TWI726998B - Colored curable resin composition, color filter and liquid crystal display device - Google Patents

Colored curable resin composition, color filter and liquid crystal display device Download PDF

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TWI726998B
TWI726998B TW106105729A TW106105729A TWI726998B TW I726998 B TWI726998 B TW I726998B TW 106105729 A TW106105729 A TW 106105729A TW 106105729 A TW106105729 A TW 106105729A TW I726998 B TWI726998 B TW I726998B
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朴昭妍
金兌昱
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南韓商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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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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  • Physics & Mathematics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
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Abstract

本發明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、包含其的濾色器和液晶顯示裝置。著色固化性樹脂組合物，是含有著色劑(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，該化合物(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。The present invention provides a colored curable resin composition capable of forming a color filter with high brightness and good solvent resistance, a color filter and a liquid crystal display device containing the same. The colored curable resin composition contains a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an epoxy compound (P) (however, with the binder resin ( B) different) coloring curable resin composition, the colorant (A) is a coloring agent containing compound (Aa), the compound (Aa) is composed of a cation having a pigment skeleton, and derived from tungsten, molybdenum, silicon and phosphorus The anion composition of the compound of at least one element and oxygen selected from the above has a content rate of the epoxy compound (P) of 0.1% by mass or more and 60% by mass or less with respect to 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 Colored curable resin compositions can be used to manufacture color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma display devices. 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 02_image001
[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[化1]
Figure 02_image001
[In the formula (1), R 1 and R 2 independently represent a phenyl group which may have a substituent. R 3 and R 4 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 by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained can be substituted by an alkyl group having 1 to 3 carbons or an alkoxy group having 1 to 3 carbons, and the -CH 2 -contained in the above saturated hydrocarbon group can be -O-, -CO- or -NR 11 -Replace. R 1 and R 3 can form a ring containing a nitrogen atom together, and R 2 and R 4 can 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 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. Z + represents + N(R 11 ) 4 , Na + or K + . R 9 and R 10 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 carbons, or an aralkyl group having 7 to 10 carbons. ] Prior Art Documents Patent Documents

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Problems to be Solved by the Invention However, the color filter obtained may have low brightness and insufficient solvent resistance. The subject of the present invention is to provide a colored curable resin composition capable of forming a color filter having 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 main points of the present invention are 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, with Binder resin (B) is different) coloring curable resin composition, the coloring agent (A) is a coloring agent containing the compound (Aa), the compound (Aa) is composed of a cation having a pigment skeleton, and derived from tungsten, molybdenum, The anion composition of a compound of at least one element selected from silicon and phosphorus and oxygen, and the content of the epoxy compound (P) relative to the total amount of the colorant (A) is 0.1% by mass or more and 60% by mass or less. [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 acid and unsaturated carboxylic anhydride ( a) A copolymer with structural unit (b) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure. [3] The coloring curable resin composition according to [1] or [2], which is composed of a cation having a pigment skeleton, and a compound 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 formula (AI).

[化2]

Figure 02_image003
[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。[化2]
Figure 02_image003
[In formula (AI), R 41 to R 44 independently represent an amino group that may be substituted, or a saturated hydrocarbon group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons, which may be substituted with a halogen atom, and the number of carbons A group in which the methylene group contained in the alkyl group of 2 to 20 is replaced by an oxygen atom, an optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group, or a hydrogen atom. R 41 and R 42 may be combined with the nitrogen atom to which they are combined to form a ring, and R 43 and R 44 may be combined with the nitrogen atom to which they are combined to form a ring. R 47 to R 54 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 combine with each other to form -NH-, -O-, -S- or -SO 2 -. In R 41 to R 44 and R 47 to R 54 , adjacent methylene groups are not replaced with oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not replaced with oxygen atoms. 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. In addition, 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 02_image005
[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[化3]
Figure 02_image005
[In the formula, ring T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as above. ]] [4] A color filter formed of the coloring curable resin composition according to any one of [1] to [3]. [5] A liquid crystal display device including the color filter described in [4]. The 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 with 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 preferred embodiments 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, unlike the binder resin (B)), the epoxy compound (P) is contained in a predetermined amount relative to the total amount of the coloring agent.

＜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)。<Coloring agent (A)> The coloring agent (A) is preferably 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) (hereinafter sometimes referred to as compound (Aa)) coloring agent. The compound (Aa) may be singly or may contain two or more kinds. In addition, as the colorant (A), a dye (Ab) may be further included.

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 this partial structure includes a structure for expressing characteristics of the 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 of the cation constituting the compound (Aa) include azo skeleton, xanthene skeleton, azine skeleton, cyanine skeleton, acridine skeleton, anthraquinone skeleton, squaraine skeleton, etc., which have an onium structure. ; Triarylmethane skeleton; One or more of the aromatic hydrocarbon rings of the triarylmethane skeleton becomes a dye skeleton of an aromatic heterocyclic ring. Among them, preferred examples include a xanthene skeleton into which an onium structure is introduced, a cyanine skeleton into which an onium structure is introduced, a squaraine skeleton into which an onium structure is introduced, a triarylmethane skeleton, and an aromatic hydrocarbon ring forming a triarylmethane skeleton. At least one dye skeleton becomes an aromatic heterocyclic ring, and more preferably one or more of the aromatic hydrocarbon rings of the triarylmethane skeleton becomes an aromatic heterocyclic dye skeleton.

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 base compound that becomes an anion is a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen. For example, two types of polybasic acids selected from tungstic acid, molybdenum acid, silicic acid, and phosphoric acid can be cited. A combination of the above (preferably 3); a homopolyacid containing at least one element selected from tungsten, molybdenum, silicon and phosphorus, and oxygen; containing two or more selected from tungsten, molybdenum, silicon and phosphorus Heteropoly acids of elements, and oxygen, etc. 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 the heteropoly acid or isopoly acid containing tungsten include Keggin type phosphotungstic acid ion α-[PW 12 O 40 ] 3- and Dawson type phosphotungstic acid ion α-[P 2 W 218 O 62 ] 6- , β-[P 2 W 18 O 62 ] 6- , Keggin-type tungstic 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 their mixtures.

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 easiness of synthesis and post-treatment, preferably phosphotungstic acid anion phosphotungstic acid ion Keggin type, Dawson type phosphotungstic acid ion; Keggin-type anion Silicotungstic acid Silicotungstic acid ion, [W 10 O 32] 4- Among other tungsten-based homopolyacid anions, phosphotungstic acid anions and tungsten-based homopolyacid anions are more preferable.

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。Examples of the compound (Aa) composed of a cation having a xanthene dye 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 Red 81, 81 :1, 81:2, 81:3, 81:4, 81:5, 169; CI Pigment Violet 1, 1:1, 1:2, 2:2, etc.

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。In addition, as a compound (Aa) composed of a cation having a triarylmethane dye skeleton and an anion derived from a compound containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus, and oxygen, 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: 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))。As the compound (Aa), a compound represented by formula (A-I) (hereinafter also referred to as (A-I)) is preferred.

[化4]

Figure 02_image007
[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。[化4]
Figure 02_image007
[In formula (AI), R 41 to R 44 independently represent a substituted amino group, or a saturated hydrocarbon group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons, which may be substituted by a halogen atom, and the number of carbons A group in which the methylene group contained in the alkyl group of 2 to 20 is replaced by an oxygen atom, an optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group, or a hydrogen atom. R 41 and R 42 may be combined with the nitrogen atom to which they are combined to form a ring, and R 43 and R 44 may be combined with the nitrogen atom to which they are combined to form a ring. R 47 to R 54 independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, 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 combine with each other to form -NH-, -O-, -S- or -SO 2 -. In R 41 to R 44 and R 47 to R 54 , adjacent methylene groups are not replaced with oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not replaced with oxygen atoms. 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. In addition, 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 02_image009
[式中，環T1 、R41 ~R44 和R47 ~R54 分別與上述同義。]][化5]
Figure 02_image009
[In the formula, ring T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as 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 condensed ring. In addition, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of monocyclic aromatic heterocyclic rings include 5-membered rings containing nitrogen atoms such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, and thiazole ring; and 5 membered rings containing no nitrogen atom such as furan ring and thiophene ring. 6-membered ring containing nitrogen atoms such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc. As the aromatic heterocyclic ring of the condensed ring, indole ring, benzimidazole ring, benzo Condensed rings containing nitrogen atoms such as thiazole rings and quinoline rings; condensed rings containing no nitrogen atoms such as benzofuran rings. Examples of the substituent that the aromatic heterocyclic ring of ring T 1 may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbons which may have substituents such as a halogen atom, and a halogen atom or a carbon number of 1 to 20. Substituents such as alkyl groups of 10 include aromatic hydrocarbon groups having 6 to 20 carbon atoms, and amino groups that may have substituents such as alkyl groups having 1 to 10 carbon atoms. Wherein the aromatic heterocyclic ring T 1 is preferably an aromatic heterocyclic containing a nitrogen atom, 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。In addition, the ring T 1 is more preferably a ring represented by the formula (Ab2-x1).

[化6]

Figure 02_image011
[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。][化6]
Figure 02_image011
[Ring T 2 represents an aromatic heterocyclic ring. R 45 and R 46 independently represent a saturated hydrocarbon group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons, and an alkyl group with 2 to 20 carbons. The methylene group contained in the alkyl group with 2 to 20 carbons is oxygenated. An atom-replaceable group, an aromatic hydrocarbon group that may have a substituent, an aralkyl group that may have a substituent, or a hydrogen atom. R 45 and R 46 may be combined to form a ring together with the nitrogen atom to which they are bonded. However, adjacent methylene groups are not replaced with oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not replaced with oxygen atoms. R 55 represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent. k1 represents 0 or 1. * Indicates the bonding end to the 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。As the aromatic heterocyclic ring of the ring T 2 , the same rings as the aromatic heterocyclic ring exemplified in the ring T 1 can be cited. Furthermore, ring T 1 is more preferably a ring represented by formula (Ab2-y1).

[化7]

Figure 02_image013
[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。][化7]
Figure 02_image013
[R 56 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. 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 have the same meaning as above. * Indicates the bonding end to the carbocation. ]

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

[化8]

Figure 02_image015
[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。][化8]
Figure 02_image015
[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 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons. 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 represents 0 or 1. * Indicates the bonding end to the carbocation. ]

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

[化9]

Figure 02_image017
[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。][化9]
Figure 02_image017
[R 60 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons. R 59 represents the same meaning as above. * Indicates the bonding end to the 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. As the linear or branched saturated hydrocarbon group, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and two Straight-chain alkyl such as decaalkyl; branched alkyl such as isopropyl, isobutyl, isopentyl, neopentyl and 2-ethylhexyl, etc. The carbon number of the saturated hydrocarbon group is preferably 1-10, more preferably 1-8, and still more preferably 1-6.

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, adamantyl, and the like. The carbon number of the cyclic saturated hydrocarbon group is preferably 3-10, and more preferably 6-10.

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 by halogen atoms or substituted or unsubstituted amino groups. Examples of the substituted or unsubstituted amino group include an amino group; 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, it is preferably substituted with a halogen atom such as forming a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit. As such a saturated hydrocarbon group having 1 to 20 carbon atoms substituted with a substituted amino group or a halogen atom, for example, a group represented by the following formula can be cited. In the following formula, * represents a bonding terminal to a nitrogen atom.

[化10]

Figure 02_image019
[化10]
Figure 02_image019

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 groups having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by R 41. In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R 57 include groups having 1 to 10 carbon atoms among the linear or branched saturated hydrocarbon groups 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。As for 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 an alkyl group is 2-10, More preferably, it is 2-8. In addition, 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, adjacent methylene groups are not replaced with oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not replaced with oxygen atoms. In a preferable specific example, the group represented by the following formula can be mentioned. In the following formula, * represents a bonding terminal to a nitrogen atom.

[化11]

Figure 02_image021
[化11]
Figure 02_image021

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 by an oxygen atom includes, for example, an alkoxyalkyl group; or (alkoxyalkoxy)alkyl, (alkoxyalkoxyalkyl) (Oxy) alkyl, (alkoxy alkoxy alkoxy alkoxy) alkyl, (alkoxy alkoxy alkoxy alkoxy alkoxy) alkyl, (alkoxy alkoxy The number of repetitions of the alkoxy unit is, for example, 1 to 6, preferably 1 to 4, and more preferably 1 to 2, and the number of repetitions of the alkoxy unit is, for example, polyalkoxyalkyl groups such as alkoxyalkoxyalkyloxyalkyloxy) alkyl groups.

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 optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 41 to R 46 , R 55 , R 56 and R 58 to R 60 preferably has a carbon number of 6 to 15, and more preferably a carbon number 6~12. Examples of the aromatic hydrocarbon group include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, naphthyl, and tolyl And xylyl group, more preferably, phenyl group can be mentioned. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; carbon atoms such as chloromethyl and trifluoromethyl. Haloalkyl with 1 to 6; Alkoxy with 1 to 6 carbons such as methoxy and ethoxy; Hydroxyl; Sulfamoyl; Alkylsulfonyl with 1 to 6 carbons such as methylsulfonyl ; C1-C6 alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl. As a specific example of the aromatic hydrocarbon group which may be substituted, the group represented by the following formula is mentioned, for example. In the following formula, * represents a bonding terminal to a nitrogen atom.

[化12]

Figure 02_image023
[化12]
Figure 02_image023

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 optionally substituted aralkyl group represented by R 41 to R 46 and R 59 include alkylene groups having 1 to 5 carbon atoms such as methylene, ethylene, and propylene, and the aromatic A group formed by combining the groups described by the hydrocarbon group, etc.

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 formed by combining R 41 and R 42 with the nitrogen atom to which they are bound, a ring formed by combining R 43 and R 44 with the nitrogen atom to which they are bound, and a nitrogen bound to and bound to R 45 and R 46 The ring formed by the atoms includes a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring and other nitrogen-containing non-aromatic 4 to 7-membered rings, preferably a pyrrolidine ring, a piperidine ring, etc. A 4- to 7-membered ring with 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 carbons or an aromatic hydrocarbon group that may have a substituent is preferable, and it is more preferable that each independently have a carbon number of 1 to The saturated hydrocarbon group of 8 or the 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 terminal to a nitrogen atom.

[化13]

Figure 02_image025
[化13]
Figure 02_image025

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 carbons, a group in which an oxygen atom is inserted between the carbon atoms of an alkyl group having 2 to 20 carbons, or an aromatic hydrocarbon group that may have a substituent. Or R 45 and R 46 are combined and form a ring together with the nitrogen atom to which they are combined. A more preferred embodiment is the following: R 45 to R 46 are 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 Combines to form a 4- to 7-membered ring with only one nitrogen atom as a heteroatom. In the following formula, * represents a bonding terminal to a nitrogen atom.

[化14]

Figure 02_image027
[化14]
Figure 02_image027

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 alkyl group having 1 to 8 carbon atoms represented by R 47 to R 54 and the group in which an oxygen atom is inserted between the carbon atoms of the alkyl group having 2 to 8 carbon atoms include those from the above-mentioned R 41 to 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 exemplified. In the following formula, * represents a bonding terminal to a carbon atom.

[化15]

Figure 02_image029
[化15]
Figure 02_image029

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 standpoint of ease of synthesis, R 47 to R 54 are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 independently of each other, and more preferably independently of each other are 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。As the cation part of the formula (Ab2), as shown in Table 1 below, cation 1 to cation 14 represented by the formula (Ab2-1) and the like can be cited. In the table, * represents the bonded end.

[化16]

Figure 02_image031
[化16]
Figure 02_image031

[表1]

Figure 02_image033
[Table 1]
Figure 02_image033

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 the bonding end.

[化17]

Figure 02_image035
[化17]
Figure 02_image035

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。In addition, as the cation part of the formula (Ab2), as shown in Table 2 below, cation 15 to cation 18 represented by the formula (Ab2-2) and the like can also be cited. In the table, * represents the bonded end.

[化18]

Figure 02_image037
[化18]
Figure 02_image037

[表2]

Figure 02_image039
[Table 2]
Figure 02_image039

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 formulas. In the formula, * represents the bonding end.

[化19]

Figure 02_image041
[化19]
Figure 02_image041

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 portion of the formula (Ab2), cation 1 to cation 6, cation 11 to cation 14 are preferable, cation 1, cation 2, or cation 12 to cation 14 are more preferable, and cation 12 is still more preferable.

作為化合物(Aa)，可列舉出由下述式表示的化合物。As a compound (Aa), the compound represented by the following formula is mentioned.

[表3]

Figure 02_image043
[table 3]
Figure 02_image043

[表4]

Figure 02_image045
[Table 4]
Figure 02_image045

其中，化合物優選為由式(Aa2-53)表示的化合物。Among them, the compound is preferably a compound represented by 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 formula (A-I) can be produced according to the method described in JP 2015-28121 A.

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。Dyestuffs (Ab) Examples of dyes include compounds with hue substances other than pigments classified in the Color Index (published by The Society of Dyers and Colourists), and well-known dyes described in the dyeing notes (Sei Dyers Co., Ltd.) .

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 dyes include azo dyes (for example, monoazo dyes, diazo dyes, azide dyes, metal complex azo dyes, etc.), anthraquinone dyes, indigo dyes, phthalocyanine dyes, and pyrazolones. Dyes, stilbene dyes, carotenoid dyes, thiazole dyes, quinoline dyes, diarylmethane dyes, triarylmethane dyes, acridine dyes, xanthene dyes, azine dyes, thiazine dyes, oxazine dyes , Cyanine dyes, indamine dyes, indophenol dyes, naphthalene dimethyl imine dyes, perylene dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, methylene amine dyes, squaraine dyes, styryl Dyes, coumarin dyes, quinoline dyes, porphyrazine dyes, nitro dyes, or nitroso dyes, etc., these are preferably organic solvent soluble. These dyes can be used individually or in combination of 2 or more types.

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。Among them, preferred are xanthene dyes, triarylmethane dyes, coumarin dyes, anthraquinone dyes, porphyrazine dyes, azo dyes, thiazine dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes, and cyanines. Dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, methyleneamine dyes, squaraine dyes, acridine dyes, styryl dyes, quinoline dyes and nitro dyes, more preferably xanthene dyes, triaryl dyes Methane dyes, coumarin dyes, anthraquinone dyes, azo dyes, and porphyrazine dyes, and xanthene dyes and azo dyes are particularly preferred. Among these, the sulfonamide of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the sulfonamide of C.I. Acid Violet 102, or the quaternary ammonium salt of C.I. Acid Violet 102 are preferable.

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 xanthene dyes, in addition to the above-exemplified compounds, for example, CI Acid Red 51 (hereinafter the expression "CI Acid Red" is omitted, only the serial number is described, and the others are the same), 52, 87, 92, 94, 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), Sulorhodamine G, the xanthene dye described in JP 2010-32999 A 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.

[化20]

Figure 02_image047
[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。][化20]
Figure 02_image047
[In formula (a1-1), R 1 to R 4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or a carbon 6 to 10 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 together form a ring containing a nitrogen atom, and R 3 and R 4 may together form a ring containing a nitrogen atom. In R 1 to R 4 , adjacent methylene groups are not replaced with oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not replaced with oxygen atoms. 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 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 + , and 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The -CH 2 -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR 8 -replacement, R 9 and R 10 can 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 carbons, or an aralkyl group having 7 to 10 carbons. ]

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。In addition, as the xanthene dye, a compound represented by formula (a1-2) (hereinafter may be referred to as "compound (a1-2)") is also preferable. The compound (a1-2) may be a tautomer.

[化21]

Figure 02_image049
[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。][化21]
Figure 02_image049
[In formula (a1-2), R 21 and R 22 independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbons, and the hydrogen atoms contained in the saturated hydrocarbon groups of R 21 and R 22 may be replaced by 6 carbon atoms. ~10 aromatic hydrocarbon group or halogen atom substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a C 1 to 3 alkoxy group, the above-mentioned R 21 , R 22 saturated hydrocarbon group contains -CH 2 -Can be replaced by -O-, -CO- or -NR 11 -. R 23 and R 24 independently represent an alkyl group having 1 to 4 carbons, an alkylsulfanyl group having 1 to 4 carbons, or an alkylsulfonyl group having 1 to 4 carbons. R 21 and R 23 may together form a ring containing a nitrogen atom, and R 22 and R 24 may together form a ring containing a nitrogen atom. p and q represent an integer from 0 to 5 independently of each other. When p is 2 or more, the plurality of R 23 may be the same or different, and when q is 2 or more, the plurality of R 24 may be the same or different. R 11 represents 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 carbons in R 21 and R 22 include groups having 1 to 10 carbons among the groups in R 8. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that can be possessed as a substituent include the same groups as those in R 1. As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example. R 21 and R 22 are preferably a monovalent saturated hydrocarbon group having 1 to 3 carbons independently of each other.

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 a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 23 and R 24 include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropyl. Sulfuryl and so on. 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 so on. As R 23 and R 24 , an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is still more preferable.

作為p和q，優選0~2的整數，優選1或2。As p and q, an integer of 0 to 2 is preferable, and 1 or 2 is preferable.

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 triarylmethane dyes 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 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。The coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. Examples of coumarin dyes 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, etc. .

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 anthraquinone dyes include CI Solvent Yellow 117 (hereinafter the expression "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。The porphyrazine dye is a compound having a porphyrazine skeleton in the molecule. In addition, when the porphyrazine 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 other dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes, etc. can be used, and a known dye is used for each. Examples of azo dyes include CI direct yellow (hereinafter the expression "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 metal complex salt azo dyes include C.I. Solvent Red 125, 130; C.I. Solvent Yellow 21, and the compounds described in JP 2010-170116 A or JP 2011-215572 A.

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, C.I. Basic Yellow 1, and the like. Examples of oxazine dyes 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, and 199, C.I. Acid Blue 249, and C.I. Basic Blue 3. Examples of quinophthalone dyes include C.I. Acid Yellow 3, C.I. Disperse Yellow 143, and the like. Examples of cyanine dyes include copper phthalocyanine (C.I. 74160) and the like. As the quinone imine dye, C.I. Basic Blue 3, C.I. Basic Blue 9 and the like can be mentioned. 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 quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, and C.I. Disperse Yellow 64. Examples of nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, and the like. Examples of azine dyes include C.I. Acid Blue 59, 102 and the like. As the indigo dye, C.I. Acid Blue 74 and the like can be mentioned.

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 producing the colored curable resin composition of the present invention, the compound (Aa) is preferably dissolved or dispersed and mixed in a solvent to prepare a colored dispersion liquid. By mixing the colored dispersion, the binder resin (B), the polymerizable compound (C), the polymerization initiator (D), etc., to prepare the 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 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, etc. These may be used alone or in plural. In the colored dispersion liquid, the content of the solvent 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 relative to 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 dispersing the compound (Aa) in a solvent to prepare a colored dispersion, it is preferable to use a dispersant. As the dispersant, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. can be used. These pigment dispersants may be used alone or in combination of two or more kinds. As a pigment dispersant, it is represented by a trade name, and includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Cerusbes (manufactured by Hypeka Co., Ltd.), and EFKA (manufactured by BASF Corporation) ), Ajisbe (manufactured by Ajinomoto Fyntec Co., Ltd.), Disperbyk (manufactured by Makkomi), etc.

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。In the colored dispersion, the content of the dispersant relative to 100 parts by mass of the compound (Aa) 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 ~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 may contain a part or all of the dye (Ab) in advance, preferably all. The amount of the dye (Ab) in the coloring 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 relative 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。In the case of preparing a colored dispersion by dispersing the compound (Aa) in a solvent, the colored dispersion may contain a part or all of the binder resin (B) contained in the colored curable resin composition, and preferably contains a part. By containing the binder resin (B) in advance, it is possible to further improve the dispersion stability when it is made into a colored curable resin composition. The content of the binder resin (B) in the colored dispersion 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 relative to 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 include a pigment (Ac) in addition to the compound (Aa) and the dye (Ab). As the pigment, for example, a pigment classified as a pigment in the Excellence Index (published by The Society of Dyers and Colourists) (however, it is 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 pigments: 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, Orange pigments such as 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214: 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, Cyan pigments such as 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265: 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. Regarding these pigments, for each color, one type of pigment or multiple types of pigments may be used, 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 treated with rosin, surface treatment using pigment derivatives introduced with acidic or basic groups, grafting treatment to the surface of the pigment using polymer compounds, etc., and microparticulation by the sulfuric acid microparticulation method, etc. Treatment, cleaning treatment using organic solvents, water, etc. for removing impurities, removal treatment using ion exchange methods such as ionic impurities, etc. The particle diameter of the pigment is preferably approximately uniform. The pigment can be made into a pigment dispersion liquid in a state uniformly dispersed in the pigment dispersant solution by carrying out the dispersion treatment by containing the pigment dispersant. Regarding the pigment, the dispersion treatment may be performed individually, or a plurality of types may be mixed and the dispersion treatment may be performed.

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 the like, and may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants can be cited. Among them, acrylic surfactants are particularly preferred. These pigment dispersants can be used alone or in combination of two or more kinds. As pigment dispersants, they are represented by trade names, and include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Ceruspas (registered trademark) (manufactured by Koeisha Chemical Co., Ltd.), and EFKA (Registered trademark) (manufactured by BASF Corporation), Ajispe (registered trademark) (manufactured by Ajinomoto Fumtec Co., Ltd.), Disperbyk (registered trademark) (manufactured by ビックケミー), 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 relative to 100 parts by mass of the pigment, more preferably 180 parts by mass or less, still more preferably 160 parts by mass or less, and particularly preferably 0 parts by mass. If the amount of the pigment dispersant used is within the above-mentioned range, when two or more kinds of pigments are used, there is a tendency to obtain a pigment dispersion in a more uniform dispersion state.

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, 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 of the compound (Aa) is within the above range, it is easier to obtain the desired spectral and color density. It should be noted that the "total amount of solid content" in this specification refers to the total amount of the components after removing the solvent from the colored curable resin composition of the present invention. The total amount of solid content and the content of each component relative to the total amount of solid content can be measured by, for example, known analytical means such as liquid chromatography and 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 included, the content of the pigment (Ac) relative to the total amount of the colorant (A) is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less , 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 soluble resin, and more preferably has a resin selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride. Addition polymer of at least one structural unit. Examples of such resins include the following resins [K1] to [K6]. Resin [K1]: At least one monomer selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms Copolymer resin [K2] of monomer (b) (hereinafter sometimes referred to as "(b)") with ethylenically unsaturated bond: (a), (b) and monomer (a) copolymerizable ( 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 copolymers of (a) with (b) and (c) [K6 ]: A resin obtained by reacting (a) with the copolymer of (b) and (c), and further reacting 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-vinyl benzoic acid; maleic acid, fumaric acid, citraconic acid, and Zhongkang Acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic 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 acid anhydrides such as bicyclo[2.2.1]hept-2-ene anhydride, etc. In addition, succinic acid mono[2-(meth)acryloyloxyethyl] ester and phthalic acid mono[2-(meth)acryloyloxyethyl] ester and other bivalent or more polybasic carboxylates can be used. Acidic unsaturated mono[(meth)acryloxyalkyl] esters; α-(hydroxymeth)acrylic acid and the like, unsaturated acrylates containing a hydroxyl group and a carboxyl group 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 this 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) refers to the polymerization of a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Sexual compounds. (b) It is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group.

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 monomers (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), and an oxetanyl group and an ethylenically unsaturated bond. The monomer (b2) (hereinafter sometimes referred to as "(b2)") and the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

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 monomers (b1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "(b1-1)") and A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-2)").

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 ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether Glyceryl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)benzene Ethylene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-Tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl) ) Styrene, 3,4,5-tris(glycidoxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)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, Cerocoide (registered trademark) 2000; manufactured by (Stock) Daicel) , 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Seikromam (registered trademark) A400; manufactured by (Stock) Daicel), 3,4-epoxycyclohexyl methyl (meth)acrylate (For example, Seikromam M100; manufactured by (Stock) Daicel), the compound represented by the formula (1), and the compound represented by the formula (2).

[化22]

Figure 02_image051
[化22]
Figure 02_image051

[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 formulas (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 by 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 the 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。As the compound represented by formula (1), compounds represented by formula (1-1) to formula (1-15) can be exemplified. Among them, preferably, compounds represented by formula (1-1) and formula (1- 3) Compounds represented by formula (1-5), formula (1-7), formula (1-9) and formula (1-11) to formula (1-15), more preferably, the compound represented by formula ( 1-1) Compounds represented by formula (1-7), formula (1-9) and formula (1-15).

[化23]

Figure 02_image053
[化23]
Figure 02_image053

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。As the compound represented by the formula (2), compounds represented by the formula (2-1) to the formula (2-15) can be cited, and among them, the compounds represented by the formula (2-1) and the formula (2- 3) Compounds represented by formula (2-5), formula (2-7), formula (2-9) and formula (2-11) ~ formula (2-15), more preferably, the compound represented by formula ( 2-1) Compounds represented by formula (2-7), formula (2-9) and formula (2-15).

[化24]

Figure 02_image055
[化24]
Figure 02_image055

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 formula (1) and the compound represented by formula (2) may each be used alone, or the compound represented by formula (1) and the compound represented by formula (2) may be used in combination. When these are used in combination, the ratio of the compound represented by the formula (1) and the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2)) is on a molar basis, It is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and still 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 tetrahydrofuran group and a (meth)acryloxy 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)。(B) is preferably (b1) in terms of being able to further improve the reliability of the resulting color filter such as heat resistance and chemical resistance, and in terms of excellent storage stability of the colored 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 of (c1) to (c6) and the like 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。(C1) Hydroxy-containing (meth)acrylates 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, etc.

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 hydroxyl-containing (meth)acrylate is preferably a hydroxyalkyl (meth)acrylate having an alkyl group having 1 to 10 carbons, more preferably having 1 to 8 carbons, more preferably 1 to 6 carbons, Particularly preferred is a hydroxyl group-containing (meth)acrylate of an alkyl group having 1 to 4 carbon atoms. Among them, specifically, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and 2-hydroxybutyl (meth)acrylate is more preferred. 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。(C2) Dicarbonylimine compounds include dicarbonylimine having aromatic hydrocarbon groups such as N-phenylmaleimide and N-tolylmaleimide, and N-cyclohexylmaleimide Imine, N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-cyclododecylmaleimide and other dicarbonylimine having alicyclic hydrocarbon groups, N -Dicarbonylimine with aralkyl groups such as benzylmaleimide, N-phenethylmaleimide, N-succinimidyl-3-maleimide benzoate, N -Succinimidyl-4-maleimidin butyrate, N-succinimidyl-6-maleimidin caproate and N-succinimidyl-3-maleimidin Acid salts and the like have dicarbonyl imines such as succinimidyl, and dicarbonyl imines such as N-(9-acridinyl) maleimines having a condensed heterocyclic group.

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 maleimide having a hydrocarbon group with 4 to 20 carbon atoms. The hydrogen atom contained in the hydrocarbon group of the above-mentioned N-substituted maleimide having a hydrocarbon group with 4 to 20 carbons may be substituted by an amino group, an alkoxy group with a carbon number of 1 to 5, a phenylamino group, a halogen atom or a hydroxyl group, etc. . Examples of the hydrocarbon group having 4 to 20 carbon atoms include alicyclic hydrocarbon groups having 4 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. As a group which substitutes the hydrogen atom contained in the said hydrocarbon group, a succinimidyl group etc. are mentioned. The monomer of the dicarbonylimine derivative is preferably an N-substituted maleimide having an alicyclic hydrocarbon group with 4 to 20 carbon atoms, and specific examples include N-cyclohexylmaleimide and N-cycloheptane Maleimines, N-cyclooctylmaleimines, and N-cyclododecylmaleimines, more preferably N-cyclohexylmaleimines.

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。(C3) (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate Base) tert-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, tricyclo[5.2.1.0 2,6 ]decane-8-yl (meth)acrylate (In this technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it is sometimes called "tricyclodecyl (meth)acrylate"), tricyclic (meth)acrylate [ 5.2.1.0 2,6 ] decene-8-yl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name), dicyclopentyloxyethyl (meth)acrylate , Isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Naphthyl ester and benzyl (meth)acrylate, etc. (C4) Dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like. (C5) Bicyclic unsaturated compounds include bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 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-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[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 include 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; vinyl-containing amides such as acrylamide and methacrylamide; vinyl acetate and other esters; 1, Dienes such as 3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

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 viewpoint of copolymerization reactivity and heat resistance, preferably hydroxy-containing (meth)acrylates and dicarbonylimine compounds are exemplified, and more preferably, (meth)acrylic acid 2-hydroxy 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)acryloyl group. A resin having such a structural unit can be obtained by making a polymer having a structural unit from (a) and (b) and a group capable of reacting with the group (a) and (b) and an ethylenically unsaturated bond The monomer addition is obtained. Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, and addition of 2-hydroxyethyl (meth)acrylate to maleic anhydride. A structural unit formed by a unit, a structural unit formed 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 ethylenic unsaturated bond, the structural unit which added carboxylic anhydride further can also be 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 monomers constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, etc. are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides The oxide (benzyl peroxide, etc.) can be used as a solvent as long as each monomer is dissolved. As the solvent (E) of the coloring curable resin composition of the present invention, the solvents described below can be cited.

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。In addition, the obtained polymer may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or a product taken out 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 reacted solution can be directly used in the preparation of the colored curable resin composition of the present invention. The manufacturing process of the colored curable resin composition of this invention can be simplified. If necessary, a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.), etc. may be used. Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic 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-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic (meth)acrylate [5.2. 1.0 2,6 ] Resins such as decyl ester/(meth)acrylic acid copolymer [K1]; (meth)glycidyl acrylate/(meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, (meth) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl Maleimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decyl ester/(meth)acrylic acid/vinyl toluene copolymer, 3-methyl-3 -(Meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer and other resins [K2]; (meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, benzene Resins such as ethylene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl(meth)acrylate/(meth)acrylic acid copolymer [K3]; make glycidyl (meth)acrylate Addition to benzyl (meth)acrylate/(meth)acrylic acid copolymer resin, adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylate Resins of acrylic copolymers, resins made by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, etc. [K4] ; Resin made by reacting (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester/(meth)acrylate glycidyl ester copolymer, making (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester Resins such as ester/styrene/glycidyl (meth)acrylate copolymer reaction [K5]; shrink (meth)acrylic acid and tricyclodecyl (meth)acrylate/(meth)acrylic acid Resins such as a copolymer reaction of glycerides and a resin obtained by further reacting tetrahydrophthalic anhydride with the obtained resin [K6]. These resins may be used alone or in combination of two or more kinds.

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 resin [K2], and more preferably has a structural unit derived from at least one monomer (a) selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride, derived from an olefinic The structural unit of the monomer (b) of unsaturated bond and cyclic ether structure, the structural unit derived from the hydroxyl-containing (meth)acrylate monomer (c1), and the monomer (c2) derived from the dicarbonylimine derivative The copolymer of the structural unit of) is more preferably a structural unit derived from at least one monomer (a) selected from acrylic acid and methacrylic acid, and is derived from 3,4-epoxy tricyclic (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 -The structural unit of at least one monomer (c1) selected from hydroxyethyl and 2-hydroxypropyl (meth)acrylate and derived from N-phenylmaleimide and N-cyclohexylmaleimide A copolymer of structural units of at least one monomer (c2) selected from N-benzylmaleimide 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 resin [K2], in terms of the content rate of the structural units derived from each monomer, in the total of all the structural units constituting the resin [K2], the structural unit derived from (a) is preferably 2 to 45 mol%, which is derived from The structural unit of (b) is 2~65 mol%, the structural unit derived from (c) is 1~95 mol%, more preferably the structural unit derived from (a) is 5-40 mol%, the structural unit derived from (b) It is 5-60 mol%, and the structural unit derived from (c) is 10-80 mol%. The monomers contained in each of (a) to (c) may be one type or two or more types. (c) is preferably two or more selected from (c1) to (c6), more preferably two or more selected from (c1) to (c3), and still more preferably (c1) and (c2).

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 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 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。In the case of combining two or more binder resins (B), a combination of resin [K1] and/or resin [K2] and resin [K4] ~ resin [K6] is preferred, and 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 weight average molecular weight in terms of polystyrene 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, still more preferably 5,000 or more and 80,000 or less, particularly preferably 6,000 or more and 50,000 or less, Especially preferably, it is 7,500 or more and 40,000 or less. If the molecular weight is within the above-mentioned range, the hardness of the coating film will increase, the residual film rate will also be high, the solubility of the unexposed part in the developing solution will be good, and the resolution of the colored pattern will tend to increase. 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 still 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, 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 it can be determined, for example, by titration using 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) relative to the total solid content is preferably 10 to 65% by mass, more preferably 15 to 60% by mass, still more preferably 20 to 55% by mass, and particularly preferably 25 ~50% by mass. If the content of the binder resin (B) is within the above-mentioned 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 acid generated by a polymerization initiator. For example, a polymerizable compound having an ethylenically unsaturated bond is exemplified, and preferably Examples include compounds 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 polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. , 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (a), (b) and (c) above. Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate Base) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate. Examples of polymerizable compounds 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, pentaerythritol deca(meth)acrylate, Four seasons pentaerythritol nine (meth) acrylate, tris (2-(meth) propylene oxyethyl) 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, preferably, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be cited.

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 of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 1-60% by mass, preferably 5-50% by mass, and more preferably 10-40% with respect to the total solid content. The mass% is more preferably 12 to 35% by mass. The content ratio of the binder resin (B) to the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) on a mass basis is usually 20:80 to 80:20, preferably 35: 65~80: 20. If the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend 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 that can initiate polymerization by generating living radicals, acids, etc. by the action of light and heat, and known polymerization initiators can be used. . The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkyl phenyl ketone compounds, triazine compounds, phosphine oxide compounds, O-oxime compounds, and biimidazole compounds, and more Preferably, it is a polymerization initiator containing an O-acetoxime compound.

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- oxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- Yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxide Cyclopentylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-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-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Corporation) can be used. Among them, it is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-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-keto-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 alkyl phenyl ketone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutane-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (the above are made by BASF Corporation) 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 can be 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)benzene Base) propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl) propan-1-one oligomer, α, α -Diethoxy acetophenone and benzyl 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, 2,4-bis(trichloromethyl) Yl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-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 Yl]-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。As an acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide can be mentioned. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) 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' -Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(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 Application Publication 62-174204, etc.) and imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 07-010913 etc.). Among them, the compounds represented by the following formulas and their mixtures are preferred.

[化25]

Figure 02_image057
[化25]
Figure 02_image057

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, o-benzyl methyl benzoate, 4-phenyl benzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4 '-Tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone And camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate and titanocene compounds. These are preferably used in combination with a polymerization initiation aid (particularly, an amine-based polymerization initiation aid) described later.

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), relative to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C), is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 1 to 30 parts by mass, 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 auxiliary agent> The polymerization initiation auxiliary agent is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by 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 amine-based polymerization initiators include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate. Ester, 4-dimethylaminobenzoic acid isoamyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester and other aminobenzoic acid esters; N,N- Dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler’s ketone), 4,4'-bis(diethylamino)benzophenone and 4,4 '-Bis(ethylmethylamino)benzophenone, of which alkylaminobenzophenones such as 4,4'-bis(diethylamino)benzophenone are 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 aids 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。As the thioxanthone-based polymerization initiation assistant, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone can be cited. Ketone 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 carboxylic acid-based polymerization initiators include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethyl sulfanyl acetic acid. Alkylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenyl Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic 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 aid is used, its content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 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 assistant 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 a solvent generally used in this field can be used alone or in combination of two or more kinds. Specifically, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule, no -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide.

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 ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexane Alcohol acetate and gamma-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 ether solvents 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 methyl propyl ether, tripropylene glycol monomethyl ether, tripropylene glycol butyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutyl 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, phenethyl 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 ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl ethyl propionate, 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, 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 glycerin.

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 amide 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。With regard to these solvents, two or more types can be combined.

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-mentioned solvents, organic solvents having a boiling point of 120°C or more and 210°C or less at 1 atm (atmospheric pressure) are preferred from the viewpoint 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 monomethyl ether are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, propylene glycol two 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) relative to the total amount of the colored curable resin composition is usually 60 to 95% by mass, preferably 65 to 92% by mass, and more preferably 70 to 90% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so there is a tendency for the display characteristics to become 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 silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms.

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 organosilicon-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray-Dow Corning Co., Ltd.), 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 Contracting Corporation).

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 surfactants having a fluorocarbon chain in the molecule. Specifically, Flourard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megofack (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (Manufactured by DIC (Stock)), Eftup (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), サーフロン (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) Manufacturing) and E5844 (manufactured by Daikin Fine Chemical Research Institute (Stock)).

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-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megfack (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Co., Ltd.) can be cited.

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。Relative to the total amount of the colored curable resin composition, the content 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, more preferably 0.001 mass% or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, particularly preferably 0.005% by mass or more and 0.07% by mass or less. If the content rate of the leveling agent is within the above-mentioned 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 an epoxy compound (P), what is necessary is just a compound which has 1 or more epoxy ethyl group. However, the epoxy compound (P) is a compound different from the binder resin (B), for example. If such an epoxy compound (P) is used, the lightness of the colored curable resin composition can be improved, and the solvent resistance can also be improved. In addition, the number of epoxy ethyl groups that the epoxy compound (P) has may be one or more, and it 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 epoxides of isoprene (co)polymers, epoxides of butadiene (co)polymers, and alkanediene (co)polymers. Epoxy and other epoxy compounds 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 cycloalkane rings with 3 to 10 carbon atoms such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; Cycloolefin rings with 5 to 10 carbon atoms such as pentene ring, cyclohexene ring, cycloheptene ring, and cyclooctene ring; bicyclo[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 with 7 to 15 carbon atoms such as decane ring (adamantane ring), etc. 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 them, cyclohexane is more preferred.

作為芳香族烴環，可列舉出苯環、萘環和蒽環等。As an aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned.

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 ethylene oxide groups is preferable, and an epoxy compound having two or more rings and two or more ethylene oxide groups is more preferable. In the epoxy compound having a ring, the number of oxirane groups relative 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 epoxy compounds having an alicyclic hydrocarbon ring and two or more epoxy ethyl groups include 1,2-epoxy-4-(2,2-bis(hydroxymethyl)-1-butanol 2-Ethoxyethyl) cyclohexane adduct and the like. As the above-mentioned epoxy compound, 3,4-epoxycyclohexane carboxylic acid 3',4'-epoxycyclohexyl methyl ester (Serocoide 2021P, manufactured by Daicel Co., Ltd.), ε-caprolactone modified 3,4-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexyl methyl ester (Serocoide 2081, manufactured by Daicel Co., Ltd.), etc.

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 epoxy ethyl groups include bisphenol A epoxy compounds, bisphenol F epoxy compounds, brominated bisphenol A epoxy compounds, 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 Methyl methane type epoxy compound; tetraphenol ethane type epoxy compound; styrene-based polymer ring such as styrene-butadiene copolymer epoxide and styrene-isoprene copolymer epoxide Oxide etc. Among them, bisphenol A type epoxy compounds and ortho-cresol novolac type epoxy compounds are particularly preferred.

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 7000 or less, more preferably 5000 or less, still more preferably 2900 or less, preferably 50 or more, more preferably 200 or more, and still 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, still more preferably 100 g/equivalent or more and 300 g/equivalent or less, particularly preferably It is 150 g/equivalent or more and 250 g/equivalent or less. The epoxy equivalent can be measured by the 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) in 100% by mass of the colored curable resin composition (solid content) is preferably 0.1% by mass or more and 25% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less 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 fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, epoxy curing agents, and curing agents as needed. Accelerators and other additives known 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 the colored curable resin composition> The colored curable resin composition of the present invention can be obtained by mixing the colorant (A), the binder resin (B), the polymerizable compound (C), and the polymerization initiator (D), for example. , Epoxy compound (P), and as required solvent (E), leveling agent, polymerization initiation aid and other ingredients are mixed to prepare. The colored 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> The coloring pattern can be formed from the coloring curable resin composition of this invention, As the 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 of applying a colored curable resin composition to a substrate, drying to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film as a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way are the color filter 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 film thickness of the produced color filter can be appropriately adjusted according to the purpose, application, etc., 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, aluminum, silver, and a silver/copper/palladium alloy thin film formed on the above 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 image elements of various colors by photolithography can be performed under known or customary equipment 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, the colored curable resin composition is applied on a substrate, and dried by heating (pre-baking) and/or under reduced pressure to remove volatile components such as the solvent and dry to obtain a smooth colored composition layer. As the coating method, a spin coating method, a slit coating method, and a slit and spin coating method can be cited.

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 coloring composition layer is exposed to light through a photomask for forming the target coloring pattern. Since parallel light can be uniformly irradiated to the entire exposure surface, and the photomask can be accurately aligned with the substrate on which the coloring 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 brought into contact with a developing solution for development, thereby forming a coloring pattern on the substrate. By development, the unexposed part of the coloring composition layer is dissolved and removed in the developer. As the developer, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The development method may be any of the rotary immersion method, the dipping method, and the spray method. Furthermore, the substrate can be inclined at an arbitrary angle during development. It is preferable to wash with water after development.

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。Preferably, the obtained colored pattern is further post-baked. The color filter having the colored pattern and colored coating film obtained in this way may be further subjected to 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 coloring 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, etc.) and solid-state imaging elements. Example

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 example, as long as there is no special description, the% and parts representing the content and the amount used are the mass basis.

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 carried out in 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 into a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little, and stirred at room temperature for 24 hours. After adding 200 parts of ice water to the reaction liquid little by little, it was allowed to stand at room temperature for 15 hours, and if the water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. After the precipitated solid was separated by filtration, it was purified by column chromatography. The purified pale yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of the compound represented by formula (C-I-18).

[化26]

Figure 02_image059
[化26]
Figure 02_image059

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 carried out in a nitrogen atmosphere. Put 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18), and 20 parts of toluene into a flask equipped with a cooling tube and a stirring device, and then add phosphorus oxychloride 12.2 parts, stirred at 95~100°C for 3 hours. Next, after the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction solution into 300 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by the liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, a filtered and dried organic layer was obtained. The solvent was distilled off the obtained organic layer using an evaporator to obtain a blue-purple solid. Furthermore, the purple solid was dried at 60°C under reduced pressure to obtain 18.4 parts of the compound represented by formula (A-II-18).

[化27]

Figure 02_image061
[化27]
Figure 02_image061

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 carried out in a nitrogen atmosphere. After putting 8 parts of the compound represented by formula (A-II-18) and 396 parts of methanol into a flask equipped with a cooling tube and a stirring device, it stirred at room temperature for 30 minutes, and prepared the cyan solution. Next, after adding 396 parts of water to the cyan solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution. 53 parts of water was put into the beaker, 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water and 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 for 30 minutes at room temperature, it was filtered to obtain a cyan solid. The obtained cyan solid was put into 200 parts of methanol and dispersed for 1 hour, and then filtered, and this operation was repeated twice. The cyan solid obtained by this operation was put into 200 parts of water and dispersed for 1 hour, followed by filtration, and this operation was repeated twice. The cyan solid obtained by this operation was dried at 60°C under reduced pressure to obtain 17.1 parts of a compound represented by formula (A-I-18).

[化28]

Figure 02_image063
[化28]
Figure 02_image063

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 coloring dispersion) In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced at 0.02 L/min to create a nitrogen atmosphere, and 3-methoxy-1 was placed -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-epoxy tricyclo[5.2.1.0 2,6 ]decyl acrylate (a compound represented by formula (II-1) and a compound represented by formula (III-1) A mixture of 50:50 in a molar ratio of the compound) 240 parts was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the dissolved solution was dropped into a flask kept at 70°C over 4 hours using a dropping funnel. On the other hand, 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate over 4 hours using another dropping funnel. The solution dripped into the flask. After dropping the polymerization initiator solution, the solution was kept at 70°C for 4 hours, and then cooled to room temperature to obtain a resin B-1b solution with a solid content of 32.6% and an acid value of 110 mg-KOH/g (in terms of solid content). The weight average molecular weight Mw of the obtained resin B-1b was 13,400, and the molecular weight distribution was 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> 10 parts of the compound represented by formula (AI-18), 2 parts of dispersant (BYK (registered trademark)-LPN6919 (manufactured by ビックケミー・ジャパン)), resin B-1b (converted solid content) 4 parts, 84 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2mm zirconia beads were mixed, and after shaking for 6 hours using a paint conditioner (manufactured by Red Devil), 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 The compound represented by formula (1-32) was obtained by the method described in Synthesis Example 3 of JP 2013-122577 A.

[化29]

Figure 02_image065
[化29]
Figure 02_image065

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 to replace it with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed and stirred 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 of acrylic acid, and 137 parts of cyclohexylmaleimide were added over 5 hours. , A mixed solution of 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate was dropped. 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 dripping was completed, it was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (B) with a type B viscosity (23°C) of 22 mPas, a solid content of 25.5%, and a solid content of 111 mg-KOH/g. -1) Solution. The weight average molecular weight Mw of the resulting 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 measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the above-mentioned binder resin was performed under the following conditions using the GPC method. Device; K2479 (made by Shimadzu Corporation) column; SHIMADZU Shim-pack GPC-80M column temperature; 40℃ solvent; THF (tetrahydrofuran) concentration of the tested solution: 25mg/mL (solvent; THF) Flow rate: 1.0mL/min Detector: RI calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) 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) colorant; 1.0 part of the compound represented by formula (1-32) (A) colorant; A1-1; colored dispersion (1) 　　　　　855 Parts (B) binder resin; resin (B-1) (in terms of solid content) 　 50 parts (C) polymerizable compound; dipentaerythritol hexaacrylate (Kaburado DPHA; manufactured by Nippon Kayaku Co., Ltd.) 　　　　　　　50 parts (D) Polymerization initiator; N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure OXE 01; manufactured by BASF Corporation) 8 parts (F) Leveling agent; polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning Co., Ltd.) 　　　　　0.2 parts (E) solvent; 580 parts of propylene glycol monomethyl ether acetate, and (P) epoxy compound; 2 1,2-Epoxy-4-(2-epoxyethyl) cyclohexane adduct of ,2-bis(hydroxymethyl)-1-butanol (EHPE3150; manufactured by Daicel Co., Ltd., molecular weight 2234 , Acid value 0mg-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) colorant; 1.0 part of the compound represented by formula (1-32) (A) colorant; A1-1; color dispersion (1) 　　　　　855 Parts (B) binder resin; resin (B-1) (in terms of solid content) 　 50 parts (C) polymerizable compound; dipentaerythritol hexaacrylate (Kaburado DPHA; manufactured by Nippon Kayaku Co., Ltd.) 　　　　　　　50 parts (D) Polymerization initiator; N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure OXE 01; manufactured by BASF Corporation) 8 parts (F) Leveling agent; polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning Co., Ltd.) 　　　　　0.2 parts (E) solvent; 580 parts of propylene glycol monomethyl ether acetate, and (P) epoxy compound; o A cresol novolak type epoxy resin (Sumie Pyashi ESCN-195XL-80; manufactured by Sumitomo Chemical Co., Ltd., molecular weight 389, acid value: 0.1 mg-KOH/g) 　5 parts were 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) colorant; 1.0 part of the compound represented by formula (1-32) (A) colorant; A1-1; color dispersion (1) 　　　　　855 Parts (B) binder resin; resin (B-1) (in terms of solid content) 　 50 parts (C) polymerizable compound; dipentaerythritol hexaacrylate (Kaburado DPHA; manufactured by Nippon Kayaku Co., Ltd.) 　　　　　　　50 parts (D) Polymerization initiator; N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure OXE 01; manufactured by BASF Corporation) 8 parts (F) Leveling agent; polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning Co., Ltd.) 　　　　　0.2 parts (E) solvent; 580 parts of propylene glycol monomethyl ether acetate, and (P) epoxy compound; double Phenolic A type epoxy resin (JER157S70; manufactured by Mitsubishi Chemical Corporation; acid value 0 mg-KOH/g) 　5 parts were mixed to obtain a colored curable resin composition 3.

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" acrylic pigment dispersant 10 parts propylene glycol monomethyl ether acetate 194 parts were mixed, the pigment was dispersed using a bead mill, and then, (A) colorant; 1-1; 3 parts of compound represented by formula (1-32) (B) binder resin; resin (B-1) (solid content conversion) 　50 parts (C) polymerizable compound; Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) polymerization initiator; OXE 01 (manufactured by BASF) and 8 parts (F) leveling agent; polyether modified silicone oil (Toray Silicone SH8400: East Li-Dow Corning Co., Ltd.) 0.2 parts of (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。<Production of color filter (coloring pattern)> The colored curable resin composition 1 was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100°C for 3 minutes to form The coloring composition layer. After cooling, the distance between the substrate on which the coloring composition layer was formed and the photomask made of quartz glass was 80 μm. Using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), the gap was set at 35 mJ/cm in an air atmosphere. Light irradiation is performed at an exposure amount of 2 (365nm standard). As the photomask, a photomask in which a pattern of 50 μm lines and gaps was formed was used. The light-irradiated coloring composition layer is immersed and developed in a developing solution (in terms of mass fraction, each containing 0.05% potassium hydroxide and 0.2% sodium butyl naphthalene sulfonate) at 25°C for 60 seconds, and then washed with water , Post-baking was performed in an oven at 230°C for 30 minutes to obtain a colored pattern. For colored curable resin compositions 2 to 4, colored patterns were obtained 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> For each of the obtained colored patterns, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon 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。<Chromaticity evaluation> For each coloring pattern obtained, the spectroscopy was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the characteristic function of the C light source was used to measure the CIE XYZ color system Xy chromaticity coordinates (x, y) in and Y in tristimulus values. The larger the Y, the higher the brightness. 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 Color Filter (Colored Coating Film)> After coating the colored curable resin composition 1 by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), it was pre-baked at 100°C for 3 minutes, The colored composition layer is formed. After cooling, the distance between the substrate on which the coloring composition layer was formed and the photomask made of quartz glass was 80 μm. Using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), the gap was set at 35 mJ/cm in an air atmosphere. The exposure amount of 2 (365nm standard) is irradiated with light to the coloring composition layer. As the photomask, a photomask in which a pattern of 50 μm lines and gaps was formed was used. The colored coating film was obtained by post-baking in an oven at 230°C for 30 minutes. Colored coating films were also obtained for colored curable resin compositions 2 to 4 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。<Solvent resistance evaluation> The chromaticity 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 immersion was measured in the same manner. As an evaluation criterion for color difference, if ΔEab* is 3 or less, there is almost no change in hue, which shows good characteristics as a color filter. If ΔEab* exceeds 3, the change in hue can be confirmed. This is when used as a color filter. Questionable benchmarks. The results are shown in Table 5.

[表5]

Figure 02_image067
產業上的可利用性[table 5]
Figure 02_image067
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)的用於提高固化物之耐溶劑性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 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) for improving the cured product The solvent-resistant coloring curable resin composition, in which the epoxy compound (P) is different from the binder resin (B), the colorant (A) is a colorant containing the compound (Aa), and the compound (Aa) has The cation of the pigment skeleton and the anion derived from the compound containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and oxygen, relative to the total amount of the colorant (A), the epoxy compound (P) is contained The rate is 0.1% by mass or more and 60% by mass or less. 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 acid and unsaturated carboxylic anhydride , And a copolymer of 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 106105729-A0305-02-0082-1
 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，
Figure 106105729-A0305-02-0083-2
 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, wherein the compound is 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): [化1]
Figure 106105729-A0305-02-0082-1
 In the formula (AI), R 41 to R 44 independently represent an amino group that may be substituted, a saturated hydrocarbon group of 1 to 20 carbons that may be substituted by a halogen atom, an alkyl group of 2 to 20 carbons, and the number of carbons 2. A group in which the methylene group contained in an alkyl group of ~20 is replaced by an oxygen atom, an optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group or a hydrogen atom, R 41 and R 42 can be combined and combined with Their combined nitrogen atoms form a ring together. R 43 and R 44 can combine and form a ring with their combined nitrogen atoms. R 47 ~ R 54 independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or the number of carbons. An alkyl group of 1-8, an oxygen atom can be inserted between the methylene groups constituting the alkyl group, R 48 and R 52 can be combined with each other to form -NH-, -O-, -S- or -SO 2 -, R In 41 to R 44 and R 47 to R 54 , the adjacent methylene groups will not be replaced with oxygen atoms at the same time, and the methylene groups at the end of the alkyl groups will not be replaced with oxygen atoms. Ring T 1 means that Aromatic heterocyclic ring with substituents. [Y] m- represents an m-valent anion containing at least one element selected from tungsten, molybdenum, silicon and phosphorus, and oxygen, and m represents an integer from 2 to 14, and more than one in one molecule In the case of cations represented by the following formula, they may have the same structure or different structures,
Figure 106105729-A0305-02-0083-2
 In the formula, rings T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as above. 一種如請求項1至3中任一項所述的著色固化性樹脂組合物所形成的濾色器。 A color filter formed of the coloring curable resin composition according to any one of claims 1 to 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 including the color filter according to claim 4.
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