酸乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙酸3-甲基-3-甲氧基丁酯、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、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸乙酯，更優選乙酸丙二醇單甲醚。溶劑可單獨使用、或使用2種以上。 Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether are preferable. , diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, lactic acid Ethyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, acetic acid Butyl ester, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, more preferably propylene glycol Monomethyl ether. The solvent may be used singly or in combination of two or more.

進而，為了提高膜厚的面內均勻性，可將所述溶劑與高沸點溶劑並用。作為高沸點溶劑，例如可列舉：苄基乙醚、二-正己醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ-丁內酯、碳酸乙二酯、碳酸丙二酯、乙二醇單苯醚乙酸酯等。高沸點溶劑可單獨使用、或使用2種以上。 Further, in order to increase the in-plane uniformity of the film thickness, the solvent may be used in combination with a high boiling point solvent. Examples of the high boiling point solvent include benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, and ethyl benzoate. , diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like. The high boiling point solvent may be used singly or in combination of two or more.

溶劑的含量並無限定，但就所獲得的該感放射線性樹脂組成物的塗布性、穩定性等的觀點而言，優選感放射線性樹脂組成物的除溶劑以外的各成分的合計濃度成為5質量%~50質量%的量，更優選所述合計濃度成為10質量%~40質量%的量。當將該感放射線性樹脂組成物製備成溶液狀態時，固體成分濃度(組成物溶液中所占的溶劑以外的成分)可對應於使用目的或所期望的膜厚值等而設定成任意的濃度(例如5質量%~50質量%)。更優選的固體成分濃度根據將塗膜形成在基板上的方法而不同，其後將對此進行敍述。以所述方式製備的組成物溶液在使用孔徑為0.5 μm左右的微孔過濾器等進行過濾後，可供於使用。 The content of the solvent is not limited, but the total concentration of each component other than the solvent of the radiation sensitive resin composition is preferably 5 from the viewpoint of the coating property and stability of the radiation-sensitive resin composition obtained. The amount of the mass % to 50% by mass is more preferably the amount of the total concentration of 10% by mass to 40% by mass. When the radiation sensitive resin composition is prepared in a solution state, the solid content concentration (component other than the solvent in the composition solution) can be set to an arbitrary concentration in accordance with the purpose of use, a desired film thickness value, or the like. (for example, 5 mass% to 50 mass%). A more preferable solid content concentration differs depending on the method of forming the coating film on the substrate, which will be described later. The composition solution prepared in the above manner is used after being filtered using a micropore filter having a pore diameter of about 0.5 μm or the like.

<顯示元件用硬化膜的形成方法> <Method of Forming Cured Film for Display Element>

該感放射線性樹脂組成物優選用於形成顯示元件用硬化膜。另外，本發明中適宜包含由該感放射線性樹脂組成物所形成的顯示元件用硬化膜。 The radiation sensitive resin composition is preferably used to form a cured film for a display element. Further, in the present invention, it is preferable to include a cured film for a display element formed of the radiation sensitive resin composition.

本發明的顯示元件用硬化膜的形成方法包括如下步驟：(1)使用該感放射線性樹脂組成物，在基板上形成塗膜；(2)對所述塗膜的至少一部分照射放射線；(3)對照射了所述放射線的塗膜進行顯影；以及(4)對經所述顯影的塗膜進行加熱。 The method for forming a cured film for a display element of the present invention comprises the steps of: (1) forming a coating film on a substrate using the radiation sensitive resin composition; (2) irradiating at least a portion of the coating film with radiation; (3) Developing a coating film irradiated with the radiation; and (4) heating the developed coating film.

根據本發明的形成方法，可形成壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。以下，對各步驟進行詳述。 According to the formation method of the present invention, a cured film for a display element which is excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance and solvent resistance can be formed. Hereinafter, each step will be described in detail.

[步驟(1)] [step 1)]

本步驟中，在透明基板的一面上形成透明導電膜，然後在該透明導電膜上形成該感放射線性樹脂組成物的塗膜。作為透明基板，例如可列舉：鈉鈣玻璃、無鹼玻璃等玻璃基板，包含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚醯亞胺等塑膠的樹脂基板等。 In this step, a transparent conductive film is formed on one surface of the transparent substrate, and then a coating film of the radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and include polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and polyimine. Plastic resin substrates, etc.

作為設置在透明基板的一面上的透明導電膜，可列舉包含氧化錫(SnO2)的NESA膜(美國必丕志(PPG)公司的註冊商標)、包含氧化銦-氧化錫(In2O3-SnO2)的ITO膜等。 Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film containing tin oxide (SnO 2 ) (registered trademark of PPE Corporation, USA), and indium oxide-tin oxide (In 2 O 3 ). -SnO 2 ) ITO film or the like.

當利用塗布法來形成塗膜時，在將該感放射線性樹脂組成物的溶液塗布在所述透明導電膜上後，優選對塗布面進行加熱(預烘烤)，由此可形成塗膜。作為塗布法中所使用的組成物溶液的固體成分濃度，優選5質量%~50質量%，更優選10質量%~40質量%，特優選15質量%~35質量%。作為該感放射線性樹脂組成物的塗布方法，例如可採用噴霧法、輥塗法、旋轉塗布法(旋塗法)、狹縫塗布法(擠壓式塗布法)、棒塗法、噴墨塗布法等適宜的方法。它們之中，優選旋塗法或狹縫塗布法。 When the coating film is formed by a coating method, after the solution of the radiation sensitive resin composition is applied onto the transparent conductive film, it is preferred to heat (pre-bake) the coated surface to form a coating film. The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 35% by mass. As a coating method of the radiation sensitive resin composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (extrusion coating method), a bar coating method, or an inkjet coating method can be employed. Suitable methods such as law. Among them, a spin coating method or a slit coating method is preferred.

作為所述預烘烤的條件，根據各成分的種類、調配比例等而不同，但優選70℃~120℃，且為1分鐘~15分鐘左右。塗膜的預烘烤後的膜厚優選0.5 μm~10 μm，更優選1.0 μm~7.0 μm左右。 The conditions for the prebaking differ depending on the type of each component, the blending ratio, and the like, but are preferably 70 ° C to 120 ° C and are about 1 minute to 15 minutes. The film thickness after prebaking of the coating film is preferably from 0.5 μm to 10 μm, more preferably from about 1.0 μm to 7.0 μm.

[步驟(2)] [Step (2)]

本步驟中，對所形成的塗膜的至少一部分照射放射線。此時，當僅對塗膜的一部分進行照射時，可利用例如經由具有規定的圖案的光罩進行照射的方法。 In this step, at least a part of the formed coating film is irradiated with radiation. At this time, when only a part of the coating film is irradiated, for example, a method of irradiating through a mask having a predetermined pattern can be used.

作為用於照射的放射線，可列舉可見光線、紫外線、遠紫外線等。其中，優選波長處於250 nm~550 nm的範圍內的放射線，更優選包含365 nm的紫外線的放射線。 Examples of the radiation used for the irradiation include visible light rays, ultraviolet rays, and far ultraviolet rays. Among them, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

放射線照射量(曝光量)作為利用照度計(OAI model 356，光學夥伴公司(Optical Associates Inc.)製造)測定所照射的放射線的波長365 nm下的強度所得的值，優選100 J/m2~5,000 J/m2，更優選200 J/m2~3,000 J/m2。 The radiation exposure amount (exposure amount) is a value obtained by measuring the intensity at a wavelength of 365 nm of the irradiated radiation by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), preferably 100 J/m 2 ~ 5,000 J/m 2 , more preferably 200 J/m 2 to 3,000 J/m 2 .

該感放射線性樹脂組成物的感光度高於先前所知的組成物，即便所述放射線照射量為700 J/m2以下，進而為600 J/m2以下，也可以獲得具有所期望的膜厚、良好的形狀、優異的密接性及高硬度的顯示元件用硬化膜。 The sensitivity of the radiation-sensitive resin composition is higher than that of the conventionally known composition, and even if the radiation irradiation amount is 700 J/m 2 or less, and further 600 J/m 2 or less, a desired film can be obtained. A cured film for a display element having a thick, good shape, excellent adhesion, and high hardness.

[步驟(3)] [Step (3)]

本步驟中，對照射放射線後的塗膜進行顯影，由此去除不需要的部分，而形成規定的圖案。作為用於顯影的顯影液，例如可列舉：氫氧化鈉、氫氧化鉀、碳酸鈉等無機鹼，氫氧化四甲基銨、氫氧化四乙基銨等四級銨鹽等鹼性化合物的水溶液。在所述鹼性化合物的水溶液中，也可以添加適量的甲醇、乙醇等水溶性有機溶劑及/或界面活性劑。 In this step, the coating film irradiated with radiation is developed to remove unnecessary portions, thereby forming a predetermined pattern. Examples of the developing solution used for development include an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate, and an aqueous solution of a basic compound such as a tetrabasic ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. . An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the aqueous solution of the basic compound.

作為顯影方法，可為浸置式顯影法、浸漬法、噴淋法等的任一種，顯影時間在常溫下優選10秒~180秒左右。顯影處理之後，例如進行30秒~90秒的流水清洗，然後利用壓縮空氣或壓縮氮氣進行風乾，由此可獲得所期望的圖案。 The development method may be any one of a dip type development method, a dipping method, and a shower method, and the development time is preferably about 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, a running water rinse is performed for 30 seconds to 90 seconds, and then air-dried with compressed air or compressed nitrogen gas, whereby a desired pattern can be obtained.

[步驟(4)] [Step (4)]

本步驟中，利用加熱板、烘箱等適當的加熱裝置對所獲得的圖案狀塗膜進行加熱，由此獲得顯示元件用硬化膜。加熱溫度為100℃~250℃左右。作為加熱時間，例如在加熱板上為5分鐘~30分鐘，在烘箱中為30分鐘~180分鐘左右。 In this step, the obtained pattern-like coating film is heated by a suitable heating means such as a hot plate or an oven to obtain a cured film for a display element. The heating temperature is about 100 ° C ~ 250 ° C. The heating time is, for example, 5 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven.

<顯示元件的製造方法> <Method of Manufacturing Display Element>

在本發明中，也適宜包含具備該顯示元件用硬化膜的顯示元件。作為顯示元件的製造方法，首先，準備一對(2片)在一面上具有透明導電膜(電極)的透明基板，在其中一片基板的透明導電膜上，使用該感放射線性樹脂組成物，根據所述方法形成間隔片或保護膜或其兩者。繼而，在這些基板的透明導電膜及間隔片或保護膜上形成具有液晶配向能力的配向膜。使這些基板的形成有配向膜之側的面變成內側，且以使各個配向膜的液晶配向方向成為正交或反平行的方式，介隔固定的間隙(單元間隙)來將這些基板相向配置，向基板的表面(配向膜)及由間隔片所劃分的單元間隙內填充液晶，然後將填充孔密封而構成液晶單元。然後，將偏光板以其偏光方向與形成在該基板的一面上的配向膜的液晶配向方向一致或正交的方式，貼合在液晶單元的兩外表面上，由此獲得本發明的顯示元件。 In the present invention, a display element including the cured film for a display element is also preferably included. As a method of manufacturing the display element, first, a pair of (two sheets) transparent substrates having a transparent conductive film (electrode) on one surface are prepared, and the radiation-sensitive resin composition is used on the transparent conductive film of one of the substrates, according to The method forms a spacer or a protective film or both. Then, an alignment film having a liquid crystal alignment ability is formed on the transparent conductive film of the substrate and the spacer or the protective film. The surfaces of the substrates on which the alignment film is formed are turned inside, and the substrates are arranged to face each other with a fixed gap (cell gap) so that the liquid crystal alignment directions of the respective alignment films are orthogonal or anti-parallel. The liquid crystal cell is formed by filling the surface of the substrate (alignment film) and the cell gap defined by the spacer with liquid crystal, and then sealing the filling hole. Then, the polarizing plate is attached to both outer surfaces of the liquid crystal cell with the polarizing direction being aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate, thereby obtaining the display element of the present invention. .

作為其他方法，與所述方法同樣地準備形成有透明導電膜、層間絕緣膜、保護膜或間隔片或其兩者、及配向膜的一對透明基板。其後，沿著一個基板的端部，使用分配器塗布紫外線硬化型密封劑，繼而，使用液晶分配器呈微小液滴狀地滴加液晶，然後在真空下進行兩基板的貼合。然後，使用高壓水銀燈對所述密封劑部照射紫外線來將兩基板密封。最後，使偏光板貼合在液晶單元的兩外表面上，由此獲得本發明的顯示元件。 As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as the above method. Thereafter, the ultraviolet curable sealant was applied to the end portion of one of the substrates using a dispenser, and then the liquid crystal was dropped in the form of fine droplets using a liquid crystal dispenser, and then the two substrates were bonded under vacuum. Then, the sealant portion is irradiated with ultraviolet rays using a high pressure mercury lamp to seal the both substrates. Finally, the polarizing plates are attached to both outer surfaces of the liquid crystal cell, whereby the display element of the present invention is obtained.

作為所述各方法中所使用的液晶，例如可列舉：向列型液晶、層列型液晶等。另外，作為用於液晶單元的外側的偏光板，可列舉：利用乙酸纖維素保護膜夾持一面使聚乙烯醇延伸配向，一面吸收碘的被稱為“H膜”的偏光膜而成的偏光板，或H膜本身構成的偏光板等。 Examples of the liquid crystal used in each of the above methods include a nematic liquid crystal, a smectic liquid crystal, and the like. In addition, as a polarizing plate which is used for the outer side of the liquid crystal cell, a polarizing film called "H film" which absorbs iodine while sandwiching the polyvinyl alcohol by a cellulose acetate protective film is used. A plate, or a polarizing plate composed of the H film itself.

[實例] [Example]

以下，根據實例對本發明進行詳述，但本發明不由該實例限定性地進行解釋。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by the examples.

<[A]鹼可溶性樹脂的合成> <[A] Synthesis of alkali-soluble resin> [合成例1](鹼可溶性樹脂(A-1)的合成) [Synthesis Example 1] (Synthesis of alkali-soluble resin (A-1))

向具備冷卻管及攪拌機的燒瓶中裝入2,2'-偶氮雙異丁腈2質量份、及乙酸丙二醇單甲醚200質量份，繼而裝入提供(a1)結構單元的甲基丙烯酸15質量份、提供(a2)結構單元的N-苯基順丁烯二醯亞胺20質量份、提供其他結構單元的甲基丙烯酸苄酯55質量份、及苯乙烯10質量份、以及作為分子量調節劑的2,4-二苯基-4-甲基-1-戊烯(日本油脂公司，Nofmer MSD)3質量份，並進行氮氣置換。其後，緩慢地攪拌並使反應溶液的溫度上升至80℃，將該溫度保持5小時來進行聚合，由此獲得共聚物溶液(固體成分濃度=33質量%)。所獲得的共聚物(A-1)的Mw=16,000。 To a flask equipped with a cooling tube and a stirrer, 2 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether were charged, followed by methacrylic acid 15 which provided the structural unit (a1) 20 parts by mass of N-phenyl maleimide, (a2) structural unit, 55 parts by mass of benzyl methacrylate providing other structural units, and 10 parts by mass of styrene, and as molecular weight adjustment 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (Nippon Oil & Fat Co., Ltd., Nofmer MSD) was replaced with nitrogen. Thereafter, the temperature of the reaction solution was gradually stirred and the temperature of the reaction solution was raised to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization, whereby a copolymer solution (solid content concentration = 33% by mass) was obtained. The obtained copolymer (A-1) had Mw = 16,000.

[合成例2](鹼可溶性樹脂(A-2)的合成) [Synthesis Example 2] (Synthesis of alkali-soluble resin (A-2))

向具備冷卻管及攪拌機的燒瓶中裝入2,2'-偶氮雙異丁腈4質量份、及二乙二醇甲基乙基醚300質量份，繼而裝入提供(a1)結構單元的甲基丙烯酸23質量份、提供其他結構單元的苯乙烯10質量份、甲基丙烯酸苄酯32質量份及甲基丙烯酸甲酯35質量份、以及作為分子量調節劑的α-甲基苯乙烯二聚物 2.7質量份，然後緩慢地攪拌，並使溶液的溫度上升至80℃，將該溫度保持4小時後，使溫度上升至100℃，將該溫度保持1小時來進行聚合，由此獲得含有共聚物的溶液(固體成分濃度=24.9%)。所獲得的共聚物的Mw為12,500。繼而，向含有共聚物的溶液中添加溴化四丁基銨1.1質量份、作為聚合抑制劑的4-甲氧基苯酚0.05質量份，在空氣環境下以90℃攪拌30分鐘後，添加甲基丙烯酸縮水甘油酯16質量份並維持90℃來進行10小時反應，由此獲得含有共聚物(A-2)的溶液(固體成分濃度=29.0%)。共聚物(A-2)的Mw為14,200。將所述含有共聚物(A-2)的溶液滴加至己烷中，由此進行再沉澱精製，針對經再沉澱的樹脂固體成分，藉由1H-NMR分析來算出甲基丙烯酸縮水甘油酯的反應率((a3)結構單元的生成率)。根據6.1 ppm附近及5.6 ppm附近的源自甲基丙烯酸縮水甘油酯的甲基丙烯醯基的波峰、與源自共聚物的甲基丙烯酸苄酯的結構單元的6.8 ppm~7.4 ppm附近的芳香環的質子的積分比的比較，算出甲基丙烯酸縮水甘油酯與共聚物中的羧基的反應率。其結果，可知進行反應的甲基丙烯酸縮水甘油酯的96莫耳%已與共聚物中的羧基產生了反應。 4 parts by mass of 2,2'-azobisisobutyronitrile and 300 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, and then charged to provide a structural unit of (a1) 23 parts by mass of methacrylic acid, 10 parts by mass of styrene providing other structural units, 32 parts by mass of benzyl methacrylate, and 35 parts by mass of methyl methacrylate, and α-methylstyrene dimerization as a molecular weight modifier 2.7 parts by mass, then slowly stirred, and the temperature of the solution was raised to 80 ° C. After the temperature was maintained for 4 hours, the temperature was raised to 100 ° C, and the temperature was maintained for 1 hour to carry out polymerization, thereby obtaining copolymerization. Solution of the substance (solid content concentration = 24.9%). The Mw of the obtained copolymer was 12,500. Then, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 ° C for 30 minutes in an air atmosphere, and then methyl group was added. 16 parts by mass of glycidyl acrylate was maintained at 90 ° C for 10 hours to obtain a solution containing a copolymer (A-2) (solid content concentration = 29.0%). The Mw of the copolymer (A-2) was 14,200. The solution containing the copolymer (A-2) was added dropwise to hexane to carry out reprecipitation purification, and the glycidyl methacrylate was calculated by 1 H-NMR analysis on the reprecipitated resin solid content. Reaction rate of ester ((a3) formation rate of structural unit). An aromatic ring near 6.8 ppm to 7.4 ppm of a peak derived from glycidyl methacrylate derived from glycidyl methacrylate in the vicinity of 6.1 ppm and around 5.6 ppm and a structural unit derived from benzyl methacrylate derived from a copolymer The reaction ratio of the glycidyl methacrylate to the carboxyl group in the copolymer was calculated by comparing the integral ratio of the protons. As a result, it was found that 96 mol% of the glycidyl methacrylate to be reacted reacted with the carboxyl group in the copolymer.

[合成例3](鹼可溶性樹脂(A-3)的合成) [Synthesis Example 3] (Synthesis of alkali-soluble resin (A-3))

向具備冷卻管及攪拌機的燒瓶中裝入2,2'-偶氮雙(2,4-二甲基戊腈)5質量份、及二乙二醇甲基乙基醚220質量份，繼而裝入提供(a1)結構單元的甲基丙烯酸12質量份、提供(a4)結構單元的甲基丙烯酸縮水甘油酯40質量份、提供其他結構單元的苯乙烯20質量份及甲基丙烯酸三環[5.2.1.02,6]癸烷-8-基酯28質量份，並進行氮氣置換，然後緩慢地攪拌，並使溶液的溫度上升至70℃，將該溫度保持5小時來進行聚合，由 此獲得含有共聚物(A-3)的溶液(固體成分濃度=31.3%)。共聚物(A-3)的Mw=12,000。 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by loading 12 parts by mass of methacrylic acid providing (a1) structural unit, 40 parts by mass of glycidyl methacrylate providing (a4) structural unit, 20 parts by mass of styrene providing other structural units, and tricyclomethacrylate [5.2] .1.0 2,6 ]oxane-8-yl ester 28 parts by mass, and subjected to nitrogen substitution, and then slowly stirred, and the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization, thereby obtaining A solution containing a copolymer (A-3) (solid content concentration = 31.3%). The copolymer (A-3) had Mw = 12,000.

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

以下表示實例及比較例中所使用的各成分的詳細情況。 The details of each component used in the examples and comparative examples are shown below.

<[B]聚合性化合物> <[B] polymerizable compound>

B-1：二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物(KAYARAD DPHA，日本化藥公司) B-1: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)

B-2：丁二酸改質季戊四醇三丙烯酸酯(Aronix TO-756，東亞合成公司) B-2: succinic acid modified pentaerythritol triacrylate (Aronix TO-756, East Asia Synthetic Company)

B-3：三羥甲基丙烷三丙烯酸酯 B-3: Trimethylolpropane triacrylate

B-4：Viscoat 802(三季戊四醇八丙烯酸酯與三季戊四醇七丙烯酸酯的混合物，大阪有機化學工業公司) B-4: Viscoat 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, Osaka Organic Chemical Industry Co., Ltd.)

<[C]光聚合起始劑> <[C] Photopolymerization initiator>

由所述式(C-1)~式(C-10)所表示的化合物 a compound represented by the formula (C-1) to formula (C-10)

<[C']光聚合起始劑> <[C'] Photopolymerization initiator>

C'-1：2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮(Irgacure 907，汽巴精化公司) C'-1: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (Irgacure 907, Ciba Specialty Chemicals)

C'-2：乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-1-(O-乙醯基肟)(Irgacure OXE02，汽巴精化公司) C'-2: Ethyl Ketone-1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl) ( Irgacure OXE02, Ciba Specialty Chemicals)

C'-3：1,2-辛二酮-1-[4-(苯硫基)-2-(O-苯甲醯基肟)](Irgacure OXE01，汽巴精化公司) C'-3: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzhydrylhydrazine)] (Irgacure OXE01, Ciba Specialty Chemicals)

C'-4：2-苄基-2-二甲氨基-1-(4-嗎啉基苯基)丁烷-1-酮 C'-4: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one

C'-5：4,4'-雙(二乙氨基)二苯甲酮 C'-5: 4,4'-bis(diethylamino)benzophenone

<[D]化合物> <[D] compound>

D-1：季戊四醇四[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯] D-1: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]

D-2：2,5-二-第三丁基對苯二酚 D-2: 2,5-di-t-butyl hydroquinone

D-3：三(3,5-二-第三丁基-4-羥基苄基)異氰脲酸酯(Adekastab AO-20，艾迪科公司) D-3: tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate (Adekastab AO-20, Adico)

D-4：1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯(Adekastab AO-330，艾迪科公司) D-4: 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (Adekastab AO-330, Adico )

D-5：雙(2,2,6,6-四甲基-4-呱啶基)癸二酸酯(TINUVIN770巴斯夫(BASF)公司) D-5: bis(2,2,6,6-tetramethyl-4-acridinyl) sebacate (TINUVIN770 BASF)

D-6：二硬脂基季戊四醇二亞磷酸酯(Adekastab PEP-8，艾迪科公司) D-6: distearyl pentaerythritol diphosphite (Adekastab PEP-8, Adico)

D-7：季戊四醇四(硫代丙酸3-月桂酯)(Adekastab AO-412S，艾迪科公司) D-7: pentaerythritol tetra (3-lauryl thiopropionate) (Adekastab AO-412S, Adico)

<[E]著色劑> <[E] colorant>

E-1：C.I.溶劑紅45 E-1: C.I. Solvent Red 45

E-2：C.I.溶劑黃82 E-2: C.I. Solvent Yellow 82

<[F]黏結助劑> <[F]bonding aid>

F-1：γ-縮水甘油氧基丙基三甲氧基矽烷 F-1: γ-glycidoxypropyltrimethoxydecane

<[G]界面活性劑> <[G] surfactant]

G-1：FTX-218(雷歐時公司) G-1: FTX-218 (Leo Time Company)

<[H]環氧化合物> <[H]epoxy compound>

H-1：苯酚酚醛清漆型環氧樹脂(Epikote 152，日本環氧樹脂公司) H-1: phenol novolac type epoxy resin (Epikote 152, Japan Epoxy Co., Ltd.)

H-2：雙酚A型環氧樹脂(Epikote 604，日本環氧樹脂公司) H-2: bisphenol A type epoxy resin (Epikote 604, Japan Epoxy Co., Ltd.)

[實例1] [Example 1]

以固體成分換算計，將作為[A]鹼可溶性樹脂的共聚物(A-3)100質量份、作為[B]聚合性化合物的(B-1)100質量份、作為[C]光聚合起始劑的(C-1)5質量份、作為[D]化合物 的(D-1)0.1質量份、作為[F]黏結助劑的(F-1)5質量份、以及作為[G]界面活性劑的(G-1)0.5質量份混合，以使固體成分濃度成為30質量%的方式添加乙酸丙二醇單甲醚後，利用孔徑為0.5 μm的微孔過濾器進行過濾，由此製成感放射線性樹脂組成物。 100 parts by mass of the copolymer (A-3) as the [A] alkali-soluble resin and 100 parts by mass of (B-1) as the [B] polymerizable compound in terms of solid content, as photopolymerization of [C] (C-1) 5 parts by mass of the starting agent, as a [D] compound 0.1 parts by mass of (D-1), 5 parts by mass of (F-1) as a [F] adhesion aid, and 0.5 parts by mass of (G-1) as a [G] surfactant, to make a solid component After adding propylene glycol monomethyl ether as a concentration of 30% by mass, the mixture was filtered through a micropore filter having a pore diameter of 0.5 μm to prepare a radiation sensitive resin composition.

[實例2~實例8及比較例1~比較例3] [Example 2 to Example 8 and Comparative Example 1 to Comparative Example 3]

將表1所示的種類及含量的各成分混合，除此以外，與實例1同樣地進行操作來製備各感放射線性樹脂組成物。再者，表1中的“-”表示未使用該成分。 Each of the radiation sensitive resin compositions was prepared in the same manner as in Example 1 except that the components of the types and contents shown in Table 1 were mixed. Further, "-" in Table 1 indicates that the component is not used.

[實例9] [Example 9]

以固體成分換算計，將作為[A]鹼可溶性樹脂的共聚物(A-1)50質量份、作為[B]聚合性化合物的(B-4)55質量份、作為[C]光聚合起始劑的(C-1)5質量份、作為[C']光聚合起始劑的(C'-4)20質量份及(C'-5)5質量份、作為[D]化合物的(D-1)0.5質量份、作為[E]著色劑的(E-1)27質量份及(E-2)8質量份、以及作為[H]環氧化合物的(H-2)15質量份混合，以使固體成分濃度成為20質量%的方式添加乙酸丙二醇單甲醚，從而製成感放射線性樹脂組成物。 50 parts by mass of the copolymer (A-1) as the [A] alkali-soluble resin and 55 parts by mass of (B-4) as the [B] polymerizable compound in terms of solid content, as photopolymerization of [C] (M-1) parts by mass of (C-1), 20 parts by mass of (C'-4) as a [C'] photopolymerization initiator, and (5' parts by mass of (C'-5), as a compound of [D] D-1) 0.5 parts by mass, (E-1) 27 parts by mass and (E-2) 8 parts by mass as the [E] colorant, and (H-2) 15 parts by mass as the [H] epoxy compound The mixture was mixed, and propylene glycol monomethyl ether was added so that the solid content concentration became 20% by mass to prepare a radiation sensitive resin composition.

[實例10~實例11] [Example 10 to Example 11]

將表1所示的種類及含量的各成分混合，除此以外，與實例9同樣地進行操作來製備各感放射線性樹脂組成物。再者，表1中的“-”表示未使用該成分。 Each of the radiation sensitive resin compositions was prepared in the same manner as in Example 9 except that the components of the types and contents shown in Table 1 were mixed. Further, "-" in Table 1 indicates that the component is not used.

<評價> <evaluation>

使用所製備的各感放射線性樹脂組成物實施以下的評價。詳細而言，針對實例1~實例4及比較例1，使用各感放射線性樹脂組成物形成顯示元件用硬化膜，並評價作為間隔片的解析度、感光度及壓縮性能。針對實例5~實例8及比較例2，使用各感放射線性樹脂組成物形成顯示元件用硬化膜，並評價作為絕緣膜的透過率、耐光性及電壓保持率。針對實例9~實例12及比較例3，使用各感放射線性樹脂組成物形成顯示元件用硬化膜，並評價作為著色圖案的耐顯影性、耐熱性及耐溶劑性。將結果示於表2。 The following evaluations were carried out using each of the prepared radiation sensitive resin compositions. Specifically, for each of the examples 1 to 4 and the comparative example 1, each of the radiation-sensitive resin compositions was used to form a cured film for a display element, and the resolution, sensitivity, and compression performance of the spacer were evaluated. In each of Examples 5 to 8 and Comparative Example 2, a cured film for a display element was formed using each of the radiation-sensitive resin compositions, and the transmittance, light resistance, and voltage holding ratio of the insulating film were evaluated. In each of Examples 9 to 12 and Comparative Example 3, a cured film for a display element was formed using each of the radiation-sensitive resin compositions, and the development resistance, heat resistance, and solvent resistance of the colored pattern were evaluated. The results are shown in Table 2.

[解析度(μm)] [resolution (μm)]

利用旋轉器將各感放射線性樹脂組成物溶液塗布在無鹼玻璃基板上後，在100℃的加熱板上進行2分鐘預烘烤，由此形成膜厚為4.0 μm的塗膜。繼而，經由具有多個直徑為8 μm~20 μm的範圍的大小不同的圓形殘留圖案的光罩，利用高壓水銀燈使曝光量在200 J/m2~1,000 J/m2的範圍內變化來對所獲得的塗膜照射放射線。其後，將23℃的0.40質量%氫氧化鉀水溶液作為顯影液，在顯影壓力為1 kgf/cm2、噴嘴直徑為1 mm的條件下噴出顯影液，由此進行噴淋顯影，然後進行1分鐘純水清洗。進而，在烘箱中以230℃進行30分鐘後烘烤，由此形成圖案狀塗膜。此時，將所形成的最小的圖案尺寸設為解析度(μm)。在12 μm以下的光罩中，只要形成有圖案，則可判斷為解析度良好。 Each of the radiation-sensitive resin composition solutions was applied onto an alkali-free glass substrate by a spinner, and then prebaked on a hot plate at 100 ° C for 2 minutes to form a coating film having a film thickness of 4.0 μm. Then, the exposure amount is changed from 200 J/m 2 to 1,000 J/m 2 by a high-pressure mercury lamp through a photomask having a plurality of circular residual patterns having different diameters ranging from 8 μm to 20 μm. The obtained coating film is irradiated with radiation. Thereafter, a 0.40 mass% potassium hydroxide aqueous solution at 23 ° C was used as a developing solution, and a developing solution was sprayed under the conditions of a developing pressure of 1 kgf/cm 2 and a nozzle diameter of 1 mm, thereby performing shower development, and then performing 1 Clean with pure water for a minute. Further, post-baking was carried out in an oven at 230 ° C for 30 minutes to form a pattern-like coating film. At this time, the minimum pattern size to be formed is set to the resolution (μm). In the mask of 12 μm or less, if a pattern is formed, it can be judged that the resolution is good.

[感光度(J/m2)] [Sensitivity (J/m 2 )]

除使用具有多個直徑為15 μm的圓形殘留圖案的光罩以外，與所述解析度的評價同樣地進行操作，而在基板上形成圓形殘留圖案。使用激光顯微鏡(VK-8500，基恩士公司)測定圓形殘留圖案的顯影前與顯影後的高度。根據該值與下述式求出殘膜率(%)。 A circular residual pattern was formed on the substrate in the same manner as the evaluation of the resolution except that a reticle having a plurality of circular residual patterns having a diameter of 15 μm was used. The height of the circular residual pattern before and after development was measured using a laser microscope (VK-8500, KEYENCE). The residual film ratio (%) was determined from this value and the following formula.

殘膜率(%)=(顯影後高度/顯影前高度)×100 Residual film rate (%) = (height after development / height before development) × 100

將該殘膜率達到90%以上的最小的曝光量設為感光度(J/m2)。當曝光量為700 J/m2以下時，可判斷為感光度良好。 The minimum exposure amount at which the residual film ratio is 90% or more is set as sensitivity (J/m 2 ). When the exposure amount is 700 J/m 2 or less, it can be judged that the sensitivity is good.

[壓縮性能] [compression performance]

與所述感光度的評價同樣地進行操作，以殘膜率達到90%以上的曝光量在基板上形成圓形殘留圖案。使用微小壓縮試驗機(Fischerscope H100C，費歇爾儀器(Fischer Instruments)公司)並利用50 μm見方狀的平面壓頭，以40 mN的負荷對該圖案進行壓縮試驗，並測定對於負荷的壓縮位移量(μm)。另外，根據40 mN的負荷時的位移量與去除了40 mN的負荷時的位移量而算出恢復率(%)。當恢復率為90%以上、且40 mN的負荷時的壓縮位移量為0.15 μm以上時，可判斷為壓縮性能良好。 In the same manner as the evaluation of the sensitivity, a circular residual pattern was formed on the substrate with an exposure amount at which the residual film ratio was 90% or more. The pattern was subjected to a compression test using a micro compression tester (Fischerscope H100C, Fischer Instruments) using a 50 μm square planar indenter at a load of 40 mN, and the amount of compression displacement for the load was measured. (μm). Further, the recovery rate (%) was calculated from the displacement amount at the load of 40 mN and the displacement amount when the load of 40 mN was removed. When the recovery rate is 90% or more and the compression displacement amount at a load of 40 mN is 0.15 μm or more, it can be judged that the compression performance is good.

[透過率(%)] [Transmission rate (%)]

不經由光罩而以800 J/m2的曝光量進行曝光，除此以外，與所述解析度的評價同樣地進行操作，針對所獲得的 顯示元件用硬化膜，使用分光光度計(150-20型雙光束，日立製作所公司)測定波長400 nm下的透過率(%)。當透過率為90%以上時，可判斷為透明性良好。 The exposure was performed in the same manner as the evaluation of the resolution, and the spectrophotometer (150-) was used for the obtained cured film for display elements, except that the exposure was performed at an exposure amount of 800 J/m 2 without using a mask. The 20-type double beam, Hitachi, Ltd.) measures the transmittance (%) at a wavelength of 400 nm. When the transmittance is 90% or more, it can be judged that the transparency is good.

[耐光性(%)] [light resistance (%)]

與所述透過率的評價同樣地進行操作來形成顯示元件用硬化膜。針對所獲得的顯示元件用硬化膜，利用紫外線(Ultraviolet，UV)照射裝置(UVX-02516S1JS01，優志旺(USHIO)公司，燈；UVL-4001M3-N1)照射500 kJ/m2的UV光，並求出照射前後的殘膜率，由此進行評價。當殘膜率為95%以上時，可判斷為耐光性(%)良好。 The cured film for display elements was formed in the same manner as the evaluation of the transmittance. For the obtained cured film for display elements, UV light of 500 kJ/m 2 was irradiated with an ultraviolet (Ultraviolet, UV) irradiation device (UVX-02516S1JS01, USHIO, lamp; UVL-4001M3-N1), and The residual film ratio before and after the irradiation was determined and evaluated. When the residual film ratio is 95% or more, it is judged that the light resistance (%) is good.

[電壓保持率(%)] [Voltage retention rate (%)]

將各感放射線性樹脂組成物旋塗在鈉玻璃基板上，該鈉玻璃基板是表面形成有防止鈉離子的溶出的SiO2膜，進而將ITO(銦-氧化錫合金)電極蒸鍍成規定形狀的基板，然後在90℃的潔淨烘箱內進行10分鐘預烘烤，而形成膜厚為2.0 μm的塗膜。繼而，不經由光罩，而以500 J/m2的曝光量對塗膜進行曝光。其後，將該基板在包含23℃的0.04質量%的氫氧化鉀水溶液的顯影液中浸漬1分鐘，進行顯影後，利用超純水加以清洗並進行風乾，進而在230℃下進行30分鐘後烘烤，使塗膜硬化而形成永久硬化膜。繼而，利用混合有0.8 mm的玻璃珠的密封劑，將形成有該像素的基板與僅將ITO電極蒸鍍成規定形狀的基板貼合，然後注入默克(Merck)製造的液晶(MLC6608)，從而製成液晶單元。繼而，將液晶單元放入至60℃的恒溫層中， 利用液晶電壓保持率測定系統(VHR-1A型，東陽技術(TOYO Corporation)公司)測定液晶單元的電壓保持率。此時的施加電壓為5.5 V的方形波，測定頻率為60 Hz。此處所謂電壓保持率，是指(16.7毫秒後的液晶單元電位差/以0毫秒施加的電壓)的值。若液晶單元的電壓保持率為90%以下，則表示液晶單元無法將16.7毫秒的時間、施加電壓保持為規定水準，而無法使液晶充分地配向，且產生殘像等的“重像(burn-in)”的可能性高。 Each of the radiation-sensitive resin compositions is spin-coated on a soda glass substrate having an SiO 2 film formed on the surface thereof to prevent elution of sodium ions, and further vapor-depositing the ITO (indium-tin oxide alloy) electrode into a predetermined shape. The substrate was then prebaked in a clean oven at 90 ° C for 10 minutes to form a film having a film thickness of 2.0 μm. Then, the coating film was exposed at a exposure amount of 500 J/m 2 without passing through a photomask. Thereafter, the substrate was immersed in a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C for 1 minute, and after development, it was washed with ultrapure water, air-dried, and further at 230 ° C for 30 minutes. Baking, the coating film is hardened to form a permanent cured film. Then, the substrate on which the pixel was formed was bonded to a substrate on which only the ITO electrode was vapor-deposited into a predetermined shape, and then injected into a liquid crystal (MLC6608) manufactured by Merck. Thereby, a liquid crystal cell is produced. Then, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, Toyo Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio means a value of (a liquid crystal cell potential difference after 16.7 milliseconds / a voltage applied at 0 milliseconds). When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the time and voltage of 16.7 milliseconds at a predetermined level, and the liquid crystal cannot be sufficiently aligned, and a "image" such as an afterimage is generated. The possibility of in)" is high.

<著色圖案的形成> <Formation of Colored Pattern>

使用旋轉塗布機，將各感放射線性樹脂組成物塗布在表面形成有防止鈉離子的溶出的SiO2膜的鈉玻璃基板上。繼而，在90℃的加熱板上進行2分鐘預烘烤，而形成預烘烤後的膜厚為2.5 μm的塗膜。將這些基板冷卻至室溫後，使用高壓水銀燈，以100 J/m2、300 J/m2、500 J/m2、700 J/m2及1,000 J/m2的曝光量經由光罩對塗膜照射包含365 nm、405 nm及436 nm的各波長的放射線來進行曝光。其後，在顯影壓力為1 kgf/cm2、噴嘴直徑為1 mm的條件下對這些基板噴出顯影液(23℃的0.04質量%氫氧化鉀水溶液)，由此進行噴淋顯影而在基板上形成200 μm×200 μm的著色圖案。進而，在180℃下進行30分鐘後烘烤而形成著色圖案。 Each of the radiation sensitive resin compositions was applied onto a soda glass substrate having a SiO 2 film on the surface where elution of sodium ions was formed using a spin coater. Then, prebaking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2.5 μm after prebaking. After cooling the substrates to room temperature, a high-pressure mercury lamp was used to pass the reticle pair at an exposure amount of 100 J/m 2 , 300 J/m 2 , 500 J/m 2 , 700 J/m 2 , and 1,000 J/m 2 . The coating film is irradiated with radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm for exposure. Thereafter, a developing solution (0.04 mass% potassium hydroxide aqueous solution at 23 ° C) was sprayed onto the substrates under conditions of a developing pressure of 1 kgf/cm 2 and a nozzle diameter of 1 mm, thereby performing shower development on the substrate. A colored pattern of 200 μm × 200 μm was formed. Further, it was baked at 180 ° C for 30 minutes to form a colored pattern.

[耐顯影性] [developability]

根據下述式算出所述著色圖案的形成過程中的顯影前後的膜厚比。 The film thickness ratio before and after development in the formation of the colored pattern was calculated according to the following formula.

顯影前後的膜厚比=(顯影後的膜厚/顯影前的膜厚)×100 Film thickness ratio before and after development = (film thickness after development / film thickness before development) × 100

將該值設為耐顯影性，將該值為95%以上的情況設為“A”(判斷為良好)，將該值未滿95%的情況、或在著色圖案的一部分中看到缺損的情況設為“B”(判斷為略微不良)，將圖案全部從基板上剝落的情況設為“C”(判斷為不良)。 This value is referred to as development resistance, and when the value is 95% or more, it is set to "A" (determined to be good), and when the value is less than 95%, or a part of the colored pattern is missing, In the case of "B" (determined to be slightly defective), the case where all the patterns were peeled off from the substrate was set to "C" (determined as defective).

[耐熱性] [heat resistance]

除以1,000 J/m2的曝光量進行曝光以外，與所述著色圖案的形成同樣地進行操作來形成著色圖案。進而在180℃下進行30分鐘追加加熱。求出追加加熱前後的顏色變化△Eab*。將該值設為耐熱性，將△Eab*未滿3的情況設為“A”(判斷為良好)，將△Eab*為3以上、未滿5的情況設為“B”(判斷為略微良好)，將△Eab*為5以上的情況設為“C”(判斷為不良)。 The coloring pattern was formed in the same manner as the formation of the colored pattern except that the exposure was performed at an exposure amount of 1,000 J/m 2 . Further, additional heating was carried out for 30 minutes at 180 °C. The color change ΔEab * before and after the additional heating was obtained. This value is referred to as heat resistance, and when ΔEab * is less than 3, it is set to "A" (determined to be good), and when ΔEab * is 3 or more and less than 5, it is set to "B" (determined to be slightly). Good), the case where ΔEab * is 5 or more is set to "C" (it is judged to be bad).

[耐溶劑性] [solvent resistance]

與所述耐熱性的評價同樣地進行操作來形成著色圖案。將該基板在60℃的N-甲基吡咯烷酮中浸漬30分鐘。將浸漬後著色圖案得以保持、且浸漬後的N-甲基吡咯烷酮完全未著色的情況設為“A”(判斷為良好)，將浸漬後著色圖案得以保持，但浸漬後的N-甲基吡咯烷酮已稍微著色的情況設為“B”(判斷為略微良好)，將浸漬後觀察到從基板上剝離的著色圖案，並且浸漬後的N-甲基吡咯烷酮已著色的情況設為“C”(判斷為不良)。 The colored pattern was formed in the same manner as the evaluation of the heat resistance. The substrate was immersed in N-methylpyrrolidone at 60 ° C for 30 minutes. After the immersion colored pattern was maintained, and the N-methylpyrrolidone after immersion was completely uncolored, it was set to "A" (determined to be good), and the immersed colored pattern was retained, but the immersed N-methylpyrrolidone In the case of being slightly colored, it was set to "B" (it was judged to be slightly good), and the colored pattern peeled off from the substrate was observed after immersion, and the case where the immersed N-methylpyrrolidone was colored was set to "C" (judging) Bad).

如根據表2的結果而明確般，可知該感放射線性樹脂組成物具有良好的解析度、感光度、壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性。 As is clear from the results of Table 2, it is understood that the radiation sensitive resin composition has good resolution, sensitivity, compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance, and solvent resistance. .

(產業上的可利用性) (industrial availability)

本發明的感放射線性樹脂組成物可容易地形成微細且精巧的圖案，並具有充分的解析度及感光度。另外，該感放射 線性樹脂組成物可形成壓縮性能、透過率、耐光性、電壓保持率、耐顯影性、耐熱性及耐溶劑性優異的顯示元件用硬化膜。因此，該感放射線性樹脂組成物適合於顯示元件用彩色濾光片，陣列用層間絕緣膜，固體攝像元件的色分解用彩色濾光片，有機EL顯示元件用彩色濾光片，電子紙等柔性顯示器用彩色濾光片，觸控面板用保護膜，金屬配線或金屬凸塊的形成、基板的加工等中所使用的光加工用抗蝕劑等。 The radiation sensitive resin composition of the present invention can easily form a fine and delicate pattern and has sufficient resolution and sensitivity. In addition, the radiation The linear resin composition can form a cured film for a display element which is excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance, and solvent resistance. Therefore, the radiation sensitive resin composition is suitable for a color filter for a display element, an interlayer insulating film for an array, a color filter for color separation of a solid-state image sensor, a color filter for an organic EL display element, an electronic paper, or the like. A color filter for a flexible display, a protective film for a touch panel, a metal wiring or a metal bump, a substrate for processing, or the like.

Claims (12)

一種感放射線性樹脂組成物，其特徵在於包含：[A]鹼可溶性樹脂；[B]具有乙烯性不飽和鍵的聚合性化合物；[C]由下述式(1)所表示的光聚合起始劑；以及[D]選自由含有受阻酚結構的化合物、含有受阻胺結構的化合物、含有亞磷酸酯結構的化合物及含有硫醚結構的化合物所組成的組群中的至少1種化合物；且相對於[A]鹼可溶性樹脂100質量份，[C]光聚合起始劑的含量為0.1質量份以上、5質量份以下， (式(1)中，R1及R4分別獨立為碳數為1~12的烷基、碳數為4~20的脂環式烴基或苯基；其中，所述苯基所具有的氫原子的一部分或全部可由碳數為1~12的烷基或碳數為1~12的烷氧基取代；R2為亞甲基或碳數為2~20的伸烷基； R3為碳數為4~20的脂環式烴基、苯基或萘基；R5為苯基、甲苯基、二甲苯基、萘基、蒽基、菲基、9-芴基、2-呋喃基或2-噻吩基；其中，這些基所具有的氫原子的一部分或全部可由碳數為1~12的烷基或碳數為1~12的烷氧基取代)。 A radiation sensitive resin composition comprising: [A] an alkali-soluble resin; [B] a polymerizable compound having an ethylenically unsaturated bond; [C] a photopolymerization represented by the following formula (1) a starting agent; and [D] at least one compound selected from the group consisting of a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing a phosphite structure, and a compound having a thioether structure; The content of the [C] photopolymerization initiator is 0.1 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. (In the formula (1), R 1 and R 4 each independently represent an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a phenyl group; wherein the hydrogen of the phenyl group A part or all of the atom may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms; R 2 is a methylene group or an alkylene group having 2 to 20 carbon atoms; and R 3 is carbon 4 to 20 alicyclic hydrocarbon groups, phenyl or naphthyl groups; R 5 is phenyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, 9-fluorenyl, 2-furyl or 2 a thienyl group; wherein a part or all of the hydrogen atoms of these groups may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms). 如申請專利範圍第1項所述的感放射線性樹脂組成物，其中：所述[A]鹼可溶性樹脂包含：(a1)選自由源自不飽和羧酸的結構單元、及源自不飽和羧酸酐的結構單元所組成的組群中的至少1種結構單元；以及(a2)由下述式(2)所表示的結構單元； (式(2)中，R6為碳數為1~12的烷基、環己基、環戊基、苯基、甲苯基、二甲苯基、萘基或苄基)。 The radiation-sensitive resin composition according to claim 1, wherein the [A] alkali-soluble resin comprises: (a1) selected from a structural unit derived from an unsaturated carboxylic acid, and derived from an unsaturated carboxylic acid. At least one structural unit of the group consisting of structural units of an acid anhydride; and (a2) a structural unit represented by the following formula (2); (In the formula (2), R 6 is an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a cyclopentyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a benzyl group). 如申請專利範圍第1項所述的感放射線性樹脂組成物，其中：所述[A]鹼可溶性樹脂包含：(a1)選自由源自不飽和羧酸的結構單元、及源自不飽 和羧酸酐的結構單元所組成的組群中的至少1種結構單元；以及(a3)由下述式(3)所表示的結構單元； (式(3)中，R7及R8為氫原子或甲基；R9為由所述式(4-1)或式(4-2)所表示的基；n為1~6的整數；式(4-1)中，R10為氫原子或甲基；式(4-1及式(4-2)中，＊表示與所述式(3)中的氧原子鍵結的部位)。 The radiation-sensitive resin composition according to claim 1, wherein the [A] alkali-soluble resin comprises: (a1) selected from a structural unit derived from an unsaturated carboxylic acid, and derived from an unsaturated carboxylic acid. At least one structural unit of the group consisting of structural units of an acid anhydride; and (a3) a structural unit represented by the following formula (3); (In the formula (3), R 7 and R 8 are a hydrogen atom or a methyl group; R 9 is a group represented by the formula (4-1) or the formula (4-2); n is an integer of 1 to 6 In the formula (4-1), R 10 is a hydrogen atom or a methyl group; in the formula (4-1 and the formula (4-2), * represents a moiety bonded to the oxygen atom in the formula (3)) . 如申請專利範圍第1項所述的感放射線性樹脂組成物，其中：所述[A]鹼可溶性樹脂包含：(a1)選自由源自不飽和羧酸的結構單元、及源自不飽和羧酸酐的結構單元所組成的組群中的至少1種結構單元；以及(a4)源自含有環氧基的不飽和化合物的結構單元。 The radiation-sensitive resin composition according to claim 1, wherein the [A] alkali-soluble resin comprises: (a1) selected from a structural unit derived from an unsaturated carboxylic acid, and derived from an unsaturated carboxylic acid. At least one structural unit of the group consisting of structural units of an acid anhydride; and (a4) a structural unit derived from an unsaturated compound containing an epoxy group. 如申請專利範圍第1項至第4項中任一項所述的感放 射線性樹脂組成物，其中：所述[B]聚合性化合物為二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯的混合物。 The sensing according to any one of claims 1 to 4 A radioactive resin composition, wherein: the [B] polymerizable compound is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. 如申請專利範圍第1項至第4項中任一項所述的感放射線性樹脂組成物，其中：所述式(1)中，R1為甲基或苯基，R2為亞甲基或伸乙基，R3為環戊基或環己基，R4為碳數為1~6的烷基或苯基，R5為甲苯基或萘基。 The radiation sensitive resin composition according to any one of claims 1 to 4, wherein, in the formula (1), R 1 is a methyl group or a phenyl group, and R 2 is a methylene group. Or an ethyl group, R 3 is a cyclopentyl group or a cyclohexyl group, R 4 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 5 is a tolyl group or a naphthyl group. 如申請專利範圍第1項至第4項中任一項所述的感放射線性樹脂組成物，其中：所述[D]化合物為所述含有受阻酚結構的化合物，且相對於[A]鹼可溶性樹脂100質量份，該[D]化合物的含量為0.01質量份以上、10質量份以下。 The radiation sensitive resin composition according to any one of claims 1 to 4, wherein: the [D] compound is the compound having a hindered phenol structure, and is relative to the [A] base The content of the [D] compound is 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the soluble resin. 如申請專利範圍第1項至第4項中任一項所述的感放射線性樹脂組成物，其中：其更包含[E]著色劑。 The radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the composition further comprises an [E] colorant. 如申請專利範圍第1項至第4項中任一項所述的感放射線性樹脂組成物，其中：其用於形成顯示元件用硬化膜。 The radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the composition is used for forming a cured film for a display element. 一種顯示元件用硬化膜的形成方法，其特徵在於包括如下步驟：(1)使用如申請專利範圍第9項所述的感放射線性樹脂組成物，在基板上形成塗膜； (2)對所述塗膜的至少一部分照射放射線；(3)對照射了所述放射線的塗膜進行顯影；以及(4)對經所述顯影的塗膜進行加熱。 A method for forming a cured film for a display element, comprising the steps of: (1) forming a coating film on a substrate using the radiation sensitive resin composition as described in claim 9; (2) irradiating at least a part of the coating film with radiation; (3) developing a coating film irradiated with the radiation; and (4) heating the developed coating film. 一種顯示元件用硬化膜，其特徵在於：其由如申請專利範圍第9項所述的感放射線性樹脂組成物形成。 A cured film for a display element, which is formed of a radiation-sensitive resin composition as described in claim 9 of the patent application. 一種顯示元件，其特徵在於：其包括如申請專利範圍第11項所述的顯示元件用硬化膜。 A display element comprising the cured film for a display element according to claim 11 of the patent application.
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