TW201932496A - Photosensitive resin composition for color filter, color filter, image display element and method for producing color filter - Google Patents

Photosensitive resin composition for color filter, color filter, image display element and method for producing color filter Download PDF

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TW201932496A
TW201932496A TW107137699A TW107137699A TW201932496A TW 201932496 A TW201932496 A TW 201932496A TW 107137699 A TW107137699 A TW 107137699A TW 107137699 A TW107137699 A TW 107137699A TW 201932496 A TW201932496 A TW 201932496A
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color filter
resin composition
photosensitive resin
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TW107137699A
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TWI794313B (en
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永井英理
木下健宏
川口恭章
柳正義
倉本拓樹
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日商昭和電工股份有限公司
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

A photosensitive resin composition for a color filter, said photosensitive resin composition comprising: a copolymer (A) which contains a structural unit (a) having an acid group and a structural unit (b) having a cyclic ether group; a compound (B) which generates an acid upon heating and/or ultraviolet light irradiation; a solvent (C); a reactive diluent (D); a photopolymerization initiator (E); and a colorant (F).

Description

彩色濾光片用感光性樹脂組成物、彩色濾光片、影像顯示元件及彩色濾光片之製造方法Photosensitive resin composition for color filter, color filter, image display element, and method for manufacturing color filter

本發明有關彩色濾光片用感光性樹脂組成物、彩色濾光片、具備其之影像顯示元件及彩色濾光片之製造方法。The present invention relates to a photosensitive resin composition for a color filter, a color filter, an image display element including the same, and a method for manufacturing a color filter.

近幾年來，基於省資源及省能源之觀點，於各種塗佈、印刷、塗料、接著劑等之領域中，已廣泛使用可藉由紫外線及電子束等之活性能量線而硬化之感光性樹脂組成物。且，於印刷配線基板等之電子材料領域中，可藉由活性能量線而硬化之感光性樹脂組成物已使用於抗焊阻劑及彩色濾光片用阻劑。進而對可硬化之感光性樹脂組成物之要求特性變的越益高度多樣化，其中要求考慮生產性之短時間硬化性、抑制被應用之構件的熱損傷之低溫硬化性。In recent years, based on the viewpoint of saving resources and energy, photosensitive resins that can be hardened by active energy rays such as ultraviolet rays and electron beams have been widely used in various fields of coating, printing, coatings, and adhesives.组合 物。 Composition. Furthermore, in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be hardened by active energy rays have been used as solder resists and resists for color filters. Furthermore, the required characteristics of the hardenable photosensitive resin composition are becoming more diverse. Among them, it is required to consider the short-term hardenability of productivity and the low-temperature hardenability of suppressing thermal damage of the applied component.

彩色濾光片一般係由玻璃基板等之透明基板、形成於透明基板上之紅(R)、綠(G)及藍(B)之像素、形成於像素邊界之黑矩陣、及形成於像素及黑矩陣上之保護膜所構成。具有此等構成之彩色濾光片通常藉由於透明基板上依序形成黑矩陣、像素及保護膜而製造。作為像素及黑矩陣(以下將像素及黑矩陣稱為「著色圖型」)之形成方法提案有各種方法。其中，使用感光性樹脂組成物作為阻劑，以重複塗佈、曝光、顯影及烘烤之光微影工法製作之顏料/染料分散法，由於可賦予耐久性優異，針孔等之缺陷少之著色圖型，故成為目前主流。A color filter is generally composed of a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the pixel boundary, and pixels and Consists of a protective film on a black matrix. A color filter having such a structure is generally manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various methods have been proposed as a method for forming the pixels and the black matrix (hereinafter, the pixels and the black matrix are referred to as "coloring patterns"). Among them, the pigment / dye dispersion method using the photosensitive resin composition as a resist and photolithography method of repeated coating, exposure, development, and baking has excellent durability, and has few defects such as pinholes. Coloring patterns have become the mainstream.

一般光微影工法所用之感光性樹脂組成物含有鹼可溶性樹脂、反應性稀釋劑、光聚合起始劑、著色劑及溶劑。顏料/染料分散法具有上述優點，但相反地由於重複形成黑矩陣、R、G、B之圖型，故要求高的耐熱性，作為可耐受高烘烤溫度之著色劑，有可使用之著色劑種類有限等之限制，而經常成為問題。The photosensitive resin composition used in the general photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment / dye dispersion method has the above advantages, but on the contrary, because the black matrix, R, G, and B patterns are repeatedly formed, high heat resistance is required. As a colorant that can withstand high baking temperatures, it can be used. Limitations such as limited colorants are often a problem.

專利文獻1中，揭示藉由使用鹼可溶性樹脂、具有乙烯性不飽和鍵之聚合性化合物、感放射線性聚合起始劑、著色劑及3-胺基苯磺酸乙酯等之化合物，而可於低溫硬化且提高保存安定性之著色組成物。Patent Document 1 discloses that compounds such as an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a colorant, and ethyl 3-aminobenzenesulfonate can be used. A colored composition that cures at low temperatures and improves storage stability.

專利文獻2中，藉由使用包含藉由鹼性物質或藉由在鹼性物質存在下之加熱而促進朝最終生成物反應之高分子前驅物、與藉由電磁波照射及加熱而產生鹼之特定鹼產生劑的感光性樹脂組成物，而可低溫硬化。
[先前技術文獻]
[專利文獻]In Patent Document 2, the use of a polymer precursor that promotes the reaction toward the final product by an alkaline substance or by heating in the presence of an alkaline substance, and the specificity that an alkali is generated by irradiation and heating with electromagnetic waves are used. The photosensitive resin composition of the alkali generator can be hardened at a low temperature.
[Prior technical literature]
[Patent Literature]

[專利文獻1] 日本特開2013-68843號公報
[專利文獻2] 日本特開2014-70148號公報[Patent Document 1] Japanese Patent Laid-Open No. 2013-68843
[Patent Document 2] Japanese Patent Application Publication No. 2014-70148

[發明欲解決之課題][Questions to be Solved by the Invention]

近幾年來，電子紙等之可撓性顯示器已普及。作為該可撓性顯示器之基板，已檢討聚對苯二甲酸乙二酯等之塑膠基板。該基板具有於烘烤時拉伸或收縮之性質，而必須使烘烤步驟低溫化。因此，專利文獻1所達成之程度就滿足上述要求而言尚不充分。且，專利文獻2中，雖低溫硬化性提高，但相反地，保存安定性低，實用化有困難。In recent years, flexible displays such as electronic paper have become popular. As a substrate of the flexible display, a plastic substrate such as polyethylene terephthalate has been reviewed. The substrate has the property of stretching or shrinking during baking, and it is necessary to reduce the temperature of the baking step. Therefore, the degree achieved in Patent Document 1 is insufficient to satisfy the above-mentioned requirements. Further, in Patent Document 2, although the low-temperature curability is improved, on the contrary, storage stability is low, and practical use is difficult.

本發明係為解決上述課題而完成者，其目的在於提供顯影性及保存安定性良好，並且即使於100℃左右之低溫下硬化亦賦予耐溶劑性優異之著色圖型之彩色濾光片用感光性樹脂組成物、及可用於調製該感光性樹脂組成物之共聚物。
且，本發明之目的在於提供具有耐溶劑性優異之著色圖型的彩色濾光片及其製造方法以及具備該彩色濾光片之影像顯示元件。

[用以解決課題之手段]The present invention has been made in order to solve the above-mentioned problems, and an object thereof is to provide a photosensitive color filter for color filters that is excellent in developability and storage stability and gives a coloring pattern excellent in solvent resistance even when cured at a low temperature of about 100 ° C. A photosensitive resin composition and a copolymer that can be used to prepare the photosensitive resin composition.
Furthermore, an object of the present invention is to provide a color filter having a colored pattern excellent in solvent resistance, a method for manufacturing the same, and an image display device including the color filter.

[Means to solve the problem]

亦即，本發明係以下述[1]～[16]表示者。
[1] 一種彩色濾光片用感光性樹脂組成物，其特徵係含有：含有具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)之共聚物(A)、藉由熱及/或紫外線照射產生酸之化合物(B)、溶劑(C)、反應性稀釋劑(D)、光聚合起始劑(E)及著色劑(F)。
[2] 如[1]之彩色濾光片用感光性樹脂組成物，其中前述具有酸基之構成單位(a)係源自含羧基之乙烯性不飽和化合物之構成單位。
[3] 如[1]或[2]之彩色濾光片用感光性樹脂組成物，其中前述具有環狀醚基之構成單位(b)係源自選自由含環氧基之(甲基)丙烯酸酯及含氧雜環丁基之(甲基)丙烯酸酯所成之群中之至少一種的構成單位。
[4] 如[1]至[3]中任一項之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)中含有之前述具有酸基之構成單位(a)之比例為5莫耳%～40莫耳%，且前述具有環狀醚基之構成單位(b)之比例為60莫耳%～95莫耳%。
[5] 如[1]至[3]中任一項之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)進而含有源自具有乙烯性不飽和基之自由基聚合性化合物之構成單位(c)。
[6] 如[5]之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)中含有之前述具有酸基之構成單位(a)之比例為5莫耳%～60莫耳%，前述具有環狀醚基之構成單位(b)之比例為5莫耳%～70莫耳%，且前述源自具有乙烯性不飽和基之自由基聚合性化合物之構成單位(c)之比例為超過0莫耳%～80莫耳%。
[7] 如[1]至[6]中任一項之彩色濾光片用感光性樹脂組成物，其中前述具有酸基之構成單位(a)之酸基係羧基。
[8] 如[1]至[7]中任一項之彩色濾光片用感光性樹脂組成物，其中前述具有環狀醚基之構成單位(b)之環狀醚基係選自由環氧基及氧雜環丁基所成之群中之至少一種。
[9] 如[1]至[8]中任一項之彩色濾光片用感光性樹脂組成物，其中前述藉由熱及/或紫外線照射產生酸之化合物(B)相對於合成前述共聚物(A)時所用之賦予前述具有環狀醚基之構成單位(b)之聚合性單體100質量份為0.05質量份～20質量份。
[10] 如[1]至[9]中任一項之彩色濾光片用感光性樹脂組成物，其中前述藉由熱及/或紫外線照射產生酸之化合物(B)係鋶鹽。
[11] 如[1]至[10]中任一項之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)之重量平均分子量為1,000～50,000且酸價為20～300KOHmg/g。
[12] 如[1]至[11]中任一項之彩色濾光片用感光性樹脂組成物，其中前述著色劑(F)含有顏料。
[13] 如[1]至[12]中任一項之彩色濾光片用感光性樹脂組成物，其中將前述彩色濾光片用感光性樹脂組成物中之前述溶劑(C)除外之成分的總和設為100質量%時，前述共聚物(A)與前述藉由熱及/或紫外線照射產生酸之化合物(B)之總和為1質量%～50質量%，前述反應性稀釋劑(D)為1質量%～60質量%，前述光聚合起始劑(E)為0.01質量%～15質量%，前述著色劑(F)為20質量%～80質量%，將前述彩色濾光片用感光性樹脂組成物中之前述溶劑(C)除外之成分的總和設為100質量份時，前述溶劑(C)為10質量份～800質量份。That is, the present invention is represented by the following [1] to [16].
[1] A photosensitive resin composition for a color filter, comprising: a copolymer (A) containing a constituent unit (a) having an acid group and a constituent unit (b) having a cyclic ether group; A compound (B), a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a coloring agent (F) which generate an acid by heat and / or ultraviolet radiation.
[2] The photosensitive resin composition for a color filter according to [1], in which the constitutional unit (a) having an acid group is a constitutional unit derived from a carboxyl group-containing ethylenically unsaturated compound.
[3] The photosensitive resin composition for a color filter according to [1] or [2], in which the aforementioned constituent unit (b) having a cyclic ether group is derived from a (methyl) group containing an epoxy group A constituent unit of at least one of the group consisting of an acrylate and an oxetanyl (meth) acrylate.
[4] The photosensitive resin composition for a color filter according to any one of [1] to [3], wherein a ratio of the aforementioned structural unit (a) having an acid group contained in the aforementioned copolymer (A) is 5 mol% to 40 mol%, and the proportion of the aforementioned constituent unit (b) having a cyclic ether group is 60 mol% to 95 mol%.
[5] The photosensitive resin composition for a color filter according to any one of [1] to [3], wherein the copolymer (A) further contains a radical polymerizable compound derived from an ethylenically unsaturated group The constituent unit (c).
[6] The photosensitive resin composition for a color filter according to [5], wherein the proportion of the above-mentioned acid unit-containing constituent unit (a) contained in the copolymer (A) is 5 mol% to 60 mol %, The proportion of the aforementioned constituent unit (b) having a cyclic ether group is 5 mol% to 70 mol%, and the aforementioned constituent unit (c) derived from a radical polymerizable compound having an ethylenically unsaturated group The ratio is more than 0 mol% to 80 mol%.
[7] The photosensitive resin composition for a color filter according to any one of [1] to [6], wherein the acid group-based carboxyl group having the acid unit as the structural unit (a).
[8] The photosensitive resin composition for a color filter according to any one of [1] to [7], wherein the cyclic ether group of the structural unit (b) having a cyclic ether group is selected from epoxy resins And at least one of the groups formed by oxetanyl and oxetanyl.
[9] The photosensitive resin composition for a color filter according to any one of [1] to [8], wherein the compound (B) that generates an acid by heat and / or ultraviolet radiation is synthesized with respect to the copolymer (A) 100 mass parts of polymerizable monomers which provide the said structural unit (b) which has a cyclic ether group are 0.05 mass parts-20 mass parts.
[10] The photosensitive resin composition for a color filter according to any one of [1] to [9], wherein the compound (B) -based sulfonium salt that generates an acid by heat and / or ultraviolet radiation is described above.
[11] The photosensitive resin composition for a color filter according to any one of [1] to [10], wherein the copolymer (A) has a weight average molecular weight of 1,000 to 50,000 and an acid value of 20 to 300 KOHmg / g.
[12] The photosensitive resin composition for a color filter according to any one of [1] to [11], wherein the colorant (F) contains a pigment.
[13] The photosensitive resin composition for a color filter according to any one of [1] to [12], wherein the components except the solvent (C) in the photosensitive resin composition for a color filter are excluded When the total amount of S is 100% by mass, the total of the copolymer (A) and the compound (B) that generates an acid by heat and / or ultraviolet irradiation is 1 to 50% by mass, and the reactive diluent (D ) Is 1% to 60% by mass, the photopolymerization initiator (E) is 0.01% to 15% by mass, the colorant (F) is 20% to 80% by mass, and the color filter is used When the total of the components except the solvent (C) in the photosensitive resin composition is 100 parts by mass, the solvent (C) is 10 to 800 parts by mass.

[14] 一種彩色濾光片，其特徵係具有由如[1]至[13]中任一項之彩色濾光片用感光性樹脂組成物之硬化物所成之著色圖型。[14] A color filter having a coloring pattern formed of a cured product of a photosensitive resin composition for a color filter according to any one of [1] to [13].

[15] 一種影像顯示元件，其特徵為具備如[14]之彩色濾光片。[15] An image display element characterized by having a color filter as in [14].

[16] 一種彩色濾光片之製造方法，其特徵係包含下述步驟：將如[1]至[13]中任一項之彩色濾光片用感光性樹脂組成物塗佈於基板上，經曝光、鹼顯影後，於150℃以下之溫度進行烘烤而形成著色圖型。

[發明效果][16] A method for manufacturing a color filter, comprising the steps of: coating the photosensitive resin composition for a color filter according to any one of [1] to [13] on a substrate, After exposure and alkali development, baking is performed at a temperature of 150 ° C or lower to form a colored pattern.

[Inventive effect]

依據本發明，可提供顯影性及保存安定性良好，並且即使於100℃左右之低溫下硬化亦賦予耐溶劑性優異之著色圖型之彩色濾光片用感光性樹脂組成物、及可用於調製該感光性樹脂組成物之共聚物。
且，依據本發明可提供具有耐溶劑性優異之著色圖型的彩色濾光片及其製造方法以及具備該彩色濾光片之影像顯示元件。According to the present invention, it is possible to provide a photosensitive resin composition for a color filter which is excellent in developability and storage stability, and which imparts a coloring pattern excellent in solvent resistance even when cured at a low temperature of about 100 ° C, and can be used for modulation. A copolymer of the photosensitive resin composition.
In addition, according to the present invention, a color filter having a colored pattern excellent in solvent resistance, a method for manufacturing the same, and an image display device including the color filter can be provided.

＜彩色濾光片用感光性樹脂組成物＞
本發明之彩色濾光片用感光性樹脂組成物含有：含有具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)之共聚物(A)、藉由熱及/或紫外線照射產生酸之化合物(B)、溶劑(C)、反應性稀釋劑(D)、光聚合起始劑(E)及著色劑(F)。<Photosensitive resin composition for color filters>
The photosensitive resin composition for a color filter of the present invention contains a copolymer (A) containing a constituent unit (a) having an acid group and a constituent unit (b) having a cyclic ether group, and heat and / or The compound (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), and the coloring agent (F) which generate an acid by ultraviolet irradiation.

＜共聚物(A)＞
＜具有酸基之構成單位(a)＞
共聚物(A)中含有之具有酸基之構成單位(a)係源自含酸基之聚合性單體之構成單位。作為酸基，舉例為羧基 (-COOH)、膦酸基(-PO(OH)2 )、磺酸基(-SO3 H)等。該等中，基於原料取得容易性或用於製造彩色濾光片時之耐溶劑性之觀點，較好為羧基。作為賦予具有酸基之構成單位(a)之聚合性單體，舉例為例如(甲基)丙烯酸、巴豆酸、桂皮酸、乙烯基磺酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基磷酸氫酯等之含羧基之乙烯性不飽和化合物。該等聚合性單體可單獨使用，亦可併用2種以上。該等中，基於取得容易性及反應性之觀點，較好為(甲基)丙烯酸。又，構成單位亦稱為單體單位。＜ Copolymer (A) ＞
＜ Constitution unit (a) with acid group ＞
The constituent unit (a) having an acid group contained in the copolymer (A) is a constituent unit derived from an acid group-containing polymerizable monomer. Examples of the acid group include a carboxyl group (-COOH), a phosphonic acid group (-PO (OH) 2 ), and a sulfonic acid group (-SO 3 H). Among these, a carboxyl group is preferable from the viewpoints of easy availability of raw materials and solvent resistance when used for manufacturing a color filter. Examples of the polymerizable monomer imparting the constituent unit (a) having an acid group include, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2- (meth) acryloxyethyl amber Acid, 2- (meth) acryloxyethyl phthalic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl Carboxylic ethylenically unsaturated compounds such as hydrogen phosphate. These polymerizable monomers may be used alone or in combination of two or more. Among these, (meth) acrylic acid is preferable from the viewpoints of easiness of obtaining and reactivity. The constituent unit is also called a monomer unit.

本發明中，藉由於共聚物(A)中含有具有酸基之構成單位(a)，可大幅改善使用共聚物(A)作為感光性材料時之鹼顯影性。In the present invention, since the copolymer (A) contains the constituent unit (a) having an acid group, the alkali developability when the copolymer (A) is used as a photosensitive material can be significantly improved.

共聚物(A)由具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)所成時，共聚物(A)中含有之具有酸基之構成單位(a)之比例較好為5莫耳%～40莫耳%，更好為10莫耳%～35莫耳%，最好為15莫耳%～30莫耳%。具有酸基之構成單位(a)之比例若為5莫耳%～40莫耳%，則成為適當之鹼顯影速度，可形成精緻著色圖型。
共聚物(A)進而含有後述其他構成單位(c)時，共聚物(A)中含有之具有酸基之構成單位(a)之比例較好為5莫耳%～60莫耳%，更好為8莫耳%～50莫耳%，最好為10莫耳%～40莫耳%。具有酸基之構成單位(a)之比例若為5莫耳%～60莫耳%，則成為適當之鹼顯影速度，可形成精緻著色圖型。When the copolymer (A) is composed of the constituent unit (a) having an acid group and the constituent unit (b) having a cyclic ether group, the proportion of the constituent unit (a) having an acid group contained in the copolymer (A) It is preferably 5 mol% to 40 mol%, more preferably 10 mol% to 35 mol%, and most preferably 15 mol% to 30 mol%. If the proportion of the structural unit (a) having an acid group is 5 mol% to 40 mol%, it will become an appropriate alkali developing speed, and a delicate coloring pattern can be formed.
When the copolymer (A) further contains other constituent units (c) described later, the proportion of the constituent units (a) having an acid group contained in the copolymer (A) is preferably 5 mol% to 60 mol%, more preferably It is 8 mol% to 50 mol%, preferably 10 mol% to 40 mol%. If the proportion of the structural unit (a) having an acid group is 5 mol% to 60 mol%, it will become an appropriate alkali developing speed, and a delicate coloring pattern can be formed.

＜具有環狀醚基之構成單位(b)＞
共聚物(A)中含有之具有環狀醚基之構成單位(b)係源自含環狀醚基之聚合性單體之構成單位(但，相當於前述具有酸基之構成單位(a)者除外)。作為環狀醚基舉例為環氧基、氧雜環丁基等。作為含環氧基之聚合性單體的具體例舉例為(甲基)丙烯酸縮水甘油酯、具有脂環式環氧基之(甲基)丙烯酸3,4-環氧基環己基甲酯及其內酯加成物(例如DAICEL股份有限公司製CYCLOMER(註冊商標)A200、M100)、3,4-環氧基環己基甲基-3’,4’-環氧基環己烷羧酸酯之單(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯基酯之環氧化物、(甲基)丙烯酸二環戊烯基氧基乙酯之環氧化物等。該等中，基於取得容易性及反應性之觀點，較好為含環氧基之(甲基)丙烯酸酯，更好為(甲基)丙烯酸縮水甘油酯。又，作為含氧雜環丁基之聚合性單體的具體例舉例為(甲基)丙烯酸(3-乙基氧雜環丁-3-基)甲酯、4-[3-(3-乙基氧雜環丁-3-基甲氧基)丙氧基]苯乙烯、4-[6-(3-乙基氧雜環丁-3-基甲氧基)己氧基]苯乙烯、4-[5-(3-乙基氧雜環丁-3-基甲氧基)戊氧基]苯乙烯、2-乙烯基-2-甲基氧雜環丁烷等。該等中，基於取得容易性及反應性之觀點，較好為含氧雜環丁基之(甲基)丙烯酸酯，更好為(甲基)丙烯酸(3-乙基氧雜環丁-3-基)甲酯。該等聚合性單體可單獨使用，亦可組合2種以上使用。<Constitutional unit (b) having a cyclic ether group>
The constituent unit (b) having a cyclic ether group contained in the copolymer (A) is a constituent unit derived from a cyclic ether group-containing polymerizable monomer (but equivalent to the aforementioned constituent unit having an acid group (a) Except those). Examples of the cyclic ether group include an epoxy group and an oxetanyl group. Specific examples of the epoxy-containing polymerizable monomer include glycidyl (meth) acrylate, 3,4-epoxy cyclohexyl methyl (meth) acrylate having an alicyclic epoxy group, and the like. Lactone adducts (e.g., CYCLOMER (registered trademark) A200, M100, manufactured by DAICEL Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate Mono (meth) acrylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, and the like. Among these, from the viewpoints of availability and reactivity, an epoxy group-containing (meth) acrylate is preferred, and a glycidyl (meth) acrylate is more preferred. Specific examples of the oxetanyl-containing polymerizable monomer include (3-ethyloxetan-3-yl) methyl (meth) acrylate and 4- [3- (3-ethyl Oxetan-3-ylmethoxy) propoxy] styrene, 4- [6- (3-ethyloxetan-3-ylmethoxy) hexyloxy] styrene, 4 -[5- (3-ethyloxetan-3-ylmethoxy) pentoxy] styrene, 2-vinyl-2-methyloxetane, and the like. Among these, from the viewpoints of availability and reactivity, a (meth) acrylic acid ester containing an oxetanyl group is preferred, and (3-ethyloxetan-3) (meth) acrylic acid is more preferred -Yl) methyl ester. These polymerizable monomers may be used alone or in combination of two or more kinds.

本發明中，藉由於共聚物(A)中含有具有環狀醚基之構成單位(b)，而大為改善使用共聚物(A)作為感光性材料時之耐溶劑性。In the present invention, since the copolymer (A) contains a constituent unit (b) having a cyclic ether group, the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

共聚物(A)由具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)構成時，共聚物(A)中含有之具有環狀醚基之構成單位(b)之比例較好為60莫耳%～95莫耳%，更好為65莫耳%～90莫耳%，最好為70莫耳%～85莫耳%。具有環狀醚基之構成單位(b)之比例若為60莫耳%～95莫耳%，則兼具硬化塗膜之耐溶劑性與共聚物(A)之保存安定性。
共聚物(A)進而含有後述其他構成單位(c)時，共聚物(A)中含有之具有環狀醚基之構成單位(b)之比例較好為5莫耳%～70莫耳%，更好為8莫耳%～60莫耳%，最好為10莫耳%～50莫耳%。具有環狀醚基之構成單位(b)之比例若為5莫耳%～70莫耳%，則兼具硬化塗膜之耐溶劑性與共聚物(A)之保存安定性。When the copolymer (A) is composed of the constituent unit (a) having an acid group and the constituent unit (b) having a cyclic ether group, the copolymer (A) contains the constituent unit (b) having a cyclic ether group. The ratio is preferably 60 mol% to 95 mol%, more preferably 65 mol% to 90 mol%, and most preferably 70 mol% to 85 mol%. If the proportion of the constituent unit (b) having a cyclic ether group is 60 mol% to 95 mol%, both the solvent resistance of the hardened coating film and the storage stability of the copolymer (A) are combined.
When the copolymer (A) further contains other constituent units (c) described later, the proportion of the constituent unit (b) having a cyclic ether group contained in the copolymer (A) is preferably 5 mol% to 70 mol%. It is more preferably 8 mol% to 60 mol%, and most preferably 10 mol% to 50 mol%. If the proportion of the constituent unit (b) having a cyclic ether group is 5 mol% to 70 mol%, both the solvent resistance of the hardened coating film and the storage stability of the copolymer (A) are combined.

＜其他構成單位(c)＞
本發明中，共聚物(A)亦可含有具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)以外之構成單位(c)(但，相當於前述具有酸基之構成單位(a)及前述具有環狀醚基之構成單位(b)者除外)。賦予該其他構成單位(c)之聚合性單體，一般為具有乙烯性不飽和基之自由基聚合性化合物，其例舉例為丁二烯等之二烯類；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸環己酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、松香(甲基)丙烯酸酯、(甲基)丙烯酸降冰片酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸1,1,1-三氟乙酯、(甲基)丙烯酸全氟乙酯、(甲基)丙烯酸三苯基甲酯、(甲基)丙烯酸枯基酯、(甲基)丙烯酸3-(N,N-二甲基胺基)丙酯、甘油單(甲基)丙烯酸酯、丁三醇單(甲基)丙烯酸酯、(甲基)丙烯酸二環戊基酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸蒽酯等之(甲基)丙烯酸酯類；降冰片烯(雙環[2.2.1]庚-2-烯)、5-甲基雙環[2.2.1]庚-2-烯、四環[4.4.0.12,5 .17,10 ]十二烷-3-烯、二環戊二烯、三環[5.2.1.02,6 ]癸-8-烯、四環[4.4.0.12,5 .17,10 .01,6 ]十二烷-3-烯、五環[6.5.1.13,6 .02,7 .09,13 ]十五烷-4-烯、5-降冰片烯-2,3-二羧酸、5-降冰片烯-2,3-二羧酸酐、(甲基)丙烯酸醯胺、(甲基)丙烯酸N,N-二甲基醯胺、(甲基)丙烯酸蒽基醯胺、N-異丙基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二丙酮(甲基)丙烯醯胺等之(甲基)丙烯酸醯胺；(甲基)丙烯酸醯替苯胺、(甲基)丙烯腈、丙烯醛、氯化乙烯、偏氯乙烯、氟化乙烯、N-乙烯基吡咯啶酮、乙烯基吡啶、乙酸乙烯酯、乙烯基甲苯等之乙烯基化合物；苯乙烯、苯乙烯之α-、o-、m-、p-烷基、硝基、氰基、醯胺衍生物；檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等之不飽和二羧酸二酯；N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-月桂基馬來醯亞胺、N-(4-羥基苯基)馬來醯亞胺等之馬來醯亞胺類；馬來酸酐、衣康酸酐等之不飽和多元酸酐。該等具有乙烯性不飽和基之自由基聚合性化合物可單獨使用，亦可組合2種以上使用。該等中，基於耐熱性及透明性之觀點，較佳為(甲基)丙烯酸甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二環戊基酯、苯乙烯、乙烯基甲苯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷基酯、降冰片烯、N-異丙基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉及二丙酮(甲基)丙烯醯胺，更好為(甲基)丙烯酸甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二環戊基酯、苯乙烯、乙烯基甲苯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷基酯及降冰片烯。＜ Other constituent units (c) ＞
In the present invention, the copolymer (A) may contain a constitutional unit (a) having an acid group and a constitutional unit (c) other than the constitutional unit (b) having a cyclic ether group (but equivalent to the aforementioned constitutional unit having an acid group) Except for the constituent unit (a) and the aforementioned constituent unit (b) having a cyclic ether group). The polymerizable monomer imparted to the other constituent unit (c) is generally a radical polymerizable compound having an ethylenically unsaturated group, and examples thereof include diene such as butadiene; methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate Ester, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol Mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid1 , 1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, (meth) acrylate) N-dimethylamino) propyl, glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl (meth) acrylate , Adamantyl (meth) acrylate (Meth) acrylates such as naphthyl (meth) acrylate and anthracene (meth) acrylate; norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2. 1] hept-2-ene, tetracyclo [4.4.0.1 2,5 .1 7,10] dodecane-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 2,6] dec -8 - ene, tetracyclo [4.4.0.1 2,5 .1 7,10 .0 1,6] dodecane-3-ene, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13 ] Pentadecan-4-ene, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, ammonium (meth) acrylate, (meth) acrylic acid N, N-dimethylfluorenamine, anthrylamine (meth) acrylate, N-isopropyl (meth) acrylamide, (meth) acrylfluorenylmorpholine, diacetone (meth) propylene Ammonium (meth) acrylate, e.g. ammonium amine; amidine (meth) acrylic acid, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, N-vinyl pyrrolidone , Vinyl pyridine, vinyl acetate, vinyl toluene and other vinyl compounds; styrene, α-, o-, m-, p-alkyl, nitro, cyano, amidine derivatives of styrene; lemon Diethyl formate, diethyl maleate, diethyl fumarate Unsaturated dicarboxylic acid diesters such as esters, diethyl itaconic acid, etc .; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimides such as maleimide; unsaturated polybasic anhydrides such as maleic anhydride and itaconic anhydride. These radically polymerizable compounds having an ethylenically unsaturated group may be used alone or in combination of two or more kinds. Among these, from the viewpoints of heat resistance and transparency, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, styrene, vinyltoluene, Isobornyl (meth) acrylate, adamantyl (meth) acrylate, norbornene, N-isopropyl (meth) acrylamide, (meth) acrylfluorenylmorpholine, and diacetone (formaldehyde) (Meth) acrylamide, more preferably methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, styrene, vinyltoluene, isobornyl (meth) acrylate Esters, adamantyl (meth) acrylate and norbornene.

共聚物(A)含有之其他構成單位(c)之比例未有特別限制，較好為超過0莫耳%～80莫耳%，更好為5莫耳%～70莫耳%，最好為10莫耳%～60莫耳%。本發明中，其他構成單位(c)並非必須，但藉由於共聚物(A)中含有其他構成單位(c)，可適當提高耐溶劑性及塗膜特性。The proportion of the other constituent units (c) contained in the copolymer (A) is not particularly limited, but preferably exceeds 0 mol% to 80 mol%, more preferably 5 mol% to 70 mol%, and most preferably 10 mol% to 60 mol%. In the present invention, the other constituent units (c) are not necessary, but the copolymer (A) contains other constituent units (c), so that the solvent resistance and the coating film characteristics can be appropriately improved.

又，本說明書中記載為(甲基)丙烯酸酯者，意指丙烯酸酯及甲基丙烯酸酯之任一者。且記載為(甲基)丙烯酸者，意指丙烯酸及甲基丙烯酸之任一者。The term "(meth) acrylate" as used in this specification means any of acrylate and methacrylate. The term "(meth) acrylic acid" means either acrylic acid or methacrylic acid.

＜共聚物(A)之製造方法＞
製造由具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)所成之共聚物(A)時所使用之賦予具有酸基之構成單位(a)之含酸基聚合性單體(a0)及賦予具有環狀醚基之構成單位(b)之含環狀醚基聚合性單體(b0)之比例並未特別限制，但較好為(a0) 5莫耳%～40莫耳%及(b0) 60莫耳%～95莫耳%，更好為(a0) 10莫耳%～35莫耳%及(b0) 65莫耳%～90莫耳%，最好為(a0) 15莫耳%～30莫耳%及(b0) 70莫耳%～85莫耳%。
製造由具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)及其他構成單位(c)所成之共聚物(A)時所使用之賦予具有酸基之構成單位(a)之含酸基聚合性單體(a0)、賦予具有環狀醚基之構成單位(b)之含環狀醚基聚合性單體(b0)及賦予其他構成單位(c)之聚合性單體(c0)之比例並未特別限制，但較好為(a0) 5莫耳%～60莫耳%、(b0) 5莫耳%～70莫耳%及(c0)超過0莫耳%～80莫耳%，更好為(a0) 8莫耳%～50莫耳%、(b0) 8莫耳%～60莫耳%及(c0) 5莫耳%～70莫耳%，最好為(a0) 10莫耳%～40莫耳%、(b0) 10莫耳%～50莫耳%及(c0) 10莫耳%～60莫耳%。<Production method of copolymer (A)>
Acid group-containing polymerization for imparting an acid group-containing constituent unit (a) for the production of a copolymer (A) composed of the acid unit-constituting unit (a) and the cyclic ether group-constituting unit (b) The ratio of the monomer (a0) and the cyclic ether group-containing polymerizable monomer (b0) to the constituent unit (b) having a cyclic ether group is not particularly limited, but it is preferably (a0) 5 mol% -40 mol% and (b0) 60 mol% to 95 mol%, more preferably (a0) 10 mol% to 35 mol% and (b0) 65 mol% to 90 mol%, the best (A0) 15 mol% to 30 mol% and (b0) 70 mol% to 85 mol%.
The acid-containing constitution unit (a) used to produce the copolymer (A) formed from the constitution unit (a) having an acid group and the constitution unit (b) having a cyclic ether group and other constitution units (c) ( a) An acid group-containing polymerizable monomer (a0), a cyclic ether group-containing polymerizable monomer (b0) imparting a constituent unit having a cyclic ether group (b), and a polymerizability imparting other constituent units (c) The proportion of the monomer (c0) is not particularly limited, but it is preferably (a0) 5 mol% to 60 mol%, (b0) 5 mol% to 70 mol%, and (c0) more than 0 mol% ~ 80 mole%, more preferably (a0) 8 mole% to 50 mole%, (b0) 8 mole% to 60 mole%, and (c0) 5 mole% to 70 mole%, preferably (A0) 10 mol% to 40 mol%, (b0) 10 mol% to 50 mol%, and (c0) 10 mol% to 60 mol%.

含酸基聚合性單體(a0)、含環狀醚基聚合性單體(b0)及賦予其他構成單位(c)之聚合性單體(c0)之共聚合反應可依據該技術領域習知之自由基聚合方法，於聚合溶劑之存在下或不存在下進行。例如該等聚合性單體依據期望溶解於溶劑後，於該溶液中添加聚合起始劑，於50℃～130℃於1小時～20小時內進行聚合反應即可。The copolymerization reaction of the acid-group-containing polymerizable monomer (a0), the cyclic ether-group-containing polymerizable monomer (b0), and the polymerizable monomer (c0) imparted to other constituent units (c) can be performed according to the conventional knowledge in the technical field. The radical polymerization method is performed in the presence or absence of a polymerization solvent. For example, after the polymerizable monomer is dissolved in a solvent as desired, a polymerization initiator is added to the solution, and the polymerization reaction may be performed at 50 ° C to 130 ° C for 1 hour to 20 hours.

作為該共聚合反應可使用之溶劑只要對反應為惰性則未特別限制，但舉例為例如乙二醇單甲醚、乙二醇單乙醚、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、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、三丙二醇單乙醚等之(聚)烷二醇單烷醚類；乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等之(聚)烷二醇單烷醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚、四氫呋喃等之其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等之酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3-甲基-3-甲氧基丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸正丁酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸乙酯等之酯類；甲苯、二甲苯等之芳香族烴類；N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等之羧酸醯胺類；二乙二醇等。該等溶劑可單獨使用，亦可組合2種以上使用。The solvent that can be used for the copolymerization reaction is not particularly limited as long as it is inert to the reaction, but examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, two (Poly) alkanediol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate (Poly) alkanediol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol Alcohol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methyl Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, acetic acid N-butyl ester, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, pyruvate Methyl esters, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate, etc .; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and other carboxylic acid amines; diethylene glycol and the like. These solvents may be used alone or in combination of two or more.

該等溶劑中，就共聚合反應結束後不去除溶劑而可直接使用作為本發明之彩色濾光片用感光性樹脂組成物之(C)成分之方面，較好為醚系溶劑，更好為丙二醇單甲醚、丙二醇單甲醚乙酸酯、二乙二醇甲醚及乙二醇單甲醚。Among these solvents, an ether-based solvent is more preferred because it can be used as the (C) component of the photosensitive resin composition for a color filter of the present invention without removing the solvent after the copolymerization reaction is completed. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether and ethylene glycol monomethyl ether.

共聚合反應所用之溶劑量並未特別限定，於將聚合性單體之總饋入量設為100質量份時，一般為30質量份～1,000質量份，更好為50質量份～800質量份。尤其藉由將溶劑量設為1,000質量份以下，可抑制鏈移動作用所致之共聚物(A)的分子量降低且可將共聚物(A)之黏度控制在適當範圍。且，藉由將溶劑量設為30質量份以上，可防止異常聚合反應，可穩定地進行聚合反應，並且亦可防止共聚物(A)之著色或膠凝化。The amount of the solvent used in the copolymerization reaction is not particularly limited. When the total feeding amount of the polymerizable monomer is 100 parts by mass, it is generally 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass. . In particular, by setting the amount of the solvent to 1,000 parts by mass or less, the decrease in the molecular weight of the copolymer (A) due to the chain shift effect can be suppressed, and the viscosity of the copolymer (A) can be controlled in an appropriate range. In addition, by setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and coloration or gelation of the copolymer (A) can also be prevented.

且，作為該共聚合反應可使用之自由基聚合起始劑並未特別限定，但舉例為例如偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)等之偶氮系自由基聚合起始劑、過氧化苯甲醯、第三丁基過氧基-2-乙基己酸酯等之有機過氧化物系自由基聚合起始劑等。該等自由基聚合起始劑可單獨使用，亦可組合2種以上使用。自由基聚合起始劑之使用量，於將聚合性單體之總饋入量設為100質量份時，一般為0.5質量份～20質量份，較好為1.0質量份～10質量份。In addition, the radical polymerization initiator that can be used as the copolymerization reaction is not particularly limited, but examples thereof include azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile). ) And other azo-based radical polymerization initiators, organic peroxide-based radical polymerization initiators such as benzamidine peroxide and third butylperoxy-2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more kinds. The amount of the radical polymerization initiator used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass when the total feeding amount of the polymerizable monomer is 100 parts by mass.

共聚物(A)之聚苯乙烯換算之重量平均分子量較好為1,000～50,000，更好為3,000～40,000。共聚物(A)之重量平均分子量為1,000以上時，作為感光性樹脂組成物使用時之鹼顯影後之著色圖型難以發生缺損。另一方面，共聚物(A)之重量平均分子量為50,000以下時，顯影時間變適當，確保實用性。The polystyrene equivalent weight average molecular weight of the copolymer (A) is preferably 1,000 to 50,000, and more preferably 3,000 to 40,000. When the weight average molecular weight of the copolymer (A) is 1,000 or more, the coloring pattern after alkali development when used as a photosensitive resin composition is unlikely to be defective. On the other hand, when the weight average molecular weight of the copolymer (A) is 50,000 or less, the development time becomes appropriate, and practicality is ensured.

又，共聚物(A)之酸價(JIS K6901 5.3)較好為20KOHmg/g～300KOHmg/g，更好為30KOHmg/g～
200KOHmg/g。共聚物(A)之酸價為20KOHmg/g以上時，彩色濾光片用感光性樹脂組成物之鹼顯影性良好。另一方面，共聚物(A)之酸價為300KOHmg/g以下時，由於曝光部分(光硬化部分)對於鹼顯影液難溶解，故圖型形狀成為良好。The acid value (JIS K6901 5.3) of the copolymer (A) is preferably from 20 KOHmg / g to 300 KOHmg / g, more preferably from 30 KOHmg / g to
200KOHmg / g. When the acid value of the copolymer (A) is 20 KOHmg / g or more, the alkali developability of the photosensitive resin composition for a color filter is good. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg / g or less, the exposed portion (light-hardened portion) is difficult to dissolve in the alkali developing solution, so the pattern shape becomes good.

進而，共聚物(A)之環狀醚基當量並未特別限制，但通常為200g/mol～2,000g/mol，較好為300g/mol～1,500g/mol，更好為480g/mol～900g/mol之範圍。共聚物(A)之環狀醚基當量為200g/mol以上時，安定性變良好。另一方面，共聚物(A)之環狀醚基當量若為2,000g/mol以下，則充分確保耐溶劑性。又，所謂環狀醚基當量係聚合物之環狀醚基每1莫耳之聚合物質量，可藉由將聚合物質量除以聚合物之環狀醚基量而求出(g/mol)。本發明中，共聚物(A)之環狀醚基當量係自聚合性單體之饋入量計算之理論值。Furthermore, the cyclic ether group equivalent of the copolymer (A) is not particularly limited, but is generally 200 g / mol to 2,000 g / mol, preferably 300 g / mol to 1,500 g / mol, and more preferably 480 g / mol to 900 g / mol range. When the cyclic ether group equivalent of the copolymer (A) is 200 g / mol or more, the stability becomes good. On the other hand, if the cyclic ether group equivalent of the copolymer (A) is 2,000 g / mol or less, the solvent resistance is sufficiently ensured. The cyclic ether group equivalent is the polymer mass per mol of the cyclic ether group of the polymer, which can be determined by dividing the polymer mass by the amount of the cyclic ether group of the polymer (g / mol). . In the present invention, the cyclic ether group equivalent of the copolymer (A) is a theoretical value calculated from the feed amount of the polymerizable monomer.

＜藉由熱及/或紫外線照射產生酸之化合物(B)＞
以下有時將藉由熱產生酸之化合物簡稱為「(B-1)熱酸產生劑」，將藉由紫外線照射產生酸之化合物簡稱為「(B-2)光酸產生劑」。作為(B-1)熱酸產生劑及(B-2)光酸產生劑，若為藉由熱及/或紫外線照射產生酸則未特別限制，但舉例為例如錪鹽、鋶鹽、鏻鹽、二偶氮鎓鹽等之鎓鹽，較佳為鋶鹽。該等中，關於(B-1)熱酸產生劑，較好為於100℃以上之加熱產生酸之可取得之SAN APRO股份有限公司製TA-100及TA-120。且關於(B-2)光酸產生劑，較好為雜質少對i線高感度之三芳基鋶鹽系之光酸產生劑，其中更好為SAN APRO股份有限公司製CPI-210系列及CPI-100系列、CPI-300系列、CPI-400系列。該等(B-1)熱酸產生劑及(B-2)光酸產生劑可單獨使用，亦可組合2種以上使用。<Compound (B) which generates acid by heat and / or ultraviolet irradiation>
Hereinafter, a compound that generates an acid by heat may be simply referred to as "(B-1) thermal acid generator", and a compound that generates an acid by ultraviolet irradiation may be simply referred to as "(B-2) photoacid generator". The (B-1) thermal acid generator and (B-2) photoacid generator are not particularly limited as long as they generate acid by heat and / or ultraviolet radiation, but examples include sulfonium salts, sulfonium salts, and sulfonium salts. Onium salts such as diazonium salts and the like are preferably sulfonium salts. Among these, the (B-1) thermal acid generator is preferably TA-100 and TA-120 manufactured by SAN APRO Co., Ltd., which can be obtained by heating at 100 ° C or higher to generate an acid. As for the (B-2) photoacid generator, a triarylsulfonium salt-based photoacid generator with low impurities and high sensitivity to i rays is preferred, and among them, the CPI-210 series and CPI made by SAN APRO Co., Ltd. are more preferable. -100 series, CPI-300 series, CPI-400 series. These (B-1) thermal acid generators and (B-2) photoacid generators may be used alone or in combination of two or more kinds.

藉由熱及/或紫外線照射產生酸之化合物(B)之調配量，相對於合成共聚物(A)時所用之賦予具有環狀醚基之構成單位(b)之聚合性單體(b0) 100質量份，較好為0.05質量份～20質量份，更好為0.1質量份～15質量份，最好為1質量份～10質量份。化合物(B)之調配量為0.05質量份以上時，易於進行感光性樹脂組成物之硬化反應。另一方面，化合物(B)之調配量為20質量份以下時，感光性樹脂組成物之保存安定性提高。
共聚物(A)與藉由熱及/或紫外線照射產生酸之化合物(B)之總和，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，較好為1質量%～50質量%，更好為5質量%～40質量%，最好為10質量%～30質量%。若為該範圍之調配量，則可提高硬化塗膜之耐溶劑性且保有保存安定性。The compounding amount of the compound (B) that generates an acid by heat and / or ultraviolet irradiation is relative to the polymerizable monomer (b0) that is used to synthesize the constituent unit (b) having a cyclic ether group used in the synthesis of the copolymer (A). 100 parts by mass, preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass. When the compounding amount of the compound (B) is 0.05 parts by mass or more, the curing reaction of the photosensitive resin composition is liable to proceed. On the other hand, when the compounding amount of the compound (B) is 20 parts by mass or less, the storage stability of the photosensitive resin composition is improved.
The sum of the copolymer (A) and the compound (B) that generates an acid by heat and / or ultraviolet radiation, and the sum of the components except the solvent (C) in the photosensitive resin composition for a color filter is 100 In the case of mass%, it is preferably 1 to 50 mass%, more preferably 5 to 40 mass%, and most preferably 10 to 30 mass%. When the blending amount is within this range, the solvent resistance of the cured coating film can be improved and the storage stability can be maintained.

＜溶劑(C)＞
本發明之彩色濾光片用感光性樹脂組成物雖亦可於自共聚合反應系單離之共聚物(A)中適當混合期望溶劑(C)而調製，但並非必定須單離共聚物(A)，亦可將共聚合反應結束時所含之溶劑直接作為溶劑(C)使用，此時，亦可根據需要進而追加期望溶劑。又，於調製彩色濾光片用感光性樹脂組成物時所用之其他成分中所含之溶劑亦可作為溶劑(C)使用。<Solvent (C)>
Although the photosensitive resin composition for a color filter of the present invention can also be prepared by appropriately mixing the desired solvent (C) with the copolymerization copolymer (A) which is a self-copolymerization reaction system, the copolymer is not necessarily required to be an ionization copolymer ( A) The solvent contained at the end of the copolymerization reaction may be used directly as the solvent (C). In this case, a desired solvent may be further added as necessary. Moreover, the solvent contained in other components used when preparing the photosensitive resin composition for color filters can also be used as a solvent (C).

溶劑(C)之調配量，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量份時，一般為10質量份～800質量份，較好為50質量份～500質量份，更好為100質量份～300質量份。若為該範圍之調配量，則可成為具有適當黏度之彩色濾光片用感光性樹脂組成物。When the total amount of the solvent (C) is 100 parts by mass when the total of the components except the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass, it is generally 10 to 800 parts by mass, preferably It is 50 to 500 parts by mass, and more preferably 100 to 300 parts by mass. If it is the compounding quantity in this range, it will become the photosensitive resin composition for color filters which has an appropriate viscosity.

＜反應性稀釋劑(D)＞
反應性稀釋劑(D)係分子內具有至少一個可聚合之乙烯性不飽和基作為聚合性官能基之化合物，其中較好為具有複數聚合性官能基之化合物。藉由於彩色濾光片用感光性樹脂組成物中含有反應性稀釋劑(D)，而提高所形成之硬化物強度及對基材之密著性。<Reactive Diluent (D)>
The reactive diluent (D) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and a compound having a plurality of polymerizable functional groups is preferred. The presence of the reactive diluent (D) in the photosensitive resin composition for color filters improves the strength of the formed cured product and the adhesion to the substrate.

作為反應性稀釋劑(D)使用之單官能單體舉例為(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、2-(甲基)丙烯醯氧基-2-羥基丙基鄰苯二甲酸酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、鄰苯二甲酸衍生物之半(甲基)丙烯酸酯等之(甲基)丙烯酸酯類；苯乙烯、α-甲基苯乙烯、α-氯甲基苯乙烯、乙烯基甲苯等之芳香族乙烯基化合物類；乙酸乙烯酯、丙酸乙烯酯等之羧酸酯類等。且該等單體可單獨使用，亦可組合2種以上使用。Examples of the monofunctional monomer used as the reactive diluent (D) are (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxylate Methyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate, (methyl Base) ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (formyl) Base) 4-hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, glycerol Mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylate 2, (Meth) acrylic esters such as 2,3,3-tetrafluoropropyl esters, semi- (meth) acrylates of phthalic acid derivatives; styrene, α-methylstyrene, α-chloromethyl Aromatic vinyl compounds such as styrene and vinyl toluene; vinyl acetate, vinyl propionate Carboxylic acid esters and the like. And these monomers can be used alone or in combination of two or more kinds.

作為使用作為反應性稀釋劑(D)之多官能單體舉例為乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸縮水甘油酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚縮水甘油醚聚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯(亦即甲苯二異氰酸酯)、三甲基六亞甲基二異氰酸酯與六亞甲基二異氰酸酯等與(甲基)丙烯酸2-羥基乙酯之反應物、三(羥基乙基)異氰尿酸酯之三(甲基)丙烯酸酯等之(甲基)丙烯酸酯類；二乙烯基苯、鄰苯二甲酸二烯丙酯、二烯丙基苯磺酸酯等之芳香族乙烯基化合物類；己二酸二乙烯基酯等之二羧酸酯類；異氰尿酸三烯丙酯、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲醚、多元醇與N-羥甲基(甲基)丙烯醯胺之縮合物等。該等單體可單獨使用，亦可組合2種以上使用。Examples of the polyfunctional monomer used as the reactive diluent (D) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylic acid. Ester, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediene Alcohol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) propenyloxydiethoxyphenyl) propane, 2,2-bis ( 4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether bis ( (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, glycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (methyl ), Urethane (meth) acrylate (i.e. toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth) acrylate Ester reactants, (meth) acrylates such as tris (hydroxyethyl) isocyanurate tris (meth) acrylates; divinylbenzene, diallyl phthalate, diene Aromatic vinyl compounds such as propylbenzenesulfonate; dicarboxylic acid esters such as divinyl adipate; triallyl isocyanurate, methylene bis (meth) acrylamide, (Meth) acrylamide methylene ether, a polycondensate of polyhydric alcohol and N-methylol (meth) acrylamide, and the like. These monomers may be used alone or in combination of two or more kinds.

反應性稀釋劑(D)之調配量，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，一般為1質量%～60質量%，較好為5質量%～50質量%，更好為10質量%～40質量%。若為該範圍之調配量，則具有作為彩色濾光片用感光性樹脂組成物之適度黏度及光硬化性。The amount of the reactive diluent (D) to be formulated is generally 1 to 60% by mass when the total amount of the components (excluding the solvent (C) in the photosensitive resin composition for color filters) is 100% by mass. It is preferably 5 mass% to 50 mass%, and more preferably 10 mass% to 40 mass%. If it is the compounding quantity in this range, it will have moderate viscosity and photocurability as a photosensitive resin composition for color filters.

＜光聚合起始劑(E)＞
作為光聚合起始劑(E)並未特別限制，可舉例為例如苯偶因、苯偶因甲醚、苯偶因乙醚、苯偶因正丁醚等之苯偶因類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、4-(1-第三丁基二氧基-1-甲基乙基)苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉-丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1等之苯乙酮類；2-甲基蒽醌、2-戊基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等之蒽醌類；呫噸酮、噻噸酮、2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮等之噻噸酮類；苯乙酮二甲基縮醛、苄基二甲基縮醛等之縮醛類；二苯甲酮、4-(1-第三丁基二氧基-1-甲基乙基)二苯甲酮、3,3’,4,4’-四(第三丁基二氧基羰基)二苯甲酮等之二苯甲酮類；醯基氧化膦類；1,2-辛二酮、1-[4-(苯硫基)-, 2-(O-苯甲醯基肟)]等之肟酯類等。該等光聚合起始劑(E)可單獨使用，亦可組合2種以上使用。<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether, and the like; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-third-butyldioxy-1-methylethyl) acetophenone , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholine Acetophenones such as butanone-1; 2-methylanthraquinone, 2-pentylanthraquinone, 2-third butylanthraquinone, 1-chloroanthraquinone, etc .; Xanthones, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and other thioxanthone; acetophenone dimethyl Acetals such as acetal, benzyldimethylacetal; benzophenone, 4- (1-third-butyldioxy-1-methylethyl) benzophenone, 3,3 ' Benzophenones such as 4,4'-tetrakis (third butyldioxycarbonyl) benzophenone; fluorenyl phosphine oxides; 1,2-octanedione, 1- [4- (benzene Thio)-, 2- (O-benzylidene oxime)] and other oxime esters. These photopolymerization initiators (E) may be used alone or in combination of two or more kinds.

光聚合起始劑(E)之調配量，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，一般為0.01質量%～15質量%，較好為0.05質量%～10質量%，更好為0.1質量%～5質量%。若為該範圍之調配量，則成為具有適當光硬化性之彩色濾光片用感光性樹脂組成物。The blending amount of the photopolymerization initiator (E) is generally 0.01 mass% to 15 masses when the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 mass%. %, Preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass. If it is the compounding quantity in this range, it will become the photosensitive resin composition for color filters which has appropriate photocurability.

本發明之彩色濾光片用感光性樹脂組成物，除上述成分以外，亦可調配用以賦予特定特性之習知偶合劑、調平劑、熱聚合抑制劑等之習知添加劑。該等添加劑之調配量，若為不損及本發明效果之範圍，則未特別限制。In addition to the above components, the photosensitive resin composition for a color filter of the present invention may be formulated with conventional additives such as a conventional coupling agent, a leveling agent, and a thermal polymerization inhibitor to impart specific characteristics. The blending amount of these additives is not particularly limited as long as it is within a range that does not impair the effects of the present invention.

＜著色劑(F)＞
著色劑(F)若為可溶解或分散於溶劑(C)者，則未特別限制，舉例為例如染料或顏料等。作為染料，基於對於溶劑(C)或鹼顯影液之溶解性、與感光性樹脂組成物中之其他成分之相互作用、耐熱性等之觀點，較好使用羧酸或磺酸等之具有酸性基之酸性染料、酸性染料之與氮化合物之鹽、酸性染料之磺醯胺體等。<Colorant (F)>
The colorant (F) is not particularly limited as long as it is soluble or dispersible in the solvent (C), and examples thereof include dyes and pigments. As the dye, from the viewpoints of solubility in a solvent (C) or an alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, and the like, it is preferable to use an acidic group such as a carboxylic acid or a sulfonic acid. Acid dyes, salts of acid dyes and nitrogen compounds, sulfonamides of acid dyes, etc.

作為此等染料之例舉例為酸性茜素紫N；酸性黑1、2、24、48；酸性藍1、7、9、25、29、40、45、62、70、74、80、83、90、92、112、113、120、129、147；酸性鉻紫K；酸性品紅；酸性綠1、3、5、25、27、50；酸性橙6、7、8、10、12、50、51、52、56、63、74、95；酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、69、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274；酸性紫6B、7、9、17、19；酸性黃1、3、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116；食品黃3及該等之衍生物等。該等中，較好為偶氮系、呫噸(xanthene)系、蒽醌系或酞青系之酸性染料。該等染料可對應於目的的像素顏色而單獨使用或組合2種以上使用。Examples of such dyes are acidic alizarin purple N; acidic black 1, 2, 24, 48; acidic blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; Acid Chrome Violet K; Acid Magenta; Acid Green 1, 3, 5, 25, 27, 50; Acid Orange 6, 7, 8, 10, 12, 50 , 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52 , 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198 , 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29 , 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes can be used singly or in combination of two or more kinds depending on the intended pixel color.

作為顏料之例舉例為C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等之黃色顏料；C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等之橙色顏料；C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等之紅色顏料；C.I.顏料藍15、15:3、15:4、15:6、60等藍色顏料；C.I.顏料紫1、19、23、29、32、36、38等紫色顏料；C.I.顏料綠7、36、58、59等之綠色顏料；C.I.顏料棕23、25等之茶色顏料；C.I.顏料黑1、7、碳黑、鈦黑、氧化鐵等之黑色顏料等。該等顏料可對應於目的的像素顏色單獨使用，亦可組合2種以上使用。Examples of pigments are CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments of 59, 61, 64, 65, 71, 73, etc .; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29 , 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments; CI Pigment Brown 23 and 25 and other brown pigments; CI Pigment Black 1, 7, carbon black, titanium black, oxidation Black pigments such as iron. These pigments may be used alone or in combination of two or more types according to the intended pixel color.

著色劑(F)亦可對應於目的之像素顏色，組合使用上述染料及顏料。The colorant (F) may be used in combination with the above-mentioned dyes and pigments in accordance with the intended pixel color.

使用顏料作為著色劑(F)時，基於提高顏料分散性之觀點，亦可於彩色濾光片用感光性樹脂組成物中調配習知分散劑。作為分散劑，較好使用經時分散安定性優異之高分子分散劑。作為高分子分散劑之例舉例為胺基甲酸酯系分散劑、聚伸乙基亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙二醇二酯系分散劑、山梨糖醇酐脂肪族酯系分散劑、脂肪族改質酯系分散劑等。作為此等高分子分散劑亦可使用以EFKA(EFKA Chemicals BV(EFKA)公司製)、Disperbyk(BYK CHEM公司製)、DISPARLON(楠本化成股份有限公司製)、SOLSPERSE(ZENECA公司製)等之商品名市售者。分散劑之調配量只要根據所使用之顏料等之種類適當設定即可。
著色劑(F)之含量係根據所使用之染料及顏料適當調整，但於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，一般較好為20質量%～80質量%，更好為30質量%～75質量%，最好為40質量%～70質量%。若為該範圍之調配量，則成為具有適當光硬化性之彩色濾光片用感光性樹脂組成物。When a pigment is used as the colorant (F), a conventional dispersant may be blended in the photosensitive resin composition for a color filter from the viewpoint of improving pigment dispersibility. As the dispersant, a polymer dispersant excellent in dispersion stability over time is preferably used. Examples of the polymer dispersant include a urethane-based dispersant, a polyethylenimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, and Yamanashi Sugar alcohol anhydride aliphatic ester-based dispersant, aliphatic modified ester-based dispersant, and the like. As these polymer dispersants, products such as EFKA (manufactured by EFKA Chemicals BV (EFKA)), Disperbyk (manufactured by BYK CHEM), DISPARLON (manufactured by Nanben Chemical Co., Ltd.), SOLSPERSE (manufactured by ZENECA), etc. A marketer. The blending amount of the dispersant may be appropriately set according to the type of the pigment or the like to be used.
The content of the colorant (F) is appropriately adjusted according to the dyes and pigments to be used. However, when the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, it is generally It is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 75% by mass, and most preferably 40% by mass to 70% by mass. If it is the compounding quantity in this range, it will become the photosensitive resin composition for color filters which has appropriate photocurability.

彩色濾光片用感光性樹脂組成物中之共聚物(A)、藉由熱及/或紫外線照射產生酸之化合物(B)、溶劑(C)、反應性稀釋劑(D)、光聚合起始劑(E)及著色劑(F)之調配量，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，共聚物(A)與藉由熱及/或紫外線照射產生酸之化合物(B)之總和為1質量%～50質量%，反應性稀釋劑(D)為1質量%～60質量%，光聚合起始劑(E)為0.01質量%～15質量%，著色劑(F)為20質量%～80質量%，將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量份時，溶劑(C)為10質量份～800質量份，且藉由熱及/或紫外線照射產生酸之化合物(B)之調配量，相對於合成共聚物(A)時所用之賦予具有環狀醚基之構成單位(b)之聚合性單體(b0)100質量份為0.05質量份～20質量份。較好，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，共聚物(A)與藉由熱及/或紫外線照射產生酸之化合物(B)之總和為5質量%～40質量%，反應性稀釋劑(D)為5質量%～50質量%，光聚合起始劑(E)為0.05質量%～10質量%，著色劑(F)為30質量%～75質量%，將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量份時，溶劑(C)為50質量份～500質量份，且藉由熱及/或紫外線照射產生酸之化合物(B)之調配量，相對於聚合性單體(b0)100質量份為0.1質量份～15質量份。更好，於將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，共聚物(A)與藉由熱及/或紫外線照射產生酸之化合物(B)之總和為10質量%～30質量%，反應性稀釋劑(D)為10質量%～40質量%，光聚合起始劑(E)為0.1質量%～5質量%，著色劑(F)為40質量%～70質量%，將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量份時，溶劑(C)為100質量份～300質量份，且藉由熱及/或紫外線照射產生酸之化合物(B)之調配量，相對於聚合性單體(b0)100質量份為1質量份～10質量份。若為該範圍之調配量，則成為具有適當黏度之彩色濾光片用感光性樹脂組成物。且，即使不含著色劑(F)之感光性樹脂組成物時，共聚物(A)、藉由熱及/或紫外線照射產生酸之化合物(B)、溶劑(C)、反應性稀釋劑(D)及光聚合起始劑(E)之調配量亦可應用上述數值範圍，亦可使用於各種塗料、接著劑、印刷墨水用黏合劑等。The copolymer (A) in the photosensitive resin composition for a color filter, the compound (B) that generates an acid by heat and / or ultraviolet radiation, the solvent (C), the reactive diluent (D), and photopolymerization When the blending amount of the initiator (E) and the coloring agent (F) is 100% by mass when the total of the components except the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the copolymer (A) The total of the compound (B) and the compound (B) that generates an acid by heat and / or ultraviolet irradiation is 1% to 50% by mass, the reactive diluent (D) is 1% to 60% by mass, and the photopolymerization initiator (E ) Is 0.01% by mass to 15% by mass, and the colorant (F) is 20% by mass to 80% by mass, and the total of components except for the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass. The solvent (C) is 10 parts by mass to 800 parts by mass, and the compounding amount of the compound (B) that generates an acid by heat and / or ultraviolet radiation is more than that given to the compound used in the synthesis of the copolymer (A). 100 parts by mass of the polymerizable monomer (b0) as the constituent unit (b) of the ether group is 0.05 to 20 parts by mass. When the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the copolymer (A) and the acid that is generated by heat and / or ultraviolet irradiation are preferably used. The total of the compound (B) is 5 to 40% by mass, the reactive diluent (D) is 5 to 50% by mass, the photopolymerization initiator (E) is 0.05 to 10% by mass, and the colorant (F) is 30% by mass to 75% by mass, and when the total amount of the components other than the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass, the solvent (C) is 50 parts by mass or more 500 parts by mass, and the compounding amount of the compound (B) that generates an acid by heat and / or ultraviolet irradiation is 0.1 to 15 parts by mass relative to 100 parts by mass of the polymerizable monomer (b0). More preferably, when the total of the components other than the solvent (C) in the photosensitive resin composition for color filters is 100% by mass, the copolymer (A) and the acid that is generated by heat and / or ultraviolet radiation The total of the compound (B) is 10% to 30% by mass, the reactive diluent (D) is 10% to 40% by mass, the photopolymerization initiator (E) is 0.1% to 5% by mass, and the colorant (F) is 40% by mass to 70% by mass, and when the total of the components except the solvent (C) in the photosensitive resin composition for a color filter is 100 parts by mass, the solvent (C) is 100 parts by mass or more 300 parts by mass, and the compounding amount of the compound (B) that generates an acid by heat and / or ultraviolet irradiation is 1 to 10 parts by mass relative to 100 parts by mass of the polymerizable monomer (b0). If it is the compounding quantity in this range, it will become the photosensitive resin composition for color filters which has an appropriate viscosity. Furthermore, even when the photosensitive resin composition does not contain a colorant (F), the copolymer (A), the compound (B) that generates an acid by heat and / or ultraviolet radiation, the solvent (C), and the reactive diluent ( The blending amount of D) and the photopolymerization initiator (E) can also be applied to the above-mentioned numerical range, and can also be used in various coatings, adhesives, and adhesives for printing inks.

＜彩色濾光片用感光性樹脂組成物之製造＞
本發明之彩色濾光片用感光性樹脂組成物可使用習知混合裝置，藉由混合上述成分而製造。且，依據期望，先調製包含共聚物(A)、藉由熱及/或紫外線照射產生酸之化合物(B)及溶劑(C)之聚合物組成物後，混合反應性稀釋劑(D)、光聚合起始劑(E)及著色劑(F)而製造。<Production of photosensitive resin composition for color filters>
The photosensitive resin composition for a color filter of the present invention can be produced by mixing the above components using a conventional mixing device. And, as desired, a polymer composition containing a copolymer (A), a compound (B) that generates an acid by heat and / or ultraviolet radiation, and a solvent (C) is first prepared, and then a reactive diluent (D), It is produced by a photopolymerization initiator (E) and a coloring agent (F).

如上述所得之彩色濾光片用感光性樹脂組成物由於具有鹼顯影性，故可較好地作為阻劑者。彩色濾光片用感光性樹脂組成物之硬化只要於250℃以下之範圍適當選擇烘烤溫度即可，但本發明中使用之共聚物(A)由於於低溫之硬化性優異，故與習知材料相較，可降低烘烤溫度。彩色濾光片用感光性樹脂組成物中使用顏料作為著色劑(F)時，即使烘烤溫度設為150℃以下亦可充分進行硬化。本發明之彩色濾光片用感光性樹脂組成物由於即使降低烘烤溫度亦可充分進行交聯反應，故就能量消耗之方面有利。且即使於耐熱性差的著色劑(F)或基板亦可使用，可獲得著色劑本來之特性，亦可應用於各種基板。基於此等見解，烘烤溫度較好設為80℃～210℃，更好設為90℃～180℃，最好為100℃～150℃。烘烤溫度過低時，難以充分改善塗膜之耐溶劑性。且，烘烤時間可適當選擇，但通常為10分鐘～4小時，較好為20分鐘～2小時。Since the photosensitive resin composition for a color filter obtained as described above has alkali developability, it can be suitably used as a resist. The curing of the photosensitive resin composition for a color filter may be performed by appropriately selecting a baking temperature within a range of 250 ° C or lower. However, the copolymer (A) used in the present invention is excellent in curing properties at low temperatures. Compared with materials, it can reduce the baking temperature. When a pigment is used as the colorant (F) in the photosensitive resin composition for a color filter, the curing can be sufficiently performed even if the baking temperature is 150 ° C or lower. Since the photosensitive resin composition for a color filter of the present invention can sufficiently perform a crosslinking reaction even if the baking temperature is reduced, it is advantageous in terms of energy consumption. In addition, it is possible to use the coloring agent (F) or the substrate having poor heat resistance, and the original characteristics of the colorant can be obtained, and it can be applied to various substrates. Based on these findings, the baking temperature is preferably 80 ° C to 210 ° C, more preferably 90 ° C to 180 ° C, and most preferably 100 ° C to 150 ° C. When the baking temperature is too low, it is difficult to sufficiently improve the solvent resistance of the coating film. The baking time can be appropriately selected, but it is usually 10 minutes to 4 hours, and preferably 20 minutes to 2 hours.

本發明之彩色濾光片用感光性樹脂組成物可較好地使用於製造組裝於有機EL顯示器、液晶顯示裝置、於CCD或CMOS等之固體攝像元件等中之彩色濾光片。The photosensitive resin composition for a color filter of the present invention can be suitably used for manufacturing a color filter incorporated in an organic EL display, a liquid crystal display device, a solid-state imaging element such as a CCD, a CMOS, or the like.

本發明之彩色濾光片用感光性樹脂組成物之顯影性及保存安定性良好，並且即使降低圖型形成時之烘烤溫度亦可獲得耐溶劑性優異之著色圖型，故作為彩色濾光片用感光性材料極為有用。且本發明之彩色濾光片用感光性樹脂組成物對於伴隨低溫硬化之可撓性顯示器之發展、製造步驟中之能量消耗減低、而且對所使用之著色劑的限制緩解亦具有貢獻。The photosensitive resin composition for a color filter of the present invention has good developability and storage stability, and can obtain a colored pattern having excellent solvent resistance even if the baking temperature during pattern formation is reduced, so it is used as a color filter. Photosensitive materials for sheets are extremely useful. In addition, the photosensitive resin composition for a color filter of the present invention also contributes to the development of a flexible display accompanied by low-temperature curing, reduction of energy consumption in manufacturing steps, and alleviation of restrictions on the coloring agent used.

＜彩色濾光片＞
其次，針對具有由本發明之彩色濾光片用感光性樹脂組成物之硬化物所成之著色圖型之彩色濾光片加以說明。本發明之彩色濾光片具有使用上述彩色濾光片用感光性樹脂組成物形成之著色圖型。彩色濾光片通常係由基板、形成於其上之RGB之像素、形成於各像素邊界之黑矩陣及形成於像素與黑矩陣上之保護膜所構成。該構成中，除了選自構成像素之R、G及B以及黑矩陣(著色圖型)中之一種以上之著色圖型係使用上述彩色濾光片用感光性樹脂組成物形成以外，其他構成可採用習知者。＜ Color filter ＞
Next, a color filter having a coloring pattern formed of a cured product of the photosensitive resin composition for a color filter of the present invention will be described. The color filter of the present invention has a coloring pattern formed using the photosensitive resin composition for a color filter. A color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix. In this configuration, in addition to one or more coloring patterns selected from R, G, and B constituting a pixel and a black matrix (coloring pattern), the configuration may be formed using the photosensitive resin composition for a color filter described above. Adopt the knower.

其次，針對彩色濾光片之製造方法之一實施形態加以說明。首先於基板上形成著色圖型。具體而言，於基板上依序形成黑矩陣及RGB之像素。基板材質並未特別限定，可適當使用玻璃基板、矽基板、聚碳酸酯基板、聚酯基板、聚醯胺基板、聚醯胺醯亞胺基板、聚醯亞胺基板、鋁基板、印刷配線基板、陣列基板等。Next, an embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on the substrate. Specifically, a black matrix and RGB pixels are sequentially formed on a substrate. The substrate material is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, and a printed wiring substrate can be appropriately used. , Array substrate, etc.

著色圖型可藉由光微影法形成。具體而言，將上述彩色濾光片用感光性樹脂組成物塗佈於基板上，形成塗佈膜後，介隔特定圖型之光罩使塗佈膜曝光，使曝光部分予以光硬化。接著，以鹼水溶液將未曝光部分顯影後，藉由烘烤，可形成特定之著色圖型。The coloring pattern can be formed by photolithography. Specifically, after the photosensitive resin composition for a color filter is coated on a substrate to form a coating film, the coating film is exposed through a photomask with a specific pattern, and the exposed portion is light-cured. Next, the unexposed portion is developed with an alkaline aqueous solution, and then a specific coloring pattern can be formed by baking.

作為彩色濾光片用感光性樹脂組成物之塗佈方法並未特別限制，可使用網版印刷法、輥塗佈法、簾流塗佈法、噴霧塗佈法、旋轉塗佈法等。且，彩色濾光片用感光性樹脂組成物塗佈後，亦可根據需要，使用循環式烘箱、紅外線加熱器、加熱板等之加熱手段進行加熱，而使溶劑(C)揮發。加熱條件並未特別限制，只要對應於所使用之彩色濾光片用感光性樹脂組成物之組成而適當設定即可。一般只要於50℃～120℃之溫度加熱30秒～30分鐘即可。The coating method of the photosensitive resin composition for color filters is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, and the like can be used. In addition, after the color filter is coated with the photosensitive resin composition, the solvent (C) may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited as long as they are appropriately set in accordance with the composition of the photosensitive resin composition for a color filter to be used. Generally, it only needs to be heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

其次，對所形成之塗膜介隔負型之遮罩照射紫外線、準分子雷射光等之活性能量線而部分曝光。所照射之能量線量只要對應於彩色濾光片用感光性樹脂組成物之組成適當選擇即可，例如較好為30mJ/cm2 ～2000mJ/cm2 。作為曝光所用之光源並未特別限制，但可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、氙氣燈、金屬鹵素燈等。Next, the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of energy rays to be irradiated may be appropriately selected in accordance with the composition of the photosensitive resin composition for a color filter, and is preferably, for example, 30 mJ / cm 2 to 2000 mJ / cm 2 . The light source used for the exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.

作為顯影所用之鹼水溶液並未特別限制，但可使用碳酸鈉、碳酸鉀、碳酸鈣、氫氧化鈉、氫氧化鉀等之水溶液；乙胺、二乙胺、二甲基乙醇胺等之胺系化合物之水溶液；四甲基銨、3-甲基-4-胺基-N,N-二乙基苯胺、3-甲基-4-胺基-N-乙基-N-β-羥基乙基苯胺、3-甲基-4-胺基-N-乙基-N-β-甲烷磺醯胺乙基苯胺、3-甲基-4-胺基-N-乙基-N-β-甲氧基乙基苯胺及該等之硫酸鹽、鹽酸鹽或對-甲苯磺酸鹽等之對-苯二胺系化合物之水溶液等。又，該等水溶液中，可根據需要添加消泡劑或界面活性劑。又，利用上述鹼水溶液顯影後，較好進行水洗及乾燥。The alkaline aqueous solution used for development is not particularly limited, but aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, and the like; amine compounds such as ethylamine, diethylamine, and dimethylethanolamine can be used Aqueous solution; tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxy Ethylanilines and the aqueous solutions of para-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate. An antifoaming agent or a surfactant may be added to these aqueous solutions as necessary. After development with the alkaline aqueous solution, washing and drying are preferably performed.

烘烤條件並未特別限制，只要根據所用之彩色濾光片用感光性樹脂組成物的組成進行加熱處理即可。以往之感光性樹脂組成物，於烘烤溫度為200℃以下時，著色圖型之耐溶劑性不足，但本發明之彩色濾光片用感光性樹脂組成物即使於150℃以下之溫度進行烘烤時，亦可形成顯示充分耐溶劑性之著色圖型。因此，可降低烘烤溫度，且於高溫烘烤時可縮短處理時間，成為製造上之較大優點。基於此等見解，烘烤溫度通常為210℃以下，較好為180℃以下，更好為150℃以下，最好為120℃以下，烘烤時間通常設為10分鐘～4小時，較好為20分鐘～2小時而進行。The baking conditions are not particularly limited as long as the heat treatment is performed according to the composition of the photosensitive resin composition for a color filter to be used. In the conventional photosensitive resin composition, when the baking temperature is 200 ° C or lower, the solvent resistance of the coloring pattern is insufficient, but the photosensitive resin composition for a color filter of the present invention is baked at a temperature of 150 ° C or lower. When baking, a colored pattern showing sufficient solvent resistance can also be formed. Therefore, the baking temperature can be reduced, and the processing time can be shortened during high-temperature baking, which is a great advantage in manufacturing. Based on these findings, the baking temperature is usually below 210 ° C, preferably below 180 ° C, more preferably below 150 ° C, most preferably below 120 ° C, and the baking time is usually set between 10 minutes and 4 hours, preferably 20 minutes to 2 hours.

藉由使用彩色濾光片之黑矩陣用感光性樹脂組成物及彩色濾光片之紅色、綠色及藍色之像素用感光性樹脂組成物依序重複如上述之塗佈、曝光、顯影及烘烤，可形成期望著色圖型。又，上述中，雖說明利用光硬化之著色圖型的形成方法，但若使用替代光聚合起始劑(E)，而調配硬化促進劑及習知環氧樹脂之感光性樹脂組成物，則藉由噴墨法塗佈後，藉由加熱亦可形成期望之著色圖型。最後，於著色圖型(RGB之各像素及黑矩陣)上形成保護膜。作為保護膜並未特別限制，只要使用習知者形成即可。The photosensitive resin composition for a black matrix using a color filter and the photosensitive resin composition for red, green, and blue pixels of a color filter are sequentially repeated as described above for coating, exposure, development, and baking. Bake to form the desired coloring pattern. In the above, although a method for forming a colored pattern using photo-hardening has been described, if a photo-initiator (E) is used instead of a photo-curing accelerator and a photosensitive resin composition of a conventional epoxy resin is blended, the After coating by the inkjet method, a desired coloring pattern can also be formed by heating. Finally, a protective film is formed on the coloring pattern (the pixels of RGB and the black matrix). The protective film is not particularly limited as long as it is formed using a known person.

如此製造之彩色濾光片由於係使用感度及顯影性優異並且可賦予耐溶劑性優異之著色圖型之彩色濾光片用感光性樹脂組成物製造，故具有色變化較少之優異著色圖型。The color filter manufactured in this way is made of a photosensitive resin composition for a color filter that is excellent in sensitivity and developability and can give a coloring pattern excellent in solvent resistance, and therefore has an excellent coloring pattern with less color change. .

＜影像顯示元件＞
本發明之影像顯示元件係具備上述彩色濾光片之影像顯示元件，作為其具體例舉例為液晶顯示元件、有機EL顯示元件、CCD元件或CMOS元件等之固體攝像元件等。本發明之影像顯示元件之製造除了使用上述彩色濾光片以外，依據常用方法進行即可。例如製造液晶顯示元件時，於基板上形成上述彩色濾光片，其次依序形成電極、間隔物等。接著，於另一片基板上形成電極等，將兩者貼合並注入特定量之液晶並密封即可。

[實施例]<Image display element>
The image display device of the present invention is an image display device provided with the above-mentioned color filter, and specific examples thereof include a liquid crystal display device, an organic EL display device, a CCD device, a solid-state imaging device such as a CMOS device, and the like. The image display device of the present invention may be manufactured in accordance with a common method except that the color filter is used. For example, when manufacturing a liquid crystal display element, the above-mentioned color filter is formed on a substrate, followed by sequentially forming electrodes, spacers, and the like. Next, an electrode or the like is formed on another substrate, and the two are bonded together and injected with a specific amount of liquid crystal and sealed.

[Example]

以下，參考實施例詳細說明本發明，但本發明並未限定於該等實施例。又，該實施例中，份及百分比只要未特別指明則全部為質量基準。且，酸價及重量平均分子量之測定法如以下。
(1)酸價：依據JIS K6901 5.3測定之共聚物(A)之酸價，意指中和該共聚物(A) 1g中所含之酸性成分所需之氫氧化鉀之mg數。
(2)重量平均分子量(Mw)係使用凝膠滲透層析儀(GPC)，以下述條件測定之標準聚苯乙烯換算重量平均分子量。
管柱：Shodex(註冊商標) LF-804+LF-804(昭和電工股份有限公司製)
管柱溫度：40℃
試料：共聚物之0.2%四氫呋喃溶液
展開溶劑：四氫呋喃
檢測器：示差折射計(Shodex RI-71S) (昭和電工股份有限公司製)
流速：1mL/minHereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this example, all parts and percentages are based on mass unless otherwise specified. The methods for measuring the acid value and weight average molecular weight are as follows.
(1) Acid value: The acid value of the copolymer (A) measured in accordance with JIS K6901 5.3 means the number of mg of potassium hydroxide required to neutralize the acid component contained in 1 g of the copolymer (A).
(2) The weight average molecular weight (Mw) is a standard polystyrene equivalent weight average molecular weight measured using a gel permeation chromatography (GPC) under the following conditions.
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Corporation)
Column temperature: 40 ℃
Sample: 0.2% tetrahydrofuran solution of copolymer Development solvent: tetrahydrofuran detector: differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Corporation)
Flow rate: 1mL / min

[合成例1]
於具備攪拌裝置、滴加漏斗、冷凝器、溫度計及氣體導入管之燒瓶中，饋入175.5g丙二醇單甲醚後，邊進行氮氣置換邊攪拌，升溫至78℃。其次，分別自滴加漏斗於燒平中滴加由作為含環狀醚基之聚合性單體(b0)之128.9g之甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯及作為含酸基聚合性單體(a0)之25.8g之甲基丙烯酸所成之單體混合物、與將13.9g之2,2’-偶氮雙(2,4-二甲基戊腈)(自由基聚合起始劑)添加並溶解於54.3g丙二醇單甲醚而成者。滴加結束後，添加10.3g丙二醇單甲醚，於78℃攪拌3小時進行共聚合反應，生成共聚物，最後，對於含環狀醚基之聚合性單體(b0)100質量份，添加1質量份之SAN APRO股份有限公司製CPI-210S，獲得試料No.1之聚合物組成物(溶劑以外之成分濃度35質量%)。所得聚合物組成物稀釋至100倍左右，使用前述GPC測定之聚合物組成物中之共聚物的重量平均分子量為6,800。且，使用所得聚合物組成物，依據JIS K6901 5.3測定之聚合物組成物中之共聚物的酸價為120.5KOHmg/g。[Synthesis example 1]
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 175.5 g of propylene glycol monomethyl ether was fed, and then stirred while replacing with nitrogen, and the temperature was raised to 78 ° C. Next, from a dropping funnel, 128.9 g of methacrylic acid (3-ethyloxetane-3-yl), which is a polymerizable monomer (b0) containing a cyclic ether group, was added dropwise to the pan. A monomer mixture of a methyl ester and 25.8 g of methacrylic acid as an acid-group-containing polymerizable monomer (a0), and 13.9 g of 2,2'-azobis (2,4-dimethylpentane) Nitrile) (radical polymerization initiator) was added and dissolved in 54.3 g of propylene glycol monomethyl ether. After the dropwise addition, 10.3 g of propylene glycol monomethyl ether was added, and the copolymer was reacted by stirring at 78 ° C for 3 hours to form a copolymer. Finally, 100 parts by mass of the cyclic ether group-containing polymerizable monomer (b0) was added by 1 CPI-210S manufactured by SAN APRO Co., Ltd. in mass parts was obtained as a polymer composition of Sample No. 1 (concentration of components other than the solvent was 35% by mass). The obtained polymer composition was diluted to about 100 times, and the weight average molecular weight of the copolymer in the polymer composition measured by the aforementioned GPC was 6,800. In addition, using the obtained polymer composition, the acid value of the copolymer in the polymer composition measured in accordance with JIS K6901 5.3 was 120.5 KOHmg / g.

[合成例2～8及比較合成例1～3]
除使用表1及2記載之原料以外，以與合成例1同樣條件進行共聚合反應，獲得試料No.2～11之聚合物組成物(溶劑以外之成分濃度35質量%)。但，比較合成例2中由於未添加含環狀醚基之聚合性單體(b0)，故藉由熱及/或紫外線照射產生酸之化合物(B)之添加量與合成例3(試料No.3)同量。所得聚合物組成物中之共聚物的重量平均分子量及酸價示於表1及2。且由聚合性單體之饋入量計算之環狀醚基當量亦示於表1及2。[Synthesis Examples 2 to 8 and Comparative Synthesis Examples 1 to 3]
Except that the raw materials described in Tables 1 and 2 were used, a copolymerization reaction was performed under the same conditions as in Synthesis Example 1 to obtain polymer compositions of Sample Nos. 2 to 11 (concentration of components other than the solvent of 35% by mass). However, in Comparative Synthesis Example 2, since the polymerizable monomer (b0) containing a cyclic ether group was not added, the addition amount of the compound (B) that generates an acid by heat and / or ultraviolet irradiation was the same as that in Synthesis Example 3 (Sample No. .3) Same amount. The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Tables 1 and 2. The cyclic ether group equivalents calculated from the feed amount of the polymerizable monomer are also shown in Tables 1 and 2.

[實施例1～8及比較例1～3]
＜彩色濾光片用感光性樹脂組成物(顏料類型)之調製＞
於填充有直徑0.5mm之氧化鋯珠粒200質量份之不鏽鋼製容器中，投入C.I顏料綠36(著色劑)100質量份、丙二醇單甲醚乙酸酯(溶劑)45質量份、日本BYK CHEM股份有限公司製Disperbyk-161(分散劑)25質量份，以塗料搖晃機混合2小時予以分散，調製綠色顏料分散液。
該綠色顏料分散液與聚合物組成物、反應性稀釋劑、光聚合起始劑及溶劑以成為表3所示之調配量予以混合，調製彩色濾光片用感光性樹脂組成物。且，表3中聚合物組成物之調配量係調製聚合物組成物時所用之溶劑除外者(共聚物(A)與藉由熱及/或紫外線照射產生酸之化合物(B)之總和)，表3中溶劑之調配量係調製聚合物組成物時所用之溶劑與追加調配之丙二醇單甲醚與調製綠色顏料分散液時所用之溶劑之合計者。如由表3之調配量所知，將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量%時，共聚物(A)與藉由熱及/或紫外線照射產生酸之化合物(B)之總和為24.4質量%，反應性稀釋劑(D)為24.4質量%，光聚合起始劑(E)為1.2質量%，著色劑(F)為40.0質量%，將彩色濾光片用感光性樹脂組成物中之溶劑(C)除外之成分的總和設為100質量份時，溶劑(C)為130.2質量份。
實施例1～8之彩色濾光片用感光性樹脂組成物係分別使用試料No.1～8之聚合物組成物而調製，比較例1～3之彩色濾光片用感光性樹脂組成物係分別使用試料No.9～11之聚合物組成物而調製。[Examples 1 to 8 and Comparative Examples 1 to 3]
<Preparation of photosensitive resin composition (pigment type) for color filters>
In a stainless steel container filled with 200 parts by mass of zirconia beads with a diameter of 0.5 mm, 100 parts by mass of CI Pigment Green 36 (colorant), 45 parts by mass of propylene glycol monomethyl ether acetate (solvent), and BYK CHEM from Japan 25 parts by mass of Disperbyk-161 (dispersant), manufactured by a joint-stock company, was mixed and dispersed with a paint shaker for 2 hours to prepare a green pigment dispersion liquid.
This green pigment dispersion liquid was mixed with a polymer composition, a reactive diluent, a photopolymerization initiator, and a solvent in the blending amounts shown in Table 3 to prepare a photosensitive resin composition for a color filter. In addition, the compounding amount of the polymer composition in Table 3 is the sum of the solvents (the sum of the copolymer (A) and the compound (B) that generates an acid by heat and / or ultraviolet radiation) used when preparing the polymer composition, The amount of the solvent in Table 3 is the total of the solvent used when preparing the polymer composition and the propylene glycol monomethyl ether and the solvent used in preparing the green pigment dispersion. When the total amount of the components except the solvent (C) in the photosensitive resin composition for a color filter is 100% by mass, the copolymer (A) and heat and / The total amount of the compound (B) that generates an acid by ultraviolet or ultraviolet irradiation is 24.4% by mass, the reactive diluent (D) is 24.4% by mass, the photopolymerization initiator (E) is 1.2% by mass, and the colorant (F) is 40.0% by mass. % When the total of the components except the solvent (C) in the photosensitive resin composition for color filters is 100 parts by mass, the solvent (C) is 130.2 parts by mass.
The photosensitive resin composition systems for color filters of Examples 1 to 8 were prepared using the polymer compositions of Sample Nos. 1 to 8, respectively. The photosensitive resin composition systems for color filters of Comparative Examples 1 to 3 were prepared. The polymer compositions of Sample Nos. 9 to 11 were used for preparation.

＜彩色濾光片用感光性樹脂組成物之評價＞
(1)鹼顯影性
將實施例1～8及比較例1～3之彩色濾光片用感光性樹脂組成物分別以曝光後厚度為2.5μm之方式旋轉塗佈於5cm見方之玻璃基板(無鹼玻璃基板)上之後，於90℃加熱3分鐘，使溶劑揮發。其次，於距離塗佈膜100μm之距離配置特定之圖型光罩，介隔該光罩使塗佈膜曝光(曝光量：150mJ/cm2 )，使曝光部分光硬化。其次，將含0.1質量%之碳酸鈉之水溶液以23℃之溫度及0.3MPa之壓力進行噴霧，使未曝光部分溶解而顯影後，於100℃烘烤20分鐘而形成特定圖型。鹼顯影後之殘渣係藉由使用日立高科技(股)製電子顯微鏡S-3400觀察鹼顯影後之圖型而確認。該評價基準如以下。
○：無殘渣
×：有殘渣
鹼顯影性之評價結果示於表4。<Evaluation of photosensitive resin composition for color filters>
(1) Alkali developability The photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated on a 5 cm square glass substrate (without a thickness of 2.5 μm after exposure, respectively). Alkaline glass substrate), and then heated at 90 ° C for 3 minutes to evaporate the solvent. Next, a specific pattern mask is arranged at a distance of 100 μm from the coating film, and the coating film is exposed (exposure amount: 150 mJ / cm 2 ) through the mask to harden the exposed portion. Next, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C. and a pressure of 0.3 MPa to dissolve and expose the unexposed portion, and then baked at 100 ° C. for 20 minutes to form a specific pattern. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The evaluation criteria are as follows.
○: No residue ×: Table 4 shows the evaluation results of the alkali developability with the residue.

(2)耐溶劑性之評價
將實施例1～8及比較例1～3之彩色濾光片用感光性樹脂組成物分別以烘烤後厚度為2.5μm之方式旋轉塗佈於5cm見方之玻璃基板(無鹼玻璃基板)上之後，於90℃加熱3分鐘，使溶劑揮發。其次，以波長365nm之光對塗佈膜曝光，使曝光部分光硬化後，於烘烤溫度100℃之乾燥器中放置20分鐘，製作硬化塗膜。於容量500mL之附蓋玻璃瓶中放入200mL丙二醇單甲醚乙酸酯，於80℃之條件下靜置。於其中浸漬附上述硬化塗膜之試驗片後，維持於80℃之狀態，靜置5分鐘。以分光光度計UV-1650PC(島津製作所股份有限公司製)測定試驗片於丙二醇單甲醚乙酸酯浸漬前後之顏色變化(ΔE*ab)。ΔE*ab之測定結果示於表4。ΔE*ab若為1.5以下則表示耐溶劑性優異。(2) Evaluation of Solvent Resistance The photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated on 5 cm square glass with a thickness of 2.5 μm after baking, respectively. The substrate (alkali-free glass substrate) was then heated at 90 ° C for 3 minutes to evaporate the solvent. Next, the coating film was exposed to light with a wavelength of 365 nm, and after the exposed portion was light-hardened, it was left in a dryer at a baking temperature of 100 ° C. for 20 minutes to prepare a hardened coating film. Put 500 mL of propylene glycol monomethyl ether acetate in a 500 mL capped glass bottle, and leave it at 80 ° C. After the test piece with the above-mentioned hardened coating film was immersed therein, the test piece was maintained at 80 ° C and left to stand for 5 minutes. The color change (ΔE * ab) of the test piece before and after immersion in propylene glycol monomethyl ether acetate was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). The measurement results of ΔE * ab are shown in Table 4. When ΔE * ab is 1.5 or less, it means that the solvent resistance is excellent.

(3)保存安定性之評價
將實施例1～8及比較例1～3之彩色濾光片用感光性樹脂組成物各等量計取於玻璃容器中，以不使灰塵進入之方式以鋁箔蓋住口部。其次將該等樣品分別於保持在23℃之恆溫器中靜置，測定樣品1個月後之重量平均分子量(Mw)，依據下述基準評價保存安定性。
Mw變化率(%)=100×(保存前Mw-保存後Mw)/保存前Mw
○：1個月後之Mw相對於保存前Mw之變化率為±20%以內
×：1個月後之Mw相對於保存前Mw之變化率超過±20%
保存安定性之評價結果示於表4。(3) Evaluation of storage stability The photosensitive resin compositions for color filters of Examples 1 to 8 and Comparative Examples 1 to 3 were each weighed into glass containers in an equal amount, and aluminum foil was used to prevent dust from entering. Cover the mouth. Next, these samples were allowed to stand in a thermostat maintained at 23 ° C., and the weight average molecular weight (Mw) of the samples after one month was measured, and the storage stability was evaluated according to the following criteria.
Mw change rate (%) = 100 × (Mw before saving-Mw after saving) / Mw before saving
○: The change rate of Mw after 1 month to Mw before storage is within ± 20% ×: The change rate of Mw after 1 month to Mw before storage exceeds ± 20%
The evaluation results of storage stability are shown in Table 4.

如表4所示，實施例1～8之彩色濾光片用感光性樹脂組成物係鹼顯影性、耐溶劑性及保存安定性全部良好。相對於此，比較例1～3之彩色濾光片用感光性樹脂組成物係耐溶劑性不充分，且比較例3之彩色濾光片用感光性樹脂組成物之鹼顯影性亦不充分。As shown in Table 4, the photosensitive resin composition for color filters of Examples 1 to 8 had good alkali developability, solvent resistance, and storage stability. On the other hand, the photosensitive resin composition for color filters of Comparative Examples 1 to 3 is insufficient in solvent resistance, and the alkali developability of the photosensitive resin composition for color filters of Comparative Example 3 is also insufficient.

如由以上結果所知，依據本發明，可提供顯影性良好，並且於低溫硬化條件下之耐溶劑性及保存安定性優異之彩色濾光片用感光性樹脂組成物。As is known from the above results, according to the present invention, it is possible to provide a photosensitive resin composition for a color filter that has good developability and excellent solvent resistance and storage stability under low-temperature curing conditions.

Claims (16)

一種彩色濾光片用感光性樹脂組成物，其特徵係含有：含有具有酸基之構成單位(a)及具有環狀醚基之構成單位(b)之共聚物(A)、藉由熱及/或紫外線照射產生酸之化合物(B)、溶劑(C)、反應性稀釋劑(D)、光聚合起始劑(E)及著色劑(F)。A photosensitive resin composition for a color filter, comprising: a copolymer (A) containing a constituent unit (a) having an acid group and a constituent unit (b) having a cyclic ether group; and The compound (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), and the coloring agent (F) which generate an acid by ultraviolet irradiation. 如請求項1之彩色濾光片用感光性樹脂組成物，其中前述具有酸基之構成單位(a)係源自含羧基之乙烯性不飽和化合物之構成單位。The photosensitive resin composition for a color filter according to claim 1, wherein the constituent unit (a) having an acid group is a constituent unit derived from a carboxyl group-containing ethylenically unsaturated compound. 如請求項1或2之彩色濾光片用感光性樹脂組成物，其中前述具有環狀醚基之構成單位(b)係源自選自由含環氧基之(甲基)丙烯酸酯及含氧雜環丁基之(甲基)丙烯酸酯所成之群中之至少一種的構成單位。The photosensitive resin composition for a color filter according to claim 1 or 2, wherein the constituent unit (b) having a cyclic ether group is derived from an epoxy group-containing (meth) acrylate and an oxygen-containing group. A structural unit of at least one of the group formed by heterobutyl (meth) acrylate. 如請求項1至3中任一項之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)中含有之前述具有酸基之構成單位(a)之比例為5莫耳%～40莫耳%，且前述具有環狀醚基之構成單位(b)之比例為60莫耳%～95莫耳%。The photosensitive resin composition for a color filter according to any one of claims 1 to 3, wherein the proportion of the aforementioned structural unit (a) having an acid group contained in the copolymer (A) is 5 mol% to 40 mol%, and the proportion of the aforementioned constituent unit (b) having a cyclic ether group is 60 mol% to 95 mol%. 如請求項1至3中任一項之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)進而含有源自具有乙烯性不飽和基之自由基聚合性化合物之構成單位(c)。The photosensitive resin composition for a color filter according to any one of claims 1 to 3, wherein the copolymer (A) further contains a constituent unit derived from a radical polymerizable compound having an ethylenically unsaturated group (c ). 如請求項5之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)中含有之前述具有酸基之構成單位(a)之比例為5莫耳%～60莫耳%，前述具有環狀醚基之構成單位(b)之比例為5莫耳%～70莫耳%，且前述源自具有乙烯性不飽和基之自由基聚合性化合物之構成單位(c)之比例為超過0莫耳%～80莫耳%。The photosensitive resin composition for a color filter according to claim 5, wherein the proportion of the aforementioned structural unit (a) having an acid group contained in the copolymer (A) is 5 mol% to 60 mol%. The proportion of the constituent unit (b) having a cyclic ether group is 5 mol% to 70 mol%, and the proportion of the aforementioned constituent unit (c) derived from the radical polymerizable compound having an ethylenically unsaturated group is more than 0 mol% to 80 mol%. 如請求項1至6中任一項之彩色濾光片用感光性樹脂組成物，其中前述具有酸基之構成單位(a)之酸基係羧基。The photosensitive resin composition for a color filter according to any one of claims 1 to 6, wherein the acid group-based carboxyl group having the acid group-containing constituent unit (a) described above. 如請求項1至7中任一項之彩色濾光片用感光性樹脂組成物，其中前述具有環狀醚基之構成單位(b)之環狀醚基係選自由環氧醚基及氧雜環丁基所成之群中之至少一種。The photosensitive resin composition for a color filter according to any one of claims 1 to 7, wherein the cyclic ether group of the constituent unit (b) having a cyclic ether group is selected from an epoxy ether group and an oxa group At least one of the groups formed by cyclobutyl. 如請求項1至8中任一項之彩色濾光片用感光性樹脂組成物，其中前述藉由熱及/或紫外線照射產生酸之化合物(B)相對於合成前述共聚物(A)時所用之賦予前述具有環狀醚基之構成單位(b)之聚合性單體100質量份為0.05質量份～20質量份。The photosensitive resin composition for a color filter according to any one of claims 1 to 8, wherein the compound (B) which generates an acid by heat and / or ultraviolet irradiation is used when synthesizing the copolymer (A). The 100 mass parts of polymerizable monomers which give the said structural unit (b) which has a cyclic ether group are 0.05 mass parts-20 mass parts. 如請求項1至9中任一項之彩色濾光片用感光性樹脂組成物，其中前述藉由熱及/或紫外線照射產生酸之化合物(B)係鋶鹽。The photosensitive resin composition for a color filter according to any one of claims 1 to 9, wherein the compound (B) is a sulfonium salt that generates an acid by heat and / or ultraviolet radiation. 如請求項1至10中任一項之彩色濾光片用感光性樹脂組成物，其中前述共聚物(A)之重量平均分子量為1,000～50,000且酸價為20～300KOHmg/g。The photosensitive resin composition for a color filter according to any one of claims 1 to 10, wherein the copolymer (A) has a weight average molecular weight of 1,000 to 50,000 and an acid value of 20 to 300 KOHmg / g. 如請求項1至11中任一項之彩色濾光片用感光性樹脂組成物，其中前述著色劑(F)含有顏料。The photosensitive resin composition for color filters according to any one of claims 1 to 11, wherein the colorant (F) contains a pigment. 如請求項1至12中任一項之彩色濾光片用感光性樹脂組成物，其中將前述彩色濾光片用感光性樹脂組成物中之前述溶劑(C)除外之成分的總和設為100質量%時，前述共聚物(A)與前述藉由熱及/或紫外線照射產生酸之化合物(B)之總和為1質量%～50質量%，前述反應性稀釋劑(D)為1質量%～60質量%，前述光聚合起始劑(E)為0.01質量%～15質量%，前述著色劑(F)為20質量%～80質量%，將前述彩色濾光片用感光性樹脂組成物中之前述溶劑(C)除外之成分的總和設為100質量份時，前述溶劑(C)為10質量份～800質量份。The photosensitive resin composition for a color filter according to any one of claims 1 to 12, wherein a total of components other than the solvent (C) in the photosensitive resin composition for the color filter is 100 At mass%, the sum of the copolymer (A) and the compound (B) that generates an acid by heat and / or ultraviolet radiation is 1 to 50% by mass, and the reactive diluent (D) is 1% by mass -60 mass%, the photopolymerization initiator (E) is 0.01 mass% to 15 mass%, the colorant (F) is 20 mass% to 80 mass%, and the photosensitive resin composition for a color filter is used When the total of the components except the solvent (C) is 100 parts by mass, the solvent (C) is 10 to 800 parts by mass. 一種彩色濾光片，其特徵係具有由如請求項1至13中任一項之彩色濾光片用感光性樹脂組成物之硬化物所成之著色圖型。A color filter having a coloring pattern formed of a cured product of a photosensitive resin composition for a color filter according to any one of claims 1 to 13. 一種影像顯示元件，其特徵為具備如請求項14之彩色濾光片。An image display element is provided with a color filter as claimed in claim 14. 一種彩色濾光片之製造方法，其特徵係包含下述步驟：將如請求項1至13中任一項之彩色濾光片用感光性樹脂組成物塗佈於基板上，經曝光、鹼顯影後，於150℃以下之溫度進行烘烤而形成著色圖型。A method for manufacturing a color filter, which comprises the following steps: coating the photosensitive resin composition for a color filter according to any one of claims 1 to 13 on a substrate, exposing and developing with alkali Thereafter, baking is performed at a temperature of 150 ° C or lower to form a colored pattern.
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