TWI791563B - Copolymer, polymer composition, photosensitive resin composition for color filter, color filter, image display element, and method for producing a color filter - Google Patents

Copolymer, polymer composition, photosensitive resin composition for color filter, color filter, image display element, and method for producing a color filter Download PDF

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TWI791563B
TWI791563B TW107125425A TW107125425A TWI791563B TW I791563 B TWI791563 B TW I791563B TW 107125425 A TW107125425 A TW 107125425A TW 107125425 A TW107125425 A TW 107125425A TW I791563 B TWI791563 B TW I791563B
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meth
acrylate
copolymer
aforementioned
constituent unit
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TW201910367A (en
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永井英理
木下健宏
川口恭章
柳正義
倉本拓樹
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日商昭和電工股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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    • 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
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C08F220/346—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links and further oxygen
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    • 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
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    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/365—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 containing further carboxylic moieties
    • 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
    • G02F1/133514—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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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    • 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
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    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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Abstract

一種濾色器用感光性樹脂組成物，其係含有：共聚物(A)、溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)及著色劑(E)，該共聚物(A)含有：具有封端異氰酸根基之構成單位(a)、具有酸基之構成單位(b)，及具有環氧基之構成單位(c)。 A photosensitive resin composition for a color filter, which contains: a copolymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E). The substance (A) contains: a constituent unit (a) having a blocked isocyanato group, a constituent unit (b) having an acid group, and a constituent unit (c) having an epoxy group.

Description

共聚物、聚合物組成物、感光性樹脂組成物、濾色器用感光性樹脂組成物、濾色器、圖像顯示元件、及濾色器之製造方法 Copolymer, polymer composition, photosensitive resin composition, photosensitive resin composition for color filter, color filter, image display element, and method for producing color filter

本發明係關於一種新穎共聚物，含有此之濾色器用感光性樹脂組成物、濾色器、具備此之圖像顯示元件及濾色器之製造方法。 The present invention relates to a novel copolymer, a photosensitive resin composition for a color filter containing the same, a color filter, an image display device having the same, and a method for manufacturing the color filter.

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, photosensitive resins that can be cured by active energy rays such as ultraviolet rays or electron rays have been widely used in the fields of various coatings, printing, paints, adhesives, etc. Composition. In addition, in the field of electronic materials such as printed wiring boards, photosensitive resin compositions curable by active energy rays are also used in solder resists, resists for color filters, and the like. In addition, the characteristics required for the curable photosensitive resin composition are gradually becoming diversified and advanced. Among them, short-time curing performance in consideration of productivity and low-temperature curing performance that suppresses thermal damage to applicable components are also required. .

濾色器一般係由玻璃基板等之適明基板、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 made of a suitable bright substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on a transparent substrate, a black matrix formed on the border of the pixel, and a It is composed of a protective film on the pixel and black substrate. A color filter with 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 pixels and black matrices (hereinafter, pixels and black matrices are referred to as "colored patterns"). Among them, the pigment/dye dispersion method, which uses a photosensitive resin composition as a resist and repeats coating, exposure, development, and baking, is produced by the photolithography method, because it can impart excellent durability, and the pinholes, etc. Coloring graphics 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。 Generally speaking, the photosensitive resin composition used in photolithography contains alkali-soluble resin, reactive diluent, photopolymerization initiator, colorant and solvent. Although the pigment/dye dispersion method has the above-mentioned advantages, on the other hand, due to the repeated formation of black matrix, R, G, and B patterns, it requires high heat resistance, and it is used as a colorant that can withstand high baking temperatures. Restrictions, such as restrictions on the types of colorants that can be used, still often cause 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 it can be cured at low temperature by using an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a colorant, and ethyl 3-aminobenzenesulfonate. 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。Patent Document 2 discloses that low-temperature curing is achieved by using a photosensitive resin composition that contains a reaction that is accelerated toward the final product by an alkaline substance or by heating in the presence of an alkaline substance. A polymer precursor, a specific base generator that generates a base by electromagnetic wave irradiation and heating.

[先前技術文獻][Prior Art Literature]

[專利文獻][Patent Document]

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

[專利文獻2] 日本特開2014-70148號公報[Patent Document 2] Japanese Unexamined Patent Publication No. 2014-70148

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，已探討感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. Plastic substrates such as polyethylene terephthalate have been studied as substrates for such flexible displays. The substrate has the property of stretching or shrinking during baking, so it is necessary to lower the temperature of the baking step. However, the level achieved in Patent Document 1 is not sufficient to satisfy the above-mentioned requirements. Moreover, although patent document 2 can improve low-temperature curability, it has low storage stability 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著色圖型之濾色器用感光性樹脂組成物、及調製該感光性樹脂組成物有用之共聚物。 　　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。The present invention has been made in order to solve the above-mentioned problems, and its object is to provide a photosensitive color filter that has good image development and storage stability, and can impart a colored pattern with excellent solvent resistance even when cured at a low temperature. A resin composition, and a copolymer useful for preparing the photosensitive resin composition. Furthermore, the object of the present invention is to provide a color filter having a colored pattern excellent in solvent resistance, a method for producing the same, and an image display device including the color filter.

即，本發明為如以下之[1]~[25]所示。 　　[1] 一種共聚物(A)，其特徵為含有：具有封端異氰酸根基之構成單位(a)、具有酸基之構成單位(b)及具有環氧基之構成單位(c)。 　　[2] 如[1]之共聚物，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]之共聚物，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、甲基乙基酮肟、2-羥基安息香酸甲酯、4-羥基安息香酸甲酯及3,5-茬酚所成群之1種以上。 　　[4] 如[1]~[3]中任一項之共聚物，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。 　　[5] 如[1]~[4]中任一項之共聚物，其中前述具有環氧基之構成單位(c)為源自含環氧基之(甲基)丙烯酸酯之構成單位。 　　[6] 如[1]~[5]中任一項之共聚物，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)1~60莫耳%、前述具有酸基之構成單位(b)5~65莫耳%及前述具有環氧基之構成單位(c)5~65莫耳%。 　　[7] 如[1]~[6]中任一項之共聚物，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)與前述具有環氧基之構成單位(c)之莫耳比率為10：90~75：25。 That is, the present invention is as shown in the following [1] to [25]. [1] A copolymer (A) characterized by comprising: a constituent unit (a) having a blocked isocyanato group, a constituent unit (b) having an acid group, and a constituent unit (c) having an epoxy group. [2] The copolymer as described in [1], wherein the aforementioned structural unit (a) having a blocked isocyanato group is a structural unit derived from a (meth)acrylate containing a blocked isocyanato group, and the aforementioned blocked isocyanato group-containing The dissociation rate of the blocked isocyanato group of the isocyanato group-terminated (meth)acrylate is 5 to 99% by mass after heating at 100°C for 30 minutes. [3] The copolymer as in [1] or [2], wherein the blocking agent of the constituent unit (a) having a blocked isocyanato group is selected from diethyl malonate, 3,5-dimethyl One or more groups of pyrazole, methyl ethyl ketone oxime, 2-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester and 3,5-diphenol. [4] The copolymer according to any one of [1] to [3], wherein the aforementioned structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid. [5] The copolymer according to any one of [1] to [4], wherein the constituent unit (c) having an epoxy group is a constituent unit derived from an epoxy group-containing (meth)acrylate. [6] The copolymer according to any one of [1] to [5], wherein the aforementioned copolymer (A) contains 1 to 60 mol% of the aforementioned structural unit (a) having a blocked isocyanato group, and the aforementioned The constituent unit (b) of acid group is 5~65 mole % and the constituent unit (c) having epoxy group is 5~65 mole %. [7] The copolymer according to any one of [1] to [6], wherein the aforementioned structural unit (a) having a blocked isocyanato group and the aforementioned structural unit having an epoxy group in the aforementioned copolymer (A) are (c) The molar ratio is 10:90~75:25.

[8]如[1]~[7]中任一項之共聚物，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]胺基]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]胺基]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]胺基]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)、源自環氧丙基甲基丙烯酸酯之構成單位(c)，及源自選自由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(e)。 [8] The copolymer according to any one of [1] to [7], wherein the aforementioned copolymer (A) contains: derived from methacrylic acid 2-(3,5-dimethylpyrazole-1- base) carbonylaminoethyl ester, 2-[O-(1'-methylpropyleneamino) carboxylamino]ethyl methacrylate, 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]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2- Methyl-1-oxyl-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3, 5-Dimethylphenoxy) carbonyl] amino] ethyl ester group of at least one kind of constituent unit (a), constituent unit (b) derived from (meth)acrylic acid, derived from glycidyl A constituent unit (c) of methacrylate, and a constituent unit (e) derived from at least one selected from the group consisting of dicyclopentyl methacrylate and meth(meth)acrylate.

[9]如[1]~[8]中任一項之共聚物，其中前述共聚物(A)更含有：具有羥基之構成單位(d)。 [9] The copolymer according to any one of [1] to [8], wherein the above-mentioned copolymer (A) further contains: a constituent unit (d) having a hydroxyl group.

[10]如[9]之共聚物，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]胺基]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 基]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]胺基]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)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)、源自2-羥基乙基甲基丙烯酸酯之構成單位(d)，及源自選自由二環戊基(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(e)。 [10] The copolymer according to [9], wherein the aforementioned copolymer (A) contains: , 2-[O-(1'-methylpropyleneamino) carboxylamino]ethyl methacrylate, malonate-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]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1-oxyl-2 -propen-1-yl)oxy]ethyl]amine At least one of the group of base]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester The constituent unit (a) derived from (meth)acrylic acid, the constituent unit (b) derived from glycidyl (meth)acrylate, the constituent unit (c) derived from 2-hydroxyethyl methacrylic acid The constituent unit (d) of ester, and the constituent unit (e) derived from at least one kind selected from the group consisting of dicyclopentyl (meth)acrylate and meth (meth)acrylate.

[11]如[8]之共聚物，其中前述共聚物(A)含有：源自甲基丙烯酸2-[O-(1’-甲基亞丙基胺基)羧基胺基]乙酯之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)，及源自二環戊基(甲基)丙烯酸酯之構成單位(e)。 [11] The copolymer according to [8], wherein the aforementioned copolymer (A) contains: a composition derived from 2-[O-(1'-methylpropyleneamino)carboxyamino]ethyl methacrylate Unit (a), constituent unit (b) derived from (meth)acrylic acid, constituent unit (c) derived from glycidyl (meth)acrylate, and constituent unit (c) derived from dicyclopentyl (meth)acrylic acid Constituent unit (e) of ester.

[12]如[8]之共聚物，其中前述共聚物(A)含有：源自甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙基酯之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)，及源自二環戊基(甲基)丙烯酸酯之構成單位(e)。 [12] The copolymer according to [8], wherein the aforementioned copolymer (A) contains: a composition derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate Unit (a), constituent unit (b) derived from (meth)acrylic acid, constituent unit (c) derived from glycidyl (meth)acrylate, and constituent unit (c) derived from dicyclopentyl (meth)acrylic acid Constituent unit (e) of ester.

[13]如[10]之共聚物，其中前述共聚物(A)含有：源自甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙基酯之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)、源自2-羥基乙基甲基丙烯酸酯之構成單位(d)，及源自二環戊基(甲基)丙烯酸酯之構成單位(e)。 [13] The copolymer according to [10], wherein the aforementioned copolymer (A) contains: a composition derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate Unit (a), constituent unit (b) derived from (meth)acrylic acid, constituent unit (c) derived from glycidyl (meth)acrylate, constituent unit derived from 2-hydroxyethyl methacrylate Structural unit (d), and structural unit (e) derived from dicyclopentyl (meth)acrylate.

[14]如[8]之共聚物，其中前述共聚物(A)含有：源自丙二酸-2-[[[2-甲基-1-側氧基-2-丙烯基]氧基]乙基]胺基]羰基]-1,3二乙基酯之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)，及源自二環戊基(甲基)丙烯酸酯之構成單位(e)。[14] The copolymer according to [8], wherein the aforementioned copolymer (A) contains: derived from malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy] Constituent unit (a) of ethyl]amino]carbonyl]-1,3 diethyl ester, structural unit (b) derived from (meth)acrylic acid, and constitutive unit (b) derived from glycidyl (meth)acrylate Structural unit (c), and structural unit (e) derived from dicyclopentyl (meth)acrylate.

[15] 如[1]~[5]中任一項之共聚物，其中前述共聚物(A)更含有：具有羥基之構成單位(d)及前述構成單位(a)~(d)以外之構成單位(e)，且 　　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%、前述具有酸基之構成單位(b)1~60莫耳%、前述具有環氧基之構成單位(c)1~70莫耳%、前述具有羥基之構成單位(d)超過0莫耳%~50莫耳%及前述構成單位(e)超過0莫耳%~80莫耳%。[15] The copolymer according to any one of [1] to [5], wherein the above-mentioned copolymer (A) further contains: a structural unit (d) having a hydroxyl group and other than the above-mentioned structural units (a) to (d) The constituent unit (e), and the aforementioned copolymer (A) contains: the aforementioned constituent unit (a) having a blocked isocyanate group (a) 1-40 mol %, the aforementioned constituent unit (b) having an acid group (b) 1-60 mole % mol%, the aforementioned constituent unit (c) having an epoxy group is 1-70 mol%, the aforementioned constituent unit (d) having a hydroxyl group is more than 0 mol% to 50 mol%, and the aforementioned constituent unit (e) is more than 0 mol% Ear % ~ 80 mole %.

[16] 如[1]~[5]中任一項之共聚物，其中前述共聚物(A)更含有：具有羥基之構成單位(d)及前述構成單位(a)~(d)以外之構成單位(e)，且 　　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)3~20莫耳%、前述具有酸基之構成單位(b)20~50莫耳%、前述具有環氧基之構成單位(c)20~40莫耳%、前述具有羥基之構成單位(d)超過0莫耳%~20莫耳%及前述構成單位(e)20~40莫耳%。[16] The copolymer according to any one of [1] to [5], wherein the above-mentioned copolymer (A) further contains: a structural unit (d) having a hydroxyl group and other than the above-mentioned structural units (a) to (d) The constituent unit (e), and the aforementioned copolymer (A) contains: the aforementioned constituent unit (a) having a blocked isocyanate group (a) 3-20 mol %, the aforementioned constituent unit (b) having an acid group (b) 20-50 mole % mol%, the aforementioned constituent unit (c) having an epoxy group is 20-40 mole%, the aforementioned constituent unit (d) having a hydroxyl group exceeds 0 mole%-20 mole%, and the aforementioned constituent unit (e) is 20-40 mole% mole %.

[17] 一種聚合物組成物，其特徵為含有：如[1]~[16]中任一項之共聚物(A)，與，溶劑(B)及反應性稀釋劑(C)之至少一者。[17] A polymer composition characterized by comprising: the copolymer (A) according to any one of [1] to [16], and at least one of solvent (B) and reactive diluent (C) By.

[18] 一種感光性樹脂組成物，其特徵為含有如：[1]~[16]中任一項之共聚物(A)、溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)。[18] A photosensitive resin composition characterized by containing the copolymer (A) of any one of [1] to [16], solvent (B), reactive diluent (C) and photopolymerizer Initiator (D).

[19] 一種濾色器用感光性樹脂組成物，其特徵為含有：如[1]~[16]中任一項之共聚物(A)、溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)及著色劑(E)。 　　[20] 如[19]之濾色器用感光性樹脂組成物，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、前述著色劑(E)3~80質量份。 　　[21] 如[19]或[20]之濾色器用感光性樹脂組成物，其中前述溶劑(B)包含：含羥基之有機溶劑。 　　[22] 如[19]~[21]中任一項之濾色器用感光性樹脂組成物，其中前述著色劑(E)包含顏料。[19] A photosensitive resin composition for a color filter, characterized by containing: the copolymer (A) of any one of [1] to [16], the solvent (B), the reactive diluent (C), A photopolymerization initiator (D) and a coloring agent (E). [20] The photosensitive resin composition for a color filter according to [19], which contains 10 parts by mass of the copolymer (A) and 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). ~100 parts by mass, 30 to 1,000 parts by mass of the aforementioned solvent (B), more than 0 to 90 parts by mass of the aforementioned reactive diluent (C), 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (D), and the aforementioned coloring Agent (E) 3~80 parts by mass. [21] The photosensitive resin composition for a color filter according to [19] or [20], wherein the solvent (B) includes: a hydroxyl group-containing organic solvent. [22] The photosensitive resin composition for color filters according to any one of [19] to [21], wherein the colorant (E) contains a pigment.

[23] 一種濾色器，其特徵為具有如[19]~ [22]中任一項之濾色器用感光性樹脂組成物之硬化物所構成之著色圖型。[23] A color filter characterized by having a colored pattern formed of a cured product of the photosensitive resin composition for a color filter according to any one of [19] to [22].

[24] 一種圖像顯示元件，其徵為具備如[23]之濾色器。[24] An image display device characterized by having a color filter as in [23].

[25] 一種濾色器之製造方法，其特徵為包含：將如[19]~[22]中任一項之濾色器用感光性樹脂組成物塗佈於基板，進行曝光，鹼顯像後，在160℃以下之溫度進行烘烤而形成著色圖型之步驟。[25] A method for manufacturing a color filter, characterized by comprising: applying the photosensitive resin composition for a color filter according to any one of [19] to [22] on a substrate, exposing, and alkali developing , the step of forming a colored pattern by baking at a temperature below 160°C.

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賦予耐溶劑性優異之著色圖型之濾色器用感光性樹脂組成物，及調製該感光性樹脂組成物有用之共聚物。 　　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 for a color filter which is excellent in developing properties and storage stability, and to impart a colored pattern with excellent solvent resistance even when cured at a low temperature, and to prepare the photosensitive resin composition Useful copolymers. Also, according to the present invention, a color filter having a colored pattern excellent in solvent resistance, a method for producing the same, and an image display device including the color filter can be provided.

＜共聚物(A)＞ 　　本發明之共聚物(A)，其特徵為含有：具有封端異氰酸根基之構成單位(a)、具有酸基之構成單位(b)及具有環氧基之構成單位(c)。<Copolymer (A)> The copolymer (A) of the present invention is characterized by containing: a constituent unit (a) having a blocked isocyanato group, a constituent unit (b) having an acid group, and a constituent unit having an epoxy group. Constituent unit (c).

＜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。<Constituent unit (a) having a blocked isocyanato group> The structural unit (a) having a blocked isocyanato group contained in the copolymer (A) is derived from a monomer containing a blocked isocyanato group. Constituent unit. Examples of such monomers include monomers having an ethylenically unsaturated bond and a blocked isocyanate group, for example, the isocyanate compound having a vinyl group, a (meth)acryloxy group, etc. in the molecule. Cyanate group, a compound obtained by capping with a capping agent. The reaction between the isocyanate compound and the blocking agent can be carried out with or without the presence of a solvent. In the case of solvents, it is necessary to use solvents which are inert to isocyanato groups. In the capping reaction, organometallic salts of tin, zinc, lead, etc., tertiary amines, etc. can be used as catalysts. The reaction can generally be carried out at -20~150°C, preferably at 0~100°C. As an example of the said isocyanate compound, the compound represented by following formula (1) is mentioned.

Figure 02_image001
Figure 02_image001

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, R 2 represents -CO-, -COOR 3 - (herein, R 3 is an alkylene group with 1 to 6 carbon atoms) or -COO-R 4 O-CONH-R 5 -(Here, R 4 is an alkylene group with 2 to 6 carbon atoms, and R 5 is an alkylene group with 2 to 12 carbon atoms that may have a substituent, or an alkylene group with 6 to 6 carbon atoms 12's extended aryl). R 2 is preferably -COOR 3 -, where R 3 is preferably an alkylene group with 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。Specific 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 ( Meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryl isocyanate, and the like. Moreover, the equimolar (1 mol: 1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. As the alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate, ethyl or n-propyl is preferable, and ethyl is more preferable. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4-(or 2,6-) tolylylene diisocyanate (TDI), 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 and the like.

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-isocyanato Acetyl cyclohexyl (meth)acrylate and methacryl isocyanate are preferred, 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。Also, in this specification, the one marked as (meth)acrylate means that it can be any one of acrylate and methacrylate, and the mark of (meth)acrylic acid means that it can be either acrylic acid or methacrylic acid. Any one of acrylic acid.

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 a blocking agent for blocking the isocyanate group in the isocyanate compound, for example, ε-caprolactamide, δ-valerolactamide, γ-butyrolactamide, β-propiolactamide Amines and other lactam series; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl Alcohols such as alcohol and cyclohexanol; butylphenols such as phenol, cresol, 2,6-stubble phenol, 3,5-stubble phenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, etc. phenylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, Phenols such as p-nitrophenol and p-chlorophenol; activated methylenes such as dimethyl malonate, diethyl malonate, methyl acetylacetate, ethyl acetylacetate, and acetylacetone Base system; thiol system such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; amine system such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; acetaniline, methoxy Acetanisidide, acetic acid amide, benzyl amide and other acid amide series; succinic imide, maleic acid imide and other acid amide series; imidazole, 2-methylimidazole, Imidazole series such as 2-ethylimidazole; pyrazole series such as pyrazole and 3,5-dimethylpyrazole; urea series such as urea, thiourea, and ethylene urea; phenyl N-phenylcarbamate, Amino formate of 2-oxazolidinone, etc.: imines of ethyleneimine, polyethyleneimine, etc.; formaldehyde oxime, acetaldehyde oxime, acetaldehyde oxime, methyl ethyl ketone oxime, methyl isobutyl Oxime series such as ketone oxime and cyclohexanone oxime; bisulfite series such as sodium bisulfite and potassium bisulfite, etc. These blocking agents may 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 blocked isocyanate group will dissociate and regenerate the isocyanate group by heating. In the present invention, the isocyanato group reacts with the reactive functional group contained in the copolymer (A) or the reactive diluent (C), that is, the acid group or the hydroxyl group, amine group, etc. contained as desired, And form a hardened product with high crosslink density.

在從後述之濾色器用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製時之烘烤溫度，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封端異氰酸根基之(甲基)丙烯酸酯之封端劑，可舉出如丙二酸二乙酯、3,5-二甲基吡唑、甲基乙基酮肟、2-羥基安息香酸甲酯、4-羥基安息香酸甲酯、3,5-茬酚、γ-丁內醯胺、1-甲氧基-2-丙醇、2,6-二甲基酚及二異丙基胺。此等封端劑之中，從低溫硬化性之觀點，以丙二酸二乙酯、3,5-二甲基吡唑、甲基乙基酮肟、2-羥基安息香酸甲酯、4-羥基安息香酸甲酯及3,5-茬酚為較佳。From the viewpoint of low-temperature curability or storage stability of the photosensitive resin composition for color filters described later, as a monomer for imparting the constituent unit (a) having a blocked isocyanato group, a compound containing blocked isocyanic acid is used. The base (meth)acrylate is preferred. The dissociation rate of the blocked isocyanate group after heat treatment at 100°C for 30 minutes is preferably 5-99% by mass, more preferably 8-97% by mass, most preferably 10-95% by mass (Meth)acrylates with blocked isocyanato groups are preferred. Also, the dissociation rate of the blocked isocyanato group of (meth)acrylate containing blocked isocyanato group is measured by HPLC analysis to prepare the (meth)acrylic acid containing blocked isocyanato group The concentration of the ester is 20% by mass of n-octanol solution, after adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to this solution, heat at 100°C for 30 The value obtained by the mass reduction ratio of the blocked isocyanato group-containing (meth)acrylate. When using (meth)acrylates containing blocked isocyanato groups with a dissociation rate within the above-mentioned range, the stability of the copolymer during synthesis can be fully ensured, and the baking temperature when making a hardened coating can be sufficiently reduced. And can fully ensure the solvent resistance of the hardened coating. Examples of blocking agents for (meth)acrylates containing blocked isocyanato groups having such a dissociation rate include diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl Ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, 3,5-butyrol, γ-butyrolactam, 1-methoxy-2-propanol, 2,6-di Methylphenol and Diisopropylamine. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketone oxime, 2-hydroxybenzoic acid methyl ester, 4- Methyl hydroxybenzoate and 3,5-styrol 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 (meth)acrylate containing a blocked isocyanato group whose dissociation temperature of the blocked isocyanato group is 80°C or higher. . When using (meth)acrylates with blocked isocyanate groups whose dissociation temperature is above 80°C, the stability of the copolymer during synthesis can be fully ensured, and unwanted crosslinking during the denaturation reaction described later can be reduced reaction. On the other hand, when the dissociation temperature of the blocked isocyanato group is 160° C. or lower, the baking temperature can be sufficiently lowered, and the solvent resistance of the cured coating film can be sufficiently ensured. Also, the dissociation temperature of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate is measured by HPLC analysis to prepare the blocked isocyanato group-containing (meth)acrylic acid The concentration of the ester is 20% by mass of n-octanol solution, and the solution is heated at a predetermined temperature after adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to this solution , the mass reduction ratio of the blocked isocyanato group-containing (meth)acrylate after 30 minutes, and the temperature at which the mass reduction ratio becomes 80% by mass or more is taken as the dissociation temperature of the blocked isocyanato group.

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。As an example of the above-mentioned blocked isocyanato group-containing (meth)acrylate, Karenz (registered trademark) MOI-DEM (methacryloxyethyl isocyanate and Reaction product of diethyl malonate, manufactured by Showa Denko Co., Ltd., dissociation temperature of blocked isocyanato group: 90°C, dissociation rate: 90% by mass), Karenz MOI represented 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 represented by the following formula (4) (reaction product of methacryloxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Denko Co., Ltd., isoblocked Dissociation temperature of cyanate group: 130°C, dissociation rate: 18% by mass) common methacrylates and corresponding acrylates, etc. These blocked isocyanato group-containing (meth)acrylates may be used alone or in combination of two or more.

Figure 02_image003
Figure 02_image003

Figure 02_image005
Figure 02_image005

Figure 02_image007
Figure 02_image007

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 constituent units (a) having blocked isocyanato groups contained in the copolymer (A) is not particularly limited, preferably 1-40 mol%, preferably 2-30 mol%, most preferably It is 3~25 mole%. When the proportion of the constituent unit (a) having a blocked isocyanato group 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。<Constituent unit (b) having an acid group> The constituent unit (b) having an acid group contained in the copolymer (A) is a constituent unit derived from a monomer containing an acid group (however, it should be The constituent unit (a) of cyanate group is excluded). Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phospho group. Among them, a carboxyl group is preferable because it is easy to obtain. Examples of the monomer that imparts the constituent unit (b) having an acid group include monomers having a polymerizable unsaturated bond and an acid group, for example, unsaturated carboxylic acid or an anhydride thereof, unsaturated sulfonic acid, unsaturated phosphonic acid wait. Specific examples of preferred monomers include (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α- Cyanocinnamic acid, maleic acid, anhydrous maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, anhydrous itaconic acid, citric acid Unsaturated carboxylic acids such as aconic acid and anhydrous citraconic acid or their anhydrides; 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, p-styrenesulfonic acid, etc. Saturated sulfonic acid; unsaturated phosphonic acid such as vinylphosphonic acid, etc. These single systems may be used alone or in combination of two or more. Among them, unsaturated carboxylic acid is preferable and (meth)acrylic acid is preferable from the viewpoint of excellent alkali developability and easy acquisition.

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, the alkali developability when the copolymer (A) is used as a photosensitive material is greatly improved by including the structural unit (b) having an acidic group in the copolymer (A).

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 ratio of the constituent units (b) with acid groups contained in the copolymer (A) is not particularly limited, preferably 1-60 mol%, more preferably 10-50 mol%, most preferably 15-40 mole %. When the ratio of the constituent unit (b) having an acidic group is 1-60 mole %, the speed suitable for alkali imaging can be achieved, and fine patterns can be formed.

＜具有環氧基之構成單位(c)＞ 　　共聚物(A)所含有之具有環氧基之構成單位(c)為源自含有環氧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)、前述具有酸基之構成單位(b)者除外)。作為賦予具有環氧基之構成單位(c)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，從聚合性及取得容易性之觀點，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。<Constituent unit (c) having an epoxy group> The structural unit (c) having an epoxy group contained in the copolymer (A) is a structural unit derived from a monomer containing an epoxy group (however, it should be Structural units (a) with blocked isocyanato groups, except the aforementioned structural units (b) having acid groups). Examples of the monomer that imparts the constituent unit (c) having an epoxy group include monomers having a polymerizable unsaturated bond and an epoxy group, for example, oxiranyl (meth)acrylate, epoxy Propyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate base) acrylate, 2-glycidoxyethyl (meth)acrylate, 3-glycidoxypropyl (meth)acrylate, glycidoxyphenyl (meth)acrylate (meth)acrylate derivatives containing epoxy groups; 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethoxy)ethyl (meth)acrylate, 3-( 3,4-epoxycyclohexylmethoxy)propyl (meth)acrylate, etc. containing alicyclic carbocyclic rings containing epoxy groups such as 3,4-epoxycyclohexane rings, etc. base) acrylate derivatives; vinyl ether compounds containing epoxy groups; allyl ether compounds containing epoxy groups, etc. These single systems may be used alone or in combination of two or more. Among these, from the viewpoints of polymerizability and ease of acquisition, oxirane-based (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (methyl) ) acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidoxypropyl (meth)acrylate , 3-glycidoxypropyl (meth) acrylate, glycidoxy phenyl (meth) acrylate and other epoxy-containing (meth) acrylates are preferred. Base (meth)acrylates are preferred.

本發明中，藉由使具有環氧基之構成單位(c)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受到大幅改善。In the present invention, by including the structural unit (c) having an epoxy group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

共聚物(A)所含有之具有環氧基之構成單位(c)之比例並無特別限制，以1~60莫耳%為佳，較佳為5~50莫耳%，最佳為10~40莫耳%。具有環氧基之構成單位(c)之比例為1~60莫耳%時，硬化塗膜之耐溶劑性與共聚物(A)之保存安定性則會併存。The proportion of the constituent units (c) having epoxy groups contained in the copolymer (A) is not particularly limited, preferably 1-60 mol%, preferably 5-50 mol%, and most preferably 10-60 mol%. 40 mole%. When the proportion of the constituent unit (c) having an epoxy group is 1-60 mol%, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) will coexist.

共聚物(A)中，具有封端異氰酸根基之構成單位(a)與具有環氧基之構成單位(c)之莫耳比率可為例如1：99~99：1，在從硬化塗膜之耐溶劑性及共聚物(A)之保存安定性之觀點，以5：95~85：15為佳，以10：90~75：25為較佳。In the copolymer (A), the molar ratio of the constituent unit (a) having a blocked isocyanate group to the constituent unit (c) having an epoxy group may be, for example, 1:99~99:1. From the viewpoint of the solvent resistance of the film and the storage stability of the copolymer (A), 5:95~85:15 is preferable, and 10:90~75:25 is more preferable.

＜具有羥基之構成單位(d)＞ 　　共聚物(A)亦可更含有：具有羥基之構成單位(d)。共聚物(A)所含有之具有羥基之構成單位(d)為源自含羥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)、前述具有酸基之構成單位(b)、前述具有環氧基之構成單位(c)者除外)。作為賦予具有羥基之構成單位(d)之單體，如具有聚合性不飽和鍵與羥基之單體，可舉出例如，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，從聚合性之觀點，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。<Constituent unit (d) having a hydroxyl group> The copolymer (A) may further contain: a structural unit (d) having a hydroxyl group. The structural unit (d) having a hydroxyl group contained in the copolymer (A) is a structural unit derived from a monomer containing a hydroxyl group (however, the structural unit (a) having a blocked isocyanato group, the aforementioned acid-containing The constituent unit (b) of the epoxy group is excluded from the aforementioned constituent unit (c) having an epoxy group). As a monomer for imparting a constituent unit (d) having a hydroxyl group, such as a monomer 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 (meth)acrylate, 4-hydroxy Butyl acrylate, etc. These single systems may 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, Hydroxyl-containing (meth)acrylate derivatives such as 3-dihydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate are preferred. 2-Hydroxyethyl (meth)acrylate is preferred.

本發明中，具有羥基之構成單位(d)並非必須者，但藉由使具有羥基之構成單位(d)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。In the present invention, the constituent unit (d) having a hydroxyl group is not essential, but when the copolymer (A) is used as a photosensitive material by including the constituent unit (d) having a hydroxyl group in the copolymer (A) The solvent resistance will be greatly improved.

共聚物(A)所含有之具有酸基之構成單位(d)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%。具有羥基之構成單位(d)之比例為超過0莫耳%~50莫耳%時，硬化塗膜之耐溶劑性與共聚物(A)之保存安定性獲得併存。The ratio of the constituent units (d) having an acid group contained in the copolymer (A) is not particularly limited, preferably exceeding 0 mol % to 50 mol %, more preferably exceeding 0 mol % to 40 mol %, preferably more than 0 mol%~30 mol%. When the ratio of the constituent unit (d) having a hydroxyl group exceeds 0 mol % to 50 mol %, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) can be coexisted.

＜其他構成單位(e)＞ 　　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)、具有酸基之構成單位(b)、具有環氧基之構成單位(c)及具有羥基之構成單位(d)，亦可一同含有與該等能共聚合之其他構成單位(e)(但，該當於前述具有封端異氰酸根基之構成單位(a)、前述具有酸基之構成單位(b)、前述具有環氧基之構成單位(c)、具有羥基之構成單位(d)者除外)。作為賦予其他構成單位(e)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、氟乙烯、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。<Other structural units (e)> In the present invention, the structural units contained in the copolymer (A) include structural units (a) having blocked isocyanato groups, structural units (b) having acidic groups, The constituent unit (c) having an epoxy group and the constituent unit (d) having a hydroxyl group may also contain other constituent units (e) that can be copolymerized together (however, it should be included in the aforementioned The constituent unit (a), the aforementioned constituent unit (b) having an acid group, the aforementioned constituent unit (c) having an epoxy group, and the constituent unit (d) having a hydroxyl group are excluded). Specific examples of monomers imparting other constituent units (e) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chloro Styrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyano Aromatic vinyl compounds such as styrene and p-acetylaminostyrene; norcamphene (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 7,10 ]dode-3-ene, 8-methyltetracyclo[4.4. 0.1 2,5 .1 7,10 ]dode-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]dode-3-ene, dicyclopentadiene, tri Cyclo[5.2.1.0 2,6 ]dec-8-ene, Tricyclo[5.2.1.0 2,6 ]dec-3-ene, Tricyclo[4.4.0.1 2,5 ]Undec-3-ene, Tricyclo [6.2.1.0 1,8 ]undec-9-ene, tricyclo[6.2.1.0 1,8 ]undec-4-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1, 6 ] Dode-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dode-3-ene, 8-ethylenetetracyclo[4.4. 0.1 2,5 .1 7,12 ]dode-3-ene, 8-ethylenetetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dode-3-ene, penta Cyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]pentadeca-4-ene, Pentacyclo[7.4.0.1 2,5 .1 9,12 .0 8,13 ]pentadeca-3 Cyclic olefins with a norcamphene structure such as -alkenes; dienes such as butadiene, isoprene, and chloroprene; 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 base) acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isopentyl (meth)acrylate ) acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate Acrylates, Cyclohexyl(meth)acrylate, Methylcyclohexyl(meth)acrylate, Ethylcyclohexyl(meth)acrylate, 1,4-Cyclohexanedimethanol mono(meth)acrylate , rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (methyl) Acrylate, 5-Ethylnorbornyl(meth)acrylate, Dicyclopentenyl(meth)acrylate, Dicyclopentyl(meth)acrylate, Dicyclopentenyloxyethylacrylate Ester isocamphoryl (meth)acrylate, adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, all Fluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, 3-(N,N-dimethylamino) Propyl(meth)acrylate, triphenylmethyl(meth)acrylate, phenyl(meth)acrylate, cumyl(meth)acrylate, 4-phenoxyphenyl(meth)acrylate base) acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono (meth)acrylate, biphenyl (meth)acrylates of oxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, etc.; (meth)acrylamide, (meth)acrylic acid N , N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di- (Meth)acrylamide such as isopropylamide and (meth)acrylic acid anthracenylamide; (meth)acrylamide benzene, (meth)acrylonitrile, acrolein, vinyl chloride, dichloromethane Vinyl compounds such as ethylene, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, etc.; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl maleate and diethyl itaconate; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide Amines, monomaleimides such as N-(4-hydroxyphenyl)maleimide, and the like. Among these, (meth)acrylate is preferable, and meth(meth)acrylate and dicyclopentyl (meth)acrylate are particularly preferable. These single systems may be used alone or in combination of two or more.

共聚物(A)所含有之其他構成單位(e)之比例並無特別限制，以超過0莫耳%~80莫耳%為佳，較佳為5~70莫耳%，最佳為10~60莫耳%。本發明中，其他構成單位(e)並非為必須者，但藉由藉由使其他構成單位(e)被包含於共聚物(A)中，可適宜地使耐溶劑性、塗膜之特性提升。The proportion of other constituent units (e) contained in the copolymer (A) is not particularly limited, preferably exceeding 0 mol % to 80 mol %, more preferably 5 to 70 mol %, and most preferably 10 to 80 mol % 60 mole %. In the present invention, the other structural unit (e) is not essential, but by including the other structural unit (e) in the copolymer (A), the solvent resistance and the characteristics of the coating film can be improved suitably .

＜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)、含酸基之單體(b0)及含環氧基之單體(c0)之比例並無特別限制，以(a0)1~60莫耳%、(b0)5~65莫耳%及(c0)5~65莫耳%為佳，較佳為(a0)5~50莫耳%、(b0)15~55莫耳%及(c0)15~55莫耳%，最佳為(a0)10~40莫耳%、(b0)25~45莫耳%及(c0)25~45莫耳%。共聚物(A)在更含有具有羥基之構成單位(d)及其他構成單位(e)之情況，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)、含環氧基之單體(c0)、含羥基之單體(d0)及其他單體(e0)之比例係以(a0)1~40莫耳%、(b0)1~60莫耳%、(c0)1~70莫耳%、(d0)超過0莫耳%~50莫耳%及(e0)超過0莫耳%~80莫耳%為佳，較佳為(a0)2~30莫耳%、(b0)10~55莫耳%、(c0)10~60莫耳%、(d0)超過0莫耳%~30莫耳%及(e0)5~60莫耳%，最佳為(a0)3~20莫耳%、(b0)20~50莫耳%、(c0)20~40莫耳%、(d0)超過0莫耳%~20莫耳%及(e0)20~40莫耳%。<Method for producing copolymer (A)> Blocked isocyanato group-containing monomer (a0), acid group-containing monomer (b0) and epoxy group-containing monomer used in the production of copolymer (A) The ratio of the monomer (c0) is not particularly limited, preferably (a0) 1-60 mol%, (b0) 5-65 mol%, and (c0) 5-65 mol%, preferably (a0 )5~50 mol%, (b0)15~55 mol% and (c0)15~55 mol%, the best are (a0)10~40 mol%, (b0)25~45 mol% And (c0) 25~45 mole%. When the copolymer (A) further contains a constituent unit (d) having a hydroxyl group and other constituent units (e), the blocked isocyanato group-containing monomer (a0) used in the production of the copolymer (A) , Acid-containing monomers (b0), epoxy-containing monomers (c0), hydroxyl-containing monomers (d0) and other monomers (e0) are based on (a0) 1~40 mol% , (b0) 1~60 mol%, (c0) 1~70 mol%, (d0) more than 0 mol%~50 mol% and (e0) more than 0 mol%~80 mol% are better , preferably (a0) 2~30 mol%, (b0) 10~55 mol%, (c0) 10~60 mol%, (d0) more than 0 mol%~30 mol% and (e0 )5~60 mol%, the best is (a0)3~20 mol%, (b0)20~50 mol%, (c0)20~40 mol%, (d0) more than 0 mol%~ 20 mol% and (e0) 20~40 mol%.

含封端異氰酸根基之單體(a0)、含酸基之單體(b0)、含環氧基之單體(c0)、含羥基之單體(d0)及其他單體(e0)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實施。例如，使此等單體溶解於依附所欲之溶劑後，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。Monomers containing blocked isocyanato groups (a0), monomers containing acid groups (b0), monomers containing epoxy groups (c0), monomers containing hydroxyl groups (d0) and other monomers (e0) The copolymerization reaction can be carried out in the presence or absence of a polymerization solvent according to the free radical polymerization method known in the technical field. For example, after dissolving these monomers in a desired solvent, a polymerization initiator is added to the solution, and a polymerization reaction is carried out at 50 to 100° C. for 1 to 20 hours. On this occasion, when the polymerization reaction is carried out at a temperature at which the blocked isocyanato group of the blocked isocyanato group-containing monomer (a0) dissociates, the isocyanate generated due to the dissociation of the blocked isocyanato group The acid group will react with the acid group to produce a gel, so the temperature is lower than the dissociation temperature of the blocked isocyanate group, preferably 20~50°C lower than the dissociation temperature of the blocked isocyanate group Preferably, the polymerization is carried out at a temperature.

作為能使用於此共聚合反應之溶劑，只要係對反應為惰性者即無特別限定，可舉出例如，乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單-n-丙基醚、二乙二醇單-n-丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單-n-丙基醚、二丙二醇單-n-丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚等之(聚)伸烷二醇單烷基醚類；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等之(聚)伸烷二醇單烷基醚乙酸酯類；二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、四氫呋喃等之其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等之酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸n-丁酯、乙酸n-丙酯、乙酸i-丙酯、乙酸n-丁酯、乙酸i-丁酯、乙酸n-戊酯、乙酸i-戊酯、丙酸n-丁酯、丁酸乙酯、丁酸n-丙酯、丁酸i-丙酯、丁酸n-丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸n-丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-酮丁酸乙酯等之酯類；甲苯、二甲苯等之芳香族烴類；N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等之羧酸醯胺類；二乙二醇等。此等溶劑係可單獨使用，亦可組合2種以上使用。The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to the reaction, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, (Poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether Other ethers such as base ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate , ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, acetate i -Propyl, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate - Esters of propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-ketobutyrate, etc. Aromatic hydrocarbons such as toluene and xylene; Carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide; Diethylene glycol, etc. These solvents may be used alone or in combination of two or more.

此等溶劑之中係以醚系溶劑為佳，以丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、二乙二醇甲基乙基醚及乙二醇單甲基醚為較佳。Among these solvents, ether-based solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, and ethylene glycol monomethyl ether are preferred.

共聚合反應使用之溶劑之量並無特別限定，將單體之投入量之合計設成100質量份時，一般為30~ 1,000質量份，較佳為50~800質量份。尤其，藉由將溶劑之量作成1,000質量份以下，可抑制因鏈轉移作用導致之共聚物(A)之分子量降低，且可將共聚物(A)之黏度控制在適當範圍。又，藉由將溶劑之量作成30質量份以上，可防止異常之聚合反應，可使聚合反應安定地進行，且同時也能防止共聚物(A)之著色或膠化。The amount of the solvent used in the copolymerization reaction is not particularly limited. When the total input amount of the monomers is 100 parts by mass, it is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass. In particular, by reducing the amount of the solvent to 1,000 parts by mass or less, the decrease in the molecular weight of the copolymer (A) due to chain transfer can be suppressed, and the viscosity of the copolymer (A) can be controlled within an appropriate range. Moreover, by making the quantity of a solvent into 30 mass parts or more, abnormal polymerization reaction can be prevented, a polymerization reaction can be made to progress stably, and coloring or gelatinization of a copolymer (A) can be prevented simultaneously.

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, t-butyl Peroxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more. The usage-amount of the polymerization initiator is generally 0.5-20 mass parts, preferably 1.0-10 mass parts when the total input amount of monomers is 100 mass parts.

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 polystyrene-equivalent weight average molecular weight 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 production method. ). When the weight average molecular weight of a copolymer (A) is 1,000 or more, it will become difficult to generate|occur|produce the defect of a colored pattern after alkali development at the time of using as a photosensitive resin composition. On the other hand, when the weight average molecular weight of a copolymer (A) is 50,000 or less, developing time becomes suitable, 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20~300 KOHmg/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 selected appropriately. When it is mixed with a photosensitive resin composition, it is preferably 20~300 KOHmg/g, more preferably 30~200KOHmg/g scope. When the acid value of a copolymer (A) is 20KOHmg/g or more, alkali developability at the time of using it as a photosensitive resin composition becomes favorable. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg/g or less, since the exposed portion (photohardened portion) to an alkaline developer is not easily dissolved, the pattern shape becomes favorable.

並且，共聚物(A)之環氧當量並無特別限制，以200~2,000g/mol為佳，較佳為300~1500g/mol，最佳為480~900g/mol之範圍。共聚物(A)之環氧當量為200g/mol以上時，安定性變得良好。另一方面，環氧當量若在2,000g/mol以下，則可充分地確保耐溶劑性。尚且，環氧當量係指聚合物之環氧基每1莫耳之聚合物之質量，且能藉由將聚合物之質量除以聚合物之環氧基量來求得者(g/ mol)。本發明中，環氧當量係從為了導入環氧基而使用之原料投入量計算而得之理論值。In addition, the epoxy equivalent of the copolymer (A) is not particularly limited, preferably 200-2,000 g/mol, more preferably 300-1500 g/mol, most preferably 480-900 g/mol. When the epoxy equivalent of a copolymer (A) is 200 g/mol or more, stability will become favorable. On the other hand, if the epoxy equivalent is at most 2,000 g/mol, solvent resistance can be sufficiently secured. Also, the epoxy equivalent refers to the mass of the epoxy group of the polymer per 1 mole of the polymer, and can be obtained by dividing the mass of the polymer by the amount of epoxy groups of the polymer (g/mol) . In the present invention, the epoxy equivalent is a theoretical value calculated from the input amount of raw materials used for introducing epoxy groups.

本發明之共聚物(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。The copolymer (A) of the present invention contains blocked isocyanato groups in the molecule. The content of the blocked isocyanato group can be selected as appropriate. Usually, the blocked isocyanato group equivalent is 400-6,000, preferably 1,000-5,000. The blocked isocyanato equivalent is the mass of polymer per 1 mole of blocked isocyanato groups contained in the polymer, and can be obtained by dividing the mass of polymer by the blocked isocyanate contained in the polymer. Calculated from the number of moles of terminal isocyanate groups (g/mol). In the present invention, the blocked isocyanate group equivalent is a theoretical value calculated from the input amount of monomers containing blocked isocyanate groups.

＜聚合物組成物＞ 　　本發明中，提供一種包含上述共聚物(A)，也包含溶劑(B)及反應性稀釋劑(C)之至少一者之聚合物組成物。溶劑(B)只要係不與共聚物(A)反應之惰性溶劑即無特別限定，可使用與在製造共聚物(A)之際所使用之溶劑相同範疇者。從可防止異常之聚合，使聚合反應安定進行之觀點，溶劑(B)係以丙二醇單甲基醚、二乙二醇等之含羥基之有機溶劑為佳。<Polymer composition> In the present invention, there is provided a polymer composition comprising the above-mentioned copolymer (A) and at least one of a solvent (B) and a reactive diluent (C). The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the copolymer (A), and the same category as the solvent used for the production of the copolymer (A) can be used. From the standpoint of preventing abnormal polymerization and stabilizing the polymerization reaction, the solvent (B) is preferably a hydroxyl-containing organic solvent such as propylene glycol monomethyl ether or diethylene glycol.

本發明之聚合物組成物係亦可對由聚合系統單離之共聚物(A)適宜混合所欲之溶劑(B)來進行調製，並不一定要將共聚物(A)由聚合系統予以單離，可直接使用共聚合反應結束時所包含之溶劑，且於此之際因應必要亦可更追加所欲之溶劑。又，調製聚合物組成物時所使用之其他成分所包含之溶劑也可使用作為溶劑(B)之成分。The polymer composition of the present invention can also be prepared by appropriately mixing the copolymer (A) isolated from the polymerization system with the desired solvent (B), and it is not necessary to separate the copolymer (A) from the polymerization system. If necessary, the solvent contained at the end of the copolymerization reaction can be used as it is, and a desired solvent can be added if necessary. Moreover, the solvent contained in the other component used when preparing a polymer composition can also be used as a component of a solvent (B).

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。The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in its molecule, among which compounds having multiple polymerizable functional groups are preferred. By using such a reactive diluent (C) in combination with the copolymer (A), the viscosity can be adjusted, and the strength of the formed cured product or the adhesion to the base material can be improved.

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 monofunctional monomers used as reactive diluents (C) include (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide Amide, Ethoxymethyl(meth)acrylamide, Propoxymethyl(meth)acrylamide, Butoxymethoxymethyl(meth)acrylamide, Methyl(methyl)acrylamide ) acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl Base (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2 -Hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethane (meth)acrylates such as 2,2,3,3-tetrafluoropropyl (meth)acrylate, hemi(meth)acrylate of phthalic acid derivatives; benzene Aromatic vinyl compounds such as ethylene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, etc.; carboxylic acid esters such as vinyl acetate, vinyl propionate, etc. 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。As the polyfunctional monomer used as reactive diluent (C), for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di( 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 base) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl(meth)acrylate, ethylenedi Alcohol Diglycidyl Ether Di(meth)acrylate, Diethylene Glycol Diglycidyl Ether Di(meth)acrylate, Diglycidyl Phthalate Di(meth)acrylate, Propylene Glycol Diglycidyl Ether Di(meth)acrylate, Triol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e. cresyl diisocyanate), trimethylhexamethylene Reaction products of diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, tri(meth)acrylate of ginseng (hydroxyethyl) isocyanurate ( Meth)acrylates; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, diallylphenylphosphonate, etc.; dicarboxylates such as divinyl adipate; Triallyl cyanurate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyvalent alcohol and N-methylol(meth)acrylamide Condensates etc. These single systems may be used alone or in combination of two or more.

聚合物組成物中之共聚物(A)、溶劑(B)及反應性稀釋劑(C)之配合量係因應使用目的適宜調整即可。聚合物組成物在包含共聚物(A)、溶劑(B)及反應性稀釋劑(C)之情況，通常係相對於共聚物(A)與反應性稀釋劑(C)之合計量100質量份，共聚物(A)為10~90質量份、溶劑(B)為30~1,000質量份、反應性稀釋劑(C)為10~90質量份，以共聚物(A)為20~80質量份、溶劑(B)為50~800質量份、反應性稀釋劑(C)為20~80質量份為佳，較佳為共聚物(A)為30~75質量份、溶劑(B)為100~700質量份、反應性稀釋劑(C)為25~70質量份。若為此範圍之配合量，則成為具有適當黏度之聚合物組成物，除了可使用於用來調製後述之濾色器用感光性樹脂組成物之外，也能使用於各種塗覆、接著劑、印刷墨用黏合劑等。The blending amounts of the copolymer (A), solvent (B) and reactive diluent (C) in the polymer composition may be appropriately adjusted according to the purpose of use. When the polymer composition contains the copolymer (A), the solvent (B) and the reactive diluent (C), it is usually 100 parts by mass relative to the total amount of the copolymer (A) and the reactive diluent (C) , the copolymer (A) is 10~90 parts by mass, the solvent (B) is 30~1,000 parts by mass, the reactive diluent (C) is 10~90 parts by mass, and the copolymer (A) is 20~80 parts by mass , Solvent (B) is 50 ~ 800 mass parts, reactive diluent (C) is 20 ~ 80 mass parts is good, preferably copolymer (A) is 30 ~ 75 mass parts, solvent (B) is 100 ~ 700 parts by mass and 25 to 70 parts by mass of the reactive diluent (C). If the compounding amount is within this range, it becomes a polymer composition with an appropriate viscosity, which can be used not only for preparing the photosensitive resin composition for color filters described later, but also for various coatings, adhesives, Adhesives for printing ink, etc.

＜感光性樹脂組成物＞ 　　本發明提供一種含有共聚物(A)、溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)之感光性樹脂組成物。作為溶劑(B)及反應性稀釋劑(C)，可使用上述者。<Photosensitive resin composition> The present invention provides a photosensitive resin composition containing a copolymer (A), a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D). As the solvent (B) and the reactive diluent (C), those mentioned above can be used.

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。The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone, 2,2-bis Methoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl ) butanone-1 and other acetophenones; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; Thioxanthones such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.; acetophenone dimethyl ketal, benzyl ketals such as dimethyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl) benzophenone, 3,3',4,4 Benzophenones such as '-tetra(t-butyldioxycarbonyl)benzophenone; acylphosphine oxides, etc. These photopolymerization initiators (D) may be used alone or in combination of two or more.

＜濾色器用感光性樹脂組成物＞ 　　本發明提供一種含有共聚物(A)、溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)及著色劑(E)之濾色器用感光性樹脂組成物。作為溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)，可使用上述者。<Photosensitive resin composition for color filter> The present invention provides a filter containing a copolymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E). A photosensitive resin composition for a color device. As a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D), those mentioned above can be used.

著色劑(E)只要係會溶解或分散於溶劑(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 coloring agent (E) is not particularly limited as long as it can be dissolved or dispersed in the solvent (B), and examples thereof include dyes, pigments, and the like. As the dye, from the viewpoints of solubility in the solvent (B) or alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., acidic dyes having carboxylic acid or sulfonic acid can be used. Acid dyes based on acid dyes, salts of acid dyes and nitrogen compounds, sulfonamides of acid dyes, etc. 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；食用黃及此等之衍生物等。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 chrome violet K; acid magenta; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; edible yellow and their derivatives, etc. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more according to the color of 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 C.I. 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, etc. yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73, etc. orange pigments; C.I. 215, 216, 224, 242, 254, 255, 264, 265, etc. red pigments; C.I. pigment blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigments; C.I. Pigment Violet 1, 19 , 23, 29, 32, 36, 38, etc. purple pigments; C.I. Pigment Green 7, 36, 58, 59, etc. Green pigments; C.I. Pigment Brown 23, 25, etc. Brown pigments; C.I. Pigment Black 1, 7, carbon Black pigments such as black, titanium black, iron oxide, 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) may be used alone or in combination of two or more according to the color of the target pixel. Furthermore, the above-mentioned dyes and pigments may 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 using a pigment as a coloring agent (E), you may mix|blend a well-known dispersing agent with a photosensitive resin composition from a viewpoint of improving a pigment dispersibility. As a dispersant, it is preferable to use a polymer dispersant excellent in dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, Sorbus Dan aliphatic ester dispersant, aliphatic denatured ester dispersant, etc. As such a polymer dispersant, for example, trade names EFKA (manufactured by EFKA chemicals BV (EFKA)), Disperbyk (manufactured by BYK-Chemie), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.) can also be used. system) and other commercially available. The compounding quantity of a dispersing agent should just be set suitably according to the kind of pigment etc. which are used.

共聚物(A)、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、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3~80質量份，以共聚物(A)為20~80質量份、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、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)、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 amount of copolymer (A), solvent (B), reactive diluent (C), photopolymerization initiator (D) and colorant (E) is relative to the amount of copolymer (A) in the photosensitive resin composition ) and the total amount of the reactive diluent (C) of 100 parts by mass, the copolymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, and the reactive diluent (C) is more than 0 mass parts ~ 90 mass parts, photopolymerization initiator (D) is 0.1 ~ 30 mass parts, coloring agent (E) is 3 ~ 80 mass parts, is 20 ~ 80 mass parts with copolymer (A), solvent ( B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, the photopolymerization initiator (D) is 0.5 to 20 parts by mass, and the colorant (E) is 5 to 70 parts by mass. Good, preferably 30-75 parts by mass of copolymer (A), 100-700 parts by mass of solvent (B), 25-70 parts by mass of reactive diluent (C), photopolymerization initiator (D) 1 to 15 parts by mass, and 10 to 60 parts by mass of the colorant (E). If the compounding quantity is within this range, it will become a photosensitive resin composition with an appropriate viscosity. Also, even in the case of a photosensitive resin composition that does not contain a colorant (E), the blending of the copolymer (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D) Quantities can also apply to the above-mentioned numerical range.

本發明之聚合物組成物及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。The polymer composition and photosensitive resin composition of the present invention may contain known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart predetermined characteristics in addition to the above-mentioned components. The compounding quantity of these additives will not be specifically limited as long as it is in the range which does not inhibit the effect of this invention.

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混合上述之成分來製造。又，根據希望，亦能預先調製包含共聚物(A)及溶劑(B)之聚合物組成物後，混合反應性稀釋劑(C)、光聚合起始劑(D)及著色劑(E)來製造。The photosensitive resin composition of the present invention can be produced by mixing the above-mentioned components using a known mixing device. Also, if desired, it is also possible to mix the reactive diluent (C), photopolymerization initiator (D) and colorant (E) after preparing a polymer composition containing the copolymer (A) and the solvent (B) in advance. 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210℃以下為佳，較佳為180℃以下，最佳為160℃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 said operation has alkali developability, it is suitable as a resist. The hardening of the photosensitive resin composition can be properly selected by selecting the baking temperature in the range below 250°C. The copolymer (A) of the present invention has excellent hardening properties at low temperatures, so it can be reduced compared with the conventional materials. baking temperature. In the case of using a pigment as the colorant (E) in the photosensitive resin composition, sufficient curability can be obtained even if the baking temperature is 160° C. or lower. The photosensitive resin composition of the present invention is advantageous in terms of energy consumption because the cross-linking reaction can proceed sufficiently even if the baking temperature is lowered. Moreover, even if it is a coloring agent (E) or a board|substrate poor in heat resistance, it becomes possible to acquire the characteristic of a coloring agent itself, and it can apply to various board|substrates. Based on this insight, the baking temperature is preferably set below 210°C, more preferably below 180°C, most preferably below 160°C. The lower limit of the baking temperature is not necessarily the same depending on the type of blocked isocyanato group contained in the copolymer (A), but it must be above the dissociation temperature of the blocked isocyanato group, usually above 80°C , preferably above 90°C, more preferably above 100°C. When the baking temperature becomes too low, it becomes difficult to fully improve the solvent resistance of a coating film. In addition, the baking time can be selected appropriately, 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 especially suitable as a color filter to be incorporated in organic EL displays (for black PDL), liquid crystal display devices, solid-state imaging devices such as CCD or CMOS, etc. The resist used. In addition, the photosensitive resin composition of the present invention can be used in various coatings, adhesives, adhesives for printing inks, etc. because it imparts a cured coating film excellent in solvent resistance, low-temperature curing properties, and the like.

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，耐溶劑性仍為優異之著色圖型，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 is extremely useful as a filter because it can form a colored pattern with good image development and storage stability, and even if the baking temperature during pattern formation is lowered, the solvent resistance is still excellent. Photosensitive material for coloring device. In addition, since the photosensitive resin composition of the present invention is cured at a low temperature, 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 colored pattern formed using the above-mentioned photosensitive resin composition. A color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed on the border of individual pixels, and a protective film formed on the pixels and the black matrix. In this structure, except that the pixel and the black matrix (colored pattern) are formed by using the above-mentioned photosensitive resin composition, the other structures can be all 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 colored pattern is formed on a substrate. Specifically, black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and can be suitably used such as glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, polyamide substrate, polyamideimide substrate, polyimide substrate, aluminum substrate , printed wiring substrates, 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。Coloring patterns can be formed by photolithography. Specifically, after the above-mentioned photosensitive resin composition is coated on a substrate to form a coating film, the coating film is exposed through a photomask of a predetermined pattern to photocure the exposed portion. After that, the unexposed part is developed with an aqueous alkali solution, and then baked to form a predetermined colored pattern.

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, roll coating, curtain coating, spray coating, and spin coating. In addition, after applying the photosensitive resin composition, if necessary, the solvent (B) may be volatilized by heating using heating means such as a circulation oven, an infrared heater, or a hot plate. The heating conditions are not particularly limited, and may be appropriately set according to the type of photosensitive resin composition to be used. Generally, it is enough to heat at a temperature of 50°C~120°C for 30 seconds to 30 minutes.

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 by irradiating active energy rays such as ultraviolet rays or excimer laser light through a negative mask. The amount of energy ray to be irradiated can be appropriately selected according to the composition of the photosensitive resin composition, for example, 30~2000mJ/cm 2 is preferable. The light source used for exposure is not particularly limited, and for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like 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。There is no particular limitation on the alkaline aqueous solution used for development, and aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; ethylamine, diethylamine, and 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 p-phenylenediamine-based compounds such as β-methoxyethylaniline and their sulfates, hydrochlorides, or p-toluenesulfonates, etc. Furthermore, a defoamer or a surfactant may be added to these aqueous solutions as necessary. In addition, after the above-mentioned image development by aqueous alkali solution, it is preferable to wash with water and dry.

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。Baking conditions are not particularly limited, and heat treatment may be performed according to the type of photosensitive resin composition used. If the conventional photosensitive resin composition is baked at a temperature below 200°C, the solvent resistance of the colored pattern will be insufficient, but even if the photosensitive resin composition of the present invention is baked at a temperature below 120°C, Still able to form pigmented patterns exhibiting adequate solvent resistance. Therefore, the baking temperature can be lowered, and the processing time can be shortened when baking at a high temperature, which is a great advantage in manufacturing. Based on this insight, the baking temperature is usually set below 210°C, preferably below 160°C, preferably below 120°C, and the baking time is usually set at 10 minutes to 4 hours, preferably at 20 minutes~ 2 hours to proceed.

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 black matrix and the photosensitive resin composition for red, green, and blue pixels, repeating the above-mentioned coating, exposure, development and baking in sequence, it can be formed Any desired coloring pattern. Also, the method of forming the colored pattern by photocuring has been described above, but if instead of the photopolymerization initiator (D), a photosensitive resin composition compounded with a hardening accelerator and a known epoxy resin is used , After coating by inkjet method, the desired color pattern can also be formed by heating. Next, a protective film is formed on the coloring pattern (each pixel of RGB and the black matrix). It does not specifically limit as a protective film, What is necessary is just to form using a well-known person.

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 produced by this operation is produced by using a photosensitive resin composition that can impart a color pattern that is excellent in sensitivity and image development, and can be cured at low temperature and has excellent solvent resistance. 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 equipped with the above-mentioned color filter, and specific examples thereof include liquid crystal display elements, organic EL display elements, CCD elements, and CMOS elements. Solid-state imaging devices, etc. The manufacture of the image display device of the present invention may be performed 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, and then electrodes, spacers, and the like are sequentially formed. Furthermore, electrodes and the like are formed on the other substrate, the two are bonded together, a predetermined amount of liquid crystal is injected, and sealing is performed. [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。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by these examples. Furthermore, in this embodiment, parts and percentages are all based on mass unless otherwise specified. In addition, the measuring method of acid value and weight average molecular weight is as follows.

(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。 (1) Acid value: the acid value of the copolymer (A) measured according to JIS K6901 5.3, and refers to the mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer (A) .

(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。 (2) Weight average molecular weight (Mw) means the weight average molecular weight in terms of standard polystyrene measured under the following conditions using gel permeation chromatography (GPC).

管柱：Shodex(註冊商標)LF-804+LF-804(昭和電工股份有限公司製) String: Shodex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.)

管柱溫度：40℃ Column temperature: 40°C

試料：共聚物之0.2%四氫呋喃溶液 Sample: 0.2% tetrahydrofuran solution of copolymer

展開溶劑：四氫呋喃 Developing solvent: tetrahydrofuran

檢測器：示差折射計(Shodex RI-71S)(昭和電工股份有限公司製) Detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.)

流速：1mL/min Flow rate: 1mL/min

[實施例1] [Example 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257.3g之二乙二醇甲基乙基醚後，實施氮取代並同時進行攪拌，且升溫至78℃。其次，將由110.0g之二環戊基甲基丙烯酸酯、17.0g之環氧丙基甲基丙 烯酸酯、28.4g之甲基丙烯酸及12.1g之甲基丙烯酸2-[O-(1’-甲基亞丙基胺基)羧基胺基]乙基酯(Karenz MOI-BM、昭和電工股份有限公司製、封端異氰酸根基之解離率：18質量%)所構成之單體混合物，與13.4g之2,2’-偶氮雙(2,4-二甲基戊腈)(聚合起始劑)，添加至78.7g之二乙二醇甲基乙基醚並使其溶解，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40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為7,500，酸價為102.3KOHmg/g。 After putting 257.3 g of diethylene glycol methyl ethyl ether into 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. Next, 110.0g of dicyclopentyl methacrylate, 17.0g of epoxypropyl methylpropane Acrylic acid ester, 28.4g of methacrylic acid and 12.1g of 2-[O-(1'-methylpropylene amino) carboxyl amino] ethyl methacrylate (Karenz MOI-BM, Showa Denko Co., Ltd. Co., Ltd., dissociation rate of blocked isocyanato group: 18% by mass) monomer mixture, and 13.4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerized Initiator) was added to 78.7 g of diethylene glycol methyl ethyl ether and dissolved, and this was dropped into the flask from the dropping funnel, respectively. After completion of the dropping, a copolymerization reaction was carried out by stirring at 78° C. for 3 hours to form a copolymer to obtain a polymer composition of Sample No. 1 (concentration of components other than the solvent: 40% by mass). The weight average molecular weight of the copolymer in the obtained polymer composition was 7,500, and the acid value was 102.3 KOHmg/g.

[實施例2~12及比較例1~3] [Examples 2 to 12 and Comparative Examples 1 to 3]

除了使用表1記載之原料以外，其他係在與實施例1相同之條件下進行共聚合反應，而取得試料No.2~15之聚合物組成物(溶劑以外之成分濃度40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。尚且，表1中，甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙基酯為昭和電工股份有限公司製Karenz MOI-BP，封端異氰酸根基之解離率：70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]胺基]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]胺基]羰基]氧基]甲基酯之封端異氰酸根基解離率：75質量%，2-丙烯酸-2-甲基-2-[[(3,5-二甲基苯氧基)羰基]胺基]乙基酯之封端異氰酸根基之解離率：28質量%。 Except for using the raw materials listed in Table 1, the copolymerization reaction was carried out under the same conditions as in Example 1 to obtain polymer compositions of sample Nos. 2 to 15 (concentration of components other than the solvent: 40% by mass). Table 1 shows the weight average molecular weight and acid value of the copolymer in the obtained polymer composition. Also, in Table 1, 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate is Karenz MOI-BP manufactured by Showa Denko Co., Ltd., and the isocyanato group is blocked Dissociation rate: 70% by mass, malonate-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 isocyanato group: 90% by mass, benzoic acid-4-[[[[2-[(2-methyl-1 Dissociation rate of blocked isocyanato group of -oxo-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester: 40% by mass, benzoin Capping of acid-2-[[[[2-[(2-methyl-1-oxyl-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester Isocyanato group dissociation rate: 75% by mass, blocked isocyanate of 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester Root dissociation rate: 28% by mass.

Figure 107125425-A0305-02-0043-1
Figure 107125425-A0305-02-0043-1

Figure 107125425-A0305-02-0044-2
Figure 107125425-A0305-02-0044-2

[實施例13~24及比較例4~6] [Examples 13-24 and Comparative Examples 4-6] <感光性樹脂組成物(顏料型)之調製> <Preparation of photosensitive resin composition (pigment type)>

藉由對填充有直徑0.5mm之氧化鋯珠200質量份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。 100 parts by mass of C.I Pigment Green 36 (colorant), 44.98 parts by mass of propylene glycol monomethyl ether acetate, and a dispersant (BYK-Chemie Disperbyk-161 (manufactured by Japan Co., Ltd.) 25 parts by mass was mixed with a paint shaker (paint shaker) for 2 hours and dispersed to prepare a green pigment dispersion.

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13~24之感光性樹脂組成物係分別使用實施例1~12(試料No.1~12)之聚合物組成物進行調製，比較例4~6之感光性樹脂組成物係分別使用比較例1~3(試料No.13~15)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。This green pigment dispersion was mixed with other ingredients shown in Table 3 (ie, polymer composition, reactive diluent, photopolymerization initiator, and solvent) to prepare a photosensitive resin composition. The blending amounts of individual components are shown in Table 3. Furthermore, the photosensitive resin compositions of Examples 13 to 24 were prepared using the polymer compositions of Examples 1 to 12 (sample Nos. 1 to 12), respectively, and the photosensitive resin compositions of Comparative Examples 4 to 6 were respectively Preparation was performed using the polymer compositions of Comparative Examples 1-3 (sample Nos. 13-15). 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 the compounding component.

Figure 02_image013
Figure 02_image013

＜感光性樹脂組成物之評價＞ (1)鹼顯像性 　　分別將實施例13~24及比較例4~6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分鐘加熱使溶劑揮發。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(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 Compositions> (1) Alkali Developability The photosensitive resin compositions of Examples 13-24 and Comparative Examples 4-6 were spin-coated so that the thickness after exposure became 2.5 μm. 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, set a distance of 100 μm from the coating film to a prescribed pattern mask, and expose the coating film through the mask (exposure amount: 150 mJ/cm 2 ) to light-cure the exposed part. Next, by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23°C and a pressure of 0.3MPa, the unexposed portion was dissolved and developed, and then baked at 100°C for 20 minutes. Form a prescribed pattern. The residue after the alkali development was confirmed by observing the pattern after the alkali development using an electron microscope S-3400 manufactured by Hitachi High-Tech Co., Ltd. The criteria for this evaluation are as follows. ◯: No residue ×: Residue exists Table 4 shows the evaluation results of the alkali developability.

(2)耐溶劑性之評價 　　分別將實施例13~24及比較例4~6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 13-24 and Comparative Examples 4-6 were spin-coated on a 5 cm square glass substrate (without Alkali glass substrate) and heated at 90° C. for 3 minutes to evaporate the solvent. Next, the coating film was exposed to light with a wavelength of 365 nm, and the exposed part was light-cured, and then placed in a dryer at a baking temperature of 100° C. for 20 minutes to form a cured coating film. Put 200mL of propylene glycol monomethyl ether acetate into a 500mL capped glass bottle, and let it stand at 80°C. After immersing the above-mentioned test piece with a cured coating film therein, it was left to stand for 5 minutes in a state maintained at 80°C. The color change (ΔE * ab) before and after immersing the test piece 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. When ΔE * ab is 1.5 or less, it can be said that the solvent resistance is excellent.

(3)保存安定性之評價 　　將實施例1~12及比較例1~3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 Examples 1 to 12 and Comparative Examples 1 to 3 were measured in equal amounts into glass containers, and the mouths were sealed with aluminum foil so that dust would not enter. Next, these samples were respectively placed in a thermostat kept at 23° C., and the weight average molecular weight (Mw) of the samples was measured one month later. The rate of change of Mw after one month is shown in Table 5. If the rate of change of Mw after one month is within 20%, it can be said that the storage stability of the copolymer is excellent.

Figure 02_image015
Figure 02_image015

Figure 02_image017
Figure 02_image017

由表4之結果可明白得知，使用試料No.1~12之聚合物組成物之實施例13~24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.1~12之聚合物組成物之實施例13~24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.13~15之聚合物組成物之比較例4~6之感光性樹脂組成物之保存安定性雖為良好，但耐溶劑性並不充分，又，比較例6之感光性樹脂組成物之鹼顯像性也不充分。From the results in Table 4, it can be clearly seen that the photosensitive resin compositions of Examples 13-24 using the polymer compositions of Sample Nos. 1-12 are good in alkali developability and solvent resistance. Moreover, since the storage stability of the copolymer is related to the storage stability of the photosensitive resin composition blended with it, it can be seen from the results in Table 5 that the implementation of the polymer composition using sample No.1~12 The photosensitive resin compositions of Examples 13-24 are also good in terms of storage stability. On the other hand, although the storage stability of the photosensitive resin compositions of Comparative Examples 4 to 6 using the polymer compositions of Sample Nos. 13 to 15 was good, the solvent resistance was not sufficient. The alkali developability of the photosensitive resin composition is also 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。又，本發明可提供在調製具有如上述特性之感光性樹脂組成物所有用之共聚物。From the above results, it can be seen that according to the present invention, a photosensitive resin composition having good image development property, solvent resistance and storage stability can be provided. Furthermore, the present invention can provide a copolymer useful in preparing a photosensitive resin composition having the above-mentioned characteristics.

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2017-150501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。Furthermore, this international application claims priority based on the Japanese patent application No. 2017-150501 filed on August 3, 2017, and the entire content of the Japanese patent application is cited in this international application .

Claims (17)

一種共聚物(A)，其特徵為含有：源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位(a)、源自(甲基)丙烯酸之構成單位(b)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)，及源自選自由二環戊基(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(e)；前述含封端異氰酸根基之(甲基)丙烯酸酯為選自由安息香酸-4-[[[[2-[(2-甲基-1-側氧基-2-丙烯-1-基)氧基]乙基]胺基]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]胺基]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]胺基]乙基酯所成群之至少一種。 A copolymer (A) characterized by comprising: a constituent unit (a) derived from (meth)acrylate containing a blocked isocyanate group, a constituent unit (b) derived from (meth)acrylic acid, a source Constituent unit (c) derived from glycidyl (meth)acrylate, and derived from dicyclopentanyl (meth)acrylate (dicyclopentanyl (meth)acrylate) and meth (meth)acrylate At least one constituent unit (e) of the group; the aforementioned (meth)acrylate containing blocked isocyanato group is selected from benzoic acid-4-[[[[2-[(2-methyl-1- Pendant oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1- Oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5-dimethyl At least one of the group of phenoxy)carbonyl]amino]ethyl esters. 如請求項1之共聚物(A)，其中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%。 Such as the copolymer (A) of claim 1, wherein the dissociation rate of the blocked isocyanato group of the (meth)acrylate containing blocked isocyanate group is 5~99% by mass after heating at 100°C for 30 minutes %. 如請求項1之共聚物(A)，其中前述共聚物(A)含有前述源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位(a)1~60莫耳%、前述源自(甲基)丙烯酸之構成單位(b)5~65莫耳%及前述源自環氧丙基(甲基)丙烯酸酯之構成單位(c)5~65莫耳%。 Such as the copolymer (A) of claim 1, wherein the aforementioned copolymer (A) contains the aforementioned structural unit (a) derived from (meth)acrylate containing blocked isocyanate group (a) 1~60 mol%, the aforementioned The structural unit (b) derived from (meth)acrylic acid is 5-65 mole % and the structural unit (c) derived from glycidyl (meth)acrylate is 5-65 mole %. 如請求項1之共聚物(A)，其中前述共聚物(A)中前述源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位(a)與前述源自環氧丙基(甲基)丙烯酸酯之構成單位(c)之莫耳比率為10：90~75：25。 Such as the copolymer (A) of claim 1, wherein in the aforementioned copolymer (A), the aforementioned constituent unit (a) derived from (meth)acrylate containing blocked isocyanato group and the aforementioned unit derived from glycidyl group The molar ratio of the constituent unit (c) of (meth)acrylate is 10:90 to 75:25. 如請求項1之共聚物(A)，其中前述共聚物(A)更含有：具有羥基之構成單位(d)。 The copolymer (A) according to claim 1, wherein the aforementioned copolymer (A) further contains: a constituent unit (d) having a hydroxyl group. 如請求項5之共聚物(A)，其中前述共聚物(A)含有：源自選自由安息香酸-4-[[[[2-[(2-甲基-1-側氧基-2-丙烯-1-基)氧基]乙基]胺基]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]胺基]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]胺基]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)、源自環氧丙基(甲基)丙烯酸酯之構成單位(c)、源自2-羥基乙基甲基丙烯酸酯之構成單位(d)，及源自選自由二環戊基(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(e)。 Such as the copolymer (A) of claim 5, wherein the aforementioned copolymer (A) contains: derived from benzoic acid-4-[[[[2-[(2-methyl-1-side oxy-2- propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1-oxyl-2-propene -1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl] At least one structural unit (a) of amino]ethyl ester group, structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate ), a constituent unit (d) derived from 2-hydroxyethyl methacrylate, and at least one type derived from the group consisting of dicyclopentyl (meth)acrylate and meth (meth)acrylate Constituent unit (e). 如請求項1之共聚物(A)，其中前述共聚物(A)更含有：具有羥基之構成單位(d)，且前述共聚物(A)含有：前述源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位(a)1~40莫耳%、前述源自不飽 和羧酸之構成單位(b)1~60莫耳%、前述源自含環氧基之(甲基)丙烯酸酯之構成單位(c)1~70莫耳%、前述具有羥基之構成單位(d)超過0莫耳%~50莫耳%及前述構成單位(e)超過0莫耳%~80莫耳%。 Such as the copolymer (A) of claim 1, wherein the aforementioned copolymer (A) further contains: a constituent unit (d) having a hydroxyl group, and the aforementioned copolymer (A) contains: the aforementioned Constituent unit (a) of (meth)acrylate is 1~40 mole%, the above-mentioned source is unsaturated and 1-60 mol% of the constituent unit (b) of carboxylic acid, 1-70 mol% of the aforementioned constituent unit (c) derived from epoxy-containing (meth)acrylate, and the aforementioned constituent unit ( d) Exceeding 0 mol % to 50 mol % and the aforementioned constituent unit (e) exceeding 0 mol % to 80 mol %. 如請求項1之共聚物(A)，其中前述共聚物(A)更含有：具有羥基之構成單位(d)，且前述共聚物(A)含有：前述源自含封端異氰酸根基之(甲基)丙烯酸酯之構成單位(a)3~20莫耳%、前述源自(甲基)丙烯酸之構成單位(b)20~50莫耳%、前述源自環氧丙基(甲基)丙烯酸酯之構成單位(c)20~40莫耳%、前述具有羥基之構成單位(d)超過0莫耳%~20莫耳%及前述構成單位(e)20~40莫耳%。 Such as the copolymer (A) of claim 1, wherein the aforementioned copolymer (A) further contains: a constituent unit (d) having a hydroxyl group, and the aforementioned copolymer (A) contains: the aforementioned The constituent unit (a) of (meth)acrylate is 3~20 mol%, the constituent unit (b) derived from (meth)acrylic acid is 20~50 mol%, the aforementioned constituent unit derived from glycidyl (methyl) ) 20-40 mol% of the constituent unit (c) of acrylate, more than 0-20 mol% of the aforementioned constituent unit (d) having a hydroxyl group, and 20-40 molar % of the aforementioned constituent unit (e). 一種聚合物組成物，其特徵為含有：如請求項1至8中任一項之共聚物(A)，與，溶劑(B)及反應性稀釋劑(C)之至少一者。 A polymer composition characterized by comprising: the copolymer (A) according to any one of claims 1 to 8, and at least one of solvent (B) and reactive diluent (C). 一種感光性樹脂組成物，其特徵為含有：如請求項1至8中任一項之共聚物(A)、溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)。 A photosensitive resin composition, characterized by containing: copolymer (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D) according to any one of claims 1 to 8 . 一種濾色器用感光性樹脂組成物，其特徵為含有：如請求項1至8中任一項之共聚物(A)、溶劑(B)、反應性稀釋 劑(C)、光聚合起始劑(D)及著色劑(E)。 A photosensitive resin composition for a color filter, characterized by containing: a copolymer (A) as in any one of claims 1 to 8, a solvent (B), a reactive diluent agent (C), photopolymerization initiator (D) and colorant (E). 如請求項11之濾色器用感光性樹脂組成物，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~未滿100質量份、前述溶劑(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、前述著色劑(E)3~80質量份。 The photosensitive resin composition for color filters according to claim 11, wherein the copolymer (A) contains 10 to less than 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). 100 parts by mass, 30 to 1,000 parts by mass of the aforementioned solvent (B), more than 0 to 90 parts by mass of the aforementioned reactive diluent (C), 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (D), and the aforementioned colorant (E) 3 to 80 parts by mass. 如請求項11之濾色器用感光性樹脂組成物，其中前述溶劑(B)包含：含羥基之有機溶劑。 The photosensitive resin composition for color filters according to claim 11, wherein the solvent (B) includes: a hydroxyl-containing organic solvent. 如請求項11之濾色器用感光性樹脂組成物，其中前述著色劑(E)包含顏料。 The photosensitive resin composition for color filters according to claim 11, wherein the colorant (E) includes a pigment. 一種濾色器，其特徵為具有由如請求項11~14中任一項之濾色器用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 colored pattern made of a cured product of the photosensitive resin composition for a color filter according to any one of Claims 11 to 14. 一種圖像顯示元件，其特徵為具備如請求項15之濾色器。 An image display element, characterized by having a color filter according to claim 15. 一種濾色器之製造方法，其特徵為包含：將如請求項11~14中任一項之濾色器用感光性樹脂組成物塗佈於基 板，進行曝光，鹼顯像後，在160℃以下之溫度進行烘烤而形成著色圖型之步驟。 A method for manufacturing a color filter, characterized by comprising: coating a photosensitive resin composition for a color filter according to any one of Claims 11 to 14 on a substrate The plate is exposed, and after alkali development, it is baked at a temperature below 160°C to form a colored pattern.
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