TW202233698A - Method for producing copolymer - Google Patents

Method for producing copolymer Download PDF

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TW202233698A
TW202233698A TW110138500A TW110138500A TW202233698A TW 202233698 A TW202233698 A TW 202233698A TW 110138500 A TW110138500 A TW 110138500A TW 110138500 A TW110138500 A TW 110138500A TW 202233698 A TW202233698 A TW 202233698A
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mass
ethylenically unsaturated
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copolymer
solvent
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TW110138500A
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木下健宏
永井英理
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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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (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
    • C08F220/26—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Polymerization Catalysts (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Provided is a method for producing a copolymer in which the molecular weight of a resin is controlled to a low molecular weight side. A method for producing a copolymer according to the present invention, which polymerizes a compound containing an ethylenically unsaturated group, comprises: a step in which a polymerization initiator and a solvent are mixed to obtain a reaction solution (1); a step for preparing a reaction solution (2) containing a compound containing an ethylenically unsaturated group; and a step in which the reaction liquid 1 and the reaction liquid 2 are dropped into the reactor and mixed. The concentration of the polymerization initiator in the reaction solution (1) is 16-50 mass%. The polymerization initiator contains 60 mass% or more of one isomer having a high solubility from among isomers comprising racemes and meso-isomers contained in the polymerization initiator. The polymerization initiator is a compound represented by general formula (1). In the formula (1), R1 and R2 are C1-6 alkyl groups or CN groups, and R1 and R2 are different; r3 and R4 are alkyl groups of C1-6; and R5 is H or a C1-6 alkoxy group.

Description

共聚物之製造方法Manufacturing method of copolymer

本發明係關於共聚物之製造方法、含有以該製造方法所得到的共聚物之感光性樹脂組成物、樹脂硬化膜、彩色濾光片及圖像顯示元件。The present invention relates to a method for producing a copolymer, a photosensitive resin composition, a cured resin film, a color filter, and an image display element containing the copolymer obtained by the method.

近年來，由省資源或省能源的觀點，在各種塗層、印刷、塗料、接著劑等之領域中，係廣為使用可藉由紫外線或電子束等之活性能量線而硬化的感光性樹脂組成物。又，在印刷配線基板等之電子材料之領域中，可藉由活性能量線而硬化的感光性樹脂組成物，亦作為用於製造阻焊劑或彩色濾光片、黑色矩陣、光間隔件、保護膜等的阻劑，而被使用。再者，近年來由於基材或發光元件之耐熱性的影響，係期望可將烘烤溫度設定在更低溫的感光性樹脂組成物。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 beams have been widely used in various fields of coating, printing, paint, adhesives, etc. composition. Also, in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are also used for the production of solder resists, color filters, black matrices, photo-spacers, protection Resistant for films, etc., and is used. In addition, in recent years, due to the influence of the heat resistance of a base material or a light-emitting element, a photosensitive resin composition in which the baking temperature can be set at a lower temperature has been desired.

同領域當中，作為用於感光性樹脂組成物之樹脂，已知有使用藉由自由基聚合所得之樹脂者，如此之樹脂之製造方法亦至今為止提出有各種者(專利文獻1、2)。工業上為了藉由自由基聚合而安定生產樹脂，一般而言亦為於溶劑中一邊滴下單體與自由基聚合起始劑一邊聚合。又，作為同領域的自由基聚合起始劑，係有偶氮系之聚合起始劑，但偶氮系之聚合起始劑多為固體者，有必要溶解於單體、溶劑等來進行聚合。 [先前技術文獻] [專利文獻] In the same field, resins obtained by radical polymerization are known as resins used for photosensitive resin compositions, and various methods for producing such resins have been proposed (Patent Documents 1 and 2). Industrially, in order to stably produce resin by radical polymerization, generally, it is also polymerized while dropping a monomer and a radical polymerization initiator in a solvent. In addition, as a radical polymerization initiator in the same field, there are azo-based polymerization initiators, but most of azo-based polymerization initiators are solid ones, and it is necessary to dissolve them in monomers, solvents, etc. to carry out polymerization. . [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2002-265390號公報 [專利文獻2]日本特開2008-266555號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2002-265390 [Patent Document 2] Japanese Patent Laid-Open No. 2008-266555

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

就安全性之觀點，較期望將單體與聚合起始劑分開滴下。惟，自由基聚合起始劑對溶劑之溶解性低，無法增加起始劑量，因此係有無法將用於感光性樹脂組成物之樹脂控制在低分子量側的問題。其結果，使用含有如此之樹脂的感光性樹脂組成物作為阻劑時，係有顯影性或耐溶劑性不足之問題。From the viewpoint of safety, it is more desirable to drop the monomer and the polymerization initiator separately. However, since the solubility of the radical polymerization initiator to the solvent is low, and the amount of the initiator cannot be increased, there is a problem that the resin used for the photosensitive resin composition cannot be controlled to the low molecular weight side. As a result, when a photosensitive resin composition containing such a resin is used as a resist, there is a problem of insufficient developability and solvent resistance.

本發明係為了解決如上述之課題而為者，其目的為提供將樹脂之分子量控制在低分子量側的共聚物之製造方法。 又，本發明之目的為提供適合用於顯影性優良的感光性樹脂組成物之共聚物之製造方法。進一步地，本發明之目的為提供適合使用作為耐溶劑性優良的樹脂硬化膜之材料的共聚物之製造方法。 [用以解決課題之手段] This invention is made in order to solve the above-mentioned subject, and the objective is to provide the manufacturing method of the copolymer which controls the molecular weight of a resin to a low molecular weight side. Moreover, the objective of this invention is to provide the manufacturing method of the copolymer suitable for the photosensitive resin composition excellent in developability. Furthermore, the objective of this invention is to provide the manufacturing method of the copolymer which is suitable for use as the material of the resin cured film excellent in solvent resistance. [means to solve the problem]

本發明包含以下態樣。 [1] 一種共聚物之製造方法，其係包含 將聚合起始劑與溶劑(稱「溶劑(ii)」)混合，得到反應液1之步驟、 調製含有含乙烯性不飽和基之化合物的反應液2之步驟，與 將反應液1與反應液2滴下混合於反應器中之步驟 的、使含乙烯性不飽和基之化合物聚合的共聚物之製造方法，其特徵為 於反應液1中，聚合起始劑之濃度為16質量%~50質量%， 前述聚合起始劑中所含有之由外消旋體(racemic body)及內消旋體(meso body)所構成的異構物當中，對前述溶劑(ii)之溶解度較高之異構物係在聚合起始劑中含有60質量%以上， 前述聚合起始劑為下述通式(1)表示之化合物， 前述含乙烯性不飽和基之化合物，至少含有不具有羧基且具有封端異氰酸基之含乙烯性不飽和基之化合物及具有羧基之含乙烯性不飽和基之化合物；

Figure 02_image001
(式(1)中，R 1及R 2各自獨立為碳數1~6之烷基或氰基，且R 1及R 2表示相異之基，R 3及R 4各自獨立表示碳數1~6之烷基，R 5表示氫原子或碳數1~6之烷氧基)。 [2] 如[1]之共聚物之製造方法，其中前述式(1)中，R 1及R 2之一者為氰基。 [3] 如[1]或[2]之共聚物之製造方法，其中前述聚合起始劑，為選自2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)及2,2’-偶氮雙(2,4-二甲基戊腈)的1種或2種以上。 [4] 如[1]~[3]中任一項之共聚物之製造方法，其中前述聚合起始劑之使用量，相對於前述含乙烯性不飽和基之化合物100質量份而言，為5~30質量份。 [5] 如[1]~[4]中任一項之共聚物之製造方法，其中前述含乙烯性不飽和基之化合物，進一步含有具有羥基之含乙烯性不飽和基之化合物。 [6] 如[1]~[5]中任一項之共聚物之製造方法，其中前述含乙烯性不飽和基之化合物，進一步含有具有環氧基之含乙烯性不飽和基之化合物。 [7] 如[1]~[6]中任一項之共聚物之製造方法，其中前述含乙烯性不飽和基之化合物中，含有不具有羧基且具有封端異氰酸基之含乙烯性不飽和基之化合物5~30莫耳%、具有羧基之含乙烯性不飽和基之化合物10~50莫耳%。 [8] 如[1]~[7]中任一項之共聚物之製造方法，其重量平均分子量為3,000~15,000。 [9] 如[1]~[8]中任一項之共聚物之製造方法，其係依序具有 將相對於前述含乙烯性不飽和基之化合物合計100質量份而言為50~500質量份的溶劑(i)昇溫至設定聚合溫度之步驟I、 將前述反應液1及前述反應液2分別滴下至前述溶劑(i)中進行共聚合之步驟II，與 於前述反應液1及反應液2之滴下結束後，進一步繼續共聚合反應1~10小時之步驟III 之共聚物之製造方法，其中 前述反應液1為前述聚合起始劑100質量份與溶劑(ii)100~525質量份之混合物， 前述反應液2，為前述含乙烯性不飽和基之化合物合計100質量份與溶劑(iii)0~500質量份之混合物。 [10] 一種感光性樹脂組成物，其含有藉由如[1]~[9]中任一項之製造方法所得到的共聚物、反應性稀釋劑、光聚合起始劑、著色劑、溶劑。 [11] 一種樹脂硬化膜，其係使如[10]之感光性樹脂組成物硬化而得到。 [12] 一種樹脂硬化膜之製造方法，其係將如[10]之感光性樹脂組成物塗佈、曝光、顯影，且於70~150℃硬化。 [13] 一種彩色濾光片，其特徵為具有由如[10]之感光性樹脂組成物之硬化物所成之著色圖型。 [14] 一種圖像顯示元件，其特徵為具備如[13]之彩色濾光片。 [發明之效果] The present invention includes the following aspects. [1] A method for producing a copolymer, comprising a step of mixing a polymerization initiator and a solvent (referred to as “solvent (ii)”) to obtain a reaction solution 1, and a reaction for preparing a compound containing an ethylenically unsaturated group The step of liquid 2, and the step of dropping and mixing the reaction liquid 1 and the reaction liquid 2 in a reactor, the method for producing a copolymer for polymerizing an ethylenically unsaturated group-containing compound is characterized in that in the reaction liquid 1, The concentration of the polymerization initiator is 16% by mass to 50% by mass. Among the isomers composed of the racemic body and the meso body contained in the polymerization initiator, The isomer with higher solubility in the aforementioned solvent (ii) is contained in a polymerization initiator in an amount of 60% by mass or more, and the aforementioned polymerization initiator is a compound represented by the following general formula (1), and the aforementioned ethylenically unsaturated A compound containing at least an ethylenically unsaturated group that does not have a carboxyl group and has a blocked isocyanate group and an ethylenically unsaturated group-containing compound that has a carboxyl group;
Figure 02_image001
(In formula (1), R 1 and R 2 are each independently an alkyl group or a cyano group having 1 to 6 carbon atoms, and R 1 and R 2 represent different groups, and R 3 and R 4 each independently represent a carbon number of 1 ~6 alkyl group, R 5 represents a hydrogen atom or an alkoxy group with a carbon number of 1~6). [2] The method for producing a copolymer according to [1], wherein in the aforementioned formula (1), one of R 1 and R 2 is a cyano group. [3] The method for producing the copolymer of [1] or [2], wherein the polymerization initiator is selected from 2,2'-azobis(4-methoxy-2,4-dimethyl) valeronitrile) and one or more of 2,2'-azobis(2,4-dimethylvaleronitrile). [4] The method for producing a copolymer according to any one of [1] to [3], wherein the amount of the polymerization initiator used is 100 parts by mass of the ethylenically unsaturated group-containing compound. 5 to 30 parts by mass. [5] The method for producing a copolymer according to any one of [1] to [4], wherein the ethylenically unsaturated group-containing compound further contains an ethylenically unsaturated group-containing compound having a hydroxyl group. [6] The method for producing a copolymer according to any one of [1] to [5], wherein the ethylenically unsaturated group-containing compound further contains an ethylenically unsaturated group-containing compound having an epoxy group. [7] The method for producing a copolymer according to any one of [1] to [6], wherein the ethylenically unsaturated group-containing compound contains an ethylenically unsaturated group containing no carboxyl group and a blocked isocyanate group. 5~30 mol% of unsaturated group compound, 10~50 mol% of ethylenically unsaturated group-containing compound with carboxyl group. [8] The method for producing a copolymer according to any one of [1] to [7], wherein the weight average molecular weight is 3,000 to 15,000. [9] The method for producing a copolymer according to any one of [1] to [8], which sequentially has 50 to 500 parts by mass relative to a total of 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound The step I of heating up the solvent (i) to the set polymerization temperature, dropping the aforementioned reaction solution 1 and the aforementioned reaction solution 2 into the aforementioned solvent (i) respectively, the step II of copolymerization, and the aforementioned step II of the aforementioned reaction solution 1 and the reaction solution After the dropping of 2 is completed, the method for producing the copolymer of step III of the step III of the copolymerization reaction is continued for 1 to 10 hours, wherein the aforementioned reaction solution 1 is 100 parts by mass of the aforementioned polymerization initiator and 100 to 525 parts by mass of the solvent (ii). The mixture, the reaction solution 2, is a mixture of 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound and 0 to 500 parts by mass of the solvent (iii). [10] A photosensitive resin composition comprising a copolymer obtained by the production method according to any one of [1] to [9], a reactive diluent, a photopolymerization initiator, a colorant, and a solvent . [11] A resin cured film obtained by curing the photosensitive resin composition according to [10]. [12] A method for producing a resin cured film, comprising coating, exposing, developing, and curing the photosensitive resin composition according to [10] at 70 to 150°C. [13] A color filter characterized by having a colored pattern formed of a cured product of the photosensitive resin composition according to [10]. [14] An image display element characterized by having the color filter according to [13]. [Effect of invention]

依照本發明，可提供將樹脂之分子量控制在低分子量側的共聚物之製造方法。又，可提供適合用於顯影性優良的感光性樹脂組成物之共聚物之製造方法。進一步地，本發明可提供適合使用作為耐溶劑性優良的樹脂硬化膜之材料的共聚物之製造方法。According to the present invention, a method for producing a copolymer in which the molecular weight of the resin is controlled to be on the low molecular weight side can be provided. Moreover, the manufacturing method of the copolymer suitable for the photosensitive resin composition excellent in developability can be provided. Furthermore, the present invention can provide a method for producing a copolymer suitable for use as a material of a resin cured film having excellent solvent resistance.

以下，詳細說明本發明之實施形態。惟，本發明不限定於以下所示之實施形態。 本說明書中表述為(甲基)丙烯酸酯者，意指可為丙烯酸酯及甲基丙烯酸酯之任意者，又，(甲基)丙烯酸之表述，意指可為丙烯酸及甲基丙烯酸之任意者。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In this specification, what is expressed as (meth)acrylate means that any one of acrylate and methacrylate can be used, and the expression of (meth)acrylic acid means that any one of acrylic acid and methacrylic acid can be used. .

＜共聚物之製造方法＞ 本實施形態之共聚物之製造方法，為使含乙烯性不飽和基之化合物聚合的共聚物之製造方法。本實施形態之共聚物之製造方法，包含將聚合起始劑與溶劑混合，而得到反應液1之步驟；調製含有特定2種以上的含乙烯性不飽和基之化合物的反應液2之步驟；與將反應液1與反應液2滴下混合於反應器中之步驟。前述反應液1中，聚合起始劑之濃度為16~50質量%。前述聚合起始劑中所含有之由外消旋體及內消旋體所構成的異構物當中，溶解度較高之異構物在聚合起始劑中係含有60質量%以上。 <Production method of copolymer> The method for producing a copolymer of the present embodiment is a method for producing a copolymer in which an ethylenically unsaturated group-containing compound is polymerized. The method for producing a copolymer of the present embodiment includes a step of obtaining a reaction solution 1 by mixing a polymerization initiator and a solvent; a step of preparing a reaction solution 2 containing two or more specific ethylenically unsaturated group-containing compounds; and the step of dropping and mixing the reaction solution 1 and the reaction solution 2 in the reactor. In the said reaction liquid 1, the density|concentration of a polymerization initiator is 16-50 mass %. Among the isomers consisting of racemates and mesomers contained in the aforementioned polymerization initiator, the isomers with higher solubility are contained in the polymerization initiator in an amount of 60% by mass or more.

[聚合起始劑] 聚合起始劑為下述通式(1)表示之化合物。 [Polymerization initiator] The polymerization initiator is a compound represented by the following general formula (1).

Figure 02_image003
Figure 02_image003

式(1)中，R 1及R 2各自獨立為碳數1~6之烷基或氰基，且R 1及R 2表示相異之基，R 3及R 4各自獨立表示碳數1~6之烷基，R 5表示氫原子或碳數1~6之烷氧基。 In formula (1), R 1 and R 2 are each independently an alkyl group or a cyano group having 1 to 6 carbon atoms, and R 1 and R 2 represent different groups, and R 3 and R 4 each independently represent a carbon number of 1 to 6. An alkyl group of 6, and R 5 represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms.

R 1及R 2所示的碳數1~6之烷基，就溶解性之觀點，較佳為碳數1~4、更佳為碳數1~2、又更佳為碳數1之甲基。 R 1及R 2表示相異之基，就分解性之觀點，較佳為碳數1~6之烷基與氰基之組合、更佳為甲基與氰基之組合。 From the viewpoint of solubility, the alkyl groups having 1 to 6 carbon atoms represented by R 1 and R 2 are preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and more preferably 1 to 1 carbon atoms. base. R 1 and R 2 represent different groups, and from the viewpoint of decomposability, a combination of an alkyl group having 1 to 6 carbon atoms and a cyano group is preferable, and a combination of a methyl group and a cyano group is more preferable.

R 3及R 4所示的碳數1~6之烷基，就溶解性之觀點，較佳為碳數1~4、更佳為碳數1~2、又更佳為碳數1之甲基。 From the viewpoint of solubility, the alkyl groups having 1 to 6 carbon atoms represented by R 3 and R 4 are preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and more preferably 1 to 1 carbon atoms. base.

R 5所示的氫原子或碳數1~6之烷氧基，就溶解性之觀點，較佳為氫原子或碳數1~4之烷氧基、更佳為氫原子或碳數1~2之烷氧基、又更佳為氫原子。 From the viewpoint of solubility, the hydrogen atom represented by R 5 or the alkoxy group having 1 to 6 carbon atoms is preferably a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. The alkoxy group of 2 is more preferably a hydrogen atom.

前述式(1)所示的化合物，具體而言，可列舉2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)。其中由於溶解性或10小時半衰期溫度適度地高，適於量產，尤以2,2’-偶氮雙(2,4-二甲基戊腈)為佳。Specifically, the compound represented by the above formula (1) includes 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile). Among them, due to its moderately high solubility or 10-hour half-life temperature, it is suitable for mass production, and 2,2'-azobis(2,4-dimethylvaleronitrile) is especially preferred.

[溶劑] 用於共聚物之製造的後述溶劑(i)、溶劑(ii)、溶劑(iii)並不特別限定，例如可列舉(聚)烯烴二醇單烷基醚乙酸酯化合物、(聚)烯烴二醇單烷基醚乙酸酯化合物、其他之醚化合物、酮化合物、酯化合物、芳香族烴化合物、羧酸醯胺化合物等。 (聚)烯烴二醇單烷基醚乙酸酯化合物，可列舉乙二醇單甲基醚、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。 (聚)烯烴二醇單烷基醚乙酸酯化合物，可列舉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。 [solvent] The following solvent (i), solvent (ii), and solvent (iii) used in the production of the copolymer are not particularly limited, and examples thereof include (poly) olefin diol monoalkyl ether acetate compounds, (poly) olefin diols Alcohol monoalkyl ether acetate compounds, other ether compounds, ketone compounds, ester compounds, aromatic hydrocarbon compounds, carboxylic acid amide compounds, and the like. (Poly) olefin glycol monoalkyl ether acetate compound, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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 monoethyl 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, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether base ether, etc. (Poly)olefin glycol monoalkyl ether acetate compound, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, etc.

其他之醚化合物，可列舉二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、四氫呋喃等。 酮化合物，可列舉甲基乙基酮、環己酮、2-庚酮、3-庚酮等。 酯化合物，可列舉2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3-甲基-3-甲氧基丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸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-側氧丁酸乙酯等。 芳香族烴化合物，可列舉甲苯、二甲苯等。 羧酸醯胺化合物，可列舉N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等。 此等之溶劑，可單獨或混合2種以上使用。 Other ether compounds include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and the like. As a ketone compound, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. are mentioned. Ester compounds include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methylpropionate Methyl oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate , n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyl acetate n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 - Ethyl oxybutyrate, etc. The aromatic hydrocarbon compound includes toluene, xylene, and the like. The carboxyamide compound includes N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. These solvents can be used alone or in combination of two or more.

此等之中，尤佳為(聚)烯烴二醇單烷基醚化合物及(聚)烯烴二醇單烷基醚乙酸酯化合物等之(聚)烯烴二醇醚系溶劑；更佳為丙二醇單甲基醚及丙二醇單甲基醚乙酸酯等之丙二醇系溶劑。Among these, (poly)olefin glycol ether-based solvents such as (poly)olefin glycol monoalkyl ether compounds and (poly)olefin glycol monoalkyl ether acetate compounds are particularly preferable; propylene glycol is more preferable Propylene glycol-based solvents such as monomethyl ether and propylene glycol monomethyl ether acetate.

溶劑之總使用量不特別限定，相對於含乙烯性不飽和基之化合物100質量份而言，較佳為30~1,000質量份、更佳為50~800質量份。特別是藉由使溶劑之使用量成為1,000質量份以下，可將聚合物之黏度控制在適切的範圍。又，藉由使溶劑之摻合量成為30質量份以上，可防止異常之聚合反應，安定地進行聚合反應，並且亦可防止聚合物之著色或凝膠化。The total usage amount of the solvent is not particularly limited, but is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated group-containing compound. In particular, by making the usage-amount of a solvent into 1,000 mass parts or less, the viscosity of a polymer can be controlled in an appropriate range. Moreover, by making the compounding quantity of a solvent into 30 mass parts or more, an abnormal polymerization reaction can be prevented, a polymerization reaction can be performed stably, and the coloring and gelation of a polymer can also be prevented.

[得到反應液1之步驟] 於將聚合起始劑與溶劑(溶劑(ii))混合而成的反應液1中，聚合起始劑之濃度為16質量%~50質量%。聚合起始劑之濃度較佳為20質量%~30質量%、更佳為20質量%~28質量%。聚合起始劑之濃度未達16質量%時，溶解於溶劑之聚合起始劑之量減少，因此無法使聚合起始劑相對於共聚物之材料的含乙烯性不飽和基之化合物的相對量增加，結果所合成的共聚物之重量平均分子量會增大。將重量平均分子量增大的共聚物使用於感光性樹脂組成物而作為阻劑使用時，係有顯影性或硬化物之耐溶劑性變得不充分的傾向。又，因為合成共聚物時之聚合起始劑之使用量被限制，故有反應產率降低，或製造時間無法縮短等，就工業量產的觀點產生問題的傾向。或者，欲增加合成共聚物時之聚合起始劑之使用量時，聚合起始劑之溶解所用的溶劑量增大，伴隨於此，最初給入於反應釜之溶劑量或用以與含乙烯性不飽和基之化合物混合使用的溶劑量係被限制。因此，同樣就量產化之觀點不佳。 [Steps to obtain reaction solution 1] In the reaction liquid 1 which mixed a polymerization initiator and a solvent (solvent (ii)), the density|concentration of a polymerization initiator is 16 mass % - 50 mass %. The concentration of the polymerization initiator is preferably 20% by mass to 30% by mass, more preferably 20% by mass to 28% by mass. When the concentration of the polymerization initiator is less than 16% by mass, the amount of the polymerization initiator dissolved in the solvent decreases, so that the relative amount of the polymerization initiator to the ethylenically unsaturated group-containing compound in the material of the copolymer cannot be adjusted. As a result, the weight-average molecular weight of the synthesized copolymer will increase. When the copolymer having an increased weight average molecular weight is used in a photosensitive resin composition as a resist, the developability and the solvent resistance of the cured product tend to be insufficient. In addition, since the amount of the polymerization initiator to be used in synthesizing the copolymer is limited, the reaction yield decreases or the production time cannot be shortened, which tends to cause problems from the viewpoint of industrial mass production. Alternatively, when the amount of the polymerization initiator used in synthesizing the copolymer is to be increased, the amount of the solvent used for dissolving the polymerization initiator is increased, and along with this, the amount of the solvent initially fed into the reaction kettle or used to mix with the ethylene-containing The amount of solvent used in combination with the compound of the sexually unsaturated group is limited. Therefore, the point of view of mass production is also not good.

前述式(1)表示之聚合起始劑，具有由外消旋體及內消旋體所構成的異構物。聚合起始劑，在前述異構物當中，對溶劑之溶解度較高之異構物係含有60質量%以上、較佳含有80質量%以上、更佳含有90質量%以上、又更佳含有95質量%以上。溶解度較高之異構物之含量未達60質量%時，溶解於溶劑之聚合起始劑之量會減少。因此，無法增加聚合起始劑相對於共聚物之材料的含乙烯性不飽和基之化合物的相對量。其結果，所合成的共聚物之重量平均分子量會增大。將重量平均分子量增大的共聚物使用於感光性樹脂組成物，而作為阻劑使用時，係有顯影性或硬化物之耐溶劑性變得不充分的傾向。又，由於合成共聚物時之聚合起始劑的使用量被限制，故有反應產率降低，或製造時間無法縮短等，就工業量產的觀點產生問題之傾向。或者，欲增加合成共聚物時之聚合起始劑的使用量時，聚合起始劑之溶解所用的溶劑量會增大，伴隨於此，最初給入於反應釜之溶劑量或用以與含乙烯性不飽和基之化合物混合使用的溶劑量係被限制，因此，同樣就量產化之觀點不佳。 前述式(1)表示之聚合起始劑之溶解度，係藉由調查於25℃條件下對溶劑(ii)之溶解量(g/100g溶劑(ii))來判斷。溶劑(ii)為丙二醇單甲基醚(PGME)時，於2,2’-偶氮雙(2,4-二甲基戊腈)係內消旋體溶解度較高、於2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)係外消旋體溶解度較高。 The polymerization initiator represented by the aforementioned formula (1) has an isomer composed of a racemate and a meso. Among the above-mentioned isomers, the isomer with higher solubility in the solvent contains 60 mass % or more, preferably 80 mass % or more, more preferably 90 mass % or more, and more preferably 95 mass % or more. mass % or more. When the content of the highly soluble isomer is less than 60% by mass, the amount of the polymerization initiator dissolved in the solvent decreases. Therefore, it is impossible to increase the relative amount of the polymerization initiator with respect to the ethylenically unsaturated group-containing compound of the material of the copolymer. As a result, the weight average molecular weight of the synthesized copolymer increases. When a copolymer having an increased weight average molecular weight is used in a photosensitive resin composition and used as a resist, the developability and the solvent resistance of the cured product tend to be insufficient. In addition, since the amount of the polymerization initiator used in synthesizing the copolymer is limited, the reaction yield is lowered, or the production time cannot be shortened, which tends to cause problems from the viewpoint of industrial mass production. Alternatively, when the amount of the polymerization initiator used in synthesizing the copolymer is to be increased, the amount of the solvent used for dissolving the polymerization initiator will increase, and along with this, the amount of the solvent initially fed into the reactor or used to mix with the Since the amount of the solvent used for mixing the ethylenically unsaturated group compound is limited, it is also unfavorable from the viewpoint of mass production. The solubility of the polymerization initiator represented by the aforementioned formula (1) was determined by examining the amount (g/100 g of solvent (ii)) dissolved in the solvent (ii) at 25°C. When the solvent (ii) is propylene glycol monomethyl ether (PGME), the solubility of the mesoform in 2,2'-azobis(2,4-dimethylvaleronitrile) is relatively high, and the Azobis(4-methoxy-2,4-dimethylvaleronitrile) racemates have higher solubility.

聚合起始劑之使用量不特別限制，相對於含乙烯性不飽和基之化合物100質量份而言，較佳為5~30質量份、更佳為7~25質量份、又更佳為8.5~23質量份。聚合起始劑之使用量若為5質量份以上，則共聚物之重量平均分子量充分地低分子量化，可得到具有良好之顯影性的感光性樹脂組成物、進而具有良好之耐溶劑性的樹脂硬化膜。聚合起始劑之使用量若為30質量份以下，可抑制使用於溶解聚合起始劑之溶劑量。因此，可充分確保最初給入於反應釜之溶劑量或用以與含乙烯性不飽和基之化合物混合使用之溶劑量，就產率提高、製造時間縮短等量產化的觀點較佳。The usage amount of the polymerization initiator is not particularly limited, and relative to 100 parts by mass of the ethylenically unsaturated group-containing compound, it is preferably 5 to 30 parts by mass, more preferably 7 to 25 parts by mass, and more preferably 8.5 parts by mass ~23 parts by mass. When the amount of the polymerization initiator used is 5 parts by mass or more, the weight-average molecular weight of the copolymer can be sufficiently lowered, and a photosensitive resin composition having good developability and further a resin having good solvent resistance can be obtained. Hardened film. When the usage-amount of a polymerization initiator is 30 mass parts or less, the amount of the solvent used for dissolving a polymerization initiator can be suppressed. Therefore, the amount of the solvent initially fed into the reactor or the amount of the solvent for mixing with the ethylenically unsaturated group-containing compound can be sufficiently secured, which is preferable from the viewpoint of mass production such as improved yield and shortened production time.

聚合起始劑之10小時半衰期溫度不特別限制，較佳為20~60℃、更佳為25~55℃。10小時半衰期溫度為20℃以上時，就操作、量產化之觀點較佳，10小時半衰期溫度為60℃以下時，就反應性、分解性之觀點較佳。The 10-hour half-life temperature of the polymerization initiator is not particularly limited, but is preferably 20 to 60°C, more preferably 25 to 55°C. When the 10-hour half-life temperature is 20°C or higher, it is preferable from the viewpoint of operation and mass production, and when the 10-hour half-life temperature is 60°C or lower, it is preferable from the viewpoint of reactivity and decomposability.

[含乙烯性不飽和基之化合物] 含乙烯性不飽和基之化合物，至少含有不具有羧基且具有封端異氰酸基之含乙烯性不飽和基之化合物及具有羧基之含乙烯性不飽和基之化合物。含乙烯性不飽和基之化合物，亦可依需要，進一步含有具有羥基之含乙烯性不飽和基之化合物或具有環氧基之含乙烯性不飽和基之化合物。 [Compounds containing ethylenically unsaturated groups] The ethylenically unsaturated group-containing compound contains at least an ethylenically unsaturated group-containing compound having no carboxyl group and a blocked isocyanate group, and an ethylenically unsaturated group-containing compound having a carboxyl group. The ethylenically unsaturated group-containing compound may further contain an ethylenically unsaturated group-containing compound having a hydroxyl group or an ethylenically unsaturated group-containing compound having an epoxy group as required.

具有封端異氰酸基之含乙烯性不飽和基之化合物，只要係不具有羧基，且具有封端異氰酸基與乙烯基及(甲基)丙烯醯氧基等之乙烯性不飽和基的化合物，則不特別限定。將所合成之共聚物作為阻劑之材料使用時，就減低烘烤溫度之觀點，係使用具有封端異氰酸基之含乙烯性不飽和基之化合物。An ethylenically unsaturated group-containing compound having a blocked isocyanate group, as long as it does not have a carboxyl group, and has an ethylenically unsaturated group such as a blocked isocyanate group and a vinyl group and a (meth)acryloyloxy group compounds are not particularly limited. When the synthesized copolymer is used as a material for the inhibitor, an ethylenically unsaturated group-containing compound having a blocked isocyanate group is used from the viewpoint of lowering the baking temperature.

具有封端異氰酸基之含乙烯性不飽和基之化合物，例如，可列舉將具有異氰酸基之含乙烯性不飽和基之化合物的異氰酸基，以封端劑封端化之化合物。The ethylenically unsaturated group-containing compound having a blocked isocyanate group, for example, the isocyanate group of the ethylenically unsaturated group-containing compound having an isocyanato group is blocked with a blocking agent. compound.

具有異氰酸基之含乙烯性不飽和基之化合物，例如，可列舉下述式(2)表示之化合物。Examples of the ethylenically unsaturated group-containing compound having an isocyanato group include compounds represented by the following formula (2).

Figure 02_image005
Figure 02_image005

上述式(2)中，R 6表示氫原子或甲基；R 7表示-CO-、-COOR 8-(此處，R 8為碳原子數1~6之伸烷基)或  -COO-R 9O-CONH-R 10-(此處，R 9為碳原子數2~6之伸烷基；R 10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)。R 6較佳為-COOR 8-，此處，R 8較佳為碳原子數1~4之伸烷基。 In the above formula (2), R 6 represents a hydrogen atom or a methyl group; R 7 represents -CO-, -COOR 8 - (here, R 8 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 9 O-CONH-R 10 -(here, R 9 is an alkylene group with 2 to 6 carbon atoms; R 10 is an alkylene group with 2 to 12 carbon atoms or a substituted alkyl group with 6 to 6 carbon atoms. 12 of the extended aryl). R 6 is preferably -COOR 8 -, and here, R 8 is preferably an alkylene group having 1 to 4 carbon atoms.

上述式(1)表示之異氰酸酯化合物，具體而言，可列舉(甲基)丙烯酸2-異氰酸基乙酯、(甲基)丙烯酸2-異氰酸基丙酯、(甲基)丙烯酸3-異氰酸基丙酯、(甲基)丙烯酸2-異氰酸基-1-甲基乙酯、(甲基)丙烯酸2-異氰酸基-1,1-二甲基乙酯、(甲基)丙烯酸4-異氰酸基環己酯、甲基丙烯醯基異氰酸酯等。又，亦可使用(甲基)丙烯酸2-羥基烷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。上述(甲基)丙烯酸2-羥基烷酯之烷基，較佳為乙基或n-丙基、更佳為乙基。上述二異氰酸酯化合物，例如可列舉六亞甲基二異氰酸酯、2,4-(或2,6-)甲苯二異氰酸酯(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(異氰酸基甲基)環己烷、離胺酸二異氰酸酯等。Specific examples of the isocyanate compound represented by the above formula (1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and 3-(meth)acrylate. -Isocyanatopropyl, (meth)acrylate 2-isocyanato-1-methylethyl, (meth)acrylate 2-isocyanato-1,1-dimethylethyl, ( 4-isocyanatocyclohexyl meth)acrylate, methacryloyl isocyanate and the like. In addition, a molar (1 mol:1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. The alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate is preferably ethyl group or n-propyl group, more preferably ethyl group. The above-mentioned diisocyanate compounds include, for example, hexamethylene diisocyanate, 2,4-(or 2,6-) toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,4-(or 2,6-) toluene diisocyanate (TDI), 5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanato) acid methyl) cyclohexane, lysine diisocyanate, etc.

此等異氰酸酯化合物之中，尤以(甲基)丙烯酸2-異氰酸基乙酯、(甲基)丙烯酸2-異氰酸基丙酯、(甲基)丙烯酸3-異氰酸基丙酯、(甲基)丙烯酸2-異氰酸基-1-甲基乙酯、(甲基)丙烯酸2-異氰酸基-1,1-二甲基乙酯、(甲基)丙烯酸4-異氰酸基環己酯及甲基丙烯醯基異氰酸酯為佳；更佳為(甲基)丙烯酸2-異氰酸基乙酯及(甲基)丙烯酸2-異氰酸基丙酯。Among these isocyanate compounds, especially 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and 3-isocyanatopropyl (meth)acrylate , (meth)acrylic acid 2-isocyanato-1-methylethyl ester, (meth)acrylic acid 2-isocyanato-1,1-dimethylethyl ester, (meth)acrylic acid 4-isocyanato Cyanocyclohexyl cyanate and methacryloyl isocyanate are preferred; 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

將異氰酸酯化合物中之異氰酸基封端化之封端劑，例如可列舉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、甲基賽珞蘇、丁基賽珞蘇、甲基卡必醇、苯甲醇、苯基賽珞蘇、呋喃甲醇、環己醇等之醇系；酚、甲酚、2,6-二甲酚、3,5-二甲酚、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、p-羥基苯甲酸酯、百里酚、p-萘酚、p-硝基酚、p-氯酚、2-羥基苯甲酸甲酯等之酚系；丙二酸二甲酯、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-十二烷基硫醇等之硫醇系；二苯基胺、苯基萘基胺、苯胺、咔唑等之胺系；乙醯苯胺、乙醯胺基苯甲醚(acetanisidide)、乙醯胺、苯甲醯胺等之酸醯胺系；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；尿素、硫代尿素、乙烯尿素等之尿素系；N-苯基胺基甲酸苯酯、2-噁唑啶酮等之胺基甲酸鹽系：伸乙亞胺、聚伸乙亞胺等之亞胺系；甲醛肟、乙醛肟、丙酮肟、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。此等之封端劑，可單獨使用、亦可組合2種以上使用。The blocking agent for blocking the isocyanate group in the isocyanate compound includes, for example, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Amide series; Methanol, Ethanol, Propanol, Butanol, Ethylene Glycol, Methyl Cerox, Butyl Cerox, Methyl Carbitol, Benzyl Alcohol, Phenyl Cerox, Furanmethanol, Cyclohexyl Alcohols such as alcohols; butylphenols such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, etc. , p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, p-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol , phenolic series such as methyl 2-hydroxybenzoate; active methylene series such as dimethyl malonate, diethyl malonate, methyl acetyl acetate, ethyl acetate, acetyl acetone, etc. ; Mercaptan series such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; amine series such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; Acid amides such as acetanisidide, acetamide, benzamide, etc.; acid amides such as succinic acid imide, maleic acid imide, etc.; imidazole, 2-methylimidazole , imidazole series such as 2-ethylimidazole; pyrazole series such as pyrazole and 3,5-dimethylpyrazole; urea series such as urea, thiourea, vinyl urea, etc.; N-phenylcarbamate benzene Carbamates of esters, 2-oxazolidinones, etc.: imines of ethyleneimine, polyethyleneimine, etc.; formaldehyde oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, Oxime series such as methyl isobutyl ketoxime, cyclohexanone oxime, etc.; bisulfite series such as sodium bisulfite, potassium bisulfite, etc. These terminal blocking agents may be used alone or in combination of two or more.

具有異氰酸基之含乙烯性不飽和基之化合物與封端劑的反應，可與有無溶劑存在無關地進行。使用溶劑時，對於異氰酸基必需使用不活性之溶劑。封端化反應時，可使用錫、鋅、鉛等之有機金屬鹽、3級胺等，作為觸媒。反應一般而言可在-20~150℃進行，較佳在0~100℃進行。The reaction between the ethylenically unsaturated group-containing compound having an isocyanato group and the blocking agent can be carried out regardless of the presence or absence of a solvent. When a solvent is used, it is necessary to use an inactive solvent for the isocyanate group. In the capping reaction, organometallic salts such as tin, zinc, and lead, tertiary amines, and the like can be used as catalysts. The reaction can generally be carried out at -20 to 150°C, preferably at 0 to 100°C.

不具有羧基且具有封端異氰酸基之含乙烯性不飽和基之化合物之使用量，相對於含乙烯性不飽和基之化合物的合計量而言，較佳為5~30莫耳%、更佳為10~25莫耳%、又更佳為15~25莫耳%。使用量為5莫耳%以上時，就耐溶劑性之觀點較佳，使用量為30莫耳%以下時，就顯影性之觀點較佳。The usage amount of the ethylenically unsaturated group-containing compound without a carboxyl group and with a blocked isocyanate group is preferably 5 to 30 mol % relative to the total amount of the ethylenically unsaturated group-containing compound. More preferably, it is 10 to 25 mol %, still more preferably 15 to 25 mol %. When the usage amount is 5 mol % or more, it is preferable from the viewpoint of solvent resistance, and when the usage amount is 30 mol % or less, it is preferable from the viewpoint of developability.

具有羧基之含乙烯性不飽和基之化合物，只要係具有羧基，與乙烯基及(甲基)丙烯醯氧基等之乙烯性不飽和基之化合物則不特別限定。將所合成之共聚物使用作為阻劑之材料時，就賦予鹼顯影性之觀點，係使用具有羧基之含乙烯性不飽和基之化合物。The ethylenically unsaturated group-containing compound having a carboxyl group is not particularly limited as long as it is a compound having a carboxyl group and an ethylenically unsaturated group such as a vinyl group and a (meth)acryloyloxy group. When the synthesized copolymer is used as a material for the inhibitor, an ethylenically unsaturated group-containing compound having a carboxyl group is used from the viewpoint of imparting alkali developability.

具有羧基之含乙烯性不飽和基之化合物，例如可列舉(甲基)丙烯酸、依康酸、巴豆酸、桂皮酸、馬來酸等之含羧基之乙烯性不飽和化合物及其取代體，就獲得性、反應性之觀點，更佳使用(甲基)丙烯酸。The ethylenically unsaturated group-containing compound having a carboxyl group includes, for example, (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid, etc., the carboxyl group-containing ethylenically unsaturated compound and its substituted products. From the viewpoint of availability and reactivity, (meth)acrylic acid is more preferably used.

具有羧基之含乙烯性不飽和基之化合物之使用量，相對於含乙烯性不飽和基之化合物之合計量而言，較佳為10~50莫耳%、更佳為15~45莫耳%、又更佳為20~40莫耳%。使用量為10~50莫耳%時，就顯影性之觀點較佳。The use amount of the ethylenically unsaturated group-containing compound having a carboxyl group is preferably 10-50 mol%, more preferably 15-45 mol%, relative to the total amount of the ethylenically unsaturated group-containing compound , and more preferably 20 to 40 mol%. When the usage amount is 10 to 50 mol %, it is preferable from the viewpoint of developability.

具有羥基之含乙烯性不飽和基之化合物，只要係不具有封端異氰酸基及羧基，且具有羥基與乙烯性不飽和基之化合物，則不特別限定。藉由使用作為共聚物之構成單體，係有助於減低作為阻劑使用時之烘烤溫度。The ethylenically unsaturated group-containing compound having a hydroxyl group is not particularly limited as long as it does not have a blocked isocyanate group and a carboxyl group and has a hydroxyl group and an ethylenically unsaturated group. By using the monomer as a constituent of the copolymer, it helps to reduce the baking temperature when used as a resist.

具有羥基之含乙烯性不飽和基之化合物，例如可列舉(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基-2-羥基丙酯、烯丙醇等。其中，就反應性之觀點，尤以(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯等之(甲基)丙烯酸羥基烷酯為佳。Examples of the ethylenically unsaturated group-containing compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylate base) 6-hydroxyhexyl acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, allyl alcohol Wait. Among them, from the viewpoint of reactivity, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxybutyl (meth)acrylate are particularly preferred. Hydroxyalkyl (meth)acrylates such as hydroxyhexyl are preferred.

使用具有羥基之含乙烯性不飽和基之化合物時之使用量，相對於含乙烯性不飽和基之化合物之合計量而言，較佳為1~20莫耳%、更佳為5~15莫耳%。使用量為1莫耳%以上且20莫耳%以下時，就耐溶劑性之觀點較佳。When using the ethylenically unsaturated group-containing compound having a hydroxyl group, the usage amount is preferably 1-20 mol %, more preferably 5-15 mol %, relative to the total amount of the ethylenically unsaturated group-containing compound Ear%. It is preferable from the viewpoint of solvent resistance that the usage-amount is 1 mol% or more and 20 mol% or less.

具有環氧基之含乙烯性不飽和基之化合物，只要係不具有封端異氰酸基、羧基及羥基，且具有環氧基與乙烯性不飽和基之化合物，則不特別限定。藉由使用作為共聚物之構成單體，係有助於減低作為阻劑使用時之烘烤溫度。The ethylenically unsaturated group-containing compound having an epoxy group is not particularly limited as long as it does not have a blocked isocyanate group, a carboxyl group, and a hydroxyl group, and has an epoxy group and an ethylenically unsaturated group. By using the monomer as a constituent of the copolymer, it helps to reduce the baking temperature when used as a resist.

具有環氧基之含乙烯性不飽和基之化合物，例如可列舉含環氧基之(甲基)丙烯酸酯。含環氧基之(甲基)丙烯酸酯之具體例子，可列舉(甲基)丙烯酸環氧丙酯、具有脂環式環氧基之(甲基)丙烯酸3,4-環氧基環己基甲酯及其內酯加成物(例如，Daicel股份有限公司製Cyclomer (註冊商標)A200、M100)、3,4-環氧基環己基甲基-3’,4’-環氧基環己烷羧酸酯之單(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯酯之環氧化物、(甲基)丙烯酸二環戊烯氧基乙酯之環氧化物等。其中特別就容易獲得、反應性之觀點，尤以(甲基)丙烯酸環氧丙酯為佳。Examples of the ethylenically unsaturated group-containing compound having an epoxy group include epoxy group-containing (meth)acrylates. Specific examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy group. Esters and lactone adducts thereof (for example, Cyclomer (registered trademark) A200, M100, manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane Mono(meth)acrylate of carboxylate, epoxide of dicyclopentenyl (meth)acrylate, epoxide of dicyclopentenyloxyethyl (meth)acrylate, etc. Among them, glycidyl (meth)acrylate is particularly preferred from the viewpoint of easy availability and reactivity.

使用具有環氧基之含乙烯性不飽和基之化合物時之使用量，相對於含乙烯性不飽和基之化合物之合計量而言，較佳為10~50莫耳%、更佳為20~45莫耳%、又更佳為25~40。使用量為10莫耳%以上時，就耐溶劑性之觀點較佳，使用量為50莫耳%以下時，就顯影性之觀點較佳。When using the ethylenically unsaturated group-containing compound having an epoxy group, the usage amount is preferably 10-50 mol%, more preferably 20-20 mol%, relative to the total amount of the ethylenically unsaturated group-containing compound 45 mol%, more preferably 25-40. When the usage amount is 10 mol % or more, it is preferable from the viewpoint of solvent resistance, and when the usage amount is 50 mol % or less, it is preferable from the viewpoint of developability.

其他之含乙烯性不飽和基之化合物，可列舉芳香族乙烯基化合物、共軛二烯化合物、(甲基)丙烯酸酯化合物、(甲基)丙烯醯胺、乙烯基化合物、不飽和二羧酸二酯化合物、單馬來醯亞胺化合物。 芳香族乙烯基化合物，可列舉降莰烯及二環戊二烯或苯乙烯、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。 共軛二烯化合物，可列舉丁二烯、異戊二烯、氯丁二烯等。 (甲基)丙烯酸酯化合物，可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸n-丙酯、甲基丙烯酸i-丙酯、(甲基)丙烯酸n-丁酯、(甲基)丙烯酸sec-丁酯、(甲基)丙烯酸異-丁酯、(甲基)丙烯酸tert-丁酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸甲基環己酯、(甲基)丙烯酸乙基環己酯、松香(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸1,1,1-三氟乙酯、(甲基)丙烯酸全氟乙酯、(甲基)丙烯酸全氟-n-丙酯、(甲基)丙烯酸全氟-異-丙酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸3-(N,N-二甲基胺基)丙酯、(甲基)丙烯酸三苯基甲酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸異丙苯酯、(甲基)丙烯酸4-苯氧基苯酯、(甲基)丙烯酸聯苯氧基乙酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸蒽酯、甲基丙烯酸n-戊酯、丙烯酸異戊酯、甲基丙烯酸n-己酯、甲基丙烯酸2-乙基己酯、丙烯酸2-乙基己酯、甲基丙烯酸n-辛酯、甲基丙烯酸異癸酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲氧基-三乙二醇丙烯酸酯、乙氧基-二乙二醇丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯(商品名：AM-90G、新中村化學工業公司製)、丙烯酸苯氧基乙酯、苯氧基-聚乙二醇丙烯酸酯(商品名：Light Acrylate P-200A、共榮社化學公司製)、丙烯酸o-苯氧基苯甲酯、丙烯酸m-苯氧基苯甲酯、丙烯酸p-苯氧基苯甲酯、α-溴(甲基)丙烯酸、β-呋喃基(甲基)丙烯酸等。 (甲基)丙烯醯胺，可列舉(甲基)丙烯醯胺、(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。 乙烯基化合物，可列舉(甲基)丙烯酸苯胺化物、(甲基)丙烯腈、丙烯醛、氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯、N-乙烯基吡咯啶酮、乙烯基吡啶、乙酸乙烯酯、乙烯基甲苯等。 不飽和二羧酸二酯化合物，可列舉檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、依康酸二乙酯等。 單馬來醯亞胺化合物，可列舉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。 Other ethylenically unsaturated group-containing compounds include aromatic vinyl compounds, conjugated diene compounds, (meth)acrylate compounds, (meth)acrylamides, vinyl compounds, and unsaturated dicarboxylic acids. Diester compound, monomaleimide compound. Aromatic vinyl compounds include norbornene, dicyclopentadiene, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, and o-chlorobenzene Ethylene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanobenzene Ethylene, p-acetylaminostyrene, etc. The conjugated diene compound includes butadiene, isoprene, chloroprene, and the like. (Meth)acrylate compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl (meth)acrylate, (meth)acrylate base) sec-butyl acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth)acrylate Cyclohexyl acrylate, methyl cyclohexyl (meth)acrylate, ethyl cyclohexyl (meth)acrylate, rosin (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, (meth)acrylic acid 1 ,1,1-Trifluoroethyl ester, (meth)acrylate perfluoroethyl, (meth)acrylate perfluoro-n-propyl, (meth)acrylate perfluoro-iso-propyl, (meth)acrylate Dicyclopentenyl acrylate, Dicyclopentenyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, 3-(N,N-dimethyl)(meth)acrylate Amino)propyl ester, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, (meth)acrylate base) biphenoxyethyl acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, n-amyl methacrylate, isoamyl acrylate, n-hexyl methacrylate, methacrylic acid 2-ethylhexyl, 2-ethylhexyl acrylate, n-octyl methacrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, methoxy-triethylene glycol acrylate , ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: AM-90G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), acrylic acid Phenoxyethyl ester, phenoxy-polyethylene glycol acrylate (trade name: Light Acrylate P-200A, manufactured by Kyōeisha Chemical Co., Ltd.), o-phenoxybenzyl acrylate, m-phenoxy acrylate Benzyl, p-phenoxybenzyl acrylate, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, etc. (Meth)acrylamide, (meth)acrylamide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-diethylamide base) acrylic acid N,N-dipropyl amide, (meth)acrylic acid N,N-di-isopropyl amide, (meth)acrylic anthryl amide and the like. Vinyl compounds include (meth)acrylic aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl Pyridine, vinyl acetate, vinyltoluene, etc. Examples of the unsaturated dicarboxylic acid diester compound include diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconic acid. Monomaleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, and N-(4-hydroxyphenyl)maleimide. Lysimide, etc.

此等之含乙烯性不飽和基之化合物，各範疇皆可單獨使用或使用2種以上。These ethylenically unsaturated group-containing compounds can be used alone or in two or more types in each category.

[調製反應液2之步驟] 於反應液2之調製中，含乙烯性不飽和基之化合物，可各種類分別準備、亦能夠以混合物之狀態準備。就控制共聚物之分子量分布的觀點，較佳為將所使用之含乙烯性不飽和基之化合物以混合物的狀態調製，而作為反應液2。 含乙烯性不飽和基之化合物為常溫(25℃)液體時，反應液2之調製係不需溶劑，但亦可依需要使用溶劑(溶劑iii)。溶劑可使用與反應液1所用的溶劑(ii)相同者。使用溶劑(iii)時的含乙烯性不飽和基之化合物的濃度，較佳為40~95質量%、更佳為50~90質量%、又更佳為60~85質量%。含乙烯性不飽和基之化合物的濃度為40質量%以上時，容易調整樹脂之固體成分。含乙烯性不飽和基之化合物的濃度為95質量%以下時，容易調整分子量。 [Procedure for preparing reaction solution 2] In the preparation of the reaction solution 2, the ethylenically unsaturated group-containing compound may be prepared separately for various types, or may be prepared in the state of a mixture. From the viewpoint of controlling the molecular weight distribution of the copolymer, the ethylenically unsaturated group-containing compound to be used is preferably prepared as a reaction solution 2 in the state of a mixture. When the ethylenically unsaturated group-containing compound is a liquid at room temperature (25°C), the preparation system of the reaction solution 2 does not require a solvent, but a solvent (solvent iii) can also be used as required. The same solvent as the solvent (ii) used in the reaction solution 1 can be used. The concentration of the ethylenically unsaturated group-containing compound when the solvent (iii) is used is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 85% by mass. When the concentration of the ethylenically unsaturated group-containing compound is 40% by mass or more, it is easy to adjust the solid content of the resin. When the concentration of the ethylenically unsaturated group-containing compound is 95% by mass or less, it is easy to adjust the molecular weight.

[共聚物] 以本實施形態之製造方法所得之共聚物之重量平均分子量可配合用途調整，但使用於各種阻劑材料時，就低溫硬化性之觀點，較佳為3000~15000、更佳為4000~10000。 [Copolymer] The weight-average molecular weight of the copolymer obtained by the production method of the present embodiment can be adjusted according to the application, but when used in various resist materials, it is preferably 3,000-15,000, more preferably 4,000-10,000 from the viewpoint of low-temperature curability.

再者，本實施形態中之重量平均分子量，意指使用凝膠滲透層析(GPC)，以下述條件所測定之以標準聚苯乙烯換算之重量平均分子量。 管柱：Shodex(註冊商標)LF-804+LF-804(昭和電工股份有限公司製) 管柱溫度：40℃ 試樣：共聚物之0.2質量%四氫呋喃溶液 展開溶劑：四氫呋喃 檢測器：示差折射計(Shodex(註冊商標)RI-71S)(昭和電工股份有限公司製) 流速：1mL/min In addition, the weight average molecular weight in this embodiment means the weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions. Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample: 0.2% by mass tetrahydrofuran solution of the copolymer Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL/min

以本實施形態之製造方法所得到的共聚物之酸值(JIS K6901 5.3)可適當選擇，但作為感光性聚合物使用時，較佳為10~300KOHmg/g、更佳為20~200KOHmg/g。The acid value (JIS K6901 5.3) of the copolymer obtained by the production method of the present embodiment can be appropriately selected, but when used as a photosensitive polymer, it is preferably 10 to 300KOHmg/g, more preferably 20 to 200KOHmg/g .

[共聚物之製造方法] 一實施形態中，更具體的共聚物之製造方法，較佳依序包含以下之步驟I~步驟III。 步驟I： 將相對於含乙烯性不飽和基之化合物100質量份為50~500質量份之溶劑(i)昇溫至特定之聚合溫度(設定聚合溫度)之步驟。 步驟II： 將前述反應液1及前述反應液2分別滴下於前述溶劑(i)之步驟。 前述反應液1為前述聚合起始劑100質量份與溶劑(ii)100~525質量份之混合物。前述反應液2為前述含乙烯性不飽和基之化合物100質量份與溶劑(iii)0~500質量份之混合物。 步驟III： 反應液1及反應液2之滴下結束後，進一步持續共聚合反應1~10小時之步驟。 [Production method of copolymer] In one embodiment, a more specific method for producing a copolymer preferably includes the following steps I to III in sequence. Step I: A step of raising the temperature of the solvent (i) in an amount of 50 to 500 parts by mass relative to 100 parts by mass of the ethylenically unsaturated group-containing compound to a specific polymerization temperature (set polymerization temperature). Step II: The step of dropping the aforementioned reaction solution 1 and the aforementioned reaction solution 2 into the aforementioned solvent (i), respectively. The aforementioned reaction solution 1 is a mixture of 100 parts by mass of the aforementioned polymerization initiator and 100 to 525 parts by mass of the solvent (ii). The aforementioned reaction solution 2 is a mixture of 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound and 0 to 500 parts by mass of the solvent (iii). Step III: After the dropping of the reaction liquid 1 and the reaction liquid 2 is completed, the step of the copolymerization reaction is further continued for 1 to 10 hours.

溶劑(i)之使用量，相對於含乙烯性不飽和基之化合物之合計量100質量份而言，較佳為50~500質量份、更佳為75~400質量份、又更佳為80~300質量份。 溶劑(ii)之使用量，相對於聚合起始劑100質量份而言，較佳為100~525質量份、更佳為230~400質量份、又更佳為250~400質量份。 溶劑(iii)之使用量，相對於含乙烯性不飽和基之化合物之合計量100質量份而言，較佳為0~100質量份、更佳為0~75質量份、又更佳為0~50質量份。 溶劑(i)~溶劑(iii)之種類可相同亦可相異，較佳為同一物。 The amount of solvent (i) used is preferably 50 to 500 parts by mass, more preferably 75 to 400 parts by mass, and more preferably 80 parts by mass relative to 100 parts by mass of the total amount of the ethylenically unsaturated group-containing compound ~300 parts by mass. The usage-amount of the solvent (ii) is preferably 100-525 parts by mass, more preferably 230-400 parts by mass, and still more preferably 250-400 parts by mass, relative to 100 parts by mass of the polymerization initiator. The amount of solvent (iii) used is preferably 0 to 100 parts by mass, more preferably 0 to 75 parts by mass, and more preferably 0 to 100 parts by mass of the total amount of the ethylenically unsaturated group-containing compound. ~50 parts by mass. The kind of solvent (i) to solvent (iii) may be the same or different, and the same thing is preferred.

步驟I~步驟III所設定之聚合溫度，較佳為50~100℃、更佳為60~90℃。The polymerization temperature set in step I to step III is preferably 50-100°C, more preferably 60-90°C.

滴下含有含乙烯性不飽和基之化合物的反應液2之時間不特別限制，通常，係花費30分鐘~300分鐘、較佳花費60分鐘~250分鐘對反應容器滴下。又，含有聚合起始劑之反應液1亦同樣地，滴下於反應容器之時間不特別限制，通常係花費30分鐘~300分鐘、較佳花費60分鐘~250分鐘滴下。再者，就作業之效率性之觀點等，亦可調整含乙烯性不飽和基之化合物與聚合起始劑之滴下時間成為相同。The time for dropping the reaction solution 2 containing the ethylenically unsaturated group-containing compound is not particularly limited, but it is usually dropped to the reaction vessel over 30 minutes to 300 minutes, preferably 60 minutes to 250 minutes. In addition, the reaction liquid 1 containing a polymerization initiator is also similarly, the time of dripping in a reaction container is not specifically limited, Usually, it is dripped over 30 minutes - 300 minutes, Preferably it is over 60 minutes - 250 minutes. In addition, from the viewpoint of work efficiency, etc., the dropping time of the ethylenically unsaturated group-containing compound and the polymerization initiator may be adjusted to be the same.

將含乙烯性不飽和基之化合物及聚合起始劑各自溶解於溶劑而藉由滴下以添加至反應容器時，滴下速度不特別限制。含有含乙烯性不飽和基之化合物的反應液2之滴下速度，當以含乙烯性不飽和基之化合物及溶劑之總量為100ml時，滴下速度通常為0.1ml/分鐘~5ml/分鐘、較佳為0.2ml/分鐘~4ml/分鐘。又，含有聚合起始劑的反應液1之滴下速度，通常為0.1ml/分鐘~5ml/分鐘、較佳為0.2ml/分鐘~4ml/分鐘。When the ethylenically unsaturated group-containing compound and the polymerization initiator are each dissolved in a solvent and added to the reaction vessel by dropping, the dropping speed is not particularly limited. The dropping rate of the reaction solution 2 containing the ethylenically unsaturated group-containing compound, when the total amount of the ethylenically unsaturated group-containing compound and the solvent is 100ml, the dropping rate is usually 0.1ml/min~5ml/min. Preferably, it is 0.2ml/min to 4ml/min. In addition, the dropping rate of the reaction solution 1 containing the polymerization initiator is usually 0.1 ml/min to 5 ml/min, preferably 0.2 ml/min to 4 ml/min.

＜感光性樹脂組成物＞ 一實施形態之感光性樹脂組成物，含有(A)共聚物、(B)反應性稀釋劑、(C)光聚合起始劑、(D)著色劑、(E)溶劑。 (A)共聚物為藉由上述製造方法所得之共聚物。 (A)共聚物之含量，相對於自感光性樹脂組成物去除(E)溶劑之成分的總和100質量份而言，較佳為3~50質量份、更佳為4~40質量份、又更佳為5~30質量份。含量為3質量份以上且50質量份以下時，就硬化性、顯影性之觀點較佳。 <Photosensitive resin composition> The photosensitive resin composition of one embodiment contains (A) a copolymer, (B) a reactive diluent, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent. (A) The copolymer is a copolymer obtained by the above-mentioned production method. The content of the (A) copolymer is preferably 3 to 50 parts by mass, more preferably 4 to 40 parts by mass, with respect to 100 parts by mass of the total of the components excluding the (E) solvent from the photosensitive resin composition. More preferably, it is 5-30 mass parts. When the content is 3 parts by mass or more and 50 parts by mass or less, it is preferable from the viewpoint of curability and developability.

[(B)反應性稀釋劑] (B)反應性稀釋劑，為分子內具有至少1個乙烯性不飽和基之化合物。就作為感光性樹脂組成物之顯影性，或作為樹脂硬化膜之耐溶劑性之觀點，特佳為具有複數個乙烯性不飽和基之化合物。藉由含有反應性稀釋劑，可調整感光性樹脂組成物之黏度，提高加工性，或提高樹脂組成物之硬化物的強度及/或對基材之密著性。具體而言，作為反應性稀釋劑，可使用以下所示之單官能單體及/或多官能單體。 [(B) Reactive Diluent] (B) The reactive diluent is a compound having at least one ethylenically unsaturated group in the molecule. From the viewpoint of developability as a photosensitive resin composition or solvent resistance as a resin cured film, a compound having a plurality of ethylenically unsaturated groups is particularly preferred. By containing the reactive diluent, the viscosity of the photosensitive resin composition can be adjusted, the processability can be improved, or the strength and/or the adhesion to the substrate of the cured product of the resin composition can be improved. Specifically, as the reactive diluent, a monofunctional monomer and/or a polyfunctional monomer shown below can be used.

單官能單體，可列舉(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基-2-羥基丙酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、鄰苯二甲酸衍生物之半(甲基)丙烯酸酯等之(甲基)丙烯酸酯類；苯乙烯、α-甲基苯乙烯、α-氯甲基苯乙烯、乙烯基甲苯等之芳香族乙烯基化合物類；乙酸乙烯酯、丙酸乙烯酯等之羧酸酯類等。此等之單官能單體，可單獨或組合2種以上使用。Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, and ethoxymethyl (meth)acrylamide Amine, Propoxymethyl (meth)acrylamide, Butoxymethoxymethyl (meth)acrylamide, Methyl (meth)acrylate, Ethyl (meth)acrylate, (methyl) ) Butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, (methyl) ) tetrahydrofuran methyl acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylates such as hemi (meth)acrylates of phthalic acid derivatives; aromatic vinyls such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, etc. base compounds; carboxylic acid esters of vinyl acetate, vinyl propionate, etc. These monofunctional monomers can be used alone or in combination of two or more.

多官能單體，可列舉乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、乙二醇二環氧丙基醚二(甲基)丙烯酸酯、二乙二醇二環氧丙基醚二(甲基)丙烯酸酯、鄰苯二甲酸二環氧丙酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚環氧丙基醚聚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯(亦即甲苯二異氰酸酯)、三甲基六亞甲基二異氰酸酯與六亞甲基二異氰酸酯等與(甲基)丙烯酸2-羥基乙酯之反應物、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、鄰苯二甲酸二烯丙酯、二烯丙基苯膦酸酯等之芳香族乙烯基化合物類；己二酸二乙烯酯等之二羧酸酯類；三聚氰酸三烯丙酯、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多元醇與N-羥甲基(甲基)丙烯醯胺之縮合物等。此等之多官能單體，可單獨或組合2種以上使用。Polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate , polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, three Methylol propane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, di- Pentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acrylooxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxy) Polyethoxyphenyl) propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethyl ether Glycol Diglycidyl Ether Di(meth)acrylate, Diglycidyl Phthalate Di(meth)acrylate, Glycerin Triacrylate, Glycerin Polyglycidyl Ether Poly(meth) Acrylates, urethane (meth)acrylates (that is, toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2-hydroxyethyl (meth)acrylate (meth)acrylates such as the reactants of (hydroxyethyl) isocyanurate, tri(meth)acrylate, etc.; divinylbenzene, diallyl phthalate, diene Aromatic vinyl compounds such as propylphenylphosphonate; dicarboxylates such as divinyl adipate; triallyl cyanurate, methylenebis(meth)acrylamide, (Meth) acrylamide methylene ether, polyol and N-methylol (meth) acrylamide condensate, etc. These polyfunctional monomers can be used alone or in combination of two or more.

作為反應性稀釋劑，於上述單體之中尤特佳包含三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯，與二季戊四醇六(甲基)丙烯酸酯當中的任一者。As a reactive diluent, among the above-mentioned monomers, Eutecto includes trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. any of .

(B)反應性稀釋劑之含量，相對於自感光性樹脂組成物去除(E)溶劑之成分的總和100質量份而言，較佳為5~50質量份、更佳為7~40質量份、又更佳為10~30質量份。含量為5質量份以上且未達50質量份時，就硬化性、顯影性之觀點較佳。The content of the (B) reactive diluent is preferably 5 to 50 parts by mass, more preferably 7 to 40 parts by mass with respect to 100 parts by mass of the total of the components excluding the (E) solvent from the photosensitive resin composition , and more preferably 10 to 30 parts by mass. When the content is 5 parts by mass or more and less than 50 parts by mass, it is preferable from the viewpoint of curability and developability.

[(C)光聚合起始劑] (C)光聚合起始劑並不特別限定，例如可列舉1,2-辛二酮,1-[4-(苯硫基)-,2-(o-苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(o-乙醯基肟)等之肟酯系；苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丁基醚等之苯偶姻類；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-苯甲基-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、苯甲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。此等之光聚合起始劑，可單獨或組合2種以上使用。 [(C) Photopolymerization Initiator] (C) The photopolymerization initiator is not particularly limited, and examples thereof include 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-benzyl oxime)], ethyl acetate Ketones, oxime esters of 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), etc.; Benzoin class of benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, etc.; acetophenone, 2,2-dimethoxy-2-phenylphenethyl ketone, 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, etc. Ketones; anthraquinones such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.; xanthone, thioxanthone, 2,4-di Methyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc. thioxanthone; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Ketals; benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetra(t-butyl) Dioxycarbonyl) benzophenone and other benzophenones; acylphosphine oxides and the like. These photopolymerization initiators can be used alone or in combination of two or more.

作為(C)光聚合起始劑，於上述化合物之中尤特別因i線(365nm)之感度高，硬化時及烘烤時之硬化物的黃變為少，因此較佳使用肟酯系者。作為肟酯系者，可列舉2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮等之苯乙酮系、1,2-辛二酮,1-[4-(苯硫基)-,2-(o-苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(o-乙醯基肟)等。此等之光聚合起始劑，例如可依作為目標之感度等，單獨或組合2種以上使用。As the (C) photopolymerization initiator, among the above-mentioned compounds, the sensitivity of i-line (365 nm) is particularly high, and the yellowing of the cured product during curing and baking is small, so oxime ester-based ones are preferably used. . Examples of oxime esters include acetophenones such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1,2-octanediones, 1-[4-(Phenylthio)-,2-(o-benzyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H -Carbazol-3-yl]-, 1-(o-acetyloxime), etc. These photopolymerization initiators can be used alone or in combination of two or more, for example, depending on the intended sensitivity and the like.

(C)光聚合起始劑之含量，相對於自感光性樹脂組成物去除(E)溶劑之成分總和100質量份而言，較佳為0.1~5質量份、更佳為0.2~4質量份、又更佳為0.3~3質量份。含量為0.1質量份以上且5質量份以下時，就硬化性、顯影性之觀點較佳。The content of the (C) photopolymerization initiator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, with respect to 100 parts by mass of the total of the components removed from the photosensitive resin composition (E) the solvent , and more preferably 0.3 to 3 parts by mass. When content is 0.1 mass part or more and 5 mass parts or less, it is preferable from a viewpoint of hardenability and developability.

[(D)著色劑] 作為(D)著色劑，可使用溶解或分散於溶劑者，例如可列舉染料及/或顏料等。(D)著色劑，例如，因應使用感光性樹脂組成物所製造的目標物之畫素的顏色等，可僅使用染料、可僅使用顏料、亦可組合染料與顏料來使用。使用感光性樹脂組成物作為彩色濾光片之材料時，依以下所示之理由，較佳使用染料來作為(D)著色劑。顏料為粒子而染料為分子。因此，使用染料作為著色劑時，相較於使用顏料的情況，於彩色濾光片中之光的散射被抑制，具備彩色濾光片之圖像顯示裝置的輝度增高。 [(D) Colorant] As (D) a coloring agent, what melt|dissolves or disperse|distributed in a solvent can be used, For example, a dye and/or a pigment etc. are mentioned. (D) The colorant, for example, may be used only by dye, only by pigment, or by combining dye and pigment, depending on the color of the pixel of the target object manufactured using the photosensitive resin composition. When using a photosensitive resin composition as a material of a color filter, it is preferable to use a dye as a (D) coloring agent for the reasons shown below. Pigments are particles and dyes are molecules. Therefore, when a dye is used as a colorant, the scattering of light in the color filter is suppressed compared with the case where a pigment is used, and the luminance of the image display device provided with the color filter is increased.

作為染料，就對溶劑及鹼顯影液之溶解性、與感光性樹脂組成物中之其他成分之相互作用、感光性樹脂組成物之耐熱性等之觀點，較佳使用具有羧酸或磺酸等之酸性基的酸性染料、與酸性染料之氮化合物之鹽、酸性染料之磺醯胺體等。特別是作為染料，較佳使用蒽醌系、偶氮系、呫噸(xanthene)系、蒽醌系或酞青素系之染料。其中尤特別因會成為可得到透過率高的樹脂硬化膜之感光性樹脂組成物，故較佳為使用蒽醌系染料與呫噸系染料當中的一者或兩者。As the dye, those having carboxylic acid, sulfonic acid, etc. are preferably used from the viewpoints of solubility in solvents and alkali developing solutions, interaction with other components in the photosensitive resin composition, and heat resistance of the photosensitive resin composition. Acid dyes with acid groups, salts with nitrogen compounds of acid dyes, sulfonamides of acid dyes, etc. In particular, as dyes, anthraquinone-based, azo-based, xanthene-based, anthraquinone-based, or phthalocyanin-based dyes are preferably used. Among them, it is particularly preferable to use one or both of anthraquinone-based dyes and xanthene-based dyes because it becomes a photosensitive resin composition from which a resin cured film with high transmittance can be obtained.

具體而言，染料可列舉酸性茜素紫 N；酸性黑1、2、24、48；酸性藍1、7、9、25、29、40、45、62、70、74、80、83、90、92、112、113、120、129、147；酸性鉻紫 K；酸性品紅；酸性綠1、3、5、25、27、50；酸性橙6、7、8、10、12、50、51、52、56、63、74、95；酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、69、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274、289、玫紅B；酸性紫6B、7、9、17、19；酸性黃1、3、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116；食品黃3、VALIFAST 藍1603、1605、1621、2606、2620、2670及此等之衍生物等。此等之染料，例如可依作為目標的畫素顏色等，單獨或組合2種以上使用。Specifically, the 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 Fuchsin; 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, 289, Rose Red B; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3, VALIFAST Blue 1603, 1605, 1621, 2606, 2620, 2670 and derivatives of these, etc. These dyes can be used alone or in combination of two or more, for example, depending on the desired pixel color or the like.

顏料可列舉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、154、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等之紫色顏料；C.I.顏料綠7、36、58、59、62等之綠色顏料；C.I.顏料棕23、25等之棕色顏料；C.I.顏料黑1、7、碳黑、鈦黑、氧化鐵等之黑色顏料等。此等之顏料，例如可依作為目標的畫素顏色等，單獨或組合2種以上使用。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 pigment; C.I. 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 and other purple pigments; C.I. Pigment Green 7, 36, 58, 59, 62, etc. green pigments; C.I. Pigment Brown 23, 25, etc. brown pigments; C.I. Pigment black 1, 7, carbon black, titanium Black pigments such as black, iron oxide, etc. These pigments can be used alone or in combination of two or more, for example, depending on the desired pixel color or the like.

使用顏料作為(D)著色劑時，就提高顏料之分散性的觀點，亦可於感光性樹脂組成物中含有公知之分散劑。 作為分散劑，較佳使用經時之分散安定性優良的高分子分散劑。高分子分散劑，可列舉胺基甲酸酯系分散劑、聚伸乙亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙二醇二酯系分散劑、山梨醇酐脂肪族酯系分散劑、脂肪族改質酯系分散劑等。高分子分散劑，亦可使用以EFKA (EFKA Chemicals B.V.(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)等之商品名所市售者。 感光性樹脂組成物中的分散劑之含量，可依所使用之顏料等之種類適當設定。 When a pigment is used as the (D) colorant, a known dispersant may be contained in the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, a polymer dispersant excellent in dispersion stability over time is preferably used. The polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, and sorbitan fats Aliphatic ester-based dispersants, aliphatic modified ester-based dispersants, etc. As the polymer dispersing agent, trade names such as EFKA (manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (manufactured by BYK-Chemie), DISPARLON (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by ZENECA) can also be used. marketer. The content of the dispersant in the photosensitive resin composition can be appropriately set according to the type of the pigment to be used.

(D)著色劑之含量，相對於自感光性樹脂組成物去除(E)溶劑之成分總和100質量份而言，較佳為20~95質量份、更佳為25~90質量份、又更佳為30~85質量份。含量為25質量份以上且90質量份以下時，就硬化性、顯影性之觀點較佳。The content of the colorant (D) is preferably 20 to 95 parts by mass, more preferably 25 to 90 parts by mass, more preferably 25 to 90 parts by mass, with respect to 100 parts by mass of the total of the components removed from the photosensitive resin composition (E) the solvent Preferably it is 30-85 mass parts. When the content is 25 parts by mass or more and 90 parts by mass or less, it is preferable from the viewpoint of curability and developability.

[(E)溶劑] 溶劑可使用與上述製造方法所用的相同者。 (E)溶劑之含量，相對於自感光性樹脂組成物去除(E)溶劑之成分總和100質量份而言，較佳為100~700質量份、更佳為200~600質量份、又更佳為300~500質量份。含量為100質量份以上且700質量份以下時，可使感光性樹脂組成物成為適切之黏度。 [(E) Solvent] As a solvent, the same thing used for the above-mentioned manufacturing method can be used. The content of the solvent (E) is preferably 100 to 700 parts by mass, more preferably 200 to 600 parts by mass, more preferably 100 to 700 parts by mass, with respect to 100 parts by mass of the total of the components of the (E) solvent removed from the photosensitive resin composition 300 to 500 parts by mass. When the content is 100 parts by mass or more and 700 parts by mass or less, the photosensitive resin composition can have an appropriate viscosity.

[其他成分] 本實施形態之感光性樹脂組成物，除了上述成分以外，為了賦予特定之特性，亦可含有偶合劑、調平劑、熱聚合抑制劑等之公知添加劑。感光性樹脂組成物中所含有的上述添加劑之含量，只要係不阻礙本發明之效果的範圍則不特別限定。 [other ingredients] The photosensitive resin composition of the present embodiment may contain known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor in order to impart specific properties in addition to the above-mentioned components. Content of the said additive contained in the photosensitive resin composition will not be specifically limited if it is a range which does not inhibit the effect of this invention.

＜感光性樹脂組成物之製造方法＞ 本實施形態之感光性樹脂組成物，可藉由將(A)共聚物、(B)反應性稀釋劑、(C)光聚合起始劑、(D)著色劑、(E)溶劑，例如使用公知之混合裝置混合而製造。 本實施形態之製造方法中，將感光性樹脂組成物中所含有的上述共聚物、溶劑、反應性稀釋劑、光聚合起始劑、著色劑之各成分混合的順序並不特別限定，例如可藉由於調製含有共聚物與溶劑之樹脂組成物後，於所得之樹脂組成物中混合反應性稀釋劑、光聚合起始劑與著色劑之方法而製造。 <Manufacturing method of photosensitive resin composition> The photosensitive resin composition of this embodiment can be prepared by mixing (A) a copolymer, (B) a reactive diluent, (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent, for example, using It is produced by mixing with a known mixing device. In the production method of the present embodiment, the order of mixing the above-mentioned copolymer, solvent, reactive diluent, photopolymerization initiator, and colorant contained in the photosensitive resin composition is not particularly limited. It is produced by a method of mixing a reactive diluent, a photopolymerization initiator, and a coloring agent in the obtained resin composition after preparing a resin composition containing a copolymer and a solvent.

本實施形態之感光性樹脂組成物，由於含有本實施形態之樹脂組成物，故可得到具有優良顯影性之樹脂硬化膜。因此，本實施形態之感光性樹脂組成物適合作為阻劑。特別是本實施形態之感光性樹脂組成物，適合作為用於製造CCD(Charged-coupled devices)或CMOS (Complementary metal-oxide-semiconductor)等之固體攝影元件、有機EL顯示器、液晶顯示裝置中所包含的透明膜、保護膜、絕緣膜、被覆膜、光間隔件、黑色矩陣、黑柱間隔件(black column spacer)、彩色濾光片等的阻劑。Since the photosensitive resin composition of the present embodiment contains the resin composition of the present embodiment, a cured resin film having excellent developability can be obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a resist. In particular, the photosensitive resin composition of the present embodiment is suitable for use in the manufacture of solid-state imaging elements, organic EL displays, and liquid crystal display devices for manufacturing CCD (Charged-coupled devices), CMOS (Complementary metal-oxide-semiconductor), etc. Transparent film, protective film, insulating film, coating film, photo spacer, black matrix, black column spacer (black column spacer), color filter and other resists.

[樹脂硬化膜] 本實施形態之樹脂硬化膜，為本實施形態之感光性樹脂組成物之硬化物。本實施形態之樹脂硬化膜，可適合地使用作為彩色濾光片之材料。以下，作為本實施形態之樹脂硬化膜之一例，列舉使用本實施形態之樹脂硬化膜之彩色濾光片為例來說明。 [resin cured film] The cured resin film of the present embodiment is a cured product of the photosensitive resin composition of the present embodiment. The resin cured film of this embodiment can be suitably used as a material of a color filter. Hereinafter, as an example of the resin cured film of this embodiment, the color filter using the resin cured film of this embodiment is mentioned as an example and demonstrated.

本實施形態之彩色濾光片，具有基板、於基板上所形成的紅(R)、綠(G)及藍(B)的畫素、形成於畫素之交界的黑色矩陣，與形成於畫素及黑色矩陣上的保護膜。本實施形態之彩色濾光片，具有包含本實施形態之感光性樹脂組成物之硬化物的畫素及黑色矩陣。本實施形態之彩色濾光片中，作為畫素及黑色矩陣以外的構成，可採用公知之構成。The color filter of the present embodiment has a substrate, red (R), green (G), and blue (B) pixels formed on the substrate, a black matrix formed at the boundary between the pixels, and a black matrix formed on the pixel. Protective film on pixel and black matrix. The color filter of the present embodiment has pixels and a black matrix including a cured product of the photosensitive resin composition of the present embodiment. In the color filter of the present embodiment, a well-known structure can be adopted as the structure other than the pixel and the black matrix.

本實施形態之彩色濾光片，例如可藉由於基板上依序形成紅(R)、綠(G)及藍(B)的畫素，與黑色矩陣之方法而製造。 基板不特別限定，可適當使用玻璃基板、矽基板、聚碳酸酯基板、聚酯基板、聚醯胺基板、聚醯胺醯亞胺基板、聚醯亞胺基板、鋁基板、印刷配線基板、陣列基板等。 The color filter of this embodiment can be manufactured by, for example, a method of sequentially forming red (R), green (G), and blue (B) pixels and a black matrix on a substrate. The substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide imide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, arrays can be appropriately used substrate, etc.

各畫素及黑色矩陣，均可使用光微影術法來形成。具體而言，係將上述感光性樹脂組成物塗佈於基板上而形成塗佈膜後，透過特定圖型之光罩將塗佈膜曝光，並使曝光部分光硬化。然後，將未曝光部分以鹼水溶液顯影後，烘烤藉以形成特定之圖型(著色圖型)。Each pixel and black matrix can be formed using photolithography. Specifically, after the above-mentioned photosensitive resin composition is applied on a substrate to form a coating film, the coating film is exposed through a photomask of a specific pattern, and the exposed part is photocured. Then, after developing the unexposed portion with an alkaline aqueous solution, it is baked to form a specific pattern (colored pattern).

感光性樹脂組成物之塗佈方法並不特別限定，可使用網版印刷法、輥塗佈法、淋幕塗佈法、噴霧塗佈法、旋轉塗佈法等。 感光性樹脂組成物塗佈後，亦可依需要，使用循環式烘箱、紅外線加熱器、加熱板等之加熱手段加熱，藉以使感光性樹脂組成物中所含有的溶劑揮發。加熱條件不特別限定，可依所使用之感光性樹脂組成物之種類而適當設定。例如，加熱溫度可為50℃~120℃，加熱時間可為30秒~30分鐘。 The coating method of the photosensitive resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc. can be used. After the photosensitive resin composition is applied, it can also be heated by heating means such as a circulating oven, an infrared heater, a hot plate, etc., as required, so as to volatilize the solvent contained in the photosensitive resin composition. The heating conditions are not particularly limited, and can be appropriately set according to the type of the photosensitive resin composition to be used. For example, the heating temperature may be 50°C to 120°C, and the heating time may be 30 seconds to 30 minutes.

將含有感光性樹脂組成物之塗佈膜曝光的方法，具體而言，可列舉透過負型之遮罩對塗佈膜照射紫外線、準分子雷射光等之活性能量線，予以部分曝光之方法。對塗佈膜照射的活性能量線量，只要依感光性樹脂組成物之組成而適當選擇即可，較佳為例如30~2000 mJ/cm 2。曝光所用之光源並不特別限定，可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、氙燈、金屬鹵化物燈等。 Specifically, the method of exposing the coating film containing the photosensitive resin composition includes a method of partially exposing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of active energy rays irradiated to the coating film may be appropriately selected depending on the composition of the photosensitive resin composition, and is preferably, for example, 30 to 2000 mJ/cm 2 . The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like can be used.

經曝光之塗佈膜的顯影所用之鹼水溶液並不特別限定，可使用碳酸鈉、碳酸鉀、碳酸鈣、氫氧化鈉、氫氧化鉀等之水溶液；乙基胺、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-苯二胺系化合物之水溶液等。此等之鹼水溶液中，亦可依需要添加消泡劑或界面活性劑。The alkaline aqueous solution used in the development of the exposed coating film is not particularly limited, and aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; ethylamine, diethylamine, dimethyl Aqueous solutions of amine compounds such as ethanolamine; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N -β-Hydroxyethylaniline, 3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- N-β-methoxyethylaniline and aqueous solutions of p-phenylenediamine-based compounds such as sulfate, hydrochloride, or p-toluenesulfonate. In these alkaline aqueous solutions, an antifoaming agent or a surfactant can also be added as required.

本實施形態中，較佳為於將經曝光之塗佈膜使用上述鹼水溶液顯影之後，進行水洗而乾燥。 烘烤顯影後的塗佈膜之條件不特別限定，係依所使用之感光性樹脂組成物之種類來進行加熱處理即可。例如，烘烤溫度可為150℃以下、較佳可為120℃以下、特佳可為100℃以下。例如，烘烤時間可為10分鐘~4小時、較佳可為20分鐘~2小時。 In this embodiment, after developing the exposed coating film using the above-mentioned alkaline aqueous solution, it is preferable to wash with water and dry. The conditions for baking and developing the coating film are not particularly limited, and the heat treatment may be performed according to the type of the photosensitive resin composition to be used. For example, the baking temperature may be 150°C or lower, preferably 120°C or lower, and particularly preferably 100°C or lower. For example, the baking time may be 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

如此地，依序重複將各畫素及黑色矩陣各自所對應的感光性樹脂組成物，進行塗佈、曝光、顯影及烘烤之步驟。藉此，可形成包含本實施形態之感光性樹脂組成物之硬化物，具有所期望之形狀的各畫素及黑色矩陣。In this way, the steps of coating, exposing, developing and baking the photosensitive resin composition corresponding to each pixel and the black matrix are sequentially repeated. Thereby, the hardened|cured material containing the photosensitive resin composition of this embodiment can be formed, and each pixel and black matrix which have a desired shape can be formed.

本實施形態之樹脂硬化膜，為具有優良保存安定性的本實施形態之感光性樹脂組成物之硬化物，因此可安定地製造。 本實施形態中，雖列舉包含本實施形態之感光性樹脂組成物之硬化物的各畫素及黑色矩陣為例來進行說明，但本實施形態之硬化物不限定於上述例子。例如，由不含著色劑之感光性樹脂組成物所成的硬化物，可適合地使用作為固體攝影元件、有機EL顯示器、液晶顯示裝置中所包含的被覆膜、保護膜、絕緣膜等。 Since the resin cured film of this embodiment is a cured product of the photosensitive resin composition of this embodiment which has excellent storage stability, it can be manufactured stably. In the present embodiment, each pixel and black matrix including the cured product of the photosensitive resin composition of the present embodiment are described as examples, but the cured product of the present embodiment is not limited to the above examples. For example, a cured product of a photosensitive resin composition containing no colorant can be suitably used as a solid-state imaging element, an organic EL display, a coating film, a protective film, an insulating film, etc. included in a liquid crystal display device.

上述實施形態中，係說明了含有本實施形態之樹脂組成物，與光聚合起始劑之感光性樹脂組成物，但亦可藉由含有硬化促進劑及公知之環氧樹脂以取代光聚合起始劑，來作為硬化性樹脂組成物。該硬化性樹脂組成物，例如可藉由以噴墨法等塗佈於基板上後進行加熱，而形成所期望之圖型。In the above-mentioned embodiment, the photosensitive resin composition containing the resin composition of the present embodiment and the photopolymerization initiator is described, but the photopolymerization initiator may be replaced by a curing accelerator and a known epoxy resin. The starting agent is used as a curable resin composition. The curable resin composition can be formed into a desired pattern by, for example, applying it to a substrate by an ink jet method or the like and then heating it.

[圖像顯示元件] 本實施形態之圖像顯示元件，具備本實施形態之樹脂硬化膜。本實施形態之圖像顯示元件，例如可列舉具有使用本實施形態之樹脂硬化膜的彩色濾光片者。 本實施形態之圖像顯示元件，具體而言，可列舉CCD或CMOS等之固體攝影元件、有機EL顯示器、液晶顯示裝置等。 [image display element] The image display element of this embodiment is equipped with the resin cured film of this embodiment. As the image display element of this embodiment, what has a color filter using the resin cured film of this embodiment is mentioned, for example. Specific examples of the image display element of the present embodiment include solid-state imaging elements such as CCD and CMOS, organic EL displays, and liquid crystal display devices.

例如製造液晶顯示元件作為本實施形態之圖像顯示元件時，係於第1基板上形成使用了本實施形態之樹脂硬化膜的彩色濾光片，接著依序形成電極、間隔件等。然後，係於第2基板上形成電極等，使第1基板之形成有彩色濾光片之面，與第2基板之形成有電極之面呈對向而貼合，於第1基板與第2基板之間注入特定量之液晶進行密封即可。 [實施例] For example, when a liquid crystal display element is manufactured as an image display element of this embodiment, the color filter using the resin cured film of this embodiment is formed on a 1st board|substrate, and electrodes, a spacer, etc. are formed in this order. Then, electrodes and the like are formed on the second substrate, so that the surface of the first substrate on which the color filter is formed faces the surface of the second substrate on which the electrodes are formed, and is bonded to the first substrate and the second substrate. A specific amount of liquid crystal can be injected between the substrates for sealing. [Example]

以下顯示實施例及比較例，以具體的說明本發明。Examples and comparative examples are shown below to specifically illustrate the present invention.

[實施例1] 於具備攪拌裝置、滴液漏斗、冷凝器、溫度計及氣體導入管之燒瓶中，置入286.5g之丙二醇單甲基醚後，一邊進行氮取代一邊攪拌，昇溫至78℃。接著，將反應液2與反應液1分別自滴液漏斗滴下至燒瓶中。前述反應液2，為含有28.3g之甲基丙烯酸二環戊酯、50.7g之甲基丙烯酸甲酯、32.1g之甲基丙烯酸及70.0g之甲基丙烯酸2-(3,5-二甲基吡唑-1-基)羰基胺基乙酯(昭和電工股份有限公司製、Karenz MOI-BP)者。前述反應液1，為將29.0g之內消旋體為99%之2,2’-偶氮雙(2,4-二甲基戊腈)(聚合起始劑、溶解度42.9g/100gPGME)添加至81.5g之丙二醇單甲基醚並溶解者。反應液1及反應液2中之聚合起始劑之濃度，分別為26.2質量%及0質量%。滴下速度在反應液1為1.8ml/分鐘、反應液2為4.4ml/分鐘。 滴下結束後，於78℃攪拌3小時進行共聚合反應，生成共聚物，最後添加丙二醇單甲基醚，使溶劑以外之成分成為35質量%，而得到試樣No.1之聚合物組成物。所得聚合物組成物中之共聚物之重量平均分子量為7,500，酸值為100KOHmg/g。 [Example 1] After placing 286.5 g of propylene glycol monomethyl ether in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, the temperature was raised to 78° C. with stirring while substituting nitrogen. Next, the reaction solution 2 and the reaction solution 1 were respectively dropped into the flask from the dropping funnel. The aforementioned reaction solution 2 contains 28.3 g of dicyclopentyl methacrylate, 50.7 g of methyl methacrylate, 32.1 g of methacrylic acid and 70.0 g of 2-(3,5-dimethyl methacrylate) Pyrazol-1-yl)carbonylaminoethyl ester (manufactured by Showa Denko Co., Ltd., Karenz MOI-BP). The aforementioned reaction solution 1 is to add 29.0 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator, solubility 42.9 g/100 g PGME) with 99% meso isomer to 81.5 g of propylene glycol monomethyl ether and dissolved. The concentrations of the polymerization initiators in the reaction liquid 1 and the reaction liquid 2 were 26.2 mass % and 0 mass %, respectively. The dropping rate was 1.8 ml/min in the reaction solution 1 and 4.4 ml/min in the reaction solution 2. After completion of the dropping, the copolymerization reaction was carried out by stirring at 78° C. for 3 hours to form a copolymer, and finally propylene glycol monomethyl ether was added so that the components other than the solvent became 35% by mass to obtain the polymer composition of Sample No. 1. The weight average molecular weight of the copolymer in the obtained polymer composition was 7,500, and the acid value was 100 KOHmg/g.

[實施例2~5、比較例3] 除了使用表1記載之組成及反應液1與反應液2之濃度以外，係與實施例1同樣地得到試樣No.1~6之聚合物組成物。 [Examples 2 to 5, Comparative Example 3] The polymer compositions of Sample Nos. 1 to 6 were obtained in the same manner as in Example 1, except that the compositions and the concentrations of the reaction liquid 1 and the reaction liquid 2 described in Table 1 were used.

[比較例1] 除了使用內消旋體與外消旋體各50%之2,2’-偶氮雙(2,4-二甲基戊腈) (聚合起始劑、溶解度17.6g/100gPGME)以外，係與實施例1同樣地實施，但聚合起始劑未完全溶解於溶劑，無法實施共聚合反應。 [Comparative Example 1] 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator, solubility 17.6g/100g PGME) was used, except that 50% of each of the meso and racemic forms was used. Example 1 was carried out in the same manner, but the polymerization initiator was not completely dissolved in the solvent, and the copolymerization reaction could not be carried out.

[比較例2] 除了使用內消旋體與外消旋體各50%之2,2’-偶氮雙(2,4-二甲基戊腈) (聚合起始劑)以外，係與實施例2同樣地實施。但是，聚合起始劑未完全溶解於溶劑，無法實施共聚合反應。 [Comparative Example 2] The procedure was carried out in the same manner as in Example 2, except that 50% of each of the meso and the racemic 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was used. . However, the polymerization initiator was not completely dissolved in the solvent, and the copolymerization reaction could not be carried out.

Figure 02_image007
Figure 02_image007

＜感光性樹脂組成物(顏料型)之調製＞ 於直徑0.5mm之填充有氧化鋯珠200g的不鏽鋼製容器中，投入C.I顏料綠36(著色劑)100質量份、丙二醇單甲基醚乙酸酯44.98質量份、分散劑(BYK-Chemie Japan股份有限公司製Disperbyk-161)25質量份。然後，以塗料振盪機混合2小時予以分散，藉以調製綠色顏料分散液。 將該綠色顏料分散液，與表2所示之其他摻合成分(亦即聚合物組成物、反應性稀釋劑、光聚合起始劑及溶劑)混合，而調製感光性樹脂組成物。各自之成分之摻合比例，係如表2所示。再者，實施例1~5、比較例3之感光性樹脂組成物，係分別使用表1記載之試樣No.1~6之聚合物組成物所調製。又，聚合物組成物之量，包含共聚物反應結束時所含有的溶劑，各試樣中所含有的溶劑量，亦一併計算於作為摻合成分之溶劑中。 <Preparation of photosensitive resin composition (pigment type)> Into a stainless steel container with a diameter of 0.5 mm filled with 200 g of zirconia beads, 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 Japan Co., Ltd.) were placed. Co., Ltd. Disperbyk-161) 25 parts by mass. Then, the green pigment dispersion liquid was prepared by mixing and dispersing with a paint shaker for 2 hours. This green pigment dispersion liquid was mixed with other admixture components shown in Table 2 (that is, a polymer composition, a reactive diluent, a photopolymerization initiator, and a solvent) to prepare a photosensitive resin composition. The blending ratios of the respective components are shown in Table 2. In addition, the photosensitive resin compositions of Examples 1 to 5 and Comparative Example 3 were prepared using the polymer compositions of Sample Nos. 1 to 6 described in Table 1, respectively. 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 calculated in the solvent as a blending component.

Figure 02_image009
Figure 02_image009

＜感光性樹脂組成物之評估＞ (1)鹼顯影性 將實施例1~5、比較例3之感光性樹脂組成物各自於5cm見方的玻璃基板(無鹼玻璃基板)上旋轉塗佈，使曝光後之厚度成為2.5μm，之後，藉由於90℃加熱3分鐘，使溶劑揮發。接著，於距塗佈膜100μm之距離，配置特定圖型之光罩，透過該光罩將塗佈膜曝光(曝光量150mJ/cm 2)，使曝光部分進行光硬化。接著，藉由將含0.1質量%之碳酸鈉的水溶液於23℃之溫度及0.3MPa之壓力下進行噴霧，將未曝光部分溶解進行顯影後，於100℃烘烤20分鐘藉以形成特定之圖型。鹼顯影後之殘渣，係藉由將鹼顯影後之圖型使用(股)日立先端科技製電子顯微鏡S-3400進行觀察來確認。該評估之基準如以下所示。 ○：無殘渣 ×：有殘渣 鹼顯影性之評估結果示於表3。 <Evaluation of Photosensitive Resin Compositions> (1) Alkali Developability The photosensitive resin compositions of Examples 1 to 5 and Comparative Example 3 were each spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) to make The thickness after exposure was 2.5 μm, and thereafter, the solvent was volatilized by heating at 90° C. for 3 minutes. Next, a photomask with a specific pattern was arranged at a distance of 100 μm from the coating film, and the coating film was exposed through the photomask (exposure amount 150 mJ/cm 2 ), and the exposed portion was photocured. 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 part was dissolved and developed, and then baked at 100°C for 20 minutes to form a specific pattern . The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi Advanced Technology Co., Ltd. The basis for this evaluation is as follows. ○: No residue ×: With residue The evaluation results of alkali developability are shown in Table 3.

(2)耐溶劑性之評估 於5cm見方的玻璃基板(無鹼玻璃基板)上，將實施例1~5、比較例3之感光性樹脂組成物分別進行旋轉塗佈，使烘烤後之厚度成為2.5μm，之後，於90℃加熱3分鐘使溶劑揮發。接著，對塗佈膜以波長365nm之光進行曝光，將曝光部分予以光硬化後，於烘烤溫度100℃之乾燥器中放置20分鐘，製作硬化塗膜。於容量500mL之附蓋玻璃瓶中置入200mL之丙二醇單甲基醚乙酸酯，於80℃之條件下靜置。於其中浸漬附上述硬化塗膜之試驗片後，於維持80℃之狀態下靜置5分鐘。以分光光度計UV-1650PC(島津製作所股份有限公司製)測定試驗片對丙二醇單甲基醚乙酸酯浸漬前後之顏色變化(ΔE*ab)。ΔE*ab之測定結果示於表3。ΔE*ab若為1.5以下則可說耐溶劑性優良。 (2) Evaluation of solvent resistance On a 5 cm square glass substrate (alkali-free glass substrate), spin-coating the photosensitive resin compositions of Examples 1 to 5 and Comparative Example 3, respectively, so that the thickness after baking is 2.5 μm, and then, at 90 The solvent was evaporated by heating at °C for 3 minutes. Next, the coating film was exposed to light with a wavelength of 365 nm, and the exposed portion was photocured, and then left to stand for 20 minutes in a drier with a baking temperature of 100° C. to prepare a cured coating film. Put 200 mL of propylene glycol monomethyl ether acetate into a 500 mL capped glass bottle, and let it stand at 80°C. After immersing the test piece to which the above-mentioned cured coating film was attached, it was left to stand for 5 minutes in a state maintained at 80°C. The color change (ΔE*ab) of the test piece before and after immersion in propylene glycol monomethyl ether acetate was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). The measurement results of ΔE*ab are shown in Table 3. When ΔE*ab is 1.5 or less, it can be said that the solvent resistance is excellent.

以上之實施例及比較例之結果示於表3。The results of the above Examples and Comparative Examples are shown in Table 3.

Figure 02_image011
Figure 02_image011

如表3所示，若使用起始劑之濃度為16%以上的反應液1，且利用使用溶解度較高的異構物含60質量%以上之聚合起始劑所得之試樣No.1~5的共聚物時，可得到顯影性與耐溶劑性優良的感光性樹脂組成物。另一方面，使用起始劑之濃度未達16%之反應液1，溶解度較高的異構物為50質量%時，係無法得到低分子量之共聚物，或者即使得到共聚物，亦無法滿足顯影性與耐溶劑性。 [產業上之可利用性] As shown in Table 3, if the reaction solution 1 with an initiator concentration of 16% or more is used, and the sample No.1~ In the case of the copolymer of 5, a photosensitive resin composition excellent in developability and solvent resistance can be obtained. On the other hand, when the concentration of the initiator is less than 16% in the reaction solution 1 and the isomer with high solubility is 50% by mass, a low molecular weight copolymer cannot be obtained, or even if a copolymer is obtained, it is not satisfactory Developability and solvent resistance. [Industrial Availability]

依照本發明，可提供將樹脂之分子量控制在低分子量側的共聚物之製造方法。又，可提供適合用於顯影性優良的感光性樹脂組成物之共聚物之製造方法。進一步地，本發明可提供適合使用作為耐溶劑性優良的樹脂硬化膜之材料的共聚物之製造方法。According to the present invention, a method for producing a copolymer in which the molecular weight of the resin is controlled to be on the low molecular weight side can be provided. Moreover, the manufacturing method of the copolymer suitable for the photosensitive resin composition excellent in developability can be provided. Furthermore, the present invention can provide a method for producing a copolymer suitable for use as a material of a resin cured film having excellent solvent resistance.

Claims (14)

一種共聚物之製造方法，其係包含 將聚合起始劑與溶劑(稱「溶劑(ii)」)混合，得到反應液1之步驟、 調製含有含乙烯性不飽和基之化合物的反應液2之步驟，與 將反應液1與反應液2滴下混合於反應器中之步驟 的使含乙烯性不飽和基之化合物聚合的共聚物之製造方法，其特徵為 於反應液1中，聚合起始劑之濃度為16質量%~50質量%， 前述聚合起始劑中所含有之由外消旋體及內消旋體所構成的異構物當中，對前述溶劑(ii)之溶解度較高之異構物係在聚合起始劑中含有60質量%以上， 前述聚合起始劑為下述通式(1)表示之化合物， 前述含乙烯性不飽和基之化合物，至少含有不具有羧基且具有封端異氰酸基之含乙烯性不飽和基之化合物及具有羧基之含乙烯性不飽和基之化合物；
Figure 03_image001
(式(1)中，R 1及R 2各自獨立為碳數1~6之烷基或氰基，且R 1及R 2表示相異之基，R 3及R 4各自獨立表示碳數1~6之烷基，R 5表示氫原子或碳數1~6之烷氧基)。 A method for producing a copolymer, comprising the steps of mixing a polymerization initiator with a solvent (referred to as "solvent (ii)") to obtain a reaction solution 1, and preparing a reaction solution 2 containing an ethylenically unsaturated group-containing compound. The method for producing a copolymer for polymerizing an ethylenically unsaturated group-containing compound with the step of dropping and mixing the reaction solution 1 and the reaction solution 2 in a reactor is characterized in that in the reaction solution 1, a polymerization initiator The concentration is 16% by mass to 50% by mass. Among the isomers composed of racemates and mesomers contained in the polymerization initiator, the solubility to the solvent (ii) is higher. The structure contains 60% by mass or more in a polymerization initiator, the polymerization initiator is a compound represented by the following general formula (1), and the ethylenically unsaturated group-containing compound contains at least no carboxyl group and has a sealing Isocyanate-terminated ethylenically unsaturated group-containing compounds and carboxyl group-containing ethylenically unsaturated group-containing compounds;
Figure 03_image001
(In formula (1), R 1 and R 2 are each independently an alkyl group or a cyano group having 1 to 6 carbon atoms, and R 1 and R 2 represent different groups, and R 3 and R 4 each independently represent a carbon number of 1 ~6 alkyl group, R 5 represents a hydrogen atom or an alkoxy group with a carbon number of 1~6). 如請求項1之共聚物之製造方法，其中前述式(1)中，R 1及R 2之一者為氰基。 The method for producing a copolymer according to claim 1, wherein in the aforementioned formula (1), one of R 1 and R 2 is a cyano group. 如請求項1或2之共聚物之製造方法，其中前述聚合起始劑，為選自2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)及2,2’-偶氮雙(2,4-二甲基戊腈)的1種或2種以上。The method for producing a copolymer of claim 1 or 2, wherein the polymerization initiator is selected from 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 2 , 2'-azobis (2,4- dimethylvaleronitrile) 1 type or 2 or more types. 如請求項1或2之共聚物之製造方法，其中前述聚合起始劑之使用量，相對於前述含乙烯性不飽和基之化合物100質量份而言，為5~30質量份。The method for producing a copolymer of claim 1 or 2, wherein the amount of the polymerization initiator used is 5 to 30 parts by mass relative to 100 parts by mass of the compound containing an ethylenically unsaturated group. 如請求項1或2之共聚物之製造方法，其中前述含乙烯性不飽和基之化合物，進一步含有具有羥基之含乙烯性不飽和基之化合物。The method for producing a copolymer according to claim 1 or 2, wherein the ethylenically unsaturated group-containing compound further contains an ethylenically unsaturated group-containing compound having a hydroxyl group. 如請求項1或2之共聚物之製造方法，其中前述含乙烯性不飽和基之化合物，進一步含有具有環氧基之含乙烯性不飽和基之化合物。The method for producing a copolymer of claim 1 or 2, wherein the ethylenically unsaturated group-containing compound further contains an ethylenically unsaturated group-containing compound having an epoxy group. 如請求項1或2之共聚物之製造方法，其中前述含乙烯性不飽和基之化合物中，含有不具有羧基且具有封端異氰酸基之含乙烯性不飽和基之化合物5~30莫耳%、具有羧基之含乙烯性不飽和基之化合物10~50莫耳%。The method for producing a copolymer according to claim 1 or 2, wherein the ethylenically unsaturated group-containing compound contains 5-30 mol of the ethylenically unsaturated group-containing compound that does not have a carboxyl group and has a blocked isocyanate group %, 10-50 mol% of compounds containing ethylenically unsaturated groups with carboxyl group. 如請求項1或2之共聚物之製造方法，其重量平均分子量為3,000~15,000。According to the method for producing the copolymer of claim 1 or 2, the weight average molecular weight is 3,000-15,000. 如請求項1或2之共聚物之製造方法，其係依序具有 將相對於前述含乙烯性不飽和基之化合物合計100質量份而言為50~500質量份的溶劑(i)昇溫至設定聚合溫度之步驟I、 將前述反應液1及前述反應液2分別滴下至前述溶劑(i)中進行共聚合之步驟II，與 於前述反應液1及反應液2之滴下結束後，進一步繼續共聚合反應1~10小時之步驟III 之共聚物之製造方法，其中 前述反應液1為前述聚合起始劑100質量份與溶劑(ii)100~525質量份之混合物， 前述反應液2，為前述含乙烯性不飽和基之化合物合計100質量份與溶劑(iii)0~500質量份之混合物。 According to the method for producing the copolymer of claim 1 or 2, it has in sequence With respect to the total of 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound, 50 to 500 parts by mass of the solvent (i) is heated to a set polymerization temperature in steps I, The aforementioned reaction solution 1 and the aforementioned reaction solution 2 are respectively dropped into the aforementioned solvent (i) to carry out the step II of copolymerization, with After the dropping of the aforementioned reaction solution 1 and reaction solution 2 is completed, step III of the copolymerization reaction is further continued for 1 to 10 hours The method for producing the copolymer, wherein The aforementioned reaction solution 1 is a mixture of 100 parts by mass of the aforementioned polymerization initiator and 100 to 525 parts by mass of the solvent (ii), The aforementioned reaction solution 2 is a mixture of 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound and 0 to 500 parts by mass of the solvent (iii). 一種感光性樹脂組成物，其含有藉由如請求項1~9中任一項之製造方法所得到的共聚物、反應性稀釋劑、光聚合起始劑、著色劑、溶劑。A photosensitive resin composition containing the copolymer obtained by the production method according to any one of claims 1 to 9, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. 一種樹脂硬化膜，其係使如請求項10之感光性樹脂組成物硬化而得到。A resin cured film obtained by curing the photosensitive resin composition of claim 10. 一種樹脂硬化膜之製造方法，其係將如請求項10之感光性樹脂組成物塗佈、曝光、顯影，且於70 ~150℃硬化。A method for producing a resin cured film, which comprises coating, exposing, developing, and curing the photosensitive resin composition as claimed in claim 10 at 70-150°C. 一種彩色濾光片，其特徵為具有由如請求項10之感光性樹脂組成物之硬化物所成之著色圖型。A color filter characterized by having a colored pattern formed by a hardened product of the photosensitive resin composition of claim 10. 一種圖像顯示元件，其特徵為具備如請求項13之彩色濾光片。An image display element characterized by having the color filter as claimed in claim 13.
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