TW201910365A - Photosensitive resin composition, and method for producing same - Google Patents

Photosensitive resin composition, and method for producing same Download PDF

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TW201910365A
TW201910365A TW107125429A TW107125429A TW201910365A TW 201910365 A TW201910365 A TW 201910365A TW 107125429 A TW107125429 A TW 107125429A TW 107125429 A TW107125429 A TW 107125429A TW 201910365 A TW201910365 A TW 201910365A
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meth
acrylate
photosensitive resin
resin composition
group
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TW107125429A
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TWI760534B (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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour 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
    • 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
    • G03F7/09—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

Abstract

A photosensitive resin composition containing: a copolymer (A) containing a structure unit (a) having a blocked isocyanate group and a structure unit (b) having an acid radical; a hydroxyl-group-containing organic solvent (B); a reactive diluent (C); and a photopolymerization initiator (D).

Description

感光性樹脂組成物及其之製造方法Photosensitive resin composition and method of manufacturing the same

本發明係關於感光性樹脂組成物及其之製造方法、濾色器及其之製造方法，以及圖像顯示元件。The present invention relates to a photosensitive resin composition and its manufacturing method, a color filter and its manufacturing method, and an image display element.

近年來從省資源或省能源之觀點，在各種塗覆(coating)、印刷、塗料、接著劑等之領域中，廣泛使用藉由紫外線或電子線等之活性能量線而能硬化之感光性樹脂組成物。又，在印刷配線基板等之電子材料之領域中，藉由活性能量線而能硬化之感光性樹脂組成物也使用於抗焊劑或濾色器用阻劑等。並且，對能硬化之感光性樹脂組成物所要求之特性也逐漸變得多樣化且高度化，其中也要求考慮到生產性之短時間硬化性，抑制所適用之構件之熱損傷之低溫硬化性。In recent years, from the viewpoint of saving resources or energy, in various fields of coating, printing, coatings, adhesives, etc., photosensitive resins that can be hardened by active energy rays such as ultraviolet rays or electronic rays are widely used Composition. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be hardened by active energy rays are also used in solder resists, color filter resists, and the like. In addition, the characteristics required for the curable photosensitive resin composition have gradually become diversified and advanced. Among them, low-temperature curability that suppresses thermal damage to applicable components in consideration of productivity and short-term curability is also required. .

濾色器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)之畫素、形成於畫素邊界上之黑色基質，及形成於畫素及黑色基質上之保護膜所構成。具有此種構成之濾色器通常係在透明基板上依序形成黑色基質、畫素及保護膜來製造。作為畫素及黑色基質(以下，將畫素及黑色基質稱為「著色圖型」)之形成方法，已提出有各種方法。其中，以使用感光性樹脂組成物作為阻劑，重複塗佈、曝光、顯像及烘烤之光微影工法所製作之顏料／染料分散法，由於能賦予耐久性優異，且針孔等之缺陷少之著色圖型，故已成為現今之主流。The 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 on the pixel boundary, and formed on Pixels and a protective film on a black matrix. A color filter having such a structure is usually manufactured by sequentially forming a black matrix, pixels and a protective film on a transparent substrate. Various methods have been proposed as methods 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 produced by the photolithography method using the photosensitive resin composition as a resist, repeated coating, exposure, development and baking, can provide excellent durability and pinholes. Coloring patterns with few defects have become the mainstream today.

一般而言，光微影工法使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／染料分散法雖然具有上述之優點，但另一方面由於係重複形成黑色基質、R、G、B之圖型，故要求高耐熱性，且有作為能承受高烘烤溫度之著色劑，可使用之著色劑之種類亦受限等之限制，仍時常造成問題。In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. Although the pigment / dye dispersion method has the above-mentioned advantages, on the other hand, the pattern of the black matrix, R, G, and B is repeatedly formed, so high heat resistance is required, and it has a coloring agent that can withstand high baking temperatures. The types of coloring agents that can be used are also limited, which often causes problems.

專利文獻1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，而能低溫硬化且保存安定性提升之著色組成物。Patent Document 1 discloses that by using an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated bond, a compound such as a radiation-sensitive polymerization initiator, a colorant, and ethyl 3-aminobenzenesulfonate, it can be hardened at low temperature. And preserve the coloring composition with improved stability.

專利文獻2揭示藉由使用一種感光性樹脂組成物而達成能低溫硬化，該感光性樹脂組成物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反應朝向最終生成物之高分子前驅物、藉由電磁波之照射及加熱而產生鹼之特定之鹼發生劑。 [先前技術文獻] [專利文獻]Patent Document 2 discloses that low-temperature hardening can be achieved by using a photosensitive resin composition that contains a basic substance or by heating in the presence of an alkaline substance to promote the reaction toward the final product Polymer precursor, a specific alkali generator that generates alkali by irradiation and heating of electromagnetic waves. [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 Literature 1] Japanese Patent Application Publication No. 2013-68843 [Patent Literature 2] Japanese Patent Application Publication No. 2014-70148

[發明所欲解決之課題][Problems to be solved by the invention]

近年來電子紙等之可撓性顯示器漸漸普及。作為此可撓性顯示器之基板，已探討關於聚對酞酸乙二酯等之塑料基板。此基板在烘烤時具有拉伸或收縮之性質，故必須要烘烤步驟之低溫化。但，專利文獻1所達成之程度，在滿足上述要求上則為不充分。又，專利文獻2雖可提升低溫硬化性，但保存安定性卻低而難以實用化。In recent years, flexible displays such as electronic paper have gradually become popular. As a substrate for this flexible display, a plastic substrate such as polyethylene terephthalate has been discussed. This substrate has the property of stretching or shrinking during baking, so it is necessary to reduce the temperature of the baking step. However, the degree achieved by Patent Document 1 is insufficient in satisfying the above requirements. In addition, although Patent Document 2 can improve the low-temperature hardenability, the storage stability is low and it is difficult to put it into practical use.

本發明係為了解決上述課題所完成者，其目的在於提供一種顯像性及保存安定性皆為良好，且即使在低溫硬化，仍可賦予耐溶劑性優異之硬化塗膜之感光性樹脂組成物、及其之製造方法。 　　又，本發明之目的在於提供具有耐溶劑性優異之著色圖型之濾色器及其之製造方法以及具備該濾色器之圖像顯示元件。 [用以解決課題之手段]The present invention has been made to solve the above-mentioned problems, and its object is to provide a photosensitive resin composition that has good developability and storage stability, and can provide a cured coating film excellent in solvent resistance even when cured at a low temperature. , And its manufacturing method. Also, the object of the present invention is to provide a color filter having a coloring pattern excellent in solvent resistance, a method of manufacturing the same, and an image display device provided with the color filter. [Means to solve the problem]

即，本發明為如以下之[1]~[15]所示。 　　[1] 一種感光性樹脂組成物，其特徵為包含：含有具有封端異氰酸根基之構成單位(a)及具有酸基之構成單位(b)之共聚物(A)、含羥基之有機溶劑(B)、反應性稀釋劑(C)，及光聚合起始劑(D)。 　　[2] 如[1]之感光性樹脂組成物，其中前述具有封端異氰酸根基之構成單位(a)為源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位，前述含封端異氰酸根基之(甲基)丙烯酸酯之封端異氰酸根基之解離率在100℃下加熱30分後為5~99質量%。 　　[3] 如[1]或[2]之感光性樹脂組成物，其中前述具有封端異氰酸根基之構成單位(a)之封端劑為選自由丙二酸二乙酯、3,5-二甲基吡唑及甲基乙基酮肟、所成群之一種以上。 　　[4] 如[1]~[3]中任一項之感光性樹脂組成物，其中前述含羥基之有機溶劑(B)為選自由乙二醇單烷基醚、二乙二醇單烷基醚、丙二醇單烷基醚、丙二醇單芳基醚、二丙二醇單烷基醚、三丙二醇單烷基醚、3-甲氧基-1-丁醇、1,3-丙二醇單烷基醚、1,3-丁二醇單烷基醚、1,4-丁二醇單烷基醚、丙三醇單烷基醚、丙三醇二烷基醚、甲醇、乙醇、丙醇、C5-6 環烷二醇、C5-6 環烷二甲醇、乳酸乙酯及二丙酮醇所成群之一種以上。 　　[5] 如[1]~[4]中任一項之感光性樹脂組成物，其中前述具有酸基之構成單位(b)為源自不飽和羧酸之構成單位。 　　[6] 如[1]~[5]中任一項之感光性樹脂組成物，其中前述共聚物(A)含有前述具有封端異氰酸根基之構成單位(a)1~40莫耳%及前述具有酸基之構成單位(b)1~60莫耳%。 　　[7] 如[1]~[6]中任一項之感光性樹脂組成物，其中前述共聚物(A)中前述具有封端異氰酸根基之構成單位(a)與前述具有酸基之構成單位(b)之莫耳比率為10:90~50:50。 　　[8] 如[1]~[7]中任一項之感光性樹脂組成物，其中前述共聚物(A)含有：源自選自由甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙基酯、甲基丙烯酸2-[O-(1’-甲基亞丙基胺基)羧基胺基]乙基酯、丙二酸-2-[[[2-甲基-1-側氧基-2-丙烯基]氧基]乙基]胺基]羰基]-1,3二乙基酯、安息香酸-4-[[[[2-[(2-甲基-1-側氧基-2-丙烯-1-基)氧基]乙基]胺]羰基]氧基]甲基酯、安息香酸-2-[[[[2-[(2-甲基-1-氧基-2-丙烯-1-基)氧基]乙基]胺]羰基]氧基]甲基酯及2-丙烯酸-2-甲基-2-[[(3,5-二甲基苯氧基)羰基]胺]乙基酯所成群之至少一種之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自選自由環氧丙基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯及甲基(甲基)丙烯酸酯所成群之至少一種之構成單位(c)。 　　[9] 如[1]~[8]中任一項之感光性樹脂組成物，其中更含有著色劑(E)，且為濾色器用。 　　[10] 如[9]之感光性樹脂組成物，其中相對於前述共聚物(A)與前述反應性稀釋劑(C)之合計量100質量份，含有前述共聚物(A)10~100質量份、前述含羥基之有機溶劑(B)30~1,000質量份、前述反應性稀釋劑(C)超過0質量份~90質量份、前述光聚合起始劑(D)0.1~30質量份及前述著色劑(E)5~80質量份。 　　[11] 如[9]或[10]之感光性樹脂組成物，其中前述著色劑(E)包含顏料。That is, the present invention is as shown in the following [1] to [15]. [1] A photosensitive resin composition characterized by comprising: a copolymer (A) containing a constitutional unit (a) having a blocked isocyanate group and a constitutional unit (b) having an acid group, and an organic group containing a hydroxyl group Solvent (B), reactive diluent (C), and photopolymerization initiator (D). [2] The photosensitive resin composition according to [1], wherein the aforementioned constitutional unit having a blocked isocyanate group (a) is a constitutional unit derived from a (meth) acrylate containing a blocked isocyanate group, The dissociation rate of the blocked isocyanate group-containing (meth) acrylate containing blocked isocyanate group is 5 to 99% by mass after heating at 100 ° C for 30 minutes. [3] The photosensitive resin composition according to [1] or [2], wherein the blocking agent of the structural unit (a) having a blocked isocyanate group is selected from diethyl malonate, 3,5 -One or more of dimethylpyrazole and methyl ethyl ketoxime. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the hydroxyl group-containing organic solvent (B) is selected from ethylene glycol monoalkyl ether and diethylene glycol monoalkyl Ether, propylene glycol monoalkyl ether, propylene glycol monoaryl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propanediol monoalkyl ether, 1 , 3-Butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerol monoalkyl ether, glycerol dialkyl ether, methanol, ethanol, propanol, C 5-6 More than one group consisting of naphthenic diol, C 5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid. [6] The photosensitive resin composition as described in any one of [1] to [5], wherein the copolymer (A) contains the aforementioned constitutional unit having a blocked isocyanate group (a) 1 to 40 mol% And the aforementioned constitutional unit (b) having an acid group is 1 to 60 mol%. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the constitutional unit (a) having the blocked isocyanate group in the copolymer (A) and the acid group having the acid group The molar ratio of constituent unit (b) is 10: 90 ~ 50: 50. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the aforementioned copolymer (A) contains: derived from 2- (3,5-dimethylpyrazole) selected from methacrylic acid -1-yl) carbonylamino ethyl ester, methacrylic acid 2- [O- (1'-methylpropylene amino) carboxyamino] ethyl ester, malonic acid-2-[[[2 -Methyl-1-oxo-2-propenyl] oxy] ethyl] amino] carbonyl] -1,3 diethyl ester, benzoic acid-4-[[[[2-[(2- Methyl-1-oxo-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester, benzoic acid-2-[[[[2-[(2-methyl Yl-1-oxy-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5- Dimethylphenoxy) carbonyl] amine] ethyl ester of at least one constituent unit (a), (meth) acrylic acid-derived constituent unit (b), derived from the group consisting of A structural unit (c) of at least one group consisting of meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate and meth (meth) acrylate. [9] The photosensitive resin composition according to any one of [1] to [8], which further contains a colorant (E) and is used for a color filter. [10] The photosensitive resin composition according to [9], which contains 10 to 100 parts by mass of the copolymer (A) relative to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). Parts, the hydroxyl group-containing organic solvent (B) 30 to 1,000 parts by mass, the reactive diluent (C) more than 0 parts by mass to 90 parts by mass, the photopolymerization initiator (D) 0.1 to 30 parts by mass and the foregoing 5 to 80 parts by mass of colorant (E). [11] The photosensitive resin composition according to [9] or [10], wherein the colorant (E) contains a pigment.

[12] 一種濾色器，其特徵為具有由如[9]~[11]中任一項之感光性樹脂組成物之硬化物所構成之著色圖型。[12] A color filter characterized by having a colored pattern composed of a cured product of the photosensitive resin composition according to any one of [9] to [11].

[13] 一種圖像顯示元件，其特徵為具備如[12]之濾色器。[13] An image display device characterized by having a color filter as described in [12].

[14] 一種濾色器之製造方法，其特徵為包含：將如[9]~[11]中任一項之感光性樹脂組成物塗佈基板，進行曝光，鹼顯像後，在160℃以下之溫度下進行烘烤而形成著色圖型之步驟。[14] A method of manufacturing a color filter, comprising: applying a photosensitive resin composition as described in any one of [9] to [11] to a substrate, performing exposure, and after alkali development, at 160 ° C The steps of baking at the following temperature to form a coloring pattern.

[15] 一種感光性樹脂組成物之製造方法，其特徵為包含：在含羥基之有機溶劑(B)之存在下，使含封端異氰酸根基之(甲基)丙烯酸酯與不飽和羧酸進行共聚合反應而合成共聚物(A)，其次，配合反應性稀釋劑(C)及光聚合起始劑(D)之步驟。 [發明之效果][15] A method for manufacturing a photosensitive resin composition, characterized by comprising: in the presence of a hydroxyl-containing organic solvent (B), a blocked isocyanate group-containing (meth) acrylate and an unsaturated carboxyl group The acid undergoes a copolymerization reaction to synthesize the copolymer (A), followed by the steps of mixing the reactive diluent (C) and the photopolymerization initiator (D). [Effect of invention]

根據本發明，可提供顯像性及保存安定性皆為良好，即使在低溫下硬化仍形成耐溶劑性優異之硬化塗膜之感光性樹脂組成物，及其之製造方法。 　　又，根據本發明，可提供具有耐溶劑性優異之著色圖型之濾色器及其之製造方法以及具備該濾色器之圖像顯示元件。According to the present invention, it is possible to provide a photosensitive resin composition that has both good developability and storage stability, and forms a cured coating film excellent in solvent resistance even when cured at a low temperature, and a method for manufacturing the same. Furthermore, according to the present invention, a color filter having a coloring pattern excellent in solvent resistance, a method of manufacturing the same, and an image display device including the color filter can be provided.

＜感光性樹脂組成物＞ 　　本發明之感光性樹脂組成物，其特徵為包含：含有具有封端異氰酸根基之構成單位(a)及具有酸基之構成單位(b)之共聚物(A)、含羥基之有機溶劑(B)、反應性稀釋劑(C)，及光聚合起始劑(D)。<Photosensitive resin composition> The photosensitive resin composition of the present invention is characterized by comprising: a copolymer (A) containing a constitutional unit (a) having a blocked isocyanate group and a constitutional unit (b) having an acid group ), Hydroxyl-containing organic solvent (B), reactive diluent (C), and photopolymerization initiator (D).

＜共聚物(A)＞ ＜具有封端異氰酸根基之構成單位(a)＞ 　　共聚物(A)所含有之具有封端異氰酸根基之構成單位(a)為源自含封端異氰酸根基之單體之構成單位。作為該單體，具有乙烯性不飽和鍵與封端異氰酸根基之單體等，可舉出例如，將分子中具有乙烯基、(甲基)丙烯醯氧基等之異氰酸酯化合物中之異氰酸根基，以封端劑進行封端化而成之化合物。異氰酸酯化合物與封端劑之反應無論有無溶劑之存在皆可進行。在使用溶劑之情況，則有必要使用對異氰酸根基為惰性之溶劑。在封端化反應之際，可使用錫、鋅、鉛等之有機金屬鹽、3級胺等作為觸媒。反應一般係可在-20~150℃下進行，以在0~100℃下進行為佳。作為上述異氰酸酯化合物之例，可舉出如下述式(1)所示之化合物。<Copolymer (A)> <Constitutional unit with blocked isocyanate groups (a)> The structural unit (a) with blocked isocyanate groups contained in the copolymer (A) is derived from blocked isocyanates Constituent unit of monomer of cyanate group. As the monomer, a monomer having an ethylenic unsaturated bond and a blocked isocyanate group, etc., for example, the difference among isocyanate compounds having a vinyl group, (meth) acryloyloxy group, etc. in the molecule The cyanate group is a compound formed by blocking with a blocking agent. The reaction of the isocyanate compound and the blocking agent can be carried out regardless of the presence of a solvent. When using solvents, it is necessary to use solvents that are inert to isocyanate groups. In the case of capping reaction, organic metal salts such as tin, zinc, lead, etc., tertiary amine, etc. can be used as a catalyst. The reaction can generally be carried out at -20 to 150 ° C, preferably at 0 to 100 ° C. Examples of the isocyanate compound include compounds represented by the following formula (1).

上述式(1)中、R1 表示氫原子或甲基，R2 表示-CO-、-COOR3 -(在此，R3 為碳原子數1~6之伸烷基)或 -COO-R4 O-CONH-R5 -(在此，R4 為碳原子數2~6之伸烷基，R5 為可具有取代基之碳原子數2~12之伸烷基或碳原子數6~12之伸芳基)。R2 係以-COOR3 -為佳，在此R3 係以碳原子數1~4之伸烷基為佳。In the above formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents -CO-, -COOR 3- (here, R 3 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 4 O-CONH-R 5- (Here, R 4 is an alkylene group having 2 to 6 carbon atoms, R 5 is an alkylene group having 2 to 12 carbon atoms or 6 to 6 carbon atoms which may have a substituent) 12 of the aryl group). R 2 is preferably -COOR 3- , where R 3 is preferably an alkylene group having 1 to 4 carbon atoms.

作為上述式(1)所示之異氰酸酯化合物，具體地可舉出如2-異氰酸根基乙基(甲基)丙烯酸酯、2-異氰酸根基丙基(甲基)丙烯酸酯、3-異氰酸根基丙基(甲基)丙烯酸酯、2-異氰酸根基-1-甲基乙基(甲基)丙烯酸酯、2-異氰酸根基-1,1-二甲基乙基(甲基)丙烯酸酯、4-異氰酸根基環己基(甲基)丙烯酸酯、甲基丙烯醯基異氰酸酯等。又，也可使用2-羥基烷基(甲基)丙烯酸酯與二異氰酸酯化合物之等莫耳(1莫耳：1莫耳)反應生成物。作為上述2-羥基烷基(甲基)丙烯酸酯之烷基，以乙基或n-丙基為佳，以乙基為較佳。作為上述二異氰酸酯化合物，可舉出例如，六亞甲基二異氰酸酯、2,4-(或2,6-)伸甲苯基二異氰酸酯(TDI)、4,4’-二苯基甲烷二異氰酸酯(MDI)、3,5,5-三甲基-3-異氰酸根基甲基環己基異氰酸酯(IPDI)、m-(或p-)二甲苯二異氰酸酯、1,3-(或1,4-)雙(異氰酸根基甲基)環己烷、賴胺酸二異氰酸酯等。Examples of the isocyanate compound represented by the above formula (1) include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3- Isocyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl ( Methacrylates, 4-isocyanatocyclohexyl (meth) acrylates, methacryloyl isocyanates, etc. Alternatively, a reaction product of moles (1 mole: 1 mole) such as 2-hydroxyalkyl (meth) acrylate and a diisocyanate compound may be used. As the alkyl group of the above 2-hydroxyalkyl (meth) acrylate, ethyl or n-propyl is preferred, and ethyl is preferred. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolyl diisocyanate (TDI), and 4,4′-diphenylmethane diisocyanate ( MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4- ) Bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, etc.

此等異氰酸酯化合物之中，以2-異氰酸根基乙基(甲基)丙烯酸酯、2-異氰酸根基丙基(甲基)丙烯酸酯、3-異氰酸根基丙基(甲基)丙烯酸酯、2-異氰酸根基-1-甲基乙基(甲基)丙烯酸酯、2-異氰酸根基-1,1-二甲基乙基(甲基)丙烯酸酯、4-異氰酸根基環己基(甲基)丙烯酸酯及甲基丙烯醯基異氰酸酯為佳，以2-異氰酸根基乙基(甲基)丙烯酸酯及2-異氰酸根基丙基(甲基)丙烯酸酯為較佳。Among these isocyanate compounds, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (methyl) Acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanate Acid-based cyclohexyl (meth) acrylate and methacryloyl isocyanate are preferred, with 2-isocyanatoethyl (meth) acrylate and 2-isocyanatopropyl (meth) acrylate Is better.

尚且，本說明書中，標示為(甲基)丙烯酸酯者係意指可為丙烯酸酯及甲基丙烯酸酯之任意一者，又，(甲基)丙烯酸之標示係意指可為丙烯酸及甲基丙烯酸之任意一者。In addition, in this specification, those marked as (meth) acrylates mean either acrylates or methacrylates, and (meth) acrylics mean that they can be acrylics and methyls. Any of acrylic.

作為將異氰酸酯化合物中之異氰酸根基予以封端化之封端劑，可舉出例如，ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺、β-丙內醯胺等之內醯胺系；甲醇、乙醇、丙醇、丁醇、乙二醇、甲基溶纖劑、丁基溶纖劑、甲基卡必醇、苄基醇、苯基溶纖劑、糠基醇、環己醇等之醇系；酚、甲酚、2,6-茬酚、3,5-茬酚、乙基酚、o-異丙基酚、p-tert-丁基酚等之丁基酚、p-tert-辛基酚、壬基酚、二壬基酚、苯乙烯化酚、2-羥基安息香酸甲酯、4-羥基安息香酸甲酯、百里酚、p-萘酚、p-硝基酚、p-氯酚等之酚系；丙二酸二甲基、丙二酸二乙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯基丙酮等之活性亞甲基系；丁基硫醇、硫酚、tert-十二基硫醇等之硫醇系；二苯基胺、苯基萘基胺、苯胺、咔唑等之胺系；乙醯苯胺、甲氧基乙醯苯胺(Acetanisidide)、乙酸醯胺、苄醯胺等之酸醯胺系；琥珀酸醯亞胺、馬來酸醯亞胺等之酸醯亞胺系；咪唑、2-甲基咪唑、2-乙基咪唑等之咪唑系；吡唑、3,5-二甲基吡唑等之吡唑系；脲、硫脲、乙烯脲等之脲系；N-苯基胺甲酸苯基酯、2-噁唑烷酮等之胺甲酸鹽系：乙烯亞胺、聚乙烯亞胺等之亞胺系；甲醛肟、乙醛肟、乙醛肟、甲基乙基酮肟、甲基異丁基酮肟、環己酮肟等之肟系；亞硫酸氫鈉、亞硫酸氫鉀等之亞硫酸氫鹽系等。此等封端劑係可單獨使用，亦可組合2種以上使用。As the blocking agent that blocks the isocyanate group in the isocyanate compound, for example, ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propionamyl Amines such as amines; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl Alcohols such as alcohol and cyclohexanol; phenol, cresol, 2,6-cropped phenol, 3,5-cropped phenol, ethyl phenol, o-isopropylphenol, p-tert-butylphenol Phenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, P-nitrophenol, p-chlorophenol and other phenols; dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetone acetone, etc. Base system; thiol series such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; diamine, phenylnaphthylamine, aniline, carbazole, etc .; acetanilide, methoxy Acetanilides (Acetanisidide), Acetamide Acetate, Benzamide Acetamide, etc .; Amber Acetylimides such as imidate, imidate maleate, etc .; imidazoles such as imidazole, 2-methylimidazole, 2-ethylimidazole; pyrazole, 3,5-dimethylpyrazole, etc. Pyrazole series; urea series such as urea, thiourea, and ethylene urea; amine formates such as phenyl N-phenylcarbamate, 2-oxazolidinone: ethyleneimine, polyethyleneimine, etc. Imines; formaldehyde oxime, acetaldehyde oxime, acetaldehyde oxime, methyl ethyl ketoxime, methyl isobutyl ketone oxime, cyclohexanone oxime, etc .; oxime; sodium bisulfite, potassium bisulfite, etc. Bisulfite series, etc. These blocking agents can be used alone or in combination of two or more.

封端劑係保護高反應性之異氰酸根基，但藉由加熱封端異氰酸根基會解離而再生成異氰酸根基。本發明中，該異氰酸根基係與共聚物(A)或反應性稀釋劑(C)所包含之反應性官能基，即，酸基或根據希望所包含之羥基、胺基等進行反應，而形成高交聯密度之硬化物。The blocking agent protects the highly reactive isocyanate group, but the isocyanate group is dissociated by heating to block the isocyanate group, and then the isocyanate group is regenerated. In the present invention, the isocyanate group reacts with the reactive functional group contained in the copolymer (A) or the reactive diluent (C), that is, an acid group, or a hydroxyl group, an amine group, etc., as desired, And form a hardened product with high crosslink density.

在從後述之感光性樹脂組成物之低溫硬化性或保存安定性之觀點，作為賦予具有封端異氰酸根基之構成單位(a)之單體，以使用含封端異氰酸根基之(甲基)丙烯酸酯為佳。以使用含有在100℃下加熱處理30分後之該封端異氰酸根基之解離率會成為5~99質量%為佳，較佳成為8~97質量%，最佳成為10~95質量%之封端異氰酸根基之(甲基)丙烯酸酯為較佳。尚且，含封端異氰酸根基之(甲基)丙烯酸酯之封端異氰酸根基之解離率係使用，藉由HPLC分析來測量調製該含封端異氰酸根基之(甲基)丙烯酸酯之濃度為20質量%之n-辛醇溶液，對此溶液添加相當於1質量%二丁基錫月桂酸酯及相當於3質量%酚噻嗪(聚合防止劑)後，在100℃下加熱30分後之該含封端異氰酸根基之(甲基)丙烯酸酯之質量減少比例而得之值。在使用含有解離率為上述範圍之封端異氰酸根基之(甲基)丙烯酸酯時，可充分確保合成時之共聚物之安定性，可充分降低製作硬化塗膜時之烘烤溫度，且可充分確保硬化塗膜之耐溶劑性。作為含有具有此種解離率之含封端異氰酸根基之(甲基)丙烯酸酯之封端劑，可舉出如γ-丁內醯胺、1-甲氧基-2-丙醇、2,6-二甲基酚、二異丙基胺、甲基乙基酮肟、3,5-二甲基吡唑及丙二酸二乙酯。從低溫硬化性之觀點，此等封端劑之中係以丙二酸二乙酯、3,5-二甲基吡唑及甲基乙基酮肟為較佳。From the viewpoint of low-temperature hardenability or storage stability of the photosensitive resin composition described later, as the monomer endowing the constitutional unit (a) having a blocked isocyanate group, a block containing a blocked isocyanate group ( Methacrylate is preferred. The dissociation rate of the blocked isocyanate group after heat treatment at 100 ° C for 30 minutes is preferably 5 to 99% by mass, preferably 8 to 97% by mass, and most preferably 10 to 95% by mass The (meth) acrylate of the blocked isocyanate group is preferred. Furthermore, the dissociation rate of the blocked isocyanate group-containing (meth) acrylate group-blocked isocyanate group is used, and the modulation of the blocked isocyanate group-containing (meth) acrylic acid is measured by HPLC analysis. The concentration of ester is 20% by mass of n-octanol solution. After adding 1% by mass of dibutyltin laurate and 3% by mass of phenolthiazine (polymerization inhibitor) to this solution, it is heated at 100 ° C for 30 The value obtained by dividing the mass reduction ratio of the (meth) acrylate containing blocked isocyanate groups. When using a (meth) acrylate containing a blocked isocyanate group with a dissociation rate within the above range, the stability of the copolymer during synthesis can be sufficiently ensured, and the baking temperature when making a cured coating film can be sufficiently reduced, and It can fully ensure the solvent resistance of the cured coating. Examples of the blocking agent containing a blocked isocyanate group-containing (meth) acrylate having such a dissociation rate include, for example, γ-butyralamide, 1-methoxy-2-propanol, and 2 , 6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, 3,5-dimethylpyrazole and diethyl malonate. From the viewpoint of low-temperature hardenability, among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are preferred.

又，以使用含封端異氰酸根基之(甲基)丙烯酸酯之封端異氰酸根基之解離溫度為80℃以上之含封端異氰酸根基之(甲基)丙烯酸酯亦為佳。在使用解離溫度為80℃以上之含封端異氰酸根基之(甲基)丙烯酸酯時，可充分確保合成時之共聚物之安定性，且可減少後述之變性反應時不想要之交聯反應。另一方面，封端異氰酸根基之解離溫度為160℃以下時，可充分降低烘烤溫度，也可充分確保硬化塗膜之耐溶劑性。尚且，含封端異氰酸根基之(甲基)丙烯酸酯之封端異氰酸根基之解離溫度係使用，藉由HPLC分析來測量調製該含封端異氰酸根基之(甲基)丙烯酸酯之濃度為20質量%之n-辛醇溶液，對此溶液添加相當於1質量%二丁基錫月桂酸酯及相當於3質量%酚噻嗪(聚合防止劑)後，在規定溫度下進行加熱，30分後之該含封端異氰酸根基之(甲基)丙烯酸酯之質量減少比例，並將該質量減少比例成為80質量%以上之溫度作為封端異氰酸根基之解離溫度。In addition, it is also preferable to use a blocked isocyanate group-containing (meth) acrylate with a blocked isocyanate group-containing (meth) acrylate having a dissociation temperature of 80 ° C. or higher. . When using a (meth) acrylate containing a blocked isocyanate group with a dissociation temperature of 80 ° C or more, the stability of the copolymer during synthesis can be sufficiently ensured, and undesired crosslinking during the denaturation reaction described later can be reduced reaction. On the other hand, when the dissociation temperature of the blocked isocyanate group is 160 ° C. or lower, the baking temperature can be sufficiently reduced, and the solvent resistance of the cured coating film can be sufficiently ensured. Moreover, the dissociation temperature of the blocked isocyanate group-containing (meth) acrylate containing blocked isocyanate group is used, and the (meth) acrylic acid group containing the blocked isocyanate group is measured by HPLC analysis. The n-octanol solution with an ester concentration of 20% by mass is added to this solution after adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) and heating at a specified temperature After 30 minutes, the mass reduction ratio of the (meth) acrylate containing blocked isocyanate groups, and the temperature at which the mass reduction ratio becomes 80% by mass or more is taken as the dissociation temperature of the blocked isocyanate groups.

作為上述含封端異氰酸根基之(甲基)丙烯酸酯之例，可舉出如下述式(2)所示之Karenz(註冊商標)MOI-DEM(甲基丙烯醯氧基乙基異氰酸酯與丙二酸二乙酯之反應生成物，昭和電工股份有限公司製，封端異氰酸根基之解離溫度：90℃，解離率：90質量%)、下述式(3)所示之Karenz MOI-BP(甲基丙烯醯氧基乙基異氰酸酯與3,5-二甲基吡唑之反應生成物、昭和電工股份有限公司製，封端異氰酸根基之解離溫度：110℃，解離率：70質量%)、下述式(4)所示之Karenz MOI-BM(甲基丙烯醯氧基乙基異氰酸酯與甲基乙基酮肟之反應生成物，昭和電工股份有限公司製，封端異氰酸根基之解離溫度：130℃，解離率：18質量%)般之甲基丙烯酸酯及對應於該等之丙烯酸酯等。此等含封端異氰酸根基之(甲基)丙烯酸酯係可單獨使用，亦可組合2種以上使用。Examples of the (meth) acrylates containing blocked isocyanate groups include Karenz (registered trademark) MOI-DEM (methacryloxyethyl isocyanate and The reaction product of diethyl malonate, manufactured by Showa Denko Co., Ltd., dissociation temperature of blocked isocyanate group: 90 ° C, dissociation rate: 90% by mass), Karenz MOI shown by the following formula (3) -BP (reaction product of methacryloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko Co., Ltd., dissociation temperature of blocked isocyanate group: 110 ° C, dissociation rate: 70% by mass), Karenz MOI-BM (reaction product of methacryloxyethyl isocyanate and methyl ethyl ketoxime, shown by the following formula (4), manufactured by Showa Denko Co., Ltd. Dissociation temperature of cyanate group: 130 ° C, dissociation rate: 18% by mass) methacrylates, acrylates corresponding to them, etc. These (meth) acrylates containing blocked isocyanate groups can be used alone or in combination of two or more.

共聚物(A)所含有之具有封端異氰酸根基之構成單位(a)之比例並無特別限制，以1~40莫耳%為佳，較佳為2~30莫耳%，最佳為3~25莫耳%。具有封端異氰酸根基之構成單位(a)之比例為1~40莫耳%時，硬化塗膜之耐溶劑性受到改善，且共聚物(A)之保存安定性亦受到保持。The proportion of the constitutional unit (a) containing blocked isocyanate groups contained in the copolymer (A) is not particularly limited, preferably 1 to 40 mol%, preferably 2 to 30 mol%, most preferably It is 3 ~ 25 mol%. When the ratio of the constituent unit (a) having blocked isocyanate groups is 1 to 40 mol%, the solvent resistance of the cured coating film is improved, and the storage stability of the copolymer (A) is also maintained.

＜具有酸基之構成單位(b)＞ 　　共聚物(A)所含有之具有酸基之構成單位(b)為源自含有酸基之單體之構成單位(但，該當於前述具有封端異氰酸根基之構成單位(a)者除外)。作為酸基，可舉出如羧基、磺酸基、二氧磷基(phospho)等，此等之中，在容易取得之面上，以羧基為佳。作為賦予具有酸基之構成單位(b)之單體，可舉出具有聚合性不飽和鍵與酸基之單體，例如，不飽和羧酸或其酐、不飽和磺酸、不飽和膦酸等。作為較佳單體之具體例，可舉出如(甲基)丙烯酸、α-溴(甲基)丙烯酸、β-呋喃基(甲基)丙烯酸、巴豆酸、丙炔酸、肉桂酸、α-氰基肉桂酸、馬來酸、無水馬來酸、馬來酸單甲酯、馬來酸單乙酯、馬來酸單異丙酯、富馬酸、伊康酸、無水伊康酸、檸康酸、無水檸康酸等之不飽和羧酸或其酐；2-丙烯醯胺-2-甲基丙烷磺酸、tert-丁基丙烯醯胺磺酸、p-苯乙烯磺酸等之不飽和磺酸；乙烯基膦酸等之不飽和膦酸等。此等單體係可單獨使用，亦可組合2種以上使用。此等之中，從鹼顯像性優異及取得容易性之觀點，以不飽和羧酸為佳，以(甲基)丙烯酸為較佳。<Constitutional unit (b) having an acid group> The constitutional unit (b) contained in the copolymer (A) having an acid group is a constitutional unit derived from a monomer containing an acid group (however, it should be different from (Except the constituent unit of cyanate group (a)). Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphorus oxide group (phospho). Among them, a carboxyl group is preferred on a surface that is easy to obtain. As the monomer imparting the structural unit (b) having an acid group, a monomer having a polymerizable unsaturated bond and an acid group can be mentioned, for example, unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid, unsaturated phosphonic acid Wait. Specific examples of preferred monomers include (meth) acrylic acid, α-bromo (meth) acrylic acid, β-furanyl (meth) acrylic acid, crotonic acid, propionic acid, cinnamic acid, and α- Cyanocinnamic acid, maleic acid, anhydrous maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic acid anhydrous, lemon Unsaturated carboxylic acids or anhydrides of itaconic acid, anhydrous citraconic acid, etc .; 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, p-styrenesulfonic acid, etc. Saturated sulfonic acid; unsaturated phosphonic acid such as vinylphosphonic acid. These single systems can be used alone or in combination of two or more. Among these, from the viewpoint of excellent alkali developability and ease of acquisition, unsaturated carboxylic acids are preferred, and (meth) acrylic acid is preferred.

本發明中，藉由使具有酸基之構成單位(b)被包含於共聚物(A)中，而將共聚物(A)使用作為感光性材料時之鹼顯像性會受到大幅改善。In the present invention, by including the structural unit (b) having an acid group in the copolymer (A), the alkali developability when the copolymer (A) is used as a photosensitive material is greatly improved.

共聚物(A)所含有之具有酸基之構成單位(b)之比例並無特別限制，以1~60莫耳%為佳，較佳為10~50莫耳%，最佳為15~40莫耳%。具有酸基之構成單位(b)之比例為1~60莫耳%時，而能成為適宜鹼顯像之速度，且變得能形成精緻之圖型。The proportion of the constituent unit (b) having acid groups contained in the copolymer (A) is not particularly limited, preferably 1 to 60 mol%, preferably 10 to 50 mol%, and most preferably 15 to 40 Moore%. When the proportion of the constituent unit (b) having an acid group is 1 to 60 mol%, it can be suitable for the speed of alkali imaging, and it can become a delicate pattern.

共聚物(A)中，具有封端異氰酸根基之構成單位(a)與具有酸基之構成單位(b)之莫耳比率可為例如，1:99~99:1，從硬化塗膜之耐溶劑性與共聚物(A)之保存安定性之觀點，較佳為5:95~75:25，最佳為10:90~50:50。In the copolymer (A), the molar ratio of the constitutional unit (a) having a blocked isocyanate group to the constitutional unit (b) having an acid group may be, for example, 1:99 to 99: 1, from the cured coating film From the viewpoint of solvent resistance and storage stability of the copolymer (A), it is preferably 5: 95 ~ 75: 25, and most preferably 10: 90 ~ 50: 50.

＜其他構成單位(c)＞ 　　本發明中，作為共聚物(A)所含有之構成單位，除了含有具有封端異氰酸根基之構成單位(a)及具有酸基之構成單位(b)，亦可一同含有與該等能共聚合之其他構成單位(c)(但，該當於前述具有封端異氰酸根基之構成單位(a)及前述具有酸基之構成單位(b)者除外)。作為其他構成單位(c)之具體例，可舉出如具有環氧基之構成單位(c-1)、具有羥基之構成單位(c-2)、(c-1)及(c-2)以外之構成單位(c-3)等。共聚物(A)所含有之其他構成單位(c)之比例並無特別限制，以0~80莫耳%為佳，較佳為0~70莫耳%，最佳為0~60莫耳%。<Other structural units (c)> In the present invention, as the structural unit contained in the copolymer (A), in addition to the structural unit (a) having a blocked isocyanate group and the structural unit (b) having an acid group, It may also contain other constituent units (c) that can be copolymerized together (however, except for the aforementioned constituent unit having a blocked isocyanate group (a) and the aforementioned constituent unit having an acid group (b)) . Specific examples of other structural units (c) include structural units (c-1) having an epoxy group, structural units (c-2), (c-1) and (c-2) having a hydroxyl group Constituent units other than (c-3), etc. The proportion of other constituent units (c) contained in the copolymer (A) is not particularly limited, preferably 0 to 80 mol%, preferably 0 to 70 mol%, most preferably 0 to 60 mol% .

作為導入具有環氧基之構成單位(c-1)所使用之單體，可舉出如具有聚合性不飽和鍵與環氧基之單體，例如，環氧乙烷基(甲基)丙烯酸酯、環氧丙基(甲基)丙烯酸酯、2-甲基環氧丙基(甲基)丙烯酸酯、2-乙基環氧丙基(甲基)丙烯酸酯、2-環氧乙烷基乙基(甲基)丙烯酸酯、2-環氧丙氧基乙基(甲基)丙烯酸酯、3-環氧丙氧基丙基(甲基)丙烯酸酯、環氧丙氧基苯基(甲基)丙烯酸酯等之包含環氧基之(甲基)丙烯酸酯衍生物；3,4-環氧基環己基(甲基)丙烯酸酯、3,4-環氧基環己基甲基(甲基)丙烯酸酯、2-(3,4-環氧基環己基)乙基(甲基)丙烯酸酯、2-(3,4-環氧基環己基甲氧基)乙基(甲基)丙烯酸酯、3-(3,4-環氧基環己基甲氧基)丙基(甲基)丙烯酸酯等之包含含有3,4-環氧基環己烷環等之環氧基之脂環式碳環之(甲基)丙烯酸酯衍生物；包含環氧基之乙烯基醚化合物；包含環氧基之烯丙基醚化合物等。此等單體係可單獨使用，亦可組合2種以上使用。此等之中係以環氧乙烷基(甲基)丙烯酸酯、環氧丙基(甲基)丙烯酸酯、2-甲基環氧丙基(甲基)丙烯酸酯、2-乙基環氧丙基(甲基)丙烯酸酯、2-環氧乙烷基乙基(甲基)丙烯酸酯、2-環氧丙氧基乙基(甲基)丙烯酸酯、3-環氧丙氧基丙基(甲基)丙烯酸酯、環氧丙氧基苯基(甲基)丙烯酸酯等之含環氧基之(甲基)丙烯酸酯為佳，以環氧丙基(甲基)丙烯酸酯為較佳。Examples of the monomer used for introducing the structural unit (c-1) having an epoxy group include monomers having a polymerizable unsaturated bond and an epoxy group, for example, ethylene oxide (meth) acrylic acid Ester, epoxypropyl (meth) acrylate, 2-methylepoxypropyl (meth) acrylate, 2-ethylepoxypropyl (meth) acrylate, 2-oxirane Ethyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, glycidoxyphenyl (meth) (Meth) acrylate derivatives containing epoxy groups such as 3) 4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (methyl) ) Acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2- (3,4-epoxycyclohexylmethoxy) ethyl (meth) acrylate , 3- (3,4-epoxycyclohexylmethoxy) propyl (meth) acrylate, etc., including alicyclic carbons containing epoxy groups such as 3,4-epoxycyclohexane rings (Meth) acrylate derivatives of the ring; vinyl ether compounds containing epoxy groups; allyl ether compounds containing epoxy groups Wait. These single systems can be used alone or in combination of two or more. Among these, ethylene oxide (meth) acrylate, epoxypropyl (meth) acrylate, 2-methylepoxypropyl (meth) acrylate, 2-ethylepoxy Propyl (meth) acrylate, 2-oxiranylethyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3-glycidoxypropyl Epoxy-containing (meth) acrylates such as (meth) acrylates, glycidoxyphenyl (meth) acrylates, etc. are preferred, and epoxypropyl (meth) acrylates are preferred .

藉由使具有環氧基之構成單位(c-1)被包含於共聚物(A)中，而將共聚物(A)使用作為感光性材料時之耐溶劑性會受到大幅改善。By including the structural unit (c-1) having an epoxy group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

將具有環氧基之構成單位(c-1)導入於共聚物(A)時，具有環氧基之構成單位(c-1)之比例並無特別限制，以超過0莫耳%~60莫耳%為佳，較佳為超過0莫耳%~50莫耳%，最佳為超過0莫耳%~40莫耳%。When the structural unit (c-1) having an epoxy group is introduced into the copolymer (A), the ratio of the structural unit (c-1) having an epoxy group is not particularly limited, and exceeds 0 mol% to 60 mol Ear% is better, preferably more than 0 mol% to 50 mol%, and most preferably more than 0 mol% to 40 mol%.

作為導入具有羥基之構成單位(c-2)所使用之單體，可舉出如具有聚合性不飽和鍵與羥基之單體，例如，2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2,3-二羥基丙基(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、4-羥基丁基丙烯酸酯、2-丙烯醯氧基乙基琥珀酸、2-丙烯醯氧基乙基六氫酞酸、2-丙烯醯氧基乙基酞酸、2-丙烯醯氧基乙基-2-羥基乙基-酞酸等。此等單體係可單獨使用，亦可組合2種以上使用。此等之中係以2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2,3-二羥基丙基(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、4-羥基丁基丙烯酸酯等之包含羥基之(甲基)丙烯酸酯衍生物為佳，以2-羥基乙基(甲基)丙烯酸酯為較佳。Examples of the monomer used for introducing the structural unit (c-2) having a hydroxyl group include monomers having a polymerizable unsaturated bond and a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate , 4-hydroxybutyl acrylate, 2-acryloxyethyl succinic acid, 2-propenyl oxyethyl hexahydrophthalic acid, 2-propenyl oxyethyl phthalic acid, 2-propenyl oxyacrylic acid Ethyl-2-hydroxyethyl-phthalic acid and so on. These single systems can be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (Meth) acrylic acid ester, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, etc. It is preferred that the (meth) acrylic acid ester derivative containing a hydroxyl group is 2-hydroxyethyl (Meth) acrylate is preferred.

藉由使具有羥基之構成單位(c-2)被包含於共聚物(A)，而將共聚物(A)使用作為感光性材料時之耐溶劑性會受到大幅改善。By including the structural unit (c-2) having a hydroxyl group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

將具有羥基之構成單位(c-2)導入於共聚物(A)時，具有羥基之構成單位(c-2)之比例並無特別限制，以超過0莫耳%~50莫耳%為佳，較佳為超過0莫耳%~40莫耳%，最佳為超過0莫耳%~30莫耳%。When the constitutional unit (c-2) having a hydroxyl group is introduced into the copolymer (A), the ratio of the constitutional unit (c-2) having a hydroxyl group is not particularly limited, and it is preferably more than 0 mol% to 50 mol% , Preferably more than 0 mol% to 40 mol%, and most preferably more than 0 mol% to 30 mol%.

作為導入具有環氧基之構成單位(c-1)及具有羥基之構成單位(c-2)以外之構成單位(c-3)所使用之單體之具體例，可舉出如，苯乙烯、α-甲基苯乙烯、o-乙烯基甲苯、m-乙烯基甲苯、p-乙烯基甲苯、o-氯苯乙烯、m-氯苯乙烯、p-氯苯乙烯、o-甲氧基苯乙烯、m-甲氧基苯乙烯、p-甲氧基苯乙烯、p-硝基苯乙烯、p-氰基苯乙烯、p-乙醯基胺基苯乙烯等之芳香族乙烯基化合物；降莰烯(雙環[2.2.1]庚-2-烯)、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、四環[4.4.0.12,5 .17,10 ]十二-3-烯、8-甲基四環[4.4.0.12,5 .17,10 ]十二-3-烯、8-乙基四環[4.4.0.12,5 .17,10 ]十二-3-烯、二環戊二烯、三環[5.2.1.02,6 ]癸-8-烯、三環[5.2.1.02,6 ]癸-3-烯、三環[4.4.0.12,5 ]十一-3-烯、三環[6.2.1.01,8 ]十一-9-烯、三環[6.2.1.01,8 ]十一-4-烯、四環[4.4.0.12,5 .17,10 .01,6 ]十二-3-烯、8-甲基四環[4.4.0.12,5 .17,10 .01,6 ]十二-3-烯、8-亞乙基四環[4.4.0.12,5 .17,12 ]十二-3-烯、8-亞乙基四環[4.4.0.12,5 .17,10 .01,6 ]十二-3-烯、五環[6.5.1.13,6 .02,7 .09,13 ]十五-4-烯、五環[7.4.0.12,5 .19,12 .08,13 ]十五-3-烯等之具有降莰烯構造之環狀烯烴；丁二烯、異戊二烯、氯丁二烯等之二烯；甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、異-丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、sec-丁基(甲基)丙烯酸酯、異-丁基(甲基)丙烯酸酯、tert-丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、新戊基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、異戊基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十二基(甲基)丙烯酸酯、環戊基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、甲基環己基(甲基)丙烯酸酯、乙基環己基(甲基)丙烯酸酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、松香(甲基)丙烯酸酯、降莰基(甲基)丙烯酸酯、5-甲基降莰基(甲基)丙烯酸酯、5-乙基降莰基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基氧基乙基丙烯酸酯異莰基(甲基)丙烯酸酯、金剛烷基(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、1,1,1-三氟乙基(甲基)丙烯酸酯、全氟乙基(甲基)丙烯酸酯、全氟-n-丙基(甲基)丙烯酸酯、全氟-異丙基(甲基)丙烯酸酯、3-(N,N-二甲基胺基)丙基(甲基)丙烯酸酯、三苯基甲基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、異丙苯基(甲基)丙烯酸酯、4-苯氧基苯基(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇單(甲基)丙烯酸酯、聯苯基氧基乙基(甲基)丙烯酸酯、萘(甲基)丙烯酸酯、蒽(甲基)丙烯酸酯等之(甲基)丙烯酸酯；(甲基)丙烯酸醯胺、(甲基)丙烯酸N,N-二甲基醯胺、(甲基)丙烯酸N,N-二乙基醯胺、(甲基)丙烯酸N,N-二丙基醯胺、(甲基)丙烯酸N,N-二-異丙基醯胺、(甲基)丙烯酸蒽基醯胺等之(甲基)丙烯酸醯胺；(甲基)丙烯酸醯胺苯、(甲基)丙烯腈、丙烯醛、氯乙烯、二氯亞乙烯、氟化乙烯基、二氟亞乙烯、N-乙烯基吡咯啶酮、乙烯基吡啶、乙酸乙烯基、乙烯基甲苯等之乙烯基化合物；檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、伊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)馬來醯亞胺等之單馬來醯亞胺等。此等之中係以(甲基)丙烯酸酯為佳，以甲基(甲基)丙烯酸酯及二環戊基(甲基)丙烯酸酯為特佳。此等單體係可單獨使用，亦可組合2種以上使用。Specific examples of the monomer used for introducing the structural unit (c-1) having an epoxy group and the structural unit (c-3) other than the structural unit (c-2) having a hydroxyl group include styrene. , Α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxybenzene Aromatic vinyl compounds such as ethylene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminoaminostyrene, etc .; Camphene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 2,5.1.10 ] Dodec -3-ene, 8-methyltetracyclo [4.4.0.1 2,5.1.10 ] Dodec -3-ene, 8-ethyl tetracyclo [4.4.0.1 2,5 .1 7,10] twelve-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 2,6] dec-8-ene, tricyclo [5.2.1.0 2,6 ] dec-3-ene, tricyclic [4.4.0.1 2,5 ] undec-3-ene, tricyclic [6.2.1.0 1,8 ] undec-9-ene, tricyclic [6.2.1.0 1,8] undec-4-ene, tetracyclo [4.4.0.1 2,5 .1 7,10 .0 1,6] twelve-3-ene, 8-methyl-tetracyclo [4.4.0.1 2, 5.1 1,6 .0 7,10] Di-3-ene, 8-ethylidene tetracyclo [4.4.0.1 2,5 .1 7,12] twelve-3-ene, 8-ethylidene tetracyclo [4.4.0.1 2,5 .1 7 , 10 .0 1,6 ] dodec-3-ene, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13 ] penta-4-ene, pentacyclo [7.4.0.1 2, 5.1 9,12 .0 8,13] pentadec-3-ene, etc. having norbornene structure of the cyclic olefin; butadiene, isoprene, chloroprene, etc. diene; methyl (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec -Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate , Benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, ten Diyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (A ) Acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (Meth) acrylate, perfluoro-isopropyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, triphenylmethyl (methyl ) Acrylate, phenyl (meth) acrylate, cumene (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, phenoxyethyl (meth) acrylate, Phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, biphenyloxyethyl (meth) acrylate, naphthalene (methyl) (Meth) acrylate such as acrylate, anthracene (meth) acrylate, etc .; (meth) acrylic acid amide , (Meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) Acrylic acid (meth) acrylate such as N, N-di-isopropylamide, (meth) acrylic acid anthracenamide; acrylic acid (meth) acrylate, (meth) acrylonitrile, acrolein , Vinyl chloride, vinylidene chloride, fluorinated vinyl, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene and other vinyl compounds; diethyl citraconic acid , Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl iconate; N-phenylmaleimide, N-cyclohexylmaleimide , N-lauryl maleimide, N- (4-hydroxyphenyl) maleimide, monomaleimide, etc. Among them, (meth) acrylate is preferred, and meth (meth) acrylate and dicyclopentyl (meth) acrylate are particularly preferred. These single systems can be used alone or in combination of two or more.

＜共聚物(A)之製造方法＞ 　　製造共聚物(A)之際所使用之含封端異氰酸根基之單體(a0)及含酸基之單體(b0)之比例並無特別限制，以(a0) 1~40莫耳%及(b0)1~60莫耳%為佳，較佳為(a0)2~30莫耳%及(b0)10~50莫耳%，最佳為(a0)3~25莫耳%及(b0)15~40莫耳%。共聚物(A)在更含其他構成單位(c)時，製造共聚物(A)之際所使用之含封端異氰酸根基之單體(a0)、含酸基之單體(b0)及其他單體(c0)之比例係以(a0)1~40莫耳%、(b0) 1~60莫耳%及(c0)超過0莫耳%~80莫耳%為佳，較佳為(a0) 2~30莫耳%、(b0)10~50莫耳%及(c0)超過0莫耳%~70莫耳%，最佳為(a0)3~25莫耳%、(b0)15~40莫耳%及(c0)超過0莫耳%~60莫耳%。<Production method of copolymer (A)> The ratio of the blocked isocyanate group-containing monomer (a0) and the acid group-containing monomer (b0) used in the production of the copolymer (A) is not particularly limited , Preferably (a0) 1 ~ 40 mol% and (b0) 1 ~ 60 mol%, preferably (a0) 2-30 mol% and (b0) 10-50 mol%, the best is (a0) 3 to 25 mol% and (b0) 15 to 40 mol%. When the copolymer (A) further contains other structural units (c), the blocked isocyanate group-containing monomer (a0) and the acid group-containing monomer (b0) used when manufacturing the copolymer (A) The ratio of (c0) and other monomers is preferably (a0) 1-40 mol%, (b0) 1-60 mol% and (c0) more than 0 mol% -80 mol%, preferably (a0) 2 to 30 mol%, (b0) 10 to 50 mol% and (c0) more than 0 mol% to 70 mol%, the best is (a0) 3 to 25 mol%, (b0) 15 to 40 mol% and (c0) more than 0 mol% to 60 mol%.

含封端異氰酸根基之單體(a0)、含酸基之單體(b0)、及其他單體(c0)之共聚合反應係可依據該技術領域中公知之自由基聚合方法，在聚合溶劑之存在下或不存在下進行，但從能防止異常聚合且使聚合反應安定進行之觀點，以在後述之含羥基之有機溶劑(B)之存在下進行為佳。藉由在含羥基之有機溶劑(B)之存在下實施共聚合反應，封端異氰酸根基即使解離產生異氰酸根基，異氰酸根基與含羥基之有機溶劑(B)之羥基會進行反應而防止異常聚合。認為在藉此而得之共聚物(A)中，將異氰酸根基予以封閉之封端劑之一部分係被含羥基之有機溶劑(B)所取代。例如，使該等單體溶解於含羥基之有機溶劑(B)後，對該溶液添加聚合起始劑，以50~100℃實施經過1~20小時之聚合反應即可。於此之際，在含封端異氰酸根基之單體(a0)之封端異氰酸根基會進行解離之溫度下進行聚合反應時，由於封端異氰酸根基解離所生成之異氰酸根基會與酸基反應而產生凝膠，故以在低於封端異氰酸根基解離溫度之溫度，較佳係以在低過於封端異氰酸根基之解離溫度20~50℃程度之溫度下進行聚合為佳。The copolymerization of monomers containing blocked isocyanate groups (a0), monomers containing acid groups (b0), and other monomers (c0) can be based on free radical polymerization methods known in the art. It is carried out in the presence or absence of a solvent, but from the viewpoint of preventing abnormal polymerization and stabilizing the polymerization reaction, it is preferably carried out in the presence of a hydroxyl-containing organic solvent (B) described later. By carrying out the copolymerization reaction in the presence of a hydroxyl-containing organic solvent (B), even if the blocked isocyanate group is dissociated to generate an isocyanate group, the isocyanate group and the hydroxyl group of the hydroxyl-containing organic solvent (B) will proceed Reaction to prevent abnormal polymerization. It is considered that in the copolymer (A) thus obtained, a part of the blocking agent that blocks the isocyanate group is replaced with a hydroxyl group-containing organic solvent (B). For example, after dissolving these monomers in an organic solvent (B) containing a hydroxyl group, a polymerization initiator may be added to the solution, and the polymerization reaction may be carried out at 50 to 100 ° C for 1 to 20 hours. On this occasion, when the blocked isocyanate group-containing monomer (a0) containing blocked isocyanate group will undergo dissociation at a temperature at which the polymerization reaction proceeds, the isocyanate generated by the dissociation of the blocked isocyanate group is generated. The acid radicals will react with the acid radicals to produce a gel, so at a temperature lower than the dissociation temperature of the blocked isocyanate group, preferably at a temperature lower than the dissociation temperature of the blocked isocyanate group by 20-50 ° C The polymerization is preferably carried out at a temperature.

又，作為能使用於此共聚合反應之聚合起始劑，並無特別限定，可舉出例如，偶氮二異丁腈、偶氮二異戊腈、過酸化苄醯基、t-丁基過氧基-2-乙基己酸酯等。此等聚合起始劑係可單獨使用，亦可組合2種以上使用。聚合起始劑之使用量在將單體之總投入量設成100質量份時，一般為0.5~20質量份，較佳為1.0~10質量份。In addition, the polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, peracidated benzyl and t-butyl Peroxy-2-ethylhexanoate, etc. These polymerization initiator systems may be used alone or in combination of two or more. When the use amount of the polymerization initiator is set to 100 parts by mass of the total input amount of the monomer, it is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.

共聚物(A)之聚苯乙烯換算之重量平均分子量並無特別限制，藉由上述製造方法，可取得具有較佳為1,000~50,000，更佳為3,000~40,000之重量平均分子量之共聚物(A)。共聚物(A)之重量平均分子量為1,000以上時，在使用作為感光性樹脂組成物時之鹼顯像後變得不易產生著色圖型之缺陷。另一方面，共聚物(A)之重量平均分子量為50,000以下時，顯像時間變得適宜，且可確保實用性。The weight-average molecular weight in terms of polystyrene of the copolymer (A) is not particularly limited, and the copolymer (A) having a weight-average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000 can be obtained by the above manufacturing method ). When the weight-average molecular weight of the copolymer (A) is 1,000 or more, it becomes less likely to cause color pattern defects after alkali development when used as a photosensitive resin composition. 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 can be ensured.

又，共聚物(A)之酸價(JIS K6901 5.3)係能適宜選擇，在配合至感光性樹脂組成物之情況，以20~300KOHmg／g為佳，較佳為30~200KOHmg／g之範圍。共聚物(A)之酸價為20KOHmg／g以上時，使用作為感光性樹脂組成物時之鹼顯像性變得良好。另一方面，共聚物(A)之酸價為300KOHmg／g以下時，由於對鹼顯像液之曝光部分(光硬化部分)不易溶解，故圖型形狀變得良好。In addition, the acid value (JIS K6901 5.3) of the copolymer (A) can be appropriately selected, and when blended with the photosensitive resin composition, it is preferably 20 to 300 KOHmg / g, preferably 30 to 200 KOHmg / g. . When the acid value of the copolymer (A) is 20 KOH mg / g or more, the alkali developability when used as a photosensitive resin composition becomes good. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg / g or less, the exposed portion (photocured portion) of the alkali developer is not easily dissolved, so the pattern shape becomes good.

本發明中，共聚物(A)係在分子中包含封端異氰酸根基。封端異氰酸根基之含量係適宜選擇即可，通常封端異氰酸根基當量係以成為400~6,000，較佳成為1,000~5,000之範圍內選擇。封端異氰酸根基當量係為相對於聚合物所包含之封端異氰酸根基每1莫耳之聚合物之質量，且係能藉由將聚合物之質量除以聚合物所包含之封端異氰酸根基之莫耳數而求得者(g／mol)。本發明中，封端異氰酸根基當量係從含封端異氰酸根基之單體之投入量計算而得之理論值。In the present invention, the copolymer (A) contains blocked isocyanate groups in the molecule. The content of the blocked isocyanate group may be appropriately selected. Usually, the equivalent of the blocked isocyanate group is selected to be 400 to 6,000, preferably 1,000 to 5,000. The equivalent of blocked isocyanate groups is the mass per 1 mole of polymer relative to the blocked isocyanate groups contained in the polymer, and can be obtained by dividing the mass of the polymer by the seal contained in the polymer. The number of moles of terminal isocyanate groups is obtained (g / mol). In the present invention, the equivalent of blocked isocyanate groups is a theoretical value calculated from the input amount of monomers containing blocked isocyanate groups.

＜含羥基之有機溶劑(B)＞ 　　含羥基之有機溶劑(B)只要係含有羥基之有機溶劑即可，可舉出例如，乙二醇單烷基醚、二乙二醇單烷基醚、丙二醇單烷基醚、丙二醇單芳基醚、二丙二醇單烷基醚、三丙二醇單烷基醚、3-甲氧基-1-丁醇、1,3-丙二醇單烷基醚、1,3-丁二醇單烷基醚、1,4-丁二醇單烷基醚、丙三醇單烷基醚、丙三醇二烷基醚、甲醇、乙醇、丙醇、C5-6 環烷二醇、C5-6 環烷二甲醇、乳酸乙酯及二丙酮醇等。在從硬化塗膜製作時之製膜性及取得容易性之觀點，此等之中係以乳酸乙酯、二丙酮醇、3-甲氧基-1-丁醇及丙二醇單甲基醚為佳，以丙二醇單甲基醚為特佳。此等含羥基之有機溶劑(B)係可單獨使用，亦可組合2種以上使用。<Hydroxy-containing organic solvent (B)> The hydroxy-containing organic solvent (B) may be any organic solvent containing a hydroxy group, and examples thereof include ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, propylene glycol monoaryl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propanediol monoalkyl ether, 1,3 -Butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerol monoalkyl ether, glycerol dialkyl ether, methanol, ethanol, propanol, C 5-6 cycloalkane Diol, C 5-6 cycloalkane dimethanol, ethyl lactate, diacetone alcohol, etc. From the viewpoints of film-forming properties and ease of acquisition at the time of hard coating film production, among these, ethyl lactate, diacetone alcohol, 3-methoxy-1-butanol, and propylene glycol monomethyl ether are preferred , Propylene glycol monomethyl ether is particularly preferred. These hydroxyl group-containing organic solvents (B) can be used alone or in combination of two or more.

本發明中，藉由將含有具有封端異氰酸根基之構成單位(a)及具有酸基之構成單位(b)之共聚物(A)與含羥基之有機溶劑(B)予以併用，而使感光性樹脂組成物之保存安定性受到改善。In the present invention, by using a copolymer (A) containing a structural unit (a) having a blocked isocyanate group and a structural unit (b) having an acid group and an organic solvent (B) containing a hydroxyl group, and The storage stability of the photosensitive resin composition is improved.

又，本發明之感光性樹脂組成物中，亦可併用含羥基之有機溶劑(B)以外之溶劑。In addition, in the photosensitive resin composition of the present invention, a solvent other than the hydroxyl group-containing organic solvent (B) may be used in combination.

＜反應性稀釋劑(C)＞ 　　反應性稀釋劑(C)為分子內具有至少一個能聚合之乙烯性不飽和基作為聚合性官能基之化合物，其中以具有複數聚合性官能基之化合物為佳。藉由將此種反應性稀釋劑(C)與共聚物(A)併用，而可調製黏度，使所形成之硬化物之強度，或對基材之密著性提升。<Reactive diluent (C)> Reactive diluent (C) 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 . By using this reactive diluent (C) in combination with the copolymer (A), the viscosity can be adjusted to increase the strength of the hardened product formed or the adhesion to the substrate.

作為使用當作反應性稀釋劑(C)之單官能單體，可舉出如(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(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基-2-羥基丙基酞酸酯、丙三醇單(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、環氧丙基(甲基)丙烯酸酯、2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、酞酸衍生物之半(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；乙酸乙烯基酯、丙酸乙烯基酯等之羧酸酯類等。又，此等單體係可單獨使用，亦可組合2種以上使用。Examples of the monofunctional monomer used as the reactive diluent (C) include (meth) acrylamide, hydroxymethyl (meth) acrylamide, and methoxymethyl (meth) acryl. Acetylamine, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (methyl ) Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2 -Hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, epoxypropyl (meth) acrylate, 2,2,2-trifluoroethane (Meth) acrylates such as (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, half (meth) acrylates of phthalic acid derivatives; benzene Aromatic vinyl compounds such as ethylene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, etc .; Carboxylic acid esters such as vinyl acid ester and vinyl propionate. In addition, these single systems may be used alone or in combination of two or more.

作為使用當作反應性稀釋劑(C)之多官能單體，可舉出如乙二醇二(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、丙三醇二(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、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、乙二醇二環氧丙基醚二(甲基)丙烯酸酯、二乙二醇二環氧丙基醚二(甲基)丙烯酸酯、酞酸二環氧丙基酯二(甲基)丙烯酸酯、丙三醇三丙烯酸酯、丙三醇聚環氧丙基醚聚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯(即，伸甲苯基二異氰酸酯)、三甲基六亞甲基二異氰酸酯與六亞甲基二異氰酸酯等與2-羥基乙基(甲基)丙烯酸酯之反應物、參(羥基乙基)異三聚氰酸酯之三(甲基)丙烯酸酯等之(甲基)丙烯酸酯類；二乙烯基苯、酞酸二烯丙酯、二烯丙基苯膦酸酯等之芳香族乙烯基化合物類；己二酸二乙烯基等之二羧酸酯類；三烯丙基三聚氰酸酯、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多價醇與N-羥甲基(甲基)丙烯醯胺之縮合物等。此等單體係可單獨使用，亦可組合2種以上使用。Examples of the multifunctional monomer used as the reactive diluent (C) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate Group) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylenedioxide Alcohol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, propylene Triol triacrylate, glycerol polyglycidyl Ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolyl diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2- (Meth) acrylates such as hydroxyethyl (meth) acrylate reactants, tri (meth) acrylates of ginseng (hydroxyethyl) isocyanurate; divinylbenzene, phthalic acid Aromatic vinyl compounds such as diallyl ester and diallyl benzene phosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylene bis (Meth) acrylamide, (meth) acrylamide methylene ether, polyvalent alcohol and N-methylol (meth) acrylamide condensate, etc. These single systems can be used alone or in combination of two or more.

＜光聚合起始劑(D)＞ 　　作為光聚合起始劑(D)，並無特別限定，可舉出例如，安息香、安息香甲基醚、安息香乙基醚、安息香丁基醚等之安息香類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、4-(1-t-丁基二氧基-1-甲基乙基)苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙烷-1-酮、2-苄基-2-二甲基胺基-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-t-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；苯乙酮二甲基縮酮、苄基二甲基縮酮等之縮酮類；二苯甲酮、4-(1-t-丁基二氧基-1-甲基乙基)二苯甲酮、3,3’,4,4’-肆(t-丁基二氧基羰基)二苯甲酮等之二苯甲酮類；醯基膦氧化物類等。此等光聚合起始劑(D)係可單獨使用，亦可組合2種以上使用。<Photopolymerization initiator (D)> The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether. ; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl Group) Acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-propane-1-one, 2-benzyl-2-dimethylamino- Acetophenones such as 1- (4-morpholinylphenyl) butanone-1; 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone Anthraquinones; thioxanthones such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; Acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone Benzophenones such as ketones, 3,3 ', 4,4'-(t-butyldioxycarbonyl) benzophenone; acetylphosphine oxides, etc. These photopolymerization initiators (D) can be used alone or in combination of two or more.

本發明之感光性樹脂組成物除了配合上述成分，為了賦予規定之特性，亦可配合公知之耦合劑、調平劑、熱聚合禁止劑等之公知之添加劑。此等添加劑之配合量只要係在不阻礙本發明之效果範圍內，即無特別限定。In addition to the above-mentioned components, the photosensitive resin composition of the present invention may be blended with well-known additives such as a well-known coupling agent, leveling agent, and thermal polymerization inhibitor in order to impart predetermined characteristics. The blending amount of these additives is not particularly limited as long as it does not hinder the effect of the present invention.

＜濾色器用感光性樹脂組成物＞ 　　又，本發明之感光性樹脂組成物中亦可使其更含有著色劑(E)而作成濾色器用感光性樹脂組成物。<Photosensitive resin composition for color filters> In addition, the photosensitive resin composition of the present invention may further contain a colorant (E) to form a photosensitive resin composition for color filters.

著色劑(E)只要係會溶解或分散於含羥基之有機溶劑(B)者即無特別限定，可舉例如，染料或顏料等。作為染料，在從對含羥基之有機溶劑(B)或鹼顯像液之溶解性、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，以使用具有羧酸或磺酸等之酸性基之酸性染料、酸性染料與氮化合物之鹽、酸性染料之磺醯胺體等為佳。The colorant (E) is not particularly limited as long as it dissolves or disperses in the hydroxyl-containing organic solvent (B), and examples thereof include dyes and pigments. As a dye, from the viewpoint of solubility in an organic solvent (B) containing a hydroxyl group or an alkali developing solution, interaction with other components in the photosensitive resin composition, heat resistance, etc., a carboxylic acid or sulfonic acid is used. Acidic acid dyes such as acids, salts of acid dyes and nitrogen compounds, and sulfonamide bodies of acid dyes are preferred.

作為此種染料之例，可舉出如酸性茜素紫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；酸性鉻媒紫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；食用黃3及該等之衍生物等。此等之中係以偶氮系、呫噸系、蒽醌系或酞花青系之酸性染料為佳。此等染料在因應作為目的畫素之顏色係可單獨使用，亦可組合2種以上使用。Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80 , 83, 90, 92, 112, 113, 120, 129, 147; acid chromium mauve 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; edible yellow 3 and their derivatives, etc. Among these, acid dyes of azo series, xanthene series, anthraquinone series or phthalocyanine series are preferred. These dyes can be used alone or in combination of two or more in the color system corresponding to the target pixel.

作為顏料之例，可舉出如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等之藍色顏料；C.I.顏料紫1、19、23、29、32、36、38等之顏料紫色顏料；C.I.顏料綠7、36、58、59等之綠色顏料；C.I.顏料褐23、25等之褐色顏料；C.I.顏料黑1、7、碳黑、鈦黑、酸化鐵等之黑色顏料等。Examples of pigments include 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, 59, 61, 64, 65, 71, 73 and other orange pigments; 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 pigment purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and carbon Black pigments such as black, titanium black, acidified iron, etc.

此等著色劑(E)在因應作為目的畫素之顏色係可單獨使用，亦可組合2種以上使用。尚且，在因應作為目的畫素之顏色，也可組合使用上述之染料及顏料。These colorants (E) can be used alone or in combination of two or more types in the color system corresponding to the target pixel. In addition, the above dyes and pigments can also be used in combination according to the color of the target pixel.

使用顏料作為著色劑(E)時，從提升顏料分散性之觀點，也可將公知之分散劑配合於感光性樹脂組成物。作為分散劑，以使用經時之分散安定性優異之高分子分散劑為佳。作為高分子分散劑之例，可舉出如胺基甲酸酯系分散劑、聚乙烯亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙二醇二酯系分散劑、花楸丹脂肪族酯系分散劑、脂肪族變性酯系分散劑等。作為此種高分子分散劑，也可使用如以商品名EFKA(EFKA chemicals BV(EFKA)公司製)、Disperbyk(BYK-Chemie公司製)、Disparlon(楠本化成股份有限公司製)、SOLSPERSE(Zeneca公司製)等所市售者。分散劑之配合量係因應使用之顏料等之種類適宜設定即可。When a pigment is used as the colorant (E), a well-known dispersant may be added to the photosensitive resin composition from the viewpoint of improving pigment dispersibility. As the dispersant, a polymer dispersant excellent in dispersion stability with time is preferably used. Examples of the polymer dispersant include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, Huadandan aliphatic ester dispersant, aliphatic modified ester dispersant, etc. As such a polymer dispersant, for example, under the trade names EFKA (manufactured by EFKA chemicals BV (EFKA)), Disperbyk (manufactured by BYK-Chemie), Disparlon (manufactured by Nanben Chemicals Co., Ltd.), SOLSPERSE (Zeneca) System), etc. The blending amount of the dispersant can be appropriately set according to the type of pigment to be used.

濾色器用感光性樹脂組成物中之共聚物(A)、含羥基之有機溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)及著色劑(E)之配合量係相對於濾色器用感光性樹脂組成物中之共聚物(A)與反應性稀釋劑(C)之合計量100質量份而言，共聚物(A)為10~100質量份、含羥基之有機溶劑(B)為30~1,000質量份、反應性稀釋劑(C)為超過0質量份~90質量份、光聚合起始劑(D)為0.1~30質量份、著色劑(E)為5~80質量份，以共聚物(A)為20~80質量份、含羥基之有機溶劑(B)為50~800質量份、反應性稀釋劑(C)為20~80質量份、光聚合起始劑(D)為0.5~20質量份、著色劑(E)為5~70質量份為佳，較佳係共聚物(A)為30~75質量份、含羥基之有機溶劑(B)為100~700質量份、反應性稀釋劑(C)為25~70質量份、光聚合起始劑(D)為1~15質量份、著色劑(E)為10~60質量份。若為此範圍之配合量，則成為具有適當黏度之濾色器用感光性樹脂組成物。又，即便在為不包含著色劑(E)之感光性樹脂組成物之情況，共聚物(A)、含羥基之有機溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)之配合量也能適用上述之數值範圍。The blending amount of the copolymer (A), hydroxyl-containing organic solvent (B), reactive diluent (C), photopolymerization initiator (D) and coloring agent (E) in the photosensitive resin composition for color filters The copolymer (A) is 10 to 100 parts by mass relative to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C) in the photosensitive resin composition for color filters. Organic solvent (B) is 30 to 1,000 parts by mass, reactive diluent (C) is more than 0 parts by mass to 90 parts by mass, photopolymerization initiator (D) is 0.1 to 30 parts by mass, and colorant (E) is 5 to 80 parts by mass, with copolymer (A) 20 to 80 parts by mass, hydroxyl group-containing organic solvent (B) 50 to 800 parts by mass, reactive diluent (C) 20 to 80 parts by mass, photopolymerization The initiator (D) is 0.5 to 20 parts by mass, the colorant (E) is preferably 5 to 70 parts by mass, preferably the copolymer (A) is 30 to 75 parts by mass, and the hydroxyl group-containing organic solvent (B) It is 100 to 700 parts by mass, the reactive diluent (C) is 25 to 70 parts by mass, the photopolymerization initiator (D) is 1 to 15 parts by mass, and the colorant (E) is 10 to 60 parts by mass. If the amount is in this range, it will become a photosensitive resin composition for a color filter with an appropriate viscosity. Moreover, even in the case of a photosensitive resin composition that does not contain a colorant (E), the copolymer (A), the hydroxyl group-containing organic solvent (B), the reactive diluent (C), and the photopolymerization initiator ( D) The blending amount can also be applied to the above numerical range.

＜感光性樹脂組成物之製造＞ 　　本發明之感光性樹脂組成物係可藉由使用公知之混合裝置來混合上述成分而進行製造。又，亦能在含羥基之有機溶劑(B)之存在下，藉由使含封端異氰酸根基之(甲基)丙烯酸酯與不飽和羧酸進行共聚合反應，而調製出包含共聚物(A)及含羥基之有機溶劑(B)之組成物後，再混合反應性稀釋劑(C)、光聚合起始劑(D)及任意成分之著色劑(E)來進行製造。<Production of photosensitive resin composition> The photosensitive resin composition of the present invention can be produced by mixing the above-mentioned components using a known mixing device. Also, in the presence of an organic solvent (B) containing a hydroxyl group, a copolymer containing a blocked isocyanate group (meth) acrylate and an unsaturated carboxylic acid can be copolymerized to prepare a copolymer After the composition of (A) and the hydroxyl group-containing organic solvent (B), a reactive diluent (C), a photopolymerization initiator (D), and an optional coloring agent (E) are mixed to manufacture.

藉由上述操作而得之感光性樹脂組成物由於具有鹼顯像性，故作為阻劑為適宜者。感光性樹脂組成物之硬化係適宜將烘烤溫度選擇在250℃以下之範圍即可，本發明之共聚物(A)由於在低溫下之硬化性優異，故在過往之材料相比較，可降低烘烤溫度。在感光性樹脂組成物中使用顏料作為著色劑(E)之情況，烘烤溫度即便係在160℃以下，仍能取得充分之硬化性。本發明之感光性樹脂組成物由於即使降低烘烤溫度，交聯反應仍可充分地進行，故在能源消費之面較為有利。又，也變得能夠使用即便係耐熱性差之著色劑(E)或基板，且也變得能取得著色劑本身之特性，而能應用於各種之基板。基於此種見解，烘烤溫度係以設成160℃以下為佳，較佳為150℃以下。烘烤溫度之下限在根據共聚物(A)所包含之封端異氰酸根基之種類不同並不一定需要一樣，但必須為該封端異氰酸根基之解離溫度以上，通常為80℃以上，以90℃以上為佳，較佳為100℃以上。烘烤溫度變得過低時，變得難以充分改善塗膜之耐溶劑性。又，烘烤時間係可適宜選擇，通常為10分~4小時，較佳為20分~2小時。Since the photosensitive resin composition obtained by the above operation has alkali developability, it is suitable as a resist. The curing of the photosensitive resin composition is suitable for selecting the baking temperature within a range of 250 ° C or less. Since the copolymer (A) of the present invention has excellent curability at a low temperature, it can be reduced compared to the previous materials Baking temperature. When a pigment is used as the coloring agent (E) in the photosensitive resin composition, even if the baking temperature is 160 ° C or lower, sufficient hardenability can be obtained. Since the photosensitive resin composition of the present invention can sufficiently proceed the crosslinking reaction even if the baking temperature is lowered, it is more advantageous in terms of energy consumption. In addition, it becomes possible to use a coloring agent (E) or a substrate that is poor in heat resistance, and it becomes possible to obtain the characteristics of the colorant itself, and can be applied to various substrates. Based on this knowledge, the baking temperature is preferably 160 ° C or lower, preferably 150 ° C or lower. The lower limit of the baking temperature is not necessarily the same according to the type of blocked isocyanate group contained in the copolymer (A), but it must be above the dissociation temperature of the blocked isocyanate group, usually above 80 ℃ It is preferably 90 ° C or higher, preferably 100 ° C or higher. When the baking temperature becomes too low, it becomes difficult to sufficiently improve the solvent resistance of the coating film. In addition, the baking time can be appropriately selected, usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

本發明之感光性樹脂組成物適宜作為各種阻劑，尤其係適宜作為為了製造組裝在有機EL顯示器(黑色PDL用)、液晶顯示裝置、CCD或CMOS等之固體攝像元件等中之濾色器所使用之阻劑。又，本發明之感光性樹脂組成物由於會賦予耐溶劑性、低溫下之硬化特性等優異之硬化塗膜，故也能使用於各種塗覆、接著劑、印刷墨用黏合劑等。The photosensitive resin composition of the present invention is suitable as various resists, and is particularly suitable for use as a color filter for assembly in solid-state imaging devices such as organic EL displays (for black PDL), liquid crystal display devices, CCDs, and CMOSs. The use of resistance agent. In addition, the photosensitive resin composition of the present invention can be used for various coatings, adhesives, adhesives for printing inks, etc. because it provides excellent cured coating films such as solvent resistance and low-temperature curing characteristics.

本發明之感光性樹脂組成物由於可形成顯像性及保存安定性皆為良好，且即使降低圖型形成時之烘烤溫度，仍可形成耐溶劑性優異之著色圖型，故極度有作為濾色器用之感光性材料。又，本發明之感光性樹脂組成物由於係伴隨低溫硬化，故對於可撓性顯示器之發展、製造步驟之能源消費減少，及緩和所使用之著色劑之限制也能產生貢獻。The photosensitive resin composition of the present invention has good developability and storage stability, and even if the baking temperature at the time of pattern formation is lowered, a colored pattern excellent in solvent resistance can be formed, so it is extremely useful Photosensitive material for color filters. In addition, since the photosensitive resin composition of the present invention is accompanied by low-temperature curing, it can also contribute to the development of flexible displays, the reduction of energy consumption in the manufacturing process, and the relaxation of restrictions on the colorants used.

＜濾色器＞ 　　其次，說明關於具有由本發明之感光性樹脂組成物之硬化物所構成之著色圖型之濾色器。本發明之濾色器具有使用上述濾色器用感光性樹脂組成物而形成之著色圖型。濾色器通常係由基板、形成於其之上之RGB畫素、形成於個別畫素之邊界上之黑色基質，及形成於畫素與黑色基質之上之保護膜所構成。於此構成中，除了畫素及黑色基質(著色圖型)係使用上述感光性樹脂組成物所形成者，其他之構成皆可採用公知者。<Color filter> Next, a color filter having a coloring pattern composed of a cured product of the photosensitive resin composition 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. The color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed on the boundary of individual pixels, and a protective film formed on the pixels and the black matrix. In this configuration, the pixel and the black matrix (colored pattern) are formed by using the above-mentioned photosensitive resin composition, and other configurations may be well-known ones.

其次，說明關於濾色器之製造方法之一種實施形態。首先，在基板上形成著色圖型。具體而言，在基板上依序形成黑色基質及RGB之畫素。基板之材質並非係受到特別限定者，可適宜使用如玻璃基板、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 of manufacturing a color filter will be described. First, a coloring pattern is formed on the substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyimide substrates, polyamidimide substrates, polyimide substrates, and aluminum substrates can be suitably used. , Printed circuit boards, array substrates, etc.

著色圖型係可藉由光微影法來形成。具體而言，將上述之感光性樹脂組成物塗佈於基板上形成塗佈膜後，通過規定圖型之光罩來曝光塗佈膜而使曝光部分光硬化。其後，將未曝光部分以鹼水溶液進行顯像後，藉由實施烘烤，而可形成規定之著色圖型。The colored pattern can be formed by photolithography. Specifically, after the above-mentioned photosensitive resin composition is applied on a substrate to form a coating film, the coating film is exposed through a mask of a predetermined pattern to photocure the exposed portion. Thereafter, after developing the unexposed portion with an alkaline aqueous solution, a predetermined coloring pattern can be formed by baking.

作為感光性樹脂組成物之塗佈方法，並無特別限定，可舉使用如網版印刷法、輥塗法、簾塗佈法、噴霧塗佈法、旋轉塗佈法等。又，塗佈感光性樹脂組成物後，因應必要亦可藉由使用循環式烤箱、紅外線加熱器、加熱板等之加熱手段進行加熱而使含羥基之有機溶劑(B)揮發。加熱條件並無別特別限定，因應使用之感光性樹脂組成物之種類而適宜設定即可。一般係以50℃~120℃之溫度進行加熱30秒~30分即可。The coating method of the photosensitive resin composition is not particularly limited, and examples thereof include screen printing method, roll coating method, curtain coating method, spray coating method, and spin coating method. In addition, after the photosensitive resin composition is applied, the organic solvent (B) containing hydroxyl group may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, a hot plate, or the like as necessary. The heating conditions are not particularly limited, and may be appropriately set according to the type of photosensitive resin composition to be used. Generally, heating at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes is sufficient.

其次，通過負型遮罩對經形成之塗膜照射紫外線、準分子雷射光等之活性能量線而部分地進行曝光。照射之能量線量係因應感光性樹脂組成物之組成而適宜選擇即可，例如，以30~2000mJ／cm2 為佳。作為曝光所使用之光源，並無特別限定，可使用如低壓水銀燈、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 to 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 according to the composition of the photosensitive resin composition, for example, 30 to 2000 mJ / cm 2 is preferable. The light source used for exposure is not particularly limited, and for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halogen lamp, etc. can be used.

作為顯像所使用之鹼水溶液，並無特別限定，可使用如碳酸鈉、碳酸鉀、碳酸鈣、氫氧化鈉、氫氧化鉀等之水溶液；乙基胺、二乙基胺、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-甲氧基乙基苯胺及此等之硫酸鹽、鹽酸鹽或p-甲苯磺酸鹽等之p-伸苯基二胺系化合物之水溶液等。尚且，此等水溶液中因應必要亦可添加消泡劑或界面活性劑。又，以在上述之由鹼水溶液所成之顯像後，進行水洗使其乾燥為佳。The alkaline aqueous solution used for development is not particularly limited, and aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; ethylamine, diethylamine, dimethylethanolamine can be used Aqueous solutions of amine compounds such as 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-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N- Aqueous solutions of β-methoxyethylaniline and these p-phenylenediamine compounds such as sulfates, hydrochlorides or p-toluenesulfonates. Furthermore, defoamers or surfactants can be added to these aqueous solutions as necessary. In addition, it is preferable to perform washing after washing with the alkali aqueous solution described above and drying.

烘烤之條件並無特別限定，因應使用之感光性樹脂組成物之種類實施加熱處理即可。過往之感光性樹脂組成物若烘烤溫度變成200℃以下時，則著色圖型之耐溶劑性會不足，但本發明之濾色器用感光性樹脂組成物即使係在120℃以下之溫度進行烘烤時，仍能形成展現充分耐溶劑性之著色圖型。因此，可降低烘烤溫度，又，在高溫下進行烘烤時可縮短處理時間，而成為在製造上之極大優點。基於此種見解，通常將烘烤溫度設在210℃以下，以設在160℃以下，較佳作成120℃以下，通常將烘烤時間設為10分~4小時，較佳設為20分~2小時來進行。The conditions for baking are not particularly limited, and heat treatment may be performed according to the type of photosensitive resin composition to be used. When the baking temperature of the past photosensitive resin composition becomes 200 ° C or lower, the solvent resistance of the colored pattern will be insufficient, but the photosensitive resin composition for color filters of the present invention is baked even at a temperature of 120 ° C or lower When baked, it can still form a coloring pattern that exhibits sufficient solvent resistance. Therefore, the baking temperature can be reduced, and the processing time can be shortened when baking at a high temperature, which becomes a great advantage in manufacturing. Based on this insight, the baking temperature is usually set to 210 ° C or lower to 160 ° C or lower, preferably 120 ° C or lower, and the baking time is usually set to 10 minutes to 4 hours, preferably 20 minutes to It takes 2 hours.

藉由使用黑色基質用之感光性樹脂組成物，及紅色、綠色、藍色之畫素用感光性樹脂組成物，依序重複如上述之塗佈、曝光、顯像及烘烤，而可形成所欲之著色圖型。尚且，上述說明了由光硬化所成之著色圖型之形成方法，但若取代光聚合起始劑(D)，而使用配合硬化促進劑及公知之環氧樹脂而成之感光性樹脂組成物，藉由噴墨法進行塗佈後，藉由加熱亦可形成所欲之著色圖型。其次，在著色圖型(RGB之各畫素及黑色基質)上形成保護膜。作為保護膜，並無特別限定，使用公知者來形成即可。By using the photosensitive resin composition for the black matrix and the photosensitive resin composition for the red, green, and blue pixels, the coating, exposure, development, and baking as described above can be repeated in sequence. The desired color pattern. Furthermore, the above describes the formation method of the color pattern formed by photo-curing, but instead of the photo-polymerization initiator (D), a photosensitive resin composition formed by blending a hardening accelerator and a known epoxy resin is used After coating by inkjet method, the desired coloring pattern can also be formed by heating. Next, a protective film is formed on the colored pattern (RGB pixels and black matrix). The protective film is not particularly limited, and may be formed using a known one.

藉此操作而製造之濾色器由於係使用會賦予感度及顯像性皆優，並且能在低溫下硬化且耐溶劑性優異之著色圖型之感光性樹脂組成物來進行製造者，故具有顏色變化少之優異著色圖型。The color filter manufactured by this operation is manufactured by using a photosensitive resin composition of a coloring pattern that imparts excellent sensitivity and visibility, and can be cured at a low temperature and has excellent solvent resistance, so it has Excellent coloring pattern with little color change.

＜圖像顯示元件＞ 　　本發明之圖像顯示元件為具備上述濾色器之圖像顯示元件，作為其具體例，可舉出如液晶顯示元件、有機EL顯示元件、CCD元件或CMOS元件等之固體攝像元件等。本發明之圖像顯示元件之製造係除了使用上述濾色器以外，其他根據常法進行即可。例如，在製造液晶顯示元件之情況，於基板上形成上述濾色器，其次依序形成電極、間隔器等。且，在另一枚之基板上形成電極等，貼合兩者並注入規定量之液晶，進行密封即可。 [實施例]<Image display element> The image display element of the present invention is an image display element provided with the above color filter. As a specific example thereof, a liquid crystal display element, an organic EL display element, a CCD element, a CMOS element, etc. may be mentioned. Solid-state imaging elements, etc. The image display device of the present invention can be manufactured according to a conventional method except for using the above-mentioned color filter. For example, in the case of manufacturing a liquid crystal display element, the above-mentioned color filter is formed on a substrate, followed by forming electrodes, spacers, etc. in order. Furthermore, an electrode or the like is formed on the other substrate, the two are bonded together, and a predetermined amount of liquid crystal is injected and sealed. [Example]

以下，參照實施例詳細說明本發明，但本發明並非係受到該等實施例所限定者。尚且，此實施例中，份及百分比在未特別界定時，皆為質量基準。又，酸價、重量平均分子量之測量法係如以下所述。 　　(1)酸價：依據JIS K6901 5.3所測量之共聚物(A)之酸價，且係意指中和該共聚物(A)1g中所包含之酸性成分所需要之氫氧化鉀之mg數。 　　(2)重量平均分子量(Mw)係意指使用凝膠滲透層析法(GPC)，以下述條件測量而得之標準聚苯乙烯換算之重量平均分子量。 　　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 　　檢出器：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 by these examples. Moreover, in this embodiment, the parts and percentages are quality standards unless otherwise defined. The measurement method of acid value and weight average molecular weight is as follows. (1) Acid value: the acid value of the copolymer (A) measured according to JIS K6901 5.3, and means the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer (A) . (2) Weight average molecular weight (Mw) means the weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions. Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40 ℃ Sample: 0.2% tetrahydrofuran solution of the copolymer Development solvent: Tetrahydrofuran detector: differential refractometer ( Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL / min

[合成例1] 　　對具備攪拌裝置、滴下漏斗、冷凝器、溫度計及氣體導入管之燒瓶放入149.3g之丙二醇單甲基醚後，實施氮取代並同時進行攪拌，且升溫至78℃。其次，將由22.4g之二環戊基甲基丙烯酸酯、17.2g之甲基丙烯酸及50.2g之甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙基酯(Karenz MOI-BP，昭和電工股份有限公司製，封端異氰酸根基之解離率：70質量%)所構成之單體混合物，與11.2g之2,2’-偶氮雙(2,4-二甲基戊腈)(聚合起始劑)添加於62.8g之丙二醇單甲基醚乙酸酯並使其溶解，並分別將此從滴下漏斗滴入於燒瓶中。滴下結束後，以78℃攪拌3小時進行共聚合反應，使共聚物生成，而取得試料No.1之聚合物組成物(溶劑以外之成分濃度35質量%)。取得之聚合物組成物中之共聚物之重量平均分子量為9,100，酸價為121.5KOHmg／g。[Synthesis Example 1] After placing 149.3 g of propylene glycol monomethyl ether in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, nitrogen substitution was performed while stirring, and the temperature was raised to 78 ° C. Secondly, 22.4g of dicyclopentyl methacrylate, 17.2g of methacrylic acid and 50.2g of methacrylic acid 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl Ester (Karenz MOI-BP, manufactured by Showa Denko Co., Ltd., dissociation rate of blocked isocyanate group: 70% by mass), and 11.2g of 2,2'-azobis (2, 4-Dimethylvaleronitrile) (polymerization initiator) was added to 62.8 g of propylene glycol monomethyl ether acetate and dissolved, and this was dropped into the flask from the dropping funnel, respectively. After completion of the dripping, the copolymerization reaction was carried out with stirring at 78 ° C. for 3 hours to generate a copolymer, and the polymer composition of Sample No. 1 (component concentration other than solvent 35 mass%) was obtained. The weight average molecular weight of the copolymer in the obtained polymer composition was 9,100, and the acid value was 121.5KOHmg / g.

[合成例2~9及比較合成例1~2] 　　除了使用表1及2記載之原料以外，其他係在與合成例1相同之條件下進行共聚合反應，而取得試料No.2~11之聚合物組成物(溶劑以外之成分濃度35質量%)。將取得之聚合物組成物中之共聚物之重量平均分子量及酸價展示於表1及2。尚且，表1及2中，甲基丙烯酸2-[O-(1’-甲基亞丙基胺基)羧基胺基]乙基酯為昭和電工股份有限公司製Karenz MOI-BM，封端異氰酸根基之解離率：18質量%)，丙二酸-2-[[[2-甲基-1-側氧基-2-丙烯基]氧基]乙基]胺基]羰基]-1,3二乙基酯為昭和電工股份有限公司製Karenz MOI-DEM，封端異氰酸根基之解離率：90質量%，安息香酸-4-[[[[2-[(2-甲基-1-側氧基-2-丙烯-1-基)氧基]乙基]胺]羰基]氧基]甲基酯之封端異氰酸根基之解離率：40質量%，安息香酸-2-[[[[2-[(2-甲基-1-氧基-2-丙烯-1-基)氧基]乙基]胺]羰基]氧基]甲基酯之封端異氰酸根基之解離率：75質量%，2-丙烯酸-2-甲基-2-[[(3,5-二甲基苯氧基)羰基]胺]乙基酯之封端異氰酸根基之解離率：28質量%。[Synthesis Examples 2 to 9 and Comparative Synthesis Examples 1 to 2] Except for using the raw materials described in Tables 1 and 2, the others were copolymerized under the same conditions as Synthesis Example 1 to obtain sample Nos. 2 to 11. Polymer composition (component concentration other than solvent 35% by mass). The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Tables 1 and 2. Moreover, in Tables 1 and 2, 2- [O- (1'-methylpropyleneamino) carboxyamino] ethyl methacrylate is Karenz MOI-BM manufactured by Showa Denko Co., Ltd. Dissociation rate of cyanate group: 18% by mass), malonic acid-2-[[[2-methyl-1-oxo-2-propenyl] oxy] ethyl] amino] carbonyl] -1 , 3 diethyl ester is Karenz MOI-DEM manufactured by Showa Denko Co., Ltd., the dissociation rate of blocked isocyanate group: 90% by mass, benzoic acid-4-[[[[[[2-[(2-methyl- 1-Penoxy-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester Dissociation rate of blocked isocyanate group: 40% by mass, benzoic acid-2- [[[[2-[(2-methyl-1-oxy-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester blocked isocyanate group Dissociation rate: 75% by mass, dissociation rate of blocked isocyanate groups of 2-acrylic acid 2-methyl-2-[[(3,5-dimethylphenoxy) carbonyl] amine] ethyl ester: 28% by mass.

[實施例1~9及比較例1~2] ＜感光性樹脂組成物(顏料型)之調製＞ 　　藉由對填充有直徑0.5mm之氧化鋯珠200g之不銹鋼製容器投入C.I顏料綠36(著色劑)100質量份、丙二醇單甲基醚乙酸酯44.98質量份、分散劑(BYK-Chemie Japan股份有限公司製Disperbyk-161)25質量份，並以塗料振盪機(paint shaker)混合2小時使其分散，而調製成綠色顏料分散液。 　　將此綠色顏料分散液，與表3所示之其他配合成分(即，聚合物組成物、反應性稀釋劑、光聚合起始劑及溶劑)進行混合而調製成感光性樹脂組成物。個別成分之配合量係如表3所示。尚且，實施例1~9之感光性樹脂組成物係分別使用試料No.1~9之聚合物組成物進行調製，比較例1~2之感光性樹脂組成物係分別使用試料No.10~11之聚合物組成物進行調製。又，聚合物組成物之量係包括共聚物反應結束時所包含之溶劑，且各試料所包含之溶劑之量也被合算在作為配合成分之溶劑中。[Examples 1 to 9 and Comparative Examples 1 to 2] <Preparation of photosensitive resin composition (pigment type)> By adding CI Pigment Green 36 (coloring) to a stainless steel container filled with 200 g of zirconia beads with a diameter of 0.5 mm Agent) 100 parts by mass, propylene glycol monomethyl ether acetate 44.98 parts by mass, 25 parts by mass of dispersant (Disperbyk-161 manufactured by BYK-Chemie Japan Co., Ltd.), and mixed with a paint shaker for 2 hours. It is dispersed and prepared as a green pigment dispersion. This green pigment dispersion liquid was mixed with other compounding ingredients shown in Table 3 (that is, a polymer composition, a reactive diluent, a photopolymerization initiator, and a solvent) to prepare a photosensitive resin composition. The blending amount of individual components is shown in Table 3. Furthermore, the photosensitive resin compositions of Examples 1-9 were prepared using the polymer compositions of Sample Nos. 1-9, respectively, and the photosensitive resin compositions of Comparative Examples 1-2 used the Sample Nos. 10-11, respectively. The polymer composition is prepared. In addition, the amount of the polymer composition includes the solvent contained at the end of the copolymer reaction, and the amount of the solvent contained in each sample is also included in the solvent as a compounding component.

＜感光性樹脂組成物之評價＞ (1)鹼顯像性 　　分別將實施例1~9及比較例1~2之感光性樹脂組成物，以曝光後之厚度成為2.5μm之方式旋轉塗佈於5cm見方之玻璃基板(無鹼玻璃基板)上後，藉由以90℃加熱3分鐘使溶劑揮發。其次，自塗佈膜起算100μm之距離設至規定之圖型光罩，通過此光罩來曝光塗佈膜(曝光量：150mJ／cm2 )，而使曝光部分光硬化。其次，在23℃之溫度及0.3MPa之壓力下藉由將包含0.1質量%之碳酸鈉之水溶液進行噴霧，使未曝光部分溶解並進行顯像後，藉由在100℃下烘烤20分鐘而形成規定之圖型。鹼顯像後之殘渣係藉由使用(股)日立高科技製電子顯微鏡S-3400進行觀察鹼顯像後之圖型而確認者。此評價之基準係如以下所示。 　　○：無殘渣 　　× ：有殘渣 　　將鹼顯像性之評價結果展示於表4。<Evaluation of photosensitive resin composition> (1) Alkali developability The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 2 were spin-coated to a thickness of 2.5 μm after exposure to After being placed on a 5 cm square glass substrate (alkali-free glass substrate), the solvent was evaporated by heating at 90 ° C for 3 minutes. Next, a distance of 100 μm from the coating film was set to a predetermined pattern mask, and the coating film was exposed through the mask (exposure amount: 150 mJ / cm 2 ) to photocure the exposed portion. Next, by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C and a pressure of 0.3 MPa to dissolve and develop the unexposed portion, by baking at 100 ° C for 20 minutes, Form a prescribed pattern. The residue after alkali imaging was confirmed by observing the pattern after alkali imaging using the Hitachi High-Technology Electron Microscope S-3400. The criteria for this evaluation are shown below. ○: No residue ×: There is a residue. Table 4 shows the evaluation results of alkali developability.

(2)耐溶劑性之評價 　　分別將實施例1~9及比較例1~2之感光性樹脂組成物，以烘烤後之厚度成為2.5μm之方式旋轉塗佈在5cm見方之玻璃基板(無鹼玻璃基板)上後，以90℃加熱3分鐘而使溶劑揮發。其次，對塗佈膜照射波長365nm之光進行曝光，而使曝光部分光硬化後，放置於烘烤溫度100℃之乾燥器中20分鐘而製成硬化塗膜。對容量500mL之附蓋之玻璃瓶放入200mL之丙二醇單甲基醚乙酸酯，並在80℃之條件下靜置。將上述之附硬化塗膜之試驗片浸漬於其中後，在維持於80℃之狀態下靜置5分鐘。使用分光光度計UV-1650PC(股份有限公司島津製作所製)測量將試驗片浸漬於丙二醇單甲基醚乙酸酯前後之色變化(ΔE＊ ab)。將ΔE＊ ab之測量結果展示於表4。ΔE＊ ab若在1.5以下，則可謂耐溶劑性優異。(2) Evaluation of solvent resistance The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 2 were spin-coated on a 5 cm square glass substrate (no After soda glass substrate), it was heated at 90 ° C for 3 minutes to volatilize the solvent. Next, the coating film was exposed to light with a wavelength of 365 nm, and the exposed portion was photocured, and then placed in a desiccator at a baking temperature of 100 ° C for 20 minutes to form a cured coating film. Put 200mL of propylene glycol monomethyl ether acetate in a glass bottle with a capacity of 500mL with a lid and let it stand at 80 ℃. After immersing the above-mentioned test piece with a cured coating film in it, it was left to stand for 5 minutes while being maintained at 80 ° C. The color change (ΔE * ab) before and after the test piece was immersed in propylene glycol monomethyl ether acetate was measured using a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Table 4 shows the measurement results of ΔE * ab. If ΔE * ab is 1.5 or less, it can be said to be excellent in solvent resistance.

(3)保存安定性之評價 　　將合成例1~9及比較合成例1~2之共聚物分別以等量計量放入玻璃容器中，使用鋁箔以灰塵不會進入之方式將口封閉。其次，將此等試樣分別靜置於保持在23℃之恆溫器之中，測量試樣1個月後之重量平均分子量(Mw)。將1個月後之Mw之變化率展示於表5。1個月後之Mw之變化率為在20%以內，則可謂共聚物之保存安定性優異。(3) Evaluation of storage stability The copolymers of Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 2 were measured in equal amounts into glass containers, and the mouth was closed with aluminum foil so that dust would not enter. Next, these samples were separately placed in a thermostat maintained at 23 ° C, and the weight average molecular weight (Mw) of the sample after 1 month was measured. The change rate of Mw after 1 month is shown in Table 5. The change rate of Mw after 1 month is within 20%, it can be said that the storage stability of the copolymer is excellent.

由表4之結果可明白得知，使用試料No.1~9之聚合物組成物之實施例1~9之感光性樹脂組成物，在鹼顯像性及耐溶劑性上皆為良好。並且，由於共聚物之保存安定性係與配合其之感光性樹脂組成物之保存安定性具有相關性，故從表5之結果可得知使用試料No.1~9之聚合物組成物之實施例1~9之感光性樹脂組成物在保存安定性上亦可謂為良好。相對於此，使用試料No.10~11之聚合物組成物之比較例1~2之感光性樹脂組成物之保存安定性雖為良好，但使用試料No.10之聚合物組成物之比較例1之感光性樹脂組成物之耐溶劑性並不充足，又，使用試料No.11之聚合物組成物之比較例2之感光性樹脂組成物之鹼顯像性及耐溶劑性並不充足。It is clear from the results in Table 4 that the photosensitive resin compositions of Examples 1 to 9 using the polymer compositions of Sample Nos. 1 to 9 are excellent in alkali developability and solvent resistance. In addition, since the storage stability of the copolymer is related to the storage stability of the photosensitive resin composition blended with it, the results of Table 5 show that the implementation of the polymer compositions using Sample Nos. 1 to 9 The photosensitive resin compositions of Examples 1 to 9 can also be said to be good in storage stability. In contrast, the storage stability of the photosensitive resin compositions of Comparative Examples 1 to 2 using the polymer compositions of Sample Nos. 10 to 11 is good, but the comparative example of using the polymer composition of Sample No. 10 The solvent resistance of the photosensitive resin composition of 1 is insufficient, and the alkali developability and solvent resistance of the photosensitive resin composition of Comparative Example 2 using the polymer composition of Sample No. 11 are insufficient.

由以上之結果，可得知根據本發明可提供顯像性良好，並且耐溶劑性及保存安定性皆優之感光性樹脂組成物。From the above results, it can be seen that according to the present invention, it is possible to provide a photosensitive resin composition having good developability and excellent solvent resistance and storage stability.

尚且，本國際申請案係基於2017年8月3日提出申請之日本國專利申請案第2017-150502號而主張優先權者，並將該日本國專利申請案之全部內容引用至本國際申請案。Moreover, this international application is based on the Japanese Patent Application No. 2017-150502 filed on August 3, 2017 and claims priority, and the entire content of the Japanese patent application is cited in this international application .

Claims (15)

一種感光性樹脂組成物，其特徵為包含：含有具有封端異氰酸根基之構成單位(a)及具有酸基之構成單位(b)之共聚物(A)、含羥基之有機溶劑(B)、反應性稀釋劑(C)，及光聚合起始劑(D)。A photosensitive resin composition characterized by comprising: a copolymer (A) containing a constitutional unit having a blocked isocyanate group (a) and a constitutional unit having an acid group (b), and an organic solvent containing a hydroxyl group (B ), Reactive diluent (C), and photopolymerization initiator (D). 如請求項1之感光性樹脂組成物，其中前述具有封端異氰酸根基之構成單位(a)為源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位，前述含封端異氰酸根基之(甲基)丙烯酸酯之封端異氰酸根基之解離率在100℃下加熱30分後為5~99質量%。The photosensitive resin composition according to claim 1, wherein the aforementioned constitutional unit having a blocked isocyanate group (a) is a constitutional unit derived from a (meth) acrylate containing a blocked isocyanate group, and the aforementioned The dissociation rate of the blocked isocyanate group of the (meth) acrylic acid group-terminated isocyanate group is 5 to 99% by mass after heating at 100 ° C for 30 minutes. 如請求項1或2之感光性樹脂組成物，其中前述具有封端異氰酸根基之構成單位(a)之封端劑為選自由丙二酸二乙酯、3,5-二甲基吡唑及甲基乙基酮肟、4-羥基安息香酸甲酯、2-羥基安息香酸甲酯及3,5-茬酚所成群之一種以上。The photosensitive resin composition according to claim 1 or 2, wherein the blocking agent of the structural unit (a) having a blocked isocyanate group is selected from diethyl malonate, 3,5-dimethylpyridine More than one group of azole and methyl ethyl ketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate and 3,5-phenol. 如請求項1~3中任一項之感光性樹脂組成物，其中前述含羥基之有機溶劑(B)為選自由乙二醇單烷基醚、二乙二醇單烷基醚、丙二醇單烷基醚、丙二醇單芳基醚、二丙二醇單烷基醚、三丙二醇單烷基醚、3-甲氧基-1-丁醇、1,3-丙二醇單烷基醚、1,3-丁二醇單烷基醚、1,4-丁二醇單烷基醚、丙三醇單烷基醚、丙三醇二烷基醚、甲醇、乙醇、丙醇、C5-6 環烷二醇、C5-6 環烷二甲醇、乳酸乙酯及二丙酮醇所成群之一種以上。The photosensitive resin composition according to any one of claims 1 to 3, wherein the hydroxyl group-containing organic solvent (B) is selected from the group consisting of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and propylene glycol monoalkyl Ether, propylene glycol monoaryl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propanediol monoalkyl ether, 1,3-butanedi Alcohol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerol monoalkyl ether, glycerol dialkyl ether, methanol, ethanol, propanol, C 5-6 cycloalkanediol, C 5-6 naphthenic dimethanol, ethyl lactate and diacetone alcohol are more than one group. 如請求項1~4中任一項之感光性樹脂組成物，其中前述具有酸基之構成單位(b)為源自不飽和羧酸之構成單位。The photosensitive resin composition according to any one of claims 1 to 4, wherein the structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid. 如請求項1~5中任一項之感光性樹脂組成物，其中前述共聚物(A)含有前述具有封端異氰酸根基之構成單位(a)1~40莫耳%及前述具有酸基之構成單位(b)1~60莫耳%。The photosensitive resin composition according to any one of claims 1 to 5, wherein the copolymer (A) contains the constituent unit (a) having a blocked isocyanate group (a) 1 to 40 mole% and the acid group The constituent unit (b) is 1 ~ 60 mol%. 如請求項1~6中任一項之感光性樹脂組成物，其中前述共聚物(A)中前述具有封端異氰酸根基之構成單位(a)與前述具有酸基之構成單位(b)之莫耳比率為10：90~50：50。The photosensitive resin composition according to any one of claims 1 to 6, wherein the aforementioned structural unit (a) having a blocked isocyanate group and the aforementioned structural unit (b) having an acid group in the copolymer (A) The molar ratio is 10: 90 ~ 50: 50. 如請求項1~7中任一項之感光性樹脂組成物，其中前述共聚物(A)含有：源自選自由甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙基酯、甲基丙烯酸2-[O-(1’-甲基亞丙基胺基)羧基胺基]乙基酯、丙二酸-2-[[[2-甲基-1-側氧基-2-丙烯基]氧基]乙基]胺基]羰基]-1,3二乙基酯、安息香酸-4-[[[[2-[(2-甲基-1-側氧基-2-丙烯-1-基)氧基]乙基]胺]羰基]氧基]甲基酯、安息香酸-2-[[[[2-[(2-甲基-1-氧基-2-丙烯-1-基)氧基]乙基]胺]羰基]氧基]甲基酯及2-丙烯酸-2-甲基-2-[[(3,5-二甲基苯氧基)羰基]胺]乙基酯所成群之至少一種之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自選自由環氧丙基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯(dicyclopentanyl (meth)acrylate)及甲基(甲基)丙烯酸酯所成群之至少一種之構成單位(c)。The photosensitive resin composition according to any one of claims 1 to 7, wherein the aforementioned copolymer (A) contains: derived from methacrylic acid 2- (3,5-dimethylpyrazol-1-yl) Carbonylaminoethyl ester, methacrylic acid 2- [O- (1'-methylpropyleneamino) carboxyamino] ethyl ester, malonic acid-2-[[[2-methyl-1 -Penoxy-2-propenyl] oxy] ethyl] amino] carbonyl] -1,3 diethyl ester, benzoic acid-4-[[[[[[[2-methyl-1- Pendant-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1-oxy 2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester and 2-acrylic acid 2-methyl-2-[[(3,5-dimethylphenoxy Group) at least one constituent unit (a), (meth) acrylic acid-derived constituent unit (b), derived from epoxypropyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate (dicyclopentanyl (meth) acrylate) and meth (meth) acrylate at least one constituent unit (c ). 如請求項1~8中任一項之感光性樹脂組成物，其中更含有著色劑(E)，且為濾色器用。The photosensitive resin composition according to any one of claims 1 to 8, which further contains a colorant (E) and is used for a color filter. 如請求項9之感光性樹脂組成物，其中相對於前述共聚物(A)與前述反應性稀釋劑(C)之合計量100質量份，含有前述共聚物(A)10~100質量份、前述含羥基之有機溶劑(B)30~1,000質量份、前述反應性稀釋劑(C)超過0質量份~90質量份、前述光聚合起始劑(D)0.1~30質量份及前述著色劑(E)5~80質量份。The photosensitive resin composition according to claim 9, which contains 10 to 100 parts by mass of the copolymer (A) and 100 parts by mass relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (C). 30 to 1,000 parts by mass of the organic solvent containing hydroxyl group (B), the reactive diluent (C) exceeds 0 to 90 parts by mass, the photopolymerization initiator (D) 0.1 to 30 parts by mass, and the colorant ( E) 5 ~ 80 parts by mass. 如請求項9或10之感光性樹脂組成物，其中前述著色劑(E)包含顏料。The photosensitive resin composition according to claim 9 or 10, wherein the aforementioned colorant (E) contains a pigment. 一種濾色器，其特徵為具有由如請求項9~11中任一項之感光性樹脂組成物之硬化物所構成之著色圖型。A color filter characterized by having a coloring pattern composed of a cured product of the photosensitive resin composition according to any one of claims 9 to 11. 一種圖像顯示元件，其特徵為具備如請求項12之濾色器。An image display element characterized by having a color filter as in claim 12. 一種濾色器之製造方法，其特徵為包含：將如請求項9~11中任一項之感光性樹脂組成物塗佈基板，進行曝光，鹼顯像後，在160℃以下之溫度下進行烘烤而形成著色圖型之步驟。A method of manufacturing a color filter, comprising: applying a photosensitive resin composition according to any one of claims 9 to 11 to a substrate, performing exposure, and performing alkali development at a temperature below 160 ° C The step of baking to form a coloring pattern. 一種感光性樹脂組成物之製造方法，其特徵為包含：在含羥基之有機溶劑(B)之存在下，使含封端異氰酸根基之(甲基)丙烯酸酯與不飽和羧酸進行共聚合反應而合成共聚物(A)，其次，配合反應性稀釋劑(C)及光聚合起始劑(D)之步驟。A method for manufacturing a photosensitive resin composition, characterized by comprising: in the presence of an organic solvent (B) containing a hydroxyl group, a (meth) acrylate containing a blocked isocyanate group and an unsaturated carboxylic acid are copolymerized Polymerization to synthesize copolymer (A), followed by the steps of blending reactive diluent (C) and photopolymerization initiator (D).
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI827406B (en) * 2021-12-21 2023-12-21 日商力森諾科股份有限公司 Polymer emulsion and storage method thereof, two-component thermosetting resin composition using the polymer emulsion, resin cured film and coating film

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113024726B (en) * 2019-12-09 2022-09-20 乐凯华光印刷科技有限公司 Pyrazole blocked isocyanate polymer and positive printing plate containing the same
CN114846366A (en) * 2019-12-25 2022-08-02 富士胶片株式会社 Color filter, method for manufacturing color filter, solid-state imaging element, and display device
JP2022077361A (en) * 2020-11-11 2022-05-23 昭和電工株式会社 Method for producing copolymer
WO2022138173A1 (en) * 2020-12-24 2022-06-30 昭和電工株式会社 Copolymer, and method for producing said copolymer
WO2022138159A1 (en) * 2020-12-24 2022-06-30 昭和電工株式会社 Copolymer and method for producing same
CN113174016B (en) * 2021-03-01 2022-04-19 广东工业大学 Low-viscosity flexible photosensitive resin for 3D printing and preparation method and application thereof
CN113388075B (en) * 2021-06-11 2023-03-24 珠海赛纳三维科技有限公司 Composition for 3D printing, 3D printing method and device
JP7221348B1 (en) 2021-09-13 2023-02-13 東洋インキＳｃホールディングス株式会社 Photosensitive coloring composition, cured film using the same, color filter, optical filter, image display device, solid-state imaging device, and infrared sensor
CN116206800B (en) * 2023-04-28 2023-07-21 乾宇微纳技术(深圳)有限公司 Medium slurry and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5357570B2 (en) * 2009-02-24 2013-12-04 東京応化工業株式会社 Photosensitive resin composition, color filter, and liquid crystal display
JP5523919B2 (en) * 2009-08-31 2014-06-18 富士フイルム株式会社 Colored composition, colored photosensitive composition, color filter, solid-state imaging device, and liquid crystal display device
JP2011081117A (en) * 2009-10-06 2011-04-21 Toppan Printing Co Ltd Coloring composition for color filter, color filter, method for producing the color filter, and liquid crystal display device and electroluminescent display device equipped with the color filter
JP5857578B2 (en) 2011-09-22 2016-02-10 Jsr株式会社 Color filter, liquid crystal display element, and method of manufacturing color filter
JP6107030B2 (en) 2012-09-28 2017-04-05 大日本印刷株式会社 Method for producing molded body and method for curing photosensitive resin composition
TWI511986B (en) * 2013-03-13 2015-12-11 Showa Denko Kk Blocked isocyanate group-containing polymer, composition comprising same and use thereof
JP2016084464A (en) * 2014-10-24 2016-05-19 昭和電工株式会社 Curable resin composition, color filter, image display element and manufacturing method of color filter

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI827406B (en) * 2021-12-21 2023-12-21 日商力森諾科股份有限公司 Polymer emulsion and storage method thereof, two-component thermosetting resin composition using the polymer emulsion, resin cured film and coating film

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