TWI711882B - Photosensitive coloring composition, cured product, coloring spacer, image display device - Google Patents

Photosensitive coloring composition, cured product, coloring spacer, image display device Download PDF

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TWI711882B
TWI711882B TW105142935A TW105142935A TWI711882B TW I711882 B TWI711882 B TW I711882B TW 105142935 A TW105142935 A TW 105142935A TW 105142935 A TW105142935 A TW 105142935A TW I711882 B TWI711882 B TW I711882B
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TW201732431A (en
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伊藤敦哉
小川善秀
斐麗華
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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
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

本發明之課題在於提供一種可形成遮光性較高、高可靠性且表面平滑性優異之圖案、尤其可較佳地用於形成著色間隔件之感光性著色組合物。本發明之感光性著色組合物含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑，並且(a)著色劑含有有機顏料及碳黑，(b)鹼可溶性樹脂含有(b-I)環氧(甲基)丙烯酸酯樹脂、與(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂，且(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元α之含有比例為12莫耳%以上。The subject of the present invention is to provide a photosensitive coloring composition that can form a pattern with high light-shielding properties, high reliability, and excellent surface smoothness, and is particularly suitable for forming colored spacers. The photosensitive coloring composition of the present invention contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) dispersion And (a) the colorant contains organic pigments and carbon black, (b) the alkali-soluble resin contains (bI) epoxy (meth)acrylate resin, and (b-II) contains side chains with ethylenic unsaturated bonds (Meth)acrylic copolymerized resin of repeating unit α and repeating unit β derived from unsaturated carboxylic acid, and (b-II) (meth)acrylic copolymerized resin content ratio of the above repeating unit α It is more than 12 mol%.

Description

感光性著色組合物、硬化物、著色間隔件、圖像顯示裝置Photosensitive coloring composition, cured product, coloring spacer, image display device

本發明係關於一種感光性著色組合物等。詳細而言，本發明係關於一種可於例如液晶顯示器等之彩色濾光片中較佳地用於著色間隔件等之形成之感光性著色組合物、將該感光性著色組合物硬化而獲得之著色間隔件、具備該著色間隔件之圖像顯示裝置。The present invention relates to a photosensitive coloring composition and the like. In detail, the present invention relates to a photosensitive coloring composition that can be preferably used for the formation of colored spacers in, for example, color filters such as liquid crystal displays, and is obtained by curing the photosensitive coloring composition Colored spacer and image display device provided with the colored spacer.

液晶顯示器(LCD)係利用藉由施加至液晶之電壓之導通/斷開而切換液晶分子之排列方式之性質。另一方面，構成LCD之單元之各構件多為藉由以光微影法為代表之利用感光性組合物之方法所形成者。基於容易形成微細之結構、對大畫面用之基板之處理亦容易等理由，今後該感光性組合物之應用範圍有進一步擴大之傾向。 然而，使用感光性組合物所製造之LCD因感光性組合物本身之電特性、或感光性組合物中所含之雜質之影響，而存在無法保持對液晶所施加之電壓，由此產生顯示器之顯示不均等問題之情形。尤其對於彩色液晶顯示器中靠近液晶層之構件、例如液晶面板中用以將2片基板之間隔保持固定之所謂柱狀間隔件、感光性間隔件等，其影響較大。 先前，於將不具有遮光性之間隔件用於TFT(Thin Film Transistor，薄膜電晶體)型LCD之情形時，存在因透過間隔件之光而使作為開關元件之TFT產生誤動作之情況。為了防止該情況，例如專利文獻1中記載有使用具有遮光性之間隔件(著色間隔件)之方法。 一方面，近年來，隨著面板結構之變化，提出有藉由光微影法一次性形成高度不同之著色間隔件之方法。例如專利文獻2中揭示有藉由組合複數種光吸收特性不同之特定之顏料種類，而確保紫外線區域與可見光區域之光吸收之平衡，可維持遮光性與液晶之電壓保持率，並且實現形狀及階差之控制、及與基板之密接性。 另一方面，專利文獻3中揭示有使用特定結構之鹼可溶性樹脂亦可實現遮光性、階差之控制、及與基板之密接性。 先前技術文獻 專利文獻 專利文獻1：日本專利特開平8-234212號公報 專利文獻2：國際公開第2013/115268號 專利文獻3：日本專利特開2013-134263號公報Liquid crystal displays (LCD) utilize the property of switching the arrangement of liquid crystal molecules by turning on/off the voltage applied to the liquid crystal. On the other hand, most of the members constituting the unit of the LCD are formed by a method using a photosensitive composition represented by photolithography. For reasons such as easy formation of fine structures and easy handling of substrates for large screens, the application range of the photosensitive composition will tend to be further expanded in the future. However, LCDs manufactured using the photosensitive composition cannot maintain the voltage applied to the liquid crystal due to the electrical properties of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition. Shows the situation of inequality problems. Particularly, it has a great influence on members close to the liquid crystal layer in color liquid crystal displays, such as so-called columnar spacers and photosensitive spacers used to maintain a fixed interval between two substrates in liquid crystal panels. In the past, when spacers that do not have light-shielding properties are used in TFT (Thin Film Transistor) LCDs, the TFT as a switching element may malfunction due to light transmitted through the spacers. In order to prevent this, for example, Patent Document 1 describes a method of using a spacer having light-shielding properties (colored spacer). On the one hand, in recent years, with changes in the panel structure, a method of forming colored spacers of different heights at one time by photolithography has been proposed. For example, Patent Document 2 discloses that by combining a plurality of specific types of pigments with different light absorption characteristics, the balance of light absorption in the ultraviolet region and the visible region can be ensured, the light-shielding property and the voltage retention rate of the liquid crystal can be maintained, and the shape and Control of the level difference and adhesion to the substrate. On the other hand, Patent Document 3 discloses that the use of an alkali-soluble resin of a specific structure can also achieve light-shielding, step control, and adhesion to the substrate. Prior Art Documents Patent Documents Patent Document 1: Japanese Patent Laid-Open No. 8-234212 Patent Document 2: International Publication No. 2013/115268 Patent Document 3: Japanese Patent Laid-Open No. 2013-134263

[發明所欲解決之問題] 近年來，隨著面板結構之變化，有進一步提高著色間隔件之遮光性之要求。作為提高遮光性之方法，可列舉使用遮光性較高之顏料之方法、或提高感光性著色組合物中之顏料含有比例之方法等。本發明者等人研究後發現，於專利文獻2所記載之感光性著色組合物中，併用遮光性較高之顏料等進一步提高了著色間隔件之遮光性，但於膜表面附近與膜底部附近交聯密度差變大，因熱硬化過程之熱收縮導致塗膜表面產生皺褶，表面平滑性變得不充分。 又，於專利文獻3所記載之使用感光性著色組合物而形成遮光性較高之著色間隔件之情形時，發現源自著色劑之雜質溶出至形成成為其上層膜之配向膜時之溶劑中，而且由於高顏料濃度且硬化成分較少，導致雜質溶出亦較多，結果存在使LCD之顯示可靠性變差等問題。 本發明係鑒於上述情況而完成者，本發明之目的在於提供一種可形成遮光性較高、高可靠性且表面平滑性優異之圖案之感光性著色組合物。 [解決問題之技術手段] 本發明者等人為了解決上述課題而進行了努力研究，結果發現，於感光性著色組合物中，藉由組合使用環氧(甲基)丙烯酸酯樹脂與特定之(甲基)丙烯酸系共聚合樹脂作為鹼可溶性樹脂，可解決上述課題，從而達成本發明。 即，本發明具有以下[1]至[9]之構成。 [1]一種感光性著色組合物，其特徵在於：其係含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑者，且 上述(a)著色劑含有有機顏料及碳黑， 上述(b)鹼可溶性樹脂含有(b-I)環氧(甲基)丙烯酸酯樹脂、與(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂，且 上述(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元α之含有比例為12莫耳%以上。 [2]如[1]所記載之感光性著色組合物，其中上述有機顏料含有選自由下述通式(1)所表示之化合物、該化合物之幾何異構物、該化合物之鹽及該化合物之幾何異構物之鹽所組成之群中之至少1種有機黑色顏料， [化1]

Figure 02_image001
(式(1)中，R11 及R16 互相獨立為氫原子、CH3 、CF3 、氟原子或氯原子； R12 、R13 、R14 、R15 、R17 、R18 、R19 及R20 與其他全部互相獨立而為氫原子、鹵素原子、R21 、COOH、COOR21 、COO- 、CONH2 、CONHR21 、CONR21 R22 、CN、OH、OR21 、COCR21 、OCONH2 、OCONHR21 、OCONR21 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 ； 且選自由R12 與R13 、R13 與R14 、R14 與R15 、R17 與R18 、R18 與R19 、及R19 與R20 所組成之群中之至少1種組合可互相直接鍵結，或者利用氧原子、硫原子、NH或NR21 橋而互相鍵結； R21 及R22 互相獨立為碳數1～12之烷基、碳數3～12之環烷基、碳數2～12之烯基、碳數3～12之環烯基或碳數2～12之炔基)。 [3]一種感光性著色組合物，其特徵在於：其係含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑者，且 上述(a)著色劑含有選自由紅色顏料及橙色顏料所組成之群中之至少一種與選自由藍色顏料及紫色顏料所組成之群中之至少一種， 上述(b)鹼可溶性樹脂含有(b-I)環氧(甲基)丙烯酸酯樹脂、與(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂，且 上述(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元α之含有比例為12莫耳%以上。 [4]如[1]至[3]中任一項所記載之感光性著色組合物，其中上述重複單元α具有下述通式(I)所表示之化學結構， [化2]
Figure 02_image003
(式(I)中，R1 及R2 分別獨立地表示氫原子或甲基；R3 表示二價連結基)。 [5]如[1]至[4]中任一項所記載之感光性著色組合物，其中上述(b-II)(甲基)丙烯酸系共聚合樹脂之含有比例相對於感光性著色組合物中之全部固形物成分為1質量%以上。 [6]如[1]至[5]中任一項所記載之感光性著色組合物，其中經硬化之塗膜之每1 μm膜厚之光學密度為1.0以上。 [7]一種硬化物，其係將如[1]至[6]中任一項所記載之感光性著色組合物硬化而獲得。 [8]一種著色間隔件，其係由如[7]所記載之硬化物所形成。 [9]一種圖像顯示裝置，其具備如[8]所記載之著色間隔件。 [發明之效果] 根據本發明，可提供一種可形成遮光性較高、高可靠性且表面平滑性優異之圖案之感光性著色組合物。又，可提供一種遮光性優異、表面平滑性優異之硬化物及著色間隔件，進而可提供一種具備此種著色間隔件之圖像顯示裝置。[Problems to be Solved by the Invention] In recent years, with changes in panel structure, there is a demand for further improvement of the light-shielding properties of colored spacers. As a method of improving the light-shielding property, a method of using a pigment with a higher light-shielding property, a method of increasing the content of the pigment in the photosensitive coloring composition, and the like can be cited. After research, the inventors found that in the photosensitive coloring composition described in Patent Document 2, the use of pigments with higher light-shielding properties further improves the light-shielding properties of the colored spacer, but near the film surface and near the bottom of the film The difference in crosslinking density becomes larger, and the surface of the coating film is wrinkled due to heat shrinkage during the thermal hardening process, and the surface smoothness becomes insufficient. In addition, in the case of using the photosensitive coloring composition described in Patent Document 3 to form a colored spacer with high light-shielding properties, it was found that the impurities derived from the coloring agent were eluted into the solvent when the alignment film was formed as the upper film Moreover, due to the high pigment concentration and less hardening components, more impurities are eluted, resulting in problems such as poor LCD display reliability. The present invention was completed in view of the above-mentioned circumstances. The object of the present invention is to provide a photosensitive coloring composition capable of forming a pattern with high light-shielding properties, high reliability, and excellent surface smoothness. [Technical Means to Solve the Problem] The inventors of the present invention conducted diligent studies to solve the above-mentioned problems, and found that in the photosensitive coloring composition, an epoxy (meth)acrylate resin and a specific ( As an alkali-soluble resin, the meth)acrylic copolymer resin can solve the above-mentioned problems, thereby achieving the invention. That is, the present invention has the following configurations [1] to [9]. [1] A photosensitive coloring composition characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) ) Solvent, and (f) dispersant, and the (a) colorant contains organic pigments and carbon black, and the (b) alkali-soluble resin contains (bI) epoxy (meth)acrylate resin, and (b- II) A (meth)acrylic copolymer resin containing a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid, and the above (b-II) (meth)acrylic The content of the repeating unit α in the copolymer resin is 12 mol% or more. [2] The photosensitive coloring composition according to [1], wherein the organic pigment contains a compound selected from the group consisting of a compound represented by the following general formula (1), geometric isomers of the compound, a salt of the compound, and the compound At least one organic black pigment in the group consisting of salts of geometric isomers, [化1]
Figure 02_image001
(In formula (1), R 11 and R 16 are independently 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 and all other each independently be a hydrogen atom, a halogen atom, R 21, COOH, COOR 21 , COO -, CONH 2, CONHR 21, CONR 21 R 22, CN, OH, OR 21, COCR 21, OCONH 2 , OCONHR 21, OCONR 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 the group consisting of R 12 and R 13, At least one combination of R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 can be directly bonded to each other, or use an oxygen atom , Sulfur atom, NH or NR 21 bridge to bond to each other; R 21 and R 22 are independently an alkyl group with 1 to 12 carbons, a cycloalkyl group with 3 to 12 carbons, an alkenyl group with 2 to 12 carbons, Cycloalkenyl having 3 to 12 carbons or alkynyl having 2 to 12 carbons). [3] A photosensitive coloring composition characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) ) Solvent and (f) dispersant, and the above-mentioned (a) colorant contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments One, the above-mentioned (b) alkali-soluble resin contains (bI) epoxy (meth)acrylate resin, and (b-II) contains a repeating unit α having an ethylenically unsaturated bond in the side chain and a compound derived from an unsaturated carboxylic acid The (meth)acrylic copolymer resin of the repeating unit β, and the content of the repeating unit α in the (b-II) (meth)acrylic copolymer resin is 12 mol% or more. [4] The photosensitive coloring composition as described in any one of [1] to [3], wherein the repeating unit α has a chemical structure represented by the following general formula (I), [化2]
Figure 02_image003
(In formula (I), R 1 and R 2 each independently represent a hydrogen atom or a methyl group; R 3 represents a divalent linking group). [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the content of (b-II) (meth)acrylic copolymer resin is relative to the photosensitive coloring composition The total solid content in it is 1% by mass or more. [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the optical density per 1 μm of the film thickness of the cured coating film is 1.0 or more. [7] A cured product obtained by curing the photosensitive coloring composition as described in any one of [1] to [6]. [8] A colored spacer formed by the hardened material as described in [7]. [9] An image display device including the colored spacer as described in [8]. [Effects of the Invention] According to the present invention, it is possible to provide a photosensitive coloring composition that can form a pattern with high light-shielding properties, high reliability, and excellent surface smoothness. In addition, it is possible to provide a cured product and a colored spacer having excellent light-shielding properties and excellent surface smoothness, and furthermore, an image display device provided with such a colored spacer can be provided.

以下，對本發明之實施形態進行具體說明，但本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變更而實施。 再者，於本發明中，所謂「(甲基)丙烯酸」意指「丙烯酸及/或甲基丙烯酸」，「(甲基)丙烯酸酯」、「(甲基)丙烯醯基」亦相同。 於本發明中，所謂「(共)聚合物」意指包括均聚物(homopolymer)與共聚物(copolymer)兩者，所謂「酸(酐)」、「(無水)…酸」意指包括酸與其酐兩者。又，於本發明中，所謂「丙烯酸系樹脂」意指含有(甲基)丙烯酸之(共)聚合物、含有具有羧基之(甲基)丙烯酸酯之(共)聚合物。 又，於本發明中，所謂「單體」係相對於所謂之高分子物質(聚合物)之用語，其含義除了狹義之單體(monomer)以外，亦包括二聚物、三聚物、低聚物等。 於本發明中，所謂「全部固形物成分」意指感光性著色組合物中或下文所述之油墨中所含之溶劑以外之全部成分。 於本發明中，所謂「重量平均分子量」係指藉由GPC(凝膠滲透層析法)所獲得之聚苯乙烯換算之重量平均分子量(Mw)。 又，於本發明中，所謂「胺值」，只要無特別說明，則表示有效固形物成分換算之胺值，為每1 g分散劑之固形物成分之鹼量與當量之KOH之質量所表示之值。再者，下文對測定方法進行說明。另一方面，所謂「酸值」，只要無特別說明，則表示有效固形物成分換算之酸值，藉由中和滴定而算出。 又，於本說明書中，「質量」所表示之百分率或份與「重量」所表示之百分率或份含義相同。 [感光性著色組合物] 本發明之感光性著色組合物含有 (a)著色劑、 (b)鹼可溶性樹脂、 (c)光聚合起始劑、 (d)乙烯性不飽和化合物、 (e)溶劑、及 (f)分散劑 作為必需成分，可視需要而進一步含有矽烷偶合劑等密接改善劑、塗佈性提高劑、顯影改良劑、紫外線吸收劑、抗氧化劑、界面活性劑、顏料衍生物等其他調配成分，通常各調配成分係以溶解或分散於溶劑中之狀態使用。 本發明之第一態樣之感光性著色組合物中，(a)著色劑含有有機顏料及碳黑。又，本發明之第二態樣之感光性著色組合物中，(a)著色劑含有選自由紅色顏料及橙色顏料所組成之群中之至少一種與選自由藍色顏料及紫色顏料所組成之群中之至少一種。進而，本發明之第三態樣之感光性著色組合物係用於形成著色間隔件。 以下，只要無特別說明，則「本發明之感光性著色組合物」係指上述第一態樣之感光性著色組合物、第二態樣之感光性著色組合物、及第三態樣之感光性著色組合物之全部。 ＜(a)著色劑＞ 本發明之感光性著色組合物所使用之(a)著色劑只要為可將感光性著色組合物或將其硬化而獲得之硬化物進行著色之色料，則無特別限定，例如可列舉顏料或染料，就耐久性之觀點而言，可較佳地使用顏料。 作為顏料，可列舉有機顏料或無機顏料，就抑制液晶之電壓保持率之降低之觀點，又，就抑制紫外線之吸收而變得容易控制形狀或階差之觀點而言，較佳為使用有機顏料。 本發明之第一態樣之感光性著色組合物所使用之(a)著色劑含有有機顏料及碳黑。由此，藉由使用紫外線之吸收較少之有機顏料，而使形狀或階差之控制變得容易，亦使表面平滑性變得良好，又，藉由除了有機顏料以外亦使用碳黑，可達成高遮光性。 有機顏料之種類並無特別限定，就密接性之觀點而言，較佳為含有選自由紅色顏料、橙色顏料、藍色顏料及紫色顏料所組成之群中之至少一種有機著色顏料。又，就遮光性之觀點而言，較佳為含有有機黑色顏料。 該等顏料之化學結構並無特別限定，除了利用偶氮系、酞菁系、喹吖啶酮系、苯并咪唑酮系、異吲哚啉酮系、二㗁𠯤系、陰丹士林系、苝系等之有機顏料以外，亦可利用各種無機顏料等。以下，以顏料編號例示可使用之顏料之具體例。以下所列舉之「C.I.顏料紅2」等用語意指色度指數(C.I.)。 作為紅色顏料，可列舉：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，較佳可列舉C.I.顏料紅48：1、122、149、168、177、179、194、202、206、207、209、224、242、254、272，進而較佳可列舉C.I.顏料紅149、177、179、194、209、224、254。再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料紅177、254、272，於藉由紫外線進行硬化之情形時，較佳為使用紫外線吸收率較低者作為紅色顏料，就該觀點而言，更佳為使用C.I.顏料紅254、272。 作為橙色(orange)顏料，可列舉：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，較佳可列舉C.I.顏料橙38、43、64、71、72。再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料橙43、64、72，於藉由紫外線進行硬化之情形時，較佳為使用紫外線吸收率較低者作為橙色顏料，就該觀點而言，更佳為使用C.I.顏料橙64、72。 作為藍色顏料，可列舉：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，較佳可列舉C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6、16、60，進而較佳可列舉C.I.顏料藍15：6。 再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料藍15：6、16、60，於藉由紫外線進行硬化之情形時，較佳為使用紫外線吸收率較低者作為藍色顏料，就該觀點而言，更佳為使用C.I.顏料藍60。 作為紫色顏料，可列舉：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，較佳可列舉C.I.顏料紫19、23、29，進而較佳可列舉C.I.顏料紫23。 再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料紫23、29，於藉由紫外線進行硬化之情形時，較佳為使用紫外線吸收率較低者作為紫色顏料，就該觀點而言，更佳為使用C.I.顏料紫29。 作為除了紅色顏料、橙色顏料、藍色顏料、紫色顏料以外可使用之有機著色顏料，例如可列舉綠色顏料、黃色顏料等。 作為綠色顏料，可列舉：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，較佳可列舉C.I.顏料綠7、36。 作為黃色顏料，可列舉：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，較佳可列舉C.I.顏料黃83、117、129、138、139、150、154、155、180、185，進而較佳可列舉C.I.顏料黃83、138、139、150、180。 該等中，就遮光性或形狀及階差之控制之觀點而言，較佳為含有以下顏料中之至少一種以上。 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、29 又，就遮光性或形狀及階差之控制之觀點而言，紅色顏料較佳為以下之(1)，橙色顏料較佳為以下之(2)，藍色顏料較佳為以下之(3)，紫色顏料較佳為以下之(4)。 (1)選自C.I.顏料紅177、254中之至少一種 (2)選自C.I.顏料橙43、64中之至少一種 (3)選自C.I.顏料藍15：6、60中之至少一種 (4)選自C.I.顏料紫23、29中之至少一種 再者，於第一態樣之感光性著色組合物中，組合複數種有機顏料而使用之情形時之該組合並無特別限定，就可見光區域之尤其長波長區域中之遮光性之觀點而言，較佳為使用藍色顏料及/或紫色顏料。尤其是由於碳黑之吸收光譜中吸光度自短波長至長波長逐漸下降，又，與有機顏料相比紫外線區域之吸光度變高，因此就兼顧遮光性與製版性之觀點而言，較佳為併用藍色顏料及/或紫色顏料與碳黑，更佳為併用藍色顏料及紫色顏料與碳黑。 另一方面，於使用少量碳黑之情形時，就遮光性之觀點而言，較佳為含有選自由紅色顏料及橙色顏料所組成之群中之至少一種與選自由藍色顏料及紫色顏料所組成之群中之至少一種，作為該具體組合例，可列舉紅色顏料與藍色顏料之組合、藍色顏料與橙色顏料之組合、藍色顏料與橙色顏料以及紫色顏料之組合等。 進而，除了該等有機著色顏料以外，可進一步使用黑色色料。作為黑色色料，可列舉碳黑等無機黑色顏料、或有機黑色顏料。 另一方面，亦可使用有機黑色顏料代替有機著色顏料。 第一態樣之感光性著色組合物含有碳黑作為黑色色料。由此藉由除了有機顏料以外亦使用碳黑，可達成高遮光性。於使用碳黑之情形時，尤其是由於有表面平滑性變差之傾向，因此藉由應用本發明，而有可改善該情況之傾向。作為碳黑之例，可列舉如以下之碳黑。 三菱化學公司製造：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公司製造：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公司製造：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)XC72R、ELFTEX(註冊商標)-8 Columbian Carbon公司製造：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 碳黑亦可使用由樹脂被覆者。若使用由樹脂被覆之碳黑，則具有提高與玻璃基板之密接性或體積電阻值之效果。作為由樹脂被覆之碳黑，例如可適宜地使用日本專利特開平09-71733號公報所記載之碳黑等。就體積電阻或介電常數之方面而言，可適宜地使用樹脂被覆碳黑。 作為供於利用樹脂進行之被覆處理之碳黑，較佳為Na與Ca之合計含量為100 ppm以下。碳黑通常以百分比之級別含有以自製造時之原料油或燃燒油(或氣體)、反應停止水或造粒水、進而反應爐之爐材等混入之Na或Ca、K、Mg、Al、Fe等作為組成之灰分。其中，通常各含有數百ppm以上之Na或Ca，藉由減少該等，而有抑制向透明電極(ITO(Indium Tin Oxides，氧化銦錫))或其他電極中之滲透，可防止電性短路之傾向。 作為減少含有該等Na或Ca之灰分之含量的方法，可藉由嚴格選擇該等之含量儘可能少之物作為製造碳黑時之原料油或燃料油(或氣體)及反應停止水以及儘可能減少調整結構(structure)之鹼性物質之添加量而實現。作為其他方法，可列舉藉由水或鹽酸等清洗由爐製造出之碳黑而將Na或Ca溶解去除之方法。 具體而言，將碳黑混合分散於水、鹽酸、或過氧化氫水中後，若添加難溶於水之溶媒，則碳黑轉移至溶媒側，與水完全分離，並且存在於碳黑中之大部分Na或Ca溶解於水或酸中而被去除。為了將Na與Ca之合計量減少為100 ppm以下，亦存在單獨藉由嚴格選擇原材料之碳黑製造過程或者單獨藉由水或酸溶解方式而實現之情形，但藉由將該兩種方式併用，可更容易地使Na與Ca之合計量成為100 ppm以下。 又，樹脂被覆碳黑較佳為pH值為6以下之所謂之酸性碳黑。由於在水中之分散直徑(附聚直徑)變小，因此可被覆至微細單元而較為適宜。進而較佳為平均粒徑為40 nm以下，鄰苯二甲酸二丁酯(DBP)吸收量為140 ml/100 g以下。藉由設為上述範圍內，而有可獲得遮光性良好之塗膜之傾向。平均粒徑意指數量平均粒徑，意指藉由粒子圖像解析求出之圓當量徑，該粒子圖像解析係對藉由電子顯微鏡觀察以數萬倍拍攝之照片拍攝數個視野，藉由圖像處理裝置計測2000～3000個左右之該等照片之粒子。 製備以樹脂被覆之碳黑之方法並無特別限定，例如適當調整碳黑及樹脂之調配量後，採用如下方法：1.將使樹脂與環己酮、甲苯、二甲苯等溶劑混合並加熱溶解而成之樹脂溶液與混合有碳黑及水之懸濁液加以混合攪拌，使碳黑與水分離後，將水去除並進行加熱混練，將所獲得之組合物成形為片狀並粉碎後，加以乾燥之方法；2.將以與上述同樣之方式製備之樹脂溶液與懸濁液加以混合攪拌並將碳黑及樹脂粒狀化後，將所獲得之粒狀物分離、加熱而去除殘存之溶劑及水之方法；3.於上述例示之溶劑中溶解順丁烯二酸、反丁烯二酸等羧酸，添加、混合碳黑並加以乾燥，去除溶劑而獲得添附羧酸之碳黑後，於其中添加樹脂並進行乾摻之方法；4.將構成進行被覆之樹脂之含反應性基單體成分與水進行高速攪拌而製備懸濁液，聚合後進行冷卻而由聚合物懸濁液獲得含反應性基之樹脂後，於其中添加碳黑並進行混練，使碳黑與反應性基進行反應(使碳黑接枝)，並進行冷卻及粉碎之方法等。 被覆處理之樹脂之種類亦無特別限定，通常為合成樹脂，進而結構中具有苯環之樹脂由於作為兩性系界面活性劑之作用更強，因此就分散性及分散穩定性之方面而言較佳。 作為具體之合成樹脂，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、環氧樹脂、烷基苯樹脂等熱硬化性樹脂；或聚苯乙烯、聚碳酸酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、改性聚苯醚、聚碸、聚對苯對苯二甲醯胺、聚醯胺醯亞胺、聚醯亞胺、聚胺基雙順丁烯二醯亞胺、聚醚碸、聚苯碸、聚芳酯、聚醚醚酮等熱塑性樹脂。樹脂對碳黑之被覆量相對於碳黑與樹脂之合計量，較佳為1～30質量%，藉由設為上述下限值以上，有可使被覆充分進行之傾向。另一方面，藉由設為上述上限值以下，有防止樹脂彼此之黏著，而製成分散性良好者之傾向。 以上述方式藉由樹脂進行被覆處理而成之碳黑可依照常規方法用作著色間隔件之遮光材，可藉由常規方法製作以該著色間隔件作為構成要素之彩色濾光片。若使用此種碳黑，則有可以較低成本達成高遮光率且表面反射率較低之著色間隔件之傾向。又，亦推測藉由以樹脂被覆碳黑表面，亦有將Ca或Na封入至碳黑中之作用。 作為碳黑以外之黑色色料，就抑制液晶之電壓保持率之降低之觀點，又，就抑制紫外線之吸收而變得容易控制形狀或階差之觀點而言，較佳為使用有機黑色顏料，尤其是就遮光性之觀點而言，較佳為使用選自由下述通式(1)所表示之化合物、該化合物之幾何異構物、該化合物之鹽及該化合物之幾何異構物之鹽所組成之群中之至少1種有機黑色顏料(以下有時簡記為「上述通式(1)所表示之有機黑色顏料」)。 [化3]

Figure 02_image005
式(1)中，R11 及R16 互相獨立為氫原子、CH3 、CF3 、氟原子或氯原子； R12 、R13 、R14 、R15 、R17 、R18 、R19 及R20 與其他全部互相獨立而為氫原子、鹵素原子、R21 、COOH、COOR21 、COO- 、CONH2 、CONHR21 、CONR21 R22 、CN、OH、OR21 、COCR21 、OCONH2 、OCONHR21 、OCONR21 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 ； 且選自由R12 與R13 、R13 與R14 、R14 與R15 、R17 與R18 、R18 與R19 、及R19 與R20 所組成之群中之至少1種組合可互相直接鍵結，或者利用氧原子、硫原子、NH或NR21 橋而互相鍵結； R21 及R22 互相獨立為碳數1～12之烷基、碳數3～12之環烷基、碳數2～12之烯基、碳數3～12之環烯基或碳數2～12之炔基。 通式(1)所表示之化合物之幾何異構物具有以下之核結構(其中省略結構式中之取代基)，很可能最穩定的是反-反異構物。 [化4]
Figure 02_image007
於通式(1)所表示之化合物為陰離子性之情形時，較佳為藉由任意公知之合適之陽離子，例如金屬、有機、無機或金屬有機陽離子，具體而言為鹼金屬、鹼土金屬、過渡金屬、一級銨、二級銨、三烷基銨等三級銨、四烷基銨等四級銨或有機金屬錯合物補償其電荷而成之鹽。又，於通式(1)所表示之化合物之幾何異構物為陰離子性之情形時，較佳為同樣之鹽。 於通式(1)之取代基及該等之定義中，由於有遮蔽率變高之傾向，因此較佳為以下。其原因在於認為以下取代基無吸收，不會對顏料之色相產生影響。 R12 、R14 、R15 、R17 、R19 及R20 互相獨立，較佳為氫原子、氟原子、或氯原子，進而較佳為氫原子。 R13 及R18 互相獨立，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 - ，進而較佳為氫原子或SO3 H。 R11 及R16 互相獨立，較佳為氫原子、CH3 或CF3 ，進而較佳為氫原子。 較佳為選自由R11 與R16 、R12 與R17 、R13 與R18 、R14 與R19 、及R15 與R20 所組成之群中之至少1種組合相同，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。 碳數1～12之烷基例如為：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、庚基、正辛基、1,1,3,3-四甲基丁基、2-乙基己基、壬基、癸基、十一烷基或十二烷基。 碳數3～12之環烷基例如為：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、側柏基(thujyl)、降
Figure 105142935-A0304-03-0013-01
基、
Figure 105142935-A0304-03-0013-01
基、降蒈基(Norcaryl)、蒈基、
Figure 105142935-001
基、降蒎基、蒎基、1-金剛烷基或2-金剛烷基。 碳數2～12之烯基例如為：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-
Figure 105142935-001
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、癸烯基或十二碳烯基。 碳數3～12之環烯基例如為：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
Figure 105142935-001
烯-8-基、4(10)-側柏烯-10-基、2-降
Figure 105142935-A0304-03-0013-01
烯-1-基、2,5-降
Figure 105142935-A0304-03-0013-01
二烯-1-基、7,7-二甲基-2,4-降蒈二烯-3-基或
Figure 105142935-A0304-03-0013-01
烯基(camphenyl)。 碳數2～12之炔基例如為：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-己二炔-5-基、1-辛炔-8-基、1-壬炔-9-基、1-癸炔-10-基或1-十二碳炔-12-基。 鹵素原子例如為：氟原子、氯原子、溴原子或碘原子。 上述通式(1)所表示之有機黑色顏料較佳為下述通式(2)所表示之化合物。 [化5]
Figure 02_image009
作為此種有機黑色顏料之具體例，可列舉商品名如下者：Irgaphor(註冊商標) Black S 0100 CF(BASF公司製造)。 該有機黑色顏料較佳為藉由下文所述之分散劑、溶劑、方法使其分散而使用。又，於分散時若存在上述通式(2)之磺酸衍生物，則存在提高分散性或保存性之情形。 作為上述通式(1)所表示之有機黑色顏料以外之黑色色料，可列舉：乙炔黑、燈黑、骨黑、石墨、鐵黑、苯胺黑、花青黑、鈦黑、苝黑等。 又，除了上述顏料以外，亦可使用染料。作為可用作色料之染料，可列舉：偶氮系染料、蒽醌系染料、酞菁系染料、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，例如可列舉：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.反應性黃2、C.I.反應性紅17、C.I.反應性紅120、C.I.反應性黑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.媒染紅7、C.I.媒染黃5、C.I.媒染黑7等。 作為蒽醌系染料，例如可列舉：C.I.還原藍4、C.I.酸性藍40、C.I.酸性綠25、C.I.反應性藍19、C.I.反應性藍49、C.I.分散紅60、C.I.分散藍56、C.I.分散藍60等。 除此以外，作為酞菁系染料，例如可列舉C.I.還原藍5等，作為醌亞胺系染料，例如可列舉C.I.鹼性藍3、C.I.鹼性藍9等，作為喹啉系染料，例如可列舉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，例如可列舉C.I.酸性黃1、C.I.酸性橙3、C.I.分散黃42等。 該等顏料較佳為以平均粒徑通常成為1 μm以下、較佳為0.5 μm以下、進而較佳為0.25 μm以下之方式分散而使用。此處，平均粒徑之基準為顏料粒子之個數。 再者，顏料之平均粒徑係根據藉由動態光散射(Dynamic Light Scattering，DLS)測得之顏料粒徑求出之值。粒徑測定係對經充分稀釋之感光性著色組合物(通常進行稀釋而而製備為顏料濃度0.005～0.2質量%左右。但若有測定機器推薦之濃度，則按照該濃度)進行，於25℃下進行測定。 第二態樣之感光性著色組合物所使用之(a)著色劑含有選自由紅色顏料及橙色顏料所組成之群中之至少一種與選自由藍色顏料及紫色顏料所組成之群中之至少一種。由此藉由本發明之第二態樣之感光性著色組合物含有特定之有機著色顏料之組合，而可達成高遮光性。 作為紅色顏料、橙色顏料、藍色顏料及紫色顏料，可適宜地使用與第一態樣中所記載者相同者。顏色之組合並無特別限定，就遮光性之觀點而言，例如可列舉：紅色顏料與藍色顏料之組合、橙色顏料與藍色顏料之組合、橙色顏料與藍色顏料以及紫色顏料之組合等。 又，第二態樣之感光性著色組合物亦可含有紅色顏料、橙色顏料、藍色顏料及紫色顏料以外之顏料，就遮光性之觀點而言，較佳為含有黑色色料。作為黑色色料，可適宜地使用與第一態樣中所記載者相同者。 第三態樣之感光性著色組合物係用於形成著色間隔件之感光性著色組合物，(a)著色劑並無特別限定。例如可列舉含有上文所述之有機著色顏料、黑色色料、染料之至少任一種者。又，作為(a)著色劑，亦可使用作為第一態樣及第二態樣所記載者，又，就遮光性之觀點而言，亦可使用含有上述通式(1)所表示之有機黑色顏料之著色劑。 ＜(b)鹼可溶性樹脂＞ 本發明所使用之(b)鹼可溶性樹脂係含有羧基或羥基之樹脂，尤其含有(b-I)環氧(甲基)丙烯酸酯樹脂、與(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂，且(b-II)(甲基)丙烯酸系共聚合樹脂中之重複單元α之含有比例為10莫耳%以上，較佳為12莫耳%以上。 於單獨使用(b-I)環氧(甲基)丙烯酸酯樹脂作為(b)鹼可溶性樹脂之情形時，通常該樹脂於主鏈具有芳香族等結構，該結構導致容易產生熱流動，產生皺褶而表面平滑性容易變差。皺褶會導致遮光性亦降低，因此無法獲得所需之遮光性而容易產生漏光等問題。 又，於著色間隔件中多數情況以高於黑矩陣之膜厚使用。又，為了設置所需之階差，較理想為感光性著色組合物具有不易熱變形之塗膜特性，但為了確保壓縮特性或可靠性，較佳為將顏料濃度設定為低於黑矩陣。其結果，於著色間隔件中，於膜表面附近與膜底部附近交聯密度之差進一步變大，而變得容易產生皺褶。又，由於此種熱變形，因此有無法確保充分之階差形成性之傾向。 為了兼顧此各種性能，認為藉由併用主鏈中不含芳香環等且熱收縮較少之丙烯酸系樹脂、尤其是玻璃轉移溫度較高且不易熱流動之含有源自不飽和羧酸之重複單元之特定之(甲基)丙烯酸系共聚合樹脂，可降低熱流動，抑制皺褶之產生，而可使表面平滑性變得良好。但由於在併用感度較低之(甲基)丙烯酸系共聚合樹脂之情形時，有可靠性變差之傾向，因此認為藉由向該(甲基)丙烯酸系共聚合樹脂中導入特定量之乙烯性不飽和鍵，可充分確保感度，使可靠性變得良好，其結果為可實現兼顧表面平滑性與可靠性。 ＜(b-I)環氧(甲基)丙烯酸酯樹脂＞ (b-I)環氧(甲基)丙烯酸酯樹脂係使環氧化合物與α,β-不飽和單羧酸及/或酯部分具有羧基之α,β-不飽和單羧酸酯之反應物及藉由該反應產生之羥基進一步與具有2個以上可與多元酸及/或其酐等之羥基進行反應之取代基之化合物進行反應而獲得之樹脂。 作為本發明所使用之(b-I)環氧(甲基)丙烯酸酯樹脂，就可靠性之觀點而言，尤其可適宜地使用下述環氧(甲基)丙烯酸酯樹脂(b1)及/或環氧(甲基)丙烯酸酯樹脂(b2)(以下有時稱為「含羧基之環氧(甲基)丙烯酸酯樹脂」)。 ＜環氧(甲基)丙烯酸酯樹脂(b1)＞ 藉由對環氧樹脂加成α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯，進而與多元酸及/或其酐進行反應而獲得之鹼可溶性樹脂。 ＜環氧(甲基)丙烯酸酯樹脂(b2)＞ 藉由對環氧樹脂加成α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯，進而與多元醇、及多元酸及/或其酐進行反應而獲得之鹼可溶性樹脂。 此處，所謂環氧樹脂係亦包括藉由熱硬化形成樹脂前之原料化合物而言，作為該環氧樹脂，可自公知之環氧樹脂中適當選擇而使用。又，環氧樹脂可使用使酚性化合物與表鹵醇進行反應而獲得之化合物。作為酚性化合物，較佳為具有二價或二價以上之酚性羥基之化合物，可為單體，亦可為聚合物。 作為成為原料之環氧樹脂之種類，可適宜地使用甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚醛清漆型環氧樹脂、作為二環戊二烯與苯酚或甲酚之加成聚合反應物與表鹵醇之反應產物之環氧樹脂、含金剛烷基之環氧樹脂、茀型環氧樹脂等，可適宜地使用此種主鏈具有芳香族環者。 又，作為環氧樹脂之具體例，可適宜地使用：雙酚A型環氧樹脂(例如三菱化學公司製造之「Epikote(註冊商標；以下相同)828」、「Epikote 1001」、「Epikote 1002」、「Epikote 1004」等)、藉由雙酚A型環氧樹脂之醇性羥基與表氯醇之反應而獲得之環氧樹脂(例如日本化藥公司製造之「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造之「Epikote 807」、「EP-4001」、「EP-4002」、「EP-4004等」)、藉由雙酚F型環氧樹脂之醇性羥基與表氯醇之反應而獲得之環氧樹脂(例如日本化藥公司製造之「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造之「YX-4000」)、苯酚酚醛清漆型環氧樹脂(例如日本化藥公司製造之「EPPN-201」、三菱化學公司製造之「EP-152」、「EP-154」、Dow Chemical公司製造之「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造之「EOCN(註冊商標；以下相同)-102S」、「EOCN-1020」、「EOCN-104S」)、異氰脲酸三縮水甘油酯(例如日產化學公司製造之「TEPIC(註冊商標)」)、三苯酚甲烷型環氧樹脂(例如日本化藥公司製造之「EPPN(註冊商標；以下相同)-501」、「EPN-502」、「EPPN-503」)、脂環式環氧樹脂(Daicel化學工業公司製造之「Celloxide 2021P」、「Celloxide(註冊商標；以下相同)EHPE」)、將藉由二環戊二烯與苯酚之反應獲得之苯酚樹脂進行縮水甘油基化而成之環氧樹脂(例如DIC公司製造之「EXA-7200」、日本化藥公司製造之「NC-7300」)、下述通式(B1)～(B4)所表示之環氧樹脂等。具體而言，作為下述通式(B1)所表示之環氧樹脂，可列舉日本化藥公司製造之「XD-1000」，作為下述通式(B2)所表示之環氧樹脂，可列舉日本化藥公司製造之「NC-3000」，作為下述通式(B4)所表示之環氧樹脂，可列舉新日鐵住金化學公司製造之「ESF-300」等。 [化6]
Figure 02_image011
於上述通式(B1)中，a表示平均值，表示0～10之數。R111 表示氫原子、鹵素原子、碳數1～8之烷基、碳數3～10之環烷基、苯基、萘基、或聯苯基中之任一者。再者，存在於1分子中之複數個R111 分別可相同亦可不同。 [化7]
Figure 02_image013
於上述通式(B2)中，b表示平均值，表示0～10之數。R121 表示氫原子、鹵素原子、碳數1～8之烷基、碳數3～10之環烷基、苯基、萘基、或聯苯基中之任一者。再者，存在於1分子中之複數個R121 分別可相同亦可不同。 [化8]
Figure 02_image015
於上述通式(B3)中，X表示下述通式(B3-1)或(B3-2)所表示之連結基。但於分子結構中含有1個以上之金剛烷結構。c表示2或3之整數。 [化9]
Figure 02_image017
[化10]
Figure 02_image019
於上述通式(B3-1)及(B3-2)中，R131 ～R134 及R135 ～R137 分別獨立地表示可具有取代基之金剛烷基、氫原子、可具有取代基之碳數1～12之烷基、或可具有取代基之苯基。﹡表示鍵結鍵。 [化11]
Figure 02_image021
於上述通式(B4)中，p及q分別獨立地表示0～4之整數，R141 及R142 分別獨立地表示碳數1～4之烷基或鹵素原子。R143 及R144 分別獨立地表示碳數1～4之伸烷基。x及y分別獨立地表示0以上之整數。 該等中，就可靠性之觀點而言，較佳為使用通式(B1)～(B4)之任一者所表示之環氧樹脂。 作為α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯，可列舉：(甲基)丙烯酸、丁烯酸、鄰乙烯基苯甲酸、間乙烯基苯甲酸、對乙烯基苯甲酸；(甲基)丙烯酸之α位鹵代烷基、烷氧基、鹵素、硝基、氰基取代體等單羧酸；2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基己二酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基丁二酸、2-(甲基)丙烯醯氧基丙基己二酸、2-(甲基)丙烯醯氧基丙基四氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、2-(甲基)丙烯醯氧基丁基丁二酸、2-(甲基)丙烯醯氧基丁基己二酸、2-(甲基)丙烯醯氧基丁基氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丁基鄰苯二甲酸、2-(甲基)丙烯醯氧基丁基順丁烯二酸；作為對(甲基)丙烯酸加成ε-己內酯、β-丙內酯、γ-丁內酯、δ-戊內酯等內酯類而成者之單體；或對(甲基)丙烯酸羥基烷基酯、季戊四醇三(甲基)丙烯酸酯加成丁二酸(酐)、鄰苯二甲酸(酐)、順丁烯二酸(酐)等酸(酐)而成之單體；(甲基)丙烯酸二聚物等。 該等中，就感度之方面而言，尤佳為(甲基)丙烯酸。 作為對環氧樹脂加成α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之方法，可使用公知之方法。例如，可於酯化觸媒之存在下，於50～150℃之溫度下使α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯與環氧樹脂進行反應。作為此處所使用之酯化觸媒，可使用：三乙胺、三甲胺、苄基二甲基胺、苄基二乙基胺等三級胺；四甲基氯化銨、四乙基氯化銨、十二烷基三甲基氯化銨等四級銨鹽等。 再者，環氧樹脂、α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯、及酯化觸媒均可單獨使用一種，亦可將兩種以上併用。 α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之使用量相對於環氧樹脂之環氧基1當量，較佳為0.5～1.2當量之範圍，進而較佳為0.7～1.1當量之範圍。藉由設為上述下限值以上，有可使不飽和基之導入量充分，且使後續之與多元酸及/或其酐之反應亦充分之傾向。又，藉由設為上述上限值以下，有可抑制α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯作為未反應物殘存之情況之傾向。 作為多元酸及/或其酐，可列舉選自順丁烯二酸、丁二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、二苯甲酮四羧酸、甲基六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、氯菌酸、甲基四氫鄰苯二甲酸、聯苯四羧酸、及該等之酐等中之一種或兩種以上。 較佳為順丁烯二酸、丁二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、聯苯四羧酸、或該等之酐。尤佳為四氫鄰苯二甲酸、聯苯四羧酸、無水四氫鄰苯二甲酸、或聯苯四羧酸二酐。 關於多元酸及/或其酐之加成反應，亦可使用公知之方法，可於與對環氧樹脂進行之α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之加成反應同樣之條件下繼續反應而獲得目標物。多元酸及/或其酐成分之加成量較佳為所產生之含羧基之環氧(甲基)丙烯酸酯樹脂之酸值成為10～150 mgKOH/g之範圍之程度，進而較佳為成為20～140 mgKOH/g之範圍之程度。藉由設為上述下限值以上，有鹼性顯影性變得良好之傾向，又，藉由設為上述上限值以下，有硬化性能變得良好之傾向。 再者，於該多元酸及/或其酐之加成反應時，可添加三羥甲基丙烷、季戊四醇、二季戊四醇等多官能醇而製成導入多分支結構者。 含羧基之環氧(甲基)丙烯酸酯樹脂通常藉由在環氧樹脂與α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之反應物中混合多元酸及/或其酐後，或者在環氧樹脂與α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之反應物中混合多元酸及/或其酐及多官能醇後進行加溫而獲得。於該情形時，多元酸及/或其酐與多官能醇之混合順序並無特別限制。藉由加溫，多元酸及/或其酐對環氧樹脂與α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之反應物及多官能醇之混合物中所存在之任一羥基進行加成反應。 含羧基之環氧(甲基)丙烯酸酯樹脂所含之重複單元之化學結構並無特別限定，例如可列舉以下所示之化學結構。 [化12]
Figure 02_image023
[化13]
Figure 02_image025
[化14]
Figure 02_image027
[化15]
Figure 02_image029
其中於上述式(C-1)～(C-15)中，X表示以下之結構。 [化16]
Figure 02_image031
(上述結構X中之R11 表示氫原子或甲基，Y表示氫原子或多元酸之殘基。又，多元酸亦可互相交聯) 作為含羧基之環氧(甲基)丙烯酸酯樹脂，除了上文所述者以外，可列舉韓國公開專利第10-2013-0022955號公報所記載者等。 環氧(甲基)丙烯酸酯樹脂之藉由凝膠滲透層析法(GPC)測得之聚苯乙烯換算之重量平均分子量(Mw)通常為1000以上，較佳為2000以上，更佳為3000以上，進而較佳為4000以上，尤佳為5000以上，且通常為10000以下，較佳為8000以下，更佳為7000以下。藉由設為上述下限值以上，有可靠性良化之傾向，又，藉由設為上述上限值以下，有溶解性變得良好之傾向。 環氧(甲基)丙烯酸酯樹脂之酸值並無特別限定，較佳為10 mg・KOH/g以上，更佳為20 mg・KOH/g以上，進而較佳為40 mg・KOH/g以上，進而更佳為60 mg・KOH/g以上，尤佳為80 mg・KOH/g以上，又，較佳為200 mg・KOH/g以下，更佳為150 mg・KOH/g以下，進而較佳為120 mg・KOH/g以下，尤佳為100 mg・KOH/g以下。藉由設為上述下限值以上，有可獲得適度之顯影溶解性之傾向，又，藉由設為上述上限值以下，有可抑制過分進行顯影而發生膜溶解之情況之傾向。 環氧(甲基)丙烯酸酯樹脂之化學結構並無特別限定，就可靠性之觀點而言，較佳為含有具有下述通式(b-I-I)所表示之重複單元結構之環氧(甲基)丙烯酸酯樹脂(以下有時簡記為「(b-I-I)環氧(甲基)丙烯酸酯樹脂」)及/或具有下述通式(b-I-II)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(以下有時簡記為「(b-I-II)環氧(甲基)丙烯酸酯樹脂」)。 [化17]
Figure 02_image033
式(b-I-I)中，R11 表示氫原子或甲基，R12 表示可具有取代基之二價烴基。式(b-I-I)中之苯環可進一步經任意取代基取代。﹡表示鍵結鍵。 [化18]
Figure 02_image035
式(b-I-II)中，R13 分別獨立地表示氫原子或甲基。R14 表示具有環狀烴基作為側鏈之二價烴基。R15 及R16 分別獨立地表示可具有取代基之二價脂肪族基。m及n分別獨立地表示0～2之整數。﹡表示鍵結鍵。 ＜(b-I-I)環氧(甲基)丙烯酸酯樹脂＞ 首先，對具有上述通式(b-I-I)所表示之重複單元結構之環氧(甲基)丙烯酸酯樹脂進行詳細說明。 [化19]
Figure 02_image037
式(b-I-I)中，R11 表示氫原子或甲基，R12 表示可具有取代基之二價烴基。式(b-I-I)中之苯環可進一步經任意取代基取代。﹡表示鍵結鍵。 (R12 ) 於上述式(b-I-I)中，R12 表示可具有取代基之二價烴基。 作為二價烴基，可列舉：二價脂肪族基、二價芳香族環基、將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基。 二價脂肪族基可列舉直鏈狀、支鏈狀、環狀者。該等中，就顯影溶解性之觀點而言，較佳為直鏈狀者，另一方面，就減少顯影液對曝光部之滲透之觀點而言，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，進而較佳為10以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為二價之直鏈狀脂肪族基之具體例，可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基等。該等中，就骨架之剛直性之觀點而言，較佳為亞甲基。 作為二價之支鏈狀脂肪族基，可列舉上文所述之二價之直鏈狀脂肪族基具有甲基、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之結構。 二價之環狀脂肪族基所具有之環數並無特別限定，通常為1以上，較佳為2以上，又，通常為12以下，較佳為10以下。藉由設為上述下限值以上，有成為強固之膜，基板密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。作為二價之環狀脂肪族基之具體例，可列舉自環己烷環、環庚烷環、環癸烷環、環十二烷環、降
Figure 105142935-A0304-03-0013-01
烷環、異
Figure 105142935-A0304-03-0013-01
烷環、金剛烷環、環十二烷環、二環戊二烯等環中去除2個氫原子而成之基。該等中，就骨架之剛直性之觀點而言，較佳為自二環戊二烯環、金剛烷環中去除2個氫原子而成之基。 作為二價脂肪族基可具有之取代基，可列舉：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、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等中，就合成容易性之觀點而言，較佳為未經取代。 又，作為二價芳香族環基，可列舉二價芳香族烴環基及二價雜芳香環基。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，進而較佳為10以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為二價芳香族烴環基中之芳香族烴環，可為單環，亦可為縮合環，例如可列舉具有1個自由原子價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、
Figure 105142935-001-2
環、聯三伸苯環、苊環、螢蒽環、茀環等之基。又，作為雜芳香環基中之雜芳香環，可為單環，亦可為縮合環，例如可列舉具有1個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、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、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、
Figure 105142935-A0304-12-xxxx-6
啉環、喹㗁啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等之基。該等中，就圖案化特性之觀點而言，較佳為苯環或萘環，更佳為苯環。 作為二價芳香族環基可具有之取代基，可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。該等中，就顯影溶解性、耐吸濕性之觀點而言，較佳為未經取代。 又，作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基，可列舉將1個以上之上文所述之二價脂肪族基與1個以上之上文所述之二價芳香族環基連結而成之基。 二價脂肪族基之個數並無特別限定，通常為1以上，較佳為2以上，且通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 二價芳香族環基之個數並無特別限定，通常為1以上，較佳為2以上，且通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基之具體例，可列舉下述式(b-I-I-A)～(b-I-I-F)所表示之基等。該等中，就骨架之剛直性與膜之疏水化之觀點而言，較佳為下述式(b-I-I-A)所表示之基。 [化20]
Figure 02_image039
如上所述，式(b-I-I)中之苯環可進一步經任意取代基取代。作為該取代基，例如可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基之個數亦無特別限定，可為1個，亦可為2個以上。 該等中，就圖案化特性之觀點而言，較佳為未經取代。 又，上述式(b-I-I)所表示之重複單元結構就合成之簡易性之觀點而言，較佳為下述式(b-I-I-1)所表示之重複單元結構。 [化21]
Figure 02_image041
式(b-I-I-1)中，R11 及R12 與上述式(b-I-I)中者含義相同。RX 表示氫原子或多元酸殘基。﹡表示鍵結鍵。式(b-I-I-1)中之苯環可進一步經任意取代基取代。 所謂多元酸殘基意指自多元酸或其酐中去除1個OH基而成之一價基。作為多元酸，可列舉選自順丁烯二酸、丁二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、二苯甲酮四羧酸、甲基六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、氯菌酸、甲基四氫鄰苯二甲酸、聯苯四羧酸中之一種或兩種以上。 該等中，就圖案化特性之觀點而言，較佳為順丁烯二酸、丁二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、聯苯四羧酸，更佳為四氫鄰苯二甲酸、聯苯四羧酸、四氫鄰苯二甲酸、聯苯四羧酸。 (b-I-I)環氧(甲基)丙烯酸酯樹脂1分子中所含之上述式(b-I-I-1)所表示之重複單元結構可為一種，亦可為兩種以上，例如可混合存在RX 為氫原子者與RX 為多元酸殘基者。 又，(b-I-I)環氧(甲基)丙烯酸酯樹脂1分子中所含之上述式(b-I-I)所表示之重複單元結構之數量並無特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，進而較佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 (b-I-I)環氧(甲基)丙烯酸酯樹脂之藉由凝膠滲透層析法(GPC)測得之聚苯乙烯換算之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為1500以上，進而較佳為2000以上，進而更佳為3000以上，尤佳為4000以上，最佳為5000以上，又，較佳為30000以下，更佳為20000以下，進而較佳為10000以下，尤佳為8000以下。藉由設為上述下限值以上，有感光性著色組合物之殘膜率變得良好之傾向，又，藉由設為上述上限值以下，有解像性變得良好之傾向。 (b-I-I)環氧(甲基)丙烯酸酯樹脂之酸值並無特別限定，較佳為10 mgKOH/g以上，更佳為20 mgKOH/g以上，進而較佳為40 mgKOH/g以上，進而更佳為50 mgKOH/g以上，尤佳為80 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，進而更佳為130 mgKOH/g以下，尤佳為100 mgKOH/g以下。藉由設為上述下限值以上，有顯影溶解性提高，解像性變得良好之傾向，又，藉由設為上述上限值以下，有感光性著色組合物之殘膜率變得良好之傾向。 以下列舉(b-I-I)環氧(甲基)丙烯酸酯樹脂之具體例。再者，例中之﹡表示鍵結鍵。 [化22]
Figure 02_image043
[化23]
Figure 02_image045
[化24]
Figure 02_image047
[化25]
Figure 02_image049
＜(b-I-II)環氧(甲基)丙烯酸酯樹脂＞ 繼而，對具有上述通式(b-I-II)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂進行詳細說明。 [化26]
Figure 02_image051
式(b-I-II)中，R13 分別獨立地表示氫原子或甲基。R14 表示具有環狀烴基作為側鏈之二價烴基。R15 及R16 分別獨立地表示可具有取代基之二價脂肪族基。m及n分別獨立地表示0～2之整數。﹡表示鍵結鍵。 (R14 ) 於上述通式(b-I-II)中，R14 表示具有環狀烴基作為側鏈之二價烴基。 作為環狀烴基，可列舉脂肪族環基或芳香族環基。 脂肪族環基所具有之環數並無特別限定，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。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 又，脂肪族環基之碳數通常為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，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為脂肪族環基中之脂肪族環之具體例，可列舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降
Figure 105142935-A0304-03-0013-01
烷環、異
Figure 105142935-A0304-03-0013-01
烷環、金剛烷環、環十二烷環等。該等中，就感光性著色組合物之殘膜率與解像性之觀點而言，較佳為金剛烷環。 另一方面，芳香族環基所具有之環數並無特別限定，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。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為芳香族環基，可列舉芳香族烴環基、雜芳香環基。又，芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，進而更佳為10以上，尤佳為12以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有圖案化特性變得良好之傾向。 作為芳香族環基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、
Figure 105142935-001-2
環、聯三伸苯環、苊環、螢蒽環、茀環等。該等中，就圖案化特性之觀點而言，較佳為茀環。 又，具有環狀烴基作為側鏈之二價烴基中之二價烴基並無特別限定，例如可列舉二價脂肪族基、二價芳香族環基、將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基。 二價脂肪族基可列舉直鏈狀、支鏈狀、環狀者。該等中，就顯影溶解性之觀點而言，較佳為直鏈狀者，另一方面，就減少顯影液對曝光部之滲透之觀點而言，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，進而較佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為二價之直鏈狀脂肪族基之具體例，可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基等。該等中，就骨架之剛直性之觀點而言，較佳為亞甲基。 作為二價之支鏈狀脂肪族基，可列舉上文所述之二價之直鏈狀脂肪族基具有甲基、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之結構。 二價之環狀脂肪族基所具有之環數並無特別限定，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，進而較佳為3以下。藉由設為上述下限值以上，有成為強固之膜，基板密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。作為二價之環狀脂肪族基之具體例，可列舉自環己烷環、環庚烷環、環癸烷環、環十二烷環、降
Figure 105142935-A0304-03-0013-01
烷環、異
Figure 105142935-A0304-03-0013-01
烷環、金剛烷環、環十二烷環等環中去除2個氫原子而成之基。該等中，就骨架之剛直性之觀點而言，較佳為自金剛烷環中去除2個氫原子而成之基。 作為二價脂肪族基可具有之取代基，可列舉：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、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等中，就合成容易性之觀點而言，較佳為未經取代。 又，作為二價芳香族環基，可列舉二價芳香族烴環基及二價雜芳香環基。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，進而較佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為二價芳香族烴環基中之芳香族烴環，可為單環，亦可為縮合環，例如可列舉具有1個自由原子價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、
Figure 105142935-001-2
環、聯三伸苯環、苊環、螢蒽環、茀環等之基。又，作為雜芳香環基中之雜芳香環，可為單環，亦可為縮合環，例如可列舉具有1個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、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、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、
Figure 105142935-A0304-12-xxxx-6
啉環、喹㗁啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等之基。該等中，就圖案化特性之觀點而言，較佳為苯環或萘環，更佳為茀環。 作為二價芳香族環基可具有之取代基，可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。該等中，就顯影溶解性之觀點而言，較佳為未經取代。 又，作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基，可列舉將1個以上之上文所述之二價脂肪族基與1個以上之上文所述之二價芳香族環基連結而成之基。 二價脂肪族基之個數並無特別限定，通常為1以上，較佳為2以上，且通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 二價芳香族環基之個數並無特別限定，通常為1以上，較佳為2以上，且通常為10以下，較佳為5以下，更佳為3以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基之具體例，可列舉上述式(b-I-I-A)～(b-I-I-F)所表示之基等。該等中，就骨架之剛直性與膜之疏水化之觀點而言，較佳為上述式(b-I-I-C)所表示之基。 作為側鏈之環狀烴基於該等二價烴基上之鍵結態樣並無特別限定，例如可列舉以該側鏈取代脂肪族基或芳香族環基之1個氫原子而成之態樣、或包括脂肪族基之1個碳原子在內而構成作為側鏈之環狀烴基之態樣。 (R15 、R16 ) 於上述通式(b-I-II)中，R15 及R16 分別獨立地表示可具有取代基之二價脂肪族基。 二價脂肪族基可列舉直鏈狀、支鏈狀、環狀者。該等中，就顯影溶解性之觀點而言，較佳為直鏈狀者，另一方面，就減少顯影液對曝光部之滲透之觀點而言，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，進而較佳為10以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，與基板之密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為二價之直鏈狀脂肪族基之具體例，可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正戊基、伸正己基、伸正庚基等。該等中，就骨架之剛直性之觀點而言，較佳為亞甲基。 作為二價之支鏈狀脂肪族基，可列舉上文所述之二價之直鏈狀脂肪族基具有甲基、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之結構。 二價之環狀脂肪族基所具有之環數並無特別限定，通常為1以上，較佳為2以上，又，通常為12以下，較佳為10以下。藉由設為上述下限值以上，有成為強固之膜，基板密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。作為二價之環狀脂肪族基之具體例，可列舉自環己烷環、環庚烷環、環癸烷環、環十二烷環、降
Figure 105142935-A0304-03-0013-01
烷環、異
Figure 105142935-A0304-03-0013-01
烷環、金剛烷環、環十二烷環、二環戊二烯等環中去除2個氫原子而成之基。該等中，就骨架之剛直性之觀點而言，較佳為自二環戊二烯環、金剛烷環中去除2個氫原子而成之基。 作為二價脂肪族基可具有之取代基，可列舉：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、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等中，就合成容易性之觀點而言，較佳為未經取代。 (m、n) 於上述通式(b-I-II)中，m及n表示0～2之整數。藉由設為上述下限值以上，有精確圖案化變得良好，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有顯影性變得良好之傾向。就顯影性之觀點而言，較佳為m及n為0，另一方面，就精確圖案化、表面粗糙之觀點而言，較佳為m及n為1以上。 又，上述通式(b-I-II)所表示之部分結構就與基板之密接性之觀點而言，較佳為下述通式(b-I-II-1)所表示之部分結構。 [化27]
Figure 02_image053
式(b-I-II-1)中，R13 、R15 、R16 、m及n與上述式(b-I-II)含義相同。Rα 表示可具有取代基之一價之環狀烴基。p為1以上之整數。式(b-I-II-1)中之苯環可進一步經任意取代基取代。﹡表示鍵結鍵。 (Rα ) 於上述通式(b-I-II-1)中，Rα 表示可具有取代基之一價之環狀烴基。 作為環狀烴基，可列舉脂肪族環基或芳香族環基。 脂肪族環基所具有之環數並無特別限定，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。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有圖案化特性變得良好之傾向。 又，脂肪族環基之碳數通常為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，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有圖案化特性變得良好之傾向。 作為脂肪族環基中之脂肪族環之具體例，可列舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降
Figure 105142935-A0304-03-0013-01
烷環、異
Figure 105142935-A0304-03-0013-01
烷環、金剛烷環、環十二烷環等。該等中，就強固之膜特性之觀點而言，較佳為金剛烷環。 另一方面，芳香族環基所具有之環數並無特別限定，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。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有圖案化特性變得良好之傾向。 作為芳香族環基，可列舉芳香族烴環基、雜芳香環基。又，芳香族環基之碳數通常為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，進而較佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有圖案化特性變得良好之傾向。 作為芳香族環基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、茀環等。該等中，就顯影溶解性之觀點而言，較佳為茀環。 作為環狀烴基可具有之取代基，可列舉：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、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等中，就合成之容易性之觀點而言，較佳為未經取代。 p表示1以上之整數，較佳為2以上，又，較佳為3以下。藉由設為上述下限值以上，有膜硬化度與殘膜率變得良好之傾向，又，藉由設為上述上限值以下，有顯影性變得良好之傾向。 該等中，就強固之膜硬化度之觀點而言，較佳為Rα 為一價脂肪族環基，更佳為金剛烷基。 如上所述，式(b-I-II-1)中之苯環可進一步經任意取代基取代。作為該取代基，例如可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基之個數亦無特別限定，可為1個，亦可為2個以上。 該等中，就圖案化特性之觀點而言，較佳為未經取代。 以下列舉上述式(b-I-II-1)所表示之部分結構之具體例。 [化28]
Figure 02_image055
[化29]
Figure 02_image057
[化30]
Figure 02_image059
[化31]
Figure 02_image061
[化32]
Figure 02_image063
又，上述通式(b-I-II)所表示之部分結構就骨架之剛直性、及膜疏水化之觀點而言，較佳為下述通式(b-I-II-2)所表示之部分結構。 [化33]
Figure 02_image065
式(b-I-II-2)中，R13 、R15 、R16 、m及n與上述式(b-I-II)含義相同。Rβ 表示可具有取代基之二價之環狀烴基。式(b-I-II-2)中之苯環可進一步經任意取代基取代。﹡表示鍵結鍵。 (Rβ ) 於上述式(b-I-II-2)中，Rβ 表示可具有取代基之二價之環狀烴基。 作為環狀烴基，可列舉脂肪族環基或芳香族環基。 脂肪族環基所具有之環數並無特別限定，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。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 又，脂肪族環基之碳數通常為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，進而較佳為30以下。藉由設為上述下限值以上，有抑制顯影時之膜粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差及顯影時之膜減少，提高解像性之傾向。 作為脂肪族環基中之脂肪族環之具體例，可列舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降
Figure 105142935-A0304-03-0013-01
烷環、異
Figure 105142935-A0304-03-0013-01
烷環、金剛烷環、環十二烷環等。該等中，就保存穩定性之觀點而言，較佳為金剛烷環。 另一方面，芳香族環基所具有之環數並無特別限定，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。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差或膜減少，解像性提高之傾向。 作為芳香族環基，可列舉芳香族烴環基、雜芳香環基。又，芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，進而較佳為10以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差或膜減少，解像性提高之傾向。 作為芳香族環基中之芳香族環之具體例，可列舉：苯環、萘環、蒽環、菲環、茀環等。該等中，就顯影性之觀點而言，較佳為茀環。 作為環狀烴基可具有之取代基，可列舉：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、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基等。該等中，就合成之簡易性之觀點而言，較佳為未經取代。 該等中，就保存穩定性及電特性之觀點而言，Rβ 較佳為二價脂肪族環基，更佳為二價金剛烷環基。 另一方面，就塗膜之低吸濕性及圖案化特性之觀點而言，Rβ 較佳為二價芳香族環基，更佳為二價茀環基。 如上所述，式(b-I-II-2)中之苯環可進一步經任意取代基取代。作為該取代基，例如可列舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基等。取代基之個數亦無特別限定，可為1個，亦可為2個以上。 又，2個苯環可經由取代基而連結。作為該情形時之取代基，可列舉：-O-、-S-、-NH-、-CH2 -等二價基。 該等中，就圖案化特性之觀點而言，較佳為未經取代。又，就使膜減少等不易產生之觀點而言，較佳為甲基取代。 以下列舉上述式(b-I-II-2)所表示之部分結構之具體例。再者，例中之﹡表示鍵結鍵。 [化34]
Figure 02_image067
[化35]
Figure 02_image069
[化36]
Figure 02_image071
[化37]
Figure 02_image073
另一方面，上述式(b-I-II)所表示之部分結構就塗膜殘膜率與圖案化特性之觀點而言，較佳為下述式(b-I-II-3)所表示之部分結構。 [化38]
Figure 02_image075
式(b-I-II-3)中，R13 、R14 、R15 、R16 、m及n與上述式(b-I-II)含義相同。RZ 表示氫原子或多元酸殘基。 所謂多元酸殘基意指自多元酸或其酐中去除1個OH基而成之一價基。再者，亦可進而再去除1個OH基，而與式(b-I-II-3)所表示之其他分子中之RZ 共用，即可經由RZ 連結複數個式(b-I-II-3)。 作為多元酸，可列舉選自順丁烯二酸、丁二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、二苯甲酮四羧酸、甲基六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、氯菌酸、甲基四氫鄰苯二甲酸、聯苯四羧酸中之一種或兩種以上。 該等中，就圖案化特性之觀點而言，較佳為順丁烯二酸、丁二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、均苯四甲酸、偏苯三甲酸、聯苯四羧酸，更佳為四氫鄰苯二甲酸、聯苯四羧酸、四氫鄰苯二甲酸、聯苯四羧酸。 (b-I-II)環氧(甲基)丙烯酸酯樹脂1分子中所含之上述式(b-I-II-3)所表示之部分結構可為一種，亦可為兩種以上，例如可混合存在RZ 為氫原子者與RZ 為多元酸殘基者。 又，(b-I-II)環氧(甲基)丙烯酸酯樹脂1分子中所含之上述式(b-I-II)所表示之部分結構之數量並無特別限定，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，進而較佳為10以下。藉由設為上述下限值以上，有容易獲得強固之膜，不易產生表面粗糙，電特性變得良好之傾向，又，藉由設為上述上限值以下，有容易抑制感度變差或膜減少，解像性提高之傾向。 (b-I-II)環氧(甲基)丙烯酸酯樹脂之藉由凝膠滲透層析法(GPC)測得之聚苯乙烯換算之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為2000以上，又，較佳為30000以下，更佳為20000以下，進而較佳為10000以下，進而更佳為7000以下，尤佳為5000以下。藉由設為上述下限值以上，有圖案化特性變得良好之傾向，又，藉由設為上述上限值以下，有容易獲得強固之膜，不易產生表面粗糙之傾向。 (b-I-II)環氧(甲基)丙烯酸酯樹脂之酸值並無特別限定，較佳為10 mgKOH/g以上，更佳為20 mgKOH/g以上，進而較佳為40 mgKOH/g以上，進而更佳為60 mgKOH/g以上，尤佳為80 mgKOH/g以上，最佳為100 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，進而較佳為120 gKOH/g以下。藉由設為上述下限值以上，有變得容易獲得強固之膜之傾向，又，藉由設為上述上限值以下，有顯影溶解性提高，解像性變得良好之傾向。 ＜(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂＞ (b-II)(甲基)丙烯酸系共聚合樹脂含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β。認為藉由具有重複單元α，可確保可靠性，又，認為藉由具有重複單元β，可將表面平滑性良化。 重複單元α只要為側鏈具有乙烯性不飽和鍵者，則無特別限定，例如，可列舉下述通式(I)所表示之化學結構者。 [化39]
Figure 02_image077
上述式(I)中，R1 及R2 分別獨立地表示氫原子或甲基。R3 表示二價連結基。 作為二價連結基，可列舉可具有取代基之伸烷基或可具有取代基之二價芳香族環基。 作為伸烷基，可列舉直鏈狀、支鏈狀或環狀之伸烷基。其碳數較佳為1以上，更佳為2以上，進而較佳為3以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下，進而更佳為8以下，尤佳為5以下。藉由設為上述下限值以上，有反應性提高之傾向，又，藉由設為上述上限值以下，有熱流動性減少之傾向。 作為伸烷基之具體例，可列舉：亞甲基、伸乙基、伸丙基、伸丁基、伸異丁基、伸環己基等。該等中，就反應性之觀點而言，較佳為亞甲基、伸乙基或伸丙基，更佳為伸丙基。 作為二價芳香族環基，可列舉二價芳香族烴環基及二價雜芳香環基。其碳數較佳為4以上，更佳為5以上，進而較佳為6以上，又，較佳為30以下，更佳為20以下，進而較佳為15以下，尤佳為10以下。藉由設為上述下限值以上，有反應性提高之傾向，又，藉由設為上述上限值以下，有熱流動性減少之傾向。 作為芳香族烴環基中之芳香族烴環，可為單環，亦可為縮合環，例如可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、
Figure 105142935-001-2
環、聯三伸苯環、苊環、螢蒽環、茀環等之基。 又，作為雜芳香環基中之雜芳香環基，可為單環，亦可為縮合環，例如可列舉：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、㗁二唑環、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、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、
Figure 105142935-A0304-12-xxxx-6
啉環、喹㗁啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等之基。 又，作為伸烷基及二價芳香族環基可具有之取代基，可列舉鹵素原子、苯基、羥基、羧基等，該等中，就反應性之觀點而言，較佳為羥基。 又，作為上述通式(I)所表示之化學結構，就反應性之觀點而言，較佳為下述通式(I-1)或(I-2)所表示之化學結構，更佳為下述通式(I-1)所表示之化學結構。 [化40]
Figure 02_image079
上述式(I-1)及式(I-2)中，R1 表示氫原子或甲基。 上述通式(I-1)或(I-2)所表示之化學結構可藉由對源自(甲基)丙烯酸之重複單元加成含環氧基之不飽和化合物而形成。 另一方面，作為源自不飽和羧酸之重複單元β，例如可列舉：源自丙烯酸之重複單元、源自甲基丙烯酸之重複單元、源自丁烯酸之重複單元、源自伊康酸之重複單元、源自順丁烯二酸之重複單元、源自反丁烯二酸之重複單元等，該等中，就熱流動性之觀點而言，較佳為源自丙烯酸之重複單元或源自甲基丙烯酸之重複單元，更佳為下述通式(II)所表示之化學結構者。 [化41]
Figure 02_image081
上述式(II)中，R3 分別獨立地表示氫原子或甲基。 又，(b-II)(甲基)丙烯酸系共聚合樹脂除了含有上述重複單元α及β以外，亦可進而含有重複單元γ。作為重複單元γ，可列舉源自(甲基)丙烯酸酯等乙烯性不飽和化合物之重複單元，例如，就可靠性或顯影時間之調整之觀點而言，較佳為具有下述式(IIIa)所表示之部分結構之重複單元。 [化42]
Figure 02_image083
式(IIIa)中，R1d ～R4d 分別獨立地表示氫原子、或碳數1～10之烷基，R5d 與R6d 分別獨立地表示氫原子、或碳數1～10之烷基。又，R5d 與R6d 可連結而形成環。R5d 與R6d 連結而形成之環較佳為脂肪族環，可為飽和或不飽和之任一種，較佳為碳數5～6。 R1d ～R4d 中之烷基之碳數通常為1以上，且通常為10以下，較佳為8以下，更佳為5以下。藉由設為上述上限值以下，有成為適當之顯影溶解性之傾向。 該等中，就溶解性之觀點而言，R1d ～R4d 較佳為氫原子。 R5d 及R6d 中之烷基之碳數通常為1以上，又，通常為10以下，較佳為8以下，更佳為5以下。藉由設為上述下限值以上，有表現出適當之溶解性之傾向，又，藉由設為上述上限值以下，有保持親水性之傾向。 該等中，就顯影溶解性之觀點而言，較佳為R5d 及R6d 為氫原子，或R5d 及R6d 連結而形成碳數5～6之脂肪族環。 於上述式(IIIa)中，較佳為具有下述式(IIIb)、(IIIc)、或(IIId)所表示之結構者。藉由導入該等部分結構，有可增加耐熱性或強度之傾向。 [化43]
Figure 02_image085
作為具有上述式(IIIa)所表示之部分結構之重複單元，就硬化性之觀點而言，較佳為下述式(III)所表示者。 [化44]
Figure 02_image087
式(III)中，R4 表示氫原子或甲基，R5 表示上述之式(IIIa)所表示之部分結構。 另一方面，作為成為重複單元γ之來源之乙烯性不飽和化合物，除了具有上述之式(IIIa)所表示之部分結構之(甲基)丙烯酸酯以外，例如亦可列舉：苯乙烯之α-烷基、鄰烷基、間烷基、對烷基、硝基、氰基、醯胺、酯衍生物等苯乙烯類；丁二烯、2,3-二甲基丁二烯、異戊二烯、氯丁二烯等二烯類；(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)丙烯酸新戊酯、(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)丙烯酸十二烷基酯、(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
Figure 105142935-A0304-03-0013-01
基酯、(甲基)丙烯酸金剛烷基酯、(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)丙烯酸蒽醌酯、(甲基)丙烯酸向日葵基酯、(甲基)丙烯酸水楊基酯、(甲基)丙烯酸呋喃基酯、(甲基)丙烯酸糠酯、(甲基)丙烯酸四氫呋喃基酯、(甲基)丙烯酸吡喃基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯乙基酯、(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)丙烯酸三苯基甲酯、(甲基)丙烯酸異丙苯酯、(甲基)丙烯酸3-(N,N-二甲胺基)丙酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等(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(甲基)丙烯醯胺類；(甲基)丙烯醯替苯胺、(甲基)丙烯醯腈、丙烯醛、氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯、N-乙烯基吡咯啶酮、乙烯基吡啶、乙酸乙烯酯等乙烯基化合物類；檸康酸二乙酯、順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等不飽和二羧酸二酯類；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-月桂基順丁烯二醯亞胺、N-(4-羥基苯基)順丁烯二醯亞胺等單順丁烯二醯亞胺類；N-(甲基)丙烯醯基鄰苯二甲醯亞胺等之類的自由基聚合性化合物。 該等中，為了賦予更優異之耐熱性及強度，有效的是使用選自苯乙烯、(甲基)丙烯酸苄酯及單順丁烯二醯亞胺中之至少一種作為乙烯性不飽和化合物。 (b-II)(甲基)丙烯酸系共聚合樹脂之製造方法並無特別限定，可藉由使分別與重複單元α～γ相對應之(甲基)丙烯酸酯化合物進行共聚合而獲得。又，亦可藉由首先獲得(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸α-乙基縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯、甲基(甲基)丙烯酸3,4-環氧環己酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚等含環氧基之(甲基)丙烯酸酯與(甲基)丙烯酸、(甲基)丙烯酸酯等乙烯性不飽和化合物之共聚物，並且對該共聚物所含之環氧基加成乙烯性不飽和單羧酸之方法而獲得。 (b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元α之含有比例通常為10莫耳%以上，較佳為12莫耳%以上，更佳為15莫耳%以上，進而較佳為18莫耳%以上，進而更佳為20莫耳%以上，尤佳為22莫耳%以上，最佳為25莫耳%以上，又，較佳為40莫耳%以下，更佳為35莫耳%以下，進而較佳為30莫耳%以下，進而更佳為25莫耳%以下。藉由設為上述下限值以上，有容易確保可靠性之傾向，又，藉由設為上述上限值以下，有容易確保表面平滑性之傾向。 又，(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元β之含有比例較佳為20莫耳%以上，更佳為30莫耳%以上，進而較佳為40莫耳%以上，最佳為50莫耳%以上，又，較佳為70莫耳%以下，更佳為60莫耳%以下，進而較佳為50莫耳%以下。藉由設為上述下限值以上，有容易確保顯影溶解性之傾向，又，藉由設為上述上限值以下，有容易確保可靠性之傾向。 又，(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元γ之含有比例通常為0莫耳%以上，較佳為10莫耳%以上，更佳為20莫耳%以上，進而較佳為30莫耳%以上，又，較佳為60莫耳%以下，更佳為50莫耳%以下，進而較佳為40莫耳%以下。藉由設為上述下限值以上，有密接性變得良好之傾向，又，藉由設為上述上限值以下，有容易確保可靠性之傾向。 (b-II)(甲基)丙烯酸系共聚合樹脂之藉由凝膠滲透層析法(GPC)測得之聚苯乙烯換算之重量平均分子量(Mw)通常為3000以上，較佳為5000以上，更佳為10000以上，進而較佳為15000以上，且通常為50000以下，較佳為30000以下，更佳為20000以下。藉由設為上述下限值以上，有可靠性變得良好之傾向，又，藉由設為上述上限值以下，有顯影溶解性變得良好之傾向。 (b-II)(甲基)丙烯酸系共聚合樹脂之酸值並無特別限定，較佳為100 mg・KOH/g以上，更佳為130 mg・KOH/g以上，進而較佳為160 mg・KOH/g以上，尤佳為180 mg・KOH/g以上，又，較佳為400 mg・KOH/g以下，更佳為300 mg・KOH/g以下，進而較佳為200 mg・KOH/g以下。藉由設為上述下限值以上，有變得容易確保顯影溶解性之傾向，又，藉由設為上述上限值以下，有變得容易確保可靠性之傾向。 於本發明之感光性著色組合物中，可含有一種含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(b-II)(甲基)丙烯酸系共聚合樹脂，又，亦可含有兩種以上。於含有兩種以上之情形時，就容易獲得本發明之效果之觀點而言，較佳為於至少一種以上之樹脂中該重複單元α之含有比例為上述範圍內。 又，另一方面，於其他態樣之感光性著色組合物中，於含有兩種以上之含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(b-II)(甲基)丙烯酸系共聚合樹脂之情形時，亦可以其全部種類之(b-II)(甲基)丙烯酸系共聚合樹脂之全部重複單元為基準，而使其中所含之重複單元α之含有比例成為上述範圍內。同樣地，可將重複單元β之含有比例設為以全部種類之(b-II)(甲基)丙烯酸系共聚合樹脂之全部重複單元為基準者。於含有重複單元γ之情形時，亦同樣地可將其含有比例設為以全部種類之(b-II)(甲基)丙烯酸系共聚合樹脂之全部重複單元為基準者。 ＜其他鹼可溶性樹脂＞ 本發明所使用之(b)鹼可溶性樹脂除了含有上述(b-I)環氧(甲基)丙烯酸酯樹脂及上述(b-II)(甲基)丙烯酸系共聚合樹脂以外，亦可含有其他鹼可溶性樹脂。 其他鹼可溶性樹脂並無限制，自感光性著色組合物通常所使用之樹脂中選擇即可。例如可列舉日本專利特開2007-271727號公報、日本專利特開2007-316620號公報、日本專利特開2007-334290號公報等所記載之黏合劑樹脂等。又，就與顏料或分散劑等之相容性之觀點而言，較佳為使用丙烯酸系樹脂，更佳可使用日本專利特開2014-137466號公報所記載者。 ＜(c)光聚合起始劑＞ (c)光聚合起始劑係具有直接吸收光，引起分解反應或奪氫反應，產生聚合活性自由基之功能之成分。視需要亦可添加聚合促進劑(鏈轉移劑)、增感色素等加成劑而使用。 作為光聚合起始劑，例如可列舉：日本專利特開昭59-152396號公報、日本專利特開昭61-151197號公報所記載之含有二茂鈦化合物之茂金屬化合物；日本專利特開2000-56118號公報所記載之六芳基聯咪唑衍生物；日本專利特開平10-39503號公報所記載之鹵甲基化㗁二唑衍生物、鹵甲基均三𠯤衍生物、N-苯基甘胺酸等N-芳基-α-胺基酸類、N-芳基-α-胺基酸鹽類、N-芳基-α-胺基酸酯類等自由基活性劑、α-胺基烷基苯酮衍生物；日本專利特開2000-80068號公報、日本專利特開2006-36750號公報等所記載之肟酯衍生物等。 具體而言，例如，作為二茂鈦衍生物類，可列舉：二(環戊二烯基)二氯化鈦、二(環戊二烯基)雙苯基鈦、二(環戊二烯基)雙(2,3,4,5,6-五氟苯-1-基)鈦、二(環戊二烯基)雙(2,3,5,6-四氟苯-1-基)鈦、二(環戊二烯基)雙(2,4,6-三氟苯-1-基)鈦、二(環戊二烯基)二(2,6-二氟苯-1-基)鈦、二(環戊二烯基)二(2,4-二氟苯-1-基)鈦、二(甲基環戊二烯基)雙(2,3,4,5,6-五氟苯-1-基)鈦、二(甲基環戊二烯基)雙(2,6-二氟苯-1-基)鈦、二(環戊二烯基)[2,6-二氟-3-(吡咯-1-基)-苯-1-基]鈦等。 又，作為聯咪唑衍生物類，可列舉：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。 又，作為鹵甲基化㗁二唑衍生物類，可列舉：2-三氯甲基-5-(2'-苯并呋喃基)-1,3,4-㗁二唑、2-三氯甲基-5-[β-(2'-苯并呋喃基)乙烯基]-1,3,4-㗁二唑、2-三氯甲基-5-[β-(2'-(6"-苯并呋喃基)乙烯基)]-1,3,4-㗁二唑、2-三氯甲基-5-呋喃基-1,3,4-㗁二唑等。 又，作為鹵甲基均三𠯤衍生物類，可列舉：2-(4-甲氧基苯基)-4,6-雙(三氯甲基)均三𠯤、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)均三𠯤、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)均三𠯤、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)均三𠯤等。 又，作為α-胺基烷基苯酮衍生物類，可列舉：2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-𠰌啉基苯基)-丁酮-1、2-苄基-2-二甲胺基-1-(4-𠰌啉基苯基)丁烷-1-酮、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、4-二乙胺基苯乙酮、4-二甲胺基苯丙酮、1,4-二甲胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙胺基苯亞甲基)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。 作為光聚合起始劑，尤其是就感度或製版性之方面而言，有效的是肟酯系化合物，於使用含有酚性羥基之鹼可溶性樹脂之情形等時，就感度之方面而言變得不利，因此尤其是此種感度優異之肟酯系化合物較為有用。由於肟酯系化合物於其結構中兼具吸收紫外線之結構、傳遞光能之結構及產生自由基之結構，因此少量即感度較高，且對熱反應而言較為穩定，可以少量獲得高感度之感光性著色組合物。 作為肟酯系化合物，例如可列舉下述通式(IV)所表示之化合物。 [化45]
Figure 02_image089
上述式(IV)中，R21a 表示氫原子、可具有取代基之烷基、或可具有取代基之芳香族環基。 R21b 表示包含芳香環或雜芳香環之任意取代基。 R22a 表示可具有取代基之烷醯基、或可具有取代基之芳醯基。 R21a 中之烷基之碳數並無特別限定，就於溶媒中之溶解性或感度之觀點而言，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。作為烷基之具體例，可列舉：甲基、乙基、丙基、環戊基乙基、丙基等。 作為烷基可具有之取代基，可列舉：芳香族環基、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-乙醯氧基胺基等，就合成容易性之觀點而言，較佳為未經取代。 作為R21a 中之芳香族環基，可列舉芳香族烴環基及雜芳香環基。芳香族環基之碳數並無特別限定，就於感光性著色組合物中之溶解性之觀點而言，較佳為5以上。又，就顯影性之觀點而言，較佳為30以下，更佳為20以下，進而較佳為12以下。 作為芳香族環基之具體例，可列舉：苯基、萘基、吡啶基、呋喃基等，該等中，就顯影性之觀點而言，較佳為苯基或萘基，更佳為苯基。 作為芳香族環基可具有之取代基，可列舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基等，就顯影性之觀點而言，較佳為羥基、羧基，更佳為羧基。 該等中，就顯影性之觀點而言，R21a 較佳為可具有取代基之烷基，更佳為未經取代之烷基，進而較佳為甲基。 又，作為R21b ，較佳可列舉可經取代之咔唑基、可經取代之9-氧硫𠮿
Figure 105142935-A0304-12-0019-3
基或可經取代之二苯硫醚基。該等中，就抑制N-甲基吡咯啶酮(NMP)溶出之觀點而言，較佳為可經取代之二苯硫醚基。 又，R22a 中之烷醯基之碳數並無特別限定，就於溶媒中之溶解性或感度之觀點而言，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，進而較佳為5以下。作為烷醯基之具體例，可列舉：乙醯基、羥乙基、丙醯基、丁醯基等。 作為烷醯基可具有之取代基，可列舉：芳香族環基、羥基、羧基、鹵素原子、胺基、醯胺基等，就合成容易性之觀點而言，較佳為未經取代。 又，R22a 中之芳醯基之碳數並無特別限定，就於溶媒中之溶解性或感度之觀點而言，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。作為芳醯基之具體例，可列舉：苯甲醯基、萘甲醯基等。 作為芳醯基可具有之取代基，可列舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基等，就合成容易性之觀點而言，較佳為未經取代。 該等中，就感度之觀點而言，R22a 較佳為可具有取代基之烷醯基，更佳為未經取代之烷醯基，進而較佳為乙醯基。 上述通式(IV)所表示之化合物中，就抑制NMP溶出之觀點而言，較佳為下述通式(V)所表示之化合物。 [化46]
Figure 02_image091
於上述通式(V)中，R23 表示可具有取代基之烷基、或可具有取代基之芳香族環基。 R24 表示可具有取代基之烷基、或可具有取代基之芳香族環基。 R25 表示羥基、羧基或下述通式(V-1)所表示之基，h表示0～5之整數。 式(V)中所示之苯環可進而具有取代基。 [化47]
Figure 02_image093
式(V-1)中，R25a 表示-O-、-S-、-OCO-或-COO-。 R25b 表示可具有取代基之伸烷基。 R25b 之伸烷基部分可被-O-、-S-、-COO-或-OCO-中斷1～5次。R25 之伸烷基部分可具有分支側鏈，亦可為伸環己基。 R25c 表示羥基或羧基。 R23 中之烷基之碳數並無特別限定，就於感光性著色組合物中之溶解性之觀點而言，較佳為1以上。又，就顯影性之觀點而言，較佳為20以下，更佳為10以下，進而較佳為8以下，進而更佳為5以下，尤佳為3以下。 作為烷基之具體例，可列舉：甲基、己基、環戊基甲基等，該等中，就顯影性之觀點而言，甲基或己基，更佳為甲基。 作為烷基可具有之取代基，可列舉：芳香族環基、羥基、羧基、鹵素原子、胺基、醯胺基等，就鹼性顯影性之觀點而言，較佳為羥基、羧基，更佳為羧基。又，就合成容易性之觀點而言，較佳為未經取代。 作為R23 中之芳香族環基，可列舉芳香族烴環基及雜芳香環基。芳香族環基之碳數並無特別限定，就於感光性著色組合物中之溶解性之觀點而言，較佳為5以上。又，就顯影性之觀點而言，較佳為30以下，更佳為20以下，進而較佳為12以下。 作為芳香族環基之具體例，可列舉：苯基、萘基、吡啶基、呋喃基等，該等中，就顯影性之觀點而言，較佳為苯基或萘基，更佳為苯基。 作為芳香族環基可具有之取代基，可列舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基等，就顯影性之觀點而言，較佳為羥基、羧基，更佳為羧基。 該等中，就顯影性之觀點而言，R23 較佳為可具有取代基之烷基，更佳為未經取代之烷基，進而較佳為甲基。 R24 中之烷基之碳數並無特別限定，就感度之觀點而言，較佳為1以上。又，就感度之觀點而言，較佳為20以下，更佳為10以下，進而較佳為5以下，尤佳為3以下。 作為烷基之具體例，可列舉：甲基、乙基、丙基等，該等中，就感度之觀點而言，較佳為甲基或乙基，更佳為甲基。 作為烷基可具有之取代基，可列舉：鹵素原子、羥基、羧基、胺基、醯胺基等，就鹼性顯影性之觀點而言，較佳為羥基、羧基，更佳為羧基，另一方面，就合成容易性之觀點而言，較佳為未經取代。 作為R24 中之芳香族環基，可列舉芳香族烴環基及雜芳香環基。其碳數較佳為30以下，更佳為12以下，且通常為4以上，較佳為6以上。藉由設為上述上限值以下，有成為高感度之傾向，藉由設為上述下限值以上，有成為低昇華性之傾向。 芳香族烴環基意指具有1個自由原子價之芳香族烴環。芳香族烴環基之芳香族烴環可為單環，亦可為縮合環，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、
Figure 105142935-001-2
環、聯三伸苯環、苊環、螢蒽環、茀環等。 又，雜芳香環基意指具有1個自由原子價之雜芳香環。雜芳香環基之雜芳香環可為單環，亦可為縮合環，例如可列舉：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、㗁二唑環、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、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、
Figure 105142935-A0304-12-xxxx-6
啉環、喹㗁啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等。 作為芳香族環基可具有之取代基，可列舉：烷基、鹵素原子、羥基、羧基等。 該等中，就感度之觀點而言，R24 較佳為可具有取代基之烷基，更佳為未經取代之烷基，進而較佳為甲基。 另一方面，就製版性之觀點而言，R24 較佳為可具有取代基之芳香族環基，更佳為可具有取代基之芳香族烴基，進而較佳為未經取代之芳香族烴基，尤佳為苯基。 R25 為羥基、羧基或上述通式(V-1)所表示之基，該等中，就感度及顯影性之觀點而言，較佳為上述通式(V-1)所表示之基。 於上述通式(V-1)中，如上文所述，R25a 表示-O-、-S-、-OCO-或-COO-，該等中，就感度及顯影性之觀點而言，較佳為-O-或-OCO-，更佳為-O-。 如上文所述，R25b 表示可具有取代基之伸烷基。 R25b 中之伸烷基之碳數並無特別限定，就於感光性著色組合物中之溶解性之觀點而言，較佳為1以上，更佳為2以上，又，較佳為20以下，更佳為10以下，進而較佳為5以下，尤佳為3以下。 伸烷基可為直鏈，亦可進行分支，亦可為含有脂肪族環者。該等中，就於感光性著色組合物中之溶解性之觀點而言，較佳為直鏈。 作為伸烷基之具體例，可列舉：亞甲基、伸乙基、伸丙基等，該等中，就於感光性著色組合物中之溶解性之觀點而言，更佳為亞甲基。 如上文所述，R25c 為羥基或羧基。就可靠性(液晶污染性)之觀點而言，R25c 較佳為羥基。 於上述通式(V)中，h表示0～5之整數。尤其是就顯影性之觀點而言，h較佳為1以上，又，較佳為4以下，更佳為3以下，進而較佳為2以下，最佳為1。 另一方面，就合成容易性之觀點而言，h較佳為0。 作為上述通式(IV)或(V)所表示之肟酯系化合物之具體例，可列舉以下者。 [化48]
Figure 02_image095
上述通式(V)所表示之肟酯系化合物之製造方法並無特別限定，例如可藉由日本專利特開2000-080068號公報所記載之方法而製造。 又，作為肟酯系化合物，亦可使用上述通式(IV)或(V)以外之化合物，例如亦可使用日本專利特開2000-80068號公報、日本專利特開2006-36750號公報、國際公開第2008/075564號、國際公開第2009/131189號、日本專利特表2014-500852號公報等所記載之肟酯衍生物等。 光聚合起始劑可單獨使用一種，亦可組合兩種以上而使用。 可視需要以提高感應感度為目的，而於光聚合起始劑中調配與圖像曝光光源之波長相對應之增感色素、聚合促進劑。作為增感色素，可列舉：日本專利特開平4-221958號公報、日本專利特開平4-219756號公報所記載之𠮿
Figure 105142935-A0304-12-0019-3
色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報所記載之具有雜環之香豆素色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報所記載之3-酮香豆素化合物；日本專利特開平6-19240號公報所記載之吡咯亞甲基色素；以及日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報所記載之具有二烷基胺基苯骨架之色素等。 該等增感色素中較佳者為含胺基之增感色素，進而較佳者為於同一分子內具有胺基及苯基之化合物。尤佳者為例如：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二苯甲酮系化合物；2-(對二甲胺基苯基)苯并㗁唑、2-(對二乙胺基苯基)苯并㗁唑、2-(對二甲胺基苯基)苯并[4,5]苯并㗁唑、2-(對二甲胺基苯基)苯并[6,7]苯并㗁唑、2,5-雙(對二乙胺基苯基)-1,3,4-㗁唑、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)嘧啶等含對二烷基胺基苯基之化合物等。其中，最佳者為4,4'-二烷基胺基二苯甲酮。 又，增感色素亦為可單獨使用一種，亦可將兩種以上併用。 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2-二甲胺基乙酯等芳香族胺；正丁胺、N-甲基二乙醇胺等脂肪族胺；下文所述之巰基化合物等。聚合促進劑可單獨使用一種，亦可組合兩種以上而使用。 ＜(d)乙烯性不飽和化合物＞ 本發明之感光性著色組合物含有(d)乙烯性不飽和化合物。藉由含有(d)乙烯性不飽和化合物而感度提高。 本發明所使用之乙烯性不飽和化合物係分子內具有至少1個乙烯性不飽和基之化合物。具體而言，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸烷基酯、丙烯腈、苯乙烯、及具有1個乙烯性不飽和鍵之羧酸與多元或一元醇之單酯等。 於本發明中，尤其理想為使用1分子中具有二個以上乙烯性不飽和基之多官能乙烯性單體。多官能乙烯性單體所具有之乙烯性不飽和基之個數並無特別限定，通常為2以上，較佳為4以上，更佳為5以上，又，較佳為8以下，更佳為7以下。藉由設為上述下限值以上，有成為高感度之傾向，藉由設為上述上限值以下，有於溶媒中之溶解性提高之傾向。 作為多官能乙烯性單體之例，例如可列舉：脂肪族聚羥基化合物與不飽和羧酸之酯；芳香族聚羥基化合物與不飽和羧酸之酯；藉由脂肪族聚羥基化合物、芳香族聚羥基化合物等多元羥基化合物、不飽和羧酸及多元羧酸之酯化反應獲得之酯等。 作為上述脂肪族聚羥基化合物與不飽和羧酸之酯，可列舉：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、季戊四醇二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、甘油丙烯酸酯等脂肪族聚羥基化合物之丙烯酸酯、將該等例示化合物之丙烯酸酯換為甲基丙烯酸酯之甲基丙烯酸酯、同樣地替代為伊康酸酯而成之伊康酸酯、替代為丁烯酸酯而成之丁烯酸酯或替代為順丁烯二酸酯而成之順丁烯二酸酯等。 作為芳香族聚羥基化合物與不飽和羧酸之酯，可列舉：對苯二酚二丙烯酸酯、對苯二酚二甲基丙烯酸酯、間苯二酚二丙烯酸酯、間苯二酚二甲基丙烯酸酯、鄰苯三酚三丙烯酸酯等芳香族聚羥基化合物之丙烯酸酯及甲基丙烯酸酯等。 作為藉由多元羧酸及不飽和羧酸與多元羥基化合物之酯化反應而獲得之酯，未必為單一物質，若列舉具有代表性之具體例，則可列舉：丙烯酸、鄰苯二甲酸、及乙二醇之縮合物；丙烯酸、順丁烯二酸、及二乙二醇之縮合物；甲基丙烯酸、對苯二甲酸及季戊四醇之縮合物；丙烯酸、己二酸、丁二醇及甘油之縮合物等。 除此以外，作為本發明所使用之多官能乙烯性單體之例，有用的是：如使多異氰酸酯化合物與含羥基之(甲基)丙烯酸酯或使多異氰酸酯化合物與多元醇及含羥基之(甲基)丙烯酸酯進行反應而獲得之(甲基)丙烯酸胺基甲酸酯類；如多元環氧化合物與羥基(甲基)丙烯酸酯或(甲基)丙烯酸之加成反應物之環氧丙烯酸酯類；伸乙基雙丙烯醯胺等丙烯醯胺類；鄰苯二甲酸二烯丙酯等烯丙酯類；鄰苯二甲酸二乙烯酯等含乙烯基之化合物等。 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(日本化藥公司製造)、U-2PPA、U-6LPA、U-10PA、U-33H、UA-53H、UA-32P、UA-1100H(新中村化學工業公司製造)、UA-306H、UA-510H、UF-8001G(協榮社化學公司製造)、UV-1700B、UV-7600B、UV-7605B、UV-7630B、UV7640B(日本合成化學公司製造)等。 該等中，就硬化性之觀點而言，作為(d)乙烯性不飽和化合物，較佳為使用(甲基)丙烯酸烷基酯，更佳為使用二季戊四醇六丙烯酸酯。 該等可單獨使用一種，亦可將兩種以上併用。 ＜(e)溶劑＞ 本發明之感光性著色組合物含有(e)溶劑。藉由含有(e)溶劑，可使顏料分散於溶劑中，又，塗佈變得容易。 本發明之感光性著色組合物通常以(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(f)分散劑、及視需要而使用之其他各種材料溶解或分散於溶劑中之狀態而使用。溶劑中，就分散性或塗佈性之觀點而言，較佳為有機溶劑。 有機溶劑中，就塗佈性之觀點而言，較佳為選擇沸點為100～300℃之範圍者，更佳為選擇沸點為120～280℃之範圍者。再者，此處所謂之沸點意指於壓力1013.25 hPa下之沸點。 作為此種有機溶劑，例如可列舉如下者。 乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丁醚、丙二醇第三丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丁醚、甲氧基甲基戊醇、二丙二醇單乙醚、二丙二醇單甲醚、3-甲基-3-甲氧基丁醇、三乙二醇單甲醚、三乙二醇單乙醚、三丙二醇甲醚之類的二醇單烷基醚類； 乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、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基醚類； 乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、甲氧基乙酸丁酯、3-甲氧基乙酸丁酯、甲氧基戊基乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、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、三乙二醇單乙醚乙酸酯、3-甲基-3-甲氧基乙酸丁酯之類的二醇烷基醚乙酸酯類； 乙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己醇二乙酸酯等二醇二乙酸酯類； 乙酸環己酯等乙酸烷基酯類； 戊基醚、二乙醚、二丙醚、二異丙醚、二丁醚、二戊醚、乙基異丁基醚、二己醚之類的醚類； 丙酮、甲基乙基酮、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； 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、苄醇之類的一元或多元醇類； 正戊烷、正辛烷、二異丁烯、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、聯環己烷之類的脂環式烴類； 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、硬脂酸丁酯、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、氯戊烷之類的鹵化烴類； 甲氧基甲基戊酮之類的醚酮類； 乙腈、苯甲腈之類的腈類等。 作為相當於上述之市售之有機溶劑，可列舉：礦油精、Varsol#2、Apco#18溶劑、Apco稀釋劑、Socal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、甲賽路蘇(「賽路蘇」為註冊商標；以下相同)、乙賽路蘇、乙賽路蘇乙酸酯、甲賽路蘇乙酸酯、二乙二醇二甲醚(均為商品名)等。 該等有機溶劑可單獨使用，亦可將兩種以上併用。 於藉由光微影法形成著色間隔件之情形時，較佳為選擇沸點為100～200℃(壓力1013.25 hPa條件下；以下關於沸點全部相同)之範圍者作為有機溶劑。更佳為具有120～170℃之沸點者。 上述有機溶劑中，就塗佈性、表面張力等之平衡良好，組合物中之構成成分之溶解度相對較高之方面而言，較佳為二醇烷基醚乙酸酯類。 又，二醇烷基醚乙酸酯類可單獨使用，亦可併用其他有機溶劑。作為所併用之有機溶劑，尤佳者為二醇單烷基醚類。其中，尤其是就組合物中之構成成分之溶解性而言，較佳為丙二醇單甲醚。再者，二醇單烷基醚類之極性較高，若添加量過多，則有顏料容易凝聚，其後獲得之著色樹脂組合物之黏度提高等保存穩定性降低之傾向，因此溶劑中之二醇單烷基醚類之比例較佳為5質量%～30質量%，更佳為5質量%～20質量%。 又，亦較佳為併用具有150℃以上之沸點之有機溶劑(以下有時稱為「高沸點溶劑」)。藉由併用此種高沸點溶劑，感光性著色組合物變得不易乾燥，具有防止組合物中之顏料之均勻之分散狀態因急遽之乾燥而受到破壞之效果。即，具有防止產生例如因狹縫噴嘴尖端之色料等之析出、固化引起之雜質缺陷的效果。就此種效果較高之方面而言，上述各種溶劑中，尤佳為二乙二醇單正丁醚、二乙二醇單正丁醚乙酸酯、及二乙二醇單乙醚乙酸酯。 有機溶劑中之高沸點溶劑之含有比例較佳為3質量%～50質量%，更佳為5質量%～40質量%，尤佳為5質量%～30質量%。藉由設為上述下限值以上，有可抑制例如於狹縫噴嘴尖端色料等析出、固化而引起雜質缺陷之情況之傾向，又，藉由設為上述上限值以下，有可抑制組合物之乾燥速度變慢，抑制減壓乾燥製程之觸控不良或預烘烤之氣孔痕跡等問題之傾向。 再者，沸點150℃以上之高沸點溶劑可為二醇烷基醚乙酸酯類，又，亦可為二醇烷基醚類，於該情形時，可不另外含有沸點150℃以上之高沸點溶劑。 作為較佳之高沸點溶劑，例如可列舉上文所述之各種溶劑中之二乙二醇單正丁醚乙酸酯、二乙二醇單乙醚乙酸酯、二丙二醇甲醚乙酸酯、1,3-丁二醇二乙酸酯、1,6-己醇二乙酸酯、甘油三乙酸酯等。 ＜(f)分散劑＞ 於本發明之感光性著色組合物中，由於對於確保品質之穩定性而言重要的是使(a)著色劑微細地分散，且使其分散狀態穩定，因此含有(f)分散劑。 作為(f)分散劑，較佳為具有官能基之高分子分散劑，進而就分散穩定性之方面而言，較佳為具有如下基等官能基之高分子分散劑：羧基；磷酸基；磺酸基；或該等之鹽之基；一級、二級或三級胺基；四級銨鹽基；源自吡啶、嘧啶、吡𠯤等含氮雜環之基。其中，尤其就於分散顏料時可以少量之分散劑進行分散之觀點而言，尤佳為具有如下基等鹼性官能基之高分子分散劑：一級、二級或三級胺基；四級銨鹽基；源自吡啶、嘧啶、吡𠯤等含氮雜環之基。 又，作為高分子分散劑，例如可列舉：胺基甲酸酯系分散劑、丙烯酸系分散劑、聚伸乙基亞胺系分散劑、聚烯丙基胺系分散劑、包含具有胺基之單體與巨單體之分散劑、聚氧乙烯烷基醚系分散劑、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、山梨糖醇酐脂肪族酯系分散劑、脂肪族改性聚酯系分散劑等。 作為此種分散劑之具體例，可列舉商品名為如下者：EFKA(註冊商標；BASF公司製造)、DISPERBYK(註冊商標；BYK-Chemie公司製造)、Disparlon(註冊商標；楠本化成公司製造)、SOLSPERSE(註冊商標；Lubrizol公司製造)、KP(信越化學工業公司製造)、Polyflow(共榮社化學公司製造)、Ajisper(註冊商標；Ajinomoto公司製造)等。 該等高分子分散劑可單獨使用一種，或者亦可將兩種以上併用。 高分子分散劑之重量平均分子量(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。 該等中，就顏料之分散性之觀點而言，(f)分散劑較佳為含有具有官能基之胺基甲酸酯系高分子分散劑及/或丙烯酸系高分子分散劑，尤佳為含有丙烯酸系高分子分散劑。 又，就分散性、保存性之方面而言，較佳為具有鹼性官能基且具有聚酯鍵及/或聚醚鍵之高分子分散劑。 作為胺基甲酸酯系及丙烯酸系高分子分散劑，例如可列舉：DISPERBYK160～166、182系列(均為胺基甲酸酯系)、DISPERBYK2000、2001、LPN21116等(均為丙烯酸系)(以上均為BYK-Chemie公司製造)。 作為胺基甲酸酯系高分子分散劑，若具體例示較佳之化學結構，則例如可列舉藉由使多異氰酸酯化合物、分子內具有1個或2個羥基之數量平均分子量300～10,000之化合物、及同一分子內具有活性氫與三級胺基之化合物進行反應而獲得之重量平均分子量1,000～200,000之分散樹脂等。藉由利用苄基氯等四級化劑對該等進行處理，可使全部或一部分三級胺基成為四級銨鹽基。 作為上述多異氰酸酯化合物之例，可列舉：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芳香族二異氰酸酯；六亞甲基二異氰酸酯、離胺酸甲酯二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、二聚酸二異氰酸酯等脂肪族二異氰酸酯；異佛酮二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、ω,ω'-二異氰酸基-二甲基環己烷等脂環族二異氰酸酯；苯二甲基二異氰酸酯、α,α,α',α'-四甲基苯二甲基二異氰酸酯等具有芳香環之脂肪族二異氰酸酯；離胺酸酯三異氰酸酯、1,6,11-十一烷三異氰酸酯、1,8-二異氰酸基-4-異氰酸基甲基辛烷、1,3,6-六亞甲基三異氰酸酯、聯環庚烷三異氰酸酯、三(異氰酸基苯基)甲烷、三(異氰酸基苯基)硫代磷酸酯等三異氰酸酯；以及該等之三聚物、水加成物、及該等之多元醇加成物等。作為多異氰酸酯，較佳為有機二異氰酸酯之三聚物，最佳為甲苯二異氰酸酯之三聚物與異佛酮二異氰酸酯之三聚物。該等可單獨使用一種，亦可將兩種以上併用。 作為異氰酸酯之三聚物之製造方法，可列舉如下方法：使用適當之三聚化觸媒、例如三級胺類、膦類、烷氧化物類、金屬氧化物、羧酸鹽類等，使上述多異氰酸酯類進行異氰酸酯基之部分三聚化，藉由添加觸媒毒而停止三聚化後，藉由溶劑萃取、薄膜蒸餾而去除未反應之多異氰酸酯，從而獲得目標之含異氰脲酸酯基之多異氰酸酯。 作為同一分子內具有1個或2個羥基之數量平均分子量300～10,000之化合物，可列舉：聚醚二醇(polyether glycol)、聚酯二醇(polyester glycol)、聚碳酸酯二醇、聚烯烴二醇等、以及該等化合物之單個末端羥基經碳數1～25之烷基進行烷氧基化而成者及該等兩種以上之混合物。 作為聚醚二醇(polyether glycol)，可列舉：聚醚二醇(polyether diol)、聚醚酯二醇(polyetherester diol)、及該等兩種以上之混合物。作為聚醚二醇(polyether diol)，可列舉使環氧烷進行均聚合或共聚合而獲得者，例如可列舉：聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚氧四亞甲基二醇、聚氧六亞甲基二醇、聚氧八亞甲基二醇及該等之兩種以上之混合物。 作為聚醚酯二醇(polyetherester diol)，可列舉藉由使含醚基之二醇或其與其他二醇之混合物與二羧酸或該等之酐進行反應、或者使聚酯二醇(polyester glycol)與環氧烷進行反應而獲得者，例如可列舉聚(聚氧四亞甲基)己二酸酯等。作為聚醚二醇(polyether glycol)，最佳為聚乙二醇、聚丙二醇、聚氧四亞甲基二醇或該等之化合物之單個末端羥基經碳數1～25之烷基進行烷氧基化而成之化合物。 作為聚酯二醇(polyester glycol)，可列舉：使二羧酸(丁二酸、戊二酸、己二酸、癸二酸、反丁烯二酸、順丁烯二酸、鄰苯二甲酸等)或該等之酐與二醇(glycol)(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、1,8-八亞甲基二醇、2-甲基-1,8-八亞甲基二醇、1,9-壬二醇等脂肪族二醇；雙羥基甲基環己烷等脂環族二醇；苯二甲醇、雙羥基乙氧基苯等芳香族二醇；N-甲基二乙醇胺等N-烷基二烷醇胺等)進行縮聚而獲得者，例如聚己二酸乙二酯、聚己二酸丁二酯、聚六亞甲基己二酸酯、聚己二酸乙二酯/己二酸丙二酯等；或者可列舉使用上述二醇(diol)類或碳數1～25之一元醇作為起始劑而獲得之聚內酯二醇或聚內酯單醇，例如聚己內酯二醇、聚甲基戊內酯及該等之兩種以上之混合物。作為聚酯二醇(polyester glycol)，最佳為聚己內酯二醇或以碳數1～25之醇作為起始劑之聚己內酯。 作為聚碳酸酯二醇，可列舉聚碳酸(1,6-己二酯)、聚碳酸(3-甲基-1,5-戊二酯)等，作為聚烯烴二醇，可列舉聚丁二烯二醇、氫化型聚丁二烯二醇、氫化型聚異戊二醇等。 該等可單獨使用一種，亦可將兩種以上併用。 同一分子內具有1個或2個羥基之化合物之數量平均分子量通常為300～10,000，較佳為500～6,000，進而較佳為1,000～4,000。 對本發明所使用之同一分子內具有活性氫與三級胺基之化合物進行說明。 作為活性氫，即直接鍵結於氧原子、氮原子或硫原子上之氫原子，可列舉羥基、胺基、硫醇基等官能基中之氫原子，其中，較佳為胺基、尤其是一級胺基之氫原子。 三級胺基並無特別限定，例如可列舉具有碳數1～4之烷基之胺基、或雜環結構，更具體而言，可列舉咪唑環或三唑環等。 若例示此種同一分子內具有活性氫與三級胺基之化合物，則可列舉：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。 又，作為三級胺基為含氮雜環結構之情形時之該含氮雜環，可列舉：吡唑環、咪唑環、三唑環、四唑環、吲哚環、咔唑環、吲唑環、苯并咪唑環、苯并三唑環、苯并㗁唑環、苯并噻唑環、苯并噻二唑環等含氮五員雜環；吡啶環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、吖啶環、異喹啉環等含氮六員雜環。該等含氮雜環中，較佳為咪唑環或三唑環。 若具體例示該等具有咪唑環與胺基之化合物，則可列舉：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，若具體例示具有三唑環與胺基之化合物，則可列舉：3-胺基-1,2,4-三唑、5-(2-胺基-5-氯苯基)-3-苯基-1H-1,2,4-三唑、4-胺基-4H-1,2,4-三唑-3,5-二醇、3-胺基-5-苯基-1H-1,3,4-三唑、5-胺基-1,4-二苯基-1,2,3-三唑、3-胺基-1-苄基-1H-2,4-三唑等。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-1,2,4-三唑。 該等可單獨使用一種，亦可將兩種以上併用。 製造胺基甲酸酯系高分子分散劑時之原料之較佳之調配比率相對於多異氰酸酯化合物100質量份，同一分子內具有1個或2個羥基之數量平均分子量300～10,000之化合物為10～200質量份，較佳為20～190質量份，進而較佳為30～180質量份，同一分子內具有活性氫與三級胺基之化合物為0.2～25質量份，較佳為0.3～24質量份。 胺基甲酸酯系高分子分散劑之製造係依照製造聚胺基甲酸酯樹脂之公知之方法而進行。作為製造時之溶媒，通常可使用：丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、異佛酮等酮類；乙酸乙酯、乙酸丁酯、乙酸賽路蘇等酯類；苯、甲苯、二甲苯、己烷等烴類；二丙酮醇、異丙醇、第二丁醇、第三丁醇等一部分醇類；二氯甲烷、氯仿等氯化物；四氫呋喃、二乙醚等醚類；二甲基甲醯胺、N-甲基吡咯啶酮、二甲基亞碸等非質子性極性溶媒等。該等可單獨使用一種，亦可將兩種以上併用。 於上述製造時，通常可使用胺基甲酸酯化反應觸媒。作為該觸媒，例如可列舉：二丁基二月桂酸錫、二辛基二月桂酸錫、二丁基二辛酸錫、辛酸亞錫等錫系觸媒；乙醯丙酮酸鐵、氯化鐵等鐵系觸媒；三乙胺、三乙二胺等三級胺系觸媒等。該等可單獨使用一種，亦可將兩種以上併用。 同一分子內具有活性氫與三級胺基之化合物之導入量以反應後之胺值計，較佳為控制為1～100 mgKOH/g之範圍內。更佳為5～95 mgKOH/g之範圍。胺值係藉由酸中和滴定鹼性胺基，使其與酸值相對於而以KOH之mg數所表示之值。若胺值低於上述範圍，則有分散能力降低之傾向，又，若胺值超出上述範圍，則有顯影性容易降低之傾向。 再者，於以上反應中異氰酸酯基殘存於高分子分散劑中之情形時，若進一步藉由醇或胺基化合物破壞異氰酸酯基，則產物之經時穩定性變高，故而較佳。 胺基甲酸酯系高分子分散劑之重量平均分子量(Mw)通常為1,000～200,000之範圍，較佳為2,000～100,000之範圍，更佳為3,000～50,000之範圍。若該分子量未達1,000，則有分散性及分散穩定性變差之傾向，若超過200,000，則有溶解性降低，分散性變差，同時反應之控制變得困難之傾向。 作為丙烯酸系高分子分散劑，較佳為使用具有官能基(此處所謂之官能基為上文作為高分子分散劑所含之官能基而說明之官能基)之含不飽和基之單體與不具有官能基之含不飽和基單體之無規共聚物、接枝共聚物、嵌段共聚物。該等共聚物可藉由公知之方法而製造。 作為具有官能基之含不飽和基之單體，可列舉如下物質作為具體例：(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、丙烯酸二聚物等具有羧基之不飽和單體；(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之四級化物等具有三級胺基、四級銨鹽基之不飽和單體。該等可單獨使用一種，亦可將兩種以上併用。 作為不具有官能基之含不飽和基之單體，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(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[艸+伯]基酯、(甲基)丙烯酸三環癸基酯、(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-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺等N-取代順丁烯二醯亞胺；丙烯腈、乙酸乙烯酯及聚(甲基)丙烯酸甲酯巨單體、聚苯乙烯巨單體、聚(甲基)丙烯酸2-羥基乙酯巨單體、聚乙二醇巨單體、聚丙二醇巨單體、聚己內酯巨單體等巨單體等。該等可單獨使用一種，亦可將兩種以上併用。 丙烯酸系高分子分散劑尤佳為包含具有官能基之A嵌段與不具有官能基之B嵌段之A-B或B-A-B嵌段共聚物，於該情形時，於A嵌段中除了包含源自上述含有官能基之含不飽和基單體之部分結構以外，亦可包含源自上述不含官能基之含不飽和基單體之部分結構，該等可以無規共聚合或嵌段共聚合之任一態樣含有於該A嵌段中。又，不含官能基之部分結構於A嵌段中之含量通常為80質量%以下，較佳為50質量%以下，進而較佳為30質量%以下。 B嵌段係包含源自上述不含官能基之含不飽和基單體之部分結構者，亦可於1個B嵌段中含有兩種以上源自單體之部分結構，該等可以無規共聚合或嵌段共聚合之任一態樣含有於該B嵌段中。 該A-B或B-A-B嵌段共聚物例如係藉由以下所示之活性聚合法而製備。 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，陰離子活性聚合法之聚合活性種為陰離子，例如以下述流程表示。 [化49]
Figure 02_image097
上述流程中，Ar1 為一價有機基，Ar2 為與Ar1 不同之一價有機基，M為金屬原子，s及t分別為1以上之整數。 自由基活性聚合法之聚合活性種為自由基，例如以下述流程表示。 [化50]
Figure 02_image099
上述流程中，Ar1 為一價有機基，Ar2 為與Ar1 不同之一價有機基，j及k分別為1以上之整數，Ra 為氫原子或一價有機基，Rb 為與Ra 不同之氫原子或一價有機基。 於合成該丙烯酸系高分子分散劑時，可採用日本專利特開平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、沢本光男、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)等所記載之公知之方法。 本發明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，構成該共聚物之A嵌段/B嵌段比較佳為1/99～80/20，尤佳為5/95～60/40(質量比)，藉由設為該範圍內，有可確保分散性與保存穩定性之平衡之傾向。 又，本發明可使用之A-B嵌段共聚物、B-A-B嵌段共聚物1 g中之四級銨鹽基之量通常較佳為0.1～10 mmol，藉由設為該範圍內，有可確保良好之分散性之傾向。 再者，於此種嵌段共聚物中，通常同在含有製造過程中所產生之胺基之情形，其胺值為1～100 mgKOH/g左右，就分散性之觀點而言，較佳為10 mgKOH/g以上，更佳為30 mgKOH/g以上，進而較佳為50 mgKOH/g以上，又，較佳為90 mgKOH/g以下，更佳為80 mgKOH/g以下，進而較佳為75 mgKOH/g以下。 此處，該等嵌段共聚物等分散劑之胺值係以相對於除分散劑試樣中之溶劑以外之固形物成分1 g之鹼量與當量之KOH之質量表示，係藉由如下方法而測定。 精確稱量0.5～1.5 g分散劑試樣置於100 mL之燒杯中，以50 mL之乙酸將其溶解。使用具備pH電極之自動滴定裝置，藉由0.1 mol/L之HClO4 乙酸溶液對該溶液進行中和滴定。以滴定pH曲線之反曲點作為滴定終點，藉由下式求出胺值。 胺值[mgKOH/g]＝(561×V)/(W×S) [其中，W表示分散劑試樣稱取量[g]，V表示滴定終點處之滴定量[mL]，S表示分散劑試樣之固形物成分濃度[質量%]] 又，該嵌段共聚物之胺值亦取決於成為該酸值之根源之酸性基之有無及種類，一般而言較低為宜，通常為10 mgKOH/g以下，其重量平均分子量(Mw)較佳為1000～100,000之範圍。藉由設為上述範圍內，有可確保良好之分散性之傾向。 於具有四級銨鹽基作為官能基之情形時，對高分子分散劑之具體之結構並無特別限定，就分散性之觀點而言，較佳為具有下述式(i)所表示之重複單元(以下有時稱為「重複單元(i)」)。 [化51]
Figure 02_image101
上述式(i)中，R31 ～R33 分別獨立為氫原子、可具有取代基之烷基、可具有取代基之芳基、或可具有取代基之芳烷基，R31 ～R33 中2個以上可互相鍵結而形成環狀結構。R34 為氫原子或甲基。X為二價連結基，Y- 為抗衡陰離子。 上述式(i)之R31 ～R33 中之可具有取代基之烷基之碳數並無特別限定，通常為1以上，又，較佳為10以下，更佳為6以下。作為烷基之具體例，可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，該等中，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、支鏈狀之任一者。又，亦可含有環己基、環己基甲基等環狀結構。 上述式(i)之R31 ～R33 中之可具有取代基之芳基之碳數並無特別限定，通常為6以上，又，較佳為16以下，更佳為12以下。作為芳基之具體例，可列舉：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。 上述式(i)之R31 ～R33 中之可具有取代基之芳烷基之碳數並無特別限定，通常為7以上，又，較佳為16以下，更佳為12以下。作為芳烷基之具體例，可列舉：苯基亞甲基、苯基伸乙基、苯基伸丙基、苯基伸丁基、苯基伸異丙基等，該等中，較佳為苯基亞甲基、苯基伸乙基、苯基伸丙基、或苯基伸丁基，更佳為苯基亞甲基、或苯基伸乙基。 該等中，就分散性之觀點而言，較佳為R31 ～R33 分別獨立為烷基或芳烷基，具體而言，較佳為R31 及R33 分別獨立為甲基或乙基，且R32 為苯基亞甲基或苯基伸乙基，進而較佳為R31 及R33 為甲基，且R32 為苯基亞甲基。 又，於上述高分子分散劑具有三級胺作為官能基之情形時，就分散性之觀點而言，較佳為具有下述式(ii)所表示之重複單元(以下有時稱為「重複單元(ii)」)。 [化52]
Figure 02_image103
上述式(ii)中，R35 及R36 分別獨立為氫原子、可具有取代基之烷基、可具有取代基之芳基、或可具有取代基之芳烷基，R35 及R36 可互相鍵結而形成環狀結構。R37 為氫原子或甲基。Z為二價連結基。 又，作為上述式(ii)之R35 及R36 中之可具有取代基之烷基，可較佳地採用作為上述式(i)之R31 ～R33 而例示者。 同樣地，作為上述式(ii)之R35 及R36 中之可具有取代基之芳基，可較佳地採用作為上述式(i)之R31 ～R33 而例示者。又，作為上述式(ii)之R35 及R36 中之可具有取代基之芳烷基，可較佳地採用作為上述式(i)之R31 ～R33 而例示者。 該等中，較佳為R35 及R36 分別獨立為可具有取代基之烷基，更佳為甲基或乙基。 作為上述式(i)之R31 ～R33 及上述式(ii)之R35 及R36 中之烷基、芳烷基或芳基可具有之取代基，可列舉：鹵素原子、烷氧基、苯甲醯基、羥基等。 於上述式(i)及(ii)中，作為二價連結基X及Z，例如可列舉碳數1～10之伸烷基、碳數6～12之伸芳基、-CONH-R43 -基、-COOR44 -基[其中，R43 及R44 為單鍵、碳數1～10之伸烷基、或碳數2～10之醚基(烷氧基烷基)]等，較佳為-COO-R44 -基。 又，於上述式(i)中，作為抗衡陰離子之Y- ，可列舉：Cl- 、Br- 、I- 、ClO4 - 、BF4 - 、CH3 COO- 、PF6 - 等。 上述式(i)所表示之重複單元之含有比例並無特別限定，就分散性之觀點而言，相對於上述式(i)所表示之重複單元之含有比例與上述式(ii)所表示之重複單元之含有比例之合計，較佳為60莫耳%以下，更佳為50莫耳%以下，進而較佳為40莫耳%以下，尤佳為35莫耳%以下，又，較佳為5莫耳%以上，更佳為10莫耳%以上，進而較佳為20莫耳%以上，尤佳為30莫耳%以上。 又，上述式(i)所表示之重複單元於高分子分散劑之總重複單元中所占之含有比例並無特別限定，就分散性之觀點而言，較佳為1莫耳%以上，更佳為5莫耳%以上，進而較佳為10莫耳%以上，又，較佳為50莫耳%以下，更佳為30莫耳%以下，進而較佳為20莫耳%以下，尤佳為15莫耳%以下。 又，上述式(ii)所表示之重複單元於高分子分散劑之總重複單元中所占之含有比例並無特別限定，就分散性之觀點而言，較佳為5莫耳%以上，更佳為10莫耳%以上，進而較佳為15莫耳%以上，尤佳為20莫耳%以上，又，較佳為60莫耳%以下，更佳為40莫耳%以下，進而較佳為30莫耳%以下，尤佳為25莫耳%以下。 又，高分子分散劑就提高相對於溶媒等黏合劑成分之相容性，提高分散穩定性之觀點而言，較佳為具有下述式(iii)所表示之重複單元(以下有時稱為「重複單元(iii)」)。 [化53]
Figure 02_image105
上述式(iii)中，R40 為伸乙基或伸丙基，R41 為可具有取代基之烷基，R42 為氫原子或甲基。n為1～20之整數。 上述式(iii)之R41 中之可具有取代基之烷基之碳數並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為6以下。作為烷基之具體例，可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，該等中，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、支鏈狀之任一者。又，亦可含有環己基、環己基甲基等環狀結構。 又，上述式(iii)中之n就相對於溶媒等黏合劑成分之相容性與分散性之觀點而言，較佳為1以上，更佳為2以上，又，較佳為10以下，更佳為5以下。 又，上述式(iii)所表示之重複單元於高分子分散劑之總重複單元中所占之含有比例並無特別限定，較佳為1莫耳%以上，更佳為2莫耳%以上，進而較佳為4莫耳%以上，又，較佳為30莫耳%以下，更佳為20莫耳%以下，進而較佳為10莫耳%以下。於為上述範圍內之情形時，有可兼顧相對於溶媒等黏合劑成分之相容性與分散穩定性之傾向。 又，高分子分散劑就提高分散劑相對於溶媒等黏合劑成分之相容性，提高分散穩定性之觀點而言，較佳為具有下述式(iv)所表示之重複單元(以下有時稱為「重複單元(iv)」)。 [化54]
Figure 02_image107
上述式(iv)中，R38 為可具有取代基之烷基、可具有取代基之芳基、或可具有取代基之芳烷基。R39 為氫原子或甲基。 上述式(iv)之R38 中之可具有取代基之烷基之碳數並無特別限定，通常為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。作為烷基之具體例，可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，該等中，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、支鏈狀之任一者。又，亦可含有環己基、環己基甲基等環狀結構。 上述式(iv)之R38 中之可具有取代基之芳基之碳數並無特別限定，通常為6以上，又，較佳為16以下，更佳為12以下，進而較佳為8以下。作為芳基之具體例，可列舉：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。 上述式(iv)之R38 中之可具有取代基之芳烷基之碳數並無特別限定，通常為7以上，又，較佳為16以下，更佳為12以下，進而較佳為10以下。作為芳烷基之具體例，可列舉：苯基亞甲基、苯基伸乙基、苯基伸丙基、苯基伸丁基、苯基伸異丙基等，該等中，較佳為苯基亞甲基、苯基伸乙基、苯基伸丙基、或苯基伸丁基，更佳為苯基亞甲基、或苯基伸乙基。 該等中，就溶劑相容性與分散穩定性之觀點而言，R38 較佳為烷基或芳烷基，更佳為甲基、乙基或苯基亞甲基。 作為R38 中之烷基可具有之取代基，可列舉鹵素原子、烷氧基等。又，作為芳基或芳烷基可具有之取代基，可列舉鏈狀之烷基、鹵素原子、烷氧基等。又，於R38 所表示之鏈狀之烷基中含有直鏈狀及支鏈狀之任一者。 又，上述式(iv)所表示之重複單元於高分子分散劑之總重複單元中所占之含有比例就分散性之觀點而言，較佳為30莫耳%以上，更佳為40莫耳%以上，進而較佳為50莫耳%以上，又，較佳為80莫耳%以下，更佳為70莫耳%以下。 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)以外之重複單元。作為此種重複單元之例，可列舉源自如下單體之重複單元：苯乙烯、α-甲基苯乙烯等苯乙烯系單體；(甲基)丙烯醯氯等(甲基)丙烯酸氯系單體；(甲基)丙烯醯胺、N-羥甲基丙烯醯胺等(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、丁烯酸縮水甘油醚；N-甲基丙烯醯基𠰌啉等單體。 高分子分散劑就進一步提高分散性之觀點而言，較佳為包含具有重複單元(i)及重複單元(ii)之A嵌段與不具有重複單元(i)及重複單元(ii)之B嵌段之嵌段共聚物。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。藉由於A嵌段中不僅導入四級銨鹽基，而且亦導入三級胺基，意外地有分散劑之分散能力顯著提高之傾向。又，B嵌段較佳為具有重複單元(iii)，更佳為進而具有重複單元(iv)。 重複單元(i)及重複單元(ii)可以無規共聚合、嵌段共聚合之任一態樣含有於A嵌段中。又，重複單元(i)及重複單元(ii)可於1個A嵌段中各含有兩種以上，於該情形時，各重複單元可以無規共聚合、嵌段共聚合之任一態樣含有於該A嵌段中。 又，於A嵌段中可含有重複單元(i)及重複單元(ii)以外之重複單元，作為此種重複單元之例，可列舉上文所述之源自(甲基)丙烯酸酯系單體之重複單元等。重複單元(i)及重複單元(ii)以外之重複單元於A嵌段中之含量較佳為0～50莫耳%，更佳為0～20莫耳%，最佳為於A嵌段中不含該重複單元。 於B嵌段中可含有重複單元(iii)及(iv)以外之重複單元，作為此種重複單元之例，可列舉源自如下單體之重複單元：苯乙烯、α-甲基苯乙烯等苯乙烯系單體；(甲基)丙烯醯氯等(甲基)丙烯酸氯系單體；(甲基)丙烯醯胺、N-羥甲基丙烯醯胺等(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、丁烯酸縮水甘油醚；N-甲基丙烯醯基𠰌啉等單體。重複單元(iii)及重複單元(iv)以外之重複單元於B嵌段中之含量較佳為0～50莫耳%，更佳為0～20莫耳%，最佳為於B嵌段中不含該重複單元。 又，就提高分散穩定性之方面而言，(f)分散劑較佳為與下文所述之顏料衍生物併用。 ＜感光性著色組合物之其他調配成分＞ 於本發明之感光性著色組合物中，除了上述成分以外，可適當調配矽烷偶合劑等密接改善劑、塗佈性提高劑、顯影改良劑、紫外線吸收劑、抗氧化劑、界面活性劑、顏料衍生物、光酸產生劑、交聯劑、聚合促進劑等。 (1)密接改善劑 為了改善與基板之密接性，亦可於本發明之感光性著色組合物中含有密接改善劑。作為密接改善劑，較佳為矽烷偶合劑、含磷酸基之化合物等。 作為矽烷偶合劑之種類，可單獨使用環氧系、(甲基)丙烯酸系、胺基系等各者中之一種，或可將兩種以上混合而使用。 作為較佳之矽烷偶合劑，例如可列舉：3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷等(甲基)丙烯醯氧基矽烷類；2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等環氧矽烷類；3-脲基丙基三乙氧基矽烷等脲基矽烷類；3-異氰酸酯基丙基三乙氧基矽烷等異氰酸酯基矽烷類，尤佳為環氧矽烷類之矽烷偶合劑。 作為含磷酸基之化合物，較佳為含(甲基)丙烯醯基之磷酸酯類，較佳為下述通式(g1)、(g2)或(g3)所表示者。 [化55]
Figure 02_image109
於上述通式(g1)、(g2)及(g3)中，R51 表示氫原子或甲基，l及l'為1～10之整數，m為1、2或3。 該等含磷酸基之化合物亦為可單獨使用一種，亦可組合兩種以上而使用。 (2)界面活性劑 為了提高塗佈性，可於本發明之感光性著色組合物中含有界面活性劑。 作為界面活性劑，例如可使用陰離子系、陽離子系、非離子系、兩性界面活性劑等各種者。其中，就對各特性造成不良影響之可能性較低之方面而言，較佳為使用非離子系界面活性劑，其中，就塗佈性之方面而言，有效的是氟系或矽系之界面活性劑。 作為此種界面活性劑，例如可列舉：TSF4460(GE Toshiba Silicones公司製造)、DFX-18(NEOS公司製造)、BYK-300、BYK-325、BYK-330(BYK-Chemie公司製造)、KP340(Shin-Etsu Silicones公司製造)、F-470、F-475、F-478、F-559(DIC公司製造)、SH7PA(Toray Silicone公司製造)、DS-401(Daikin公司製造)、L-77(Nippon Unicar公司製造)、FC4430(住友3M公司製造)等。 再者，界面活性劑可使用一種，亦可以任意組合及比率併用兩種以上。 (3)顏料衍生物 為了提高分散性、保存性，可於本發明之感光性著色組合物中含有顏料衍生物作為分散助劑。 作為顏料衍生物，可列舉：偶氮系、酞菁系、喹吖啶酮系、苯并咪唑酮系、喹酞酮系、異吲哚啉酮系、二㗁𠯤系、蒽醌系、陰丹士林系、苝系、紫環酮系、二酮吡咯并吡咯系、二㗁𠯤系等衍生物，其中，較佳為酞菁系、喹酞酮系。 作為顏料衍生物之取代基，可列舉磺酸基、磺醯胺基及其四級鹽、鄰苯二甲醯亞胺甲基、二烷基胺基烷基、羥基、羧基、醯胺基等直接或經由烷基、芳基、雜環基等鍵結於顏料骨架上者，較佳為磺酸基。又，該等取代基可對一個顏料骨架取代複數個。 作為顏料衍生物之具體例，可列舉：酞菁之磺酸衍生物、喹酞酮之磺酸衍生物、蒽醌之磺酸衍生物、喹吖啶酮之磺酸衍生物、二酮吡咯并吡咯之磺酸衍生物、二㗁𠯤之磺酸衍生物等。該等可單獨使用一種，亦可將兩種以上併用。 (4)光酸產生劑 所謂光酸產生劑係可藉由紫外線而產生酸之化合物，藉由進行曝光時產生之酸之作用，因存在例如三聚氰胺化合物等交聯劑，故而會進行交聯反應。該光酸產生劑中，較佳為對溶劑之溶解性、尤其是對感光性著色組合物所使用之溶劑之溶解性較大者，例如可列舉：二苯基錪、二甲苯基錪、苯基對茴香基錪、雙(間硝基苯基)錪、雙(對第三丁基苯基)錪、雙(對氯苯基)錪、雙(正十二烷基)錪、對異丁基苯基對甲苯基錪、對異丙基苯基對甲苯基錪等二芳基錪；或三苯基鋶等三芳基鋶之氯化物、溴化物；或氟硼酸鹽、六氟磷酸鹽、六氟砷酸鹽、芳香族磺酸鹽、四(五氟苯基)硼酸鹽等；或正丁基三苯基硼酸二苯基苯甲醯甲基鋶等鋶有機硼錯合物類；或2-甲基-4,6-雙(三氯甲基)三𠯤、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)三𠯤等三𠯤化合物等，但並不僅限於此。 (5)交聯劑 可進而於本發明之感光性著色組合物中添加交聯劑，例如可使用三聚氰胺或胍胺系之化合物。作為該等交聯劑，例如可列舉下述通式(6)所表示之三聚氰胺或胍胺系之化合物。 [化56]
Figure 02_image111
式(6)中，R61 表示-NR66 R67 基或碳數6～12之芳基，於R61 為-NR66 R67 基之情形時，R62 、R63 、R64 、R65 、R66 及R67 之一表示-CH2 OR68 基，並且於R61 為碳數6～12之芳基之情形時，R62 、R63 、R64 及R65 之一表示-CH2 OR68 基，R62 、R63 、R64 、R65 、R66 及R67 中剩餘者互相獨立地表示氫或-CH2 OR68 基，此處，R68 表示氫原子或碳數1～4之烷基。 此處，碳數6～12之芳基典型而言為苯基、1-萘基或2-萘基，於該等苯基或萘基上可鍵結有烷基、烷氧基、鹵素原子等取代基。烷基及烷氧基可分別為碳數1～6左右。R68 所表示之烷基較佳為上述中之甲基或乙基，尤佳為甲基。 相當於通式(6)之三聚氰胺系化合物、即下述通式(6-1)之化合物中包含六羥甲基三聚氰胺、五羥甲基三聚氰胺、四羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、五甲氧基甲基三聚氰胺、四甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺等。 [化57]
Figure 02_image113
式(6-1)中，於R62 、R63 、R64 、R65 、R66 及R67 之一為芳基之情形時，R62 、R63 、R64 及R65 之一表示-CH2 OR68 基，R62 、R63 、R64 、R65 、R66 及R67 中剩餘者互相獨立地表示氫原子或-CH2 OR68 基，此處，R68 表示氫原子或烷基。 又，相當於通式(6)之胍胺系化合物、即通式(6)中之R61 為芳基之化合物中包含四羥甲基苯并胍胺、四甲氧基甲基苯并胍胺、三甲氧基甲基苯并胍胺、四乙氧基甲基苯并胍胺等。 進而，亦可使用具有羥甲基或羥甲基烷基醚基之交聯劑。以下列舉其例。 2,6-雙(羥基甲基)-4-甲基苯酚、4-第三丁基-2,6-雙(羥基甲基)苯酚、5-乙基-1,3-雙(羥基甲基)全氫-1,3,5-三𠯤-2-酮(通稱為N-乙基二羥甲基三𠯤酮)或其二甲醚體、二羥甲基三亞甲基脲或其二甲醚體、3,5-雙(羥基甲基)全氫-1,3,5-㗁二𠯤-4-酮(通稱為dimethyloluron)或其二甲醚體、四羥甲基乙二醛二烷基脲或其四甲醚體。 再者，該等交聯劑可單獨使用一種，亦可組合兩種以上而使用。使用交聯劑時之量相對於感光性著色組合物之全部固形物成分較佳為0.1～15質量%，尤佳為0.5～10質量%。 (6)巰基化合物 作為聚合促進劑，又，為了提高與基板之密接性，亦可添加巰基化合物。 作為巰基化合物之種類，可列舉：2-巰基苯并噻唑、2-巰基苯并㗁唑、2-巰基苯并咪唑、己二硫醇、癸二硫醇、1,4-二甲硫基苯、丁二醇雙硫代丙酸酯、丁二醇雙硫代乙醇酸酯、乙二醇雙硫代乙醇酸酯、三羥甲基丙烷三硫代乙醇酸酯、丁二醇雙硫代丙酸酯、三羥甲基丙烷三硫代丙酸酯、三羥甲基丙烷三硫代乙醇酸酯、季戊四醇四硫代丙酸酯、季戊四醇四硫代乙醇酸酯、三羥基乙基三硫代丙酸酯、乙二醇雙(3-巰基丁酸酯)、丁二醇雙(3-巰基丁酸酯)、1,4-雙(3-巰基丁醯氧基)丁烷、三羥甲基丙烷三(3-巰基丁酸酯)、季戊四醇四(3-巰基丁酸酯)、季戊四醇三(3-巰基丁酸酯)、乙二醇雙(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、三羥甲基丙烷三(3-巰基異丁酸酯)、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮等具有雜環之巰基化合物或脂肪族多官能巰基化合物等。該等可單獨使用各者之一種，或可將兩種以上混合而使用。 ＜感光性著色組合物中之成分調配量＞ 於本發明之感光性著色組合物中，(a)著色劑之含有比例相對於感光性著色組合物中之全部固形物成分量，通常為10質量%以上，更佳為20質量%以上，進而較佳為30質量%以上，進而更佳為35質量%以上，尤佳為40質量%以上，又，通常較佳為60質量%以下，更佳為50質量%以下，進而較佳為48質量%以下，尤佳為46質量%以下。藉由將(a)著色劑之含有比例設為上述下限值以上，有可獲得充分之光學密度(optical density，OD)之傾向，又，藉由設為上述上限值以下，有容易獲得充分之製版特性之傾向。 又，於(a)著色劑含有有機顏料之情形時，有機顏料相對於(a)著色劑之含有比例較佳為1質量%以上，更佳為5質量%以上，進而較佳為10質量%以上，進而更佳為30質量%以上，尤佳為50質量%以上，最佳為70質量%以上，又，通常為100質量%以下，較佳為99質量%以下，更佳為95質量%以下，進而較佳為90質量%以下，進而更佳為85質量%以下，尤佳為80質量%以下。藉由設為上述下限值以上，有可獲得充分之光學密度(OD)之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 又，於(a)著色劑含有有機著色顏料之情形時，有機著色顏料相對於(a)著色劑之含有比例較佳為1質量%以上，更佳為5質量%以上，進而較佳為10質量%以上，進而更佳為30質量%以上，尤佳為50質量%以上，最佳為70質量%以上，又，通常為100質量%以下，較佳為99質量%以下，更佳為95質量%以下，進而較佳為90質量%以下，進而更佳為85質量%以下，尤佳為80質量%以下。藉由設為上述下限值以上，有可獲得充分之光學密度(OD)之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 又，於(a)著色劑含有選自由紅色顏料及橙色顏料所組成之群中之至少一種顏料之情形時，選自由紅色顏料及橙色顏料所組成之群中之至少一種顏料相對於(a)著色劑之含有比例較佳為1質量%以上，更佳為2質量%以上，進而較佳為3質量%以上，又，較佳為30質量%以下，更佳為20質量%以下，進而較佳為15質量%以下，進而更佳為10質量%以下，尤佳為7質量%以下，最佳為5質量%以下。藉由設為上述下限值以上，有可獲得充分之光學密度(OD)之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 又，於(a)著色劑含有選自由藍色顏料及紫色顏料所組成之群中之至少一種顏料之情形時，選自由藍色顏料及紫色顏料所組成之群中之至少一種顏料相對於(a)著色劑之含有比例較佳為20質量%以上，更佳為30質量%以上，進而較佳為40質量%以上，進而更佳為50質量%以上，尤佳為60質量%以上，最佳為65質量%以上，又，較佳為90質量%以下，更佳為80質量%以下，進而較佳為70質量%以下。藉由設為上述下限值以上，有可確保遮光性之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 於(a)著色劑含有黑色色料之情形時，黑色色料相對於(a)著色劑之含有比例較佳為5質量%以上，更佳為10質量%以上，進而較佳為15質量%以上，尤佳為20質量%以上，又，較佳為50質量%以下，更佳為40質量%以下，進而較佳為35質量%以下，進而更佳為30質量%以下。藉由設為上述下限值以上，有可獲得充分之光學密度(OD)之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 進而，於(a)著色劑含有有機黑色顏料之情形時，黑色有機顏料相對於(a)著色劑之含有比例較佳為1質量%以上，更佳為5質量%以上，進而更佳為10質量%以上，尤佳為20質量%以上，又，較佳為50質量%以下，更佳為40質量%以下，進而較佳為30質量%以下，尤佳為20質量%以下。藉由設為上述下限值以上，有可獲得充分之光學密度(OD)之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 於(a)著色劑含有碳黑之情形時，碳黑相對於(a)著色劑之含有比例較佳為5質量%以上，更佳為10質量%以上，進而較佳為15質量%以上，尤佳為20質量%以上，又，較佳為50質量%以下，更佳為40質量%以下，進而較佳為35質量%以下，尤佳為30質量%以下。藉由設為上述下限值以上，有可獲得充分之光學密度(OD)之傾向，藉由設為上述上限值以下，有可確保製版特性之傾向。 (b)鹼可溶性樹脂之含有比例相對於本發明之感光性著色組合物之全部固形物成分通常為5質量%以上，較佳為10質量%以上，更佳為20質量%以上，進而較佳為25質量%以上，且通常為85質量%以下，較佳為80質量%以下，更佳為70質量%以下，進而較佳為60質量%以下，進而更佳為50質量%以下，尤佳為40質量%以下。藉由將(b)鹼可溶性樹脂之含有比例設為上述下限值以上，有可抑制未曝光部分相對於顯影液之溶解性降低，而抑制顯影不良之傾向。又，藉由設為上述上限值以下，有可抑制顯影液對曝光部之滲透性變高之情況，而可抑制像素之銳利性或密接性降低之傾向。 (b-I)環氧(甲基)丙烯酸酯樹脂之含有比例相對於本發明之感光性著色組合物之全部固形物成分，通常為3質量%以上，較佳為6質量%以上，更佳為8質量%以上，且通常為40質量%以下，較佳為30質量%以下，更佳為20質量%以下，進而較佳為15質量%以下。藉由設為上述下限值以上，有可確保可靠性之傾向，又，藉由設為上述上限值以下，有可確保表面平滑性之傾向。 (b)鹼可溶性樹脂中所含之(b-I)環氧(甲基)丙烯酸酯樹脂之含有比例通常為10質量%以上，較佳為20質量%以上，更佳為25質量%以上，進而較佳為30質量%以上，尤佳為40質量%以上，且通常為90質量%以下，較佳為80質量%以下，更佳為70質量%以下，進而較佳為60質量%以下，進而更佳為50質量%以下，尤佳為40質量%以下。藉由設為上述下限值以上，有可確保可靠性之傾向，又，藉由設為上述上限值以下，有可確保表面平滑性之傾向。 (b-II)(甲基)丙烯酸系共聚合樹脂之含有比例相對於本發明之感光性著色組合物之全部固形物成分，通常為1質量%以上，較佳為3質量%以上，更佳為6質量%以上，進而較佳為8質量%以上，且通常為40質量%以下，較佳為30質量%以下，更佳為20質量%以下，進而較佳為15質量%以下。藉由設為上述下限值以上，有可確保表面平滑性之傾向，又，藉由設為上述上限值以下，有可確保可靠性之傾向。 (b)鹼可溶性樹脂中所含之(b-II)(甲基)丙烯酸系共聚合樹脂之含有比例通常為10質量%以上，較佳為20質量%以上，更佳為25質量%以上，進而較佳為30質量%以上，尤佳為40質量%以上，且通常為80質量%以下，較佳為70質量%以下，更佳為60質量%以下，進而較佳為50質量%以下，尤佳為40質量%以下。藉由設為上述下限值以上，有可確保表面平滑性之傾向，又，藉由設為上述上限值以下，有可確保可靠性之傾向。 (c)光聚合起始劑之含有比例相對於本發明之感光性著色組合物之全部固形物成分，通常為0.1質量%以上，較佳為0.5質量%以上，更佳為1質量%以上，進而較佳為2質量%以上，進而更佳為3質量%以上，尤佳為4質量%以上，且通常為15質量%以下，較佳為10質量%以下，更佳為8質量%以下，進而較佳為7質量%以下。藉由將(c)光聚合起始劑之含有比例設為上述下限值以上，有可抑制感度降低之傾向，藉由設為上述上限值以下，有可抑制未曝光部分相對於顯影液之溶解性降低，而抑制顯影不良之傾向。 於將(c)光聚合起始劑與聚合促進劑一併使用之情形時，聚合促進劑之含有比例相對於本發明之感光性著色組合物之全部固形物成分，較佳為0.05質量%以上，且通常為10質量%以下，較佳為5質量%以下，聚合促進劑較佳為以相對於(c)光聚合起始劑100質量份通常為0.1～50質量份、尤其是0.1～20質量份之比例使用。藉由將聚合促進劑之含有比例設為上述下限值以上，有可抑制對曝光光線之感度降低之傾向，藉由設為上述上限值以下，有可抑制未曝光部分相對於顯影液之溶解性降低，而抑制顯影不良之傾向。 又，增感色素於本發明之感光性著色組合物中所占之調配比例就感度之觀點而言，於感光性著色組合物中之全部固形物成分中，通常為20質量%以下，較佳為15質量%以下，進而較佳為10質量%以下。 (d)乙烯性不飽和化合物之含有比例相對於本發明之感光性著色組合物之全部固形物成分通常為30質量%以下，較佳為20質量%以下，更佳為15質量%以下。藉由將(d)乙烯性不飽和化合物之含有比例設為上述上限值以下，有抑制顯影液對曝光部之滲透性變高之情況，而容易獲得良好之圖像之傾向。再者，(d)乙烯性不飽和化合物之含有比例之下限值通常為1質量%以上，較佳為5質量%以上。 再者，本發明之感光性著色組合物藉由使用(e)溶劑，而以其固形物成分濃度成為通常為5質量%以上、較佳為10質量%以上、更佳為15質量%以上、進而較佳為20質量%以上且通常為50質量%以下、較佳為30質量%以下之方式進行調液。 (f)分散劑之含有比例於感光性著色組合物之固形物成分中通常為1質量%以上，較佳為3質量%以上，更佳為5質量%以上，且通常為30質量%以下，較佳為20質量%以下，更佳為15質量%以下，進而較佳為10質量%以下。又，(f)分散劑相對於(a)著色劑100質量份之含有比例通常為5質量份以上，更佳為10質量份以上，進而較佳為15質量份以上，且通常為50質量份以下，尤佳為30質量份以下。藉由將(f)分散劑之含有比例設為上述下限值以上，有容易獲得充分之分散性之傾向，藉由設為上述上限值以下，有可抑制因其他成分之比例相對減少而導致感度、製版性等降低之情況之傾向。 於使用密接改善劑之情形時，其含有比例相對於感光性著色組合物中之全部固形物成分，通常為0.1～5質量%，較佳為0.2～3質量%，進而較佳為0.4～2質量%。藉由將密接改善劑之含有比例設為上述下限值以上，有可充分獲得改善密接性之效果之傾向，藉由設為上述上限值以下，有可抑制感度降低、顯影後殘留殘渣而成為缺陷之情況之傾向。 又，於使用界面活性劑之情形時，其含有比例相對於感光性著色組合物中之全部固形物成分，通常為0.001～10質量%，較佳為0.005～1質量%，進而較佳為0.01～0.5質量%，最佳為0.03～0.3質量%。藉由將界面活性劑之含量設為上述下限值以上，有容易表現出塗佈膜之平滑性、均一性之傾向，藉由設為上述上限值以下，有容易表現出塗佈膜之平滑性、均一性，亦可抑制其他特性變差之傾向。 ＜感光性著色組合物之物性＞ 本發明之感光性著色組合物可適宜地用於形成著色間隔件，就用作著色間隔件之觀點而言，較佳為呈黑色。又，將感光性著色組合物硬化而成之塗膜之每1 μm膜厚之光學密度(OD)較佳為1.0以上，更佳為1.2以上，進而較佳為1.5以上，尤佳為1.8以上，且通常為4.0以下，較佳為3.0以下，更佳為2.5以下。 ＜感光性著色組合物之製造方法＞ 本發明之感光性著色組合物(以下有時稱為「抗蝕劑」)可依照常規方法而製造。 通常較佳為使用塗料調節器、砂磨機、球磨機、輥磨機、石磨機、噴射磨機、均質機等對(a)著色劑預先進行分散處理。由於藉由分散處理將(a)著色劑微粒化，因此抗蝕劑之塗佈特性提高。 分散處理通常較佳為藉由併用(a)著色劑、(e)溶劑、及(f)分散劑、以及(b)鹼可溶性樹脂之一部分或全部之系統進行(以下有時將供於分散處理之混合物、及藉由該處理而獲得之組合物稱為「油墨」或「顏料分散液」)。尤其是若使用高分子分散劑作為(f)分散劑，則可抑制所獲得之油墨及抗蝕劑之經時增黏(分散穩定性優異)，故而較佳。 如上所述，於製造抗蝕劑之步驟中，較佳為製造至少含有(a)著色劑、(e)溶劑、及(f)分散劑之顏料分散液。作為顏料分散液可使用之(a)著色劑、(e)有機溶劑、及(f)分散劑，分別可較佳地採用作為感光性著色組合物可使用者而記載者。 再者，於對含有調配於感光性著色組合物中之全部成分之液體進行分散處理之情形時，由於分散處理時產生放熱，因此存在高反應性之成分改性之可能性。因此，較佳為藉由含有高分子分散劑之系統進行分散處理。 於藉由砂磨機使(a)著色劑分散之情形時，可較佳地使用0.1～8 mm左右之粒徑之玻璃珠或氧化鋯珠。分散處理條件如下：溫度通常為0℃至100℃，較佳為室溫至80℃之範圍。分散時間根據液之組成及分散處理裝置之尺寸等而合適時間有所不同，因此適當進行調節。分散標準為以抗蝕劑之20度鏡面光澤度(JIS Z8741)成為50～300之範圍之方式控制油墨之光澤。於抗蝕劑之光澤度較低之情形時，較多情況下分散處理不充分，而殘留粗糙之顏料(色料)粒子，存在顯影性、密接性、解像性等變得不充分之可能性。又，若進行分散處理直至光澤值超過上述範圍，則由於顏料破碎而產生大量超微粒，因此反而有分散穩定性受損之傾向。 又，分散於油墨中之顏料之分散粒徑通常為0.03～0.3 μm，可藉由動態光散射法等進行測定。 繼而，將藉由上述分散處理而獲得之油墨與抗蝕劑中所含之上述其他成分加以混合而製成均勻之溶液。於抗蝕劑之製造步驟中，由於較多情況下微細之污物會混入至液中，因此較理想為藉由過濾器等對所獲得之抗蝕劑進行過濾處理。 [硬化物] 藉由將本發明之感光性著色組合物硬化，可獲得硬化物。將感光性著色組合物硬化而成之硬化物可適宜地用作著色間隔件。 [著色間隔件] 繼而，依照使用本發明之感光性著色組合物之著色間隔件之製造方法對其進行說明。 (1)支持體 作為用以形成著色間隔件之支持體，只要有適度之強度，則其材質並無特別限定。主要使用透明基板，作為材質，例如可列舉：聚對苯二甲酸乙二酯等聚酯系樹脂、聚丙烯、聚乙烯等聚烯烴系樹脂、聚碳酸酯、聚甲基丙烯酸甲酯、聚碸等熱塑性樹脂製片材；環氧樹脂、不飽和聚酯樹脂、聚(甲基)丙烯酸系樹脂等熱硬化性樹脂片材、或各種玻璃等。其中，就耐熱性之觀點而言，較佳為玻璃、耐熱性樹脂。又，亦存在於基板之表面成膜ITO、IZO(Indium Zinc Oxide，氧化銦鋅)等透明電極之情形。除了透明基板以外，亦可於TFT陣列上形成。 為了改良接著性等表面物性，可視需要對支持體進行電暈放電處理、臭氧處理、矽烷偶合劑或胺基甲酸酯系樹脂等各種樹脂之薄膜形成處理等。 透明基板之厚度通常設為0.05～10 mm之範圍，較佳設為0.1～7 mm之範圍。又，於進行各種樹脂之薄膜形成處理之情形時，其膜厚通常為0.01～10 μm之範圍，較佳為0.05～5 μm之範圍。 (2)著色間隔件 本發明之感光性著色組合物係用於與公知之彩色濾光片用感光性著色組合物同樣之用途，以下，依照使用本發明之感光性著色組合物之黑色光間隔件之形成方法之具體例對用作著色間隔件(黑色光間隔件)之情形進行說明。 通常，藉由塗佈等方法以膜狀或圖案狀將感光性著色組合物供給於應設置黑色光間隔件之基板上，將溶劑加以乾燥。其次，藉由進行曝光-顯影之光微影法等方法進行圖案形成。其後，視需要進行追加曝光或熱硬化處理，藉此於該基板上形成黑色光間隔件。 (3)著色間隔件之形成 [1]對基板之供給方法 本發明之感光性著色組合物通常以溶解或分散於溶劑中之狀態供給至基板上。作為其供給方法，可藉由先前公知之方法進行，例如旋轉塗佈法、線棒塗佈法、流塗法、模塗法、輥塗法、噴塗法等。又，亦可藉由噴墨法或印刷法等，以圖案狀供給。其中，若藉由模塗法，則就可大幅削減塗佈液之使用量，且完全不會受利用旋轉塗佈法時附著之霧等之影響，可抑制雜質產生等綜合觀點而言較佳。 塗佈量根據用途而有所不同，例如於黑色光間隔件之情形時，乾燥膜厚通常為0.5 μm～10 μm之範圍，較佳為1 μm～9 μm之範圍，尤佳為1 μm～7 μm之範圍。又，重要的是乾燥膜厚或最終形成之間隔件之高度於基板全域上均勻。於偏差較大之情形時，會於液晶面板上產生不均缺陷。 但於藉由光微影法將本發明之感光性著色組合物一次性形成高度不同之黑色光間隔件之情形時，最終形成之黑色光間隔件之高度不同。 再者，可使用玻璃基板等公知之基板作為基板。又，基板表面為平面為宜。 [2]乾燥方法 將感光性著色組合物溶液供給至基板上後之乾燥較佳為利用使用加熱板、IR(infrared，紅外線)烘箱、對流烘箱之乾燥方法。又，亦可組合不提高溫度而於減壓腔室內進行乾燥之減壓乾燥法。 乾燥之條件可根據溶劑成分之種類、所使用之乾燥機之性能等而適當選擇。乾燥時間根據溶劑成分之種類、所使用之乾燥機之性能等，通常可於40℃～130℃之溫度下15秒～5分鐘之範圍內選擇，較佳為於50℃～110℃之溫度下30秒～3分鐘之範圍內選擇。 [3]曝光方法 曝光係於感光性著色組合物之塗佈膜上重疊負光罩圖案，經由該光罩圖案照射紫外線或可見光線之光源而進行。於使用曝光光罩進行曝光之情形時，可利用使曝光光罩靠近感光性著色組合物之塗佈膜之方法，或將曝光光罩配置於偏離感光性著色組合物之塗佈膜之位置，並投影經由該曝光光罩之曝光之光之方法。又，亦可利用不使用光罩圖案之藉由雷射光進行之掃描曝光方式。此時，為了防止由氧引起之光聚合性層之感度降低，可視需要於脫氧環境下進行，或於在光聚合性層上形成聚乙烯醇層等隔氧層後進行曝光。 作為本發明之較佳之態樣，於藉由光微影法同時形成高度不同之黑色光間隔件之情形時，例如使用具有遮光部(透光率0%)與作為複數個開口部之相對於平均透光率最高之開口部(完全透過開口部)平均透光率較小之開口部(中間透過開口部)的曝光光罩。藉由該方法，利用中間透過開口部與完全透過開口部之平均透光率之差、即曝光量之差而產生殘膜率之差異。 已知有例如利用具有微小之多角形之遮光單元的矩陣狀遮光圖案製作中間透過開口部之方法等。又，已知有作為吸收體，藉由鉻系、鉬系、鎢系、矽系等材料之膜對透光率進行控制而製作之方法等。 上述曝光所使用之光源並無特別限定。作為光源，例如可列舉：氙氣燈、鹵素燈、鎢絲燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、中壓水銀燈、低壓水銀燈、碳弧燈、螢光燈等燈光源，或氬離子雷射、YAG(Yttrium Aluminum Garnet，釔-鋁-石榴石)雷射、準分子雷射、氮雷射、氦-鎘雷射、藍紫色半導體雷射、近紅外半導體雷射等雷射光源等。於照射特定波長之光而使用之情形時，亦可利用光學濾光片。 作為光學濾光片，例如可為可藉由薄膜控制曝光波長中之透光率之類型，作為該情形時之材質，例如可列舉：Cr化合物(Cr之氧化物、氮化物、氮氧化物、氟化物等)、MoSi、Si、W、Al等。 作為曝光量，通常為1 mJ/cm2 以上，較佳為5 mJ/cm2 以上，更佳為10 mJ/cm2 以上，且通常為300 mJ/cm2 以下，較佳為200 mJ/cm2 以下，更佳為150 mJ/cm2 以下。 又，於近接曝光方式之情形時，曝光對象與光罩圖案之距離通常為10 μm以上，較佳為50 μm以上，更佳為75 μm以上，且通常為500 μm以下，較佳為400 μm以下，更佳為300 μm以下。 [4]顯影方法 進行上述曝光後，藉由使用鹼性化合物之水溶液、或有機溶劑之顯影，可於基板上形成圖像圖案。該水溶液中可進而含有界面活性劑、有機溶劑、緩衝劑、錯合劑、染料或顏料。 作為鹼性化合物，可列舉：氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、磷酸鈉、磷酸鉀、磷酸氫鈉、磷酸氫鉀、磷酸二氫鈉、磷酸二氫鉀、氫氧化銨等無機鹼性化合物；或單、二或三乙醇胺、單、二或三甲胺、單、二或三乙胺、單或二異丙胺、正丁胺、單、二或三異丙醇胺、伸乙基亞胺、伸乙基二亞胺、四甲基氫氧化銨(TMAH)、膽鹼等有機鹼性化合物。該等鹼性化合物可為兩種以上之混合物。 作為上述界面活性劑，例如可列舉：聚氧乙烯烷基醚類、聚氧乙烯烷基芳基醚類、聚氧乙烯烷基酯類、山梨糖醇酐烷基酯類、單甘油酯烷基酯類等非離子系界面活性劑；烷基苯磺酸鹽類、烷基萘磺酸鹽類、烷基硫酸鹽類、烷基磺酸鹽類、磺基丁二酸酯鹽類等陰離子性界面活性劑；烷基甜菜鹼類、胺基酸類等兩性界面活性劑。 作為有機溶劑，例如可列舉：異丙醇、苄醇、乙基賽路蘇、丁基賽路蘇、苯基賽路蘇、丙二醇、二丙酮醇等。有機溶劑可單獨使用，亦可與水溶液併用。 顯影處理之條件並無特別限制，通常可於顯影溫度為10～50℃之範圍，其中較佳為15～45℃、尤佳為20～40℃下，藉由浸漬顯影法、噴射顯影法、毛刷顯影法、超音波顯影法等任一顯影方法進行。 [5]追加曝光及熱硬化處理 可視需要藉由與上述曝光方法同樣之方法對顯影後之基板進行追加曝光，又，亦可進行熱硬化處理。關於此時之熱硬化處理條件，溫度可於100℃～280℃之範圍、較佳為150℃～250℃之範圍內選擇，時間は可於5分鐘～60分鐘之範圍內選擇。 本發明之著色間隔件之大小或形狀等係根據應用其之彩色濾光片之規格等而適當調整，本發明之感光性著色組合物尤其是對藉由光微影法同時形成間隔件與輔助間隔件高度不同之黑色光間隔件有用，於該情形時，間隔件之高度通常為2～7 μm左右，輔助間隔件通常具有較間隔件低0.2～1.5 μm左右之高度。 又，本發明之著色間隔件之每1 μm之光學密度(OD)就遮光性之觀點而言，較佳為1.2以上，更佳為1.5以上，進而較佳為1.8以上，且通常為4.0以下，較佳為3.0以下。此處，光學密度(OD)係藉由下文所述之方法測得之值。 [彩色濾光片] 本發明之彩色濾光片具備如上所述之本發明之著色間隔件，例如係於作為透明基板之玻璃基板上積層黑矩陣與紅色、綠色、藍色之像素著色層及表塗層，並於形成著色間隔件後形成配向膜而製造。 可將此種具有本發明之著色間隔件之彩色濾光片與液晶驅動側基板進行貼合而形成液晶單元，於形成之液晶單元中注入液晶，藉此製造具備本發明之著色間隔件之液晶顯示裝置等圖像顯示裝置。 [實施例] 繼而，列舉實施例及比較例更具體地說明本發明，但本發明只要不超過其主旨，則並不限定於以下實施例。 以下之實施例及比較例所使用之感光性著色組合物之構成成分如下所述。 ＜有機黑色顏料＞ BASF公司製造，Irgaphor(註冊商標) Black S 0100 CF(具有下述式(2)所表示之化學結構) [化58]
Figure 02_image115
＜鹼可溶性樹脂-A＞ 一面對丙二醇單甲醚乙酸酯145質量份進行氮氣置換一面加以攪拌，並升溫至120℃。於其中滴加苯乙烯10質量份、甲基丙烯酸縮水甘油酯85.2質量份及具有三環癸烷骨架之單丙烯酸酯(日立化成公司製造之FA-513M)66質量份，以及歷經3小時滴加2,2'-偶氮雙-2-甲基丁腈8.47質量份，進而於90℃下繼續攪拌2小時。其次將反應容器內置換為空氣，於丙烯酸43.2質量份中投入三(二甲胺基甲基)苯酚0.7質量份及對苯二酚0.12質量份，於100℃下持續反應12小時。其後，添加四氫鄰苯二甲酸酐(THPA)56.2質量份、三乙胺0.7質量份，於100℃下反應3.5小時。由此獲得之鹼可溶性樹脂-A之藉由GPC測得之重量平均分子量Mw約為8400，酸值為80 mgKOH/g。 ＜鹼可溶性樹脂-B＞ 一面對丙二醇單甲醚乙酸酯217.6質量份與丙二醇單甲醚53.9質量份之混合液進行氮氣置換一面加以攪拌，升溫至120℃。歷經3小時於其中滴加甲基丙烯酸苄酯3.52質量份、甲基丙烯酸58.5質量份、具有三環癸烷骨架之單丙烯酸酯FA-513M(日立化成公司製造)66.1質量份及2,2'-偶氮雙-2-甲基丁腈3.8質量份之混合液，進而於90℃下繼續攪拌2小時。其次，將反應容器內置換為空氣，投入甲基丙烯酸縮水甘油酯27.3質量份、三(二甲胺基甲基)苯酚0.6質量份及對苯二酚0.1質量份，於100℃下持續反應12小時。由此獲得之鹼可溶性樹脂-B之重量平均分子量Mw為16500，酸值為176 mgKOH/g。 ＜鹼可溶性樹脂-C＞ 一面對丙二醇單甲醚乙酸酯303.5質量份與丙二醇單甲醚75.9質量份之混合液進行氮氣置換一面加以攪拌，升溫至120℃。歷經3小時於其中滴加苯乙烯10.4質量份、甲基丙烯酸34.4質量份、具有三環癸烷骨架之單丙烯酸酯FA-513M(日立化成公司製造)66.1質量份及2,2'-偶氮雙-2-甲基丁腈8.7質量份之混合液，進而於90℃下繼續攪拌2小時。其次，將反應容器內置換為空氣，投入甲基丙烯酸縮水甘油酯9.9質量份、三(二甲胺基甲基)苯酚0.2質量份及對苯二酚0.04質量份，於100℃下持續反應12小時。由此獲得之鹼可溶性樹脂-C之重量平均分子量Mw為7200，酸值為86 mgKOH/g。 ＜鹼可溶性樹脂-D＞ 日本化藥公司製造之「ZCR-1642H」(Mw＝6500，酸值＝98 mgKOH/g) ＜鹼可溶性樹脂-E＞ [化59]
Figure 02_image117
將上述結構之環氧化合物(環氧當量264)50 g、丙烯酸13.65 g、甲氧基乙酸丁酯60.5 g、三苯基膦0.936 g、及對甲氧基苯酚0.032 g裝入至安裝有溫度計、攪拌機、冷卻管之燒瓶中，一面加以攪拌一面於90℃下反應至酸值成為5 mgKOH/g以下為止。反應需要12小時，獲得環氧丙烯酸酯溶液。 將上述環氧丙烯酸酯溶液25質量份及三羥甲基丙烷(TMP)0.76質量份、聯苯四羧酸二酐(BPDA)3.3質量份、四氫鄰苯二甲酸酐(THPA)3.5質量份裝入至安裝有溫度計、攪拌機、冷卻管之燒瓶中，一面加以攪拌一面緩慢升溫至105℃而進行反應。 於樹脂溶液變得透明時，以甲氧基乙酸丁酯進行稀釋，以固形物成分成為50質量%之方式進行製備，而獲得酸值113 mgKOH/g、藉由GPC測得之聚苯乙烯換算之重量平均分子量(Mw)2600、雙鍵當量520 g/mol之含羧基之環氧甲基丙烯酸酯樹脂(鹼可溶性樹脂-E)。 ＜鹼可溶性樹脂-F＞ 一面對丙二醇單甲醚乙酸酯214.5質量份與丙二醇單甲醚53.6質量份之混合液進行氮氣置換一面加以攪拌，升溫至120℃。歷經3小時於其中滴加甲基丙烯酸苄酯68.7質量份、甲基丙烯酸43.9質量份、具有三環癸烷骨架之單丙烯酸酯FA-513M(日立化成公司製造)22.0質量份及2,2'-偶氮雙-2-甲基丁腈1.4質量份之混合液，進而於90℃下繼續攪拌2小時。其次，將反應容器內置換為空氣，投入甲基丙烯酸縮水甘油酯21.3質量份、三(二甲胺基甲基)苯酚0.5質量份及對苯二酚0.1質量份，於100℃下持續反應12小時。由此獲得之鹼可溶性樹脂-F之重量平均分子量Mw為44100，酸值為130 mgKOH/g。 ＜鹼可溶性樹脂-G＞ 一面對丙二醇單甲醚乙酸酯210.1質量份與丙二醇單甲醚52.5質量份之混合液進行氮氣置換一面加以攪拌，升溫至120℃。歷經3小時於其中滴加甲基丙烯酸苄酯3.52質量份、甲基丙烯酸68.8質量份、具有三環癸烷骨架之單丙烯酸酯FA-513M(日立化成公司製造)39.7質量份及2,2'-偶氮雙-2-甲基丁腈3.3質量份之混合液，進而於90℃下繼續攪拌2小時。其次，將反應容器內置換為空氣，投入甲基丙烯酸縮水甘油酯38.4質量份、三(二甲胺基甲基)苯酚0.8質量份及對苯二酚0.1質量份，於100℃下持續反應12小時。由此獲得之鹼可溶性樹脂-G之重量平均分子量Mw為19100，酸值為198 mgKOH/g。 ＜分散劑-I＞ BYK-Chemie公司製造之「DISPERBYK-LPN21116」(包含側鏈具有四級銨鹽基及三級胺基之A嵌段與不具有四級銨鹽基及三級胺基之B嵌段的丙烯酸系A-B嵌段共聚物。胺值為70 mgKOH/g，酸值為1 mgKOH/g以下) 於分散劑-I之A嵌段中含有下述式(1a)及(2a)之重複單元，於B嵌段中含有下述式(3a)之重複單元。下述式(1a)、(2a)、及(3a)之重複單元於分散劑-I之總重複單元中所占之含有比例分別為11.1莫耳%、22.2莫耳%、6.7莫耳%。 [化60]
Figure 02_image119
＜分散劑-II＞ BYK-Chemie公司製造之「DISPERBYK-167」(胺基甲酸酯系高分子分散劑) ＜顏料衍生物＞ Lubrizol公司製造之「Solsperse12000」 ＜溶劑-I＞ PGMEA：丙二醇單甲醚乙酸酯 ＜溶劑-II＞ MB：3-甲氧基丁醇 ＜光聚合起始劑＞ 下述結構之化合物 [化61]
Figure 02_image121
＜光聚合性單體＞ DPHA：日本化藥公司製造之二季戊四醇六丙烯酸酯 ＜添加劑＞ 日本化藥公司製造，KAYAMER PM-21(含甲基丙烯醯基之磷酸酯) ＜界面活性劑＞ DIC公司製造之MEGAFAC F-559 ＜每單位膜厚之光學密度(單位OD值)之測定＞ 每單位膜厚之光學密度係藉由以下順序進行測定。 首先，以最終膜厚成為2 μm之方式藉由旋轉塗佈機將所製備之感光性著色組合物塗佈於玻璃基板上，減壓乾燥1分鐘後，於加熱板溫度80℃下乾燥70秒。經過曝光及顯影步驟後於烘箱溫度230℃下加熱20分鐘，藉此獲得抗蝕劑塗佈基板。藉由透過濃度計Gretag Macbeth D200-II測定所獲得之基板之光學密度(OD)，藉由Ryoka Systems公司製造之非接觸表面/層剖面形狀計測系統VertScan(R)2.0測定膜厚，根據光學密度(OD)及膜厚算出每單位膜厚之光學密度。再者，OD值係表示遮光能力之數值，數值越大表示遮光性越高。 ＜NMP溶出試驗＞ N-甲基吡咯啶酮(NMP)溶出試驗係藉由以下順序進行。 首先，以最終膜厚成為2 μm之方式藉由旋轉塗佈機將所製備之感光性著色組合物塗佈於玻璃基板上，減壓乾燥1分鐘後，於加熱板溫度80℃下乾燥70秒。經過曝光及顯影步驟後於烘箱溫度230℃下加熱20分鐘而獲得抗蝕劑塗佈基板。自所製作之抗蝕劑塗佈基板切下2塊測定用基板(2.5 cm×1.0 cm見方)，浸漬於裝有N-甲基吡咯啶酮(NMP)8 mL之10 mL用小瓶中。然後，以將該裝有測定用基板之小瓶於80℃之熱浴中靜置40分鐘之狀態實施NMP溶出試驗。靜置40分鐘後自熱浴中將小瓶取出，藉由分光光度計(島津製作所公司製造之「UV-3100PC」)於300～800 nm之波長範圍內以1 nm為間隔對該NMP溶出溶液測定吸光度。光源使用鹵素燈及氘燈(切換波長360 nm)，檢測器使用光電倍增器，以狹縫寬度2 nm作為測定條件。又，將試樣溶液(NMP溶出溶液)置於1 cm見方之石英皿進行測定。所謂吸光度係分光法中表示光通過某物體時光強度會衰減何種程度之無因次量，由以下之式所定義。 A(吸光度)＝-log10 (I/I0 ) (I：透過光強度、I0 ：入射光強度) 又，自相同之光源分別向試樣溶液與NMP單獨液入射光時，可將透過NMP單獨液之光強度視為I0 ，將透過試樣溶液之光強度視為I。因此，上式之(I/I0 )表示透光率，吸光度A為以對數表現透過率之倒數而得之值。吸光度A係算出試樣溶液所含之物質之濃度等時所使用之表述。於吸光度A＝0之情形時，表示完全未吸收光之狀態(透過率100%)，於吸光度A＝∞之情形時，表示光完全未透過之狀態(透過率0%)。即，吸光度越強，表示抗蝕劑塗膜成分越多地溶出至NMP中，NMP耐性越差。算出所測得之吸光度之光譜面積(nm)，將面積值未達20(nm)評價為○，將為20(nm)以上評價為×，對NMP耐性進行評價。作為本評價基準之吸光度之光譜面積可以各波長下之吸光度之和表示，意指所溶出之抗蝕劑成分之總和。 NMP耐性評價基準：利用吸光度之光譜面積值進行之判定(波長300～800 nm) ○：未達20(nm) ×：20(nm)以上 ＜表面平滑性之評價＞ 表面平滑性及下述之表面粗度之評價係藉由以下順序進行。 首先，以最終膜厚成為3 μm之方式藉由旋轉塗佈機將所製備之感光性著色組合物塗佈於玻璃基板上，減壓乾燥1分鐘後，於加熱板溫度80℃下乾燥70秒。經過曝光及顯影步驟後於烘箱溫度230℃下加熱20分鐘而獲得抗蝕劑塗佈基板。對於所製作之抗蝕劑塗佈基板，藉由光學顯微鏡於70 μm×70 μm之視野下觀察加熱後之表面有無皺褶產生。再者，評價基準如以下所述。 ○：於圖案之表面未觀察到微米級之皺褶 ×：於圖案之表面明顯存在微米級之皺褶 ＜表面粗度之評價＞ 對於上述＜表面平滑性之評價＞中所製作之抗蝕劑塗佈基板，藉由Ryoka Systems公司製造之三維非接觸表面形狀計測系統Micromap，使用50倍之光學透鏡，以Focus模式於70 μm×70 μm之視野中測定表面粗度Sa(算術平均粗糙度，μm)。 ＜顏料分散液1、3及4之製備＞ 以成為表1所記載之質量比之方式將表1所記載之顏料、分散劑、分散助劑、鹼可溶性樹脂、及溶劑加以混合。藉由塗料振盪機於25～45℃之範圍內對該混合液進行3小時之分散處理。使用0.5 mm
Figure 02_image123
之氧化鋯珠作為珠粒，添加分散液之2.5倍之質量。分散結束後，藉由過濾器將珠粒與分散液分離，而製備顏料分散液1、3及4。 [表1]
Figure 105142935-A0304-0001
 ＜顏料分散液2(被覆碳黑分散液)＞ 碳黑係藉由通常之油爐法而製造。其中，使用Na、Ca、S分量較少之乙烯焦油作為原料油，燃燒用使用焦爐煤氣。進而，使用經離子交換樹脂處理之純水作為反應停止水。使用均質機，以5,000～6,000 rpm將所獲得之碳黑540 g與純水14500 g一併攪拌30分鐘而獲得漿料。將該漿料轉移至附螺旋型攪拌機之容器中，一面以約1,000 rpm加以混合一面逐量添加溶解有環氧樹脂「Epikote 828」(三菱化學公司製造)60 g之甲苯600 g。於約15分鐘內分散於水中之碳黑全部轉移至甲苯側，成為約1 mm之粒。 繼而，藉由60目金屬線網甩掉水後，置入真空乾燥機中，於70℃下乾燥7小時，而將甲苯與水完全去除。 以成為表1所記載之質量比之方式將所獲得之被覆碳黑、分散劑、顏料衍生物及溶劑加以混合。 藉由攪拌機將其充分攪拌而進行預混。繼而，藉由塗料振盪機於25～45℃之範圍內進行6小時之分散處理。使用0.5 mm
Figure 02_image123
之氧化鋯珠作為珠粒，添加與分散液相同之質量。分散結束後，藉由過濾器將珠粒與分散液分離，而製備顏料分散液2。 [實施例1～6、比較例1～3] 以固形物成分比率成為表2之調配比例之方式添加各成分，進而以固形物成分成為22質量%之方式添加PGMEA，加以攪拌而使其溶解，從而製備感光性著色組合物。將所製備之組合物之固形物成分比率示於表2。又，將藉由上文所述之方法測得之單位OD值、NMP溶出試驗、表面平滑性及表面粗糙度之評價結果示於表2。再者，表2中之感光性著色組合物之質量份表示固形物成分之質量份。 [表2]
Figure 105142935-A0304-0002
 表2之實施例1與比較例1及2之比較揭示出，包含(b-I)環氧(甲基)丙烯酸酯樹脂與(b-II)含有12莫耳%以上之具有乙烯性不飽和鍵之重複單元α且含有源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂的感光性著色組合物可確保較高之遮光性，同時可靠性與表面平滑性優異。另一方面，重複單元α未達12莫耳%之比較例1之可靠性不良，又，不含(b-II)(甲基)丙烯酸系共聚合樹脂之比較例2之表面平滑性不良。 於如比較例2般主要之樹脂成分為(b-I)環氧(甲基)丙烯酸酯樹脂之情形時，認為由其結構引起之熱流動導致表面平滑性變得不良。因此認為，藉由除了環氧(甲基)丙烯酸酯樹脂以外亦使用不易熱流動之含有源自不飽和羧酸之重複單元的(甲基)丙烯酸系共聚合樹脂，熱流動減少而改善表面平滑性。但由於此種(甲基)丙烯酸系共聚合樹脂通常與環氧(甲基)丙烯酸酯樹脂相比感度較低，故而存在硬化性降低，如比較例1般可靠性變差之情形。因此認為，藉由提高(甲基)丙烯酸系共聚合樹脂中之具有乙烯性不飽和鍵之重複單元α之含有比例，可確保充分之硬化性，兼顧可靠性與表面平滑性。 又，實施例1～3之比較揭示出，於著色劑含有有機顏料與碳黑之情形，或含有選自由紅色顏料及橙色顏料所組成之群中之至少一種與選自由藍色顏料及紫色顏料所組成之群中之至少一種之情形時，不論具體之顏料種類為何，均可確保較高之遮光性，同時可靠性與表面平滑性優異。 相對於此，著色劑僅為紫外線吸收性較高之碳黑之比較例3的表面平滑性不充分。 另一方面，實施例2與4之比較揭示出，不論(b-I)環氧(甲基)丙烯酸酯樹脂之種類為何，可靠性均優異。另一方面，實施例1、5、6之比較揭示出，若(b-II)樹脂中之具有乙烯性不飽和鍵之重複單元α之含有比例為12莫耳%以上，則不論其具體之含有比例之值如何，可靠性與表面平滑性均優異。 已使用特定之態樣對本發明進行了詳細說明，但業者明白，可不脫離本發明之意圖與範圍而進行各種變更及變形。再者，本申請案基於2015年12月24日提出申請之日本專利申請案(日本專利特願2015-252149)，藉由引用而援引其全部內容。 [產業上之可利用性] 根據本發明之感光性著色組合物，可提供一種遮光性較高、高可靠性且表面平滑性優異之硬化物及著色間隔件，進而，可提供具備此種著色間隔件之圖像顯示裝置。因此，本發明於感光性著色組合物、硬化物、著色間隔件及圖像顯示裝置之各領域內，產業上之可利用性極高。Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist. Furthermore, in the present invention, the term "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth)acrylate" and "(meth)acrylic acid" are also the same. In the present invention, the so-called "(co)polymer" means to include both homopolymer and copolymer, and the so-called "acid (anhydride)", "(anhydrous)...acid" means to include acid Both with its anhydride. In addition, in the present invention, the "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylate having a carboxyl group. In addition, in the present invention, the so-called "monomer" refers to the so-called high-molecular substance (polymer), and its meaning includes dimers, trimers, and oligomers in addition to monomers in the narrow sense. Polymer etc. In the present invention, the "all solid components" means all components other than the solvent contained in the photosensitive coloring composition or the ink described below. In the present invention, the "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography). In addition, in the present invention, the so-called "amine value", unless otherwise specified, means the amine value in terms of effective solid content, which is expressed by the amount of alkali per 1 g of the dispersant and the mass of equivalent KOH The value. In addition, the measurement method will be described below. On the other hand, the so-called "acid value", unless otherwise specified, means the acid value in terms of effective solid content, which is calculated by neutralization titration. In addition, in this specification, the percentage or part indicated by "mass" and the percentage or part indicated by "weight" have the same meaning. [Photosensitive coloring composition] The photosensitive coloring composition of the present invention contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) Solvents and (f) dispersants are essential components, and may further contain adhesion improvers such as silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc., if necessary Other formulation ingredients are usually used in a state of being dissolved or dispersed in a solvent. In the photosensitive coloring composition of the first aspect of the present invention, the (a) colorant contains an organic pigment and carbon black. Furthermore, in the photosensitive coloring composition of the second aspect of the present invention, (a) the colorant contains at least one selected from the group consisting of red pigments and orange pigments and selected from the group consisting of blue pigments and purple pigments At least one of the group. Furthermore, the photosensitive coloring composition of the 3rd aspect of this invention is used for forming a colored spacer. Hereinafter, unless otherwise specified, the "photosensitive coloring composition of the present invention" refers to the photosensitive coloring composition of the first aspect, the photosensitive coloring composition of the second aspect, and the photosensitive coloring composition of the third aspect. All of the sexual coloring composition. <(a) Coloring agent> The (a) coloring agent used in the photosensitive coloring composition of the present invention is not particularly limited as long as it can color the photosensitive coloring composition or the cured product obtained by curing it The limitation includes, for example, a pigment or a dye, and from the viewpoint of durability, a pigment can be preferably used. Examples of pigments include organic pigments and inorganic pigments. From the viewpoint of suppressing the decrease in the voltage retention rate of liquid crystals, and from the viewpoint of suppressing the absorption of ultraviolet rays and making it easier to control the shape or level difference, it is preferable to use organic pigments. . The (a) colorant used in the photosensitive coloring composition of the first aspect of the present invention contains an organic pigment and carbon black. Thus, by using organic pigments that absorb less ultraviolet light, the shape or level difference can be easily controlled, and the surface smoothness can be improved. Furthermore, by using carbon black in addition to organic pigments, Achieve high shading properties. The type of organic pigment is not particularly limited. From the viewpoint of adhesion, it is preferable to contain at least one organic coloring pigment selected from the group consisting of red pigments, orange pigments, blue pigments, and purple pigments. Moreover, it is preferable to contain an organic black pigment from a viewpoint of light-shielding property. The chemical structure of these pigments is not particularly limited, except for the use of azo series, phthalocyanine series, quinacridone series, benzimidazolone series, isoindolinone series, bis-㗁𠯤 series, indanthrene series In addition to organic pigments such as, perylene, etc., various inorganic pigments can also be used. Hereinafter, specific examples of pigments that can be used are illustrated by the pigment number. The terms "C.I. Pigment Red 2" listed below mean chromaticity index (C.I.). Examples of red pigments include CI 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, preferably CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, 272 can be cited, and CI Pigment Red 149 is more preferred. , 177, 179, 194, 209, 224, 254. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Red 177, 254, and 272. In the case of curing by ultraviolet light, it is preferable to use a red pigment with a lower ultraviolet absorption rate. From this viewpoint, it is more preferable to use CI Pigment Red 254 and 272. Examples of orange pigments include CI 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, C.I. Pigment Orange 38, 43, 64, 71, and 72 are preferred. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Orange 43, 64, and 72. In the case of curing by ultraviolet light, it is preferable to use the one with lower ultraviolet absorption rate as the orange pigment From this viewpoint, it is more preferable to use CI Pigment Orange 64 and 72. Examples of blue pigments include: CI 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, preferably C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and more preferably C.I. Pigment Blue 15:6. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Blue 15: 6, 16, 60. In the case of curing by ultraviolet light, it is preferable to use the one with lower ultraviolet absorption rate as As for the blue pigment, from this viewpoint, it is more preferable to use CI Pigment Blue 60. Examples of purple pigments include: CI 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 them, C.I. Pigment Violet 19, 23, and 29 are preferable, and C.I. Pigment Violet 23 is more preferable. Furthermore, in terms of dispersibility and light-shielding properties, it is preferable to use CI Pigment Violet 23 and 29. In the case of curing by ultraviolet light, it is preferable to use a purple pigment with a lower ultraviolet absorption rate. From this viewpoint, it is more preferable to use CI Pigment Violet 29. Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments. 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, 55. Among them, C.I. Pigment Green 7, 36 is preferable. Examples of yellow pigments include: CI 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, and 185 are preferably cited, and C.I. Pigment Yellow 83, 138, 139, 150, and 180 are more preferably cited. Among these, it is preferable to contain at least one or more of the following pigments from the viewpoint of light-shielding properties or control of shape and level difference. Red Pigment: CI Pigment Red 177, 254, 272 Orange Pigment: CI Pigment Orange 43, 64, 72 Blue Pigment: CI Pigment Blue 15: 6, 60 Violet Pigment: CI Pigment Violet 23, 29 Also, it is shading or shape From the viewpoint of the control of the level difference, the red pigment is preferably the following (1), the orange pigment is preferably the following (2), the blue pigment is preferably the following (3), and the purple pigment is preferably the following Of (4). (1) At least one selected from CI Pigment Red 177, 254 (2) At least one selected from CI Pigment Orange 43, 64 (3) At least one selected from CI Pigment Blue 15: 6, 60 (4) At least one selected from CI Pigment Violet 23 and 29. Furthermore, in the photosensitive coloring composition of the first aspect, when a plurality of organic pigments are combined and used, the combination is not particularly limited, as far as the visible light region is concerned. In particular, from the viewpoint of light-shielding properties in the long-wavelength region, it is preferable to use a blue pigment and/or a violet pigment. Especially since the absorbance in the absorption spectrum of carbon black gradually decreases from short wavelengths to long wavelengths, and the absorbance in the ultraviolet region is higher than that of organic pigments, it is preferable to use it in combination from the viewpoint of both light-shielding properties and plate-making properties. A blue pigment and/or a purple pigment and carbon black are more preferably used in combination with a blue pigment and a purple pigment and carbon black. On the other hand, when a small amount of carbon black is used, from the viewpoint of light-shielding properties, it is preferable to contain at least one selected from the group consisting of red pigments and orange pigments and those selected from blue pigments and purple pigments. At least one of the composition group, as the specific combination 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, etc. can be cited. Furthermore, in addition to these organic coloring pigments, black colorants can be further used. As the black colorant, inorganic black pigments such as carbon black or organic black pigments can be cited. On the other hand, organic black pigments can also be used instead of organic colored pigments. The photosensitive coloring composition of the first aspect contains carbon black as a black colorant. Therefore, by using carbon black in addition to organic pigments, high shading properties can be achieved. In the case of using carbon black, the surface smoothness tends to deteriorate in particular, and therefore, there is a tendency to improve the situation by applying the present invention. As an example of carbon black, the following carbon black can be mentioned. Manufactured 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 , OIL11B, OIL30B, OIL31B Degussa company manufacture: Printex (registered trademark, the same below) 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 Manufactured by Cabot: Monarch (registered trademark, the same hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99 , REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55 R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8 Columbian Carbon company manufacture: RAVEN (registered trademark, the same below) 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, RAVEN5750, RAVEN5000, RAVEN carbon black Can be used with resin coating. If carbon black coated with resin is used, it has the effect of improving the adhesion with the glass substrate or the volume resistance. As carbon black coated with resin, for example, carbon black described in JP 09-71733 A, etc. can be suitably used. In terms of volume resistance or dielectric constant, resin-coated carbon black can be suitably used. As carbon black to be used for coating treatment with resin, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black usually contains Na or Ca, K, Mg, Al, raw material oil or combustion oil (or gas) at the time of manufacture, reaction stop water or granulation water, and furnace materials of the reaction furnace in percentage levels. Fe etc. are used as the ash of the composition. Among them, each usually contains hundreds of ppm or more of Na or Ca. By reducing these, the penetration into transparent electrodes (ITO (Indium Tin Oxides, indium tin oxide)) or other electrodes can be suppressed, and electrical short circuits can be prevented. The tendency. As a method to reduce the content of ash containing the Na or Ca, it is possible to strictly select the content as little as possible as the feedstock oil or fuel oil (or gas) and reaction stop water and exhaust gas for carbon black production. It can be achieved by reducing the amount of alkaline substances added to adjust the structure. As another method, a method of dissolving and removing Na or Ca by washing carbon black produced in a furnace with water, hydrochloric acid, or the like. Specifically, after mixing and dispersing carbon black in water, hydrochloric acid, or hydrogen peroxide water, if a solvent that is hardly soluble in water is added, the carbon black is transferred to the solvent side, completely separated from the water, and is present in the carbon black. Most of Na or Ca is dissolved in water or acid to be removed. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be achieved by the carbon black manufacturing process of strictly selecting raw materials alone or by water or acid dissolution alone, but by combining the two methods , It is easier to make the total amount of Na and Ca 100 ppm or less. In addition, the resin-coated carbon black is preferably a so-called acid carbon black having a pH of 6 or less. Since the dispersion diameter (agglomeration diameter) in water becomes smaller, it is more suitable for being able to coat fine cells. More preferably, the average particle diameter is 40 nm or less, and the dibutyl phthalate (DBP) absorption is 140 ml/100 g or less. By setting it within the above range, there is a tendency to obtain a coating film with good light-shielding properties. The average particle size refers to the number average particle size, which refers to the equivalent circle diameter obtained by analyzing the particle image. The particle image analysis is to take several fields of view of the photo taken at tens of thousands of times by observation of the electron microscope. The image processing device measures about 2000 to 3000 particles of these photos. The method of preparing resin-coated carbon black is not particularly limited. For example, after appropriately adjusting the blending amount of carbon black and resin, the following methods are used: 1. Mix the resin with solvents such as cyclohexanone, toluene, and xylene and heat to dissolve it The resulting resin solution is mixed with a suspension containing carbon black and water. After the carbon black is separated from the water, the water is removed and heated and kneaded. The obtained composition is shaped into a sheet and crushed. The method of drying; 2. The resin solution and suspension prepared in the same manner as above are mixed and stirred, and the carbon black and resin are granulated, and then the obtained granules are separated and heated to remove the remaining Solvent and water method; 3. Dissolve carboxylic acid such as maleic acid and fumaric acid in the above-exemplified solvent, add, mix and dry carbon black, remove the solvent to obtain carboxylic acid-added carbon black , The method of adding resin to it and dry blending; 4. Mixing the reactive group-containing monomer component of the resin to be coated with water at high speed to prepare a suspension, and then cooling after polymerization to form a polymer suspension After the resin containing the reactive group is obtained, carbon black is added to it and kneaded, the carbon black is reacted with the reactive group (the carbon black is grafted), and methods such as cooling and crushing are performed. The type of resin to be coated is also not particularly limited. It is usually a synthetic resin, and the resin with a benzene ring in the structure is more effective as an amphoteric surfactant, so it is better in terms of dispersibility and dispersion stability . As specific synthetic resins, thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glycolphthalate resin, epoxy resin, and alkylbenzene resin can be used; or polystyrene Ethylene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfide, poly(p-phenylene terephthalamide), polyamide imide, Thermoplastic resins such as polyimide, polyamino bismaleimide, polyether sulfide, polyphenylene sulfide, polyarylate, polyether ether ketone, etc. The coating amount of the carbon black by the resin is preferably 1 to 30% by mass relative to the total amount of the carbon black and the resin, and by setting it to be more than the above lower limit value, the coating tends to be sufficiently advanced. On the other hand, by setting it below the above upper limit value, there is a tendency for resins to be prevented from adhering to each other and the dispersibility is good. Carbon black coated with resin in the above-mentioned manner can be used as a light-shielding material for colored spacers in accordance with a conventional method, and a color filter with the colored spacer as a constituent element can be manufactured by a conventional method. If this kind of carbon black is used, there is a tendency that a colored spacer with a high shading rate and a low surface reflectance can be achieved at a lower cost. In addition, it is also speculated that by coating the surface of carbon black with resin, it also has the effect of enclosing Ca or Na in carbon black. As a black colorant other than carbon black, it is preferable to use organic black pigments from the viewpoint of suppressing the decrease in the voltage retention rate of the liquid crystal, and from the viewpoint of suppressing the absorption of ultraviolet rays and making it easy to control the shape or the level difference. Especially from the viewpoint of light-shielding properties, it is preferable to use a compound selected from the group consisting of the compound represented by the following general formula (1), the geometric isomer of the compound, the salt of the compound, and the salt of the geometric isomer of the compound At least one organic black pigment in the group consisting of (hereinafter sometimes abbreviated as "organic black pigment represented by the above general formula (1)"). [化3]
Figure 02_image005
In formula (1), R11 And R16 Independent of each other as hydrogen atom, CH3 , CF3 , Fluorine atom or chlorine atom; R12 , R13 , R14 , R15 , R17 , R18 , R19 And R20 It is independent of all others and is hydrogen atom, halogen atom, Rtwenty one , COOH, COORtwenty one , COO- , CONH2 , CONHRtwenty one , CONRtwenty one Rtwenty two , CN, OH, ORtwenty one , COCRtwenty one , OCONH2 , OCONHRtwenty one , OCONRtwenty one Rtwenty two , NO2 , NH2 , NHRtwenty one , NRtwenty one Rtwenty two , NHCORtwenty two , NRtwenty one CORtwenty two , N=CH2 , N=CHRtwenty one , N=CRtwenty one Rtwenty two , SH, SRtwenty one , SORtwenty one , SO2 Rtwenty one , SO3 Rtwenty one , SO3 H, SO3 - , SO2 NH2 , SO2 NHRtwenty one Or SO2 NRtwenty one Rtwenty two ; And choose free R12 With R13 , R13 With R14 , R14 With R15 , R17 With R18 , R18 With R19 , And R19 With R20 At least one combination in the group can be directly bonded to each other, or use oxygen atom, sulfur atom, NH or NRtwenty one Bridge and bond to each other; Rtwenty one And Rtwenty two Independently of each other are an alkyl group with 1 to 12 carbons, a cycloalkyl group with 3 to 12 carbons, an alkenyl group with 2 to 12 carbons, a cycloalkenyl group with 3 to 12 carbons, or an alkynyl group with 2 to 12 carbons. The geometric isomers of the compound represented by the general formula (1) have the following nuclear structure (wherein the substituents in the structural formula are omitted), and the most stable is probably the trans-trans isomer. [化4]
Figure 02_image007
When the compound represented by the general formula (1) is anionic, it is preferably by any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, Transition metal, tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complex compound to compensate its charge. In addition, when the geometric isomer of the compound represented by the general formula (1) is anionic, the same salt is preferred. In the substituents of the general formula (1) and these definitions, since the shielding rate tends to increase, the following are preferred. The reason is that the following substituents are believed to have no absorption and will not affect the hue of the pigment. R12 , R14 , R15 , R17 , R19 And R20 Independent of each other, a hydrogen atom, a fluorine atom, or a chlorine atom is preferable, and a hydrogen atom is more preferable. R13 And R18 Independent of each other, preferably hydrogen atom, NO2 , OCH3 , OC2 H5 , Bromine atom, chlorine atom, CH3 , C2 H5 , N(CH3 )2 , N(CH3 )(C2 H5 ), N(C2 H5 )2 , Α-naphthyl, β-naphthyl, SO3 H or SO3 - , More preferably hydrogen atom or SO3 H. R11 And R16 Independent of each other, preferably hydrogen atom, CH3 Or CF3 , More preferably a hydrogen atom. Preferably selected from R11 With R16 , R12 With R17 , R13 With R18 , R14 With R19 , And R15 With R20 At least one combination in the group is the same, more preferably R11 With R16 Same, R12 With R17 Same, R13 With R18 Same, R14 With R19 Same, and R15 With R20 the same. Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, 2-methylbutyl, N-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2- Ethylhexyl, nonyl, decyl, undecyl or dodecyl. Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl ,drop
Figure 105142935-A0304-03-0013-01
base,
Figure 105142935-A0304-03-0013-01
Base, norcaryl, norcaryl,
Figure 105142935-001
Group, norpinyl, pinyl, 1-adamantyl or 2-adamantyl. Examples of alkenyl groups having 2 to 12 carbon atoms are vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene En-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-
Figure 105142935-001
1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl , Hexenyl, octenyl, nonenyl, decenyl or dodecenyl. Cycloalkenyl groups having 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, and 3-cyclohexene-1-yl. Base, 2,4-cyclohexadien-1-yl, 1-pair
Figure 105142935-001
En-8-yl, 4(10)-thujene-10-yl, 2-nor
Figure 105142935-A0304-03-0013-01
En-1-yl, 2,5-nor
Figure 105142935-A0304-03-0013-01
Dien-1-yl, 7,7-dimethyl-2,4-norcardien-3-yl or
Figure 105142935-A0304-03-0013-01
Alkenyl (camphenyl). Examples of alkynyl groups having 2 to 12 carbon atoms are: 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl Base, 1,4-pentadien-3-yl, 1,3-pentadien-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-pentene-4-yne -1-yl, trans-3-methyl-2-pentene-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyne -9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The organic black pigment represented by the above general formula (1) is preferably a compound represented by the following general formula (2). [化5]
Figure 02_image009
As a specific example of such an organic black pigment, the following trade name can be mentioned: Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation). The organic black pigment is preferably dispersed and used by the dispersant, solvent, and method described below. In addition, if the sulfonic acid derivative of the general formula (2) is present during dispersion, the dispersibility or storage properties may be improved. Examples of black colorants other than the organic black pigment represented by the general formula (1) include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyan black, titanium black, and perylene black. In addition to the above-mentioned pigments, dyes may also be used. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine Department of dyes and so on. As the azo dyes, for example, CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, etc. Examples of anthraquinone dyes include: CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60 and so on. In addition, examples of phthalocyanine dyes include CI Vat Blue 5, and examples of quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9, and examples of quinoline dyes include Examples include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, and the like. Examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, and the like. These pigments are preferably dispersed and used so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle size is the number of pigment particles. Furthermore, the average particle size of the pigment is a value obtained from the pigment particle size measured by Dynamic Light Scattering (DLS). The particle size measurement is performed on a fully diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring device, follow this concentration) at 25°C Measure under. (A) The colorant used in the photosensitive coloring composition of the second aspect contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and purple pigments One kind. Thus, by the photosensitive coloring composition of the second aspect of the present invention containing a combination of specific organic coloring pigments, high light-shielding properties can be achieved. As the red pigment, orange pigment, blue pigment, and purple pigment, the same ones described in the first aspect can be suitably used. The combination of colors is not particularly limited. From the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of an orange pigment and a blue pigment, a combination of an orange pigment, a blue pigment, and a purple pigment, etc. . In addition, the photosensitive coloring composition of the second aspect may also contain pigments other than red pigments, orange pigments, blue pigments, and purple pigments. From the viewpoint of light-shielding properties, it is preferable to contain a black colorant. As the black color material, the same as those described in the first aspect can be suitably used. The photosensitive coloring composition of the third aspect is a photosensitive coloring composition for forming color spacers, and the (a) colorant is not particularly limited. For example, those containing at least one of the above-mentioned organic coloring pigments, black colorants, and dyes can be cited. In addition, as the coloring agent (a), those described in the first aspect and the second aspect may also be used, and from the viewpoint of light-shielding properties, organic compounds represented by the general formula (1) may also be used. Coloring agent for black pigments. <(b) Alkali-soluble resin> The (b) alkali-soluble resin used in the present invention is a resin containing a carboxyl group or a hydroxyl group, especially containing (bI) epoxy (meth)acrylate resin and (b-II) containing side (Meth)acrylic copolymer resins in which the chain has repeating units α of ethylenically unsaturated bonds and repeating units β derived from unsaturated carboxylic acids, and (b-II) among the (meth)acrylic copolymers The content ratio of the repeating unit α is 10 mol% or more, preferably 12 mol% or more. When (bI) epoxy (meth)acrylate resin is used alone as (b) alkali-soluble resin, usually the resin has an aromatic structure in the main chain, and this structure tends to generate heat flow and cause wrinkles. Surface smoothness tends to deteriorate. The wrinkles will also reduce the shading properties, so the required shading properties cannot be obtained and problems such as light leakage are likely to occur. In addition, in many cases, colored spacers are used with a film thickness higher than that of the black matrix. In addition, in order to set the required level difference, it is preferable that the photosensitive coloring composition has a coating film characteristic that is not easily deformed by heat. However, in order to ensure compression characteristics and reliability, it is preferable to set the pigment concentration to be lower than the black matrix. As a result, in the colored spacer, the difference in crosslinking density between the vicinity of the film surface and the vicinity of the film bottom is further increased, and wrinkles are likely to occur. In addition, due to such thermal deformation, there is a tendency that sufficient step formation properties cannot be ensured. In order to take into account these various properties, it is considered that the use of acrylic resins that do not contain aromatic rings in the main chain and have less heat shrinkage, especially those containing repeating units derived from unsaturated carboxylic acids that have a high glass transition temperature and are not easy to heat flow The specific (meth)acrylic copolymer resin can reduce heat flow, suppress the generation of wrinkles, and make the surface smooth. However, when the (meth)acrylic copolymer resin with low sensitivity is used in combination, the reliability tends to deteriorate. Therefore, it is considered that a specific amount of ethylene is introduced into the (meth)acrylic copolymer resin. Sexually unsaturated bonds can fully ensure sensitivity and improve reliability. As a result, it is possible to achieve both surface smoothness and reliability. <(bI) Epoxy (meth)acrylate resin> (bI) Epoxy (meth)acrylate resin is an α in which the epoxy compound and α,β-unsaturated monocarboxylic acid and/or ester portion have a carboxyl group , β-unsaturated monocarboxylic acid ester reactant and the hydroxyl group produced by the reaction is further reacted with a compound having two or more substituents that can react with the hydroxyl group of the polybasic acid and/or its anhydride, etc. Resin. As the (bI) epoxy (meth)acrylate resin used in the present invention, from the viewpoint of reliability, the following epoxy (meth)acrylate resin (b1) and/or cyclic Oxygen (meth)acrylate resin (b2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin"). <Epoxy (meth)acrylate resin (b1)> By adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group to epoxy resin, it is combined with polybasic acid And/or an alkali-soluble resin obtained by reacting with its anhydride. <Epoxy (meth)acrylate resin (b2)> By adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group to epoxy resin, it is combined with polyol , And alkali-soluble resin obtained by reacting with polybasic acid and/or its anhydride. Here, the term "epoxy resin" also includes a raw material compound before forming 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 epihalohydrin can be used. The phenolic compound is preferably a compound having a phenolic hydroxyl group having a divalent or higher valence, and may be a monomer or a polymer. As the types of epoxy resins used as raw materials, cresol novolak type epoxy resins, phenol novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and triphenol methane can be suitably used. Type epoxy resin, biphenol novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin as the reaction product of the addition polymerization reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin , Adamantyl-containing epoxy resins, sulphur-type epoxy resins, etc., those having an aromatic ring in the main chain can be suitably used. In addition, as a specific example of the epoxy resin, a bisphenol A type epoxy resin (for example, "Epikote (registered trademark; the same hereinafter) 828", "Epikote 1001", and "Epikote 1002" manufactured by Mitsubishi Chemical Corporation can be suitably used. , "Epikote 1004", etc.), epoxy resins obtained by the reaction between the alcoholic hydroxyl group of bisphenol A epoxy resin and epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76℃)), bisphenol F resin (such as "Epikote 807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Mitsubishi Chemical Corporation), and bisphenol Epoxy resin obtained by the reaction of alcoholic hydroxyl group of F-type epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (Epoxy equivalent 350, softening point 66°C)), bisphenol S Type epoxy resin, biphenyl glycidyl ether (e.g. "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (e.g. "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154", "DEN-438" manufactured by Dow Chemical), (ortho, meta, and p) cresol novolac type epoxy resins (e.g. "EOCN( Registered trademark; the same below) -102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co.), triphenol methane Type epoxy resin (for example, "EPPN (registered trademark; the same below)-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resin (manufactured by Daicel Chemical Industry Co., Ltd.) "Celloxide 2021P", "Celloxide (registered trademark; the same below) EHPE"), an epoxy resin made by glycidylating a phenol resin obtained by the reaction of dicyclopentadiene and phenol (such as DIC "EXA-7200" manufactured by Nippon Kayaku Corporation "NC-7300"), epoxy resin represented by the following general formulas (B1) to (B4), etc. Specifically, the epoxy resin represented by the following general formula (B1) includes "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and the epoxy resin represented by the following general formula (B2) includes The "NC-3000" manufactured by Nippon Kayaku Co., Ltd., as the epoxy resin represented by the following general formula (B4), includes "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., etc. [化6]
Figure 02_image011
In the above general formula (B1), a represents an average value and represents a number from 0 to 10. R111 It represents any of 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. Furthermore, there are multiple Rs in 1 molecule111 They can be the same or different. [化7]
Figure 02_image013
In the above general formula (B2), b represents an average value and represents a number from 0 to 10. R121 It represents any of 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. Furthermore, there are multiple Rs in 1 molecule121 They can be the same or different. [化8]
Figure 02_image015
In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, the molecular structure contains more than one adamantane structure. c represents an integer of 2 or 3. [化9]
Figure 02_image017
[化10]
Figure 02_image019
In the above general formulas (B3-1) and (B3-2), R131 ~R134 And R135 ~R137 Each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group with 1 to 12 carbons which may have a substituent, or a phenyl group which may have a substituent. ﹡Indicating bonding key. [化11]
Figure 02_image021
In the above general formula (B4), p and q each independently represent an integer from 0 to 4, and R141 And R142 Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. R143 And R144 Each independently represents an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more. Among these, from the viewpoint of reliability, it is preferable to use an epoxy resin represented by any one of general formulas (B1) to (B4). Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, ortho-vinyl benzoic acid, m-vinyl benzoic acid, P-vinyl benzoic acid; (meth)acrylic acid α-position halogenated alkyl, alkoxy, halogen, nitro, cyano substituents and other monocarboxylic acids; 2-(meth)acryloyloxyethyl succinic acid , 2-(meth)acryloxyethyl adipic acid, 2-(meth)acryloxyethyl phthalic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid Dicarboxylic acid, 2-(meth)acryloxyethyl maleic acid, 2-(meth)acryloxypropyl succinic acid, 2-(meth)acryloxypropyl hexyl Diacid, 2-(meth)acryloxypropyl tetrahydrophthalic acid, 2-(meth)acryloxypropyl phthalic acid, 2-(meth)acryloxypropyl Alkyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutane Hydroxyphthalic acid, 2-(meth)acryloxybutyl phthalic acid, 2-(meth)acryloxybutyl maleic acid; as an addition to (meth)acrylic acid ε -Caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone and other lactone monomers; or hydroxyalkyl (meth)acrylate, pentaerythritol tris (methyl) ) Acrylic acid ester is added with succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride) and other acids (anhydrides); (meth)acrylic acid dimers. Among these, (meth)acrylic acid is particularly preferable in terms of sensitivity. As a method of adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group can be reacted with epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150°C . As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine can be used; tetramethylammonium chloride, tetraethyl chloride Quaternary ammonium salts such as ammonium, dodecyl trimethyl ammonium chloride, etc. Furthermore, epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having carboxyl group, and esterification catalyst may be used alone or in combination of two or more. The usage amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of epoxy resin. It is preferably in the range of 0.7 to 1.1 equivalents. By setting it to the above lower limit or more, the introduction amount of the unsaturated group can be made sufficient, and the subsequent reaction with the polybasic acid and/or its anhydride tends to be sufficient. Moreover, by setting it as the said upper limit or less, there exists a tendency to suppress that an α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. Examples of polybasic acids and/or their anhydrides include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic acid. , Trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endo-methylene tetrahydro phthalic acid, chlorosonic acid, methyl tetrahydro phthalic acid, biphenyl tetracarboxylic acid One or two or more of carboxylic acid and these anhydrides. Preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyl tetracarboxylic acid Acid, or anhydrides of these. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrous tetrahydrophthalic acid, or biphenyltetracarboxylic dianhydride. Regarding the addition reaction of polybasic acid and/or its anhydride, well-known methods can also be used. It can be used with epoxy resin α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid with carboxyl group The addition reaction of the acid ester continues under the same conditions to obtain the target compound. The addition amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the produced carboxyl-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mgKOH/g, and is more preferably The extent of the range of 20～140 mgKOH/g. By setting it as the above lower limit value or more, the alkali developability tends to become good, and by setting it as the above upper limit value or less, the curing performance tends to become better. Furthermore, during the addition reaction of the polybasic acid and/or its anhydride, polyfunctional alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol can be added to produce a multi-branched structure introduced. Carboxyl-containing epoxy (meth)acrylate resins are usually prepared by mixing polybasic acids in the reactants of epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group And/or its anhydride, or in the reactant of epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group, mixed polybasic acid and/or its anhydride and polybasic acid It is obtained by heating after functional alcohol. In this case, the mixing order of the polybasic acid and/or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride reacts to the mixture of epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group and polyfunctional alcohol Any hydroxyl group present undergoes an addition reaction. The chemical structure of the repeating unit contained in the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited. For example, the chemical structure shown below can be cited. [化12]
Figure 02_image023
[化13]
Figure 02_image025
[化14]
Figure 02_image027
[化15]
Figure 02_image029
Among them, in the above formulas (C-1) to (C-15), X represents the following structure. [化16]
Figure 02_image031
(R in the above structure X11 Represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom or a residue of a polyacid. In addition, polybasic acids may be cross-linked with each other.) As the carboxyl group-containing epoxy (meth)acrylate resin, in addition to the above, those described in Korean Patent Publication No. 10-2013-0022955 and the like can be cited. The weight average molecular weight (Mw) of epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 1000 or more, preferably 2000 or more, more preferably 3000 Above, it is more preferably 4000 or more, more preferably 5000 or more, and usually 10000 or less, preferably 8000 or less, and more preferably 7000 or less. By setting it as above the above lower limit value, reliability tends to be improved, and by setting it as below the above upper limit value, there is a tendency for solubility to become better. The acid value of the epoxy (meth)acrylate resin is not particularly limited. It is preferably 10 mg·KOH/g or more, more preferably 20 mg·KOH/g or more, and still more preferably 40 mg·KOH/g or more , And more preferably 60 mg·KOH/g or more, more preferably 80 mg·KOH/g or more, more preferably 200 mg·KOH/g or less, more preferably 150 mg·KOH/g or less, and more It is preferably 120 mg·KOH/g or less, and particularly preferably 100 mg·KOH/g or less. By setting it as above the lower limit value, there is a tendency to obtain a moderate development solubility, and by setting it as below the upper limit value, there is a tendency to suppress the occurrence of film dissolution due to excessive development. The chemical structure of epoxy (meth)acrylate resin is not particularly limited. From the viewpoint of reliability, it is preferable to contain epoxy (methyl) having a repeating unit structure represented by the following general formula (bII) Acrylate resin (hereinafter sometimes abbreviated as "(bII) epoxy (meth)acrylate resin") and/or epoxy (meth)acrylic acid having a partial structure represented by the following general formula (bI-II) Ester resin (hereinafter sometimes abbreviated as "(bI-II) epoxy (meth)acrylate resin"). [化17]
Figure 02_image033
In formula (b-I-I), R11 Represents a hydrogen atom or a methyl group, R12 Represents a divalent hydrocarbon group that may have a substituent. The benzene ring in formula (b-I-I) may be further substituted with any substituent. ﹡Indicating bonding key. [化18]
Figure 02_image035
In formula (b-I-II), R13 Each independently represents a hydrogen atom or a methyl group. R14 Represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R15 And R16 Each independently represents a divalent aliphatic group which may have a substituent. m and n each independently represent an integer of 0-2. ﹡Indicating bonding key. <(b-I-I) Epoxy (meth)acrylate resin> First, the epoxy (meth)acrylate resin having the repeating unit structure represented by the general formula (b-I-I) will be described in detail. [化19]
Figure 02_image037
In formula (b-I-I), R11 Represents a hydrogen atom or a methyl group, R12 Represents a divalent hydrocarbon group that may have a substituent. The benzene ring in formula (b-I-I) may be further substituted with any substituent. ﹡Indicating bonding key. (R12 ) In the above formula (b-I-I), R12 Represents a divalent hydrocarbon group that may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups. Examples of the divalent aliphatic group include linear, branched, and cyclic ones. Among these, from the viewpoint of development solubility, the linear one is preferable, and on the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, the cyclic one is preferable. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. Specific examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and the like. Among them, from the viewpoint of the rigidity of the skeleton, a methylene group is preferred. As the divalent branched aliphatic group, the divalent linear aliphatic group described above has methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl, tertiary butyl, etc. are used as side chain structures. The number of rings possessed by the divalent cycloaliphatic group is not particularly limited, and it is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. By setting it above the above lower limit value, it becomes a strong film and the substrate adhesion tends to become better. Moreover, by setting it below the above upper limit value, it is easy to suppress deterioration of sensitivity and film reduction during development. The tendency to improve the resolution. Specific examples of the divalent cyclic aliphatic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, and
Figure 105142935-A0304-03-0013-01
Alkyl ring, iso
Figure 105142935-A0304-03-0013-01
Alkyl ring, adamantane ring, cyclododecane ring, dicyclopentadiene and other rings are formed by removing two hydrogen atoms. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring and an adamantane ring is preferable. Examples of the substituents that the divalent aliphatic group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, isoamyl Alkyl groups with 1 to 5 carbon atoms, such as methoxy groups; alkoxy groups with 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted. Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent heteroaromatic ring group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. As the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group, it may be a single ring or a condensed ring. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and perylene ring having one free valence , Fused tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 105142935-001-2
The base of ring, terphenylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. In addition, the heteroaromatic ring in the heteroaromatic ring group may be a single ring or a condensed ring. For example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, Pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furan Pyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyridine ring, pyrimidine ring, tricyclic ring, Quinoline ring, isoquinoline ring,
Figure 105142935-A0304-12-xxxx-6
A group such as a quinoline ring, a quinoline ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, and a azulene ring. Among them, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, it is preferable to be unsubstituted from the viewpoint of development solubility and moisture absorption resistance. In addition, as a group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups, there can be mentioned one or more divalent aliphatic groups described above and one The above-mentioned divalent aromatic ring group is connected. The number of divalent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. The number of divalent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. Specific examples of the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following formulas (b-I-I-A) to (b-I-I-F). Among these, the group represented by the following formula (b-I-I-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film. [化20]
Figure 02_image039
As mentioned above, the benzene ring in formula (b-I-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 may be one or two or more. Among them, from the viewpoint of patterning characteristics, it is preferable to be unsubstituted. Furthermore, the repeating unit structure represented by the above formula (b-I-I) is preferably a repeating unit structure represented by the following formula (b-I-I-1) from the viewpoint of ease of synthesis. [化21]
Figure 02_image041
In formula (b-I-I-1), R11 And R12 It has the same meaning as in the above formula (b-I-I). RX Represents a hydrogen atom or a polyacid residue. ﹡Indicating bonding key. The benzene ring in formula (b-I-I-1) may be further substituted with any substituent. The so-called polybasic acid residue means a monovalent group formed by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. One of benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endo-methylene tetrahydrophthalic acid, chlorsaconic acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid Or two or more. Among them, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, homo Pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, biphenyltetracarboxylic acid. (b-I-I) The repeating unit structure represented by the above formula (b-I-I-1) contained in 1 molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R may be mixedX For the hydrogen atom and RX Those who are polyacid residues. In addition, the number of the repeating unit structure represented by the formula (bII) contained in 1 molecule of the (bII) epoxy (meth)acrylate resin is not particularly limited, and is preferably 1 or more, more preferably 3 or more, Moreover, it is preferably 20 or less, and more preferably 15 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and it is less likely to cause surface roughness. Moreover, by setting it below the above upper limit value, it is easy to suppress the deterioration of sensitivity and film reduction during development, thereby improving The tendency of resolving. (bII) The weight average molecular weight (Mw) of epoxy (meth)acrylate resin in terms of polystyrene as measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more Preferably it is 1500 or more, more preferably 2000 or more, still more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, more preferably 30000 or less, more preferably 20000 or less, and still more preferably 10000 Below, 8000 or less is particularly preferable. By setting it as the above-mentioned lower limit or more, the residual film rate of a photosensitive coloring composition tends to become favorable, and by setting it as below the said upper limit, there exists a tendency for resolution to become favorable. (bII) The acid value of the epoxy (meth)acrylate resin is not particularly limited. It is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and still more It is preferably 50 mgKOH/g or more, more preferably 80 mgKOH/g or more, more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 130 mgKOH/g or less, and particularly preferably Below 100 mgKOH/g. By setting it above the above lower limit value, the developing solubility is improved and the resolution tends to become better. Moreover, by setting it below the above upper limit value, the residual film rate of the photosensitive coloring composition becomes better. The tendency. Specific examples of (b-I-I) epoxy (meth)acrylate resin are listed below. Furthermore, in the example, * means a bonding key. [化22]
Figure 02_image043
[化23]
Figure 02_image045
[化24]
Figure 02_image047
[化25]
Figure 02_image049
<(b-I-II) Epoxy (meth)acrylate resin> Next, the epoxy (meth)acrylate resin which has a partial structure represented by the said general formula (b-I-II) is demonstrated in detail. [化26]
Figure 02_image051
In formula (b-I-II), R13 Each independently represents a hydrogen atom or a methyl group. R14 Represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R15 And R16 Each independently represents a divalent aliphatic group which may have a substituent. m and n each independently represent an integer of 0-2. ﹡Indicating bonding key. (R14 ) In the above general formula (b-I-II), R14 Represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. As the cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group can be cited. The number of rings possessed by the aliphatic ring group is not particularly limited. It is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and it is less likely to cause surface roughness. Moreover, by setting it below the above upper limit value, it is easy to suppress the deterioration of sensitivity and film reduction during development, thereby improving The tendency of resolving. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and it is less likely to cause surface roughness. Moreover, by setting it below the above upper limit value, it is easy to suppress the deterioration of sensitivity and film reduction during development, thereby improving The tendency of resolving. Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, and
Figure 105142935-A0304-03-0013-01
Alkyl ring, iso
Figure 105142935-A0304-03-0013-01
Alkane ring, adamantane ring, cyclododecane ring, etc. Among these, from the viewpoint of the residual film rate and resolution of the photosensitive coloring composition, an adamantane ring is preferred. On the other hand, the number of rings of the aromatic ring group is not particularly limited, and 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 Is 4 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and it is less likely to cause surface roughness. Moreover, by setting it below the above upper limit value, it is easy to suppress the deterioration of sensitivity and film reduction during development, thereby improving The tendency of resolving. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and a heteroaromatic ring 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, still more preferably 10 or more, particularly preferably 12 or more, more preferably 40 or less, and more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. By setting it as above the above lower limit value, a strong film tends to be easily obtained, and surface roughness tends not to occur easily, and by setting it below the above upper limit value, there is a tendency for patterning characteristics to become better. Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetrabenzene ring, pyrene ring, benzopyrene ring,
Figure 105142935-001-2
Ring, bis-terylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. Among them, from the viewpoint of patterning characteristics, the ring is preferable. In addition, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and combining one or more divalent aliphatic groups with A group formed by connecting more than one divalent aromatic ring group. Examples of the divalent aliphatic group include linear, branched, and cyclic ones. Among these, from the viewpoint of development solubility, the linear one is preferable, and on the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, the cyclic one is preferable. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. Specific examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and the like. Among them, from the viewpoint of the rigidity of the skeleton, a methylene group is preferred. As the divalent branched aliphatic group, the divalent linear aliphatic group described above has methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl, tertiary butyl, etc. are used as side chain structures. The number of rings of the divalent cycloaliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it above the above lower limit value, it becomes a strong film and the substrate adhesion tends to become better. Moreover, by setting it below the above upper limit value, it is easy to suppress deterioration of sensitivity and film reduction during development. The tendency to improve the resolution. Specific examples of the divalent cyclic aliphatic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, and
Figure 105142935-A0304-03-0013-01
Alkyl ring, iso
Figure 105142935-A0304-03-0013-01
Alkyl ring, adamantane ring, cyclododecane ring and other rings are formed by removing two hydrogen atoms. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable. Examples of the substituents that the divalent aliphatic group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, isoamyl Alkyl groups with 1 to 5 carbon atoms, such as methoxy groups; alkoxy groups with 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted. Moreover, as a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent heteroaromatic ring group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. As the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group, it may be a single ring or a condensed ring. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and perylene ring having one free valence , Fused tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 105142935-001-2
The base of ring, terphenylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. In addition, the heteroaromatic ring in the heteroaromatic ring group may be a single ring or a condensed ring. For example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, Pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furan Pyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyridine ring, pyrimidine ring, tricyclic ring, Quinoline ring, isoquinoline ring,
Figure 105142935-A0304-12-xxxx-6
A group such as a quinoline ring, a quinoline ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, and a azulene ring. Among them, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring is preferable, and a sulphur ring is more preferable. Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, it is preferable to be unsubstituted from the viewpoint of development solubility. In addition, as a group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups, there can be mentioned one or more divalent aliphatic groups described above and one The above-mentioned divalent aromatic ring group is connected. The number of divalent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. The number of divalent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. Specific examples of the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the above formulas (b-I-I-A) to (b-I-I-F). Among them, the group represented by the above formula (b-I-I-C) is preferred from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film. The cyclic hydrocarbon as a side chain is not particularly limited based on the bonding state of the divalent hydrocarbon group. For example, the side chain may be substituted for one hydrogen atom of an aliphatic group or an aromatic ring group. , Or including one carbon atom of an aliphatic group to form a cyclic hydrocarbon group as a side chain. (R15 , R16 ) In the above general formula (b-I-II), R15 And R16 Each independently represents a divalent aliphatic group which may have a substituent. Examples of the divalent aliphatic group include linear, branched, and cyclic ones. Among these, from the viewpoint of development solubility, the linear one is preferable, and on the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, the cyclic one is preferable. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, it is difficult to produce surface roughness, and the adhesion to the substrate tends to become good. Moreover, by setting it below the above upper limit value, it is easy to suppress the sensitivity change Poor and film reduction during development, increasing the tendency of resolution. Specific examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and the like. Among them, from the viewpoint of the rigidity of the skeleton, a methylene group is preferred. As the divalent branched aliphatic group, the divalent linear aliphatic group described above has methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The second butyl, tertiary butyl, etc. are used as side chain structures. The number of rings possessed by the divalent cycloaliphatic group is not particularly limited, and it is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. By setting it above the above lower limit value, it becomes a strong film and the substrate adhesion tends to become better. Moreover, by setting it below the above upper limit value, it is easy to suppress deterioration of sensitivity and film reduction during development. The tendency to improve the resolution. Specific examples of the divalent cyclic aliphatic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, and
Figure 105142935-A0304-03-0013-01
Alkyl ring, iso
Figure 105142935-A0304-03-0013-01
Alkyl ring, adamantane ring, cyclododecane ring, dicyclopentadiene and other rings are formed by removing two hydrogen atoms. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring and an adamantane ring is preferable. Examples of the substituents that the divalent aliphatic group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, isoamyl Alkyl groups with 1 to 5 carbon atoms, such as methoxy groups; alkoxy groups with 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted. (m, n) In the above general formula (b-I-II), m and n represent an integer of 0-2. By setting it as above the lower limit value, accurate patterning becomes good, and surface roughness tends to be less likely to occur, and by setting it as below the upper limit value, there is a tendency for developability to become better. From the viewpoint of developability, m and n are preferably 0. On the other hand, from the viewpoint of precise patterning and surface roughness, m and n are preferably 1 or more. In addition, the partial structure represented by the general formula (b-I-II) is preferably a partial structure represented by the following general formula (b-I-II-1) from the viewpoint of adhesion to the substrate. [化27]
Figure 02_image053
In formula (b-I-II-1), R13 , R15 , R16 , M and n have the same meanings as in the above formula (b-I-II). Rα Represents a cyclic hydrocarbon group that may have a monovalent substituent. p is an integer of 1 or more. The benzene ring in formula (b-I-II-1) may be further substituted with any substituent. ﹡Indicating bonding key. (Rα ) In the above general formula (b-I-II-1), Rα Represents a cyclic hydrocarbon group that may have a monovalent substituent. As the cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group can be cited. The number of rings possessed by 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, and more preferably 3 or less. By setting it as above the above lower limit value, a strong film tends to be easily obtained, and surface roughness tends not to occur easily, and by setting it below the above upper limit value, there is a tendency for patterning characteristics to become better. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. By setting it as above the above lower limit value, a strong film tends to be easily obtained, and surface roughness tends not to occur easily, and by setting it below the above upper limit value, there is a tendency for patterning characteristics to become better. Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, and
Figure 105142935-A0304-03-0013-01
Alkyl ring, iso
Figure 105142935-A0304-03-0013-01
Alkane ring, adamantane ring, cyclododecane ring, etc. Among them, an adamantane ring is preferred from the viewpoint of strong film properties. On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting it as above the above lower limit value, a strong film tends to be easily obtained, and surface roughness tends not to occur easily, and by setting it below the above upper limit value, there is a tendency for patterning characteristics to become better. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and a heteroaromatic ring group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting it as above the above lower limit value, a strong film tends to be easily obtained, and surface roughness tends not to occur easily, and by setting it below the above upper limit value, there is a tendency for patterning characteristics to become better. 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 sulphur ring. Among these, from the viewpoint of developing solubility, a sage ring is preferable. Examples of substituents that the cyclic hydrocarbon group may have include hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, pentyl, isopentyl, etc. Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy; hydroxy; nitro; cyano; carboxyl, etc. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted. p represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. By setting it as the above-mentioned lower limit or more, the film hardening degree and residual film rate tend to become favorable, and by setting it as below the said upper limit, there exists a tendency for developability to become favorable. Among them, from the viewpoint of a strong film hardening degree, R is preferredα It is a monovalent aliphatic ring group, more preferably an adamantyl group. As mentioned above, the benzene ring in formula (b-I-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 may be one or two or more. Among them, from the viewpoint of patterning characteristics, it is preferable to be unsubstituted. Specific examples of the partial structure represented by the above formula (b-I-II-1) are listed below. [化28]
Figure 02_image055
[化29]
Figure 02_image057
[化30]
Figure 02_image059
[化31]
Figure 02_image061
[化32]
Figure 02_image063
In addition, the partial structure represented by the above general formula (b-I-II) is preferably the partial structure represented by the following general formula (b-I-II-2) from the standpoint of rigidity of the skeleton and hydrophobization of the film. [化33]
Figure 02_image065
In formula (b-I-II-2), R13 , R15 , R16 , M and n have the same meanings as in the above formula (b-I-II). Rβ Represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (b-I-II-2) may be further substituted with any substituent. ﹡Indicating bonding key. (Rβ ) In the above formula (b-I-II-2), Rβ Represents a divalent cyclic hydrocarbon group which may have a substituent. As the cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group can be cited. The number of rings possessed by the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and it is less likely to cause surface roughness. Moreover, by setting it below the above upper limit value, it is easy to suppress the deterioration of sensitivity and film reduction during development, thereby improving The tendency of resolving. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less. By setting it above the above lower limit value, there is a tendency to suppress film roughness during development, and by setting it below the above upper limit value, it is easy to suppress deterioration of sensitivity and film reduction during development, thereby improving resolution tendency. Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, and
Figure 105142935-A0304-03-0013-01
Alkyl ring, iso
Figure 105142935-A0304-03-0013-01
Alkane ring, adamantane ring, cyclododecane ring, etc. Among these, from the viewpoint of storage stability, an adamantane ring is preferred. On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and the surface roughness tends to be less likely to occur. Moreover, by setting it below the above upper limit value, it is easy to suppress deterioration of sensitivity or film reduction and improve resolution The tendency. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and a heteroaromatic ring 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, still more preferably 10 or more, more preferably 40 or less, more preferably 30 or less, and more preferably It is 20 or less, particularly preferably 15 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and the surface roughness tends to be less likely to occur. Moreover, by setting it below the above upper limit value, it is easy to suppress deterioration of sensitivity or film reduction and improve resolution The tendency. 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 sulphur ring. Among these, from the viewpoint of developability, a sage ring is preferable. Examples of substituents that the cyclic hydrocarbon group may have include hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, pentyl, isopentyl, etc. Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy; hydroxy; nitro; cyano; carboxyl, etc. Among these, from the viewpoint of ease of synthesis, it is preferable to be unsubstituted. Among these, in terms of storage stability and electrical characteristics, Rβ Preferably, it is a divalent aliphatic ring group, and more preferably is a divalent adamantane ring group. On the other hand, in terms of low moisture absorption and patterning characteristics of the coating film, Rβ Preferably, it is a divalent aromatic ring group, and more preferably is a divalent fluorine ring group. As mentioned above, the benzene ring in formula (b-I-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 also not particularly limited, and may be one or two or more. In addition, two benzene rings may be connected via a substituent. In this case, the substituents include: -O-, -S-, -NH-, -CH2 -Equivalent divalent base. Among them, from the viewpoint of patterning characteristics, it is preferable to be unsubstituted. In addition, from the viewpoint of making it difficult to produce film reduction, etc., methyl substitution is preferred. Specific examples of the partial structure represented by the above formula (b-I-II-2) are listed below. Furthermore, in the example, * means a bonding key. [化34]
Figure 02_image067
[化35]
Figure 02_image069
[化36]
Figure 02_image071
[化37]
Figure 02_image073
On the other hand, the partial structure represented by the above formula (b-I-II) is preferably the partial structure represented by the following formula (b-I-II-3) from the viewpoint of the residual film rate and patterning characteristics of the coating film. [化38]
Figure 02_image075
In formula (b-I-II-3), R13 , R14 , R15 , R16 , M and n have the same meanings as in the above formula (b-I-II). RZ Represents a hydrogen atom or a polyacid residue. The so-called polybasic acid residue means a monovalent group formed by removing one OH group from a polybasic acid or its anhydride. Furthermore, one OH group can be further removed, and the R in other molecules represented by formula (b-I-II-3)Z Share, you can use RZ Connect multiple formulas (b-I-II-3). Examples of polybasic acids include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. One of benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endo-methylene tetrahydrophthalic acid, chlorsaconic acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid Or two or more. Among them, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, homo Pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, biphenyltetracarboxylic acid. (b-I-II) The partial structure represented by the above formula (b-I-II-3) contained in 1 molecule of the epoxy (meth)acrylate resin may be one type or two or more types, for example, R may be mixedZ For the hydrogen atom and RZ Those who are polyacid residues. In addition, the number of partial structures represented by the above formula (bI-II) contained in one molecule of the (bI-II) epoxy (meth)acrylate resin is not particularly limited, and is preferably 1 or more, and more preferably 3 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting it above the above lower limit value, it is easy to obtain a strong film, and the surface roughness is less likely to occur, and the electrical properties tend to become better. Moreover, by setting it below the above upper limit value, it is easy to suppress the deterioration of sensitivity or the film Decrease, the tendency to improve resolution. (bI-II) The weight average molecular weight (Mw) of epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more , More preferably 2,000 or more, more preferably 30,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less, still more preferably 7,000 or less, and particularly preferably 5,000 or less. By setting it as above the lower limit value, the patterning characteristics tend to become better, and by setting it as the value below the upper limit value, it is easy to obtain a strong film, and there is a tendency that surface roughness is less likely to occur. (bI-II) The acid value of the epoxy (meth)acrylate resin is not particularly limited, and is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and still more preferably 40 mgKOH/g or more, Still more preferably 60 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, most preferably 100 mgKOH/g or more, more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and more preferably Preferably it is 120 gKOH/g or less. By setting it as above the above lower limit value, it tends to be easier to obtain a strong film, and by setting it as below the above upper limit value, there is a tendency that the developing solubility is improved and the resolution becomes better. <(b-II) (Meth)acrylic copolymer resin containing repeating unit α with ethylenically unsaturated bond in side chain and repeating unit β derived from unsaturated carboxylic acid> (b-II) (Methyl) The acrylic copolymer resin contains a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid. It is considered that by having the repeating unit α, reliability can be ensured, and it is considered that by having the repeating unit β, the surface smoothness can be improved. The repeating unit α is not particularly limited as long as it has an ethylenically unsaturated bond in the side chain. For example, a chemical structure represented by the following general formula (I) can be mentioned. [化39]
Figure 02_image077
In the above formula (I), R1 And R2 Each independently represents a hydrogen atom or a methyl group. R3 Represents a bivalent linking base. As a divalent linking group, the alkylene group which may have a substituent, or the divalent aromatic ring group which may have a substituent is mentioned. Examples of the alkylene group include linear, branched, or cyclic alkylene groups. The carbon number is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, more preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and even more preferably 8 or less, It is particularly preferably 5 or less. The reactivity tends to be improved by setting it above the above lower limit value, and the thermal fluidity tends to decrease by setting it below the above upper limit value. Specific examples of alkylene include methylene, ethylene, propylene, butylene, isobutylene, cyclohexylene, and the like. Among them, from the viewpoint of reactivity, methylene, ethylene or propylene is preferred, and propylene is more preferred. Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent heteroaromatic ring group. The carbon number is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less. The reactivity tends to be improved by setting it above the above lower limit value, and the thermal fluidity tends to decrease by setting it below the above upper limit value. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, and pyrene ring , Benzopyrene ring,
Figure 105142935-001-2
The base of ring, terphenylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. In addition, the heteroaromatic ring group in the heteroaromatic ring group may be a single ring or a condensed ring, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole Ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furan Bifuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, pyrimidine ring, tricyclic ring, quinoline ring, iso Quinoline ring,
Figure 105142935-A0304-12-xxxx-6
A group such as a quinoline ring, a quinoline ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, and a azulene ring. Moreover, as the substituent which the alkylene group and the divalent aromatic ring group may have, a halogen atom, a phenyl group, a hydroxyl group, a carboxyl group, etc. are mentioned, Among these, a hydroxyl group is preferable from a viewpoint of reactivity. Furthermore, as the chemical structure represented by the above general formula (I), from the viewpoint of reactivity, the chemical structure represented by the following general formula (I-1) or (I-2) is preferred, and more preferably The chemical structure represented by the following general formula (I-1). [化40]
Figure 02_image079
In the above formula (I-1) and formula (I-2), R1 Represents a hydrogen atom or a methyl group. The chemical structure represented by the general formula (I-1) or (I-2) can be formed by adding an epoxy group-containing unsaturated compound to a repeating unit derived from (meth)acrylic acid. On the other hand, as the repeating unit β derived from unsaturated carboxylic acid, for example, repeating unit derived from acrylic acid, repeating unit derived from methacrylic acid, repeating unit derived from crotonic acid, and itaconic acid derived The repeating unit, the repeating unit derived from maleic acid, the repeating unit derived from fumaric acid, etc., among them, from the viewpoint of thermal fluidity, the repeating unit derived from acrylic acid or The repeating unit derived from methacrylic acid is more preferably one having a chemical structure represented by the following general formula (II). [化41]
Figure 02_image081
In the above formula (II), R3 Each independently represents a hydrogen atom or a methyl group. In addition, the (b-II) (meth)acrylic copolymer resin may further contain a repeating unit γ in addition to the above-mentioned repeating units α and β. Examples of the repeating unit γ include repeating units derived from ethylenically unsaturated compounds such as (meth)acrylates. For example, from the viewpoint of reliability and adjustment of the development time, it preferably has the following formula (IIIa) The repeating unit of the partial structure shown. [化42]
Figure 02_image083
In formula (IIIa), R1d ~R4d Each independently represents a hydrogen atom or an alkyl group with 1 to 10 carbons, R5d With R6d Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Again, R5d With R6d Can be connected to form a ring. R5d With R6d The ring formed by connection is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5-6 carbon atoms. R1d ~R4d The carbon number of the alkyl group is usually 1 or more, and usually 10 or less, preferably 8 or less, and more preferably 5 or less. By setting it as the upper limit or less mentioned above, there exists a tendency which becomes suitable development solubility. Among these, in terms of solubility, R1d ~R4d Preferably it is a hydrogen atom. R5d And R6d The carbon number of the alkyl group is usually 1 or more, and usually 10 or less, preferably 8 or less, and more preferably 5 or less. By setting it above the above lower limit value, there is a tendency to exhibit proper solubility, and by setting it below the above upper limit value, there is a tendency to maintain hydrophilicity. Among them, from the viewpoint of developing solubility, R is preferred5d And R6d Is a hydrogen atom, or R5d And R6d Link to form an aliphatic ring with 5-6 carbon atoms. In the above-mentioned formula (IIIa), those having a structure represented by the following formula (IIIb), (IIIc), or (IIId) are preferred. By introducing these partial structures, there is a tendency to increase heat resistance or strength. [化43]
Figure 02_image085
As the repeating unit having the partial structure represented by the above formula (IIIa), from the viewpoint of curability, it is preferably represented by the following formula (III). [化44]
Figure 02_image087
In formula (III), R4 Represents a hydrogen atom or a methyl group, R5 It represents the partial structure represented by the above formula (IIIa). On the other hand, as the ethylenically unsaturated compound that becomes the source of the repeating unit γ, in addition to the (meth)acrylate having the partial structure represented by the above-mentioned formula (IIIa), for example, styrene α- Alkyl, o-alkyl, m-alkyl, p-alkyl, nitro, cyano, amide, ester derivatives and other styrenes; butadiene, 2,3-dimethylbutadiene, isoprene Dienes such as ene and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid N-butyl ester, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, Hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth)acrylate Base) cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isopropyl (meth)acrylate
Figure 105142935-A0304-03-0013-01
Base ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth) ) Anthracene acrylate, anthraquinone (meth)acrylate, sunflower (meth)acrylate, salicyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, Tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, toluene (meth)acrylate, (meth)acrylic acid -1,1,1-trifluoroethyl, perfluoroethyl (meth)acrylate, perfluoron-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, (meth)acrylate Phenyl methyl ester, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) Acrylic acid-2-hydroxypropyl ester and other (meth)acrylates; (meth)acrylamide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-di Ethyl amide, N,N-dipropyl amide (meth)acrylate, N,N-diisopropyl amide (meth)acrylate, anthracenyl amide (meth)acrylate, etc. (meth) Acrylic amines; (meth)acrylic aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, ethylene Vinyl pyridine, vinyl acetate and other vinyl compounds; diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itconate and other unsaturated dicarboxylic acids Esters; N-phenylmaleimide, N-cyclohexylmaleimide, N-lauryl maleimide, N-(4-hydroxyphenyl)maleimide Monomaleimides such as enediimines; radically polymerizable compounds such as N-(meth)acrylonitrile phthalimides. Among these, in order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth)acrylate, and monomaleimide as the ethylenically unsaturated compound. (b-II) The method for producing the (meth)acrylic copolymer resin is not particularly limited, and it can be obtained by copolymerizing (meth)acrylate compounds corresponding to the repeating units α to γ, respectively. In addition, it can also be obtained by first obtaining glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and methyl (meth)acrylate. Epoxy-containing (meth)acrylates such as 3,4-epoxycyclohexyl acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and (meth)acrylic acid, (meth)acrylates, etc. It is a copolymer of ethylenically unsaturated compound and obtained by adding ethylenically unsaturated monocarboxylic acid to the epoxy group contained in the copolymer. (b-II) The content ratio of the repeating unit α in the (meth)acrylic copolymer resin is usually 10 mol% or more, preferably 12 mol% or more, more preferably 15 mol% or more, and further Preferably it is 18 mol% or more, further more preferably 20 mol% or more, particularly preferably 22 mol% or more, most preferably 25 mol% or more, and more preferably 40 mol% or less, more preferably It is 35 mol% or less, more preferably 30 mol% or less, and still more preferably 25 mol% or less. By setting it as the above-mentioned lower limit value or more, reliability tends to be easy to ensure, and by setting it as below the said upper limit value, there exists a tendency to easily ensure surface smoothness. In addition, the content ratio of the repeating unit β in the (b-II) (meth)acrylic copolymer resin is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% % Or more, preferably 50 mol% or more, more preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less. By setting it to more than the above lower limit value, it tends to be easier to ensure the development solubility, and by setting it to be less than the above upper limit value, it tends to be easier to ensure reliability. In addition, the content of the repeating unit γ in the (b-II) (meth)acrylic copolymer resin is usually 0 mol% or more, preferably 10 mol% or more, and more preferably 20 mol% or more , More preferably 30 mol% or more, more preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. By setting it as the above-mentioned lower limit value or more, adhesiveness tends to become good, and by setting it as below the said upper limit value, there exists a tendency to ensure reliability easily. (b-II) The weight average molecular weight (Mw) of (meth)acrylic copolymer resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 3000 or more, preferably 5000 or more , More preferably 10,000 or more, still more preferably 15,000 or more, and usually 50,000 or less, preferably 30,000 or less, more preferably 20,000 or less. By setting it as the above-mentioned lower limit or more, reliability tends to become good, and by setting it as below the said upper limit, there exists a tendency for developing solubility to become good. (b-II) The acid value of the (meth)acrylic copolymer resin is not particularly limited. It is preferably 100 mg·KOH/g or more, more preferably 130 mg·KOH/g or more, and more preferably 160 mg・KOH/g or more, more preferably 180 mg·KOH/g or more, more preferably 400 mg·KOH/g or less, more preferably 300 mg·KOH/g or less, and still more preferably 200 mg·KOH/ g or less. By setting it as the above lower limit value or more, it tends to be easier to ensure the development solubility, and by setting it as the above upper limit value or less, it tends to be easier to ensure reliability. In the photosensitive coloring composition of the present invention, a (b-II) (meth)acrylic system containing a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid may be contained The copolymer resin may also contain two or more types. In the case of containing two or more types, it is preferable that the content ratio of the repeating unit α in at least one type of resin is within the above-mentioned range from the viewpoint of easily obtaining the effects of the present invention. On the other hand, in the photosensitive coloring composition of another aspect, it contains two or more types of repeating units α containing ethylenically unsaturated bonds in side chains and repeating units β derived from unsaturated carboxylic acids ( In the case of b-II) (meth)acrylic copolymer resins, all repeating units of all types of (b-II) (meth)acrylic copolymer resins may be used as the basis, and the contained The content ratio of the repeating unit α is within the above range. Similarly, the content ratio of the repeating unit β may be based on all the repeating units of all types of (b-II) (meth)acrylic copolymer resins. When the repeating unit γ is included, the content ratio can be set to be based on all the repeating units of all types of (b-II) (meth)acrylic copolymer resins. <Other alkali-soluble resins> The (b) alkali-soluble resin used in the present invention contains the (bI) epoxy (meth)acrylate resin and the (b-II) (meth)acrylic copolymer resin, in addition to It may also contain other alkali-soluble resins. Other alkali-soluble resins are not limited, and may be selected from resins generally used in photosensitive coloring compositions. For example, the binder resins described in Japanese Patent Application Publication No. 2007-271727, Japanese Patent Application Publication No. 2007-316620, Japanese Patent Application Publication No. 2007-334290, and the like can be cited. Moreover, from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use acrylic resins, and it is more preferable to use those described in JP 2014-137466 A. <(c) Photopolymerization initiator> (c) The photopolymerization initiator is a component having the function of directly absorbing light, causing decomposition reaction or hydrogen abstraction reaction, and generating polymerization active free radicals. If necessary, addition agents such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added and used. As the photopolymerization initiator, for example, a metallocene compound containing a titanocene compound described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Japanese Patent Laid-Open No. 2000 -Hexaarylbiimidazole derivatives described in No. 56118; halomethylated oxadiazole derivatives, halomethyl serotriazole derivatives, N-phenyl described in Japanese Patent Laid-Open No. 10-39503 N-aryl-α-amino acids such as glycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radical activators, α-amino acids Alkyl phenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750, etc. Specifically, for example, as the titanocene derivatives, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)bisphenyl titanium, bis(cyclopentadienyl) )Bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-tetrafluorophenyl-1-yl)titanium , Bis(cyclopentadienyl)bis(2,4,6-trifluorophenyl-1-yl)titanium, bis(cyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium , Bis(cyclopentadienyl)bis(2,4-difluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene -1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium, bis(cyclopentadienyl)(2,6-difluoro-3 -(Pyrrol-1-yl)-phenyl-1-yl]titanium and the like. In addition, examples of biimidazole 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. Moreover, as the halomethylated oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloro Methyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6" -Benzofuranyl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc. Also, as halomethyl The derivatives of serotris, including: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)sstris, 2-(4-methoxynaphthyl)-4 ,6-Bis (trichloromethyl) tris, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl) tris, 2-(4-ethoxycarbonyl) Naphthyl)-4,6-bis(trichloromethyl)s-tris, etc. In addition, examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(form (Sulfuryl)phenyl)-2-𠰌olinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌linephenyl)-butanone-1, 2-benzyl 2-Dimethylamino-1-(4-𠰌linephenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5-bis(4-diethylaminobenzoic acid) Methyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzyl)coumarin, 4-(diethylamino)chalcone, etc. As the start of photopolymerization In particular, oxime ester compounds are effective in terms of sensitivity and plate-making properties. When alkali-soluble resins containing phenolic hydroxyl groups are used, they become disadvantageous in terms of sensitivity. This kind of oxime ester compound with excellent sensitivity is more useful. Because the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates free radicals in its structure, a small amount means a higher sensitivity and is resistant to heat. The reaction is relatively stable, and a high-sensitivity photosensitive coloring composition can be obtained in a small amount. Examples of the oxime ester compound include compounds represented by the following general formula (IV).
Figure 02_image089
In the above formula (IV), R21a It represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group. R21b Represents any substituent containing an aromatic ring or a heteroaromatic ring. R22a It represents an alkane group which may have a substituent, or an aryl group which may have a substituent. R21a The carbon number of the alkyl group is not particularly limited. From the viewpoint of solubility or sensitivity in the solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, More preferably, it is 10 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, and propyl. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and 4-(2-methoxy-1-methyl)ethoxy-2 -Methylphenyl, N-acetoxy-N-acetoxyamino group, etc., from the viewpoint of ease of synthesis, preferably unsubstituted. As R21a Examples of the aromatic ring group include aromatic hydrocarbon ring groups and heteroaromatic ring groups. The carbon number of the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the photosensitive coloring composition, it is preferably 5 or more. Moreover, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. Specific examples of aromatic ring groups include phenyl, naphthyl, pyridyl, furanyl, etc. Among them, from the viewpoint of developability, phenyl or naphthyl is preferred, and benzene is more preferred. base. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferred, and more preferred are carboxyl. Among these, in terms of developability, R21a It is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group. Also, as R21b , Preferably include substituted carbazolyl and substituted 9-oxysulfur 𠮿
Figure 105142935-A0304-12-0019-3
Group or diphenyl sulfide group which may be substituted. Among these, from the viewpoint of suppressing the elution of N-methylpyrrolidone (NMP), a substituted diphenyl sulfide group is preferred. Again, R22a The carbon number of the alkyl group is not particularly limited. From the viewpoint of solubility or sensitivity in the solvent, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less , More preferably 10 or less, and still more preferably 5 or less. As a specific example of an alkane group, an acetyl group, a hydroxyethyl group, a propionyl group, a butyryl group, etc. are mentioned. Examples of the substituent that the alkano group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amido group. From the viewpoint of ease of synthesis, it is preferably unsubstituted. Again, R22a The carbon number of the aryl group is not particularly limited. From the viewpoint of solubility or sensitivity in a solvent, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less , More preferably 10 or less. As a specific example of an aryl group, a benzyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like. From the viewpoint of ease of synthesis, it is preferably unsubstituted. Among these, in terms of sensitivity, R22a It is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group. Among the compounds represented by the general formula (IV), from the viewpoint of suppressing the elution of NMP, the compound represented by the following general formula (V) is preferred. [化46]
Figure 02_image091
In the above general formula (V), Rtwenty three It represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. Rtwenty four It represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. R25 It represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (V-1), and h represents an integer of 0-5. The benzene ring shown in formula (V) may further have a substituent. [化47]
Figure 02_image093
In formula (V-1), R25a Represents -O-, -S-, -OCO- or -COO-. R25b Represents an alkylene group which may have a substituent. R25b The alkylene part can be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. R25 The alkylene moiety may have branched side chains or cyclohexylene. R25c Represents a hydroxyl group or a carboxyl group. Rtwenty three The carbon number of the alkyl group is not particularly limited, but from the viewpoint of solubility in the photosensitive coloring composition, it is preferably 1 or more. Moreover, from the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 5 or less, and particularly preferably 3 or less. Specific examples of the alkyl group include a methyl group, a hexyl group, a cyclopentylmethyl group, and the like. Among these, a methyl group or a hexyl group is more preferably a methyl group from the viewpoint of developability. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, etc. From the viewpoint of alkali developability, hydroxyl groups and carboxyl groups are preferred, and more It is preferably a carboxyl group. Furthermore, from the viewpoint of ease of synthesis, it is preferably unsubstituted. As Rtwenty three Examples of the aromatic ring group include aromatic hydrocarbon ring groups and heteroaromatic ring groups. The carbon number of the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the photosensitive coloring composition, it is preferably 5 or more. Moreover, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. Specific examples of aromatic ring groups include phenyl, naphthyl, pyridyl, furanyl, etc. Among them, from the viewpoint of developability, phenyl or naphthyl is preferred, and benzene is more preferred. base. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferred, and more preferred are carboxyl. Among these, in terms of developability, Rtwenty three It is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group. Rtwenty four The carbon number of the alkyl group is not particularly limited, but from the viewpoint of sensitivity, it is preferably 1 or more. Moreover, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and the like. Among these, from the viewpoint of sensitivity, a methyl group or an ethyl group is preferable, and a methyl group is more preferable. Examples of substituents that the alkyl group may have include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, amide groups, and the like. From the viewpoint of alkali developability, hydroxyl groups and carboxyl groups are preferred, and carboxyl groups are more preferred. On the one hand, from the viewpoint of ease of synthesis, it is preferably unsubstituted. As Rtwenty four Examples of the aromatic ring group include aromatic hydrocarbon ring groups and heteroaromatic ring groups. The carbon number is preferably 30 or less, more preferably 12 or less, and usually 4 or more, preferably 6 or more. By setting it below the above upper limit value, the sensitivity tends to be high, and by setting it above the above lower limit value, it tends to be low sublimability. The aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having 1 free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group can be a single ring or a condensed ring, including: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 105142935-001-2
Ring, bis-terylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. In addition, the heteroaromatic ring group means a heteroaromatic ring having one free valence. The heteroaromatic ring of the heteroaromatic ring group may be a single ring or a condensed ring, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, 㗁Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring,
Figure 105142935-A0304-12-xxxx-6
A quinoline ring, a quinoline ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, a azulene ring, etc. Examples of the substituent that the aromatic ring group may have include an alkyl group, a halogen atom, a hydroxyl group, and a carboxyl group. Among these, in terms of sensitivity, Rtwenty four It is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group. On the other hand, from the viewpoint of platemaking property, Rtwenty four An aromatic ring group which may have a substituent is preferable, an aromatic hydrocarbon group which may have a substituent is more preferable, an unsubstituted aromatic hydrocarbon group is more preferable, and a phenyl group is especially preferable. R25 It is a hydroxyl group, a carboxyl group, or the group represented by the said general formula (V-1), Among these, the group represented by the said general formula (V-1) is preferable from a viewpoint of sensitivity and developability. In the above general formula (V-1), as described above, R25a It represents -O-, -S-, -OCO-, or -COO-. Among these, from the viewpoint of sensitivity and developability, -O- or -OCO- is preferable, and -O- is more preferable. As mentioned above, R25b Represents an alkylene group which may have a substituent. R25b The number of carbon atoms in the alkylene group is not particularly limited, but from the viewpoint of solubility in the photosensitive coloring composition, it is preferably 1 or more, more preferably 2 or more, and more preferably 20 or less, and more It is preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less. The alkylene group may be linear or branched, or may contain an aliphatic ring. Among these, from the viewpoint of solubility in the photosensitive coloring composition, a linear chain is preferred. Specific examples of the alkylene group include: methylene group, ethylene group, propylene group, etc. Among these, from the viewpoint of solubility in the photosensitive coloring composition, methylene group is more preferable . As mentioned above, R25c It is a hydroxyl group or a carboxyl group. From the viewpoint of reliability (liquid crystal contamination), R25c Preferably it is a hydroxyl group. In the above general formula (V), h represents an integer of 0-5. In particular, from the viewpoint of developability, h is preferably 1 or more, more preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, most preferably 1. On the other hand, from the viewpoint of ease of synthesis, h is preferably zero. Specific examples of the oxime ester-based compound represented by the above general formula (IV) or (V) include the following. [化48]
Figure 02_image095
The method for producing the oxime ester compound represented by the general formula (V) is not particularly limited, and it can be produced, for example, by the method described in JP 2000-080068 A. In addition, as the oxime ester compound, compounds other than the above-mentioned general formula (IV) or (V) may also be used. For example, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, and International The oxime ester derivatives described in Publication No. 2008/075564, International Publication No. 2009/131189, Japanese Patent Application Publication No. 2014-500852, etc. The photopolymerization initiator may be used alone or in combination of two or more kinds. If necessary, for the purpose of improving the sensitivity, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be formulated in the photopolymerization initiator. As a sensitizing dye, there may be mentioned: 頮 described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756
Figure 105142935-A0304-12-0019-3
Pigments; Coumarin pigments with heterocycles described in Japanese Patent Laid-open No. Hei 3-239703 and Japanese Patent Laid-Open No. 5-289335; Japanese Patent Laid-Open No. Hei 3-239703 and Japanese Patent Laid-Open No. 5-289335 The 3-ketocoumarin compound described in Japanese Patent Publication No. 6-19240; the pyrromethene pigment described in Japanese Patent Application Laid-Open No. 6-19240; and Japanese Patent Application Publication No. 47-2528 and Japanese Patent Application Publication No. 54- 155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Application Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication Sho 60-88005, Japanese Patent Laid-open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japan Dye having a dialkylaminobenzene skeleton described in Japanese Patent Laid-Open No. 5-210240 and Japanese Patent Laid-Open No. 4-288818. Among these sensitizing dyes, preferred are amine-containing sensitizing dyes, and more preferred are compounds having an amine group and a phenyl group in the same molecule. Particularly preferred ones are, for example: 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone Benzophenone compounds such as ketone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-( P-Dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole Azole, 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-diethyl) Aminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylamine) Phenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl) Pyrimidine and other compounds containing p-dialkylamino phenyl groups. Among them, the best one is 4,4'-dialkylaminobenzophenone. In addition, a sensitizing dye may be used individually by 1 type, and may use 2 or more types together. As the polymerization accelerator, for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate; aliphatic amines such as n-butylamine and N-methyldiethanolamine; The sulfhydryl compounds and so on. A polymerization accelerator may be used individually by 1 type, and may be used in combination of 2 or more types. <(d) Ethylene Unsaturated Compound> The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. Sensitivity is improved by containing (d) ethylenically unsaturated compound. The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and monoesters of carboxylic acid having one ethylenically unsaturated bond and polyvalent or monohydric alcohols, etc. . In the present invention, it is particularly desirable to use a multifunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule. The number of ethylenically unsaturated groups possessed by the multifunctional ethylenic monomer is not particularly limited, but it is usually 2 or more, preferably 4 or more, more preferably 5 or more, more preferably 8 or less, and more preferably 7 or less. By setting it above the above lower limit value, there is a tendency for high sensitivity, and by setting it below the above upper limit value, the solubility in the solvent tends to improve. Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; by aliphatic polyhydroxy compounds, aromatic Polyhydroxy compounds such as polyhydroxy compounds, unsaturated carboxylic acids and esters obtained by esterification of polycarboxylic acids, etc. Examples of esters of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and other aliphatic polyhydroxy compound acrylates, the The acrylate of the exemplified compounds is replaced by the methacrylate of methacrylate, it is similarly replaced by itconate, the crotonate is replaced by crotonate, or Maleic acid ester made of maleic acid ester, etc. Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include: hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethyl Acrylate and methacrylate of aromatic polyhydroxy compounds such as acrylate and pyrogallol triacrylate. The ester obtained by the esterification reaction of polybasic carboxylic acid and unsaturated carboxylic acid and polybasic hydroxy compound is not necessarily a single substance. If representative specific examples are cited, acrylic acid, phthalic acid, and Condensate of ethylene glycol; Condensate of acrylic acid, maleic acid, and diethylene glycol; Condensate of methacrylic acid, terephthalic acid and pentaerythritol; Condensate of acrylic acid, adipic acid, butanediol and glycerin Condensate, etc. In addition, as an example of the multifunctional ethylenic monomer used in the present invention, it is useful to combine a polyisocyanate compound with a hydroxyl-containing (meth)acrylate or a polyisocyanate compound with a polyol and a hydroxyl-containing (Meth) acrylic esters are reacted to obtain (meth) acrylic urethanes; such as epoxy acrylics which are the addition reactants of polyepoxy compounds and hydroxyl (meth) acrylates or (meth) acrylic acid Esters; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate. As said (meth)acrylic urethanes, for example, 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 Shinnakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.) ), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Corporation), etc. Among these, from the viewpoint of curability, (d) the ethylenically unsaturated compound is preferably an alkyl (meth)acrylate, and more preferably dipentaerythritol hexaacrylate. These can be used alone or in combination of two or more. <(e) Solvent> The photosensitive coloring composition of the present invention contains (e) a solvent. By containing the (e) solvent, the pigment can be dispersed in the solvent, and coating becomes easy. The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and if necessary The other materials used are dissolved or dispersed in the solvent. Among the solvents, an organic solvent is preferred from the viewpoint of dispersibility or coatability. Among the organic solvents, it is preferable to select a boiling point in the range of 100 to 300°C, and more preferably to select a boiling point in the range of 120 to 280°C from the viewpoint of coating properties. Furthermore, the so-called boiling point here means the boiling point at a pressure of 1013.25 hPa. Examples of such organic solvents include the following. 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 methyl butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene two Glycol dialkyl ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl 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, methoxy butyl acetate, 3-methoxy butyl acetate, methoxy pentyl acetate, 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, triethylene glycol monoethyl ether acetate, 3-methyl-3- Glycol alkyl ether acetates such as butyl methoxyacetate; ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, etc. Alcohol diacetates; alkyl acetates such as cyclohexyl acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl Ethers and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isopropyl ketone Ketones such as butyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentanone; ethanol, propanol, butanone Alcohol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol and other mono- or poly- Alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, Alicyclic hydrocarbons such as methylcyclohexene and bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; pentyl formate, ethyl formate, ethyl acetate, acetic acid Butyl ester, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate , Ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone and other chain or cyclic esters; 3-methoxypropionic acid, Alkoxycarboxylic acids such as 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; among acetonitrile and benzonitrile Nitriles, etc. Examples of commercially available organic solvents equivalent to the above include: mineral spirits, Varsol#2, Apco#18 solvent, Apco diluent, Socal solvent No.1 and No.2, Solvesso#150, Shell TS28 solvent, card Alcohol, Ethyl Carbitol, Butyl Carbitol, Alcerosol ("Selousu" is a registered trademark; the same below), Betaloxol, Betaloxol acetate, Alcerosol Acetate, diethylene glycol dimethyl ether (all trade names), etc. These organic solvents may be used alone or in combination of two or more kinds. In the case of forming the colored spacer by photolithography, it is preferable to select a boiling point in the range of 100 to 200°C (under the pressure of 1013.25 hPa; the following boiling points are all the same) as the organic solvent. More preferably, it has a boiling point of 120-170°C. Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred in terms of good balance of coatability, surface tension, etc., and relatively high solubility of constituent components in the composition. In addition, glycol alkyl ether acetates may be used alone, or other organic solvents may be used in combination. As the organic solvent used in combination, diol monoalkyl ethers are particularly preferred. Among them, propylene glycol monomethyl ether is particularly preferred in terms of the solubility of the constituent components in the composition. Furthermore, glycol monoalkyl ethers have high polarity. If the amount of addition is too large, the pigments tend to agglomerate, and the viscosity of the colored resin composition obtained thereafter will increase. The storage stability tends to decrease. Therefore, the second solvent The ratio of the alcohol monoalkyl ethers is preferably 5 mass% to 30 mass %, more preferably 5 mass% to 20 mass %. In addition, it is also preferable to use an organic solvent having a boiling point of 150°C or higher (hereinafter sometimes referred to as a "high boiling point solvent"). By using such a high boiling point solvent in combination, the photosensitive coloring composition becomes difficult to dry, and it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed due to rapid drying. That is, it has the effect of preventing the occurrence of impurity defects caused by precipitation and solidification of the color material at the tip of the slit nozzle. In terms of such a higher effect, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it to more than the above lower limit value, there is a tendency that, for example, the precipitation and solidification of the colorant at the tip of the slit nozzle and causing impurity defects can be suppressed, and by setting it below the above upper limit value, it is possible to suppress combination The drying speed of the material becomes slower, which suppresses the tendency of poor touch during the reduced pressure drying process or the pore marks of pre-baking. Furthermore, the high boiling point solvent with a boiling point above 150°C may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, the high boiling point solvent with a boiling point above 150°C may not be included. . As a preferable high boiling point solvent, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1 ,3-Butanediol diacetate, 1,6-hexanol diacetate, glycerol triacetate, etc. <(f) Dispersant> In the photosensitive coloring composition of the present invention, since it is important to ensure the stability of quality that the (a) colorant is finely dispersed and the dispersion state is stabilized, it contains ( f) Dispersant. As the (f) dispersant, a polymer dispersant having a functional group is preferred, and in terms of dispersion stability, a polymer dispersant having a functional group such as the following groups is preferred: carboxyl group; phosphoric acid group; sulfonate Acid groups; or groups of these salts; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; groups derived from pyridine, pyrimidine, pyrimidine and other nitrogen-containing heterocyclic rings. Among them, especially from the viewpoint that a small amount of dispersing agent can be used for dispersing pigments, it is particularly preferable to use polymer dispersants with basic functional groups such as the following groups: primary, secondary or tertiary amine groups; quaternary ammonium Base; derived from pyridine, pyrimidine, pyridine and other nitrogen-containing heterocyclic groups. In addition, as polymer dispersants, for example, urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, and those containing amine groups Dispersant for monomers and macromonomers, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan aliphatic ester Dispersant, aliphatic modified polyester dispersant, etc. As specific examples of such dispersants, the following product names can be cited: EFKA (registered trademark; manufactured by BASF Corporation), DISPERBYK (registered trademark; manufactured by BYK-Chemie Corporation), Disparlon (registered trademark; manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark; manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha 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. The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less. Among them, from the viewpoint of the dispersibility of the pigment, (f) the dispersant preferably contains a urethane-based polymer dispersant and/or an acrylic polymer dispersant having a functional group, and is particularly preferred Contains acrylic polymer dispersant. Moreover, in terms of dispersibility and storage properties, a polymer dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferred. Examples of urethane-based and acrylic-based polymer dispersants include: DISPERBYK160-166, 182 series (all are urethane-based), DISPERBYK2000, 2001, LPN21116, etc. (all are acrylic-based) (above All manufactured by BYK-Chemie). As a urethane-based polymer dispersant, if a preferable chemical structure is specifically exemplified, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, And a dispersion resin with a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound with active hydrogen and a tertiary amine group in the same molecule. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amine groups can be turned into quaternary ammonium bases. Examples of the above-mentioned polyisocyanate compounds include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5- Aromatic diisocyanates such as diisocyanate and toluidine diisocyanate; hexamethylene diisocyanate, methyl lysine diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Aliphatic diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanate-dimethylcyclohexane, etc. ; Aliphatic diisocyanates with aromatic rings such as xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate; lysine triisocyanate, 1,6,11- Undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate Cyanatophenyl) methane, tris(isocyanatophenyl) phosphorothioate and other triisocyanates; and these trimers, water adducts, and these polyol adducts. The polyisocyanate is preferably a trimer of organic diisocyanate, most preferably a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate. These can be used alone or in combination of two or more. As a method of producing isocyanate terpolymers, the following methods can be cited: using appropriate trimerization catalysts, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., Polyisocyanates undergo partial trimerization of isocyanate groups. After the trimerization is stopped by adding catalyst poison, unreacted polyisocyanates are removed by solvent extraction and thin film distillation to obtain the target isocyanurate containing Based polyisocyanate. As a compound with a number average molecular weight of 300 to 10,000 having 1 or 2 hydroxyl groups in the same molecule, examples include: polyether glycol, polyester glycol, polycarbonate diol, and polyolefin Diols, etc., as well as those formed by alkoxylation of a single terminal hydroxyl group of these compounds with a C1-C25 alkyl group, and mixtures of these two or more. Examples of polyether glycol include polyether diol, polyetherester diol, and a mixture of two or more of these. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, and polyoxytetramethylene. Base glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and mixtures of two or more of these. As the polyetherester diol (polyetherester diol), an ether group-containing diol or a mixture of other diols and dicarboxylic acid or these anhydrides can be reacted, or polyester diol (polyester diol) Glycol) is obtained by reacting with alkylene oxide, and examples thereof include poly(polyoxytetramethylene) adipate. As polyether glycol, the most preferred is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or these compounds. The single terminal hydroxyl group is alkoxylated via an alkyl group with 1-25 carbon atoms. Compounds formed by radicalization. Examples of polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid). Etc.) or such anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol) Alcohol, 1,4-butanediol, 2,3-butanediol, 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-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5 -Hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic diols; dihydroxymethyl ring Alicyclic diols such as hexane; aromatic diols such as benzenedimethanol and bishydroxyethoxybenzene; N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.) obtained by condensation polymerization, such as poly Ethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene adipate/propylene adipate, etc.; or the use of the above diols (diol ) Or polylactone diols or polylactone monools obtained by using monohydric alcohols with 1 to 25 carbon atoms as initiators, such as polycaprolactone diol, polymethylvalerolactone and two of these A mixture of the above. As polyester glycol, the most preferred is polycaprolactone diol or polycaprolactone using an alcohol with 1 to 25 carbon atoms as the initiator. Examples of polycarbonate diols include polycarbonate (1,6-hexanediol), polycarbonates (3-methyl-1,5-pentanediol), etc., and examples of polyolefin diols include polybutylene Alkylene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. These can be used alone or in combination of two or more. The number average molecular weight of a compound having 1 or 2 hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000. The compound having active hydrogen and tertiary amine group in the same molecule used in the present invention will be described. The active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group. Among them, an amino group is preferred, especially The hydrogen atom of the primary amino group. The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and 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- Propylenediamine, 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-butanediamine, N,N- Diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc. In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indole Azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing five-membered heterocycles; pyridine ring, pyridine ring, pyrimidine ring, three 𠯤 ring, quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing six-membered heterocycles. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferred. Specific examples of these compounds having an imidazole ring and an amino group include: 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl) Imidazole and so on. Furthermore, if a compound having a triazole ring and an amino group is specifically exemplified, 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-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3 -Amino-1,2,4-triazole. These can be used alone or in combination of two or more. The preferable blending ratio of the raw materials when manufacturing the urethane-based polymer dispersant is 10 to 100 parts by mass of the polyisocyanate compound, and the number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is from 10 to 10,000. 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass, 0.2-25 parts by mass, preferably 0.3-24 parts by mass of the compound having active hydrogen and tertiary amine group in the same molecule Copies. The production of the urethane-based polymer dispersant is carried out in accordance with a known method for producing polyurethane resins. As a solvent in the manufacture, usually: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone and other ketones; ethyl acetate, butyl acetate, acetoacetate Esters such as Lusu; hydrocarbons such as benzene, toluene, xylene, hexane; some alcohols such as diacetone alcohol, isopropanol, second butanol, and tertiary butanol; chlorides such as dichloromethane and chloroform; Ethers such as tetrahydrofuran and diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfide. These can be used alone or in combination of two or more. In the above production, usually a urethane reaction catalyst can be used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron acetopyruvate, iron chloride Iron-based catalysts; tertiary amine-based catalysts such as triethylamine and triethylenediamine. These can be used alone or in combination of two or more. The introduction amount of the compound having active hydrogen and tertiary amine group in the same molecule is based on the amine value after the reaction, and is preferably controlled within the range of 1-100 mgKOH/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 by titrating the basic amine group by acid neutralization and making it relative to the acid value. If the amine value is less than the above range, the dispersibility tends to decrease, and if the amine value exceeds the above range, the developability tends to decrease easily. Furthermore, in the case where the isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further destroyed by alcohol or an amine compound, the stability of the product over time becomes higher, which is preferable. 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. If the molecular weight is less than 1,000, the dispersibility and dispersion stability will tend to deteriorate, and if it exceeds 200,000, the solubility will decrease, the dispersibility will deteriorate, and the reaction control tends to become difficult. As the acrylic polymer dispersant, it is preferable to use an unsaturated group-containing monomer having a functional group (the so-called functional group is the functional group described above as the functional group contained in the polymer dispersant) and Random copolymers, graft copolymers, and block copolymers of unsaturated group-containing monomers without functional groups. These copolymers can be produced by known methods. As the unsaturated group-containing monomer having a functional group, the following can be cited as specific examples: (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)propylene Unsaturated monomers with carboxyl groups such as oxyethyl phthalic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, acrylic acid dimer; dimethylamine (meth)acrylate Unsaturated monomers with tertiary amino groups and quaternary ammonium salt groups, such as ethyl ester, diethylamino ethyl (meth)acrylate, and quaternary compounds thereof. These may be used alone or in combination of two or more. Examples of unsaturated group-containing monomers without functional groups include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, N-Butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid ring Hexyl ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, iso[艸+primary](meth)acrylate , Tricyclodecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene; N-cyclohexylbutane N-substituted maleimines such as enediimines, N-phenyl maleimines, N-benzyl maleimines; acrylonitrile, vinyl acetate and poly( Methyl meth)acrylate macromonomer, polystyrene macromonomer, poly(meth)acrylate 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone Giant monomers and other giant monomers. These may be used alone or in combination of two or more. The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer containing an A block with a functional group and a B block without a functional group. In this case, in addition to the A block containing the above In addition to the partial structure of the functional group-containing unsaturated group-containing monomer, it may also include the partial structure derived from the above-mentioned non-functional group-containing unsaturated group-containing monomer, which can be either random copolymerization or block copolymerization. One aspect is contained in the A block. In addition, the content of the partial structure containing no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. The B block contains partial structures derived from the above-mentioned unsaturated group-containing monomers without functional groups, and one B block may contain two or more partial structures derived from monomers. These can be random Any aspect of copolymerization or block copolymerization is contained in the B block. 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, a cationic living polymerization method, and a free radical living polymerization method. Among them, the polymerization active species of the anionic living polymerization method is an anion, which is represented by the following flow, for example. [化49]
Figure 02_image097
In the above process, Ar1 Is a monovalent organic base, Ar2 For and Ar1 Different monovalent organic groups, M is a metal atom, and s and t are each an integer of 1 or more. The polymerization active species of the radical living polymerization method is a free radical, which is represented by the following scheme, for example. [化50]
Figure 02_image099
In the above process, Ar1 Is a monovalent organic base, Ar2 For and Ar1 Different monovalent organic groups, j and k are integers above 1, Ra Is a hydrogen atom or a monovalent organic group, Rb For and Ra Different hydrogen atoms or monovalent organic groups. When synthesizing the acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002, or P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews can be used. et al, Macromolecules, 14, 1601(1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977(1985), 18, 1037(1986), right hand Koichi, Hatada Koichi, polymer processing , 36, 366 (1987), Higashimura Toshinobu, Sawmoto Mitsuo, Collection of Polymer Essays, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Known methods described in Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987). The acrylic polymer dispersant that can be used in the present invention can be an AB block copolymer or a BAB block copolymer. The A block/B block constituting the copolymer is preferably 1/99～80/20 It is particularly preferred that it is 5/95 to 60/40 (mass ratio). By setting it within this range, there is a tendency to ensure a balance between dispersibility and storage stability. In addition, the amount of quaternary ammonium salt groups in 1 g of AB block copolymers and BAB block copolymers that can be used in the present invention is usually preferably 0.1-10 mmol. By setting it within this range, it is possible to ensure good The tendency of dispersion. Furthermore, in such a block copolymer, it is usually the same as in the case of containing an amine group generated during the manufacturing process, and its amine value is about 1-100 mgKOH/g. From the viewpoint of dispersibility, it is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, more preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, and still more preferably 75 Below mgKOH/g. Here, the amine value of the dispersants such as the block copolymers is expressed in terms of the amount of base and the equivalent of KOH relative to the solid content of 1 g excluding the solvent in the dispersant sample, by the following method And determined. Accurately weigh 0.5 ~ 1.5 g of the dispersant sample into a 100 mL beaker, and dissolve it with 50 mL of acetic acid. Use an automatic titration device with a pH electrode, with 0.1 mol/L HClO4 The acetic acid solution neutralizes the solution. With the inflection point of the titration pH curve as the end point of the titration, the amine value is calculated by the following formula. Amine value [mgKOH/g]=(561×V)/(W×S) [Where, W represents the weighed amount of dispersant sample [g], V represents the titer at the end of the titration [mL], and S represents dispersion The solid content concentration of the agent sample [mass%]] In addition, the amine value of the block copolymer also depends on the existence and type of the acidic group that is the source of the acid value. Generally speaking, lower is better, usually The weight average molecular weight (Mw) of 10 mgKOH/g or less is preferably in the range of 1000 to 100,000. By setting it within the above range, there is a tendency to ensure good dispersibility. In the case of having a quaternary ammonium salt group as the functional group, the specific structure of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferable to have the repetition represented by the following formula (i) Unit (hereinafter sometimes referred to as "repeating unit (i)"). [化51]
Figure 02_image101
In the above formula (i), R31 ~R33 Each independently is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, R31 ~R33 Two or more of them may be bonded to each other to form a ring structure. R34 It is a hydrogen atom or a methyl group. X is the bivalent linking base, Y- It is the counter anion. R in the above formula (i)31 ~R33 The carbon number of the alkyl group which may have a substituent is not particularly limited, and is usually 1 or more, and preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Furthermore, it may be either linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group. R in the above formula (i)31 ~R33 The carbon number of the aryl group which may have a substituent is not particularly limited, and is usually 6 or more, and more preferably 16 or less, and more preferably 12 or less. Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthryl, etc. Among these, benzene is preferred. Group, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl. R in the above formula (i)31 ~R33 The carbon number of the aralkyl group which may have a substituent is not particularly limited, and it is usually 7 or more, and is preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, phenylisopropylidene, etc. Among them, phenylmethylene is preferred. Group, phenylethylene group, phenylethylene group, or phenylethylene group, more preferably phenylmethylene group or phenylethylene group. Among them, from the viewpoint of dispersibility, R is preferred31 ~R33 Each independently is an alkyl group or an aralkyl group, specifically, R is preferred31 And R33 Each independently is methyl or ethyl, and R32 Is phenylmethylene or phenylethylene, more preferably R31 And R33 Is methyl, and R32 It is phenylmethylene. Furthermore, when the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, it preferably has a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as "repeating Unit (ii)"). [化52]
Figure 02_image103
In the above formula (ii), R35 And R36 Each independently is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, R35 And R36 Can be bonded to each other to form a ring structure. R37 It is a hydrogen atom or a methyl group. Z is a divalent linking group. Also, as R in the above formula (ii)35 And R36 The alkyl group, which may have a substituent, can be preferably used as R in the above formula (i)31 ~R33 And the exemplifier. Similarly, as R in the above formula (ii)35 And R36 The aryl group, which may have a substituent, can be preferably used as R in the above formula (i)31 ~R33 And the exemplifier. Also, as R in the above formula (ii)35 And R36 The aralkyl group, which may have a substituent, can be preferably used as R in the above formula (i)31 ~R33 And the exemplifier. Among them, R is preferred35 And R36 Each is independently an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group. As R in the above formula (i)31 ~R33 And the R of the above formula (ii)35 And R36 Examples of the substituents that the alkyl group, aralkyl group, or aryl group may have include halogen atoms, alkoxy groups, benzyl groups, and hydroxyl groups. In the above formulas (i) and (ii), as the divalent linking group X and Z, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -CONH-R43 -Base, -COOR44 -Base [where R43 And R44 It is a single bond, an alkylene group with 1 to 10 carbons, or an ether group (alkoxyalkyl) with 2 to 10 carbons], etc., preferably -COO-R44 -base. Also, in the above formula (i), Y as the counter anion- , Can enumerate: Cl- , Br- , I- , ClO4 - , BF4 - , CH3 COO- , PF6 - Wait. The content ratio of the repeating unit represented by the above formula (i) is not particularly limited. From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (i) is the same as that represented by the above formula (ii) The total content ratio of the repeating unit is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and more preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more. In addition, the content ratio of the repeating unit represented by the above formula (i) in the total repeating units of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 1 mol% or more, and more It is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 50 mol% or less, more preferably 30 mol% or less, and still more preferably 20 mol% or less, especially It is 15 mol% or less. In addition, the content ratio of the repeating unit represented by the above formula (ii) in the total repeating units of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 5 mol% or more, and more Preferably it is 10 mol% or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, more preferably 60 mol% or less, more preferably 40 mol% or less, and still more preferred It is 30 mol% or less, particularly preferably 25 mol% or less. In addition, the polymer dispersing agent preferably has a repeating unit represented by the following formula (iii) (hereinafter sometimes referred to as "Repeat unit (iii)"). [化53]
Figure 02_image105
In the above formula (iii), R40 Ethylene or propylene, R41 Is an alkyl group which may have substituents, R42 It is a hydrogen atom or a methyl group. n is an integer of 1-20. R of the above formula (iii)41 The carbon number of the optionally substituted alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Furthermore, it may be either linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group. In addition, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and more preferably 10 or less from the viewpoint of compatibility and dispersibility with respect to the binder component such as a solvent. More preferably, it is 5 or less. In addition, the content ratio of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, and it is preferably 1 mol% or more, more preferably 2 mol% or more, It is more preferably 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. When it is within the above range, there is a tendency that compatibility with a binder component such as a solvent and dispersion stability can be balanced. In addition, the polymer dispersant preferably has a repeating unit represented by the following formula (iv) from the viewpoint of improving the compatibility of the dispersant with the binder components such as the solvent and improving the dispersion stability. Called "repeat unit (iv)"). [化54]
Figure 02_image107
In the above formula (iv), R38 It is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R39 It is a hydrogen atom or a methyl group. R in the above formula (iv)38 The carbon number of the alkyl group which may have a substituent is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 4 or more, and more preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, methyl, ethyl, propyl, Butyl, pentyl, or hexyl, more preferably methyl, ethyl, propyl, or butyl. Furthermore, it may be either linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group. R in the above formula (iv)38 The carbon number of the aryl group which may have a substituent is not particularly limited, and is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less. Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthryl, etc. Among these, benzene is preferred. Group, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl. R in the above formula (iv)38 The carbon number of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. Specific examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, phenylisopropylidene, etc. Among them, phenylmethylene is preferred. Group, phenylethylene group, phenylethylene group, or phenylethylene group, more preferably phenylmethylene group or phenylethylene group. Among these, in terms of solvent compatibility and dispersion stability, R38 Preferably it is an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group. As R38 Examples of the substituents that the alkyl group may have include a halogen atom and an alkoxy group. 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. Also, in R38 The chain-shaped alkyl group shown includes either linear or branched chain. In addition, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating unit of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol from the viewpoint of dispersibility % Or more, more preferably 50 mol% or more, more preferably 80 mol% or less, more preferably 70 mol% or less. The polymer dispersant may also 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 monomers such as styrene and α-methylstyrene; (meth)acrylic acid chlorides such as (meth)acrylic chloride Monomers; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Ether; N-methacryloyl 𠰌line and other monomers. From the viewpoint of further improving the dispersibility of the polymer dispersant, it is preferable to include A block having repeating unit (i) and repeating unit (ii) and B not having repeating unit (i) and repeating unit (ii) Block copolymers. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Due to the introduction of not only quaternary ammonium salt groups but also tertiary amine groups in the A block, unexpectedly there is a tendency for the dispersing ability of the dispersant to be significantly improved. In addition, the B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv). The repeating unit (i) and the repeating unit (ii) may be contained in the A block in either of random copolymerization and block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may each contain two or more in one A block. In this case, each repeating unit may be random copolymerized or block copolymerized. Contained in the A block. In addition, the A block may contain repeating units other than repeating unit (i) and repeating unit (ii). Examples of such repeating units include the above-mentioned (meth)acrylate-derived monomers Body repeating unit, etc. The content of repeating units other than repeating unit (i) and repeating unit (ii) in the A block is preferably 0-50 mol%, more preferably 0-20 mol%, and most preferably in the A block Does not contain this repeating unit. The B block may contain repeating units other than repeating units (iii) and (iv). Examples of such repeating units include repeating units derived from the following monomers: styrene, α-methylstyrene, etc. Styrenic monomers; (meth)acrylic acid chloride monomers such as (meth)acrylic acid chloride; (meth)acrylic acid amine monomers such as (meth)acrylic acid amine, N-methylol acrylamide, etc. Body; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloyl 𠰌line and other monomers. The content of repeating unit (iii) and repeating units other than repeating unit (iv) in the B block is preferably 0-50 mol%, more preferably 0-20 mol%, and most preferably in the B block Does not contain this repeating unit. In addition, in terms of improving dispersion stability, the (f) dispersant is preferably used in combination with the pigment derivatives described below. <Other components of the photosensitive coloring composition> In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, adhesion improvers such as silane coupling agents, coatability improvers, development improvers, and ultraviolet absorbers can be appropriately formulated Agents, antioxidants, surfactants, pigment derivatives, photoacid generators, crosslinking agents, polymerization accelerators, etc. (1) Adhesion improving agent In order to improve the adhesiveness to the substrate, the photosensitive coloring composition of the present invention may contain an adhesion improving agent. As the adhesion improving agent, a silane coupling agent, a phosphoric acid group-containing compound, and the like are preferred. As the type of silane coupling agent, one of epoxy-based, (meth)acrylic-based, amine-based, etc. may be used alone, or two or more may be mixed and used. As a preferable silane coupling agent, for example, (meth)acrylic acid such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. Oxyoxysilanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silanes such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane; Urea-based silanes such as 3-ureidopropyltriethoxysilane; 3-isocyanatopropyltriethoxysilane Isocyanate-based silanes, especially epoxy silane coupling agents. As the phosphoric acid group-containing compound, a (meth)acrylic acid group-containing phosphoric acid ester is preferred, and one represented by the following general formula (g1), (g2) or (g3) is preferred. [化55]
Figure 02_image109
In the above general formulas (g1), (g2) and (g3), R51 Represents a hydrogen atom or a methyl group, l and l'are integers of 1-10, and m is 1, 2 or 3. These phosphoric acid group-containing compounds may be used alone or in combination of two or more. (2) Surfactant In order to improve coating properties, a surfactant may be contained in the photosensitive coloring composition of the present invention. As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, it is preferable to use non-ionic surfactants in terms of the possibility of adversely affecting each characteristic. Among them, in terms of coatability, fluorine-based or silicon-based surfactants are effective. Surfactant. Examples of such surfactants include: TSF4460 (manufactured by GE Toshiba Silicones), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 ( Shin-Etsu Silicones), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicone), DS-401 (manufactured by Daikin), L-77 ( Nippon Unicar Corporation), FC4430 (Sumitomo 3M Corporation), etc. Furthermore, one type of surfactant may be used, or two or more types may be used in any combination and ratio. (3) Pigment derivative In order to improve the dispersibility and storage properties, the photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid. Examples of pigment derivatives include: azo series, phthalocyanine series, quinacridone series, benzimidazolone series, quinophthalone series, isoindolinone series, bis-㗁𠯤 series, anthraquinone series, anion Derivatives such as danslin series, perylene series, percyclic ketone series, diketopyrrolopyrrole series, and diacetone series, among which phthalocyanine series and quinophthalone series are preferred. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and its quaternary salt, phthaliminomethyl, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group, etc. Those bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., are preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted for one pigment skeleton. Specific examples of pigment derivatives include: phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolo The sulfonic acid derivatives of pyrrole, the sulfonic acid derivatives of dioxane, etc. These may be used alone or in combination of two or more. (4) Photoacid generators The so-called photoacid generators are compounds that can generate acid by ultraviolet rays. By the action of the acid generated during exposure, crosslinking reaction occurs due to the presence of crosslinking agents such as melamine compounds. . Among the photoacid generators, those having greater solubility in solvents, especially solvents used in the photosensitive coloring composition, are preferred. Examples include: diphenyl iodonium, xylyl iodonium, benzene P-anisyl iodonium, bis(m-nitrophenyl) iodonium, bis(p-tertiary butylphenyl) iodonium, bis(p-chlorophenyl) iodonium, bis(n-dodecyl) iodonium, p-isobutyl Diaryl iodonium such as phenyl-p-tolyl iodonium, p-isopropyl phenyl-p-tolyl iodonium, etc.; or chlorides and bromides of triaryl alumium such as triphenyl sulfonium; or fluoroborate, hexafluorophosphate, Hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc.; or organic boron complexes such as n-butyl triphenyl borate, diphenyl benzyl methyl sulfonate; or 2-methyl-4,6-bis(trichloromethyl)tris, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)tris, and other tris compounds, etc., But it is not limited to this. (5) Cross-linking agent A cross-linking agent can be further added to the photosensitive coloring composition of the present invention. For example, a melamine or guanamine-based compound can be used. Examples of such crosslinking agents include melamine or guanamine-based compounds represented by the following general formula (6). [化56]
Figure 02_image111
In formula (6), R61 Represents -NR66 R67 Group or aryl group with 6 to 12 carbons, in R61 For-NR66 R67 In the basic situation, R62 , R63 , R64 , R65 , R66 And R67 One means -CH2 OR68 Base, and in R61 In the case of an aryl group with 6 to 12 carbons, R62 , R63 , R64 And R65 One means -CH2 OR68 Base, R62 , R63 , R64 , R65 , R66 And R67 The remainder of each independently represents hydrogen or -CH2 OR68 Base, here, R68 Represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Here, the aryl group with 6 to 12 carbons is typically phenyl, 1-naphthyl or 2-naphthyl, and these phenyl or naphthyl groups may be bonded with alkyl, alkoxy, or halogen atoms And other substituents. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. R68 The alkyl group represented is preferably the above-mentioned methyl or ethyl group, and particularly preferably a methyl group. The melamine compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1) contains hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, and hexamethoxymethyl melamine , Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc. [化57]
Figure 02_image113
In formula (6-1), in R62 , R63 , R64 , R65 , R66 And R67 When one is aryl, R62 , R63 , R64 And R65 One means -CH2 OR68 Base, R62 , R63 , R64 , R65 , R66 And R67 The remainder of each independently represents a hydrogen atom or -CH2 OR68 Base, here, R68 Represents a hydrogen atom or an alkyl group. Moreover, it corresponds to the guanamine compound of the general formula (6), that is, R in the general formula (6)61 The aryl compounds include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine and the like. Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are listed below. 2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl) ) Perhydro-1,3,5-tris-2-one (commonly known as N-ethyl dimethylol tris ketone) or its dimethyl ether body, dimethylol trimethylene urea or its dimethyl Ether body, 3,5-bis(hydroxymethyl)perhydro-1,3,5-㗁di𠯤-4-one (commonly known as dimethyloluron) or its dimethyl ether body, tetramethylolglyoxane Base urea or its tetramethyl ether body. Moreover, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more types. The amount when the crosslinking agent is used is preferably from 0.1 to 15% by mass, and particularly preferably from 0.5 to 10% by mass relative to the total solid content of the photosensitive coloring composition. (6) Mercapto compound As a polymerization accelerator, a mercapto compound may be added in order to improve the adhesion to the substrate. The types of mercapto compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexamethylene dithiol, decane dithiol, 1,4-dimethylthiobenzene , Butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithioglycolate Ester, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithioglycolate Propionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutanoyloxy)butane, trimethylol Propane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanedi Alcohol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3, 5-Tris-2,4,6(1H,3H,5H)-triketone and other heterocyclic mercapto compounds or aliphatic polyfunctional mercapto compounds, etc. One of these may be used alone, or two or more of them may be mixed and used. <The amount of component blending in the photosensitive coloring composition> In the photosensitive coloring composition of the present invention, the content ratio of (a) colorant relative to the total amount of solid components in the photosensitive coloring composition is usually 10 mass % Or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, particularly preferably 40% by mass or more, and generally preferably 60% by mass or less, more preferably It is 50% by mass or less, more preferably 48% by mass or less, and particularly preferably 46% by mass or less. By setting the content ratio of (a) colorant to above the above lower limit, there is a tendency to obtain a sufficient optical density (OD), and by setting it below the above upper limit, it is easy to obtain The tendency of sufficient plate-making characteristics. In addition, when (a) the colorant contains an organic pigment, the content ratio of the organic pigment to the (a) colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass Above, more preferably 30% by mass or more, more preferably 50% by mass or more, most preferably 70% by mass or more, and usually 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass Hereinafter, it is more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less. By setting it above the above lower limit value, a sufficient optical density (OD) tends to be obtained, and by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics. Moreover, when the (a) colorant contains an organic color pigment, the content ratio of the organic color pigment to the (a) colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10 Mass% or more, more preferably 30 mass% or more, particularly preferably 50 mass% or more, most preferably 70 mass% or more, and usually 100 mass% or less, preferably 99 mass% or less, more preferably 95 mass% or less % By mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less. By setting it above the above lower limit value, a sufficient optical density (OD) tends to be obtained, and by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics. In addition, when (a) the colorant contains at least one pigment selected from the group consisting of red pigments and orange pigments, at least one pigment selected from the group consisting of red pigments and orange pigments is relative to (a) The content of the coloring agent is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, more preferably 30% by mass or less, more preferably 20% by mass or less, and more It is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 7% by mass or less, and most preferably 5% by mass or less. By setting it above the above lower limit value, a sufficient optical density (OD) tends to be obtained, and by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics. Moreover, when (a) the colorant contains at least one pigment selected from the group consisting of blue pigments and purple pigments, at least one pigment selected from the group consisting of blue pigments and purple pigments is relative to ( a) The content of the colorant is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, particularly preferably 60% by mass or more, most preferably It is preferably 65% by mass or more, more preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. By setting it above the above lower limit value, there is a tendency to ensure light-shielding properties, and by setting it below the above upper limit value, there is a tendency to ensure plate making characteristics. When (a) the colorant contains a black colorant, the content of the black colorant relative to the (a) colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass Above, it is particularly preferably 20% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and still more preferably 30% by mass or less. By setting it above the above lower limit value, a sufficient optical density (OD) tends to be obtained, and by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics. Furthermore, when the (a) colorant contains an organic black pigment, the content ratio of the black organic pigment to the (a) colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10 Mass% or more, particularly preferably 20% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less. By setting it above the above lower limit value, a sufficient optical density (OD) tends to be obtained, and by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics. When (a) the coloring agent contains carbon black, the content ratio of the carbon black to the (a) coloring agent is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, It is particularly preferably 20% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and particularly preferably 30% by mass or less. By setting it above the above lower limit value, a sufficient optical density (OD) tends to be obtained, and by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics. (b) The content ratio of the alkali-soluble resin relative to the total solid content of the photosensitive coloring composition of the present invention is usually 5 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more, and more preferably It is 25% by mass or more, and usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less, especially It is 40% by mass or less. By setting the content ratio of (b) alkali-soluble resin to the above lower limit or more, it is possible to suppress the decrease in the solubility of the unexposed part with respect to the developing solution, thereby suppressing poor development. In addition, by setting it below the above upper limit value, the penetration of the developer into the exposed portion may be suppressed from increasing, and the sharpness or adhesion of the pixels tends to be suppressed from decreasing. (bI) The content of the epoxy (meth)acrylate resin is usually 3% by mass or more, preferably 6% by mass or more, and more preferably 8% relative to the total solid content of the photosensitive coloring composition of the present invention. Mass% or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. By setting it as above the lower limit value, reliability tends to be ensured, and by setting it as below the upper limit value, there is a tendency for surface smoothness to be ensured. (b) The content of (bI) epoxy (meth)acrylate resin contained in the alkali-soluble resin is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, and more It is preferably 30% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more It is preferably 50% by mass or less, and particularly preferably 40% by mass or less. By setting it as above the lower limit value, reliability tends to be ensured, and by setting it as below the upper limit value, there is a tendency for surface smoothness to be ensured. (b-II) The content ratio of the (meth)acrylic copolymer resin relative to the total solid components of the photosensitive coloring composition of the present invention is usually 1% by mass or more, preferably 3% by mass or more, more preferably It is 6% by mass or more, more preferably 8% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. By setting it as above the lower limit value, there is a tendency that surface smoothness can be ensured, and by setting it as below the upper limit value, there is a tendency that reliability can be ensured. (b) The content of (b-II) (meth)acrylic copolymer resin contained in the alkali-soluble resin is usually 10% by mass or more, preferably 20% by mass or more, and more preferably 25% by mass or more, It is more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less, It is particularly preferably 40% by mass or less. By setting it as above the lower limit value, there is a tendency that surface smoothness can be ensured, and by setting it as below the upper limit value, there is a tendency that reliability can be ensured. (c) The content of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more relative to the total solid components of the photosensitive coloring composition of the present invention. It is more preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 4% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less, More preferably, it is 7 mass% or less. By setting the content ratio of (c) photopolymerization initiator to the above lower limit or more, there is a tendency to suppress the decrease in sensitivity, and by setting it below the above upper limit, it is possible to suppress the unexposed portion relative to the developer The solubility is reduced, and the tendency of poor development is suppressed. When (c) the photopolymerization initiator and the polymerization accelerator are used together, the content of the polymerization accelerator is preferably 0.05% by mass or more relative to the total solid components of the photosensitive coloring composition of the present invention , And usually 10% by mass or less, preferably 5% by mass or less, and the polymerization accelerator is preferably 0.1-50 parts by mass, especially 0.1-20 parts by mass relative to 100 parts by mass of the (c) photopolymerization initiator. Use in proportion to mass parts. By setting the content ratio of the polymerization accelerator to more than the above lower limit, there is a tendency that the sensitivity to exposure light can be suppressed, and by setting the content below the above upper limit, it is possible to suppress the unexposed part relative to the developer. The solubility is reduced, and the tendency of poor development is suppressed. In addition, the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is generally 20% by mass or less in the total solid components in the photosensitive coloring composition from the viewpoint of sensitivity. It is 15% by mass or less, and more preferably 10% by mass or less. (d) The content of the ethylenically unsaturated compound is generally 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less relative to the total solid content of the photosensitive coloring composition of the present invention. By setting the content ratio of the (d) ethylenically unsaturated compound to the above upper limit or less, there is a tendency that the permeability of the developer to the exposed portion is suppressed from increasing, and a good image tends to be easily obtained. In addition, the lower limit of the content of (d) ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more. Furthermore, the photosensitive coloring composition of the present invention uses the solvent (e), so that the solid content concentration thereof is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, Furthermore, it is more preferable to adjust the liquid by 20 mass% or more, and 50 mass% or less normally, Preferably it is 30 mass% or less. (f) The content ratio of the dispersant in the solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less, It is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. In addition, the content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass Below, 30 parts by mass or less are particularly preferable. By setting the content ratio of the dispersant (f) above the above lower limit, it tends to be easy to obtain sufficient dispersibility. By setting it below the above upper limit, it is possible to suppress the relative decrease in the ratio of other components. The tendency of the situation that leads to a decrease in sensitivity and plate making performance. In the case of using an adhesion improving agent, its content relative to the total solid components in the photosensitive coloring composition is usually 0.1 to 5 mass%, preferably 0.2 to 3 mass%, and more preferably 0.4 to 2 quality%. By setting the content ratio of the adhesion improver to more than the above lower limit, there is a tendency that the effect of improving the adhesion can be sufficiently obtained. By setting it below the above upper limit, it is possible to suppress the decrease in sensitivity and residual residue after development. The tendency to become a defect. In addition, when a surfactant is used, its content relative to the total solid components in the photosensitive coloring composition is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.01 ~0.5% by mass, most preferably 0.03~0.3% by mass. By setting the content of the surfactant to be more than the above lower limit, the smoothness and uniformity of the coating film tends to be easily expressed. By setting it below the above upper limit, the coating film tends to be easily expressed Smoothness and uniformity can also suppress the tendency of other characteristics to deteriorate. <Physical properties of photosensitive coloring composition> The photosensitive coloring composition of the present invention can be suitably used to form a colored spacer, and from the viewpoint of use as a colored spacer, it is preferably black. In addition, the optical density (OD) per 1 μm film thickness of the coating film formed by curing the photosensitive coloring composition is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.5 or more, particularly preferably 1.8 or more , And generally 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less. <The manufacturing method of the photosensitive coloring composition> The photosensitive coloring composition of this invention (it may be called "resist" below) can be manufactured in accordance with a conventional method. It is generally preferable to use a paint conditioner, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, etc. to disperse the (a) colorant in advance. Since the (a) colorant is atomized by the dispersion treatment, the coating characteristics of the resist are improved. The dispersion treatment is usually preferably performed by a system that uses (a) a colorant, (e) a solvent, and (f) a dispersant, and (b) part or all of an alkali-soluble resin (hereinafter sometimes used for dispersion treatment) The mixture and the composition obtained by this treatment are called "ink" or "pigment dispersion"). In particular, if a polymer dispersant is used as the (f) dispersant, it is possible to suppress the increase in viscosity of the obtained ink and resist over time (excellent in dispersion stability), which is preferable. As described above, in the step of producing a resist, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. The (a) colorant, (e) organic solvent, and (f) dispersant that can be used as the pigment dispersion liquid can preferably be those described as the user of the photosensitive coloring composition. Furthermore, when the liquid containing all the components blended in the photosensitive coloring composition is subjected to dispersion treatment, since heat is generated during the dispersion treatment, there is a possibility of modification of highly reactive components. Therefore, it is preferable to perform the dispersion treatment by a system containing a polymer dispersant. When the (a) colorant is dispersed by a sand mill, it is preferable to use glass beads or zirconia beads with a particle size of about 0.1-8 mm. The dispersion treatment conditions are as follows: the temperature is usually 0°C to 100°C, preferably in the range of room temperature to 80°C. The appropriate time varies depending on the composition of the liquid and the size of the dispersion processing device, so it is adjusted appropriately. The dispersion standard is to control the gloss of the ink so that the 20-degree specular gloss of the resist (JIS Z8741) is in the range of 50 to 300. When the gloss of the resist is low, the dispersion treatment is often insufficient, and coarse pigment (colorant) particles remain, and the developability, adhesion, resolution, etc. may become insufficient Sex. In addition, if the dispersion treatment is performed until the gloss value exceeds the above-mentioned range, a large number of ultrafine particles are generated due to the crushing of the pigment, and therefore the dispersion stability tends to be impaired. In addition, the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, which can be measured by a dynamic light scattering method or the like. Then, the ink obtained by the aforementioned dispersion treatment and the aforementioned other components contained in the resist are mixed to form a uniform solution. In the resist manufacturing step, since fine dirt is often mixed into the liquid, it is preferable to filter the obtained resist with a filter or the like. [Cured product] A cured product can be obtained by curing the photosensitive coloring composition of the present invention. The cured product obtained by curing the photosensitive coloring composition can be suitably used as a coloring spacer. [Colored Spacer] Next, it will be described in accordance with the manufacturing method of the colored spacer using the photosensitive coloring composition of the present invention. (1) Support As the support used to form the colored spacer, the material is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used. Examples of materials include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polycarbonate Thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, etc., or various glasses. Among them, from the viewpoint of heat resistance, glass and heat-resistant resin are preferred. In addition, there are also cases where transparent electrodes such as ITO and IZO (Indium Zinc Oxide) are deposited on the surface of the substrate. In addition to a transparent substrate, it can also be formed on a TFT array. In order to improve the surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agent or urethane resin, etc., if necessary. The thickness of the transparent substrate is usually set in the range of 0.05-10 mm, preferably in the range of 0.1-7 mm. In addition, in the case of performing thin film formation processing of various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably in the range of 0.05 to 5 μm. (2) Coloring spacer The photosensitive coloring composition of the present invention is used for the same purposes as the known photosensitive coloring composition for color filters. Hereinafter, according to the black light spacing using the photosensitive coloring composition of the present invention A specific example of the method of forming the member will be described when it is used as a colored spacer (black light spacer). Generally, the photosensitive coloring composition is supplied on the substrate on which the black photo spacer is to be provided in a film or pattern by a method such as coating, and the solvent is dried. Secondly, pattern formation is performed by methods such as exposure-development photolithography. After that, additional exposure or thermal curing treatment is performed as needed, thereby forming a black photo spacer on the substrate. (3) Formation of colored spacers [1] Supply method to substrate The photosensitive coloring composition of the present invention is usually supplied on the substrate in a state of being dissolved or dispersed in a solvent. The supply method can be performed by a conventionally known method, such as spin coating, wire bar coating, flow coating, die coating, roll coating, spray coating, and the like. In addition, it may be supplied in a pattern by an inkjet method, a printing method, or the like. Among them, if the die coating method is used, the amount of coating liquid used can be greatly reduced, and it will not be affected by the fog attached when using the spin coating method, and it is preferable from a comprehensive viewpoint that the generation of impurities can be suppressed. . The coating amount varies depending on the application. For example, in the case of a black photo spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably in the range of 1 μm to 9 μm, and particularly preferably in the range of 1 μm to 1 μm. Range of 7 μm. In addition, it is important that the thickness of the dried film or the height of the finally formed spacer is uniform across the entire substrate. When the deviation is large, uneven defects will occur on the liquid crystal panel. However, when the photosensitive coloring composition of the present invention is formed into black photo spacers with different heights at one time by photolithography, the heights of the black photo spacers finally formed are different. Furthermore, a well-known substrate such as a glass substrate can be used as the substrate. In addition, the surface of the substrate is preferably flat. [2] Drying method Drying after supplying the photosensitive coloring composition solution on the substrate is preferably a drying method using a hot plate, IR (infrared) oven, or convection oven. In addition, it is also possible to combine a reduced-pressure drying method of drying in a reduced-pressure chamber without increasing the temperature. The drying conditions can be appropriately selected according to the type of solvent components, the performance of the dryer used, etc. The drying time depends on the type of solvent, the performance of the dryer used, etc. It can usually be selected within the range of 15 seconds to 5 minutes at a temperature of 40℃～130℃, preferably at a temperature of 50℃～110℃ Choose from 30 seconds to 3 minutes. [3] Exposure method Exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet or visible light through the mask pattern. When an exposure mask is used for exposure, the exposure mask can be approached to the coating film of the photosensitive coloring composition, or the exposure mask can be arranged at a position away from the coating film of the photosensitive coloring composition. And the method of projecting the exposed light through the exposure mask. In addition, a scanning exposure method by laser light without using a mask pattern can also be used. At this time, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, it may be carried out in a deoxidizing environment as necessary, or exposure may be carried out after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer. As a preferred aspect of the present invention, when forming black light spacers with different heights at the same time by photolithography, for example, using a light-shielding portion (transmittance 0%) and a plurality of openings as opposed to The exposure mask for the opening with the highest average light transmittance (completely through the opening) and the opening with the lower average light transmittance (the middle through opening). With this method, the difference in the residual film rate is generated by the difference in the average light transmittance between the middle through opening and the complete through opening, that is, the difference in exposure. For example, a method of making a light-shielding pattern in a matrix with a light-shielding unit having a minute polygonal shape is known. In addition, as an absorber, a method of controlling the light transmittance by a film made of a chromium-based, molybdenum-based, tungsten-based, silicon-based, or other material is known. The light source used for the above exposure is not particularly limited. Examples of light sources include light sources such as xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps, or argon ion Lasers, YAG (Yttrium Aluminum Garnet, Yttrium Aluminum Garnet) lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, near-infrared semiconductor lasers and other laser light sources, etc. . When irradiating light of a specific wavelength for use, an optical filter can also be used. As an optical filter, for example, the light transmittance in the exposure wavelength can be controlled by a thin film. As the material in this case, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, Fluoride, etc.), MoSi, Si, W, Al, etc. As the amount of exposure, usually 1 mJ/cm2 Above, preferably 5 mJ/cm2 Above, more preferably 10 mJ/cm2 Above, and usually 300 mJ/cm2 Below, preferably 200 mJ/cm2 Below, more preferably 150 mJ/cm2 the following. Moreover, in the case of the proximity exposure mode, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm Below, it is more preferably 300 μm or less. [4] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution may further contain surfactants, organic solvents, buffers, complexing agents, dyes or pigments. Examples of basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic alkaline compounds; or mono, di or triethanolamine, mono, di or trimethylamine, mono, di or tri Ethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline and other organic Basic compound. These basic compounds may be a mixture of two or more kinds. As the above-mentioned surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl Non-ionic surfactants such as esters; anionic such as alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates, etc. Surfactant; amphoteric surfactants such as alkyl betaines and amino acids. Examples of the organic solvent include isopropanol, benzyl alcohol, ethyl siloxol, butyl siloxol, phenyl siloxol, propylene glycol, and diacetone alcohol. The organic solvent can be used alone or in combination with the aqueous solution. The conditions of the development treatment are not particularly limited. Usually, the development temperature can be in the range of 10-50°C, preferably 15-45°C, and particularly preferably 20-40°C, by immersion developing method, spray developing method, Any development methods such as brush development method and ultrasonic development method are performed. [5] Additional exposure and thermal hardening treatment Optionally, the developed substrate may be additionally exposed by the same method as the above-mentioned exposure method, and thermal hardening treatment may also be performed. Regarding the thermal hardening treatment conditions at this time, the temperature can be selected in the range of 100°C to 280°C, preferably 150°C to 250°C, and the time can be selected in the range of 5 minutes to 60 minutes. The size or shape of the colored spacer of the present invention is appropriately adjusted according to the specifications of the color filter to which it is applied. The photosensitive coloring composition of the present invention is particularly useful for forming spacers and auxiliary components simultaneously by photolithography. Black optical spacers with different spacer heights are useful. In this case, the height of the spacer is usually about 2-7 μm, and the auxiliary spacer usually has a height about 0.2-1.5 μm lower than the spacer. In addition, the optical density (OD) per 1 μm of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, still more preferably 1.8 or more, and usually 4.0 or less from the viewpoint of light-shielding. , Preferably 3.0 or less. Here, the optical density (OD) is the value measured by the method described below. [Color filter] The color filter of the present invention is provided with the color spacer of the present invention as described above, for example, a black matrix and red, green, and blue pixel colored layers are laminated on a glass substrate as a transparent substrate, and The surface coating is manufactured by forming an alignment film after forming colored spacers. The color filter with the colored spacer of the present invention and the liquid crystal drive side substrate can be bonded to form a liquid crystal cell, and liquid crystal can be injected into the formed liquid crystal cell, thereby manufacturing a liquid crystal with the colored spacer of the present invention Image display devices such as display devices. [Examples] Next, examples and comparative examples are given to explain the present invention more specifically, but the present invention is not limited to the following examples as long as it does not exceed the gist. The constituent components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows. <Organic black pigment> Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (has a chemical structure represented by the following formula (2)) [Chemical 58]
Figure 02_image115
<Alkali-soluble resin-A> While replacing 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, the mixture was stirred and heated to 120°C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and the mixture was dropped after 3 hours 8.47 parts by mass of 2,2'-azobis-2-methylbutyronitrile, and further stirring at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were put into 43.2 parts by mass of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 100°C for 3.5 hours. The weight average molecular weight Mw measured by GPC of the alkali-soluble resin-A thus obtained is about 8,400, and the acid value is 80 mgKOH/g. <Alkali-soluble resin-B> While replacing the mixed solution of 217.6 parts by mass of propylene glycol monomethyl ether acetate and 53.9 parts by mass of propylene glycol monomethyl ether with nitrogen, the mixture was stirred and the temperature was raised to 120°C. Over 3 hours, 3.52 parts by mass of benzyl methacrylate, 58.5 parts by mass of methacrylic acid, and 66.1 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2' -A mixture of 3.8 parts by mass of azobis-2-methylbutyronitrile, and further stirring at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 27.3 parts by mass of glycidyl methacrylate, 0.6 parts by mass of tris(dimethylaminomethyl)phenol, and 0.1 parts by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hour. The weight average molecular weight Mw of the alkali-soluble resin-B thus obtained was 16,500 and the acid value was 176 mgKOH/g. <Alkali-soluble resin-C> While replacing the mixed solution of 303.5 parts by mass of propylene glycol monomethyl ether acetate and 75.9 parts by mass of propylene glycol monomethyl ether with nitrogen, the mixture was stirred and heated to 120°C. Over 3 hours, 10.4 parts by mass of styrene, 34.4 parts by mass of methacrylic acid, 66.1 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) and 2,2'-azo The mixed solution of 8.7 parts by mass of bis-2-methylbutyronitrile was further stirred at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air, 9.9 parts by mass of glycidyl methacrylate, 0.2 parts by mass of tris(dimethylaminomethyl)phenol, and 0.04 parts by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hour. The weight average molecular weight Mw of the alkali-soluble resin-C thus obtained was 7200, and the acid value was 86 mgKOH/g. <Alkali-soluble resin-D> "ZCR-1642H" manufactured by Nippon Kayaku Corporation (Mw=6500, acid value=98 mgKOH/g) <Alkali-soluble resin-E> [Chem 59]
Figure 02_image117
The epoxy compound of the above structure (epoxy equivalent 264) 50 g, acrylic acid 13.65 g, methoxy butyl acetate 60.5 g, triphenyl phosphine 0.936 g, and p-methoxyphenol 0.032 g are loaded into the thermometer. , In a flask with a stirrer and a cooling tube, while stirring, react at 90°C until the acid value becomes less than 5 mgKOH/g. The reaction required 12 hours to obtain an epoxy acrylate solution. 25 parts by mass of the epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) Put it into a flask equipped with a thermometer, a stirrer, and a cooling tube, and while stirring it, slowly raise the temperature to 105°C for reaction. When the resin solution becomes transparent, it is diluted with butyl methoxyacetate and prepared so that the solid content becomes 50% by mass to obtain an acid value of 113 mgKOH/g, measured by GPC in terms of polystyrene The weight average molecular weight (Mw) of 2600, double bond equivalent of 520 g/mol of carboxyl-containing epoxy methacrylate resin (alkali-soluble resin-E). <Alkali-soluble resin-F> While replacing the mixture of 214.5 parts by mass of propylene glycol monomethyl ether acetate and 53.6 parts by mass of propylene glycol monomethyl ether with nitrogen, the mixture was stirred and the temperature was raised to 120°C. Over 3 hours, 68.7 parts by mass of benzyl methacrylate, 43.9 parts by mass of methacrylic acid, and 22.0 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) with a tricyclodecane skeleton were added dropwise and 2,2' -A mixture of 1.4 parts by mass of azobis-2-methylbutyronitrile, and further stirring at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air, 21.3 parts by mass of glycidyl methacrylate, 0.5 parts by mass of tris(dimethylaminomethyl)phenol, and 0.1 parts by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hour. The weight average molecular weight Mw of the alkali-soluble resin-F thus obtained was 44,100 and the acid value was 130 mgKOH/g. <Alkali-soluble resin-G> While replacing a mixture of 210.1 parts by mass of propylene glycol monomethyl ether acetate and 52.5 parts by mass of propylene glycol monomethyl ether with nitrogen, the mixture was stirred and heated to 120°C. Over 3 hours, 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, 39.7 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) and 2,2' -A mixture of 3.3 parts by mass of azobis-2-methylbutyronitrile, and further stirring at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 38.4 parts by mass of glycidyl methacrylate, 0.8 parts by mass of tris(dimethylaminomethyl)phenol, and 0.1 parts by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hour. The weight average molecular weight Mw of the alkali-soluble resin-G thus obtained was 19100 and the acid value was 198 mgKOH/g. <Dispersant-I> "DISPERBYK-LPN21116" manufactured by BYK-Chemie (consisting of A block with quaternary ammonium salt group and tertiary amine group in the side chain and one without quaternary ammonium salt group and tertiary amine group Acrylic AB block copolymer of B block. The amine value is 70 mgKOH/g and the acid value is less than 1 mgKOH/g. The A block of Dispersant-I contains the following formulas (1a) and (2a) The repeating unit contains the repeating unit of the following formula (3a) in the B block. The proportions of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. [化60]
Figure 02_image119
<Dispersant-II> "DISPERBYK-167" (urethane polymer dispersant) manufactured by BYK-Chemie <Pigment derivative> "Solsperse12000" manufactured by Lubrizol <Solvent-I> PGMEA: Propylene glycol mono Methyl ether acetate <Solvent-II> MB: 3-Methoxybutanol <Photopolymerization initiator> The compound of the following structure [Chem. 61]
Figure 02_image121
<Photopolymerizable monomer> DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Additive> manufactured by Nippon Kayaku Co., Ltd., KAYAMER PM-21 (phosphate containing methacrylic acid group) <Interface active agent> DIC MEGAFAC F-559 manufactured by the company <Measurement of optical density per unit film thickness (unit OD value)> Optical density per unit film thickness is measured by the following procedure. First, apply the prepared photosensitive coloring composition on a glass substrate with a spin coater so that the final film thickness becomes 2 μm, dry under reduced pressure for 1 minute, and then dry at a hot plate temperature of 80°C for 70 seconds . After the exposure and development steps, it is heated at an oven temperature of 230° C. for 20 minutes, thereby obtaining a resist coated substrate. The optical density (OD) of the obtained substrate was measured by Gretag Macbeth D200-II densitometer, and the film thickness was measured by the non-contact surface/layer profile measurement system VertScan(R)2.0 manufactured by Ryoka Systems. According to the optical density (OD) and film thickness to calculate the optical density per unit film thickness. Furthermore, the OD value represents the value of the shading ability, and the larger the value, the higher the shading ability. <NMP dissolution test> The N-methylpyrrolidone (NMP) dissolution test was performed in the following procedure. First, apply the prepared photosensitive coloring composition on a glass substrate with a spin coater so that the final film thickness becomes 2 μm, dry under reduced pressure for 1 minute, and then dry at a hot plate temperature of 80°C for 70 seconds . After exposure and development steps, it is heated at an oven temperature of 230° C. for 20 minutes to obtain a resist coated substrate. Two measurement substrates (2.5 cm×1.0 cm square) were cut from the prepared resist-coated substrate and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). Then, the NMP elution test was carried out in a state where the vial containing the substrate for measurement was allowed to stand in a hot bath at 80°C for 40 minutes. After standing for 40 minutes, remove the vial from the hot bath, and measure the NMP dissolution solution with a spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation) in the wavelength range of 300 to 800 nm at 1 nm intervals Absorbance. The light source uses a halogen lamp and a deuterium lamp (switching wavelength of 360 nm), a detector uses a photomultiplier, and a slit width of 2 nm is used as the measurement condition. In addition, the sample solution (NMP elution solution) was placed in a 1 cm square quartz cuvette for measurement. The so-called absorbance spectroscopy is a dimensionless quantity that indicates how much light intensity attenuates when light passes through an object, and is defined by the following formula. A(Absorbance)=-log10 (I/I0 ) (I: transmitted light intensity, I0 : Incident light intensity) In addition, when light is incident on the sample solution and the NMP single solution from the same light source, the light intensity passing through the NMP single solution can be regarded as I0 , The light intensity transmitted through the sample solution is regarded as I. Therefore, the above formula (I/I0 ) Represents the transmittance, and the absorbance A is a value obtained by expressing the reciprocal of the transmittance in logarithm. Absorbance A is an expression used when calculating the concentration of substances contained in a sample solution. In the case of absorbance A=0, it means that no light is absorbed at all (transmittance 100%), and in the case of absorbance A=∞, it means that light is not transmitted at all (transmittance 0%). That is, the stronger the absorbance, the more the resist coating film components are eluted into NMP, and the NMP resistance is worse. The spectral area (nm) of the measured absorbance was calculated, and the area value less than 20 (nm) was evaluated as ○, and if the area value was greater than 20 (nm), it was evaluated as ×, and the NMP resistance was evaluated. The spectral area of absorbance, which is the criterion of this evaluation, can be expressed as the sum of absorbance at each wavelength, which means the sum of the eluted resist components. NMP resistance evaluation criteria: Judgment by absorbance spectral area value (wavelength 300～800 nm) ○: Less than 20 (nm) ×: 20 (nm) or more <Evaluation of surface smoothness> Surface smoothness and the following The evaluation of the surface roughness was performed in the following procedure. First, apply the prepared photosensitive coloring composition on a glass substrate with a spin coater so that the final film thickness becomes 3 μm, dry under reduced pressure for 1 minute, and then dry at a hot plate temperature of 80°C for 70 seconds . After exposure and development steps, it is heated at an oven temperature of 230° C. for 20 minutes to obtain a resist coated substrate. For the produced resist-coated substrate, observe whether there are wrinkles on the surface after heating with an optical microscope in a field of view of 70 μm×70 μm. In addition, the evaluation criteria are as follows. ○: No micron-level wrinkles are observed on the surface of the pattern ×: Micron-level wrinkles are clearly present on the surface of the pattern <Evaluation of surface roughness> For the resist produced in the above <Evaluation of surface smoothness> Coating the substrate, using the three-dimensional non-contact surface shape measurement system Micromap manufactured by Ryoka Systems, using a 50x optical lens, the surface roughness Sa (arithmetic mean roughness, arithmetic mean roughness, is measured in a field of view of 70 μm×70 μm in Focus mode, μm). <Preparation of Pigment Dispersion Liquids 1, 3, and 4> The pigments, dispersants, dispersion aids, alkali-soluble resins, and solvents described in Table 1 were mixed so as to achieve the mass ratios described in Table 1. Disperse the mixed solution for 3 hours in the range of 25-45°C with a paint shaker. Use 0.5 mm
Figure 02_image123
The zirconia beads are used as beads and added 2.5 times the mass of the dispersion. After the dispersion, the beads and the dispersion are separated by a filter to prepare pigment dispersions 1, 3, and 4. [Table 1]
Figure 105142935-A0304-0001
 <Pigment Dispersion Liquid 2 (Coated Carbon Black Dispersion Liquid)> Carbon black is produced by a normal oil furnace method. Among them, ethylene tar with less Na, Ca, and S content is used as feedstock oil, and coke oven gas is used for combustion. Furthermore, pure water treated with an ion exchange resin was used as reaction stop water. Using a homogenizer, 540 g of the obtained carbon black and 14,500 g of pure water were stirred at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. The slurry was transferred to a container with a screw-type mixer, and while mixing at about 1,000 rpm, 600 g of toluene in which 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added in portions. The carbon black dispersed in the water was transferred to the toluene side within about 15 minutes, becoming about 1 mm particles. Then, after shaking off the water with a 60-mesh metal wire net, it was placed in a vacuum dryer and dried at 70°C for 7 hours to completely remove toluene and water. The obtained coated carbon black, dispersant, pigment derivative, and solvent were mixed so as to become the mass ratio described in Table 1. It is premixed by fully stirring it with a mixer. Then, a dispersion treatment was performed for 6 hours in the range of 25-45°C with a paint shaker. Use 0.5 mm
Figure 02_image123
The zirconia beads are used as beads and added with the same mass as the dispersion. After the dispersion is completed, the beads and the dispersion are separated by a filter to prepare the pigment dispersion 2. [Examples 1 to 6, Comparative Examples 1 to 3] Each component was added so that the solid content ratio became the blending ratio in Table 2, and then PGMEA was added so that the solid content became 22% by mass, and stirred and dissolved , Thereby preparing a photosensitive coloring composition. Table 2 shows the solid content ratio of the prepared composition. In addition, the evaluation results of unit OD value, NMP dissolution test, surface smoothness and surface roughness measured by the method described above are shown in Table 2. In addition, the parts by mass of the photosensitive coloring composition in Table 2 represent the parts by mass of the solid content. [Table 2]
Figure 105142935-A0304-0002
 The comparison of Example 1 in Table 2 with Comparative Examples 1 and 2 reveals that (bI) epoxy (meth)acrylate resin and (b-II) containing more than 12 mol% of ethylenically unsaturated bonds The photosensitive coloring composition of the (meth)acrylic copolymer resin having the repeating unit α and containing the repeating unit β derived from an unsaturated carboxylic acid can ensure high light-shielding properties while being excellent in reliability and surface smoothness. On the other hand, the reliability of Comparative Example 1 in which the repeating unit α was less than 12 mol% was poor, and the surface smoothness of Comparative Example 2 not containing (b-II) (meth)acrylic copolymer resin was poor. In the case where the main resin component is (b-I) epoxy (meth)acrylate resin as in Comparative Example 2, it is considered that the surface smoothness becomes poor due to the heat flow caused by the structure. Therefore, it is believed that by using (meth)acrylic copolymer resins containing repeating units derived from unsaturated carboxylic acids that are not easy to heat flow in addition to epoxy (meth)acrylate resins, heat flow is reduced and surface smoothness is improved. Sex. However, since such (meth)acrylic copolymer resins are generally lower in sensitivity than epoxy (meth)acrylate resins, curability may be lowered, and reliability may deteriorate as in Comparative Example 1. Therefore, it is considered that by increasing the content ratio of the repeating unit α having an ethylenically unsaturated bond in the (meth)acrylic copolymer resin, sufficient curability can be ensured, and both reliability and surface smoothness can be achieved. Furthermore, the comparison of Examples 1 to 3 reveals that when the colorant contains organic pigments and carbon black, or contains at least one selected from the group consisting of red pigments and orange pigments and selected from blue pigments and purple pigments In the case of at least one of the groups, regardless of the specific pigment type, high light-shielding properties can be ensured, and the reliability and surface smoothness are excellent. On the other hand, the surface smoothness of Comparative Example 3 in which the coloring agent is only carbon black with high ultraviolet absorption is insufficient. On the other hand, the comparison of Examples 2 and 4 revealed that regardless of the type of (b-I) epoxy (meth)acrylate resin, the reliability is excellent. On the other hand, the comparison of Examples 1, 5, and 6 reveals that if the content of the repeating unit α having ethylenic unsaturated bonds in the resin (b-II) is 12 mol% or more, no matter what Regardless of the value of the content ratio, both reliability and surface smoothness are excellent. The present invention has been described in detail using specific aspects, but the industry understands that various changes and modifications can be made without departing from the intent and scope of the present invention. In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2015-252149) filed on December 24, 2015, and the entire content is incorporated by reference. [Industrial Applicability] According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a colored spacer with high light-shielding properties, high reliability, and excellent surface smoothness. Furthermore, it is possible to provide a colored spacer with such coloring. Image display device for spacers. Therefore, the present invention has extremely high industrial applicability in various fields of photosensitive coloring compositions, cured products, colored spacers, and image display devices.

Claims (9)

一種感光性著色組合物，其特徵在於：其係含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑者，並且上述(a)著色劑含有有機顏料及碳黑，上述(b)鹼可溶性樹脂含有(b-I)環氧(甲基)丙烯酸酯樹脂、與(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂，且上述(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元α之含有比例為12莫耳%以上。 A photosensitive coloring composition characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, And (f) a dispersant, and the above (a) colorant contains organic pigments and carbon black, the above (b) alkali-soluble resin contains (bI) epoxy (meth)acrylate resin, and (b-II) contains A (meth)acrylic copolymer resin having a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid, and the above (b-II) (meth)acrylic copolymer resin The content ratio of the above repeating unit α is 12 mol% or more. 如請求項1之感光性著色組合物，其中上述有機顏料含有選自由下述通式(1)所表示之化合物、該化合物之幾何異構物、該化合物之鹽及該化合物之幾何異構物之鹽所組成之群中之至少1種有機黑色顏料，
Figure 105142935-A0305-02-0133-1
 式(1)中，R11及R16互相獨立為氫原子、CH3、CF3、氟原子或氯原子；R12、R13、R14、R15、R17、R18、R19及R20與其他全部互相獨立而為 氫原子、鹵素原子、R21、COOH、COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OCONH2、OCONHR21、OCONR21R22、NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22、N=CH2、N=CHR21、N=CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21或SO2NR21R22；且選自由R12與R13、R13與R14、R14與R15、R17與R18、R18與R19、及R19與R20所組成之群中之至少1種組合可互相直接鍵結，或者利用氧原子、硫原子、NH或NR21橋而互相鍵結；R21及R22互相獨立為碳數1~12之烷基、碳數3~12之環烷基、碳數2~12之烯基、碳數3~12之環烯基或碳數2~12之炔基。 The photosensitive coloring composition according to claim 1, wherein the organic pigment contains a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a geometric isomer of the compound At least one organic black pigment in the group of salt,
Figure 105142935-A0305-02-0133-1
 In the formula (1), R 11 and R 16 are independently 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 and all other each independently be a hydrogen atom, a halogen atom, R 21, COOH, COOR 21 , COO -, CONH 2, CONHR 21, CONR 21 R 22, CN, OH, OR 21, COCR 21, OCONH 2, OCONHR 21, OCONR 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 the group consisting of R 12 and R 13, R At least one combination of 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 can be directly bonded to each other, or an oxygen atom, Sulfur atom, NH or NR 21 bridge and bond to each other; R 21 and R 22 are independently an alkyl group with 1 to 12 carbons, cycloalkyl with 3 to 12 carbons, alkenyl with 2 to 12 carbons, Cycloalkenyl with 3-12 or alkynyl with 2-12 carbons. 一種感光性著色組合物，其特徵在於：其係含有(a)著色劑、(b)鹼可溶性樹脂、(c)光聚合起始劑、(d)乙烯性不飽和化合物、(e)溶劑、及(f)分散劑者，並且上述(a)著色劑含有選自由紅色顏料及橙色顏料所組成之群中之至少一種、與選自由藍色顏料及紫色顏料所組成之群中之至少一種，上述(b)鹼可溶性樹脂含有(b-I)環氧(甲基)丙烯酸酯樹脂、與(b-II)含有側鏈具有乙烯性不飽和鍵之重複單元α及源自不飽和羧酸之重複單元β之(甲基)丙烯酸系共聚合樹脂，且上述(b-II)(甲基)丙烯酸系共聚合樹脂中之上述重複單元α之含有比例為12莫耳%以上。 A photosensitive coloring composition characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, And (f) a dispersant, and the above-mentioned (a) colorant contains at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and purple pigments, The above-mentioned (b) alkali-soluble resin contains (bI) epoxy (meth)acrylate resin, and (b-II) contains a repeating unit α with an ethylenically unsaturated bond in the side chain and a repeating unit derived from an unsaturated carboxylic acid β (meth)acrylic copolymer resin, and the content ratio of the repeating unit α in the (b-II) (meth)acrylic copolymer resin is 12 mol% or more. 如請求項1至3中任一項之感光性著色組合物，其中上述重複單元α具有下述通式(I)所表示之化學結構，
Figure 105142935-A0305-02-0135-2
 式(I)中，R1及R2分別獨立地表示氫原子或甲基；R3表示二價連結基。 The photosensitive coloring composition according to any one of claims 1 to 3, wherein the repeating unit α has a chemical structure represented by the following general formula (I),
Figure 105142935-A0305-02-0135-2
 In formula (I), R 1 and R 2 each independently represent a hydrogen atom or a methyl group; R 3 represents a divalent linking group. 如請求項1至3中任一項之感光性著色組合物，其中上述(b-II)(甲基)丙烯酸系共聚合樹脂之含有比例相對於感光性著色組合物中之全部固形物成分為1質量%以上。 The photosensitive coloring composition according to any one of claims 1 to 3, wherein the content ratio of the (b-II) (meth)acrylic copolymer resin with respect to all solid components in the photosensitive coloring composition is 1% by mass or more. 如請求項1至3中任一項之感光性著色組合物，其中經硬化之塗膜之每1μm膜厚之光學密度為1.0以上。 The photosensitive coloring composition according to any one of claims 1 to 3, wherein the optical density per 1 μm of the film thickness of the cured coating film is 1.0 or more. 一種硬化物，其係將如請求項1至6中任一項之感光性著色組合物硬化而獲得。 A hardened product obtained by hardening the photosensitive coloring composition according to any one of claims 1 to 6. 一種著色間隔件，其由如請求項7之硬化物所形成。 A colored spacer, which is formed of a hardened material as in Claim 7. 一種圖像顯示裝置，其具備如請求項8之著色間隔件。An image display device provided with a colored spacer as in Claim 8.
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