TW201800849A - colored curable resin composition comprising the dye solution color filters and liquid crystal display devices - Google Patents

colored curable resin composition comprising the dye solution color filters and liquid crystal display devices Download PDF

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TW201800849A
TW201800849A TW106105729A TW106105729A TW201800849A TW 201800849 A TW201800849 A TW 201800849A TW 106105729 A TW106105729 A TW 106105729A TW 106105729 A TW106105729 A TW 106105729A TW 201800849 A TW201800849 A TW 201800849A
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朴昭妍
金兌昱
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東友精細化工有限公司
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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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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    • G02—OPTICS
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    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
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    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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Abstract

The present invention provides a colored curable resin composition capable of forming a color filter having high brightness and good solvent resistance. The present invention relates to the colored curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D) and an epoxy compound (P), which is different from the binder resin (B), wherein the colorant (A) comprises a compound (Aa) composed of a cation having a dye skeleton and an anion derived from a compound including at least one element selected from a group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen, and the content of the epoxy compound (P) is 0.1 to 60 mass% based on the total amount of the colorant (A).

Description

著色固化性樹脂組合物、濾色器和液晶顯示裝置Colored curable resin composition, color filter and liquid crystal display device

發明領域 本發明涉及著色固化性樹脂組合物、濾色器和液晶顯示裝置。FIELD OF THE INVENTION The present invention relates to a coloring curable resin composition, a color filter, and a liquid crystal display device.

發明背景 著色固化性樹脂組合物可用於製造在液晶顯示裝置、電致發光顯示裝置和等離子體顯示器顯示裝置等顯示裝置中使用的濾色器。作為這樣的著色固化性樹脂組合物，已知有包含由下式表示的著色劑、樹脂、聚合性化合物和聚合引發劑的組合物(專利文獻1)。BACKGROUND OF THE INVENTION A colored curable resin composition can be used for manufacturing a color filter used in a display device such as a liquid crystal display device, an electroluminescent display device, and a plasma display device. As such a coloring curable resin composition, a composition containing a coloring agent represented by the following formula, a resin, a polymerizable compound, and a polymerization initiator is known (Patent Document 1).

[化1]

Figure TW201800849AD00001
[式(1)中，R1 和R2 相互獨立地表示可具有取代基的苯基。 R3 和R4 相互獨立地表示碳數1~10的1價飽和烴基，該飽和烴基中所含的氫原子可以被碳數6~10的芳香族烴基或鹵素原子取代，該芳香族烴基中所含的氫原子可以被碳數1~3的烷基或碳數1~3的烷氧基取代，上述飽和烴基中所含的-CH2 -可以被-O-、-CO-或-NR11 -替換。 R1 和R3 可一起形成含有氮原子的環，R2 和R4 可一起形成含有氮原子的環。 R5 表示-OH、-SO3 H、-SO3 - Z+ 、-CO2 H、-CO2 - Z+ 、-CO2 R8 、-SO3 R8 或-SO2 NR9 R10 。 R6 和R7 相互獨立地表示氫原子或碳數1~6的烷基。 m表示0~4的整數。在m為2以上的整數的情況下，多個R5 可以彼此相同，也可不同。 R8 表示碳數1~20的1價飽和烴基，該飽和烴基中所含的氫原子可以被鹵素原子取代。 Z+ 表示+ N(R11 )4 、Na+ 或K+ 。 R9 和R10 相互獨立地表示氫原子或碳數1~20的1價的飽和烴基，R9 和R10 可相互結合而形成含有氮原子的3~10元環的雜環。 4個R11 相互獨立地表示氫原子、碳數1~20的1價飽和烴基或碳數7~10的芳烷基。] 現有技術文獻 專利文獻[Chemical 1]
Figure TW201800849AD00001
[In the formula (1), R 1 and R 2 each independently represent a phenyl group which may have a substituent. R 3 and R 4 each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group or halogen atom having 6 to 10 carbon atoms. The hydrogen atom contained may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. The -CH 2 -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -NR. 11 -Replace. R 1 and R 3 may form a ring containing a nitrogen atom together, and R 2 and R 4 may form a ring containing a nitrogen atom together. R 5 represents -OH, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO 2 NR 9 R 10. R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer from 0 to 4. When m is an integer of 2 or more, a plurality of R 5 may be the same as or different from each other. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. Z + means + N (R 11 ) 4 , Na + or K + . R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R 9 and R 10 may be combined with each other to form a 3 to 10 membered heterocyclic ring containing a nitrogen atom. The four R 11 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ] Prior Art Literature Patent Literature

專利文獻1：日本特開2013-50693號公報Patent Document 1: Japanese Patent Application Publication No. 2013-50693

發明要解決的課題 但是，在得到的濾色器中，有時其明度低，另外其耐溶劑性不充分。本發明的課題在於提供能夠形成明度高、耐溶劑性良好的濾色器的著色固化性樹脂組合物。 用於解決課題的手段Problem to be Solved by the Invention However, in the obtained color filter, the brightness may be low and the solvent resistance may be insufficient. An object of the present invention is to provide a coloring curable resin composition capable of forming a color filter with high brightness and good solvent resistance. Means to solve the problem

即，本發明涉及的要點如以下所述。 [1] 著色固化性樹脂組合物，其為含有著色劑(A)、黏結劑樹脂(B)、聚合性化合物(C)、聚合引發劑(D)和環氧化合物(P)(不過，與黏結劑樹脂(B)不同)的著色固化性樹脂組合物， 著色劑(A)為包含化合物(Aa)的著色劑，化合物(Aa)由具有色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成， 相對於著色劑(A)的總量，環氧化合物(P)的含有率為0.1質量%以上且60質量%以下。 [2] [1]所述的著色固化性樹脂組合物，其中，黏結劑樹脂(B)為具有來自從不飽和羧酸和不飽和羧酸酐中選擇的至少1種的單體的結構單元(a)、和來自具有烯屬不飽和鍵和環狀醚結構的單體的結構單元(b)的共聚物。 [3] [1]或[2]所述的著色固化性樹脂組合物，其中，由具有色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成的化合物(Aa)為由式(A-I)表示的化合物。That is, the gist of this invention is as follows. [1] A colored curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an epoxy compound (P) (however, and The coloring curable resin composition is different from the binder resin (B). The coloring agent (A) is a coloring agent containing a compound (Aa). The compound (Aa) is composed of a cation having a pigment skeleton, and is derived from a compound containing tungsten, molybdenum, The content of the epoxy compound (P) is 0.1% by mass or more and 60% by mass or less based on the anion composition of at least one element selected from silicon and phosphorus and an oxygen compound. [2] The colored curable resin composition according to [1], wherein the binder resin (B) is a structural unit having at least one monomer selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides ( a) A copolymer with a structural unit (b) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure. [3] The colored curable resin composition according to [1] or [2], wherein the colored curable resin composition is a cation having a pigment skeleton and derived from a cation containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen. The compound (Aa) composed of the anion of the compound is a compound represented by the formula (AI).

[化2]

Figure TW201800849AD00002
[式(A-I)中，R41 ~R44 相互獨立地表示可被取代的氨基、或可被鹵素原子取代的碳數1~20的飽和烴基、碳數2~20的烷基、該碳數2~20的烷基中所含的亞甲基被氧原子替換的基團、可具有取代基的芳香族烴基、可具有取代基的芳烷基或氫原子。R41 與R42 可結合並與它們結合的氮原子一起形成環，R43 與R44 可結合並與它們結合的氮原子一起形成環。 R47 ~R54 相互獨立地表示氫原子、鹵素原子、硝基、羥基、或碳數1~8的烷基，在構成該烷基的亞甲基間可***氧原子。R48 與R52 可相互結合而形成-NH-、-O-、-S-或-SO2 -。在R41 ~R44 和R47 ~R54 中，鄰接的亞甲基不會同時被替換為氧原子，另外，烷基的末端的亞甲基也不會被替換為氧原子。 環T1 表示可具有取代基的芳香族雜環。 [Y]m- 表示含有選自鎢、鉬、矽、和磷中的至少1個元素、和氧的m價的陰離子。 m表示2~14的整數。 再有，在1個分子中含有多個由下述式表示的陽離子的情況下，它們可以為相同的結構，也可以為不同的結構。[Chemical 2]
Figure TW201800849AD00002
[In the formula (AI), R 41 to R 44 independently represent an amino group which may be substituted or a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and the carbon number which may be substituted with a halogen atom. A group in which the methylene group contained in the 2 to 20 alkyl group is replaced with an oxygen atom, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R 41 and R 42 may be combined and form a ring with the nitrogen atom to which they are bonded, and R 43 and R 44 may be combined and form a ring with the nitrogen atom to which they are bonded. R 47 to R 54 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group. R 48 and R 52 may be combined with each other to form -NH-, -O-, -S-, or -SO 2- . In R 41 to R 44 and R 47 to R 54 , the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group of the alkyl group is not replaced with an oxygen atom. Ring T 1 represents an aromatic heterocyclic ring which may have a substituent. [Y] m- represents an m-valent anion containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus, and oxygen. m represents an integer from 2 to 14. When a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[化3]

Figure TW201800849AD00003
[式中，環T1 、R41 ~R44 和R47 ~R54 分別與上述同義。]] [4] 由[1]~[3]的任一項所述的著色固化性樹脂組合物形成的濾色器。 [5] 液晶顯示裝置，其包含[4]所述的濾色器。 發明的效果[Chemical 3]
Figure TW201800849AD00003
[In the formula, the rings T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as described above. ]] [4] A color filter formed from the colored curable resin composition according to any one of [1] to [3]. [5] A liquid crystal display device including the color filter according to [4]. Effect of the invention

根據本發明，能夠形成高明度、耐溶劑性良好的濾色器。According to the present invention, a color filter having high brightness and good solvent resistance can be formed.

較佳實施例之詳細說明 本發明的著色固化性樹脂組合物含有著色劑(A)、黏結劑樹脂(B)、聚合性化合物(C)、聚合引發劑(D)和環氧化合物(P)(不過，與黏結劑樹脂(B)不同)，相對於著色劑的總量，含有規定量的環氧化合物(P)。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The colored curable resin composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an epoxy compound (P). (However, it is different from the binder resin (B)), and contains a predetermined amount of the epoxy compound (P) with respect to the total amount of the colorant.

＜著色劑(A)＞ 著色劑(A)優選為包含由具有色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成的化合物(Aa)(以下有時稱為化合物(Aa))的著色劑。化合物(Aa)可單獨、也可包含2種以上。另外，作為著色劑(A)，可進一步包含染料(Ab)。<Colorant (A)> The colorant (A) preferably contains a compound consisting of a cation having a pigment skeleton and an anion derived from a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen ( Aa) (hereinafter sometimes referred to as compound (Aa)). The compound (Aa) may be used alone or in combination of two or more. The colorant (A) may further include a dye (Ab).

化合物(Aa)中的色素骨架是指選擇性地吸收可見光線(波長：400~750nm)而具有固有顏色的化合物的部分結構，該部分結構中包含用於顯現具有固有顏色的特徵的結構。The pigment skeleton in the compound (Aa) refers to a partial structure of a compound that selectively absorbs visible light (wavelength: 400 to 750 nm) and has an inherent color, and the partial structure includes a structure for expressing a characteristic with an inherent color.

作為構成化合物(Aa)的陽離子具有的色素骨架，可列舉出偶氮骨架、呫噸骨架、吖嗪骨架、菁骨架、吖啶骨架、蒽醌骨架和方酸骨架等中具有鎓結構的色素骨架；三芳基甲烷骨架；使三芳基甲烷骨架的芳香族烴環的1個以上成為了芳香族雜環的色素骨架等。其中，優選地可列舉出導入了鎓結構的呫噸骨架、導入了鎓結構的菁骨架、導入了鎓結構的方酸骨架、三芳基甲烷骨架和使三芳基甲烷骨架的芳香族烴環的1個以上成為了芳香族雜環的色素骨架，更優選地可列舉出使三芳基甲烷骨架的芳香族烴環的1個以上成為了芳香族雜環的色素骨架。Examples of the pigment skeleton possessed by the cation constituting the compound (Aa) include a pigment skeleton having an onium structure among azo skeleton, xanthene skeleton, azine skeleton, cyanine skeleton, acridine skeleton, anthraquinone skeleton, and cubic acid skeleton. A triarylmethane skeleton; a pigment skeleton having one or more aromatic hydrocarbon rings of a triarylmethane skeleton as an aromatic heterocyclic ring. Among them, preferred examples include a xanthene skeleton into which an onium structure is introduced, a cyanide skeleton into which an onium structure is introduced, a squaric acid skeleton into which an onium structure is introduced, a triarylmethane skeleton, and 1 More than one pigment | dye skeleton which became an aromatic heterocyclic ring, More preferably, the pigment | dye skeleton which made one or more aromatic hydrocarbon rings of a triarylmethane skeleton into an aromatic heterocyclic ring is mentioned.

成為陰離子的基礎化合物為含有選自鎢、鉬、矽和磷中的至少1個元素和氧的化合物，例如可列舉出選自鎢酸、鉬酸、矽酸和磷酸中的多元酸的2種以上(優選地3種)的組合；含有選自鎢、鉬、矽和磷中的至少1個元素、和氧的同多酸；含有選自鎢、鉬、矽和磷中的2個以上的元素、和氧的雜多酸等。其中，作為優選的化合物，可列舉出選自鎢酸、鉬酸和磷酸中的2種以上(優選地3種)的組合；或者含有鎢的雜多酸和含有鎢的同多酸，更優選地，可列舉出磷鎢酸、矽鎢酸和鎢系同多酸。The basic compound that becomes an anion is a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen. Examples include two types of polybasic acids selected from tungstic acid, molybdic acid, silicic acid, and phosphoric acid. A combination of the above (preferably 3 types); an isopoly acid containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus; and oxygen; containing two or more of the group selected from tungsten, molybdenum, silicon, and phosphorus; Elements, and heteropoly acids such as oxygen. Among them, preferred compounds include a combination of two or more (preferably three) selected from tungstic acid, molybdic acid, and phosphoric acid; or a heteropoly acid containing tungsten and a homopoly acid containing tungsten, more preferably Examples include phosphotungstic acid, silicotungstic acid, and tungsten homopolyacids.

作為含有鎢的雜多酸或同多酸的陰離子，例如可列舉出Keggin型磷鎢酸離子α-[PW12 O40 ]3- 、Dawson型磷鎢酸離子α-[P2 W218 O62 ]6- 、β-[P2 W18 O62 ]6- 、Keggin型矽鎢酸離子α-[SiW12 O40 ]4- 、β-[SiW12 O40 ]4- 、γ-[SiW12 O40 ]4- 、[P2 W17 O61 ]10- 、[P2 W15 O56 ]12- 、[H2 P2 W12 O48 ]12- 、[NaP5 W30 O110 ]14- 、α-[SiW9 O34 ]10- 、γ-[SiW10 O36 ]8- 、α-[SiW11 O39 ]8- 、β-[SiW11 O39 ]8- 、[W6 O19 ]2- 、[W10 O32 ]4- 、WO4 2- 和它們的混合物。Examples of the anion of a heteropoly acid or an isopoly acid containing tungsten include Keggin-type phosphotungstate ion α- [PW 12 O 40 ] 3- and Dawson-type phosphotungstate ion α- [P 2 W 218 O 62 ] 6- , β- [P 2 W 18 O 62 ] 6- , Keggin-type silicotungstic acid ion α- [SiW 12 O 40 ] 4- , β- [SiW 12 O 40 ] 4- , γ- [SiW 12 O 40 ] 4- , [P 2 W 17 O 61 ] 10- , [P 2 W 15 O 56 ] 12- , [H 2 P 2 W 12 O 48 ] 12- , [NaP 5 W 30 O 110 ] 14 - , Α- [SiW 9 O 34 ] 10- , γ- [SiW 10 O 36 ] 8- , α- [SiW 11 O 39 ] 8- , β- [SiW 11 O 39 ] 8- , [W 6 O 19 ] 2- , [W 10 O 32 ] 4- , WO 4 2- and mixtures thereof.

陰離子也優選為來自由選自矽和磷中的至少1個元素、和氧構成的化合物的陰離子。 作為來自由選自矽和磷中的至少1個元素、和氧構成的化合物的陰離子，可列舉出SiO3 2- 、PO4 3- 。The anion is also preferably an anion derived from a compound composed of at least one element selected from silicon and phosphorus, and oxygen. Examples of the anion derived from a compound composed of at least one element selected from silicon and phosphorus and oxygen include SiO 3 2- and PO 4 3- .

從合成和後處理的容易程度出發，優選Keggin型磷鎢酸離子、Dawson型磷鎢酸離子等磷鎢酸陰離子；Keggin型矽鎢酸離子等矽鎢酸陰離子、[W10 O32 ]4- 等鎢系同多酸陰離子，其中，更優選磷鎢酸陰離子、鎢系同多酸陰離子。From the ease of synthesis and post-treatment, preferred are phosphotungstic acid anions such as Keggin-type phosphotungstic acid ions and Dawson-type phosphotungstic acid ions; silicotungstic acid anions such as Keggin-type tungstic acid ions, [W 10 O 32 ] 4- The iso-tungsten-based homopolyacid anion, among them, a phosphotungstic acid anion and a tungsten-based isopolyacid anion are more preferred.

作為由具有呫噸色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成的化合物(Aa)，可列舉出C.I.顏料紅81、81：1、81：2、81：3、81：4、81：5、169；C.I.顏料紫1、1：1、1：2、2、2：2等。As the compound (Aa) composed of a cation having a xanthene pigment skeleton and an anion derived from a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen, CI Pigment Red 81, 81 : 1, 81: 2, 81: 3, 81: 4, 81: 5, 169; CI Pigment Violet 1, 1: 1, 1: 2, 2, 2: 2 and so on.

另外，作為由具有三芳基甲烷色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成的化合物(Aa)，可列舉出C.I.顏料藍1、1：2、1：3、2、2：1、2：2、3、8、9、10、10：1、11、12、18、19、24、24：1、53、56、56：1、57、58、59、61、62等。Examples of the compound (Aa) composed of a cation having a triarylmethane pigment skeleton and an anion derived from a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen, include CI Pigment Blue. 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 18, 19, 24, 24: 1, 53, 56, 56, 56: 1, 57, 58, 59, 61, 62, etc.

作為化合物(Aa)，優選由式(A-I)表示的化合物(以下也稱為(A-I))。The compound (Aa) is preferably a compound represented by the formula (A-I) (hereinafter also referred to as (A-I)).

[化4]

Figure TW201800849AD00004
[式(A-I)中，R41 ~R44 相互獨立地表示可被取代的氨基、或者可被鹵素原子取代的碳數1~20的飽和烴基、碳數2~20的烷基、該碳數2~20的烷基中所含的亞甲基被氧原子替換的基團、可具有取代基的芳香族烴基、可具有取代基的芳烷基或氫原子。R41 與R42 可結合並與它們結合的氮原子一起形成環，R43 與R44 可結合並與它們結合的氮原子一起形成環。 R47 ~R54 相互獨立地表示氫原子、鹵素原子、硝基、羥基、碳數1~8的烷基，在構成該烷基的亞甲基間可***氧原子。R48 與R52 可相互結合而形成-NH-、-O-、-S-或-SO2 -。 R41 ~R44 和R47 ~R54 中，鄰接的亞甲基不會同時被替換為氧原子，另外，烷基的末端的亞甲基也不會被替換為氧原子。 環T1 表示可具有取代基的芳香族雜環。 [Y]m- 表示含有選自鎢、鉬、矽和磷中的至少1個元素、和氧的m價的陰離子。 m表示2~14的整數。 再有，在1個分子中含有多個由下述式表示的陽離子的情況下，它們可以為相同的結構，也可以為不同的結構。[Chemical 4]
Figure TW201800849AD00004
[In the formula (AI), R 41 to R 44 independently represent an amino group which may be substituted or a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and the carbon number which may be substituted with a halogen atom. A group in which the methylene group contained in the 2 to 20 alkyl group is replaced with an oxygen atom, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R 41 and R 42 may be combined and form a ring with the nitrogen atom to which they are bonded, and R 43 and R 44 may be combined and form a ring with the nitrogen atom to which they are bonded. R 47 to R 54 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group. R 48 and R 52 may be combined with each other to form -NH-, -O-, -S-, or -SO 2- . In R 41 to R 44 and R 47 to R 54 , the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group of the alkyl group is not replaced with an oxygen atom. Ring T 1 represents an aromatic heterocyclic ring which may have a substituent. [Y] m- represents an m-valent anion containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus, and oxygen. m represents an integer from 2 to 14. When a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[化5]

Figure TW201800849AD00005
[式中，環T1 、R41 ~R44 和R47 ~R54 分別與上述同義。]][Chemical 5]
Figure TW201800849AD00005
[In the formula, the rings T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as described above. ]]

環T1 的芳香族雜環可以為單環，也可以為稠合環。另外，芳香族雜環優選為5~10元環，更優選為5~9元環。作為單環的芳香族雜環，例如可列舉出吡咯環、噁唑環、吡唑環、咪唑環、噻唑環等含有氮原子的5元環；呋喃環、噻吩環等不含氮原子的5元環；吡啶環、嘧啶環、噠嗪環、吡嗪環等含有氮原子的6元環等，作為稠合環的芳香族雜環，可列舉出吲哚環、苯並咪唑環、苯並噻唑環、喹啉環等含有氮原子的稠合環；苯並呋喃環等不含氮原子的稠合環等。 作為環T1 的芳香族雜環可具有的取代基，可列舉出鹵素原子、氰基、可具有鹵素原子等取代基的碳數1~20的烷基、可具有鹵素原子或碳數1~10的烷基等取代基的碳數6~20的芳香族烴基、可具有碳數1~10的烷基等取代基的氨基等。 其中，環T1 的芳香族雜環優選為含有氮原子的芳香族雜環，更優選為含有氮原子的5元環的芳香族雜環。The aromatic heterocyclic ring of ring T 1 may be a monocyclic ring or a fused ring. The aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; and a 5-membered ring containing no nitrogen atom such as a furan ring and a thiophene ring. 6-membered ring containing nitrogen atom, such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc. As the aromatic heterocyclic ring of the fused ring, indole ring, benzimidazole ring, benzo Nitrogen-containing fused rings such as thiazole ring and quinoline ring; fused rings containing no nitrogen atom such as benzofuran ring and the like. Examples of the substituent that the aromatic heterocyclic ring of ring T 1 may have include a halogen atom, a cyano group, and an alkyl group having 1 to 20 carbon atoms, which may have a substituent such as a halogen atom, and may have a halogen atom or 1 to carbon number. An aromatic hydrocarbon group having 6 to 20 carbon atoms, such as an alkyl group having 10 substituents, an amino group that may have a substituent, such as an alkyl group having 1 to 10 carbon atoms, and the like. Among them, the aromatic heterocyclic ring of ring T 1 is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

另外，環T1 更優選為由式(Ab2-x1)表示的環。The ring T 1 is more preferably a ring represented by the formula (Ab2-x1).

[化6]

Figure TW201800849AD00006
[環T2 表示芳香族雜環。 R45 和R46 相互獨立地表示可具有取代基的碳數1~20的飽和烴基、碳數2~20的烷基、該碳數2~20的烷基中所含的亞甲基被氧原子替換的基團、可具有取代基的芳香族烴基、可具有取代基的芳烷基或氫原子。R45 與R46 可結合並與它們結合的氮原子一起形成環。 不過，鄰接的亞甲基不會同時被替換為氧原子，另外，烷基的末端的亞甲基也不會被替換為氧原子。R55 表示碳數1~20的飽和烴基、或可具有取代基的芳香族烴基。 k1表示0或1。 ＊表示與碳陽離子的鍵合端。][Chemical 6]
Figure TW201800849AD00006
[Ring T 2 represents an aromatic heterocyclic ring. R 45 and R 46 independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and a methylene group contained in the alkyl group having 2 to 20 carbon atoms which may have a substituent. Atom-replacement group, aromatic hydrocarbon group which may have substituent, aralkyl group which may have substituent or hydrogen atom. R 45 and R 46 may be bonded together with the nitrogen atom to which they are bonded to form a ring. However, the adjacent methylene group will not be replaced with an oxygen atom at the same time, and the terminal methylene group of the alkyl group will not be replaced with an oxygen atom. R 55 represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent. k1 means 0 or 1. * Indicates a bonding end with a carbocation. ]

作為環T2 的芳香族雜環，可列舉出與環T1 中例示的芳香族雜環同樣的環。 進而，環T1 更優選為由式(Ab2-y1)表示的環。Examples of the aromatic heterocyclic ring of ring T 2 include the same ring as the aromatic heterocyclic ring exemplified for ring T 1 . Furthermore, the ring T 1 is more preferably a ring represented by the formula (Ab2-y1).

[化7]

Figure TW201800849AD00007
[R56 表示氫原子、碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。 X2表示氧原子、-NR57 -或硫原子。 R57 表示氫原子或碳數1~10的烷基。 R45 和R46 與上述同義。 ＊表示與碳陽離子的鍵合端。][Chemical 7]
Figure TW201800849AD00007
[R 56 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. X2 represents an oxygen atom, -NR 57- , or a sulfur atom. R 57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 45 and R 46 are synonymous with the above. * Indicates a bonding end with a carbocation. ]

另外，環T1 也優選為由式(Ab2-x2)表示的環。The ring T 1 is also preferably a ring represented by the formula (Ab2-x2).

[化8]

Figure TW201800849AD00008
[環T3 表示具有氮原子的5~10元環的芳香族雜環。 R58 表示碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。 R59 表示氫原子、可具有取代基的碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的芳烷基。 k2表示0或1。 ＊表示與碳陽離子的鍵合端。][Chemical 8]
Figure TW201800849AD00008
[Ring T 3 represents a 5- to 10-membered aromatic heterocyclic ring having a nitrogen atom. R 58 represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. R 59 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or an aralkyl group which may have a substituent. k2 means 0 or 1. * Indicates a bonding end with a carbocation. ]

另外，環T1 進一步也優選為由式(Ab2-y2)表示的環。The ring T 1 is more preferably a ring represented by the formula (Ab2-y2).

[化9]

Figure TW201800849AD00009
[R60 表示氫原子、碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。 R59 表示與上述同義。 ＊表示與碳陽離子的鍵合端。][Chemical 9]
Figure TW201800849AD00009
[R 60 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. R 59 is synonymous with the above. * Indicates a bonding end with a carbocation. ]

由R41 ~R46 、R55 、R56 和R58 ~R60 表示的碳數1~20的飽和烴基可以為直鏈、分支鏈和環狀的任一種。作為直鏈或分支鏈的飽和烴基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、辛基、壬基、癸基、十二烷基、十六烷基和二十烷基等直鏈狀烷基；異丙基、異丁基、異戊基、新戊基和2-乙基己基等分支鏈狀烷基等。該飽和烴基的碳數優選為1~10，更優選為1~8，進一步優選為1~6。The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 may be any of linear, branched, and cyclic chains. Examples of the linear or branched saturated hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl and di Linear alkyl groups such as decadecyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The carbon number of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

由R41 ~R46 、R55 、R56 和R58 ~R60 表示的環狀的飽和烴基可以為單環，也可為多環。作為該環狀的飽和烴基，可列舉出環丙基、環丁基、環戊基、環己基和金剛烷基等。該環狀的飽和烴基的碳數優選為3~10，更優選為6~10。The cyclic saturated hydrocarbon group represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3 to 10, and more preferably 6 to 10.

R41 ~R46 、R55 、R56 和R58 ~R60 的飽和烴基可以被鹵素原子或者取代或未取代的氨基取代。作為取代或未取代的氨基，例如可列舉出氨基；二甲基氨基和二乙基氨基等烷基氨基。作為鹵素原子，可列舉出氟、氯、溴和碘等。鹵素原子為氟原子的情況下，優選如形成三氟甲基單元、五氟乙基單元和七氟丙基單元等全氟烷基單元那樣鹵素原子取代。 作為這樣的用取代氨基或鹵素原子取代了的碳數1~20的飽和烴基，例如可列舉出由下述式表示的基團。下述式中，＊表示與氮原子的鍵合端。The saturated hydrocarbon groups of R 41 to R 46 , R 55 , R 56 and R 58 to R 60 may be substituted with a halogen atom or a substituted or unsubstituted amino group. Examples of the substituted or unsubstituted amino group include an amino group; and an alkylamino group such as a dimethylamino group and a diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted such as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit. Examples of such a saturated hydrocarbon group having 1 to 20 carbon atoms substituted with a substituted amino group or a halogen atom include a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

[化10]

Figure TW201800849AD00010
[Chemical 10]
Figure TW201800849AD00010

作為由R47 ~R54 表示的碳數1~8的烷基，可列舉出作為由R41 表示的飽和烴基例示的直鏈或分支鏈的飽和烴基中碳數1~8的基團。 另外，作為由R57 表示的碳數1~10的烷基，可列舉出作為由R41 表示的飽和烴基例示的直鏈或分支鏈的飽和烴基中碳數1~10的基團。Examples of the alkyl group having 1 to 8 carbon atoms represented by R 47 to R 54 include a carbon group having 1 to 8 carbon atoms in the straight or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R 41 . Examples of the alkyl group having 1 to 10 carbon atoms represented by R 57 include a group having 1 to 10 carbon atoms in a straight or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R 41 .

就由R41 ~R54 表示的烷基而言，該烷基中所含的亞甲基可以被氧原子替換。烷基的優選的碳數為2~10，更優選為2~8。另外***了氧原子時，末端與氧原子之間、或氧原子與氧原子之間的碳數例如為1~5，優選為2~3，更優選為2。不過，鄰接的亞甲基不會同時被替換為氧原子，另外，烷基的末端的亞甲基也不會被替換為氧原子。在優選的具體例中，可列舉出由下述式表示的基團。下述式中，＊表示與氮原子的鍵合端。In the alkyl group represented by R 41 to R 54 , the methylene group contained in the alkyl group may be replaced by an oxygen atom. The preferable carbon number of the alkyl group is 2 to 10, and more preferably 2 to 8. When an oxygen atom is inserted, the number of carbons between the terminal and the oxygen atom, or between the oxygen atom and the oxygen atom is, for example, 1 to 5, preferably 2 to 3, and more preferably 2. However, the adjacent methylene group will not be replaced with an oxygen atom at the same time, and the terminal methylene group of the alkyl group will not be replaced with an oxygen atom. Preferable specific examples include a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

[化11]

Figure TW201800849AD00011
[Chemical 11]
Figure TW201800849AD00011

在這樣的烷基中所含的亞甲基被氧原子替換了的基團中，例如包含烷氧基烷基；或者(烷氧基烷氧基)烷基、(烷氧基烷氧基烷氧基)烷基、(烷氧基烷氧基烷氧基烷氧基)烷基、(烷氧基烷氧基烷氧基烷氧基烷氧基)烷基、(烷氧基烷氧基烷氧基烷氧基烷氧基烷氧基)烷基等聚烷氧基烷基等，烷氧基單元的重複數例如為1~6，優選為1~4，更優選為1~2。The group in which the methylene group contained in such an alkyl group is replaced with an oxygen atom includes, for example, an alkoxyalkyl group; or (alkoxyalkoxy) alkyl, (alkoxyalkoxyalkane) (Oxy) alkyl, (alkoxyalkoxyalkoxyalkoxy) alkyl, (alkoxyalkoxyalkoxyalkoxyalkoxy) alkyl, (alkoxyalkoxy Polyalkoxyalkyl groups such as alkoxyalkoxyalkoxyalkoxy) alkyl groups and the like have repeating numbers of alkoxy units of, for example, 1 to 6, preferably 1 to 4, and more preferably 1 to 2.

另外，由R41 ~R46 、R55 、R56 和R58 ~R60 表示的可具有取代基的碳數6~20的芳香族烴基的碳數優選為6~15，更優選為碳數6~12。作為該芳香族烴基，可列舉出苯基、甲苯基、二甲苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等，優選地可列舉出苯基、萘基、甲苯基和二甲苯基，更優選地，可列舉出苯基。另外，該芳香族烴基可具有1或2個以上的取代基，作為該取代基，可列舉出氟原子、氯原子、碘原子和溴原子等鹵素原子；氯甲基和三氟甲基等碳數1~6的鹵代烷基；甲氧基和乙氧基等碳數1~6的烷氧基；羥基；氨磺醯基；甲基磺醯基等碳數1~6的烷基磺醯基；甲氧基羰基和乙氧基羰基等碳數1~6的烷氧基羰基等。作為可被取代的芳香族烴基的具體例，例如可列舉出由下述式表示的基團。下述式中，＊表示與氮原子的鍵合端。In addition, the carbon number of the aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 is preferably 6 to 15, and more preferably the carbon number. 6 ~ 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, and a phenyl group, a naphthyl group, and a tolyl group are preferable. And xylyl, more preferably, phenyl is mentioned. The aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; and carbons such as a chloromethyl group and a trifluoromethyl group. 1 to 6 haloalkyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; sulfamoyl groups; methylsulfonyl groups having 1 to 6 carbon alkyl groups ; 1 to 6 carbon alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups. Specific examples of the aromatic hydrocarbon group which may be substituted include a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

[化12]

Figure TW201800849AD00012
[Chemical 12]
Figure TW201800849AD00012

作為由R41 ~R46 、R59 表示的可具有取代基的芳烷基，可列舉出亞甲基、亞乙基、亞丙基等碳數1~5的亞烷基與作為上述芳香族烴基說明的基團結合而成的基團等。Examples of the aralkyl group which may have a substituent represented by R 41 to R 46 and R 59 include an alkylene group having 1 to 5 carbon atoms such as methylene, ethylene, and propylene, and the aromatic group. A group in which a group described by a hydrocarbon group is combined.

作為R41 和R42 結合且與它們結合的氮原子一起形成的環、R43 和R44 結合且與它們結合的氮原子一起形成的環、以及R45 和R46 結合且與它們結合的氮原子一起形成的環，可列舉出吡咯烷環、嗎啉環、呱啶環、呱嗪環等含氮非芳香族4~7元環，優選地可列舉出吡咯烷環、呱啶環等只具有1個氮原子作為雜原子的4~7元環。As a ring in which R 41 and R 42 are bonded and formed with a nitrogen atom to which they are bonded, a ring in which R 43 and R 44 are bonded and formed with a nitrogen atom to which they are bonded, and a nitrogen which is bonded to and bonded to R 45 and R 46 Examples of the ring formed by the atoms include a nitrogen-containing non-aromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholine ring, a pyridine ring, and a pyrazine ring, and preferably a pyrrolidine ring, a pyridine ring, and the like A 4- to 7-membered ring having one nitrogen atom as a heteroatom.

其中，作為R41 ~R44 、R55 、R56 、R58 和R59 ，優選碳數1~20的飽和烴基或可具有取代基的芳香族烴基，更優選相互獨立地為碳數1~8的飽和烴基或由下述式表示的芳香族烴基。R55 進一步優選為由下述式表示的芳香族烴基。下述式中，＊表示與氮原子的鍵合端。Among them, as R 41 to R 44 , R 55 , R 56 , R 58, and R 59 , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable, and 1 to 3 carbon atoms are more preferably independent of each other. A saturated hydrocarbon group of 8 or an aromatic hydrocarbon group represented by the following formula. R 55 is more preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

[化13]

Figure TW201800849AD00013
[Chemical 13]
Figure TW201800849AD00013

R45 ~R46 優選相互獨立地為碳數1~20的飽和烴基、在碳數2~20的烷基的碳原子間***了氧原子的基團、或可具有取代基的芳香族烴基，或者R45 與R46 結合並與它們結合的氮原子一起形成環。更優選的方案是下述方案：R45 ~R46 相互獨立地為碳數1~8的飽和烴基、烷氧基烷基、或由下述式表示的芳香族烴基，或者R45 與R46 結合而形成只具有1個氮原子作為雜原子的4~7元環。下述式中，＊表示與氮原子的鍵合端。R 45 to R 46 are preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a group having an oxygen atom inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent, Or R 45 is bonded to R 46 and forms a ring with the nitrogen atom to which they are bonded. A more preferred embodiment is one in which R 45 to R 46 are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula, or R 45 and R 46 Combine to form a 4- to 7-membered ring with only one nitrogen atom as a heteroatom. In the following formula, * represents a bonding end with a nitrogen atom.

[化14]

Figure TW201800849AD00014
[Chemical 14]
Figure TW201800849AD00014

另外，作為由R47 ~R54 表示的碳數1~8的烷基和在碳數2~8的烷基的碳原子間***了氧原子的基團，可列舉出從與上述R41 ~R46 對應的基團中選擇了碳數8以下的基團的基團，更優選地，可列舉出由下述式表示的基團。下述式中，＊表示與碳原子的鍵合端。In addition, examples of the group having an alkyl group having 1 to 8 carbon atoms represented by R 47 to R 54 and an oxygen atom inserted between the carbon atoms of the alkyl group having 2 to 8 carbon atoms include R 41 to R 41 to R 54 . Among the groups corresponding to R 46, a group having a carbon number of 8 or less is selected, and more preferably, a group represented by the following formula is used. In the following formula, * represents a bonding end with a carbon atom.

[化15]

Figure TW201800849AD00015
[Chemical 15]
Figure TW201800849AD00015

從合成的容易程度方面出發，R47 ~R54 優選相互獨立地為氫原子、鹵素原子或碳數1~8的烷基，更優選相互獨立地為氫原子、甲基、氟原子或氯原子。From the viewpoint of ease of synthesis, R 47 to R 54 are preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom. .

作為式(Ab2)的陽離子部分，可列舉出如下述表1中所示那樣由式(Ab2-1)表示的陽離子1~陽離子14等。表中，＊表示鍵合端。Examples of the cation part of the formula (Ab2) include cations 1 to 14 and the like represented by the formula (Ab2-1) as shown in Table 1 below. In the table, * indicates a bonding end.

[化16]

Figure TW201800849AD00016
[Chemical 16]
Figure TW201800849AD00016

[表1]

Figure TW201800849AD00017
[Table 1]
Figure TW201800849AD00017

表1中，Ph1~Ph9表示由下述式表示的基團。式中，＊表示鍵合端。In Table 1, Ph1 to Ph9 represent groups represented by the following formulas. In the formula, * represents a bonding end.

[化17]

Figure TW201800849AD00018
[Chemical 17]
Figure TW201800849AD00018

另外，作為式(Ab2)的陽離子部分，也可列舉出如下述表2中所示那樣由式(Ab2-2)表示的陽離子15~陽離子18等。表中，＊表示鍵合端。Examples of the cation moiety of the formula (Ab2) include cation 15 to cation 18 represented by the formula (Ab2-2) as shown in Table 2 below. In the table, * indicates a bonding end.

[化18]

Figure TW201800849AD00019
[Chemical 18]
Figure TW201800849AD00019

[表2]

Figure TW201800849AD00020
[Table 2]
Figure TW201800849AD00020

表2中，Ph1、Ph10、Ph11表示由下述式表示的基團。式中，＊表示鍵合端。In Table 2, Ph1, Ph10, and Ph11 represent groups represented by the following formula. In the formula, * represents a bonding end.

[化19]

Figure TW201800849AD00021
[Chemical 19]
Figure TW201800849AD00021

其中，作為式(Ab2)的陽離子部分，優選陽離子1~陽離子6、陽離子11~陽離子14，更優選陽離子1、陽離子2、或陽離子12~陽離子14，進一步優選陽離子12。Among them, as the cation part of the formula (Ab2), cation 1 to cation 6 and cation 11 to cation 14 are preferred, cation 1, cation 2, or cation 12 to cation 14 is more preferred, and cation 12 is more preferred.

作為化合物(Aa)，可列舉出由下述式表示的化合物。Examples of the compound (Aa) include compounds represented by the following formula.

[表3]

Figure TW201800849AD00022
[table 3]
Figure TW201800849AD00022

[表4]

Figure TW201800849AD00023
[Table 4]
Figure TW201800849AD00023

其中，化合物優選為由式(Aa2-53)表示的化合物。Among these, the compound is preferably a compound represented by the formula (Aa2-53).

由式(A-I)表示的化合物能夠按照日本特開2015-28121號公報中記載的方法製造。The compound represented by the formula (A-I) can be produced by a method described in Japanese Patent Application Laid-Open No. 2015-28121.

染料(Ab) 作為染料，例如可列舉出在色指數(The Society of Dyers and Colourists出版)中歸類在顏料以外的具有色調的物質的化合物、染色筆記(色染社)中記載的公知的染料。Dyes (Ab) Examples of the dye include a compound classified in the color index (published by The Society of Dyers and Colourists) as a substance having a color tone other than pigments, and a well-known dye described in Dyeing Notes (Dyeing Society) .

作為染料，例如可列舉出偶氮染料(例如單偶氮染料、重氮染料、疊氮染料、金屬絡鹽偶氮染料等)、蒽醌染料、靛藍系染料、酞菁染料、吡唑啉酮染料、均二苯乙烯染料、類胡蘿蔔素染料、噻唑染料、喹啉染料、二芳基甲烷染料、三芳基甲烷染料、吖啶染料、呫噸染料、吖嗪染料、噻嗪染料、噁嗪染料、菁染料、吲達胺染料、靛酚染料、萘二甲醯亞胺染料、苝染料、萘醌染料、醌亞胺染料、次甲基染料、亞甲胺染料、方酸染料、苯乙烯基染料、香豆素染料、喹啉染料、四氮雜卟啉染料、硝基染料、或亞硝基染料等，這些優選為有機溶劑可溶性。這些染料可以單獨使用或者將2種以上組合使用。Examples of the dye include azo dyes (for example, monoazo dyes, diazo dyes, azido dyes, metal complex salt azo dyes, etc.), anthraquinone dyes, indigo dyes, phthalocyanine dyes, and pyrazolinones. Dyes, homostilbene dyes, carotenoid dyes, thiazole dyes, quinoline dyes, diarylmethane dyes, triarylmethane dyes, acridine dyes, xanthene dyes, azine dyes, thiazine dyes, oxazine dye , Cyanine dye, indamine dye, indophenol dye, naphthalene dimethyl imine dye, fluorene dye, naphthoquinone dye, quinone imine dye, methine dye, methyleneamine dye, cubic acid dye, styryl Dyes, coumarin dyes, quinoline dyes, tetraazaporphyrin dyes, nitro dyes, or nitroso dyes, etc., these are preferably organic solvent soluble. These dyes can be used alone or in combination of two or more.

其中，優選呫噸染料、三芳基甲烷染料、香豆素染料、蒽醌染料、四氮雜卟啉染料、偶氮染料、噻嗪染料、噁嗪染料、酞菁染料、喹酞酮染料、菁染料、萘醌染料、醌亞胺染料、次甲基染料、亞甲胺染料、方酸染料、吖啶染料、苯乙烯基染料、喹啉染料和硝基染料，更優選呫噸染料、三芳基甲烷染料、香豆素染料、蒽醌染料、偶氮染料和四氮雜卟啉染料，特別優選呫噸染料、偶氮染料。 這些中，優選C.I.酸性紅289的磺醯胺化物、C.I.酸性紅289的季銨鹽、C.I.酸性紫102的磺醯胺化物或C.I.酸性紫102的季銨鹽。Of these, xanthene dye, triarylmethane dye, coumarin dye, anthraquinone dye, tetraazaporphyrin dye, azo dye, thiazine dye, oxazine dye, phthalocyanine dye, quinophthalone dye, and cyanine are preferred. Dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, methyleneamine dyes, squaric acid dyes, acridine dyes, styryl dyes, quinoline dyes, and nitro dyes, more preferably xanthene dyes, triaryls Methane dyes, coumarin dyes, anthraquinone dyes, azo dyes and tetraazaporphyrin dyes, xanthene dyes and azo dyes are particularly preferred. Among these, C.I. acid red 289 sulfonamidate, C.I. acid red 289 quaternary ammonium salt, C.I. acid violet 102 sulfonamide and C.I. acid violet 102 quaternary ammonium salt are preferred.

作為呫噸染料，除了上述例示的化合物以外，例如也可列舉出C.I.酸性紅51(以下省略表述“C.I.酸性紅”，只記載序號，其他也同樣)、52、87、92、94、388，C.I.酸性紫9、30，C.I.鹼性紅1(若丹明6G)、2、3、4、8，C.I.鹼性紅10(若丹明B)、11，C.I.鹼性紫10、11、25，C.I.溶劑紅218，C.I.媒染紅27，C.I.活性紅36(玫瑰紅B)，磺基若丹明G，日本特開2010-32999號公報中記載的呫噸染料和專利第4492760號公報中記載的呫噸染料等。As the xanthene dye, in addition to the compounds exemplified above, for example, CI Acid Red 51 (hereinafter, the expression "CI Acid Red" is omitted and only the serial number is described, the same is true), 52, 87, 92, 94, and 388. CI acid violet 9, 30, CI basic red 1 (rhodamine 6G), 2, 3, 4, 8, CI basic red 10 (rhodamine B), 11, CI basic violet 10, 11, 25 , CI solvent red 218, CI mordant red 27, CI reactive red 36 (rose red B), sulforhodamine G, xanthene dye described in Japanese Patent Application Laid-Open No. 2010-32999 and patent No. 4492760 Xanthene dyes and so on.

呫噸染料更優選為由以下的式(a1-1)表示的化合物(以下也稱為化合物(a1-1))。化合物(a1-1)可以為其互變異構體。The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as a compound (a1-1)). The compound (a1-1) may be a tautomer thereof.

[化20]

Figure TW201800849AD00024
[式(a1-1)中，R1 ~R4 相互獨立地表示氫原子、可具有取代基的碳數1~20的1價的飽和烴基、或者可具有取代基的碳數6~10的1價的芳香族烴基，該飽和烴基中所含的亞甲基(-CH2 -)可被-O-、-CO-或-NR11 -替換。R1 和R2 可一起形成包含氮原子的環，R3 和R4 可一起形成包含氮原子的環。 R1 ~R4 中，鄰接的亞甲基不會同時被替換為氧原子，另外，烷基的末端的亞甲基也不會被替換為氧原子。 R5 表示-OH、-SO3 - 、-SO3 H、-SO3 - Z+ 、-CO2 H、-CO2 - Z+ 、-CO2 R8 、-SO3 R8 或-SO2 NR9 R10 。 R6 和R7 相互獨立地表示氫原子或碳數1~6的烷基。 m表示0~5的整數。m為2以上時，多個R5 可以相同，也可不同。 a表示0或1的整數。 X表示鹵素原子。 Z+ 表示+ N(R11 )4 、Na+ 或K+ ，4個R11 可以相同，也可不同。 R8 表示碳數1~20的1價的飽和烴基，該飽和烴基中所含的氫原子可以被鹵素原子取代。 R9 和R10 相互獨立地表示氫原子或可具有取代基的碳數1~20的1價的飽和烴基，該飽和烴基中所含的-CH2 -可被-O-、-CO-、-NH-或-NR8 -替換，R9 和R10 可相互結合而形成含有氮原子的3~10元環的雜環。 R11 表示氫原子、碳數1~20的1價的飽和烴基或碳數7~10的芳烷基。][Chemical 20]
Figure TW201800849AD00024
[In the formula (a1-1), R 1 to R 4 independently of each other represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. A monovalent aromatic hydrocarbon group, and the methylene group (-CH 2- ) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -NR 11- . R 1 and R 2 may form a ring containing a nitrogen atom together, and R 3 and R 4 may form a ring containing a nitrogen atom together. In R 1 to R 4 , the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group of the alkyl group is not replaced with an oxygen atom. R 5 represents -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO 2 NR 9 R 10 . R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer from 0 to 5. When m is 2 or more, a plurality of R 5 may be the same or different. a represents an integer of 0 or 1. X represents a halogen atom. Z + represents + N (R 11 ) 4 , Na + or K + . The four R 11 may be the same or different. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH 2 -contained in the saturated hydrocarbon group may be -O-, -CO-, -NH- or -NR 8 -is substituted, and R 9 and R 10 may be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

另外，作為呫噸染料，也優選由式(a1-2)表示的化合物(以下有時稱為“化合物(a1-2)”)。化合物(a1-2)可以為其互變異構體。Moreover, as a xanthene dye, the compound represented by Formula (a1-2) (henceforth a "compound (a1-2)") is also preferable. Compound (a1-2) may be its tautomer.

[化21]

Figure TW201800849AD00025
[式(a1-2)中，R21 和R22 相互獨立地表示碳數1~10的1價的飽和烴基，該R21 、R22 的飽和烴基中所含的氫原子可以被碳數6~10的芳香族烴基或鹵素原子取代，該芳香族烴基中所含的氫原子可以被碳數1~3的烷氧基取代，上述R21 、R22 的飽和烴基中所含的-CH2 -可以被-O-、-CO-或-NR11 -替換。 R23 和R24 相互獨立地表示碳數1~4的烷基、碳數1~4的烷基硫烷基或碳數1~4的烷基磺醯基。 R21 和R23 可一起形成含有氮原子的環，R22 和R24 可一起形成含有氮原子的環。 p和q相互獨立地表示0~5的整數。p為2以上時，多個R23 可以相同，也可不同，q為2以上時，多個R24 可以相同，也可不同。R11 表示與上述相同的含義。][Chemical 21]
Figure TW201800849AD00025
[In the formula (a1-2), R 21 and R 22 independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group of R 21 and R 22 may be 6 carbon atoms. ~ 10 Aromatic hydrocarbon groups or halogen atoms are substituted. The hydrogen atoms contained in the aromatic hydrocarbon groups may be substituted by alkoxy groups having 1 to 3 carbon atoms. -CH 2 contained in the saturated hydrocarbon groups of R 21 and R 22 described above. -Can be replaced by -O-, -CO- or -NR 11- . R 23 and R 24 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. R 21 and R 23 may form a ring containing a nitrogen atom together, and R 22 and R 24 may form a ring containing a nitrogen atom together. p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R 23 may be the same or different, and when q is 2 or more, a plurality of R 24 may be the same or different. R 11 has the same meaning as described above. ]

作為R21 和R22 中的碳數1~10的1價的飽和烴基，可列舉出R8 中的基團中碳數1~10的基團。 作為可作為取代基具有的碳數6~10的芳香族烴基，可列舉出與R1 中的基團相同的基團。 作為碳數1~3的烷氧基，例如可列舉出甲氧基、乙氧基、丙氧基等。 R21 和R22 優選相互獨立地為碳數1~3的1價的飽和烴基。Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 21 and R 22 include a group having 1 to 10 carbon atoms in the group in R 8 . Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that can be used as a substituent include the same groups as those in R 1 . Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. R 21 and R 22 are each preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

作為R23 和R24 中的碳數1~4的烷基，可列舉出甲基、乙基、丙基、丁基、異丙基、異丁基、仲丁基、叔丁基等。 作為R23 和R24 中的碳數1~4的烷基硫烷基，可列舉出甲基硫烷基、乙基硫烷基、丙基硫烷基、丁基硫烷基和異丙基硫烷基等。 作為R23 和R24 中的碳數1~4的烷基磺醯基，可列舉出甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基和異丙基磺醯基等。 作為R23 和R24 ，優選碳數1~4的烷基，更優選甲基、乙基，進一步優選甲基。Examples of the alkyl group having 1 to 4 carbon atoms in R 23 and R 24 include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 23 and R 24 include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, and isopropyl group. Sulfanyl and the like. Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 23 and R 24 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropyl Sulfonyl and others. R 23 and R 24 are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and still more preferably a methyl group.

作為p和q，優選0~2的整數，優選1或2。As p and q, integers of 0 to 2 are preferred, and 1 or 2 is preferred.

三芳基甲烷染料優選為包含具有3個芳香族烴基結合於一個碳原子的結構的化合物的染料。作為三芳基甲烷染料，例如可列舉出C.I.溶劑藍2、4、5、43、124；C.I.鹼性紫3、14、25；C.I.鹼性藍1、5、7、11、26和日本專利第4492760號公報中記載的三芳基甲烷染料等。The triarylmethane dye is preferably a dye containing a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. Examples of the triarylmethane dye include CI solvent blue 2, 4, 5, 43, 124; CI basic violet 3, 14, 25; CI basic blue 1, 5, 7, 11, 26, and Japanese Patent No. Triarylmethane dyes and the like described in Japanese Patent No. 4492760.

香豆素染料為包含在分子內具有香豆素骨架的化合物的染料。作為香豆素染料，可列舉出例如C.I.酸性黃227、250；C.I.分散黃82、184；C.I.溶劑橙112；C.I.溶劑黃160、172；日本專利第1299948號公報中記載的香豆素染料等。Coumarin dye is a dye containing a compound having a coumarin skeleton in its molecule. Examples of the coumarin dye include CI acid yellow 227, 250; CI disperse yellow 82, 184; CI solvent orange 112; CI solvent yellow 160, 172; coumarin dyes described in Japanese Patent No. 1299948, and the like .

作為蒽醌染料，可列舉出C.I.溶劑黃117(以下省略表述“C.I.溶劑黃”，只記載序號)、163、167、189、 C.I.溶劑橙77、86、 C.I.溶劑紅111、143、145、146、150、151、155、168、169、172、175、181、207、222、227、230、245、247、 C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60、 C.I.溶劑藍14、18、35、36、45、58、59、59：1、63、68、69、78、79、83、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139、 C.I.溶劑綠3、28、29、32、33、 C.I.酸性紅80、 C.I.酸性綠25、27、28、41、 C.I.酸性紫34、 C.I.酸性藍25、27、40、45、78、80、112、 C.I.分散黃51、 C.I.分散紫26、27、 C.I.分散藍1、14、56、60、 C.I.直接藍40、 C.I.媒染紅3、11、 C.I.媒染藍8等。Examples of the anthraquinone dye include CI Solvent Yellow 117 (hereinafter, the “CI Solvent Yellow” is omitted, and only the serial number is described), 163, 167, 189, CI Solvent Orange 77, 86, CI Solvent Red 111, 143, 145, 146 , 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100 , 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI Solvent Green 3, 28, 29, 32, 33, CI Acid Red 80, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112, CI Disperse Yellow 51, CI Disperse Violet 26, 27, CI Disperse Blue 1, 14, 56, 60, CI Direct Blue 40. CI Mordant Red 3, 11, CI Mordant Blue 8, etc.

四氮雜卟啉染料為在分子內具有四氮雜卟啉骨架的化合物。另外，四氮雜卟啉染料為酸性染料或鹼性染料的情況下，可以與任意的陽離子或陰離子形成鹽。A tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in a molecule. When the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

作為其他的染料，可使用偶氮染料、噻唑染料、噁嗪染料、酞菁染料、喹酞酮染料等，各自使用公知的染料。 作為偶氮染料，例如可列舉出C.I.直接黃(以下省略表述“C.I.直接黃”，只記載序號)2、33、34、35、39、50、69、70、71、86、93、94、95、98、102、109、129、136、141； C.I.直接橙41、46、56、61、64、70、96、97、106、107； C.I.直接紅79、82、83、84、97、98、99、106、107、172、173、176、177、179、181、182、204、207、211、213、218、221、222、232、233、243、246、250； C.I.直接紫47、52、54、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104； C.I.直接藍51、57、71、81、84、85、90、93、94、95、98、100、101、113、149、150、153、160、162、163、164、166、167、170、172、188、192、193、194、196、198、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275； C.I.直接綠27、34、37、65、67、68、69、72、77、79、82； C.I.酸性紅1、3、4、6、8、11、12、14、18、26、27、33、37、53、57、88、106、108、111、114、131、137、138、151、154、158、159、173、184、186、215、257、266、296、337； C.I.酸性橙7、10、12、19、20、22、28、30、52、56、74、127； C.I.酸性紫11、56、58； C.I.酸性黃1、17、18、23、25、36、38、42、44、54、59、72、78、151； C.I.酸性棕2、4、13、248； C.I.酸性藍92、102、113、117； C.I.鹼性紅17、22、23、25、29、30、38、39、46、46：1、82； C.I.鹼性橙2、24、25； C.I.鹼性紫18； C.I.鹼性黃15、24、25、32、36、41、73、80； C.I.鹼性棕1； C.I.鹼性藍41、54、64、66、67、129等。As another dye, an azo dye, a thiazole dye, an oxazine dye, a phthalocyanine dye, a quinophthalone dye, etc. can be used, and a well-known dye is used for each. Examples of the azo dye include CI Direct Yellow (hereinafter, the “CI Direct Yellow” is omitted and only the serial number is described) 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95, 98, 102, 109, 129, 136, 141; CI Direct Orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107; CI Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221, 222, 232, 233, 243, 246, 250; CI Direct Purple 47 , 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275; CI Direct Green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82; CI Acid Red 1, 3 , 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159 , 173, 184, 186, 215, 257, 266, 296, 337; CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; CI Acid Violet 11, 56 , 58; CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; CI Acid Brown 2, 4, 13, 248; CI Acid Blue 92, 102, 113, 117; CI Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82; CI Basic Orange 2, 24, 25; CI Basic Violet 18; CI Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; CI Basic Brown 1; CI Basic Blue 41, 54, 64, 66, 67, 129, etc.

作為金屬絡鹽偶氮染料，可列舉出C.I.溶劑紅125、130；C.I.溶劑黃21、和日本特開2010-170116號公報或日本特開2011-215572號公報記載的化合物等。Examples of the metal complex salt azo dye include compounds described in C.I. Solvent Red 125 and 130; C.I. Solvent Yellow 21; and Japanese Patent Application Laid-Open No. 2010-170116 or Japanese Patent Application Laid-Open No. 2011-215572.

作為噻唑染料，可列舉出C.I.直接黃54、C.I.鹼性黃1等。 作為噁嗪染料，可列舉出C.I.直接藍97、99、106、107、108、109、190、293等。 作為酞菁染料，可列舉出C.I.直接藍86、87、189、199，C.I.酸性藍249，C.I.鹼性藍3等。 作為喹酞酮染料，可列舉出C.I.酸性黃3、C.I. 分散黃143等。 作為菁染料，可列舉出銅酞菁(C.I.74160)等。 作為醌亞胺染料，可列舉出C.I.鹼性藍3、C.I.鹼性藍9等。 作為次甲基染料，可列舉出C.I.鹼性紅13、14；C.I.鹼性橙21；C.I.鹼性紫16、39；C.I.鹼性黃11、13、21、23、28等。 作為喹啉染料，可列舉出C.I.溶劑黃33、C.I.酸性黃3、C.I.分散黃64等。 作為硝基染料，可列舉出C.I.酸性黃1、C.I.酸性橙3、C.I.分散黃42等。 作為吖嗪染料，可列舉出C.I. 酸性藍59、102等。 作為靛藍染料，可列舉出C.I. 酸性藍74等。Examples of the thiazole dye include C.I. direct yellow 54 and C.I. basic yellow 1. Examples of the oxazine dye include C.I. Direct Blue 97, 99, 106, 107, 108, 109, 190, 293, and the like. Examples of the phthalocyanine dye include C.I. Direct Blue 86, 87, 189, 199, C.I. Acid Blue 249, C.I. Basic Blue 3, and the like. Examples of the quinophthalone dye include C.I. Acid Yellow 3, C.I. Disperse Yellow 143, and the like. Examples of the cyanine dye include copper phthalocyanine (C.I. 74160). Examples of the quinone imine dye include C.I. Basic Blue 3, C.I. Basic Blue 9 and the like. Examples of methine dyes include C.I. Basic Red 13, 14; C.I. Basic Orange 21; C.I. Basic Violet 16, 39; C.I. Basic Yellow 11, 13, 21, 23, 28, and the like. Examples of the quinoline dye include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, and the like. Examples of the nitro dye include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42. Examples of the azine dye include C.I. Acid Blue 59, 102, and the like. Examples of the indigo dye include C.I. Acid Blue 74 and the like.

著色分散液 製造本發明的著色固化性樹脂組合物時，就化合物(Aa)而言，優選使其在溶劑中溶解或分散、混合而製備著色分散液。通過將著色分散液、和黏結劑樹脂(B)、聚合性化合物(C)、聚合引發劑(D)等混合而製備著色固化性樹脂組合物，從而能夠進一步提高由該著色固化性樹脂組合物形成的濾色器的耐熱性。Colored dispersion liquid When the colored curable resin composition of the present invention is produced, the compound (Aa) is preferably dissolved or dispersed in a solvent and mixed to prepare a colored dispersion liquid. By mixing a colored dispersion liquid with a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and the like to prepare a colored curable resin composition, the colored curable resin composition can be further improved. The heat resistance of the formed color filter.

作為溶劑，只要是可以作為著色固化性樹脂組合物的溶劑(E)使用的溶劑，則可以使用任何溶劑。溶劑為例如醚酯溶劑，更優選地，可列舉出將亞烷基二醇或聚亞烷基二醇的一個羥基醚化、將剩餘的羥基酯化而成的溶劑，例如丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二甘醇單乙基醚乙酸酯、二甘醇單丁基醚乙酸酯、二丙二醇甲基醚乙酸酯等。這些可單獨使用或者包含多種。 著色分散液中，相對於化合物(Aa)1質量份，溶劑的含量例如為1~50質量份，優選為2~30質量份，更優選為3~10質量份。As the solvent, any solvent can be used as long as it is a solvent that can be used as the solvent (E) of the colored curable resin composition. The solvent is, for example, an ether ester solvent, and more preferably, a solvent obtained by etherifying one hydroxyl group of an alkylene glycol or polyalkylene glycol and esterifying the remaining hydroxyl group, such as propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like. These may be used alone or in combination. The content of the solvent in the colored dispersion liquid is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass, based on 1 part by mass of the compound (Aa).

使化合物(Aa)分散於溶劑、製備著色分散液時，優選使用分散劑。作為分散劑，能夠使用陽離子系、陰離子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等的公知的顏料分散劑。這些顏料分散劑可以單獨使用，也可以將2種以上組合使用。作為顏料分散劑，以商品名表示，可列舉出KP(信越化學工業(股)製造)、フローレン(共榮社化學(股)製造)、ソルスパース(ゼネカ(股)製造)、EFKA(BASF公司製造)、アジスパー(味之素ファインテクノ(股)製造)、Disperbyk(ビックケミー公司製造)等。When the compound (Aa) is dispersed in a solvent and a colored dispersion liquid is prepared, a dispersant is preferably used. As the dispersant, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Froeren (manufactured by Kyoeisha Chemical Co., Ltd.), ソ ル ス パ ー ス (manufactured by Seika Corporation), and EFKA (manufactured by BASF) ), Ajax (manufactured by Ajinomoto Funkin Co., Ltd.), Disperbyk (manufactured by Teknik Co., Ltd.), and the like.

該著色分散液中，分散劑的含量，相對於化合物(Aa)100質量份，例如為1~1000質量份，優選為3~100質量份，更優選為5~50質量份，特別優選為10~30質量份。The content of the dispersant in the colored dispersion liquid is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 100 parts by mass of the compound (Aa). ~ 30 parts by mass.

著色分散液可預先包含染料(Ab)的一部分或全部，優選地包含全部。相對於化合物(Aa)100質量份，著色分散液中的染料(Ab)的量例如為0.1~20質量份，優選為0.5~10質量份，更優選為1~5質量份。The colored dispersion liquid may contain a part or all of the dye (Ab) in advance, and preferably contains all. The amount of the dye (Ab) in the colored dispersion liquid is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the compound (Aa).

使化合物(Aa)在溶劑中分散而製備著色分散液的情況下，著色分散液可預先包含著色固化性樹脂組合物中含有的黏結劑樹脂(B)的一部分或全部，優選地包含一部分。通過預先含有黏結劑樹脂(B)，能夠進一步改善製成著色固化性樹脂組合物時的分散穩定性。著色分散液中的黏結劑樹脂(B)的含量，相對於化合物(Aa)100質量份，例如為1~300質量份，優選為10~100質量份，更優選為20~70質量份。When the colored dispersion liquid is prepared by dispersing the compound (Aa) in a solvent, the colored dispersion liquid may previously contain a part or all of the binder resin (B) contained in the colored curable resin composition, and preferably a part thereof. By containing the binder resin (B) in advance, it is possible to further improve the dispersion stability when the colored curable resin composition is prepared. The content of the binder resin (B) in the colored dispersion liquid is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass based on 100 parts by mass of the compound (Aa).

著色劑(A)除了化合物(Aa)和染料(Ab)以外，可進一步包含顏料(Ac)。作為顏料，例如可列舉出色指數(The Society of Dyers and Colourists出版)中分類為顏料的顏料(不過，與化合物(Aa)不同)，可以例示如下顏料。The colorant (A) may further contain a pigment (Ac) in addition to the compound (Aa) and the dye (Ab). Examples of the pigment include pigments classified as pigments in the Outstanding Index (published by The Society of Dyers and Colourists) (however, different from the compound (Aa)), and the following pigments can be exemplified.

綠色顏料：C.I.顏料綠7、36、58等 黃色顏料：C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、129、137、138、139、147、148、150、153、154、166、173、185、194、214等 橙色顏料：C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等 紅色顏料：C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等 青色顏料：C.I.顏料藍15、15：3、15：4、15：6、60等 紫色顏料：C.I.顏料紫1、19、23、29、32、36、38等 就這些顏料而言，對於各色，可使用1種顏料或多種顏料，也可將各色的顏料組合。Green pigment: CI pigment green 7, 36, 58 and other yellow pigments: CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other orange pigments: CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other red pigments: CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other cyan pigments: CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other purple pigments: CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. As for these pigments, one type or a plurality of types of pigments may be used for each color, or the pigments of each color may be combined.

顏料根據需要可實施松香處理、使用了導入了酸性基或者鹼性基的顏料衍生物等的表面處理、採用高分子化合物等的對顏料表面的接枝處理、採用硫酸微粒化法等的微粒化處理、或者用於將雜質除去的採用有機溶劑、水等的清洗處理、採用離子性雜質的離子交換法等的除去處理等。顏料的粒徑優選為大致均一。對於顏料，通過含有顏料分散劑而進行分散處理，從而能夠製成在顏料分散劑溶液中均一地分散的狀態的顏料分散液。對於顏料，可各自單獨地進行分散處理，也可將多種混合而進行分散處理。The pigment can be subjected to rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc., pigment surface grafting treatment using polymer compounds, and micronization using sulfuric acid micronization method. Treatment, or cleaning treatment using an organic solvent, water, or the like for removing impurities, removal treatment using an ion exchange method using ionic impurities, and the like. The particle diameter of the pigment is preferably substantially uniform. The pigment can be prepared as a pigment dispersion in a state where it is uniformly dispersed in the pigment dispersant solution by performing a dispersion treatment by containing a pigment dispersant. Each of the pigments may be subjected to a dispersion treatment individually, or a plurality of pigments may be mixed to perform the dispersion treatment.

作為顏料分散劑，可列舉出表面活性劑等，可以為陽離子系、陰離子系、非離子系、兩性的任一種的表面活性劑。具體地，可列舉出聚酯系、多胺系、丙烯酸系等的表面活性劑等。其中，特別優選丙烯酸系表面活性劑。這些顏料分散劑可單獨使用或者將二種以上組合使用。作為顏料分散劑，用商品名表示，可列舉出KP(信越化學工業(股)製造)、フローレン(共榮社化學(股)製造)、ソルスパース(註冊商標)(ゼネカ(股)製造)、EFKA(註冊商標)(BASF公司製造)、アジスパー(註冊商標)(味之素ファインテクノ(股)製造)、Disperbyk(註冊商標)(ビックケミー公司製造)等。Examples of the pigment dispersant include surfactants, and may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specific examples include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. Among these, an acrylic surfactant is particularly preferable. These pigment dispersants can be used alone or in combination of two or more. As the pigment dispersant, it is represented by a trade name, and examples thereof include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), florence (manufactured by Kyoeisha Chemical Co., Ltd.), ソ ル ス パ ー ス (registered trademark) (manufactured by ゼ ネ カ (股)), EFKA (Registered trademark) (manufactured by BASF Corporation), asia (registered trademark) (manufactured by Ajinomoto Fusion Co., Ltd.), Disperbyk (registered trademark) (manufactured by ビ 克 ケ ミ ー 公司), and the like.

使用顏料分散劑的情況下，相對於顏料100質量份，其使用量優選為200質量份以下，更優選為180質量份以下，進一步優選為160質量份以下，特別優選為0質量份。如果顏料分散劑的使用量在上述的範圍內，使用2種以上的顏料的情況下，具有得到更為均勻的分散狀態的顏料分散液的傾向。When a pigment dispersant is used, the amount used is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, still more preferably 160 parts by mass or less, and particularly preferably 0 parts by mass with respect to 100 parts by mass of the pigment. When the use amount of the pigment dispersant is within the above range, when two or more kinds of pigments are used, there is a tendency that a pigment dispersion liquid in a more uniform dispersed state is obtained.

相對於固體成分的總量，著色固化性樹脂組合物中的著色劑(A)的含有率通常為10質量%以上且70質量%以下，優選為15質量%以上且60質量%以下，更優選為20質量%以上且55質量%以下，特別優選為25質量%以上且50質量%以下。如果上述化合物(Aa)的含有率為上述的範圍內，更容易獲得所期望的分光、色濃度。應當說明，本說明書中“固體成分的總量”是指從本發明的著色固化性樹脂組合物中將溶劑除去後的成分的合計量。固體成分的總量和相對於固體成分總量的各成分的含量例如能夠採用液相色譜、氣相色譜等公知的分析手段測定。 染料(Ab)與化合物(Aa)的質量比(染料(Ab)/化合物(Aa))優選為0.001以上且0.5以下，更優選為0.005以上且0.4以下，進一步優選為0.01以上且0.3以下。 包含顏料(Ac)的情況下，相對於上述著色劑(A)的總量，顏料(Ac)的含有率優選為70質量%以下，更優選為60質量%以下，進一步優選為50質量%以下，特別優選為0質量%。The content of the coloring agent (A) in the colored curable resin composition is usually 10% by mass or more and 70% by mass or less, preferably 15% by mass or more and 60% by mass or less with respect to the total amount of the solid content, and more preferably It is 20% by mass or more and 55% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less. If the content rate of the said compound (Aa) exists in the said range, it becomes easier to obtain a desired spectroscopic and color density. In addition, the "total amount of solid content" in this specification means the total amount of the component which removed the solvent from the coloring curable resin composition of this invention. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured, for example, by a known analysis means such as liquid chromatography or gas chromatography. The mass ratio of the dye (Ab) to the compound (Aa) (dye (Ab) / compound (Aa)) is preferably 0.001 or more and 0.5 or less, more preferably 0.005 or more and 0.4 or less, and still more preferably 0.01 or more and 0.3 or less. When the pigment (Ac) is contained, the content of the pigment (Ac) is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less based on the total amount of the colorant (A). It is particularly preferably 0% by mass.

＜黏結劑樹脂(B)＞ 本發明的著色固化性樹脂組合物中所含的黏結劑樹脂(B)優選為堿可溶性樹脂，更優選具有來自從不飽和羧酸和不飽和羧酸酐中選擇的至少一種的結構單元的加成聚合物。作為這樣的樹脂，可列舉出下述樹脂[K1]~[K6]。 樹脂[K1]：選自不飽和羧酸和不飽和羧酸酐中的至少一種的單體(a)(以下有時稱為“(a)”)和具有碳數2~4的環狀醚結構和烯屬不飽和鍵的單體(b)(以下有時稱為“(b)”)的共聚物 樹脂[K2]：(a)、(b)和可與(a)共聚的單體(c)(不過，與(a)和(b)不同)(以下有時稱為“(c)”)的共聚物 樹脂[K3]：(a)與(c)的共聚物 樹脂[K4]：通過使(b)與(a)和(c)的共聚物反應而得到的樹脂 樹脂[K5]：通過使(a)與(b)和(c)的共聚物反應而得到的樹脂 樹脂[K6]：通過使(a)與(b)和(c)的共聚物反應、進而使羧酸酐反應而得到的樹脂。<Binder resin (B)> The binder resin (B) contained in the colored curable resin composition of the present invention is preferably a fluorene-soluble resin, and more preferably one selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Additive polymer of at least one structural unit. Examples of such resins include the following resins [K1] to [K6]. Resin [K1]: a monomer (a) (hereinafter sometimes referred to as "(a)") selected from at least one of unsaturated carboxylic acid and unsaturated carboxylic anhydride and a cyclic ether structure having 2 to 4 carbon atoms Copolymer resin [K2] with an ethylenically unsaturated monomer (b) (hereinafter sometimes referred to as "(b)"): (a), (b), and a monomer copolymerizable with (a) ( c) (However, different from (a) and (b)) (hereinafter sometimes referred to as "(c)") copolymer resin [K3]: (a) and (c) copolymer resin [K4]: Resin resin obtained by reacting (b) with copolymers of (a) and (c) [K5]: Resin resin obtained by reacting (a) with copolymers of (b) and (c) [K6] ]: A resin obtained by reacting (a) with a copolymer of (b) and (c), and further reacting a carboxylic anhydride.

作為(a)，可列舉出丙烯酸、甲基丙烯酸、巴豆酸以及鄰-、間-、對-乙烯基苯甲酸等不飽和單羧酸； 馬來酸、富馬酸、檸康酸、中康酸、衣康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸和1,4-環己烯二羧酸等不飽和二羧酸； 甲基-5-降冰片烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯和5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基的雙環不飽和化合物； 馬來酸酐、檸康酸酐、衣康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐和5,6-二羧基雙環[2.2.1]庚-2-烯酐等不飽和二羧酸酐等。 此外，可使用琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯和鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上的多元羧酸的不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸等在同一分子中含有羥基和羧基的不飽和丙烯酸酯類等。 這些中，單體(a)優選為不飽和單羧酸，更優選為丙烯酸和甲基丙烯酸。Examples of (a) include acrylic acid, methacrylic acid, crotonic acid, and unsaturated monocarboxylic acids such as o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, and Zhongkang Acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5- Carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene , 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] Bicyclic unsaturated compounds containing carboxyl groups such as hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride , 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxyl Unsaturated dicarboxylic anhydrides such as bicyclo [2.2.1] heptan-2-ene anhydride. In addition, a two- or more-valent polycarboxylic acid such as mono [2- (meth) acryloxyethyl] succinate and mono [2- (meth) acryloxyethyl] phthalate can be used. Unsaturated mono [(meth) acryloxyalkyl] esters of acids; unsaturated acrylic esters such as α- (hydroxymethyl) acrylic acid containing hydroxyl and carboxyl groups in the same molecule. Among these, the monomer (a) is preferably an unsaturated monocarboxylic acid, and more preferably acrylic acid and methacrylic acid.

應當說明，本說明書中，表述“(甲基)丙烯酸”表示選自丙烯酸和甲基丙烯酸中的至少1種。表述“(甲基)丙烯酸酯”等也同樣。It should be noted that in the present specification, the expression "(meth) acrylic acid" means at least one selected from acrylic acid and methacrylic acid. The same applies to the expression "(meth) acrylate" and the like.

(b)是指具有碳數2~4的環狀醚結構(例如，選自環氧乙烷環、氧雜環丁烷環和四氫呋喃環中的至少1種)和烯屬不飽和鍵的聚合性化合物。(b)優選為具有碳數2~4的環狀醚結構和(甲基)丙烯醯氧基的單體。(b) A polymerization of a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Sexual compounds. (b) A monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

作為(b)，可列舉出具有環氧乙基和烯屬不飽和鍵的單體(b1)(以下有時稱為“(b1)”)、具有氧雜環丁基和烯屬不飽和鍵的單體(b2)(以下有時稱為“(b2)”)和具有四氫呋喃基和烯屬不飽和鍵的單體(b3)(以下有時稱為“(b3)”)。Examples of (b) include a monomer (b1) (hereinafter sometimes referred to as "(b1)") having an epoxyethyl group and an ethylenically unsaturated bond, and an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as "(b2)") and monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuryl group and an ethylenically unsaturated bond.

作為(b1)，可列舉出具有直鏈狀或分支鏈狀的脂肪族不飽和烴被環氧化的結構的單體(b1-1)(以下有時稱為“(b1-1)”)和具有脂環式不飽和烴被環氧化的結構的單體(b1-2)(以下有時稱為“(b1-2)”)。Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and A monomer (b1-2) (hereinafter referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

作為(b1-1)，優選具有縮水甘油基和烯屬不飽和鍵的單體。作為(b1-1)，具體地，可列舉出(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、縮水甘油基乙烯基醚、鄰-乙烯基苄基縮水甘油基醚、間-乙烯基苄基縮水甘油基醚、對-乙烯基苄基縮水甘油基醚、α-甲基-鄰-乙烯基苄基縮水甘油基醚、α-甲基-間-乙烯基苄基縮水甘油基醚、α-甲基-對-乙烯基苄基縮水甘油基醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯和2,4,6-三(縮水甘油氧基甲基)苯乙烯。As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl Vinyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl Glyceryl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) benzene Ethylene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) ) Styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.

作為(b1-2)，可列舉出乙烯基環己烯一氧化物、1,2-環氧-4-乙烯基環己烷(例如，セロキサイド(註冊商標)2000；(股)大賽璐製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，サイクロマー(註冊商標)A400；(股)大賽璐製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，サイクロマーM100；(股)大賽璐製造)、由式(1)表示的化合物和由式(2)表示的化合物。Examples of (b1-2) include vinylcyclohexene monoxide and 1,2-epoxy-4-vinylcyclohexane (for example, セ ロ キ サ イ ド (registered trademark) 2000; (share) manufactured by Daicel) 3,4-epoxycyclohexyl methyl (meth) acrylate (for example, Micro (R) A400; (manufactured by Daicel)), 3,4-epoxy cyclohexyl methyl (meth) acrylate (E.g., Micro-M100; manufactured by Daicel), a compound represented by the formula (1), and a compound represented by the formula (2).

[化22]

Figure TW201800849AD00026
[Chemical 22]
Figure TW201800849AD00026

[式(1)和式(2)中，Ra 和Rb 相互獨立地表示氫原子或碳數1~4的烷基，該烷基中所含的氫原子可以被羥基取代。 Xa 和Xb 相互獨立地表示單鍵、＊-RC -、＊-RC -O-、＊-RC -S-或＊-RC -NH-。RC 表示碳數1~6的亞烷基。＊表示與O的鍵合端。][In the formulae (1) and (2), R a and R b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X a and X b each independently represents a single bond, * - R C -, * - R C -O -, * - R C -S- or * -R C -NH-. R C represents an alkylene group having 1 to 6 carbon atoms. * Indicates a bonding end with O. ]

作為由式(1)表示的化合物，可列舉出由式(1-1)~式(1-15)表示的化合物，其中，優選地可列舉出由式(1-1)、式(1-3)、式(1-5)、式(1-7)、式(1-9)和式(1-11)~式(1-15)表示的化合物，更優選地可列舉出由式(1-1)、式(1-7)、式(1-9)和式(1-15)表示的化合物。Examples of the compound represented by the formula (1) include compounds represented by the formulae (1-1) to (1-15). Among them, preferred examples include the compounds represented by the formula (1-1), the formula (1- 3), the formula (1-5), the formula (1-7), the formula (1-9), and the compounds represented by the formula (1-11) to the formula (1-15), and more preferably a compound represented by the formula ( 1-1), compounds represented by formula (1-7), formula (1-9) and formula (1-15).

[化23]

Figure TW201800849AD00027
[Chemical 23]
Figure TW201800849AD00027

作為由式(2)表示的化合物，可列舉出由式(2-1)~式(2-15)表示的化合物，其中，優選地可列舉出由式(2-1)、式(2-3)、式(2-5)、式(2-7)、式(2-9)和式(2-11)~式(2-15)表示的化合物，更優選地可列舉出由式(2-1)、式(2-7)、式(2-9)和式(2-15)表示的化合物。Examples of the compound represented by the formula (2) include compounds represented by the formulae (2-1) to (2-15). Among them, preferably, the compounds represented by the formula (2-1), the formula (2- 3), the compound represented by the formula (2-5), the formula (2-7), the formula (2-9), and the formula (2-11) to the formula (2-15), and more preferably a compound represented by the formula ( 2-1), compounds represented by formula (2-7), formula (2-9), and formula (2-15).

[化24]

Figure TW201800849AD00028
[Chemical 24]
Figure TW201800849AD00028

由式(1)表示的化合物和由式(2)表示的化合物可各自單獨地使用，也可將由式(1)表示的化合物與由式(2)表示的化合物並用。將這些並用的情況下，由式(1)表示的化合物和由式(2)表示的化合物的比率(由式(1)表示的化合物：由式(2)表示的化合物)以摩爾基準計，優選為5：95~95：5，更優選為10：90~90：10，進一步優選為20：80~80：20。The compound represented by the formula (1) and the compound represented by the formula (2) may be used individually, or the compound represented by the formula (1) and the compound represented by the formula (2) may be used in combination. When these are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is on a molar basis, It is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

作為(b2)，更優選具有氧雜環丁基和(甲基)丙烯醯氧基的單體。 作為(b3)，更優選具有四氫呋喃基和(甲基)丙烯醯氧基的單體。As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acrylfluorenyl group is more preferable.

在能夠進一步提高得到的濾色器的耐熱性、耐化學品性等的可靠性的方面，(b)優選為(b1)，在著色固化性樹脂組合物的保存穩定性優異的方面，(b1)優選為(b1-2)。In order to further improve reliability such as heat resistance and chemical resistance of the obtained color filter, (b) is preferably (b1), and in terms of excellent storage stability of the color-curable resin composition, (b1) ) Is preferably (b1-2).

作為(c)，能夠使用以下的(c1)~(c6)的單體等。As (c), the following monomers (c1) to (c6) can be used.

作為(c1)含有羥基的(甲基)丙烯酸酯，可列舉出(甲基)丙烯酸2-羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、1,3-丁二醇(甲基)丙烯酸酯、1,4-丁二醇(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯、3-甲基戊二醇(甲基)丙烯酸酯等。Examples of the (c1) hydroxyl-containing (meth) acrylate include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) Acrylate, 3-methylpentanediol (meth) acrylate, and the like.

含有羥基的(甲基)丙烯酸酯優選為具有碳數1~10的烷基的(甲基)丙烯酸羥基烷基酯，更優選為具有碳數1~8、更優選地碳數1~6、特別優選地碳數1~4的烷基的含有羥基的(甲基)丙烯酸酯。 其中，具體地，優選為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯，更優選為(甲基)丙烯酸2-羥基乙酯。The hydroxy-containing (meth) acrylate is preferably a hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms, more preferably having a carbon number of 1 to 8, more preferably 1 to 6, Particularly preferred is a hydroxyl-containing (meth) acrylate of an alkyl group having 1 to 4 carbon atoms. Among them, specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate is preferable, and 2-hydroxy (meth) acrylate is more preferable. Hydroxyethyl ester.

作為(c2)二羰基亞胺化合物，可列舉出N-苯基馬來醯亞胺、N-甲苯基馬來醯亞胺等具有芳香族烴基的二羰基亞胺、N-環己基馬來醯亞胺、N-環庚基馬來醯亞胺、N-環辛基馬來醯亞胺、N-環十二烷基馬來醯亞胺等具有脂環式烴基的二羰基亞胺、N-苄基馬來醯亞胺、N-苯乙基馬來醯亞胺等具有芳烷基的二羰基亞胺、N-琥珀醯亞氨基-3-馬來醯亞胺苯甲酸鹽、N-琥珀醯亞氨基-4-馬來醯亞胺丁酸鹽、N-琥珀醯亞氨基-6-馬來醯亞胺己酸鹽和N-琥珀醯亞氨基-3-馬來醯亞胺丙酸鹽等具有琥珀醯亞氨基等的二羰基亞胺、N-(9-吖啶基)馬來醯亞胺等具有稠合雜環基的二羰基亞胺等。Examples of the (c2) dicarbonylimine compound include dicarbonylimine having an aromatic hydrocarbon group such as N-phenylmaleimide, N-tolylmaleimide, and N-cyclohexylmaleimide. Imide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-cyclododecylmaleimide, dicarbonylimine having alicyclic hydrocarbon group, N -Dicarbonylimines having an aralkyl group such as benzylmaleimide, N-phenethylmaleimide, N-succinimidylimino-3-maleimide benzoate, N -Succinimidyl-4-maleimidine butyrate, N-succinimidyl-6-maleimide hexanoate, and N-succinimidyl-3-maleimide propyl Dicarbonylimines having succinimidylimide and the like, dicarbonylimines having fused heterocyclic groups such as N- (9-acridyl) maleimide, and the like.

上述二羰基亞胺衍生物的單體優選為具有碳數4~20的烴基的N取代馬來醯亞胺。上述具有碳數4~20的烴基的N取代馬來醯亞胺中的烴基中所含的氫原子可以被氨基、碳數1~5的烷氧基、苯基氨基、鹵素原子或羥基等取代。 作為上述碳數4~20的烴基，可列舉出碳數4~20的脂環式烴基、碳數6~20的芳香族烴基和碳數7~20的芳烷基。作為將上述烴基中所含的氫原子取代的基團，可列舉出琥珀醯亞氨基等。 二羰基亞胺衍生物的單體優選為具有碳數4~20的脂環式烴基的N取代馬來醯亞胺，具體地可列舉出N-環己基馬來醯亞胺、N-環庚基馬來醯亞胺、N-環辛基馬來醯亞胺和N-環十二烷基馬來醯亞胺，更優選地可列舉出N-環己基馬來醯亞胺。The monomer of the dicarbonylimine derivative is preferably an N-substituted maleimidine having a hydrocarbon group having 4 to 20 carbon atoms. The hydrogen atom contained in the above-mentioned N-substituted maleimide having a hydrocarbon group having 4 to 20 carbon atoms may be substituted with an amino group, an alkoxy group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, or a hydroxyl group. . Examples of the hydrocarbon group having 4 to 20 carbon atoms include an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Examples of the group in which a hydrogen atom contained in the hydrocarbon group is substituted include succinimide and the like. The monomer of the dicarbonylimine derivative is preferably an N-substituted maleimide having an alicyclic hydrocarbon group having 4 to 20 carbon atoms. Specific examples include N-cyclohexylmaleimide and N-cycloheptyl. As the maleimide, N-cyclooctylmaleimide, and N-cyclododecylmaleimide, N-cyclohexylmaleimide is more preferable.

作為(c3)(甲基)丙烯酸酯，可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯(該技術領域中，作為慣用名，稱為“(甲基)丙烯酸雙環戊酯”。另外，有時稱為“(甲基)丙烯酸三環癸酯”)、(甲基)丙烯酸三環[5.2.1.02,6 ]癸烯-8-基酯(該技術領域中，作為慣用名，稱為“(甲基)丙烯酸雙環戊烯酯”)、(甲基)丙烯酸雙環戊氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯和(甲基)丙烯酸苄酯等。 作為(c4)二羧酸二酯，可列舉出馬來酸二乙酯、富馬酸二乙酯和衣康酸二乙酯等。 作為(c5)雙環不飽和化合物，可列舉出雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-叔-丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(叔-丁氧基羰基)雙環[2.2.1]庚-2-烯和5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等。 (c6)可列舉出苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯基甲苯和對-甲氧基苯乙烯等含有乙烯基的芳香族化合物；丙烯腈、甲基丙烯腈等含有乙烯基的腈；氯乙烯和偏氯乙烯等鹵代烴；丙烯醯胺和甲基丙烯醯胺等含有乙烯基的醯胺；醋酸乙烯酯等酯；1,3-丁二烯、異戊二烯和2,3-二甲基-1,3-丁二烯的二烯等。Examples of (c3) (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and (formyl) T-butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) ) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclic [5.2.1.0 2,6 ] decane-8-yl ester (In this technical field, as a common name, it is called "dicyclopentyl (meth) acrylate." It may also be called "tricyclodecyl (meth) acrylate".) 5.2.1.0 2,6 ] decene-8-yl ester (in this technical field, as a common name, it is called "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate , Isobornyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid Naphthyl ester and benzyl (meth) acrylate. Examples of the (c4) dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconic acid. Examples of the (c5) bicyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [ 2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxy Bicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2 .1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonyl bicyclic [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclic [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, and 5,6-bis (cyclo Hexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like. (c6) Examples of aromatic compounds containing vinyl groups, such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, and p-methoxystyrene; Vinyl-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinylamines containing vinyl groups such as acrylamide and methacrylamide; esters such as vinyl acetate; 1, 3-butadiene, isoprene, and diene of 2,3-dimethyl-1,3-butadiene, and the like.

這些中，從共聚反應性和耐熱性的觀點出發，優選地可列舉出含有羥基的(甲基)丙烯酸酯和二羰基亞胺化合物，更優選地，可列舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺和N-苄基馬來醯亞胺。Among these, from the viewpoints of copolymerization reactivity and heat resistance, a hydroxyl group-containing (meth) acrylate and a dicarbonylimine compound are preferably exemplified, and more preferably, a 2-hydroxy (meth) acrylic acid is exemplified. Ethyl ester, 2-hydroxypropyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide.

具有烯屬不飽和鍵的結構單元優選為具有(甲基)丙烯醯基的結構單元。具有這樣的結構單元的樹脂可以通過使具有來自(a)、(b)的結構單元的聚合物與具有可與(a)、(b)具有的基團反應的基團和烯屬不飽和鍵的單體加成而得到。 作為這樣的結構單元，可列舉出使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸單元而成的結構單元、使(甲基)丙烯酸2-羥基乙酯加成於馬來酸酐單元而成的結構單元、使(甲基)丙烯酸加成於(甲基)丙烯酸縮水甘油酯單元而成的結構單元等。另外，這些結構單元具有羥基的情況下，作為具有烯屬不飽和鍵的結構單元，也可列舉出進一步使羧酸酐加成而成的結構單元。The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acrylfluorenyl group. The resin having such a structural unit can be obtained by allowing a polymer having a structural unit derived from (a) and (b) to have a group and an ethylenically unsaturated bond which can react with a group having (a) and (b). Obtained by the addition of monomers. Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic unit, and adding 2-hydroxyethyl (meth) acrylate to maleic anhydride. A structural unit formed by a unit, a structural unit obtained by adding (meth) acrylic acid to a glycidyl (meth) acrylate unit, and the like. Moreover, when these structural units have a hydroxyl group, as a structural unit which has an ethylenically unsaturated bond, the structural unit which added the carboxylic anhydride further is mentioned.

具有來自(a)的結構單元的聚合物例如能夠通過在聚合引發劑的存在下、在溶劑中使構成聚合物的結構單元的單體進行聚合而製造。對聚合引發劑和溶劑等並無特別限定，能夠使用該領域中通常使用的聚合引發劑和溶劑。例如，作為聚合引發劑，可列舉出偶氮化合物(2,2’-偶氮二異丁腈、2,2’-偶氮二(2,4-二甲基戊腈)等)、有機過氧化物(過氧化苯甲醯等)，作為溶劑，只要將各單體溶解即可，作為本發明的著色固化性樹脂組合物的溶劑(E)，可列舉出後述的溶劑等。A polymer having a structural unit derived from (a) can be produced, for example, by polymerizing a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, the solvent, and the like are not particularly limited, and a polymerization initiator and a solvent generally used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.), organic compounds, and the like. An oxide (such as benzamidine peroxide) may be a solvent as long as each monomer is dissolved. Examples of the solvent (E) of the colored curable resin composition of the present invention include solvents described below.

再有，得到的聚合物可以直接地使用反應後的溶液，也可使用濃縮或稀釋的溶液，還可以使用採用再沉澱等方法作為固體(粉體)取出的產物。特別地，在該聚合時作為溶劑，通過使用本發明的著色固化性樹脂組合物中所含的溶劑，能夠將反應後的溶液直接在本發明的著色固化性樹脂組合物的製備中使用，因此能夠簡化本發明的著色固化性樹脂組合物的製造工序。 根據需要，可使用羧酸或羧酸酐與環狀醚的反應催化劑(例如三(二甲基氨基甲基)苯酚等)和阻聚劑(例如氫醌等)等。 作為羧酸酐，可列舉出馬來酸酐、檸康酸酐、衣康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐和5,6-二羧基雙環[2.2.1]庚-2-烯酐等。The obtained polymer may be used directly after the reaction, a concentrated or diluted solution may be used, and a product obtained as a solid (powder) by a method such as reprecipitation may also be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used directly in the preparation of the colored curable resin composition of the present invention, and therefore, The manufacturing process of the colored curable resin composition of this invention can be simplified. If necessary, a reaction catalyst (for example, tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.), and the like for a reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether can be used. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, etc. .

作為黏結劑樹脂(B)，可以使用(甲基)丙烯酸3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6 ]癸酯/(甲基)丙烯酸共聚物等樹脂[K1]；(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6 ]癸酯/(甲基)丙烯酸/N-環己基馬來醯亞胺共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6 ]癸酯/(甲基)丙烯酸/乙烯基甲苯共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2]；(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸苄酯/(甲基)丙烯酸三環癸酯/(甲基)丙烯酸共聚物等樹脂[K3]；使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物的樹脂、使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物的樹脂、使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物的樹脂等樹脂[K4]；使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯的共聚物反應而成的樹脂、使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯的共聚物反應而成的樹脂等樹脂[K5]；使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯的共聚物反應、使四氫鄰苯二甲酸酐進一步與所得的樹脂反應而成的樹脂等樹脂[K6]。這些樹脂可以單獨地使用，也可將2種以上組合。As the binder resin (B), 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic copolymer, 3,4-epoxy tricyclic (meth) acrylate can be used [5.2. 1.0 2,6 ] decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer, (meth) Glycidyl acrylate / styrene / (meth) acrylic copolymer, 3,4-epoxy tricyclic (meth) acrylate [5.2.1.0 2,6 ] decyl / (meth) acrylic acid / N-cyclohexyl Maleimide imine copolymer, 3,4-epoxy tricyclic (meth) acrylic acid [5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3 -(Meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymers [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzene Resins such as ethylene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; glycidyl (meth) acrylate Resin added to benzyl (meth) acrylate / (meth) acrylic copolymer to shrink (meth) acrylic acid Glyceryl ester is added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic copolymer resin, and glycidyl (meth) acrylate is added to tricyclodecyl (meth) acrylate / Resins such as benzyl (meth) acrylate / (meth) acrylic copolymer resins [K4]; copolymerization of (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate And other resins [K5]; resins obtained by reacting (meth) acrylic acid with a tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer; Resins such as (meth) acrylic acid and copolymers of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and resins obtained by further reacting tetrahydrophthalic anhydride with the obtained resin [ K6]. These resins may be used alone or in combination of two or more.

其中，黏結劑樹脂(B)優選為樹脂[K2]，更優選為具有來自從不飽和羧酸和不飽和羧酸酐中選擇的至少1種的單體(a)的結構單元、來自具有烯屬不飽和鍵和環狀醚結構的單體(b)的結構單元、來自含有羥基的(甲基)丙烯酸酯單體(c1)的結構單元、和來自二羰基亞胺衍生物的單體(c2)的結構單元的共聚物，進一步優選為具有來自從丙烯酸和甲基丙烯酸中選擇的至少1種的單體(a)的結構單元、來自從(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6 ]癸酯和(甲基)丙烯酸3,4-環氧環己基甲酯中選擇的至少1種的單體(b)的結構單元、來自從(甲基)丙烯酸2-羥基乙酯和(甲基)丙烯酸2-羥基丙酯中選擇的至少1種的單體(c1)的結構單元、和來自從N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、和N-苄基馬來醯亞胺中選擇的至少1種的單體(c2)的結構單元的共聚物。Among them, the binder resin (B) is preferably a resin [K2], more preferably a structural unit having a monomer derived from at least one monomer (a) selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride, and derived from an olefinic compound. The structural unit of the monomer (b) having an unsaturated bond and a cyclic ether structure, the structural unit derived from a hydroxyl group-containing (meth) acrylate monomer (c1), and the monomer derived from a dicarbonylimine derivative (c2) The copolymer of the structural unit) is more preferably a structural unit derived from at least one monomer (a) selected from acrylic acid and methacrylic acid, and is derived from a 3,4-epoxy tricyclic ring derived from (meth) acrylic acid. [5.2.1.0 2,6 ] The structural unit of at least one monomer (b) selected from decyl ester and 3,4-epoxycyclohexyl methyl (meth) acrylate, derived from (meth) acrylic acid 2 -A structural unit of at least one monomer (c1) selected from -hydroxyethyl ester and 2-hydroxypropyl (meth) acrylate, and derived from N-phenylmaleimide, N-cyclohexylmale A copolymer of structural units of at least one monomer (c2) selected from fluoreneimine and N-benzylmaleimide.

樹脂[K2]中，就來自各個單體的結構單元的含有率而言，在構成樹脂[K2]的全部結構單元的合計中，優選來自(a)的結構單元為2~45摩爾%，來自(b)的結構單元為2~65摩爾%，來自(c)的結構單元為1~95摩爾%，更優選來自(a)的結構單元為5~40摩爾%，來自(b)的結構單元為5~60摩爾%，來自(c)的結構單元為10~80摩爾%。 (a)~(c)的各自中所含的單體可以為1種，也可為2種以上。(c)優選為選自(c1)~(c6)中的2種以上，更優選為選自(c1)~(c3)中的2種以上，進一步優選為(c1)和(c2)。In the resin [K2], in terms of the content rate of the structural unit derived from each monomer, in the total of all the structural units constituting the resin [K2], it is preferable that the structural unit derived from (a) is 2 to 45 mol%. The structural unit of (b) is 2 to 65 mol%, the structural unit derived from (c) is 1 to 95 mol%, and the structural unit derived from (a) is 5 to 40 mol%, and the structural unit derived from (b) It is 5 to 60 mol%, and the structural unit derived from (c) is 10 to 80 mol%. The monomers contained in each of (a) to (c) may be one kind, or two or more kinds. (c) Two or more types selected from (c1) to (c6) are preferred, two or more types selected from (c1) to (c3) are more preferred, and (c1) and (c2) are more preferred.

來自(c1)的結構單元的含有率，在來自(c)的全部結構單元的合計中，優選為1~60摩爾%，更優選為10~50摩爾%，進一步優選為20~40摩爾%。 來自(c2)的結構單元的含有率，在來自(c)的全部結構單元的合計中，優選為30~90摩爾%，更優選為40~80摩爾%，進一步優選為50~70摩爾%。The content rate of the structural unit derived from (c1) is preferably 1 to 60 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% in the total of all the structural units derived from (c). The content rate of the structural unit derived from (c2) is preferably 30 to 90 mol%, more preferably 40 to 80 mol%, and still more preferably 50 to 70 mol% in the total of all the structural units derived from (c).

將2種以上的黏結劑樹脂(B)組合的情況下，優選樹脂[K1]和/或樹脂[K2]與樹脂[K4]~樹脂[K6]的組合，更優選樹脂[K1]和/或樹脂[K2]與樹脂[K4]的組合。When two or more binder resins (B) are combined, the resin [K1] and / or the resin [K2] and the resin [K4] to the resin [K6] are preferably combined, and the resin [K1] and / or Combination of resin [K2] and resin [K4].

黏結劑樹脂(B)的聚苯乙烯換算的重均分子量優選為3,000以上且100,000以下，更優選為4,000以上且100,000以下，進一步優選為5,000以上且80,000以下，特別優選為6,000以上且50,000以下，尤其優選為7,500以上且40,000以下。如果分子量在上述的範圍內，具有塗膜硬度提高、殘膜率也高、未曝光部的對於顯影液的溶解性良好、著色圖案的解析度提高的傾向。黏結劑樹脂(B)的分子量分佈[重均分子量(Mw)/數均分子量(Mn)]優選為1.1~6，更優選為1.2~4，進一步優選為1.3~3。The polystyrene equivalent weight average molecular weight of the binder resin (B) is preferably 3,000 or more and 100,000 or less, more preferably 4,000 or more and 100,000 or less, even more preferably 5,000 or more and 80,000 or less, and particularly preferably 6,000 or more and 50,000 or less, Especially preferably, it is 7,500 or more and 40,000 or less. When the molecular weight is within the above range, the coating film hardness is increased, the residual film ratio is also high, the solubility of the unexposed portion to the developing solution is good, and the resolution of the colored pattern tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and even more preferably 1.3 to 3.

黏結劑樹脂(B)的酸值(固體成分換算)優選為30~200mg-KOH/g，更優選為35mg-KOH/g以上，進一步優選為40mg-KOH/g以上，特別優選為180mg-KOH/g以下，尤其優選為150mg-KOH/g以下。酸值為作為中和黏結劑樹脂(B)1g所需的氫氧化鉀的量(mg)所測定的值，例如能夠使用氫氧化鉀水溶液進行滴定而求出。The acid value (in terms of solid content) of the binder resin (B) is preferably 30 to 200 mg-KOH / g, more preferably 35 mg-KOH / g or more, still more preferably 40 mg-KOH / g or more, and particularly preferably 180 mg-KOH. / g or less, particularly preferably 150 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the binder resin (B), and can be determined by, for example, titration with an aqueous potassium hydroxide solution.

黏結劑樹脂(B)的合計的含有率，相對於固體成分的總量，優選為10~65質量%，更優選為15~60質量%，進一步優選為20~55質量%，特別優選為25~50質量%。如果黏結劑樹脂(B)的含有率在上述的範圍內，著色圖案形成容易，具有著色圖案的解析度和殘膜率提高的傾向。The total content of the binder resin (B) is preferably 10 to 65 mass%, more preferably 15 to 60 mass%, still more preferably 20 to 55 mass%, and particularly preferably 25 to the total solid content. ~ 50% by mass. When the content of the binder resin (B) is within the above range, the colored pattern is easily formed, and the resolution of the colored pattern and the residual film rate tend to increase.

＜聚合性化合物(C)＞ 聚合性化合物(C)是能夠利用由聚合引發劑產生的活性自由基和/或酸聚合的化合物，可列舉出例如具有烯屬不飽和鍵的聚合性化合物，優選地可列舉出具有(甲基)丙烯酸酯結構的化合物。聚合性化合物(C)優選為具有3個以上的烯屬不飽和鍵的聚合性化合物，更優選為具有5個~6個烯屬不飽和鍵的聚合性化合物。<Polymerizable Compound (C)> The polymerizable compound (C) is a compound that can be polymerized using living radicals and / or acids generated by a polymerization initiator, and examples thereof include polymerizable compounds having an ethylenically unsaturated bond, and are preferred. Examples of the compound include a compound having a (meth) acrylate structure. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

作為具有1個烯屬不飽和鍵的聚合性化合物，可列舉出壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯烷酮、上述的(a)、(b)和(c)。 作為具有2個烯屬不飽和鍵的聚合性化合物，可列舉出1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、雙酚A的雙(丙烯醯氧基乙基)醚和3-甲基戊二醇二(甲基)丙烯酸酯。 作為具有3個以上的烯屬不飽和鍵的聚合性化合物，可列舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、三(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯、乙二醇改性季戊四醇四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯和己內酯改性二季戊四醇六(甲基)丙烯酸酯。 這些中，優選地可列舉出二季戊四醇五(甲基)丙烯酸酯和二季戊四醇六(甲基)丙烯酸酯。Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexylcarbitol acrylate , 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (a), (b), and (c) above. Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di (methyl) Acrylate), triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, Pentaerythritol nine (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified Dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone Ester modified dipentaerythritol hexa (meth) acrylate. Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

聚合性化合物(C)的重均分子量優選為150以上且2,900以下，更優選為250以上且1,500以下。The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

相對於固體成分的總量，本發明的著色固化性樹脂組合物中的聚合性化合物(C)的含有率通常為1~60質量%，優選為5~50質量%，更優選為10~40質量%，進一步優選為12~35質量%。黏結劑樹脂(B)與聚合性化合物(C)的含量比(黏結劑樹脂(B)：聚合性化合物(C))以質量基準計，通常為20：80~80：20，優選為35：65~80：20。如果聚合性化合物(C)的含量在上述的範圍內，則具有著色圖案形成時的殘膜率和濾色器的耐化學品性提高的傾向。The content rate of the polymerizable compound (C) in the colored curable resin composition of the present invention is generally 1 to 60% by mass, preferably 5 to 50% by mass, and more preferably 10 to 40 with respect to the total amount of the solid content. The mass% is more preferably 12 to 35 mass%. The content ratio of the binder resin (B) to the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) is usually 20:80 to 80:20 on a mass basis, and preferably 35: 65 ~ 80: 20. When content of a polymerizable compound (C) exists in the said range, there exists a tendency for the residual film rate at the time of coloring pattern formation, and the chemical resistance of a color filter to improve.

＜聚合引發劑(D)＞ 聚合引發劑(D)只要是能夠利用光、熱的作用而產生活性自由基、酸等，引發聚合的化合物，則並無特別限定，能夠使用公知的聚合引發劑。 作為聚合引發劑(D)，優選為包含選自烷基苯基酮化合物、三嗪化合物、醯基氧化膦化合物、O-醯基肟化合物和聯咪唑化合物中的至少一種的聚合引發劑，更優選為包含O-醯基肟化合物的聚合引發劑。<Polymerization Initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by the action of light and heat to generate active radicals, acids, and the like, and a known polymerization initiator can be used. . The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, a fluorenyl phosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound, and more preferably A polymerization initiator containing an O-fluorenyl oxime compound is preferable.

作為O-醯基肟化合物，可列舉出N-苯甲醯氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-｛2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲氧基)苯甲醯基｝-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺和N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺。可使用Irgacure(註冊商標)OXE01、OXE02(以上為BASF公司製造)、N-1919(ADEKA公司製造)等市售品。其中，優選為選自N-苯甲醯氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺和N-苯甲醯氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺中的至少1種，更優選N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺。Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzyloxy 1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylsulfanylphenyl) -3 -Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3- Alkyl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6-fluorene 2-methyl-4- (3,3-dimethyl-2,4-dioxo Heteropentylmethoxy) benzylfluorenyl-9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA) can be used. Among them, it is preferably selected from N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzyloxy-1- ( 4-phenylsulfanylphenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane At least one of 1-one-2-imine, more preferably N-benzyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine.

作為烷基苯基酮化合物，可列舉出2-甲基-2-嗎啉代-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲基氨基-1-(4-嗎啉代苯基)-2-苄基丁烷-1-酮和2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮。可使用Irgacure 369、907、379(以上為BASF公司製造)等市售品。Examples of the alkylphenyl ketone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (above manufactured by BASF) can be used.

烷基苯基酮化合物可以為2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮的低聚物、α,α-二乙氧基苯乙酮和苯偶醯二甲基縮酮。The alkyl phenyl ketone compound may be 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) benzene Yl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer, α, α -Diethoxyacetophenone and benzophenone dimethyl ketal.

作為三嗪化合物，可列舉出2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基氨基-2-甲基苯基)乙烯基]-1,3,5-三嗪和2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪。Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, and 2,4-bis (trichloromethyl) ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperidyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene Group] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1, 3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine.

作為醯基氧化膦化合物，可列舉出2,4,6-三甲基苯甲醯基二苯基氧化膦。可使用Irgacure(註冊商標)819(BASF公司製造)等市售品。Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

作為聯咪唑化合物，具體地，可列舉出2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基聯咪唑(例如，參照日本特開平6-75372號公報、日本特開平6-75373號公報等)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)聯咪唑(例如，參照日本特公昭48-38403號公報、日本特開昭62-174204號公報等)和4,4’,5,5’-位的苯基被烷氧羰基取代的咪唑化合物(例如，參照日本特開平07-010913號公報等)。其中，優選由下述式表示的化合物和它們的混合物。Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2, 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2, 2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5' -Tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204 and the like) and imidazole compounds in which the 4,4 ', 5,5'-phenyl group is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 07-010913). Among them, a compound represented by the following formula and a mixture thereof are preferred.

[化25]

Figure TW201800849AD00029
[Chemical 25]
Figure TW201800849AD00029

作為其他的聚合引發劑，可列舉出苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚等苯偶姻化合物；二苯甲酮、鄰-苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、3,3’,4,4’-四(叔-丁基過氧羰基)二苯甲酮和2,4,6-三甲基二苯甲酮等二苯甲酮化合物；9,10-菲醌、2-乙基蒽醌和樟腦醌等醌化合物；10-丁基-2-氯吖啶酮、苯偶醯、苯基乙醛酸甲酯和二茂鈦化合物等。這些優選與後述的聚合引發助劑(特別是胺系聚合引發助劑)組合使用。Examples of other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzophenone, methyl o-benzylidenebenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4 '-Tetrakis (t-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone And quinone compounds such as camphor quinone; 10-butyl-2-chloroacridone, benzodiazone, methyl phenylglyoxylate and titanocene compounds. These are preferably used in combination with a polymerization initiation aid described later (particularly, an amine-based polymerization initiation aid).

聚合引發劑(D)的含量，相對於黏結劑樹脂(B)和聚合性化合物(C)的合計量100質量份，通常為0.1~40質量份，優選為0.1~30質量份，更優選為1~30質量份，進一步優選為1~20質量份。The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass with respect to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). 1 to 30 parts by mass, and more preferably 1 to 20 parts by mass.

＜聚合引發助劑＞ 聚合引發助劑是為了促進用聚合引發劑(D)引發了聚合的聚合性化合物(C)的聚合而使用的化合物或増感劑。本發明的著色固化性樹脂組合物包含聚合引發助劑的情況下，通常與聚合引發劑(D)組合使用。作為聚合引發助劑，可列舉出胺系聚合引發助劑、烷氧基蒽系聚合引發助劑、噻噸酮系聚合引發助劑和羧酸系聚合引發助劑。<Polymerization Initiation Aid> The polymerization initiation aid is a compound or a sensitizer used to promote the polymerization of the polymerizable compound (C) in which the polymerization is initiated with the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation aid, it is usually used in combination with a polymerization initiator (D). Examples of the polymerization initiation aid include amine-based polymerization initiation aids, alkoxyanthracene-based polymerization initiation aids, thioxanthone-based polymerization initiation aids, and carboxylic acid-based polymerization initiation aids.

作為胺系聚合引發助劑，可列舉出三乙醇胺、甲基二乙醇胺和三異丙醇胺等鏈烷醇胺；4-二甲基氨基苯甲酸甲酯、4-二甲基氨基苯甲酸乙酯、4-二甲基氨基苯甲酸異戊酯、苯甲酸2-二甲基氨基乙酯和4-二甲基氨基苯甲酸2-乙基己酯等氨基苯甲酸酯；N,N-二甲基對甲苯胺、4,4’-雙(二甲基氨基)二苯甲酮(通稱米蚩酮)、4,4’-雙(二乙基氨基)二苯甲酮和4,4’-雙(乙基甲基氨基)二苯甲酮，其中優選4,4’-雙(二乙基氨基)二苯甲酮等烷基氨基二苯甲酮。其中，優選烷基氨基二苯甲酮，優選4,4’-雙(二乙基氨基)二苯甲酮。可使用EAB-F(保土谷化學工業(股)製造)等市售品。Examples of the amine-based polymerization initiation aid include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; N, N- Dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as mignonone), 4,4'-bis (diethylamino) benzophenone, and 4,4 Among these, '-bis (ethylmethylamino) benzophenone is preferred, and alkylaminobenzophenone such as 4,4'-bis (diethylamino) benzophenone is preferred. Among them, alkylaminobenzophenone is preferred, and 4,4'-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

作為烷氧基蒽系聚合引發助劑，可列舉出9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽和2-乙基-9,10-二丁氧基蒽。Examples of the alkoxyanthracene-based polymerization initiation aid include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2 -Ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

作為噻噸酮系聚合引發助劑，可列舉出2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮和1-氯-4-丙氧基噻噸酮。Examples of the thioxanthone-based polymerization initiation aid include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. Ketones and 1-chloro-4-propoxythioxanthone.

作為羧酸系聚合引發助劑，可列舉出苯基硫烷基醋酸、甲基苯基硫烷基醋酸、乙基苯基硫烷基醋酸、甲基乙基苯基硫烷基醋酸、二甲基苯基硫烷基醋酸、甲氧基苯基硫烷基醋酸、二甲氧基苯基硫烷基醋酸、氯苯基硫烷基醋酸、二氯苯基硫烷基醋酸、N-苯基甘氨酸、苯氧基醋酸、萘硫基醋酸、N-萘基甘氨酸和萘氧基醋酸。Examples of the carboxylic acid-based polymerization initiation aid include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethyl Phenylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenyl Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid.

使用聚合引發助劑的情況下，其含量相對於黏結劑樹脂(B)及聚合性化合物(C)的合計量100質量份，優選為0.1~30質量份，更優選為1~20質量份。如果聚合引發助劑的含量在該範圍內，能夠以更高感度形成著色圖案，濾色器的生產率傾向於提高。When a polymerization initiation adjuvant is used, its content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). If the content of the polymerization initiation aid is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to increase.

＜溶劑(E)＞ 對溶劑(E)並無限定，能夠單獨使用該領域中通常使用的溶劑或者將2種以上組合使用。具體地，可列舉出酯溶劑(在分子內包含-COO-、不含-O-的溶劑)、醚溶劑(在分子內包含-O-、不含-COO-的溶劑)、醚酯溶劑(在分子內包含-COO-和-O-的溶劑)、酮溶劑(在分子內包含-CO-、不含-COO-的溶劑)、醇溶劑(在分子內包含OH、不含-O-、-CO-和-COO-的溶劑)、芳香族烴溶劑、醯胺溶劑和二甲基亞碸。<Solvent (E)> The solvent (E) is not limited, and solvents commonly used in this field can be used alone or in combination of two or more kinds. Specific examples include ester solvents (solvents containing -COO- and -O-free in the molecule), ether solvents (solvents containing -O- and -COO-free in the molecule), and ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and -COO-free in the molecule), alcohol solvents (containing OH in the molecule, -O- free, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, and dimethyl sulfene.

作為酯溶劑，可列舉出乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、醋酸乙酯、醋酸丁酯、醋酸異丁酯、甲酸戊酯、醋酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯和γ-丁內酯。Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexane Alcohol acetate and γ-butyrolactone.

作為醚溶劑，可列舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、二丙二醇單甲基醚、二丙二醇正丙基醚、二丙二醇丁基醚、二丙二醇甲基丙基醚、三丙二醇單甲基醚、三丙二醇丁基醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二噁烷、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇甲基乙基醚、二甘醇二丙基醚、二甘醇二丁基醚、茴香醚、苯***和甲基茴香醚。Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol n-propyl ether , Dipropylene glycol butyl ether, dipropylene glycol methylpropyl ether, tripropylene glycol monomethyl ether, tripropylene glycol butyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutane Alcohol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, anisole, phenyl ether and methyl anisole.

作為醚酯溶劑，可列舉出甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二甘醇單乙基醚乙酸酯、二甘醇單丁基醚乙酸酯和二丙二醇甲基醚乙酸酯和丙二醇二乙酸酯。Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate and propylene glycol diacetate.

作為酮溶劑，可列舉出4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮和異佛爾酮。Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, and isophorone.

作為醇溶劑，可列舉出甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇和甘油。Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

作為芳香族烴溶劑，可列舉出苯、甲苯、二甲苯和1,3,5-三甲基苯。Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

作為醯胺溶劑，可列舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮。Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

就這些溶劑而言，可將二種以上組合。These solvents may be used in combination of two or more kinds.

上述的溶劑中，從塗布性、乾燥性的方面出發，優選1atm(大氣壓)下的沸點為120℃以上、210℃以下的有機溶劑。其中，優選丙二醇單甲基醚乙酸酯、乳酸乙酯、丙二醇單甲基醚、3-乙氧基丙酸乙酯、乙二醇單甲基醚、乙二醇單丁基醚、二甘醇單甲基醚、二甘醇單乙基醚、乙酸3-甲氧基丁酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、丙二醇二乙酸酯、N,N-二甲基甲醯胺和N-甲基吡咯烷酮，更優選丙二醇單甲基醚乙酸酯、丙二醇單甲基醚、乙二醇單丁基醚、二丙二醇甲基醚乙酸酯、乳酸乙酯、乙酸3-甲氧基丁酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯、N,N-二甲基甲醯胺、N-甲基吡咯烷酮、4-羥基-4-甲基-2-戊酮和丙二醇二乙酸酯。Among the above solvents, organic solvents having a boiling point of 1 atm (atmospheric pressure) of 120 ° C. or higher and 210 ° C. or lower are preferred from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, propylene glycol di Acetate, N, N-dimethylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl Ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N-dimethylformamide, N-methylpyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate.

相對於著色固化性樹脂組合物的總量，溶劑(E)的含有率通常為60~95質量%，優選為65~92質量%，更優選為70~90質量%。如果溶劑(E)的含量在上述的範圍內，塗布時的平坦性變得良好，另外，由於形成了濾色器時色濃度不會不足，因此具有顯示特性變得良好的傾向。The content of the solvent (E) is usually 60 to 95% by mass, preferably 65 to 92% by mass, and more preferably 70 to 90% by mass with respect to the total amount of the colored curable resin composition. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating will be good, and the color density will not be insufficient when the color filter is formed, so that the display characteristics tend to be good.

＜流平劑＞ 作為流平劑，可列舉出有機矽系表面活性劑、氟系表面活性劑和具有氟原子的有機矽系表面活性劑。<Leveling agent> Examples of the leveling agent include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom.

作為有機矽系表面活性劑，可列舉出在分子內具有矽氧烷鍵的表面活性劑。具體地，可列舉出Toray Silicone DC3PA、SH7PA、DC11PA、SH21PA、SH28PA、SH29PA、SH30PA、SH8400(東麗-道康寧(股)製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452和TSF4460(邁圖高新材料日本合同會社製造)。Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industrial (stock) manufacturing), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Advanced Materials Japan Contracts).

作為氟系表面活性劑，可列舉出在分子內具有氟碳鏈的表面活性劑。具體地，可列舉出フロラード(註冊商標)FC430、FC431(住友3M(股)製造)、メガファック(註冊商標)F142D、F171、F172、F173、F177、F183、F554、R30、RS-718-K(DIC(股)製造)、エフトップ(註冊商標)EF301、EF303、EF351、EF352(三菱綜合材料電子化成(股)製造)、サーフロン(註冊商標)S381、S382、SC101、SC105(旭硝子(股)製造)和E5844((股)大金精細化工研究所製造)。Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include Fluoro (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M, Ltd.), Fluoro (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (Manufactured by DIC), エ フ ト ッ 注册 (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Co., Ltd.), フ ー ロ ン (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) (Manufacturing) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

作為具有氟原子的有機矽系表面活性劑，可列舉出在分子內具有矽氧烷鍵和氟碳鏈的表面活性劑。具體地，可列舉出メガファック(註冊商標)R08、BL20、F475、F477和F443(DIC(股)製造)。Examples of the organosilicon surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in a molecule. Specific examples include メ ガ (メ ガ) (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC).

相對於著色固化性樹脂組合物的總量，流平劑的含有率通常為0.0005質量%以上且0.6質量%以下，優選為0.001質量%以上且0.5質量%以下，更優選為0.001質量%以上且0.2質量%以下，進一步優選為0.002質量%以上且0.1質量%以下，特別優選為0.005質量%以上且0.07質量%以下。如果流平劑的含有率在上述的範圍內，則能夠使濾色器的平坦性變得良好。The content rate of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, and more preferably 0.001 mass% or more with respect to the total amount of the colored curable resin composition. 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and particularly preferably 0.005 mass% or more and 0.07 mass% or less. When the content rate of the leveling agent is within the above range, the flatness of the color filter can be improved.

環氧化合物(P) 作為環氧化合物(P)，只要是具有1個以上的環氧乙基的化合物即可。不過，環氧化合物(P)是例如與黏結劑樹脂(B)不同的化合物。如果使用這樣的環氧化合物(P)，能夠提高著色固化性樹脂組合物的明度，另外能夠提高耐溶劑性。再有，環氧化合物(P)具有的環氧乙基的數目只要為1個以上即可，可以為2個以上，也可以為3個以上。Epoxy compound (P) As the epoxy compound (P), any compound having one or more epoxy ethyl groups may be used. However, the epoxy compound (P) is, for example, a compound different from the binder resin (B). When such an epoxy compound (P) is used, the lightness of a colored curable resin composition can be improved, and solvent resistance can also be improved. The number of epoxyethyl groups in the epoxy compound (P) may be one or more, and may be two or more, or three or more.

上述環氧化合物(P)的酸值優選為不到30mg-KOH/g，更優選為20mg-KOH/g以下，進一步優選為10mg-KOH/g以下，特別優選為0mg-KOH/g。The acid value of the epoxy compound (P) is preferably less than 30 mg-KOH / g, more preferably 20 mg-KOH / g or less, still more preferably 10 mg-KOH / g or less, and particularly preferably 0 mg-KOH / g.

作為上述環氧化合物(P)，可列舉出異戊二烯的(共)聚合物的環氧化物、丁二烯的(共)聚合物的環氧化物等烷烴二烯(共)聚合物的環氧化物等不具有環的環氧化合物；具有環的環氧化合物。作為該環，可列舉出脂環式烴環、芳香族烴環。這些可以為雜環，但優選為烴環。Examples of the epoxy compound (P) include an epoxide of a (co) polymer of isoprene and an epoxide of a alkanediene (co) polymer such as an epoxide of a (co) polymer of butadiene. Epoxy compounds, such as epoxides, that do not have a ring; epoxy compounds that have a ring. Examples of the ring include an alicyclic hydrocarbon ring and an aromatic hydrocarbon ring. These may be heterocyclic rings, but are preferably hydrocarbon rings.

作為脂環式烴環，可列舉出環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環等碳數3~10的環烷烴環；環戊烯環、環己烯環、環庚烯環、環辛烯環等碳數5~10的環烯烴環；雙環[2.2.1]庚烷環(降冰片烷環)、1,7,7-三甲基雙環[2.2.1]庚烷環(異冰片烷環)、雙環[2.2.2]辛烷環、三環[5.2.1.02,6 ]癸烷環、三環[3.3.1.13,7 ]癸烷環(金剛烷環)等碳數7~15的多環的脂環式烴環等。 脂環式烴環優選為碳數4~9的環烷烴環，更優選為碳數5~8的環烷烴環。其中，更優選環己烷。Examples of the alicyclic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. Cyclic olefin rings with 5 to 10 carbons, such as pentene ring, cyclohexene ring, cycloheptene ring, and cyclooctene ring; bicyclic [2.2.1] heptane ring (norbornane ring), 1,7,7 -Trimethylbicyclo [2.2.1] heptane ring (isobornane ring), bicyclo [2.2.2] octane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo [3.3.1.1 3,7 ] Polycyclic alicyclic hydrocarbon rings having 7 to 15 carbons such as decane ring (adamantane ring). The alicyclic hydrocarbon ring is preferably a cycloalkane ring having 4 to 9 carbon atoms, and more preferably a cycloalkane ring having 5 to 8 carbon atoms. Among these, cyclohexane is more preferable.

作為芳香族烴環，可列舉出苯環、萘環和蒽環等。Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring.

作為具有環的環氧化合物，優選具有1個以上的環和2個以上的環氧乙基的化合物，更優選具有2個以上的環和2個以上的環氧乙基的環氧化合物。在具有環的環氧化合物中，相對於環的數目1的環氧乙基的數目優選為0.8~1.2，更優選為0.9~1.1。As the epoxy compound having a ring, a compound having one or more rings and two or more epoxy ethyl groups is preferred, and an epoxy compound having two or more rings and two or more epoxy ethyl groups is more preferred. In the epoxy compound having a ring, the number of ethylene oxide groups with respect to the number of rings is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

作為具有脂環式烴環和2個以上的環氧乙基的環氧化合物，可列舉出2,2-雙(羥基甲基)-1-丁醇的1,2-環氧-4-(2-環氧乙基)環己烷加成物等。 作為上述環氧化合物，也可列舉出3,4-環氧環己烷羧酸3',4'-環氧環己基甲酯(セロキサイド2021P、大賽璐株式會社製造)、ε-己內酯改性3,4-環氧環己烷羧酸3',4'-環氧環己基甲酯(セロキサイド2081、大賽璐株式會社製造)等。Examples of the epoxy compound having an alicyclic hydrocarbon ring and two or more epoxyethyl groups include 1,2-epoxy-4- (2,2-bis (hydroxymethyl) -1-butanol). 2-epoxyethyl) cyclohexane adduct. Examples of the epoxy compound include 3,4-epoxycyclohexanecarboxylic acid 3 ', 4'-epoxycyclohexyl methyl ester (Merolite 2021P, manufactured by Daicel Corporation), and ε-caprolactone modification. 3 ', 4'-epoxycyclohexyl methyl ester of 3,4-epoxycyclohexanecarboxylic acid (produce 2081, manufactured by Daicel Corporation), and the like.

作為具有芳香族烴環和2個以上的環氧乙基的環氧化合物，可列舉出雙酚A型環氧化合物、雙酚F型環氧化合物、溴化雙酚A型環氧化合物和溴化雙酚F型環氧化合物等雙酚型環氧化合物；苯酚酚醛清漆型環氧化合物和甲酚酚醛清漆型環氧化合物等酚醛清漆型環氧化合物；聯苯型環氧化合物；三羥基苯基甲烷型環氧化合物；四酚乙烷型環氧化合物；苯乙烯-丁二烯共聚物的環氧化物和苯乙烯-異戊二烯共聚物的環氧化物等苯乙烯系聚合物的環氧化物等。其中，特別優選雙酚A型環氧化合物和鄰甲酚酚醛清漆型環氧化合物。Examples of the epoxy compound having an aromatic hydrocarbon ring and two or more epoxyethyl groups include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a brominated bisphenol A type epoxy compound, and bromine. Bisphenol-type epoxy compounds such as bisphenol F-type epoxy compounds; novolac-type epoxy compounds such as phenol novolac-type epoxy compounds and cresol novolac-type epoxy compounds; biphenyl-type epoxy compounds; trihydroxybenzene Methane epoxy compound; tetraphenol ethane epoxy compound; epoxy of styrene-butadiene copolymer and epoxy of styrene-isoprene copolymer Oxides, etc. Among these, a bisphenol A type epoxy compound and an o-cresol novolac type epoxy compound are particularly preferable.

環氧化合物(P)的重均分子量優選為7000以下，更優選為5000以下，進一步優選為2900以下，優選為50以上，更優選為200以上，進一步優選為350以上。The weight average molecular weight of the epoxy compound (P) is preferably 7,000 or less, more preferably 5,000 or less, even more preferably 2900 or less, preferably 50 or more, more preferably 200 or more, and even more preferably 350 or more.

環氧化合物(P)的環氧當量優選為30g/當量以上且400g/當量以下，更優選為50g/當量以上且350g/當量以下，進一步優選為100g/當量以上且300g/當量以下，特別優選為150g/當量以上且250g/當量以下。環氧當量能夠採用JISK7236中規定的方法測定。The epoxy equivalent of the epoxy compound (P) is preferably 30 g / equivalent or more and 400 g / equivalent or less, more preferably 50 g / equivalent or more and 350 g / equivalent or less, even more preferably 100 g / equivalent or more and 300 g / equivalent or less, and particularly preferably It is 150 g / equivalent or more and 250 g / equivalent or less. The epoxy equivalent can be measured by a method specified in JISK7236.

環氧化合物(P)的含有率，在著色固化性樹脂組合物(固體成分)100質量%中，優選為0.1質量%以上且25質量%以下，更優選為0.5質量%以上且20質量%以下，進一步優選為1質量%以上且15質量%以下，特別優選為2質量%以上且10質量%以下。The content of the epoxy compound (P) is preferably 0.1% by mass or more and 25% by mass or less, and more preferably 0.5% by mass or more and 20% by mass or less in 100% by mass of the colored curable resin composition (solid content). It is more preferably 1% by mass or more and 15% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less.

＜其他成分＞ 本發明的著色固化性樹脂組合物，根據需要，可包含填充劑、其他的高分子化合物、密合促進劑、抗氧化劑、光穩定劑、鏈轉移劑、環氧固化劑、固化促進劑等該技術領域中公知的添加劑。<Other components> The colored curable resin composition of the present invention may contain a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, an epoxy curing agent, and a curing agent, if necessary. Accelerators and other well-known additives in this technical field.

＜著色固化性樹脂組合物的製造方法＞ 本發明的著色固化性樹脂組合物例如能夠通過將著色劑(A)、黏結劑樹脂(B)、聚合性化合物(C)、聚合引發劑(D)、環氧化合物(P)、以及根據需要的溶劑(E)、流平劑、聚合引發助劑和其他成分混合而製備。對於混合後的著色固化性樹脂組合物，優選用孔徑0.01~10μm左右的過濾器過濾。<The manufacturing method of a coloring curable resin composition> The coloring curable resin composition of this invention can be made by coloring (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), for example. , An epoxy compound (P), and a solvent (E), a leveling agent, a polymerization initiator, and other components, if necessary, and prepared by mixing. The coloring curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

＜濾色器的製造方法＞ 由本發明的著色固化性樹脂組合物能夠形成著色圖案，作為其製造方法，可列舉出光刻法、噴墨法、印刷法等，優選列舉出光刻法。光刻法是將著色固化性樹脂組合物塗布於基板，乾燥而形成著色組合物層，經由光掩模將該著色組合物層曝光、顯影的方法。光刻法中，通過在曝光時不使用光掩模和/或不顯影，從而能夠形成作為上述著色組合物層的固化物的著色塗膜。這樣形成的著色圖案、著色塗膜為本發明的濾色器。<The manufacturing method of a color filter> A colored pattern can be formed from the colored curable resin composition of this invention, As a manufacturing method, a photolithography method, an inkjet method, a printing method, etc. are mentioned, Preferably, a photolithography method is mentioned. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the coloring composition layer can be formed by using no photomask and / or no development during exposure. The colored pattern and colored coating film thus formed are the color filters of the present invention.

製作的濾色器的膜厚，能夠根據目的、用途等適當調整，通常為0.1~30μm，優選為0.1~20μm，更優選為0.5~6μm。The thickness of the produced color filter can be appropriately adjusted according to the purpose, application, and the like, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

作為基板，可使用玻璃板、樹脂板、矽、在上述基板上形成了鋁、銀、銀/銅/鈀合金薄膜等的產物。在這些基板上可形成另外的濾色器層、樹脂層、電晶體、電路等。As the substrate, a glass plate, a resin plate, silicon, or a product obtained by forming an aluminum, silver, silver / copper / palladium alloy film, or the like on the substrate can be used. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

採用光刻法的各色圖元的形成能夠在公知或慣用的裝置、條件下進行。例如，能夠如下所述製作。The formation of each color element using the photolithography method can be performed under a known or conventional apparatus and conditions. For example, it can be produced as follows.

首先，將著色固化性樹脂組合物塗布在基板上，通過加熱乾燥(預烘焙)和/或減壓乾燥，從而將溶劑等揮發成分除去而乾燥，得到平滑的著色組合物層。作為塗布方法，可列舉出旋塗法、狹縫塗布法以及狹縫和旋轉塗布法。First, a colored curable resin composition is coated on a substrate, and then dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as solvents and drying, thereby obtaining a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

接下來，經由用於形成目標的著色圖案的光掩模對著色組合物層進行曝光。由於可以對曝光面全體均勻地照射平行光線，能夠進行光掩模與形成了著色組合物層的基板的正確對位，因此優選使用掩模對準器和步進器等曝光裝置進行曝光。通過使曝光後的著色組合物層與顯影液接觸而顯影，從而在基板上形成著色圖案。通過顯影，著色組合物層的未曝光部在顯影液中溶解而被除去。 作為顯影液，優選氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物的水溶液。 显影方法可以是旋覆浸没法、浸渍法和喷雾法的任一种。進而，在顯影時可使基板傾斜任意的角度。顯影後優選進行水洗。Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. Since the entire exposure surface can be uniformly irradiated with parallel light rays, and the photomask can be accurately aligned with the substrate on which the colored composition layer is formed, it is preferable to perform exposure using an exposure device such as a mask aligner and a stepper. The coloring composition layer after exposure is developed by contacting with the developing solution, thereby forming a coloring pattern on the substrate. By the development, the unexposed part of the coloring composition layer is dissolved in the developing solution and removed. As the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The development method may be any of a spin-on immersion method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development. After development, washing with water is preferred.

優選對得到的著色圖案進一步進行後烘焙。對於具有這樣得到的著色圖案、著色塗膜的濾色器，為了賦予各種特性，可進一步進行表面塗覆處理。The obtained colored pattern is preferably further post-baked. The color filter having the coloring pattern and the colored coating film obtained in this manner may be further subjected to a surface coating treatment in order to impart various characteristics.

由本發明的著色固化性樹脂組合物形成的濾色器可用作在顯示裝置(例如，液晶顯示裝置、有機EL裝置、電子紙等)和固體攝像元件中使用的濾色器。 實施例The color filter formed from the colored curable resin composition of the present invention can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, and the like) and solid-state imaging elements. Examples

以下通過實施例對本發明更詳細地進行說明，但本發明不受這些實施例限定。示例中，只要無特別說明，表示含量乃至使用量的%和份為質量基準。Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by these examples. In the examples, as long as there is no special description, the percentages and parts indicating the content and even the amount used are based on mass.

合成例1(顏料合成例) 以下的反應在氮氣氛下進行。在具備冷卻管和攪拌裝置的燒瓶中投入N-甲基苯胺(東京化成工業株式會社製造)15.3份和N,N-二甲基甲醯胺60份後，將混合溶液冰冷。在冰冷下歷時30分鐘一點點地加入60%氫化鈉(東京化成工業株式會社製造)5.7份後，邊升溫到室溫邊攪拌了1小時。一點點地將4,4’-二氟二苯甲酮(東京化成工業株式會社製造)10.4份加入反應液中，在室溫下攪拌了24小時。將反應液一點點地加入冰水200份後，在室溫下靜置15小時，如果將水通過傾析除去，則作為殘渣得到了黏稠固體。在該黏稠固體中加入了甲醇60份後，在室溫下攪拌了15小時。將析出的固體過濾分離後，用柱色譜精製。將精製的淡黃色固體在減壓下在60℃下乾燥，得到了由式(C-I-18)表示的化合物9.8份。Synthesis Example 1 (Pigment Synthesis Example) The following reactions were performed under a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little over 30 minutes under ice cooling, the mixture was stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little, and the mixture was stirred at room temperature for 24 hours. After 200 parts of ice water was added to the reaction solution little by little, it was left to stand at room temperature for 15 hours. If water was removed by decantation, a thick solid was obtained as a residue. After 60 parts of methanol was added to this viscous solid, it was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and then purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to obtain 9.8 parts of a compound represented by the formula (C-I-18).

[化26]

Figure TW201800849AD00030
[Chemical 26]
Figure TW201800849AD00030

以下的反應在氮氣氛下進行。在具備冷卻管和攪拌裝置的燒瓶中投入由式(B-I-7)表示的化合物8.2份、由式(C-I-18)表示的化合物10份和甲苯20份後，接下來，加入***12.2份，在95~100℃下攪拌了3小時。接下來，將反應混合物冷卻到室溫後，用異丙醇170份稀釋。接下來，將稀釋的反應溶液注入飽和食鹽水300份中後，加入甲苯100份，攪拌了30分鐘。接著，停止攪拌，靜置30分鐘，結果分離為有機層與水層。通過分液操作將水層廢棄後，將有機層用飽和食鹽水300份清洗。在有機層中加入適當量的芒硝，攪拌了30分鐘後，得到了過濾、乾燥的有機層。使用蒸發器對得到的有機層進行溶劑餾除，得到了青紫色固體。進而，在減壓下在60℃下對青紫色固體進行乾燥，得到了由式(A-II-18)表示的化合物18.4份。The following reactions were performed under a nitrogen atmosphere. 8.2 parts of a compound represented by formula (BI-7), 10 parts of a compound represented by formula (CI-18), and 20 parts of toluene were put into a flask equipped with a cooling tube and a stirring device, and then phosphorus oxychloride was added. 12.2 parts, stirred at 95 to 100 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped and the mixture was left to stand for 30 minutes. As a result, the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer, and after stirring for 30 minutes, a filtered and dried organic layer was obtained. The obtained organic layer was subjected to solvent distillation using an evaporator to obtain a blue-violet solid. Furthermore, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 18.4 parts of a compound represented by the formula (A-II-18).

[化27]

Figure TW201800849AD00031
[Chemical 27]
Figure TW201800849AD00031

以下的反應在氮氣氛下進行。在具備冷卻管和攪拌裝置的燒瓶中投入由式(A-II-18)表示的化合物8份、甲醇396份後，在室溫下攪拌30分鐘，製備了青色溶液。接下來，在青色溶液中投入水396份後，進而在室溫下攪拌30分鐘，得到了反應溶液。在燒杯中投入水53份，進而將Keggin型磷鎢酸(Aldrich公司製造)11.8份和甲醇53份投入該水中，在空氣氣氛下、室溫下混合，製備了磷鎢酸溶液。 歷時1小時將得到的磷鎢酸溶液滴入前面製備的反應溶液中。進而在室溫下攪拌了30分鐘後，過濾，得到了青色固體。將得到的青色固體投入甲醇200份中，使其分散1小時後，進行過濾，將該操作反複了2次。將通過該操作得到的青色固體投入水200部中，使其分散1小時後，進行過濾，將該操作反複了2次。將通過該操作得到的青色固體在減壓下在60℃下乾燥，得到了由式(A-I-18)表示的化合物17.1份。The following reactions were performed under a nitrogen atmosphere. After putting 8 parts of a compound represented by formula (A-II-18) and 396 parts of methanol into a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes to prepare a cyan solution. Next, 396 parts of water was added to the cyan solution, and the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution. 53 parts of water was put into a beaker, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and they were mixed in an air atmosphere at room temperature to prepare a phosphotungstic acid solution. The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. After further stirring at room temperature for 30 minutes, it was filtered to obtain a cyan solid. The obtained cyan solid was put into 200 parts of methanol, and after dispersing for 1 hour, filtration was performed, and this operation was repeated twice. The cyan solid obtained by this operation was put into 200 parts of water, dispersed for 1 hour, and then filtered, and this operation was repeated twice. The cyan solid obtained by this operation was dried under reduced pressure at 60 ° C to obtain 17.1 parts of a compound represented by the formula (A-I-18).

[化28]

Figure TW201800849AD00032
[Chemical 28]
Figure TW201800849AD00032

合成例2(著色分散液所使用的樹脂) 在具備回流冷凝器、滴液漏斗和攪拌器的燒瓶內，使氮以0.02L/分流入而成為氮氣氛，放入3-甲氧基-1-丁醇200份和乙酸3-甲氧基丁酯105份，邊攪拌邊加熱到70℃。接下來，將甲基丙烯酸60份、丙烯酸3,4-環氧三環[5.2.1.02,6 ]癸酯(由式(II-1)表示的化合物和由式(III-1)表示的化合物的摩爾比50：50的混合物)240份溶解於乙酸3-甲氧基丁酯140份，製備溶液，使用滴液漏斗、歷時4小時將該溶解液滴入保溫於70℃的燒瓶內。另一方面，使用另外的滴液漏斗歷時4小時將聚合引發劑2,2’-偶氮二(2,4-二甲基戊腈)30份溶解於乙酸3-甲氧基丁酯225份的溶液滴入燒瓶內。聚合引發劑的溶液的滴入結束後，在70℃保持4小時，然後冷卻到室溫，得到了固體成分32.6%、酸值110mg-KOH/g(固體成分換算)的樹脂B-1b溶液。得到的樹脂B-1b的重均分子量Mw為13,400，分子量分佈為2.50。Synthesis Example 2 (Resin used for colored dispersion) In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced at 0.02 L / min to form a nitrogen atmosphere, and 3-methoxy-1 was placed therein. -200 parts of butanol and 105 parts of 3-methoxybutyl acetate, heated to 70 ° C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl acrylate (a compound represented by formula (II-1) and a compound represented by formula (III-1) 240 parts of a compound having a molar ratio of 50:50) were dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a flask held at 70 ° C. using a dropping funnel over 4 hours. On the other hand, 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate using another dropping funnel over 4 hours. The solution was dropped into the flask. After the dripping of the solution of the polymerization initiator was completed, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a resin B-1b solution having a solid content of 32.6% and an acid value of 110 mg-KOH / g (in terms of solid content). The obtained resin B-1b had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

＜著色分散液的製備＞ 將由式(A-I-18)表示的化合物10份、分散劑(BYK(註冊商標)-LPN6919(ビックケミー・ジャパン公司製造))2份、樹脂B-1b(固體成分換算)4份、丙二醇單甲基醚乙酸酯84份和0.2mm的氧化鋯珠粒300份混合，使用塗料調理器(Red Devil公司製造)，振盪6小時後，通過過濾將氧化鋯珠粒除去，從而製備了著色分散液(1)。<Preparation of Colored Dispersion Liquid> 10 parts of a compound represented by the formula (AI-18), 2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by ビ 克 ケ ミ ー ・ ジ ャ パ ン)), and resin B-1b (solid content conversion) 4 parts, 84 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2 mm zirconia beads were mixed, and after using a paint conditioner (manufactured by Red Devil) for 6 hours, the zirconia beads were removed by filtration. Thus, a colored dispersion liquid (1) was prepared.

合成例3 採用日本特開2013-122577號公報的合成例3中記載的方法得到了由式(1-32)表示的化合物。Synthesis Example 3 A compound represented by Formula (1-32) was obtained by a method described in Synthesis Example 3 of Japanese Patent Application Laid-Open No. 2013-122577.

[化29]

Figure TW201800849AD00033
[Chemical 29]
Figure TW201800849AD00033

合成例4 在具備回流冷凝器、滴液漏斗和攪拌器的燒瓶內，使適量氮流入而置換為氮氣氛，放入乳酸乙酯141份、丙二醇單甲基醚乙酸酯178份，邊攪拌邊加熱到85℃。接下來，歷時5小時將丙烯酸38份、丙烯酸3,4-環氧三環[5.2.1.02,6 ]癸-8和9-基酯的混合物25份、環己基馬來醯亞胺137份、甲基丙烯酸2-羥基乙酯50份、丙二醇單甲基醚乙酸酯338份的混合溶液滴入。另一方面，歷時6小時滴入將2,2-偶氮二異丁腈5份溶解於丙二醇單甲基醚乙酸酯88份中的混合溶液。滴入結束後，在相同溫度下保持了4小時後，冷卻到室溫，得到了B型黏度(23℃)22mPas、固體成分25.5%、固體成分酸值111mg-KOH/g的共聚物(B-1)溶液。生成的共聚物的重均分子量Mw為7700，分散度為2.1。Synthesis Example 4 In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced into the flask and replaced with a nitrogen atmosphere. 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed while stirring. While heating to 85 ° C. Next, 38 parts of acrylic acid, 25 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 2,6 ] dec-8 and 9-yl ester, and 137 parts of cyclohexylmaleimide were prepared over 5 hours. A mixed solution of 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate was added dropwise. On the other hand, a mixed solution in which 5 parts of 2,2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (B having a B-type viscosity (23 ° C) of 22 mPas, a solid content of 25.5%, and a solid content acid value of 111 mg-KOH / g. -1) solution. The weight average molecular weight Mw of the produced copolymer was 7,700, and the degree of dispersion was 2.1.

對於上述的黏結劑樹脂的重均分子量(Mw)和數均分子量(Mn)的測定，使用GPC法，在以下的條件下進行。 裝置；K2479((股)島津製作所製造) 柱；SHIMADZU Shim-pack GPC-80M 柱溫度；40℃ 溶劑；THF(四氫呋喃) 被檢測液濃度：25mg/mL(溶劑；THF) 流速：1.0mL/min 檢測器：RI 校正用標準物質：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(東曹(股)製造) 將上述得到的聚苯乙烯換算的重均分子量和數均分子量之比作為分散度(Mw/Mn)。The weight average molecular weight (Mw) and number average molecular weight (Mn) of the above-mentioned binder resin were measured using the GPC method under the following conditions. Device; K2479 (manufactured by Shimadzu Corporation) column; SHIMADZU Shim-pack GPC-80M column temperature; 40 ° C solvent; THF (tetrahydrofuran) Test solution concentration: 25mg / mL (solvent; THF) Flow rate: 1.0mL / min Detector: RI Calibration Standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The weight average of polystyrene conversion obtained above The ratio of the molecular weight to the number average molecular weight is taken as the degree of dispersion (Mw / Mn).

實施例1 (著色固化性樹脂組合物1的製備) 將(A)著色劑；由式(1-32)表示的化合物　　　1.0份 (A)著色劑；A1-1；著色分散液(1) 　　　　　855份 (B)黏結劑樹脂；樹脂(B-1)(固體成分換算)　 50份 (C) 聚合性化合物；二季戊四醇六丙烯酸酯(カヤラッドDPHA；日本化藥(股)製造) 　　　　　　　50份 (D) 聚合引發劑；N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺(Irgacure OXE 01；BASF公司製造) 8份 (F) 流平劑；聚醚改性矽油(Toray Silicone SH8400：東麗-道康寧(股)製造) 　　　　　0.2份 (E)溶劑；丙二醇單甲基醚乙酸酯 　580份，和 (P)環氧化合物；2,2-雙(羥基甲基)-1-丁醇的1,2-環氧-4-(2-環氧乙基)環己烷加成物(EHPE3150；大賽璐(股)製造、分子量2234、酸值0mg-KOH/g) 　5份 混合，得到了著色固化性樹脂組合物1。Example 1 (Preparation of colored curable resin composition 1) (A) A colorant; 1.0 part of a compound represented by Formula (1-32) (A) A colorant; A1-1; A colored dispersion (1) 855 Parts (B) binder resin; resin (B-1) (in terms of solid content) 50 parts (C) polymerizable compound; dipentaerythritol hexaacrylate (carbamate DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator; N-benzyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF) 8 parts (F) Leveling agent; polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.2 part (E) solvent; 580 parts of propylene glycol monomethyl ether acetate, and (P) epoxy compound; 2 1,2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 1,2-bis (hydroxymethyl) -1-butanol (EHPE3150; manufactured by Daicel, Inc., molecular weight 2234 (Acid value: 0 mg-KOH / g) 5 parts were mixed to obtain a colored curable resin composition 1.

實施例2 (著色固化性樹脂組合物2的製備) 將(A)著色劑；由式(1-32)表示的化合物　　　1.0份 (A)著色劑；A1-1；著色分散液(1)　　　　　855份 (B)黏結劑樹脂；樹脂(B-1)(固體成分換算)　50份 (C) 聚合性化合物；二季戊四醇六丙烯酸酯(カヤラッドDPHA；日本化藥(股)製造) 　　　　　　　50份 (D) 聚合引發劑；N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺(Irgacure OXE 01；BASF公司製造) 8份 (F) 流平劑；聚醚改性矽油(Toray Silicone SH8400：東麗-道康寧(股)製造) 　　　　　0.2份 (E)溶劑；丙二醇單甲基醚乙酸酯 　580份，和 (P) 環氧化合物；鄰甲酚酚醛清漆型環氧樹脂(スミエポキシESCN-195XL-80；住友化學(股)製造、分子量389、酸值：0.1mg-KOH/g) 　5份 混合，得到了著色固化性樹脂組合物2。Example 2 (Preparation of colored curable resin composition 2) (A) a colorant; 1.0 part of a compound represented by formula (1-32) (A) a colorant; A1-1; a colored dispersion liquid (1) 855 Parts (B) binder resin; resin (B-1) (solid content conversion) 50 parts (C) polymerizable compound; dipentaerythritol hexaacrylate (carbamate DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator; N-benzyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF) 8 parts (F) Leveling agent; polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.2 part (E) solvent; 580 parts of propylene glycol monomethyl ether acetate, and (P) epoxy compound; o 5 parts of cresol novolac epoxy resin (SUSHI ESCN-195XL-80; manufactured by Sumitomo Chemical Co., Ltd., molecular weight 389, acid value: 0.1 mg-KOH / g) was mixed to obtain a colored curable resin composition 2.

實施例3 (著色固化性樹脂組合物3的製備) 將(A)著色劑；由式(1-32)表示的化合物　　　1.0份 (A)著色劑；A1-1；著色分散液(1)　　　　　855份 (B)黏結劑樹脂；樹脂(B-1)(固體成分換算)　50份 (C) 聚合性化合物；二季戊四醇六丙烯酸酯(カヤラッドDPHA；日本化藥(股)製造) 　　　　　　　50份 (D) 聚合引發劑；N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺(Irgacure OXE 01；BASF公司製造) 8份 (F) 流平劑；聚醚改性矽油(Toray Silicone SH8400：東麗-道康寧(股)製造) 　　　　　0.2份 (E)溶劑；丙二醇單甲基醚乙酸酯 　580份，和 (P)環氧化合物；雙酚A型環氧樹脂(JER157S70；三菱化學(股)製造；酸值 0mg-KOH/g) 　5份 混合，得到了著色固化性樹脂組合物3。Example 3 (Preparation of colored curable resin composition 3) (A) a coloring agent; 1.0 part of a compound represented by the formula (1-32) (A) a coloring agent; A1-1; a coloring dispersion (1) 855 Parts (B) binder resin; resin (B-1) (solid content conversion) 50 parts (C) polymerizable compound; dipentaerythritol hexaacrylate (carbamate DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator; N-benzyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF) 8 parts (F) Leveling agent; polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.2 part (E) solvent; 580 parts of propylene glycol monomethyl ether acetate, and (P) epoxy compound; bis Phenol A type epoxy resin (JER157S70; manufactured by Mitsubishi Chemical Corporation; acid value 0 mg-KOH / g) 5 parts were mixed, and the colored curable resin composition 3 was obtained.

比較例1 將(A)著色劑；C.I.顏料藍15：6(顏料)　　　29.3份 丙烯酸系顏料分散劑　　　　　　　　　　　10份 丙二醇單甲基醚乙酸酯 　　　　　　 194份 混合，使用珠磨機使顏料分散，接著， 將(A)著色劑；1-1；由式(1-32)表示的化合物 3份 (B)黏結劑樹脂；樹脂(B-1)(固體成分換算) 　50份 (C)聚合性化合物；二季戊四醇六丙烯酸酯(日本化藥(股)製造) 50份 (D) 聚合引發劑；OXE 01(BASF公司製造)　　8份 (F) 流平劑；聚醚改性矽油(Toray Silicone SH8400：東麗-道康寧(股)製造) 　　　　　0.2份 (E)溶劑；丙二醇單甲基醚乙酸酯 　　488份和 (E)溶劑；丙二醇單甲基醚 　　　　　　　171份 混合，得到了著色固化性樹脂組合物4。Comparative Example 1 (A) colorant; CI Pigment Blue 15: 6 (pigment) 29.3 parts of acrylic pigment dispersant 10 parts of propylene glycol monomethyl ether acetate 194 parts were mixed, and the pigment was dispersed using a bead mill, and then, (A) a colorant; 1-1; 3 parts of a compound represented by the formula (1-32) (B) a binder resin; resin (B-1) (solid content conversion) 50 parts (C) a polymerizable compound; Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) polymerization initiator; OXE 01 (manufactured by BASF) 8 parts (F) leveling agent; polyether modified silicone oil (Toray Silicone SH8400: East Li-Dow Corning Co., Ltd. 0.2 part (E) solvent; 488 parts of propylene glycol monomethyl ether acetate and (E) solvent; 171 parts of propylene glycol monomethyl ether were mixed to obtain a colored curable resin composition 4.

＜濾色器(著色圖案)的製作＞ 在5cm見方的玻璃基板(Eagle 2000；康寧公司製造)上採用旋塗法塗布著色固化性樹脂組合物1後，在100℃下預烘焙3分鐘，形成了著色組合物層。放冷後，使形成了該著色組合物層的基板與石英玻璃製光掩模的間隔為80μm，使用曝光機(TME-150RSK；トプコン(股)製造)，在大氣氣氛下、以35mJ/cm2 的曝光量(365nm基準)進行光照射。作為光掩模，使用了形成了50μm線和間隙圖案的光掩模。將光照射後的著色組合物層在顯影液(以質量分率計，分別包含氫氧化鉀0.05%和丁基萘磺酸鈉0.2%的水溶液)中在25℃下浸漬顯影60秒，水洗後，在烘箱中、於230℃下進行30分鐘後烘焙，得到了著色圖案。 對於著色固化性樹脂組合物2~4，也同樣地得到了著色圖案。<Preparation of a color filter (colored pattern)> A 5 cm-square glass substrate (Eagle 2000; manufactured by Corning Corporation) was used to apply the colored curable resin composition 1 by spin coating, and then pre-baked at 100 ° C for 3 minutes to form A coloring composition layer is provided. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the photomask made of quartz glass was 80 μm, using an exposure machine (TME-150RSK; manufactured by Tektronix Co., Ltd.) in an atmosphere of 35 mJ / cm Light exposure was performed at an exposure amount of 2 (based on 365 nm). As the photomask, a photomask in which a 50 μm line and gap pattern was formed was used. The coloring composition layer after light irradiation was immersed and developed in a developing solution (in terms of mass fraction, an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfonate) at 25 ° C for 60 seconds. After baking in an oven at 230 ° C. for 30 minutes, a colored pattern was obtained. The colored curable resin compositions 2 to 4 also obtained colored patterns in the same manner.

＜膜厚測定＞ 對於得到的各著色圖案，使用膜厚測定裝置(DEKTAK3；日本真空技術(股)製造))測定了膜厚。將結果示於表5中。<Film thickness measurement> The thickness of each obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). The results are shown in Table 5.

＜色度評價＞ 對於得到的各著色圖案，使用測色機(OSP-SP-200；奧林巴斯(股)製造)測定分光，使用C光源的特性函數，測定了CIE的XYZ表色系中的xy色度座標(x、y)和三刺激值中的Y。Y越大，表示明度越高。將結果示於表5中。<Colorimetric Evaluation> For each of the obtained colored patterns, spectrometry was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and a characteristic function of a C light source was used to measure the XYZ color system of CIE Xy chromaticity coordinates (x, y) in Y and Y in tristimulus values. The larger Y is, the higher the brightness is. The results are shown in Table 5.

＜濾色器(著色塗膜)的製備＞ 在5cm見方的玻璃基板(Eagle 2000；康寧公司製造)上採用旋塗法塗布著色固化性樹脂組合物1後，在100℃下預烘焙3分鐘，形成了著色組合物層。放冷後，使形成了該著色組合物層的基板與石英玻璃製光掩模的間隔為80μm，使用曝光機(TME-150RSK；トプコン(股)製造)，在大氣氣氛下、以35mJ/cm2 的曝光量(365nm基準)對著色組合物層進行光照射。作為光掩模，使用了形成了50μm線和間隙圖案的光掩模。通過在烘箱中、230℃下進行30分鐘後烘焙，從而得到了著色塗膜。 對於著色固化性樹脂組合物2~4也同樣地得到了著色塗膜。<Preparation of a color filter (colored coating film)> After the colored curable resin composition 1 was applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Corporation) by a spin coating method, pre-baked at 100 ° C for 3 minutes, A colored composition layer was formed. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the photomask made of quartz glass was 80 μm, using an exposure machine (TME-150RSK; manufactured by Tektronix Co., Ltd.) in an atmosphere of 35 mJ / cm An exposure amount (based on 365 nm) of 2 was used to irradiate the colored composition layer with light. As the photomask, a photomask in which a 50 μm line and gap pattern was formed was used. A post-baking was performed at 230 ° C. for 30 minutes in an oven to obtain a colored coating film. The colored curable resin compositions 2 to 4 also obtained colored coating films in the same manner.

＜耐溶劑性評價＞ 使用測色機(OSP-SP-200；OLYMPUS公司製造)測定了得到的著色塗膜的色度。接著，將得到的著色塗膜在23℃下保持恒定的大幅過量的N-甲基-2-吡咯烷酮中浸漬30分鐘，同樣地測定了浸漬後的著色塗膜的色度。 作為色差的評價標準，如果ΔEab＊為3以下，則幾乎沒有發現色調變化，顯示出作為濾色器時良好的特性，如果ΔEab＊超過3，則能夠確認色調變化，這是作為濾色器時具有問題的基準。將結果示於表5中。<Evaluation of Solvent Resistance> The color of the obtained colored coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). Next, the obtained colored coating film was immersed in a large excess of N-methyl-2-pyrrolidone kept constant at 23 ° C. for 30 minutes, and the chromaticity of the colored coating film after the immersion was measured in the same manner. As a criterion for evaluating the color difference, if ΔEab * is 3 or less, there is almost no change in hue, which shows good characteristics when used as a color filter. If ΔEab * exceeds 3, the change in hue can be confirmed. Problematic benchmark. The results are shown in Table 5.

[表5]

Figure TW201800849AD00034
產業上的可利用性[table 5]
Figure TW201800849AD00034
Industrial availability

採用本發明的著色固化性樹脂組合物，能夠形成具有高明度、並且耐溶劑性良好的濾色器。According to the colored curable resin composition of the present invention, a color filter having high brightness and good solvent resistance can be formed.

(無)(no)

Claims (5)

一種固化性樹脂組合物，其為含有著色劑(A)、黏結劑樹脂(B)、聚合性化合物(C)、聚合引發劑(D)和環氧化合物(P)的著色固化性樹脂組合物，其中，環氧化合物(P)與黏結劑樹脂(B)不同，著色劑(A)為包含化合物(Aa)的著色劑，化合物(Aa)由具有色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成，相對於著色劑(A)的總量，環氧化合物(P)的含有率為0.1質量%以上且60質量%以下。A curable resin composition which is a colored curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an epoxy compound (P). Among them, the epoxy compound (P) is different from the binder resin (B), the colorant (A) is a coloring agent containing the compound (Aa), and the compound (Aa) is composed of a cation having a pigment skeleton, and An anion composition of at least one element selected from molybdenum, silicon, and phosphorus and an oxygen compound. The content of the epoxy compound (P) is 0.1% by mass or more and 60% by mass or less based on the total amount of the colorant (A). . 如請求項1所述的著色固化性樹脂組合物，其中，黏結劑樹脂(B)為具有來自從不飽和羧酸和不飽和羧酸酐中選擇的至少1種的單體的結構單元(a)、和來自具有烯屬不飽和鍵和環狀醚結構的單體的結構單元(b)的共聚物。The colored curable resin composition according to claim 1, wherein the binder resin (B) is a structural unit (a) having at least one monomer selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides. And a copolymer of a structural unit (b) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure. 如請求項1所述的著色固化性樹脂組合物，其中，由具有色素骨架的陽離子、和來自含有從鎢、鉬、矽和磷中選擇的至少1個元素和氧的化合物的陰離子構成的化合物(Aa)為由式(A-I)表示的化合物： [化1]
Figure TW201800849AC00001
式(A-I)中，R41 ~R44 相互獨立地表示可被取代的氨基、或可被鹵素原子取代的碳數1~20的飽和烴基、碳數2~20的烷基、該碳數2~20的烷基中所含的亞甲基被氧原子替換的基團、可具有取代基的芳香族烴基、可具有取代基的芳烷基或氫原子，R41 與R42 可結合並與它們結合的氮原子一起形成環，R43 與R44 可結合並與它們結合的氮原子一起形成環， R47 ~R54 相互獨立地表示氫原子、鹵素原子、硝基、羥基、或碳數1~8的烷基，在構成該烷基的亞甲基間可***氧原子，R48 與R52 可相互結合而形成-NH-、-O-、-S-或-SO2 -， R41 ~R44 和R47 ~R54 中，鄰接的亞甲基不會同時被替換為氧原子，另外，烷基的末端的亞甲基也不會被替換為氧原子， 環T1 表示可具有取代基的芳香族雜環。 [Y]m- 表示含有選自鎢、鉬、矽和磷中的至少1個元素、和氧的m價的陰離子， m表示2~14的整數， 再有，在1個分子中含有多個由下述式表示的陽離子的情況下，它們可以為相同的結構，也可以為不同的結構， [化2]
Figure TW201800849AC00002
式中，環T1 、R41 ~R44 和R47 ~R54 分別與上述同義。The colored curable resin composition according to claim 1, which is a compound composed of a cation having a pigment skeleton and an anion derived from a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen. (Aa) is a compound represented by formula (AI):
Figure TW201800849AC00001
In the formula (AI), R 41 to R 44 independently represent an amino group which may be substituted, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and the carbon number 2 A group in which a methylene group contained in an alkyl group of ~ 20 is replaced by an oxygen atom, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom, R 41 and R 42 may be combined and combined with The nitrogen atoms to which they bind together form a ring. R 43 and R 44 can combine to form a ring with the nitrogen atom to which they bind. R 47 to R 54 independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a carbon number. An alkyl group of 1 to 8 can insert an oxygen atom between the methylene groups constituting the alkyl group, and R 48 and R 52 can be combined with each other to form -NH-, -O-, -S-, or -SO 2- , R and 41 ~ R 44 R 47 ~ R 54, the adjacent methylene group is replaced not simultaneously an oxygen atom, additionally, a methylene group end is not replaced by an oxygen atom, T 1 represents the ring may Aromatic heterocyclic ring having a substituent. [Y] m- represents an m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen, m represents an integer of 2 to 14, and more than one is contained in one molecule. In the case of cations represented by the following formulas, they may have the same structure or different structures. [化 2]
Figure TW201800849AC00002
In the formula, the rings T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as those described above. 如請求項1~3中的任一項所述的著色固化性樹脂組合物形成的濾色器。The color filter formed by the colored curable resin composition as described in any one of Claims 1-3. 一種液晶顯示裝置，其包含如請求項4所述的濾色器。A liquid crystal display device includes the color filter according to claim 4.
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