TWI781283B - Colored photosensitive resin composition, bank, organic electroluminescent element, image display device and lighting - Google Patents

Colored photosensitive resin composition, bank, organic electroluminescent element, image display device and lighting Download PDF

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TWI781283B
TWI781283B TW108102757A TW108102757A TWI781283B TW I781283 B TWI781283 B TW I781283B TW 108102757 A TW108102757 A TW 108102757A TW 108102757 A TW108102757 A TW 108102757A TW I781283 B TWI781283 B TW I781283B
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ring
mass
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TW201937283A (en
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利光恵理子
中谷和裕
斎藤恵子
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日商三菱化學股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K50/865—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. light-blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

Abstract

Provided is a colored photosensitive resin composition having good ink repellency and exhibiting good linearity. The colored photosensitive resin composition of the present invention comprises (A) an ethylenic unsaturated compound, (B) a photopolymerization initiator, (C) an alkali soluble resin, (D) a liquid-repellent agent, and (E) a coloring agent, the content of (E) the coloring agent in the solid content of the colored photosensitive resin composition being 20wt% or less, and (C) the alkali soluble resin containing (c1) an acryl copolymerized resin having an ethylenic unsaturated group in a side chain and (c2) epoxy(meth)acrylate resin.

Description

有色感光性樹脂組成物、分隔壁、有機電致發光元件、影像 顯示裝置及照明 Colored photosensitive resin composition, partition wall, organic electroluminescent element, image Display Devices and Lighting

本發明係關於一種用以形成分隔壁的有色感光性樹脂組成物，更關於一種由有色感光性樹脂組成物所構成之分隔壁、具備該分隔壁之有機電致發光元件、包含該有機電致發光元件的影像顯示裝置及照明。 本發明將2018年1月26日向日本特許廳提出申請的日本特願2018-011096的說明書、申請專利範圍及摘要的所有內容以及本說明書中引用之文獻等所揭示之內容的一部分或全部引用至此，而作為本說明書揭示的內容。The present invention relates to a colored photosensitive resin composition for forming a partition wall, and more to a partition wall made of the colored photosensitive resin composition, an organic electroluminescent element with the partition wall, and an organic electroluminescent element including the organic electroluminescent element. Image display device and lighting of light-emitting elements. The present invention incorporates part or all of the content disclosed in Japanese Patent Application No. 2018-011096 filed with the Japan Patent Office on January 26, 2018, all contents of the scope of claims and abstract, and documents cited in this specification. , and as the content disclosed in this specification.

以往，有機電致顯示器及有機電致照明等所包含的有機電致發光元件，係在基板上形成分隔壁(Bank)後，在被分隔壁圍住的區域內積層各種功能層以進行製造。藉由使用感光性樹脂組成物的光微影法之形成的方法來作為易於形成這種分隔壁之方法，已為人所知。Conventionally, organic electroluminescent elements included in organic electroluminescent displays and organic electroluminescent lighting are manufactured by forming partition walls (banks) on a substrate, and then laminating various functional layers in regions surrounded by the partition walls. As a method for easily forming such a partition wall, a method of forming a photolithography method using a photosensitive resin composition is known.

又，作為在被分隔壁圍住的區域內積層各種功能層的方法，已為人所知的有先調製包含構成功能層之材料的印墨，接著將所調製之印墨注入被分隔壁圍住的區域內。該方法之中，噴墨法因為可輕易將既定量的印墨正確注入既定處，因此多被採用。Also, as a method of laminating various functional layers in a region surrounded by partition walls, it is known to first prepare ink containing materials constituting the functional layer, and then inject the prepared ink into the region surrounded by partition walls. within the area where you live. Among these methods, the inkjet method is often used because it can easily and accurately inject a given amount of ink into a given place.

再者，使用印墨形成功能層的情況，以防止印墨附著於分隔壁以及防止注入相鄰區域之間的印墨彼此混合為目的等，有時要求賦予分隔壁撥墨性(撥液性)。 又，近年來除了撥墨性以外，亦對於分隔壁要求各種特性，而開發各種感光性樹脂組成物。例如，從提升對比及防止反射的觀點來看，要求有色分隔壁。專利文獻1中記載，在負型感光性樹脂組成物中，使用黑色有機顏料與特定的鹼可溶性樹脂，使該組成物的固體成分酸價在特定範圍內，藉此可形成同時具有微細線圖案與微小接觸孔的分隔壁，而對於顯影中所使用的鹼顯影液，所含有之黑色有機顏料的分散性良好，且保存穩定性良好。 [先前技術文獻] [專利文獻]Furthermore, when using ink to form a functional layer, it is sometimes required to impart ink repellency (liquid repellency) ). Moreover, in recent years, in addition to ink repellency, various characteristics have been required for a partition, and various photosensitive resin compositions have been developed. For example, from the viewpoint of improving contrast and preventing reflection, colored partition walls are required. Patent Document 1 describes that in a negative photosensitive resin composition, a black organic pigment and a specific alkali-soluble resin are used, and the solid content of the composition has an acid value within a specific range, thereby forming a fine line pattern. The partition wall of the tiny contact hole, and the black organic pigment contained in the alkaline developer used in the development has good dispersibility and good storage stability. [Prior Art Document] [Patent Document]

[專利文獻1] 國際公開第2013/069789號[Patent Document 1] International Publication No. 2013/069789

[發明所欲解決之課題][Problem to be Solved by the Invention]

近年致力於開發有色分隔壁，例如，為了使用含有溶劑溶解性低之成分的印墨來形成既定膜厚的功能層，必須在被有色分隔壁圍住的區域中大量注入稀薄的印墨，自然需要一種厚膜的有色分隔壁。由於有色分隔壁所要求的遮光性係膜厚整體的遮光性，因此在厚膜的分隔壁中，會有每單位膜厚的遮光性變低、亦即著色劑之含有比例會變低的傾向。 在這種厚膜的有色分隔壁中，為了防止相鄰區域之間的印墨彼此混合等，而要求其呈現充分的撥墨性。再者，被分隔壁圍住之區域的功能層理當成為影像顯示裝置的像素，然若分隔壁之邊緣部非直線或是具有殘渣而導致直線性不足，則無法均勻地形成功能層，反而成為發光不均的原因，因此要求分隔壁之邊緣部的直線性良好。In recent years, efforts have been devoted to the development of colored partitions. For example, in order to form a functional layer with a predetermined film thickness using printing inks containing low solvent solubility components, it is necessary to inject a large amount of thin ink into the area surrounded by colored partitions. Naturally, A thick film colored partition is desired. Since the light-shielding property required for a colored partition is the light-shielding property of the entire film thickness, in a thick-film partition, the light-shielding property per unit film thickness tends to be lower, that is, the content ratio of the colorant tends to be lower. . Such thick-film colored partitions are required to exhibit sufficient ink repellency in order to prevent inks between adjacent regions from mixing with each other. Furthermore, the functional layer in the area surrounded by the partition wall should be the pixel of the image display device. However, if the edge of the partition wall is not straight or has residues, resulting in insufficient linearity, the functional layer cannot be formed uniformly, and instead becomes Because of uneven light emission, the linearity of the edge of the partition wall is required to be good.

本案發明人等研究的結果，發現專利文獻1之有色感光性樹脂組成物中，降低著色劑的含有比例雖使直線性良好，但難以得到充分的撥墨性。 於是本發明之目的在於提供一種撥墨性高且直線性良好的有色感光性樹脂組成物。 又，本發明之目的在於提供一種使用該有色感光性樹脂組成物形成的分隔壁、具備該分隔壁之有機電致發光元件、包含該有機電致發光元件之影像顯示裝置及照明。 [解決課題之手段]As a result of research by the inventors of the present application, they found that in the colored photosensitive resin composition of Patent Document 1, it was difficult to obtain sufficient ink repellency even though the linearity was improved by reducing the content ratio of the colorant. Therefore, an object of the present invention is to provide a colored photosensitive resin composition having high ink repellency and good linearity. Furthermore, the object of the present invention is to provide a partition formed using the colored photosensitive resin composition, an organic electroluminescence element having the partition, an image display device and lighting including the organic electroluminescence element. [Means to solve the problem]

本案發明人等精心探討的結果，發現即使在含有撥液劑的有色感光性樹脂組成物中著色劑的含有比例少的情況，藉由併用特定的鹼可溶性樹脂，即可解決上述課題，進而完成本發明。 亦即本發明之要旨如下。As a result of careful research, the inventors of the present invention found that even if the content ratio of the colorant in the colored photosensitive resin composition containing the liquid-repellent agent is small, the above-mentioned problems can be solved by using a specific alkali-soluble resin together, and the completed this invention. That is, the gist of the present invention is as follows.

[1] 一種有色感光性樹脂組成物，其係含有(A)乙烯屬不飽和化合物、(B)光聚合起始劑、(C)鹼可溶性樹脂、(D)撥液劑以及(E)著色劑的有色感光性樹脂組成物，其特徵為： 該(E)著色劑的含有比例，在該有色感光性樹脂組成物的總固體成分中為20質量%以下， 該(C)鹼可溶性樹脂含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂以及(c2)環氧(甲基)丙烯酸酯樹脂。[1] A colored photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent, and (E) a coloring The colored photosensitive resin composition of the coloring agent is characterized in that: the content ratio of the (E) coloring agent is 20% by mass or less in the total solid content of the colored photosensitive resin composition, and the (C) alkali-soluble resin contains (c1) Acrylic copolymer resin and (c2) epoxy (meth)acrylate resin which have an ethylenically unsaturated group in a side chain.

[2] 如[1]之有色感光性樹脂組成物，其中該(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂具有以下述通式(I)所表示之部分結構。[2] The colored photosensitive resin composition according to [1], wherein the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the following general formula (I).

[化學式1]

Figure 02_image001
[chemical formula 1]
Figure 02_image001

(式(I)中，R1 及R2 分別獨立表示氫原子或甲基。＊表示鍵結處。)(In formula (I), R 1 and R 2 independently represent a hydrogen atom or a methyl group. * represents a bond.)

[3] 如[1]或[2]之有色感光性樹脂組成物，其中該(c2)環氧(甲基)丙烯酸酯樹脂包含選自具有以下述通式(i)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂、具有以下述通式(ii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂以及具有以下述通式(iii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂所構成之群組的至少1種。[3] The colored photosensitive resin composition as described in [1] or [2], wherein the (c2) epoxy (meth)acrylate resin is composed of Epoxy (meth)acrylate resin, epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii), and epoxy resin having a partial structure represented by the following general formula (iii) At least 1 sort(s) of the group which consists of (meth)acrylate resin.

[化學式2]

Figure 02_image003
[chemical formula 2]
Figure 02_image003

(式(i)中，Ra 表示氫原子或甲基，Rb 表示可具有取代基的2價烴基。式(i)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。)(In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group that may have a substituent. The benzene ring in formula (i) may also be substituted by any substituent. * represents a bond place.)

[化學式3]

Figure 02_image005
[chemical formula 3]
Figure 02_image005

(式(ii)中，Rc 分別獨立表示氫原子或甲基。Rd 表示具有環狀烴基作為側鏈的2價烴基。＊表示鍵結處。)(In formula (ii), R c each independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.)

[化學式4]

Figure 02_image007
[chemical formula 4]
Figure 02_image007

(式(iii)中，Re 表示氫原子或甲基，γ表示單鍵、-CO-、可具有取代基的伸烷基、或亦可具有取代基的2價環狀烴基。式(iii)中的苯環更可由任意的取代基取代。＊表示鍵結處。)(In formula (iii), Re represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group that may have a substituent, or a divalent cyclic hydrocarbon group that may also have a substituent. Formula (iii ) The benzene ring in ) can be substituted by any substituent. * indicates the bond.)

[4] 如[1]至[3]中任1項之有色感光性樹脂組成物，其中該(D)撥液劑具有交聯基。 [5] 如[1]至[4]中任1項之有色感光性樹脂組成物，其中更含有鏈轉移劑。[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the liquid repellent (D) has a crosslinking group. [5] The colored photosensitive resin composition according to any one of [1] to [4], which further contains a chain transfer agent.

[6] 一種分隔壁，係由如[1]至[5]中任1項之有色感光性樹脂組成物所構成。 [7] 一種有機電致發光元件，具備如[6]之分隔壁。 [8] 一種影像顯示裝置，包含如[7]之有機電致發光元件。 [9] 一種照明，包含如[7]之有機電致發光元件。 [發明之效果][6] A partition composed of the colored photosensitive resin composition according to any one of [1] to [5]. [7] An organic electroluminescent device comprising the partition wall described in [6]. [8] An image display device comprising the organic electroluminescence element of [7]. [9] A lighting comprising the organic electroluminescence element of [7]. [Effect of Invention]

根據本發明，可提供一種撥墨性高且直線性良好的有色感光性樹脂組成物。According to the present invention, it is possible to provide a colored photosensitive resin composition having high ink repellency and good linearity.

以下詳細說明本發明。另外，以下的記載為本發明之實施態樣的一例，本發明只要不超出其主旨，則不限於該等實施態樣。 另外，本發明中，「(甲基)丙烯酸」係指「丙烯酸及/或甲基丙烯酸」，又，「總固體成分」係指有色感光性樹脂組成物中溶劑以外的所有成分。再者，本發明中使用「~」所表示之數值範圍，係指包含「~」的前後所記載之數值以作為下限值及上限值的範圍。 又，本發明中，「(共)聚合物」係包含均聚合物(Homopolymer)與共聚合物(Copolymer)兩者，又，「(酸)酐」、「(無水)…酸」係指包含酸與其酸酐之兩者。 本發明中，分隔壁材係指堤材、壁材、牆材，相同地，分隔壁係指堤、壁、牆。 本發明中，重量平均分子量係指以GPC(Gel Permeation Chromatography)在聚苯乙烯換算下的重量平均分子量(Mw)。The present invention will be described in detail below. In addition, the following description is an example of embodiment of this invention, Unless this invention deviates from the summary, it is not limited to these embodiment. In addition, in the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "total solid content" means all components in the colored photosensitive resin composition except the solvent. Furthermore, the numerical range represented by "~" in the present invention refers to a range including the numerical values described before and after "~" as the lower limit and the upper limit. Also, in the present invention, "(co)polymer" includes both homopolymer (Homopolymer) and copolymer (Copolymer), and "(acid) anhydride" and "(anhydrous)...acid" refer to Both acids and their anhydrides. In the present invention, a partition wall material refers to a dike material, a wall material, and a wall material, and similarly, a partition wall refers to a dike, a wall, or a wall. In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene by GPC (Gel Permeation Chromatography).

[1]有色感光性樹脂組成物 本發明之有色感光性樹脂組成物，係含有(A)乙烯屬不飽和化合物、(B)光聚合起始劑、(C)鹼可溶性樹脂、(D)撥液劑及(E)著色劑的有色感光性樹脂組成物，其特徵為該(E)著色劑的含有比例，在總固體成分中為20質量%以下，該(C)鹼可溶性樹脂含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂以及(c2)環氧(甲基)丙烯酸酯樹脂。因應需求可更包含其他成分，例如亦可包含溶劑及鏈轉移劑。[1] Colored photosensitive resin composition The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) A colored photosensitive resin composition comprising a liquid agent and (E) a colorant, wherein the content ratio of the (E) colorant is 20% by mass or less in the total solid content, and the (C) alkali-soluble resin contains (c1 ) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain; and (c2) an epoxy (meth)acrylate resin. Other components may be included as required, for example, solvents and chain transfer agents may also be included.

本發明中分隔壁，例如，係用以劃分主動式驅動型有機電致發光元件中的功能層(有機層、發光部)，且為藉由將作為用以構成功能層之材料的印墨吐出至經劃分之區域(像素區域)並進行乾燥，用來形成包含功能層及分隔壁的像素等中所使用。In the present invention, the partition wall is, for example, used to divide the functional layers (organic layer, light-emitting part) in the active driving type organic electroluminescent element, and is formed by ejecting ink as a material for constituting the functional layer. To the divided area (pixel area) and dry it, it is used to form a pixel including a functional layer and a partition wall.

[1-1]有色感光性樹脂組成物的成分及組成 針對構成本發明之有色感光性樹脂組成物的成分及其組成進行說明。 本發明之有色感光性樹脂組成物含有(A)乙烯屬不飽和化合物、(B)光聚合起始劑、(C)鹼可溶性樹脂、(D)撥液劑以及(E)著色劑，通常還更含有溶劑。[1-1] Components and Composition of Colored Photosensitive Resin Composition Components and composition thereof constituting the colored photosensitive resin composition of the present invention will be described. The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellant, and (E) a colorant, and usually Contains more solvents.

[1-1-1] (A)成分；乙烯屬不飽和化合物 本發明之有色感光性樹脂組成物含有(A)乙烯屬不飽和化合物。藉由包含(A)乙烯屬不飽和化合物，被認為可成為高感度。 作為此處所使用之乙烯屬不飽和化合物，雖係指分子內具有1個以上之乙烯屬不飽和鍵的化合物，但從聚合性、交聯性及可隨之放大對於曝光部與非曝光部的顯影液之溶解性差異等的觀點來看，較佳係分子內具有2個以上乙烯屬不飽和鍵的化合物，又，更佳係該不飽和鍵源自(甲基)丙烯醯氧基，亦即(甲基)丙烯酸酯化物。[1-1-1] (A) Component; Ethylenically unsaturated compound The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound. It is considered that high sensitivity can be achieved by including (A) an ethylenically unsaturated compound. As used herein, the ethylenically unsaturated compound refers to a compound having one or more ethylenically unsaturated bonds in the molecule, but from the perspective of polymerizability, crosslinkability, and enlarging the ratio between the exposed part and the non-exposed part From the viewpoint of the difference in the solubility of the developer, etc., it is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and it is more preferable that the unsaturated bond is derived from a (meth)acryloxyl group. That is (meth) acrylate.

本發明中，特別期望使用1分子中具有2個以上乙烯屬不飽和鍵的多官能乙烯屬單體。多官能乙烯屬單體所具有的乙烯屬不飽和基的數量並未特別限定，較佳為2個以上，更佳為3個以上，再佳為5個以上，又，較佳為15個以下，更佳為10個以下，再佳為8個以下，特佳為7個以下。藉由使其在該下限值以上，會有聚合性提升而成為高感度的傾向，藉由使其在該上限值以下，會有顯影性變得更好的傾向。多官能乙烯屬單體所具有作為乙烯屬不飽和基的數量，例如為2~15個，較佳為2~10個，更佳為3~8個，再佳為5~7個。 作為乙烯屬不飽和化合物的具體例，舉例如脂肪族多羥基化合物與不飽和羧酸的酯；芳香族多羥基化合物與不飽和羧酸的酯；脂肪族多羥基化合物、芳香族多羥基化合物等的多元羥基化合物與不飽和羧酸及多元羧酸藉由酯化反應所得之酯等。In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and is preferably 15 or less , more preferably less than 10, more preferably less than 8, and most preferably less than 7. When it is more than this lower limit, there exists a tendency for polymerizability to improve and become high sensitivity, and when it is less than this upper limit, it exists in the tendency for developability to become better. The number of ethylenically unsaturated groups in the polyfunctional vinylic monomer is, for example, 2 to 15, preferably 2 to 10, more preferably 3 to 8, and even more preferably 5 to 7. Specific examples of ethylenically unsaturated compounds include esters of aliphatic polyols and unsaturated carboxylic acids; esters of aromatic polyols and unsaturated carboxylic acids; aliphatic polyols, aromatic polyols, etc. Polyhydric hydroxyl compounds and unsaturated carboxylic acids and polycarboxylic acids obtained by esterification.

作為該脂肪族多羥基化合物與不飽和羧酸的酯，舉例如乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基乙烷三丙烯酸酯、新戊四醇二丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇四丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇六丙烯酸酯、甘油丙烯酸酯等的脂肪族多羥基化合物的丙烯酸酯、將該等例示化合物的丙烯酸酯替換為甲基丙烯酸酯的甲基丙烯酸酯化物、同樣地替換為伊康酸酯的伊康酸酯化物、替換為巴豆酸酯的巴豆酸酯化物或替換為馬來酸酯的馬來酸酯化物等。Examples of esters of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. , neopentylthritol diacrylate, neopentylthritol triacrylate, neopentylthritol tetraacrylate, diperythritol tetraacrylate, diperythritol pentaacrylate, diperythritol hexaacrylate Acrylates of aliphatic polyols such as esters and glycerin acrylates, methacrylates in which the acrylates of these exemplified compounds are replaced by methacrylates, and itaconate esters in which itaconate is similarly replaced Compounds, crotonate esters replaced by crotonate esters or maleate esters replaced by maleate esters, etc.

作為芳香族多羥基化合物與不飽和羧酸的酯，舉例如氫醌二丙烯酸酯、氫醌二甲基丙烯酸酯、間苯二酚二丙烯酸酯、間苯二酚二甲基丙烯酸酯、焦五倍子酚三丙烯酸酯等的芳香族多羥基化合物的丙烯酸酯及甲基丙烯酸酯等。 作為藉由脂肪族多羥基化合物、芳香族多羥基化合物等的多元羥基化合物與不飽和羧酸及多元羧酸的酯化反應所得到的酯，不一定要為單一物質，若舉出作為代表的具體例，舉例如丙烯酸、酞酸及乙二醇的縮合物；丙烯酸、馬來酸及二乙二醇的縮合物；甲基丙烯酸、對酞酸及新戊四醇的縮合物；丙烯酸、己二酸、丁二醇及甘油的縮合物等。Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyroquinone Acrylates and methacrylates of aromatic polyols such as phenol triacrylate, etc. The ester obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids does not necessarily have to be a single substance. Specific examples, such as condensation products of acrylic acid, phthalic acid and ethylene glycol; condensation products of acrylic acid, maleic acid and diethylene glycol; condensation products of methacrylic acid, terephthalic acid and neopentyl glycol; Condensates of diacid, butanediol and glycerin, etc.

其他，作為本發明中所使用的多官能乙烯屬單體的例子，使聚異氰酸酯化物、含羥基之(甲基)丙烯酸酯或聚異氰酸酯化物與多元醇及含羥基之(甲基)丙烯酸酯反應所得之(甲基)丙烯酸胺基甲酸酯類；多價環氧化物與含羥基之(甲基)丙烯酸酯或(甲基)丙烯酸的加成反應物之類的環氧丙烯酸酯類；乙烯基雙丙烯醯胺等的丙烯醯胺類；酞酸二烯丙酯等的烯丙酯類；酞酸二乙烯酯等的含乙烯基之化合物等係為有用。 作為上述(甲基)丙烯酸胺基甲酸酯類，例如，可列舉DPHA-40H、UX-5000、UX-5002D-P20、UX-5003D、UX-5005(日本化藥公司製)、U-2PPA、U-6LPA、U-10PA、U-33H、UA-53H、UA-32P、UA-1100H(新中村化學工業公司製)、UA-306H、UA-510H、UF-8001G(共榮公司化學公司製)、UV-1700B、UV-7600B、UV-7605B、UV-7630B、UV7640B(日本合成化學工業公司製)等。In addition, as an example of the polyfunctional vinylic monomer used in the present invention, polyisocyanate, hydroxyl-containing (meth)acrylate or polyisocyanate is reacted with polyol and hydroxyl-containing (meth)acrylate The resulting (meth)acrylate urethanes; epoxy acrylates such as addition reactants of polyvalent epoxides and hydroxyl-containing (meth)acrylates or (meth)acrylic acid; vinyl Acrylamides such as bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful. Examples of the above-mentioned urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoei Chemical Co., Ltd. ), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), etc.

該等之中，從適當錐角與感度的觀點來看，作為(A)乙烯屬不飽和化合物，較佳係使用酯(甲基)丙烯酸酯類或(甲基)丙烯酸胺基甲酸酯類，更佳係使用二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、2-參(甲基)丙烯醯氧基甲基乙基酞酸、新戊四醇四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯的二元酸酐加成物、新戊四醇三(甲基)丙烯酸酯的二元酸酐加成物等。 該等可單獨使用1種，亦可併用2種以上。Among them, it is preferable to use ester (meth)acrylates or urethane (meth)acrylates as (A) ethylenically unsaturated compounds from the viewpoint of appropriate cone angle and sensitivity, It is more preferable to use dipentylthritol hexa(meth)acrylate, dipentylthritol penta(meth)acrylate, 2-paraffin (meth)acryloxymethylethyl phthalic acid, neopentyl Tetraol tetra(meth)acrylate, neopentylthritol tri(meth)acrylate, dibasic anhydride adducts of dipentyl penta(meth)acrylate, neopentylthritol tri(meth)acrylate ) Dibasic anhydride adducts of acrylates, etc. These may be used individually by 1 type, and may use 2 or more types together.

本發明中，(A)乙烯屬不飽和化合物的分子量並未特別限定，從感度、撥墨性、錐角的觀點來看，較佳為100以上，更佳為150以上，再佳為200以上，再更佳為300以上，特佳為400以上，最佳為500以上，較佳為1000以下，更佳為700以下。作為(A)乙烯屬不飽和化合物的分子量，例如為100~1000，較佳為150~700，更佳為200~700，再佳為300~700，再更佳為400~700，特佳為500~700。 又，(A)乙烯屬不飽和化合物的碳數並未特別限定，從感度、撥墨性、錐角的觀點來看，較佳為7以上，更佳為10以上，再佳為15以上，再更佳為20以上，特佳為25以上，較佳為50以下，更佳為40以下，再佳為35以下，特佳為30以下。作為(A)乙烯屬不飽和化合物的碳數，例如，可列舉7~50，較佳為10~40，更佳為15~35，再佳為20~30，再更佳為25~30。 又，從感度、撥墨性、錐角的觀點來看，較佳為酯(甲基)丙烯酸酯類、環氧(甲基)丙烯酸酯類以及(甲基)丙烯酸胺基甲酸酯類，其中，新戊四醇四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等3官能以上的酯(甲基)丙烯酸酯類、2,2,2-參(甲基)丙烯醯氧基甲基乙基酞酸、二新戊四醇五(甲基)丙烯酸酯的二元酸酐加成物等的對於3官能以上之酯(甲基)丙烯酸酯類加成酸酐的產物，在感度、撥墨性、錐角的面向上更佳。In the present invention, the molecular weight of the (A) ethylenically unsaturated compound is not particularly limited, but is preferably at least 100, more preferably at least 150, and still more preferably at least 200, from the viewpoints of sensitivity, ink repellency, and cone angle. , more preferably above 300, particularly preferably above 400, most preferably above 500, preferably below 1000, more preferably below 700. The molecular weight of the (A) ethylenically unsaturated compound is, for example, 100-1000, preferably 150-700, more preferably 200-700, further preferably 300-700, still more preferably 400-700, and most preferably 500~700. Also, the carbon number of (A) the ethylenically unsaturated compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, and still more preferably 15 or more, from the viewpoints of sensitivity, ink repellency, and taper angle. More preferably, it is 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, and most preferably 30 or less. (A) The carbon number of an ethylenically unsaturated compound is 7-50, for example, Preferably it is 10-40, More preferably, it is 15-35, More preferably, it is 20-30, More preferably, it is 25-30. Also, from the viewpoint of sensitivity, ink repellency, and taper angle, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred, among which , Neopentylthritol tetra(meth)acrylate, Neopentylthritol tri(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Dineopentylthritol penta(meth)acrylate, etc. Three or more functional esters (meth)acrylates, 2,2,2-paraffinyl (meth)acryloxymethylethyl phthalic acid, di-neopentaerythritol penta (meth)acrylate binary Products such as acid anhydride adducts to trifunctional or higher ester (meth)acrylates are more preferable in terms of sensitivity, ink repellency, and taper angle.

本發明之有色感光性樹脂組成物中的(A)乙烯屬不飽和化合物的含有比例無特別限定，在總固體成分中，通常為1質量%以上，較佳為5質量%以上，更佳為10質量%以上，再佳為15質量%以上，通常為80質量%以下，較佳為60質量%以下，更佳為40質量%以下，再佳為20質量%以下。藉由使其在該下限值以上，會有曝光時的感度及錐角變好的傾向，藉由使其在該上限值以下，會有顯影性變好的傾向。作為(A)乙烯屬不飽和化合物在有色感光性樹脂組成物之總固體成分中的含有比例，例如為1~80質量%，較佳為5~60質量%，更佳為10~40質量%，再佳為15~20質量%。The content ratio of the (A) ethylenically unsaturated compound in the colored photosensitive resin composition of the present invention is not particularly limited, but it is usually at least 1% by mass, preferably at least 5% by mass, and more preferably at least 5% by mass of the total solid content. 10 mass % or more, more preferably 15 mass % or more, usually 80 mass % or less, preferably 60 mass % or less, more preferably 40 mass % or less, even more preferably 20 mass % or less. The sensitivity and taper angle at the time of exposure tend to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The ratio of the (A) ethylenically unsaturated compound to the total solid content of the colored photosensitive resin composition is, for example, 1 to 80% by mass, preferably 5 to 60% by mass, more preferably 10 to 40% by mass , preferably 15-20% by mass.

又，相對於(C)鹼可溶性樹脂100質量份，(A)乙烯屬不飽和化合物的含有比例並未特別限定，通常為1質量份以上，較佳為5質量份以上，更佳為10質量份以上，再佳為15質量份以上，特佳為20質量份以上，通常為150質量份以下，較佳為100質量份以下，更佳為70質量份以下，再佳為50質量份以下，特佳為30質量份以下。藉由使其在該下限值以上，會有曝光時感度變好、錐角變好的傾向，藉由使其在該上限值以下，會有顯影性變好的傾向。相對於(C)鹼可溶性樹脂100質量份，(A)乙烯屬不飽和化合物的含有比例，例如為1~150質量份，較佳為5~100質量份，更佳為10~70質量份，再佳為15~50質量份，再更佳為20~30質量份。Also, the ratio of the (A) ethylenically unsaturated compound to 100 parts by mass of the alkali-soluble resin (C) is not particularly limited, but is usually at least 1 part by mass, preferably at least 5 parts by mass, and more preferably at least 10 parts by mass. more than 15 parts by mass, more preferably more than 20 parts by mass, usually less than 150 parts by mass, preferably less than 100 parts by mass, more preferably less than 70 parts by mass, more preferably less than 50 parts by mass, Most preferably, it is 30 mass parts or less. By making it more than this lower limit, there exists a tendency for the sensitivity at the time of exposure to become favorable and a taper angle to become favorable, and by making it below this upper limit, it exists in the tendency for developability to improve. With respect to 100 mass parts of (C) alkali-soluble resin, the content rate of (A) ethylenically unsaturated compound is, for example, 1-150 mass parts, Preferably it is 5-100 mass parts, More preferably, it is 10-70 mass parts, More preferably, it is 15 to 50 parts by mass, and even more preferably, it is 20 to 30 parts by mass.

[1-1-2] (B)成分；光聚合起始劑 本發明之有色感光性樹脂組成物含有(B)光聚合起始劑。光聚合起始劑，只要是可藉由活性光線使該(A)乙烯屬不飽和化合物所具有的乙烯屬不飽和鍵聚合的化合物，則未特別限定，可使用習知的光聚合起始劑。[1-1-2] Component (B); photopolymerization initiator The colored photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that can polymerize the ethylenically unsaturated bond of the (A) ethylenically unsaturated compound by active light rays, and a known photopolymerization initiator can be used .

本發明之有色感光性樹脂組成物中，作為(B)光聚合起始劑，可使用此領域中通常使用的光聚合起始劑。作為這樣的光聚合起始劑，例如，舉例如日本特開昭59-152396號公報、日本特開昭61-151197號公報記載的含二茂鈦化合物的茂金屬化合物；日本特開2000-56118號公報記載的六芳基雙咪唑衍生物；日本特開平10-39503號公報記載的鹵甲基化噁二唑衍生物、鹵甲基-s-三嗪衍生物、N-苯基甘胺酸等的N-芳基-α-胺基酸類、N-芳基-α-胺基酸鹽類、N-芳基-α-胺基酸酯類等的自由基活性劑、α-胺基烷基苯酮衍生物；日本特開2000-80068號公報、日本特開2006-36750號公報等記載的肟酯系化合物等。In the colored photosensitive resin composition of this invention, the photoinitiator normally used in this field can be used as (B) photoinitiator. As such a photopolymerization initiator, for example, a metallocene compound containing a titanocene compound described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118 Hexaarylbisimidazole derivatives described in Japanese Patent Publication No. 10-39503; Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine Free radical activators such as N-aryl-α-amino acids, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, etc., α-aminoalkanes phenyl phenone derivatives; oxime ester compounds described in JP-A-2000-80068, JP-A-2006-36750, and the like.

具體而言，例如，作為二茂鈦衍生物類，舉例如二氯二茂鈦、二環戊二烯基鈦雙苯基、二環戊二烯基鈦雙(2,3,4,5,6-五氟苯基)、二環戊二烯基鈦雙(2,3,5,6-四氟苯基)、二環戊二烯基鈦雙(2,4,6-三氟苯基)、二環戊二烯基鈦二(2,6-二氟苯基)、二環戊二烯基鈦二(2,4-二氟苯基)、二(甲基環戊二烯基)鈦雙(2,3,4,5,6-五氟苯基)、二(甲基環戊二烯基)鈦雙(2,6-二氟苯基)、二環戊二烯基鈦[2,6-二-氟-3-(吡咯-1-基)-苯基]等。Specifically, for example, as titanocene derivatives, dichloro titanocene, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5, 6-pentafluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl ), dicyclopentadienyl titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium bis(2,4-difluorophenyl), bis(methylcyclopentadienyl) Titanium bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), dicyclopentadienyltitanium[ 2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl] and the like.

又，作為雙咪唑衍生物類，舉例如2-(2’-氯苯基)-4,5-二苯基咪唑二聚物、2-(2’-氯苯基)-4,5-雙(3’-甲氧基苯基)咪唑二聚物、2-(2’-氟苯基)-4,5-二苯基咪唑二聚物、2-(2’-甲氧基苯基)-4,5-二苯基咪唑二聚物、(4’-甲氧基苯基)-4,5-二苯基咪唑二聚物等。In addition, examples of bisimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis (3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.

又，作為鹵甲基化噁二唑衍生物類，舉例如2-三氯甲基-5-(2’-苯并呋喃基)-1,3,4-噁二唑、2-三氯甲基-5-[β-(2’-苯并呋喃基)乙烯基]-1,3,4-噁二唑、2-三氯甲基-5-[β-(2’-(6’’-苯并呋喃基)乙烯基)]-1,3,4-噁二唑、2-三氯甲基-5-呋喃基-1,3,4-噁二唑等。In addition, examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethane Base-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6'' -benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc.

又，作為鹵甲基-s-三嗪衍生物類，舉例如2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)-s-三嗪等。Moreover, as halomethyl-s-triazine derivatives, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -Methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s -triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine and the like.

又，作為α-胺基烷基苯酮衍生物類，舉例如2-甲基-1[4-(甲基硫基)苯基]-2-嗎啉基丙-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1,2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)丁-1-酮、苯甲酸4-二甲胺基乙酯、苯甲酸4-二甲胺基異戊酯、4-二乙胺基苯乙酮、4-二甲胺基丙醯苯、2-乙基己基-1,4-二甲胺基苯甲酸酯、2,5-雙(4-二乙胺基亞苄基)環己酮、7-二乙胺基-3-(4-二乙胺基苯甲醯基)香豆素、4-(二乙胺基)查耳酮等。In addition, examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl Base-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butyl -1-ketone, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminoacylbenzene, 2- Ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-di Ethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

作為光聚合起始劑，在感度及製版性的點上，肟酯系化合物特別有效，在使用包含酚性羥基之鹼可溶性樹脂的情況等，感度的點上變得不利，因此這種感度優良的肟酯系化合物特別有用。肟酯系化合物，其結構之中一併具有吸收紫外線的結構、傳遞光能量的結構與產生自由基的結構，因此少量即可為高感度且對於熱反應穩定，且少量即可得到高感度的有色感光性樹脂組成物。As a photopolymerization initiator, oxime ester-based compounds are particularly effective in terms of sensitivity and plate-making properties, but in the case of using an alkali-soluble resin containing a phenolic hydroxyl group, etc., the sensitivity becomes disadvantageous, so this sensitivity is excellent. Oxime ester compounds are particularly useful. Oxime ester compounds have a structure that absorbs ultraviolet rays, transmits light energy, and generates free radicals. Therefore, a small amount can be highly sensitive and stable to thermal reactions, and a small amount can obtain high-sensitivity Colored photosensitive resin composition.

作為肟酯系化合物，例如，可列舉以下述通式(IV)所表示之化合物。As an oxime ester type compound, the compound represented by following general formula (IV) is mentioned, for example.

[化學式5]

Figure 02_image009
[chemical formula 5]
Figure 02_image009

上述式(IV)中，R21a 表示氫原子、亦可具有取代基的烷基、或亦可具有取代基的芳香環基。 R21b 表示包含芳香環的任意取代基。 R22a 表示亦可具有取代基的烷醯基或是亦可具有取代基的芳醯基。 n表示0或1的整數。In the above formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents an arbitrary substituent including an aromatic ring. R 22a represents an alkacyl group which may have a substituent or an aryl group which may have a substituent. n represents an integer of 0 or 1.

R21a 中的烷基的碳數並未特別限定，從對於溶劑之溶解性及感度的觀點來看，通常為1以上，較佳為2以上，又，通常為20以下，較佳為15以下，更佳為10以下。作為烷基的具體例，舉例如甲基、乙基、丙基、環戊基乙基、丙基等。 烷基可具有的取代基，舉例如芳香環基、羥基、羧基、鹵素原子、胺基、醯胺基、4-(2-甲氧基-1-甲基)乙氧基-2-甲基苯基或N-乙醯基-N-乙醯氧胺基等，從合成容易性的觀點來看，較佳為無取代。The carbon number of the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility and sensitivity to solvents, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less , more preferably 10 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, propyl and the like. Substituents that the alkyl group may have include, for example, an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, and 4-(2-methoxy-1-methyl)ethoxy-2-methyl A phenyl group or an N-acetyl-N-acetyloxyamino group is preferably unsubstituted from the viewpoint of ease of synthesis.

作為R21a 中的芳香環基，舉例如芳香烴環基及芳香雜環基。芳香環基的碳數並未特別限定，從對於有色感光性樹脂組成物之溶解性的觀點來看，較佳為5以上。又，從顯影性的觀點來看，較佳為30以下，更佳為20以下，再佳為12以下。The aromatic ring group in R 21a includes, for example, an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored photosensitive resin composition. Moreover, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.

作為芳香環基的具體例，舉例如苯基、萘基、吡啶基、呋喃基等，該等之中，從顯影性的觀點來看，較佳為苯基或萘基，更佳為苯基。 作為芳香環基可具有的取代基，舉例如羥基、羧基、鹵素原子、胺基、醯胺基、烷基、烷氧基、該等的取代基所連結之基團等，從顯影性的觀點來看，較佳為烷基、烷氧基、將該等連結之基團，更佳為經連結的烷氧基。 該等之中，從感度的觀點來看，R21a 較佳為亦可具有取代基的烷基或亦可具有取代基的芳香環基。Specific examples of the aromatic ring group include phenyl, naphthyl, pyridyl, furyl, etc. Among them, phenyl or naphthyl is preferred from the viewpoint of developability, and phenyl is more preferred. . Examples of substituents that the aromatic ring group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amido groups, alkyl groups, alkoxy groups, and groups to which these substituents are linked. From the viewpoint of developability In view of these, it is preferably an alkyl group, an alkoxy group, and a group linking them, and more preferably a linked alkoxy group. Among them, from the viewpoint of sensitivity, R 21a is preferably an alkyl group which may also have a substituent or an aromatic ring group which may also have a substituent.

又，作為R21b ，較佳舉例如亦可被取代的咔唑基、亦可被取代的噻噸酮基或亦可被取代的二苯硫醚基。該等之中，從感度的觀點來看，較佳為亦可被取代的咔唑基。Moreover, R 21b is preferably, for example, a carbazolyl group which may be substituted, a thioxanthone group which may be substituted, or a diphenylsulfide group which may be substituted. Among these, a carbazolyl group which may also be substituted is preferred from the viewpoint of sensitivity.

又，R22a 中的烷醯基的碳數並未特別限定，從對於溶劑之溶解性及感度的觀點來看，通常為2以上，較佳為3以上，又，通常為20以下，較佳為15以下，更佳為10以下，再佳為5以下。作為烷醯基的具體例，舉例如乙醯基(acetyl)、乙醯基(ethanoyl)、丙醯基、丁醯基等。 作為烷醯基可具有的取代基，舉例如芳香環基、羥基、羧基、鹵素原子、胺基、醯胺基等，從合成容易性的觀點來看，較佳為無取代。In addition, the carbon number of the alkyl group in R22a is not particularly limited, but from the viewpoint of solubility and sensitivity to solvents, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably It is 15 or less, more preferably 10 or less, still more preferably 5 or less. Specific examples of the alkylyl group include acetyl, ethanoyl, propionyl, butyryl and the like. Examples of substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amine group, and an amido group, and are preferably unsubstituted from the viewpoint of ease of synthesis.

又，R22a 中的芳醯基的碳數並未特別限定，從對於溶劑的溶解性及感度的觀點來看，通常為7以上，較佳為8以上，又，通常為20以下，較佳為15以下，更佳為10以下。作為芳醯基的具體例，舉例如苯甲醯基、萘甲醯基等。 作為芳醯基可具有的取代基，舉例如羥基、羧基、鹵素原子、胺基、醯胺基、烷基等，從合成容易性的觀點來看，較佳為無取代。 該等之中，從感度的觀點來看，R22a 較佳為亦可具有取代基的烷醯基，更佳為無取代的烷醯基，再佳為乙醯基。In addition, the carbon number of the aryl group in R22a is not particularly limited, but from the viewpoint of solubility and sensitivity to solvents, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Specific examples of the aryl group include benzoyl, naphthyl, and the like. The substituent that the aryl group may have includes, for example, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, an alkyl group, and the like, and is preferably unsubstituted from the viewpoint of ease of synthesis. Among them, from the viewpoint of sensitivity, R 22a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably an acetyl group.

光聚合起始劑可單獨使用1種，亦可組合2種以上使用。 光聚合起始劑中，可因應需求，以提高感應感度為目的，摻合與影像曝光光源之波長對應的增感色素、聚合促進劑。作為增感色素，可舉例如日本特開平4-221958號公報、日本特開平4-219756號公報記載的呫噸色素、日本特開平3-239703號公報、日本特開平5-289335號公報記載的具有雜環的香豆素色素、日本特開平3-239703號公報、日本特開平5-289335號公報記載的3-酮基香豆素化合物、日本特開平6-19240號公報記載的吡咯亞甲基色素，其他舉例如日本特開昭47-2528號公報、日本特開昭54-155292號公報、日本特公昭45-37377號公報、日本特開昭48-84183號公報、日本特開昭52-112681號公報、日本特開昭58-15503號公報、日本特開昭60-88005號公報、日本特開昭59-56403號公報、日本特開平2-69號公報、日本特開昭57-168088號公報、日本特開平5-107761號公報、日本特開平5-210240號公報、日本特開平4-288818號公報記載的具有二烷胺基苯骨架的色素等。A photoinitiator may be used individually by 1 type, and may use it in combination of 2 or more types. In the photopolymerization initiator, sensitizing pigments and polymerization accelerators corresponding to the wavelength of the image exposure light source can be blended for the purpose of increasing the sensitivity according to the needs. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, and JP-A-5-289335. Coumarin dyes having a heterocycle, JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, pyrromethenes described in JP-A-6-19240 Base pigments, other examples such as Japanese Patent Application No. 47-2528, Japanese Patent Application No. 54-155292, Japanese Patent Application No. 45-37377, Japanese Patent Application No. 48-84183, and Japanese Patent Application No. 52 -JP-A-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-2-69, JP-A-57- Dye having a dialkylaminobenzene skeleton described in JP-A-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like.

該等的增感色素之中，較佳為含胺基的增感色素，更佳為在同一分子內具有胺基及苯基的化合物。特別佳為例如4,4’-二甲胺基二苯甲酮、4,4’-二乙胺基二苯甲酮、2-胺基二苯甲酮、4-胺基二苯甲酮、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4-二胺基二苯甲酮等的二苯甲酮系化合物；2-(對二甲胺基苯基)苯并噁唑、2-(對二乙胺基苯基)苯并噁唑、2-(對二甲胺基苯基)苯并[4,5]苯并噁唑、2-(對二甲胺基苯基)苯并[6,7]苯并噁唑、2,5-雙(對二乙胺基苯基)-1,3,4-噁唑、2-(對二甲胺基苯基)苯并噻唑、2-(對二乙胺基苯基)苯并噻唑、2-(對二甲胺基苯基)苯并咪唑、2-(對二乙胺基苯基)苯并咪唑、2,5-雙(對二乙胺基苯基)-1,3,4-噻二唑、(對二甲胺基苯基)吡啶、(對二乙胺基苯基)吡啶、(對二甲胺基苯基)喹啉、(對二乙胺基苯基)喹啉、(對二甲胺基苯基)嘧啶、(對二乙胺基苯基)嘧啶等的對二烷胺基苯基含有化合物等。其中最佳為4,4’-二烷胺基二苯甲酮。 增感色素亦可單獨使用1種，亦可併用2種以上。Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, Benzophenone compounds such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, etc.; 2-(p Dimethylaminophenyl)benzoxazole, 2-(p-Diethylaminophenyl)benzoxazole, 2-(p-Dimethylaminophenyl)benzo[4,5]benzoxazole , 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2- (p-Dimethylaminophenyl)benzothiazole, 2-(p-Diethylaminophenyl)benzothiazole, 2-(p-Dimethylaminophenyl)benzimidazole, 2-(p-Diethylamine phenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylamino Phenyl)pyridine, (p-Dimethylaminophenyl)quinoline, (p-Diethylaminophenyl)quinoline, (p-Dimethylaminophenyl)pyrimidine, (p-Diethylaminophenyl)pyrimidine etc. p-dialkylaminophenyl containing compounds etc. Among them, 4,4'-dialkylaminobenzophenone is the best. The sensitizing dye may be used alone or in combination of two or more.

作為聚合促進劑，例如，可使用對二甲胺基苯甲酸乙酯、苯甲酸2-二甲胺基乙酯等的芳香族胺、正丁胺、N-甲基二乙醇胺等的脂肪族胺等。聚合促進劑可單獨使用1種，亦可組合2種以上使用。As the polymerization accelerator, for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine can be used. Wait. A polymerization accelerator may be used individually by 1 type, and may use it in combination of 2 or more types.

本發明之有色感光性樹脂組成物中的(B)光聚合起始劑的含有比例並未特別限定，在有色感光性樹脂組成物的總固體成分中，通常為0.01質量%以上，較佳為0.1質量%以上，更佳為1質量%以上，再佳為2質量%以上，特佳為3質量%以上，通常為25質量%以下，較佳為20質量%以下，更佳為15質量%以下，再佳為10質量%以下，再更佳為7質量%以下，特佳為5質量%以下。藉由使其在該下限值以上，會有在顯影時形成塗膜而不發生膜損、且可產生充分之撥墨性的傾向，又，藉由使其在該上限值以下，會有易於形成預期圖案形狀的傾向。作為(B)光聚合起始劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.01~25質量%，0.01~20質量%，更佳為0.1~15質量%，再佳為1~10質量%，再更佳為2~7質量%，特佳為3~5質量%。The content ratio of the (B) photopolymerization initiator in the colored photosensitive resin composition of the present invention is not particularly limited, but it is usually 0.01% by mass or more in the total solid content of the colored photosensitive resin composition, preferably 0.1 mass % or more, more preferably 1 mass % or more, still more preferably 2 mass % or more, especially preferably 3 mass % or more, usually 25 mass % or less, preferably 20 mass % or less, more preferably 15 mass % It is not more than 10% by mass, more preferably not more than 7% by mass, and most preferably not more than 5% by mass. By making it more than the lower limit, there will be a tendency to form a coating film during development without film damage, and sufficient ink repellency can be produced. Also, by making it below the upper limit, it will There is a tendency to easily form a desired pattern shape. The ratio of the (B) photopolymerization initiator to the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 25% by mass, 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably It is 1 to 10% by mass, more preferably 2 to 7% by mass, and most preferably 3 to 5% by mass.

又，在有色感光性樹脂組成物中，相對於(A)乙烯屬不飽和化合物，(B)光聚合起始劑的摻合比，係相對於(A)乙烯屬不飽和化合物100質量份，較佳為1質量份以上，更佳為5質量份以上，再佳為10質量份以上，再更佳為15質量份以上，特佳為20質量份以上，又，較佳為200質量份以下，更佳為100質量份以下，再佳為50質量份以下，特佳為30質量份以下。藉由使其在該下限值以上，會有成為適當感度的傾向，又，藉由使其在該上限值以下，會有易於形成預期圖案形狀的傾向。相對於(A)乙烯屬不飽和化合物100質量份，(B)光聚合起始劑的摻合比，例如為1~200質量份，較佳為5~100質量份，更佳為10~100質量份，再佳為15~50質量份，再更佳為20~30質量份。Also, in the colored photosensitive resin composition, the blending ratio of (B) photopolymerization initiator with respect to (A) ethylenically unsaturated compound is based on 100 parts by mass of (A) ethylenically unsaturated compound, Preferably at least 1 part by mass, more preferably at least 5 parts by mass, more preferably at least 10 parts by mass, even more preferably at least 15 parts by mass, particularly preferably at least 20 parts by mass, and more preferably at least 200 parts by mass , more preferably at most 100 parts by mass, even more preferably at most 50 parts by mass, and most preferably at most 30 parts by mass. By making it more than this lower limit, it exists in the tendency which becomes suitable sensitivity, and also exists in the tendency which becomes easy to form a desired pattern shape by making it below this upper limit. The blending ratio of (B) photopolymerization initiator to 100 parts by mass of (A) ethylenically unsaturated compound is, for example, 1-200 parts by mass, preferably 5-100 parts by mass, more preferably 10-100 parts by mass parts by mass, more preferably 15 to 50 parts by mass, more preferably 20 to 30 parts by mass.

又，較佳係與上述光聚合起始劑併用鏈轉移劑。作為鏈轉移劑，舉例如含巰基之化合物及四氯化碳等，從會有鏈轉移效果高的傾向來看，較佳係使用具有巰基的化合物。這是因為藉由S-H鍵能小而容易引發鍵斷裂，而被認為易於引起抓氫反應(hydrogen abstraction)或鏈轉移反應。其對於提升感度及表面硬化性有效。Moreover, it is preferable to use a chain transfer agent together with the said photoinitiator. As the chain transfer agent, for example, a mercapto group-containing compound, carbon tetrachloride, etc., it is preferable to use a compound having a mercapto group since the chain transfer effect tends to be high. This is because the S-H bond energy is small and bond breakage is likely to occur, which is considered to be easy to cause hydrogen abstraction reaction (hydrogen abstraction) or chain transfer reaction. It is effective for improving sensitivity and surface hardening.

作為含巰基之化合物，舉例如2-巰基苯并噻唑、2-巰基苯并咪唑、2-巰基苯并噁唑、3-巰基-1,2,4-***、2-巰基-4(3H)-喹唑啉、β-巰基萘、1,4-二甲基巰基苯等的具有芳香環的含巰基之化合物；己二硫醇、癸二硫醇、丁二醇雙(3-巰基丙酸酯)、丁二醇雙氫硫乙酸酯、乙二醇雙(3-巰基丙酸酯)、乙二醇雙氫硫乙酸酯、三羥甲基丙烷參(3-巰基丙酸酯)、三羥甲基丙烷參氫硫乙酸酯、參羥乙基參硫基丙酸酯、新戊四醇肆(3-巰基丙酸酯)、新戊四醇參(3-巰基丙酸酯)、丁二醇雙(3-巰基丁酸酯)、乙二醇雙(3-巰基丁酸酯)、三羥甲基丙烷參(3-巰基丁酸酯)、新戊四醇肆(3-巰基丁酸酯)、新戊四醇參(3-巰基丁酸酯)、1,3,5-參(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮等的脂肪族系的含巰基之化合物，特別是具有多個巰基的化合物等。As mercapto-containing compounds, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H )-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other mercapto-containing compounds with aromatic rings; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropane Ester), Butanediol Dihydrothioacetate, Ethylene Glycol Bis(3-Mercaptopropionate), Ethylene Glycol Dihydrothioacetate, Trimethylolpropane Ginseng (3-Mercaptopropionate ), trimethylolpropane ginseng thioacetate, ginseng hydroxyethyl ginseng thiopropionate, neopentylthritol four (3-mercaptopropionate), neopentylthritol ginseng (3-mercaptopropionic acid ester), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptobutyrate), neopentylthritol ( 3-mercaptobutyrate), neopentylthritol ginseng (3-mercaptobutyrate), 1,3,5-ginseng (3-mercaptobutoxyethyl)-1,3,5-triazine-2 , 4,6(1H,3H,5H)-triketone and other aliphatic mercapto-containing compounds, especially compounds with multiple mercapto groups.

其中較佳係在具有芳香環的含巰基之化合物之中，較佳為2-巰基苯并噻唑、2-巰基苯并咪唑，而在脂肪族系的含巰基之化合物之中，較佳為三羥甲基丙烷參(3-巰基丙酸酯)、新戊四醇肆(3-巰基丙酸酯)、新戊四醇參(3-巰基丙酸酯)、三羥甲基丙烷參(3-巰基丁酸酯)、新戊四醇肆(3-巰基丁酸酯)、新戊四醇參(3-巰基丁酸酯)、1,3,5-參(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮。Among the mercapto group-containing compounds with aromatic rings, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto group-containing compounds, three Methylolpropane Ginseng (3-Mercaptopropionate), Neopentylthritol Ginseng (3-Mercaptopropionate), Neopentylthritol Ginseng (3-Mercaptopropionate), Trimethylolpropane Ginseng (3 -Mercaptobutyrate), Neopentylthritol (3-mercaptobutyrate), Neopentylthritol ginseng (3-mercaptobutyrate), 1,3,5-ginseng (3-mercaptobutoxyethyl base)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

又，從感度的面向來看，較佳為脂肪族系的含巰基之化合物，具體而言，更佳為三羥甲基丙烷參(3-巰基丙酸酯)、新戊四醇肆(3-巰基丙酸酯)、新戊四醇參(3-巰基丙酸酯)、三羥甲基丙烷參(3-巰基丁酸酯)、新戊四醇肆(3-巰基丁酸酯)、新戊四醇參(3-巰基丁酸酯)、1,3,5-參(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮，更佳為新戊四醇肆(3-巰基丙酸酯)、新戊四醇肆(3-巰基丁酸酯)。 該等各種皆可單獨使用1種，或混合2種以上使用。Also, from the viewpoint of sensitivity, aliphatic mercapto-containing compounds are preferred, and specifically, trimethylolpropane (3-mercaptopropionate), neopentylthritol (3 -Mercaptopropionate), Neopentylthritol Ginseng (3-Mercaptopropionate), Trimethylolpropane Ginseng (3-Mercaptobutyrate), Neopentylthritol (3-Mercaptobutyrate), Neopentylthritol ginseng (3-mercaptobutyrate), 1,3,5-ginseng (3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, more preferably neopentylthritol (3-mercaptopropionate), neopentylthritol (3-mercaptobutyrate). These various types may be used individually by 1 type, or may mix and use 2 or more types.

該等之中，從提高錐角的觀點來看，適宜將選自2-巰基苯并噻唑、2-巰基苯并咪唑以及2-巰基苯并噁唑所構成之群組的1個或2個以上與光聚合起始劑組合，以作為光聚合起始劑系使用。例如，可使用2-巰基苯并噻唑，亦可使用2-巰基苯并咪唑，亦可併用2-巰基苯并噻唑與2-巰基苯并咪唑。 又，從感度的觀點來看，較佳係使用選自新戊四醇肆(3-巰基丙酸酯)、新戊四醇肆(3-巰基丁酸酯)所構成之群組的1個或2個以上。再者，從感度的觀點來看，較佳係將選自2-巰基苯并噻唑、2-巰基苯并咪唑以及2-巰基苯并噁唑所構成之群組的1個或2個以上、選自新戊四醇肆(3-巰基丙酸酯)、新戊四醇肆(3-巰基丁酸酯)所構成之群組的1個或2個以上與光聚合起始劑組合以使用。Among them, from the viewpoint of increasing the cone angle, one or two selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole are suitable. The above is used in combination with a photopolymerization initiator as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination. Also, from the viewpoint of sensitivity, it is preferable to use one selected from the group consisting of neopentylthritol (3-mercaptopropionate) and neopentylthritol (3-mercaptobutyrate). or 2 or more. Furthermore, from the viewpoint of sensitivity, it is preferable to use one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, One or two or more selected from the group consisting of neopentylthritol (3-mercaptopropionate) and neopentylthritol (3-mercaptobutyrate) are used in combination with a photopolymerization initiator .

本發明之有色感光性樹脂組成物中的鏈轉移劑的含有比例並未特別限定，在有色感光性樹脂組成物的總固體成分中，通常為0.01質量%以上，較佳為0.1質量%以上，更佳為0.5質量%以上，再佳為0.8質量%以上，通常為5質量%以下，較佳為4質量%以下，更佳為3質量%以下，再佳為2質量%以下。藉由使其在該下限值以上，會有感度變高的傾向，又，藉由使其在該上限值以下，會有易於形成預期圖案的傾向。作為鏈轉移劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.01~5質量%，較佳為0.1~4質量%，更佳為0.5~3質量%，再佳為0.8~2質量%。The content ratio of the chain transfer agent in the colored photosensitive resin composition of the present invention is not particularly limited, but it is usually at least 0.01% by mass, preferably at least 0.1% by mass, in the total solid content of the colored photosensitive resin composition. More preferably, it is at least 0.5% by mass, still more preferably at least 0.8% by mass, usually at most 5% by mass, preferably at most 4% by mass, more preferably at most 3% by mass, and even more preferably at most 2% by mass. There exists a tendency for sensitivity to become high by making it more than this lower limit, and also there exists a tendency for formation of a desired pattern to be easy by making it below this upper limit. The content ratio of the chain transfer agent in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 5% by mass, preferably 0.1 to 4% by mass, more preferably 0.5 to 3% by mass, and even more preferably 0.8% by mass. ~2% by mass.

又，在有色感光性樹脂組成物中，相對於(B)光聚合起始劑，鏈轉移劑的含有比例，係相對於(B)光聚合起始劑100質量份，較佳為5質量份以上，更佳為10質量份以上，再佳為15質量份以上，特佳為20質量份以上，又，較佳為500質量份以下，更佳為300質量份以下，再佳為100質量份以下，特佳為50質量份以下。藉由使其在該下限值以上，會有成為高感度的傾向，又，藉由使其在該上限值以下，會有容易形成預期圖案的傾向。相對於(B)光聚合起始劑100質量份，作為鏈轉移劑的含有比例，例如為5~500質量份，較佳為10~300質量份，更佳為15~100質量份，再佳為20~50質量份。In addition, in the colored photosensitive resin composition, the content ratio of the chain transfer agent is preferably 5 parts by mass relative to 100 parts by mass of the photopolymerization initiator (B) relative to the photopolymerization initiator (B). Above, more preferably at least 10 parts by mass, more preferably at least 15 parts by mass, particularly preferably at least 20 parts by mass, more preferably at most 500 parts by mass, more preferably at most 300 parts by mass, even more preferably at least 100 parts by mass Below, especially preferably 50 mass parts or less. There exists a tendency for it to become high sensitivity by making it more than this lower limit value, and it exists in the tendency for a desired pattern to be formed easily by making it below this upper limit value. Relative to (B) 100 parts by mass of the photopolymerization initiator, the content ratio of the chain transfer agent is, for example, 5 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 15 to 100 parts by mass, and even more preferably 20 to 50 parts by mass.

[1-1-3] (C)成分；鹼可溶性樹脂 本發明之有色感光性樹脂組成物含有(C)鹼可溶性樹脂。本發明中，作為鹼可溶性樹脂，只要可由顯影液進行顯影，則無特別限定，但作為顯影液較佳為鹼顯影液，因此較佳係使用含羧基或羥基的樹脂，從顯影性優良的觀點來看，較佳為含有羧基的樹脂。 又，因為可得到適當錐角的分隔壁、抑制因顯影或分隔壁之熱熔融導致撥液劑的流出而能夠保持撥墨性等的理由，較佳為具有乙烯屬不飽和基的鹼可溶性樹脂。[1-1-3] (C) Component; Alkali-Soluble Resin The colored photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. In the present invention, the alkali-soluble resin is not particularly limited as long as it can be developed by a developer. However, the developer is preferably an alkali developer. Therefore, it is preferable to use a resin containing a carboxyl group or a hydroxyl group. From the viewpoint of excellent developability From this point of view, resins containing carboxyl groups are preferred. Also, an alkali-soluble resin having an ethylenically unsaturated group is preferred because it can obtain a partition wall with an appropriate taper angle, suppress the outflow of the liquid-repellent agent due to development or thermal melting of the partition wall, and maintain ink repellency. .

本發明之有色感光性樹脂組成物的(C)鹼可溶性樹脂包含(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂(以下有時稱為「(c1)丙烯酸共聚合樹脂」)。(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂，因為骨架柔軟，在曝光時產生之自由基在膜內的自由度高，而能夠抑制膜表面的氧導致自由基失活，進而使得膜表面的硬化性提高，因而認為易於在表面附近捕捉撥液劑。並且進一步認為可藉由側鏈的乙烯屬不飽和基充分捕捉在膜表面定向的撥液劑。藉由在膜表面充分捕捉的撥液劑而提高撥墨性，抑制印墨附著於分隔壁以及注入相鄰區域間的印墨彼此混合，因此認為會讓有機電致發光元件在各個像素均勻發光。 另一方面，本發明之有色感光性樹脂組成物的(C)鹼可溶性樹脂更包含(c2)環氧(甲基)丙烯酸酯樹脂。(c2)環氧(甲基)丙烯酸酯樹脂，因為骨架剛直，與基板的密合性不會過高，因此認為可抑制分隔壁之邊緣部的殘渣，更可抑制拖尾(trail)，而使分隔壁之邊緣部成為直線。如此，若可使分隔壁邊緣部的直線性良好，可在被分隔壁圍住的區域中均勻地形成功能層，因此認為可抑制發光不均。再者，因為亦可抑制電阻不均，而認為難以發生成為壽命惡化之原因的電流集中。 因此本發明之有色感光性樹脂組成物中，作為(C)鹼可溶性樹脂，包含(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂與(c2)環氧(甲基)丙烯酸酯樹脂的兩者，藉此認為可兼具撥墨性與直線性兩者。The (C) alkali-soluble resin of the colored photosensitive resin composition of the present invention includes (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain (hereinafter sometimes referred to as "(c1) acrylic copolymer resin") . (c1) The acrylic copolymer resin having an ethylenically unsaturated group in the side chain, because the skeleton is soft, the free radicals generated during exposure have a high degree of freedom in the film, and can inhibit the oxygen on the film surface from causing free radical deactivation, Furthermore, since the curability of the film surface is improved, it is considered that the liquid-repelling agent is easily captured near the surface. And it is further believed that the liquid repellent oriented on the film surface can be fully captured by the ethylenically unsaturated group of the side chain. The ink repellency is improved by the liquid repellant fully captured on the surface of the film, and the adhesion of the ink to the partition wall and the mixing of the ink injected into the adjacent areas are suppressed, so it is considered that the organic electroluminescent element will emit light uniformly in each pixel . On the other hand, the (C) alkali-soluble resin of the colored photosensitive resin composition of the present invention further includes (c2) epoxy (meth)acrylate resin. (c2) Epoxy (meth)acrylate resin, because the skeleton is rigid, the adhesion with the substrate will not be too high, so it is considered that the residue at the edge of the partition wall can be suppressed, and the tailing (trail) can be suppressed, and Make the edge of the partition wall into a straight line. In this way, if the linearity of the edge portion of the partition wall can be improved, the functional layer can be uniformly formed in the region surrounded by the partition wall, so it is considered that uneven light emission can be suppressed. Furthermore, since the resistance unevenness can also be suppressed, it is considered that the current concentration which becomes the cause of life deterioration is hard to generate|occur|produce. Therefore, in the colored photosensitive resin composition of the present invention, as (C) an alkali-soluble resin, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain and (c2) an epoxy (meth)acrylate Both resins are considered to have both ink repellency and linearity.

以下詳述(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂。The (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain will be described in detail below.

[(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂] (c1)丙烯酸共聚合樹脂，於側鏈具有乙烯屬不飽和基。藉由具有乙烯屬不飽和基，因曝光所引發的光硬化而成為穩固的膜，被認為即使在顯影時撥液劑亦難以流出。[(c1) Acrylic copolymer resin having an ethylenically unsaturated group in a side chain] (c1) An acrylic copolymer resin having an ethylenically unsaturated group in a side chain. Since it has an ethylenically unsaturated group, it becomes a stable film by photohardening by exposure, and it is considered that a liquid repellent is hard to flow out even at the time of development.

(以通式(I)所表示之部分結構) (c1)丙烯酸共聚合樹脂所具有的、包含具有乙烯屬不飽和基之側鏈的部分結構並未特別限定，從伴隨膜的柔軟性自由基因而易於發散的觀點來看，例如，較佳係具有以下述通式(I)所表示之部分結構。(Partial structure represented by the general formula (I)) (c1) The partial structure of the acrylic copolymer resin including a side chain having an ethylenically unsaturated group is not particularly limited. On the other hand, from the viewpoint of easy divergence, for example, it is preferable to have a partial structure represented by the following general formula (I).

[化學式6]

Figure 02_image001
[chemical formula 6]
Figure 02_image001

式(I)中，R1 及R2 分別獨立表示氫原子或甲基。＊表示鍵結處。In formula (I), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. ＊Indicates a bond.

又，以該式(I)所表示之部分結構之中，從感度及鹼顯影性的觀點來看，較佳係以下述通式(I’)所表示之部分結構。Also, among the partial structures represented by the formula (I), preferred are partial structures represented by the following general formula (I') from the viewpoint of sensitivity and alkali developability.

[化學式7]

Figure 02_image012
[chemical formula 7]
Figure 02_image012

式(I’)中，R1 及R2 分別獨立表示氫原子或甲基。RX 表示氫原子或多元酸殘基。In formula (I'), R 1 and R 2 independently represent a hydrogen atom or a methyl group. R X represents a hydrogen atom or a polybasic acid residue.

多元酸殘基，係指從多元酸或其酸酐去除1個OH基的1價基團。作為多元酸，舉例如選自馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、二苯甲酮四羧酸、甲基六氫酞酸、橋聯亞甲基四氫酞酸、氯橋酸、甲基四氫酞酸、聯苯四羧酸的1種或2種以上。 該等之中，從圖案化特性的觀點來看，較佳為馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、聯苯四羧酸，更佳為四氫酞酸、聯苯四羧酸。The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or an acid anhydride thereof. As the polybasic acid, for example, selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, One or more kinds of methylhexahydrophthalic acid, bridged methylene tetrahydrophthalic acid, chloro-bridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid are preferable from the viewpoint of patterning properties. , biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid.

(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂所包含的、以該通式(I)所表示之部分結構的含有比例無特別限定，較佳為10莫耳%以上，更佳為20莫耳%以上，再佳為30莫耳%以上，再更佳為40莫耳%以上，特佳為50莫耳%以上，最佳為65莫耳%以上，又，較佳為95莫耳%以下，更佳為90莫耳%以下，再佳為85莫耳%以下，再更佳為80莫耳%以下，特佳為75莫耳%以下，最佳為70莫耳%以下。藉由使其在該下限值以上，會有撥墨性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。作為(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂所包含的、以該通式(I)所表示之部分結構的含有比例，例如為10~95莫耳%，較佳為20~85莫耳%，更佳為30~80莫耳%，再佳為40~75莫耳%，再更佳為50~70莫耳%。(c1) The proportion of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mole % or more, more preferably Preferably more than 20 mol%, more preferably more than 30 mol%, more preferably more than 40 mol%, especially preferably more than 50 mol%, most preferably more than 65 mol%, and more preferably Less than 95 mole %, more preferably less than 90 mole %, more preferably less than 85 mole %, more preferably less than 80 mole %, most preferably less than 75 mole %, most preferably less than 70 mole % the following. There exists a tendency for ink repellency to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit. (c1) The proportion of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is, for example, 10 to 95 mole %, preferably 20-85 mol%, more preferably 30-80 mol%, even more preferably 40-75 mol%, even more preferably 50-70 mol%.

(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂所包含的、以該通式(I’)所表示之部分結構的含有比例並未特別限定，較佳為10莫耳%以上，更佳為20莫耳%以上，再佳為30莫耳%以上，再更佳為40莫耳%以上，特佳為50莫耳%以上，最佳為65莫耳%以上，又，較佳為95莫耳%以下，更佳為90莫耳%以下，再佳為85莫耳%以下，再更佳為80莫耳%以下，特佳為75莫耳%以下，最佳為70莫耳%以下。藉由使其在該下限值以上，會有容易進行鹼顯影的傾向，又，藉由使其在該上限值以下，會有可確保顯影密合性的傾向。作為(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂所包含的、該通式(I’)所表示之部分結構的含有比例，例如為10~95莫耳%，較佳為20~80莫耳%，更佳為30~75莫耳%，再佳為40~70莫耳%，再更佳為50~65莫耳%。(c1) The proportion of the partial structure represented by the general formula (I') included in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more , more preferably more than 20 mole %, more preferably more than 30 mole %, more preferably more than 40 mole %, especially preferably more than 50 mole %, most preferably more than 65 mole %, and more Preferably less than 95 mol%, more preferably less than 90 mol%, more preferably less than 85 mol%, even more preferably less than 80 mol%, particularly preferably less than 75 mol%, most preferably less than 70 mol% Ear % below. Alkali image development tends to be made easy by making it more than the said lower limit, and there exists a tendency for image development adhesiveness to be securable by making it below the said upper limit. (c1) The content ratio of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is, for example, 10 to 95 mol%, preferably 20-80 mol%, more preferably 30-75 mol%, even more preferably 40-70 mol%, even more preferably 50-65 mol%.

(以通式(II)所表示之部分結構) (c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂包含以該通式(I)所表示之部分結構的情況中，其他包含於其中的部分結構並未特別限定，從顯影密合性的觀點來看，例如，較佳為具有以下述通式(II)所表示的部分結構。(Partial structure represented by the general formula (II)) (c1) In the case where the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains the partial structure represented by the general formula (I), others are contained in Among them, the partial structure is not particularly limited, but preferably has a partial structure represented by the following general formula (II) from the viewpoint of image development adhesiveness, for example.

[化學式8]

Figure 02_image014
[chemical formula 8]
Figure 02_image014

上述式(II)中，R3 表示氫原子或甲基，R4 表示亦可具有取代基的烷基、亦可具有取代基的芳基(芳香環基)、或亦可具有取代基的烯基。In the above formula (II), R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group which may also have a substituent, an aryl group (aromatic ring group) which may also have a substituent, or an alkene group which may also have a substituent base.

(R4 ) 該式(II)中，R4 表示亦可具有取代基的烷基、亦可具有取代基的芳基、或亦可具有取代基的烯基。 作為R4 中的烷基，舉例如直鏈狀、分支鏈狀或環狀的烷基。其碳數較佳為1以上，更佳為3以上，再佳為5以上，特佳為8以上，又，較佳為20以下，更佳為18以下，再佳為16以下，再更佳為14以下，特佳為12以下。藉由使其在該下限值以上，會有膜強度提高，顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。(R 4 ) In the formula (II), R 4 represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group. Examples of the alkyl group in R 4 include linear, branched or cyclic alkyl groups. The carbon number is preferably at least 1, more preferably at least 3, even more preferably at least 5, particularly preferably at least 8, more preferably at least 20, more preferably at most 18, even more preferably at least 16, and even more preferably Below 14, especially below 12. By making it more than this lower limit, there exists a tendency for film intensity|strength to improve and image development adhesiveness to improve, and by making it below this upper limit, there exists a tendency for the residue to reduce.

作為烷基的具體例，舉例如甲基、乙基、環己基、二環戊基、十二烷基等。該等之中，從顯影性的觀點來看，較佳為二環戊基或十二烷基，更佳為二環戊基。 又，作為烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。Specific examples of the alkyl group include methyl group, ethyl group, cyclohexyl group, dicyclopentyl group, dodecyl group and the like. Among these, dicyclopentyl or dodecyl is preferable from the viewpoint of developability, and dicyclopentyl is more preferable. In addition, examples of substituents that the alkyl group may have include methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer, phenyl, carboxyl , acryl group, methacryl group, and the like, and from the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferable.

作為R4 中的芳基(芳香環基)，舉例如1價的芳香烴環基及1價的芳香雜環基。其碳數較佳為6以上，又，較佳為24以下，更佳為22以下，再佳為20以下，再更佳為18以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。 作為芳香烴環基中的芳香烴環，可為單環，亦可為縮合環，例如，舉例如苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、苯并菲環、聯伸三苯基環、苊萘環、熒蒽環、茀環等的基團。 又，作為芳香雜環基中的芳香雜環基，可為單環，亦可為縮合環，例如，舉例如呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、噁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異噁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡嗪環、噠嗪環、嘧啶環、三嗪環、喹啉環、異喹啉環、㖕啉環、喹噁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等的基團。該等之中，從顯影性的觀點來看，較佳為苯環基、或萘環基，更佳為苯環基。 又，作為芳基可具有的取代基，舉例如甲基、乙基、丙基、甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。The aryl group (aromatic ring group) in R 4 includes, for example, a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably at least 6, and preferably at most 24, more preferably at most 22, even more preferably at most 20, and even more preferably at most 18. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit. As the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group, it can be a single ring or a condensed ring, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzene ring, etc. Groups such as pyrene ring, triphenylene ring, triphenylene ring, acenaphthylnaphthalene ring, fluoranthene ring, and fluorene ring. In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, etc. ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furan Furan ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, iso Groups such as quinoline ring, zeoline ring, quinoxaline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. Among these, a phenyl ring group or a naphthyl ring group is preferable from the viewpoint of developability, and a benzene ring group is more preferable. In addition, examples of substituents that the aryl group may have include methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer Ethylene glycol group, phenyl group, carboxyl group, and the like are preferably hydroxyl group and oligoethylene glycol group from the viewpoint of developability.

作為R4 中的烯基，舉例如直鏈狀、分支鏈狀或環狀的烯基。其碳數為2以上，又，較佳為22以下，更佳為20以下，再佳為18以下，再更佳為16以下，特佳為14以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。The alkenyl group in R 4 includes, for example, linear, branched or cyclic alkenyl groups. The carbon number is at least 2, preferably at most 22, more preferably at most 20, even more preferably at most 18, even more preferably at most 16, most preferably at most 14. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

作為烯基的具體例，舉例如乙烯基、烯丙基、2-丙烯-2-基、2-丁烯-1-基、3-丁烯-1-基、2-戊烯-1-基、3-戊烯-2-基、己烯基、環丁烯基、環戊烯基、環己烯基等。該等之中，從顯影性的觀點來看，較佳為乙烯基或烯丙基，更佳為乙烯基。Specific examples of alkenyl include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl , 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Among them, from the viewpoint of developability, vinyl or allyl is preferred, and vinyl is more preferred.

又，作為烯基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。In addition, examples of substituents that an alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligoglycol, phenyl, carboxyl etc. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.

如此，R4 表示亦可具有取代基的烷基、亦可具有取代基的芳基、或亦可具有取代基的烯基，但該等之中，從顯影性與膜強度的觀點來看，較佳為烷基或烯基，更佳為烷基。 In this way, R represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group, but among these, from the viewpoint of developability and film strength, Preferably it is an alkyl or alkenyl group, more preferably an alkyl group.

(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂中的、以該通式(II)所表示之部分結構的含有比例並未特別限定，較佳為1莫耳%以上，更佳為5莫耳%以上，再佳為10莫耳%以上，特佳為20莫耳%以上，又，較佳為70莫耳%以下，更佳為60莫耳%以下，再佳為50莫耳%以下，特佳為40莫耳%以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。(c1) The content ratio of the partial structure represented by the general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol % or more, more preferably Preferably at least 5 mol%, more preferably at least 10 mol%, particularly preferably at least 20 mol%, more preferably less than 70 mol%, more preferably less than 60 mol%, even more preferably 50 mol% Mole % or less, especially preferably less than 40 Mole %. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

(以通式(III)所表示之部分結構) (c1)丙烯酸共聚合樹脂包含以該通式(I)所表示之部分結構的情況中，作為其他包含於其中的部分結構，從耐熱性、膜強度的觀點來看，較佳為包含以下述通式(III)所表示之部分結構。(Partial structure represented by general formula (III)) (c1) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), as other partial structures contained therein, from heat resistance, From the viewpoint of film strength, it is preferable to include a partial structure represented by the following general formula (III).

[化學式9]

Figure 02_image016
[chemical formula 9]
Figure 02_image016

上述式(III)中，R5 表示氫原子或甲基，R6 表示亦可具有取代基的烷基、亦可具有取代基的烯基、亦可具有取代基的炔基、羥基、羧基、鹵素原子、亦可具有取代基的烷氧基、硫醇基、或亦可具有取代基的硫化烷基。t表示0~5的整數。In the above formula (III), R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkyl group that may also have a substituent, an alkenyl group that may also have a substituent, an alkynyl group that may also have a substituent, a hydroxyl group, a carboxyl group, A halogen atom, an alkoxy group which may have a substituent, a thiol group, or a sulfurized alkyl group which may have a substituent. t represents an integer from 0 to 5.

(R6 ) 該式(III)中，R6 表示亦可具有取代基的烷基、亦可具有取代基的烯基、亦可具有取代基的炔基、羥基、羧基、鹵素原子、亦可具有取代基的烷氧基、硫醇基、或亦可具有取代基的硫化烷基。 作為R6 中的烷基，舉例如直鏈狀、分支鏈狀或環狀的烷基。其碳數較佳為1以上，更佳為3以上，再佳為5以上，又，較佳為20以下，更佳為18以下，再佳為16以下，再更佳為14以下，特佳為12以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。(R 6 ) In the formula (III), R 6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, or An alkoxy group which has a substituent, a thiol group, or a sulfurized alkyl group which may have a substituent. Examples of the alkyl group in R 6 include linear, branched or cyclic alkyl groups. The carbon number is preferably at least 1, more preferably at least 3, even more preferably at least 5, more preferably at most 20, more preferably at most 18, even more preferably at most 16, even more preferably at most 14, especially preferably 12 or less. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

作為烷基的具體例，舉例如甲基、乙基、環己基、二環戊基、十二烷基等。該等之中，從顯影性與膜強度的觀點來看，較佳為二環戊基或十二烷基，更佳為二環戊基。 又，作為烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。Specific examples of the alkyl group include methyl group, ethyl group, cyclohexyl group, dicyclopentyl group, dodecyl group and the like. Among these, dicyclopentyl or dodecyl is preferable from the viewpoint of developability and film strength, and dicyclopentyl is more preferable. In addition, examples of substituents that the alkyl group may have include methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer, phenyl, carboxyl , acryl group, methacryl group, and the like, and from the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferable.

作為R6 中的烯基，舉例如直鏈狀、分支鏈狀或環狀的烯基。其碳數較佳為2以上，又，較佳為22以下，更佳為20以下，再佳為18以下，再更佳為16以下，特佳為14以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。The alkenyl group in R 6 includes, for example, linear, branched or cyclic alkenyl groups. The carbon number is preferably at least 2, preferably at most 22, more preferably at most 20, even more preferably at most 18, even more preferably at most 16, and most preferably at most 14. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

作為烯基的具體例，舉例如乙烯基、烯丙基、2-丙烯-2-基、2-丁烯-1-基、3-丁烯-1-基、2-戊烯-1-基、3-戊烯-2-基、己烯基、環丁烯基、環戊烯基、環己烯基等。該等之中，從顯影性的觀點來看，較佳為乙烯基或烯丙基，更佳為乙烯基。Specific examples of alkenyl include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl , 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Among them, from the viewpoint of developability, vinyl or allyl is preferred, and vinyl is more preferred.

又，作為烯基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。In addition, examples of substituents that an alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligoglycol, phenyl, carboxyl etc. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.

作為R6 中的炔基，舉例如直鏈狀、分支鏈狀或環狀的炔基。其碳數較佳為2以上，又，較佳為22以下，更佳為20以下，再佳為18以下，再更佳為16以下，特佳為14以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。The alkynyl group in R 6 includes, for example, straight-chain, branched-chain or cyclic alkynyl groups. The carbon number is preferably at least 2, preferably at most 22, more preferably at most 20, even more preferably at most 18, even more preferably at most 16, and most preferably at most 14. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

作為炔基的具體例，舉例如1-丙炔-3-基、1-丁炔-4-基、1-戊炔-5-基、2-甲基-3-丁炔-2-基、1,4-戊二炔-3-基、1,3-戊二炔-5-基、1-己炔-6-基等。Specific examples of the alkynyl group include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, etc.

又，作為炔基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。In addition, examples of substituents that the alkynyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligomer, phenyl, carboxyl etc. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.

作為R6 中的鹵素原子，舉例如氟原子、氯原子、溴原子、碘原子，該等之中，從撥墨性的觀點來看，較佳為氟原子。The halogen atom in R 6 includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferred from the viewpoint of ink repellency.

作為R6 中的烷氧基，舉例如直鏈狀、分支鏈狀或環狀的烷氧基。其碳數較佳為1以上，又，較佳為20以下，更佳為18以下，再佳為16以下，再更佳為14以下，特佳為12以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。Examples of the alkoxy group in R 6 include linear, branched or cyclic alkoxy groups. The carbon number is preferably at least 1, preferably at most 20, more preferably at most 18, even more preferably at most 16, even more preferably at most 14, and most preferably at most 12. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

作為烷氧基的具體例，舉例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基等。Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and the like.

又，作為烷氧基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。In addition, examples of substituents that an alkoxy group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligomer, phenyl, The carboxyl group, acryl group, methacryl group, etc. are preferably a hydroxyl group and an oligoglycol group from the viewpoint of developability.

R6 中的硫化烷基，舉例如直鏈狀、分支鏈狀或環狀的硫化烷基。其碳數較佳為1以上，又，較佳為20以下，更佳為18以下，再佳為16以下，再更佳為14以下，特佳為12以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。The sulfurized alkyl group in R6 is, for example, a linear, branched or cyclic sulfurized alkyl group. The carbon number is preferably at least 1, preferably at most 20, more preferably at most 18, even more preferably at most 16, even more preferably at most 14, and most preferably at most 12. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit.

作為硫化烷基的具體例，舉例如硫化甲烷基、硫化乙烷基、硫化丙烷基、硫化丁烷基等。該等之中，從顯影性的觀點來看，較佳為硫化甲烷基或硫化乙烷基。Specific examples of alkyl sulfide include methyl sulfide, ethyl sulfide, propyl sulfide, butyl sulfide, and the like. Among these, methylsulfide or ethylsulfide is preferable from the viewpoint of developability.

又，作為硫化烷基中的烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等，從顯影性的觀點來看，較佳為羥基、寡聚乙二醇基。In addition, examples of substituents that the alkyl group in the sulfurized alkyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligethylene glycol, etc. , phenyl group, carboxyl group, acryl group, methacryl group, etc., from the viewpoint of developability, preferably a hydroxyl group and an oligoglycol group.

如此，R6 雖表示亦可具有取代基的烷基、亦可具有取代基的烯基、亦可具有取代基的炔基、羥基、羧基、鹵素原子、烷氧基、羥基烷基、硫醇基、或亦可具有取代基的硫化烷基，但該等之中，從顯影性的觀點來看，較佳為羥基或羧基，更佳為羧基。 In this way, R represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group or a sulfide alkyl group which may have a substituent, among these, a hydroxyl group or a carboxyl group is preferable from the viewpoint of developability, and a carboxyl group is more preferable.

該式(III)中，t雖表示0~5的整數，但從製造容易性的觀點來看， t較佳為0。In this formula (III), although t represents an integer of 0 to 5, t is preferably 0 from the viewpoint of ease of manufacture.

(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂中的、以該通式(III)所表示之部分結構的含有比例並未特別限定，較佳為1莫耳%以上，更佳為2莫耳%以上，再佳為5莫耳%以上，特佳為8莫耳%以上，又，較佳為50莫耳%以下，更佳為40莫耳%以下，再佳為30莫耳%以下，特佳為20莫耳%以下。藉由使其在該下限值以上，具有顯影密合性提升的傾向，又，藉由使其在該上限值以下，具有殘渣減少的傾向。(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂中，以該通式(III)所表示之部分結構的含有比例，例如為1~50莫耳%，2~40莫耳%，更佳為5~30莫耳%，再佳為8~20莫耳%。 (以通式(IV)所表示之部分結構)(c1) The content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol % or more, more preferably Preferably it is more than 2 mol%, more preferably more than 5 mol%, especially preferably more than 8 mol%, and more preferably less than 50 mol%, more preferably less than 40 mol%, even more preferably 30 mol% Mole % or less, especially preferably less than 20 Mole %. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for residue to reduce by making it below this upper limit. (c1) In the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, the proportion of the partial structure represented by the general formula (III) is, for example, 1 to 50 mol %, 2 to 40 mol % , more preferably 5-30 mol%, and more preferably 8-20 mol%. (partial structure represented by general formula (IV))

(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂具有以該通式(I)所表示之部分結構的情況，作為其他包含於其中的部分結構，從顯影性的觀點來看，較佳係具有以下述通式(IV)所表示之部分結構。(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (I), as other partial structures contained therein, from the viewpoint of developability, It preferably has a partial structure represented by the following general formula (IV).

[化學式10]

Figure 02_image018
[chemical formula 10]
Figure 02_image018

上述式(IV)中，R7 表示氫原子或甲基。In the above formula (IV), R 7 represents a hydrogen atom or a methyl group.

(c1)於側鏈具有乙烯屬不飽和基之丙烯酸共聚合樹脂中含有以該通式(IV)所表示之部分結構的情況，其含有比例並未特別限定，較佳為5莫耳%以上，更佳為10莫耳%以上，再佳為20莫耳%以上，又，較佳為80莫耳%以下，更佳為70莫耳%以下，再佳為60%莫耳以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有顯影密合性提升的傾向。(c1)於側鏈具有乙烯屬不飽和基之丙烯酸共聚合樹脂中含有以該通式(IV)所表示之部分結構的情況，其含有比例，例如為5~80莫耳%，較佳為10~70莫耳%，更佳為20~60莫耳%。(c1) When the partial structure represented by the general formula (IV) is contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, the proportion thereof is not particularly limited, but is preferably 5 mol % or more , more preferably more than 10 mol%, more preferably more than 20 mol%, and more preferably less than 80 mol%, more preferably less than 70 mol%, even more preferably less than 60% mol. It exists in the tendency for developability to improve by making it more than this lower limit, and it exists in the tendency for image development adhesiveness to improve by making it below this upper limit. (c1) When the partial structure represented by the general formula (IV) is contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, the content ratio thereof is, for example, 5 to 80 mol%, preferably 10-70 mol%, more preferably 20-60 mol%.

另一方面，(c1)丙烯酸共聚合樹脂的酸價並未特別限定，較佳為10mgKOH/g以上，更佳為30mgKOH/g以上，再佳為40mgKOH/g以上，再更佳為50mgKOH/g以上，特佳為60mgKOH/g以上，又，較佳為150mgKOH/g以下，更佳為140mgKOH/g以下，再佳為130mgKOH/g以下，再更佳為120mgKOH/g以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有顯影密合性提升的傾向。作為(c1)丙烯酸共聚合樹脂的酸價，例如為10~150mgKOH/g，較佳為30~140mgKOH/g，更佳為50~130mgKOH/g，再佳為60~120mgKOH/g。On the other hand, (c1) the acid value of the acrylic copolymer resin is not particularly limited, but is preferably at least 10 mgKOH/g, more preferably at least 30 mgKOH/g, even more preferably at least 40 mgKOH/g, even more preferably at least 50 mgKOH/g Above, especially preferably above 60 mgKOH/g, more preferably below 150 mgKOH/g, more preferably below 140 mgKOH/g, even more preferably below 130 mgKOH/g, even more preferably below 120 mgKOH/g. It exists in the tendency for developability to improve by making it more than this lower limit, and it exists in the tendency for image development adhesiveness to improve by making it below this upper limit. (c1) The acid value of the acrylic copolymer resin is, for example, 10-150 mgKOH/g, preferably 30-140 mgKOH/g, more preferably 50-130 mgKOH/g, even more preferably 60-120 mgKOH/g.

(c1)丙烯酸共聚合樹脂的重量平均分子量(Mw)並未特別限定，通常為1000以上，較佳為2000以上，更佳為4000以上，再佳為6000以上，再更佳為7000以上，特佳為8000以上，又，通常為30000以下，較佳為20000以下，更佳為15000以下，再佳為10000以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。作為(c1)丙烯酸共聚合樹脂的重量平均分子量(Mw)、例如為1000~30000，較佳為2000~20000，更佳為4000~15000，再佳為6000~15000，再更佳為7000~10000，特佳為8000~10000。(c1) The weight-average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more. It is preferably at least 8,000, and usually at most 30,000, preferably at most 20,000, more preferably at most 15,000, and still more preferably at most 10,000. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit. (c1) The weight average molecular weight (Mw) of the acrylic copolymer resin is, for example, 1,000 to 30,000, preferably 2,000 to 20,000, more preferably 4,000 to 15,000, further preferably 6,000 to 15,000, and still more preferably 7,000 to 10,000 , the best is 8000~10000.

(C)鹼可溶性樹脂所包含的(c1)丙烯酸共聚合樹脂的含有比例並未特別限定，較佳為10質量%以上，更佳為30質量%以上，再佳為50質量%以上，特佳為70質量%以上，又，95質量%以下，更佳為90質量%以下，再佳為85質量%以下。藉由使其在該下限值以上，會有撥墨性提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。作為(C)鹼可溶性樹脂所包含的(c1)丙烯酸共聚合樹脂的含有比例，例如為10~95質量%，較佳為30~90質量%，更佳為50~85質量%，再佳為70~85質量%。(C) The proportion of the (c1) acrylic copolymer resin included in the alkali-soluble resin is not particularly limited, but is preferably at least 10% by mass, more preferably at least 30% by mass, still more preferably at least 50% by mass, particularly preferably It is 70 mass % or more, and 95 mass % or less, More preferably, it is 90 mass % or less, More preferably, it is 85 mass % or less. There exists a tendency for ink repellency to improve by making it more than this lower limit, and there exists a tendency for the residue to reduce by making it below this upper limit. The proportion of the (c1) acrylic copolymer resin included in the (C) alkali-soluble resin is, for example, 10 to 95% by mass, preferably 30 to 90% by mass, more preferably 50 to 85% by mass, and even more preferably 70~85% by mass.

又，(c1)丙烯酸共聚合樹脂的含有比例，相對於(c1)丙烯酸共聚合樹脂與(c2)環氧(甲基)丙烯酸酯樹脂的總質量，較佳為10質量%以上，更佳為30質量%以上，再佳為50質量%以上，特佳為70質量%以上，又，較佳為95質量%以下，更佳為90質量%以下，再佳為85質量%以下。藉由使其在該下限值以上，具有撥墨性提升的傾向，又，藉由使其在該上限值以下，具有殘渣減少的傾向。相對於(c1)丙烯酸共聚合樹脂與(c2)環氧(甲基)丙烯酸酯樹脂的總質量，(c1)丙烯酸共聚合樹脂的含有比例，例如為10~95質量%，較佳為30~90質量%，更佳為50~85質量%，再佳為70~85質量%。In addition, the content ratio of (c1) acrylic copolymer resin is preferably 10 mass % or more with respect to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin, more preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 70% by mass or more, and more preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less. There exists a tendency for ink repellency to improve by making it more than this lower limit, and there exists a tendency for residue to reduce by making it below this upper limit. With respect to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin, the content ratio of (c1) acrylic copolymer resin is, for example, 10 to 95% by mass, preferably 30 to 95% by mass. 90% by mass, more preferably 50-85% by mass, even more preferably 70-85% by mass.

以下詳述(c1)丙烯酸共聚合樹脂的具體例。作為(c1)丙烯酸共聚合樹脂，舉例如例如於(c1-a)側鏈具有乙烯屬不飽和基的羧基共聚物。Specific examples of (c1) acrylic copolymer resin will be described in detail below. As (c1) acrylic copolymer resin, the carboxyl copolymer which has an ethylenically unsaturated group in a side chain in (c1-a), for example is mentioned.

於(c1-a)側鏈具有乙烯屬不飽和基的含羧基之共聚物 (c1-a-1)不飽和羧酸與含有2個以上乙烯屬不飽和基之化合物的共聚物 作為於側鏈具有乙烯屬不飽和基的含羧基之共聚物，例如，舉例如使(甲基)丙烯酸烯丙酯、(甲基)丙烯酸3-烯丙氧基-2-羥丙酯、(甲基)丙烯酸桂醯酯、(甲基)丙烯酸巴豆醯酯、(甲基)丙烯酸甲基烯丙酯、N,N-二烯丙基(甲基)丙烯醯胺等的含有2個以上乙烯屬不飽和基的化合物、或是(甲基)丙烯酸乙烯酯、(甲基)丙烯酸1-氯乙烯酯、(甲基)丙烯酸2-苯基乙烯酯、(甲基)丙烯酸1-丙烯酯、巴豆酸乙烯酯、乙烯基(甲基)丙烯醯胺等的含有2個以上乙烯屬不飽和基的化合物，與(甲基)丙烯酸等的不飽和羧酸共聚合或是進一步與不飽和羧酸酯等共聚合所得之共聚物等，來讓前者的含有2個以上之乙烯屬不飽和基的化合物在整體中所占的比例為10~90莫耳%、較佳為30~80莫耳%左右。Carboxyl-containing copolymers having ethylenically unsaturated groups in (c1-a) side chains (c1-a-1) Copolymers of unsaturated carboxylic acids and compounds containing two or more ethylenically unsaturated groups as side chains Carboxyl-containing copolymers having ethylenically unsaturated groups, such as, for example, allyl (meth)acrylate, 3-allyloxy-2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Cinnamyl, crotonyl (meth)acrylate, methallyl (meth)acrylate, N,N-diallyl (meth)acrylamide, etc. containing 2 or more ethylenically unsaturated groups Compounds, or vinyl (meth)acrylate, 1-chlorovinyl (meth)acrylate, 2-phenylvinyl (meth)acrylate, 1-propenyl (meth)acrylate, vinyl crotonate Compounds containing two or more ethylenically unsaturated groups, such as vinyl (meth)acrylamide, are copolymerized with unsaturated carboxylic acids such as (meth)acrylic acid or further copolymerized with unsaturated carboxylic acid esters, etc. In the obtained copolymer, etc., the proportion of the former compound containing two or more ethylenically unsaturated groups in the whole is 10-90 mol%, preferably about 30-80 mol%.

另外，該共聚物的酸價，從顯影性的觀點來看，較佳為30~250mgKOH/g，重量平均分子量(Mw)，從顯影溶解性的觀點來看，較佳為1000~30000。In addition, the acid value of the copolymer is preferably 30 to 250 mgKOH/g from the viewpoint of developability, and the weight average molecular weight (Mw) is preferably 1000 to 30000 from the viewpoint of development solubility.

(c1-a-2)包含經含環氧基之不飽和化合物改質之羧基的共聚物 又，作為於側鏈具有乙烯屬不飽和基的含羧基之共聚物，例如，舉例如使含環氧基之不飽和化合物與含羧基之共聚物反應，而對於含羧基之共聚物的部分羧基加成含環氧基之不飽和化合物的環氧基而進行改質的含經改質之羧基的共聚物。 作為該含羧基之共聚物，從圖案化之性能的觀點來看，較佳為含羧基之共聚物的(甲基)丙烯酸酯-(甲基)丙烯酸共聚物以及苯乙烯-(甲基)丙烯酸酯-(甲基)丙烯酸共聚物等。 又，作為該含環氧基之不飽和化合物，舉例如烯丙基縮水甘油醚、(甲基)丙烯酸縮水甘油酯、α-乙基(甲基)丙烯酸縮水甘油酯、巴豆酸縮水甘油酯、異巴豆酸縮水甘油酯、巴豆基縮水甘油醚、伊康酸單烷基單縮水甘油酯、富馬酸單烷基單縮水甘油酯、馬來酸單烷基單縮水甘油酯等的含脂肪族環氧基之不飽和化合物、以及(甲基)丙烯酸3,4-環氧環己基甲酯、 (甲基)丙烯酸2,3-環氧環戊基甲酯、(甲基)丙烯酸7,8-環氧[三環[5.2.1.0]癸-2-基]氧基乙酯等的含脂環式環氧基之不飽和化合物。 接著，使該等的含環氧基之不飽和化合物與含羧基之共聚物所具有之羧基的5~90莫耳%、較佳為30~70莫耳%左右反應，藉此可得。另外，反應可藉由習知的方法實施。(c1-a-2) A copolymer containing a carboxyl group modified by an epoxy group-containing unsaturated compound Also, as a carboxyl group-containing copolymer having an ethylenically unsaturated group in a side chain, for example, a ring-containing Oxygen-containing unsaturated compounds are reacted with carboxyl-containing copolymers, and modified carboxyl-containing compounds are modified by adding epoxy groups of epoxy-containing unsaturated compounds to part of the carboxyl groups of carboxyl-containing copolymers copolymer. As the carboxyl group-containing copolymer, from the viewpoint of patterning performance, (meth)acrylate-(meth)acrylic acid copolymers and styrene-(meth)acrylic acid copolymers of carboxyl group-containing copolymers are preferable. Ester-(meth)acrylic acid copolymer, etc. Further, examples of the epoxy group-containing unsaturated compound include allyl glycidyl ether, glycidyl (meth)acrylate, α-ethyl (meth)glycidyl acrylate, glycidyl crotonate, Glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconic acid, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, etc. Unsaturated compounds of epoxy groups, and 3,4-epoxycyclohexylmethyl (meth)acrylate, 2,3-epoxycyclopentylmethyl (meth)acrylate, 7,8 (meth)acrylate - an unsaturated compound containing an alicyclic epoxy group such as epoxy[tricyclo[5.2.1.0]dec-2-yl]oxyethyl ester. Next, it can be obtained by reacting these epoxy group-containing unsaturated compounds with 5-90 mol %, preferably about 30-70 mol %, of the carboxyl groups contained in the carboxyl group-containing copolymer. In addition, the reaction can be carried out by a known method.

另外，該包含經含環氧基之不飽和化合物改質之羧基的共聚物的酸價，從顯影性的觀點來看，較佳為30~250mgKOH/g，從顯影性與膜強度的觀點來看，重量平均分子量(Mw)較佳為1000~300000。In addition, the acid value of the copolymer containing a carboxyl group modified by an epoxy group-containing unsaturated compound is preferably 30 to 250 mgKOH/g from the viewpoint of developability and film strength. See, the weight average molecular weight (Mw) is preferably 1,000 to 300,000.

(c1-a-3)包含經不飽和羧酸改質之環氧基及羧基的(共)聚合物 又，作為於側鏈具有乙烯屬不飽和基的含羧基之共聚物，例如舉例如含有改質環氧基及羧基之共聚物，其係經使(甲基)丙烯酸等的不飽和羧酸，與前述的含脂肪族環氧基之不飽和化合物或含脂環式環氧基之不飽和化合物或是進一步與不飽和羧酸酯或苯乙烯等共聚合而得到共聚物，來讓前者的含羧基之不飽和化合物在整體中所占的比例為10~90莫耳%、較佳為30~80莫耳%左右，再使所得之共聚物與(甲基)丙烯酸等的不飽和羧酸反應，以對於該共聚物的環氧基加成不飽和羧酸的羧基而改質。(c1-a-3) A (co)polymer containing an epoxy group and a carboxyl group modified by an unsaturated carboxylic acid Also, as a carboxyl group-containing copolymer having an ethylenically unsaturated group in a side chain, for example, it contains Copolymer of modified epoxy group and carboxyl group, which is obtained by combining unsaturated carboxylic acid such as (meth)acrylic acid with the above-mentioned unsaturated compound containing aliphatic epoxy group or unsaturated compound containing alicyclic epoxy group. Saturated compounds or further copolymerized with unsaturated carboxylic acid esters or styrene to obtain copolymers, so that the proportion of the former carboxyl-containing unsaturated compounds in the whole is 10~90 mole%, preferably 30~80 mol%, and then react the obtained copolymer with unsaturated carboxylic acid such as (meth)acrylic acid to modify the epoxy group of the copolymer by adding the carboxyl group of the unsaturated carboxylic acid.

另外，該包含經不飽和羧酸改質之環氧基及羧基的共聚物的酸價，從顯影性的觀點來看，較佳為30~250mgKOH/g，從顯影性與膜強度的觀點來看，重量平均分子量(Mw)較佳為1000~300000。In addition, the acid value of the copolymer containing epoxy groups and carboxyl groups modified by unsaturated carboxylic acid is preferably 30 to 250 mgKOH/g from the viewpoint of developability and film strength. See, the weight average molecular weight (Mw) is preferably 1,000 to 300,000.

(c1-a-4)包含經酸改質之環氧基的共聚物 又，作為於側鏈具有乙烯屬不飽和基的含羧基之(共)聚合物，舉例如包含經酸改質之環氧基的(共)聚合物，其係由對於含環氧基之(甲基)丙烯酸酯與乙烯屬不飽和化合物的共聚物，於該共聚物所具有之環氧基的至少一部分加成乙烯屬不飽和單羧酸，再於由加成所生成之羥基的至少一部分加成多元酸(酐)而得。 具體而言，舉例如包含經酸改質之環氧基的(共)聚合物，其係由對於(甲基)丙烯酸縮水甘油酯等的含環氧基之(甲基)丙烯酸酯5~99莫耳%與(甲基)丙烯酸酯等的乙烯屬不飽和化合物通常為1~95莫耳%的共聚物，於共聚物所包含之環氧基的通常10~100莫耳%加成乙烯屬不飽和單羧酸，再於由加成時產生之羥基的通常10~100莫耳%進一步加成多元酸(酐)而得-。(c1-a-4) A copolymer containing an acid-modified epoxy group. As a carboxyl-containing (co)polymer having an ethylenically unsaturated group in a side chain, for example, an acid-modified ring Oxygen-based (co)polymers, which are copolymers of epoxy-group-containing (meth)acrylates and ethylenically unsaturated compounds, and ethylene is added to at least a part of the epoxy groups contained in the copolymer It is an unsaturated monocarboxylic acid obtained by adding polybasic acid (anhydride) to at least a part of the hydroxyl groups formed by the addition. Specifically, for example, a (co)polymer containing an acid-modified epoxy group is composed of epoxy-containing (meth)acrylates such as glycidyl (meth)acrylate 5-99 Mole % and ethylenically unsaturated compounds such as (meth)acrylates are usually 1 to 95 mole % copolymers, usually 10 to 100 mole % of epoxy groups contained in the copolymer are added with vinyl Unsaturated monocarboxylic acid is obtained by adding polybasic acid (anhydride) to usually 10~100 mol% of the hydroxyl group generated during the addition.

此處，該共聚物中的含環氧基之(甲基)丙烯酸酯的共聚合比例並未特別限定，通常為5莫耳%以上，較佳為10莫耳%以上，更佳為20莫耳%以上，再佳為30莫耳%以上，再更佳為40莫耳%以上，特佳為50莫耳%以上，通常為90莫耳%以下，較佳為85莫耳%以下，更佳為80莫耳%以下。藉由使其在該下限值以上，會有撥墨性提升的傾向，又，藉由使其在該上限值以下，會有殘渣提升的傾向。作為該共聚物中的含環氧基之(甲基)丙烯酸酯的共聚合比例，例如為5~90莫耳%，較佳為10~90莫耳%，更佳為20~85莫耳%，再佳為30~85莫耳%，再更佳為40~80莫耳%，特佳為50~80莫耳%。 另一方面，該共聚物中的乙烯屬不飽和化合物的共聚合比例並未特別限定，通常為1莫耳%以上，較佳為5莫耳%以上，更佳為10莫耳%以上，再更佳為20莫耳%以上，特佳為30莫耳%以上，通常為90莫耳%以下，較佳為80莫耳%以下，更佳為70莫耳%以下，再佳為60莫耳%以下，特佳為50莫耳%以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有撥墨性及顯影性提升的傾向。作為該共聚物中的乙烯屬不飽和化合物的共聚合比例，例如為1~90莫耳%，較佳為5~80莫耳%，更佳為10~70莫耳%，再佳為20~60莫耳%，再更佳為30~50莫耳%。Here, the copolymerization ratio of the epoxy group-containing (meth)acrylate in the copolymer is not particularly limited, but it is usually more than 5 mol%, preferably more than 10 mol%, more preferably 20 mol%. More than mol%, more preferably more than 30 mol%, more preferably more than 40 mol%, especially preferably more than 50 mol%, usually less than 90 mol%, preferably less than 85 mol%, more preferably Preferably it is less than 80 mole%. By making it more than this lower limit, ink repellency tends to improve, and also by making it below this upper limit, there exists a tendency for residue to improve. The copolymerization ratio of the epoxy group-containing (meth)acrylate in the copolymer is, for example, 5-90 mol%, preferably 10-90 mol%, more preferably 20-85 mol%. , more preferably 30-85 mole%, more preferably 40-80 mole%, especially preferably 50-80 mole%. On the other hand, the copolymerization ratio of the ethylenically unsaturated compound in the copolymer is not particularly limited, but is usually at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, and then More preferably more than 20 mol%, especially preferably more than 30 mol%, usually less than 90 mol%, preferably less than 80 mol%, more preferably less than 70 mol%, and even more preferably 60 mol% % or less, especially preferably less than 50 mole %. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for ink repellency and developability to improve by making it below this upper limit. As the copolymerization ratio of the ethylenically unsaturated compound in the copolymer, for example, it is 1-90 mole %, preferably 5-80 mole %, more preferably 10-70 mole %, and even more preferably 20-90 mole %. 60 mole%, more preferably 30~50 mole%.

作為含環氧基之(甲基)丙烯酸酯，舉例如(甲基)丙烯酸縮水甘油酯、α-乙基(甲基)丙烯酸縮水甘油酯等的含脂肪族環氧基之(甲基)丙烯酸酯；3,4-環氧環己基(甲基)丙烯酸甲酯、2,3-環氧環戊基(甲基)丙烯酸甲酯、7,8-環氧[三環[5.2.1.0]癸-2-基]氧基(甲基)丙烯酸乙酯等的含脂環式環氧基之(甲基)丙烯酸酯。Examples of the epoxy group-containing (meth)acrylate include aliphatic epoxy group-containing (meth)acrylic acid such as glycidyl (meth)acrylate and α-ethyl glycidyl (meth)acrylate. esters; 3,4-epoxycyclohexyl (meth)acrylate methyl ester, 2,3-epoxycyclopentyl (meth)acrylate methyl ester, 7,8-epoxy[tricyclo[5.2.1.0]decane Alicyclic epoxy group-containing (meth)acrylates such as -2-yl]oxy ethyl (meth)acrylate.

此處，作為(甲基)丙烯酸酯等的乙烯屬不飽和化合物，例如，較佳係使用具有以下述通式(V)所表示之部分結構的單(甲基)丙烯酸酯的1種或2種以上。Here, as ethylenically unsaturated compounds such as (meth)acrylates, for example, one or two mono(meth)acrylates having a partial structure represented by the following general formula (V) are preferably used. more than one species.

[化學式11]

Figure 02_image020
[chemical formula 11]
Figure 02_image020

式(V)中，R1d ~R4d 分別獨立表示氫原子、或碳數1~10的烷基，R5d 與R6d 分別獨立表示氫原子、或碳數1~10的烷基。又，R5d 與R6d 亦可連結而形成環。R5d 與R6d 連結所形成的環，較佳為脂肪族環，可為飽和或不飽和的任一者，較佳為碳數5~6。In formula (V), R 1d to R 4d independently represent a hydrogen atom or an alkyl group with 1 to 10 carbons, and R 5d and R 6d independently represent a hydrogen atom or an alkyl group with 1 to 10 carbons. In addition, R 5d and R 6d may be connected to form a ring. The ring formed by linking R 5d and R 6d is preferably an aliphatic ring, which may be either saturated or unsaturated, and preferably has 5-6 carbon atoms.

R1d ~R4d 中的烷基的碳數通常為1以上，通常為10以下，較佳為8以下，更佳為5以下。藉由使其在該上限值以下，會有成為適當之顯影溶解性的傾向。 該等之中，從溶解性的觀點來看，R1d ~R4d 較佳為氫原子。The carbon number of the alkyl group in R 1d to R 4d is usually 1 or more, usually 10 or less, preferably 8 or less, more preferably 5 or less. By making it below this upper limit, there exists a tendency for appropriate image development solubility to become. Among these, R 1d to R 4d are preferably hydrogen atoms from the viewpoint of solubility.

R5d 及R6d 中的烷基的碳數通常為1以上，又，通常為10以下，較佳為8以下，更佳為5以下。藉由使其在該下限值以上，會有顯影密合性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。 該等之中，從顯影溶解性的觀點來看，較佳係R5d 及R6d 為氫原子，或是R5d 及R6d 連結而形成碳數5~6的脂肪族環。The carbon number of the alkyl group in R 5d and R 6d is usually 1 or more, and usually 10 or less, preferably 8 or less, more preferably 5 or less. There exists a tendency for image development adhesiveness to improve by making it more than this lower limit, and also there exists a tendency for film strength to improve by making it below this upper limit. Among them, from the viewpoint of developing solubility, R 5d and R 6d are preferably hydrogen atoms, or R 5d and R 6d are linked to form an aliphatic ring having 5 to 6 carbon atoms.

該式(V)之中，較佳為具有以下式(Va)、(Vb)、或(Vc)所表示之結構的單(甲基)丙烯酸酯。藉由導入該等的部分結構，會有可增加單(甲基)丙烯酸酯之耐熱性及強度的傾向。另外，該等的單(甲基)丙烯酸酯可使用1種，亦可以任意的組合及比例併用2種以上。Among the formula (V), preferred is a mono(meth)acrylate having a structure represented by the following formula (Va), (Vb), or (Vc). The introduction of such partial structures tends to increase the heat resistance and strength of mono(meth)acrylate. Moreover, these mono(meth)acrylates may use 1 type, and may use 2 or more types together in arbitrary combinations and ratios.

[化學式12]

Figure 02_image022
[chemical formula 12]
Figure 02_image022

作為具有以該式(V)所表示之部分結構的單(甲基)丙烯酸酯，可使用各種習知者，但從膜強度的觀點來看，特佳為以下述通式(VI)所表示者。As the mono(meth)acrylate having a partial structure represented by the formula (V), various known ones can be used, but the mono(meth)acrylate represented by the following general formula (VI) is particularly preferable from the viewpoint of film strength. By.

[化學式13]

Figure 02_image024
[chemical formula 13]
Figure 02_image024

式(VI)中，R7d 表示氫原子或甲基，R8d 表示以該式(V)的部分結構。In the formula (VI), R 7d represents a hydrogen atom or a methyl group, and R 8d represents a partial structure of the formula (V).

另一方面，作為乙烯屬不飽和化合物，具有以該式(V)所表示之部分結構的單(甲基)丙烯酸酯以外的乙烯屬不飽和化合物，例如，舉例如苯乙烯的α-、鄰、間、對烷基、硝基、氰基、醯胺、酯衍生物等的苯乙烯類；丁二烯、2,3-二甲基丁二烯、異戊二烯、氯丁二烯等的二烯類；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸新戊基、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸二環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸蒽酯、(甲基)丙烯酸蒽基壬酯、(甲基)丙烯酸向日葵酯、(甲基)丙烯酸柳酯、(甲基)丙烯酸呋喃酯、(甲基)丙烯酸糠酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸哌喃酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯乙酯、(甲基)丙烯酸甲苯酯、(甲基)丙烯酸-1,1,1-三氟乙酯、(甲基)丙烯酸全氟乙酯、(甲基)丙烯酸全氟正丙酯、(甲基)丙烯酸全氟異丙酯、(甲基)丙烯酸三苯甲酯、(甲基)丙烯酸枯酯、(甲基)丙烯酸3-(N,N-二甲胺基)丙酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯等的(甲基)丙烯酸酯類、(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)丙烯酸蒽基醯胺等的(甲基)丙烯醯胺類；(甲基)丙烯酸醯胺苯、(甲基)丙烯醯腈、丙烯醛、氯化乙烯、氯化亞乙烯、氟化乙烯、氟化亞乙烯、N-乙烯基吡咯啶酮、乙烯吡啶、乙酸乙烯酯等的乙烯基化合物類；焦檸檬酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、伊康酸二乙酯等的不飽和二羧酸二酯類；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)馬來醯亞胺等的單馬來醯亞胺類；N-(甲基)丙烯醯基酞醯亞胺等之類的自由基聚合性化合物。On the other hand, as the ethylenically unsaturated compound, there are ethylenically unsaturated compounds other than mono(meth)acrylate having a partial structure represented by the formula (V), for example, α-, o-, , m-, p-alkyl, nitro, cyano, amide, ester derivatives and other styrenes; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, etc. Dienes; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate Base) second butyl acrylate, third butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ( 2-methylcyclohexyl methacrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, ( Propargyl methacrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, anthracenyl nonyl (meth)acrylate, sunflower (meth)acrylate, Willyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyryl (meth)acrylate, benzyl (meth)acrylate, ( Phenylethyl methacrylate, Cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, Perfluoroethyl (meth)acrylate, Perfluoro(meth)acrylate n-propyl ester, perfluoroisopropyl (meth)acrylate, trityl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino) (meth)acrylate (Meth)acrylates such as propyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylamide, (meth)acrylic acidN,N -Dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-di-isopropylamide (Meth)acrylamides such as (meth)acrylamide, (meth)acrylic acid anthracylamide, etc.; (meth)acrylamide benzene, (meth)acrylonitrile, acrolein, vinyl chloride, chlorinated Vinyl compounds such as vinylidene, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, etc.; diethyl pyrocitrate, diethyl maleate, fumaric acid Unsaturated dicarboxylic acid diesters such as diethyl ester and diethyl itonate; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide , monomaleimides such as N-(4-hydroxyphenyl)maleimide; radically polymerizable compounds such as N-(meth)acrylphthalimide and the like.

該等之中，從膜強度的觀點來看，作為乙烯屬不飽和化合物，較佳係使用選自苯乙烯、(甲基)丙烯酸苄酯及單馬來醯亞胺所構成之群組之中的至少1種。此情況中，從膜強度與顯影性的觀點來看，選自苯乙烯、(甲基)丙烯酸苄酯及單馬來醯亞胺所構成之群組之中的至少1種的共聚合比例，通常為1莫耳%以上，較佳為3莫耳%以上，又，通常為70莫耳%以下，較佳為50莫耳%以下，更佳為30莫耳%以下，再佳為10莫耳%以下。Among them, from the viewpoint of film strength, it is preferable to use a compound selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide as the ethylenically unsaturated compound. at least 1 species of . In this case, from the viewpoint of film strength and developability, the copolymerization ratio of at least one selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide, Usually more than 1 mol%, preferably more than 3 mol%, and usually less than 70 mol%, preferably less than 50 mol%, more preferably less than 30 mol%, even more preferably 10 mol% Ear % below.

作為對於含環氧基之(甲基)丙烯酸酯與乙烯屬不飽和化合物的共聚物所包含的環氧基進行加成的乙烯屬不飽和單羧酸，可使用習知者，從硬化性的觀點來看，較佳為(甲基)丙烯酸。對於該共聚物所包含的環氧基加成乙烯屬不飽和單羧酸的量，通常係該共聚物所包含的環氧基的10莫耳%以上，較佳為30莫耳%以上，更佳為50莫耳%以上，再佳為70莫耳%以上，通常為100莫耳%以下。藉由使乙烯屬不飽和單羧酸的加成比例在該下限值以上，會有可提高硬化性的傾向。另外，作為對於該共聚物加成乙烯屬不飽和單羧酸的方法，可採用習知的方法。作為對於該共聚物所包含之環氧基加成乙烯屬不飽和單羧酸的量，例如，共聚物所包含之環氧基的10~100莫耳%，較佳為30~100莫耳%，更佳為50~100莫耳%，再佳為70~100莫耳%。As the ethylenically unsaturated monocarboxylic acid to which the epoxy group contained in the epoxy group-containing (meth)acrylate copolymer and the ethylenically unsaturated compound is added, known ones can be used, starting from hardening From a viewpoint, (meth)acrylic acid is preferable. The amount of ethylenically unsaturated monocarboxylic acid added to the epoxy group contained in the copolymer is usually more than 10 mol% of the epoxy group contained in the copolymer, preferably more than 30 mol%, more preferably It is preferably at least 50 mol%, more preferably at least 70 mol%, and usually not more than 100 mol%. There exists a tendency for curability to be improved by making the addition ratio of an ethylenically unsaturated monocarboxylic acid more than the said lower limit. In addition, as a method of adding an ethylenically unsaturated monocarboxylic acid to the copolymer, a known method can be employed. As the amount of ethylenically unsaturated monocarboxylic acid added to the epoxy group contained in the copolymer, for example, 10 to 100 mol % of the epoxy group contained in the copolymer, preferably 30 to 100 mol % , more preferably 50-100 mol%, more preferably 70-100 mol%.

作為對於該共聚物加成乙烯屬不飽和單羧酸時所產生之羥基進行加成之多元酸(酐)，並無特別限定，可單獨使用1種習知者，亦可以任意的組合及比例併用2種以上。藉由加成這樣的成分，可將鹼可溶性賦予共聚物。The polybasic acid (anhydride) that is added to the hydroxyl group generated when ethylenically unsaturated monocarboxylic acid is added to the copolymer is not particularly limited, and a conventional one may be used alone or in any combination and ratio. Use 2 or more kinds together. Alkali solubility can be imparted to a copolymer by adding such a component.

多元酸(酐)的加成量，通常係對於該共聚物加成乙烯屬不飽和單羧酸時所產生之羥基的1莫耳%以上，較佳為5莫耳%以上，更佳為10莫耳%以上，再佳為30莫耳%以上，再更佳為50莫耳%以上，特佳為60莫耳%以上。又，通常為100莫耳%以下，較佳為90莫耳%以下，更佳為80莫耳%以下，再佳為70莫耳%以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。另外，作為對於該共聚物加成乙烯屬不飽和單羧酸時所產生之羥基加成多元酸(酐)的方法，可任意採用習知的方法。作為對於該共聚物加成乙烯屬不飽和單羧酸時所產生之羥基加成多元酸(酐)的量，例如為1~100莫耳%，5~90莫耳%，更佳為10~80莫耳%，再佳為30~80莫耳%，再更佳為50~70莫耳%，特佳為60~70莫耳%。The addition amount of polybasic acid (anhydride) is usually more than 1 mole %, preferably more than 5 mole %, more preferably 10 mole % of the hydroxyl group produced when the copolymer is added with ethylenically unsaturated monocarboxylic acid. Mole % or more, more preferably more than 30 mole %, more preferably more than 50 mole %, especially preferably more than 60 mole %. Moreover, it is usually not more than 100 mol%, preferably not more than 90 mol%, more preferably not more than 80 mol%, and still more preferably not more than 70 mol%. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit. In addition, as a method of adding a polybasic acid (anhydride) to a hydroxyl group generated when an ethylenically unsaturated monocarboxylic acid is added to the copolymer, a known method can be adopted arbitrarily. The amount of hydroxyl-added polybasic acid (anhydride) produced when ethylenically unsaturated monocarboxylic acid is added to the copolymer is, for example, 1 to 100 mol%, 5 to 90 mol%, more preferably 10 to 90 mol%. 80 mole %, more preferably 30-80 mole %, more preferably 50-70 mole %, especially preferably 60-70 mole %.

由以上的含環氧基之共聚物的乙烯屬不飽和單羧酸及多元酸(酐)而來的改質物中，對於在多元酸(酐)加成後所產生之羧基的一部分加成(甲基)丙烯酸縮水甘油酯或具有乙烯不飽和基的縮水甘油醚化合物，藉此可更提升光感度。又，對於多元酸(酐)加成後所產生之羧基的一部分加成不具有乙烯屬不飽和基的縮水甘油醚化合物，藉此可提升顯影性。再者，亦可在多元酸(酐)加成後，再使該等的兩者加成。In the modified product derived from the above-mentioned ethylenically unsaturated monocarboxylic acid and polybasic acid (anhydride) of the epoxy group-containing copolymer, a part of the carboxyl group generated after the addition of the polybasic acid (anhydride) is added ( Glycidyl methacrylate or a glycidyl ether compound having an ethylenically unsaturated group can further enhance the photosensitivity. Moreover, the developability can be improved by adding the glycidyl ether compound which does not have an ethylenically unsaturated group to some of the carboxyl groups produced after the addition of a polybasic acid (anhydride). In addition, after adding polybasic acid (anhydride), you may add these two again.

另外，作為上述包含經酸改質之環氧基的共聚物，例如，舉例如日本特開平8-297366號公報或日本特開2001-89533號公報之樹脂。又，上述改質物的重量平均分子量(Mw)無特別限定，通常為3000以上，較佳為5000以上，又，通常為100000以下，較佳為50000以下，更佳為30000以下，再佳為20000以下，特佳為15000以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。作為上述改質物的重量平均分子量(Mw)，例如為3000~100000，較佳為3000~50000，更佳為5000~30000，再佳為5000~20000，再更佳為5000~15000。 又，分子量分布[重量平均分子量(Mw)/數量平均分子量(Mn)]，從硬化性的觀點來看，較佳為2.0~5.0。In addition, as the copolymer containing the above-mentioned acid-modified epoxy group, for example, resins such as JP-A-8-297366 or JP-A-2001-89533 are exemplified. Also, the weight average molecular weight (Mw) of the above-mentioned modified substance is not particularly limited, but it is usually not less than 3000, preferably not less than 5000, and usually not more than 100000, preferably not more than 50000, more preferably not more than 30000, and more preferably not more than 20000. The best is below 15,000. When it is more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the residue tends to decrease. The weight average molecular weight (Mw) of the modified substance is, for example, 3,000-100,000, preferably 3,000-50,000, more preferably 5,000-30,000, further preferably 5,000-20,000, and still more preferably 5,000-15,000. Also, the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 2.0 to 5.0 from the viewpoint of curability.

又，包含經酸改質之環氧基的共聚物的酸價並未特別限定，較佳為30mgKOH/g以上，更佳為40mgKOH/g以上，再佳為50mgKOH/g以上，又，較佳為150mgKOH/g以下，更佳為130mgKOH/g以下，再佳為120mgKOH/g以下，再更佳為110mgKOH/g以下，特佳為100mgKOH/g以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。作為包含經酸改質之環氧基的共聚物的酸價，例如為30~150mgKOH/g，較佳為40~130mgKOH/g，更佳為40~120mgKOH/g，再佳為50~110mgKOH/g，再更佳為50~100mgKOH/g。Also, the acid value of the copolymer comprising acid-modified epoxy groups is not particularly limited, but it is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, further preferably 50 mgKOH/g or more, and preferably It is 150 mgKOH/g or less, more preferably 130 mgKOH/g or less, still more preferably 120 mgKOH/g or less, still more preferably 110 mgKOH/g or less, particularly preferably 100 mgKOH/g or less. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit. The acid value of the copolymer comprising acid-modified epoxy groups is, for example, 30-150 mgKOH/g, preferably 40-130 mgKOH/g, more preferably 40-120 mgKOH/g, and more preferably 50-110 mgKOH/g. g, more preferably 50-100 mgKOH/g.

接著詳述(c2)環氧(甲基)丙烯酸酯樹脂。Next, the (c2) epoxy (meth)acrylate resin will be described in detail.

[(c2)環氧(甲基)丙烯酸酯樹脂] (c2)環氧(甲基)丙烯酸酯樹脂係為對於環氧樹脂加成乙烯屬不飽和單羧酸或酯化物，任意地使含有異氰酸酯基之化合物反應後，再使多元酸或其酸酐反應而得到的樹脂。例如，舉例如藉由於環氧樹脂的環氧基使不飽和單羧酸的羧基進行開環加成，透過酯鍵(-COO-)對於環氧化物加成乙烯屬不飽和鍵，並且於此時產生的羥基加成多元酸酐之一邊的羧基。又，舉例如加成多元酸酐時，同時添加多元醇而進行加成的產物。[(c2) Epoxy (meth)acrylate resin] (c2) Epoxy (meth)acrylate resin is an epoxy resin in which an ethylenically unsaturated monocarboxylic acid or esterified product is added, optionally containing isocyanate Resin obtained by reacting polybasic acid or its anhydride after reacting the base compound. For example, an ethylenically unsaturated bond is added to an epoxide through an ester bond (-COO-) by, for example, ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, and here When the hydroxyl group produced is added to the carboxyl group on one side of the polybasic anhydride. Moreover, for example, when adding a polybasic acid anhydride, the thing which added and added polyhydric alcohol simultaneously is mentioned.

又，使上述反應所得之樹脂的羧基進一步與反應所得之具有官能基之化合物反應所得之樹脂亦包含於上述(c2)環氧(甲基)丙烯酸酯樹脂。 如此，環氧(甲基)丙烯酸酯樹脂，在化學結構中實際上不含有環氧基，且並不限於「(甲基)丙烯酸酯」，但因為係以環氧化物(環氧樹脂)為原料，且以「(甲基)丙烯酸酯」為代表例，因此依照慣用如此進行命名。Moreover, the resin obtained by making the carboxyl group of the resin obtained by the said reaction react further with the compound which has a functional group obtained by the reaction is also contained in the said (c2) epoxy (meth)acrylate resin. In this way, epoxy (meth)acrylate resin does not actually contain epoxy groups in its chemical structure, and is not limited to "(meth)acrylate", but because it is based on epoxy (epoxy resin) The raw material is "(meth)acrylate" as a representative example, so it is named according to the usual practice.

此處，環氧樹脂係指亦包含因熱硬化而形成樹脂的習知原料化合物，作為該環氧樹脂，可從習知的環氧樹脂之中適當選擇而使用。又，環氧樹脂，可使用使酚性化合物與環氧氯丙烷反應所得之化合物。作為酚性化合物，舉例如具有2價以上之酚性羥基的化合物，可為單體亦可為聚合物。 具體而言，例如，可較佳地使用雙酚A環氧樹脂、雙酚F環氧樹脂、雙酚S環氧樹脂、苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、聯苯酚醛清漆環氧樹脂、參酚環氧樹脂、酚與二環戊烷的聚合環氧樹脂、二羥基茀型環氧樹脂、二羥基伸烷氧基茀型環氧樹脂、9,9-雙(4’-羥基苯基)茀的二縮水甘油醚化物、1,1-雙(4’-羥基苯基)金剛烷的二縮水甘油醚化物等，像這樣於主鏈具有芳香環者。Here, the epoxy resin refers to a known raw material compound that also forms a resin by thermosetting, and as the epoxy resin, it can be appropriately selected from known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenolic compound with epichlorohydrin can be used. The phenolic compound includes, for example, a compound having a divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, biphenol novolak epoxy resin, Varnish epoxy resin, ginseng phenolic epoxy resin, polymerized epoxy resin of phenol and dicyclopentane, dihydroxy fluorine type epoxy resin, dihydroxy alkeneoxy fluorine type epoxy resin, 9,9-bis(4 Diglycidyl ether compounds of '-hydroxyphenyl) terrene, diglycidyl ether compounds of 1,1-bis(4'-hydroxyphenyl) adamantane, etc., which have an aromatic ring in the main chain.

其中，從硬化膜強度高的觀點來看，較佳為雙酚A環氧樹脂、苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、苯酚與二環戊二烯的聚合環氧樹脂、9,9-雙(4’-羥基苯基)茀的二縮水甘油醚化物等，再佳為雙酚A環氧樹脂。 作為環氧樹脂的具體例，例如，可較佳地使用雙酚A型環氧樹脂(例如，三菱化學公司製的「jER(註冊商標，以下相同)828」、「jER1001」、「jER1002」、「jER1004」等)、由雙酚A型環氧樹脂的醇性羥基與環氧氯丙烷的反應所得之環氧樹脂(例如，日本化藥公司製的「NER-1302」(環氧當量323，軟化點76℃))、雙酚F型樹脂(例如，三菱化學公司製的「jER807」、「EP-4001」、「EP-4002」、「EP-4004」等)、由雙酚F型環氧樹脂的醇性羥基與環氧氯丙烷的反應所得之環氧樹脂(例如，日本化藥公司製的「NER-7406」(環氧當量350，軟化點66℃))、雙酚S型環氧樹脂、聯苯縮水甘油醚(例如，三菱化學公司製的「YX-4000」)、苯酚酚醛清漆型環氧樹脂(例如，日本化藥公司製的「EPPN-201」、三菱化學公司製的「EP-152」、「EP-154」、Dow Chemical公司製的「DEN-438」)、(鄰、間、對)甲酚酚醛清漆型環氧樹脂(例如，日本化藥公司製的「EOCN(註冊商標，以下相同)-102S」、「EOCN-1020」、「EOCN-104S」)、三縮水甘油異三聚氰酸酯(例如，日產化學公司製的「TEPIC(註冊商標)」)、參酚甲烷型環氧樹脂(例如，日本化藥公司製的「EPPN(註冊商標，以下相同)-501」、「EPPN-502」、「EPPN-503」)、脂環式環氧樹脂(DAICEL公司製的「CELLOXIDE(註冊商標，以下相同)2021P」、「CELLOXIDE EHPE」)、將二環戊二烯與酚的反應而來的酚樹脂進行縮水甘油化而成的環氧樹脂(例如，DIC公司製的「EXA-7200」、日本化藥公司製的「NC-7300」)、以下述通式(C1)~(C4)所表示之環氧樹脂等。具體而言，舉例如日本化藥公司製的「XD-1000」作為以下述通式(C1)所表示之環氧樹脂，日本化藥公司製的「NC-3000」作為以下述通式(C2)所表示之環氧樹脂，新日鐵住金化學公司製的「ESF-300」等作為以下述通式(C4)所表示之環氧樹脂。Among them, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, Diglycidyl ether compound of 9,9-bis(4'-hydroxyphenyl) terpene, etc., more preferably bisphenol A epoxy resin. As a specific example of the epoxy resin, for example, a bisphenol A type epoxy resin (for example, "jER (registered trademark, the same below) 828", "jER1001", "jER1002" manufactured by Mitsubishi Chemical Corporation, etc. can be preferably used. "jER1004", etc.), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol A epoxy resins with epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, Softening point 76°C)), bisphenol F-type resin (for example, "jER807", "EP-4001", "EP-4002", "EP-4004" manufactured by Mitsubishi Chemical Corporation, etc.), bisphenol F-type ring Epoxy resin obtained by reacting the alcoholic hydroxyl group of epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S-ring epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154", "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o-, m-, p-) cresol novolak type epoxy resin (for example, "EOCN" manufactured by Nippon Kayaku Co., Ltd. (registered trademark, the same below)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), Phenolmethane-type epoxy resins (for example, "EPPN (registered trademark, the same below)-501", "EPPN-502", and "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins (DAICEL "CELLOXIDE (registered trademark, hereinafter the same) 2021P" and "CELLOXIDE EHPE" manufactured by the company), epoxy resins obtained by glycidylating phenol resins obtained by the reaction of dicyclopentadiene and phenol (for example, DIC "EXA-7200" manufactured by the company, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (C1) to (C4), etc. Specifically, "XD-1000" produced by Nippon Kayaku Co., Ltd. is an epoxy resin represented by the following general formula (C1), and "NC-3000" produced by Nippon Kayaku Co., Ltd. is an epoxy resin represented by the following general formula (C2 ) as the epoxy resin represented by the following general formula (C4), "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., etc.

[化學式14]

Figure 02_image026
[chemical formula 14]
Figure 02_image026

上述通式(C1)中，a為平均值，表示0~10的數值。R111 分別獨立表示氫原子、鹵素原子、碳數1~8的烷基、碳數3~10的環烷基、苯基、萘基、或聯苯基。另外，1分子中存在的複數R111 分別可相同，亦可不同。In the above-mentioned general formula (C1), a is an average value and represents a numerical value from 0 to 10. R 111 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. In addition, the plurality of R 111 present in one molecule may be the same or different.

[化學式15]

Figure 02_image028
[chemical formula 15]
Figure 02_image028

上述通式(C2)中，b為平均值，表示0~10的數值。R121 分別獨立表示氫原子、鹵素原子、碳數1~8的烷基、碳數3~10的環烷基、苯基、萘基、或聯苯基。另外，1分子中存在的複數R121 分別可相同，亦可不同。In the above-mentioned general formula (C2), b is an average value and represents a numerical value from 0 to 10. R 121 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbons, a cycloalkyl group with 3 to 10 carbons, a phenyl group, a naphthyl group, or a biphenyl group. In addition, the plurality of R 121 present in one molecule may be the same or different.

[化學式16]

Figure 02_image030
[chemical formula 16]
Figure 02_image030

上述通式(C3)中，X表示以下述通式(C3-1)或(C3-2)所表示之連結基團。其中，分子結構中包含1個以上的金剛烷結構。c表示2或3。In the above general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2). Among them, the molecular structure contains one or more adamantane structures. c means 2 or 3.

[化學式17]

Figure 02_image032
[chemical formula 17]
Figure 02_image032

上述通式(C3-1)及(C3-2)中，R131 ~R134 及R135 ~R137 分別獨立表示亦可具有取代基的金剛烷基、氫原子、亦可具有取代基的碳數1~12的烷基、或亦可具有取代基的苯基。＊表示鍵結處。In the above general formulas (C3-1) and (C3-2), R 131 ~ R 134 and R 135 ~ R 137 independently represent an adamantyl group that may also have a substituent, a hydrogen atom, and a carbon that may also have a substituent An alkyl group having a number of 1 to 12, or a phenyl group which may have a substituent. ＊Indicates a bond.

[化學式18]

Figure 02_image034
[chemical formula 18]
Figure 02_image034

上述通式(C4)中，p及q分別獨立表示0~4的整數，R141 及R142 分別獨立表示碳數1~4的烷基或鹵素原子。R143 及R144 分別獨立表示碳數1~4的伸烷基。x及y分別獨立表示0以上的整數。In the above general formula (C4), p and q independently represent an integer of 0 to 4, and R 141 and R 142 independently represent an alkyl group or a halogen atom having 1 to 4 carbon atoms. R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.

該等之中，較佳係使用以通式(C1)~(C4)的任一者所表示的環氧樹脂。Among these, it is preferable to use the epoxy resin represented by any one of general formula (C1)-(C4).

作為乙烯屬不飽和單羧酸，舉例例如(甲基)丙烯酸、巴豆酸、馬來酸、富馬酸、伊康酸、焦檸檬酸等，以及新戊四醇三(甲基)丙烯酸酯琥珀酸酐加成物、新戊四醇三(甲基)丙烯酸酯四氫酞酸酐加成物、二新戊四醇五(甲基)丙烯酸酯琥珀酸酐加成物、二新戊四醇五(甲基)丙烯酸酯酞酸酐加成物、二新戊四醇五(甲基)丙烯酸酯四氫酞酸酐加成物、(甲基)丙烯酸與ε-己內酯的反應產物等。其中，從感度的觀點來看，較佳為(甲基)丙烯酸。Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, pyrocitric acid, and neopentylthritol tri(meth)acrylate succinic acid. Anhydride adducts, neopentylthritol tri(meth)acrylate tetrahydrophthalic anhydride adducts, diperythritol penta(meth)acrylate succinic anhydride Base) acrylate phthalic anhydride adducts, dipentyl penta(meth)acrylate tetrahydrophthalic anhydride adducts, reaction products of (meth)acrylic acid and ε-caprolactone, etc. Among them, (meth)acrylic acid is preferable from the viewpoint of sensitivity.

作為多元酸(酐)，舉例例如琥珀酸、馬來酸、伊康酸、酞酸、四氫酞酸、3-甲基四氫酞酸、4-甲基四氫酞酸、3-乙基四氫酞酸、4-乙基四氫酞酸、六氫酞酸、3-甲基六氫酞酸、4-甲基六氫酞酸、3-乙基六氫酞酸、4-乙基六氫酞酸、苯偏三酸、苯均四酸、二苯甲酮四羧酸、聯苯四羧酸、及該等的酸酐等。其中，從排出氣體的觀點來看，較佳為琥珀酸酐、馬來酸酐、四氫酞酸酐、或六氫酞酸酐，更佳為琥珀酸酐或四氫酞酸酐。Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyl Tetrahydrophthalic acid, 4-ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethyl Hexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and their anhydrides. Among these, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable from the viewpoint of exhaust gas.

藉由使用多元醇，使(c2)環氧(甲基)丙烯酸酯樹脂的分子量增加，可在分子中導入分支，會有可取得分子量與黏度之平衡的傾向。又，可增加酸基在分子中的導入率，會有容易取得感度及密合性等之平衡的傾向。 作為多元醇，例如，較佳為選自三羥甲基丙烷、二三羥甲基丙烷、新戊四醇、二新戊四醇、三羥甲基乙烷、1,2,3-丙三醇之中的1種或2種以上的多元醇。By using polyhydric alcohol, the molecular weight of (c2) epoxy (meth)acrylate resin can be increased, branches can be introduced into the molecule, and there is a tendency that a balance between molecular weight and viscosity can be achieved. Also, the rate of introduction of acid groups into the molecule can be increased, and the balance between sensitivity and adhesiveness tends to be easily achieved. As the polyhydric alcohol, for example, preferably selected from trimethylolpropane, ditrimethylolpropane, neopentylthritol, dipenteoerythritol, trimethylolethane, 1,2,3-propane One or more polyhydric alcohols among alcohols.

作為環氧(甲基)丙烯酸酯樹脂，除了前述以外，舉例如韓國公開專利第10-2013-0022955號公報中所記載的環氧(甲基)丙烯酸酯樹脂等。As an epoxy (meth)acrylate resin, the epoxy (meth)acrylate resin etc. which are described in Korean Laid-Open Patent No. 10-2013-0022955 other than the above are mentioned, for example.

(c2)環氧(甲基)丙烯酸酯樹脂的酸價並未特別限定，較佳為10mgKOH/g以上，更佳為30mgKOH/g以上，再佳為50mgKOH/g以上，再更佳為70mgKOH/g以上，特佳為80mgKOH/g以上，又，較佳為200mgKOH/g以下，更佳為180mgKOH/g以下，再佳為150mgKOH/g以下，再更佳為120mgKOH/g以下，特佳為110mgKOH/g以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。作為(c2)環氧(甲基)丙烯酸酯樹脂的酸價，例如為10~200mgKOH/g，較佳為30~180mgKOH/g，更佳為50~150mgKOH/g，再佳為70~120mgKOH/g，再更佳為80~110mgKOH/g。(c2) The acid value of the epoxy (meth)acrylate resin is not particularly limited, preferably more than 10mgKOH/g, more preferably more than 30mgKOH/g, more preferably more than 50mgKOH/g, and more preferably 70mgKOH/g More than g, preferably more than 80mgKOH/g, preferably less than 200mgKOH/g, more preferably less than 180mgKOH/g, more preferably less than 150mgKOH/g, more preferably less than 120mgKOH/g, most preferably less than 110mgKOH /g or less. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit. The acid value of (c2) epoxy (meth)acrylate resin is, for example, 10-200 mgKOH/g, preferably 30-180 mgKOH/g, more preferably 50-150 mgKOH/g, and more preferably 70-120 mgKOH/g. g, more preferably 80~110mgKOH/g.

(c2)環氧(甲基)丙烯酸酯樹脂的重量平均分子量(Mw)並未特別限定，通常為1000以上，較佳為2000以上，更佳為3000以上，再佳為4000以上，再更佳為5000以上，特佳為6000以上，最佳為7000以上，又，通常為30000以下，較佳為20000以下，更佳為15000以下，再佳為10000以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有殘渣減少的傾向。作為(c2)環氧(甲基)丙烯酸酯樹脂的重量平均分子量(Mw)，例如為1000~30000，較佳為2000~20000，更佳為3000~20000，再佳為4000~15000，再更佳為5000~15000，特佳為6000~10000，最佳為7000~10000。(c2) The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin is not particularly limited, but it is usually more than 1000, preferably more than 2000, more preferably more than 3000, more preferably more than 4000, and more preferably It is 5,000 or more, particularly preferably 6,000 or more, most preferably 7,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and most preferably 10,000 or less. When it is more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the residue tends to decrease. As (c2) the weight average molecular weight (Mw) of epoxy (meth)acrylate resin is, for example, 1000~30000, preferably 2000~20000, more preferably 3000~20000, more preferably 4000~15000, more preferably The best is 5000~15000, the best is 6000~10000, and the best is 7000~10000.

(C)鹼可溶性樹脂所包含的(c2)環氧(甲基)丙烯酸酯樹脂的含有比例並未特別限定，較佳為5質量%以上，更佳為10質量%以上，再佳為15質量%以上，再更佳為18質量%以上，又，較佳為90質量%以下，更佳為70質量%以下，再佳為50質量%以下，特佳為30質量%以下。藉由使其在該下限值以上，會有殘渣減少的傾向，又，藉由使其在該上限值以下，會有撥墨性提升的傾向。作為(C)鹼可溶性樹脂所包含的(c2)環氧(甲基)丙烯酸酯樹脂的含有比例，例如為5~90質量%，較佳為10~70質量%，更佳為15~50質量%，再佳為18~30質量%。(C) The content ratio of (c2) epoxy (meth)acrylate resin contained in alkali-soluble resin is not specifically limited, Preferably it is 5 mass % or more, More preferably, it is 10 mass % or more, More preferably, it is 15 mass % % or more, more preferably at least 18% by mass, more preferably at most 90% by mass, more preferably at most 70% by mass, even more preferably at most 50% by mass, and most preferably at most 30% by mass. There exists a tendency for the residue to reduce by making it more than this lower limit, and there exists a tendency for ink repellency to improve by making it below this upper limit. The content ratio of (c2) epoxy (meth)acrylate resin contained as (C) alkali-soluble resin is, for example, 5-90 mass %, Preferably it is 10-70 mass %, More preferably, it is 15-50 mass % %, preferably 18-30% by mass.

又，(c2)環氧(甲基)丙烯酸酯樹脂的含有比例，相對於(c1)丙烯酸共聚合樹脂與(c2)環氧(甲基)丙烯酸酯樹脂的總質量，較佳為5質量%以上，更佳為10質量%以上，再佳為15質量%以上，特佳為20質量%以上，又，較佳為90質量%以下，更佳為70質量%以下，再佳為50質量%以下，特佳為30質量%以下，再特佳為25質量%以下。藉由使其在該下限值以上，會有殘渣減少的傾向，又，藉由使其在該上限值以下，會有撥墨性提升的傾向。相對於(c1)丙烯酸共聚合樹脂與(c2)環氧(甲基)丙烯酸酯樹脂的總質量，(c2)環氧(甲基)丙烯酸酯樹脂的含有比例，例如為5~90質量%，較佳為5~70質量%，更佳為10~50質量%，再佳為15~30質量%，再更佳為20~25質量%。Also, the content ratio of (c2) epoxy (meth)acrylate resin is preferably 5% by mass relative to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin. Above, more preferably at least 10% by mass, more preferably at least 15% by mass, particularly preferably at least 20% by mass, more preferably at most 90% by mass, more preferably at most 70% by mass, even more preferably at least 50% by mass At most, it is at most 30% by mass, and at most preferably it is at most 25% by mass. There exists a tendency for the residue to reduce by making it more than this lower limit, and there exists a tendency for ink repellency to improve by making it below this upper limit. With respect to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin, the content ratio of (c2) epoxy (meth)acrylate resin is, for example, 5 to 90% by mass, Preferably it is 5-70 mass %, More preferably, it is 10-50 mass %, More preferably, it is 15-30 mass %, More preferably, it is 20-25 mass %.

(c2)環氧(甲基)丙烯酸酯樹脂，可由以往習知的方法合成。具體而言，可使用使該環氧樹脂溶解於有機溶劑，在觸媒與熱聚合抑制劑的共存下，加入該具有乙烯屬不飽和鍵的酸或酯化物，使其進行加成反應，再加入多元酸或其酸酐以持續反應之方法。(c2) Epoxy (meth)acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin can be dissolved in an organic solvent, and the acid or ester compound having an ethylenically unsaturated bond is added in the presence of a catalyst and a thermal polymerization inhibitor to perform an addition reaction, and then The method of adding polybasic acid or its anhydride to continue the reaction.

此處，作為反應中使用的有機溶劑，舉例如甲乙酮、環己酮、二乙二醇***乙酸酯、丙二醇單甲醚乙酸酯等的有機溶劑的1種或2種以上。又，作為上述觸媒，舉例如三乙胺、苄基二甲胺、三苄胺等的3級胺類、氯化四甲銨、氯化甲基三乙銨、氯化四乙銨、氯化四丁銨、氯化三甲基苄銨等的4級銨鹽類、三苯基膦等的磷化合物、三苯銻等的銻化氫類等的1種或2種以上。再者，作為熱聚合抑制劑，舉例如氫醌、氫醌單甲醚、甲基氫醌等的1種或2種以上。Here, as the organic solvent used in the reaction, one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate are exemplified. In addition, examples of the aforementioned catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, chlorine One or two or more kinds of quaternary ammonium salts such as tetrabutylammonium chloride and trimethylbenzyl ammonium chloride, phosphorus compounds such as triphenylphosphine, and antimonides such as triphenylantimony. In addition, as a thermal polymerization inhibitor, 1 type or 2 or more types of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, etc. are mentioned, for example.

又，作為具有乙烯屬不飽和鍵的酸或酯化物，可為相對於環氧樹脂之環氧基的1化學當量，通常係成為0.7~1.3化學當量，較佳係成為0.9~1.1化學當量的量。又，作為加成反應時的溫度，通常可為60~150℃，較佳可為80~120℃的溫度。再者，作為多元酸(酐)的使用量，可為相對於該加成反應中所產生之羥基的1化學當量，通常係成為0.1~1.2化學當量，較佳係成為0.2~1.1化學當量的量。Also, as an acid or ester compound having an ethylenically unsaturated bond, it may be 1 chemical equivalent to the epoxy group of the epoxy resin, usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents quantity. Moreover, as a temperature at the time of an addition reaction, it can be 60-150 degreeC normally, Preferably it can be 80-120 degreeC. Furthermore, the usage amount of the polybasic acid (anhydride) may be 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents relative to 1 chemical equivalent of the hydroxyl group produced in the addition reaction. quantity.

(c2)環氧(甲基)丙烯酸酯樹脂之中，從膜強度及直線性的觀點來看，較佳係包含選自具有以下述通式(i)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂、具有以下述通式(ii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂、以及具有以下述通式(iii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂所構成之群組的至少1種。(c2) Among the epoxy (meth)acrylate resins, from the viewpoint of film strength and linearity, it is preferable to contain epoxy (meth)acrylates having a partial structure represented by the following general formula (i). base) acrylate resin, epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii), and epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) ) at least one of the group consisting of acrylate resins.

[化學式19]

Figure 02_image003
[chemical formula 19]
Figure 02_image003

式(i)中，Ra 表示氫原子或甲基，Rb 表示亦可具有取代基的2價烴基。式(i)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. ＊Indicates a bond.

[化學式20]

Figure 02_image005
[chemical formula 20]
Figure 02_image005

式(ii)中，Rc 分別獨立表示氫原子或甲基。Rd 表示具有環狀烴基作為側鏈的2價烴基。＊表示鍵結處。In formula (ii), R c each independently represent a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. ＊Indicates a bond.

[化學式21]

Figure 02_image007
[chemical formula 21]
Figure 02_image007

式(iii)中，Re 表示氫原子或甲基，γ表示單鍵、-CO-、亦可具有取代基的伸烷基、或亦可具有取代基的2價環狀烴基。式(iii)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。In formula (iii), R e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group that may have a substituent, or a divalent cyclic hydrocarbon group that may have a substituent. The benzene ring in formula (iii) may be further substituted with any substituent. ＊Indicates a bond.

該等之中，首先詳述具有以下述通式(i)所表示之部分結構環氧(甲基)丙烯酸酯樹脂(以下有時稱為「環氧(甲基)丙烯酸酯樹脂(c2-1)」)。Among these, epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (c2-1) having a partial structure represented by the following general formula (i) will be described in detail. )”).

[化學式22]

Figure 02_image003
[chemical formula 22]
Figure 02_image003

式(i)中，Ra 表示氫原子或甲基，Rb 表示亦可具有取代基的2價烴基。式(i)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. ＊Indicates a bond.

(Rb ) 該式(i)中，Rb 表示亦可具有取代基的2價烴基。 作為2價烴基，舉例如2價脂肪族基、2價芳香環基、將1個以上的2價脂肪族基與1個以上的2價芳香環基連結的基團。(R b ) In the formula (i), R b represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

2價脂肪族基，舉例如直鏈狀、分支鏈狀、環狀者。該等之中，從顯影溶解性的觀點來看，較佳為直鏈狀者，另一方面，從降低顯影液對於曝光部之浸透的觀點來看，較佳為環狀者。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為20以下，更佳為15以下，再佳為10以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有感度提升的傾向。Examples of divalent aliphatic groups include straight-chain, branched-chain, and cyclic ones. Among them, from the viewpoint of image development solubility, a linear one is preferable, and on the other hand, a cyclic one is preferable from the viewpoint of reducing penetration of a developing solution into an exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When it is more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the sensitivity tends to be improved.

作為2價的直鏈狀脂肪族基的具體例，舉例如亞甲基、伸乙基、正伸丙基、正伸丁基、正伸己基、正伸庚基等。該等之中，從感度及製造成本的觀點來看，較佳為亞甲基。 作為2價的分支鏈狀脂肪族基的具體例，舉例如在前述2價的直鏈狀脂肪族基中，具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等作為側鏈的結構。 2價的環狀脂肪族基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為2價的環狀的脂肪族基的具體例，舉例如從環己烷環、環庚烷環、環癸烷環、環十二烷環、降莰烷環、異莰烷環、金剛烷環等的環去除2個氫原子的基團。該等之中，從膜強度與顯影性的觀點來看，較佳為從金剛烷環去除2個氫原子的基團。Specific examples of the divalent straight-chain aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexylene, and n-heptyl. Among them, methylene is preferable from the viewpoint of sensitivity and production cost. Specific examples of the divalent branched-chain aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl among the aforementioned divalent straight-chain aliphatic groups. Group, second butyl, third butyl, etc. as side chain structure. The number of rings that the divalent cycloaliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. Specific examples of divalent cyclic aliphatic groups include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, A ring such as a ring is a group in which two hydrogen atoms have been removed. Among them, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of film strength and developability.

作為2價脂肪族基可具有的取代基，舉例如甲氧基、乙氧基等的碳數1~5的烷氧基；羥基；硝基；氰基；羧基等。該等之中，從合成容易性的觀點來看，較佳為無取代。Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. Among these, no substitution is preferred from the viewpoint of easiness of synthesis.

又，作為2價芳香環基，舉例如2價的芳香烴環基及2價的芳香雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為20以下，更佳為15以下，再佳為10以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned, for example. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為2價芳香烴環基中的芳香烴環，可為單環，亦可為縮合環。2價的芳香烴環基，例如，舉例如具有2個自由價的苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、苯并菲環、聯伸三苯基環、苊萘環、熒蒽環、茀環等的基團。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. A divalent aromatic hydrocarbon ring group, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring, a triphenylene ring, etc. , groups that extend triphenyl rings, acenaphthyl rings, fluoranthene rings, fenhe rings, etc.

又，作為芳香雜環基中的芳香雜環，可為單環，亦可為縮合環。作為2價的芳香雜環基，舉例例如，具有2個自由價的呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、噁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異噁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡嗪環、噠嗪環、嘧啶環、三嗪環、喹啉環、異喹啉環、㖕啉環、喹噁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等的基團。該等之中，從製造成本的觀點來看，較佳為具有2個自由價的苯環或萘環，更佳為具有2個自由價的苯環。In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indazole rings, and Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzo Isoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, phenoline ring, quinoxaline ring ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. Among them, from the viewpoint of production cost, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

作為2價芳香環基可具有的取代基，舉例如羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。該等之中，從硬化性的觀點來看，較佳為無取代。As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group etc. are mentioned, for example. Among these, no substitution is preferred from the viewpoint of curability.

又，作為將1個以上的2價脂肪族基與1個以上的2價芳香環基連結的基團，舉例如將1個以上的前述2價脂肪族基與1個以上的前述2價芳香環基連結的基團。 2價脂肪族基的數量並未特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。 2價芳香環基的數量並未特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。Also, as a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups, for example, one or more aforementioned divalent aliphatic groups are linked to one or more aforementioned divalent aromatic ring groups. The group linked by the ring group. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為將1個以上的2價脂肪族基與1個以上的2價芳香環基連結之基團的具體例，舉例如以下式(i-A)~(i-F)所表示之基團等。該等之中，從骨架的剛直性與膜之疏水化的觀點來看，較佳為以下式(i-A)所表示之基團。Specific examples of groups in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups represented by the following formulas (i-A) to (i-F). Among them, a group represented by the following formula (i-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane.

[化學式23]

Figure 02_image040
[chemical formula 23]
Figure 02_image040

如上所述，式(i)中的苯環亦可更由任意的取代基取代。作為該取代基，舉例例如羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基的數量亦無特別限定，較佳為1個，亦可為2個以上。 該等之中，從硬化性的觀點來看，較佳為無取代。As mentioned above, the benzene ring in formula (i) may be further substituted with any substituent. As this substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group etc. are mentioned, for example. The number of substituents is also not particularly limited, and is preferably 1, and may be 2 or more. Among these, no substitution is preferred from the viewpoint of curability.

又，以該式(i)所表示之部分結構，從顯影溶解性的觀點來看，較佳為以下式(i-1)所表示之部分結構。In addition, the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of image development solubility.

[化學式24]

Figure 02_image042
[chemical formula 24]
Figure 02_image042

式(i-1)中，Ra 及Rb 與該式(i)中同義。RY 表示氫原子或多元酸殘基。＊表示鍵結處。式(i-1)中的苯環亦可更由任意的取代基取代。In formula (i-1), R a and R b have the same meaning as in formula (i). RY represents a hydrogen atom or a residue of a polybasic acid. ＊Indicates a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

多元酸殘基，係指從多元酸或其酸酐去除1個OH基的1價基團。作為多元酸，舉例如選自馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、二苯甲酮四羧酸、甲基六氫酞酸、橋聯亞甲基四氫酞酸、氯橋酸、甲基四氫酞酸、聯苯四羧酸的1種或2種以上。 該等之中，從圖案化特性的觀點來看，較佳為馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、聯苯四羧酸，更佳為四氫酞酸、聯苯四羧酸。The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or an acid anhydride thereof. As the polybasic acid, for example, selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, One or more kinds of methylhexahydrophthalic acid, bridged methylene tetrahydrophthalic acid, chloro-bridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid are preferable from the viewpoint of patterning properties. , biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid.

環氧(甲基)丙烯酸酯樹脂(c2-1)1分子中所包含的、以該式(i-1)所表示之重複單元結構可為1種、亦可為2種以上。The repeating unit structure represented by this formula (i-1) contained in 1 molecule of epoxy (meth)acrylate resin (c2-1) may be 1 type, and may be 2 or more types.

又，環氧(甲基)丙烯酸酯樹脂(c2-1)1分子中所包含的、以該式(i)所表示之部分結構的數量並未特別限定，較佳為1以上，更佳為2以上，再佳為3以上，又，較佳為10以下，更佳為8以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。Also, the number of partial structures represented by the formula (i) included in one molecule of the epoxy (meth)acrylate resin (c2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, and more preferably 10 or less, more preferably 8 or less. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit.

又，環氧(甲基)丙烯酸酯樹脂(c2-1)1分子中所包含的、以該式(i-1)所表示之部分結構的數量並未特別限定，較佳為1以上，更佳為2以上，再佳為3以上，又，較佳為10以下，更佳為8以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。Also, the number of partial structures represented by the formula (i-1) included in one molecule of the epoxy (meth)acrylate resin (c2-1) is not particularly limited, but is preferably 1 or more, more preferably It is preferably at least 2, more preferably at least 3, more preferably at most 10, more preferably at most 8. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit.

以下舉出環氧(甲基)丙烯酸酯樹脂(c2-1)的具體例。Specific examples of the epoxy (meth)acrylate resin (c2-1) are given below.

[化學式25]

Figure 02_image044
[chemical formula 25]
Figure 02_image044

[化學式26]

Figure 02_image046
[chemical formula 26]
Figure 02_image046

[化學式27]

Figure 02_image048
[chemical formula 27]
Figure 02_image048

[化學式28]

Figure 02_image050
[chemical formula 28]
Figure 02_image050

[化學式29]

Figure 02_image052
[chemical formula 29]
Figure 02_image052

[化學式30]

Figure 02_image054
[chemical formula 30]
Figure 02_image054

[化學式31]

Figure 02_image056
[chemical formula 31]
Figure 02_image056

接著詳述具有以下述通式(ii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂(以下有時稱為「環氧(甲基)丙烯酸酯樹脂(c2-2)」)。Next, the epoxy (meth)acrylate resin (it may be called "epoxy (meth)acrylate resin (c2-2)" hereafter) which has a partial structure represented by following general formula (ii) is demonstrated in full detail.

[化學式32]

Figure 02_image058
[chemical formula 32]
Figure 02_image058

式(ii)中，Rc 分別獨立表示氫原子或甲基。Rd 表示具有環狀烴基作為側鏈的2價烴基。＊表示鍵結處。In formula (ii), R c each independently represent a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. ＊Indicates a bond.

(Rd ) 該式(ii)中，Rd 表示具有環狀烴基作為側鏈的2價烴基。 作為環狀烴基，舉例如脂肪族環基或芳香環基。(R d ) In the formula (ii), R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned, for example.

脂肪族環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下，更佳為3以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 又，脂肪族環基的碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為30以下，再佳為20以下，特佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. the following. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為脂肪族環基中的脂肪族環的具體例，舉例如環己烷環、環庚烷環、環癸烷環、環十二烷環、降莰烷環、異莰烷環、金剛烷環、環十二烷環等。該等之中，從膜強度與顯影性的觀點來看，較佳為金剛烷環。Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. , Cyclododecane ring, etc. Among them, an adamantane ring is preferable from the viewpoint of film strength and developability.

另一方面，芳香環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，通常為10以下，較佳為5以下，更佳為4以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。On the other hand, the number of rings in the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably 4 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為芳香環基，舉例如芳香烴環基、芳香雜環基。又，芳香環基的碳數通常為4以上，較佳為6以上，更佳為8以上，再佳為10以上，特佳為12以上，又，較佳為40以下，更佳為30以下，再佳為20以下，特佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。The aromatic ring group includes, for example, an aromatic hydrocarbon ring group and an aromatic heterocyclic group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less , preferably below 20, especially below 15. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為芳香環基中的芳香環的具體例，舉例如苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、苯并菲環、聯伸三苯基環、苊萘環、熒蒽環、茀環等。該等之中，從圖案化特性的觀點來看，較佳為茀環。Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring, a triphenylene ring, and a triphenylene ring. Base ring, acenaphthaphthalene ring, fluoranthene ring, fenene ring, etc. Among them, from the viewpoint of patterning properties, a fennel ring is preferable.

又，具有環狀烴基作為側鏈的2價烴基中，2價烴基並未特別限定，例如，舉例如2價脂肪族基、2價芳香環基、將1個以上的2價脂肪族基與1個以上的2價芳香環基連結之基團。In addition, among divalent hydrocarbon groups having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, for example, a divalent aliphatic group, a divalent aromatic ring group, a combination of one or more divalent aliphatic groups and A group in which one or more divalent aromatic ring groups are linked.

2價脂肪族基，舉例如直鏈狀、分支鏈狀、環狀者。該等之中，從提升顯影性的觀點來看，較佳為直鏈狀者，另一方面，從膜強度的觀點來看，較佳為環狀者。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為25以下，更佳為20以下，再佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。Examples of divalent aliphatic groups include straight-chain, branched-chain, and cyclic ones. Among these, from the viewpoint of improving developability, a linear one is preferable, and on the other hand, a cyclic one is preferable from the viewpoint of film strength. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為2價的直鏈狀脂肪族基的具體例，舉例如亞甲基、伸乙基、正伸丙基、正伸丁基、正伸己基、正伸庚基等。該等之中，從感度的觀點來看，較佳為亞甲基。 作為2價的分支鏈狀脂肪族基的具體例，舉例如在前述2價的直鏈狀脂肪族基上，具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等以作為側鏈的結構。Specific examples of the divalent straight-chain aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexylene, and n-heptyl. Among these, methylene is preferable from the viewpoint of sensitivity. Specific examples of divalent branched chain aliphatic groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Group, second butyl, third butyl, etc. as side chain structure.

2價的環狀的脂肪族基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下，更佳為3以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為2價的環狀的脂肪族基的具體例，舉例如從環己烷環、環庚烷環、環癸烷環、環十二烷環、降莰烷環、異莰烷環、金剛烷環等的環去除2個氫原子的基團。該等之中，從膜強度的觀點來看，較佳為從金剛烷環去除2個氫原子的基團。Specific examples of divalent cyclic aliphatic groups include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, A ring such as a ring is a group in which two hydrogen atoms have been removed. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferred from the viewpoint of film strength.

作為2價脂肪族基可具有的取代基，舉例如甲氧基、乙氧基等的碳數1~5的烷氧基；羥基；硝基；氰基；羧基等。該等之中，從合成容易性的觀點來看，較佳為無取代。Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. Among these, no substitution is preferred from the viewpoint of easiness of synthesis.

又，作為2價芳香環基，舉例如2價的芳香烴環基及2價的芳香雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，再佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned, for example. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為2價的芳香烴環基中的芳香烴環，可為單環，亦可為縮合環。作為2價的芳香烴環基，例如，舉例如具有2個自由價的苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、苯并菲環、聯伸三苯基環、苊萘環、熒蒽環、茀環等的基團。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the divalent aromatic hydrocarbon ring group, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, triphenylene ring, etc. Groups such as rings, triphenyl rings, acenaphthyl rings, fluoranthene rings, and fenene rings.

又，作為芳香雜環基中的芳香雜環，可為單環，亦可為縮合環。作為2價的芳香雜環基，舉例例如具有2個自由價的呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、噁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異噁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡嗪環、噠嗪環、嘧啶環、三嗪環、喹啉環、異喹啉環、㖕啉環、喹噁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等的基團。該等之中，從製造成本的觀點來看，較佳為具有2個自由價的苯環或萘環，更佳為具有2個自由價的苯環。In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, and indole rings having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benziso Oxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, phenoline ring, quinoxaline ring , phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. Among them, from the viewpoint of production cost, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

作為2價芳香環基可具有的取代基，舉例如羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。該等之中，從硬化性的觀點來看，較佳為無取代。As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group etc. are mentioned, for example. Among these, no substitution is preferred from the viewpoint of curability.

又，作為將1個以上的2價脂肪族基與1個以上的2價芳香環基連結之基團，舉例如將1個以上的前述2價脂肪族基與1個以上的前述2價芳香環基連結之基團。 2價脂肪族基的數量並未特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。 2價芳香環基的數量並未特別限定，通常為1以上，較佳為2以上，通常為10以下，較佳為5以下，更佳為3以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。Also, as a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups, for example, one or more aforementioned divalent aliphatic groups and one or more aforementioned divalent aromatic ring groups are combined. A group linked by a ring group. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為將1個以上的2價脂肪族基與1個以上的2價芳香環基連結之基團的具體例，舉例如以該式(i-A)~(i-F)所表示之基團等。該等之中，從兼具膜強度與感度的觀點來看，較佳為以該式(i-C)所表示之基團。Specific examples of groups in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups represented by the formulas (i-A) to (i-F). Among them, the group represented by the formula (i-C) is preferable from the viewpoint of achieving both film strength and sensitivity.

對於該等的2價烴基，作為側鏈的環狀烴基的鍵結態樣並未特別限定，舉例例如以該側鏈取代脂肪族基或芳香環基的1個氫原子的態樣或是包含脂肪族基的1個碳原子而構成作為側鏈之環狀烴基的態樣。For these divalent hydrocarbon groups, the bonding state of the cyclic hydrocarbon group as the side chain is not particularly limited, for example, the state of substituting the side chain for one hydrogen atom of an aliphatic group or an aromatic ring group or containing One carbon atom of the aliphatic group constitutes a form of a cyclic hydrocarbon group as a side chain.

又，以該式(ii)所表示之部分結構，從感度的觀點來看，較佳為以下式(ii-1)所表示的部分結構。Also, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of sensitivity.

[化學式33]

Figure 02_image060
[chemical formula 33]
Figure 02_image060

式(ii-1)中，Rc 與該式(ii)同義。Rα 表示亦可具有取代基的1價環狀烴基。n為1以上的整數。式(ii-1)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。In the formula (ii-1), R c has the same meaning as the formula (ii). R α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with any substituent. ＊Indicates a bond.

(Rα ) 該式(ii-1)中，Rα 表示亦可具有取代基的1價環狀烴基。 作為環狀烴基，舉例如脂肪族環基或芳香環基。(R α ) In the formula (ii-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned, for example.

脂肪族環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，又，通常為6以下，較佳為4以下，更佳為3以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 又，脂肪族環基的碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為30以下，再佳為20以下，特佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. the following. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為脂肪族環基中的脂肪族環的具體例，舉例如環己烷環、環庚烷環、環癸烷環、環十二烷環、降莰烷環、異莰烷環、金剛烷環等。該等之中，從兼具膜強度與顯影性的觀點來看，較佳為金剛烷環。Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. Wait. Among them, an adamantane ring is preferable from the viewpoint of achieving both film strength and developability.

另一方面，芳香環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，通常為10以下，較佳為5以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 作為芳香環基，舉例如芳香烴環基、芳香雜環基。又，芳香環基的碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，再佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The aromatic ring group includes, for example, an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Also, the carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為芳香環基中的芳香環的具體例，舉例如苯環、萘環、蒽環、菲環、茀環等。該等之中，從兼具膜強度與顯影性的觀點來看，較佳為茀環。Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, from the viewpoint of achieving both film strength and developability, fennel ring is preferable.

作為環狀烴基可具有的取代基，舉例如羥基、甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等的碳數1~5的烷基；甲氧基、乙氧基等的碳數1~5的烷氧基；硝基；氰基；羧基等。該等之中，從合成容易性的觀點來看，較佳為無取代。Examples of substituents that the cyclic hydrocarbon group may have include hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy groups; nitro groups; cyano groups; carboxyl groups, etc. Among these, no substitution is preferred from the viewpoint of easiness of synthesis.

n表示1以上的整數，較佳為2以上，又，較佳為3以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有膜強度提升的傾向。n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. There exists a tendency for developability to improve by making it more than this lower limit, and there exists a tendency for film strength to improve by making it below this upper limit.

該等之中，從兼具膜強度與顯影性的觀點來看，Rα 較佳為1價的脂肪族環基，更佳為金剛烷基。Among them, R α is preferably a monovalent aliphatic ring group, more preferably an adamantyl group, from the viewpoint of achieving both film strength and developability.

如上所述，式(ii-1)中的苯環亦可更由任意的取代基取代。作為該取代基，舉例例如羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基的數量亦無特別限定，較佳為1個，亦可為2個以上。該等之中，從硬化性的觀點來看，較佳為無取代。As mentioned above, the benzene ring in formula (ii-1) may be further substituted with any substituent. As this substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group etc. are mentioned, for example. The number of substituents is also not particularly limited, and is preferably 1, and may be 2 or more. Among these, no substitution is preferred from the viewpoint of curability.

以下舉出以該式(ii-1)所表示之部分結構的具體例。Specific examples of the partial structure represented by the formula (ii-1) are given below.

[化學式34]

Figure 02_image062
[chemical formula 34]
Figure 02_image062

[化學式35]

Figure 02_image064
[chemical formula 35]
Figure 02_image064

[化學式36]

Figure 02_image066
[chemical formula 36]
Figure 02_image066

[化學式37]

Figure 02_image068
[chemical formula 37]
Figure 02_image068

[化學式38]

Figure 02_image070
[chemical formula 38]
Figure 02_image070

又，以該式(ii)所表示之部分結構，從顯影密合性的觀點來看，較佳為以下式(ii-2)所表示的部分結構。Moreover, it is preferable that the partial structure represented by this formula (ii) is the partial structure represented by the following formula (ii-2) from a viewpoint of image development adhesiveness.

[化學式39]

Figure 02_image072
[chemical formula 39]
Figure 02_image072

式(ii-2)中，Rc 與該式(ii)同義。Rβ 表示亦可具有取代基的2價環狀烴基。式(ii-2)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。In the formula (ii-2), R c has the same meaning as the formula (ii). R β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. ＊Indicates a bond.

(Rβ ) 該式(ii-2)中，Rβ 表示亦可具有取代基的2價環狀烴基。 作為環狀烴基，舉例如脂肪族環基或芳香環基。(R β ) In the formula (ii-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned, for example.

脂肪族環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 又，脂肪族環基的碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為35以下，再佳為30以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 作為脂肪族環基中的脂肪族環的具體例，舉例如環己烷環、環庚烷環、環癸烷環、環十二烷環、降莰烷環、異莰烷環、金剛烷環等。該等之中，從兼具膜強度與顯影性的觀點來看，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. Wait. Among them, an adamantane ring is preferable from the viewpoint of achieving both film strength and developability.

另一方面，芳香環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，通常為10以下，較佳為5以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 作為芳香環基，舉例如芳香烴環基、芳香雜環基。又，芳香環基的碳數通常為4以上，較佳為6以上，更佳為8以上，再佳為10以上，又，較佳為40以下，更佳為30以下，再佳為20以下，特佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The aromatic ring group includes, for example, an aromatic hydrocarbon ring group and an aromatic heterocyclic group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and more preferably 20 or less , preferably below 15. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為芳香環基中的芳香環的具體例，舉例如苯環、萘環、蒽環、菲環、茀環等。該等之中，從膜強度與顯影性的觀點來看，較佳為茀環。Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, from the viewpoint of film strength and developability, fennel ring is preferable.

作為環狀烴基可具有的取代基，舉例如羥基、甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等的碳數1~5的烷基；甲氧基、乙氧基等的碳數1~5的烷氧基；硝基；氰基；羧基等。該等之中，從合成簡易性的觀點來看，較佳為無取代。Examples of substituents that the cyclic hydrocarbon group may have include hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy groups; nitro groups; cyano groups; carboxyl groups, etc. Among these, no substitution is preferred from the viewpoint of the ease of synthesis.

該等之中，從兼具膜強度與顯影性的觀點來看，Rβ 較佳為2價的脂肪族環基，更佳為2價的金剛烷環基。 另一方面，從兼具膜強度與顯影性的觀點來看，Rβ 較佳為2價芳香環基，更佳為2價的茀環基。Among them, R β is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, from the viewpoint of achieving both film strength and developability. On the other hand, R β is preferably a divalent aromatic ring group, more preferably a divalent fenene ring group, from the viewpoint of achieving both film strength and developability.

如上所述，式(ii-2)中的苯環亦可更由任意的取代基取代。作為該取代基，舉例例如羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基的數量亦無特別限定，可為1個，亦可為2個以上。該等之中，從硬化性的觀點來看，較佳為無取代。As mentioned above, the benzene ring in formula (ii-2) may be further substituted with any substituent. As this substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group etc. are mentioned, for example. The number of substituents is not particularly limited either, and may be one or two or more. Among these, no substitution is preferred from the viewpoint of curability.

以下舉出以該式(ii-2)所表示之部分結構的具體例。Specific examples of the partial structure represented by the formula (ii-2) are given below.

[化學式40]

Figure 02_image074
[chemical formula 40]
Figure 02_image074

[化學式41]

Figure 02_image076
[chemical formula 41]
Figure 02_image076

[化學式42]

Figure 02_image078
[chemical formula 42]
Figure 02_image078

[化學式43]

Figure 02_image080
[chemical formula 43]
Figure 02_image080

另一方面，以該式(ii)所表示之部分結構，從顯影性的觀點來看，較佳為以下式(ii-3)所表示的部分結構。On the other hand, the partial structure represented by this formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of developability.

[化學式44]

Figure 02_image082
[chemical formula 44]
Figure 02_image082

式(ii-3)中，Rc 及Rd 與以該式(ii)同義。RZ 表示氫原子或多元酸殘基。In formula (ii-3), R c and R d have the same meaning as in formula (ii). R Z represents a hydrogen atom or a polybasic acid residue.

多元酸殘基，係指從多元酸或其酸酐去除1個OH基的1價基團。作為多元酸，舉例如選自馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、二苯甲酮四羧酸、甲基六氫酞酸、橋聯亞甲基四氫酞酸、氯橋酸、甲基四氫酞酸、聯苯四羧酸之中的1種或2種以上。 該等之中，從圖案化特性的觀點來看，較佳為馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、聯苯四羧酸，更佳為四氫酞酸、聯苯四羧酸。The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or an acid anhydride thereof. As the polybasic acid, for example, selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, One or more of methyl hexahydrophthalic acid, bridging methylene tetrahydrophthalic acid, chloro-bridged acid, methyl tetrahydrophthalic acid, and biphenyltetracarboxylic acid. Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid are preferable from the viewpoint of patterning properties. , biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid.

環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-3)所表示之部分結構可為1種，亦可為2種以上。The partial structure represented by this formula (ii-3) contained in 1 molecule of epoxy (meth)acrylate resin (c2-2) may be 1 type, and may be 2 or more types.

又，環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii)所表示之部分結構的數量並未特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，更佳為15以下，再佳為10以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii)所表示之部分結構的數量，例如為1~20，較佳為3~15，更佳為3~10。Also, the number of partial structures represented by the formula (ii) included in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. There exists a tendency for sensitivity to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, more preferably The best is 3~10.

又，環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-1)所表示之部分結構的數量並未特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，更佳為15以下，再佳為10以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-1)所表示之部分結構的數量，例如為1~20，較佳為3~15，更佳為3~10。Also, the number of partial structures represented by the formula (ii-1) included in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, more preferably Preferably, it is 3 or more, and more preferably, it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less. There exists a tendency for sensitivity to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15 , more preferably 3~10.

又，環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-2)所表示之部分結構的數量並未特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，更佳為15以下，再佳為10以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-2)所表示之部分結構的數量，例如為1~20，較佳為3~15，更佳為3~10。Also, the number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, more preferably Preferably, it is 3 or more, and more preferably, it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less. There exists a tendency for sensitivity to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15 , more preferably 3~10.

又，環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-3)所表示之部分結構的數量並未特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，更佳為15以下，再佳為10以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為環氧(甲基)丙烯酸酯樹脂(c2-2)1分子中所包含的、以該式(ii-3)所表示之部分結構的數量，例如為1~20，較佳為3~15，更佳為3~10。Also, the number of partial structures represented by the formula (ii-3) included in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, more preferably Preferably, it is 3 or more, and more preferably, it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less. There exists a tendency for sensitivity to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15 , more preferably 3~10.

接著詳述具有以下述通式(iii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂(以下有時稱為「環氧(甲基)丙烯酸酯樹脂(c2-3)」)。Next, an epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (c2-3)") having a partial structure represented by the following general formula (iii) will be described in detail.

[化學式45]

Figure 02_image007
[chemical formula 45]
Figure 02_image007

式(iii)中，Re 表示氫原子或甲基，γ表示單鍵、-CO-、亦可具有取代基的伸烷基、或亦可具有取代基的2價環狀烴基。式(iii)中的苯環亦可更由任意的取代基取代。＊表示鍵結處。In formula (iii), R e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group that may have a substituent, or a divalent cyclic hydrocarbon group that may have a substituent. The benzene ring in formula (iii) may be further substituted with any substituent. ＊Indicates a bond.

(γ) 該式(iii)中，γ表示單鍵、-CO-、亦可具有取代基的伸烷基、或亦可具有取代基的2價環狀烴基。(γ) In the formula (iii), γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

伸烷基可為直鏈、亦可為分支鏈，但從顯影溶解性的觀點來看，較佳為直鏈，從顯影密合性的觀點來看，較佳為分支鏈。其碳數並未特別限定，通常為1以上，較佳為2以上，又，通常為6以下，較佳為4以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。The alkylene group may be a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of image development solubility, and is preferably a branched chain from the viewpoint of image development adhesiveness. The carbon number is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit.

作為伸烷基的具體例，舉例如亞甲基、伸乙基、伸丙基、伸丁基、伸己基、伸庚基，從兼具膜強度與顯影性的觀點來看，較佳為伸乙基或伸丙基，更佳為伸丙基。Specific examples of the alkylene group include methylene, ethylene, propylidene, butylene, hexylene, and heptyl. From the viewpoint of both film strength and developability, alkene is preferred. Ethyl or propylidene, more preferably propylidene.

作為伸烷基可具有的取代基，舉例如甲氧基、乙氧基等的碳數1~5的烷氧基；羥基；硝基；氰基；羧基等。該等之中，從合成容易性的觀點來看，較佳為無取代。Examples of substituents that the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Among these, no substitution is preferred from the viewpoint of easiness of synthesis.

作為2價環狀烴基，舉例如2價的脂肪族環基或2價芳香環基。As a divalent cyclic hydrocarbon group, a divalent aliphatic ring group or a divalent aromatic ring group is mentioned, for example.

脂肪族環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，又，通常為10以下，較佳為5以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 又，脂肪族環基的碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為35以下，再佳為30以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 作為脂肪族環基中的脂肪族環的具體例，舉例如環己烷環、環庚烷環、環癸烷環、環十二烷環、降莰烷環、異莰烷環、金剛烷環等。該等之中，從兼具膜強度與顯影性的觀點來看，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. Wait. Among them, an adamantane ring is preferable from the viewpoint of achieving both film strength and developability.

另一方面，芳香環基所具有之環的數量並未特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，通常為10以下，較佳為5以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 作為芳香環基，舉例如芳香烴環基、芳香雜環基。又，芳香環基的碳數通常為4以上，較佳為6以上，更佳為8以上，再佳為10以上，又，較佳為40以下，更佳為30以下，再佳為20以下，再更佳為15以下。藉由使其在該下限值以上，會有膜強度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。 作為芳香環基中的芳香環的具體例，舉例如苯環、萘環、蒽環、菲環、茀環等。該等之中，從兼具膜強度與顯影性的觀點來看，較佳為茀環。On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The aromatic ring group includes, for example, an aromatic hydrocarbon ring group and an aromatic heterocyclic group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and more preferably 20 or less , and more preferably 15 or less. There exists a tendency for film strength to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, from the viewpoint of achieving both film strength and developability, fennel ring is preferable.

作為環狀烴基可具有的取代基，舉例如甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等的碳數1~5的烷基；甲氧基、乙氧基等的碳數1~5的烷氧基；羥基；硝基；氰基；羧基等。該等之中，從合成簡易性的觀點來看，較佳為無取代。Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. Alkyl group with 1~5 carbons; alkoxy group with 1~5 carbons such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group, etc. Among these, no substitution is preferred from the viewpoint of the ease of synthesis.

又，該等之中，從顯影性的觀點來看，γ較佳為亦可具有取代基的伸烷基，更佳為二甲基亞甲基。Moreover, among these, from the viewpoint of developability, γ is preferably an alkylene group which may have a substituent, more preferably a dimethylmethylene group.

如上所述，式(iii)中的苯環亦可更由任意的取代基取代。作為該取代基，舉例例如羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基的數量亦無特別限定，較佳為1個，亦可為2個以上。該等之中，從硬化性的觀點來看，較佳為無取代。As mentioned above, the benzene ring in formula (iii) may be further substituted with any substituent. As this substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group etc. are mentioned, for example. The number of substituents is also not particularly limited, and is preferably 1, and may be 2 or more. Among these, no substitution is preferred from the viewpoint of curability.

另一方面，以該式(iii)所表示之部分結構，從顯影溶解性的觀點來看，較佳為以下式(iii-1)所表示的部分結構。On the other hand, the partial structure represented by this formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of image development solubility.

[化學式46]

Figure 02_image085
[chemical formula 46]
Figure 02_image085

式(iii-1)中，Re 及γ與該式(iii)同義。RW 表示氫原子或多元酸殘基。＊表示鍵結處。式(iii-1)中的苯環亦可更由任意的取代基取代。In the formula (iii-1), R e and γ have the same meaning as the formula (iii). R W represents a hydrogen atom or a polybasic acid residue. ＊Indicates a bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.

多元酸殘基，係指從多元酸或其酸酐去除1個OH基的1價基團。作為多元酸，舉例如選自馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、二苯甲酮四羧酸、甲基六氫酞酸、橋聯亞甲基四氫酞酸、氯橋酸、甲基四氫酞酸、聯苯四羧酸之中的1種或2種以上。 該等之中，從圖案化特性的觀點來看，較佳為馬來酸、琥珀酸、伊康酸、酞酸、四氫酞酸、六氫酞酸、苯均四酸、苯偏三酸、聯苯四羧酸，更佳為四氫酞酸、聯苯四羧酸。The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or an acid anhydride thereof. As the polybasic acid, for example, selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, One or more of methyl hexahydrophthalic acid, bridging methylene tetrahydrophthalic acid, chloro-bridged acid, methyl tetrahydrophthalic acid, and biphenyltetracarboxylic acid. Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid are preferable from the viewpoint of patterning properties. , biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid.

又，環氧(甲基)丙烯酸酯樹脂(c2-3)1分子中所包含的、以該式(iii)所表示之重複單元結構的數量並未特別限定，較佳為1以上，更佳為5以上，再佳為10以上，又，較佳為18以下，更佳為15以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為環氧(甲基)丙烯酸酯樹脂(c2-3)1分子中所包含的、以該式(iii)所表示之重複單元結構的數量，例如為1~18，較佳為5~18，更佳為10~15。Also, the number of repeating unit structures represented by the formula (iii) contained in 1 molecule of the epoxy (meth)acrylate resin (c2-3) is not particularly limited, preferably 1 or more, more preferably 5 or more, more preferably 10 or more, and more preferably 18 or less, more preferably 15 or less. There exists a tendency for sensitivity to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The number of repeating unit structures represented by the formula (iii) included in the epoxy (meth)acrylate resin (c2-3) 1 molecule is, for example, 1 to 18, preferably 5 to 18, More preferably, it is 10-15.

又，環氧(甲基)丙烯酸酯樹脂(c2-3)1分子中所包含的，以該式(iii-1)所表示之重複單元結構的數量並未特別限定，較佳為1以上，更佳為3以上，再佳為5以上，又，較佳為18以下，更佳為15以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有顯影性提升的傾向。作為環氧(甲基)丙烯酸酯樹脂(c2-3)1分子中所包含的、以該式(iii-1)所表示之重複單元結構的數量，例如為1~18，較佳為3~18，更佳為5~15。Also, the number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-3) is not particularly limited, but is preferably 1 or more, More preferably, it is 3 or more, Still more preferably, it is 5 or more, Also, it is more preferable that it is 18 or less, More preferably, it is 15 or less. There exists a tendency for sensitivity to improve by making it more than this lower limit, and there exists a tendency for developability to improve by making it below this upper limit. The number of repeating unit structures represented by the formula (iii-1) included in the epoxy (meth)acrylate resin (c2-3) 1 molecule is, for example, 1 to 18, preferably 3 to 18, more preferably 5-15.

以下舉出環氧(甲基)丙烯酸酯樹脂(c2-3)的具體例。Specific examples of the epoxy (meth)acrylate resin (c2-3) are given below.

[化學式47]

Figure 02_image087
[chemical formula 47]
Figure 02_image087

[化學式48]

Figure 02_image089
[chemical formula 48]
Figure 02_image089

如上所述，本發明中的(C)鹼可溶性樹脂，包含(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂及(c2)環氧(甲基)丙烯酸酯樹脂，但除了該等以外，亦可包含其他鹼可溶性樹脂。As described above, the (C) alkali-soluble resin in the present invention includes (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain and (c2) an epoxy (meth)acrylate resin. In addition to other alkali-soluble resins, etc. may be included.

又，(C)成分的鹼可溶性樹脂的平均酸價並未特別限定，較佳為10mgKOH/g以上，更佳為20mgKOH/g以上，再佳為30mgKOH/g以上，又，較佳為200mgKOH/g以下，更佳為150mgKOH/g以下，再佳為100mgKOH/g以下，再更佳為70mgKOH/g以下，特佳為50mgKOH/g以下。藉由使其在該下限值以上，會有顯影性提升的傾向，又，藉由使其在該上限值以下，會有顯影密合性提升的傾向。(C)成分的鹼可溶性樹脂的平均酸價可藉由中和滴定測量。作為(C)成分的鹼可溶性樹脂的平均酸價，例如為10~200mgKOH/g，較佳為10~150mgKOH/g，更佳為20~100mgKOH/g，再佳為20~70mgKOH/g，再更佳為30~50mgKOH/g。Also, the average acid value of the alkali-soluble resin of component (C) is not particularly limited, but is preferably at least 10 mgKOH/g, more preferably at least 20 mgKOH/g, still more preferably at least 30 mgKOH/g, and more preferably at least 200 mgKOH/g. g or less, more preferably 150 mgKOH/g or less, even more preferably 100 mgKOH/g or less, still more preferably 70 mgKOH/g or less, particularly preferably 50 mgKOH/g or less. It exists in the tendency for developability to improve by making it more than this lower limit, and it exists in the tendency for image development adhesiveness to improve by making it below this upper limit. (C) The average acid value of the alkali-soluble resin of component can be measured by neutralization titration. The average acid value of the alkali-soluble resin as the component (C) is, for example, 10 to 200 mgKOH/g, preferably 10 to 150 mgKOH/g, more preferably 20 to 100 mgKOH/g, and more preferably 20 to 70 mgKOH/g. More preferably 30~50mgKOH/g.

本發明之有色感光性樹脂組成物中的(C)鹼可溶性樹脂的含有比例並未特別限定，在總固體成分中，通常為5質量%以上，較佳為10質量%以上，更佳為20質量%以上，再佳為30質量%以上，再更佳為40質量%以上，特佳為50質量%以上，最佳為60質量%以上，又，通常為90質量%以下，較佳為80質量%以下，更佳為70質量%以下。藉由使其在該下限值以上，會有分隔壁的形狀變好的傾向，又，藉由使其在該上限值以下，會有感度提升的傾向。作為(C)鹼可溶性樹脂在有色感光性樹脂組成物之總固體成分中的含有比例，例如為5~90質量%，較佳為10~90質量%，更佳為20~80質量%，再佳為30~80質量%，再更佳為40~80質量%，特佳為50~70質量%，最佳為60~70質量%。The content ratio of the (C) alkali-soluble resin in the colored photosensitive resin composition of the present invention is not particularly limited, but it is usually at least 5% by mass, preferably at least 10% by mass, and more preferably at least 20% by mass of the total solid content. More than 30% by mass, more preferably more than 30% by mass, more preferably more than 40% by mass, particularly preferably more than 50% by mass, most preferably more than 60% by mass, and usually less than 90% by mass, preferably 80% by mass Mass % or less, more preferably 70 mass % or less. There exists a tendency for the shape of a partition to improve by making it more than this lower limit, and there exists a tendency for sensitivity to improve by making it below this upper limit. (C) The content ratio of the alkali-soluble resin in the total solid content of the colored photosensitive resin composition is, for example, 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and then Preferably it is 30-80 mass %, more preferably 40-80 mass %, especially preferably 50-70 mass %, most preferably 60-70 mass %.

又，總固體成分中，(A)乙烯屬不飽和化合物及(C)鹼可溶性樹脂的含有比例的總和較佳為10質量%以上，更佳為30質量%以上，再佳為60質量%以上，再更佳為80質量%以上，又，較佳為100質量%以下，更佳為95質量%以下，再佳為90質量%以下。藉由使其在該下限值以上，會有感度提升的傾向，又，藉由使其在該上限值以下，會有分隔壁的形狀變好的傾向。在有色感光性樹脂組成物之總固體成分中，(A)乙烯屬不飽和化合物及(C)鹼可溶性樹脂之含有比例的總和，例如為10~100質量%，較佳為30~95質量%，更佳為60~95質量%，再佳為80~90質量%。In addition, in the total solid content, the sum of the content ratios of (A) ethylenically unsaturated compounds and (C) alkali-soluble resins is preferably at least 10% by mass, more preferably at least 30% by mass, and still more preferably at least 60% by mass. , more preferably at least 80% by mass, more preferably at most 100% by mass, more preferably at most 95% by mass, even more preferably at most 90% by mass. There exists a tendency for the sensitivity to improve by making it more than this lower limit value, and also there exists a tendency for the shape of a partition to improve by making it below this upper limit value. In the total solid content of the colored photosensitive resin composition, the total content ratio of (A) ethylenically unsaturated compound and (C) alkali-soluble resin is, for example, 10 to 100% by mass, preferably 30 to 95% by mass , more preferably 60-95% by mass, more preferably 80-90% by mass.

[1-1-4](D)成分；撥液劑 本發明之有色感光性樹脂組成物含有(D)撥液劑。藉由含有(D)撥液劑，可賦予所得之分隔壁的表面撥墨性，因此認為可防止所得之分隔壁與各個有機層的發光部(像素)混色。[1-1-4] Component (D); liquid repellent The colored photosensitive resin composition of the present invention contains (D) a liquid repellent. Since ink repellency can be imparted to the surface of the partition obtained by containing (D) liquid repellent, it is considered that the partition obtained and the light-emitting part (pixel) of each organic layer can be prevented from mixing colors.

作為撥液劑，舉例如聚矽氧含有化合物及氟系化合物，較佳舉例如具有交聯基的撥液劑(以下有時稱為「含交聯基之撥液劑」)。作為交聯基，舉例如環氧基或乙烯屬不飽和基，從抑制撥液成分流出至顯影液的觀點來看，較佳為乙烯屬不飽和基。 使用含交聯基之撥液劑的情況中，在將所形成之塗膜曝光時，可加速在其表面的交聯反應，撥液劑在顯影處理中難以流出，結果認為可使所得之分隔壁呈現高撥墨性。The liquid repellent includes, for example, a silicone-containing compound and a fluorine-based compound, preferably a liquid repellent having a crosslinking group (hereinafter sometimes referred to as a "crosslinking group-containing liquid repellent"). As a crosslinking group, an epoxy group or an ethylenically unsaturated group is mentioned, for example, Ethylenically unsaturated group is preferable from a viewpoint of suppressing the outflow of a liquid-repellent component to a developing solution. In the case of using a liquid-repelling agent containing a cross-linking group, when the formed coating film is exposed to light, the cross-linking reaction on the surface can be accelerated, and the liquid-repelling agent is difficult to flow out during the development process. The next door shows high ink repellency.

使用氟系化合物作為撥液劑的情況中，該氟化物在分隔壁的表面上定向，而會有發揮防止滲墨及混色之效果的傾向。更詳細而言，具有氟原子的基團，會有發揮防止印墨排斥、印墨超過分隔壁而進入相鄰區域導致滲墨或混色之效果的傾向。In the case of using a fluorine-based compound as the liquid repellant, the fluorine compound is oriented on the surface of the partition and tends to exhibit the effect of preventing bleeding and color mixing. More specifically, the group having a fluorine atom tends to exert the effect of preventing ink repelling, and the ink goes beyond the partition wall and enters the adjacent area to cause ink bleeding or color mixing.

作為撥液劑之氟系化合物的具體例，可舉例例如全氟烷磺酸、全氟烷羧酸、全氟烷基伸烷基氧化物加成物、全氟烷基三烷基銨鹽、包含全氟烷基與親水基的寡聚物、包含全氟烷基與親油基的寡聚物、包含全氟烷基、親水基與親油基的寡聚物、包含全氟烷基與親水基的胺基甲酸酯、全氟烷酯、全氟烷基磷酸酯等的含氟之有機化合物。 又，該等的化合物，較佳係具有環氧基作為交聯基，或是具有乙烯屬不飽和基以作為取代基。 作為該等的具有交聯基的含氟化合物的市售品，可使用下述商品名稱的市售含氟有機化合物：DIC公司製「MEGAFACE (註冊商標，以下相同)F116」、「MEGAFACE F120」、「MEGAFACE F142D」、「MEGAFACE F144D」、「MEGAFACE F150」、「MEGAFACE F160」、「MEGAFACE F171」、「MEGAFACE F172」、「MEGAFACE F173」、「MEGAFACE F177」、「MEGAFACE F178A」、「MEGAFACE F178K」、「MEGAFACE F179」、「MEGAFACE F183」、「MEGAFACE F184」、「MEGAFACE F191」、「MEGAFACE F812」、「MEGAFACE F815」、「MEGAFACE F824」、「MEGAFACE F833」、「MEGAFACE RS101」、「MEGAFACE RS102」「MEGAFACE RS105」、「MEGAFACE RS201」、「MEGAFACE RS202」、「MEGAFACE RS301」、「MEGAFACE RS303」、「MEGAFACE RS304」、「MEGAFACE RS401」、「MEGAFACE RS402」、「MEGAFACE RS501」、「MEGAFACE RS502」、「MEGAFACE RS-72-K」、「DEFENSA(註冊商標，以下相同)MCF300」、「DEFENSA MCF310」、「DEFENSA MCF312」、「DEFENSA MCF323」、3M Japan公司製「FLUORAD FC430」、「FLUORAD FC431」、「FC-4430」、「FC4432」、AGC公司製「AsahiGuard(註冊商標)AG710」、AGC SEIMI CHEMICAL公司製「SURFLON (註冊商標，以下相同)S-382」、「SURFLON SC-101」、「SURFLON SC-102」、「SURFLON SC-103」、「SURFLON SC-104」、「SURFLON SC-105」、「SURFLON SC-106」、大金工業公司製「OPTOOL(註冊商標)DAC-HP」等。Specific examples of the fluorine compound as the liquid repellant include, for example, perfluoroalkanesulfonic acid, perfluoroalkanecarboxylic acid, perfluoroalkylene oxide adducts, perfluoroalkyltrialkylammonium salts, including Oligomers of perfluoroalkyl and hydrophilic groups, oligomers of perfluoroalkyl and lipophilic groups, oligomers of perfluoroalkyl, hydrophilic and lipophilic groups, perfluoroalkyl and hydrophilic Fluorine-containing organic compounds such as urethanes, perfluoroalkyl esters, and perfluoroalkyl phosphates. Moreover, these compounds preferably have an epoxy group as a crosslinking group, or have an ethylenically unsaturated group as a substituent. As commercial products of such fluorine-containing compounds having a crosslinking group, commercially available fluorine-containing organic compounds with the following trade names: "MEGAFACE (registered trademark, the same hereinafter) F116" and "MEGAFACE F120" manufactured by DIC Corporation can be used. , "MEGAFACE F142D", "MEGAFACE F144D", "MEGAFACE F150", "MEGAFACE F160", "MEGAFACE F171", "MEGAFACE F172", "MEGAFACE F173", "MEGAFACE F177", "MEGAFACE F178A", "MEGAFACE F178K" , "MEGAFACE F179", "MEGAFACE F183", "MEGAFACE F184", "MEGAFACE F191", "MEGAFACE F812", "MEGAFACE F815", "MEGAFACE F824", "MEGAFACE F833", "MEGAFACE RS101", "MEGAFACE RS102" "MEGAFACE RS105", "MEGAFACE RS201", "MEGAFACE RS202", "MEGAFACE RS301", "MEGAFACE RS303", "MEGAFACE RS304", "MEGAFACE RS401", "MEGAFACE RS402", "MEGAFACE RS501", "MEGAFACE RS502", "MEGAFACE RS-72-K", "DEFENSA (registered trademark, the same below) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", 3M Japan Corporation "FLUORAD FC430", "FLUORAD FC431", "FC-4430", "FC4432", "AsahiGuard (registered trademark) AG710" manufactured by AGC Corporation, "SURFLON (registered trademark, the same below) S-382" manufactured by AGC SEIMI CHEMICAL Corporation, "SURFLON SC-101", "SURFLON SC-102", "SURFLON SC-103", "SURFLON SC-104", "SURFLON SC-105", "SURFLON SC-106", "OPTOOL (registered trademark) DAC-HP" manufactured by Daikin Industries, Ltd., etc.

如此，使用氟系化合物作為撥液劑的情況中，撥液劑中含有氟原子的比例並未特別限制，氟原子含量較佳為1質量%以上，更佳為5質量%以上，又，較佳為50質量%以下，更佳為25質量%以下。藉由使其在該下限值以上，會有呈現高接觸角的傾向，又，藉由使其在該上限值以下，會有可抑制撥液劑往像素部流出的傾向。作為撥液劑中含有氟原子的比例，例如為1~50質量%，較佳為5~25質量%。Thus, in the case of using a fluorine-based compound as the liquid-repellent agent, the proportion of fluorine atoms contained in the liquid-repellent agent is not particularly limited, and the content of fluorine atoms is preferably at least 1% by mass, more preferably at least 5% by mass, and more preferably It is preferably at most 50% by mass, more preferably at most 25% by mass. By making it more than this lower limit, it exists in the tendency for a high contact angle to appear, and also by making it below this upper limit, it exists in the tendency for a liquid-repellent agent to be suppressed to flow out to a pixel part. The ratio of fluorine atoms contained in the liquid-repellent agent is, for example, 1 to 50% by mass, preferably 5 to 25% by mass.

撥液劑的分子量並未特別限制，可為低分子量的化合物，亦可為高分子量體。高分子量體的撥液劑，可抑制因為後烘烤所造成之撥液劑的流動性，而能夠抑制撥液劑從堤流出，因而較佳，從此觀點來看，撥液劑的數量平均分子量較佳為100以上，更佳為500以上，再佳為100000以下，更佳為10000以下。作為撥液劑的分子量，例如，作為數量平均分子量，為100~100000、較佳為500~10000。The molecular weight of the liquid repelling agent is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. The liquid repellent of high molecular weight can suppress the fluidity of the liquid repellent caused by post-baking, and can inhibit the liquid repellent from flowing out from the embankment, so it is better. From this point of view, the number average molecular weight of the liquid repellent Preferably it is 100 or more, more preferably 500 or more, still more preferably 100,000 or less, more preferably 10,000 or less. The molecular weight of the liquid repellent is, for example, 100 to 100,000, preferably 500 to 10,000 as a number average molecular weight.

本發明之有色感光性樹脂組成物中的(D)撥液劑的含有比例並未特別限定，在總固體成分中，通常為0.01質量%以上，較佳為0.1質量%以上，更佳為0.5質量%以上，又，通常為5質量%以下，較佳為3質量%以下，更佳為2質量%以下。藉由使其在該下限值以上，會有呈現高撥墨性的傾向，又，藉由使其在該上限值以下，會有可抑制撥液劑往像素部流出的傾向。作為(D)撥液劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.01~5質量%，較佳為0.1~3質量%，更佳為0.5~2質量%。The content ratio of the (D) liquid-repelling agent in the colored photosensitive resin composition of the present invention is not particularly limited, but it is usually at least 0.01% by mass, preferably at least 0.1% by mass, and more preferably at least 0.5% by mass in the total solid content. % by mass or more, and usually not more than 5 mass %, preferably not more than 3 mass %, more preferably not more than 2 mass %. There exists a tendency for high ink repellency to be exhibited by making it more than this lower limit, and there exists a tendency for a liquid-repellent agent to be suppressed to flow out to a pixel part by making it below this upper limit. The content ratio of (D) liquid repellent in the total solid content of the colored photosensitive resin composition is, for example, 0.01-5% by mass, preferably 0.1-3% by mass, more preferably 0.5-2% by mass.

另一方面，本發明之有色感光性樹脂組成物，可與(D)撥液劑一起使用界面活性劑，又，亦可使用界面活性劑代替(D)撥液劑。界面活性劑，其使用目的是提升作為有色感光性樹脂組成物之塗布液的塗布性以及塗膜的顯影性等，其中，較佳為氟系或聚矽氧系的界面活性劑。 從顯影時特別具有從未曝光部去除有色感光性樹脂組成物之殘渣的作用，而且具有呈現潤濕性之功能，聚矽氧系界面活性劑為較佳；更佳為聚醚改質聚矽氧系界面活性劑。On the other hand, in the colored photosensitive resin composition of the present invention, a surfactant can be used together with the (D) liquid repellent, and a surfactant can also be used instead of the (D) liquid repellent. Surfactants are used for the purpose of improving the applicability of the coating solution as the colored photosensitive resin composition and the developability of the coating film. Among them, fluorine-based or polysiloxane-based surfactants are preferred. It has the function of removing the residue of the colored photosensitive resin composition from the unexposed part during development, and has the function of exhibiting wettability. Polysiloxane-based surfactants are preferred; more preferably polyether-modified polysilicon Oxygen-based surfactants.

作為氟系界面活性劑，較佳為在末端、主鏈及側鏈的至少任一部位具有氟烷基或氟伸烷基的化合物。具體而言，舉例如1,1,2,2-四氟辛基(1,1,2,2-四氟丙基)醚、1,1,2,2-四氟辛基己醚、八乙二醇二(1,1,2,2-四氟丁基)醚、六乙二醇二(1,1,2,2,3,3-六氟戊基)醚、八丙二醇二(1,1,2,2-四氟丁基)醚、六丙二醇二(1,1,2,2,3,3-六氟戊基)醚、全氟十二基磺酸鈉、1,1,2,2,8,8,9,9,10,10-十氟十二烷、1,1,2,2,3,3-六氟癸烷等。作為該等的市售品，例如，舉例如BM Chemie公司製「BM-1000」、「BM-1100」、DIC公司製「MEGAFACE F142D」、「MEGAFACE F172」、「MEGAFACE F173」、「MEGAFACE F183」、「MEGAFACE F470」、「MEGAFACE F475」、3M Japan公司製「FC430」、NEOS公司製「DFX-18」等。As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group at least any one of a terminal, a main chain, and a side chain is preferable. Specifically, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octafluorooctyl Ethylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis(1 ,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Such commercially available products include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie, "MEGAFACE F142D", "MEGAFACE F172", "MEGAFACE F173" and "MEGAFACE F183" manufactured by DIC Corporation , "MEGAFACE F470", "MEGAFACE F475", "FC430" manufactured by 3M Japan Corporation, "DFX-18" manufactured by NEOS Corporation, etc.

又，作為聚矽氧系界面活性劑，例如，舉例如TORAY・Dow Corning公司製「DC3PA」、「SH7PA」、「DC11PA」、「SH21PA」、「SH28PA」、「SH29PA」、「8032Additive」、「SH8400」、BYK公司製「BYK323」、「BYK330」等的市售品。 作為界面活性劑，亦可包含氟系界面活性劑及聚矽氧系界面活性劑以外的添加劑，此外，作為界面活性劑，舉例如非離子性、陰離子性、陽離子性、兩性界面活性劑等。In addition, examples of polysiloxane-based surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", " Commercially available products such as SH8400", "BYK323" and "BYK330" manufactured by BYK Corporation. Surfactants may contain additives other than fluorine-based surfactants and silicone-based surfactants, and examples of surfactants include nonionic, anionic, cationic, and amphoteric surfactants.

作為上述非離子性界面活性劑，例如，舉例如聚氧乙烯烷醚類、聚氧乙烯聚氧丙烯烷醚類、聚氧乙烯烷基苯醚類、聚氧乙烯烷酯類、聚氧乙烯脂肪酸酯類、甘油脂肪酸酯類、聚氧乙烯甘油脂肪酸酯類、新戊四醇脂肪酸酯類、聚氧乙烯新戊四醇脂肪酸酯類、山梨糖醇脂肪酸酯類、聚氧乙烯山梨糖醇脂肪酸酯類、山梨醇脂肪酸酯類、聚氧乙烯山梨醇脂肪酸酯類等。作為該等的市售品，例如，可列舉花王公司製的「EMULGEN (註冊商標，以下相同)104P」、「EMULGEN A60」等的聚氧乙烯系界面活性劑等。Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acids Esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, neopentylitol fatty acid esters, polyoxyethylene neopentylitol fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters Classes, sorbitol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Examples of such commercially available products include polyoxyethylene-based surfactants such as "EMULGEN (registered trademark, the same hereinafter) 104P" and "EMULGEN A60" manufactured by Kao Corporation.

又，作為上述陰離子性界面活性劑，舉例例如烷基磺酸鹽類、烷基苯磺酸鹽類、烷基萘磺酸鹽類、聚氧乙烯烷醚磺酸鹽類、烷基硫酸鹽類、烷基硫酸酯鹽類、高級醇硫酸酯鹽類、脂肪族醇硫酸酯鹽類、聚氧乙烯烷醚硫酸鹽類、聚氧乙烯烷基苯醚硫酸鹽類、烷基磷酸酯鹽類、聚氧乙烯烷醚磷酸鹽類、聚氧乙烯烷基苯醚磷酸鹽類、特殊高分子系界面活性劑等。其中，較佳為特殊高分子系界面活性劑，更佳為特殊多元羧酸型高分子系界面活性劑。作為這樣的陰離子性界面活性劑，可使用市售品，例如，烷基硫酸酯鹽類中舉例如花王公司製「AIMAR(註冊商標)10」等，烷基萘磺酸鹽類中舉例如花王公司製「PELEX(註冊商標)NB-L」等，特殊高分子系界面活性劑中舉例如花王公司製「HOMOGENOL (註冊商標，以下相同)L-18」、「HOMOGENOL L-100」等。In addition, examples of the above-mentioned anionic surfactants include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkyl ether sulfonates, and alkyl sulfates. , Alkyl sulfates, Higher alcohol sulfates, Aliphatic alcohol sulfates, Polyoxyethylene alkyl ether sulfates, Polyoxyethylene alkyl phenyl ether sulfates, Alkyl phosphate salts, Polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants, etc. Among them, a special polymeric surfactant is preferred, and a special polycarboxylic acid type polymeric surfactant is more preferred. As such an anionic surfactant, commercially available products can be used, for example, the alkyl sulfate ester salts such as "AIMAR (registered trademark) 10" manufactured by Kao Corporation, etc., the alkyl naphthalene sulfonates such as Kao "PELEX (registered trademark) NB-L" manufactured by the company, etc., and "HOMOGENOL (registered trademark, the same hereinafter) L-18" and "HOMOGENOL L-100" manufactured by Kao Corporation are examples of special polymer surfactants.

再者，作為上述陽離子性界面活性劑，舉例如4級銨鹽類、咪唑啉衍生物類、烷胺鹽類等，又，作為兩性界面活性劑，舉例如甜菜鹼型化合物類、咪唑鹽類、咪唑啉類、胺基酸類等。該等之中，較佳為4級銨鹽類、更佳為硬脂醯基三甲基銨鹽類。作為市售品，例如，烷胺鹽類舉例如花王公司製「ACETAMIN(註冊商標)24」等，4級銨鹽類舉例如花王公司製「QUARTAMIN (註冊商標，以下相同)24P」、「QUARTAMIN 86W」等。Furthermore, examples of the aforementioned cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts, and examples of amphoteric surfactants include betaine-type compounds and imidazolium salts. , imidazolines, amino acids, etc. Among these, quaternary ammonium salts are preferred, and stearyl trimethyl ammonium salts are more preferred. As commercially available products, for example, alkylamine salts such as "ACETAMIN (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "QUARTAMIN (registered trademark, the same below) 24P" manufactured by Kao Corporation, "QUARTAMIN 86W", etc.

又，界面活性劑亦可使用2種以上的組合，舉例例如聚矽氧系界面活性劑/氟系界面活性劑、聚矽氧系界面活性劑/特殊高分子系界面活性劑、氟系界面活性劑/特殊高分子系界面活性劑的組合等。其中，較佳為聚矽氧系界面活性劑/氟系界面活性劑的組合。該聚矽氧系界面活性劑/氟系界面活性劑的組合中，例如，舉例如NEOS公司製「DFX-18」、BYK公司製「BYK-300」或「BYK-330」/AGC SEIMI CHEMICAL公司製「S-393」、信越Silicone公司製「KP340」/DIC公司製「F-478」或「F-475」、TORAY・Dow Corning公司製「SH7PA」/大金公司製「DS-401」、NUC公司製「L-77」/3M Japan公司製「FC4430」等。In addition, a combination of two or more surfactants can be used, for example, silicone-based surfactant/fluorine-based surfactant, silicone-based surfactant/special polymer-based surfactant, fluorine-based surfactant agent/special polymer surfactant combination, etc. Among them, a combination of polysiloxane-based surfactant/fluorine-based surfactant is preferable. Among the silicone-based surfactant/fluorine-based surfactant combinations, for example, "DFX-18" manufactured by NEOS Corporation, "BYK-300" or "BYK-330" manufactured by BYK Corporation/AGC SEIMI CHEMICAL "S-393" manufactured by Shin-Etsu Silicone Co., Ltd. "KP340" manufactured by DIC Corporation/"F-478" or "F-475" manufactured by DIC Corporation, "SH7PA" manufactured by TORAY・Dow Corning Corporation/"DS-401" manufactured by Daikin Corporation, "L-77" manufactured by NUC Corporation / "FC4430" manufactured by 3M Japan Corporation, etc.

[1-1-5](E)著色劑 本發明之有色感光性樹脂組成物包含(E)著色劑。藉由包含(E)著色劑，可得到適當的光吸收性，特別是在形成有色分隔壁等的遮光構件之用途中使用的情況下，可得到適當的遮光性。[1-1-5] (E) Coloring agent The colored photosensitive resin composition of this invention contains (E) coloring agent. Appropriate light absorption can be obtained by including (E) a coloring agent, and when using it for the use which forms light-shielding members, such as a colored partition especially, appropriate light-shielding property can be acquired.

本發明中所使用的(E)著色劑的種類並未特別限制，可使用顏料、亦可使用染料。該等之中，從耐久性的觀點來看，較佳係使用顏料。The kind of (E) coloring agent used in this invention is not specifically limited, A pigment and a dye can also be used. Among them, it is preferable to use a pigment from the viewpoint of durability.

(E)著色劑所包含的顏料可為單獨1種，亦可為2種以上。特別是，從在可見光區域中均勻遮光的觀點來看，較佳為2種以上。 可作為(E)著色劑使用的顏料，其種類並未特別限定，舉例例如有機顏料或無機顏料。該等之中，從控制有色感光性樹脂組成物之穿透波長而有效率地硬化的觀點來看，較佳係使用有機顏料。 作為有機顏料，舉例如有機著色顏料或有機黑色顏料。此處，有機著色顏料係指呈現黑色以外之顏色的有機顏料，舉例如紅色顏料、橙色顏料、藍色顏料、紫色顏料、綠色顏料、黃色顏料等。(E) The pigment contained in a coloring agent may be single 1 type, and may be 2 or more types. In particular, from the viewpoint of uniform light shielding in the visible light region, two or more types are preferred. The type of the pigment that can be used as the (E) colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among them, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the colored photosensitive resin composition and efficiently curing it. As an organic pigment, an organic colored pigment or an organic black pigment is mentioned, for example. Here, the organic colored pigment refers to an organic pigment that exhibits a color other than black, such as a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, a yellow pigment, and the like.

有機顏料之中，從遮光性及紫外線吸收性的觀點來看，較佳為使用有機著色顏料。 有機著色顏料可單獨使用1種，亦可併用2種以上。特別是用於遮光性之用途的情況中，較佳為組合使用顏色不同的有機著色顏料，再佳為使用呈現接近黑色之有機著色顏料的組合。Among organic pigments, it is preferable to use organic coloring pigments from the viewpoint of light-shielding properties and ultraviolet absorbing properties. An organic coloring pigment may be used individually by 1 type, and may use 2 or more types together. In particular, when it is used for light-shielding applications, it is preferable to use a combination of organic coloring pigments having different colors, and it is more preferable to use a combination of organic coloring pigments showing close to black.

該等有機顏料的化學結構並未特別限定，舉例如偶氮系、酞花青系、喹吖酮系、苯并咪唑酮系、異吲哚啉酮系、雙噁嗪系、茚烷陰丹系、苝系等。以下，以顏料號數表示可使用之顏料的具體例。以下舉例的「C.I.顏料紅2」等的用語表示比色指數(C.I.)。The chemical structures of these organic pigments are not particularly limited, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, bisoxazine-based, indanindan Department, perylene system, etc. Hereinafter, the specific example of the pigment which can be used is shown by the pigment number. The terms such as "C.I. Pigment Red 2" exemplified below mean color index (C.I.).

作為紅色顏料，舉例如C.I.顏料紅1、2、3、4、5、6，7、8、9、12、14、15、16、17、21、22、23、31、32、37、38、41、47、48、48：1、48：2、48：3、48：4、49、49：1、49：2、50：1、52：1、52：2、53、53：1、53：2、53：3、57、57：1、57：2、58：4、60、63、63：1、63：2、64、64：1、68、69、81、81：1、81：2、81：3、81：4、83、88、90：1、101、101：1、104、108、108：1、109、112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、258、259、260、262、263、264、265、266、267、268、269、270、271、272、273、274、275、276。其中，從遮光性、分散性的觀點來看，較佳可舉例如C.I.顏料紅48：1、122、149、168、177、179、194、202、206、207、209、224、242、254，再佳可舉例如C.I.顏料紅177、209、224、254。另外，從分散性及遮光性的觀點來看，較佳為使用C.I.顏料紅177、254、272，以紫外線使有色感光性樹脂組成物硬化的情況中，較佳係使用紫外線吸收率低者作為紅色顏料，從此觀點來看，較佳係使用C.I.顏料紅254、272。Examples of red pigments include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38 , 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1 , 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1 , 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146 ,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202 ,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250 ,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276. Among them, preferred examples include C.I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 from the viewpoint of light-shielding properties and dispersibility. , more preferably for example C.I. Pigment Red 177, 209, 224, 254. In addition, it is preferable to use C.I. Pigment Red 177, 254, and 272 from the viewpoint of dispersibility and light-shielding properties. When curing a colored photosensitive resin composition with ultraviolet rays, it is preferable to use one with a low ultraviolet absorption rate as As the red pigment, from this point of view, C.I. Pigment Red 254 and 272 are preferably used.

作為橙色(橘)顏料，舉例如C.I.顏料橙1、2、5、13、16、17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79。其中，從分散性及遮光性的觀點來看，較佳係使用C.I.顏料橙13、43、64、72，以紫外線使有色感光性樹脂組成物硬化的情況中，較佳係使用紫外線吸收率低者作為橙色顏料，從此觀點來看，較佳為C.I.顏料橙64、72。Examples of orange (tangerine) pigments include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, it is preferable to use C.I. Pigment Orange 13, 43, 64, and 72 from the viewpoint of dispersibility and light-shielding properties, and when the colored photosensitive resin composition is cured by ultraviolet rays, it is preferable to use a resin with a low ultraviolet absorption rate. As the orange pigment, C.I. Pigment Orange 64 and 72 are preferable from this point of view.

作為藍色顏料，舉例如C.I.顏料藍1、1：2、9、14、15、15：1、15：2、15：3、15：4、15：6、16、17、19、25、27、28、29、33、35、36、56、56：1、60、61、61：1、62、63、66、67、68、71、72、73、74、75、76、78、79。其中，從遮光性的觀點來看，較佳可舉例如C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6、60，再佳可舉例如C.I.顏料藍15：6。 另外，從分散性及遮光性的觀點來看，較佳為使用C.I.顏料藍15：6、16、60，以紫外線使有色感光性樹脂組成物硬化的情況中，較佳為使用紫外線吸收率低者作為藍色顏料，從此觀點來看，較佳為使用C.I.顏料藍60。Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, from the viewpoint of light-shielding properties, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferable, and C.I. Pigment Blue is more preferable. 15:6. In addition, it is preferable to use C.I. Pigment Blue 15:6, 16, or 60 from the viewpoint of dispersibility and light-shielding properties, and when curing the colored photosensitive resin composition with ultraviolet light, it is preferable to use a product with a low ultraviolet absorption rate. As the blue pigment, it is preferable to use C.I. Pigment Blue 60 from this point of view.

作為紫色顏料，舉例如C.I.顏料紫1、1：1、2、2：2、3、3：1、3：3、5、5：1、14、15、16、19、23、25、27、29、31、32、37、39、42、44、47、49、50。其中，從遮光性的觀點來看，較佳可舉例如C.I.顏料紫19、23，再佳可舉例如C.I.顏料紫23。 另外，從分散性及遮光性的觀點來看，較佳為使用C.I.顏料紫23、29，以紫外線使有色感光性樹脂組成物硬化的情況中，較佳為使用紫外線吸收率低者作為紫色顏料，從此觀點來看，較佳為使用C.I.顏料紫29。As purple pigments, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27 , 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, C.I. Pigment Violet 19 and 23 are preferable, and C.I. Pigment Violet 23 is more preferable from the viewpoint of light-shielding properties. In addition, it is preferable to use C.I. Pigment Violet 23 and 29 from the viewpoint of dispersibility and light-shielding properties. When curing a colored photosensitive resin composition with ultraviolet rays, it is preferable to use one with a low ultraviolet absorption rate as a purple pigment. , from this point of view, it is preferable to use C.I. Pigment Violet 29.

除了紅色顏料、橙色顏料、藍色顏料、紫色顏料以外，作為其他可使用的有機著色顏料，例如，舉例如綠色顏料、黃色顏料等。 作為綠色顏料，舉例如C.I.顏料綠1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55。其中，較佳舉例如C.I.顏料綠7、36。 作為黃色顏料，舉例如C.I.顏料黃1、1：1、2、3、4、5、6、9、10、12、13、14、16、17、24、31、32、34、35、35：1、36、36：1、37、37：1、40、41、42、43、48、53、55、61、62、62：1、63、65、73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、126、127、127：1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191：1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208。其中，較佳可舉例如C.I.顏料黃83、117、129、138、139、150、154、155、180、185，再佳可舉例如C.I.顏料黃83、138、139、150、180。In addition to red pigments, orange pigments, blue pigments, and violet pigments, other usable organic coloring pigments include, for example, green pigments, yellow pigments, and the like. Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55. Among them, C.I. Pigment Green 7 and 36 are preferable examples. Examples of yellow pigments include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83 ,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134 ,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170 ,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199 , 200, 202, 203, 204, 205, 206, 207, 208. Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable, and C.I. Pigment Yellow 83, 138, 139, 150, 180 are more preferable.

該等之中，從遮光性及形狀控制的觀點來看，較佳係使用選自紅色顏料、橙色顏料、藍色顏料及紫色顏料所構成之群組中的至少1種。Among them, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and purple pigments from the viewpoint of light-shielding properties and shape control.

該等之中，從遮光性及形狀控制的觀點來看，較佳係包含以下顏料之中的至少1種以上。 紅色顏料：C.I.顏料紅177、254、272 橙色顏料：C.I.顏料橙43、64、72 藍色顏料：C.I.顏料藍15：6、60 紫色顏料：C.I.顏料紫23、29Among them, it is preferable to contain at least one or more of the following pigments from the viewpoint of light-shielding property and shape control. Red Pigment: C.I. Pigment Red 177, 254, 272 Orange Pigment: C.I. Pigment Orange 43, 64, 72 Blue Pigment: C.I. Pigment Blue 15: 6, 60 Violet Pigment: C.I. Pigment Violet 23, 29

又，併用2種以上有機著色顏料的情況中，針對有機著色顏料的組合並未特別限定，從遮光性的觀點來看，較佳係含有選自紅色顏料及橙色顏料所構成之群組中的至少1種與選自藍色顏料及紫色顏料所構成之群組中的至少1種。 另外，顏色的組合並未特別限定，從遮光性的觀點來看，例如，舉例如紅色顏料與藍色顏料的組合、藍色顏料與橙色顏料的組合、藍色顏料與橙色顏料與紫色顏料的組合等。Also, in the case of using two or more organic coloring pigments in combination, the combination of organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, it is preferable to contain one selected from the group consisting of red pigments and orange pigments. at least one and at least one selected from the group consisting of blue pigments and purple pigments. In addition, the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a purple pigment combination etc.

再者，除了該等的有機著色顏料以外，亦可使用黑色顏料。又，除了有機著色顏料以外，亦可更使用黑色顏料。 作為黑色顏料，舉例如無機黑色顏料及有機黑色顏料，但從遮光性的觀點來看，較佳為含有碳黑及/或有機黑色顏料。In addition, a black pigment can also be used other than these organic coloring pigments. Moreover, you may use a black pigment other than an organic coloring pigment. As a black pigment, an inorganic black pigment and an organic black pigment are mentioned, for example, However, From a light-shielding viewpoint, it is preferable to contain carbon black and/or an organic black pigment.

黑色顏料之中，從抑制紫外線的吸收而可輕易控制形狀及段差的觀點來看，較佳係使用有機黑色顏料，特別是從遮光性的觀點來看，較佳係使用包含選自以下述通式(1)所表示之化合物(以下亦稱為「化合物(1)」)、化合物(1)的幾何異構物、化合物(1)的鹽、以及化合物(1)的幾何異構物的鹽所構成之群組中之至少1種的有機黑色顏料(以下有時亦稱為「以通式(1)所表示之有機黑色顏料」)。Among the black pigments, it is preferable to use organic black pigments from the viewpoint of suppressing the absorption of ultraviolet rays to easily control the shape and level difference, and especially from the viewpoint of light-shielding properties, it is preferable to use organic black pigments selected from the group consisting of: Compound represented by formula (1) (hereinafter also referred to as "compound (1)"), geometric isomer of compound (1), salt of compound (1), and salt of geometric isomer of compound (1) At least one organic black pigment (hereinafter sometimes referred to as "the organic black pigment represented by the general formula (1)") in the formed group.

[化學式49]

Figure 02_image091
[chemical formula 49]
Figure 02_image091

式(1)中，R11 及R16 分別獨立表示氫原子、CH3 、CF3 、氟原子或氯原子； R12 、R13 、R14 、R15 、R17 、R18 、R19 及R20 分別獨立表示氫原子、鹵素原子、R21 、COOH、COOR21 、COO- 、CONH2 、CONHR21 、CONR21 R22 、CN、OH、OR21 、COCR21 、OOCNH2 、OOCNHR21 、OOCNR21 R22 、NO2 、NH2 、NHR21 、NR21 R22 、NHCOR22 、NR21 COR22 、N＝CH2 、N＝CHR21 、N＝CR21 R22 、SH、SR21 、SOR21 、SO2 R21 、SO3 R21 、SO3 H、SO3 - 、SO2 NH2 、SO2 NHR21 或SO2 NR21 R22 ；且選自R12 與R13 、R13 與R14 、R14 與R15 、R17 與R18 、R18 與R19 、及R19 與R20 所構成之群組的至少1個組合，亦可互相直接鍵結，或亦可藉由氧原子、硫原子、NH或NR21 橋接互相鍵結；R21 及R22 分別獨立表示碳數1~12的烷基、碳數3~12的環烷基、碳數2~12的烯基、碳數3~12的環烯基或碳數2~12的炔基。In formula (1), R 11 and R 16 independently represent a hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 independently represent hydrogen atom, halogen atom, R 21 , COOH, COOR 21 , COO - , CONH 2 , CONHR 21 , CONR 21 R 22 , CN, OH, OR 21 , COCR 21 , OOCNH 2 , OOCNHR 21 , OOCNR 21 R 22 , NO 2 , NH 2 , NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 , N=CH 2 , N=CHR 21 , N=CR 21 R 22 , SH, SR 21 , SOR 21 , SO 2 R 21 , SO 3 R 21 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 21 or SO 2 NR 21 R 22 ; and selected from R 12 and R 13 , R 13 and R 14 , at least one combination of the group consisting of R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 may be directly bonded to each other, or may be bonded via an oxygen atom , sulfur atom, NH or NR 21 are bridged and bonded to each other; R 21 and R 22 independently represent alkyl with 1 to 12 carbons, cycloalkyl with 3 to 12 carbons, alkenyl with 2 to 12 carbons, carbon Cycloalkenyl with 3 to 12 carbons or alkynyl with 2 to 12 carbons.

化合物(1)及化合物(1)的幾何異構物，具有以下的核心結構(其中省略結構式中的取代基)，其中順-反異構物應為最穩定。Compound (1) and the geometric isomers of compound (1) have the following core structure (wherein the substituents in the structural formula are omitted), and the cis-trans isomer should be the most stable.

[化學式50]

Figure 02_image093
[chemical formula 50]
Figure 02_image093

化合物(1)為陰離子性的情況，較佳係藉由任意習知適合的陽離子補償其電荷的鹽，該陽離子例如為金屬、有機、無機或有機金屬陽離子，具體係以鹼金屬、鹼土類金屬、過渡金屬、一級銨、二級銨、三烷基銨等的三級銨、四烷基銨等的四級銨或有機金屬錯合物進行補償的鹽。又，化合物(1)的幾何異構物為陰離子性的情況，較佳為相同的鹽。In the case that the compound (1) is anionic, it is preferably a salt whose charge is compensated by any known suitable cation, such as a metal, organic, inorganic or organometallic cation, specifically an alkali metal, alkaline earth metal , transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexes for compensation. Also, when the geometric isomer of compound (1) is anionic, the same salt is preferred.

通式(1)的取代基及該等的定義中，從遮蔽率變高的傾向來看，較佳如下。這被認為係因為以下的取代基無吸收，而不會影響顏料的色相。 R12 、R14 、R15 、R17 、R19 及R20 分別獨立，較佳為氫原子、氟原子或氯原子，再佳為氫原子。 R13 及R18 分別獨立，較佳為氫原子、NO2 、OCH3 、OC2 H5 、溴原子、氯原子、CH3 、C2 H5 、N(CH3 )2 、N(CH3 )(C2 H5 )、N(C2 H5 )2 、α-萘基、β-萘基、SO3 H或SO3 - ，再佳為氫原子或SO3 H，特佳為氫原子。Among the substituents of the general formula (1) and their definitions, the following are preferable from the viewpoint of the tendency that the shielding ratio becomes high. This is considered to be because the following substituents have no absorption and do not affect the hue of the pigment. R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently, preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom. R 13 and R 18 are independent, preferably hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 )(C 2 H 5 ), N(C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 - , more preferably a hydrogen atom or SO 3 H, especially preferably a hydrogen atom .

R11 及R16 分別獨立，較佳為氫原子、CH3 或CF3 ，再佳為氫原子。 較佳係選自R11 與R16 、R12 與R17 、R13 與R18 、R14 與R19 、及R15 與R20 所構成之群組中的至少1個組合相同，更佳為R11 與R16 相同、R12 與R17 相同、R13 與R18 相同、R14 與R19 相同、且R15 與R20 相同。R 11 and R 16 are independent, preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom. Preferably at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably R11 is the same as R16 , R12 is the same as R17 , R13 is the same as R18 , R14 is the same as R19 , and R15 is the same as R20 .

碳數1~12的烷基，例如甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、2-甲基丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、正己基、正庚基、正辛基、1,1,3,3-四甲基丁基、2-乙基己基、壬基、癸基、十一基或十二基。Alkyl groups with 1 to 12 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, third-butyl, 2-methylbutyl, n-butyl Pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2- Ethylhexyl, nonyl, decyl, undecyl or dodecyl.

碳數3~12的環烷基，例如環丙基、環丙基甲基、環丁基、環戊基、環己基、環己基甲基、三甲基環己基、

Figure 02_image095
基(thujyl)、降莰基、莰基、降蒈基(norcaryl)、蒈基(caryl)、薄荷腦基(menthyl)、降菔基(Norpinyl)、蒎烷基(pinyl)、金剛烷-1-基或金剛烷-2-基。Cycloalkyl with 3 to 12 carbons, such as cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl,
Figure 02_image095
Thujyl, Norcamyl, Camphenyl, Norcaryl, Caryl, Menthyl, Norpinyl, Pinyl, Adamantane-1 -yl or adamantane-2-yl.

碳數2~12的烯基，例如乙烯基、烯丙基、2-丙烯-2-基、2-丁烯-1-基、3-丁烯-1-基、1,3-丁二烯-2-基、2-戊烯-1-基、3-戊烯-2-基、2-薄荷腦基-1-丁烯-3-基、2-甲基-3-丁烯-2-基、3-甲基-2-丁烯-1-基、1,4-戊二烯-3-基、己烯基、辛烯基、壬烯基、癸烯基或十二烯基。Alkenyl with 2~12 carbons, such as vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene -2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-menthol-1-buten-3-yl, 2-methyl-3-butene-2- 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

碳數3~12的環烯基，例如2-環丁烯-1-基、2-環戊烯-1-基、2-環己烯-1-基、3-環己烯-1-基、2,4-環己二烯-1-基、1-對䓝烯-8-基、4(10)-側柏烯-10-基、2-降莰烯-1-基、2,5-二環庚二烯-1-基、7,7-二甲基-2,4-降蒈二烯-3-基或莰烯基(camphenyl)。Cycloalkenyl with 3~12 carbons, such as 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl , 2,4-cyclohexadien-1-yl, 1-p-pentene-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5 - bicycloheptadien-1-yl, 7,7-dimethyl-2,4-norcaren-3-yl or camphenyl.

碳數2~12的炔基，例如為1-丙炔-3-基、1-丁炔-4-基、1-戊炔-5-基、2-甲基-3-丁炔-2-基、1,4-戊二炔-3-基、1,3-戊二炔-5-基、1-己炔-6-基、順-3-甲基-2-戊烯-4-炔-1-基、反-3-甲基-2-戊烯-4-炔-1-基、1,3-六二炔-5-基、1-辛炔-8-基、1-壬炔-9-基、1-癸炔-10-基或1-十二炔-12-基。Alkynyl with 2 to 12 carbons, such as 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2- Base, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yne -1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyne -9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

鹵素原子為例如氟原子、氯原子、溴原子或碘原子。The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

該以通式(1)所表示之有機黑色顏料，較佳為包含選自以下述通式(2)所表示之化合物(以下亦稱為「化合物(2)」)及化合物(2)的幾何異構物所構成之群組中之至少1種的有機黑色顏料。The organic black pigment represented by general formula (1) preferably comprises a compound (hereinafter also referred to as "compound (2)") and compound (2) selected from compounds represented by general formula (2) below. An organic black pigment of at least one type in the group consisting of isomers.

[化學式51]

Figure 02_image097
[chemical formula 51]
Figure 02_image097

作為這樣的有機黑色顏料的具體例，舉例如商品名Irgaphor(註冊商標)Black S 0100 CF(BASF公司製)。 該有機黑色顏料，較佳係藉由後述分散劑、溶劑、方法分散而使用。又，分散時若存在化合物(1)的磺酸衍生物，特別是化合物(2)的磺酸衍生物，則會有分散性及保存性提升的情況，因此有機黑色顏料較佳係包含該等的磺酸衍生物。As a specific example of such an organic black pigment, a brand name Irgaphor (registered trademark) Black S 0100 CF (made by BASF Corporation) is mentioned, for example. The organic black pigment is preferably used by dispersing it with a dispersant, a solvent, and a method described later. Also, if there is a sulfonic acid derivative of compound (1), especially a sulfonic acid derivative of compound (2) during dispersion, the dispersibility and storage stability will be improved, so the organic black pigment preferably contains these sulfonic acid derivatives.

作為以該通式(1)所表示之有機黑色顏料以外的有機黑色顏料，舉例例如苯胺黑及苝黑等。Examples of organic black pigments other than the organic black pigment represented by the general formula (1) include aniline black, perylene black, and the like.

另一方面，作為無機黑色顏料，舉例如碳黑、乙炔黑、燈黑、骨黑、石墨、鐵黑、花青黑、鈦黑等。該等之中，從遮光性、影像特性的觀點來看，較佳可使用碳黑。作為碳黑的例子，舉例如下的碳黑。On the other hand, examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, titanium black, and the like. Among them, carbon black is preferably used from the viewpoint of light-shielding properties and image characteristics. As an example of carbon black, the following carbon black is exemplified.

三菱化學公司製：MA7、MA8、MA11、MA77、MA100、MA100R、MA100S、MA220、MA230、MA600、MCF88、＃5、＃10、＃20、＃25、＃30、＃32、＃33、＃40、＃44、＃45、＃47、＃50、＃52、＃55、＃650、＃750、＃850、＃900、＃950、＃960、＃970、＃980、＃990、＃1000、＃2200、＃2300、＃2350、＃2400、＃2600、＃2650、＃3030、＃3050、＃3150、＃3250、＃3400、＃3600、＃3750、＃3950、＃4000、＃4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31B Degussa公司製：Printex(註冊商標，以下相同)3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170 CABOT公司製：Monarch(註冊商標，以下相同)120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL(註冊商標，以下相同)99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN(註冊商標，以下相同)XC72R、ELFTEX(註冊商標)-8 BIRLA公司製：RAVEN(註冊商標，以下相同)11、RAVEN14、RAVEN15、RAVEN16、RAVEN22、RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000。Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B . , Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color0 Black FW2 Color Black S160, Color Black S170 Manufactured by CABOT: Monarch (registered trademark, hereinafter the same) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter the same) 99 , REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark)-8 Made by BIRLA: RAVEN (registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000。

亦可使用被樹脂所被覆的碳黑。若使用被樹脂所被覆的碳黑，則會有對於玻璃基板的密合性及體積電阻值提升的效果。作為被樹脂被覆的碳黑，較佳可使用例如日本特開平09-71733號公報所記載之碳黑等。從體積電阻及介電常數的觀點來看，較佳係使用樹脂被覆碳黑。Carbon black coated with resin can also be used. When carbon black coated with resin is used, the adhesiveness to the glass substrate and the effect of improving the volume resistance value are obtained. As the carbon black coated with the resin, for example, carbon black described in JP-A-09-71733, etc. can be preferably used. From the viewpoint of volume resistance and dielectric constant, it is preferable to use resin-coated carbon black.

作為用於進行樹脂之被覆處理的碳黑，較佳係Na與Ca的總含量在100ppm以下。碳黑通常含有灰分，而該灰分的組成係從製造時的原料油、燃燒油(或氣體)、反應停止水或造粒水、甚至是反應爐的爐材等混入的Na、Ca、K、Mg、Al、Fe等。其中，一般係分別含有Na及Ca數百ppm以上，但藉由減少此等成分，會有抑制對於透明電極(ITO)及其他電極的浸透，而可防止電性短路的傾向。As the carbon black used for resin coating treatment, the total content of Na and Ca is preferably 100 ppm or less. Carbon black usually contains ash, and the composition of the ash is Na, Ca, K, Mg, Al, Fe, etc. Among them, Na and Ca are generally contained in hundreds of ppm or more, but by reducing these components, there is a tendency to suppress penetration into transparent electrodes (ITO) and other electrodes, and prevent electrical short circuits.

作為減少包含該等Na及Ca之灰分的含量的方法，可嚴謹選擇該等成分含量極少的原料以作為製造碳黑時的原料油及燃油(或氣體)以及反應終止水，以及可將用以調整結構的鹼物質之添加量極力減少。作為其另一方法，舉例如以水或鹽酸等清洗從爐製造出來的碳黑而將Na及Ca溶解並去除的方法。As a method of reducing the content of ash containing these Na and Ca, raw materials with very little content of these components can be carefully selected as raw material oil and fuel oil (or gas) and reaction terminated water when producing carbon black, and can be used for The amount of alkali substances to adjust the structure is reduced as much as possible. Another method thereof is, for example, a method of washing carbon black produced from a furnace with water or hydrochloric acid to dissolve and remove Na and Ca.

具體而言，若將碳黑混合分散於水、鹽酸、或過氧化氫水之後，添加難溶於水的溶劑，則碳黑轉移至溶劑側，在與水完全分離的同時，幾乎所有存在於碳黑中的Na及Ca幾乎溶解於水或酸而被去除。為了將Na與Ca的總量降低至100ppm以下，雖然有時亦單獨使用嚴謹選擇原材料的碳黑製造過程或是單獨使用以水或酸溶解的方式，但藉由併用這兩種方式，可更容易使Na與Ca的總量在100ppm以下。Specifically, if carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide water, and a solvent that is poorly soluble in water is added, the carbon black is transferred to the solvent side, and while it is completely separated from water, almost all of the Na and Ca in carbon black are almost dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to less than 100ppm, although the carbon black manufacturing process that carefully selects raw materials or the method of dissolving in water or acid is used alone, it can be more effective by using these two methods together. It is easy to make the total amount of Na and Ca 100 ppm or less.

又，樹脂被覆碳黑，較佳為pH6以下的所謂酸性碳黑。因為在水中的分散直徑(黏聚物(agglomerate)直徑)小，可進行細微單元的被覆，因而較佳。更佳為平均粒徑在40nm以下、酞酸二丁酯(DBP)吸收量在140mL/100g以下。藉由在該範圍內，會有可得到遮光性良好之塗膜的傾向。平均粒徑係指數量平均粒徑，係指藉由電子顯微鏡觀察，拍攝多個以數萬倍拍攝的影像，再由影像處理裝置對該等影像中的2000~3000個左右的粒子進行量測之由粒子影像解析所求得的等效圓直徑。Also, the resin-coated carbon black is preferably a so-called acid carbon black with a pH of 6 or less. It is preferable because the dispersion diameter (agglomerate diameter) in water is small and coating of fine units is possible. More preferably, the average particle diameter is below 40nm, and the absorption of dibutyl phthalate (DBP) is below 140mL/100g. By being within this range, there exists a tendency for the coating film with favorable light-shielding property to be obtained. The average particle size refers to the quantitative average particle size, which refers to the observation of electron microscopes, taking multiple images taken at tens of thousands of times, and then measuring about 2,000 to 3,000 particles in these images by an image processing device The equivalent circle diameter obtained from particle image analysis.

調製被樹脂被覆之碳黑的方法並無特別限定，例如，可在適當調整碳黑及樹脂的摻合量之後，採用1.將使樹脂與環己酮、甲苯、二甲苯等的溶劑混合並使其加熱溶解的樹脂溶液、使碳黑及水混合的懸濁液混合攪拌，使碳黑與水分離後，去除水以進行加熱揉合而得到組成物，再使該組成物形成片狀，並且進行粉碎後，再使其乾燥的方法；2.將與上述相同地調製的樹脂溶液與懸濁液混合攪拌，使碳黑及樹脂粒狀化之後，將所得之粒狀物分離、加熱，去除殘存之溶劑及水的方法；3.使馬來酸、富馬酸等的羧酸溶解於上述例示的溶劑中，添加碳黑，進行混合並使其乾燥，去除溶劑得到羧酸浸染碳黑後，對其添加樹脂以進行乾式混合的方法；4.將構成被覆樹脂的含反應性基之單體成分與水高速攪拌，以調製懸濁液，使其聚合後冷卻，從聚合物懸濁液得到含有反應性基之樹脂後，將碳黑添加至其中並進行揉合，使碳黑與反應性基進行反應(使碳黑接枝)、再進行冷卻及粉碎的方法等。The method of preparing resin-coated carbon black is not particularly limited. For example, after properly adjusting the blending amount of carbon black and resin, 1. mixing the resin with a solvent such as cyclohexanone, toluene, xylene, and The heat-dissolved resin solution and the suspension mixed with carbon black and water were mixed and stirred to separate the carbon black and water, and then the water was removed to heat and knead to obtain a composition, and then the composition was formed into a sheet, And the method of drying after pulverization; 2. Mixing and stirring the resin solution and the suspension prepared in the same manner as above, and granulating the carbon black and resin, separating and heating the obtained granules, The method of removing the remaining solvent and water; 3. Dissolving carboxylic acids such as maleic acid and fumaric acid in the above-mentioned solvents, adding carbon black, mixing and drying, and removing the solvent to obtain carboxylic acid impregnated carbon black After that, add resin to it for dry mixing method; 4. Stir the reactive group-containing monomer components constituting the coating resin with water at high speed to prepare a suspension, polymerize it and cool it, and suspend it from the polymer After the resin containing the reactive group is obtained, carbon black is added to it and kneaded, the carbon black and the reactive group are reacted (grafting the carbon black), and then cooled and pulverized.

被覆處理的樹脂，其種類亦無特別限定，一般為合成樹脂，而結構中具有苯環的樹脂，其作為兩性系界面活性劑的效果更強，因此從分散性及分散穩定性的觀點來看更佳。 作為具體的合成樹脂，可使用酚樹脂、三聚氰胺樹脂、二甲苯樹脂、鄰苯二甲酸二烯丙酯樹脂、甘酞樹脂(glyptal resin)、環氧樹脂、烷基苯樹脂等的熱硬化性樹脂，或聚苯乙烯、聚碳酸酯、聚對酞酸乙二酯、聚對酞酸丁二酯、改質聚伸苯基氧化物、聚碸、聚對苯二甲醯對苯二胺、聚醯胺醯亞胺、聚醯亞胺、聚胺基雙馬來醯亞胺、聚醚碸、聚苯碸、聚芳酯、聚醚醚酮等的熱塑性樹脂。被覆樹脂的量，相對於碳黑與樹脂的總量，較佳為1~30質量%。藉由使其在該下限值以上，會有可充分被覆的傾向。另一方面，藉由使其在該上限值以下，會有可防止樹脂彼此黏著而分散性良好的傾向。The type of resin to be coated is not particularly limited. It is generally a synthetic resin, and a resin with a benzene ring in its structure has a stronger effect as an amphoteric surfactant. Therefore, from the perspective of dispersibility and dispersion stability better. As specific synthetic resins, thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins can be used. , or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene oxide, polypyrene, polyparaphenylene terephthalamide, poly Thermoplastic resins such as amidoimide, polyimide, polyaminobismaleimide, polyether, polyphenylene, polyarylate, polyether ether ketone, etc. The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of carbon black and resin. There exists a tendency for sufficient covering to be possible by making it more than this lower limit. On the other hand, by making it below this upper limit, it exists in the tendency for resins to be prevented from sticking together and dispersibility to be favorable.

如此以樹脂進行被覆處理的碳黑，可依照一般方法將其作為有色分隔壁的著色劑使用。若使用這樣的碳黑，則會有可以低成本形成高遮光率且表面反射率低之有色分隔壁的傾向。又，亦推測藉由以樹脂被覆碳黑表面，會有將包含Na及Ca的灰分封入碳黑之中的效果。Carbon black coated with a resin in this way can be used as a colorant for colored partition walls according to a general method. When such carbon black is used, it tends to be possible to form a colored partition having a high light-shielding rate and low surface reflectance at low cost. In addition, it is also speculated that by covering the surface of carbon black with a resin, there is an effect of encapsulating ash including Na and Ca in carbon black.

該等的顏料，較佳係分散使用，以使平均粒徑通常為1μm以下，較佳為0.5μm以下，再佳為0.25μm以下。此處平均粒徑的基準為顏料粒子的數量。 又，顏料的平均粒徑，係從以動態光散射(DLS)所測量之顏料粒徑求得的值。粒徑測量，係在25℃下對於經充分稀釋的有色感光性樹脂組成物(通常進行稀釋以將顏料濃度調製為0.005~0.2質量%左右。然而，若有來自測量設備所建議之濃度，則依照其濃度)進行測量。These pigments are preferably used in dispersion so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. The basis of the average particle diameter here is the number of pigment particles. In addition, the average particle diameter of a pigment is a value calculated|required from the particle diameter of the pigment measured by dynamic light scattering (DLS). Particle size measurement is based on the fully diluted colored photosensitive resin composition at 25°C (usually diluted to adjust the pigment concentration to about 0.005~0.2% by mass. However, if there is a concentration recommended from the measurement equipment, then according to its concentration).

又，除了上述的有機著色顏料、黑色顏料以外，亦可使用染料。可作為著色劑使用的染料，舉例如偶氮系染料、蒽醌系染料、酞花青系染料、醌亞胺系染料、喹啉系染料、硝基系染料、羰基系染料、次甲基系染料等。 作為偶氮系染料，舉例例如C.I.酸性黃11、C.I.酸性橙7、C.I.酸性紅37、C.I.酸性紅180、C.I.酸性藍29、C.I.直接紅28、C.I.直接紅83、C.I.直接黃12、C.I.直接橙26、C.I.直接綠28、C.I.直接綠59、C.I.活性黃2、C.I.活性紅17、C.I.活性紅120、C.I.活性黑5、C.I.分散橙5、C.I.分散紅58、C.I.分散藍165、C.I.鹼性藍41、C.I. 鹼性紅18、C.I.媒介紅7、C.I. 媒介黃5、C.I. 媒介黑7等。Moreover, besides the above-mentioned organic coloring pigments and black pigments, dyes can also be used. Dyes that can be used as coloring agents include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes Dyes etc. Examples of azo dyes include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Active Yellow 2, C.I. Active Red 17, C.I. Active Red 120, C.I. Active Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Alkaline Sexual Blue 41, C.I. Basic Red 18, C.I. Medium Red 7, C.I. Medium Yellow 5, C.I. Medium Black 7, etc.

作為蒽醌系染料，舉例例如C.I.還原藍4、C.I.酸性藍40、C.I.酸性綠25、C.I.活性藍19、C.I.活性藍49、C.I.分散紅60、C.I.分散藍56、C.I.分散藍60等。 其他，作為酞花青系染料，舉例例如C.I.還原藍5等，作為醌亞胺系染料，舉例例如C.I.鹼性藍3、C.I.鹼性藍9等，作為喹啉系染料，舉例例如C.I.溶劑黃33、C.I.酸性黃3、C.I.分散黃64等，作為硝基系染料，舉例例如C.I.酸性黃1、C.I.酸性橙3、C.I.分散黃42等。Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60. In addition, as phthalocyanine dyes, for example, C.I. Vat Blue 5, etc., as quinone imine dyes, for example, C.I. Basic Blue 3, C.I. Basic Blue 9, etc., as quinoline dyes, for example, C.I. Solvent Yellow 33. C.I. Acid Yellow 3, C.I. Disperse Yellow 64, etc. Examples of nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42.

本發明之有色感光性樹脂組成物中的(E)著色劑的含有比例，在總固體成分中為20質量%以下。如此，在著色劑的含有比例少的情況下，認為著色劑不會阻礙撥液劑在表面的定向，在塗布乾燥時成為大量撥液劑定向於塗膜表面的狀態，而無法充分鍵結於膜表面的撥液劑大多在顯影時流失，又，即使加熱硬化撥液劑亦不會從膜內部補充至表面，因此會有所得之分隔壁的撥墨性變低的傾向。因此，著色劑的含有比例少的情況中，如前所述，認為可藉由使用特定的鹼可溶性樹脂，以化學鍵穩固地捕捉在塗膜表面定向的撥液劑，而能夠提高撥墨性。The content rate of (E) coloring agent in the colored photosensitive resin composition of this invention is 20 mass % or less in total solid content. In this way, when the content ratio of the coloring agent is small, it is considered that the coloring agent does not hinder the orientation of the liquid-repelling agent on the surface, and when the coating is dried, a large amount of the liquid-repelling agent is oriented on the surface of the coating film, and cannot be sufficiently bonded to the surface of the coating film. The liquid repellant on the surface of the film is mostly lost during development, and the liquid repellent is not replenished from the inside of the film to the surface even if it is heated and hardened, so the ink repellency of the resulting partition tends to be lowered. Therefore, when the content ratio of the coloring agent is small, as mentioned above, it is considered that the liquid-repelling agent oriented on the surface of the coating film can be stably captured with a chemical bond by using a specific alkali-soluble resin, thereby improving the ink-repelling property.

又，著色劑的含有比例高的情況中，會有發生表面粗糙的情況。這被認為是因為著色劑多而導致到達塗膜表面與塗膜內部的紫外線量不同，使得光硬化性產生差異，在後烘烤時表面與內部的收縮性不同，因此在塗膜表面發生表面粗糙。表面粗糙嚴重的情況，在分隔壁上積層電極或其他有機層時難以製作均勻的層，因此較佳係抑制表面粗糙，但因為本發明之有色感光性樹脂組成物中著色劑的含有比例低，所以塗膜表面與塗膜內部的光硬化性的差異變少，因而認為可抑制表面粗糙。Moreover, when the content rate of a coloring agent is high, surface roughness may generate|occur|produce. This is considered to be due to the difference in the amount of ultraviolet light reaching the surface of the coating film and the inside of the coating film due to the large amount of colorant, resulting in a difference in photocurability, and the difference in shrinkage between the surface and the inside of the coating film during post-baking, so that surface damage occurs on the surface of the coating film. rough. In the case of severe surface roughness, it is difficult to form a uniform layer when laminating electrodes or other organic layers on the partition wall. Therefore, it is preferable to suppress surface roughness. However, since the colorant content in the colored photosensitive resin composition of the present invention is low, Therefore, the difference in photocurability between the surface of the coating film and the interior of the coating film is reduced, and it is considered that surface roughness can be suppressed.

本發明之有色感光性樹脂組成物中的(E)著色劑的含有比例，在總固體成分中，只要在20質量%以下則無特別限定，較佳為18質量%以下，更佳為15質量%以下，再佳為12質量%以下，特佳為10質量%以下，又，較佳為2質量%以上，更佳為3質量%以上，再佳為4質量%以上，特佳為5質量%以上。藉由使其在該上限值以下，因為可相對地增加鹼可溶性樹脂、乙烯屬不飽和化合物，而會有塗膜的硬化性、撥墨性提升的傾向，又，藉由使其在該下限值以上，會有可確保遮光性的傾向。作為(E)著色劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為2~20質量%，較佳為2~18質量%，更佳為3~15質量%，再佳為4~12質量%，再更佳為5~10質量%。The content ratio of the (E) colorant in the colored photosensitive resin composition of the present invention is not particularly limited as long as it is 20% by mass or less in the total solid content, but is preferably 18% by mass or less, more preferably 15% by mass % or less, more preferably less than 12 mass %, particularly preferably less than 10 mass %, more preferably at least 2 mass %, more preferably at least 3 mass %, even more preferably at least 4 mass %, most preferably at least 5 mass % %above. By making it below the upper limit, since the alkali-soluble resin and the ethylenically unsaturated compound can be relatively increased, the curability of the coating film and the ink repellency tend to be improved. There exists a tendency for the light-shielding property to be securable if it is more than a lower limit. The ratio of the (E) colorant to the total solid content of the colored photosensitive resin composition is, for example, 2 to 20% by mass, preferably 2 to 18% by mass, more preferably 3 to 15% by mass, and even more preferably 4 to 12% by mass, more preferably 5 to 10% by mass.

[1-1-6](F)分散劑 本發明之有色感光性樹脂組成物中，為了使(E)著色劑細微分散，且使其分散狀態穩定化，較佳係包含(F)分散劑。 作為(F)分散劑，較佳為具有官能基的高分子分散劑，再者，從分散穩定性的面向來看，較佳為具有羧基；磷酸基；磺酸基；或該等的鹽基；一級、二級或三級胺基；四級銨鹽基；源自吡啶、嘧啶、嘧啶等的含氮雜環之基團等之官能基的高分子分散劑。其中，尤其是從在將顏料分散時可以少量的分散劑進行分散的觀點來看，特佳為具有一級、二級或三級胺基；四級銨鹽基；源自吡啶、嘧啶、吡嗪等的含氮雜環之基團等的鹼性官能基的高分子分散劑。[1-1-6] (F) Dispersant In the colored photosensitive resin composition of the present invention, in order to finely disperse the (E) colorant and stabilize the dispersed state, it is preferable to contain (F) a dispersant . The (F) dispersant is preferably a polymer dispersant having a functional group, and furthermore, from the perspective of dispersion stability, it is preferably a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a salt group thereof ; primary, secondary or tertiary amine groups; quaternary ammonium bases; polymer dispersants derived from functional groups such as nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, and pyrimidine. Among them, especially from the point of view that a small amount of dispersant can be dispersed when the pigment is dispersed, it is particularly preferable to have a primary, secondary or tertiary amine group; a quaternary ammonium base; derived from pyridine, pyrimidine, pyrazine A polymer dispersant with basic functional groups such as nitrogen-containing heterocyclic groups.

又，作為高分子分散劑，舉例例如胺基甲酸酯系分散劑、丙烯酸系分散劑、聚乙亞胺系分散劑、聚烯丙胺系分散劑、具有胺基之單體與巨分子單體所構成之分散劑、聚氧乙烯烷醚系分散劑、聚氧乙烯二酯系分散劑、聚醚磷酸系分散劑、聚酯磷酸系分散劑、山梨糖醇脂肪族酯系分散劑、脂肪族改質聚酯系分散劑等。Also, examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, monomers having amine groups, and macromonomers. Dispersants composed of polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitol aliphatic ester dispersants, aliphatic Modified polyester dispersant, etc.

作為這樣的分散劑的具體例，舉例如商品名稱EFKA(註冊商標，BASF公司製)、DISPERBYK(註冊商標，BYK公司製)、DISPARLON (註冊商標，楠本化成公司製)、SOLSPERSE(註冊商標，LUBRIZOL公司製)、KP(信越化學工業公司製)、POLYFLOW(共榮公司化學公司製)、AJISPER(註冊商標，味之素公司製)等。 該等的高分子分散劑可單獨使用1種使用，或亦可併用2種以上。Specific examples of such dispersants include trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK Corporation), DISPARLON (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by LUBRIZOL Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.), etc. These polymer dispersants may be used alone or in combination of two or more.

高分子分散劑的重量平均分子量(Mw)通常為700以上，較佳為1000以上，又通常為100,000以下，較佳為50,000以下。 該等之中，從顏料分散性的觀點來看，(F)分散劑較佳為包含具有官能基的胺基甲酸酯系高分子分散劑及/或丙烯酸系高分子分散劑，特佳為包含丙烯酸系高分子分散劑。 又，從分散性、保存性的面向來看，較佳為具有鹼性官能基並具有聚酯鍵及/或聚醚鍵的高分子分散劑。The weight average molecular weight (Mw) of the polymer dispersant is usually above 700, preferably above 1000, and usually below 100,000, preferably below 50,000. Among them, from the viewpoint of pigment dispersibility, the (F) dispersant preferably contains a functional group-containing urethane-based polymer dispersant and/or an acrylic-based polymer dispersant, and is particularly preferably Contains acrylic polymer dispersant. Also, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferable.

作為胺基甲酸酯系及丙烯酸系高分子分散劑，舉例如例如DISPERBYK-160~167、182系列(皆為胺基甲酸酯系)、DISPERBYK-2000、2001、BYK-LPN21116等(皆為丙烯酸系)(以上皆為BYK公司製)。 作為胺基甲酸酯系高分子分散劑，若具體例示較佳的化學結構，舉例例如使聚異氰酸酯化物、分子內具有1個或2個羥基且數量平均分子量為300~10,000的化合物、在相同分子內具有活性氫與3級胺基的化合物反應所得到的、重量平均分子量1,000~200,000的分散樹脂等。藉由以氯甲苯等的四級化劑處理該等樹脂，可使一部分或全部的3級胺基成為4級銨鹽基。As urethane-based and acrylic polymer dispersants, for example, DISPERBYK-160~167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116, etc. (all Acrylic system) (all of the above are manufactured by BYK Corporation). As a urethane-based polymer dispersant, if a preferred chemical structure is specifically exemplified, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000, in the same Dispersion resins with a weight average molecular weight of 1,000 to 200,000 obtained by reacting compounds with active hydrogen and tertiary amine groups in the molecule, etc. By treating these resins with a quaternization agent such as chlorotoluene, a part or all of the tertiary amine groups can be converted into quaternary ammonium groups.

作為上述的聚異氰酸酯化物的例子，舉例如對苯二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、萘-1,5-二異氰酸酯、聯甲苯胺二異氰酸酯等的芳香族二異氰酸酯、二異氰酸六亞甲酯、離胺酸甲酯二異氰酸酯、二異氰酸2,4,4-三甲基六亞甲酯、二聚酸二異氰酸酯等的脂肪族二異氰酸酯、異佛爾酮二異氰酸酯、4,4’-亞甲基雙(異氰酸環己酯)、ω,ω’-二異氰酸酯二甲基環己烷等的脂環族二異氰酸酯、二異氰酸苯二甲酯、二異氰酸α,α,α’,α’-四甲基苯二甲酯等的具有芳香環的脂肪族二異氰酸酯、離胺酸酯三異氰酸酯、1,6,11-十一烷三異氰酸酯、1,8-二異氰酸酯-4-異氰酸酯甲基辛烷、三異氰酸1,3,6-六亞甲酯、雙環庚烷三異氰酸酯、參(異氰酸酯苯基甲烷)、參(異氰酸酯苯基)硫基磷酸酯等的三異氰酸酯、及該等的三聚物、水加成物、以及該等的多元醇加成物等。作為聚異氰酸酯，較佳為有機二異氰酸酯的三聚物，最佳為甲苯二異氰酸酯的三聚物與異佛爾酮二異氰酸酯的三聚物。 該等可單獨使用1種，亦可併用2種以上。Examples of the aforementioned polyisocyanates include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5- Aromatic diisocyanate such as diisocyanate and benzylidine diisocyanate, hexamethylene diisocyanate, methyl lysine diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), ω,ω'-diisocyanate dimethylcyclohexane Cycloaliphatic diisocyanate, xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate and other aliphatic diisocyanates with aromatic rings, iono Amino ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, dicyclohepta Triisocyanates such as alkane triisocyanate, ginseng (isocyanate phenylmethane), ginseng (isocyanate phenyl) thiophosphate, etc., and their trimers, water adducts, and these polyol adducts, etc. . The polyisocyanate is preferably a trimer of organic diisocyanate, most preferably a trimer of toluene diisocyanate and trimer of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

作為異氰酸酯之三聚物的製造方法，舉例如對於該聚異氰酸酯類，使用適當的三聚化觸媒，例如第3級胺類、膦類、烷氧化物類、金屬氧化物、羧酸鹽類等，進行異氰酸酯基的部分三聚化，再藉由添加觸媒毒而使三聚化停止後，對於未反應的聚異氰酸酯進行溶劑萃取，藉由薄膜蒸餾將其去除，而得到作為目標的含異三聚氰酸酯(isocyanurate)基的聚異氰酸酯之方法。As a method for producing a trimer of isocyanate, for example, using an appropriate trimerization catalyst for the polyisocyanate, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates etc., carry out partial trimerization of isocyanate groups, and then stop the trimerization by adding catalyst poison, carry out solvent extraction for unreacted polyisocyanate, and remove it by thin film distillation to obtain the target polyisocyanate containing A method for isocyanurate-based polyisocyanates.

作為在相同分子內具有1個或2個羥基的數量平均分子量300~10,000的化合物，舉例如聚醚二醇、聚酯二醇、聚碳酸酯二醇、聚烯烴二醇等，及以碳數1~25的烷基對該等化合物之單側末端羥基進行烷氧基化者，以及該等2種以上的混合物。 作為聚醚二醇，舉例如聚醚二醇、聚醚酯二醇、及該等2種以上的混合物。作為聚醚二醇，舉例如使伸烷基氧化物單獨或共聚合而得者，例如聚乙二醇、聚丙二醇、聚乙烯-丙二醇、聚氧基伸丁二醇、聚氧基六亞甲二醇、聚氧基八亞甲二醇及該等的2種以上的混合物。Examples of compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, etc., and The alkyl group of 1~25 is alkoxylated to the terminal hydroxyl group of one side of these compounds, and the mixture of two or more kinds of these compounds. As polyether diol, polyether diol, polyether ester diol, and the mixture of these 2 or more types are mentioned, for example. Examples of polyether diols include those obtained by independently or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxybutylene glycol, polyoxyhexamethylene diol, etc. Alcohol, polyoxy octamethylene glycol, and a mixture of two or more of these.

作為聚醚酯二醇，舉例如使含有醚基之二醇或其他二醇的混合物與二羧酸或該等的酸酐反應，或是使聚酯二醇與伸烷基氧化物反應所得者，例如聚(聚氧基四亞甲基)己二酸等。作為聚醚二醇，最佳為以碳數1~25的烷基對於聚乙二醇、聚丙二醇、聚氧基伸丁二醇或該等的化合物之單側末端羥基進行烷氧基化的化合物。Examples of polyether ester diols include those obtained by reacting ether group-containing diols or mixtures of other diols with dicarboxylic acids or their anhydrides, or by reacting polyester diols with alkylene oxides, For example, poly(polyoxytetramethylene) adipic acid and the like. As the polyether diol, it is best to use an alkyl group with 1 to 25 carbons to alkoxylate the terminal hydroxyl group of polyethylene glycol, polypropylene glycol, polyoxybutylene glycol or the compound on one side. .

作為聚酯二醇，舉例如使二羧酸(琥珀酸、戊二酸、己二酸、壬二酸、富馬酸、馬來酸、酞酸等)或該等的酸酐與二醇(乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、3-甲基-1,5-戊二醇、新戊二醇、2-甲基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、1,5-戊二醇、1,6-己二醇、2-甲基-2,4-戊二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,8-辛二醇、2-甲基-1,8-辛二醇、1,9-壬二醇等的脂肪族二醇、雙羥基甲基環己烷等的脂環族二醇、苯二甲基二醇、雙羥基乙氧基苯等的芳香族二醇、N-甲基二乙醇胺等的N-烷基二烷醇胺等)聚縮合而得者，例如聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸1,6己二醇酯、聚己二酸乙二醇/丙二醇酯等，或使用該二醇類或碳數1~25的一元醇作為起始劑所得到的聚內酯二醇或聚內酯一元醇，例如聚己內酯乙二醇、聚甲基戊內酯及該等的2種以上的混合物。作為聚酯二醇，最佳為以聚己內酯乙二醇或碳數1~25的醇作為起始劑的聚己內酯。As the polyester diol, for example, dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, etc.) Diol, Diethylene Glycol, Triethylene Glycol, Propylene Glycol, Dipropylene Glycol, Tripropylene Glycol, 1,2-Butanediol, 1,3-Butanediol, 1,4-Butanediol, 2,3-Butanediol Diol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2- Butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-tris Methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2- Aliphatic diols such as methyl-1,8-octanediol and 1,9-nonanediol, alicyclic diols such as bishydroxymethylcyclohexane, xylylene glycol, bishydroxyethyl Aromatic diols such as oxybenzene, N-alkyldialkanolamines such as N-methyldiethanolamine, etc.), such as polyethylene adipate, polybutylene adipate Alcohol ester, 1,6-hexylene adipate, polyethylene glycol/propylene adipate, etc., or polyols obtained by using the glycols or monohydric alcohols with 1 to 25 carbons as initiators Lactone diol or polylactone monoalcohol, such as polyethylene caprolactone glycol, polymethylvalerolactone, and mixtures of two or more thereof. As the polyester diol, polycaprolactone using polycaprolactone glycol or an alcohol having 1 to 25 carbon atoms as an initiator is most preferable.

作為聚碳酸酯二醇，舉例如聚(1,6-伸己基)碳酸酯、聚(3-甲基-1,5-伸戊基)碳酸酯等，作為聚烯烴二醇，舉例如聚丁二烯二醇、加氫型聚丁二烯二醇、加氫型聚異戊二烯二醇等。 該等可單獨使用1種，亦可併用2種以上。Examples of polycarbonate diols include poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc., examples of polyolefin diols include polybutylene Diene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, and the like. These may be used individually by 1 type, and may use 2 or more types together.

在相同分子內具有1個或2個羥基之化合物的數量平均分子量，通常為300~10,000，較佳為500~6,000，再佳為1,000~4,000。The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is usually 300-10,000, preferably 500-6,000, more preferably 1,000-4,000.

說明本發明中所使用的在相同分子內具有活性氫與3級胺基之化合物。 作為活性氫，亦即，與氧原子、氮原子或硫原子直接鍵結的氫原子，舉例如羥基、胺基、硫醇基等的官能基中的氫原子，其中較佳為胺基，特別是1級胺基的氫原子。A compound having an active hydrogen and a tertiary amine group in the same molecule used in the present invention will be described. As active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, for example, a hydrogen atom in a functional group such as a hydroxyl group, an amine group, a thiol group, etc., wherein an amine group is preferred, especially is a hydrogen atom of a primary amine group.

3級胺基無特別限定，例如，舉例如具有碳數1~4之烷基的胺基，或是雜環結構，更具體舉例如咪唑環或***環等。 若例示這種在相同分子內具有活性氫與3級胺基的化合物，舉例如N,N-二甲基-1,3-丙二胺、N,N-二乙基-1,3-丙二胺、N,N-二丙基-1,3-丙二胺、N,N-二丁基-1,3-丙二胺、N,N-二甲基乙二胺、N,N-二乙基乙二胺、N,N-二丙基乙二胺、N,N-二丁基乙二胺、N,N-二甲基-1,4-丁二胺、N,N-二乙基-1,4-丁二胺、N,N-二丙基-1,4-丁二胺、N,N-二丁基-1,4-丁二胺等。The tertiary amino group is not particularly limited, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring. Examples of such compounds having active hydrogen and tertiary amine groups in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propane Diamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N- Diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butylenediamine, N,N-di Ethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

又，在3級胺基為含氮雜環結構的情況中，作為該含氮雜環，舉例如吡唑環、咪唑環、***環、四唑環、吲哚環、咔唑環、吲唑環、苯并咪唑環、苯并***環、苯并噁唑環、苯并噻唑環、苯并噻二唑環等的含氮五元雜環、吡啶環、噠嗪環、嘧啶環、三嗪環、喹啉環、吖啶環、異喹啉環等的含氮六元雜環。該等的含氮雜環之中，較佳為咪唑環或***環。Also, when the tertiary amino group is a nitrogen-containing heterocyclic ring structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indole ring, Nitrogen-containing five-membered heterocycles such as azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, Nitrogen-containing six-membered heterocyclic rings such as triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferred.

若具體例示該等具有咪唑環與胺基的化合物，舉例如1-(3-胺基丙基)咪唑、組胺酸、2-胺基咪唑、1-(2-胺基乙基)咪唑等。又，若具體例示具有***環與胺基之化合物，舉例如3-胺基-1,2,4-***、5-(2-胺基-5-氯苯基)-3-苯基-1H-1,2,4-***、4-胺基-4H-1,2,4-***-3,5-二醇、3-胺基-5-苯基-1H-1,3,4-***、5-胺基-1,4-二苯基-1,2,3-***、3-胺基-1-苄基-1H-2,4-***等。其中，較佳為N,N-二甲基-1,3-丙二胺、N,N-二乙基-1,3-丙二胺、1-(3-胺基丙基)咪唑、3-胺基-1,2,4-***。 該等可單獨使用1種，亦可併用2種以上。Specific examples of such compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole, etc. . In addition, if a compound having a triazole ring and an amino group is specifically exemplified, such as 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl -1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3 ,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. Among them, N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, 1-(3-aminopropyl)imidazole, 3 -Amino-1,2,4-triazole. These may be used individually by 1 type, and may use 2 or more types together.

製造胺基甲酸酯系高分子分散劑時，原料較佳的摻合比例，係相對於聚異氰酸酯化物100質量份，在相同分子內具有1個或2個羥基的、數量平均分子量300~10,000的化合物為10~200質量份，較佳為20~190質量份，再佳為30~180質量份，在相同分子內具有活性氫與3級胺基的化合物則為0.2~25質量份，較佳為0.3~24質量份。When producing urethane-based polymer dispersants, the preferred blending ratio of raw materials is relative to 100 parts by mass of polyisocyanate compound, which has 1 or 2 hydroxyl groups in the same molecule and has a number average molecular weight of 300~10,000. The compound is 10~200 parts by mass, preferably 20~190 parts by mass, more preferably 30~180 parts by mass, and the compound with active hydrogen and tertiary amine groups in the same molecule is 0.2~25 parts by mass, which is relatively Preferably, it is 0.3 to 24 parts by mass.

胺基甲酸酯系高分子分散劑的製造，可藉由製造聚胺基甲酸酯樹脂的習知方法進行。作為製造時的溶劑，通常可使用丙酮、甲乙酮、甲基異丁酮、環戊酮、環己酮，異佛爾酮等的酮類、乙酸乙酯、乙酸丁酯、乙酸賽路蘇等的酯類、苯、甲苯、二甲苯、己烷等的烴類、二丙酮醇、異丙醇、第二丁醇、第三丁醇等一部分的醇類、氯化亞甲基、氯仿等的氯化物、四氫呋喃、二***等的醚類、二甲基甲醯胺、N-甲基吡咯啶酮、二甲基亞碸等的非質子性極性溶劑等。該等可單獨使用1種，亦可併用2種以上。The urethane-based polymer dispersant can be produced by a known method for producing polyurethane resin. As a solvent during production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, ethyl acetate, butyl acetate, celuxo acetate, etc. Esters, hydrocarbons such as benzene, toluene, xylene, and hexane, some alcohols such as diacetone alcohol, isopropanol, 2-butanol, and 3-butanol, and chlorine such as methylene chloride and chloroform Compounds, ethers such as tetrahydrofuran and diethyl ether, aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide, etc. These may be used individually by 1 type, and may use 2 or more types together.

上述製造時，通常係使用胺基甲酸酯化反應觸媒。作為該觸媒，舉例例如二月桂酸二丁錫、二月桂酸二辛錫、二辛酸二丁錫、辛酸亞錫等的錫系、乙醯丙酮鐵、氯化亞鐵等的鐵系、三乙胺、三乙二胺等的3級胺系等。該等可單獨使用1種，亦可併用2種以上。During the above-mentioned production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron-based catalysts such as iron acetylacetonate and ferrous chloride; Tertiary amines such as ethylamine and triethylenediamine, etc. These may be used individually by 1 type, and may use 2 or more types together.

在相同分子內具有活性氫與3級胺基的化合物，其導入量較佳係反應後的胺價控制在1~100mgKOH/g的範圍內。更佳為5~95mgKOH/g的範圍。胺價係以酸對於鹼性胺基進行中和滴定，與酸價對應而以KOH的mg數所表示的值。藉由使其在該下限值以上，會有分散能力優化的傾向，又，藉由使其在該上限值以下，會有顯影性優化的傾向。For compounds with active hydrogen and tertiary amine groups in the same molecule, it is better to control the amine value after the reaction within the range of 1~100mgKOH/g. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value through neutralization titration of an acid against a basic amine group. By making it more than this lower limit, there exists a tendency for a dispersibility to optimize, and also by making it below this upper limit, there exists a tendency for developability to optimize.

另外，以上的反應中，高分子分散劑中殘存異氰酸酯基的情況中，若進一步以醇或胺基化合物破壞異氰酸酯基，則產物的耐久穩定性變高，因而較佳。 胺基甲酸酯系高分子分散劑的重量平均分子量(Mw)通常為1000~200000，較佳為2000~100000，更佳為3000~50000的範圍。藉由使其在該下限值以上，會有分散性及分散穩定性優化的傾向，藉由使其在該上限值以下，會有溶解性提升、分散性優化的傾向。In addition, in the above reaction, when the isocyanate group remains in the polymer dispersant, it is preferable to destroy the isocyanate group with an alcohol or an amine compound because the durable stability of the product will increase. The weight-average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably in the range of 2,000 to 100,000, and more preferably in the range of 3,000 to 50,000. By setting it above the lower limit, the dispersibility and dispersion stability tend to be optimized, and by setting it below the upper limit, the solubility improves and the dispersibility tends to be optimized.

作為丙烯酸系高分子分散劑，較佳係使用具有官能基(此處所指的官能基，係上述作為高分子分散劑所含有之官能基)的含有不飽和基之單體與不具有官能基的含有不飽和基之單體的無規共聚物、接枝共聚物、嵌段共聚物。該等的共聚物可由習知的方法製造。As the acrylic polymer dispersant, it is preferable to use monomers containing unsaturated groups with functional groups (the functional groups referred to here are the functional groups contained in the above-mentioned polymer dispersants) and monomers without functional groups. Random copolymers, graft copolymers, and block copolymers of monomers containing unsaturated groups. These copolymers can be produced by known methods.

作為具有官能基的含有不飽和基之單體，舉例如(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基酞酸、2-(甲基)丙烯醯氧基乙基六氫酞酸、丙烯酸二聚物等的具有羧基的不飽和單體、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯及該等的4級化物等的具有3級胺基、4級銨鹽基的不飽和單體以作為具體例。該等可單獨使用1種，亦可併用2種以上。Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloxyethylsuccinic acid, and 2-(meth)acryloxyethylphthalic acid. , 2-(meth)acryloxyethyl hexahydrophthalic acid, unsaturated monomers with carboxyl groups such as acrylic acid dimers, dimethylaminoethyl (meth)acrylate, (meth)acrylic acid di Unsaturated monomers having tertiary amino groups and quaternary ammonium groups, such as ethylaminoethyl ester and their quaternary compounds, are given as specific examples. These may be used individually by 1 type, and may use 2 or more types together.

作為不具有官能基的含有不飽和基之單體，舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、異(甲基)丙烯酸丙酯、n-(甲基)丙烯酸丁酯、異(甲基)丙烯酸丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸苄酯、苯基(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基甲酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、三環癸烷(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、N-乙烯基吡咯啶酮、苯乙烯及其衍生物、α-甲基苯乙烯、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-苄基馬來醯亞胺等的N-取代馬來醯亞胺、丙烯腈、乙酸乙烯酯及聚(甲基)丙烯酸甲酯巨分子單體、聚苯乙烯巨分子單體、聚(甲基)丙烯酸2-羥乙酯巨分子單體、聚乙二醇巨分子單體、聚丙二醇巨分子單體、聚己內酯巨分子單體等的巨分子單體等。該等可單獨使用1種，亦可併用2種以上。Examples of unsaturated group-containing monomers that do not have functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n -Butyl (meth)acrylate, butyl iso(meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Cyclohexyl, Phenoxyethyl (meth)acrylate, Phenoxymethyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Isocamphoryl (meth)acrylate, Tricyclodecane Alkane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-substituted maleimides such as N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, Polystyrene macromer, poly(2-hydroxyethyl meth)acrylate macromer, polyethylene glycol macromer, polypropylene glycol macromer, polycaprolactone macromer, etc. Macromolecules etc. These may be used individually by 1 type, and may use 2 or more types together.

丙烯酸系高分子分散劑，特佳為具有官能基之A嵌段與不具有官能基之B嵌段所構成之A-B或B-A-B嵌段共聚物，但此情況下，在A嵌段中，除了源自上述包含官能基的含有不飽和基之單體的部分結構以外，亦可包含源自上述不包含官能基的含有不飽和基之單體的部分結構，該等可以無規共聚合或嵌段共聚合的任一態樣含有於該A嵌段之中。又，不包含官能基之部分結構在A嵌段中的含量，通常為80質量%以下，較佳為50質量%以下，再佳為30質量%以下。The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer composed of an A block with a functional group and a B block without a functional group, but in this case, in the A block, except for the source In addition to the partial structure of the above-mentioned unsaturated group-containing monomer containing a functional group, a partial structure derived from the above-mentioned unsaturated group-containing monomer not containing a functional group may also be included, and these may be randomly copolymerized or block Any form of copolymerization is contained in this A block. Also, the content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, further preferably 30% by mass or less.

B嵌段係由源自上述不包含官能基的含有不飽和基之單體的部分結構所構成，但亦可為在1個B嵌段中含有源自2種以上之單體的部分結構，該等可以無規共聚合或嵌段共聚合的任一態樣含有於該B嵌段之中。 該A-B或B-A-B嵌段共聚物，例如係由以下所示的活性聚合法所調製。 活性聚合法中，有陰離子活性聚合法、陽離子活性聚合法、自由基活性聚合法，其中，在陰離子活性聚合法中，聚合活性種為陰離子，例如下述機制中所示。The B block is composed of a partial structure derived from the above-mentioned unsaturated group-containing monomer that does not contain a functional group, but one B block may contain a partial structure derived from two or more monomers, These may be contained in the B block in any form of random copolymerization or block copolymerization. This A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method shown below. The living polymerization method includes an anionic living polymerization method, cationic living polymerization method, and radical living polymerization method. In the anionic living polymerization method, the polymerization active species is an anion, as shown in the following mechanism, for example.

[化學式52]

Figure 02_image099
[chemical formula 52]
Figure 02_image099

上述機制中，Ar1 為1價的有機基、Ar2 為與Ar1 不同的1價的有機基、M為金屬原子、s及t分別為1以上的整數。In the above mechanism, Ar 1 is a monovalent organic group, Ar 2 is a monovalent organic group different from Ar 1 , M is a metal atom, and s and t are each an integer of 1 or more.

自由基活性聚合法中，聚合活性種為自由基，例如下述機制中所示。In the radical living polymerization method, the polymerization active species is a radical, as shown in the following mechanism, for example.

[化學式53]

Figure 02_image101
[chemical formula 53]
Figure 02_image101

上述機制中，Ar1 為1價的有機基、Ar2 為與Ar1 不同的1價的有機基、j及k分別為1以上的整數，Ra 為氫原子或1價的有機基、Rb 為與Ra 不同的氫原子或1價的有機基。In the above mechanism, Ar 1 is a monovalent organic group, Ar 2 is a monovalent organic group different from Ar 1 , j and k are each an integer of 1 or more, R a is a hydrogen atom or a monovalent organic group, R b is a hydrogen atom or a monovalent organic group different from R a .

在合成該丙烯酸系高分子分散劑時，可採用日本特開平9-62002號公報或P.Lutz,P.Masson et al,Polym. Bull. 12, 79 (1984)、B.C.Anderson, G.D.Andrews et al,Macromolecules,14,1601(1981)、K.Hatada,K.Ute,et al,Polym. J. 17,977(1985),18,1037(1986)、右手浩一、畑田耕一，高分子加工，36,366(1987)、東村敏延、澤本光男，高分子論文集，46,189(1989)、 M.Kuroki,T.Aida,J. Am. Chem. Sic,109,4737(1987)、相田卓三、井上祥平、有機合成化學，43,300(1985)，D.Y.Sogoh，W.R.Hertler et al，Macromolecules，20,1473(1987)等的習知方法。When synthesizing the acrylic polymer dispersant, Japanese Patent Application No. 9-62002 or P.Lutz, P.Masson et al, Polym. Bull. 12, 79 (1984), B.C.Anderson, G.D.Andrews et al can be used. , Macromolecules, 14, 1601(1981), K.Hatada, K.Ute, et al, Polym. J. 17,977(1985), 18, 1037(1986), Koichi Right, Koichi Hatada, Polymer Processing, 36,366(1987 ), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989), M.Kuroki, T.Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985), D.Y. Sogoh, W.R. Hertler et al, Macromolecules, 20, 1473 (1987) etc., are known methods.

本發明中可使用之丙烯酸系高分子分散劑，可為A-B嵌段共聚物，亦可為B-A-B嵌段共聚物，構成該共聚物的A嵌段/B嵌段的比例為1/99~80/20，特佳為5/95~60/40(質量比)，藉由使其在該範圍內，會有可確保分散性與保存穩定性之平衡的傾向。 又，在本發明中可使用的A-B嵌段共聚物、B-A-B嵌段共聚物，在1g中，4級銨鹽基的量通常較佳為0.1~10mmol，藉由使其在該範圍內，會有可確保良好分散性的傾向。The acrylic polymer dispersant that can be used in the present invention can be an A-B block copolymer or a B-A-B block copolymer, and the ratio of the A block/B block constituting the copolymer is 1/99~80 /20, particularly preferably 5/95 to 60/40 (mass ratio), by making it within this range, there is a tendency that a balance between dispersibility and storage stability can be ensured. Also, in the A-B block copolymer and B-A-B block copolymer that can be used in the present invention, the amount of the quaternary ammonium base is usually preferably 0.1 to 10 mmol in 1 g, and by making it within this range, it will There is a tendency that good dispersibility can be ensured.

另外，在這樣的嵌段共聚物中，通常具有在製造過程產生之胺基含有於其中的情況，其胺價為1~100mgKOH/g左右，從分散性的觀點來看，較佳為10mgKOH/g以上，更佳為30mgKOH/g以上，再佳為50mgKOH/g以上，又，較佳為90mgKOH/g以下，更佳為80mgKOH/g以下，再佳為75mgKOH/g以下。 此處，該等嵌段共聚物等的分散劑之胺價，係以將分散劑樣品中的溶劑去除後固體成分每1克的鹼量與當量之KOH的質量表示，其係以下述方法測量。 在100mL的燒杯中，精密秤量分散劑樣品0.5~1.5g，並以50mL的乙酸溶解。使用具備pH電極的自動滴定裝置，以0.1mol/L的HClO4 乙酸溶液對該溶液進行中和滴定。將滴定pH曲線的反曲點作為滴定終點，以下式求得胺價。In addition, such block copolymers usually contain amine groups generated during the production process, and the amine value is about 1 to 100 mgKOH/g, preferably 10 mgKOH/g from the viewpoint of dispersibility. g or more, more preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, even more preferably 75 mgKOH/g or less. Here, the amine value of the dispersant such as the block copolymer is expressed by the mass of the alkali amount and equivalent KOH per 1 gram of the solid content after removing the solvent in the dispersant sample, and it is measured by the following method . In a 100mL beaker, accurately weigh 0.5~1.5g of the dispersant sample and dissolve it in 50mL of acetic acid. Using an automatic titration device equipped with a pH electrode, the solution was neutralized and titrated with a 0.1 mol/L HClO 4 acetic acid solution. Using the inflection point of the titration pH curve as the end point of the titration, the amine value was obtained by the following formula.

胺價[mgKOH/g]＝(561×V)/(W×S)［其中，W表示分散劑樣品的秤取量[g]，V表示滴定終點的滴定量[mL]，S表示分散劑樣品的固體成分濃度[質量%]］ 又，該嵌段共聚物的酸價，雖亦與該酸價之來源的酸性基之有無以及其種類相關，但一般係越低越好，通常在10mgKOH/g以下，其重量平均分子量(Mw)較佳係在1000~100,000的範圍。藉由使其在該範圍內，會有可確保良好分散性的傾向。Amine value [mgKOH/g]=(561×V)/(W×S) [Wherein, W represents the weighed amount of the dispersant sample [g], V represents the titration amount at the titration end point [mL], and S represents the dispersant The solid content concentration of the sample [mass %]] Also, although the acid value of the block copolymer is also related to the presence or absence of the acidic group and the type of the source of the acid value, generally the lower the better, usually 10mgKOH /g or less, the weight average molecular weight (Mw) is preferably in the range of 1000 to 100,000. By setting it as this range, there exists a tendency for favorable dispersibility to be ensured.

具有4級銨鹽基作為官能基的情況，關於高分子分散劑的具體結構並未特別限定，從分散性的觀點來看，較佳為具有以下式(i)所表示之重複單元(以下有時亦稱為「重複單元(i)」)。In the case of having a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferred to have a repeating unit represented by the following formula (i) (hereinafter: also referred to as "repeating unit (i)").

[化學式54]

Figure 02_image103
[chemical formula 54]
Figure 02_image103

上述式(i)中，R31 ~R33 分別獨立表示氫原子、亦可具有取代基的烷基、亦可具有取代基的芳基、或亦可具有取代基的芳烷基； R31 ~R33 之中的2個以上亦可互相鍵結而形成環狀結構； R34 為氫原子或甲基； X為2價的連結基團； Y- 為成對陰離子。In the above formula (i), R 31 ~ R 33 independently represent a hydrogen atom, an alkyl group that may also have a substituent, an aryl group that may also have a substituent, or an aralkyl group that may also have a substituent; R 31 ~ Two or more of R 33 may be bonded to each other to form a ring structure; R 34 is a hydrogen atom or a methyl group; X is a divalent linking group; Y - is a paired anion.

上述式(i)的R31 ~R33 中，亦可具有取代基的烷基，其碳數並未特別限定，較佳為1以上，又，較佳為10以下，更佳為6以下。作為烷基的具體例，舉例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，該等之中，較佳為甲基、乙基、丙基、丁基、戊基、或己基，更佳為甲基、乙基、丙基、或丁基。又，可為直鏈狀、分枝狀任一者。又，可包含環己基、環己基甲基等的環狀結構。In R 31 to R 33 of the above formula (i), the alkyl group which may have a substituent has no particular limitation on its carbon number, but is preferably 1 or more, and is preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be linear or branched. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl may be included.

上述式(i)的R31 ~R33 中，亦可具有取代基的芳基，其碳數並未特別限定，通常為6以上，又，較佳為16以下，更佳為12以下。作為芳基的具體例，舉例如苯基、甲基苯基、乙基苯基、二甲基苯基、二乙基苯基、萘基、蒽基等，該等之中，較佳為苯基、甲基苯基、乙基苯基、二甲基苯基、或二乙基苯基，更佳為苯基、甲基苯基、或乙基苯基。Among R 31 to R 33 of the above formula (i), the aryl group which may have a substituent has a carbon number that is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less. Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, etc. Among them, benzene radical, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

上述式(i)的R31 ~R33 中，亦可具有取代基的芳烷基，其碳數並未特別限定，通常為7以上，又，較佳為16以下，更佳為12以下。作為芳烷基的具體例，舉例如苯甲基(benzyl)、苯乙基(phenethyl)、苯基丙基、苯丁基、苯基異丙基等，該等之中，較佳為苯甲基、苯乙基、苯丙基、或苯丁基，更佳為苯甲基、或苯乙基。In R 31 to R 33 of the above formula (i), the aralkyl group which may have a substituent has no particular limitation on its carbon number, but is usually 7 or more, and preferably 16 or less, more preferably 12 or less. Specific examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylisopropyl, etc. Among them, benzyl is preferred. Base, phenethyl, phenylpropyl, or phenbutyl, more preferably benzyl, or phenethyl.

該等之中，從分散性的觀點來看，R31 ~R33 較佳係分別獨立為烷基或芳烷基，具體而言，較佳係R31 及R33 分別獨立為甲基或乙基、且R32 為苯甲基或苯乙基，更佳係R31 及R33 為甲基、且R32 為苯甲基。Among these, from the viewpoint of dispersibility, R 31 to R 33 are preferably independently alkyl or aralkyl, specifically, R 31 and R 33 are preferably independently methyl or ethyl. and R 32 is benzyl or phenethyl, more preferably R 31 and R 33 are methyl, and R 32 is benzyl.

又，該高分子分散劑具有3級胺作為官能基的情況，從分散性的觀點來看，較佳係具有以下式(ii)所表示之重複單元(以下有時稱為「重複單元(ii)」)。Also, when the polymer dispersant has a tertiary amine as a functional group, it is preferable to have a repeating unit represented by the following formula (ii) from the viewpoint of dispersibility (hereinafter sometimes referred to as "repeating unit (ii) )”).

[化學式55]

Figure 02_image105
[chemical formula 55]
Figure 02_image105

上述式(ii)中，R35 及R36 分別獨立為氫原子、亦可具有取代基的烷基、亦可具有取代基的芳基、或亦可具有取代基的芳烷基； R35 及R36 亦可互相鍵結而形成環狀結構； R37 為氫原子或甲基； Z為2價的連結基團。In the above formula (ii), R 35 and R 36 are independently a hydrogen atom, an alkyl group that may also have a substituent, an aryl group that may also have a substituent, or an aralkyl group that may also have a substituent; R 35 and R 36 can also bond with each other to form a ring structure; R 37 is a hydrogen atom or a methyl group; Z is a divalent linking group.

作為上述式(ii)的R35 及R36 中亦可具有取代基的烷基，較佳可採用上述式(i)中例示為R31 ~R33 者。 作為上述式(ii)的R35 及R36 中亦可具有取代基的芳基，較佳可採用上述式(i)中例示為R31 ~R33 者。 作為上述式(ii)的R35 及R36 中亦可具有取代基的芳烷基，較佳可採用上述式(i)中例示為R31 ~R33 者。As the alkyl group that may have a substituent in R 35 and R 36 of the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) can be preferably used. As the aryl group that may have a substituent in R 35 and R 36 of the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) can be preferably used. As the aralkyl group which may have a substituent in R 35 and R 36 of the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) can be preferably used.

該等之中，R35 及R36 較佳係分別獨立為亦可具有取代基的烷基，更佳為甲基或乙基。Among them, R 35 and R 36 are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.

作為上述式(i)的R31 ~R33 及上述式(ii)的R35 及R36 中的烷基、芳烷基或芳基可具有的取代基，舉例如鹵素原子、烷氧基、苯甲醯基、羥基等。Examples of substituents that the alkyl, aralkyl, or aryl groups in R 31 to R 33 of the above formula (i) and R 35 and R 36 of the above formula (ii) may have include halogen atoms, alkoxy groups, Benzoyl, hydroxyl, etc.

上述式(i)及(ii)中，作為2價的連結基團X及Z，舉例例如碳數1~10的伸烷基、碳數6~12的伸芳基、-CONH-R43 -基、-COOR44 -基［其中，R43 及R44 為單鍵、碳數1~10的伸烷基、或碳數2~10的醚基(烷氧基烷基)］等，較佳為-COO-R44 -基。 又，上述式(i)中，作為成對陰離子的Y- ，舉例如Cl- 、Br- 、I- 、ClO4 - 、BF4 - 、CH3 COO- 、PF6 - 等。In the above formulas (i) and (ii), as the divalent linking groups X and Z, for example, an alkylene group having 1 to 10 carbons, an arylylene group having 6 to 12 carbons, -CONH-R 43 - group, -COOR 44 - group [wherein R 43 and R 44 are single bonds, alkylene groups with 1 to 10 carbons, or ether groups (alkoxyalkyl groups) with 2 to 10 carbons], etc., preferably is -COO-R 44 -group. In addition, in the above formula (i), Y - as the pair anion includes, for example, Cl - , Br - , I - , ClO 4 - , BF 4 - , CH 3 COO - , PF 6 - and the like.

以該式(i)所表示之重複單元的含有比例並未特別限定，從分散性的觀點來看，相對於以該式(i)所表示之重複單元的含有比例與以該式(ii)所表示之重複單元的含有比例的總和，較佳為60莫耳%以下，更佳為50莫耳%以下，再佳為40莫耳%以下，特佳為35莫耳%以下，又，較佳為5莫耳%以上，更佳為10莫耳%以上，再佳為20莫耳%以上，特佳為30莫耳%以上。The content ratio of the repeating unit represented by the formula (i) is not particularly limited. From the viewpoint of dispersibility, the content ratio of the repeat unit represented by the formula (i) is the same as that of the formula (ii) The sum of the content ratios of the repeating units represented is preferably at most 60 mol%, more preferably at most 50 mol%, even more preferably at most 40 mol%, and most preferably at most 35 mol%. Preferably it is at least 5 mol%, more preferably at least 10 mol%, even more preferably at least 20 mol%, and most preferably at least 30 mol%.

又，以該式(i)所表示之重複單元在高分子分散劑之所有重複單元中所占的含有比例並未特別限定，從分散性的觀點來看，較佳為1莫耳%以上，更佳為5莫耳%以上，再佳為10莫耳%以上，又，較佳為50莫耳%以下，更佳為30莫耳%以下，再佳為20莫耳%以下，特佳為15莫耳%以下。In addition, the content ratio of the repeating unit represented by the formula (i) in all the repeating units of the polymer dispersant is not particularly limited, but it is preferably 1 mol% or more from the viewpoint of dispersibility, More preferably at least 5 mol %, more preferably at least 10 mol %, more preferably less than 50 mol %, more preferably less than 30 mol %, more preferably less than 20 mol %, especially preferably at least 50 mol % Below 15 mol%.

又，以該式(ii)所表示之重複單元在高分子分散劑的所有重複單元中所占的含有比例並未特別限定，從分散性的觀點來看，較佳為5莫耳%以上，更佳為10莫耳%以上，再佳為15莫耳%以上，特佳為20莫耳%以上，又，較佳為60莫耳%以下，更佳為40莫耳%以下，再佳為30莫耳%以下，特佳為25莫耳%以下。Also, the content ratio of the repeating unit represented by the formula (ii) in all the repeating units of the polymer dispersant is not particularly limited, but it is preferably 5 mol% or more from the viewpoint of dispersibility, More preferably at least 10 mol %, more preferably at least 15 mol %, especially preferably at least 20 mol %, and more preferably at least 60 mol %, more preferably at least 40 mol %, even more preferably at least 20 mol % Less than 30 mol%, especially preferably less than 25 mol%.

又，高分子分散劑，從提高對於溶劑等的黏結劑成分的相溶性、提升分散穩定性的觀點來看，較佳係具有以下式(iii)所表示之重複單元(以下有時稱為「重複單元(iii)」)。In addition, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter sometimes referred to as " repeating unit (iii)").

[化學式56]

Figure 02_image107
[chemical formula 56]
Figure 02_image107

上述式(iii)中，R40 為伸乙基或伸丙基；R41 表示亦可具有取代基的烷基；R42 表示氫原子或甲基；n為1~20的整數。In the above formula (iii), R 40 is ethyl or propylene; R 41 represents an alkyl group that may also have a substituent; R 42 represents a hydrogen atom or a methyl group; n is an integer of 1 to 20.

上述式(iii)的R41 中，亦可具有取代基的烷基，其碳數並未特別限定，可為1以上，較佳為2以上，又，較佳為10以下，更佳為6以下。作為烷基的具體例，舉例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，該等之中，較佳為甲基、乙基、丙基、丁基、戊基、或己基，更佳為甲基、乙基、丙基、或丁基。又，可為直鏈狀、分枝狀任一者。又，亦可包含環己基、環己基甲基等的環狀結構。In R41 of the above-mentioned formula (iii), the alkyl group that may also have a substituent is not particularly limited in its carbon number and may be 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 the following. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be linear or branched. Moreover, the ring structure, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

又，上述式(iii)中的n，從對於溶劑等黏結劑成分之相溶性與分散性的觀點來看，可為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下。In addition, n in the above formula (iii) may be 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less.

又，以該式(iii)所表示之重複單元在高分子分散劑的所有重複單元中所占的含有比例並未特別限定，較佳為1莫耳%以上，更佳為2莫耳%以上，再佳為4莫耳%以上，又，較佳為30莫耳%以下，更佳為20莫耳%以下，再佳為10莫耳%以下。在該範圍內的情況中，會有可兼具對於溶劑等黏結劑成分之相溶性與分散穩定性的傾向。Also, the proportion of the repeating unit represented by the formula (iii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more , more preferably at least 4 mol%, and more preferably at most 30 mol%, more preferably at most 20 mol%, even more preferably at most 10 mol%. When it is within this range, compatibility with respect to binder components, such as a solvent, and dispersion stability tend to be compatible.

又，高分子分散劑，從提高相對於分散劑之溶劑等黏結劑成分的相溶性、提升分散穩定性這樣的觀點來看，較佳係具有以下式(iv)所表示之重複單元(以下有時稱為「重複單元(iv)」)。In addition, the polymer dispersant preferably has a repeating unit represented by the following formula (iv) from the viewpoint of improving compatibility with binder components such as a solvent of the dispersant and improving dispersion stability (hereinafter: referred to as "repeating unit (iv)").

[化學式57]

Figure 02_image109
[chemical formula 57]
Figure 02_image109

上述式(iv)中，R38 為亦可具有取代基的烷基、亦可具有取代基的芳基、或亦可具有取代基的芳烷基；R39 表示氫原子或甲基。In the above formula (iv), R 38 is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; R 39 represents a hydrogen atom or a methyl group.

上述式(iv)的R38 之中，亦可具有取代基的烷基，其碳數並未特別限定，可為1以上，較佳為2以上，更佳為4以上，又，較佳為10以下，更佳為8以下。作為烷基的具體例，舉例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，該等之中，較佳為甲基、乙基、丙基、丁基、戊基、或己基，更佳為甲基、乙基、丙基、或丁基。又，可為直鏈狀、分枝狀任一者。又，亦可包含環己基、環己基甲基等的環狀結構。In R38 of the above formula (iv), the alkyl group that may also have a substituent has no particular limitation on its carbon number, and may be 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Moreover, it may be linear or branched. Moreover, the ring structure, such as a cyclohexyl group and a cyclohexylmethyl group, may be included.

上述式(iv)的R38 之中，亦可具有取代基的芳基，其碳數並未特別限定，通常為6以上，又，較佳為16以下，更佳為12以下，再佳為8以下。作為芳基的具體例，舉例如苯基、甲基苯基、乙基苯基、二甲基苯基、二乙基苯基、萘基、蒽基等，該等之中，較佳為苯基、甲基苯基、乙基苯基、二甲基苯基、或二乙基苯基，更佳為苯基、甲基苯基、或乙基苯基。Among R 38 in the above formula (iv), the aryl group that may also have a substituent has a carbon number that is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, etc. Among them, benzene radical, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

上述式(iv)的R38 之中，亦可具有取代基的芳烷基，其碳數並未特別限定，通常為7以上，又，較佳為16以下，更佳為12以下，再佳為10以下。作為芳烷基的具體例，舉例如苯甲基(benzyl)、苯乙基(phenethyl)、苯丙基、苯丁基、苯基異丙基等，該等之中，較佳為苯甲基、苯乙基、苯丙基、或苯丁基，更佳為苯甲基、或苯乙基。Among R38 of the above formula (iv), the aralkyl group that may also have a substituent has a carbon number that is not particularly limited, but is usually 7 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. Specific examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenbutyl, phenylisopropyl, etc. Among them, benzyl is preferred. , phenethyl, phenylpropyl, or phenbutyl, more preferably benzyl, or phenethyl.

該等之中，從溶劑相溶性與分散穩定性的觀點來看，R38 較佳為烷基、或芳烷基，更佳為甲基、乙基、或苯甲基。 作為R38 之中的烷基可具有的取代基，舉例如鹵素原子、烷氧基等。又，作為芳基或芳烷基可具有的取代基，舉例如鏈狀的烷基、鹵素原子、烷氧基等。又，R38 所示的鏈狀的烷基中，包含直鏈狀及分支鏈狀的任一者。Among them, from the viewpoint of solvent compatibility and dispersion stability, R 38 is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group, or a benzyl group. The substituent that the alkyl group in R 38 may have includes, for example, a halogen atom, an alkoxy group, and the like. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain alkyl group, a halogen atom, an alkoxy group etc. are mentioned, for example. In addition, the chained alkyl group represented by R38 includes any of linear and branched chains.

又，以該式(iv)所表示之重複單元在高分子分散劑的所有重複單元中所占的含有比例，從分散性的觀點來看，較佳為30莫耳%以上，更佳為40莫耳%以上，再佳為50莫耳%以上，又，較佳為80莫耳%以下，更佳為70莫耳%以下。In addition, the proportion of the repeating unit represented by the formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mole % or more, more preferably 40 mole % from the viewpoint of dispersibility. Mole % or more, more preferably 50 Mole % or more, and more preferably 80 Mole % or less, more preferably 70 Mole % or less.

高分子分散劑，亦可具有重複單元(i)、重複單元(ii)、重複單元(iii)及重複單元(iv)以外的重複單元。作為這種重複單元的例子，舉例如源自下述單體的重複單元：苯乙烯、α-甲基苯乙烯等的苯乙烯系單體；(甲基)丙烯丙烯醯氯等的(甲基)丙烯酸鹽系單體；(甲基)丙烯醯胺、N-羥甲基丙烯醯胺等的(甲基)丙烯醯胺系單體；乙酸乙烯酯；丙烯腈；烯丙基縮水甘油醚、巴豆酸縮水甘油醚；N-甲基丙烯醯基嗎啉等。The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii) and repeating unit (iv). Examples of such repeating units include repeating units derived from the following monomers: styrene-based monomers such as styrene and α-methylstyrene; ) acrylate-based monomers; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, Crotonic acid glycidyl ether; N-methacryl morpholine, etc.

高分子分散劑，從更提高分散性的觀點來看，較佳為A嵌段與B嵌段的嵌段共聚物，該A嵌段具有重複單元(i)及重複單元(ii)，該B嵌段不具有重複單元(i)及重複單元(ii)。該嵌段共聚物，較佳為A-B嵌段共聚物或B-A-B嵌段共聚物。在A嵌段中，不僅導入4級銨鹽基，亦導入3級胺基，藉此意外地會有顯著提升分散劑之分散能力的傾向。又，B嵌段較佳係具有重複單元(iii)，更佳係更具有重複單元(iv)。The polymer dispersant, from the point of view of improving dispersibility, is preferably a block copolymer of A block and B block, the A block has repeating unit (i) and repeating unit (ii), and the B block The block does not have repeating unit (i) and repeating unit (ii). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. In the A block, not only the quaternary ammonium group but also the tertiary amine group are introduced, thereby unexpectedly tending to significantly improve the dispersing ability of the dispersant. Also, the B block preferably has the repeating unit (iii), and more preferably has the repeating unit (iv).

重複單元(i)及重複單元(ii)可以無規共聚合、嵌段共聚合的任一態樣包含於A嵌段中。又，重複單元(i)及重複單元(ii)，在1個A嵌段中可分別含有2種以上，此情況中，各重複單元可以無規共聚合、嵌段共聚合的任一態樣包含於該A嵌段中。The repeating unit (i) and the repeating unit (ii) may be included in the A block in any form of random copolymerization or block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may each contain two or more types in one A block. In this case, each repeating unit may be random copolymerized or block copolymerized. included in the A block.

又，A嵌段中亦可包含重複單元(i)及重複單元(ii)以外的重複單元，而作為這種重複單元的例子，舉例如前述源自(甲基)丙烯酸酯系單體的重複單元等。重複單元(i)及重複單元(ii)以外的重複單元在A嵌段中的含量，較佳為0~50莫耳%，更佳為0~20莫耳%，但最佳係A嵌段中不含有此重複單元。In addition, repeating units other than repeating unit (i) and repeating unit (ii) may also be included in the A block, and as an example of such a repeating unit, for example, the repeating unit derived from the aforementioned (meth)acrylate monomer unit etc. The content of repeating units other than repeating unit (i) and repeating unit (ii) in the A block is preferably 0-50 mole %, more preferably 0-20 mole %, but the best is the A block does not contain this repeating unit.

B嵌段中亦可包含重複單元(iii)及(iv)以外的重複單元，作為這種重複單元的例子，舉例如源自苯乙烯、α-甲基苯乙烯等的苯乙烯系單體；(甲基)丙烯醯氯等的(甲基)丙烯酸鹽系單體；(甲基)丙烯醯胺、N-羥甲基丙烯醯胺等的(甲基)丙烯醯胺系單體；乙酸乙烯酯；丙烯腈；烯丙基縮水甘油醚、巴豆酸縮水甘油醚；N-甲基丙烯醯基嗎啉等單體的重複單元。重複單元(iii)及重複單元(iv)以外的重複單元在B嵌段中的含量，較佳為0~50莫耳%，更佳為0~20莫耳%，但最佳係B嵌段中不含有此重複單元。Repeating units other than repeating units (iii) and (iv) may also be included in the B block, as examples of such repeating units, for example, styrene-based monomers derived from styrene, α-methylstyrene, etc.; (Meth)acrylate-based monomers such as (meth)acryl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate ester; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryl morpholine and other monomer repeating units. The content of repeating units other than repeating unit (iii) and repeating unit (iv) in the B block is preferably 0-50 mole%, more preferably 0-20 mole%, but the best is the B block does not contain this repeating unit.

本發明之有色感光性樹脂組成物含有(F)分散劑的情況，其含有比例並未特別限定，在有色感光性樹脂組成物的總固體成分中，較佳為0.1質量%以上，更佳為0.5質量%以上，再佳為1質量%以上，特佳為1.5質量%以上，又，較佳為8質量%以下，更佳為5質量%以下，再佳為3質量%以下，特佳為2質量%以下。藉由使其在該下限值以上，會有可抑制凝集物導致殘渣發生的傾向，又，藉由使其在該上限值以下，會有感度及顯影性提升的傾向。有色感光性樹脂組成物含有(F)分散劑的情況中，(F)分散劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.1~8質量%，較佳為0.1~5質量%，更佳為1~3質量%，再佳為1.5~2質量%。 [1-1-7]紫外線吸收劑When the colored photosensitive resin composition of the present invention contains (F) a dispersant, the content ratio is not particularly limited, but it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably at least 1% by mass, particularly preferably at least 1.5% by mass, more preferably at most 8% by mass, more preferably at most 5% by mass, even more preferably at most 3% by mass, and most preferably at least 3% by mass. 2% by mass or less. There exists a tendency for the generation|occurrence|production of the residue by an aggregate to be suppressed by making it more than this lower limit, and there exists a tendency for sensitivity and developability to improve by making it below this upper limit. When the colored photosensitive resin composition contains the (F) dispersant, the content ratio of the (F) dispersant in the total solid content of the colored photosensitive resin composition is, for example, 0.1 to 8% by mass, preferably 0.1 to 8% by mass. 5% by mass, more preferably 1-3% by mass, even more preferably 1.5-2% by mass. [1-1-7] UV absorber

本發明之有色感光性樹脂組成物亦可含有紫外線吸收劑。紫外線吸收劑的添加目的，係以紫外線吸收劑吸收曝光中所使用之光源的特定波長，藉此控制光硬化分布。藉由添加紫外線吸收劑，可得到改善顯影後的錐角及形狀、使顯影後殘留於非曝光部之殘渣消失等的效果。作為紫外線吸收劑，從阻礙(B)光聚合起始劑之光吸收的觀點來看，例如可使用在波長250nm至400nm之間具有吸收最大值的化合物。 作為紫外線吸收劑，期望為苯并***系化合物及/或三嗪系化合物。藉由包含苯并***系化合物及/或三嗪系化合物，起始劑在膜底部的光吸收率減少，底部尺寸變小，因此認為可得到錐角增大的效果。The colored photosensitive resin composition of the present invention may also contain an ultraviolet absorber. The purpose of adding the ultraviolet absorber is to control the photohardening distribution by absorbing the specific wavelength of the light source used in the exposure by the ultraviolet absorber. By adding a UV absorber, effects such as improving the taper angle and shape after development, and disappearing residue remaining in the non-exposed portion after development can be obtained. As the ultraviolet absorber, from the viewpoint of inhibiting the light absorption of the (B) photopolymerization initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used. As the ultraviolet absorber, a benzotriazole-based compound and/or a triazine-based compound is desirable. By including the benzotriazole-based compound and/or the triazine-based compound, the light absorptivity of the initiator at the bottom of the film decreases, and the size of the bottom becomes smaller, so the effect of increasing the cone angle is considered to be obtained.

苯并***系化合物之中，從錐狀的觀點來看，較佳為以下述通式(Z1)記載的苯并***化合物。Among the benzotriazole-based compounds, a benzotriazole compound represented by the following general formula (Z1) is preferable from the viewpoint of the cone shape.

[化學式58]

Figure 02_image111
[chemical formula 58]
Figure 02_image111

上述式(Z1)中，R1e 及R2e 分別獨立表示氫原子、亦可具有取代基的烷基、以下述通式(Z2)所表示之基團、或以下述通式(Z3)所表示之基團。R3e 表示氫原子或鹵素原子。In the above formula (Z1), R 1e and R 2e independently represent a hydrogen atom, an alkyl group that may have a substituent, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3) group. R 3e represents a hydrogen atom or a halogen atom.

[化學式59]

Figure 02_image113
[chemical formula 59]
Figure 02_image113

上述式(Z2)中，R4e 表示亦可具有取代基的伸烷基，R5e 表示亦可具有取代基的烷基。In the above formula (Z2), R 4e represents an alkylene group which may have a substituent, and R 5e represents an alkyl group which may also have a substituent.

[化學式60]

Figure 02_image115
[chemical formula 60]
Figure 02_image115

上述式(Z3)中，R6e 表示亦可具有取代基的伸烷基，R7e 表示氫原子或甲基。In the above formula (Z3), R 6e represents an alkylene group which may have a substituent, and R 7e represents a hydrogen atom or a methyl group.

(R1e 及R2e ) 該式(Z1)中，R1e 及R2e 分別獨立表示氫原子、亦可具有取代基的烷基、以通式(Z2)所表示之基團，或以通式(Z3)所表示之基團。 作為烷基，舉例如直鏈狀、分支鏈狀或環狀的烷基。其碳數較佳為1以上，更佳為2以上，再佳為4以上，又，較佳為10以下，更佳為6以下，再佳為4以下。(R 1e and R 2e ) In the formula (Z1), R 1e and R 2e independently represent a hydrogen atom, an alkyl group that may have a substituent, a group represented by the general formula (Z2), or a group represented by the general formula The group represented by (Z3). Examples of the alkyl group include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less.

作為烷基的具體例，舉例如甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基等。該等之中，較佳為第三丁基。 又，作為烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等。Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and the like. Among these, tertiary butyl is preferred. In addition, examples of substituents that the alkyl group may have include methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer, phenyl, carboxyl , acryl, methacryl, etc.

(R3e ) 該式(Z1)中，R3e 表示氫原子或鹵素原子。 作為鹵素原子，舉例如氟原子、氯原子、溴原子、碘原子等。 該等之中，從合成容易性的觀點來看，R3e 較佳為氫原子。(R 3e ) In the formula (Z1), R 3e represents a hydrogen atom or a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. Among these, R 3e is preferably a hydrogen atom from the viewpoint of easiness of synthesis.

(R4e ) 該式(Z2)中，R4e 表示亦可具有取代基的伸烷基。 作為伸烷基，舉例如直鏈狀、分支鏈狀或環狀的伸烷基。其碳數通常為1以上，較佳為2以上，又，較佳為6以下，更佳為4以下，再佳為3以下。(R 4e ) In the formula (Z2), R 4e represents an alkylene group which may have a substituent. Examples of the alkylene group include linear, branched or cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, still more preferably 3 or less.

作為伸烷基的具體例，舉例如亞甲基、伸乙基、伸丙基、伸丁基等。該等之中，較佳為伸乙基。 又，作為伸烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等。Specific examples of the alkylene group include a methylene group, an ethylene group, a propylidene group, and a butylene group. Among these, ethylene is preferred. In addition, examples of substituents that the alkylene group may have include methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer, phenyl, Carboxyl, acryl, methacryl, etc.

該等之中，R4e 較佳為伸乙基。Among them, R 4e is preferably ethylene.

(R5e ) 該式(Z2)中，R5e 表示亦可具有取代基的烷基。 作為烷基，舉例如直鏈狀、分支鏈狀或環狀的烷基。其碳數較佳為4以上，更佳為5以上，再佳為7以上，又，較佳為15以下，更佳為10以下，再佳為9以下。(R 5e ) In the formula (Z2), R 5e represents an alkyl group which may have a substituent. Examples of the alkyl group include linear, branched or cyclic alkyl groups. The carbon number is preferably at least 4, more preferably at least 5, even more preferably at least 7, and is preferably at most 15, more preferably at most 10, and still more preferably at most 9.

作為烷基的具體例，舉例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基等。 又，作為烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等。 該等之中，從錐狀的觀點來看，R5e 較佳為庚基、辛基、壬基。Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and the like. In addition, examples of substituents that the alkyl group may have include methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer, phenyl, carboxyl , acryl, methacryl, etc. Among these, R 5e is preferably a heptyl group, an octyl group, or a nonyl group from the viewpoint of conical shape.

(R6e ) 作為伸烷基，舉例如直鏈狀、分支鏈狀或環狀的伸烷基。其碳數通常為1以上，較佳為2以上，又，較佳為6以下，更佳為4以下，再佳為3以下。(R 6e ) Examples of the alkylene group include linear, branched or cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, still more preferably 3 or less.

作為伸烷基的具體例，舉例如亞甲基、伸乙基、伸丙基、伸丁基等。該等之中，較佳為伸乙基。 又，作為伸烷基可具有的取代基，舉例如甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、寡聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基等。Specific examples of the alkylene group include a methylene group, an ethylene group, a propylidene group, and a butylene group. Among these, ethylene is preferred. In addition, examples of substituents that the alkylene group may have include methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligomer, phenyl, Carboxyl, acryl, methacryl, etc.

該等之中，從錐狀的觀點來看，較佳係R1e 為第三丁基、R2e 為以通式(Z2)所表示之基團(但R4e 為亞甲基、及R5e 為碳數7~9的烷基)、R3e 為氫原子的化合物，或是R1e 為氫原子、R2e 為以通式(Z3)所表示之基團(但R6e 為亞甲基、及R7e 為甲基)、R3e 為氫原子的化合物，更佳係R1e 為第三丁基、R2e 為以通式(Z2)所表示之基團(但R4e 為亞甲基、及R5e 為碳數7~9的烷基)、R3e 為氫原子的化合物。Among them, from the point of view of cone shape, it is preferable that R 1e is a tert-butyl group, R 2e is a group represented by the general formula (Z2) (but R 4e is a methylene group, and R 5e is an alkyl group with 7 to 9 carbons), R 3e is a compound of a hydrogen atom, or R 1e is a hydrogen atom, R 2e is a group represented by the general formula (Z3) (but R 6e is methylene, and R 7e is a methyl group), R 3e is a compound of a hydrogen atom, more preferably R 1e is a tertiary butyl group, R 2e is a group represented by general formula (Z2) (but R 4e is a methylene group, And R 5e is an alkyl group with 7 to 9 carbons), R 3e is a compound of a hydrogen atom.

作為其他苯并***系化合物，舉例如2-(5甲基-2-羥基苯基)苯并***、2-(2-羥基-5-第三丁基苯基)-2H-苯并***、辛基-3[3-第三丁基-4-羥基-5-(5-氯-2H-苯并***-2-基)苯基]丙酸酯與2-乙基己基-3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并***-2-基)苯基]丙酸酯的混合物、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-2H-苯并***、2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯并***、2-(3,5-二-第三戊基-2-羥基苯基)苯并***、2-(2’-羥基-5’-第三辛基苯基)苯并***、2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯乙基)酚、2-(2H-苯并***-2-基)-6-(1-甲基-1-苯乙基)-4-(1,1,3,3-四甲基丁基)酚。As other benzotriazole compounds, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzo Triazole, octyl-3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl- Mixture of 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro Benzotriazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl) benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl) benzo Triazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenethyl)phenol, 2-(2H-benzotriazol-2-yl )-6-(1-methyl-1-phenethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

作為市售的苯并***系化合物，舉例如例如SUMISORB (註冊商標，以下相同)200、SUMISORB250、SUMISORB300、SUMISORB340、SUMISORB350(住友化學製)、JF77、JF78、JF79、JF80、JF83(城北化學工業製)、TINUVIN(註冊商標，以下相同)PS、TINUVIN99-2、TINUVIN109、TINUVIN384-2、TINUVIN 326、TINUVIN900、「TINUVIN 928」、TINUVIN928、TINUVIN1130(BASF製)、EVERSORB70、EVERSORB71、EVERSORB72、EVERSORB73、EVERSORB74、EVERSORB75、EVERSORB76、EVERSORB234、EVERSORB77、EVERSORB78、EVERSORB80、EVERSORB81(台灣永光化學工業製)、TOMISORB (註冊商標，以下相同)100、TOMISORB600(API Corporation製)、SEESORB(註冊商標，以下相同)701、SEESORB702、SEESORB703、SEESORB704、SEESORB706、SEESORB707、SEESORB709(SHIPRO化成製)、RUVA-93(大塚化學股份有限公司)等。Examples of commercially available benzotriazole-based compounds include SUMISORB (registered trademark, the same below) 200, SUMISORB250, SUMISORB300, SUMISORB340, SUMISORB350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (Songhoku Chemical Co., Ltd. TINUVIN (registered trademark, the same below) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (by BASF), EVERSORB70, EVERSORB71, EVERSORB72, 4EVERSORB73, , EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Yongguang Chemical Industry), TOMISORB (registered trademark, hereinafter the same) 100, TOMISORB600 (API Corporation), SEESORB (registered trademark, hereinafter the same) 701, SEESORB702 , SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by SHIPRO Chemicals), RUVA-93 (Otsuka Chemical Co., Ltd.), etc.

作為三嗪系化合物，舉例如2-[4,6-二(2,4-二甲苯基)-1,3,5-三嗪-2-基]-5-辛基氧基酚、2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-[3-(十二氧基)-2-羥基丙氧基]酚、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪與(2-乙基己基)環氧丙酸酯的反應產物、2,4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三嗪等。該等之中，從錐角與曝光感度的觀點來看，較佳為羥基苯基三嗪化合物。 作為市售的三嗪系化合物，可舉例例如TINUVIN400、TINUVIN405、TINUVIN460、TINUVIN477、TINUVIN479(BASF製)等。Examples of triazine compounds include 2-[4,6-bis(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2- [4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy ]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl) ring Oxypropionate reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine Wait. Among them, a hydroxyphenyltriazine compound is preferable from the viewpoint of a cone angle and exposure sensitivity. As a commercially available triazine compound, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (made by BASF) etc. are mentioned, for example.

作為其他紫外線吸收劑，舉例如二苯甲酮化合物、苯甲酸酯化物、桂皮酸衍生物、萘衍生物、蒽及其衍生物、二萘化合物、啡啉化合物、染料等。 更具體而言，舉例例如SUMISORB130(住友化學製)、EVERSORB10、EVERSORB11、EVERSORB12(台灣永光化學工業製)、TOMISORB800(API Corporation製)、SEESORB100、SEESORB101、SEESORB101S、SEESORB102、SEESORB103、SEESORB105、SEESORB106、SEESORB107、SEESORB151(SHIPRO化成製)等的二苯甲酮化合物；SUMISORB 400(住友化學製)、柳酸苯酯等的苯甲酸酯化物；桂皮酸2-乙基己酯、桂皮酸對甲氧基2-乙基己酯、桂皮酸甲氧基異丙酯、桂皮酸甲氧基異戊酯等的桂皮酸衍生物；α-萘酚、β-萘酚、α-萘酚甲醚、α-萘酚***、1,2-二羥基萘、1,3-二羥基萘、1,4-二羥基萘、1,5-二羥基萘、1,6-二羥基萘、1,7-二羥基萘、1,8-二羥基萘、2,3-二羥基萘、2,6-二羥基萘、2,7-二羥基萘等的萘衍生物；蒽、9,10-二羥基蒽等的蒽及其衍生物；偶氮系染料、二苯甲酮系染料、胺基酮系染料、喹啉系染料、蒽醌系染料、二苯基氰基丙烯酸酯系染料、三嗪系染料、對胺基苯甲酸系染料等的染料等。該等之中，從曝光感度的觀點來看，較佳係使用桂皮酸衍生物、萘衍生物，特佳係使用桂皮酸衍生物。Examples of other ultraviolet absorbers include benzophenone compounds, benzoate esters, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, binaphthyl compounds, phenanthroline compounds, and dyes. More specifically, for example, SUMISORB130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongguang Chemical Industry), TOMISORB800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB10 Benzophenone compounds such as SEESORB 151 (manufactured by SHIPRO Chemicals); benzoate esters such as SUMISORB 400 (manufactured by Sumitomo Chemical), phenyl salicylate, etc.; 2-ethylhexyl cinnamate, p-methoxy 2 cinnamate - Cinnamic acid derivatives such as ethylhexyl ester, methoxyisopropyl cinnamate, methoxyisoamyl cinnamate, etc.; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthalene Phenol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene , 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other naphthalene derivatives; anthracene, 9,10-dihydroxyanthracene and other anthracene and its derivatives; azo-based dyes, benzophenone-based dyes, aminoketone-based dyes, quinoline-based dyes, anthraquinone-based dyes, diphenylcyanoacrylate-based dyes, triazine-based dyes, p-amine dyes such as benzoic acid-based dyes, etc. Among them, from the viewpoint of exposure sensitivity, it is preferable to use a cinnamic acid derivative or a naphthalene derivative, and it is particularly preferable to use a cinnamic acid derivative.

該等之中，從錐狀的觀點來看，較佳為苯并***化合物及/或羥基苯基三嗪化合物，特佳為苯并***化合物。Among these, benzotriazole compounds and/or hydroxyphenyltriazine compounds are preferable from the viewpoint of cone shape, and benzotriazole compounds are particularly preferable.

作為紫外線吸收劑，可單獨使用1種化合物，亦可併用2種類以上的化合物。As the ultraviolet absorber, one type of compound may be used alone, or two or more types of compounds may be used in combination.

本發明之有色感光性樹脂組成物含有紫外線吸收劑的情況，其含有比例並未特別限定，在有色感光性樹脂組成物的總固體成分中，通常為0.01質量%以上，較佳為0.05質量%以上，更佳為0.1質量%以上，再佳為0.5質量%以上，特佳為1質量%以上，又，通常為15質量%以下，較佳為10質量%以下，更佳為5質量%以下，再佳為3質量%以下。藉由使其在該下限值以上，會有錐角變大的傾向，又，藉由使其在該上限值以下，會有成為高感度的傾向。有色感光性樹脂組成物含有紫外線吸收劑的情況中，紫外線吸收劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.01~15質量%，較佳為0.05~10質量%，更佳為0.1~5質量%，再佳為0.5~3質量%，再更佳為1~3質量%。When the colored photosensitive resin composition of the present invention contains an ultraviolet absorber, the content ratio is not particularly limited, but it is usually 0.01% by mass or more, preferably 0.05% by mass in the total solid content of the colored photosensitive resin composition. Above, more preferably at least 0.1% by mass, still more preferably at least 0.5% by mass, particularly preferably at least 1% by mass, and usually at most 15% by mass, preferably at most 10% by mass, more preferably at most 5% by mass , more preferably 3% by mass or less. By setting it above the lower limit, the taper angle tends to become large, and by setting it below the upper limit, the sensitivity tends to become high. When the colored photosensitive resin composition contains an ultraviolet absorber, the content ratio of the ultraviolet absorber in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 15% by mass, preferably 0.05 to 10% by mass, More preferably, it is 0.1-5 mass %, More preferably, it is 0.5-3 mass %, More preferably, it is 1-3 mass %.

又，本發明之有色感光性樹脂組成物含有紫外線吸收劑的情況中，作為相對於(B)光聚合起始劑的摻合比，係相對於(B)光聚合起始劑100質量份，紫外線吸收劑的摻合量通常為1質量份以上，較佳為10質量份以上，更佳為30質量份以上，再佳為50質量份以上，特佳為80質量份以上，通常為500質量份以下，較佳為300質量份以下，更佳為200質量份以下，再佳為100質量份以下。藉由使其在該下限值以上，會有錐角變大的傾向，又，藉由使其在該上限值以下，會有成為高感度的傾向。相對於(B)光聚合起始劑100質量份，紫外線吸收劑的摻合量例如為1~500質量份，較佳為10~300質量份，更佳為30~200質量份，再佳為50~100質量份，再更佳為80~100質量份。In addition, when the colored photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio with respect to (B) photopolymerization initiator is relative to 100 parts by mass of (B) photopolymerization initiator, The blending amount of the ultraviolet absorber is usually at least 1 part by mass, preferably at least 10 parts by mass, more preferably at least 30 parts by mass, still more preferably at least 50 parts by mass, particularly preferably at least 80 parts by mass, usually 500 parts by mass Parts or less, preferably less than 300 parts by mass, more preferably less than 200 parts by mass, even more preferably less than 100 parts by mass. By setting it above the lower limit, the taper angle tends to become large, and by setting it below the upper limit, the sensitivity tends to become high. With respect to 100 parts by mass of (B) photopolymerization initiator, the blending amount of the ultraviolet absorber is, for example, 1 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, and even more preferably 50-100 parts by mass, more preferably 80-100 parts by mass.

[1-1-8]聚合抑制劑 本發明之有色感光性樹脂組成物，較佳係含有聚合抑制劑。藉由含有聚合抑制劑，其阻礙自由基聚合，因此會有可使所得之分隔壁的錐角變大的傾向。 作為聚合抑制劑，舉例如氫醌、氫醌單甲醚、甲氫醌、甲氧苯酚、2,6-二-第三丁基-4-甲酚(BHT)等。該等之中，從抑制聚合之能力的觀點來看，較佳為氫醌、甲基氫醌或甲氧苯酚，更佳為甲氫醌。[1-1-8] Polymerization inhibitor The colored photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, since radical polymerization is inhibited, there exists a tendency for the taper angle of the obtained partition to become large. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT), and the like. Among these, hydroquinone, methylhydroquinone, or methoxyphenol is preferable, and methylhydroquinone is more preferable from the viewpoint of the ability to inhibit polymerization.

聚合抑制劑較佳係含有1種或2種以上。通常在製造(C)鹼可溶性樹脂時，有時會在該樹脂中包含聚合抑制劑，亦可將其作為本發明之聚合抑制劑使用，除了樹脂中所包含的聚合抑制劑以外，亦可在製造有色感光性樹脂組成物時添加與其相同或不同的聚合抑制劑。It is preferable to contain 1 type or 2 or more types of polymerization inhibitors. In general, when (C) alkali-soluble resin is produced, a polymerization inhibitor is sometimes included in the resin, and it can also be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor contained in the resin, it can also be included in When producing a colored photosensitive resin composition, the same or different polymerization inhibitors are added.

有色感光性樹脂組成物含有聚合抑制劑的情況，其含有比例並未特別限定，在有色感光性樹脂組成物的總固體成分中，通常為0.0005質量%以上，較佳為0.001質量%以上，更佳為0.01質量%以上，又通常為0.1質量%以下，較佳為0.08質量%以下，更佳為0.05質量%以下。藉由使其在該下限值以上，會有可提高錐角的傾向，又，藉由使其在該上限值以下，會有可保持高感度的傾向。有色感光性樹脂組成物含有聚合抑制劑的情況中，聚合抑制劑在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.0005~0.1質量%，較佳為0.001~0.08質量%，更佳為0.01~0.05質量%。When the colored photosensitive resin composition contains a polymerization inhibitor, the content ratio is not particularly limited, but it is usually 0.0005% by mass or more, preferably 0.001% by mass or more, and more preferably 0.001% by mass or more in the total solid content of the colored photosensitive resin composition. It is preferably at least 0.01% by mass, and usually at most 0.1% by mass, preferably at most 0.08% by mass, more preferably at most 0.05% by mass. By making it more than the lower limit, the taper angle tends to be increased, and by making it below the upper limit, it tends to maintain high sensitivity. When the colored photosensitive resin composition contains a polymerization inhibitor, the content ratio of the polymerization inhibitor in the total solid content of the colored photosensitive resin composition is, for example, 0.0005 to 0.1% by mass, preferably 0.001 to 0.08% by mass, More preferably, it is 0.01 to 0.05% by mass.

[1-1-9]熱聚合起始劑 再者，本發明之有色感光性樹脂組成物中，亦可含有熱聚合起始劑。藉由含有熱聚合起始劑，會有可提高膜之交聯度的傾向。作為這樣的熱聚合起始劑的具體例，舉例例如偶氮系化合物、有機過氧化物及過氧化氫等。該等可單獨使用1種，亦可併用2種以上。[1-1-9] Thermal polymerization initiator Furthermore, the colored photosensitive resin composition of the present invention may contain a thermal polymerization initiator. There exists a tendency for the crosslinking degree of a film to be raised by containing a thermal-polymerization initiator. As a specific example of such a thermal-polymerization initiator, an azo compound, an organic peroxide, hydrogen peroxide, etc. are mentioned, for example. These may be used individually by 1 type, and may use 2 or more types together.

另外，期待提升感度及增加膜之交聯密度而在光聚合起始劑中併用熱聚合起始劑的情況，該等的含有比例的總和，較佳係成為光聚合起始劑在有色感光性樹脂組成物之總固體成分中的含有比例，又，作為光聚合起始劑與熱聚合起始劑的併用比例，從感度的觀點來看，相對於光聚合起始劑100質量份，較佳係使熱聚合起始劑為5~300質量份。In addition, in the case where a thermal polymerization initiator is used together with a photopolymerization initiator in anticipation of increasing the sensitivity and increasing the crosslink density of the film, the sum of these proportions is preferably used as the photopolymerization initiator in the color photosensitive The content ratio in the total solid content of the resin composition, and as the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator, it is preferable from the viewpoint of sensitivity to 100 parts by mass of the photopolymerization initiator The thermal polymerization initiator is 5 to 300 parts by mass.

[1-1-10]胺基化合物 本發明之有色感光性樹脂組成物中，為了促進熱硬化，亦可包含胺基化合物。此情況中，作為有色感光性樹脂組成物中的胺基化合物的含量，在有色感光性樹脂組成物的總固體成分中，通常為40質量%以下，較佳為30質量%以下。又，通常為0.5質量%以上，較佳為1質量%以上。藉由使其在該上限值以下，會有可維持保存穩定性的傾向，藉由使其在該下限值以上，會有可確保充分之熱硬化性的傾向。有色感光性樹脂組成物含有胺基化合物的情況中，胺基化合物在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.5~40質量%，較佳為1~30質量%。[1-1-10] Amino compound The colored photosensitive resin composition of the present invention may contain an amine compound in order to accelerate thermosetting. In this case, the content of the amino compound in the colored photosensitive resin composition is usually 40% by mass or less, preferably 30% by mass or less in the total solid content of the colored photosensitive resin composition. Moreover, it is usually 0.5 mass % or more, Preferably it is 1 mass % or more. There exists a tendency for storage stability to be maintained by making it below this upper limit, and there exists a tendency for sufficient thermosetting property to be ensured by making it more than this lower limit. When the colored photosensitive resin composition contains an amino compound, the content ratio of the amino compound in the total solid content of the colored photosensitive resin composition is, for example, 0.5-40% by mass, preferably 1-30% by mass.

作為胺基化合物，舉例例如具有至少2個羥甲基或對羥甲基進行碳數1~8之醇縮合改質的烷氧基甲基以作為官能基的胺基化合物。具體而言，舉例例如三聚氰胺與甲醛聚縮合的三聚氰胺樹脂；使苯胍胺與甲醛聚縮合的苯胍胺樹脂；使甘脲與甲醛聚縮合的甘脲樹脂；使尿素與甲醛聚縮合的尿素樹脂；使三聚氰胺、苯胍胺、甘脲或尿素等的2種以上與甲醛共聚縮合的樹脂；將上述樹脂的羥甲基進行醇縮合改質的改質樹脂等。該等可單獨使用1種，亦可併用2種以上。作為胺基化合物，其中，較佳為三聚氰胺樹脂及其改質樹脂，更佳為羥甲基的改質比例在70%以上的改質樹脂，特佳為80%以上的改質樹脂。As the amino compound, for example, an amino compound having at least two methylol groups or an alkoxymethyl group modified by alcohol condensation having 1 to 8 carbon atoms as a functional group is exemplified. Specifically, for example, melamine resin obtained by polycondensing melamine and formaldehyde; benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensing glycoluril and formaldehyde; urea resin obtained by polycondensing urea and formaldehyde ; A resin obtained by copolymerizing and condensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde; a modified resin obtained by modifying the methylol groups of the above resins with alcohol condensation. These may be used individually by 1 type, and may use 2 or more types together. As the amino compound, among them, melamine resin and its modified resin are preferred, the modified resin with a methylol modified ratio of 70% or more is more preferred, and the modified resin with 80% or more is particularly preferred.

作為上述胺基化合物的具體例，作為三聚氰胺樹脂及其改質樹脂，舉例例如SITECH公司製的「CYMEL」(註冊商標)300、301、303、350、736、738、370、771、325、327、703、701、266、267、285、232、235、238、1141、272、254、202、1156、1158、及三和化學公司製的「NIKALAC」(註冊商標)MW-390、MW-100LM、MX-750LM、MW-30M、MX-45、MX-302等。又、作為上述苯胍胺樹脂及其改質樹脂，舉例例如SITECH公司製的「CYMEL」(註冊商標)1123、1125、1128等。又、作為上述甘脲樹脂及其改質樹脂，舉例例如SITECH公司製的「CYMEL」(註冊商標)1170、1171、1174、1172、以及三和化學公司製的「NIKALAC 」(註冊商標)MX-270等。又，作為上述尿素樹脂及其改質樹脂，舉例例如SITECH公司製的「UFR」(註冊商標)65、300、以及三和化學公司製的「NIKALAC 」(註冊商標)MX-290等。Specific examples of the above-mentioned amino compounds include melamine resins and modified resins thereof, such as "CYMEL" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by SITECH Corporation. . , MX-750LM, MW-30M, MX-45, MX-302, etc. Moreover, as said benzoguanamine resin and its modified resin, "CYMEL" (registered trademark) 1123, 1125, 1128 etc. manufactured by Sitech Corporation are mentioned, for example. In addition, as the above-mentioned glycoluril resin and its modified resin, for example, "CYMEL" (registered trademark) 1170, 1171, 1174, 1172 manufactured by SITECH Corporation, and "NIKALAC" (registered trademark) MX- 270 etc. In addition, examples of the urea resin and its modified resin include "UFR" (registered trademark) 65 and 300 manufactured by Sitech Corporation, and "NIKALAC" (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd., and the like.

[1-1-11]塗布性提升劑、顯影改良劑 本發明之有色感光性樹脂組成物中，為了提升塗布性及顯影溶解性，亦可含有塗布性提升劑及顯影改良劑。作為塗布性提升劑或顯影改良劑，例如，可使用習知的陽離子性、陰離子性、非離子性、氟系、聚矽氧系界面活性劑。又，作為顯影改良劑，可使用有機羧酸或其酸酐等習知者。又，其含量，從感度的觀點來看，相對於感光性樹脂組成物的總固體成分，通常為20質量%以下，較佳為10質量%以下。[1-1-11] Coatability enhancer and development improver The colored photosensitive resin composition of the present invention may contain a coatability enhancer and a development improver in order to improve coatability and development solubility. As the applicability enhancer or development improver, for example, known cationic, anionic, nonionic, fluorine-based, silicone-based surfactants can be used. Moreover, as a development improving agent, a well-known thing, such as an organic carboxylic acid or its anhydride, can be used. Moreover, its content is usually 20 mass % or less with respect to the total solid content of a photosensitive resin composition from a viewpoint of sensitivity, Preferably it is 10 mass % or less.

[1-1-12]矽烷偶合劑 本發明之有色感光性樹脂組成物中，為了改善與基板的密合性，添加矽烷偶合劑亦佳。作為矽烷偶合劑的種類，可使用環氧系、甲基丙烯酸系、胺基系、咪唑系等各個種類，從提升密合性的觀點來看，特佳為環氧系、咪唑系的矽烷偶合劑。其含量，從密合性的觀點來看，相對於有色感光性樹脂組成物的總固體成分，通常為20質量%以下，較佳為15質量%以下。[1-1-12] Silane coupling agent In the colored photosensitive resin composition of the present invention, it is also preferable to add a silane coupling agent in order to improve the adhesion with the substrate. As the type of silane coupling agent, various types such as epoxy-based, methacrylic-based, amino-based, and imidazole-based can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred. mixture. The content thereof is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content of the colored photosensitive resin composition from the viewpoint of adhesion.

[1-1-13]無機填充劑 又，本發明之有色感光性樹脂組成物中亦可更含有無機填充劑，其目的係提升作為硬化物之強度並且提升與鹼可溶性樹脂適度之相互作用(基質結構的形成)而使塗膜具有優良之平坦性、以及提升錐角等。作為這種無機填充劑，舉例例如滑石、二氧化矽、氧化鋁、硫酸鋇、氧化鎂、氧化鈦或是以各種矽烷偶合劑對該等進行表面處理者等。[1-1-13] Inorganic filler In addition, the colored photosensitive resin composition of the present invention may further contain an inorganic filler, the purpose of which is to increase the strength of the hardened product and to enhance the appropriate interaction with the alkali-soluble resin ( The formation of the matrix structure) makes the coating film have excellent flatness, and enhances the taper angle, etc. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesia, titanium oxide, and those subjected to surface treatment with various silane coupling agents.

作為該等無機填充劑的平均粒徑，通常為0.005~2μm，較佳為0.01~1μm。此處本實施形態中所指的平均粒徑，係以BECKMANCOULTER公司製等的雷射繞射散射粒度分布測量裝置所測量的值。此等無機填充劑中，特別是摻合氧化矽溶膠及氧化矽溶膠改質物，會有分散穩定性與提升錐角的效果優良的傾向，因此較佳。本發明之有色感光性樹脂組成物包含該等無機填充劑的情況中，作為其含量，從感度的觀點來看，在總固體成分中，通常為5質量%以上，較佳為10質量%以上，通常為80質量%以下，較佳為70質量%以下。The average particle size of these inorganic fillers is usually 0.005 to 2 μm, preferably 0.01 to 1 μm. Here, the average particle diameter referred to in this embodiment is a value measured with a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter Co., Ltd. or the like. Among these inorganic fillers, especially blending of silica sol and silica sol-modified substances tends to be excellent in dispersion stability and the effect of increasing the cone angle, so it is preferable. When the colored photosensitive resin composition of the present invention contains these inorganic fillers, the content thereof is usually at least 5% by mass, preferably at least 10% by mass, of the total solid content from the viewpoint of sensitivity. , usually 80% by mass or less, preferably 70% by mass or less.

[1-1-14]密合性提升劑 本發明之有色感光性樹脂組成物中，以賦予與基板之密合性為目的，亦可使其含有磷酸系乙烯屬單體。作為磷酸系乙烯屬單體，較佳為含有(甲基)丙烯醯氧基之磷酸酯類，更佳為以下述通式(g1)、(g2)、(g3)所表示者。[1-1-14] Adhesion Improver The colored photosensitive resin composition of the present invention may contain a phosphate-based vinyl monomer for the purpose of imparting adhesiveness to the substrate. Phosphate-based vinyl monomers are preferably phosphoric acid esters containing a (meth)acryloxy group, more preferably those represented by the following general formulas (g1), (g2), and (g3).

[化學式61]

Figure 02_image117
[chemical formula 61]
Figure 02_image117

上述通式(g1)、(g2)、(g3)中，R51 表示氫原子或甲基，l及l’表示1~10的整數，m為1、2或3。In the above-mentioned general formulas (g1), (g2), and ( g3 ), R represents a hydrogen atom or a methyl group, l and l' represent an integer of 1 to 10, and m is 1, 2 or 3.

該等的磷酸系乙烯屬單體可單獨使用1種，亦可組合2種以上使用。使用該等磷酸系乙烯屬單體的情況，其含有比例，在有色感光性樹脂組成物的總固體成分中，通常為0.02質量%以上，更佳為0.05質量%以上，再佳為0.1質量%以上，特佳為0.2質量%以上。又4質量%以下，更佳為3質量%以下，再佳為2質量%以下，特佳為1質量%以下。藉由使其在該下限值以上，會有與基板之密合性的改善效果變得充分的傾向，藉由使其在該上限值以下，會有容易抑制與基板之密合性惡化的傾向。有色感光性樹脂組成物含有磷酸系乙烯屬單體的情況中，磷酸系乙烯屬單體在有色感光性樹脂組成物之總固體成分中的含有比例，例如為0.02~4質量%，較佳為0.05~3質量%，更佳為0.1~2質量%，再佳為0.2~1質量%。These phosphate-based vinyl monomers may be used alone or in combination of two or more. When using such phosphate-based vinyl monomers, the content ratio thereof is usually at least 0.02% by mass, more preferably at least 0.05% by mass, and still more preferably at least 0.1% by mass, based on the total solid content of the colored photosensitive resin composition. or more, particularly preferably 0.2% by mass or more. 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and most preferably 1% by mass or less. By setting it above the lower limit, the effect of improving the adhesion with the substrate tends to be sufficient, and by setting it below the upper limit, it becomes easy to suppress the deterioration of the adhesion with the substrate. Propensity. When the colored photosensitive resin composition contains a phosphate-based vinyl monomer, the content ratio of the phosphate-based vinyl monomer in the total solid content of the colored photosensitive resin composition is, for example, 0.02 to 4% by mass, preferably 0.05-3% by mass, more preferably 0.1-2% by mass, even more preferably 0.2-1% by mass.

[1-1-15]溶劑 本發明之有色感光性樹脂組成物，通常含有溶劑，其係在將前述各成分溶解或分散於溶劑的狀態下使用。作為該溶劑，並無特別限制，舉例例如以下記載的有機溶劑。[1-1-15] Solvent The colored photosensitive resin composition of the present invention usually contains a solvent, and is used in a state where the aforementioned components are dissolved or dispersed in the solvent. It does not specifically limit as this solvent, For example, the organic solvent described below is mentioned.

乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單正丁醚、丙二醇第三丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丁醚、甲氧基甲基戊醇、二丙二醇單***、二丙二醇單甲醚、3-甲基-3-甲氧基丁醇、3-甲氧基-1-丁醇、三乙二醇單甲醚、三乙二醇單***、三丙二醇甲醚之類的二醇單烷醚類；乙二醇二甲醚、乙二醇二***、二乙二醇二甲醚、二乙二醇乙基甲醚、二乙二醇二***、二乙二醇二丙醚、二乙二醇二丁醚、二丙二醇二甲醚之類的二醇二烷醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、甲氧基丁基乙酸酯、3-甲氧基丁基乙酸酯、甲氧基戊基乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單正丁醚乙酸酯、二丙二醇單甲醚乙酸酯、三乙二醇單甲醚乙酸酯、三乙二醇單***乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲氧基-1-丁基乙酸酯之類的二醇烷醚乙酸酯類；乙二醇二乙酸酯、1,3-伸丁基二醇二乙酸酯、1,6-己醇二乙酸酯等的二醇二乙酸酯類；環己醇乙酸酯等的烷基乙酸酯類；戊醚、二***、二丙醚、二異丙醚、二丁醚、二戊醚、乙基異丁醚、二己醚之類的醚類；丙酮、甲乙酮、甲基戊基酮、甲基異丙基酮、甲基異戊基酮、二異丙基酮、二異丁基酮、甲基異丁基酮、環己酮、乙基戊基酮、甲基丁基酮、甲基己基酮、甲基壬基酮、甲氧基甲基戊酮之類的酮類；甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丁二醇、二乙二醇、二丙二醇、三乙二醇、甲氧基甲基戊醇、甘油、苄醇之類的1價或多元醇類；正戊烷、正辛烷、二異伸丁基、正己烷、己烯、異戊二烯、二戊烯、十二烷之類的脂肪族烴類；環己烷、甲基環己烷、甲基環己烯、雙環己基之類的脂環式烴類；苯、甲苯、二甲苯、異丙苯之類的芳香族烴類；甲酸戊酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、乙酸戊酯、異丁酸甲酯、乙二醇乙酸酯、丙酸乙酯、丙酸丙酯、丁酸丁酯、丁酸異丁酯、異丁酸甲酯、辛酸乙酯、硬脂酸丁脂、苯甲酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、γ-丁內酯之類的鏈狀或環狀酯類；3-甲氧基丙酸、3-乙氧基丙酸之類的烷氧基羧酸類；氯丁烷、氯戊烷之類的鹵代烴類；甲氧基甲基戊酮之類的醚酮類；乙腈、苯甲腈之類的腈類：四氫呋喃、二甲基四氫呋喃、二甲氧基四氫呋喃之類的四氫呋喃類等。Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tertiary butyl ether, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxy Glycol monoalkyl ethers such as butanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether , ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol di Glycol dialkyl ethers such as methyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentylacetate Ester, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate Diol alkanes such as ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate Ether acetates; glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, etc.; cyclohexanol ethyl alcohol Alkyl acetates such as acid esters; ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether; acetone, Methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone , methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone and other ketones; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol Monovalent or polyhydric alcohols such as alcohol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; n-pentane, n-octane , diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane and other aliphatic hydrocarbons; cyclohexane, methylcyclohexane, methylcyclohexene, bicyclo Alicyclic hydrocarbons such as hexyl; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate ester, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate lipid, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as propyl oxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; 3-methoxypropionic acid, 3-ethoxypropionic acid, etc. Alkoxy carboxylic acids; halogenated hydrocarbons such as chlorobutane and chloropentane; methoxymethylpentanone and the like nitriles such as acetonitrile and benzonitrile: tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran, etc.

作為與上述相當的市售溶劑，舉例如礦精、BARUSORU＃2、APCO＃18溶劑、APCO稀釋劑、SOKAL溶劑No.1及No.2、SOLVESSO＃150、Shell TS28 溶劑、卡必醇、乙基卡必醇、丁基卡必醇、甲基賽路蘇、乙基賽路蘇、乙基賽路蘇乙酸酯、甲基賽路蘇乙酸酯、DIGLYME(皆為商品名稱)等。Commercially available solvents equivalent to the above include mineral concentrate, BARUSORU #2, APCO #18 solvent, APCO diluent, SOKAL solvent No.1 and No.2, SOLVESSO #150, Shell TS28 solvent, carbitol, ethyl alcohol, Acyl carbitol, butyl carbitol, methyl celuso, ethyl celuso, ethyl celuso acetate, methyl celuso acetate, DIGLYME (all are trade names), etc.

上述溶劑，可使有色感光性樹脂組成物中的各成分溶解或分散，其可因應本發明之有色感光性樹脂組成物的使用方法選擇，但從塗布性的觀點來看，較佳係選擇在大氣壓下(1013.25hPa)的沸點在60~280℃之範圍者。更佳為具有70~260℃之沸點者，例如較佳為丙二醇單甲醚、3-甲氧基-1-丁醇、丙二醇單甲醚乙酸酯、3-甲氧基-1-丁基乙酸酯。The above-mentioned solvent can dissolve or disperse the components in the colored photosensitive resin composition, and it can be selected according to the usage method of the colored photosensitive resin composition of the present invention. The boiling point at atmospheric pressure (1013.25hPa) is in the range of 60~280℃. More preferably, it has a boiling point of 70~260°C, such as propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl Acetate.

該等的溶劑可單獨使用1種或混和2種以上使用。又，該等的溶劑，較佳係使用來讓在有色感光性樹脂組成物中的總固體成分的含有比例通常為10質量%以上，較佳為15質量%以上，更佳為20質量%以上，通常為90質量%以下，較佳為50質量%以下，更佳為40質量%以下，再佳為35質量%以下。藉由使其在該下限值以上，會有可抑制發生塗布不均的傾向，又，藉由使其在該上限值以下，會有可抑制產生異物、收縮等的傾向。例如，可以在有色感光性樹脂組成物中的總固體成分之含有比例成為10~90質量%，較佳為10~50質量%，更佳為15~40質量%，再佳為20~35質量%的方式使用溶劑。These solvents can be used individually by 1 type or in mixture of 2 or more types. In addition, these solvents are preferably used so that the content ratio of the total solid content in the colored photosensitive resin composition is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more , usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less. By making it more than this lower limit, there exists a tendency for the generation|occurrence|production of coating unevenness to be suppressed, and by making it below this upper limit, there exists a tendency for the generation|occurrence|production of a foreign material, shrinkage, etc. to be suppressed. For example, the content ratio of the total solid content in the colored photosensitive resin composition may be 10 to 90% by mass, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, even more preferably 20 to 35% by mass % way to use solvents.

[1-2]有色感光性樹脂組成物的調製方法 本發明之有色感光性樹脂組成物，係以攪拌機混合上述各成分而調製。 例如，包含顏料等的無須溶劑之成分作為(E)著色劑的情況中，較佳係預先使用塗料振盪器、砂磨機、球磨機、輥研磨機、石磨、噴射磨機、均質機等進行分散處理。藉由分散處理可使(E)著色劑微粒子化，因此會提升有色感光性樹脂組成物的塗布特性。[1-2] Preparation method of colored photosensitive resin composition The colored photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components with a mixer. For example, in the case of (E) a colorant containing a solvent-free component such as a pigment, it is preferable to carry out the process in advance using a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. Distributed processing. Since the (E) colorant can be made into fine particles by the dispersion treatment, the coating properties of the colored photosensitive resin composition can be improved.

分散處理，通常係由併用(E)著色劑、溶劑及(F)分散劑的系統進行，較佳係與該等任意併用(C)鹼可溶性樹脂的一部分或全部的系統進行(以下，有時將提供至分散處理的混合物以及由該處理所得之組成物稱為「印墨」或「顏料分散液」)。尤其若使用高分子分散劑作為(F)分散劑，可抑制所得之印墨及有色感光性樹脂組成物的黏度隨著時間增加(分散穩定性優良)，因而較佳。 如此，在製造有色感光性樹脂組成物的工序中，較佳係製造至少含有(E)著色劑、溶劑及(F)分散劑的顏料分散液。 作為可用於顏料分散液的(E)著色劑、有機溶劑及(F)分散劑，較佳為採用上述記載可用於有色感光性樹脂組成物者。又，作為顏料分散液中的(E)著色劑的各著色劑的含有比例，較佳為採用上述記載的有色感光性樹脂組成物中的含有比例。Dispersion treatment is usually carried out by a system using (E) a colorant, a solvent, and (F) a dispersant in combination, and it is preferably carried out with a system in which any or all of (C) an alkali-soluble resin is used in combination (hereinafter, sometimes The mixture subjected to the dispersion treatment and the composition resulting from the treatment are called "ink" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the (F) dispersant because it can suppress the increase in viscosity of the obtained ink and colored photosensitive resin composition over time (excellent dispersion stability). Thus, in the process of manufacturing a colored photosensitive resin composition, it is preferable to manufacture the pigment dispersion liquid containing at least (E) coloring agent, a solvent, and (F) dispersing agent. As the (E) colorant, organic solvent, and (F) dispersant that can be used for the pigment dispersion liquid, those that can be used for the colored photosensitive resin composition according to the above description are preferable. Moreover, as the content ratio of each coloring agent of (E) coloring agent in a pigment dispersion liquid, it is preferable to adopt the content ratio in the colored photosensitive resin composition described above.

以砂磨機使(E)著色劑分散的情況中，較佳係使用粒徑為0.1~8mm左右的玻璃珠或二氧化鋯珠。分散處理條件，溫度通常為0℃至100℃，較佳為室溫至80℃的範圍。分散時間，根據液體的組成及分散處理裝置的尺寸等而有不同的適當時間，因此會適當調整。分散的目標係控制印墨的光澤以使有色感光性樹脂組成物的20度鏡面光澤度(JIS Z8741)在50~300的範圍內。When dispersing the (E) colorant with a sand mill, it is preferable to use glass beads or zirconia beads with a particle diameter of about 0.1 to 8 mm. Dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, preferably in the range of room temperature to 80°C. Dispersion time is appropriately adjusted depending on the composition of the liquid and the size of the dispersion treatment device, etc. The goal of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the colored photosensitive resin composition is within the range of 50-300.

又，分散於印墨中之顏料的分散粒徑通常為0.03~0.3μm，其係由動態光散射法等測量。 接著，將由上述分散處理所得之印墨與有色感光性樹脂組成物中所包含的上述其他成分混合，以作為均勻的溶液。有色感光性樹脂組成物的製造工序中，有時在液體中混入微細雜質，因此期望以過濾器等對所得之有色感光性樹脂組成物進行過濾處理。Also, the dispersed particle size of the pigment dispersed in the printing ink is usually 0.03 to 0.3 μm, which is measured by a dynamic light scattering method or the like. Next, the printing ink obtained by the above-mentioned dispersion treatment is mixed with the above-mentioned other components contained in the colored photosensitive resin composition to form a uniform solution. In the production process of the colored photosensitive resin composition, since fine impurities may be mixed in the liquid, it is desirable to filter the obtained colored photosensitive resin composition with a filter or the like.

[2]分隔壁及其形成方法 本發明之有色感光性樹脂組成物，較佳係可用於形成分隔壁，尤其是用以劃分有機電致發光元件之有機層的分隔壁。本發明之分隔壁，係由本發明之有色感光性樹脂組成物所構成。 使用以上說明之有色感光性樹脂組成物形成分隔壁的方法並未特別限制，可採用以往習知的方法。作為分隔壁的形成方法，舉例例如包含塗布工序，將有色感光性樹脂組成物塗布於基板上以形成感光性樹脂組成物層；及曝光工序，對感光性樹脂組成物層進行曝光之方法。作為這樣的分隔壁的形成方法的具體例，舉例如噴墨法與光微影法。[2] Partition wall and its forming method The colored photosensitive resin composition of the present invention is preferably used to form a partition wall, especially a partition wall for dividing the organic layer of an organic electroluminescence element. The partition wall of the present invention is composed of the colored photosensitive resin composition of the present invention. The method of forming the partition using the colored photosensitive resin composition described above is not particularly limited, and conventionally known methods can be used. The method for forming the partition wall includes, for example, a coating step of applying a colored photosensitive resin composition on a substrate to form a photosensitive resin composition layer; and an exposure step of exposing the photosensitive resin composition layer. As a specific example of the formation method of such a partition, an inkjet method and a photolithography method are mentioned, for example.

噴墨法中，使用以溶劑稀釋等來調整黏度的有色感光性樹脂組成物作為印墨，沿著既定的分隔壁圖案，以噴墨法將印墨液滴吐出至基板上，藉此將有色感光性樹脂組成物塗布於基板上，形成未硬化的分隔壁圖案。接著，對未硬化的分隔壁的圖案進行曝光，而在基板上形成硬化的分隔壁。對於未硬化之分隔壁圖案進行曝光，除了不使用光罩以外，係以與後述光微影法中的曝光工序相同的工序進行。In the inkjet method, a colored photosensitive resin composition whose viscosity is adjusted by diluting with a solvent is used as the ink, and ink droplets are ejected onto the substrate by the inkjet method along a predetermined partition wall pattern, whereby the colored The photosensitive resin composition is coated on the substrate to form an unhardened partition wall pattern. Next, the pattern of the uncured partition walls is exposed to form cured partition walls on the substrate. The exposure of the uncured partition wall pattern is performed in the same process as the exposure process in the photolithography method described later, except that a photomask is not used.

光微影法中，將有色感光性樹脂組成物塗布於基板上形成有分隔壁的整個區域，而形成有色感光性樹脂組成物層。將所形成之有色感光性樹脂組成物層對應既定的分隔壁圖案曝光後，將經曝光的有色感光性樹脂組成物層顯影，而在基板上形成分隔壁。In the photolithography method, a colored photosensitive resin composition is applied to the entire region on the substrate where the partition walls are formed to form a colored photosensitive resin composition layer. After exposing the formed colored photosensitive resin composition layer corresponding to the predetermined partition wall pattern, the exposed colored photosensitive resin composition layer is developed to form partition walls on the substrate.

光微影法中，在基板上塗布有色感光性樹脂組成物的塗布工序中，在應形成分隔壁的基板上，使用輥塗布機、反向塗布機、棒塗布機等的接觸轉印型塗布裝置或旋塗機(旋轉式塗布裝置)、融流塗布機等的非接觸型塗布裝置塗布感光性樹脂組成物，並因應需求藉由乾燥去除溶劑，而形成有色感光性樹脂組成物層。In photolithography, in the coating process of coating a colored photosensitive resin composition on a substrate, contact transfer coating using a roll coater, reverse coater, bar coater, etc. A non-contact coating device such as a spin coater (rotary coating device), melt flow coater, etc. applies a photosensitive resin composition, and if necessary, removes the solvent by drying to form a colored photosensitive resin composition layer.

接著，在曝光工序中利用負型光罩，對有色感光性樹脂組成物照射紫外線、準分子雷射光等的活性能量線，以對應分隔壁的圖案將有色感光性樹脂組成物層進行部分曝光。曝光係可使用高壓水銀燈、超高壓水銀燈、氙氣燈、碳電弧燈等的發出紫外線之光源。曝光量根據有色感光性樹脂組成物的組成而有所不同，較佳為例如10~400mJ/cm2 左右。Next, in the exposure step, the colored photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask to partially expose the colored photosensitive resin composition layer in a pattern corresponding to the partition walls. For the exposure system, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the colored photosensitive resin composition, but is preferably, for example, about 10 to 400 mJ/cm 2 .

接著，顯影工序中，以顯影液將對應分隔壁之圖案進行曝光的有色感光性樹脂組成物層進行顯影，而形成分隔壁。顯影方法並未特別限制，可使用浸漬法、噴霧法等。作為顯影液的具體例，舉例如二甲基苄胺、單乙醇胺、二乙醇胺、三乙醇胺等的有機系顯影液，或是氫氧化鈉、氫氧化鉀、碳酸鈉、氨、4級銨鹽等的水溶液。又，顯影液中可添加消泡劑或界面活性劑。Next, in the developing process, the colored photosensitive resin composition layer exposed corresponding to the pattern of the partition wall is developed with a developer to form the partition wall. The image development method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of developers include organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. of aqueous solution. In addition, an antifoaming agent or a surfactant may be added to the developer.

之後，對顯影後的分隔壁實施後烘烤，以進行加熱硬化。後烘烤較佳為150~250℃、15~60分鐘。Thereafter, post-baking is performed on the developed partition to heat-harden it. The post-baking is preferably at 150~250° C. for 15~60 minutes.

用於形成分隔壁的基板並未特別限制，係配合使用形成有分隔壁之基板所製造的有機電致發光元件的種類適當選擇。作為較佳的基板材料，舉例如玻璃及各種樹脂材料。作為樹脂材料的具體例，舉例如聚對酞酸乙二酯等的聚酯；聚乙烯及聚丙烯等的聚烯烴；聚碳酸酯；聚(甲基)丙烯酸樹脂；聚碸；聚醯亞胺。該等的基板材料之中，從耐熱性優良來看，較佳為玻璃或聚醯亞胺。又，因應所製造之有機電致發光元件的種類，亦可在形成有分隔壁的基板表面上預先設置ITO或ZnO等的透明電極層。The substrate for forming the partition wall is not particularly limited, and it is appropriately selected according to the type of the organic electroluminescent element manufactured using the substrate on which the partition wall is formed. As preferred substrate materials, for example, glass and various resin materials. Specific examples of resin materials include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resins; . Among these substrate materials, glass or polyimide is preferable because of its excellent heat resistance. Also, depending on the type of organic electroluminescent element to be manufactured, a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the partition walls are formed.

分隔壁的形狀等並未特別限定，在使用含有溶劑溶解性低之成分的印墨形成既定膜厚之功能層時，較佳為厚膜。作為此情況中的分隔壁的膜厚，較佳為5μm以上，更佳為7μm以上，再佳為8μm以上，特佳為10μm以上，通常為20μm以下。作為分隔壁的膜厚，舉例例如5~20μm，較佳為7~20μm，更佳為8~20μm，再佳為10~20μm。The shape of the partition wall is not particularly limited, and when a functional layer having a predetermined film thickness is formed using an ink containing a component with low solvent solubility, a thick film is preferable. The film thickness of the partition wall in this case is preferably 5 μm or more, more preferably 7 μm or more, further preferably 8 μm or more, particularly preferably 10 μm or more, and usually 20 μm or less. The film thickness of the partition is, for example, 5 to 20 μm, preferably 7 to 20 μm, more preferably 8 to 20 μm, further preferably 10 to 20 μm.

[3]有機電致發光元件 本發明之有機電致發光元件具備本發明之分隔壁。 使用具備由以上說明之方法所製造之分隔壁圖案的基板，來製造各種有機電致發光元件。形成有機電致發光元件的方法並未特別限定，較佳為以上述方法於基板上形成分隔壁之圖案後，在基板上被分隔壁圍住的區域內注入印墨而形成像素等的有機層，藉此製造有機電致發光元件。 作為有機電致發光元件的型態，舉例如底部發光型及頂部發光型。 底部發光型中，例如，在積層有透明電極的玻璃基板上形成分隔壁，在被分隔壁圍住的開口部中積層電洞輸送層、發光層、電子輸送層、金屬電極層以進行製作。另一方面，頂部發光型中，例如，在積層有金屬電極層的玻璃基板上形成分隔壁，於被分隔壁圍住的開口部中積層電子輸送層、發光層、電洞輸送層、透明電極層以進行製作。[3] Organic electroluminescence element The organic electroluminescence element of the present invention includes the partition wall of the present invention. Various organic electroluminescence elements were produced using the substrate provided with the partition pattern produced by the method described above. The method of forming the organic electroluminescent element is not particularly limited, and it is preferable to form the pattern of the partition wall on the substrate by the above method, and then inject ink into the area surrounded by the partition wall on the substrate to form organic layers such as pixels , thereby fabricating organic electroluminescent elements. Types of organic electroluminescent elements include bottom emission type and top emission type, for example. In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode are stacked in an opening surrounded by the partition wall. layer for production.

分隔壁為拖尾形狀的情況，用以形成有機層的印墨會在分隔壁的拖尾部分被排斥，而會有用以形成有機層的印墨無法充分被覆由分隔所壁圍住之區域的情況。相對於此，藉由形成無拖尾的良好形狀，由用以形成有機層的印墨可充分被覆由分隔壁所圍住的區域。藉此，例如，可消除有機EL顯示元件中的暈影問題。In the case where the partition wall has a trailing shape, the ink used to form the organic layer will be repelled at the trailing part of the partition wall, and the ink used to form the organic layer may not be able to sufficiently cover the area surrounded by the partition wall Condition. In contrast, by forming a good shape without smearing, the ink used to form the organic layer can sufficiently cover the area surrounded by the partition walls. Thereby, for example, the problem of vignetting in an organic EL display element can be eliminated.

作為形成有機層形成用之印墨時所使用的溶劑，可使用水、有機溶劑及該等的混合溶劑。有機溶劑，只要可從注入印墨後所形成之皮膜去除，則無特別限定。作為有機溶劑的具體例，舉例如甲苯、二甲苯、苯甲醚、均三甲苯、四氫萘、環己苯、丙酮、甲乙酮、甲基異丁酮、環己酮、甲醇、乙醇、異丙醇、乙酸乙酯、乙酸丁酯、3-苯氧基甲苯等。又，印墨中亦可添加界面活性劑、抗氧化劑、黏度調整劑、紫外線吸收劑等。As the solvent used when forming the ink for forming the organic layer, water, an organic solvent, and a mixed solvent of these can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after injecting the ink. Specific examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl Alcohol, ethyl acetate, butyl acetate, 3-phenoxytoluene, etc. In addition, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, etc. can also be added to the ink.

作為在由分隔壁所圍住之區域內注入印墨的方法，噴墨法可輕易將少量印墨注入既定處，因而較佳。用於形成有機層的印墨，係因應欲製造的有機電致發光元件的種類而適當選擇。以噴墨法注入印墨的情況，印墨的黏度，只要可使印墨從噴墨頭良好地吐出，則無特別限定，較佳為4~20mPa・s，更佳為5~10mPa・s。印墨的黏度，可藉由調整印墨中的固體成分含量、變更溶劑、添加黏度調整劑等來進行調整。As a method of injecting ink into the area surrounded by the partition wall, an inkjet method is preferable because it can easily inject a small amount of ink into a predetermined place. The ink used for forming the organic layer is appropriately selected according to the type of organic electroluminescent device to be produced. In the case of injecting ink by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected from the inkjet head well, but it is preferably 4~20mPa・s, more preferably 5~10mPa・s . The viscosity of the ink can be adjusted by adjusting the solid content of the ink, changing the solvent, adding a viscosity modifier, etc.

另外，作為發光層，舉例如日本特開2009-146691號公報及日本專利第5734681號公報中所記載的有機電致發光層。又，亦可使用日本專利第5653387號公報及日本專利第5653101號公報中所記載的量子點。In addition, examples of the light-emitting layer include organic electroluminescent layers described in JP-A-2009-146691 and JP-A-5734681. In addition, quantum dots described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[4]影像顯示裝置 本發明之影像顯示裝置包含本發明之有機電致發光元件。只要包含本發明之有機電致發光元件，則就影像顯示裝置的型式及結構並無特別限制，例如可使用主動式驅動型有機電致發光元件並以一般方法進行組裝。例如，可以「有機EL顯示器」(Ohmsha公司，2004年8月20日發行，時任靜士、安達千波矢、村田英幸著)所記載之方法，形成本發明之影像顯示裝置。例如，亦可將發出白光的有機電致發光元件與彩色濾波器組合而顯示影像，亦可將RGB等的發光顏色不同的有機電致發光元件組合而顯示影像。[4] Image display device The image display device of the present invention includes the organic electroluminescent device of the present invention. As long as the organic electroluminescent element of the present invention is included, the type and structure of the image display device are not particularly limited. For example, an active driving type organic electroluminescent element can be used and assembled in a general method. For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha Corporation, published on August 20, 2004, by Seishi Oma, Chihaya Adachi, and Hideyuki Murata at the time). For example, an image may be displayed by combining an organic electroluminescence element emitting white light and a color filter, or an image may be displayed by combining an organic electroluminescence element having different emission colors such as RGB.

[5]照明 本發明之照明包含本發明之有機電致發光元件。關於型式及結構未特別限制，可使用本發明之有機電致發光元件並以一般方法組裝。作為有機電致發光元件，可為單純矩陣驅動方式，亦可為主動矩陣驅動方式。 為了使本發明之照明發出白光，亦可使用發出白光的有機電致發光元件。又，亦可組合發光色不同的有機電致發光元件並使各顏色混色為白色而構成，亦可構成來調整混色比例，進而賦予調色功能。 [實施例][5] Lighting The lighting of the present invention includes the organic electroluminescence device of the present invention. The type and structure are not particularly limited, and the organic electroluminescent element of the present invention can be used and assembled by a general method. As an organic electroluminescence element, it may be a simple matrix driving method, or may be an active matrix driving method. In order to make the lighting of the present invention emit white light, organic electroluminescent elements emitting white light can also be used. In addition, organic electroluminescent elements having different luminescent colors may be combined to make the colors mixed into white, and the color mixing ratio may be adjusted to provide a color-matching function. [Example]

以下舉出具體實施例就本發明之有色感光性樹脂組成物進行說明，本發明只要不超出其主旨，則不限於以下的實施例。The colored photosensitive resin composition of the present invention will be described with reference to specific examples below, and the present invention is not limited to the following examples unless the gist thereof is exceeded.

＜鹼可溶性樹脂-I＞ 對於以丙烯酸二環戊甲酯/苯乙烯/縮水甘油甲基丙烯酸酯(莫耳比：0.3/0.1/0.6)作為構成單體的共聚合樹脂，以相對於縮水甘油甲基丙烯酸酯相等的量加成丙烯酸而進行反應，再對其加成四氫酞酸酐進行反應，使其相對於上述共聚合樹脂1莫耳為0.39莫耳，得到鹼可溶性的丙烯酸共聚合樹脂。以GPC進行測量、在聚苯乙烯換算下的重量平均分子量(Mw)為9000，固體成分酸價為80mgKOH/g。相當於(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂。<Alkali-soluble resin-I> For a copolymer resin containing dicyclopentylmethyl acrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as a constituent monomer, the ratio of glycidol Acrylic acid was added in an equal amount to methacrylate to react, and then tetrahydrophthalic anhydride was added to react so that it was 0.39 moles relative to 1 mole of the above-mentioned copolymer resin to obtain an alkali-soluble acrylic copolymer resin. . When measured by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 9,000, and the solid content acid value was 80 mgKOH/g. It corresponds to (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain.

＜鹼可溶性樹脂-II＞ 日本化藥公司製「ZCR-1642H」(Mw6500，酸價98mgKOH/g)。相當於(c2)環氧(甲基)丙烯酸酯樹脂。<Alkali-soluble resin-II> "ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (Mw6500, acid value: 98 mgKOH/g). Corresponds to (c2) epoxy (meth)acrylate resin.

＜鹼可溶性樹脂-III＞＜Alkali-soluble resin-III＞

[化學式62]

Figure 02_image119
[chemical formula 62]
Figure 02_image119

將上述結構的環氧化物(環氧當量264)50g、丙烯酸13.65g、甲氧基丁基乙酸酯60.5g、三苯基膦0.936g及對甲氧苯酚0.032g置入裝設有溫度計、攪拌機、冷卻管的燒瓶內，一邊攪拌、一邊於90℃下使其反應至酸價成為5mgKOH/g以下。反應需12小時，得到環氧丙烯酸酯溶液。Put 50g of epoxide (epoxy equivalent 264) of the above structure, 13.65g of acrylic acid, 60.5g of methoxybutyl acetate, 0.936g of triphenylphosphine and 0.032g of p-methoxyphenol into a thermometer, In the flask of a stirrer and a cooling tube, it was made to react at 90 degreeC, stirring, until the acid value became 5 mgKOH/g or less. The reaction takes 12 hours to obtain an epoxy acrylate solution.

將上述環氧丙烯酸酯溶液25質量份、三羥甲丙烷(TMP)0.74質量份、聯苯四羧酸二酐(BPDA)3.95質量份、四氫酞酸酐(THPA)2.7質量份置入裝設有溫度計、攪拌機、冷卻管的燒瓶中，一邊攪拌，一邊緩慢升溫至105℃以使其反應，得到鹼可溶性樹脂-III。以GPC測量、於聚苯乙烯換算下的重量平均分子量(Mw)為4100，固體成分酸價為112mgKOH/g。相當於(c2)環氧(甲基)丙烯酸酯樹脂。Put 25 parts by mass of the above-mentioned epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) into the device In a flask equipped with a thermometer, a stirrer, and a cooling tube, the temperature was gradually raised to 105°C while stirring to allow a reaction to obtain an alkali-soluble resin-III. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4100, and the solid content acid value was 112 mgKOH/g. Corresponds to (c2) epoxy (meth)acrylate resin.

＜鹼可溶性樹脂-IV＞ 對於以丙烯酸二環戊甲酯/苯乙烯/縮水甘油甲基丙烯酸酯(莫耳比：2/5/93)作為構成單體的共聚合樹脂，以與縮水甘油甲基丙烯酸酯相等的量加成丙烯酸而使其反應，再加成四氫酞酸酐讓相對於上述共聚合樹脂1莫耳成為莫耳比0.1，得到鹼可溶性樹脂-IV。以GPC測量、在聚苯乙烯換算下的重量平均分子量(Mw)為7700，固體成分酸價為28.5mgKOH/g。相當於(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂。<Alkali-soluble resin-IV> For a copolymer resin composed of dicyclopentylmethyl acrylate/styrene/glycidyl methacrylate (molar ratio: 2/5/93) Acrylic acid was added and reacted in an amount equal to the base acrylate, and tetrahydrophthalic anhydride was added so that the molar ratio was 0.1 with respect to 1 mole of the above-mentioned copolymer resin to obtain alkali-soluble resin-IV. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 7700, and the solid content acid value was 28.5 mgKOH/g. It corresponds to (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain.

＜鹼可溶性樹脂-V＞ 以丙烯酸環己基甲酯/甲基丙烯酸(莫耳比：85/15)作為構成單體的鹼可溶性丙烯酸共聚合樹脂。以GPC測量、在聚苯乙烯換算下的重量平均分子量(Mw)為12300，固體成分酸價為94mgKOH/g。<Alkali-soluble resin-V> Alkali-soluble acrylic acid copolymer resin which uses cyclohexyl methyl acrylate/methacrylic acid (molar ratio: 85/15) as a constituent monomer. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 12300, and the acid value of solid content was 94 mgKOH/g.

＜鹼可溶性樹脂-VI＞ 以甲基丙烯酸甲酯/甲基丙烯酸(莫耳比：82/18)作為構成單體的鹼可溶性丙烯酸共聚合樹脂。以GPC測量、在聚苯乙烯換算下的重量平均分子量(Mw)為11400，固體成分酸價為97mgKOH/g。<Alkali-soluble resin-VI> Alkali-soluble acrylic copolymer resin which uses methyl methacrylate/methacrylic acid (molar ratio: 82/18) as a constituent monomer. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 11400, and the acid value of solid content was 97 mgKOH/g.

＜有機黑色顏料＞ BASF公司製，「Irgaphor(註冊商標) Black S 0100 CF」(具有以下式(1-1)所表示之化學結構)<Organic black pigment> "Irgaphor (registered trademark) Black S 0100 CF" manufactured by BASF Corporation (has a chemical structure represented by the following formula (1-1))

[化學式63]

Figure 02_image121
[chemical formula 63]
Figure 02_image121

＜分散劑-I＞ BYK公司製「BYK-LPN21116」(於側鏈具有4級銨鹽基及3級胺基的A嵌段與不具有4級銨鹽基及3級胺基的B嵌段所構成之丙烯酸系A-B嵌段共聚物。胺價為70mgKOH/g。酸價為1mgKOH/g以下)。 分散劑-I的A嵌段中，包含下式(1a)及(2a)的重複單元，B嵌段中包含下式(3a)的重複單元。下式(1a)、(2a)、及(3a)的重複單元在分散劑-I的所有重複單元中所占的含有比例分別為11.1莫耳%、22.2莫耳%、6.7莫耳%。<Dispersant-I> "BYK-LPN21116" manufactured by BYK Corporation (A block with a quaternary ammonium group and a tertiary amine group in the side chain and a B block without a quaternary ammonium group and a tertiary amine group The formed acrylic A-B block copolymer. The amine value is 70mgKOH/g. The acid value is 1mgKOH/g or less). The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The proportions of repeating units of the following formulas (1a), (2a), and (3a) in all repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[化學式64]

Figure 02_image123
[chemical formula 64]
Figure 02_image123

＜顏料衍生物＞ Lubrizol公司製「Solsperse12000」<Pigment derivative> "Solsperse 12000" manufactured by Lubrizol

＜溶劑-I＞ PGMEA：丙二醇單甲醚乙酸酯 ＜溶劑-II＞ MB：3-甲氧基-1-丁醇 ＜光聚合性單體＞ DPHA：日本化藥公司製 二新戊四醇六丙烯酸酯<Solvent-I> PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-II> MB: 3-Methoxy-1-butanol <Photopolymerizable Monomer> DPHA: Nippon Kayaku Co., Ltd. dipenteoerythritol Hexaacrylate

＜光聚合起始劑＞ 使用具有以下化學結構的化合物。<Photopolymerization Initiator> A compound having the following chemical structure was used.

[化學式65]

Figure 02_image125
[chemical formula 65]
Figure 02_image125

＜撥液劑＞ DIC公司製 MEGAFACE RS-72-K(氟系，具有乙烯屬雙鍵寡聚物)<Liquid repellant> MEGAFACE RS-72-K manufactured by DIC Corporation (fluorine-based, ethylene double bond oligomer)

＜添加劑-I＞ 昭和電工公司製 Karenz MT PE1(新戊四醇肆(3-巰基丁酸酯)<Additive-I> Showa Denko Karenz MT PE1 (neopentylthritol (3-mercaptobutyrate)

＜添加劑-II＞ 日本化藥公司製 KAYAMER PM-21(含有甲基丙烯醯基的磷酸酯)<Additive-II> Nippon Kayaku Co., Ltd. KAYAMER PM-21 (phosphate ester containing methacryloyl group)

＜顏料分散液I~III的調製＞ 將表1之顏料、分散劑、分散助劑、鹼可溶性樹脂及溶劑混合成為表1之質量比。以塗料振盪機於25~45℃的範圍將該混合液進行3小時分散處理。作為珠粒，可使用0.5mmφ的二氧化鋯珠，其添加量為混合液之2.5倍的質量。分散結束後，藉由過濾器將珠粒與分散液分離，調製顏料分散液I~III。 另外，表1中的分散劑、鹼可溶性樹脂的摻合比例、固體成分換算值、溶劑的摻合比例中，亦包含源自分散劑及鹼可溶性樹脂之溶劑的量。<Preparation of Pigment Dispersion Liquids I to III> The pigments, dispersants, dispersion aids, alkali-soluble resins, and solvents in Table 1 were mixed to obtain the mass ratios in Table 1. The mixed solution was dispersed for 3 hours in the range of 25~45°C with a paint shaker. As the beads, 0.5 mmφ zirconia beads can be used, and the amount added is 2.5 times the mass of the mixed solution. After the dispersion is completed, the beads and the dispersion liquid are separated by a filter to prepare pigment dispersion liquids I~III. In Table 1, the blending ratio of the dispersant and the alkali-soluble resin, the solid content conversion value, and the blending ratio of the solvent also include the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[表1]

Figure 108102757-A0304-0001
[Table 1]
Figure 108102757-A0304-0001

[實施例1~9以及比較例1~3] 使用上述調製之顏料分散液，將各成分混合而成為表2及表3之摻合比例，將其攪拌以使其溶解，調製實施例1~9及比較例1~3的有色感光性樹脂組成物。使用所得之有色感光性樹脂組成物，以後述方法評估性能。 另外，表2及表3中的鹼可溶性樹脂、撥液劑的摻合比例，固體成分換算值，溶劑的摻合比例中，亦包含源自鹼可溶性樹脂、撥液劑的溶劑的量。另一方面，顏料分散液的摻合比例並非固體成分換算值，其係包含溶劑的總量。[Examples 1 to 9 and Comparative Examples 1 to 3] Using the pigment dispersion liquid prepared above, mix the components to obtain the blending ratios in Table 2 and Table 3, stir them to dissolve them, and prepare Examples 1 to 3. 9 and the colored photosensitive resin compositions of Comparative Examples 1 to 3. Using the obtained colored photosensitive resin composition, performance was evaluated by the method described later. In addition, the blending ratio of the alkali-soluble resin and the liquid-repelling agent in Table 2 and Table 3, the solid content conversion value, and the blending ratio of the solvent also include the amount of the solvent derived from the alkali-soluble resin and the liquid-repelling agent. On the other hand, the blending ratio of the pigment dispersion is not a solid content conversion value, but includes the total amount of the solvent.

[表2]

Figure 108102757-A0304-0002
[Table 2]
Figure 108102757-A0304-0002

[表3]

Figure 108102757-A0304-0003
[table 3]
Figure 108102757-A0304-0003

以下說明評估性能的方法。The method for evaluating performance is explained below.

＜製作測量用基板＞ 使用旋塗機，在玻璃基板上塗布上述各種有色感光性樹脂組成物，讓加熱硬化後厚度成為10.0μm。之後，在100℃下，以加熱板加熱乾燥90秒，得到塗膜基板。不對其進行曝光處理，使用將0.04質量%的KOH及0.07質量%的EMULGEN A-60(花王公司製界面活性劑)溶解的水溶液作為顯影液，於24℃下進行噴霧顯影，讀取塗膜完全顯影去除的時間，將其作為對照時間。 接著，以相同的順序得到塗膜基板，不使用曝光光罩，在曝光量50mJ/cm2 下進行紫外線曝光。此時波長365nm中的強度為45mW/cm2 。使用該顯影液，以對照時間的1.2倍的顯影時間，於24℃下對該基板進行噴霧顯影後，以純水洗淨10秒。在烘箱中，於230℃下將該基板加熱硬化30分鐘，得到測量用基板。<Preparation of substrates for measurement> Using a spin coater, the above-mentioned various colored photosensitive resin compositions were coated on glass substrates so as to have a thickness of 10.0 μm after heat curing. Thereafter, it was heated and dried on a hot plate at 100° C. for 90 seconds to obtain a coated film substrate. Without exposure treatment, use an aqueous solution of 0.04% by mass KOH and 0.07% by mass of EMULGEN A-60 (surfactant manufactured by Kao Corporation) as a developing solution, spray development at 24°C, and read that the coating film is complete. The time for developing and removing was used as the control time. Next, a coated film substrate was obtained in the same procedure, and ultraviolet exposure was performed at an exposure amount of 50 mJ/cm 2 without using an exposure mask. At this time, the intensity at a wavelength of 365 nm was 45 mW/cm 2 . Using this developing solution, the substrate was subjected to spray development at 24° C. for a development time 1.2 times that of the control time, and then washed with pure water for 10 seconds. The substrate was heated and hardened at 230° C. for 30 minutes in an oven to obtain a substrate for measurement.

＜光學濃度(OD)的測量＞ 以穿透濃度計(GretagMacbeth公司製「D200-II」)測量該測量用基板的光學濃度(OD)。再者，對於測量處的膜厚，以菱化系統公司製非接觸表面・層剖面形狀測量系統VertScan(R)2.0進行測量，從光學濃度(OD)及膜厚，算出每單位膜厚(1μm)的光學濃度(單元OD、OD/μm)。其結果顯示於表2及表3。<Measurement of Optical Density (OD)> The optical density (OD) of the substrate for measurement was measured with a transmission densitometer ("D200-II" manufactured by GretagMacbeth). Furthermore, the film thickness at the measurement site was measured with the non-contact surface and layer cross-sectional shape measurement system VertScan(R) 2.0 manufactured by Ryoka Systems Co., Ltd., and the film thickness per unit (1 μm) was calculated from the optical density (OD) and the film thickness. ) optical density (unit OD, OD/μm). The results are shown in Table 2 and Table 3.

＜PGMEA接觸角的測量＞ 使用協和界面科學公司製Drop Master 500接觸角測量裝置，在23℃、濕度50%的條件下，將PGMEA(丙二醇單甲醚乙酸酯)0.7μL滴下至該測量用基板上，測量1秒後的接觸角，結果顯示於表2及表3。接觸角大者表示撥墨性高。<Measurement of contact angle of PGMEA> Using a drop master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd., 0.7 μL of PGMEA (propylene glycol monomethyl ether acetate) was dropped on the measurement surface at 23° C. and a humidity of 50%. On the substrate, the contact angle after 1 second was measured, and the results are shown in Table 2 and Table 3. A larger contact angle means higher ink repellency.

＜製作分隔壁＞ 使用旋塗機，在玻璃基板上塗布上述各種有色感光性樹脂組成物，讓加熱硬化後厚度成為10.0μm。之後，在100℃下以加熱板加熱乾燥90秒。使用光罩對於所得之塗膜進行紫外線曝光。曝光量為50mJ/cm2 ，曝光間隙為16μm。此時波長365nm中的強度為45mW/cm2 。作為光罩，係使用具有格子狀開口部的光罩(以40μm間隔具有複數80μm×280μm之被覆部的光罩)。接著，以與該＜測量用基板作成＞相同的條件，以對照時間1.2倍的顯影時間進行顯影後，以純水洗淨10秒。在烘箱中，於230℃下使該基板加熱硬化30分鐘，得到附有格狀分隔壁的基板。<Preparation of Partition Walls> Using a spin coater, the above-mentioned various colored photosensitive resin compositions were coated on a glass substrate, and the thickness was 10.0 μm after heating and hardening. Thereafter, it was heated and dried on a hot plate at 100° C. for 90 seconds. The obtained coating film was exposed to ultraviolet rays using a photomask. The exposure amount was 50 mJ/cm 2 , and the exposure gap was 16 μm. At this time, the intensity at a wavelength of 365 nm was 45 mW/cm 2 . As the mask, a mask having a lattice-shaped opening (a mask having a plurality of covering portions of 80 μm×280 μm at intervals of 40 μm) was used. Next, under the same conditions as in this <preparation of the substrate for measurement>, after developing with a development time 1.2 times the control time, it was washed with pure water for 10 seconds. The substrate was heated and cured at 230° C. for 30 minutes in an oven to obtain a substrate with lattice partition walls.

＜分隔壁圖案邊緣部的直線性評估＞ 以SEM在6000倍下觀察該附有格狀分隔壁之基板的分隔壁表面，評估分隔壁邊緣部的直線性。分隔壁之邊緣部為直線且無殘渣則評估為「A」，分隔壁之邊緣部具有不規則的拖尾而非直線、或是發現殘渣的情況則評估為「B」，結果顯示於表2及表3。<Evaluation of Linearity of Partition Wall Pattern Edge> The surface of the partition wall of the substrate with grid-shaped partition walls was observed with SEM at 6000 magnifications, and the linearity of the partition wall edge part was evaluated. If the edge of the dividing wall is straight and there is no residue, it is evaluated as "A". If the edge of the dividing wall has irregular tails instead of straight lines, or residues are found, it is evaluated as "B". The results are shown in Table 2 and Table 3.

＜基板表面狀態的評估＞ 以目視觀察該測量用基板的表面狀態，評估表面是否粗糙。表面具有充分光澤則評估為「A」，無光澤的情況則為「B」。結果顯示於表2及表3。 具有光澤的情況，則為接近鏡面反射之狀態，亦即粗糙度低的均勻表面狀態，另一方面，無光澤的情況為發生不規則反射的狀態，亦即粗糙度高、表面粗糙的狀態。<Evaluation of Surface State of Substrate> The surface state of the substrate for measurement was visually observed to evaluate whether or not the surface was rough. The evaluation was "A" when the surface had sufficient gloss, and "B" when there was no gloss. The results are shown in Table 2 and Table 3. In the case of gloss, it is a state close to specular reflection, that is, a uniform surface state with low roughness. On the other hand, in the case of matte, it is a state of irregular reflection, that is, a state with high roughness and rough surface.

從表2可知，實施例1及2的有色感光性樹脂組成物，係著色劑的含有比例在總固體成分中為20質量%以下、並且含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂及(c2)環氧(甲基)丙烯酸酯樹脂者，其遮光性良好，PGMEA接觸角高，呈現良好的撥墨性，且分隔壁之邊緣部的直線性良好。又可得知基板表面狀態亦佳，具有光澤、無表面粗糙。As can be seen from Table 2, the colored photosensitive resin compositions of Examples 1 and 2 have a colorant content of 20% by mass or less in the total solid content and contain (c1) a colorant having an ethylenically unsaturated group in the side chain. Acrylic resin and (c2) epoxy (meth)acrylate resin have good light-shielding properties, high PGMEA contact angle, good ink repellency, and good linearity at the edge of the partition wall. It can also be seen that the surface condition of the substrate is also good, with gloss and no surface roughness.

另一方面，比較例2的有色感光性樹脂組成物，著色劑的含有比例在總固體成分中超過20質量%，亦即過量含有著色劑，儘管不包含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂，仍呈現PGMEA接觸角高之良好的撥墨性，且分隔壁之邊緣部的直線性良好。由此可得知過量含有著色劑的情況中，並不存在撥墨性與直線性的課題。另外，基板表面無光澤，且發生表面粗糙。On the other hand, in the colored photosensitive resin composition of Comparative Example 2, the content ratio of the colorant in the total solid content exceeds 20% by mass, that is, the colorant is excessively contained, although (c1) having vinyl in the side chain is not included. The acrylic resin with unsaturated groups still exhibits good ink repellency with a high PGMEA contact angle, and the linearity of the edge of the partition wall is good. From this, it can be seen that there are no problems of ink repellency and linearity when the coloring agent is excessively contained. In addition, the surface of the substrate was matted, and surface roughness occurred.

相對於此，可得知比較例1的有色感光性樹脂組成物，雖係使比較例2中著色劑的含有比例變更為20質量%以下，分隔壁之邊緣部的直線性仍為良好，但PGMEA的接觸角低而撥墨性不佳。從比較例2與比較例1的比較來看，可得知著色劑的含有比例在總固體成分中若在20質量%以下，則PGMEA的接觸角變低，而產生撥墨性不佳的課題。這被認為是因為著色劑的含有比例變低導致撥液劑在表面的配向變多，無法與膜表面充分鍵結的撥液劑變多，而在顯影時流失。On the other hand, in the colored photosensitive resin composition of Comparative Example 1, although the content ratio of the colorant in Comparative Example 2 was changed to 20% by mass or less, the linearity of the edge portion of the partition wall was still good, but PGMEA has a low contact angle and poor ink repellency. From the comparison of Comparative Example 2 and Comparative Example 1, it can be seen that if the content of the coloring agent is less than 20% by mass in the total solid content, the contact angle of PGMEA becomes low, and the problem of poor ink repellency occurs. . This is considered to be because the lower content of the coloring agent leads to more alignment of the liquid-repelling agent on the surface, and more liquid-repelling agent that cannot be sufficiently bonded to the film surface is lost during development.

該比較例1雖不含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂，且含有(c2)環氧(甲基)丙烯酸酯樹脂，相對於此，如比較例3，可得知當含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂且不含有(c2)環氧(甲基)丙烯酸酯樹脂，PGMEA接觸角高而撥墨性良好，但另一方面分隔壁之邊緣部的直線性會不佳。 這被認為是因為含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂，因為其柔軟的骨架而在曝光時產生之自由基在膜內的自由度高，可抑制膜表面的氧導致自由基失活，使得膜表面的硬化性高，再者，因為於側鏈具有乙烯屬不飽和基，可充分捕捉在膜表面上配向的撥液劑，因此在顯影時不會流出而殘留於膜表面，結果PGMEA接觸角高而撥墨性變好。然而，由於不含有以具有剛直骨架而有著對於基板的密合性不會過度提高的傾向之(c2)環氧(甲基)丙烯酸酯樹脂，而認為對於基板的密合性過度提高，分隔壁之邊緣部的直線性並不充分。Although this Comparative Example 1 does not contain (c1) an acrylic resin having an ethylenically unsaturated group in the side chain, and contains (c2) an epoxy (meth)acrylate resin, as in Comparative Example 3, it can be seen that When containing (c1) an acrylic resin having an ethylenically unsaturated group in the side chain and not containing (c2) an epoxy (meth)acrylate resin, the contact angle of PGMEA is high and the ink repellency is good, but on the other hand, the separation wall The linearity of the edge portion will be poor. This is considered to be because the acrylic copolymer resin containing (c1) having an ethylenically unsaturated group in the side chain has a high degree of freedom in the film due to its soft skeleton, which can suppress the free radicals generated on the film surface. Oxygen causes free radicals to deactivate, making the hardening of the film surface high. Furthermore, because the side chain has an ethylenically unsaturated group, it can fully capture the liquid repellent aligned on the film surface, so it will not flow out during development. Remains on the surface of the film, resulting in a high PGMEA contact angle and better ink repellency. However, since it does not contain (c2) epoxy (meth)acrylate resin, which tends not to increase the adhesion to the substrate due to the rigid skeleton, it is considered that the adhesion to the substrate is excessively improved, and the partition wall The linearity of the edge portion is not sufficient.

相對於此，實施例1及實施例2的有色感光性樹脂組成物，著色劑的含有比例在總固體成分中為20質量%以下，藉由含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂，因為其柔軟的骨架，在曝光時產生之自由基在膜內的自由度高，可抑制因為膜表面的氧導致自由基失活，膜表面的硬化性提高，再者，因為於側鏈具有乙烯屬不飽和基而可充分捕捉在膜表面上配向的撥液劑，在顯影時不會流出而殘留於膜表面，因而認為PGMEA接觸角高而撥墨性變得良好。又，藉由含有(c2)環氧(甲基)丙烯酸酯樹脂，因為該芳香環等的剛直骨架使得基板上之羥基及矽醇基的鍵結力變弱，未曝光部變得容易顯影，而認為可使分隔壁邊緣部的直線性變得良好。又，藉由使著色劑的含有比例在總固體成分中為20質量%以下，由於膜表面與內部之硬化性的差異變少，於加熱硬化時，膜表面與內部的收縮差亦變少，基板表面狀態變得良好，而認為能夠抑制表面粗糙。On the other hand, in the colored photosensitive resin compositions of Examples 1 and 2, the content ratio of the colorant in the total solid content is 20% by mass or less, and by containing (c1) having an ethylenically unsaturated group in the side chain The acrylic resin, because of its soft skeleton, has a high degree of freedom in the film of free radicals generated during exposure, which can inhibit the inactivation of free radicals caused by oxygen on the film surface, and improve the hardening of the film surface. The side chain has an ethylenically unsaturated group and can sufficiently capture the liquid repellent that is aligned on the film surface, and does not flow out and remain on the film surface during development. Therefore, it is considered that the contact angle of PGMEA is high and the ink repellency becomes good. In addition, by containing (c2) epoxy (meth)acrylate resin, since the rigid skeleton of the aromatic ring and the like weakens the bonding force between the hydroxyl group and the silanol group on the substrate, the unexposed part becomes easy to develop, On the other hand, it is considered that the linearity of the edge portion of the partition wall can be improved. In addition, by making the content of the coloring agent 20% by mass or less in the total solid content, since the difference in curability between the surface and the inside of the film is reduced, the shrinkage difference between the surface and the inside of the film is also reduced during heat curing. The state of the substrate surface becomes favorable, and it is considered that surface roughness can be suppressed.

又實施例3~6係使用含有(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂作為分散樹脂的顏料分散液，PGMEA接觸角亦高而撥墨性良好，又，分隔壁之邊緣部的直線性亦良好，基板表面狀態亦良好，而抑制了表面粗糙。從實施例3與實施例4的比較來看，(c1)丙烯酸共聚合樹脂的比例高者會有PGMEA的接觸角變高的傾向。又，從實施例3、5及6的比較可得知，著色劑的含有比例在總固體成分中若為20質量%以下則無特別限定，PGMEA接觸角亦高而撥墨性良好，基板表面狀態亦良好，而會抑制表面粗糙。In addition, Examples 3 to 6 are pigment dispersions that use (c1) an acrylic resin having an ethylenically unsaturated group in the side chain as a dispersion resin, and the PGMEA contact angle is also high and the ink repellency is good. The straightness of the substrate is also good, and the surface condition of the substrate is also good, and the surface roughness is suppressed. From the comparison of Example 3 and Example 4, the contact angle of PGMEA tends to be high in the case where the ratio of (c1) acrylic copolymer resin is high. Also, from the comparison of Examples 3, 5, and 6, it can be seen that the content of the coloring agent is not particularly limited if it is 20% by mass or less in the total solid content, and the contact angle of PGMEA is also high and the ink repellency is good. The state is also good, and surface roughness is suppressed.

實施例7係在實施例3中變更著色劑的種類者，從實施例3與實施例7的比較可得知，無論著色劑的種類，PGMEA接觸角也高且撥墨性良好，分隔壁之邊緣部的直線性亦良好，基板表面狀態亦良好，會抑制表面粗糙。Embodiment 7 is the person who changed the kind of coloring agent in embodiment 3. From the comparison of embodiment 3 and embodiment 7, it can be known that regardless of the kind of coloring agent, PGMEA contact angle is also high and the ink repellency is good. The linearity of the edge portion is also good, and the surface condition of the substrate is also good, and surface roughness is suppressed.

實施例8，係在實施例3中變更(c2)環氧(甲基)丙烯酸酯樹脂的種類者，從實施例3與8的比較可得知，無論(c2)環氧(甲基)丙烯酸酯樹脂的種類，分隔壁之邊緣部的直線性皆為良好。 又實施例9係在實施例3中將作為(c1)於側鏈具有乙烯屬不飽和基之丙烯酸樹脂的鹼可溶性樹脂-I的一部分變更為鹼可溶性樹脂-IV者，從實施例3及9的比較可得知，無論(c1)於側鏈具有乙烯屬不飽和基的丙烯酸樹脂的種類，PGMEA接觸角皆高而撥墨性良好。Embodiment 8 is the person who changes the type of (c2) epoxy (meth)acrylate resin in embodiment 3. From the comparison of embodiment 3 and 8, it can be known that no matter (c2) epoxy (meth)acrylic acid The type of ester resin and the linearity of the edge of the partition wall were all good. In Example 9, in Example 3, a part of the alkali-soluble resin-I, which is an acrylic resin having an ethylenically unsaturated group in the side chain (c1), was changed to an alkali-soluble resin-IV, from Examples 3 and 9 It can be seen that regardless of the type of acrylic resin (c1) having an ethylenically unsaturated group in the side chain, the PGMEA contact angle is high and the ink repellency is good.

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Claims (11)

一種有色感光性樹脂組成物，其係含有(A)乙烯屬不飽和化合物、(B)光聚合起始劑、(C)鹼可溶性樹脂、(D)撥液劑以及(E)著色劑的有色感光性樹脂組成物，其特徵為：該(E)著色劑的含有比例，在該有色感光性樹脂組成物的總固體成分中為20質量%以下，該(C)鹼可溶性樹脂含有：(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂；以及(c2)環氧(甲基)丙烯酸酯樹脂；其中相對於(C)鹼可溶性樹脂的總量，(c2)環氧(甲基)丙烯酸酯樹脂的含有比例為70質量%以下。 A colored photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid-repelling agent, and (E) a colorant. The photosensitive resin composition is characterized in that: the content ratio of the (E) colorant is 20% by mass or less in the total solid content of the colored photosensitive resin composition, and the (C) alkali-soluble resin contains: (c1 ) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain; and (c2) epoxy (meth)acrylate resin; wherein relative to the total amount of (C) alkali-soluble resin, (c2) epoxy (meth)acrylate resin base) The content ratio of the acrylate resin is 70% by mass or less. 如申請專利範圍第1項之有色感光性樹脂組成物，其中該(c1)於側鏈具有乙烯屬不飽和基的丙烯酸共聚合樹脂具有以下述通式(I)所表示之部分結構；
Figure 108102757-A0305-02-0148-1
 (式(I)中，R1及R2分別獨立表示氫原子或甲基；＊表示鍵結處)。 Such as the colored photosensitive resin composition of claim 1, wherein the (c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the following general formula (I);
Figure 108102757-A0305-02-0148-1
 (In formula (I), R 1 and R 2 independently represent a hydrogen atom or a methyl group; * represents a bond). 如申請專利範圍第1項之有色感光性樹脂組成物，其中該(c2)環氧(甲基)丙烯酸酯樹脂包含：選自具有以下述通式(i)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂；具有以下述通式(ii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂；以及具有以下述通式(iii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂所構成之群組的至少1種；
Figure 108102757-A0305-02-0149-2
 (式(i)中，Ra表示氫原子或甲基，Rb表示亦可具有取代基的2價烴基；式(i)中的苯環亦可更由任意的取代基取代；＊表示鍵結處)；
Figure 108102757-A0305-02-0149-3
 (式(ii)中，Rc分別獨立表示氫原子或甲基；Rd表示具有環狀烴基作為側鏈的2價烴基；＊表示鍵結處)；
Figure 108102757-A0305-02-0150-4
 (式(iii)中，Re表示氫原子或甲基，γ表示單鍵、-CO-、亦可具有取代基的伸烷基、或亦可具有取代基的2價環狀烴基；式(iii)中的苯環亦可更由任意的取代基取代；＊表示鍵結處)。 Such as the colored photosensitive resin composition of item 1 of the patent scope of the application, wherein the (c2) epoxy (meth)acrylate resin comprises: epoxy ( Meth)acrylate resin; Epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii); and epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) base) at least one of the group consisting of acrylate resins;
Figure 108102757-A0305-02-0149-2
 (In the formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group that may also have a substituent; the benzene ring in the formula (i) may also be substituted by any substituent; * represents a bond junction);
Figure 108102757-A0305-02-0149-3
 (In formula (ii), Rc independently represents a hydrogen atom or a methyl group; Rd represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain; * represents a bond);
Figure 108102757-A0305-02-0150-4
 (In the formula (iii), Re represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group that may also have a substituent, or a divalent cyclic hydrocarbon group that may also have a substituent; the formula ( The benzene ring in iii) may be further substituted by any substituent; * indicates a bonding position). 如申請專利範圍第2項之有色感光性樹脂組成物，其中該(c2)環氧(甲基)丙烯酸酯樹脂包含：選自具有以下述通式(i)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂；具有以下述通式(ii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂；以及具有以下述通式(iii)所表示之部分結構的環氧(甲基)丙烯酸酯樹脂所構成之群組的至少1種；[化學式2]
Figure 108102757-A0305-02-0151-5
 (式(i)中，Ra表示氫原子或甲基，Rb表示亦可具有取代基的2價烴基；式(i)中的苯環亦可更由任意的取代基取代；＊表示鍵結處)；
Figure 108102757-A0305-02-0151-6
 (式(ii)中，Rc分別獨立表示氫原子或甲基；Rd表示具有環狀烴基作為側鏈的2價烴基；＊表示鍵結處)；[化學式4]
Figure 108102757-A0305-02-0152-7
 (式(iii)中，Re表示氫原子或甲基，γ表示單鍵、-CO-、亦可具有取代基的伸烷基、或亦可具有取代基的2價環狀烴基；式(iii)中的苯環亦可更由任意的取代基取代；＊表示鍵結處)。 Such as the colored photosensitive resin composition of item 2 of the scope of application for patents, wherein the (c2) epoxy (meth)acrylate resin comprises: epoxy ( Meth)acrylate resin; Epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii); and epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) base) at least one of the group consisting of acrylate resins; [chemical formula 2]
Figure 108102757-A0305-02-0151-5
 (In the formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group that may also have a substituent; the benzene ring in the formula (i) may also be substituted by any substituent; * represents a bond junction);
Figure 108102757-A0305-02-0151-6
 (In formula (ii), Rc independently represents a hydrogen atom or a methyl group; Rd represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain; * represents a bond); [Chemical formula 4]
Figure 108102757-A0305-02-0152-7
 (In the formula (iii), Re represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group that may also have a substituent, or a divalent cyclic hydrocarbon group that may also have a substituent; the formula ( The benzene ring in iii) may be further substituted by any substituent; * indicates a bonding position). 如申請專利範圍第1至4項中任1項之有色感光性樹脂組成物，其中該(E)著色劑為有機顏料。 The colored photosensitive resin composition according to any one of items 1 to 4 of the scope of application, wherein the (E) colorant is an organic pigment. 如申請專利範圍第1至4項中任1項之有色感光性樹脂組成物，其中該(D)撥液劑具有交聯基。 The colored photosensitive resin composition according to any one of items 1 to 4 of the scope of the patent application, wherein the liquid repellent (D) has a crosslinking group. 如申請專利範圍第1至4項中任1項之有色感光性樹脂組成物，其中更含有鏈轉移劑。 Such as the colored photosensitive resin composition of any one of items 1 to 4 of the scope of the patent application, which further contains a chain transfer agent. 一種分隔壁，係由如申請專利範圍第1至7項中任1項之有色感光性樹脂組成物所構成。 A partition wall is composed of a colored photosensitive resin composition according to any one of items 1 to 7 in the scope of the patent application. 一種有機電致發光元件，具備如申請專利範圍第8項之分隔壁。 An organic electroluminescent element is provided with a partition wall as described in item 8 of the scope of the patent application. 一種影像顯示裝置，包含如申請專利範圍第9項之有機電致發光元件。 An image display device, comprising the organic electroluminescence element as claimed in claim 9 of the patent application. 一種照明，包含如申請專利範圍第9項之有機電致發光元件。 A lighting comprising the organic electroluminescent element as claimed in item 9 of the scope of the patent application.
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