TW202225842A - Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device - Google Patents

Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device Download PDF

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TW202225842A
TW202225842A TW110135753A TW110135753A TW202225842A TW 202225842 A TW202225842 A TW 202225842A TW 110135753 A TW110135753 A TW 110135753A TW 110135753 A TW110135753 A TW 110135753A TW 202225842 A TW202225842 A TW 202225842A
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coloring composition
photosensitive coloring
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沢井良尚
力武信夫
三島康太郎
宮下賀子
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日商三菱化學股份有限公司
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F2/00—Processes of polymerisation
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

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Abstract

Provided is a photosensitive coloring composition that causes little roughness of the surface of an electrode following a heat treatment. This photosensitive coloring composition is characterized: by containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent and (f) a dispersing agent; in that the coloring agent (a) contains a compound represented by a specific general formula (I), a geometric isomer of the compound, a salt of the compound or a salt of a geometric isomer of the compound; in that the dispersing agent (f) contains an acrylic copolymer (f1) which contains repeating units represented by specific general formulae (1), (2) and (3) and does not contain a repeating unit having a quaternary ammonium group; and in that the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solids content in the photosensitive coloring composition.

Description

感光性著色組合物、硬化物、有機電致發光元件及圖像顯示裝置Photosensitive coloring composition, cured product, organic electroluminescence element, and image display device

本發明係關於一種感光性著色組合物、硬化物、有機電致發光元件及圖像顯示裝置。 本案基於2020年9月28日於日本提出申請之特願2020-162460號、及2021年2月18日於日本提出申請之特願2021-024490號主張優先權，並將其內容引用至本文中。 The present invention relates to a photosensitive coloring composition, a cured product, an organic electroluminescence element, and an image display device. This case claims priority based on Japanese Patent Application No. 2020-162460 filed in Japan on September 28, 2020 and Japanese Patent Application No. 2021-024490 filed in Japan on February 18, 2021, the contents of which are incorporated herein by reference .

液晶顯示器(LCD)利用了液晶分子之排列方式會因對液晶施加之電壓之接通、斷開而改變之性質。構成LCD之單元之各構件大多藉由以光微影法為代表之利用感光性組合物的方法而形成。該感光性組合物由於易形成微細結構，且亦易對大畫面用基板進行處理等，故其應用範圍進一步擴大。A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules changes when a voltage applied to the liquid crystal is turned on and off. Each member constituting a cell of an LCD is often formed by a method using a photosensitive composition typified by a photolithography method. Since this photosensitive composition is easy to form a fine structure, and it is easy to handle the board|substrate for large screens, etc., its application range is further expanded.

包含有機電致發光元件(亦稱為有機電致發光、有機EL)之圖像顯示裝置由於對比度或視角等視認性或響應性優異，且能夠實現低耗電化、薄型輕量化、及顯示器本體之可撓性化，故作為下一代平板顯示器(FPD)備受關注。 有機電致發光元件具有如下構造：於至少一個電極具有透光性之一對電極間夾持有包含發光層或各種功能層之有機層。圖像顯示裝置係藉由驅動每一像素都配置了有機電致發光元件之面板來進行圖像顯示。 一直以來，此種有機電致發光元件係於基板上形成間隔壁(觸排)後，於由間隔壁所包圍包圍之區域內積層發光層或各種功能層而製造。 Image display devices including organic electroluminescence elements (also referred to as organic electroluminescence, organic EL) have excellent visibility or responsiveness due to contrast, viewing angle, etc., and can achieve low power consumption, thinness and weight, and display body. Because of its flexibility, it is attracting attention as a next-generation flat panel display (FPD). The organic electroluminescence element has a structure in which an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes, at least one of which is light-transmitting. The image display device performs image display by driving a panel in which each pixel is configured with an organic electroluminescence element. Conventionally, such an organic electroluminescence device is manufactured by forming a partition wall (contact bank) on a substrate, and then laminating a light-emitting layer or various functional layers in a region surrounded by the partition wall.

於由間隔壁所包圍之區域內成膜發光層等時，主要應用如下蒸鍍法：於真空狀態下使材料昇華，並使其附著於基板上而成膜。 又，近年來，藉由流延法、旋轉塗佈法、噴墨印刷法等濕式製程進行成膜之方法受到關注。尤其是噴墨印刷法可減少製成大面積時之膜厚不均，並且能夠藉由在塗佈時進行分塗而謀求顯示器之高精細化、材料使用量之削減、良率之提高，故適合作為大型面板中之有機層之成膜方法。 When forming a light-emitting layer or the like in the region surrounded by the partition walls, the following vapor deposition method is mainly used: the material is sublimated in a vacuum state, and the material is adhered to the substrate to form a film. In addition, in recent years, a method of forming a film by a wet process such as a casting method, a spin coating method, and an ink jet printing method has attracted attention. In particular, the inkjet printing method can reduce the uneven thickness of the film when it is made into a large area, and can achieve high-definition display, reduction of material usage, and improvement of yield by sub-coating during coating. It is suitable as a film forming method for organic layers in large panels.

作為易於形成間隔壁之方法，已知有藉由使用感光性組合物之光微影法形成之方法。又，作為對間隔壁賦予遮光性以抑制像素間之漏光之方法，已知有使感光性組合物中含有著色劑之方法。As a method of easily forming a partition wall, a method of forming by a photolithography method using a photosensitive composition is known. Moreover, as a method of providing light-shielding property to a partition and suppressing the light leakage between pixels, the method of containing a coloring agent in a photosensitive composition is known.

專利文獻1中對藉由使用特定之有機黑色顏料與鹼可溶性樹脂而抑制釋氣產生之著色感光性樹脂組合物進行了記載。 [先前技術文獻] [專利文獻] Patent Document 1 describes a colored photosensitive resin composition that suppresses the generation of outgassing by using a specific organic black pigment and an alkali-soluble resin. [Prior Art Literature] [Patent Literature]

[專利文獻1]國際公開第2018/101314號[Patent Document 1] International Publication No. 2018/101314

[發明所欲解決之問題][Problems to be Solved by Invention]

於有機電致發光元件中存在頂部發光型與底部發光型之面板形態。於頂部發光之情形時，使用銀等反射電極作為電極並於其上製作間隔壁等硬化物，但於加熱處理時感光性組合物中之成分會發揮作用，而有時引起金屬電極之腐蝕或遷移等。當電極表面產生凹凸(以下，亦記載為表面粗糙)時，於該部分上無法均勻地形成發光層，從而於製作有機電致發光元件時，有可能因短路等而導致顯示不良。There are top emission type and bottom emission type panel forms in organic electroluminescence devices. In the case of top emission, a reflective electrode such as silver is used as an electrode and a hardened material such as a partition wall is formed on it, but the components in the photosensitive composition will play a role during heat treatment, which may cause corrosion or corrosion of the metal electrode. Migration, etc. When unevenness (hereinafter, also referred to as surface roughness) occurs on the electrode surface, the light-emitting layer cannot be uniformly formed on the portion, and there is a possibility of display failure due to short circuit or the like when producing an organic electroluminescent device.

本發明人等進行研究，結果發現，專利文獻1中所記載之著色感光性樹脂組合物會使電極表面粗糙，於實用上存在問題。As a result of studies by the present inventors, the colored photosensitive resin composition described in Patent Document 1 has been found to cause a rough electrode surface, which is a problem in practical use.

本發明係鑒於上述情況而成者，其目的在於提供一種加熱處理後較少產生電極表面粗糙之感光性著色組合物，且提供一種無顯示不良且可靠性較高之有機發光元件、圖像顯示裝置。 [解決問題之技術手段] The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a photosensitive coloring composition that is less likely to produce electrode surface roughness after heat treatment, and to provide an organic light-emitting element and image display with no display defects and high reliability device. [Technical means to solve problems]

本發明人進行了努力研究，結果發現，藉由使用特定之分散劑與著色劑，可解決上述課題，從而完成本發明。 即，本發明之主旨如下所述。 As a result of diligent studies, the present inventors found that the above-mentioned problems can be solved by using a specific dispersing agent and a coloring agent, and completed the present invention. That is, the gist of the present invention is as follows.

[1]一種感光性著色組合物，其特徵在於：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，且 上述(a)著色劑含有選自由下述通式(I)所表示之化合物、上述化合物之幾何異構物、上述化合物之鹽、及上述化合物之幾何異構物之鹽所組成之群中之至少一種， 上述(f)分散劑含有如下丙烯酸系共聚物(f1)，其至少含有下述通式(1)、(2)及(3)所表示之重複單元，且不具有包含四級銨基之重複單元， 且相對於感光性著色組合物之全部固形物成分量，感光性著色組合物中之氯原子之含量為0.05質量%以下。 [1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent , and (f) a dispersant, and The coloring agent (a) above contains a compound selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the above compound, a salt of the above compound, and a salt of the geometric isomer of the above compound. at least one, The above-mentioned (f) dispersant contains the following acrylic copolymer (f1), which at least contains repeating units represented by the following general formulae (1), (2) and (3), and does not have repeating quaternary ammonium groups. unit, And content of the chlorine atom in a photosensitive coloring composition is 0.05 mass % or less with respect to the total solid content of a photosensitive coloring composition.

[化1]

Figure 02_image001
[hua 1]
Figure 02_image001

(式(I)中，R 1及R 6相互獨立地為氫原子、CH 3、CF 3、氟原子或氯原子； R 2、R 3、R 4、R 5、R 7、R 8、R 9及R 10係與其他全部相互獨立，為氫原子、鹵素原子、R 11、COOH、COOR 11、COO -、CONH 2、CONHR 11、CONR 11R 12、CN、OH、OR 11、COCR 11、OOCNH 2、OOCNHR 11、OOCNR 11R 12、NO 2、NH 2、NHR 11、NR 11R 12、NHCOR 12、NR 11COR 12、N=CH 2、N=CHR 11、N=CR 11R 12、SH、SR 11、SOR 11、SO 2R 11、SO 3R 11、SO 3H、SO 3 -、SO 2NH 2、SO 2NHR 11或SO 2NR 11R 12； 選自由R 2與R 3、R 3與R 4、R 4與R 5、R 7與R 8、R 8與R 9、及R 9與R 10所組成之群中之至少1個組合亦可相互直接鍵結，或者藉由氧原子、硫原子、NH或NR 11橋聯而相互鍵結； R 11及R 12相互獨立地為碳數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) (In formula (I), R 1 and R 6 are independently hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom; R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 are independent of all others, and are hydrogen atom, halogen atom, R 11 , COOH, COOR 11 , COO − , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N=CH 2 , N=CHR 11 , N=CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 11 or SO 2 NR 11 R 12 ; selected from R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and at least one combination of R 9 and R 10 in the group formed by They are bonded to each other by bridges of oxygen atoms, sulfur atoms, NH or NR 11 ; R 11 and R 12 are independently each other an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with a carbon number of 3 to 12, and a cycloalkyl group with 2 to 12 carbon atoms. 12 alkenyl, cycloalkenyl with 3 to 12 carbons or alkynyl with 2 to 12 carbons)

[化2]

Figure 02_image003
[hua 2]
Figure 02_image003

(式(1)中，R 31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； R 32為氫原子或甲基； *表示鍵結鍵) (In formula (1), R 31 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; R 32 is a hydrogen atom or a methyl group; * represents a bond )

[化3]

Figure 02_image005
[hua 3]
Figure 02_image005

(式(2)中，R 33為亞甲基、伸乙基或伸丙基，R 34為可具有取代基之烷基，R 35為氫原子或甲基； n為1～20之整數； *表示鍵結鍵) (In formula (2), R 33 is a methylene group, an ethylidene group or a propylidene group, R 34 is an alkyl group which may have a substituent, R 35 is a hydrogen atom or a methyl group; n is an integer from 1 to 20; *represents a bond key)

[化4]

Figure 02_image007
[hua 4]
Figure 02_image007

(式(3)中，R 36及R 37分別獨立地為氫原子、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，R 36及R 37可相互鍵結而形成環狀結構； R 38為氫原子或甲基； Z為二價連結基； *表示鍵結鍵) [2]如[1]中所記載之感光性著色組合物，其中上述(a)著色劑包含有機著色顏料。 [3]一種感光性著色組合物，其特徵在於：其含有(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，且 硬化後之塗膜之每1 μm膜厚之光學密度為0.5以上， 上述(f)分散劑含有如下丙烯酸系共聚物(f1)，其至少含有下述通式(1)、(2)及(3)所表示之重複單元，且不具有包含四級銨基之重複單元， 且相對於感光性著色組合物之全部固形物成分量，感光性著色組合物中之氯原子之含量為0.05質量%以下。 (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R 36 and R 37 can be bonded to each other to form a cyclic structure; R 38 is a hydrogen atom or a methyl group; Z is a divalent linking group; * represents a bond) [2] The photosensitive coloring composition as described in [1], wherein The above-mentioned (a) colorant contains an organic color pigment. [3] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) A solvent and (f) a dispersant, and the optical density per 1 μm thickness of the cured coating film is 0.5 or more, and the above (f) dispersant contains the following acrylic copolymer (f1), which contains at least the following general The repeating units represented by the formulae (1), (2) and (3) do not have repeating units containing a quaternary ammonium group, and the photosensitive coloring composition is based on the total solid content of the photosensitive coloring composition. The content of chlorine atoms in it is 0.05 mass % or less.

[化5]

Figure 02_image009
[hua 5]
Figure 02_image009

(式(1)中，R 31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； R 32為氫原子或甲基； *表示鍵結鍵) (In formula (1), R 31 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; R 32 is a hydrogen atom or a methyl group; * represents a bond )

[化6]

Figure 02_image011
[hua 6]
Figure 02_image011

(式(2)中，R 33為亞甲基、伸乙基或伸丙基，R 34為可具有取代基之烷基，R 35為氫原子或甲基； n為1～20之整數； *表示鍵結鍵) (In formula (2), R 33 is a methylene group, an ethylidene group or a propylidene group, R 34 is an alkyl group which may have a substituent, R 35 is a hydrogen atom or a methyl group; n is an integer from 1 to 20; *represents a bond key)

[化7]

Figure 02_image013
[hua 7]
Figure 02_image013

(式(3)中，R 36及R 37分別獨立地為氫原子、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，R 36及R 37可相互鍵結而形成環狀結構； R 38為氫原子或甲基； Z為二價連結基； *表示鍵結鍵) [4]如[3]中所記載之感光性著色組合物，其中上述(a)著色劑包含選自由紅色顏料及橙色顏料所組成之群中之至少一種、及選自由藍色顏料及紫色顏料所組成之群中之至少一種。 [5]如[1]至[4]中任一項所記載之感光性著色組合物，其中上述丙烯酸系共聚物(f1)為嵌段共聚物。 [6]如[1]至[5]中任一項所記載之感光性著色組合物，其中上述丙烯酸系共聚物(f1)之胺值為90 mgKOH/g以上。 [7]如[1]至[6]中任一項所記載之感光性著色組合物，其中相對於感光性著色組合物之全部固形物成分量，包含10質量%以上之上述(a)著色劑。 [8]如[1]至[7]中任一項所記載之感光性著色組合物，其係用於形成有機電致發光元件之間隔壁。 [9]一種硬化物，其係使如[1]至[8]中任一項所記載之感光性著色組合物硬化而成。 [10]一種有機電致發光元件，其包含如[9]中所記載之硬化物。 [11]一種圖像顯示裝置，其包含如[10]中所記載之有機電致發光元件。 [發明之效果] (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R 36 and R 37 can be bonded to each other to form a cyclic structure; R 38 is a hydrogen atom or a methyl group; Z is a divalent linking group; * represents a bond) [4] The photosensitive coloring composition as described in [3], wherein 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 violet pigments. [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the acrylic copolymer (f1) is a block copolymer. [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the amine value of the acrylic copolymer (f1) is 90 mgKOH/g or more. [7] The photosensitive coloring composition according to any one of [1] to [6], which contains 10% by mass or more of the coloring (a) above with respect to the total solid content of the photosensitive coloring composition. agent. [8] The photosensitive coloring composition according to any one of [1] to [7], which is used for forming a partition wall between organic electroluminescence elements. [9] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [8]. [10] An organic electroluminescence element comprising the cured product as described in [9]. [11] An image display device comprising the organic electroluminescence element as described in [10]. [Effect of invention]

根據本發明，可提供一種加熱處理後較少於電極上產生表面粗糙之感光性著色組合物。According to the present invention, it is possible to provide a photosensitive coloring composition in which surface roughness is less likely to occur on an electrode after heat treatment.

以下，具體地說明本發明之實施方式，但本發明並不限定於以下之實施方式，可於其主旨之範圍內進行各種變更而實施。 於本發明中，所謂「(甲基)丙烯酸」意指「丙烯酸及/或甲基丙烯酸」，關於「(甲基)丙烯酸酯」、「(甲基)丙烯醯基」亦同樣。 Hereinafter, the embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. In the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acryloyl group".

所謂「(共)聚合物」意指包含均聚物(homopolymer)與共聚物(copolymer)這兩者，所謂「酸(酸酐)」、「(無水)…酸」意指包含酸與其酸酐這兩者。 於本發明中，所謂「丙烯酸系樹脂」意指包含(甲基)丙烯酸之(共)聚合物、包含具有羧基之(甲基)丙烯酸酯之(共)聚合物。 The term "(co)polymer" refers to both a homopolymer and a copolymer, and the term "acid (anhydride)" and "(anhydrous) ... acid" refers to both an acid and an anhydride thereof. By. In the present invention, the "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing a (meth)acrylate having a carboxyl group.

於本發明中，所謂「單體」係與高分子物質(聚合物)相對之用語，意指除了狹義之單體(monomer)以外，還包含二聚物、三聚物、低聚物之含義。 於本發明中，所謂「全部固形物成分量」意指感光性著色組合物中或顏料分散液中所含之溶劑以外之全部成分量。溶劑以外之成分即便於常溫下為液體，該成分亦不含於溶劑中，而包含於全部固形物成分量中。 於本發明中，所謂「重量平均分子量」意指利用GPC(凝膠滲透層析法)之聚苯乙烯換算之重量平均分子量(Mw)。 於本發明中，只要無特別說明，則「胺值」表示有效固形物成分換算之胺值，且係以與分散劑之每1 g固形物成分之鹼量相當之KOH的質量表示之值。再者，關於測定方法於下文中加以說明。只要無特別說明，則「酸值」表示有效固形物成分換算之酸值，且係藉由中和滴定算出。 In the present invention, the so-called "monomer" is a term relative to a macromolecular substance (polymer), which means that in addition to the narrowly defined monomer (monomer), it also includes the meaning of dimer, trimer, and oligomer. . In the present invention, the term "total solid content" means the total amount of components other than the solvent contained in the photosensitive coloring composition or the pigment dispersion liquid. Even if the components other than the solvent are liquid at normal temperature, the components are not included in the solvent, but are included in the total solid content. In the present invention, the "weight average molecular weight" means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, unless otherwise specified, the "amine value" means the amine value in terms of effective solid content, and is a value expressed by the mass of KOH corresponding to the amount of alkali per 1 g of the solid content of the dispersant. In addition, the measurement method is demonstrated below. Unless otherwise specified, the "acid value" means the acid value in terms of effective solid content, and is calculated by neutralization titration.

關於顏料，所謂「C.I.」意指色指數。Regarding the pigment, the so-called "C.I." means the color index.

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。In this specification, the percentage or part represented by "mass" has the same meaning as the percentage or part represented by "weight".

[感光性著色組合物] 本發明之感光性著色組合物含有如下成分作為必需成分： (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 (f)分散劑。 作為第一態樣，含有選自由通式(I)所表示之化合物、通式(I)所表示之化合物之幾何異構物、通式(I)所表示之化合物之鹽、或通式(I)所表示之化合物之幾何異構物之鹽所組成之群中之至少一種作為(a)著色劑。 作為第二態樣，使本發明之感光性著色組合物硬化而成之塗膜之每1 μm膜厚之光學密度為0.5以上。 又，視需要進而包含矽烷偶合劑等密接提昇劑、界面活性劑、顏料衍生物、光酸產生劑、交聯劑、巰基化合物、聚合抑制劑等其他調配成分，通常，各調配成分係於溶解或分散於溶劑中之狀態下使用。 [Photosensitive Coloring Composition] The photosensitive coloring composition of the present invention contains the following components as essential components: (a) Colorants (b) Alkali-soluble resin (c) Photopolymerization initiator (d) ethylenically unsaturated compounds (e) Solvent (f) Dispersants. As a first aspect, the compound containing the compound represented by the general formula (I), the geometric isomer of the compound represented by the general formula (I), the salt of the compound represented by the general formula (I), or the general formula ( At least one of the group consisting of salts of geometric isomers of the compounds represented by I) is used as the (a) colorant. As a 2nd aspect, the optical density per 1 micrometer of film thickness of the coating film obtained by hardening the photosensitive coloring composition of this invention is 0.5 or more. In addition, other formulation components such as adhesion promoters such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors may be further included if necessary. Or use it in a state of being dispersed in a solvent.

＜(a)著色劑＞ 本發明之感光性著色組合物含有(a)著色劑。藉由含有(a)著色劑，可獲得適度之光吸收性，尤其於用於形成間隔壁等遮光構件之用途之情形時可獲得適度之遮光性。 於第一態樣中，含有選自由通式(I)所表示之化合物、通式(I)所表示之化合物之幾何異構物、通式(I)所表示之化合物之鹽、及通式(I)所表示之化合物之幾何異構物之鹽所組成之群中之至少一種作為(a)著色劑。 通式(I)所表示之化合物(以下，亦稱為「化合物(I)」)為有機黑色顏料。推測藉由具有含有芳香環之剛直骨架，而使得加熱處理時所產生之含有氯之氣體難以滲透至塗膜中。又，由於紫外線之透過率較高，故所塗佈之感光性組合物容易進行光硬化，從該等方面考慮較有用。 <(a) Colorant> The photosensitive coloring composition of this invention contains (a) a coloring agent. By containing (a) a coloring agent, moderate light-absorptive property can be acquired, and moderate light-shielding property can be acquired especially when it is used for the use of forming a light-shielding member, such as a partition. In the first aspect, the compound containing the compound represented by the general formula (I), the geometric isomer of the compound represented by the general formula (I), the salt of the compound represented by the general formula (I), and the general formula At least one of the group consisting of salts of geometric isomers of the compounds represented by (I) is used as the (a) colorant. The compound represented by the general formula (I) (hereinafter, also referred to as "compound (I)") is an organic black pigment. It is presumed that by having a rigid skeleton including an aromatic ring, it is difficult for the chlorine-containing gas generated during the heat treatment to permeate into the coating film. In addition, since the transmittance of ultraviolet rays is high, the photosensitive composition to be applied is easily photocured, which is useful from these points of view.

[化8]

Figure 02_image015
[hua 8]
Figure 02_image015

式(I)中，R 11及R 16分別獨立地表示氫原子、CH 3、CF 3、氟原子或氯原子； R 12、R 13、R 14、R 15、R 17、R 18、R 19及R 20分別獨立地表示氫原子、鹵素原子、R 21、COOH、COOR 21、COO -、CONH 2、CONHR 21、CONR 21R 22、CN、OH、OR 21、COCR 21、OOCNH 2、OOCNHR 21、OOCNR 21R 22、NO 2、NH 2、NHR 21、NR 21R 22、NHCOR 22、NR 21COR 22、N=CH 2、N=CHR 21、N=CR 21R 22、SH、SR 21、SOR 21、SO 2R 21、SO 3R 21、SO 3H、SO 3 -、SO 2NH 2、SO 2NHR 21或SO 2NR 21R 22； 選自由R 12與R 13、R 13與R 14、R 14與R 15、R 17與R 18、R 18與R 19、及R 19與R 20所組成之群中之至少1個組合可相互直接鍵結，或者可藉由氧原子、硫原子、NH或NR 21橋聯而相互鍵結； R 21及R 22分別獨立地表示碳數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。 In formula (I), R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 independently represent 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 , OOCNH 2 , OOCNHR 21 , OOCNR 21 R 22 , NO 2 , NH 2 , NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 , N=CH 2 , N=CHR 21 , N=CR 21 R 22 , SH, SR 21 , SOR 21 , SO 2 R 21 , SO 3 R 21 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 21 or SO 2 NR 21 R 22 ; selected from R 12 and R 13 , 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 in the group consisting of at least one combination can be directly bonded to each other, or can be directly bonded to each other through oxygen atoms, sulfur Atoms, NH or NR 21 are bridged and bonded to each other; R 21 and R 22 independently represent 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 having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.

化合物(I)及化合物(I)之幾何異構物具有以下之核結構(其中，結構式中之取代基省略)，且反式-反式異構物可能最穩定。Compound (I) and geometric isomers of compound (I) have the following core structures (wherein the substituents in the structural formula are omitted), and trans-trans isomers are probably the most stable.

[化9]

Figure 02_image017
[Chemical 9]
Figure 02_image017

於化合物(I)為陰離子性之情形時，較佳為利用任意公知之適當之陽離子例如金屬、有機、無機或金屬有機陽離子、具體而言，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，於化合物(I)之幾何異構物為陰離子性之情形時，較佳為同樣之鹽。When the compound (I) is anionic, it is preferable to use any known suitable cations such as metal, organic, inorganic or metal-organic cations, specifically, alkali metals, alkaline earth metals, transition metals, primary ammonium, Tertiary ammonium such as tertiary ammonium, trialkyl ammonium, quaternary ammonium such as tetraalkyl ammonium, or salts formed by organometallic complexes to compensate for their charge. Moreover, when the geometric isomer of compound (I) is anionic, the same salt is preferable.

於通式(I)之取代基及該等之定義中，從有遮蔽率增高之傾向方面考慮，較佳為以下者。其原因在於，認為以下之取代基不具有吸收，不會影響顏料之色相。 R 12、R 14、R 15、R 17、R 19及R 20分別獨立地較佳為氫原子、氟原子、或氯原子，進而較佳為氫原子。 R 13及R 18分別獨立地較佳為氫原子、NO 2、OCH 3、OC 2H 5、溴原子、氯原子、CH 3、C 2H 5、N(CH 3) 2、N(CH 3)(C 2H 5)、N(C 2H 5) 2、α-萘基、β-萘基、SO 3H或SO 3 -，進而較佳為氫原子或SO 3H，尤佳為氫原子。 Among the substituents of the general formula (I) and their definitions, the following ones are preferred from the viewpoint that the shielding ratio tends to increase. The reason is that the following substituents do not have absorption and do not affect the hue of the pigment. R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R 13 and R 18 are each independently preferably hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 )(C 2 H 5 ), N(C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 − , more preferably a hydrogen atom or SO 3 H, particularly preferably hydrogen atom.

R 11及R 16分別獨立地較佳為氫原子、CH 3或CF 3，進而較佳為氫原子。 較佳為選自由R 11與R 16、R 12與R 17、R 13與R 18、R 14與R 19、及R 15與R 20所組成之群中之至少1個組合相同，更佳為R 11與R 16相同，R 12與R 17相同，R 13與R 18相同，R 14與R 19相同，且R 15與R 20相同。 R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom. Preferably, at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is the same as R 20 .

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、正庚基、正辛基、1,1,3,3-四甲基丁基、2-乙基己基、壬基、癸基、十一烷基或十二烷基。The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-butyl Pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2- Ethylhexyl, nonyl, decyl, undecyl or dodecyl.

碳數3～12之環烷基例如為環丙基、環丙基甲基、環丁基、環戊基、環己基、甲基環己基、三甲基環己基、側柏基(thujyl)、降𦯉基、𦯉基、降蒈基、蒈基、䓝基、降蒎基、蒎基、金剛烷-1-基或金剛烷-2-基。The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norpyridyl, norpyridyl, norpyridyl, pyridyl, pyridyl, norpinyl, pinonyl, adamantan-1-yl or adamantan-2-yl.

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-甲基-1-丁烯-3-基、2-甲基-3-丁烯-2-基、3-甲基-2-丁烯-1-基、1,4-戊二烯-3-基、己烯基、辛烯基、壬烯基、癸烯基或十二烯基。Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 1,3-butadiene. -2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-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.

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-對薄荷烯-8-基、4(10)-側柏烯-10-基、2-降莰烯-1-基、2,5-降𦯉二烯-1-基、7,7-二甲基-2,4-降蒈二烯-3-基或莰烯基。The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, and 3-cyclohexen-1-yl , 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujene-10-yl, 2-norbornen-1-yl, 2,5 - norrcadien-1-yl, 7,7-dimethyl-2,4-norcarbadien-3-yl or 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1-十二炔-12-基。Examples of alkynyl groups having 2 to 12 carbon atoms include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn- 1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn- 9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

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

上述通式(I)所表示之化合物較佳為包含選自由下述通式(II)所表示之化合物(以下，亦稱為「化合物(II)」)、及化合物(II)之幾何異構物所組成之群中之至少一種之化合物。The compound represented by the aforementioned general formula (I) preferably includes a compound (hereinafter, also referred to as "compound (II)") represented by the following general formula (II), and geometric isomerism of compound (II) A compound of at least one of a group of things.

[化10]

Figure 02_image019
[Chemical 10]
Figure 02_image019

作為此種化合物，例如，就商品名而言，可例舉Irgaphor(註冊商標) Black S 0100 CF(BASF公司製造)。Examples of such a compound include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) as a trade name.

該有機黑色顏料較佳為藉由下述方法進行分散而使用。又，若於分散時存在化合物(I)之磺酸衍生物、或化合物(I)之幾何異構物之磺酸衍生物、尤其是化合物(II)之磺酸衍生物、或化合物(II)之幾何異構物之磺酸衍生物，則存在分散性或保存性提高之情形。The organic black pigment is preferably dispersed and used by the following method. In addition, if there is a sulfonic acid derivative of compound (I), or a sulfonic acid derivative of a geometric isomer of compound (I), especially a sulfonic acid derivative of compound (II), or compound (II) during dispersion The sulfonic acid derivatives of the geometric isomers may have improved dispersibility or storage.

於本發明之第一態樣中，(A)著色劑除了通式(I)之化合物以外，還可含有其他著色劑。作為其他著色劑，較佳為顏料，顏料可為有機顏料，亦可為無機顏料。從高電阻、低介電常數之觀點考慮，更佳為有機顏料，尤其進而較佳為下述有機著色顏料。 有機著色顏料之中，從使可見光區域之高波長區域之透過率變均勻之觀點考慮，較佳為使用化合物(I)與藍色顏料。較佳為顏料藍B60、15：6、16，更佳為顏料藍B60。 另一方面，從使整個可見光區域之透過率變均勻之觀點考慮，較佳為除了化合物(I)以外，還使用選自由紅色顏料及橙色顏料所組成之群中之至少一種、及選自由藍色顏料及紫色顏料所組成之群中之至少一種。 In the first aspect of the present invention, the (A) colorant may contain other colorants in addition to the compound of the general formula (I). As another colorant, a pigment is preferable, and the pigment may be an organic pigment or an inorganic pigment. From the viewpoints of high resistance and low dielectric constant, organic pigments are more preferred, and the following organic coloring pigments are still more preferred. Among the organic coloring pigments, it is preferable to use the compound (I) and a blue pigment from the viewpoint of uniformizing the transmittance in the high wavelength region of the visible light region. Pigment blue B60, 15:6, 16 are preferred, and pigment blue B60 is more preferred. On the other hand, from the viewpoint of making the transmittance of the entire visible light region uniform, it is preferable to use, in addition to the compound (I), 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 At least one of the group consisting of color pigments and purple pigments.

於第二態樣中，本發明之感光性著色組合物之硬化後之塗膜之每1 μm膜厚之光學密度(以下，有時稱為「每單位膜厚之OD」)為0.5以上。藉由含有(a)著色劑，且將每單位膜厚之OD設為上述下限值以上，所獲得之硬化物、尤其是間隔壁之遮光性增高。In the second aspect, the optical density per 1 μm of the film thickness of the coating film after curing of the photosensitive coloring composition of the present invention (hereinafter, sometimes referred to as “OD per unit film thickness”) is 0.5 or more. By containing (a) a coloring agent, and making the OD per film thickness more than the said lower limit, the light-shielding property of the obtained hardened|cured material, especially a partition becomes high.

每單位膜厚之OD可藉由測定使感光性著色組合物硬化而成之塗膜之光學密度與膜厚，並將光學密度除以膜厚而算出。塗膜之製作條件並無特別限定，例如可採用下述實施例中所記載之條件。 於將每單位膜厚之OD設為上述下限值以上時，例如只要適當調整(a)著色劑之種類、或全部固形物成分量中之含有比率即可。 The OD per unit film thickness can be calculated by measuring the optical density and film thickness of the coating film obtained by curing the photosensitive coloring composition, and dividing the optical density by the film thickness. The production conditions of the coating film are not particularly limited, and for example, the conditions described in the following examples can be adopted. When making the OD per unit film thickness more than the said lower limit, what is necessary is just to adjust suitably the kind of (a) coloring agent, or the content rate in the whole solid content amount, for example.

於本發明之第二態樣中，感光性著色組合物中可使用之(a)著色劑之種類並無特別限定，可使用顏料，亦可使用染料。其中，從耐久性之觀點考慮，較佳為使用顏料。In the second aspect of the present invention, the type of the (a) colorant that can be used in the photosensitive coloring composition is not particularly limited, and a pigment or a dye may be used. Among them, it is preferable to use a pigment from the viewpoint of durability.

(a)著色劑中所含之顏料可為單獨一種，亦可為兩種以上。尤其從同時實現於可見區域中均勻地遮光、及每單位膜厚之OD之觀點考慮，較佳為兩種以上。 可用作(a)著色劑之顏料之種類並無特別限定，例如可例舉有機著色顏料或黑色顏料。此處，所謂有機著色顏料意指呈現黑色以外之顏色之有機顏料，例如可例舉：紅色顏料、橙色顏料、藍色顏料、紫色顏料、綠色顏料、黃色顏料。 (a) The pigment contained in the colorant may be one type alone or two or more types. In particular, from the viewpoint of achieving uniform light shielding in the visible region and OD per unit film thickness at the same time, two or more types are preferred. The kind of the pigment that can be used as the (a) colorant is not particularly limited, and examples thereof include organic coloring pigments and black pigments. Here, the organic color pigment means an organic pigment that exhibits a color other than black, and examples thereof include red pigment, orange pigment, blue pigment, violet pigment, green pigment, and yellow pigment.

顏料之中，從高電阻、低介電常數之觀點考慮，較佳為使用有機著色顏料。又，從遮光性之觀點考慮，較佳為使用化合物(I)或其他黑色顏料。Among the pigments, organic coloring pigments are preferably used from the viewpoints of high resistance and low dielectric constant. Moreover, it is preferable to use a compound (I) or another black pigment from a light-shielding viewpoint.

有機著色顏料可單獨使用一種，亦可併用兩種以上。尤其從將每單位膜厚之OD設為0.5以上之觀點考慮，更佳為組合使用顏色不同之有機著色顏料，進而較佳為使用呈現接近黑色之顏色之有機著色顏料之組合。An organic coloring pigment may be used individually by 1 type, and may use 2 or more types together. In particular, from the viewpoint of setting the OD per unit film thickness to 0.5 or more, it is more preferable to use a combination of organic coloring pigments having different colors, and it is more preferable to use a combination of organic coloring pigments exhibiting a color close to black.

該等有機著色顏料之化學結構並無特別限定，例如可例舉：偶氮系、酞菁系、喹吖酮系、苯并咪唑酮系、異吲哚啉酮系、二㗁 𠯤系、陰丹士林系、苝系。以下，以顏料編號表示可使用之顏料之具體例。以下所例舉之「C.I.顏料紅2」等中之「C.I.」意指色指數。The chemical structure of these organic coloring pigments is not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, bismuth-based, anionic Danshiline series, perylene series. Below, the specific example of the pigment which can be used is shown by the pigment number. "C.I." in "C.I. Pigment Red 2" and the like exemplified below means a color index.

作為紅色顏料，可例舉：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。從遮光性、分散性之觀點考慮，較佳為可例舉：C.I.顏料紅48：1、122、149、168、177、179、194、202、206、207、209、224、242、254，進而較佳為可例舉：C.I.顏料紅177、209、224、254。從分散性或遮光性方面考慮，較佳為C.I.顏料紅177、254、272，於利用紫外線使感光性著色組合物硬化之情形時，作為紅色顏料，較佳為紫外線吸收率較低者，就該觀點而言，更佳為C.I.顏料紅254、272。Examples of red pigments include: C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200 , 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249 , 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 . From the viewpoint of light-shielding property and dispersibility, C.I. Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, More preferably, C.I. Pigment Red 177, 209, 224, 254 can be mentioned. C.I. Pigment Red 177, 254, and 272 are preferred from the viewpoint of dispersibility and light-shielding properties. When the photosensitive coloring composition is cured by ultraviolet rays, the red pigment is preferably one with a lower ultraviolet absorptivity. From this viewpoint, C.I. Pigment Red 254 and 272 are more preferable.

作為橙色(orange)顏料，可例舉：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。從分散性或遮光性之觀點考慮，較佳為C.I.顏料橙13、43、64、72，於利用紫外線使感光性著色組合物硬化之情形時，作為橙色顏料，較佳為紫外線吸收率較低者，就該觀點而言，更佳為C.I.顏料橙64、72。Examples of orange pigments include C.I. 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. From the viewpoint of dispersibility or light-shielding properties, C.I. Pigment Orange 13, 43, 64, and 72 are preferred, and when the photosensitive coloring composition is cured by ultraviolet rays, the orange pigments are preferably low in ultraviolet absorptivity. and C.I. Pigment Orange 64 and 72 are more preferable from this viewpoint.

作為藍色顏料，可例舉：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。從遮光性之觀點考慮，較佳為可例舉：C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6、60，進而較佳為可例舉C.I.顏料藍15：6。從分散性或遮光性方面考慮，較佳為C.I.顏料藍15：6、16、60，於利用紫外線使感光性著色組合物硬化之情形時，作為藍色顏料，較佳為紫外線吸收率較低者，就該觀點而言，更佳為C.I.顏料藍60。Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. From the viewpoint of light-shielding properties, preferably, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, and more preferably C.I. Pigment Blue 15:6. C.I. Pigment Blue 15:6, 16, 60 is preferable from the viewpoint of dispersibility or light-shielding property, and when the photosensitive coloring composition is cured by ultraviolet rays, it is preferable that the blue pigment has a low ultraviolet absorption rate. Furthermore, from this viewpoint, C.I. Pigment Blue 60 is more preferable.

作為紫色顏料，可例舉：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。從遮光性之觀點考慮，較佳為可例舉：C.I.顏料紫19、23、29，進而較佳為可例舉C.I.顏料紫23。從分散性或遮光性方面考慮，較佳為C.I.顏料紫23、29，於利用紫外線使感光性著色組合物硬化之情形時，作為紫色顏料，較佳為紫外線吸收率較低者，就該觀點而言，更佳為C.I.顏料紫29。Examples of purple pigments include: C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25 , 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. From the viewpoint of light-shielding properties, C.I. Pigment Violet 19, 23, and 29 are preferably used, and C.I. Pigment Violet 23 is more preferably used. C.I. Pigment Violet 23 and 29 are preferred from the viewpoint of dispersibility and light-shielding properties. In the case of curing the photosensitive coloring composition with ultraviolet rays, the purple pigment is preferably one with a lower ultraviolet absorption rate. More preferably, it is C.I. Pigment Violet 29.

作為綠色顏料，可例舉：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、58、59。較佳為可例舉C.I.顏料綠7、36。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 , 58, 59. Preferable examples include C.I. Pigment Green 7 and 36.

作為黃色顏料，可例舉：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。較佳為可例舉：C.I.顏料黃83、117、129、138、139、150、154、155、180、185，進而較佳為可例舉：C.I.顏料黃83、138、139、150、180。Examples of yellow pigments include: C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 , 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81 , 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133 , 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169 , 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198 , 199, 200, 202, 203, 204, 205, 206, 207, 208. Preferred examples include: C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferred examples include: C.I. Pigment Yellow 83, 138, 139, 150, 180 .

從控制硬化物之遮光性、或形狀及階差之觀點考慮，較佳為選自由紅色顏料、橙色顏料、藍色顏料及紫色顏料所組成之群中之至少一種。From the viewpoint of controlling the light-shielding property, or the shape and level difference of the cured product, it is preferably at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments.

從控制硬化物之遮光性、或形狀及階差之觀點考慮，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 It is preferable to contain at least 1 type or more of the following pigments from a viewpoint of controlling the light-shielding property of hardened|cured material, or a shape and a level difference. Red Pigment: C.I. Pigment Red 177, 254, 272 Orange Pigment: C.I. Pigment Orange 43, 64, 72 Blue Pigment: C.I. Pigment Blue 15:6, 60 Purple Pigment: C.I. Pigment Violet 23, 29

關於併用兩種以上有機著色顏料時之有機著色顏料之組合並無特別限定，從遮光性之觀點考慮，較佳為併用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。 關於顏色之組合，並無特別限定，從遮光性之觀點考慮，例如可例舉：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、橙色顏料及紫色顏料之組合。 The combination of organic coloring pigments when two or more organic coloring pigments are used together is not particularly limited, but from the viewpoint of light-shielding properties, it is preferable to use together at least one selected from the group consisting of red pigments and orange pigments, and At least one of the group consisting of blue pigments and purple pigments. The combination of colors is not particularly limited, and from the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment; a combination of a blue pigment and an orange pigment; a combination of a blue pigment, an orange pigment, and a violet pigment may be mentioned. combination.

可使用有機著色顏料、通式(I)所表示之有機黑色顏料以外之有機黑色顏料、或無機黑色顏料。 作為通式(I)所表示之有機黑色顏料以外之有機黑色顏料，例如可例舉苯胺黑或苝黑。 An organic coloring pigment, an organic black pigment other than the organic black pigment represented by the general formula (I), or an inorganic black pigment can be used. Examples of organic black pigments other than the organic black pigment represented by the general formula (I) include aniline black and perylene black.

作為無機黑色顏料，例如可例舉國際公開第2018/101314號中所記載之無機黑色顏料。As an inorganic black pigment, the inorganic black pigment described in International Publication No. 2018/101314 can be mentioned, for example.

於使用該等著色劑時，當於著色劑中含有氯原子之情形時，可藉由以氯量不會過度增加之方式調整添加量而使用。When these colorants are used, when chlorine atoms are contained in the colorant, they can be used by adjusting the addition amount so that the amount of chlorine does not increase excessively.

該等顏料較佳為以平均粒徑通常成為1 μm以下、較佳為成為0.5 μm以下、進而較佳為成為0.25 μm以下之方式進行分散而使用。此處，平均粒徑之基準為顏料粒子之數量。 再者，於本發明之感光性著色組合物中，顏料之平均粒徑係根據藉由動態光散射(DLS)測定之顏料粒徑而求出之值。對經充分稀釋之感光性著色組合物(通常進行稀釋而製備為顏料濃度0.005～0.2質量%左右。但若存在由測定機器所推薦之濃度，則依據該濃度)進行粒徑測定，且於25℃下進行測定。 These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the reference of the average particle size is the number of pigment particles. In addition, in the photosensitive coloring composition of this invention, the average particle diameter of a pigment is the value calculated|required from the pigment particle diameter measured by dynamic light scattering (DLS). The sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2 mass %. However, if there is a concentration recommended by the measuring machine, the particle size is measured according to the concentration), and at 25 Measured at °C.

於本發明之第二態樣之感光性著色組合物中，可單獨使用一種有機著色顏料、黑色顏料等著色劑，亦可併用兩種以上。In the photosensitive coloring composition of the second aspect of the present invention, one coloring agent such as an organic coloring pigment and a black pigment may be used alone, or two or more kinds may be used in combination.

除了上述有機著色顏料、黑色顏料以外，還可使用染料。作為可用作著色劑之染料，例如可例舉國際公開第2018/101314號中所記載之染料。In addition to the above-mentioned organic color pigments and black pigments, dyes can also be used. As a dye which can be used as a coloring agent, the dye described in International Publication No. 2018/101314 can be mentioned, for example.

＜(b)鹼可溶性樹脂＞ 作為本發明中所使用之(b)鹼可溶性樹脂，只要為包含羧基或羥基之樹脂，則並無特別限定，例如可例舉：環氧(甲基)丙烯酸酯系樹脂、丙烯酸系樹脂、含羧基環氧樹脂、含羧基聚胺酯樹脂、酚醛清漆系樹脂、聚乙烯基酚系樹脂。其中，從優異之製版性之觀點考慮，可適宜地使用如下樹脂： (b1)環氧(甲基)丙烯酸酯系樹脂 (b2)丙烯酸系共聚樹脂。 該等可單獨使用一種或併用兩種以上。 <(b) Alkali-soluble resin> The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth)acrylate-based resins, acrylic-based resins, Carboxyl epoxy resin, carboxyl group-containing polyurethane resin, novolac resin, polyvinyl phenol resin. Among them, from the viewpoint of excellent plate-making properties, the following resins can be suitably used: (b1) Epoxy (meth)acrylate resin (b2) Acrylic copolymer resin. These can be used individually by 1 type or in combination of 2 or more types.

＜(b1)環氧(甲基)丙烯酸酯系樹脂＞ (b1)環氧(甲基)丙烯酸酯系樹脂係進而使如下羥基與如下化合物反應所獲得之樹脂，上述羥基係藉由環氧化合物(環氧樹脂)、與在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而生成，上述化合物具有2個以上能夠與上述多元酸及/或其酸酐等之羥基反應之取代基。 於使多元酸及/或其酸酐與羥基反應前，使具有2個以上能夠與羥基反應之取代基之化合物反應，其後使多元酸及/或其酸酐反應所獲得之樹脂亦包含於上述(b1)環氧(甲基)丙烯酸酯系樹脂中。 <(b1) Epoxy (meth)acrylate resin> (b1) Epoxy (meth)acrylate-based resin is a resin obtained by further reacting the following hydroxyl groups with the following compounds, which are obtained by reacting an epoxy compound (epoxy resin) with an α,β-unsaturated mono The carboxylic acid and/or ester moiety is produced by the reaction of α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the compound has two or more substituents that can react with hydroxyl groups such as the polybasic acid and/or its anhydride. Before reacting a polybasic acid and/or its acid anhydride with a hydroxyl group, a compound having two or more substituents capable of reacting with a hydroxyl group is reacted, and then the resin obtained by reacting the polybasic acid and/or its acid anhydride is also included in the above ( b1) In epoxy (meth)acrylate resin.

進而使具有可能夠反應之官能基之化合物、與上述反應中所獲得之樹脂之羧基反應所獲得之樹脂亦包含於上述(b1)環氧(甲基)丙烯酸酯系樹脂中。 如此，環氧(甲基)丙烯酸酯系樹脂於化學結構上實質上不具有環氧基，且並不限定於「(甲基)丙烯酸酯」，但由於環氧化合物(環氧樹脂)為原料，且「(甲基)丙烯酸酯」為代表例，故依據慣例如此命名。 Furthermore, the compound which has a functional group which can react, and the resin obtained by reacting with the carboxyl group of the resin obtained by the said reaction are also contained in the said (b1) epoxy (meth)acrylate type resin. In this way, epoxy (meth)acrylate-based resins do not substantially have epoxy groups in chemical structure, and are not limited to "(meth)acrylates", but since epoxy compounds (epoxy resins) are raw materials , and "(meth)acrylate" is a representative example, so it is named according to the convention.

從顯影性、可靠性之觀點考慮，作為本發明中所使用之(b1)環氧(甲基)丙烯酸酯系樹脂，可尤其適宜地使用下述環氧(甲基)丙烯酸酯系樹脂(b1-1)及/或環氧(甲基)丙烯酸酯系樹脂(b1-2)(以下有時稱為「含羧基環氧(甲基)丙烯酸酯系樹脂」)。 又，作為(b1)環氧(甲基)丙烯酸酯系樹脂，從釋氣之觀點考慮，可更適宜地使用主鏈具有芳香族環者。 From the viewpoint of developability and reliability, as the epoxy (meth)acrylate resin (b1) used in the present invention, the following epoxy (meth)acrylate resin (b1) can be particularly suitably used -1) and/or epoxy (meth)acrylate resin (b1-2) (hereinafter may be referred to as "carboxy group-containing epoxy (meth)acrylate resin"). Moreover, as (b1) epoxy (meth)acrylate resin, from a viewpoint of outgassing, what has an aromatic ring in a main chain can be used more suitably.

＜環氧(甲基)丙烯酸酯系樹脂(b1-1)＞ 藉由如下方法獲得之鹼可溶性樹脂：使環氧樹脂加成α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯，任意使含異氰酸基化合物反應，其後進而與多元酸及/或其酸酐反應。 ＜環氧(甲基)丙烯酸酯系樹脂(b1-2)＞ 藉由如下方法獲得之鹼可溶性樹脂：使環氧樹脂加成α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯，任意使含異氰酸基化合物反應，其後進而與多元醇、及多元酸及/或其酸酐反應。 <Epoxy (meth)acrylate resin (b1-1)> Alkali-soluble resin obtained by the following method: adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group to epoxy resin, optionally reacting isocyanate group-containing compound, Then, it reacts with a polybasic acid and/or its acid anhydride. <Epoxy (meth)acrylate resin (b1-2)> Alkali-soluble resin obtained by the following method: adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group to epoxy resin, optionally reacting isocyanate group-containing compound, Then, it reacts with a polyhydric alcohol, a polybasic acid, and/or its acid anhydride.

此處，所謂環氧樹脂亦包括藉由熱硬化形成樹脂以前之原料化合物在內加以表述，作為該環氧樹脂，可自公知之環氧樹脂中適當選擇使用。又，環氧樹脂可使用使酚性化合物與表鹵醇反應所獲得之化合物。作為酚性化合物，較佳為具有二元或者二元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，例如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複加成反應物和表鹵醇之反應產物之環氧樹脂、含金剛烷基環氧樹脂、茀型環氧樹脂，其中，可更適宜地使用主鏈具有芳香族環者。 Here, the term "epoxy resin" includes the raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins. Moreover, the compound obtained by making a phenolic compound react with an epihalohydrin can be used for an epoxy resin. The phenolic compound is preferably a compound having a divalent or more divalent phenolic hydroxyl group, and may be a monomer or a polymer. As the kind of epoxy resin used as a raw material, for example, cresol novolac epoxy resin, phenol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, trisphenol epoxy resin can be suitably used Methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin as the reaction product of the complex addition reactant of dicyclopentadiene and phenol or cresol and epihalohydrin Among resins, adamantyl-containing epoxy resins, and pyrene-type epoxy resins, those having an aromatic ring in the main chain can be preferably used.

作為環氧樹脂，例如可適宜地使用雙酚A型環氧樹脂(例如三菱化學公司製造之「jER(註冊商標，下同)828」、「jER1001」、「jER1002」、「jER1004」等)、藉由雙酚A型環氧樹脂之醇性羥基與表氯醇之反應所獲得之環氧樹脂(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「jER807」、「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所獲得之環氧樹脂(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」、陶氏化學公司製造之「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，下同)-102S」、「EOCN-1020」、「EOCN-104S」)、異氰尿酸三縮水甘油酯(例如日產化學公司製造之「TEPIC(註冊商標)」)、三酚甲烷型環氧樹脂(例如日本化藥公司製造之「EPPN(註冊商標，下同)-501」、「EPPN-502」、「EPPN-503」)、脂環式環氧樹脂(大賽璐公司製造之「Celloxide(註冊商標，下同)2021P」、「Celloxide EHPE」)、對由二環戊二烯與苯酚之反應所獲得之苯酚樹脂進行縮水甘油化而成之環氧樹脂(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。具體而言，例如可例舉：作為下述通式(B1)所表示之環氧樹脂之日本化藥公司製造之「XD-1000」、作為下述通式(B2)所表示之環氧樹脂之日本化藥公司製造之「NC-3000」、作為下述通式(B3)所表示之環氧樹脂之大阪有機化學工業公司製造之「E-201」、作為下述通式(B4)所表示之環氧樹脂之新日鐵住金化學公司製造之「ESF-300」。As the epoxy resin, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, the same below) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation), Epoxy resin obtained by the reaction of alcoholic hydroxyl group of bisphenol A epoxy resin with epichlorohydrin (such as "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent weight 323, softening point 76°C)) , Bisphenol F type resin (such as "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), through the alcoholic hydroxyl group of bisphenol F type epoxy resin Epoxy resin obtained by reaction with epichlorohydrin (such as "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S-type epoxy resin, biphenyl glycidol Ethers (such as "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac epoxy resins (such as "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" manufactured by Mitsubishi Chemical Corporation, "EP- 154", "DEN-438" manufactured by Dow Chemical Company), (ortho, meta, para) cresol novolac epoxy resin (such as "EOCN (registered trademark, the same below)-102S manufactured by Nippon Kayaku Co., Ltd.) ", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (such as "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenol methane epoxy resin (such as Nippon Kayaku) "EPPN (registered trademark, the same below)-501", "EPPN-502", "EPPN-503"), cycloaliphatic epoxy resin ("Celloxide (registered trademark, the same below) manufactured by Daicel) 2021P", "Celloxide EHPE"), epoxy resins (such as "EXA-7200" manufactured by DIC Corporation, Nippon Kayaku Co., Ltd. "NC-7300" manufactured by the company, epoxy resin represented by the following general formulas (B1) to (B4). Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B1), and an epoxy resin represented by the following general formula (B2) may, for example, be mentioned. "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd., which is an epoxy resin represented by the following general formula (B3), and "E-201", which is an epoxy resin represented by the following general formula (B4) "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. is the epoxy resin indicated.

[化11]

Figure 02_image021
[Chemical 11]
Figure 02_image021

於上述通式(B1)中，a為平均值，表示0～10之數，R 111分別獨立地表示氫原子、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。再者，1分子中所存在之複數個R 111分別可相同亦可不同。 In the above general formula (B1), a is an average value and represents a number from 0 to 10, and R 111 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and a cycloalkane having 3 to 10 carbon atoms. phenyl, naphthyl, or biphenyl. In addition, the plurality of R 111 present in one molecule may be the same or different, respectively.

[化12]

Figure 02_image023
[Chemical 12]
Figure 02_image023

於上述通式(B2)中，b1及b2分別獨立地為平均值，表示0～10之數，R 121分別獨立地表示氫原子、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。再者，1分子中所存在之複數個R 121分別可相同亦可不同。 In the above general formula (B2), b1 and b2 are each independently an average value and represent a number from 0 to 10, and R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon number 3 ~10 of cycloalkyl, phenyl, naphthyl, or biphenyl. In addition, the plurality of R 121 present in one molecule may be the same or different, respectively.

[化13]

Figure 02_image025
[Chemical 13]
Figure 02_image025

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。其中，分子結構中包含1個以上金剛烷結構。c表示2或3。In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). Among them, one or more adamantane structures are included in the molecular structure. c means 2 or 3.

[化14]

Figure 02_image027
[Chemical 14]
Figure 02_image027

於上述通式(B3-1)及(B3-2)中，R 131～R 134及R 135～R 137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。 In the above general formulas (B3-1) and (B3-2), R 131 to R 134 and R 135 to R 137 each independently represent an optionally substituted adamantyl group, a hydrogen atom, and an optionally substituted carbon In the alkyl group of numbers 1 to 12, or the phenyl group which may have a substituent, * represents a bond.

[化15]

Figure 02_image029
[Chemical 15]
Figure 02_image029

於上述通式(B4)中，p及q分別獨立地表示0～4之整數，R 141及R 142分別獨立地表示碳數1～4之烷基或鹵素原子，R 143及R 144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。 In the above general formula (B4), p and q each independently represent an integer of 0 to 4, R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 143 and R 144 are each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or more.

其中，較佳為使用通式(B1)～(B4)中之任一者所表示之環氧樹脂。Among them, the epoxy resin represented by any one of the general formulae (B1) to (B4) is preferably used.

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，可例舉：(甲基)丙烯酸、丁烯酸、鄰、間或對乙烯苯甲酸、(甲基)丙烯酸之α位鹵烷基、烷氧基、鹵素、硝基、氰基取代物等單羧酸、2-(甲基)丙烯醯氧基乙基琥珀酸、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)丙烯醯氧基丙基琥珀酸、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)丙烯醯氧基丁基琥珀酸、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、作為於丙烯酸上加成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、或於(甲基)丙烯酸羥基烷基酯、季戊四醇三(甲基)丙烯酸酯上加成琥珀酸(酐)、鄰苯二甲酸(酐)、順丁烯二酸(酐)等酸(酸酐)而成之單體、(甲基)丙烯酸二聚物等。 其中，從感度方面考慮，尤佳為(甲基)丙烯酸。 As α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group, (meth)acrylic acid, crotonic acid, ortho-, meta- or para-vinyl benzoic acid, (meth)acrylic acid, Monocarboxylic acids such as α-haloalkyl, alkoxy, halogen, nitro, and cyano substituents of acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)propylene Ethyloxyethyladipic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(methyl) ) Acrylooxyethyl maleic acid, 2-(meth)acrylooxypropyl succinic acid, 2-(meth)acrylooxypropyl adipic acid, 2-(methyl) Acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2- (Meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-( Meth)acryloyloxybutylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, ε-caprolactone, β-propiolactone, γ- Monomers of lactones such as butyrolactone and delta-valerolactone, or adding succinic acid (anhydride), o-hydroxyalkyl (meth)acrylate and pentaerythritol tri(meth)acrylate to Monomers made from acids (acid anhydrides) such as phthalic acid (anhydride) and maleic acid (anhydride), (meth)acrylic acid dimers, and the like. Among them, (meth)acrylic acid is particularly preferred from the viewpoint of sensitivity.

作為使環氧樹脂加成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反應。作為此處所使用之酯化觸媒，可使用三乙基胺、三甲基胺、苄基二甲基胺、苄基二乙基胺等三級胺；氯化四甲基銨、氯化四乙基銨、氯化十二烷基三甲基銨等四級銨鹽等。As a method of adding an α,β-unsaturated monocarboxylic acid or an 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 monocarboxylate having a carboxyl group can be reacted with epoxy resin in the presence of an esterification catalyst at a temperature of 50-150°C. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine can be used; tetramethylammonium chloride, tetramethylammonium chloride Ethyl ammonium, dodecyl trimethyl ammonium chloride and other quaternary ammonium salts, etc.

關於環氧樹脂、α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯、及酯化觸媒之各成分，可分別選擇各成分之一種使用，亦可併用兩種以上。 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。藉由將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設為上述下限值以上，可抑制不飽和基之導入量之不充分，有隨後之與多元酸及/或其酸酐之反應亦容易變充分之傾向。另一方面，藉由設為上述上限值以下，可抑制α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯之未反應物之殘留，確認到容易使硬化特性變良好之傾向。 Regarding the components of epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having carboxyl group, and esterification catalyst, one of the components can be selected and used separately, or they can be used in combination two or more. The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin, and more preferably It is in the range of 0.7 to 1.1 equivalents. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be more than the above lower limit value, the insufficient amount of unsaturated group introduced can be suppressed, and there are The subsequent reaction with the polybasic acid and/or its acid anhydride also tends to be sufficient. On the other hand, by setting the above upper limit value or less, the remaining unreacted products of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and it has been confirmed that it is easy to make Tendency to improve hardening properties.

作為多元酸及/或其酸酐，例如可例舉：順丁烯二酸、琥珀酸、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、氯橋酸、甲基四氫鄰苯二甲酸、聯苯四羧酸、及該等之酸酐。As a polybasic acid and/or its acid anhydride, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid can be mentioned. , trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro bridge acid, methyltetrahydrophthalic acid, biphenyltetrahydrophthalic acid Carboxylic acids, and their anhydrides.

較佳為順丁烯二酸、琥珀酸、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、或該等之酸酐。尤佳為四氫鄰苯二甲酸、聯苯四羧酸、四氫鄰苯二甲酸酐、或聯苯四羧酸二酐。Preferably maleic acid, succinic acid, itonic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid , or such anhydrides. Especially preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

多元酸及/或其酸酐之加成反應可使用公知之方法進行，可在與α,β-不飽和單羧酸或具有羧基之α,β-不飽和單羧酸酯對環氧樹脂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/或其酸酐成分之加成量較佳為如所生成之含羧基環氧(甲基)丙烯酸酯系樹脂之酸值達到10～150 mgKOH/g之範圍的程度，進而較佳為如達到20～140 mgKOH/g之範圍之程度。藉由設為上述下限值以上，有鹼性顯影性變良好之傾向。藉由設為上述上限值以下，有硬化性能變良好之傾向。The addition reaction of the polybasic acid and/or its acid anhydride can be carried out using a known method. Continue the reaction to obtain the target under the same conditions as the reaction. The addition amount of the polybasic acid and/or its acid anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin reaches the range of 10 to 150 mgKOH/g, and more preferably Such as to reach the extent of the range of 20 ~ 140 mgKOH/g. By setting it as the said lower limit or more, there exists a tendency for alkali developability to become favorable. There exists a tendency for hardenability to become favorable by setting it as the said upper limit or less.

亦可於多元酸及/或其酸酐之加成反應時，添加三羥甲基丙烷、二-三羥甲基丙烷、季戊四醇、二季戊四醇、三羥甲基乙烷、1,2,3-丙烷三醇等多官能醇(多元醇)，導入多分支結構。於該情形時，多元酸及/或其酸酐與多官能醇之混合順序並無特別限制。藉由加熱，多元酸及/或其酸酐會對存在於環氧樹脂與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、和多官能醇之混合物中之任一羥基進行加成反應。Trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propane can also be added during the addition reaction of polybasic acid and/or its acid anhydride Polyfunctional alcohols (polyols) such as triols are introduced into multi-branched structures. In this case, the mixing order of the polybasic acid and/or its acid anhydride and the polyfunctional alcohol is not particularly limited. By heating, polybasic acids and/or their anhydrides will react to the reactants existing in epoxy resins and α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with carboxyl groups, and polyfunctional alcohols. Any hydroxyl group in the mixture undergoes an addition reaction.

藉由使用多元醇，有可使(b1)環氧(甲基)丙烯酸酯樹脂之分子量增大，向分子中導入分支，可取得分子量與黏度之平衡之傾向。又，有可增加向分子中之酸基之導入率，容易取得感度或密接性等之平衡之傾向。By using a polyol, the molecular weight of the (b1) epoxy (meth)acrylate resin can be increased, a branch can be introduced into the molecule, and the molecular weight and viscosity can be balanced. In addition, the introduction rate of the acid group into the molecule can be increased, and the balance of sensitivity and adhesiveness tends to be easily achieved.

作為含羧基環氧(甲基)丙烯酸酯系樹脂，除了上述樹脂以外，例如還可例舉韓國公開專利第10-2013-0022955號公報中所記載者。As a carboxyl group-containing epoxy (meth)acrylate resin, other than the above-mentioned resins, for example, those described in Korean Laid-Open Patent Publication No. 10-2013-0022955 can be exemplified.

含羧基環氧(甲基)丙烯酸酯系樹脂之藉由凝膠滲透層析法(GPC)測定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1500以上，更佳為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30000以下，較佳為20000以下，更佳為15000以下。上述上限及下限可任意地組合。例如較佳為1000～30000，更佳為1500～20000，進而較佳為1500～15000，更進而較佳為2000～15000。藉由設為上述下限值以上，有可抑制對於顯影液之溶解性變得過高之傾向。藉由設為上述上限值以下，有容易使對於顯影液之溶解性變良好之傾向。The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably It is 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1000-30000 are preferable, 1500-20000 are more preferable, 1500-15000 are still more preferable, and 2000-15000 are still more preferable. By setting it as the said lower limit or more, the tendency for the solubility with respect to a developer to become too high can be suppressed. By setting it below the said upper limit, there exists a tendency for the solubility with respect to a developer to become favorable easily.

含羧基環氧(甲基)丙烯酸酯系樹脂之酸值並無特別限定，較佳為20 mgKOH/g以上，更佳為40 mgKOH/g以上，進而較佳為60 mgKOH/g以上，更進而較佳為80 mgKOH/g以上，尤佳為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130 mgKOH/g以下，尤佳為120 mgKOH/g以下。上述上限及下限可任意地組合。例如，較佳為20 mgKOH/g～200 mgKOH/g，更佳為60 mgKOH/g～150 mgKOH/g，進而較佳為80 mgKOH/g～130 mgKOH/g，更進而較佳為100 mgKOH/g～130 mgKOH/g。藉由設為上述下限值以上，有顯影溶解性提高，解像性變良好之傾向。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良好之傾向。The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, more preferably 60 mgKOH/g or more, and further Preferably it is 80 mgKOH/g or more, more preferably 100 mgKOH/g or more, and more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, further preferably 130 mgKOH/g or less, especially 120 mgKOH/g or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 20 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 150 mgKOH/g, more preferably 80 mgKOH/g to 130 mgKOH/g, and still more preferably 100 mgKOH/g. g～130 mgKOH/g. By setting it as the said lower limit or more, developing solubility improves and there exists a tendency for resolution to become favorable. There exists a tendency for the residual film ratio of a photosensitive coloring composition to become favorable by making it below the said upper limit.

環氧(甲基)丙烯酸酯系樹脂之化學結構並無特別限定，從顯影性、可靠性之觀點考慮，較佳為含有具有下述通式(b1-I)所表示之部分結構之環氧(甲基)丙烯酸酯系樹脂(以下，有時簡稱為「(b1-I)環氧(甲基)丙烯酸酯系樹脂」)及/或具有下述通式(b1-II)所表示之部分結構之環氧(甲基)丙烯酸酯系樹脂(以下，有時簡稱為「(b1-II)環氧(甲基)丙烯酸酯系樹脂」)。The chemical structure of the epoxy (meth)acrylate resin is not particularly limited, but from the viewpoint of developability and reliability, it is preferable to contain an epoxy resin having a partial structure represented by the following general formula (b1-I) (Meth)acrylate-based resin (hereinafter, sometimes abbreviated as "(b1-I) epoxy (meth)acrylate-based resin") and/or a moiety represented by the following general formula (b1-II) Structured epoxy (meth)acrylate resin (hereinafter, it may be abbreviated as "(b1-II) epoxy (meth)acrylate resin").

[化16]

Figure 02_image031
[Chemical 16]
Figure 02_image031

式(b1-I)中，R 11表示氫原子或甲基，R 12表示可具有取代基之二價烴基，k表示1或2，*表示鍵結鍵。 式(b1-I)中之苯環可進而經任意之取代基取代。 In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in the formula (b1-I) may be further substituted with any substituent.

[化17]

Figure 02_image033
[Chemical 17]
Figure 02_image033

式(b1-II)中，R 13分別獨立地表示氫原子或甲基，R 14表示具有環狀烴基作為側鏈之二價烴基，R 15及R 16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。 In formula (b1-II), R 13 each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R 15 and R 16 each independently represent the second group which may have a substituent Valence aliphatic group, m and n each independently represent an integer of 0 to 2, and * represents a bond.

＜(b1-I)環氧(甲基)丙烯酸酯系樹脂＞ 首先，對具有上述通式(b1-I)所表示之部分結構之環氧(甲基)丙烯酸酯系樹脂詳細加以說明。 <(b1-I) Epoxy (meth)acrylate resin> First, the epoxy (meth)acrylate resin which has a partial structure represented by the said general formula (b1-I) is demonstrated in detail.

[化18]

Figure 02_image035
[Chemical 18]
Figure 02_image035

式(b1-I)中，R 11表示氫原子或甲基，R 12表示可具有取代基之二價烴基，k表示1或2，*表示鍵結鍵。 式(b1-I)中之苯環可進而經任意之取代基取代。 In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in the formula (b1-I) may be further substituted with any substituent.

(R 12) 於上述式(b1-I)中，R 12表示可具有取代基之二價烴基。 作為二價烴基，可例舉：二價脂肪族基、二價芳香族環基、連結1個以上之二價脂肪族基與1個以上之二價芳香族環基而成之基。 (R 12 ) In the above formula (b1-I), R 12 represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may, for example, be a divalent aliphatic group, a divalent aromatic ring group, or a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

二價脂肪族基可例舉：直鏈狀、支鏈狀、環狀脂肪族基。其中，從顯影溶解性之觀點考慮，較佳為直鏈狀脂肪族基。另一方面，從減少顯影液向曝光部之滲透之觀點考慮，較佳為環狀脂肪族基。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。上述上限及下限可任意地組合。例如，較佳為1～20，更佳為1～15，進而較佳為1～10。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。The divalent aliphatic group may, for example, be a linear, branched or cyclic aliphatic group. Among them, a linear aliphatic group is preferred from the viewpoint of developing solubility. On the other hand, a cyclic aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1-20 are preferable, 1-15 are more preferable, and 1-10 are still more preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

作為二價直鏈狀脂肪族基，例如可例舉：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。其中，從骨架之剛直性之觀點考慮，較佳為亞甲基。 作為二價支鏈狀脂肪族基，可例舉於上述二價直鏈狀脂肪族基上例如具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基作為側鏈之結構。 二價環狀脂肪族基所具有之環之數量並無特別限定，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。上述上限及下限可任意地組合。例如，較佳為1～12，更佳為1～10，進而較佳為2～10。藉由設為上述下限值以上，有成為牢固之膜，基板密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 作為二價環狀脂肪族基，例如可例舉自環己烷環、環庚烷環、環癸環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環、環十二烷環、二環戊二烯、二環戊烷等環上去除2個氫原子而成之基。其中，從骨架之剛直性之觀點考慮，較佳為自二環戊二烯環、二環戊烷環、金剛烷環上去除2個氫原子而成之基。 As a divalent linear aliphatic group, a methylene group, an ethylidene group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, and a n-heptide group are mentioned, for example. Among them, a methylene group is preferred from the viewpoint of rigidity of the skeleton. Examples of the divalent branched chain aliphatic group include those having, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second Butyl and tertiary butyl as the structure of the side chain. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1-12 are preferable, 1-10 are more preferable, and 2-10 are still more preferable. By setting it as the said lower limit or more, it becomes a firm film and there exists a tendency for the board|substrate adhesiveness to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. As the divalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norcane ring, an isobornane ring, an adamantane ring, and a cyclodecane ring can be mentioned. A group formed by removing two hydrogen atoms from a ring such as dioxane ring, dicyclopentadiene, and dicyclopentane. Among them, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, and an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

作為二價脂肪族基可具有之取代基，例如可例舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基。其中，從合成容易性之觀點考慮，較佳為未經取代。As a substituent which the divalent aliphatic group may have, for example, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group may be mentioned. Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.

作為二價芳香族環基，可例舉二價芳香族烴環基及二價芳香族雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。上述上限及下限可任意地組合。例如，較佳為4～20，更佳為5～15，進而較佳為6～10。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。As a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

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。作為芳香族烴環基，例如可例舉：具有2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 110135753-A0304-12-01
環、聯三伸苯環、苊環、螢蒽環、茀環。 又，作為芳香族雜環基中之芳香族雜環，可為單環，亦可為縮合環。作為芳香族雜環基，例如可例舉：具有2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、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。 其中，從圖案特性之觀點考慮，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,
Figure 110135753-A0304-12-01
Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring. Moreover, as an aromatic heterocyclic ring in an aromatic heterocyclic group, a monocyclic ring may be sufficient, and a condensed ring may be sufficient as it. Examples of the aromatic heterocyclic group include a furan ring having two free valences, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline phenoline ring, phenanthrene ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among them, from the viewpoint of pattern characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

作為二價芳香族環基可具有之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。其中，從顯影溶解性之觀點考慮，較佳為未經取代。As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group are mentioned, for example. Among them, unsubstituted is preferable from the viewpoint of developing solubility.

作為連結1個以上之二價脂肪族基與1個以上之二價芳香族環基而成之基，可例舉連結1個以上之上述二價脂肪族基與1個以上之上述二價芳香族環基而成之基。 二價脂肪族基之數量並無特別限定，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。例如，較佳為1～10，更佳為1～5，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 二價芳香族環基之數量並無特別限定，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。例如，較佳為1～10，更佳為1～5，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 As a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic groups may, for example, be linked. The base of the ring group. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

作為連結1個以上之二價脂肪族基與1個以上之二價芳香族環基而成之基，例如可例舉下述式(b1-I-A)～(b1-I-F)所表示之基。其中，從骨架之剛直性與膜之疏水化之觀點考慮，較佳為下述式(b1-I-A)所表示之基。As a group which connects one or more divalent aliphatic groups and one or more divalent aromatic ring groups, for example, groups represented by the following formulae (b1-I-A) to (b1-I-F) can be mentioned. Among them, a group represented by the following formula (b1-I-A) is preferred from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

[化19]

Figure 02_image037
[Chemical 19]
Figure 02_image037

於上述式(b1-I)中，k表示1或2。從密接性、圖案性之觀點考慮，k較佳為1。從耐NMP(N-methyl-2-pyrrolidone，N-甲基-2-吡咯啶酮)性之觀點考慮，k較佳為2。於(b1-I)環氧(甲基)丙烯酸酯中亦可含有k為1之部分結構與k為2之部分結構這兩者。In the above formula (b1-I), k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1. From the viewpoint of NMP (N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone) resistance, k is preferably 2. Both the partial structure in which k is 1 and the partial structure in which k is 2 may be contained in (b1-I) epoxy (meth)acrylate.

式(b1-I)中之苯環可進而經任意之取代基取代。作為式(b1-I)中之苯環所容許之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。於式(b1-I)中之苯環具有取代基之情形時，其取代基之數量並無特別限定，可為1個，亦可為2個以上。 從圖案特性之觀點考慮，式(b1-I)中之苯環較佳為未經取代。 The benzene ring in the formula (b1-I) may be further substituted with any substituent. Examples of acceptable substituents for the benzene ring in the formula (b1-I) include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. When the benzene ring in formula (b1-I) has a substituent, the number of the substituent is not particularly limited, and may be one or two or more. From the viewpoint of pattern characteristics, the benzene ring in the formula (b1-I) is preferably unsubstituted.

從合成之簡易性之觀點考慮，式(b1-I)所表示之部分結構較佳為下述式(b1-I-1)所表示之部分結構。From the viewpoint of simplicity of synthesis, the partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1).

[化20]

Figure 02_image039
[hua 20]
Figure 02_image039

式(b1-I-1)中，R 11、R 12及k與上述式(b1-I)之R 11、R 12及k含義相同，R X表示氫原子或多元酸殘基，*表示鍵結鍵。式(b1-I-1)中之苯環可進而經任意之取代基取代。 In the formula (b1-I-1), R 11 , R 12 and k have the same meanings as R 11 , R 12 and k in the above formula (b1-I), R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond key. The benzene ring in the formula (b1-I-1) may be further substituted with an arbitrary substituent.

所謂多元酸殘基意指自多元酸或其酸酐去除1個OH基而成之一價基。作為多元酸，例如可例舉：順丁烯二酸、琥珀酸、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、氯橋酸、甲基四氫鄰苯二甲酸、聯苯四羧酸。 從圖案特性之觀點考慮，較佳為順丁烯二酸、琥珀酸、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、聯苯四羧酸。 The polybasic acid residue means a valent group obtained by removing one OH group from a polybasic acid or its acid anhydride. As the polybasic acid, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid may be mentioned. , benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro bridge acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid. From the viewpoint of pattern characteristics, maleic acid, succinic acid, itonic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid are preferred. Formic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

式(b1-I-1)中之苯環可進而經任意之取代基取代。作為取代基，可較佳地採用關於式(b1-I)中之苯環所例舉者。The benzene ring in the formula (b1-I-1) may be further substituted with an arbitrary substituent. As the substituent, those exemplified with respect to the benzene ring in the formula (b1-I) can be preferably used.

(b1-I)環氧(甲基)丙烯酸酯系樹脂1分子中所含之上述式(b1-I-1)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R X為氫原子者與R X為多元酸殘基者。 (b1-I) The partial structure represented by the above formula (b1-I-1) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types, for example, may be mixed R X is a hydrogen atom and R X is a polyacid residue.

又，(b1-I)環氧(甲基)丙烯酸酯系樹脂1分子中所含之上述式(b1-I)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，進而較佳為15以下。較佳為1～20，更佳為1～15，進而較佳為3～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。In addition, the number of the partial structures represented by the above formula (b1-I) contained in one molecule of the epoxy (meth)acrylate resin (b1-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less. Preferably it is 1-20, More preferably, it is 1-15, More preferably, it is 3-15. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

(b1-I)環氧(甲基)丙烯酸酯系樹脂之藉由凝膠滲透層析法(GPC)測定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，更進而較佳為3000以上，尤佳為4000以上，最佳為5000以上，且通常為30000以下，較佳為20000以下，更佳為15000以下。上述上限及下限可任意地組合。例如，較佳為1000～30000，更佳為1500～2000，進而較佳為1500～15000，更進而較佳為2000～1500。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良好之傾向。藉由設為上述上限值以下，有對於顯影液之溶解性變良好之傾向。(b1-I) The weight average molecular weight (Mw) of epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, but preferably 1000 or more , more preferably 1500 or more, more preferably 2000 or more, still more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 the following. The above upper limit and lower limit can be arbitrarily combined. For example, 1000-30000 are preferable, 1500-2000 are more preferable, 1500-15000 are still more preferable, and 2000-1500 are still more preferable. By setting it as the said lower limit or more, there exists a tendency for the residual film rate of a photosensitive coloring composition to become favorable. By setting it below the said upper limit, the solubility with respect to a developer tends to become favorable.

(b1-I)環氧(甲基)丙烯酸酯系樹脂之酸值並無特別限定，較佳為20 mgKOH/g以上，更佳為40 mgKOH/g以上，進而較佳為60 mgKOH/g以上，更進而較佳為80 mgKOH/g以上，尤佳為100 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，更進而較佳為130 mgKOH/g以下，尤佳為120 mgKOH/g以下。上述上限及下限可任意地組合。例如，較佳為20 mgKOH/g～200 mgKOH/g，更佳為60 mgKOH/g～150 mgKOH/g，進而較佳為80 mgKOH/g～130 mgKOH/g，更進而較佳為100 mgKOH/g～130 mgKOH/g。藉由設為上述下限值以上，有顯影溶解性提高，解像性變良好之傾向。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良好之傾向。The acid value of the (b1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and still more preferably 60 mgKOH/g or more , more preferably 80 mgKOH/g or more, more preferably 100 mgKOH/g or more, and more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 130 mgKOH/g or less, particularly preferably 120 mgKOH/g or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 20 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 150 mgKOH/g, more preferably 80 mgKOH/g to 130 mgKOH/g, and still more preferably 100 mgKOH/g. g～130 mgKOH/g. By setting it as the said lower limit or more, developing solubility improves and there exists a tendency for resolution to become favorable. There exists a tendency for the residual film ratio of a photosensitive coloring composition to become favorable by making it below the said upper limit.

以下例舉(b1-I)環氧(甲基)丙烯酸酯系樹脂之具體例。再者，例中之*表示鍵結鍵。Specific examples of the (b1-I) epoxy (meth)acrylate-based resin are listed below. Furthermore, * in the example represents a bond bond.

[化21]

Figure 02_image041
[Chemical 21]
Figure 02_image041

[化22]

Figure 02_image043
[Chemical 22]
Figure 02_image043

[化23]

Figure 02_image045
[Chemical 23]
Figure 02_image045

[化24]

Figure 02_image047
[Chemical 24]
Figure 02_image047

＜(b1-II)環氧(甲基)丙烯酸酯系樹脂＞ 對具有上述通式(b1-II)所表示之部分結構之環氧(甲基)丙烯酸酯系樹脂詳細加以說明。 <(b1-II) Epoxy (meth)acrylate resin> The epoxy (meth)acrylate type resin which has the partial structure represented by the said general formula (b1-II) is demonstrated in detail.

[化25]

Figure 02_image049
[Chemical 25]
Figure 02_image049

式(b1-II)中，R 13分別獨立地表示氫原子或甲基，R 14表示具有環狀烴基作為側鏈之二價烴基，R 15及R 16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。 In formula (b1-II), R 13 each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R 15 and R 16 each independently represent the second group which may have a substituent Valence aliphatic group, m and n each independently represent an integer of 0 to 2, and * represents a bond.

(R 14) 於上述通式(b1-II)中，R 14表示具有環狀烴基作為側鏈之二價烴基。 作為環狀烴基，可例舉脂肪族環基或芳香族環基。 (R 14 ) In the above general formula (b1-II), R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

脂肪族環基所具有之環之數量並無特別限定，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。例如，較佳為1～10，更佳為1～5，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 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。上述上限及下限可任意地組合。例如，較佳為4～40，更佳為4～30，進而較佳為6～20，尤佳為8～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 作為脂肪族環基中之脂肪族環，例如可例舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環、環十二烷環。其中，從感光性著色組合物之殘膜率與解像性之觀點考慮，較佳為金剛烷環。 The number of rings possessed by the alicyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. 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, further preferably 20 or less, particularly preferably 15 or less . The above upper limit and lower limit can be arbitrarily combined. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, 8-15 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norcane ring, an isobornane ring, and an adamantane ring. , cyclododecane ring. Among them, an adamantane ring is preferable from the viewpoint of the residual film ratio and the resolution of the photosensitive coloring composition.

芳香族環基所具有之環之數量並無特別限定，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。上述上限及下限可任意地組合。例如，較佳為1～10，更佳為1～5，進而較佳為1～4，更進而較佳為2～4，尤佳為3～4。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。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，更進而較佳為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。上述上限及下限可任意地組合。例如，較佳為4～40，更佳為6～40，進而較佳為8～30，更進而較佳為10～20，尤佳為12～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有圖案特性變良好之傾向。 作為芳香族環基中之芳香族環，例如可例舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 110135753-A0304-12-01
環、聯三伸苯環、苊環、螢蒽環、茀環。其中，從圖案特性之觀點考慮，較佳為茀環。 The number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, more preferably 4 or less . The above upper limit and lower limit can be arbitrarily combined. For example, 1-10 are preferable, 1-5 are more preferable, 1-4 are still more preferable, 2-4 are still more preferable, 3-4 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. As the aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group may, for example, be mentioned. Moreover, 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, and more preferably 40 or less, more preferably It is 30 or less, more preferably 20 or less, particularly preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 4-40 are preferable, 6-40 are more preferable, 8-30 are still more preferable, 10-20 are still more preferable, 12-15 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, there exists a tendency for a pattern characteristic to become favorable. As the aromatic ring in the aromatic ring group, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzopyrene ring,
Figure 110135753-A0304-12-01
Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring. Among them, from the viewpoint of pattern characteristics, a pylon is preferable.

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，例如可例舉：二價脂肪族基、二價芳香族環基、連結1個以上之二價脂肪族基與1個以上之二價芳香族環基而成之基。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 bivalent aliphatic group, a bivalent aromatic ring group, a A group consisting of one or more divalent aromatic ring groups.

二價脂肪族基可例舉：直鏈狀、支鏈狀、環狀脂肪族基。其中，從顯影溶解性之觀點考慮，較佳為直鏈狀脂肪族基，另一方面，從減少顯影液向曝光部之滲透之觀點考慮，較佳為環狀脂肪族基。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。上述上限及下限可任意地組合。例如，較佳為1～25，更佳為3～20，進而較佳為6～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。The divalent aliphatic group may, for example, be a linear, branched or cyclic aliphatic group. Among them, a linear aliphatic group is preferred from the viewpoint of developing solubility, and a cyclic aliphatic group is preferred from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and more preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1-25 are preferable, 3-20 are more preferable, and 6-15 are still more preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

作為二價直鏈狀脂肪族基，例如可例舉：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。其中，從骨架之剛直性之觀點考慮，較佳為亞甲基。 作為二價支鏈狀脂肪族基，例如可例舉於上述二價直鏈狀脂肪族基上具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基作為側鏈之結構。 二價環狀脂肪族基所具有之環之數量並無特別限定，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。例如，較佳為1～10，更佳為1～5，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有成為牢固之膜，基板密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 作為二價環狀脂肪族基，例如可例舉自環己烷環、環庚烷環、環癸環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環、環十二烷環之環上去除2個氫原子而成之基。其中，從骨架之剛直性之觀點考慮，較佳為自金剛烷環上去除2個氫原子而成之基。 As a divalent linear aliphatic group, a methylene group, an ethylidene group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, and a n-heptide group are mentioned, for example. Among them, a methylene group is preferred from the viewpoint of rigidity of the skeleton. Examples of the divalent branched-chain aliphatic group include the above-mentioned divalent straight-chain aliphatic groups having methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second Butyl and tertiary butyl as the structure of the side chain. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, it becomes a firm film and there exists a tendency for the board|substrate adhesiveness to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. As the divalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norcane ring, an isobornane ring, an adamantane ring, and a cyclodecane ring can be mentioned. A base formed by removing two hydrogen atoms from a dioxane ring. Among them, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred from the viewpoint of rigidity of the skeleton.

作為二價脂肪族基可具有之取代基，例如可例舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基。其中，從合成容易性之觀點考慮，較佳為未經取代。As a substituent which the divalent aliphatic group may have, for example, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group may be mentioned. Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.

作為二價芳香族環基，可例舉二價芳香族烴環基及二價芳香族雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，進而較佳為15以下。例如，較佳為4～30，更佳為5～20，進而較佳為6～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。As a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

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。作為芳香族烴環基，例如可例舉：具有2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 110135753-A0304-12-01
環、聯三伸苯環、苊環、螢蒽環、茀環。 作為芳香族雜環基中之芳香族雜環，可為單環，亦可為縮合環。作為芳香族雜環基，例如可例舉：具有2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、㖕啉環、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。其中，從圖案特性之觀點考慮，較佳為具有2個自由原子價之苯環或萘環，更佳為具有2個自由原子價之苯環。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring having two free valences, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a condensed tetraphenyl ring, a pyrene ring, a benzopyrene ring,
Figure 110135753-A0304-12-01
Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, perylene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring having two free valences, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzene Isoxazole, benzisothiazole, benzimidazole, pyridine, pyridine, pyridine, pyrimidine, tris, quinoline, isoquinoline, quinoline, quinoline Linen ring, phenanthrene ring, benzimidazole ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among them, from the viewpoint of pattern characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

作為二價芳香族環基可具有之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。其中，從顯影溶解性之觀點考慮，較佳為未經取代。As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group are mentioned, for example. Among them, unsubstituted is preferable from the viewpoint of developing solubility.

作為連結1個以上之二價脂肪族基與1個以上之二價芳香族環基而成之基，可例舉連結1個以上之上述二價脂肪族基與1個以上之上述二價芳香族環基而成之基。 二價脂肪族基之數量並無特別限定，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。例如，較佳為1～10，更佳為1～5，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 二價芳香族環基之數量並無特別限定，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。例如，較佳為1～10，更佳為1～5，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度變差或顯影時之膜減少，使解像性提高之傾向。 As a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic groups can be exemplified. The base of the ring group. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

作為連結1個以上之二價脂肪族基與1個以上之二價芳香族環基而成之基，例如可例舉上述式(b1-I-A)～(b1-I-F)所表示之基。其中，從骨架之剛直性與膜之疏水化之觀點考慮，較佳為上述式(b1-I-C)所表示之基。As a group which connects one or more divalent aliphatic groups and one or more divalent aromatic ring groups, groups represented by the above formulae (b1-I-A) to (b1-I-F) may, for example, be mentioned. Among them, the group represented by the above formula (b1-I-C) is preferred from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

作為側鏈之環狀烴基對於該等二價烴基之鍵結態樣並無特別限定，例如可例舉：脂肪族基或芳香族環基之1個氫原子經作為側鏈之環狀烴基取代之態樣、或包含脂肪族基之1個碳原子在內構成作為側鏈之環狀烴基之態樣。The cyclic hydrocarbon group as the side chain is not particularly limited to the bonding state of these divalent hydrocarbon groups. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain. form, or form a cyclic hydrocarbon group as a side chain including one carbon atom of an aliphatic group.

(R 15、R 16) 於通式(b1-II)中，R 15及R 16分別獨立地表示可具有取代基之二價脂肪族基。 (R 15 , R 16 ) In the general formula (b1-II), R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent.

二價脂肪族基可例舉：直鏈狀、支鏈狀、環狀脂肪族基。其中，從顯影溶解性之觀點考慮，較佳為直鏈狀脂肪族基，另一方面，從減少顯影液向曝光部之滲透之觀點考慮，較佳為環狀脂肪族基。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。例如，較佳為1～20，更佳為3～15，進而較佳為6～10。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙，對基板之密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度變差或顯影時之膜減少，使解像性提高之傾向。The divalent aliphatic group may, for example, be a linear, branched or cyclic aliphatic group. Among them, a linear aliphatic group is preferred from the viewpoint of developing solubility, and a cyclic aliphatic group is preferred from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, 1-20 are preferable, 3-15 are more preferable, 6-10 are still more preferable. By setting it as the said lower limit or more, a firm film is easy to be obtained, the surface roughness which arises at the time of image development is hard to generate|occur|produce, and there exists a tendency for the adhesiveness to a board|substrate to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve.

作為二價直鏈狀脂肪族基，例如可例舉：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。其中，從骨架之剛直性之觀點考慮，較佳為亞甲基。 作為二價支鏈狀脂肪族基，可例舉於上述二價直鏈狀脂肪族基上例如具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基作為側鏈之結構。 二價環狀脂肪族基所具有之環之數量並無特別限定，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。例如，較佳為1～12，更佳為2～10。藉由設為上述下限值以上，有成為牢固之膜，基板密接性變良好之傾向。藉由設為上述上限值以下，有容易抑制感度變差或顯影時之膜減少，使解像性提高之傾向。 作為二價環狀脂肪族基，例如可例舉自環己烷環、環庚烷環、環癸環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環、環十二烷環、二環戊二烯環上去除2個氫原子而成之基。其中，從骨架之剛直性之觀點考慮，較佳為自二環戊二烯環、金剛烷環上去除2個氫原子而成之基。 As a divalent linear aliphatic group, a methylene group, an ethylidene group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, and a n-heptide group are mentioned, for example. Among them, a methylene group is preferred from the viewpoint of rigidity of the skeleton. Examples of the divalent branched chain aliphatic group include those having, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second Butyl and tertiary butyl as the structure of the side chain. The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. For example, 1-12 are preferable, and 2-10 are more preferable. By setting it as the said lower limit or more, it becomes a firm film and there exists a tendency for the board|substrate adhesiveness to become favorable. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. As the divalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norcane ring, an isobornane ring, an adamantane ring, and a cyclodecane ring can be mentioned. A group formed by removing two hydrogen atoms from a dioxane ring and a dicyclopentadiene ring. Among them, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring and an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

作為二價脂肪族基可具有之取代基，例如可例舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基。其中，從合成容易性之觀點考慮，較佳為未經取代。As a substituent which the divalent aliphatic group may have, for example, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group may be mentioned. Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.

(m、n) 於通式(b1-II)中，m及n分別獨立地表示0～2之整數。藉由設為上述下限值以上，有圖案適性變良好，不易產生顯影時所產生之表面粗糙之傾向，又，藉由設為上述上限值以下，有顯影性變良好之傾向。從顯影性之觀點考慮，m及n較佳為0。另一方面，從圖案適性、顯影時所產生之表面粗糙之觀點考慮，m及n較佳為1以上。 (m, n) In the general formula (b1-II), m and n each independently represent an integer of 0 to 2. By setting it as the said lower limit or more, pattern suitability becomes favorable, and it exists in the tendency for surface roughness which arises at the time of image development to become hard to generate|occur|produce, and it exists in the tendency for developability to become favorable by setting it as said upper limit or less. From the viewpoint of developability, m and n are preferably 0. On the other hand, m and n are preferably 1 or more from the viewpoint of pattern suitability and surface roughness generated at the time of development.

從對基板之密接性之觀點考慮，通式(b1-II)所表示之部分結構較佳為下述通式(b1-II-1)所表示之部分結構。From the viewpoint of the adhesiveness to the substrate, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1).

[化26]

Figure 02_image051
[Chemical 26]
Figure 02_image051

式(b1-II-1)中，R 13、R 15、R 16、m及n與式(b1-II)含義相同，R α表示可具有取代基之一價環狀烴基，p表示1以上之整數，*表示鍵結鍵。式(b1-II-1)中之苯環可進而經任意之取代基取代。 In formula (b1-II-1), R 13 , R 15 , R 16 , m and n have the same meanings as in formula (b1-II), R α represents an optionally substituted monovalent cyclic hydrocarbon group, and p represents 1 or more Integer, * indicates the bond key. The benzene ring in the formula (b1-II-1) may be further substituted with an arbitrary substituent.

(R α) 於通式(b1-II-1)中，R α表示可具有取代基之一價環狀烴基。 作為環狀烴基，可例舉脂肪族環基或芳香族環基。 (R α ) In the general formula (b1-II-1), R α represents a valent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

脂肪族環基所具有之環之數量並無特別限定，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。例如，較佳為1～6，更佳為1～4，進而較佳為1～3，尤佳為2～3。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有圖案特性變良好之傾向。 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。上述上限及下限可任意地組合。例如，較佳為4～40，更佳為4～30，進而較佳為6～20，尤佳為8～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有圖案特性變良好之傾向。 作為脂肪族環基中之脂肪族環，例如可例舉：環己烷環、環庚烷環、環癸環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環、環十二烷環。其中，從牢固之膜特性之觀點考慮，較佳為金剛烷環。 The number of rings possessed by the alicyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. For example, 1-6 are preferable, 1-4 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, there exists a tendency for a pattern characteristic to become favorable. 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, further preferably 20 or less, particularly preferably 15 or less . The above upper limit and lower limit can be arbitrarily combined. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, 8-15 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, there exists a tendency for a pattern characteristic to become favorable. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norcane ring, an isobornane ring, an adamantane ring, Cyclododecane ring. Among them, an adamantane ring is preferred from the viewpoint of firm film properties.

芳香族環基所具有之環之數量並無特別限定，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。上述上限及下限可任意地組合。例如，較佳為1～10，更佳為1～5，進而較佳為2～5，尤佳為3～5。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有圖案特性變良好之傾向。 作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。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。上述上限及下限可任意地組合。例如，較佳為4～30，更佳為5～20，進而較佳為6～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向，又，藉由設為上述上限值以下，有圖案特性變良好之傾向。 作為芳香族環基中之芳香族環，可例舉：苯環、萘環、蒽環、菲環、茀環。其中，從顯影溶解性之觀點考慮，較佳為茀環。 The number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1-10 are preferable, 1-5 are more preferable, 2-5 are still more preferable, 3-5 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, there exists a tendency for a pattern characteristic to become favorable. As the aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group may, for example, be mentioned. Moreover, the carbon number of an aromatic ring group is 4 or more normally, Preferably it is 5 or more, More preferably, it is 6 or more, Furthermore, it is preferable that it is 30 or less, More preferably, it is 20 or less, More preferably, it is 15 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By setting it as the said lower limit or more, a firm film tends to be obtained easily, and the surface roughness which arises at the time of image development tends not to generate|occur|produce, and it exists in the tendency for pattern characteristics to become favorable by setting it as the said upper limit or less. As an aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a perylene ring are mentioned. Among them, a perylene ring is preferable from the viewpoint of developing solubility.

作為環狀烴基可具有之取代基，例如可例舉：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。其中，從合成容易性之觀點考慮，較佳為未經取代。Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, and the like. Alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; carboxyl groups. Among them, unsubstituted is preferred from the viewpoint of ease of synthesis.

p表示1以上之整數，但較佳為2以上，又，較佳為3以下。例如，較佳為1～3，更佳為2～3。藉由設為上述下限值以上，有膜硬化度與殘膜率變良好之傾向。藉由設為上述上限值以下，有顯影性變良好之傾向。p represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. For example, 1-3 are preferable, and 2-3 are more preferable. By setting it as the said lower limit or more, there exists a tendency for a film hardening degree and a residual film rate to become favorable. By setting it below the said upper limit, there exists a tendency for developability to become favorable.

其中，從牢固之膜硬化度之觀點考慮，R α較佳為一價脂肪族環基，更佳為金剛烷基。 Among them, R α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group, from the viewpoint of a firm film hardening degree.

式(b1-II-1)中之苯環可進而經任意之取代基取代。作為式(b1-II-1)中之苯環所容許之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。於式(b1-II-1)中之苯環具有取代基之情形時，取代基之數量並無特別限定，可為1個，亦可為2個以上。 從圖案特性之觀點考慮，式(b1-II-1)中之苯環較佳為未經取代。 The benzene ring in the formula (b1-II-1) may be further substituted with an arbitrary substituent. Examples of acceptable substituents for the benzene ring in the formula (b1-II-1) include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. When the benzene ring in the formula (b1-II-1) has a substituent, the number of the substituents is not particularly limited, and may be one or two or more. From the viewpoint of pattern characteristics, the benzene ring in the formula (b1-II-1) is preferably unsubstituted.

以下例舉式(b1-II-1)所表示之部分結構之具體例。Specific examples of the partial structure represented by the formula (b1-II-1) are shown below.

[化27]

Figure 02_image053
[Chemical 27]
Figure 02_image053

[化28]

Figure 02_image055
[Chemical 28]
Figure 02_image055

[化29]

Figure 02_image057
[Chemical 29]
Figure 02_image057

[化30]

Figure 02_image059
[Chemical 30]
Figure 02_image059

[化31]

Figure 02_image061
[Chemical 31]
Figure 02_image061

從骨架之剛直性、及膜疏水化之觀點考慮，通式(b1-II)所表示之部分結構較佳為下述通式(b1-II-2)所表示之部分結構。The partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2) from the viewpoints of the rigidity of the skeleton and the hydrophobization of the membrane.

[化32]

Figure 02_image063
[Chemical 32]
Figure 02_image063

式(b1-II-2)中，R 13、R 15、R 16、m及n與式(b1-II)含義相同，R β表示可具有取代基之二價環狀烴基，*表示鍵結鍵。 式(b1-II-2)中之苯環可進而經任意之取代基取代。 In formula (b1-II-2), R 13 , R 15 , R 16 , m and n have the same meanings as in formula (b1-II), R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond key. The benzene ring in the formula (b1-II-2) may be further substituted with any substituent.

(R β) 於式(b1-II-2)中，R β表示可具有取代基之二價環狀烴基。 作為環狀烴基，可例舉脂肪族環基或芳香族環基。 (R β ) In formula (b1-II-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

脂肪族環基所具有之環之數量並無特別限定，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。例如，較佳為1～10，更佳為2～5。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 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。上述上限及下限可任意地組合。例如，較佳為4～40，更佳為6～35，進而較佳為8～30。藉由設為上述下限值以上，有抑制顯影時之膜粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或顯影時之膜減少，解像性提高之傾向。 作為脂肪族環基中之脂肪族環，例如可例舉：環己烷環、環庚烷環、環癸環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環、環十二烷環。其中，從顯影時之膜減少、解像性之觀點考慮，較佳為金剛烷環。 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 10 or less, preferably 5 or less. For example, 1-10 are preferable, and 2-5 are more preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and more preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 4-40 are preferable, 6-35 are more preferable, 8-30 are still more preferable. By setting it as the said lower limit or more, there exists a tendency for the film roughness at the time of image development to be suppressed. By setting it below the said upper limit value, it becomes easy to suppress the deterioration of a sensitivity and the film reduction at the time of image development, and there exists a tendency for a resolution to improve. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norcane ring, an isobornane ring, an adamantane ring, Cyclododecane ring. Among them, an adamantane ring is preferred from the viewpoints of film reduction and resolution at the time of development.

另一方面，芳香族環基所具有之環之數量並無特別限定，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。上述上限及下限可任意地組合。例如，較佳為1～10，更佳為1～5，進而較佳為2～5，尤佳為3～5。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或膜減少，解像性提高之傾向。 作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。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。上述上限及下限可任意地組合。例如，較佳為4～40，更佳為6～30，進而較佳為8～20，尤佳為10～15。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或膜減少，解像性提高之傾向。 作為芳香族環基中之芳香族環，例如可例舉：苯環、萘環、蒽環、菲環、茀環。其中，從顯影性之觀點考慮，較佳為茀環。 On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1-10 are preferable, 1-5 are more preferable, 2-5 are still more preferable, 3-5 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, the deterioration of a sensitivity and a film reduction are easily suppressed, and there exists a tendency for the resolution to improve. As the aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group may, for example, be mentioned. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, more preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 4-40 are preferable, 6-30 are more preferable, 8-20 are still more preferable, 10-15 are especially preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, the deterioration of a sensitivity and a film reduction are easily suppressed, and there exists a tendency for the resolution to improve. As an aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a perylene ring are mentioned, for example. Among them, from the viewpoint of developability, a perylene ring is preferable.

作為環狀烴基可具有之取代基，例如可例舉：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。其中，從合成之簡易性之觀點考慮，較佳為未經取代。Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, and the like. Alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; carboxyl groups. Among them, unsubstituted is preferable from the viewpoint of easiness of synthesis.

其中，從膜減少之抑制、解像性之觀點考慮，R β較佳為二價脂肪族環基，更佳為二價金剛烷環基。 另一方面，從圖案特性之觀點考慮，R β較佳為二價芳香族環基，更佳為二價茀環基。 Among them, R β is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group, from the viewpoints of film reduction suppression and resolution. On the other hand, from the viewpoint of pattern characteristics, R β is preferably a divalent aromatic ring group, more preferably a divalent perylene ring group.

式(b1-II-2)中之苯環可進而經任意之取代基取代。作為式(b1-II-2)中之苯環所容許之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。於式(b1-II-2)中之苯環具有取代基之情形時，取代基之數量並無特別限定，可為1個，亦可為2個以上。 又，2個苯環亦可經由取代基連結。作為該情形時之取代基，可例舉：-O-、-S-、-NH-、-CH 2-等二價基。 從圖案特性之觀點考慮，式(b1-II-2)中之苯環較佳為未經取代。又，從不易產生膜減少等之觀點考慮，式(b1-II-2)中之苯環較佳為被取代為甲基。 The benzene ring in the formula (b1-II-2) may be further substituted with any substituent. Examples of acceptable substituents for the benzene ring in the formula (b1-II-2) include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. When the benzene ring in the formula (b1-II-2) has a substituent, the number of the substituents is not particularly limited, and may be one or two or more. In addition, two benzene rings may be linked via a substituent. As a substituent in this case, divalent groups, such as -O-, -S-, -NH-, -CH2- , are mentioned. From the viewpoint of pattern characteristics, the benzene ring in the formula (b1-II-2) is preferably unsubstituted. In addition, it is preferable that the benzene ring in the formula (b1-II-2) is substituted with a methyl group from the viewpoint of less occurrence of film reduction and the like.

以下例舉上述式(b1-II-2)所表示之部分結構之具體例。再者，例中之*表示鍵結鍵。Specific examples of the partial structure represented by the above formula (b1-II-2) are shown below. Furthermore, * in the example represents a bond bond.

[化33]

Figure 02_image065
[Chemical 33]
Figure 02_image065

[化34]

Figure 02_image067
[Chemical 34]
Figure 02_image067

[化35]

Figure 02_image069
[Chemical 35]
Figure 02_image069

[化36]

Figure 02_image071
[Chemical 36]
Figure 02_image071

從塗膜殘膜率與圖案特性之觀點考慮，式(b1-II)所表示之部分結構較佳為下述式(b1-II-3)所表示之部分結構。The partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoints of the residual coating film ratio and the pattern characteristics.

[化37]

Figure 02_image073
[Chemical 37]
Figure 02_image073

式(b1-II-3)中，R 13、R 14、R 15、R 16、m及n與式(b1-II)含義相同，R Z表示氫原子或多元酸殘基。 In formula (b1-II-3), R 13 , R 14 , R 15 , R 16 , m and n have the same meanings as in formula (b1-II), and R Z represents a hydrogen atom or a polybasic acid residue.

所謂多元酸殘基意指自多元酸去除1個OH基而成之一價基。再者，亦可進而去除另1個OH基，與式(b1-II-3)所表示之其他分子中之R Z共用，即，複數個式(b1-II-3)亦可經由R Z連結。 作為多元酸，例如可例舉：順丁烯二酸、琥珀酸、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、氯橋酸、甲基四氫鄰苯二甲酸、聯苯四羧酸。 其中，從圖案特性之觀點考慮，較佳為順丁烯二酸、琥珀酸、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、聯苯四羧酸。 The polybasic acid residue means a valent group obtained by removing one OH group from a polybasic acid. Furthermore, another OH group can be further removed and shared with R Z in other molecules represented by formula (b1-II-3), that is, multiple formulas (b1-II-3) can also be passed through R Z link. As the polybasic acid, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid may be mentioned. , benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chloro bridge acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid. Among them, from the viewpoint of pattern characteristics, maleic acid, succinic acid, itonic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, Benzenetricarboxylic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

(b1-II)環氧(甲基)丙烯酸酯系樹脂1分子中所含之式(b1-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R Z為氫原子者與R Z為多元酸殘基者。 (b1-II) The partial structure represented by the formula (b1-II-3) contained in 1 molecule of epoxy (meth)acrylate resin may be one kind or two or more kinds, for example, R may be mixed Where Z is a hydrogen atom and R Z is a polyacid residue.

(b1-II)環氧(甲基)丙烯酸酯系樹脂1分子中所含之式(b1-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。例如，較佳為1～20，更佳為1～15，進而較佳為3～10。藉由設為上述下限值以上，有容易獲得牢固之膜，不易產生顯影時所產生之表面粗糙之傾向。藉由設為上述上限值以下，有容易抑制感度之惡化或膜減少，解像性提高之傾向。(b1-II) The number of partial structures represented by formula (b1-II) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more , and it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, 1-20 are preferable, 1-15 are more preferable, and 3-10 are still more preferable. By setting it as the said lower limit or more, it becomes easy to obtain a firm film, and there exists a tendency for the surface roughness which arises at the time of image development to become hard to generate|occur|produce. By setting it below the said upper limit, the deterioration of a sensitivity and a film reduction are easily suppressed, and there exists a tendency for the resolution to improve.

(b1-II)環氧(甲基)丙烯酸酯系樹脂之藉由凝膠滲透層析法(GPC)測定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，更進而較佳為3000以上，尤佳為4000以上，最佳為5000以上，且通常為10000以下，較佳為8000以下，更佳為7000以下。上述上限及下限可任意地組合。例如，較佳為1000～10000，更佳為1500～10000，進而較佳為1500～8000，更進而較佳為2000～8000，尤佳為2000～7000。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良好之傾向。藉由設為上述上限值以下，有對於顯影液之溶解性變良好之傾向。(b1-II) The weight average molecular weight (Mw) of epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, but preferably 1000 or more , more preferably 1500 or more, more preferably 2000 or more, still more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, and usually 10000 or less, preferably 8000 or less, more preferably 7000 the following. The above upper limit and lower limit can be arbitrarily combined. For example, 1000-10000 are preferable, 1500-10000 are more preferable, 1500-8000 are more preferable, 2000-8000 are still more preferable, 2000-7000 are especially preferable. By setting it as the said lower limit or more, there exists a tendency for the residual film rate of a photosensitive coloring composition to become favorable. By setting it below the said upper limit, the solubility with respect to a developer tends to become favorable.

(b1-II)環氧(甲基)丙烯酸酯系樹脂之酸值並無特別限定，較佳為20 mgKOH/g以上，更佳為40 mgKOH/g以上，進而較佳為60 mgKOH/g以上，更進而較佳為80 mgKOH/g以上，尤佳為100 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為150 mgKOH/g以下，更進而較佳為130 mgKOH/g以下，尤佳為120 mgKOH/g以下。上述上限及下限可任意地組合。例如，較佳為20 mgKOH/g～200 mgKOH/g，更佳為60 mgKOH/g～150 mgKOH/g，進而較佳為80 mgKOH/g～130 mgKOH/g，更進而較佳為100 mgKOH/g～130 mgKOH/g。藉由設為上述下限值以上，有顯影溶解性提高，解像性變良好之傾向。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良好之傾向。The acid value of the epoxy (meth)acrylate resin (b1-II) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and still more preferably 60 mgKOH/g or more , more preferably 80 mgKOH/g or more, more preferably 100 mgKOH/g or more, and more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 130 mgKOH/g or less, particularly preferably 120 mgKOH/g or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 20 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 150 mgKOH/g, more preferably 80 mgKOH/g to 130 mgKOH/g, and still more preferably 100 mgKOH/g. g～130 mgKOH/g. By setting it as the said lower limit or more, developing solubility improves and there exists a tendency for resolution to become favorable. There exists a tendency for the residual film ratio of a photosensitive coloring composition to become favorable by making it below the said upper limit.

含羧基環氧(甲基)丙烯酸酯系樹脂可單獨使用一種，亦可混合使用兩種以上之樹脂。 亦可將含羧基環氧(甲基)丙烯酸酯系樹脂之一部分置換成其他黏合劑樹脂來使用。即，亦可併用含羧基環氧(甲基)丙烯酸酯系樹脂與其他黏合劑樹脂。於該情形時，較佳為將(b)鹼可溶性樹脂中之含羧基環氧(甲基)丙烯酸酯系樹脂之比率設為50質量%以上，更佳為設為60質量%以上，進而較佳為設為70質量%以上，尤佳為設為80質量%以上，且通常為100質量%以下。 The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more. A part of the carboxyl group-containing epoxy (meth)acrylate resin may be substituted with other binder resin and used. That is, a carboxyl group-containing epoxy (meth)acrylate resin and another binder resin may be used in combination. In this case, the ratio of the carboxyl group-containing epoxy (meth)acrylate resin in the (b) alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably Preferably it is 70 mass % or more, More preferably, it is 80 mass % or more, and it is usually 100 mass % or less.

從與顏料或分散劑等之相溶性之觀點考慮，作為(b)鹼可溶性樹脂，較佳為使用(b2)丙烯酸系共聚樹脂，可較佳地使用日本專利特開2014-137466號公報中所記載之丙烯酸系共聚樹脂。From the viewpoint of compatibility with pigments, dispersants, etc., as the (b) alkali-soluble resin, it is preferable to use (b2) an acrylic copolymer resin. The described acrylic copolymer resin.

作為丙烯酸系共聚樹脂，例如可例舉具有1個以上羧基之乙烯性不飽和單體(以下，有時稱為「不飽和單體(b2-1)」)、與其他能夠共聚之乙烯性不飽和單體(以下，有時稱為「不飽和單體(b2-2)」)之共聚物。 作為不飽和單體(b2-1)，例如可例舉：(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、桂皮酸等不飽和單羧酸；順丁烯二酸、順丁烯二酸酐、反丁烯二酸、檸康酸、檸康酸酐、甲基反丁烯二酸等不飽和二羧酸或其酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等二元以上之多元羧酸之單[(甲基)丙烯醯氧基烷基]酯；ω-羧基聚己內酯單(甲基)丙烯酸酯等於兩末端具有羧基與羥基之聚合物之單(甲基)丙烯酸酯；對乙烯苯甲酸。 該等不飽和單體(b2-1)可單獨使用或可混合使用兩種以上。 Examples of acrylic copolymer resins include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter, sometimes referred to as "unsaturated monomers (b2-1)"), and other copolymerizable ethylenically unsaturated monomers. A copolymer of saturated monomer (hereinafter, sometimes referred to as "unsaturated monomer (b2-2)"). Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic acid, and the like. Acid anhydride, fumaric acid, citraconic acid, citraconic anhydride, methyl fumaric acid and other unsaturated dicarboxylic acids or their anhydrides; succinic acid mono[2-(meth)acryloyloxyethyl] Mono[(meth)acryloyloxyalkyl]esters of polycarboxylic acids with more than two valences, such as mono[2-(meth)acryloyloxyethyl]phthalate; ω-carboxypolyester Caprolactone mono(meth)acrylate is equal to mono(meth)acrylate of a polymer having carboxyl and hydroxyl groups at both ends; p-vinyl benzoic acid. These unsaturated monomers (b2-1) may be used alone or in combination of two or more.

作為不飽和單體(b2-2)，例如可例舉：N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等N-取代順丁烯二醯亞胺； 苯乙烯、α-甲基苯乙烯、對羥基苯乙烯、對羥基-α-甲基苯乙烯、對乙烯基苄基縮水甘油醚、苊等芳香族乙烯系化合物； Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. ; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthene;

(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、聚乙二醇(聚合度2～10)甲醚(甲基)丙烯酸酯、聚丙二醇(聚合度2～10)甲醚(甲基)丙烯酸酯、聚乙二醇(聚合度2～10)單(甲基)丙烯酸酯、聚丙二醇(聚合度2～10)單(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異𦯉酯、(甲基)丙烯酸三環[5.2.1.0 2,6]癸-8-基酯、(甲基)丙烯酸二環戊烯酯、單(甲基)丙烯酸甘油酯、(甲基)丙烯酸4-羥基苯酯、對異丙苯基苯酚之環氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、3-[(甲基)丙烯醯氧基甲基]氧雜環丁烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基氧雜環丁烷等(甲基)丙烯酸酯； Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl meth)acrylate, polyethylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polyethylene glycol ( Polymerization degree 2~10) Mono(meth)acrylate, Polypropylene glycol (Polymerization degree 2~10) Mono(meth)acrylate, Cyclohexyl(meth)acrylate, Iso(meth)acrylate, ( Tricyclo[5.2.1.0 2,6 ]dec-8-yl meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxybenzene (meth)acrylate Ester, ethylene oxide modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[ (Meth)acrylates such as (meth)acryloyloxymethyl]oxetane, 3-[(meth)acrylooxymethyl]-3-ethyloxetane, etc.;

環己基乙烯醚、異𦯉基乙烯醚、三環[5.2.1.0 2,6]癸-8-基乙烯醚、五環十五烷基乙烯醚、3-(乙烯氧基甲基)-3-乙基氧雜環丁烷等乙烯醚； 聚苯乙烯、(甲基)丙烯酸聚甲酯、(甲基)丙烯酸聚正丁酯、聚矽氧烷等於聚合物分子鏈之末端具有單(甲基)丙烯醯基之巨單體。 該等不飽和單體(b2-2)可單獨使用或可混合使用兩種以上。 Cyclohexyl vinyl ether, iso(vinyl vinyl ether), tricyclo[5.2.1.0 2,6 ]dec-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3- Ethyl oxetane and other vinyl ethers; polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane are equal to the end of the polymer molecular chain with a mono(methyl) ) acrylic acid-based giant monomer. These unsaturated monomers (b2-2) may be used alone or in combination of two or more.

於不飽和單體(b2-1)與不飽和單體(b2-2)之共聚物中，不飽和單體(b2-1)之共聚比率較佳為5～50質量%，進而較佳為10～40質量%。藉由在此種範圍內使不飽和單體(b2-1)共聚，有可獲得鹼性顯影性及保存穩定性優異之感光性著色組合物之傾向。In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50% by mass, and more preferably 10 to 40 mass %. By copolymerizing the unsaturated monomer (b2-1) within such a range, there is a tendency that a photosensitive coloring composition excellent in alkali developability and storage stability can be obtained.

作為不飽和單體(b2-1)與不飽和單體(b2-2)之共聚物，例如可例舉：日本專利特開平7-140654號公報、日本專利特開平8-259876號公報、日本專利特開平10-31308號公報、日本專利特開平10-300922號公報、日本專利特開平11-174224號公報、日本專利特開平11-258415號公報、日本專利特開2000-56118號公報、日本專利特開2004-101728號公報中所揭示之共聚物。 不飽和單體(b2-1)與不飽和單體(b2-2)之共聚物可藉由公知之方法而製造，例如亦可藉由日本專利特開2003-222717號公報、日本專利特開2006-259680號公報、國際公開第2007/029871號公報中所揭示之方法，控制其結構或Mw、Mw/Mn。 As the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 11-258415 The copolymer disclosed in Japanese Patent Laid-Open No. 2004-101728. The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method, for example, Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open The methods disclosed in 2006-259680 Gazette and International Publication No. 2007/029871 Gazette control the structure or Mw and Mw/Mn.

除此以外，亦可使用國際公開第2016/194619號、國際公開第2017/154439號中所記載之樹脂。In addition to this, resins described in International Publication No. 2016/194619 and International Publication No. 2017/154439 can also be used.

＜(c)光聚合起始劑＞ (c)光聚合起始劑係具有如下功能之成分：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。亦可視需要添加聚合促進劑(鏈轉移劑)、增感色素等添加劑使用。 作為光聚合起始劑，例如可例舉：日本專利特開昭59-152396號公報、日本專利特開昭61-151197號公報中所記載之包含二茂鈦化合物之茂金屬化合物；日本專利特開2000-56118號公報中所記載之六芳基聯咪唑衍生物類；日本專利特開平10-39503號公報記載之鹵甲基化㗁二唑衍生物類、鹵甲基對稱三𠯤衍生物類；α-胺基烷基苯酮衍生物類；日本專利特開2000-80068號公報、日本專利特開2006-36750號公報等中所記載之肟酯系化合物。 <(c) Photopolymerization Initiator> (c) The photopolymerization initiator is a component with the following functions: directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and generates a polymerization active radical. Additives such as polymerization accelerators (chain transfer agents) and sensitizing dyes can also be added as needed. As the photopolymerization initiator, for example, metallocene compounds containing titanocene compounds described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Japanese Patent Laid-Open No. 61-151197 Hexaarylbiimidazole derivatives described in the publication No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl symmetric triazole derivatives described in Japanese Patent Laid-Open No. 10-39503 α-aminoalkylphenone derivatives; Oxime ester compounds described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, and the like.

作為茂金屬化合物，例如可例舉：二環戊二烯基二氯化鈦、二環戊二烯基二苯基鈦、二環戊二烯基雙(2,3,4,5,6-五氟苯基)鈦、二環戊二烯基雙(2,3,5,6-四氟苯基)鈦、二環戊二烯基雙(2,4,6-三氟苯基)鈦、二環戊二烯基二(2,6-二氟苯基)鈦、二環戊二烯基二(2,4-二氟苯基)鈦、二(甲基環戊二烯基)雙(2,3,4,5,6-五氟苯基)鈦、二(甲基環戊二烯基)雙(2,6-二氟苯基)鈦、二環戊二烯基[2,6-二氟-3-(吡咯-1-基)苯基]鈦。As the metallocene compound, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6- Pentafluorophenyl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienylbis(2,4,6-trifluorophenyl)titanium , dicyclopentadienyl bis (2,6-difluorophenyl) titanium, dicyclopentadienyl bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-Pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, dicyclopentadienyl[2, 6-Difluoro-3-(pyrrol-1-yl)phenyl]titanium.

作為六芳基聯咪唑衍生物類，例如可例舉：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。Examples of hexaarylbiimidazole 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'-methoxyphenyl)-4,5-diphenylimidazole dimer.

作為鹵甲基化㗁二唑衍生物類，例如可例舉：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。As halomethylated oxadiazole derivatives, for example, 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl 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.

作為鹵甲基對稱三𠯤衍生物類，例如可例舉：2-(4-甲氧基苯基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)對稱三𠯤。Examples of halomethyl symmetric tris' derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetric tris, 2-(4-methoxyphenyl) Naphthyl)-4,6-bis(trichloromethyl)symmetric tris 𠯤, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl) symmetric tris 𠯤, 2-( 4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)symmetric tris.

作為α-胺基烷基苯酮衍生物類，例如可例舉：2-甲基-1[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)丁烷-1-酮、苯甲酸4-二甲胺基乙酯、苯甲酸4-二甲胺基異戊酯、4-二乙胺基苯乙酮、4-二甲胺基苯丙酮、基苯甲酸2-乙基己基-1,4-二甲基胺酯、2,5-雙(4-二乙胺基亞苄基)環己酮、7-二乙胺基-3-(4-二乙胺基苯甲醯基)香豆素、4-(二乙胺基)查耳酮。As α-aminoalkylphenone derivatives, for example, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl Alkyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone Alkan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, benzene 2-ethylhexyl-1,4-dimethylamine formate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylamino) Ethylaminobenzyl)coumarin, 4-(diethylamino)chalcone.

作為光聚合起始劑，尤其是從感度或製版性方面考慮，有效的是肟酯系化合物，例如於使用包含酚性羥基之鹼可溶性樹脂之情形時，此種感度優異之肟酯系化合物尤其有用。肟酯系化合物由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，故少量即感度較高，且對熱反應較穩定，少量即可獲得高感度之感光性著色組合物。As a photopolymerization initiator, oxime ester-based compounds are particularly effective from the viewpoint of sensitivity and plate-making properties. For example, when an alkali-soluble resin containing a phenolic hydroxyl group is used, such an oxime-ester-based compound having excellent sensitivity is especially effective. it works. Oxime ester compounds have a structure that absorbs ultraviolet rays, transmits light energy and generates free radicals, so a small amount of them has higher sensitivity and is more stable to thermal reaction. A small amount can obtain high sensitivity photosensitivity coloring composition.

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

[化38]

Figure 02_image075
[Chemical 38]
Figure 02_image075

上述式(IV)中，R 21a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。 R 21b表示包含芳香環之任意取代基。 R 22a表示可具有取代基之烷醯基、或可具有取代基之芳醯基。 n表示0或1之整數。 In the above formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents an arbitrary substituent including an aromatic ring. R 22a represents an optionally substituted alkane group or an optionally substituted aryl group. n represents an integer of 0 or 1.

R 21a中之烷基之碳數並無特別限定，從對溶劑之溶解性或感度之觀點考慮，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。例如為1～20，較佳為1～15，更佳為2～10。作為烷基，可例舉：甲基、乙基、丙基、環戊基乙基。 作為烷基可具有之取代基，例如可例舉：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，從合成容易性之觀點考慮，較佳為未經取代。 The number of carbon atoms of the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility in a solvent or sensitivity, 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. For example, it is 1-20, Preferably it is 1-15, More preferably, it is 2-10. As an alkyl group, a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group are mentioned. Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, and a 4-(2-methoxy-1-methyl)ethoxy group. The -2-methylphenyl group or the N-acetyl-N-acetoxyamino group is preferably unsubstituted from the viewpoint of ease of synthesis.

作為R 21a中之芳香族環基，可例舉芳香族烴環基及芳香族雜環基。芳香族環基之碳數並無特別限定，從對感光性著色組合物之溶解性之觀點考慮，較佳為5以上。又，從顯影性之觀點考慮，較佳為30以下，更佳為20以下，進而較佳為12以下。例如為5～30，較佳為5～20，更佳為5～12以下。 As the aromatic ring group in R 21a , an aromatic hydrocarbon ring group and an aromatic heterocyclic group may, for example, be mentioned. Although the carbon number of an aromatic ring group is not specifically limited, From a viewpoint of solubility to a photosensitive coloring composition, 5 or more are preferable. Moreover, from a viewpoint of developability, 30 or less are preferable, 20 or less are more preferable, and 12 or less are still more preferable. For example, it is 5-30, Preferably it is 5-20, More preferably, it is 5-12 or less.

作為芳香族環基，例如可例舉：苯基、萘基、吡啶基、呋喃基，其中，從顯影性之觀點考慮，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，例如可例舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基、烷氧基、該等取代基連結而成之基，從顯影性之觀點考慮，較佳為烷基、烷氧基、連結該等而成之基，更佳為進行連結而成之烷氧基。 其中，從顯影性之觀點考慮，R 21a較佳為可具有取代基之芳香族環基，進而較佳為如下芳香族環基，其於取代基上具有進行連結而成之烷氧基。 As an aromatic ring group, a phenyl group, a naphthyl group, a pyridyl group, and a furanyl group are mentioned, for example, Among them, a phenyl group or a naphthyl group is preferable from the viewpoint of developability, and a phenyl group is more preferable. Examples of substituents that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked. From a viewpoint, an alkyl group, an alkoxy group, and the group formed by linking these are preferable, and the alkoxy group formed by linking is more preferable. Among them, from the viewpoint of developability, R 21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having an alkoxy group linked to the substituent.

又，作為R 21b，可例舉：可經取代之咔唑基、可經取代之9-氧硫𠮿

Figure 110135753-A0304-12-02
基、可經取代之二苯硫醚基。其中，從感度之觀點考慮，較佳為可經取代之咔唑基。從電可靠性之觀點考慮，較佳為可經取代之二苯硫醚基。 Moreover, as R <21b >, the carbazolyl group which may be substituted, the 9-oxosulfan which may be substituted may be mentioned.
Figure 110135753-A0304-12-02
group, a diphenyl sulfide group which may be substituted. Among them, from the viewpoint of sensitivity, a substituted carbazolyl group is preferred. From the viewpoint of electrical reliability, a diphenyl sulfide group which may be substituted is preferred.

又，R 22a中之烷醯基之碳數並無特別限定，從對溶劑之溶解性或感度之觀點考慮，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。例如為2～20，較佳為2～15，更佳為3～10，進而較佳為3～5。作為烷醯基，可例舉：乙醯基、丙醯基、丁醯基。 作為烷醯基可具有之取代基，例如可例舉：芳香族環基、羥基、羧基、鹵素原子、胺基、醯胺基，從合成容易性之觀點考慮，較佳為未經取代。 In addition, the number of carbon atoms of the alkanoyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, still more preferably 5 or less. For example, it is 2-20, Preferably it is 2-15, More preferably, it is 3-10, More preferably, it is 3-5. As an alkane group, an acetyl group, a propionyl group, and a butyryl group are mentioned. Examples of the substituent which the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

又，R 22a中之芳醯基之碳數並無特別限定，從對溶劑之溶解性或感度之觀點考慮，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。例如為7～20，較佳為7～15，更佳為8～10。作為芳醯基，可例舉苯甲醯基、萘甲醯基。 作為芳醯基可具有之取代基，例如可例舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基，從合成容易性之觀點考慮，較佳為未經取代。 其中，從感度之觀點考慮，R 22a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。 In addition, the number of carbon atoms of the aryl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. For example, it is 7-20, Preferably it is 7-15, More preferably, it is 8-10. As the aryl group, a benzyl group and a naphthyl group may, for example, be mentioned. Examples of the substituent which the aryl aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted. Among them, from the viewpoint of sensitivity, R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and still more preferably an acetyl group.

從減少由著色劑所引起之液晶層之污染方面考慮，亦可適宜地使用日本專利特開2016-133574號公報中所記載之起始劑。From the viewpoint of reducing the contamination of the liquid crystal layer caused by the colorant, the initiator described in Japanese Patent Laid-Open No. 2016-133574 can also be suitably used.

光聚合起始劑可單獨使用一種，亦可併用兩種以上。 為了提高感應感度，可視需要於光聚合起始劑中調配對應於圖像曝光之光源之波長之增感色素、聚合促進劑。作為增感色素，例如可例舉：日本專利特開平4-221958號公報、日本專利特開平4-219756號公報中所記載之𠮿

Figure 110135753-A0304-12-02
色素、日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中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號公報中所記載之3-酮香豆素化合物、日本專利特開平6-19240號公報中所記載之吡咯亞甲基色素、日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本專利特公昭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號公報中所記載之具有二烷基胺基苯骨架之色素。 A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together. In order to improve the sensitivity, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the light source for image exposure can be formulated into the photopolymerization initiator as needed. Examples of the sensitizing dye include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756.
Figure 110135753-A0304-12-02
Pigments, Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, Coumarin pigments with heterocycles, Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. Hei 5- 3-ketocoumarin compounds described in Gazette No. 289335, pyrrolomethylene dyes described in Japanese Patent Laid-Open No. 6-19240, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 47-2528 Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, Japanese Patent Laid-Open No. 52-112681 Japanese Patent Laid-Open No. 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 The dye having a dialkylaminobenzene skeleton described in the gazette, Japanese Patent Laid-Open No. 5-210240, and Japanese Patent Laid-Open No. 4-288818.

該等增感色素之中，較佳為含胺基之增感色素，更佳為於同一分子內具有胺基及苯基之化合物。作為較佳之增感色素，例如可例舉：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化合物。其中，尤佳為4,4'-二烷基胺基二苯甲酮。 增感色素可單獨使用一種，亦可併用兩種以上。 Among these sensitizing dyes, an amino group-containing sensitizing dye is preferred, and a compound having an amino group and a phenyl group in the same molecule is more preferred. As preferred sensitizing dyes, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4 - Benzophenones such as aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone Series compounds; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4 ,5]Benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3, 4-oxazole, 2-(p-dimethylaminophenyl) benzothiazole, 2-(p-diethylaminophenyl) benzothiazole, 2-(p-dimethylaminophenyl) benzimidazole, 2-(p-Diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine , (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) Ethylaminophenyl) pyrimidine and other p-dialkylaminophenyl compounds. Among them, 4,4'-dialkylaminobenzophenone is particularly preferred. One of the sensitizing dyes may be used alone, or two or more of them may be used in combination.

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；正丁基胺、N-甲基二乙醇胺等脂肪族胺；下述巰基化合物。聚合促進劑可單獨使用一種，亦可併用兩種以上。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 thiol compound. A polymerization accelerator may be used individually by 1 type, and may use 2 or more types together.

＜(d)乙烯性不飽和化合物＞ 本發明之感光性著色組合物包含(d)乙烯性不飽和化合物。藉由包含(d)乙烯性不飽和化合物，感度提高。 本發明中所使用之乙烯性不飽和化合物為分子內具有至少1個乙烯性不飽和基之化合物。具體而言，例如可例舉：(甲基)丙烯酸、(甲基)丙烯酸烷基酯、丙烯腈、苯乙烯、具有1個乙烯性不飽和鍵之羧酸、多元或一元醇之單酯。 <(d) Ethylenically unsaturated compound> The photosensitive coloring composition of this invention contains (d) an ethylenically unsaturated compound. By including (d) an ethylenically unsaturated compound, the sensitivity is improved. The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, (meth)acrylic acid, (meth)acrylic-acid alkyl ester, acrylonitrile, styrene, the carboxylic acid which has one ethylenically unsaturated bond, the monoester of a polyhydric or monohydric alcohol are mentioned, for example.

於本發明中，尤其理想為使用1分子中具有2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數量並無特別限定，通常為2個以上，較佳為4個以上，更佳為5個以上，又，較佳為8個以下，更佳為7個以下。上述上限及下限可任意地組合。例如，較佳為2～8個，更佳為2～7個，進而較佳為4～7個，尤佳為5～7個。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，有對溶劑之溶解性提高之傾向。 作為多官能乙烯性單體之例，例如可例舉：脂肪族多羥基化合物與不飽和羧酸之酯；芳香族多羥基化合物與不飽和羧酸之酯；藉由脂肪族多羥基化合物、芳香族多羥基化合物等多元羥基化合物與不飽和羧酸及多元性羧酸之酯化反應所獲得之酯。 In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, More preferably, it is seven or less. The above upper limit and lower limit can be arbitrarily combined. For example, 2-8 pieces are preferable, 2-7 pieces are more preferable, 4-7 pieces are still more preferable, 5-7 pieces are especially preferable. By making it more than the said lower limit, there exists a tendency for high sensitivity. Solubility with respect to a solvent tends to improve by setting it as the said upper limit or less. 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; The ester obtained by the esterification of polyhydric hydroxy compounds such as polyhydric hydroxy compounds with unsaturated carboxylic acid and polyhydric carboxylic acid.

作為脂肪族多羥基化合物與不飽和羧酸之酯，例如可例舉：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、丙烯酸甘油酯等脂肪族多羥基化合物之丙烯酸酯、將該等丙烯酸酯替換為甲基丙烯酸酯而成之甲基丙烯酸酯、替換為伊康酸酯而成之伊康酸酯、替換為丁烯酸酯而成之丁烯酸酯、替換為順丁烯二酸酯而成之順丁烯二酸酯。Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates of aliphatic polyhydroxy compounds such as acrylates, pentaerythritol diacrylates, pentaerythritol triacrylates, pentaerythritol tetraacrylates, dipentaerythritol tetraacrylates, dipentaerythritol pentaacrylates, dipentaerythritol hexaacrylates, glycerol acrylates, etc. These acrylates are replaced by methacrylates, methacrylates, iconates, Iconates, crotonates, crotonates, cis-butyrates Maleic acid ester made of alkalic acid ester.

作為芳香族多羥基化合物與不飽和羧酸之酯，例如可例舉：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多羥基化合物之丙烯酸酯及甲基丙烯酸酯。Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol diacrylate. Acrylates and methacrylates of aromatic polyhydroxy compounds such as methacrylates and pyrogallol triacrylates.

作為藉由多元性羧酸及不飽和羧酸與多元羥基化合物之酯化反應所獲得之酯，未必為單一物，例如可例舉：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。The ester obtained by the esterification reaction of polybasic carboxylic acid and unsaturated carboxylic acid and polyhydric hydroxy compound is not necessarily a single substance, for example, condensate of acrylic acid, phthalic acid, and ethylene glycol; Condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butylene glycol and glycerin.

除此以外，作為本發明中所使用之多官能乙烯性單體，例如較有用的是如使聚異氰酸酯化合物與含羥基(甲基)丙烯酸酯、或使聚異氰酸酯化合物與多元醇及含羥基(甲基)丙烯酸酯反應所獲得之胺基甲酸酯(甲基)丙烯酸酯類；如多元環氧化合物與(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化合物。In addition, as the polyfunctional vinylic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate, or a polyisocyanate compound and a polyol and a hydroxyl group (meth)acrylate are useful. Urethane (meth)acrylates obtained by meth)acrylate reaction; such as epoxy acrylates of addition reactants of polyvalent epoxy compounds and (meth)acrylates or (meth)acrylic acid Acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate.

作為胺基甲酸酯(甲基)丙烯酸酯類，例如可例舉：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(共榮社化學公司製造)、UV-1700B、UV-7600B、UV-7605B、UV-7630B、UV7640B(三菱化學公司製造)。Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U- 2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (Kyoeisha Chemical Co., Ltd.) Company), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (Mitsubishi Chemical Corporation).

其中，從硬化性之觀點考慮，作為(d)乙烯性不飽和化合物，較佳為使用脂肪族多羥基化合物與不飽和羧酸之酯類或胺基甲酸酯(甲基)丙烯酸酯類；如使聚異氰酸酯化合物與含羥基(甲基)丙烯酸酯、或使聚異氰酸酯化合物與多元醇及含羥基(甲基)丙烯酸酯反應所獲得之胺基甲酸酯(甲基)丙烯酸酯類，更佳為使用(甲基)丙烯酸烷基酯，進而較佳為使用二季戊四醇六丙烯酸酯。 該等可單獨使用一種，亦可併用兩種以上。 Among them, from the viewpoint of curability, as the (d) ethylenically unsaturated compound, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates are preferably used; For example, urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate, or by reacting a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylate, are more It is preferable to use an alkyl (meth)acrylate, and it is more preferable to use dipentaerythritol hexaacrylate. These may be used individually by 1 type, and may use 2 or more types together.

＜(e)溶劑＞ 本發明之感光性著色組合物包含(e)溶劑。藉由包含(e)溶劑，可使(a)著色劑分散或溶解於溶劑中，又，容易塗佈。 本發明之感光性著色組合物通常係於(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、及視需要使用之其他各種材料溶解或分散於溶劑中之狀態下使用。溶劑之中，從分散性或塗佈性之觀點考慮，較佳為有機溶劑。 <(e) Solvent> The photosensitive coloring composition of this invention contains (e) a solvent. By including the (e) solvent, the (a) colorant can be dispersed or dissolved in the solvent, and coating can be facilitated. The photosensitive coloring composition of the present invention is usually composed of (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and a visual Use in a state where various other materials to be used are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.

有機溶劑之中，從塗佈性之觀點考慮，較佳為選擇沸點為100～300℃者，更佳為120～280℃者。再者，此處所述之沸點係指壓力1013.25 hPa下之沸點，以下關於沸點均同樣。Among the organic solvents, those having a boiling point of 100 to 300°C are preferably selected from the viewpoint of coatability, and more preferably those having a boiling point of 120 to 280°C. Furthermore, the boiling point mentioned here refers to the boiling point under a pressure of 1013.25 hPa, and the same applies to the boiling point below.

作為此種有機溶劑，例如可例舉：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-甲氧基丁醇、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； As such an organic solvent, for example, 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 mononormal Butyl ether, propylene glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl amyl alcohol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether Glycol monoalkyl such as ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether ethers; Of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether Glycol dialkyl ethers of the class;

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、乙酸甲氧基丁酯、乙酸3-甲氧基丁酯、乙酸甲氧基戊酯、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、乙酸3-甲基-3-甲氧基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； 環己醇乙酸酯等乙酸烷基酯類； 戊醚、二乙醚、二丙醚、二異丙醚、二丁醚、二戊醚、乙基異丁醚、二己醚之類的醚類； 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 ethyl Acetate, Propylene Glycol Monobutyl Ether Acetate, Methoxybutyl Acetate, 3-Methoxybutyl Acetate, Methoxy Amyl Acetate, Diethylene Glycol Monomethyl Ether Acetate, Diethylene Glycol Mono Diethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, acetic acid 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl ester; Glycol diacetate such as ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

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； Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone , ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentyl ketone and other ketones; Ethanol, Propanol, Butanol, Hexanol, Cyclohexanol, Ethylene Glycol, Propylene Glycol, Butylene Glycol, Diethylene Glycol, Dipropylene Glycol, Triethylene Glycol, Methoxymethyl Amyl Alcohol, Glycerin, Benzyl Alcohol Monohydric or polyhydric alcohols such as; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane;

苯、甲苯、二甲苯、異丙苯之類的芳香族烴類； 甲酸戊酯、乙基甲酸酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、乙酸戊酯、甲基異丁酸酯、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。 Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl 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 Ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, gamma-butyrolactone, etc. Chain or cyclic esters; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile.

作為市售之有機溶劑，例如可使用礦油精、Varsol#2、Apco#18 solvent、Apcothinner、Socalsolvent No.1及No.2、Solvesso#150、Shell TS28 solvent、卡必醇、乙基卡必醇、丁基卡必醇、甲基溶纖劑(「Cellosolve」為註冊商標。下同)、乙基溶纖劑、乙基溶纖劑乙酸酯、甲基溶纖劑乙酸酯、二乙二醇二甲醚(diglyme)(均為商品名)。 該等有機溶劑可單獨使用，亦可併用兩種以上。 As a commercially available organic solvent, for example, mineral spirits, Varsol#2, Apco#18 solvent, Apcothinner, Socalsolvent No.1 and No.2, Solvesso#150, Shell TS28 solvent, carbitol, ethyl carbitol can be used Alcohol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark. The same below), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Dimethyl Cellosolve Ethylene glycol dimethyl ether (diglyme) (all trade names). These organic solvents may be used alone or in combination of two or more.

於藉由光微影法形成間隔壁之情形時，作為有機溶劑，較佳為選擇沸點為100～240℃者，更佳為120～200℃者，進而較佳為120℃～170℃者。When the partition wall is formed by photolithography, it is preferable to select a boiling point of 100-240 degreeC as an organic solvent, More preferably, it is 120-200 degreeC, More preferably, it is 120-170 degreeC.

上述有機溶劑之中，從塗佈性、表面張力等之平衡性良好，組合物中之構成成分之溶解度相對較高方面考慮，較佳為二醇烷基醚乙酸酯類。 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，尤佳為二醇單烷基醚類。從組合物中之構成成分之溶解性考慮，較佳為丙二醇單甲醚。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，其後所獲得之感光性著色組合物之黏度上升等保存穩定性降低之傾向，故溶劑中之二醇單烷基醚類之比率較佳為5質量%～30質量%，更佳為5質量%～20質量%。 Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension, etc., and relatively high solubility of the constituent components in the composition. The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent to be used together, glycol monoalkyl ethers are particularly preferred. Propylene glycol monomethyl ether is preferred from the viewpoint of solubility of the constituents in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate easily, and the viscosity of the photosensitive coloring composition obtained thereafter tends to decrease in storage stability, so the diol in the solvent tends to decrease. 5 mass % - 30 mass % are preferable, and, as for the ratio of monoalkyl ethers, 5 mass % - 20 mass % are more preferable.

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」)。藉由併用高沸點溶劑，感光性著色組合物不易乾燥，但有防止因急劇乾燥而組合物中之顏料之均勻分散狀態受到破壞之效果。即，例如有防止於狹縫噴嘴前端因著色劑等之析出、固化而產生異物缺陷之效果。從此種效果較高方面考慮，上述各種溶劑之中，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。It is also preferable to use together an organic solvent having a boiling point of 150° C. or higher (hereinafter, sometimes referred to as a “high-boiling point solvent”). By using a high boiling point solvent together, the photosensitive coloring composition is not easily dried, but has the effect of preventing the uniform dispersion state of the pigment in the composition from being damaged due to rapid drying. That is, for example, there is an effect of preventing foreign matter defects due to precipitation and curing of colorants and the like at the tip of the slit nozzle. 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 preferable from the viewpoint of high effect.

於併用高沸點溶劑之情形時，有機溶劑中之高沸點溶劑之含有比率較佳為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，例如有可抑制於狹縫噴嘴前端色料等析出、固化而引起異物缺陷之傾向，又，藉由設為上述上限值以下，有可抑制組合物之乾燥溫度變慢，抑制減壓乾燥製程之產距不良、或預烘烤之氣孔痕跡等問題之傾向。When a high boiling point solvent is used in combination, the content ratio 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, particularly preferably 5% by mass to 30% by mass %. By setting the above lower limit value or more, for example, the precipitation and curing of colorants at the front end of the slit nozzle and the tendency to cause foreign matter defects can be suppressed, and by setting the above upper limit value or less, the composition can be suppressed. The drying temperature becomes slower, which suppresses the tendency of problems such as poor production distance in the vacuum drying process, or stomata marks in the pre-baking process.

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，上述各種溶劑之中，例如可例舉：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、三乙酸甘油酯。 The high boiling point solvent having a boiling point of 150° C. or higher may be glycol alkyl ether acetates, or may be glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150°C or higher may be additionally contained. As a preferred high boiling point solvent, among the above-mentioned various solvents, 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, triacetin.

＜(f)分散劑＞ 本發明之感光性著色組合物含有(f)分散劑。藉由含有(f)分散劑，可使(a)著色劑穩定地分散。 本發明之感光性著色組合物中之(f)分散劑含有具有下述通式(1)～(3)所表示之重複單元之丙烯酸系共聚物(f1)(以下，有時稱為「分散劑(f1)」)，且不具有包含四級銨基之重複單元。 <(f) Dispersant> The photosensitive coloring composition of this invention contains (f) a dispersing agent. By containing the (f) dispersant, the (a) colorant can be stably dispersed. The (f) dispersant in the photosensitive coloring composition of the present invention contains an acrylic copolymer (f1) having repeating units represented by the following general formulas (1) to (3) (hereinafter, sometimes referred to as "dispersion" agent (f1)"), and does not have a repeating unit containing a quaternary ammonium group.

[化39]

Figure 02_image077
[Chemical 39]
Figure 02_image077

(式(1)中，R 31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； R 32為氫原子或甲基； *表示鍵結鍵) (In formula (1), R 31 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; R 32 is a hydrogen atom or a methyl group; * represents a bond )

[化40]

Figure 02_image079
[Chemical 40]
Figure 02_image079

(式(2)中，R 33為亞甲基、伸乙基或伸丙基，R 34為可具有取代基之烷基，R 35為氫原子或甲基； n為1～20之整數； *表示鍵結鍵) (In formula (2), R 33 is a methylene group, an ethylidene group or a propylidene group, R 34 is an alkyl group which may have a substituent, R 35 is a hydrogen atom or a methyl group; n is an integer from 1 to 20; *represents a bond key)

[化41]

Figure 02_image081
[Chemical 41]
Figure 02_image081

(式(3)中，R 36及R 37分別獨立地為氫原子、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，R 36及R 37可相互鍵結而形成環狀結構； R 38為氫原子或甲基； Z為二價連結基； *表示鍵結鍵) (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R 36 and R 37 Can be bonded to each other to form a cyclic structure; R 38 is a hydrogen atom or a methyl group; Z is a divalent linking group; * represents a bond)

從提高對於溶劑或鹼可溶性樹脂之相溶性，提高分散穩定性之觀點考慮，分散劑(f1)具有下述通式(1)所表示之重複單元。The dispersant (f1) has a repeating unit represented by the following general formula (1) from the viewpoint of improving compatibility with a solvent or an alkali-soluble resin and improving dispersion stability.

[化42]

Figure 02_image083
[Chemical 42]
Figure 02_image083

(式(1)中，R 31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； R 32為氫原子或甲基； *表示鍵結鍵) (In formula (1), R 31 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; R 32 is a hydrogen atom or a methyl group; * represents a bond )

(R 31) 於上述式(1)中，作為R 31中之烷基，可例舉：直鏈狀、支鏈狀、或環狀烷基，從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，較佳為直鏈狀，又，從對於顏料之親和性之觀點考慮，較佳為支鏈狀。 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，進而較佳為6以下。上述上限及下限可任意地組合。例如，較佳為1～10，更佳為2～8，進而較佳為4～6。藉由設為上述下限值以上，有提高對於顏料之親和性之傾向。藉由設為上述上限值以下，有提高對於溶劑或鹼可溶性樹脂之相溶性，改善分散性之傾向。 作為烷基，例如可例舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、乙基己基，從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，較佳為甲基、乙基，更佳為甲基。 作為烷基可具有之取代基，例如可例舉：甲氧基、乙氧基等烷氧基；氟原子、氯原子、溴原子等鹵素原子；苯基、萘基等芳基，從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，較佳為未經取代，從對於顏料之親和性之觀點考慮，較佳為苯基。 (R 31 ) In the above formula (1), the alkyl group in R 31 may, for example, include linear, branched, or cyclic alkyl groups, and from the viewpoint of compatibility with solvents or alkali-soluble resins Considering that, a straight-chain form is preferable, and a branched-chain form is preferable from the viewpoint of affinity with a pigment. The number of carbon atoms in the alkyl group is not particularly limited, but 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, and still more preferably 6 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 1-10 are preferable, 2-8 are more preferable, 4-6 are still more preferable. By setting it as the said lower limit or more, there exists a tendency for the affinity with respect to a pigment to improve. By setting it as the said upper limit or less, the compatibility with respect to a solvent or alkali-soluble resin improves, and there exists a tendency for dispersibility to improve. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl, and from the viewpoint of compatibility with solvents or alkali-soluble resins, A methyl group and an ethyl group are preferable, and a methyl group is more preferable. Examples of substituents that the alkyl group may have include alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine, chlorine, and bromine atoms; aryl groups such as phenyl and naphthyl. From the viewpoint of compatibility with the alkali-soluble resin, it is preferably unsubstituted, and from the viewpoint of affinity for pigments, it is preferably a phenyl group.

作為R 31中之芳基，可例舉一價芳香族烴環基、一價芳香族雜環基。 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10以下。藉由設為上述上限值以下，有提高對於顏料之親和性之傾向。作為芳基，例如可例舉：苯基、萘基、蒽基，從分散性之觀點考慮，較佳為苯基、萘基，更佳為苯基。 作為芳基可具有之取代基，例如可例舉：甲基、乙基等烷基；甲氧基、乙氧基等烷氧基；氟原子、氯原子、溴原子等鹵素原子；苯基、萘基等芳基；苄基、苯乙基等芳烷基，從分散性之觀點考慮，較佳為未經取代。 As an aryl group in R31 , a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group are mentioned. The number of carbon atoms in the aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. By setting it below the said upper limit, there exists a tendency for the affinity with respect to a pigment to improve. As an aryl group, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example, From a viewpoint of dispersibility, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. Examples of substituents that the aryl group may have include: alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, Aryl groups such as naphthyl and aralkyl groups such as benzyl and phenethyl are preferably unsubstituted from the viewpoint of dispersibility.

其中，從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，作為R 31，較佳為可具有取代基之烷基，更佳為甲基、丁基、乙基己基、或苄基。 Among them, R 31 is preferably an alkyl group which may have a substituent, more preferably a methyl group, a butyl group, an ethylhexyl group, or a benzyl group, from the viewpoint of compatibility with a solvent or an alkali-soluble resin.

從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，分散劑(f1)具有下述通式(2)所表示之重複單元。From the viewpoint of compatibility with a solvent or an alkali-soluble resin, the dispersant (f1) has a repeating unit represented by the following general formula (2).

[化43]

Figure 02_image085
[Chemical 43]
Figure 02_image085

(式(2)中，R 33為亞甲基、伸乙基或伸丙基，R 34為可具有取代基之烷基，R 35為氫原子或甲基； n為1～20之整數； *表示鍵結鍵) (In formula (2), R 33 is a methylene group, an ethylidene group or a propylidene group, R 34 is an alkyl group which may have a substituent, R 35 is a hydrogen atom or a methyl group; n is an integer from 1 to 20; *represents a bond key)

於上述式(2)中，R 33為亞甲基、伸乙基、或伸丙基，但從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，較佳為伸乙基。 於上述式(2)中，R 34係可具有取代基之烷基，但從對於溶劑或鹼可溶性樹脂之相溶性之觀點考慮，較佳為甲基或乙基。 In the above formula (2), R 33 is a methylene group, an ethylidene group, or a propylidene group, but from the viewpoint of compatibility with a solvent or an alkali-soluble resin, it is preferably an ethylidene group. In the above formula (2), R 34 is an alkyl group which may have a substituent, but is preferably a methyl group or an ethyl group from the viewpoint of compatibility with a solvent or an alkali-soluble resin.

於上述式(2)中，n為1～20之整數，但較佳為1以上，更佳為2以上，又，較佳為10以下，更佳為5以下。例如，較佳為1～10，更佳為1～5，進而較佳為2～5。藉由設為上述下限值以上，有對於溶劑或鹼可溶性樹脂之相溶性改善之傾向。藉由設為上述上限值以下，有提高對於顏料之親和性，改善分散性之傾向。In the above formula (2), n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, and more preferably 10 or less, more preferably 5 or less. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable. By setting it as the said lower limit or more, there exists a tendency for the compatibility with a solvent or alkali-soluble resin to improve. By setting it below the said upper limit, affinity with respect to a pigment improves and there exists a tendency for dispersibility to improve.

分散劑(f1)具有上述通式(3)所表示之重複單元。從電極之表面粗糙之觀點考慮，可適宜地使用。The dispersant (f1) has a repeating unit represented by the above-mentioned general formula (3). From the viewpoint of the surface roughness of the electrode, it can be suitably used.

[化44]

Figure 02_image087
[Chemical 44]
Figure 02_image087

(式(3)中，R 36及R 37分別獨立地為氫原子、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，R 36及R 37可相互鍵結而形成環狀結構； R 38為氫原子或甲基； Z為二價連結基； *表示鍵結鍵) (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R 36 and R 37 Can be bonded to each other to form a cyclic structure; R 38 is a hydrogen atom or a methyl group; Z is a divalent linking group; * represents a bond)

於上述式(3)中，R 36及R 37分別獨立地為氫原子、可具有取代基之烷基、或可具有取代基之芳基、或可具有取代基之芳烷基。作為可具有取代基之烷基、可具有取代基之芳基，可較佳地採用作為上述式(1)中之R 31所例舉者。 In the above formula (3), R 36 and R 37 are each independently 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. As the alkyl group which may have a substituent and the aryl group which may have a substituent, those exemplified as R 31 in the above formula (1) can be preferably used.

於上述式(3)中，R 36及R 37可相互鍵結而形成環狀結構；作為環狀結構，例如可例舉5～7員環之含氮雜環單環或該等之2個縮合而成之縮合環。含氮雜環較佳為不具有芳香族性者，更佳為飽和環。具體而言，可例舉以下者。 In the above formula (3), R 36 and R 37 may be bonded to each other to form a cyclic structure; as the cyclic structure, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or two of these can be exemplified. Condensed ring formed by condensation. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and is more preferably a saturated ring. Specifically, the following can be mentioned.

[化45]

Figure 02_image089
[Chemical 45]
Figure 02_image089

(該等環狀結構可進而具有取代基； *表示鍵結鍵) (These cyclic structures may further have substituents; *represents a bond key)

(Z) 於上述式(3)中，Z為二價連結基。 作為二價連結基，例如可例舉：單鍵、碳數1～10之伸烷基、碳數6～12之伸芳基、-CONH-R 39-基、-COOR 40-基(其中，R 39及R 40分別獨立地為單鍵、碳數1～10之伸烷基、或碳數2～10之醚基(烷氧基烷基))，從分散性之觀點考慮，較佳為-COOR 7-基。R 40之中，從分散液之經時穩定性之觀點考慮，較佳為碳數1～10之伸烷基，更佳為碳數1～5之伸烷基，進而較佳為碳數1～3之伸烷基。 (Z) In the above formula (3), Z is a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a -CONH-R 39 - group, and a -COOR 40 - group (wherein, R 39 and R 40 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms), and from the viewpoint of dispersibility, preferably -COOR 7 -base. Among R 40 , from the viewpoint of the stability over time of the dispersion liquid, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and an alkylene group having 1 to 5 carbon atoms is still more preferred. ~3 alkylene groups.

分散劑(f1)中之通式(1)所表示之重複單元(以下，有時稱為「重複單元(1)」)之含有比率並無特別限定，於全部重複單元中較佳為20莫耳%以上，更佳為30莫耳%以上，進而較佳為40莫耳%以上，更進而較佳為50莫耳%以上，尤佳為60莫耳%以上，又，較佳為90莫耳%以下，更佳為85莫耳%以下，進而較佳為80莫耳%以下，尤佳為75莫耳%以下。上述上限及下限可任意地組合。例如，較佳為20莫耳%～90莫耳%，更佳為30莫耳%～90莫耳%，進而較佳為40莫耳%～80莫耳%，更進而較佳為50莫耳%～80莫耳%，尤佳為60莫耳%～80莫耳%。藉由設為上述下限值以上，有提高對於顏料之親和性之傾向。藉由設為上述上限值以下，有提高對於溶劑或鹼可溶性樹脂之相溶性之傾向。The content ratio of the repeating unit represented by the general formula (1) in the dispersant (f1) (hereinafter, sometimes referred to as "repeating unit (1)") is not particularly limited, but is preferably 20 moles in all repeating units. % or more, more preferably more than 30 mol%, more preferably more than 40 mol%, more preferably more than 50 mol%, particularly preferably more than 60 mol%, and more preferably 90 mol% mol % or less, more preferably 85 mol % or less, still more preferably 80 mol % or less, particularly preferably 75 mol % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 20 mol % to 90 mol %, more preferably 30 mol % to 90 mol %, more preferably 40 mol % to 80 mol %, more preferably 50 mol % %～80mol%, preferably 60mol%～80mol%. By setting it as the said lower limit or more, there exists a tendency for the affinity with respect to a pigment to improve. By setting it below the said upper limit, there exists a tendency for the compatibility with a solvent or alkali-soluble resin to improve.

分散劑(f1)中之上述通式(2)所表示之重複單元(以下，有時稱為「重複單元(2)」)之含有比率並無特別限定，於全部重複單元中較佳為1莫耳%以上，更佳為2莫耳%以上，進而較佳為2.5莫耳%以上，尤佳為3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15莫耳%以下，更進而較佳為10莫耳%以下，尤佳為8莫耳%以下。上述上限及下限可任意地組合。例如，較佳為1莫耳%～30莫耳%，更佳為1莫耳%～20莫耳%，進而較佳為1莫耳%～15莫耳%，更進而較佳為1莫耳%～10莫耳%，尤佳為2莫耳%～10莫耳%。藉由設為上述下限值以上，有提高對於溶劑或鹼可溶性樹脂之相溶性之傾向。藉由設為上述上限值以下，有提高對於顏料之親和性之傾向。The content ratio of the repeating unit represented by the general formula (2) in the dispersant (f1) (hereinafter, sometimes referred to as "repeating unit (2)") is not particularly limited, but is preferably 1 in all repeating units Molar % or more, more preferably 2 mol % or more, more preferably 2.5 mol % or more, more preferably 3 mol % or more, and preferably 30 mol % or less, more preferably 20 mol % % or less, more preferably 15 mol % or less, more preferably 10 mol % or less, particularly preferably 8 mol % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 1 mol % to 30 mol %, more preferably 1 mol % to 20 mol %, more preferably 1 mol % to 15 mol %, still more preferably 1 mol % % to 10 mol %, preferably 2 mol % to 10 mol %. By setting it as the said lower limit or more, there exists a tendency for the compatibility with a solvent or alkali-soluble resin to improve. By setting it below the said upper limit, there exists a tendency for the affinity with respect to a pigment to improve.

分散劑(f1)中之上述通式(3)所表示之重複單元(以下，有時稱為「重複單元(3)」)之含有比率並無特別限定，於全部重複單元中較佳為10莫耳%以上，更佳為20莫耳%以上，進而較佳為25莫耳%以上，尤佳為30莫耳%以上，又，較佳為50莫耳%以下，更佳為45莫耳%以下，進而較佳為40莫耳%以下，尤佳為35莫耳%以下。上述上限及下限可任意地組合。例如，較佳為10莫耳%～50莫耳%，更佳為20莫耳%～40莫耳%，進而較佳為25莫耳%～35莫耳%，尤佳為30莫耳%～35莫耳%。藉由設為上述下限值以上，有分散性變良好之傾向。藉由設為上述上限值以下，有分散液之經時穩定性變良好之傾向。The content ratio of the repeating unit represented by the general formula (3) in the dispersant (f1) (hereinafter, sometimes referred to as "repeating unit (3)") is not particularly limited, but is preferably 10 in all repeating units. Molar % or more, more preferably 20 mol % or more, more preferably 25 mol % or more, more preferably 30 mol % or more, and more preferably 50 mol % or less, more preferably 45 mol % % or less, more preferably 40 mol % or less, particularly preferably 35 mol % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 10 mol % to 50 mol %, more preferably 20 mol % to 40 mol %, more preferably 25 mol % to 35 mol %, particularly preferably 30 mol % to 30 mol %. 35 mol%. By setting it as the said lower limit or more, there exists a tendency for a dispersibility to become favorable. By setting it below the said upper limit, there exists a tendency for the time-dependent stability of a dispersion liquid to become favorable.

分散劑(f1)能夠以無規共聚、嵌段共聚中之任一種態樣含有，但從分散性之觀點考慮，較佳為嵌段共聚物，嵌段共聚物較佳為包含：A嵌段，其包含具有親溶劑基之重複單元；及B嵌段，其包含具有顏料吸附基之重複單元。The dispersing agent (f1) can be contained in any form of random copolymerization and block copolymerization, but from the viewpoint of dispersibility, it is preferably a block copolymer, and the block copolymer preferably contains: A block , which includes repeating units having solvophilic groups; and B blocks, which include repeating units having pigment-adsorbing groups.

分散劑(f1)較佳為於A嵌段中含有重複單元(1)、重複單元(2)，且能夠以無規共聚、嵌段共聚中之任一種態樣含有。又，重複單元(1)或重複單元(2)可於A嵌段中分別含有兩種以上，於該情形時，各重複單元可於A嵌段中以無規共聚、嵌段共聚中之任一種態樣含有。The dispersing agent (f1) preferably contains the repeating unit (1) and the repeating unit (2) in the A block, and can be contained in any aspect of random copolymerization and block copolymerization. In addition, the repeating unit (1) or repeating unit (2) may respectively contain two or more kinds in the A block. In this case, each repeating unit may be randomly copolymerized or block copolymerized in the A block. A form contains.

於A嵌段中可含有重複單元(1)及(2)以外之重複單元，作為此種重複單元，可例舉來自苯乙烯、α-甲基苯乙烯等苯乙烯系單體；(甲基)丙烯醯氯等(甲基)丙烯酸鹽系單體；(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-甲基丙烯醯基嗎啉之重複單元。The A block may contain repeating units other than repeating units (1) and (2). Examples of such repeating units include styrene-based monomers derived from styrene and α-methylstyrene; (methyl styrene) ) (meth)acrylate-based monomers such as acryloyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide, N-methylol acrylamide, etc.; vinyl acetate; acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; repeating unit of N-methacryloyl morpholine.

其中，含有具有重複單元(1)、重複單元(2)之A嵌段、及具有重複單元(3)之B嵌段之嵌段共聚物更佳為A-B嵌段共聚物或A-B-A嵌段共聚物。Among them, the block copolymer containing the A block having the repeating unit (1), the repeating unit (2), and the B block having the repeating unit (3) is more preferably an A-B block copolymer or an A-B-A block copolymer .

分散劑(f1)之胺值並無特別限定，較佳為50 mgKOH/g以上，更佳為80 mgKOH/g以上，進而較佳為90 mgKOH/g以上，尤佳為100 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為160 mgKOH/g以下，進而較佳為140 mgKOH/g以下，尤佳為130 mgKOH/g以下。上述上限及下限可任意地組合。例如，較佳為50 mgKOH/g～200 mgKOH/g，更佳為80 mgKOH/g～160 mgKOH/g，進而較佳為100 mgKOH/g～140 mgKOH/g，尤佳為100 mgKOH/g～130 mgKOH/g。藉由設為上述下限值以上，有可抑制電極之表面粗糙之傾向。藉由設為上述上限值以下，有分散液之經時穩定性改善之傾向。胺值係以與分散劑(f1)之每1 g固形物成分之鹼量相當之KOH的質量表示。The amine value of the dispersant (f1) is not particularly limited, but is preferably 50 mgKOH/g or more, more preferably 80 mgKOH/g or more, further preferably 90 mgKOH/g or more, particularly preferably 100 mgKOH/g or more, Moreover, 200 mgKOH/g or less is preferable, 160 mgKOH/g or less is more preferable, 140 mgKOH/g or less is still more preferable, 130 mgKOH/g or less is especially preferable. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 50 mgKOH/g to 200 mgKOH/g, more preferably 80 mgKOH/g to 160 mgKOH/g, further preferably 100 mgKOH/g to 140 mgKOH/g, particularly preferably 100 mgKOH/g to 130 mgKOH/g. By making it more than the said lower limit, the tendency for the surface roughness of an electrode can be suppressed. By setting it below the said upper limit, there exists a tendency for the time-dependent stability of a dispersion liquid to improve. The amine value is represented by the mass of KOH corresponding to the alkali amount per 1 g of solid content of the dispersant (f1).

分散劑(f1)之酸值並無特別限定，從分散性之觀點考慮，較佳為10 mgKOH/g以下，更佳為5 mgKOH/g以下，進而較佳為1 mgKOH/g，尤佳為0 mgKOH/g。The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10 mgKOH/g or less, more preferably 5 mgKOH/g or less, still more preferably 1 mgKOH/g, particularly preferably 0 mgKOH/g.

分散劑(f1)之重量平均分子量並無特別限定，較佳為3000以上，更佳為5000以上，進而較佳為7000以上，又，較佳為100000以下，更佳為50000以下，進而較佳為10000以下。上述上限及下限可任意地組合。例如，較佳為3000～100000，更佳為5000～50000，進而較佳為7000～10000。藉由設為上述下限值以上，有分散性改善之傾向。藉由設為上述上限值以下，有分散液之經時穩定性改善之傾向。The weight-average molecular weight of the dispersing agent (f1) is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, more preferably 7,000 or more, and more preferably 100,000 or less, more preferably 50,000 or less, still more preferably is less than 10000. The above upper limit and lower limit can be arbitrarily combined. For example, 3000-100000 are preferable, 5000-50000 are more preferable, and 7000-10000 are still more preferable. By setting it as the said lower limit or more, there exists a tendency for dispersibility to improve. By setting it below the said upper limit, there exists a tendency for the time-dependent stability of a dispersion liquid to improve.

分散劑(f1)中之氯原子之含量並無特別限定，較佳為1.0質量%以下，更佳為0.5質量%以下，進而較佳為0.2質量%以下，尤佳為實質上不含氯原子，即為0.1質量%以下。藉由設為上述上限值以下，有表面粗糙得以抑制之傾向。The content of chlorine atoms in the dispersant (f1) is not particularly limited, but is preferably 1.0 mass % or less, more preferably 0.5 mass % or less, still more preferably 0.2 mass % or less, and particularly preferably substantially free of chlorine atoms , that is, 0.1 mass % or less. By setting it below the said upper limit, there exists a tendency for surface roughness to be suppressed.

分散劑(f1)之製造方法並無特別限定，可採用公知之方法。例如可例舉：日本專利特開平01-299014號公報、日本專利特開2017-019937號公報、日本專利特開2018-172530號公報、日本專利特開2018-203795號公報、日本專利特開2019-099801號公報、國際公開第2019/079659號公報中所記載之方法。The manufacturing method of a dispersing agent (f1) is not specifically limited, A well-known method can be employ|adopted. For example: Japanese Patent Laid-Open No. 01-299014, Japanese Patent Laid-Open No. 2017-019937, Japanese Patent Laid-Open No. 2018-172530, Japanese Patent Laid-Open No. 2018-203795, Japanese Patent Laid-Open No. 2019 - The method described in Gazette No. 099801 and International Publication No. 2019/079659.

本發明之感光性著色組合物中之(f)分散劑亦可含有分散劑(f1)以外之分散劑(以下，有時稱為「其他分散劑」)。The (f) dispersing agent in the photosensitive coloring composition of this invention may contain the dispersing agent (henceforth "other dispersing agent") other than the dispersing agent (f1).

作為其他分散劑，從分散穩定性方面考慮，例如較佳為具有羧基；或該等之鹼基；一級、二級或三級胺基；四級銨鹽基；來自吡啶、嘧啶、吡𠯤等含氮雜環之基作為官能基之分散劑。其中，更佳為具有鹼性官能基例如一級、二級或三級胺基；四級銨鹽基；來自吡啶、嘧啶、吡𠯤等含氮雜環之基之分散劑。 又，從於使顏料分散時能夠以少量之分散劑進行分散之觀點考慮，較佳為高分子分散劑。 As other dispersants, from the viewpoint of dispersion stability, for example, it is preferable to have carboxyl groups; or bases thereof; primary, secondary or tertiary amine groups; quaternary ammonium salt groups; The nitrogen-containing heterocyclic group acts as a dispersant for the functional group. Among them, more preferred are dispersants with basic functional groups such as primary, secondary or tertiary amine groups; quaternary ammonium salt groups; groups derived from pyridine, pyrimidine, pyridine and other nitrogen-containing heterocycles. Moreover, when dispersing a pigment, it is preferable that it is a polymeric dispersing agent from a viewpoint of being able to disperse|distribute with a small amount of dispersing agent.

作為高分子分散劑，例如可例舉：分散劑(f1)以外之丙烯酸系分散劑、胺基甲酸酯系分散劑、聚乙烯亞胺系分散劑、聚烯丙胺系分散劑、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、山梨醇酐脂肪族酯系分散劑、脂肪族改性聚酯系分散劑。Examples of polymer dispersants include acrylic dispersants other than dispersants (f1), urethane-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, and amine-containing dispersants. Base monomer and macromonomer dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan aliphatic dispersant Ester-based dispersant, aliphatic modified polyester-based dispersant.

作為此種高分子分散劑，例如以商品名可例舉：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)。As such a polymer dispersant, for example, trade names include: 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 Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyeisha Chemical Corporation), Ajisper (registered trademark. manufactured by Ajinomoto Corporation).

作為胺基甲酸酯系及丙烯酸系高分子分散劑，例如可例舉：DISPERBYK160～166、182系列(均為胺基甲酸酯系)、DISPERBYK2000、2001、BYK-LPN21116(均為丙烯酸系)(以上均為BYK-Chemie公司製造)。Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK160 to 166, 182 series (all of which are urethane-based), DISPERBYK2000, 2001, and BYK-LPN21116 (all of which are acrylic-based) (All of the above are manufactured by BYK-Chemie Corporation).

其他分散劑可使用一種，亦可併用兩種以上。As for the other dispersants, one type may be used, or two or more types may be used in combination.

＜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，還可適當調配矽烷偶合劑等密接提昇劑、界面活性劑、顏料衍生物、光酸產生劑、交聯劑、巰基化合物、聚合抑制劑等添加劑。 <Other preparation components of the photosensitive coloring composition> In the photosensitive coloring composition of the present invention, in addition to the above-mentioned components, adhesion promoters such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors may be appropriately formulated additives, etc.

(1)密接提昇劑 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提昇劑。作為密接提昇劑，較佳為矽烷偶合劑、含磷酸基化合物。 作為矽烷偶合劑之種類，可單獨使用一種環氧系、(甲基)丙烯酸系、胺基系等各種矽烷偶合劑，或者可混合使用兩種以上。 (1) Adhesion enhancer In order to improve the adhesiveness with a board|substrate, an adhesiveness improvement agent may be contained in the photosensitive coloring composition of this invention. As the adhesion promoter, a silane coupling agent and a phosphoric acid group-containing compound are preferable. As a kind of silane coupling agent, various silane coupling agents, such as an epoxy type, (meth)acrylic type, and an amino type, can be used individually by 1 type, or 2 or more types can be mixed and used.

作為矽烷偶合劑，例如可例舉：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。 作為含磷酸基化合物，較佳為含(甲基)丙烯醯基磷酸酯類，且較佳為下述通式(g1)、(g2)或(g3)所表示者。 Examples of silane coupling agents include (meth)acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane. Silanes; 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 3-glycidyloxypropyltriethoxysilane and other epoxysilanes; 3-ureidopropyltriethoxysilane and other ureidosilanes; 3-isocyanatopropyltriethoxysilane, etc. Isocyanatosilanes. Particularly preferred are silane coupling agents such as epoxy silanes. The phosphoric acid group-containing compound is preferably a (meth)acryloyl group-containing phosphoric acid ester, and is preferably represented by the following general formula (g1), (g2) or (g3).

[化46]

Figure 02_image091
[Chemical 46]
Figure 02_image091

於上述通式(g1)、(g2)及(g3)中，R 51表示氫原子或甲基，l及l'為1～10之整數，m為1、2或3。 該等含磷酸基化合物可單獨使用一種，亦可併用兩種以上。 In the above general formulae (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, 1 and 1' are integers of 1 to 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)界面活性劑 為了提高塗佈性，本發明之感光性著色組合物亦可含有界面活性劑。 (2) Surfactant In order to improve coatability, the photosensitive coloring composition of this invention may contain surfactant.

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界面活性劑。其中，從對各特性造成不良影響之可能性較低方面考慮，較佳為使用非離子系界面活性劑，其中，氟系或矽系界面活性劑於塗佈性方面較有效。 作為此種界面活性劑，例如可例舉：TSF4460(邁圖高新材料公司製造)、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-554、F-559(DIC公司製造)、SH7PA(東麗道康寧公司製造)、DS-401(大金公司製造)、L-77(Nippon Unicar公司製造)、FC4430(3M公司製造)。 界面活性劑可使用一種，亦能夠以任意之組合及比率併用兩種以上。 As the surfactant, for example, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant from the viewpoint of low possibility of adversely affecting the properties, and among them, a fluorine-based or silicon-based surfactant is more effective in coating properties. As such a surfactant, for example, TSF4460 (manufactured by Momentive High-tech Materials Co., Ltd.), DFX-18 (manufactured by NEOS Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie Co., Ltd.), KP340 (manufactured by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (Daikin) Company), L-77 (Nippon Unicar Company), FC4430 (3M Company). One type of surfactant may be used, or two or more types may be used in combination in any combination and ratio.

(3)顏料衍生物 為了提高分散性、保存性，於本發明之感光性著色組合物中亦可含有顏料衍生物作為分散助劑。 作為顏料衍生物，例如可例舉：偶氮系、酞菁系、喹吖酮系、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、芘酮系、吡咯并吡咯二酮系、二㗁𠯤系之衍生物，其中較佳為酞菁系、喹酞酮系。 作為顏料衍生物之取代基，例如可例舉：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而成者，較佳為磺酸基。又，該等取代基可於一個顏料骨架上進行複數個取代。 (3) Pigment derivatives In order to improve dispersibility and storage stability, a pigment derivative may be contained in the photosensitive coloring composition of this invention as a dispersing aid. As pigment derivatives, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxaquinone-based, anthraquinone-based, Derivatives of indanthrene series, perylene series, pyrene series, diketopyrrolopyrrole series, and bismuth series, among which phthalocyanine series and quinophthalone series are preferred. Examples of substituents of pigment derivatives include sulfonic acid groups, sulfonamido groups and quaternary salts thereof, phthalimidomethyl, dialkylaminoalkyl, hydroxyl, carboxyl, An amino group or the like is directly or via an alkyl group, an aryl group, a heterocyclic group, or the like bonded to the pigment skeleton, preferably a sulfonic acid group. Also, these substituents may be substituted in plural on one pigment skeleton.

作為顏料衍生物，例如可例舉：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、喹吖酮之磺酸衍生物、吡咯并吡咯二酮之磺酸衍生物、二㗁𠯤之磺酸衍生物。該等可單獨使用一種，亦可併用兩種以上。Examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and sulfonic acid derivatives of diketopyrrolopyrrole. Sulfonic acid derivatives, sulfonic acid derivatives of two 㗁𠯤. These may be used individually by 1 type, and may use 2 or more types together.

(4)巰基化合物 又，為了提高對基板之密接性，亦可添加巰基化合物作為聚合促進劑。 (4) Sulfhydryl compounds Moreover, in order to improve the adhesiveness to a board|substrate, you may add a mercapto compound as a polymerization accelerator.

作為巰基化合物，例如可例舉：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、1,4-二甲基巰基苯、丁二醇雙硫代丙酸酯、丁二醇雙巰基乙酸酯、乙二醇雙巰基乙酸酯、三羥甲基丙烷三巰基乙酸酯、丁二醇雙硫代丙酸酯、三羥甲基丙烷三硫代丙酸酯、三羥甲基丙烷三巰基乙酸酯、季戊四醇四硫代丙酸酯、季戊四醇四巰基乙酸酯、三羥乙基三硫代丙酸酯、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、脂肪族多官能巰基化合物。該等可單獨使用各種巰基化合物中之一種，或者可混合使用兩種以上。Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, and 1,4-dimethylmercaptobenzene. , Butylene Glycol Dithioglycolate, Butylene Glycol Dithioglycolate, Ethylene Glycol Dithioglycolate, Trimethylolpropane Trimercaptoacetate, Butylene Glycol Dithioglycolate, Trimethylolpropane Trithiopropionate, Trimethylolpropane Trimercaptoacetate, Pentaerythritol Tetrathioglycolate, Pentaerythritol Tetrathioglycolate, Trimethylolpropane Trithioglycolate, Ethylene Glycol Diol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutanoyloxy)butane, trimethylolpropane tris(3 - mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptobutyrate) mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris𠯤- 2,4,6(1H,3H,5H)-triketone and other mercapto compounds having heterocycles, aliphatic polyfunctional mercapto compounds. These may be used alone or in combination of two or more of various mercapto compounds.

(5)聚合抑制劑 從硬化物之形狀控制之觀點考慮，於本發明之感光性著色組合物中亦可含有聚合抑制劑。認為藉由含有聚合抑制劑，其阻礙塗佈膜下層之自由基聚合，故可控制錐角(支持體與硬化物於硬化物剖面所成之角度)。 作為聚合抑制劑，例如可例舉：對苯二酚、對苯二酚單甲醚、甲基對苯二酚、甲氧基苯酚、2,6-二第三丁基-4-甲酚(BHT)。其中，從形狀控制之觀點考慮，較佳為2,6-二第三丁基-4-甲酚。又，從對人體之安全性尤其優異之觀點考慮，較佳為對苯二酚單甲醚、甲基對苯二酚。 聚合抑制劑可單獨使用一種，或者可混合使用兩種以上。 於製造(b)鹼可溶性樹脂時，有時於樹脂中包含聚合抑制劑，可使用其作為本發明之聚合抑制劑，於樹脂中除了聚合抑制劑以外，還可於感光性著色組合物製造時添加與其相同或不同之聚合抑制劑。 (5) Polymerization inhibitor From the viewpoint of shape control of the cured product, a polymerization inhibitor may be contained in the photosensitive coloring composition of the present invention. It is considered that by containing a polymerization inhibitor, it inhibits the radical polymerization of the lower layer of the coating film, so that the taper angle (the angle formed by the support body and the cured product in the cross section of the cured product) can be controlled. As the polymerization inhibitor, for example, hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol ( BHT). Among them, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control. Moreover, from a viewpoint of being especially excellent in safety to a human body, hydroquinone monomethyl ether and methyl hydroquinone are preferable. A polymerization inhibitor may be used individually by 1 type, or may be used in mixture of 2 or more types. In the production of the (b) alkali-soluble resin, a polymerization inhibitor may be contained in the resin, and this can be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor in the resin, it can also be used in the production of the photosensitive coloring composition. Add the same or different polymerization inhibitor.

於感光性著色組合物包含聚合抑制劑之情形時，其含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，通常為0.0005質量%以上，較佳為0.001質量%以上，更佳為0.01質量%以上，又，通常為0.3質量%以下，較佳為0.2質量%以下，更佳為0.1質量%以下。上述上限及下限可任意地組合。例如，較佳為0.0005質量%～0.3質量%，更佳為0.001質量%～0.2質量%，進而較佳為0.01質量%～0.1質量%。藉由設為上述下限值以上，有可控制硬化物之形狀之傾向。藉由設為上述上限值以下，有可維持所需之感度之傾向。When the photosensitive coloring composition contains a polymerization inhibitor, its content ratio is not particularly limited, but is usually 0.0005 mass % or more, preferably 0.001 mass % or more with respect to the total solid content of the photosensitive coloring composition , more preferably 0.01 mass % or more, and usually 0.3 mass % or less, preferably 0.2 mass % or less, more preferably 0.1 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 0.0005 mass % to 0.3 mass %, more preferably 0.001 mass % to 0.2 mass %, and still more preferably 0.01 mass % to 0.1 mass %. By making it more than the said lower limit, there exists a tendency for the shape of hardened|cured material to be controllable. By setting it below the said upper limit, there exists a tendency for a desired sensitivity to be maintained.

＜感光性著色組合物中之各成分之含有比率＞ 本發明之感光性著色組合物中之(a)著色劑之含有比率並無特別限定，相對於全部固形物成分量，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，更進而較佳為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25質量%以下。上述上限及下限可任意地組合。例如，較佳為5質量%～50質量%，更佳為10質量%～40質量%，進而較佳為15質量%～40質量%，更進而較佳為15質量%～30質量%，尤佳為15質量%～25質量%。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，有可減少分散劑量，可抑制表面粗糙之傾向。 <The content ratio of each component in the photosensitive coloring composition> The content ratio of the colorant (a) in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably with respect to the total solid content. 15 mass % or more, more preferably 20 mass % or more, and more preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less, particularly preferably 25 mass % or less . The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, still more preferably 15% by mass to 40% by mass, still more preferably 15% by mass to 30% by mass, especially Preferably it is 15 mass % - 25 mass %. By setting it as the said lower limit or more, there exists a tendency for the light-shielding property to be ensured. By setting it as the said upper limit or less, the dispersing amount can be reduced and there exists a tendency for surface roughness to be suppressed.

於第一態樣中，相對於感光性著色組合物之全部固形物成分量，感光性著色組合物中之化合物(I)之含有比率較佳為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，通常為50質量%以下，較佳為40質量%以下，更佳為30質量%以下，尤佳為25質量%以下。上述上限及下限可任意地組合。例如，較佳為5質量%～70質量%，更佳為20質量%～70質量%，進而較佳為20質量%～60質量%，尤佳為20質量%～50質量%。藉由設為上述下限值以上，有抑制硬化所需之紫外線光之損耗，且遮光性增高之傾向。藉由設為上述上限值以下，有可減少分散劑量，可抑制表面粗糙之傾向。In the first aspect, the content ratio of the compound (I) in the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more with respect to the total solid content of the photosensitive coloring composition. , more preferably 15 mass % or more, more preferably 20 mass % or more, and usually 50 mass % or less, preferably 40 mass % or less, more preferably 30 mass % or less, particularly preferably 25 mass % or less . The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5% by mass to 70% by mass, more preferably 20% by mass to 70% by mass, still more preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass. By setting it as the said lower limit or more, there exists a tendency for the loss of ultraviolet light required for hardening to be suppressed, and a light-shielding property to become high. By setting it as the said upper limit or less, the dispersing amount can be reduced and there exists a tendency for surface roughness to be suppressed.

於第一態樣中，於(a)著色劑包含化合物(I)及其他顏料之情形時，其含有比率之合計並無特別限定，(a)著色劑中之化合物(I)之含有比率較佳為10質量%以上，更佳為20質量%以上，進而較佳為30質量%以上，又，較佳為90質量%以下，更佳為80質量%以下，尤佳為70質量%以下。上述上限及下限可任意地組合。例如，較佳為10質量%～90質量%，更佳為20質量%～80質量%，進而較佳為30質量%～70質量%。藉由設為上述下限值以上，有遮光性增高，可設為接近黑色之色調之傾向。藉由設為上述上限值以下，有顯影時之殘渣減少，元件製作時之可靠性變良好之傾向。In the first aspect, when (a) the colorant contains the compound (I) and other pigments, the total content ratio is not particularly limited, and (a) the content ratio of the compound (I) in the colorant is relatively 10 mass % or more is preferable, 20 mass % or more is more preferable, 30 mass % or more is more preferable, and 90 mass % or less is preferable, 80 mass % or less is more preferable, 70 mass % or less is especially preferable. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass. By making it more than the said lower limit, the light-shielding property becomes high, and there exists a tendency for the color tone to be close to black. By setting it below the said upper limit, the residue at the time of image development is reduced, and there exists a tendency for the reliability at the time of element manufacture to become favorable.

於第一態樣中，於(a)著色劑包含化合物(I)及有機著色顏料之情形時，其含有比率之合計並無特別限定，(a)著色劑中之化合物(I)之含有比率較佳為10質量%以上，更佳為20質量%以上，進而較佳為30質量%以上，又，較佳為90質量%以下，更佳為80質量%以下，尤佳為70質量%以下。上述上限及下限可任意地組合。例如，較佳為10質量%～90質量%，更佳為20質量%～80質量%，進而較佳為30質量%～70質量%。藉由設為上述下限值以上，有遮光性增高，可設為接近黑色之色調之傾向。藉由設為上述上限值以下，有顯影時之殘渣減少，元件製作時之可靠性變良好之傾向。In the first aspect, when (a) the colorant contains the compound (I) and an organic colored pigment, the total content ratio is not particularly limited, and (a) the content ratio of the compound (I) in the colorant It is preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 30 mass % or more, and more preferably 90 mass % or less, more preferably 80 mass % or less, particularly preferably 70 mass % or less . The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass. By making it more than the said lower limit, the light-shielding property becomes high, and there exists a tendency for the color tone to be close to black. By setting it below the said upper limit, the residue at the time of image development is reduced, and there exists a tendency for the reliability at the time of element manufacture to become favorable.

於感光性著色組合物包含有機著色顏料之情形時，其含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，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，通常為50質量%以下，較佳為40質量%以下，更佳為30質量%以下，尤佳為25質量%以下。上述上限及下限可任意地組合。例如，較佳為5質量%～70質量%，更佳為20質量%～70質量%，進而較佳為20質量%～60質量%，尤佳為20質量%～50質量%。藉由設為上述下限值以上，有遮光性增高之傾向。藉由設為上述上限值以下，有可減少分散劑量，可抑制表面粗糙之傾向。When the photosensitive coloring composition contains an organic coloring pigment, the content ratio thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass relative to the total solid content of the photosensitive coloring composition. or more, more preferably 15 mass % or more, particularly preferably 20 mass % or more, and usually 50 mass % or less, preferably 40 mass % or less, more preferably 30 mass % or less, particularly preferably 25 mass % the following. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5% by mass to 70% by mass, more preferably 20% by mass to 70% by mass, still more preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass. By making it more than the said lower limit, there exists a tendency for light-shielding property to become high. By setting it as the said upper limit or less, the dispersing amount can be reduced and there exists a tendency for surface roughness to be suppressed.

於(a)著色劑包含紅色顏料及/或橙色顏料之情形時，紅色顏料及橙色顏料之含有比率之合計並無特別限定，於(a)著色劑中較佳為5質量%以上，更佳為8質量%以上，進而較佳為10質量%以上，尤佳為12質量%以上，又，較佳為40質量%以下，更佳為30質量%以下，尤佳為20質量%以下。上述上限及下限可任意地組合。例如，較佳為5質量%～40質量%，更佳為8質量%～40質量%，進而較佳為10質量%～30質量%，尤佳為12質量%～20質量%。藉由設為上述下限值以上，有可設為接近黑色之色調之傾向。藉由設為上述上限值以下，有成為高感度之傾向。In the case where the (a) colorant contains a red pigment and/or an orange pigment, the total content ratio of the red pigment and the orange pigment is not particularly limited, but in (a) the colorant is preferably 5% by mass or more, more preferably It is 8 mass % or more, more preferably 10 mass % or more, particularly preferably 12 mass % or more, and more preferably 40 mass % or less, more preferably 30 mass % or less, particularly preferably 20 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5% by mass to 40% by mass, more preferably 8% by mass to 40% by mass, still more preferably 10% by mass to 30% by mass, and particularly preferably 12% by mass to 20% by mass. By setting it as the said lower limit or more, there exists a tendency for the color tone to be close to black. By setting it below the said upper limit, there exists a tendency for high sensitivity.

於(a)著色劑包含藍色顏料及/或紫色顏料之情形時，藍色顏料及紫色顏料之含有比率之合計並無特別限定，於(a)著色劑中較佳為30質量%以上，更佳為50質量%以上，進而較佳為70質量%以上，尤佳為80質量%以上，又，較佳為95質量%以下，更佳為92質量%以下，尤佳為90質量%以下。上述上限及下限可任意地組合。例如，較佳為30質量%～95質量%，更佳為50質量%～95質量%，進而較佳為70質量%～92質量%，尤佳為80質量%～90質量%。藉由設為上述下限值以上，有可設為接近黑色之色調之傾向。藉由設為上述上限值以下，有感度、遮光性變良好之傾向。When (a) the colorant contains a blue pigment and/or a violet pigment, the total content ratio of the blue pigment and the violet pigment is not particularly limited, but in (a) the colorant is preferably 30% by mass or more, It is more preferably 50 mass % or more, further preferably 70 mass % or more, particularly preferably 80 mass % or more, and more preferably 95 mass % or less, more preferably 92 mass % or less, particularly preferably 90 mass % or less . The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 30% by mass to 95% by mass, more preferably 50% by mass to 95% by mass, still more preferably 70% by mass to 92% by mass, and particularly preferably 80% by mass to 90% by mass. By setting it as the said lower limit or more, there exists a tendency for the color tone to be close to black. By setting it below the said upper limit, there exists a tendency for sensitivity and light-shielding property to become favorable.

於(a)著色劑包含紅色顏料及/或橙色顏料與藍色顏料及/或紫色顏料這兩者之情形時，紅色顏料及/或橙色顏料之含有比率並無特別限定，相對於藍色顏料及/或紫色顏料之含量較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上，尤佳為8質量%以上，又，較佳為300質量%以下，更佳為100質量%以下，尤佳為50質量%以下。上述上限及下限可任意地組合。例如，較佳為1質量%～300質量%，更佳為3質量%～100質量%，進而較佳為5質量%～100質量%，尤佳為8質量%～50質量%。藉由設為上述下限值以上，有抑制藍色光之透過，遮光性增高之傾向。藉由設為上述上限值以下，有可設為接近黑色之色調之傾向。When (a) the colorant contains both the red pigment and/or the orange pigment and the blue pigment and/or the violet pigment, the content ratio of the red pigment and/or the orange pigment is not particularly limited, relative to the blue pigment and/or the content of the purple pigment is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, particularly preferably 8 mass% or more, and preferably 300 mass% or less, More preferably, it is 100 mass % or less, and even more preferably 50 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 1% by mass to 300% by mass, more preferably 3% by mass to 100% by mass, still more preferably 5% by mass to 100% by mass, and particularly preferably 8% by mass to 50% by mass. By setting it as the said lower limit or more, the permeation|transmission of blue light is suppressed and there exists a tendency for the light-shielding property to become high. By setting it below the said upper limit, there exists a tendency for the color tone to be close to black.

於感光性著色組合物包含有機黑色顏料之情形時，其含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，較佳為3質量%以上，更佳為5質量%以上，進而較佳為10質量%以上，尤佳為20質量%以上，又，較佳為60質量%以下，更佳為50質量%以下，尤佳為40質量%以下。上述上限及下限可任意地組合。例如，較佳為3質量%～60質量%，更佳為5質量%～60質量%，進而較佳為10質量%～50質量%，尤佳為20質量%～40質量%。藉由設為上述下限值以上，有遮光性增高之傾向。若為上述上限值以下，則有可減少分散劑量，可抑制表面粗糙之傾向。When the photosensitive coloring composition contains an organic black pigment, the content ratio thereof is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass relative to the total solid content of the photosensitive coloring composition Above, more preferably 10 mass % or more, particularly preferably 20 mass % or more, and more preferably 60 mass % or less, more preferably 50 mass % or less, particularly preferably 40 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 3% by mass to 60% by mass, more preferably 5% by mass to 60% by mass, still more preferably 10% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass. By making it more than the said lower limit, there exists a tendency for light-shielding property to become high. If it is below the said upper limit, there exists a tendency for the amount of dispersing to be reduced and surface roughness to be suppressed.

於感光性著色組合物包含碳黑作為無機黑色顏料之情形時，其含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上，又，較佳為30質量%以下，更佳為20質量%以下，尤佳為10質量%以下。上述上限及下限可任意地組合。例如，較佳為1質量%～30質量%，更佳為3質量%～20質量%，進而較佳為3質量%～10質量%。藉由設為上述下限值以上，有遮光性增高之傾向。藉由設為上述上限值以下，有可形成高電阻、低介電常數之硬化物之傾向。When the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content ratio thereof is not particularly limited, but is preferably 1 mass % or more with respect to the total solid content of the photosensitive coloring composition, more preferably 3 mass % or more, more preferably 5 mass % or more, and more preferably 30 mass % or less, more preferably 20 mass % or less, particularly preferably 10 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and still more preferably 3% by mass to 10% by mass. By making it more than the said lower limit, there exists a tendency for light-shielding property to become high. By setting it below the said upper limit, there exists a tendency for the hardened|cured material of high resistance and low dielectric constant to be formed.

於(a)著色劑包含黑色顏料及有機著色顏料之情形時，其含有比率之合計並無特別限定，(a)著色劑中之黑色顏料之含有比率較佳為10質量%以上，更佳為20質量%以上，進而較佳為30質量%以上，又，較佳為90質量%以下，更佳為80質量%以下，尤佳為70質量%以下。上述上限及下限可任意地組合。例如，較佳為10質量%～90質量%，更佳為20質量%～80質量%，進而較佳為30質量%～70質量%。藉由設為上述下限值以上，有遮光性增高，可設為接近黑色之色調之傾向。藉由設為上述上限值以下，有顯影時之殘渣減少，元件製作時之可靠性變良好之傾向。When (a) the colorant contains a black pigment and an organic color pigment, the total content ratio is not particularly limited, and the content ratio of the black pigment in the (a) colorant is preferably 10% by mass or more, more preferably 20 mass % or more, more preferably 30 mass % or more, and more preferably 90 mass % or less, more preferably 80 mass % or less, particularly preferably 70 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass. By making it more than the said lower limit, the light-shielding property becomes high, and there exists a tendency for the color tone to be close to black. By setting it below the said upper limit, the residue at the time of image development is reduced, and there exists a tendency for the reliability at the time of element manufacture to become favorable.

(b)鹼可溶性樹脂之含有比率並無特別限定，相對於本發明之感光性著色組合物之全部固形物成分量，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30質量%以上，尤佳為40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，更佳為55質量%以下。上述上限及下限可任意地組合。例如，較佳為5質量%～80質量%，更佳為10質量%～70質量%，進而較佳為20質量%～60質量%，更進而較佳為30質量%～60質量%，特別較佳為30質量%～55質量%，尤佳為40質量%～55質量%。藉由設為上述下限值以上，有可抑制未曝光部分對於顯影液之溶解性降低，抑制顯影不良之傾向。藉由設為上述上限值以下，有可維持適當之感度，抑制曝光部之由顯影液所引起之溶解，且可抑制圖案之鮮明性或密接性降低之傾向。(b) The content rate of the alkali-soluble resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass relative to the total solid content of the photosensitive coloring composition of the present invention. mass % or more, more preferably 30 mass % or more, particularly preferably 40 mass % or more, and usually 85 mass % or less, preferably 80 mass % or less, more preferably 70 mass % or less, and still more preferably 60 mass % mass % or less, more preferably 55 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, still more preferably 30% by mass to 60% by mass, especially Preferably it is 30 mass % - 55 mass %, Especially preferably, it is 40 mass % - 55 mass %. By setting it as the said lower limit or more, it exists in the tendency which can suppress the fall of the solubility with respect to a developing solution of an unexposed part and suppress image development failure. By setting it below the said upper limit, a suitable sensitivity can be maintained, the melt|dissolution by a developing solution of an exposure part can be suppressed, and the tendency for the sharpness or adhesiveness of a pattern to fall can be suppressed.

(b1)環氧(甲基)丙烯酸酯系樹脂之含有比率並無特別限定，相對於本發明之感光性著色組合物之全部固形物成分量，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，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，尤佳為55質量%以下。上述上限及下限可任意地組合。例如，較佳為5質量%～80質量%，更佳為10質量%～70質量%，進而較佳為20質量%～60質量%，更進而較佳為30質量%～60質量%，特別較佳為30質量%～55質量%，尤佳為40質量%～55質量%。藉由設為上述下限值以上，有可確保未曝光部分對於顯影液之溶解性之傾向。藉由設為上述上限值以下，有可維持適當之感度，抑制曝光部之由顯影液所引起之溶解，且可抑制圖案之鮮明性或密接性降低之傾向。The content ratio of (b1) epoxy (meth)acrylate resin is not particularly limited, but is usually 5 mass % or more, preferably 10 mass % with respect to the total solid content of the photosensitive coloring composition of the present invention % or more, more preferably 15 mass % or more, more preferably 20 mass % or more, still more preferably 30 mass % or more, particularly preferably 40 mass % or more, and usually 80 mass % or less, preferably 70 mass % % or less, more preferably 60 mass % or less, particularly preferably 55 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, still more preferably 30% by mass to 60% by mass, especially Preferably it is 30 mass % - 55 mass %, Especially preferably, it is 40 mass % - 55 mass %. By setting it as the said lower limit or more, there exists a tendency for the solubility with respect to a developing solution of an unexposed part to be ensured. By setting it below the said upper limit, a suitable sensitivity can be maintained, the melt|dissolution by a developing solution of an exposure part can be suppressed, and the tendency for the sharpness or adhesiveness of a pattern to fall can be suppressed.

(b)鹼可溶性樹脂中所含之(b1)環氧(甲基)丙烯酸酯系樹脂之含有比率並無特別限定，通常為20質量%以上，較佳為30質量%以上，更佳為40質量%以上，且通常為100質量%以下，較佳為90質量%以下，更佳為80質量%以下。上述上限及下限可任意地組合。例如，較佳為20質量%～90質量%，更佳為30質量%～80質量%，進而較佳為40質量%～80質量%。藉由設為上述下限值以上，有可確保未曝光部分對於顯影液之溶解性之傾向。藉由設為上述上限值以下，有可維持適當之感度，抑制曝光部之由顯影液所引起之溶解，且可抑制圖案之鮮明性或密接性降低之傾向。(b) The content ratio of the (b1) epoxy (meth)acrylate resin contained in the alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more The mass % or more is usually 100 mass % or less, preferably 90 mass % or less, and more preferably 80 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and still more preferably 40% by mass to 80% by mass. By setting it as the said lower limit or more, there exists a tendency for the solubility with respect to a developing solution of an unexposed part to be ensured. By setting it below the said upper limit, a suitable sensitivity can be maintained, the melt|dissolution by a developing solution of an exposure part can be suppressed, and the tendency for the sharpness or adhesiveness of a pattern to fall can be suppressed.

(c)光聚合起始劑之含有比率並無特別限定，相對於本發明之感光性著色組合物之全部固形物成分量，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，更佳為3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6質量%以下。上述上限及下限可任意地組合。例如，較佳為0.1質量%～15質量%，更佳為0.5質量%～15質量%，進而較佳為1質量%～10質量%，更進而較佳為2質量%～8質量%，尤佳為3質量%～6質量%。藉由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對於顯影液之溶解性降低，抑制顯影不良之傾向。(c) The content ratio of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.1% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention. 1 mass % or more, more preferably 2 mass % or more, more preferably 3 mass % or more, and usually 15 mass % or less, preferably 10 mass % or less, more preferably 8 mass % or less, still more preferably It is 6 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, still more preferably 2% by mass to 8% by mass, especially Preferably it is 3 mass % - 6 mass %. By setting it as the said lower limit or more, there exists a tendency for a sensitivity fall to be suppressed. By setting it below the said upper limit, the solubility with respect to a developing solution of an unexposed part can be suppressed from falling, and there exists a tendency for development failure to be suppressed.

於和(c)光聚合起始劑一起使用聚合促進劑之情形時，聚合促進劑之含有比率並無特別限定，相對於本發明之感光性著色組合物之全部固形物成分量，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。又，相對於(c)光聚合起始劑100質量份，聚合促進劑通常以0.1～50質量份、尤其是0.1～20質量份之比率使用。藉由將聚合促進劑之含有比率設為上述下限值以上，有可抑制對於曝光之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對於顯影液之溶解性降低，抑制顯影不良之傾向。 於和(c)光聚合起始劑一起使用增感色素之情形時，其含有比率並無特別限定，從感度之觀點考慮，相對於感光性著色組合物中之全部固形物成分量，通常為20質量%以下，較佳為15質量%以下，更佳為10質量%以下。 In the case where a polymerization accelerator is used together with the (c) photopolymerization initiator, the content ratio of the polymerization accelerator is not particularly limited, and the content of the polymerization accelerator with respect to the total solid content of the photosensitive coloring composition of the present invention is preferably 0.05 mass % or more, and 10 mass % or less normally, Preferably it is 5 mass % or less. Moreover, a polymerization accelerator is usually used in the ratio of 0.1-50 mass parts, especially 0.1-20 mass parts with respect to 100 mass parts of (c) photopolymerization initiators. By making the content ratio of a polymerization accelerator more than the said lower limit, the tendency for the sensitivity to the light of exposure to fall can be suppressed. By setting it below the said upper limit, the solubility with respect to a developing solution of an unexposed part can be suppressed from falling, and there exists a tendency for development failure to be suppressed. When the sensitizing dye is used together with the (c) photopolymerization initiator, its content ratio is not particularly limited, but from the viewpoint of sensitivity, it is usually 20 mass % or less, preferably 15 mass % or less, more preferably 10 mass % or less.

(d)乙烯性不飽和化合物之含有比率並無特別限定，相對於本發明之感光性著色組合物之全部固形物成分量，通常為1質量%以上，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，又，通常為30質量%以下，較佳為25質量%以下，更佳為20質量%以下。上述上限及下限可任意地組合。例如，較佳為1質量%～30質量%，更佳為5質量%～20質量%，進而較佳為10質量%～20質量%。藉由設為上述下限值以上，有可維持適當之感度，抑制曝光部之由顯影液所引起之溶解，且可抑制圖案之鮮明性或密接性降低之傾向。藉由設為上述上限值以下，有容易抑制顯影液對曝光部之滲透性增高，獲得良好之圖像之傾向。(d) The content rate of the ethylenically unsaturated compound is not particularly limited, but is usually 1 mass % or more, preferably 5 mass % or more, more preferably 1 mass % or more with respect to the total solid content of the photosensitive coloring composition of the present invention. It is 10 mass % or more, more preferably 15 mass % or more, and usually 30 mass % or less, preferably 25 mass % or less, more preferably 20 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 20% by mass, and still more preferably 10% by mass to 20% by mass. By setting it as the said lower limit or more, a suitable sensitivity can be maintained, the dissolution by a developing solution of an exposure part can be suppressed, and the tendency for the sharpness or adhesiveness of a pattern to fall can be suppressed. By setting it as the said upper limit or less, it exists in the tendency for the permeability|transmittance of a developing solution to an exposure part to increase easily, and to obtain a favorable image.

本發明之感光性著色組合物係藉由使用(e)溶劑，以全部固形物成分量之含有比率較佳為成為5質量%以上，更佳為成為10質量%以上，進而較佳為成為15質量%以上，又，較佳為成為50質量%以下，更佳為成為30質量%以下，進而較佳為成為25質量%以下之方式配製。上述上限及下限可任意地組合。例如以較佳為成為5質量%～50質量%，更佳為成為10質量%～30質量%，進而較佳為成為15質量%～25質量%之方式配製。The photosensitive coloring composition of the present invention is preferably 5 mass % or more, more preferably 10 mass % or more, and still more preferably 15 mass % or more by using the solvent (e) in the content ratio of the total solid content. It is more preferably 50 mass % or less, more preferably 30 mass % or less, and still more preferably 25 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably prepared to be 5 to 50 mass %, more preferably 10 to 30 mass %, and still more preferably 15 to 25 mass %.

(f)分散劑之含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，通常為1質量%以上，較佳為2質量%以上，更佳為3質量%以上，又，通常為20質量%以下，較佳為15質量%以下，更佳為10質量%以下，進而較佳為7質量%以下。上述上限及下限可任意地組合。例如，較佳為1質量%～20質量%，更佳為2質量%～15質量%，進而較佳為3質量%～10質量%，尤佳為3質量%～7質量%。藉由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，有可抑制電極表面之表面粗糙之傾向。(f) The content ratio of the dispersant is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, relative to the total solid content of the photosensitive coloring composition, Moreover, it is usually 20 mass % or less, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 7 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, still more preferably 3% by mass to 10% by mass, and particularly preferably 3% by mass to 7% by mass. By setting it as the said lower limit or more, sufficient dispersibility tends to be easily obtained. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode surface to be suppressed.

分散劑(f1)之含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，通常為1質量%以上，較佳為2質量%以上，更佳為3質量%以上，又，通常為20質量%以下，較佳為15質量%以下，更佳為10質量%以下，進而較佳為7質量%以下。上述上限及下限可任意地組合。例如，較佳為1質量%～20質量%，更佳為2質量%～15質量%，進而較佳為3質量%～10質量%，尤佳為3質量%～7質量%。藉由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，有可抑制電極表面之表面粗糙之傾向。The content ratio of the dispersing agent (f1) is not particularly limited, but is usually 1 mass % or more, preferably 2 mass % or more, more preferably 3 mass % or more with respect to the total solid content of the photosensitive coloring composition, Moreover, it is usually 20 mass % or less, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 7 mass % or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, still more preferably 3% by mass to 10% by mass, and particularly preferably 3% by mass to 7% by mass. By setting it as the said lower limit or more, sufficient dispersibility tends to be easily obtained. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode surface to be suppressed.

分散劑(f1)之含有比率並無特別限定，於(f)分散劑中通常為20質量%以上，較佳為40質量%以上，更佳為60質量%以上，進而較佳為80質量%以上，又，通常為100質量%以下。藉由設為上述下限值以上，有可抑制電極表面之表面粗糙之傾向。The content ratio of the dispersing agent (f1) is not particularly limited, but in the dispersing agent (f), it is usually 20 mass % or more, preferably 40 mass % or more, more preferably 60 mass % or more, and still more preferably 80 mass % More than that, it is usually 100 mass % or less. By making it more than the said lower limit, there exists a tendency for the surface roughness of an electrode surface to be suppressed.

(f)分散劑相對於(a)著色劑100質量份之含有比率並無特別限定，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。上述上限及下限可任意地組合。例如，較佳為5質量份～50質量份，更佳為10質量份～50質量份，進而較佳為15質量份～30質量份。藉由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，有可抑制電極表面之表面粗糙之傾向。The content ratio of the (f) dispersant to 100 parts by mass of the colorant (a) is not particularly limited, but 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 or less, particularly preferably 30 parts by mass or less. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 5 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 50 parts by mass, and still more preferably 15 parts by mass to 30 parts by mass. By setting it as the said lower limit or more, sufficient dispersibility tends to be easily obtained. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode surface to be suppressed.

(b)鹼可溶性樹脂相對於(d)乙烯性不飽和化合物100質量份之含有比率並無特別限定，通常為100質量份以上，較佳為200質量份以上，更佳為250質量份以上，進而較佳為300質量份以上，尤佳為350質量份以上，又，通常為700質量份以下，較佳為500質量份以下，更佳為450質量份以下，進而較佳為400質量份以下。上述上限及下限可任意地組合。例如，較佳為100質量份～700質量份，更佳為200質量份～700質量份，進而較佳為250質量份～500質量份，更進而較佳為250質量份～450質量份，尤佳為250質量份～400質量份。藉由設為上述下限值以上，有呈現無剝離等之適當之溶解顯影狀態之傾向。藉由設為上述上限值以下，有可獲得對於顯影液之適當之溶解時間之傾向。The content ratio of the (b) alkali-soluble resin to 100 parts by mass of the (d) ethylenically unsaturated compound is not particularly limited, but is usually 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 250 parts by mass or more, Furthermore, it is preferably 300 parts by mass or more, particularly preferably 350 parts by mass or more, and usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and still more preferably 400 parts by mass or less . The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 100 parts by mass to 700 parts by mass, more preferably 200 parts by mass to 700 parts by mass, still more preferably 250 parts by mass to 500 parts by mass, still more preferably 250 parts by mass to 450 parts by mass, especially Preferably it is 250 mass parts - 400 mass parts. By setting it as the said lower limit or more, there exists a tendency for the suitable dissolving and developing state without peeling etc. to be exhibited. By setting it below the said upper limit, there exists a tendency for the suitable dissolution time with respect to a developer to be obtained.

於使用密接提昇劑之情形時，其含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，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%。藉由設為上述下限值以上，有可充分地獲得密接性之提高效果之傾向。藉由設為上述上限值以下，有可抑制感度降低，或顯影後殘渣殘留而成為缺陷之傾向。In the case of using an adhesion promoter, its content ratio is not particularly limited, but is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably based on the total solid content of the photosensitive coloring composition. Preferably it is 0.4-2 mass %. By setting it as the said lower limit or more, there exists a tendency for the improvement effect of adhesiveness to be fully acquired. By setting it below the said upper limit value, there exists a tendency for a sensitivity fall or residue to remain after image development to become a defect and to be suppressed.

於使用界面活性劑之情形時，其含有比率並無特別限定，相對於感光性著色組合物之全部固形物成分量，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%。藉由設為上述下限值以上，有容易表現塗佈膜之平滑性、均勻性之傾向。藉由設為上述上限值以下，有容易表現塗佈膜之平滑性、均勻性，亦可抑制其他特性惡化之傾向。In the case of using a surfactant, its content ratio is not particularly limited, but is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.001 to 10% by mass relative to the total solid content of the photosensitive coloring composition. Preferably it is 0.01-0.5 mass %, Most preferably, it is 0.03-0.3 mass %. By making it more than the said lower limit, there exists a tendency for the smoothness and uniformity of a coating film to be easily expressed. By setting it below the said upper limit, the smoothness and uniformity of a coating film are easy to express, and there exists a tendency for the deterioration of other characteristics to also be suppressed.

＜感光性著色組合物中之氯原子含量＞ 關於本發明之感光性著色組合物，相對於感光性著色組合物之全部固形物成分量，感光性著色組合物中之氯原子之含量為0.05質量%以下。 於製作間隔壁時，伴有如下所述之步驟：進行加熱處理，使感光性著色組合物硬化。此時，存在電極表面產生表面粗糙之情形。表面粗糙可利用光學顯微鏡進行觀察，又，表面粗糙度亦增高。當電極表面產生表面粗糙之情形時，無法於該部分均勻地形成發光層，從而於製作有機電致發光元件時有可能因短路等導致顯示不良。推測其原因在於：於加熱處理時、尤其是於焙燒時，感光性著色組合物發生分解、揮發、或昇華，其中之氯原子對銀等金屬電極發揮作用，導致腐蝕或蝕刻等，藉由將氯原子之含量設為一定值以下，可抑制表面粗糙。 <The content of chlorine atoms in the photosensitive coloring composition> About the photosensitive coloring composition of this invention, content of the chlorine atom in the photosensitive coloring composition is 0.05 mass % or less with respect to the total solid content of the photosensitive coloring composition. When producing a partition wall, it is accompanied by the process of heat-processing and hardening a photosensitive coloring composition. At this time, there are cases where surface roughness occurs on the surface of the electrode. The surface roughness can be observed with an optical microscope, and the surface roughness is also increased. When the surface of the electrode is rough, the light-emitting layer cannot be uniformly formed in the portion, and the display failure may be caused by short circuit or the like during the production of the organic electroluminescent device. The reason for this is presumed to be that the photosensitive coloring composition is decomposed, volatilized, or sublimated during heat treatment, especially during firing, and chlorine atoms therein act on metal electrodes such as silver, causing corrosion or etching. When the content of chlorine atoms is set to a certain value or less, surface roughness can be suppressed.

感光性著色組合物中之氯原子主要含於(a)著色劑、(b)鹼可溶性樹脂、(f)分散劑等構成材料中，但有時亦會含有於其他材料中。為了使氯原子之含量落入本發明所規定之數值範圍內，可減少一種構成材料之氯含量，或者亦可設計成減少各材料中之氯含量，以落入規定之數值範圍內。Chlorine atoms in the photosensitive coloring composition are mainly contained in constituent materials such as (a) colorants, (b) alkali-soluble resins, and (f) dispersants, but may be contained in other materials. In order to make the content of chlorine atoms fall within the numerical range specified in the present invention, the chlorine content of one constituent material may be reduced, or the chlorine content of each material may be designed to be reduced so as to fall within the specified numerical range.

感光性著色組合物中之氯原子之含量並無特別限定，相對於感光性著色組合物之全部固形物成分量為0.05質量%以下，較佳為0.04質量%以下，更佳為0.03質量%以下，進而較佳為0.01質量%以下。藉由設為上述上限值以下，有可抑制電極之表面粗糙之傾向。 感光性著色組合物中之氯原子之含量並無特別限定，通常為0.0005質量%以上，較佳為0.001質量%以上，更佳為0.002質量%。藉由設為上述下限值以上，於在製造各構成材料時可緩和精製方面較有效。 上述上限及下限可任意地組合。例如較佳為0.0005～0.05質量%，更佳為0.0005～0.04質量%，進而較佳為0.001～0.03質量%，尤佳為0.002～0.01質量%。 The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is 0.05 mass % or less, preferably 0.04 mass % or less, and more preferably 0.03 mass % or less with respect to the total solid content of the photosensitive coloring composition. , more preferably 0.01 mass % or less. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode to be suppressed. Although content of the chlorine atom in a photosensitive coloring composition is not specifically limited, Usually, it is 0.0005 mass % or more, Preferably it is 0.001 mass % or more, More preferably, it is 0.002 mass %. By setting it as the said lower limit or more, it is effective in the point which can ease refinement|purification at the time of manufacture of each constituent material. The above upper limit and lower limit can be arbitrarily combined. For example, 0.0005-0.05 mass % is preferable, 0.0005-0.04 mass % is more preferable, 0.001-0.03 mass % is still more preferable, 0.002-0.01 mass % is especially preferable.

感光性著色組合物中之氯原子之含量並無特別限定，相對於包含溶劑之感光性著色組合物之總質量，較佳為100 μg/g以下，更佳為80 μg/g以下，進而較佳為50 μg/g以下，更進而較佳為30 μg/g以下，尤佳為10 μg/g以下。藉由設為上述上限值以下，有可良好地抑制電極之表面粗糙之傾向。 感光性著色組合物中之氯原子之含量並無特別限定，通常為0.5 μg/g以上，較佳為1.0 μg/g以上，更佳為2.0 μg/g以上。藉由設為下限值以上，於在製造各構成材料時可緩和精製方面較有效。 上述上限及下限可任意地組合。例如，較佳為0.5～100 μg/g，更佳為0.5～80 μg/g，進而較佳為1.0～50 μg/g，更進而較佳為1.0～30 μg/g，尤佳為2.0～10 μg/g。 The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 100 μg/g or less, more preferably 80 μg/g or less, and more preferably 100 μg/g or less with respect to the total mass of the photosensitive coloring composition containing the solvent. It is preferably 50 μg/g or less, more preferably 30 μg/g or less, and still more preferably 10 μg/g or less. By setting it below the said upper limit value, there exists a tendency for the surface roughness of an electrode to be suppressed favorably. The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.5 μg/g or more, preferably 1.0 μg/g or more, and more preferably 2.0 μg/g or more. By setting it as the lower limit value or more, it is effective in that the purification can be eased when producing each constituent material. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 0.5 to 100 μg/g, more preferably 0.5 to 80 μg/g, still more preferably 1.0 to 50 μg/g, still more preferably 1.0 to 30 μg/g, particularly preferably 2.0 to 2.0 μg/g. 10 μg/g.

感光性著色組合物中之氯原子之含量並無特別限定，相對於感光性著色組合物之(a)著色劑之含量100質量%，較佳為0.20質量%以下，更佳為0.15質量%以下，進而較佳為0.10質量%以下，更進而較佳為0.05質量%以下，尤佳為0.03質量%以下。藉由設為上述上限值以下，有可抑制電極之表面粗糙之傾向。 感光性著色組合物中之氯原子之含量並無特別限定，通常為0.001質量%以上，較佳為0.005質量%以上，更佳為0.010質量%。藉由設為下限值以上，於在製造各構成材料時可緩和精製方面較有效。 上述上限及下限可任意地組合。例如，相對於感光性著色組合物之(a)著色劑之含量100質量%，較佳為0.001～0.20質量%，更佳為0.001～0.15質量%，進而較佳為0.005～0.10質量%，更進而較佳為0.005～0.05質量%，尤佳為0.010～0.03質量%。 The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.20% by mass or less, more preferably 0.15% by mass or less with respect to 100% by mass of the content of the colorant (a) in the photosensitive coloring composition. , more preferably 0.10 mass % or less, still more preferably 0.05 mass % or less, and still more preferably 0.03 mass % or less. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode to be suppressed. Although content of the chlorine atom in a photosensitive coloring composition is not specifically limited, Usually, it is 0.001 mass % or more, Preferably it is 0.005 mass % or more, More preferably, it is 0.010 mass %. By setting it as the lower limit value or more, it is effective in that the purification can be eased when producing each constituent material. The above upper limit and lower limit can be arbitrarily combined. For example, it is preferably 0.001 to 0.20 mass %, more preferably 0.001 to 0.15 mass %, still more preferably 0.005 to 0.10 mass % with respect to 100 mass % of the content of the (a) colorant in the photosensitive coloring composition, and more preferably More preferably, it is 0.005 to 0.05 mass %, particularly preferably 0.010 to 0.03 mass %.

感光性著色組合物中之氯原子之含量例如可藉由燃燒離子層析法(Combustion ion chromatography)等進行測定。The content of chlorine atoms in the photosensitive coloring composition can be measured, for example, by combustion ion chromatography (Combustion ion chromatography).

＜感光性著色組合物之物性＞ 關於本發明之感光性著色組合物，其塗膜之膜厚每1 μm之光學密度(OD)於第一態樣中並無特別限定，較佳為0.5以上。於第二態樣中為0.5以上。更佳為0.7以上，進而較佳為1.0以上，更進而較佳為1.3以上，尤佳為1.5以上，且通常為4.0以下，較佳為3.0以下，更佳為2.0以下。上述上限及下限可任意地組合。於第一態樣及第二態樣之任一者中亦例如較佳為0.5～4.0，更佳為0.7～4.0，進而較佳為1.0～3.0，更進而較佳為1.3～3.0，尤佳為1.5～2.0。藉由設為上述下限值以上，有可獲得充分之遮光性之傾向。藉由設為上述上限值以下，有電極之表面粗糙變良好之傾向。 <Physical properties of photosensitive coloring composition> Regarding the photosensitive coloring composition of the present invention, the optical density (OD) per 1 μm of the film thickness of the coating film is not particularly limited in the first aspect, but is preferably 0.5 or more. In the second aspect, it is 0.5 or more. More preferably, it is 0.7 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, particularly preferably 1.5 or more, and usually 4.0 or less, preferably 3.0 or less, more preferably 2.0 or less. The above upper limit and lower limit can be arbitrarily combined. In any one of the first aspect and the second aspect, for example, it is preferably 0.5 to 4.0, more preferably 0.7 to 4.0, still more preferably 1.0 to 3.0, still more preferably 1.3 to 3.0, particularly preferably is 1.5 to 2.0. By setting it as the said lower limit or more, there exists a tendency for sufficient light-shielding property to be acquired. There exists a tendency for the surface roughness of an electrode to become favorable by making it below the said upper limit.

塗膜之膜厚每1 μm之光學密度(OD)只要使用使本發明之感光性著色組合物硬化而成之塗膜測定即可，且可使用於230℃下進行20分鐘加熱硬化而成之塗膜進行測定。 所謂光學密度係指受光部之分光感度特性由ISO 5-3標準中之ISO視覺密度表示之透過光學密度。通常，作為光源，可使用CIE(國際照明委員會)所規定之A光源。作為可於透過光學密度之測定中使用之測定器，例如可例舉Sakata Inx Engineering公司之X-Rite 361T(V)。 The optical density (OD) per 1 μm of the film thickness of the coating film can be measured by using the coating film obtained by curing the photosensitive coloring composition of the present invention, and it can be used for heat curing at 230° C. for 20 minutes. The coating film was measured. The so-called optical density refers to the transmission optical density expressed by the ISO visual density in the ISO 5-3 standard for the spectral sensitivity characteristics of the light-receiving part. In general, as the light source, A light source specified by CIE (Commission Internationale de Illumination) can be used. As a measuring device which can be used for the measurement of transmission optical density, X-Rite 361T(V) of Sakata Inx Engineering can be mentioned, for example.

＜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係依據常法製造。 通常，(a)著色劑較佳為預先使用塗料調節器、砂磨機、球磨機、輥磨機、石磨機、噴射磨機、均質機等進行分散處理。藉由分散處理，(a)著色劑經微粒子化，故抗蝕劑之塗佈特性提高。 <The manufacturing method of the photosensitive coloring composition> The photosensitive coloring composition of this invention is manufactured according to an ordinary method. Usually, the (a) colorant is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. (a) The colorant is micronized by the dispersion treatment, so that the coating properties of the resist are improved.

分散處理通常較佳為利用併用(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、及藉由分散處理所獲得之組合物稱為「顏料分散液」)。尤其是若使用高分子分散劑作為(f)分散劑，則所獲得之顏料分散液及感光性著色組合物之經時之增黏得以抑制，即分散穩定性優異，故較佳。 如此，於製造感光性著色組合物之步驟中，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。 作為顏料分散液中可使用之(a)著色劑、(e)溶劑、及(f)分散劑，可分別較佳地採用作為可用於感光性著色組合物者所記載者。又，作為顏料分散液中之(a)著色劑之各著色劑之含有比率，亦可較佳地採用作為感光性著色組合物中之含有比率所記載者。 The dispersion treatment is usually preferably performed using a system in which (a) a colorant, (e) a solvent, (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used together (hereinafter, it may be used for the dispersion treatment in some cases). The mixture and the composition obtained by dispersion treatment are called "pigment dispersion"). In particular, when a polymer dispersant is used as the (f) dispersant, the viscosity increase over time of the obtained pigment dispersion liquid and the photosensitive coloring composition is suppressed, that is, the dispersion stability is excellent, which is preferable. In this way, in the step of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion liquid, those described as those usable in the photosensitive coloring composition can be preferably used, respectively. Moreover, as the content ratio of each coloring agent of (a) coloring agent in a pigment dispersion liquid, what was described as a content ratio in a photosensitive coloring composition can also be used suitably.

於對含有調配至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，因分散處理時產生之放熱，故高反應性成分有可能改性。因此，較佳為利用包含高分子分散劑之系統進行分散處理。 於利用砂磨機使(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。關於分散處理條件，溫度通常為0℃至100℃，較佳為室溫至80℃之範圍。關於分散時間，根據液體之組成及分散處理裝置之尺寸等不同而存在不同之適宜時間，故適當加以調節。分散之標準為：以感光性著色組合物之20度鏡面光澤度(JIS Z8741)達到50～300之範圍之方式，控制顏料分散液之光澤。於感光性著色組合物之光澤度較低之情形時，分散處理不充分，殘留粗糙之顏料(色料)粒子之情形較多，顯影性、密接性、解像性等有可能變得不充分。若進行分散處理直至光澤值超過上述範圍，則顏料粉碎而產生大量超微粒子，故反而有分散穩定性受損之傾向。 分散於顏料分散液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進行測定。 In the case of performing dispersion treatment on a liquid containing all the components formulated in the photosensitive coloring composition, there is a possibility that the highly reactive component may be modified due to heat generation during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment using a system containing a polymer dispersant. In the case of dispersing the (a) colorant with a sand mill, glass beads or zirconia beads with a particle size of about 0.1 to 8 mm can be preferably used. Regarding the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, and preferably in the range of room temperature to 80°C. Regarding the dispersion time, there is a different suitable time depending on the composition of the liquid and the size of the dispersion treatment device, so it is appropriately adjusted. The standard of dispersion is to control the gloss of the pigment dispersion liquid so that the 20-degree specular gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300. When the glossiness of the photosensitive coloring composition is low, the dispersion treatment is not sufficient, and there are many cases where rough pigment (color material) particles remain, and developability, adhesion, resolution, etc. may become insufficient. . If the dispersion treatment is performed until the gloss value exceeds the above-mentioned range, the pigment is pulverized to generate a large amount of ultrafine particles, so that the dispersion stability tends to be impaired instead. The dispersed particle size of the pigment dispersed in the pigment dispersion liquid is usually 0.03-0.3 μm, which can be measured by dynamic light scattering method.

其次，將藉由上述分散處理所獲得之顏料分散液、及感光性著色組合物中所含之上述其他成分混合，製成均勻之溶液或分散液。於感光性著色組合物之製造步驟中，微細之污物有時會混入至液體中，故所獲得之感光性著色組合物較理想為利用過濾器等進行過濾處理。Next, the pigment dispersion liquid obtained by the above-mentioned dispersion treatment and the above-mentioned other components contained in the photosensitive coloring composition are mixed to prepare a uniform solution or dispersion liquid. In the production process of the photosensitive coloring composition, since fine dirt may be mixed into the liquid, the obtained photosensitive coloring composition is preferably filtered with a filter or the like.

[硬化物] 藉由使本發明之感光性著色組合物硬化，可獲得本發明之硬化物。使本發明之感光性著色組合物硬化而成之硬化物可適宜地用作間隔壁。 [hardened product] The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention. The hardened|cured material which hardened the photosensitive coloring composition of this invention can be used suitably as a partition.

[間隔壁] 本發明之感光性著色組合物可適宜地用於形成間隔壁、尤其是用以劃分有機電致發光元件之有機層之間隔壁。作為有機電致發光元件中所使用之有機層，例如可例舉：如日本專利特開2016-165396號公報中所記載之電洞注入層、電洞傳輸層或電洞注入層上之電洞傳輸層中所使用之有機層。 [partition wall] The photosensitive coloring composition of this invention can be used suitably for forming a partition, especially for dividing the partition of the organic layer of an organic electroluminescent element. As the organic layer used in the organic electroluminescence device, for example, as described in Japanese Patent Laid-Open No. 2016-165396, the hole injection layer, the hole transport layer, or the hole on the hole injection layer can be mentioned. The organic layer used in the transport layer.

其次，對使用本發明之感光性著色組合物之間隔壁，依據其製造方法加以說明。Next, the partition wall using the photosensitive coloring composition of this invention is demonstrated based on the manufacturing method.

(1)支持體 作為用以形成間隔壁之支持體，只要有適度之強度，則其材質並無特別限定。主要使用基板，作為材質，例如可例舉：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)丙烯酸樹脂等熱硬化性樹脂片材；各種玻璃。其中，從耐熱性之觀點考慮，較佳為玻璃、耐熱性樹脂。又，亦存在於基板之表面成膜有ITO(Indium Tin Oxide，氧化銦錫)、IZO(Indium Zinc Oxide，氧化銦鋅)等透明電極；或銀、金、鉑、鋁、鎂之類的金屬電極之情形。除了上述基板以外，亦能夠形成於TFT(Thin Film Transistor，薄膜電晶體)陣列上。 (1) Support body The material of the support for forming the partition is not particularly limited as long as it has an appropriate strength. Substrates are mainly used, and as materials, for example, polyester-based resins such as polyethylene terephthalate; polyolefin-based resins such as polypropylene and polyethylene; polycarbonate, polymethyl methacrylate, and polysilicon and other thermoplastic resin sheets; epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin and other thermosetting resin sheets; various glasses. Among them, from the viewpoint of heat resistance, glass and heat-resistant resin are preferred. In addition, there are also transparent electrodes such as ITO (Indium Tin Oxide, indium tin oxide), IZO (Indium Zinc Oxide, indium zinc oxide) formed on the surface of the substrate; or metals such as silver, gold, platinum, aluminum, and magnesium. The situation of the electrodes. In addition to the above-mentioned substrate, it can also be formed on a TFT (Thin Film Transistor, thin film transistor) array.

為了改良接著性等表面物性，亦可視需要對支持體例如進行電暈放電處理、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。 基板之厚度通常設為0.05～10 mm，較佳為設為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。 In order to improve surface physical properties such as adhesiveness, the support may be subjected to, for example, corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent or a urethane resin, if necessary. The thickness of the substrate is usually set in the range of 0.05 to 10 mm, preferably in the range of 0.1 to 7 mm. Moreover, when performing the thin-film formation process of various resin, the range of the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2)間隔壁 本發明之感光性著色組合物被用於和公知之彩色濾光片用感光性著色組合物同樣之用途，以下，依據使用本發明之感光性著色組合物之間隔壁之形成方法的具體例對用作間隔壁之情形加以說明。 (2) Partition wall The photosensitive coloring composition of the present invention is used in the same application as the known photosensitive coloring composition for color filters, and the following will be based on a specific example of the method of forming a partition using the photosensitive coloring composition of the present invention. The case where it is used as a partition wall will be described.

通常，藉由塗佈等方法將感光性著色組合物以膜狀或圖案狀供於應設置間隔壁之基板上，並使溶劑乾燥。繼而，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，藉此於基板上形成間隔壁。Usually, the photosensitive coloring composition is supplied in the form of a film or a pattern on the board|substrate which should provide a partition by methods, such as coating, and a solvent is dried. Then, pattern formation is performed by methods, such as the photolithography method which performs exposure-development. After that, additional exposure or thermosetting treatment is performed as necessary to form partition walls on the substrate.

(3)間隔壁之形成 [1]向基板之供給方法 本發明之感光性著色組合物通常係於溶解或分散於溶劑中之狀態下向基板上供給。作為其供給方法，可藉由先前公知之方法例如旋轉塗佈法、線棒塗佈法、流塗法、模嘴塗佈法、輥塗法、噴塗法而進行。又，例如可藉由噴墨法或印刷法，以圖案狀供給。其中，根據模嘴塗佈法，塗佈液之使用量大幅削減，且完全不存在利用旋轉塗佈法時附著之霧等之影響，抑制異物產生等，就綜合性觀點而言較佳。 (3) Formation of partition walls [1] Supply method to substrate The photosensitive coloring composition of this invention is usually supplied on a board|substrate in the state which melt|dissolved or disperse|distributed in a solvent. As the supply method, it can be performed by a conventionally known method, for example, a spin coating method, a wire bar coating method, a flow coating method, a die coating method, a roll coating method, and a spray coating method. Also, for example, it can be supplied in a pattern by an ink jet method or a printing method. Among them, according to the die coating method, the usage amount of the coating liquid can be greatly reduced, the influence of fog and the like adhering in the spin coating method is completely eliminated, and the generation of foreign matter can be suppressed, which is preferable from a comprehensive viewpoint.

塗佈量根據用途而有所不同，例如於間隔壁之情形時，以乾燥膜厚計，以通常成為0.5 μm～10 μm、較佳為成為1 μm～9 μm、尤佳為成為1 μm～7 μm之方式塗佈。重要的是乾燥膜厚或最終形成之間隔壁之高度於整個基板上較均勻。藉由不均較小，可均勻地製作發光層，且可抑制發光時之顯示不良。The coating amount varies depending on the application. For example, in the case of a partition wall, the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 1 μm. Coating at 7 μm. It is important that the dry film thickness or the height of the final formed partitions is relatively uniform over the entire substrate. Since the unevenness is small, the light-emitting layer can be produced uniformly, and display failure at the time of light emission can be suppressed.

於使用本發明之感光性著色組合物，藉由光微影法一起形成高度不同之間隔壁之情形時，最終形成之間隔壁之高度不同。When using the photosensitive coloring composition of this invention, when the partition walls with different heights are formed together by the photolithography method, the heights of the partition walls finally formed are different.

再者，作為基板，可使用玻璃基板、陣列基板等公知之基板。基板表面較適宜為平面。In addition, as a board|substrate, a well-known board|substrate, such as a glass substrate and an array substrate, can be used. The substrate surface is preferably flat.

[2]乾燥方法 向基板上供給感光性著色組合物後之乾燥較佳為利用加熱板、IR(Infrared Radiation，紅外線輻射)烘箱、對流烘箱之乾燥方法。亦可組合減壓乾燥法，其不提高溫度，於減壓室內進行乾燥。 [2] Drying method The drying after supplying the photosensitive coloring composition on the substrate is preferably a drying method using a hot plate, an IR (Infrared Radiation) oven, or a convection oven. It is also possible to combine the drying method under reduced pressure, which does not increase the temperature and conducts drying in a reduced pressure chamber.

乾燥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，通常於40℃～130℃之溫度下於15秒鐘～5分鐘之範圍內選擇，較佳為於50℃～110℃之溫度下於30秒鐘～3分鐘之範圍內選擇。The drying conditions can be appropriately selected according to the type of solvent components, the performance of the dryer to be used, and the like. The drying time depends on the type of solvent components, the performance of the dryer used, etc., usually within the range of 15 seconds to 5 minutes at a temperature of 40°C to 130°C, preferably at a temperature of 50°C to 110°C Select within the range of 30 seconds to 3 minutes.

[3]曝光方法 曝光係於感光性著色組合物之塗佈膜上使負型遮罩圖案重疊，並介隔該遮罩圖案，照射紫外線或可見光之光源而進行。於使用曝光遮罩進行曝光之情形時，可利用使曝光遮罩接近感光性著色組合物之塗佈膜之方法；或將曝光遮罩配置於遠離感光性著色組合物之塗佈膜之位置，介隔曝光遮罩投影曝光之光之方法。亦可利用不使用遮罩圖案之利用雷射光之掃描曝光方式。視需要為了防止由氧所引起之光聚合性層之感度降低，亦可於脫氧氣氛下進行曝光，或者於光聚合性層上形成聚乙烯醇層等隔氧層後進行曝光。 [3] Exposure method The exposure is performed by overlapping the negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating the light source of ultraviolet rays or visible light through the mask pattern. In the case of exposure using an exposure mask, a method of making the exposure mask close to the coating film of the photosensitive coloring composition; or disposing the exposure mask at a position away from the coating film of the photosensitive coloring composition, A method of projecting exposure light through an exposure mask. A scanning exposure method using laser light without using a mask pattern can also be used. If necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, exposure may be performed in a deoxidized atmosphere, or exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

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間隔壁之情形時，例如使用如下曝光遮罩，其具有遮光部(光透過率0%)、及作為複數個開口部之平均光透過率相對於平均光透過率最高之開口部(完全透過開口部)較小之開口部(中間透過開口部)。藉由該方法，藉由中間透過開口部與完全透過開口部之平均光透過率之差、即曝光量之差，產生殘膜率之差異。 例如已知有利用具有微小之多邊形遮光單元之矩陣狀遮光圖案製作中間透過開口部之方法。又，例如已知有作為吸收體，利用鉻系、鉬系、鎢系、矽系材料之膜，控制光透過率而製作之方法。 As a preferred aspect of the present invention, in the case of simultaneously forming partitions with different heights by photolithography, for example, an exposure mask having a light-shielding portion (light transmittance of 0%) and a plurality of The average light transmittance of the openings is smaller than the openings (completely transmitted openings) with the highest average light transmittances (intermediately transmitted openings). According to this method, the difference in residual film ratio is generated by the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. For example, there is known a method of forming an intermediate transmission opening using a matrix-shaped light-shielding pattern having minute polygonal light-shielding elements. In addition, for example, there is known a method of producing by controlling the light transmittance by using a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material as an absorber.

上述曝光所使用之光源並無特別限定。作為光源，例如可例舉：氙燈、鹵素燈、鎢燈、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、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。於照射特定波長之光而使用之情形時，亦可利用濾光器。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 lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; or argon ion lasers , YAG (Yttrium Aluminum Garnet, yttrium aluminum garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser and other laser light sources. When used by irradiating light of a specific wavelength, a filter can also be used.

作為濾光器，例如可為能夠利用薄膜控制曝光波長下之光透過率之類型，作為該情形時之材質，例如可例舉：Cr化合物(Cr之氧化物、氮化物、氮氧化物、氟化物等)、MoSi、Si、W、Al。The optical filter can be, for example, a type that can control the light transmittance at the exposure wavelength with a thin film, and as a material in this case, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, fluorine compounds, etc.), MoSi, Si, W, Al.

作為曝光量，並無特別限定，通常為1 mJ/cm 2以上，較佳為5 mJ/cm 2以上，更佳為10 mJ/cm 2以上，且通常為300 mJ/cm 2以下，較佳為200 mJ/cm 2以下，更佳為150 mJ/cm 2以下。 於接近曝光方式之情形時，作為曝光對象與遮罩圖案之距離，並無特別限定，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。 The exposure amount is not particularly limited, but is usually 1 mJ/cm 2 or more, preferably 5 mJ/cm 2 or more, more preferably 10 mJ/cm 2 or more, and usually 300 mJ/cm 2 or less, preferably It is 200 mJ/cm 2 or less, more preferably 150 mJ/cm 2 or less. In the case of the close exposure method, the distance between the exposure object and the mask pattern is not particularly limited, but is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, Preferably it is 400 micrometers or less, More preferably, it is 300 micrometers or less.

[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。鹼性化合物之水溶液亦可進而含有例如界面活性劑、有機溶劑、緩衝劑、錯合劑、染料或顏料。 [4] Development method After the above-mentioned exposure, an image pattern can be formed on the substrate by developing using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the basic compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

作為鹼性化合物，可例舉：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；單、二或三乙醇胺、單、二或三甲基胺、單、二或三乙基胺、單或二異丙基胺、正丁基胺、單、二或三異丙醇胺、伸乙亞胺、乙二亞胺、氫氧化四甲基銨(TMAH)、膽鹼等有機鹼性化合物。該等鹼性化合物亦可為兩種以上之混合物。Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and sodium phosphate. , potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds; mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimide, tetramethylammonium hydroxide (TMAH), bile Alkali and other organic basic compounds. These basic compounds may also be a mixture of two or more kinds.

作為界面活性劑，例如可例舉：聚氧乙烯烷基醚類、聚氧乙烯烷基芳醚類、聚氧乙烯烷基酯類、山梨醇酐烷基酯類、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、磺基琥珀酸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。As surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters can be mentioned. Nonionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates and other anionic surfactants; Amphoteric surfactants such as alkyl betaines and amino acids.

作為有機溶劑，例如可例舉：異丙醇、苄醇、乙基溶纖劑、丁基溶纖劑、苯基溶纖劑、丙二醇、二丙酮醇。該等有機溶劑亦可併用兩種以上。又，有機溶劑可單獨使用，亦可與水或鹼性化合物之水溶液併用。As an organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol are mentioned, for example. These organic solvents may be used in combination of two or more. In addition, the organic solvent may be used alone or in combination with water or an aqueous solution of a basic compound.

顯影處理之條件並無特別限制，通常，顯影溫度為10～50℃，較佳為15～45℃，更佳為20～40℃。顯影方法例如可利用浸漬顯影法、噴霧顯影法、毛刷顯影法、超音波顯影法。The conditions of the development treatment are not particularly limited, but the development temperature is usually 10 to 50°C, preferably 15 to 45°C, and more preferably 20 to 40°C. As a development method, a dip development method, a spray development method, a brush development method, and an ultrasonic development method can be utilized, for example.

[5]追加曝光及熱硬化處理 亦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。亦可於顯影後、或追加曝光後，進行熱硬化處理(亦稱為焙燒)。關於熱硬化處理條件，溫度較佳為100℃～280℃，更佳為150℃～250℃，時間為5分鐘～60分鐘。 [5] Additional exposure and thermal curing If necessary, the developed substrate may be additionally exposed by the same method as the above-mentioned exposure method. After development, or after additional exposure, thermosetting treatment (also referred to as baking) may be performed. Regarding the thermal curing conditions, the temperature is preferably 100°C to 280°C, more preferably 150°C to 250°C, and the time is 5 minutes to 60 minutes.

使用本發明之感光性著色組合物作為間隔壁時之大小或形狀等係根據應用其之有機電致發光元件之規格等而適當調整，由本發明之感光性著色組合物形成之間隔壁之高度通常為0.5～10 μm左右。 又，從遮光性之觀點考慮，作為本發明之間隔壁之每1 μm之光學密度(OD)較佳為0.7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。又，較佳為4.0以下，更佳為3.0以下。上述上限及下限可任意地組合。例如，較佳為0.7～4.0，更佳為1.2～4.0，進而較佳為1.5～3.0，尤佳為1.8～3.0。此處，光學密度(OD)係藉由下述方法測定之值。 When using the photosensitive coloring composition of the present invention as a partition wall, the size, shape, etc. are appropriately adjusted according to the specifications of the organic electroluminescent element to which it is applied, and the height of the partition wall formed by the photosensitive coloring composition of the present invention is usually is about 0.5 to 10 μm. Furthermore, from the viewpoint of light-shielding properties, the optical density (OD) per 1 μm of the partition walls of the present invention is preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, particularly preferably 1.8 or more. Moreover, it is preferable that it is 4.0 or less, and it is more preferable that it is 3.0 or less. The above upper limit and lower limit can be arbitrarily combined. For example, 0.7-4.0 are preferable, 1.2-4.0 are more preferable, 1.5-3.0 are still more preferable, 1.8-3.0 are especially preferable. Here, the optical density (OD) is a value measured by the following method.

[有機電致發光元件] 本發明之有機電致發光元件具備本發明之硬化物例如間隔壁。 例如，使用具備藉由上述方法製造之間隔壁圖案之基板，製造各種有機電致發光元件。形成有機電致發光元件之方法並無特別限定，較佳為於藉由上述方法基板上形成間隔壁之圖案後，藉由使功能材料於真空狀態下昇華，使之附著於基板上之由間隔壁所包圍之區域內而成膜之蒸鍍法、或流延法、旋轉塗佈法、噴墨印刷法等濕式製程形成像素等之有機層，藉此製造有機電致發光元件。 [Organic Electroluminescent Device] The organic electroluminescence element of the present invention includes the cured product of the present invention, for example, a partition wall. For example, various organic electroluminescence elements are produced using a substrate having a partition pattern produced by the above method. The method of forming the organic electroluminescence device is not particularly limited, and preferably after forming the pattern of the partition wall on the substrate by the above method, the functional material is sublimated in a vacuum state, so that it is attached to the substrate between Organic layers such as pixels are formed by wet processes such as vapor deposition, casting, spin coating, and inkjet printing to form a film in the region surrounded by the partition walls, thereby producing organic electroluminescent devices.

作為有機電致發光元件之類型，可例舉底部發光型或頂部發光型。 關於底部發光型，例如係於積層有透明電極之玻璃基板上形成間隔壁，於由間隔壁所包圍之開口部積層電洞傳輸層、發光層、電子傳輸層、金屬電極層而製作。另一方面，關於頂部發光型，例如係於積層有金屬電極層作為反射層之玻璃基板上形成間隔壁，於由間隔壁所包圍之開口部積層電子傳輸層、發光層、電洞傳輸層、透明電極層而製作。 再者，作為發光層，可例舉如日本專利特開2009-146691號公報或日本專利第5734681號公報中所記載之有機電致發光層。又，亦可使用如日本專利第5653387號公報或日本專利第5653101號公報中所記載之量子點。 As the type of the organic electroluminescence element, a bottom emission type or a top emission type can be exemplified. For the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in the opening surrounded by the partition wall. On the other hand, as for the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated as a reflective layer, and an electron transport layer, a light emitting layer, a hole transport layer, an electron transport layer, a light emitting layer, a hole transport layer, transparent electrode layer. In addition, as a light-emitting layer, the organic electroluminescent layer described in Unexamined-Japanese-Patent No. 2009-146691 or Unexamined-Japanese-Patent No. 5734681 is mentioned, for example. In addition, quantum dots as described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101 can also be used.

層構成並不限定於此，例如，從發光效率之觀點考慮，電洞傳輸層、電子傳輸層之各層亦可為包含雙層以上之積層構成。各層之厚度並無特別限定，從發光效率或亮度之觀點考慮，通常為1～500 nm。The layer structure is not limited to this. For example, from the viewpoint of luminous efficiency, each of the hole transport layer and the electron transport layer may have a laminated structure including two or more layers. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

有機電致發光元件可於每一開口部劃分RGB(Red Green Blue，紅綠藍)各色而形成，亦可於1個開口部積層二色以上。從可靠性提高之觀點考慮，有機電致發光元件亦可具備密封層。密封層具有防止空氣中之水分吸附於有機電致發光元件，降低發光效率之功能。從光提取效率提高之觀點考慮，有機電致發光元件亦可於和空氣之界面處具備低反射膜。藉由將低反射膜配置於空氣與元件之界面，可期待縮小折射率之差距，抑制於界面之反射。於此種低反射膜中例如可應用蛾眼構造、超多層膜之技術。The organic electroluminescence element can be formed by dividing RGB (Red Green Blue, red, green and blue) colors in each opening, and can also be formed by laminating two or more colors in one opening. From the viewpoint of improving reliability, the organic electroluminescence element may be provided with a sealing layer. The sealing layer has the function of preventing moisture in the air from being adsorbed on the organic electroluminescent element and reducing the luminous efficiency. From the viewpoint of improving the light extraction efficiency, the organic electroluminescence element may also have a low reflection film at the interface with the air. By arranging the low-reflection film at the interface between the air and the element, it is expected to narrow the difference in refractive index and suppress reflection at the interface. For such a low-reflection film, for example, a moth-eye structure and a technique of a super multilayer film can be applied.

於使用有機電致發光元件作為圖像顯示裝置之像素之情形時，必須防止某像素之發光層之光洩漏至其他像素，進而於電極等為金屬之情形時，必須防止伴隨外光反射之圖像品質之降低，故較佳為對構成有機電致發光元件之間隔壁賦予遮光性。 又，於有機電致發光元件中，必須對間隔壁之上表面及下表面賦予電極，故從絕緣性之觀點考慮，間隔壁較佳為高電阻、低介電常數。因此，於為了對間隔壁賦予遮光性而使用著色劑之情形時，較佳為使用高電阻且低介電常數之上述有機顏料。 When using an organic electroluminescent element as a pixel of an image display device, it is necessary to prevent the light from the light-emitting layer of one pixel from leaking to other pixels, and when the electrode is made of metal, it is necessary to prevent the image accompanying the reflection of external light. In order to reduce the image quality, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescence element. In addition, in the organic electroluminescence element, electrodes must be provided on the upper and lower surfaces of the partition walls, so from the viewpoint of insulating properties, the partition walls preferably have high resistance and low dielectric constant. Therefore, when a colorant is used in order to impart light-shielding properties to the partition wall, it is preferable to use the above-mentioned organic pigment having a high electrical resistance and a low dielectric constant.

[圖像顯示裝置] 作為本發明之圖像顯示裝置，可例舉包含本發明之硬化物之間隔壁或具有本發明之有機電致發光元件之有機EL顯示裝置。 有機EL顯示裝置只要係包含上述有機電致發光元件者，則圖像顯示裝置之型號或構造並無特別限制，例如可使用主動驅動型有機電致發光元件並依據常法組裝。例如可藉由如「有機EL顯示器」(Ohmsha，2004年8月20日發行，時任靜士、安達千波矢、村田英幸著)中所記載之方法而形成。例如可組合發出白色光之有機電致發光元件與彩色濾光片而進行圖像顯示，亦可組合RGB等發光顏色不同之有機電致發光元件而進行圖像顯示。 [image display device] As the image display device of the present invention, an organic EL display device including a partition wall of the cured product of the present invention or an organic EL display device having the organic electroluminescence element of the present invention can be exemplified. The type or structure of the image display device is not particularly limited as long as the organic EL display device includes the above-mentioned organic electroluminescence device, for example, an active driving type organic electroluminescence device can be used and assembled according to a conventional method. For example, it can be formed by the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, then by Shizuoka, Chihaya Adachi, Hideyuki Murata). For example, an organic electroluminescent element that emits white light and a color filter can be combined to perform image display, and an organic electroluminescent element of different emitting colors such as RGB can be combined to perform image display.

[照明] 包含本發明之硬化物之有機電致發光元件可用於照明。照明之型號或結構並無特別限制，可使用包含本發明之硬化物之有機電致發光元件並依據常法組裝。作為有機電致發光元件，可設為單純矩陣驅動方式，亦可設為主動矩陣驅動方式。 為了使照明發出白色光，亦可使用發出白色光之有機電致發光元件。又，可構成為組合發光顏色不同之有機電致發光元件，混合各色而成為白色，亦可構成為可調整混色比率而賦予調色功能。 [實施例] [illumination] The organic electroluminescent element containing the hardened|cured material of this invention can be used for illumination. The type or structure of the lighting is not particularly limited, and an organic electroluminescence element including the cured product of the present invention can be used and assembled according to a conventional method. As the organic electroluminescence element, a simple matrix driving method or an active matrix driving method may be used. In order to make the illumination emit white light, an organic electroluminescence element that emits white light can also be used. In addition, it may be configured to combine organic electroluminescent elements with different emission colors, and to mix each color to make white, or it may be configured to adjust the color mixing ratio to provide a toning function. [Example]

以下，例舉實施例及比較例更具體地說明本發明，但本發明只要不超出其主旨，則並不限定於以下之實施例。 以下之實施例及比較例中所使用之感光性著色組合物之構成成分、以及該等之評價方法如下所述。 Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. The components of the photosensitive coloring composition used in the following Examples and Comparative Examples, and the evaluation methods thereof are as follows.

＜鹼可溶性樹脂-I＞ 將日本化藥公司製造之「XD1000」(二環戊二烯-苯酚聚合物之聚縮水甘油醚，環氧當量252)300質量份、丙烯酸87質量份、對甲氧基苯酚0.2質量份、三苯基膦5質量份、及丙二醇單甲醚乙酸酯255質量份添加至反應容器中，於100℃下進行攪拌直至酸值達到3.0 mgKOH/g。繼而進而添加四氫鄰苯二甲酸酐145質量份，於120℃下進行4小時反應。如此獲得之鹼可溶性樹脂-I之藉由GPC測定之重量平均分子量Mw為2600，酸值為106 mgKOH/g。 <Alkali-soluble resin-I> "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, 252 epoxy equivalent) manufactured by Nippon Kayaku Co., Ltd., 300 parts by mass, 87 parts by mass of acrylic acid, 0.2 part by mass of p-methoxyphenol, 3 parts by mass 5 parts by mass of phenylphosphine and 255 parts by mass of propylene glycol monomethyl ether acetate were added to the reaction container, and the mixture was stirred at 100° C. until the acid value reached 3.0 mgKOH/g. Next, 145 parts by mass of tetrahydrophthalic anhydride was further added, and the reaction was performed at 120° C. for 4 hours. The weight-average molecular weight Mw of the alkali-soluble resin-I thus obtained measured by GPC was 2600, and the acid value was 106 mgKOH/g.

＜鹼可溶性樹脂-II＞<Alkali-soluble resin-II>

[化47]

Figure 02_image093
[Chemical 47]
Figure 02_image093

上述結構之環氧化合物(環氧當量248)50.0質量份、丙烯酸14.2質量份、乙酸甲氧基丁酯52.6質量份、三苯基膦1.29質量份、及對甲氧基苯酚0.044質量份加入至安裝有溫度計、攪拌機、冷凝管之燒瓶中，一面攪拌一面於90℃下進行反應直至酸值達到5 mgKOH/g以下。反應需要12小時，獲得環氧丙烯酸酯溶液。 於上述環氧丙烯酸酯溶液中，將乙酸甲氧基丁酯42.9質量份、三羥甲基丙烷(TMP)1.98質量份、聯苯四羧酸二酐(BPDA)24.9質量份、四氫鄰苯二甲酸酐(THPA)5.39質量份加入至安裝有溫度計、攪拌機、冷凝管之燒瓶中，一面攪拌一面緩慢升溫至105℃而進行反應。 於樹脂溶液呈現透明時，利用乙酸甲氧基丁酯進行稀釋，以固形物成分成為50質量%之方式製備，獲得酸值100 mgKOH/g、重量平均分子量(Mw)12000之鹼可溶性樹脂(II)。 50.0 parts by mass of epoxy compound (epoxy equivalent 248) of the above structure, 14.2 parts by mass of acrylic acid, 52.6 parts by mass of methoxybutyl acetate, 1.29 parts by mass of triphenylphosphine, and 0.044 parts by mass of p-methoxyphenol were added to In a flask equipped with a thermometer, a stirrer and a condenser, the reaction was carried out at 90°C while stirring until the acid value reached 5 mgKOH/g or less. The reaction required 12 hours to obtain an epoxy acrylate solution. In the above-mentioned epoxy acrylate solution, 42.9 parts by mass of methoxybutyl acetate, 1.98 parts by mass of trimethylolpropane (TMP), 24.9 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and tetrahydrophthalic acid were added. 5.39 parts by mass of diformic anhydride (THPA) was added to a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was gradually raised to 105° C. while stirring to perform a reaction. When the resin solution was transparent, it was diluted with methoxybutyl acetate, and the solid content was 50% by mass to obtain an alkali-soluble resin (II) with an acid value of 100 mgKOH/g and a weight-average molecular weight (Mw) of 12,000. ).

＜鹼可溶性樹脂-III＞ 日本化藥公司製造之「ZCR-8035H」(重量平均分子量Mw＝7000，酸值＝82 mgKOH/g)。具有下述式(C-1)所表示之部分結構。 <Alkali-soluble resin-III> "ZCR-8035H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw=7000, acid value=82 mgKOH/g). It has a partial structure represented by the following formula (C-1).

[化48]

Figure 02_image095
[Chemical 48]
Figure 02_image095

＜顏料-I＞ 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) ＜Pigment-I＞ Irgaphor (registered trademark) Black S 0100 CF (with a chemical structure represented by the following formula (2)), manufactured by BASF Corporation

[化49]

Figure 02_image097
[Chemical 49]
Figure 02_image097

＜顏料-II＞ C.I.顏料橙64 ＜顏料-III＞ C.I.顏料紫29 ＜顏料-IV＞ C.I.顏料藍60 ＜Pigment-II＞ C.I. Pigment Orange 64 ＜Pigment-III＞ C.I. Pigment Violet 29 ＜Pigment-IV＞ C.I. Pigment Blue 60

＜分散劑-I＞ 甲基丙烯酸系A-B二嵌段共聚物，其包含：A嵌段，其包含具有親溶劑基之重複單元；及B嵌段，其包含具有顏料吸附基之重複單元。具有下述式(a)～(f)之重複單元。胺值為120 mgKOH/g。重量平均分子量為9000。於分散劑中實質上不含氯原子。 ＜Dispersant-I＞ A methacrylic acid-based A-B diblock copolymer comprising: an A block comprising repeating units having a solvophilic group; and a B block comprising repeating units having a pigment adsorption group. A repeating unit having the following formulae (a) to (f). The amine value was 120 mgKOH/g. The weight average molecular weight was 9000. The dispersant contains substantially no chlorine atoms.

下述式(a)～(f)之重複單元於全部重複單元中之含有比率分別為(a)33.3莫耳%、(b)13.3莫耳%、(c)6.7莫耳%、(d)6.7莫耳%、(e)6.7莫耳%、(f)33.3莫耳%。The content ratios of the repeating units of the following formulae (a) to (f) in all repeating units are (a) 33.3 mol %, (b) 13.3 mol %, (c) 6.7 mol %, (d) 6.7 mol%, (e) 6.7 mol%, (f) 33.3 mol%.

[化50] A嵌段

Figure 02_image099
[Chem. 50] A block
Figure 02_image099

[化51] B嵌段

Figure 02_image101
[Chem. 51] B block
Figure 02_image101

＜分散劑-II＞ 甲基丙烯酸系A-B二嵌段共聚物，其包含：A嵌段，其包含具有親溶劑基之重複單元；及B嵌段，其包含具有顏料吸附基之重複單元。具有下述式(h)～(n)之重複單元。胺值為70 mgKOH/g。將胺基四級化前之重量平均分子量為9000。分散劑中之氯原子之含量為2.1質量%。 ＜Dispersant-II＞ A methacrylic acid-based A-B diblock copolymer comprising: an A block comprising repeating units having a solvophilic group; and a B block comprising repeating units having a pigment adsorption group. Repeating units having the following formulae (h) to (n). The amine value was 70 mgKOH/g. The weight average molecular weight before quaternization of the amine groups was 9000. The content of chlorine atoms in the dispersant was 2.1% by mass.

下述式(h)～(n)之重複單元於全部重複單元中之含有比率分別為(h)33.3莫耳%、(i)13.3莫耳%、(j)6.7莫耳%、(k)6.7莫耳%、(l)6.7莫耳%、(m)24.0莫耳%、(n)9.3莫耳%。The content ratios of the repeating units of the following formulae (h) to (n) in all repeating units are (h) 33.3 mol %, (i) 13.3 mol %, (j) 6.7 mol %, (k) 6.7 mol%, (l) 6.7 mol%, (m) 24.0 mol%, (n) 9.3 mol%.

[化52] A嵌段

Figure 02_image103
[Chem. 52] A block
Figure 02_image103

[化53] B嵌段

Figure 02_image105
[Chem. 53] B block
Figure 02_image105

＜溶劑-I＞ PGMEA：丙二醇單甲醚乙酸酯 ＜溶劑-II＞ MB：3-甲氧基-1-丁醇 ＜溶劑-III＞ MBA：3-乙酸甲氧基丁酯 <Solvent-I> PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-II> MB: 3-Methoxy-1-butanol <Solvent-III> MBA: 3-Methoxybutyl acetate

＜光聚合起始劑-I＞ 具有以下化學結構之肟酯系光聚合起始劑 <Photopolymerization Initiator-I> Oxime ester-based photopolymerization initiator with the following chemical structure

[化54]

Figure 02_image107
[Chemical 54]
Figure 02_image107

＜乙烯性不飽和化合物＞ DPHA-40H：日本化藥公司製造 胺基甲酸酯丙烯酸酯 ＜界面活性劑＞ DIC公司製造 MEGAFAC F-559 <ethylenically unsaturated compound> DPHA-40H: Nippon Kayaku Co., Ltd. urethane acrylate ＜Surfactant＞ Made by DIC Corporation MEGAFAC F-559

＜黏度評價＞ 所製備之顏料分散液之黏度係利用東機產業公司製造之RE-85L型黏度計(測定條件：23℃、20 rpm)進行測定。 <Viscosity evaluation> The viscosity of the prepared pigment dispersion liquid was measured using the RE-85L type viscometer (measurement conditions: 23 degreeC, 20 rpm) manufactured by Toki Sangyo Co., Ltd.

＜氯原子含量之測定＞ 藉由燃燒離子層析法(Combustion ion chromatography)進行測定。利用三菱化學分析科技公司(現日東精工分析科技公司)之燃燒吸收離子層析(CIC)裝置AQF2100H，藉由校準曲線法，對感光性著色組合物中之氯原子含量進行定量。 <Determination of chlorine atom content> The measurement is carried out by combustion ion chromatography (Combustion ion chromatography). The content of chlorine atoms in the photosensitive coloring composition was quantified by the calibration curve method using the combustion absorption ion chromatography (CIC) apparatus AQF2100H of Mitsubishi Chemical Analytical Technology Corporation (now Nitto Seiko Analytical Technology Corporation).

＜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以如下之順序進行測定。 首先，利用旋轉塗佈機，將所製備之感光性著色組合物以焙燒後之膜厚成為1.5 μm之方式塗佈於玻璃基板上，進行1分鐘減壓乾燥後，利用加熱板於100℃下進行120秒鐘乾燥。對所獲得之塗佈膜，不使用曝光遮罩而進行曝光。照射光源係使用波長365 nm下之強度為40 mW/cm 2之高壓水銀燈，曝光量設為50 mJ/cm 2。繼而於烘箱中以230℃加熱30分鐘以使之硬化，藉此獲得抗蝕劑塗敷基板1。 使用X-Rite公司製造之361T(V)透過濃度計(照明光源之色溫度：約2850 K(相當於CIE標準光源A)、受光部之分光感度特性：ISO 5-3標準中之ISO視覺密度(visual density))測定所獲得之抗蝕劑塗敷基板1之光學密度(OD值)，利用Ryoka Systems公司製造之非接觸表面、層剖面形狀測量系統VertScan(R)2.0來測定膜厚，根據光學密度(OD值)及膜厚算出每單位膜厚(1 μm)之光學密度(單位OD值)。再者，OD值係表示遮光能力之數值，數值越大，表示越為高遮光性。 <Measurement of optical density per unit film thickness (unit OD value)> The optical density per unit film thickness was measured in the following procedure. First, using a spin coater, the prepared photosensitive coloring composition was applied on a glass substrate so that the film thickness after firing was 1.5 μm, dried under reduced pressure for 1 minute, and then heated at 100° C. using a hot plate. Dry for 120 seconds. The obtained coating film was exposed without using an exposure mask. The irradiation light source was a high-pressure mercury lamp with an intensity of 40 mW/cm 2 at a wavelength of 365 nm, and the exposure amount was set to 50 mJ/cm 2 . Then, it was hardened by heating at 230 degreeC for 30 minutes in an oven, and the resist-coated board|substrate 1 was obtained by this. Use the 361T(V) transmission densitometer manufactured by X-Rite company (color temperature of illumination light source: about 2850 K (equivalent to CIE standard light source A), spectral sensitivity characteristics of light receiving part: ISO visual density in ISO 5-3 standard (visual density)) to measure the optical density (OD value) of the obtained resist-coated substrate 1, and use the non-contact surface and layer profile measurement system VertScan(R) 2.0 manufactured by Ryoka Systems to measure the film thickness, according to Optical density (OD value) and film thickness The optical density (unit OD value) per unit film thickness (1 μm) was calculated. Furthermore, the OD value is a numerical value representing the light-shielding ability, and the larger the numerical value, the higher the light-shielding ability.

＜電極表面粗糙評價＞ 於在玻璃基板上之整個面蒸鍍有膜厚60 nm之銀薄膜之電極基板上，利用旋轉塗佈機將各感光性著色組合物以焙燒後之膜厚成為1.5 μm之方式進行塗佈，進行1分鐘減壓乾燥後，利用加熱板於100℃下進行120秒鐘乾燥。其次，於所獲得之塗膜基板上使用能夠形成每邊為50 μm之正方形開口圖案之光罩，利用高壓水銀燈，截止330 nm以下之波長並以曝光間隙5 μm進行50 mJ/cm 2之紫外線曝光。此時之波長365 nm下之光強度為40 mW/cm 2。繼而，將2.38質量%之TMAH(氫氧化四甲基銨)水溶液作為顯影液，於25℃下實施顯影液水壓0.05 MPa之噴淋顯影60秒鐘，其後利用純水沖掉顯影液以停止顯影，並利用水洗噴霧進行60秒鐘洗淨。 藉由該等操作對開口部分進行顯影去除，獲得間隔壁經圖案化之電極基板。將形成有該圖案之基板於烘箱中以230℃加熱(焙燒)30分鐘而使圖案硬化。 利用光學顯微鏡以200倍觀察所獲得之形成有50 μm開口圖案之電極基板，確認於開口圖案內電極表面有無形狀變化(表面粗糙)。以A、B、C之順序表示表面粗糙良好之程度，且A最為良好。 A：加熱硬化後，電極表面未產生表面粗糙。 B：加熱硬化後，電極表面產生一些表面粗糙，但實用上並無問題，可容許。 C：加熱硬化後，電極表面可見凹凸，產生表面粗糙，實用上存在問題，難以容許。 <Evaluation of electrode surface roughness> On the electrode substrate on which the silver thin film with a film thickness of 60 nm was vapor-deposited on the entire surface of the glass substrate, each photosensitive coloring composition was baked to a thickness of 1.5 μm using a spin coater. The coating was carried out in the same manner, and after drying under reduced pressure for 1 minute, drying was performed at 100° C. for 120 seconds on a hot plate. Next, a photomask capable of forming a square opening pattern of 50 μm on each side was used on the obtained coated substrate, and a high-pressure mercury lamp was used to cut off the wavelength below 330 nm and conduct ultraviolet rays of 50 mJ/cm 2 with an exposure gap of 5 μm. exposure. The light intensity at the wavelength of 365 nm at this time was 40 mW/cm 2 . Then, a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution was used as a developing solution, and spray development with a developing solution water pressure of 0.05 MPa was performed at 25° C. for 60 seconds, and then the developing solution was rinsed out with pure water. The development was stopped, and washing was performed for 60 seconds with a water washing spray. Through these operations, the opening portion is developed and removed to obtain an electrode substrate with a patterned partition wall. The substrate on which the pattern was formed was heated (fired) in an oven at 230° C. for 30 minutes to harden the pattern. The obtained electrode substrate having an opening pattern of 50 μm was observed with an optical microscope at a magnification of 200, and the presence or absence of shape change (surface roughness) on the electrode surface in the opening pattern was confirmed. In the order of A, B, and C, the degree of good surface roughness is indicated, and A is the best. A: No surface roughness occurred on the electrode surface after heat curing. B: After heating and hardening, some surface roughness occurred on the electrode surface, but there was no practical problem and it was acceptable. C: After heating and hardening, irregularities are seen on the surface of the electrode, resulting in surface roughness, which is a practical problem and cannot be tolerated.

＜發光特性評價＞ 使用通常之光微影技術與鹽酸蝕刻，將於玻璃上以70 nm之厚度沈積氧化銦錫(ITO)透明導電膜而成者形成為陽極，於形成有該陽極之基板上，利用旋轉塗佈機，將各感光性著色組合物以焙燒後之膜厚成為1.5 μm之方式進行塗佈，進行1分鐘減壓乾燥後，利用加熱板於100℃下進行120秒鐘乾燥。其次，於所獲得之塗膜基板上，使用曝光遮罩(以縱60 μm、橫100 μm之間距具有複數個長方形狀之被覆部(縱40 μm×橫80 μm)者)，利用截止了330 nm以下之波長之高壓水銀燈，以曝光間隙5 μm進行50 mJ/cm 2之紫外線曝光。此時之波長365 nm下之光強度為40 mW/cm 2。繼而，將2.38質量%之TMAH(氫氧化四甲基銨)水溶液作為顯影液，於25℃下實施顯影液水壓0.05 MPa之噴淋顯影60～120秒鐘，其後利用純水沖掉顯影液而停止顯影，利用水洗噴霧進行60秒鐘洗淨。噴淋顯影時間設為將塗膜之未曝光部溶解去除之時間之1.2倍以上。 藉由該等操作對開口部分進行顯影去除，獲得間隔壁經圖案化之電極基板。將形成有該圖案之基板於烘箱中以230℃加熱(焙燒)30分鐘而使圖案硬化。 <Evaluation of Light Emitting Characteristics> An anode formed by depositing a transparent conductive film of indium tin oxide (ITO) with a thickness of 70 nm on glass was formed on the glass using a normal photolithography technique and hydrochloric acid etching, and then the anode was formed on the substrate on which the anode was formed. , each photosensitive coloring composition was applied by a spin coater so that the film thickness after baking was 1.5 μm, and after drying under reduced pressure for 1 minute, drying was performed on a hot plate at 100° C. for 120 seconds. Next, on the obtained coated substrate, using an exposure mask (those having a plurality of rectangular covering portions (length 40 μm × width 80 μm) at a pitch of 60 μm in length and 100 μm in width), using a cut-off 330 A high-pressure mercury lamp with wavelengths below nm was used for UV exposure at 50 mJ/cm 2 with an exposure gap of 5 μm. The light intensity at the wavelength of 365 nm at this time was 40 mW/cm 2 . Next, a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution was used as a developing solution, and at 25° C., a spray development with a developing solution water pressure of 0.05 MPa was performed for 60 to 120 seconds, and then the development was rinsed out with pure water. The liquid was removed to stop the development, and washing was performed for 60 seconds with a water washing spray. The shower development time was set to be 1.2 times or more the time for dissolving and removing the unexposed part of the coating film. Through these operations, the opening portion is developed and removed to obtain an electrode substrate with a patterned partition wall. The substrate on which the pattern was formed was heated (fired) in an oven at 230° C. for 30 minutes to harden the pattern.

＜有機電致發光元件之製作＞ 於所製作之間隔壁經圖案化之電極基板上之整個面，以作為電洞注入層之氧化鉬成為膜厚10 nm、作為電洞傳輸層之N-([1,1'-聯苯]-4-基)-9,9-二甲基-N-[4-(9-苯基-9H-咔唑-3-基)苯基]-9H-茀-2-胺成為膜厚60 nm、作為發光層之三(8-羥基喹啉)鋁成為膜厚60 nm、作為電子注入層之8-羥基喹啉鋰成為膜厚1 nm、作為陰極之鋁成為膜厚80 nm之方式藉由真空蒸鍍法依序積層，而製作有機電致發光元件。 其次，於中央具有凹部之密封玻璃之該凹部貼附乾燥劑，於凹部之周圍之框部分塗佈UV硬化樹脂。以密封玻璃之凹部覆蓋上述電極基板上之有機電致發光元件之全部的方式進行配置，將密封玻璃貼附於上述電極基板，對UV硬化樹脂照射UV使其硬化，進行中空構造之密封，藉此製作有機電致發光元件評價用器件。 <Production of organic electroluminescence device> On the entire surface of the patterned electrode substrate of the produced partition wall, molybdenum oxide as a hole injection layer is formed into a film thickness of 10 nm, and N-([1,1'-biphenyl] as a hole transport layer -4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-pyridin-2-amine into a film thickness of 60 nm , the third (8-quinolinolato) aluminum as the light-emitting layer has a film thickness of 60 nm, the 8-hydroxyquinoline lithium as the electron injection layer has a film thickness of 1 nm, and the aluminum as the cathode has a film thickness of 80 nm. The organic electroluminescent element is fabricated by sequentially stacking layers by a vacuum evaporation method. Next, a desiccant is attached to the concave portion of the sealing glass having a concave portion in the center, and UV curing resin is applied to the frame portion around the concave portion. The concave portion of the sealing glass is arranged so that the entire organic electroluminescence element on the electrode substrate is covered, the sealing glass is attached to the electrode substrate, the UV curing resin is irradiated with UV to be cured, and the hollow structure is sealed by In this way, a device for evaluating organic electroluminescence elements was produced.

＜有機電致發光元件之發光特性評價＞ 測定於所製作之元件通電電流密度10 mA/cm 2之直流電流時之電壓值(驅動電壓)。 於製作單元時，以電流密度10 mA/cm 2通電時之電壓值(驅動電壓) A：電壓 6.5 V以下 B：電壓 高於6.5 V 繼而，對所製作之元件於60℃環境下對電流密度50 mA/cm 2之直流電流進行定電流驅動時，將自初始亮度至成為90%之值為止之時間(h)設為驅動壽命而進行測定。 至相對於初始亮度成為90%之亮度為止之時間(壽命) A：長於25小時 B：25小時以下 <Evaluation of Light Emitting Characteristics of Organic Electroluminescence Element> The voltage value (driving voltage) when a direct current with a current density of 10 mA/cm 2 was applied to the fabricated element was measured. When fabricating the cell, the voltage value (driving voltage) when the current density is 10 mA/cm 2 when energized A: The voltage is less than 6.5 V B: The voltage is higher than 6.5 V In the case of constant current driving with a DC current of 50 mA/cm 2 , the time (h) from the initial luminance to the value of 90% was set as the driving life and measured. Time until the brightness becomes 90% of the initial brightness (lifetime) A: More than 25 hours B: Less than 25 hours

＜顏料分散液1～3之製備＞ 以成為表1中所記載之質量比之方式混合表1中所記載之顏料、分散劑、鹼可溶性樹脂、及溶劑。利用塗料振盪器於25～45℃之範圍內對該混合液進行3小時分散處理。使用0.5 mmϕ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，利用過濾器使珠粒與分散液分離，製備顏料分散液1～3。 再者，表1中之溶劑之量亦包括來自分散劑及鹼可溶性樹脂之溶劑的量。又，將藉由上述方法測定之顏料分散液之黏度之評價結果示於表1。 <Preparation of Pigment Dispersions 1 to 3> The pigments, dispersants, alkali-soluble resins, and solvents described in Table 1 were mixed so as to have the mass ratios described in Table 1. The mixed solution was dispersed in the range of 25 to 45°C for 3 hours using a paint shaker. Use 0.5 mmϕ zirconia beads as beads, and add 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare Pigment Dispersion Liquids 1 to 3. Furthermore, the amount of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. In addition, Table 1 shows the evaluation result of the viscosity of the pigment dispersion liquid measured by the said method.

[表1]    顏料分散液1 顏料分散液2 顏料分散液3 調配比率(質量份) 顏料 顏料-I 100 100    顏料-II       9 顏料-III       31 顏料-IV       60 分散劑(固形物成分換算) 分散劑-I 20    20 分散劑-II    20    鹼可溶性樹脂(固形物成分換算) 鹼可溶性樹脂-I 50 50    鹼可溶性樹脂-III       33 溶劑 溶劑-I 408 408 368 溶劑-II 102 102 92 顏料分散液之黏度(mPa・s) 5.6 5.5 20.7 [Table 1] Pigment Dispersion 1 Pigment dispersion 2 Pigment Dispersion 3 Blending ratio (parts by mass) pigment Pigment-I 100 100 Pigment-II 9 Pigment-III 31 Pigment-IV 60 Dispersant (solid content conversion) Dispersant-I 20 20 Dispersant-II 20 Alkali-soluble resin (solid content conversion) Alkali Soluble Resin-I 50 50 Alkali Soluble Resin-III 33 solvent Solvent-I 408 408 368 Solvent-II 102 102 92 Viscosity of Pigment Dispersion (mPa·s) 5.6 5.5 20.7

[實施例1、2、比較例1] 以各成分之固形物成分於全部固形物成分量中所占之含有比率成為表2中所記載之值的方式添加各成分，進而以PGMEA/MB/MBA＝72/20/8、全部固形物成分量之含有比率成為17質量%之方式添加溶劑，進行攪拌、溶解，製備實施例1、2及比較例1之感光性著色組合物。又，將藉由上述方法測定之氯原子含量、或單位OD值、電極之表面粗糙之評價結果示於表2及表3。 [Examples 1, 2, Comparative Example 1] Each component was added so that the content ratio of the solid content of each component to the total solid content was the value described in Table 2, and further, PGMEA/MB/MBA=72/20/8, all solids were added. A solvent was added so that the content ratio of the component amount might be 17 mass %, and the photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1 were prepared by stirring and dissolving. In addition, Table 2 and Table 3 show the results of the evaluation of the chlorine atom content, the unit OD value, and the surface roughness of the electrode measured by the above-mentioned method.

[表2]    實施例1 比較例1 調配比率 (質量份，固形物成分換算值) 顏料分散液1 37.4    顏料分散液2    37.4 顏料分散液3       鹼可溶性樹脂-II 41.1 41.1 乙烯性不飽和化合物 17.4 17.4 光聚合起始劑-I 4.0 4.0 界面活性劑 0.1 0.1 感光性著色組合物之固形物成分中之顏料含有比率(質量%) 22.0 22.0 感光性著色組合物之固形物成分濃度(質量%) 17.0 17.0 氯原子含量 感光性著色組合物中之氯原子含有比率 (μg/g) 6.1 154 感光性著色組合物之固形物成分中之氯原子含有比率 (質量%) 0.0036 0.0906 評價結果 單位OD[/μm] 0.9 0.9 電極之表面粗糙評價 A C 發光特性/驅動電壓[V](判定) 7.5 V(B) 7.1 V(B) 發光特性/壽命[時間](判定) 29 hr(A) 25 hr(B) [Table 2] Example 1 Comparative Example 1 Mixing ratio (parts by mass, solid content conversion value) Pigment Dispersion 1 37.4 Pigment dispersion 2 37.4 Pigment Dispersion 3 Alkali Soluble Resin-II 41.1 41.1 ethylenically unsaturated compounds 17.4 17.4 Photopolymerization Initiator-I 4.0 4.0 Surfactant 0.1 0.1 Pigment content ratio (mass %) in solid content of photosensitive coloring composition 22.0 22.0 Solid content concentration (mass %) of photosensitive coloring composition 17.0 17.0 Chlorine atom content Chlorine atom content ratio in photosensitive coloring composition (μg/g) 6.1 154 Chlorine atom content ratio (mass %) in solid content of photosensitive coloring composition 0.0036 0.0906 Evaluation results Unit OD[/μm] 0.9 0.9 Surface roughness evaluation of electrodes A C Light emission characteristics/driving voltage [V] (judgment) 7.5V(B) 7.1 V(B) Luminescence characteristics/life [time] (judgment) 29 hours(A) 25 hours (B)

確認到使用有比較例1之感光性著色組合物之基板於銀(電極)表面形成凹凸，較粗糙。認為其原因在於，由於分散劑-II中所含之氯原子量較多，故於感光性著色組合物中亦較多地含有，焙燒時產生含有氯之氣體，與銀(電極)表面反應，於表面形成凹凸。 另一方面，關於使用有實施例1之感光性著色組合物之基板，未觀察到銀(電極)表面之形成有凹凸之情況。認為其原因在於，於分散劑-I中無氯原子量，其結果為，感光性著色組合物中之含量亦較少，故不會於銀(電極)表面產生粗糙，獲得正常之電極基板。 於有機電致發光元件之發光特性方面，實施例1與比較例1相比壽命較長。認為其原因在於，由於氯量較少，故發光元件之經時劣化得以抑制。 It was confirmed that the substrate using the photosensitive coloring composition of Comparative Example 1 had irregularities formed on the surface of the silver (electrode) and was relatively rough. The reason for this is considered to be that since the chlorine atomic weight contained in the dispersant-II is large, it is also contained in the photosensitive coloring composition in a large amount, and a gas containing chlorine is generated during baking, which reacts with the surface of silver (electrode) and is The surface is uneven. On the other hand, about the board|substrate using the photosensitive coloring composition of Example 1, the formation of unevenness|corrugation on the silver (electrode) surface was not observed. The reason is considered to be that there is no chlorine atomic weight in the dispersant-I, and as a result, the content in the photosensitive coloring composition is also small, so that no roughness occurs on the silver (electrode) surface, and a normal electrode substrate is obtained. In terms of the light-emitting characteristics of the organic electroluminescent element, Example 1 has a longer lifetime than Comparative Example 1. The reason for this is considered to be that the deterioration over time of the light-emitting element is suppressed due to the small amount of chlorine.

[表3]    實施例2 調配比率 (質量份，固形物成分換算值) 顏料分散液1    顏料分散液2    顏料分散液3 33.7 鹼可溶性樹脂-II 44.8 乙烯性不飽和化合物 17.4 光聚合起始劑-I 4.0 界面活性劑 0.1 感光性著色組合物之固形物成分中之顏料含有比率(質量%) 22.0 感光性著色組合物之固形物成分濃度(質量%) 17.0 氯原子含量 感光性著色組合物中之氯原子含有比率 (μg/g) 11.1 感光性著色組合物之固形物成分中之氯原子含有比率 (質量%) 0.0065 評價結果 單位OD[/μm] 0.9 電極之表面粗糙評價 B 發光特性/驅動電壓[V](判定) 6.1 V(A) 發光特性/壽命[時間](判定) 24 hr(B) [table 3] Example 2 Mixing ratio (parts by mass, solid content conversion value) Pigment Dispersion 1 Pigment dispersion 2 Pigment Dispersion 3 33.7 Alkali Soluble Resin-II 44.8 ethylenically unsaturated compounds 17.4 Photopolymerization Initiator-I 4.0 Surfactant 0.1 Pigment content ratio (mass %) in solid content of photosensitive coloring composition 22.0 Solid content concentration (mass %) of photosensitive coloring composition 17.0 Chlorine atom content Chlorine atom content ratio in photosensitive coloring composition (μg/g) 11.1 Chlorine atom content ratio (mass %) in solid content of photosensitive coloring composition 0.0065 Evaluation results Unit OD[/μm] 0.9 Surface roughness evaluation of electrodes B Light emission characteristics/driving voltage [V] (judgment) 6.1 V(A) Luminescence characteristics/life [time] (judgment) 24 hours (B)

關於使用有實施例2之感光性著色組合物之基板，銀(電極)表面之凹凸亦為實質上無問題之水準。認為與實施例2相比，實施例1之銀(電極)表面粗糙情況良好之原因在於，由於顏料-I為包含芳香環之剛直之骨架，故連微量之氯原子亦不會釋出至膜外。About the board|substrate using the photosensitive coloring composition of Example 2, the unevenness|corrugation of the silver (electrode) surface is a level which does not have a problem substantially. It is considered that the reason why the surface roughness of the silver (electrode) of Example 1 is better than that of Example 2 is that since Pigment-I is a rigid skeleton containing an aromatic ring, even a trace amount of chlorine atoms will not be released to the film outside.

於有機電致發光元件之發光特性方面，實施例2之初始驅動電壓降低，良好。又，與實施例1相比良好。With regard to the light-emitting characteristics of the organic electroluminescent element, the initial driving voltage of Example 2 was reduced and was good. Moreover, compared with Example 1, it is favorable.

Claims (11)

一種感光性著色組合物，其特徵在於：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，且 上述(a)著色劑含有選自由下述通式(I)所表示之化合物、上述化合物之幾何異構物、上述化合物之鹽、及上述化合物之幾何異構物之鹽所組成之群中之至少一種， 上述(f)分散劑含有丙烯酸系共聚物(f1)，該丙烯酸系共聚物(f1)至少含有下述通式(1)、(2)及(3)所表示之重複單元，且不具有包含四級銨基之重複單元， 且相對於感光性著色組合物之全部固形物成分量，感光性著色組合物中之氯原子之含量為0.05質量%以下， [化1]
Figure 03_image109
(式(I)中，R 1及R 6相互獨立地為氫原子、CH 3、CF 3、氟原子或氯原子； R 2、R 3、R 4、R 5、R 7、R 8、R 9及R 10係與其他全部相互獨立，為氫原子、鹵素原子、R 11、COOH、COOR 11、COO -、CONH 2、CONHR 11、CONR 11R 12、CN、OH、OR 11、COCR 11、OOCNH 2、OOCNHR 11、OOCNR 11R 12、NO 2、NH 2、NHR 11、NR 11R 12、NHCOR 12、NR 11COR 12、N=CH 2、N=CHR 11、N=CR 11R 12、SH、SR 11、SOR 11、SO 2R 11、SO 3R 11、SO 3H、SO 3 -、SO 2NH 2、SO 2NHR 11或SO 2NR 11R 12； 選自由R 2與R 3、R 3與R 4、R 4與R 5、R 7與R 8、R 8與R 9、及R 9與R 10所組成之群中之至少1個組合亦可相互直接鍵結，或者藉由氧原子、硫原子、NH或NR 11橋聯而相互鍵結； R 11及R 12相互獨立地為碳數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) [化2]
Figure 03_image111
(式(1)中，R 31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； R 32為氫原子或甲基； *表示鍵結鍵) [化3]
Figure 03_image113
(式(2)中，R 33為亞甲基、伸乙基或伸丙基，R 34為可具有取代基之烷基，R 35為氫原子或甲基； n為1～20之整數； *表示鍵結鍵) [化4]
Figure 03_image115
(式(3)中，R 36及R 37分別獨立地為氫原子、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，R 36及R 37可相互鍵結而形成環狀結構； R 38為氫原子或甲基； Z為二價連結基； *表示鍵結鍵)。 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 a compound selected from the group consisting of compounds represented by the following general formula (I), geometric isomers of the above-mentioned compounds, salts of the above-mentioned compounds, and salts of geometric isomers of the above-mentioned compounds At least one of the group consisting of, the above-mentioned (f) dispersant contains an acrylic copolymer (f1), and the acrylic copolymer (f1) contains at least the following general formulas (1), (2) and (3) The repeating unit represented does not have a repeating unit containing a quaternary ammonium group, and the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition, [ 1]
Figure 03_image109
(In formula (I), R 1 and R 6 are independently hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom; R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 are independent of all others, and are hydrogen atom, halogen atom, R 11 , COOH, COOR 11 , COO − , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N=CH 2 , N=CHR 11 , N=CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 11 or SO 2 NR 11 R 12 ; selected from R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and at least one combination of R 9 and R 10 in the group formed by They are bonded to each other by bridges of oxygen atoms, sulfur atoms, NH or NR 11 ; R 11 and R 12 are independently each other an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with a carbon number of 3 to 12, and a cycloalkyl group with 2 to 12 carbon atoms. 12 alkenyl, cycloalkenyl with 3 to 12 carbons or alkynyl with 2 to 12 carbons) [Chem. 2]
Figure 03_image111
(In formula (1), R 31 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; R 32 is a hydrogen atom or a methyl group; * represents a bond ) [化3]
Figure 03_image113
(In formula (2), R 33 is a methylene group, an ethylidene group or a propylidene group, R 34 is an alkyl group which may have a substituent, R 35 is a hydrogen atom or a methyl group; n is an integer from 1 to 20; *represents a bond bond) [化4]
Figure 03_image115
(In formula (3), R 36 and R 37 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R 36 and R 37 They can be bonded to each other to form a cyclic structure; R 38 is a hydrogen atom or a methyl group; Z is a divalent linking group; * represents a bonding bond). 如請求項1之感光性著色組合物，其中上述(a)著色劑包含有機著色顏料。The photosensitive coloring composition according to claim 1, wherein the colorant (a) above contains an organic coloring pigment. 一種感光性著色組合物，其特徵在於：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，且 硬化後之塗膜之每1 μm膜厚之光學密度為0.5以上， 上述(f)分散劑含有丙烯酸系共聚物(f1)，該丙烯酸系共聚物(f1)至少含有下述通式(1)、(2)及(3)所表示之重複單元，且不具有包含四級銨基之重複單元， 且相對於感光性著色組合物之全部固形物成分量，感光性著色組合物中之氯原子之含量為0.05質量%以下， [化5]
Figure 03_image117
(式(1)中，R 31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； R 32為氫原子或甲基； *表示鍵結鍵) [化6]
Figure 03_image119
(式(2)中，R 33為亞甲基、伸乙基或伸丙基，R 34為可具有取代基之烷基，R 35為氫原子或甲基； n為1～20之整數； *表示鍵結鍵) [化7]
Figure 03_image121
(式(3)中，R 36及R 37分別獨立地為氫原子、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，R 36及R 37可相互鍵結而形成環狀結構； R 38為氫原子或甲基； Z為二價連結基； *表示鍵結鍵)。 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 optical density per 1 μm of film thickness of the cured coating film is 0.5 or more, the above (f) dispersant contains an acrylic copolymer (f1), and the acrylic copolymer (f1) contains at least the following The repeating units represented by the general formulae (1), (2) and (3) do not have repeating units containing a quaternary ammonium group, and are photosensitive coloring with respect to the total solid content of the photosensitive coloring composition The content of chlorine atoms in the composition is 0.05% by mass or less, [Chem. 5]
Figure 03_image117
(In formula (1), R 31 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; R 32 is a hydrogen atom or a methyl group; * represents a bond ) [hua 6]
Figure 03_image119
(In formula (2), R 33 is a methylene group, an ethylidene group or a propylidene group, R 34 is an alkyl group which may have a substituent, R 35 is a hydrogen atom or a methyl group; n is an integer from 1 to 20; *represents a bond bond) [化7]
Figure 03_image121
(In formula (3), R 36 and R 37 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R 36 and R 37 They can be bonded to each other to form a cyclic structure; R 38 is a hydrogen atom or a methyl group; Z is a divalent linking group; * represents a bonding bond). 如請求項3之感光性著色組合物，其中上述(a)著色劑包含選自由紅色顏料及橙色顏料所組成之群中之至少一種、及選自由藍色顏料及紫色顏料所組成之群中之至少一種。The photosensitive coloring composition according to claim 3, wherein the (a) colorant comprises 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 at least one. 如請求項1至4中任一項之感光性著色組合物，其中上述丙烯酸系共聚物(f1)為嵌段共聚物。The photosensitive coloring composition according to any one of claims 1 to 4, wherein the acrylic copolymer (f1) is a block copolymer. 如請求項1至5中任一項之感光性著色組合物，其中上述丙烯酸系共聚物(f1)之胺值為90 mgKOH/g以上。The photosensitive coloring composition according to any one of claims 1 to 5, wherein the amine value of the acrylic copolymer (f1) is 90 mgKOH/g or more. 如請求項1至6中任一項之感光性著色組合物，其中相對於感光性著色組合物之全部固形物成分量，包含10質量%以上之上述(a)著色劑。The photosensitive coloring composition in any one of Claims 1-6 which contains the said (a) coloring agent in 10 mass % or more with respect to the total solid content of the photosensitive coloring composition. 如請求項1至7中任一項之感光性著色組合物，其係用於形成有機電致發光元件之間隔壁。The photosensitive coloring composition according to any one of claims 1 to 7, which is used for forming a partition wall between organic electroluminescent elements. 一種硬化物，其係使如請求項1至8中任一項之感光性著色組合物硬化而成。A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 8. 一種有機電致發光元件，其包含如請求項9之硬化物。An organic electroluminescence element comprising the cured product of claim 9. 一種圖像顯示裝置，其包含如請求項10之有機電致發光元件。An image display device comprising the organic electroluminescence element as claimed in claim 10.
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