TWI770067B - Colored curable resin composition, color filter and displayer - Google Patents

Colored curable resin composition, color filter and displayer Download PDF

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TWI770067B
TWI770067B TW106134182A TW106134182A TWI770067B TW I770067 B TWI770067 B TW I770067B TW 106134182 A TW106134182 A TW 106134182A TW 106134182 A TW106134182 A TW 106134182A TW I770067 B TWI770067 B TW I770067B
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市岡賢二
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日商住友化學股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • C09B67/0038—Mixtures of anthraquinones
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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

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Abstract

A colored curable resin composition comprises a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a triarylmethane colorant, a xanthene dye, and an anthraquinone dye.

Description

著色硬化性樹脂組成物、彩色濾光片及顯示装置 Colored curable resin composition, color filter, and display device

本發明係關於著色硬化性樹脂組成物。 The present invention relates to a colored curable resin composition.

作為形成液晶顯示裝置等或固體攝像元件等所包含之彩色濾光片之著色硬化性樹脂組成物，於日本國特許出願公開第2015-199912號公報中，係記載一種含有三芳基甲烷染料與二苯并哌喃染料作為著色劑之著色硬化性樹脂組成物。 Japanese Patent Application Laid-Open No. 2015-199912 discloses a coloring curable resin composition for forming color filters included in liquid crystal display devices, etc., solid-state imaging devices, etc., which contains a triarylmethane dye and a diarylmethane dye. A benzopyran dye is used as a coloring curable resin composition as a colorant.

本發明係提供以下[1]至[5]。 The present invention provides the following [1] to [5].

[1]一種著色硬化性樹脂組成物，其係含有：著色劑、樹脂、聚合性化合物及聚合起始劑；前述著色劑，含有：三芳基甲烷著色劑、二苯并哌喃染料、以及蒽醌染料。 [1] A colorable curable resin composition containing: a colorant, a resin, a polymerizable compound, and a polymerization initiator; the colorant containing: a triarylmethane colorant, a dibenzopyran dye, and an anthracene Quinone dyes.

[2]如[1]所述之著色硬化性樹脂組成物，其中前述蒽醌染料的含量，相對於前述三芳基甲烷著色劑100質量份為0.5至50質量份。 [2] The colorable curable resin composition according to [1], wherein the content of the anthraquinone dye is 0.5 to 50 parts by mass relative to 100 parts by mass of the triarylmethane colorant.

[3]如[2]所述之著色硬化性樹脂組成物，其中前述蒽醌染料的含量，相對於前述三芳基甲烷著色劑100質量份為1.0至13.5質量份。 [3] The colorable curable resin composition according to [2], wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass relative to 100 parts by mass of the triarylmethane colorant.

[4]一種彩色濾光片，其係由[1]至[3]中任一項所述之著色硬化性樹脂組成物所形成。 [4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].

[5]一種顯示裝置，其係包含[4]所述之彩色濾光片。 [5] A display device comprising the color filter described in [4].

本發明之著色硬化性樹脂組成物，係含有：著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)。本發明之著色硬化性樹脂組成物，較佳係含有溶劑(E)及/或勻染劑(F)，此外，可含有抗氧化劑(H)及其他成分。著色劑(A)，含有：三芳基甲烷著色劑(Aa1)、二苯并哌喃染料(Aa2)、以及蒽醌染料(Aa3)。本發明之著色硬化性樹脂組成物，由於具有上述構成，可製造高對比的彩色濾光片。 The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorable curable resin composition of the present invention preferably contains a solvent (E) and/or a leveling agent (F), and may also contain an antioxidant (H) and other components. The colorant (A) contains a triarylmethane colorant (Aa1), a dibenzopyran dye (Aa2), and an anthraquinone dye (Aa3). Since the colored curable resin composition of the present invention has the above-mentioned constitution, a high-contrast color filter can be produced.

〈著色劑(A)〉 <Colorant (A)>

著色劑(A)，含有：三芳基甲烷著色劑(Aa1)、二苯并哌喃染料(Aa2)、以及蒽醌染料(Aa3)。且亦可含有與三芳基甲烷著色劑(Aa1)、二苯并哌喃染料(Aa2)、以及蒽醌染料(Aa3)不同之染料(以下有時稱為「染料(Aa4)」)。 The colorant (A) contains a triarylmethane colorant (Aa1), a dibenzopyran dye (Aa2), and an anthraquinone dye (Aa3). In addition, a dye (hereinafter sometimes referred to as "dye (Aa4)") different from the triarylmethane colorant (Aa1), the dibenzopyran dye (Aa2), and the anthraquinone dye (Aa3) may be contained.

(三芳基甲烷著色劑(Aa1)) (Triarylmethane Colorant (Aa1))

三芳基甲烷著色劑(Aa1)，為包含分子內具有三芳基甲烷骨架之化合物的著色劑。該著色劑可列舉出染料及顏 料，亦可為色澱化顏料。三芳基甲烷著色劑(Aa1)，較佳為含有以式(A-I)所表示之化合物及該互變異構物(以下有時將此等總稱為「化合物(A-I)」)之染料。 The triarylmethane colorant (Aa1) is a colorant including a compound having a triarylmethane skeleton in the molecule. Examples of the colorant include dyes and pigments, and may be laked pigments. The triarylmethane colorant (Aa1) is preferably a dye containing the compound represented by the formula (A-I) and the tautomer (hereinafter, these may be collectively referred to as "compound (A-I)").

使用化合物(A-I)時，三芳基甲烷著色劑(Aa1)中之化合物(A-I)的含有率，較佳為50質量%以上，尤佳為70質量%以上，更佳為90質量%以上。當中，三芳基甲烷著色劑(Aa1)較佳係僅使用化合物(A-I)。 When the compound (A-I) is used, the content of the compound (A-I) in the triarylmethane colorant (Aa1) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. Among them, it is preferable to use only the compound (A-I) as the triarylmethane colorant (Aa1).

Figure 106134182-A0202-12-0003-1
Figure 106134182-A0202-12-0003-1

[式(A-I)中，[Y2]m-表示m價的陰離子；R41至R44互為獨立地表示氫原子、可經取代之碳數1至20的飽和烴基、於構成碳數2至20的烷基之碳原子間***有氧原子之基、可經取代之芳基、或可經取代之芳烷基；R41與R42可鍵結並與此等所鍵結之氮原子一同形成環，R43與R44可鍵結並與此等所鍵結之氮原子一同形成環；R45至R52互為獨立地表示氫原子、鹵素原子、硝基、羥基、碳數1至8的飽和烴基、或於構成碳數2至8的烷基之碳原子間***有氧原子之基，或是R46與R50相互鍵結而形成-O-、-NH-、-S-或-SO2-；Y1表示可經取代之芳基、或可經取代之雜芳基；當以式(A-I)所表示之化合物含有複數個陽離子時，複數個陽離子可互為相同結構或相異結構；m表示任意的自然數] [In formula (AI), [Y 2 ] m- represents an m-valent anion; R 41 to R 44 independently represent a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and each of which constitutes a carbon number of 2 A group in which an oxygen atom is inserted between the carbon atoms of the alkyl group to 20, an aryl group which may be substituted, or an aralkyl group which may be substituted; R 41 and R 42 may be bonded and with these bonded nitrogen atoms Form a ring together, R 43 and R 44 can bond and form a ring together with these bonded nitrogen atoms; R 45 to R 52 independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carbon number of 1 A saturated hydrocarbon group of to 8, or a group in which an oxygen atom is inserted between the carbon atoms constituting an alkyl group of 2 to 8 carbon atoms, or R 46 and R 50 are bonded to each other to form -O-, -NH-, -S -or -SO 2 -; Y 1 represents a substituted aryl group or a substituted heteroaryl group; when the compound represented by formula (AI) contains multiple cations, the multiple cations may have the same structure as each other or dissimilar structure; m represents any natural number]

[Y2]m-表示m價的陰離子。以[Y2]m-所表示之陰離子，只要是可與染料陽離子形成對離子之陰離子即可，並無特別限定，較佳為含硼陰離子、含鋁陰離子、含氟陰離子、氯陰離子等之鹵素陰離子，以及具有選自由鎢、鉬、矽及磷所組成之群組的至少1種元素與氧原子之陰離子。 [Y 2 ] m- represents an m-valent anion. The anion represented by [Y 2 ] m- is not particularly limited as long as it can form a counter ion with the dye cation, and is preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, a chloride anion, or the like. Halogen anions, and anions having at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and an oxygen atom.

含硼陰離子及含鋁陰離子，例如可列舉出以式(4)所表示之陰離子。 Examples of boron-containing anions and aluminum-containing anions include anions represented by formula (4).

[W1-M-W2]Θ (4) [W 1 -MW 2 ] Θ (4)

[式(4)中，W1及W2互為獨立地表示從具有2個1價的質子供予性取代基之化合物中釋出質子而成之基；M表示硼或鋁] [In formula (4), W 1 and W 2 independently represent a group obtained by releasing a proton from a compound having two monovalent proton-donating substituents; M represents boron or aluminum]

關於式(4)，具有2個1價的質子供予性取代基之化合物，可列舉出具有2個1價的質子供予性取代基(例如羥基、羧基)之化合物，例如可列舉出二羥基萘、可具有取代基之2,2'-聯苯酚、可具有取代基之3-羥基-2-萘甲酸、可具有取代基之2-羥基-1-萘甲酸、可具有取代基之1-羥基-2-萘甲酸、可具有取代基之二萘酚、可具有取代基之柳酸、可具有取代基之苯甲酸或可具有取代基之苦杏仁酸。 In the formula (4), compounds having two monovalent proton-donating substituents include compounds having two monovalent proton-donating substituents (eg, a hydroxyl group and a carboxyl group). For example, two Hydroxynaphthalene, optionally substituted 2,2'-biphenol, optionally substituted 3-hydroxy-2-naphthoic acid, optionally substituted 2-hydroxy-1-naphthoic acid, optionally substituted 1 -Hydroxy-2-naphthoic acid, optionally substituted dinaphthol, optionally substituted salicylic acid, optionally substituted benzoic acid, or optionally substituted mandelic acid.

所謂從該化合物中釋出質子而成之基，為從該化合物中的複數個質子供予性取代基中，質子全部解離而成之基，意指具有O-或COO-之基。 The group formed by releasing a proton from the compound is a group formed by dissociating all protons from a plurality of proton-donating substituents in the compound, and means a group having O - or COO - .

該化合物，較佳為可具有取代基之兒茶酚、 可具有取代基之2,3-二羥基萘、可具有取代基之2,2'-聯苯酚、可具有取代基之3-羥基-2-萘甲酸、可具有取代基之2-羥基-1-萘甲酸、可具有取代基之1-羥基-2-萘甲酸、可具有取代基之二萘酚、可具有取代基之柳酸、可具有取代基之苯甲酸或可具有取代基之苦杏仁酸。 The compound is preferably catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, 3-hydroxy- 2-naphthoic acid, optionally substituted 2-hydroxy-1-naphthoic acid, optionally substituted 1-hydroxy-2-naphthoic acid, optionally substituted dinaphthol, optionally substituted salicylic acid, Benzoic acid which may have a substituent or mandelic acid which may have a substituent.

前述各化合物中，取代基可列舉出飽和烴基(烷基、環烷基等)、鹵素原子、羥基、胺基、硝基、烷氧基等。 In each of the aforementioned compounds, the substituents include saturated hydrocarbon groups (alkyl, cycloalkyl, etc.), halogen atoms, hydroxyl groups, amino groups, nitro groups, alkoxy groups, and the like.

可具有取代基之柳酸，可列舉出柳酸、3-甲基柳酸、3-三級丁基柳酸、3-甲氧基柳酸、3-硝基柳酸、4-三氟甲基柳酸、3,5-二(三級丁基)柳酸、3-胺基柳酸、4-胺基柳酸、5-胺基柳酸、6-胺基柳酸等之單胺基柳酸；3-羥基柳酸(2,3-二羥基苯甲酸)、4-羥基柳酸(2,4-二羥基苯甲酸)、5-羥基柳酸(2,5-二羥基苯甲酸)、6-羥基柳酸(2,6-二羥基苯甲酸)等之單羥基柳酸；4,5-二羥基柳酸、4,6-二羥基柳酸等之二羥基柳酸；3-氯柳酸、4-氯柳酸、5-氯柳酸、6-氯柳酸、3-溴柳酸、4-溴柳酸、5-溴柳酸、6-溴柳酸等之單鹵素柳酸；3,5-二氯柳酸、3,5-二溴柳酸、3,5-二碘柳酸等之二鹵素柳酸；3,5,6-三氯柳酸等之三鹵素柳酸等。 The salicylic acid which may have a substituent includes salicylic acid, 3-methyl salicylic acid, 3-tert-butyl salicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, and 4-trifluoromethane. Monoamine group of salicylic acid, 3,5-bis(tertiary butyl) salicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, etc. Salic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid) , Monohydroxysalicylic acid such as 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid); Monohalogen salicylic acid such as salicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid, etc. ; 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-diiodosalicylic acid, etc., dihalosalicylic acid; 3,5,6-triclosalic acid, etc. Wait.

可具有取代基之苯甲酸，可列舉出以下述結構式所表示之化合物等。 The benzoic acid which may have a substituent, the compound etc. which are represented by the following structural formula are mentioned.

Figure 106134182-A0202-12-0006-2
Figure 106134182-A0202-12-0006-2

可具有取代基之苦杏仁酸，可列舉出以下述結構式所表示之化合物等。 As mandelic acid which may have a substituent, the compound etc. which are represented by the following structural formula are mentioned.

Figure 106134182-A0202-12-0006-3
Figure 106134182-A0202-12-0006-3

以式(4)所表示之陰離子，較佳是以下述式所表示之陰離子，可列舉出具有表1所記載之陰離子(BC-1)至陰離子(BC-24)、以及分別以式(BC-25)、式(BC-26)、式(BC-27)及式(BC-28)所表示之陰離子(BC-25)至陰離子(BC-28)等。 The anion represented by the formula (4) is preferably an anion represented by the following formula, and examples thereof include the anions (BC-1) to (BC-24) described in Table 1, and those represented by the formula (BC-24), respectively. -25), formula (BC-26), formula (BC-27) and formula (BC-28) represented by anion (BC-25) to anion (BC-28) and the like.

Figure 106134182-A0202-12-0006-4
Figure 106134182-A0202-12-0006-4

[式中，M表示硼或鋁] [In the formula, M represents boron or aluminum]

Figure 106134182-A0202-12-0007-5
Figure 106134182-A0202-12-0007-5

Figure 106134182-A0202-12-0007-6
Figure 106134182-A0202-12-0007-6

[式(BC-25)中，M表示硼或鋁] [In formula (BC-25), M represents boron or aluminum]

Figure 106134182-A0202-12-0007-7
Figure 106134182-A0202-12-0007-7

[式(BC-26)中，M表示硼或鋁] [In formula (BC-26), M represents boron or aluminum]

Figure 106134182-A0202-12-0008-8
Figure 106134182-A0202-12-0008-8

[式(BC-27)中，M表示硼或鋁] [In formula (BC-27), M represents boron or aluminum]

Figure 106134182-A0202-12-0008-9
Figure 106134182-A0202-12-0008-9

[式(BC-28)中，M表示硼或鋁] [In formula (BC-28), M represents boron or aluminum]

以式(4)所表示之陰離子，較佳為陰離子(BC-1)、陰離子(BC-2)、陰離子(BC-3)、陰離子(BC-25)、陰離子(BC-26)、陰離子(BC-27)，尤佳為陰離子(BC-1)、陰離子(BC-2)、陰離子(BC-25)，更佳為陰離子(BC-1)、陰離子(BC-2)。具有此等陰離子的任一者之以式(A-I)所表示之化合物，具有對有機溶劑之溶解性優異之傾向。 The anion represented by the formula (4) is preferably an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC-26), an anion (BC-2). BC-27), particularly preferably anion (BC-1), anion (BC-2), anion (BC-25), more preferably anion (BC-1), anion (BC-2). The compound represented by formula (A-I) having any of these anions tends to have excellent solubility in organic solvents.

含氟陰離子，例如可列舉出以式(6)、(7)、(8)、(9)所表示之基。 As a fluorine-containing anion, the group represented by Formula (6), (7), (8), (9) is mentioned, for example.

Figure 106134182-A0202-12-0008-10
Figure 106134182-A0202-12-0008-10

[式(6)中，W3及W4互為獨立地表示氟原子或是碳數1至4的氟烷基，或者是W3及W4成為一體而表示碳數1至4的氟烷二基] [In formula (6), W 3 and W 4 independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or W 3 and W 4 are integrated to represent a fluorocarbon having 1 to 4 carbon atoms two bases]

Figure 106134182-A0202-12-0009-11
Figure 106134182-A0202-12-0009-11

[式(7)中，W5、W6及W7互為獨立地表示氟原子或是碳數1至4的氟烷基] [In formula (7), W 5 , W 6 and W 7 each independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms]

ΘO3S-Ya-SO3 Θ (8) Θ O 3 SY a -SO 3 Θ (8)

[式(8)中，Ya表示碳數1至4的氟烷二基] [In formula (8), Y a represents a fluoroalkanediyl group having 1 to 4 carbon atoms]

Yb-SO3 Θ (9) Y b -SO 3 Θ (9)

[式(9)中，Yb表示碳數1至4的氟烷基] [In formula (9), Y b represents a fluoroalkyl group having 1 to 4 carbon atoms]

式(6)、(7)及(9)中，碳數1至4的氟烷基較佳為全氟烷基。該全氟烷基，可列舉出-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、或-C(CF3)3。 In formulas (6), (7) and (9), the fluoroalkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF ( CF 3 ) 2 , or -C(CF 3 ) 3 .

式(6)及(8)中，碳數1至4的氟烷二基可列舉出全氟烷二基，較佳可列舉出-CF2-、-CF2CF2-、-CF2CF2CF2-、-C(CF3)2-、-CF2CF2CF2CF2-等。 In formulas (6) and (8), the fluoroalkanediyl having 1 to 4 carbon atoms includes perfluoroalkanediyl, and preferably -CF 2 -, -CF 2 CF 2 -, and -CF 2 CF are exemplified. 2 CF 2 -, -C(CF 3 ) 2 -, -CF 2 CF 2 CF 2 CF 2 - and the like.

以式(6)所表示之陰離子(以下有時稱為「陰離子(6)」)，可列舉出分別以式(6-1)至式(6-6)所表示之陰離子(以下有時稱為「陰離子(6-1)至陰離子(6-6)」)。 The anion represented by the formula (6) (hereinafter sometimes referred to as "anion (6)") includes the anions represented by the formula (6-1) to the formula (6-6) (hereinafter sometimes referred to as the formula (6-6). is "anion (6-1) to anion (6-6)").

Figure 106134182-A0202-12-0010-12
Figure 106134182-A0202-12-0010-12

以式(7)所表示之陰離子(以下有時稱為「陰離子(7)」)，可列舉出以下述式(7-1)所表示之陰離子(7-1)。 Examples of the anion represented by the formula (7) (hereinafter sometimes referred to as "anion (7)") include the anion (7-1) represented by the following formula (7-1).

Figure 106134182-A0202-12-0010-13
Figure 106134182-A0202-12-0010-13

以式(8)所表示之陰離子(以下有時稱為「陰離子(8)」)，可列舉出分別以式(8-1)至式(8-4)所表示之陰離子(以下有時稱為「陰離子(8-1)」至「陰離子(8-4)」)。 The anion represented by the formula (8) (hereinafter sometimes referred to as "anion (8)") includes the anions represented by the formula (8-1) to the formula (8-4) (hereinafter sometimes referred to as the formula (8-4). are "anion (8-1)" to "anion (8-4)").

ΘO3S-CF2-SO3 Θ (8-1) ΘO3S-CF2CF2CF2-SO3 Θ (8-3) Θ O 3 S-CF 2 -SO 3 Θ (8-1) Θ O 3 S-CF 2 CF 2 CF 2 -SO 3 Θ (8-3)

ΘO3S-CF2CF2-SO3 Θ (8-2) ΘO3S-CF2CF2CF2CF2-SO3 Θ (8-4) Θ O 3 S-CF 2 CF 2 -SO 3 Θ (8-2) Θ O 3 S-CF 2 CF 2 CF 2 CF 2 -SO 3 Θ (8-4)

以式(9)所表示之陰離子(以下有時稱為「陰離子(9)」)，可列舉出分別以式(9-1)至式(9-4)所表示之陰離子(以下有時稱為「陰離子(9-1)」至「陰離子(9-4)」)。 The anion represented by formula (9) (hereinafter sometimes referred to as "anion (9)") includes anions (hereinafter sometimes referred to as formula (9-1) to formula (9-4), respectively). are "anion (9-1)" to "anion (9-4)").

F3C-SO3 Θ (9-1) F3CF2CF2C-SO3 Θ (9-3) F 3 C-SO 3 Θ (9-1) F 3 CF 2 CF 2 C-SO 3 Θ (9-3)

F3CF2C-SO3 Θ (9-2) F3CF2CF2CF2C-SO3 Θ (9-4) F 3 CF 2 C-SO 3 Θ (9-2) F 3 CF 2 CF 2 CF 2 C-SO 3 Θ (9-4)

[Y2]m-，較佳為含氟陰離子、多酸陰離子，尤佳為以式(6)所表示之陰離子、[PW12O40]3-、[P2W18O62]6-、 [SiW12O40]4-及[W10O32]4-，更佳為以式(6-1)至式(6-5)所表示之陰離子、[PW12O40]3-、及[P2W18O62]6-，特佳為以式(6-2)所表示之陰離子以及[PW12O40]3-。 [Y 2 ] m- is preferably a fluorine-containing anion, a polyacid anion, particularly preferably an anion represented by the formula (6), [PW 12 O 40 ] 3- , [P 2 W 18 O 62 ] 6- , [SiW 12 O 40 ] 4- and [W 10 O 32 ] 4- , more preferably an anion represented by formula (6-1) to formula (6-5), [PW 12 O 40 ] 3- , and [P 2 W 18 O 62 ] 6- , particularly preferably an anion represented by the formula (6-2) and [PW 12 O 40 ] 3- .

m表示任意的自然數，等於陰離子[Y2]m-所具有之負的電荷。陽離子側的m，係以使陰離子[Y2]m-與陽離子的電荷成為相等之方式來決定。m較佳為1至10的自然數。 m represents an arbitrary natural number, which is equal to the negative charge possessed by the anion [Y 2 ] m- . The m on the cation side is determined so that the charges of the anion [Y 2 ] m- and the cation become equal. m is preferably a natural number from 1 to 10.

以R41至R44所表示之碳數1至20的飽和烴基，可為直鏈狀、分枝鏈狀及環狀中之任一種。此外，該飽和烴基的碳數較佳為1至10，尤佳為1至8，更佳為1至6，特佳為1至4。 The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 41 to R 44 may be any of linear, branched and cyclic. Furthermore, the carbon number of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, particularly preferably 1 to 4.

前述直鏈狀或分枝鏈狀的飽和烴基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、辛基、壬基、癸基等之直鏈狀烷基；異丙基、異丁基、2-乙基己基等之分枝鏈狀烷基。直鏈狀或分枝鏈狀之飽和烴的碳數，較佳為1至8，尤佳為1至6，更佳為1至4。 The straight-chain or branched-chain saturated hydrocarbon groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl; iso- Branched chain alkyl of propyl, isobutyl, 2-ethylhexyl, etc. The carbon number of the linear or branched saturated hydrocarbon is preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4.

前述環狀的飽和烴基，可為單環或多環。該環狀的飽和烴基，可列舉出環丙基、環丁基、環戊基、環己基、金剛烷基等。環狀飽和烴基的碳數，較佳為3至10，尤佳為6至10。 The aforementioned cyclic saturated hydrocarbon group may be monocyclic or polycyclic. The cyclic saturated hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably from 3 to 10, particularly preferably from 6 to 10.

R41至R44之飽和烴基的氫原子，可藉由取代基所取代。該取代基，可列舉出取代或非取代的胺基或鹵素原子。取代胺基，可列舉出二甲基胺基等之二烷基胺基等，鹵素原子可列舉出氟原子、氯原子、溴原子、碘原子。 氫原子藉由取代或非取代的胺基或鹵素原子所取代之飽和烴基，例如可列舉出以下述式所表示之基。下述式中，*表示與氮原子之鍵結鍵。 The hydrogen atom of the saturated hydrocarbon group of R 41 to R 44 may be substituted by a substituent. Examples of the substituent include substituted or unsubstituted amine groups and halogen atoms. Examples of the substituted amino group include dialkylamine groups such as a dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of saturated hydrocarbon groups in which hydrogen atoms are substituted with substituted or unsubstituted amine groups or halogen atoms include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

Figure 106134182-A0202-12-0012-14
Figure 106134182-A0202-12-0012-14

以R41至R44所表示之基中，於構成碳數2至20的烷基之亞甲基(碳原子)之間***有氧原子之基，例如可列舉出以下述式所表示之基。下述式中，*表示與氮原子之鍵結鍵。當中，於構成該烷基之亞甲基之間***有氧原子之基，較佳為碳數2至10之基，尤佳為碳數2至6之基。***有氧原子之烷基，較佳為直鏈烷基。此外，氧原子間的碳數，較佳為1至4個，尤佳為2至3個。 Among the groups represented by R 41 to R 44 , groups in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms include, for example, groups represented by the following formulae . In the following formula, * represents a bond with a nitrogen atom. Among them, the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and particularly preferably a group having 2 to 6 carbon atoms. The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. Further, the number of carbon atoms between oxygen atoms is preferably 1 to 4, and particularly preferably 2 to 3.

Figure 106134182-A0202-12-0012-15
Figure 106134182-A0202-12-0012-15

R41至R44中，芳基的碳數較佳為6至20，尤 佳為6至10，芳烷基的碳數較佳為7至20，尤佳為7至10。 In R 41 to R 44 , the carbon number of the aryl group is preferably 6 to 20, particularly preferably 6 to 10, and the carbon number of the aralkyl group is preferably 7 to 20, particularly preferably 7 to 10.

R41至R44的芳基，可列舉出苯基、萘基、甲苯甲醯基等。 The aryl group of R 41 to R 44 includes a phenyl group, a naphthyl group, a tolyl group and the like.

R41至R44之芳烷基中的芳基，可列舉出苯基、萘基等，芳烷基可列舉出此等芳基的鍵結鍵與烷二基鍵結之基。前述烷二基的碳數較佳為1至10，尤佳為1至5，較佳為直鏈狀烷二基。前述烷二基，具體可列舉出亞甲基、伸乙基、伸丙基、丁二基、戊二基等，芳烷基可列舉出苯甲基、苯乙基、萘甲基、萘乙基等。 Examples of the aryl group in the aralkyl group of R 41 to R 44 include a phenyl group, a naphthyl group, and the like, and the aralkyl group includes a group in which a bond of these aryl groups and an alkanediyl group are bonded. The carbon number of the aforementioned alkanediyl group is preferably 1 to 10, particularly preferably 1 to 5, and is preferably a linear alkanediyl group. Specific examples of the alkanediyl group include methylene group, ethylidene group, propylidene group, butanediyl group, pentanediyl group, and the like, and the aralkyl group includes benzyl group, phenethyl group, naphthylmethyl group, and naphthylethyl group. Base et al.

以R41至R44所表示之基中，於芳基及芳烷基中，取代基可列舉出氟原子、氯原子、碘原子等之鹵素原子；甲氧基、乙氧基等之碳數1至6的烷氧基；羥基；甲基磺醯基等之碳數1至6的烷基磺醯基；甲氧羰基、乙氧羰基等之碳數2至6的烷氧羰基等。 Among the groups represented by R 41 to R 44 , in the aryl group and the aralkyl group, the substituents include halogen atoms such as fluorine atom, chlorine atom, iodine atom, etc.; carbon number such as methoxy group, ethoxy group, etc. Alkoxy groups of 1 to 6; hydroxyl; alkylsulfonyl groups of 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups of 2 to 6 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, and the like.

可經取代之芳基的具體例，可列舉出以下述式所表示之基。下述式中，*表示與氮原子之鍵結鍵。 Specific examples of the aryl group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

Figure 106134182-A0202-12-0014-16
Figure 106134182-A0202-12-0014-16

可經取代之芳烷基的具體例，可列舉出亞甲基、伸乙基等之伸烷基鍵結於前述芳基的鍵結鍵之基。 Specific examples of the aralkyl group which may be substituted include a group in which an alkylene group such as a methylene group and an ethylidene group is bonded to the bonding bond of the aforementioned aryl group.

R41與R42可鍵結並與此等所鍵結之氮原子一同形成環，以及R43與R44可鍵結並與此等所鍵結之氮原子一同形成環，可列舉出吡咯啶(Pyrrolidine)等之5員環；嗎福林(Morpholine)環、哌啶(Piperidine)環、哌嗪(Piperazine)環等之6員環等。 R 41 and R 42 may bond and form a ring together with these bonded nitrogen atoms, and R 43 and R 44 may bond and form a ring with these bonded nitrogen atoms, and pyrrolidine can be exemplified (Pyrrolidine) and other 5-membered rings; Morpholine (Morpholine) ring, piperidine (Piperidine) ring, piperazine (Piperazine) ring and other 6-membered rings.

R41至R44，從合成容易度之點來看，較佳係互為獨立地為可經取代之碳數1至20的飽和烴基、可經取代之芳基、或可經取代之芳烷基，尤佳係互為獨立地為碳數1至8的飽和烴基或以下述式所表示之基。下述式中，*表示與氮原子之鍵結鍵。 R 41 to R 44 are preferably independently substituted saturated hydrocarbon groups having 1 to 20 carbon atoms, optionally substituted aryl groups, or optionally substituted aralkanes, from the viewpoint of ease of synthesis. The groups are preferably, independently of each other, a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Figure 106134182-A0202-12-0015-17
Figure 106134182-A0202-12-0015-17

以R45至R52所表示之飽和烴基，可為直鏈狀、分枝鏈狀及環狀中之任一種，較佳為鏈狀。以R45至R52所表示之飽和烴基，可列舉出以R41至R44所表示之飽 和烴基中所例示之基中之碳數1至8之基。 The saturated hydrocarbon group represented by R 45 to R 52 may be any of linear, branched and cyclic, preferably chain. The saturated hydrocarbon group represented by R 45 to R 52 includes a group having 1 to 8 carbon atoms among the groups exemplified in the saturated hydrocarbon group represented by R 41 to R 44 .

於構成該烷基之亞甲基(碳原子)之間***有氧原子之基，尤佳為碳數2至8之基。***有氧原子之烷基，較佳為直鏈烷基。氧原子間的碳數，較佳為1至4個，尤佳為2至3個。例如可列舉出以下述式所表示之基。下述式中，*表示與碳原子之鍵結鍵。 A group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting the alkyl group is particularly preferably a group having 2 to 8 carbon atoms. The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3. For example, the group represented by the following formula is mentioned. In the following formula, * represents a bond with a carbon atom.

Figure 106134182-A0202-12-0016-18
Figure 106134182-A0202-12-0016-18

R45至R52，從合成容易度之點來看，較佳係互為獨立地為氫原子、鹵素原子或碳數1至8的飽和烴基，尤佳係互為獨立地為氫原子、甲基、氟原子或氯原子。 R 45 to R 52 are preferably independently a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and are particularly preferably independently a hydrogen atom, methyl group, fluorine atom or chlorine atom.

R46與R50可相互鍵結而形成-O-、-NH-、-S-或-SO2-。 R 46 and R 50 may bond with each other to form -O-, -NH-, -S- or -SO 2 -.

Y1表示可經取代之芳基、或可經取代之雜芳基。 Y 1 represents an aryl group which may be substituted, or a heteroaryl group which may be substituted.

芳基可為單環及縮合環中之任一種，可列舉出苯基、甲苯基、二甲苯基、萘基、蒽基(Anthranyl)、菲基(Phenanthryl)、聯苯基、聯三苯基等之碳數6至20的芳香族烴基。 The aryl group may be either a single ring or a condensed ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a biphenyl group, and a bitriphenyl group. Aromatic hydrocarbon groups with 6 to 20 carbon atoms.

雜芳基為來自芳香族雜環之取代基。前述芳香族雜環可為單環及縮合環中之任一種，較佳為5至10員環，尤佳為5至9員環。 A heteroaryl group is a substituent derived from an aromatic heterocycle. The aforementioned aromatic heterocycle may be either a monocyclic ring or a condensed ring, preferably a 5- to 10-membered ring, particularly preferably a 5- to 9-membered ring.

單環的芳香族雜環，可列舉出吡咯環(Pyrrole)、噁唑(Oxazole)環、吡唑(Pyrazole)環、咪唑 (Imidazole)環、噻唑(Thiazole)環等之具有氮原子之5員環；呋喃(Furan)環、噻吩(Thiophene)環等之具有氧原子或硫原子之5員環；吡啶(Pyridine)環、嘧啶(Pyrimidine)環、噠嗪(Pyridazine)環、吡嗪(Pyrazine)環等之具有氮原子之6員環等。縮合環的芳香族雜環，可列舉出吲哚(Indole)環、苯并咪唑環、苯并噻唑環、喹啉(Quinoline)環等之具有氮原子之縮合環；苯并呋喃等之具有氧原子或硫原子之等。可經取代之雜芳基，尤佳為以式(Ab2-x1)所表示之基。 The monocyclic aromatic heterocyclic ring includes five members having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring. Ring; Furan (Furan) ring, Thiophene (Thiophene) ring and other 5-membered rings with oxygen atom or sulfur atom; Pyridine (Pyridine) ring, pyrimidine (Pyrimidine) ring, pyridazine (Pyridazine) ring, Pyrazine A 6-membered ring having a nitrogen atom, etc., is included in the ring. The aromatic heterocycle of the condensed ring includes a condensed ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; and an oxygen atom such as benzofuran. atom or sulfur atom etc. The heteroaryl group which may be substituted is particularly preferably a group represented by the formula (Ab2-x1).

Figure 106134182-A0202-12-0017-19
Figure 106134182-A0202-12-0017-19

[環T2表示芳香族雜環；R53及R54互為獨立地表示可經取代之碳數1至20的飽和烴基、於構成碳數2至20的烷基之碳原子間***有氧原子之基、可經取代之芳基、或可經取代之芳烷基、或是氫原子；R55表示氫原子、碳數1至20的飽和烴基、或可經取代之芳基；k1表示0或1；*表示與碳陽離子之鍵結鍵] [Ring T 2 represents an aromatic heterocycle; R 53 and R 54 independently represent a substituted saturated hydrocarbon group with 1 to 20 carbon atoms, and oxygen is inserted between the carbon atoms constituting the alkyl group with 2 to 20 carbon atoms Atomic group, aryl group that can be substituted, aralkyl group that can be substituted, or hydrogen atom; R 55 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group that can be substituted; k1 represents 0 or 1; * indicates a bond with a carbocation]

環T2表示芳香族雜環，較佳表示碳數2至9的芳香族雜環。 Ring T 2 represents an aromatic heterocycle, preferably an aromatic heterocycle having 2 to 9 carbon atoms.

R53至R55的詳細內容如後述。 Details of R 53 to R 55 will be described later.

化合物(A-I)，尤佳是以式(A-II)所表示之化合物。 The compound (A-I) is particularly preferably a compound represented by the formula (A-II).

Figure 106134182-A0202-12-0018-20
Figure 106134182-A0202-12-0018-20

[式(A-II)中，[Y2]m-、R41至R52及m與前述相同；R53及R54互為獨立地表示氫原子、可經取代之碳數1至20的飽和烴基、於構成碳數2至20的烷基之碳原子間***有氧原子之基、可經取代之芳基、或可經取代之芳烷基；R55表示氫原子、碳數1至20的飽和烴基、或可經取代之芳基；X表示氧原子、-NR57-或硫原子；R57表示氫原子或碳數1至10的烷基；當以式(A-II)所表示之化合物含有複數個陽離子時，複數個陽離子可互為相同結構或相異結構] [In formula (A-II), [Y 2 ] m- , R 41 to R 52 and m are the same as described above; R 53 and R 54 independently represent a hydrogen atom, a substituted carbon number of 1 to 20 A saturated hydrocarbon group, a group in which an oxygen atom is inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, an aryl group that may be substituted, or an aralkyl group that may be substituted; R 55 represents a hydrogen atom, a carbon number of 1 to 20 A saturated hydrocarbon group of 20, or an aryl group that can be substituted; X 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; when represented by formula (A-II) When the compound represented contains multiple cations, the multiple cations may have the same structure or different structures]

R53及R54，可列舉出與R41至R44中所例示之基為相同之基。 R 53 and R 54 include the same groups as those exemplified for R 41 to R 44 .

以R55所表示之碳數1至20的飽和烴基，可列舉出與R41至R44的飽和烴基中所例示之基為相同之基。當中較佳為碳數1至10的烷基，尤佳為碳數1至8的烷基，更佳為碳數1至6的烷基，特佳為碳數1至4的烷基。 Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 55 include the same groups as those exemplified in the saturated hydrocarbon group of R 41 to R 44 . Among them, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is particularly preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

以R55所表示之於構成上述烷基之碳原子間***有氧原子之基，可列舉出與R41至R44中所例示之基為相同之基。***有氧原子之烷基，較佳為直鏈烷基。此外，氧原子間的碳數，較佳為1至4個，尤佳為2至3個。 The group represented by R 55 in which an oxygen atom is inserted between carbon atoms constituting the above-mentioned alkyl group includes the same groups as those exemplified in R 41 to R 44 . The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. Further, the number of carbon atoms between oxygen atoms is preferably 1 to 4, and particularly preferably 2 to 3.

R55中，芳基的碳數較佳為6至20，尤佳為6至10。該芳基，可列舉出與R41至R44中所例示之芳基為相同之基，較佳為苯基。 In R 55 , the carbon number of the aryl group is preferably from 6 to 20, particularly preferably from 6 to 10. Examples of the aryl group include the same groups as the aryl groups exemplified in R 41 to R 44 , and preferably a phenyl group.

R55中，芳基所具有之取代基，可列舉出氟原子、氯原子、碘原子等之鹵素原子；甲氧基、乙氧基等之碳數1至6的烷氧基；羥基；胺磺醯基；甲基磺醯基等之碳數1至6的烷基磺醯基；甲氧羰基、乙氧羰基等之碳數2至6的烷氧羰基等。 In R 55 , the substituents possessed by the aryl group include halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; amines Sulfonyl; alkylsulfonyl having 1 to 6 carbons such as methylsulfonyl; alkoxycarbonyl having 2 to 6 carbons such as methoxycarbonyl, ethoxycarbonyl and the like.

R55，從合成容易度之點來看，較佳為碳數1至10的飽和烴基或可經取代之芳基，尤佳為碳數1至8的烷基，或是可經鹵素原子、碳數1至4的烷氧基、羥基、或甲基磺醯基取代之芳基，更佳為以下述式所表示之基。下述式中，*表示與碳原子之鍵結鍵。 R 55 is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group that may be substituted, particularly preferably an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, or a halogen atom, The aryl group substituted with an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a methylsulfonyl group is more preferably a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

Figure 106134182-A0202-12-0020-21
Figure 106134182-A0202-12-0020-21

R57，較佳為碳數1至4的烷基，尤佳為甲基。 R 57 is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.

X表示氧原子、-NR57-或硫原子。含有X之環狀結構，例如可列舉出以下述式所表示之基。式中，R53至R55分別與上述同義，*表示與碳陽離子之鍵結鍵。當中，X較佳為氧原子或硫原子，尤佳為硫原子。 X represents an oxygen atom, -NR 57 - or a sulfur atom. Examples of the cyclic structure containing X include groups represented by the following formulae. In the formula, R 53 to R 55 are respectively synonymous with the above, and * represents a bond with a carbocation. Among them, X is preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.

Figure 106134182-A0202-12-0020-22
Figure 106134182-A0202-12-0020-22

式(A-I)所具有之陽離子，為式(A-I-1)所表示之陽離子，可列舉出具有表2所示之取代基之陽離子1至陽離子27。 The cations of formula (A-I) are cations represented by formula (A-I-1), and cations 1 to 27 having substituents shown in Table 2 are exemplified.

Figure 106134182-A0202-12-0021-23
Figure 106134182-A0202-12-0021-23

Figure 106134182-A0202-12-0021-25
Figure 106134182-A0202-12-0021-25

表2中，Ph1至Ph12意指以下述式所表示之基。 In Table 2, Ph1 to Ph12 mean groups represented by the following formulae.

Figure 106134182-A0202-12-0022-26
Figure 106134182-A0202-12-0022-26

式(A-I)中的陽離子，較佳為陽離子1至陽離子6、陽離子11及陽離子12，尤佳為陽離子1、陽離子2及陽離子12。 The cations in the formula (A-I) are preferably cation 1 to cation 6, cation 11 and cation 12, and particularly preferably cation 1, cation 2 and cation 12.

當以式(A-II)所表示之化合物含有複數個陽離子時，複數個陽離子可互為相同結構或相異結構。 When the compound represented by the formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

(二苯并哌喃染料(Aa2)) (Dibenzopyran dye (Aa2))

二苯并哌喃染料(Aa2)，為含有分子內具有二苯并哌喃骨架之化合物之染料。二苯并哌喃染料(Aa2)，可列舉出C.I.酸性紅51(以下省略C.I.酸性紅的記載，僅記載編號。其他亦同)、52、87、92、94、289、388；C.I.酸性紫9、30、102；C.I.鹼性紅1(玫瑰紅6G)、2、3、4、8；C.I.鹼性紅10(玫瑰紅B)、11；C.I.鹼性紫10、11、25；C.I.溶劑紅218；C.I.媒染紅媒染紅27；C.I.活性紅36(孟加拉玫瑰素B)、磺基玫瑰紅G、日本特開2010-32999號公報所記載之二苯并哌喃染料及日本特許第4492760號公報所記 載之二苯并哌喃染料等。當中較佳為溶解於有機溶劑之二苯并哌喃染料。 Dibenzopyran dye (Aa2) is a dye containing a compound having a dibenzopyran skeleton in the molecule. Dibenzopyran dyes (Aa2) include C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted, and only the number is described. The same applies to others), 52, 87, 92, 94, 289, 388; C.I. Acid Violet 9, 30, 102; C.I. Basic Red 1 (Rose Red 6G), 2, 3, 4, 8; C.I. Basic Red 10 (Rose Red B), 11; C.I. Basic Violet 10, 11, 25; C.I. Solvent Red 218; C.I. Mordant Red Mordant Red 27; C.I. Reactive Red 36 (Rose Bengal B), Sulfo Rose Bengal G, Dibenzopyran dyes described in Japanese Patent Laid-Open No. 2010-32999 and Japanese Patent No. 4492760 Dibenzopyran dyes and the like described in the gazette. Among them, dibenzopyran dyes dissolved in organic solvents are preferred.

此等當中，二苯并哌喃染料(Aa2)較佳為含有以式(1a)所表示之化合物及該互變異構物(以下有時將此等總稱為「化合物(1a)」)之染料。使用化合物(1a)時，二苯并哌喃染料(A2)中之化合物(1a)的含量，較佳為50質量%以上，尤佳為70質量%以上，更佳為90質量%以上。當中，二苯并哌喃染料(A2)較佳係僅使用化合物(1a)。 Among these, the dibenzopyran dye (Aa2) is preferably a dye containing the compound represented by the formula (1a) and the tautomer (hereinafter, these may be collectively referred to as "compound (1a)"). . When the compound (1a) is used, the content of the compound (1a) in the dibenzopyran dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. Among them, it is preferable to use only the compound (1a) as the dibenzopyran dye (A2).

Figure 106134182-A0202-12-0023-27
Figure 106134182-A0202-12-0023-27

[式(1a)中，R1至R4互為獨立地表示氫原子、碳數1至20之1價的飽和烴基、或可具有取代基之碳數6至10之1價的芳香族烴基，該飽和烴基所含有之氫原子，可經碳數6至10的芳香族烴基、或鹵素原子所取代，該芳香族烴基所含有之氫原子，可經碳數1至3的烷氧基所取代，前述飽和烴基所含有之-CH2-，可經-O-、-CO-或-NR11-置換；R1與R2可成為一體而形成含有氮原子之環，R3與R4可成為一體而形成含有氮原子之環；R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10；R6及R7互為獨立地表示氫原子或碳數1至6的烷基； m表示0至5的整數；m為2以上的整數時，複數個R5可為相同或相異；a表示0或1的整數；X0表示鹵素原子；R8表示碳數1至20之1價的飽和烴基，該飽和烴基所含有之氫原子，可經鹵素原子所取代；Z+表示+N(R11)4、Na+或K+；R9及R10互為獨立地表示氫原子或可具有取代基之碳數1至20之1價的飽和烴基，該飽和烴基所含有之-CH2-，可經-O-、-CO-、-NH-或-NR8-置換；R9及R10可相互鍵結而形成含有氮原子之3至10員環的雜環；+N(R11)4中的4個R11，係互為獨立地表示氫原子、碳數1至20之1價的飽和烴基或碳數7至10的芳烷基] [In formula (1a), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms that may have a substituent , the hydrogen atom contained in the saturated hydrocarbon group may be replaced by an aromatic hydrocarbon group with a carbon number of 6 to 10 or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be replaced by an alkoxy group with a carbon number of 1 to 3 Substitution, the -CH 2 - contained in the aforementioned saturated hydrocarbon group can be replaced by -O-, -CO- or -NR 11 -; R 1 and R 2 can be integrated to form a ring containing nitrogen atoms, R 3 and R 4 Can be integrated to form a ring containing nitrogen 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 of 0 to 5; m is 2 or more When the integer of R 5 can be the same or different; a represents an integer of 0 or 1; X0 represents a halogen atom; R 8 represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, and the hydrogen contained in the saturated hydrocarbon group Atom, which may be substituted by a halogen atom; Z + represents + N(R 11 ) 4 , Na + or K + ; R 9 and R 10 independently represent a hydrogen atom or a substituent with 1 to 20 carbon atoms. Monovalent saturated hydrocarbon group, the -CH 2 - contained in the saturated hydrocarbon group can be replaced by -O-, -CO-, -NH- or -NR 8 -; R 9 and R 10 can be bonded to each other to form nitrogen-containing A 3- to 10-membered heterocyclic ring of atoms; 4 R 11 in + N(R 11 ) 4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or a monovalent saturated hydrocarbon group with 7 to 20 carbon atoms. 10 aralkyl]

表示R1至R4之1價的芳香族烴基，可列舉出苯基、甲苯基、二甲苯基、三甲苯基、丙基苯基及丁基苯基等。 A phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, a butylphenyl group, etc. are mentioned as a monovalent aromatic hydrocarbon group which shows R< 1 >-R< 4 >.

該芳香族烴基可具有之取代基，可列舉出鹵素原子、-R8、-OH、-OR8、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2R8、SR8、-SO2R8、-SO3R8或-SO2NR9R10。此等當中，取代基較佳為-SO3 -、-SO3H、-SO3 -Z+及-SO2NR9R10，尤佳為-SO3 -Z+及-SO2NR9R10。此時之-SO3 -Z+，較佳為-SO3 -+N(R11)4。當R1至R4為此等基時，從含有化合物(1a)之本發明之著色硬化性樹脂組成物中，可形成雜質的產生較少且耐熱性優異之彩色濾光片。 The substituent which the aromatic hydrocarbon group may have includes halogen atom, -R 8 , -OH, -OR 8 , -SO 3 - , -SO 3 H, -SO 3 - Z + , -CO 2 H, - CO 2 R 8 , SR 8 , -SO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 . Among these, the substituents are preferably -SO 3 - , -SO 3 H, -SO 3 - Z + and -SO 2 NR 9 R 10 , particularly preferably -SO 3 - Z + and -SO 2 NR 9 R 10 . In this case, -SO 3 - Z + is preferably -SO 3 -+ N(R 11 ) 4 . When R 1 to R 4 are such groups, from the colored curable resin composition of the present invention containing the compound (1a), a color filter with less generation of impurities and excellent heat resistance can be formed.

R1與R2成為一體所形成之環，以及R3與R4 成為一體所形成之環，例如可列舉出以下所示者。 The ring formed by the integration of R 1 and R 2 and the ring formed by the integration of R 3 and R 4 include, for example, those shown below.

Figure 106134182-A0202-12-0025-28
Figure 106134182-A0202-12-0025-28

表示R8至R11之1價的飽和烴基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十六烷基、二十烷基等之直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、2-乙基己基等之分枝鏈狀烷基；環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等之碳數3至20的脂環式飽和烴基。 The monovalent saturated hydrocarbon group representing R 8 to R 11 includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Linear alkyl groups such as hexadecyl, eicosyl, etc.; branched chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc.; cyclopropyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms.

-OR8，可列舉出甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基及二十烷氧基等。 -OR 8 includes methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and eicosane Oxygen, etc.

-CO2R8，可列舉出甲氧羰基、乙氧羰基、丙氧羰基、三級丁氧羰基、己氧羰基及二十烷氧羰基等。 -CO 2 R 8 includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, hexyloxycarbonyl, eicosyloxycarbonyl, and the like.

SR8，可列舉出甲基氫硫基、乙基氫硫基、丁基氫硫基、己基氫硫基、癸基氫硫基及二十烷基氫硫基等。 As SR 8 , methyl thiosulfanyl, ethyl sulfhydryl, butyl sulfhydryl, hexyl sulfhydryl, decyl sulfhydryl, eicosyl sulfhydryl, and the like are exemplified.

-SO2R8，可列舉出甲基磺醯基、乙基磺醯基、丁基磺醯基、己基磺醯基、癸基磺醯基及二十烷基磺醯基等。 -SO 2 R 8 includes methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, eicosylsulfonyl, and the like.

-SO3R8，可列舉出甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、三級丁氧基磺醯基、己氧基磺醯基及二十烷氧基磺醯基等。 -SO 3 R 8 , methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary butoxysulfonyl, hexyloxysulfonyl, and eicosyloxy Sulfonyl, etc.

-SO2NR9R10，可列舉出胺磺醯基；N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、 N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-二級丁基胺磺醯基、N-三級丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N-(3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基等之N-1取代胺磺醯基；N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-三級丁基甲基胺磺醯基、N,N-丁基乙基胺磺醯基、N,N-雙(1-甲基丙基)胺磺醯基、N,N-庚基甲基胺磺醯基等之N,N-2取代胺磺醯基等。 -SO 2 NR 9 R 10 , sulfasulfonyl; Sulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-second-butylaminesulfonyl, N-tertiary-butylaminesulfonyl, N-amylaminesulfonyl Acyl, N-(1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) amine Sulfonyl, N-(2,2-dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl) sulfamoyl base, N-(3-methylbutyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl Sulfonyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4 -Dimethylpentyl) sulfamoyl, N-octyl sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethyl)hexyl sulfamoyl N-1-substituted sulfamoyl group, N-(1,1,2,2-tetramethylbutyl) sulfamoyl group, etc.; N,N-dimethylsulfamoyl group, N,N- Ethylmethylaminosulfonyl, N,N-diethylaminosulfonyl, N,N-propylmethylaminosulfonyl, N,N-isopropylmethylaminosulfonyl, N, N-tertiary butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethyl N,N-2 substituted sulfamoyl groups such as sulfamoyl groups, etc.

表示R9或R10之1價的飽和烴基中之取代基，可列舉出羥基及鹵素原子。 The substituent in the monovalent saturated hydrocarbon group representing R 9 or R 10 includes a hydroxyl group and a halogen atom.

R5較佳為-CO2H、-CO2 -Z+、-CO2R8、-SO3 -、-SO3 -Z+、-SO3H或-SO2NHR9，尤佳為-SO3 -、-SO3 -Z+、-SO3H或-SO2NHR9。 R 5 is preferably -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 - , -SO 3 - Z + , -SO 3 H or -SO 2 NHR 9 , particularly preferably - SO 3 - , -SO 3 - Z + , -SO 3 H or -SO 2 NHR 9 .

m較佳為1至4，尤佳為1或2。 m is preferably 1 to 4, particularly preferably 1 or 2.

表示R6及R7之碳數1至6的烷基，可為直鏈或分枝鏈，可列舉出甲基、乙基、丙基、丁基、戊基、己基。 The alkyl group having 1 to 6 carbon atoms representing R 6 and R 7 may be a straight chain or a branched chain, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

表示R11之芳烷基，可列舉出苯甲基、苯基乙基、苯 基丁基等。 The aralkyl group representing R 11 includes a benzyl group, a phenylethyl group, a phenylbutyl group, and the like.

Z+為+N(R11)4、Na+或K+，較佳為+N(R11)4。 Z + is + N(R 11 ) 4 , Na + or K + , preferably + N(R 11 ) 4 .

前述+N(R11)4，於4個R11中，較佳係至少2個為碳數5至20之1價的飽和烴基。4個R11的合計碳數較佳為20至80，尤佳為20至60。於化合物(1a)中存在有+N(R11)4時，若R11為此等基，則從含有化合物(1a)之本發明之著色硬化性樹脂組成物中，可形成雜質少之彩色濾光片。 In the aforementioned + N(R 11 ) 4 , among the four R 11 , at least two of them are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R 11s is preferably from 20 to 80, particularly preferably from 20 to 60. When + N(R 11 ) 4 is present in the compound (1a), if R 11 is such a group, the color curable resin composition of the present invention containing the compound (1a) can form a color with few impurities filter.

化合物(1a)的較佳例子，可列舉出以式(2a)所表示之化合物及該互變異構物(以下有時將此等總稱為「化合物(2a)」)。使用化合物(2a)時，二苯并哌喃染料(A2)中之化合物(2a)的含量，較佳為50質量%以上，尤佳為70質量%以上，更佳為90質量%以上。 Preferable examples of the compound (1a) include the compound represented by the formula (2a) and the tautomer (hereinafter, these may be collectively referred to as "compound (2a)"). When the compound (2a) is used, the content of the compound (2a) in the dibenzopyran dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more.

Figure 106134182-A0202-12-0027-29
Figure 106134182-A0202-12-0027-29

[式(2a)中，R21至R24互為獨立地表示氫原子、-R26或可具有取代基之可具有碳數6至10之1價的取代基之芳香族烴基；R11與R22可成為一體而形成含有氮原子之環，R23與R24可成為一體而形成含有氮原子之環；R25表示-SO3 -、-SO3H、-SO3 -Z1+或-SO2NHR26；m1表示0至5的整數；m1為2以上的整數時，複數個R25可為相同或相異；a1表示0或1的整數； X1表示鹵素原子；R26表示碳數1至20之1價的飽和烴基；Z1+表示+N(R27)4、Na+或K+；+N(R27)4中的4個R27，係互為獨立地表示碳數1至20之1價的飽和烴基或苯甲基] [In formula (2a), R 21 to R 24 each independently represent a hydrogen atom, -R 26 or an aromatic hydrocarbon group which may have a substituent which may have a monovalent substituent of 6 to 10 carbon atoms; R 11 and R 22 can be integrated to form a ring containing nitrogen atoms, R 23 and R 24 can be integrated to form a ring containing nitrogen atoms; R 25 represents -SO 3 - , -SO 3 H, -SO 3 - Z1 + or - SO 2 NHR 26 ; m1 represents an integer from 0 to 5; when m1 is an integer of 2 or more, a plurality of R 25 may be the same or different; a1 represents an integer of 0 or 1; X1 represents a halogen atom; R 26 represents the carbon number Monovalent saturated hydrocarbon group of 1 to 20; Z1 + represents + N(R 27 ) 4 , Na + or K + ; 4 R 27 in + N(R 27 ) 4 independently represent carbon number 1 Monovalent saturated hydrocarbon group or benzyl group to 20]

表示R21至R24之1價的芳香族烴基，可列舉出與前述R1至R4中所列舉之芳香族烴基為相同之基；該芳香族烴基所含有之氫原子，可經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26所取代。 The monovalent aromatic hydrocarbon group representing R 21 to R 24 can be the same as the aromatic hydrocarbon group exemplified in the aforementioned R 1 to R 4 ; the hydrogen atom contained in the aromatic hydrocarbon group can be represented by -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 .

R21至R24的組合，較佳係R21及R23為氫原子，R22及R24為碳數6至10之1價的芳香族烴基，且該芳香族烴基所含有之氫原子經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26所取代者。更佳的組合，係R21及R23為氫原子，R22及R24為碳數6至10之1價的芳香族烴基，且該芳香族烴基所含有之氫原子經-SO3 -Z1+或-SO2NHR26所取代者。當R21至R24為此等基時，從含有化合物(2a)之本發明之著色硬化性樹脂組成物，可形成耐熱性優異之彩色濾光片。 The combination of R 21 to R 24 is preferably that R 21 and R 23 are hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 . A more preferable combination is that R 21 and R 23 are hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups with 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO 3 - Z1 + or - SO 2 NHR 26 superseded. When R 21 to R 24 are such groups, a color filter excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

R21與R22成為一體所形成之含有氮原子之環，以及R23與R24成為一體所形成之含有氮原子之環，可列舉出與R1與R2成為一體所形成之環為相同之環。當中較佳為脂肪族雜環。該脂肪族雜環例如可列舉出以下所示者。 The ring containing a nitrogen atom formed by the integration of R 21 and R 22 , and the ring containing a nitrogen atom formed by the integration of R 23 and R 24 , are the same as the ring formed by the integration of R 1 and R 2 . ring. Among them, an aliphatic heterocycle is preferred. Examples of the aliphatic heterocycle include those shown below.

Figure 106134182-A0202-12-0028-30
Figure 106134182-A0202-12-0028-30

表示R26及R27之碳數1至20之1價的飽和烴基，可列舉出與R8至R11中作為飽和烴基所列舉之基為相同之基。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R 26 and R 27 include the same groups as those exemplified as the saturated hydrocarbon group among R 8 to R 11 .

當R21至R24為-R26時，-R26較佳係互為獨立地為甲基或乙基。-SO3R26及-SO2NHR26中的R26，較佳為碳數3至20之分枝鏈狀烷基，尤佳為碳數6至12之分枝鏈狀烷基，更佳為2-乙基己基。當R26為此等基時，從含有化合物(2a)之本發明之著色硬化性樹脂組成物，可形成雜質的產生少之彩色濾光片。 When R 21 to R 24 are -R 26 , -R 26 is preferably independently methyl or ethyl. R 26 in -SO 3 R 26 and -SO 2 NHR 26 is preferably a branched chain alkyl group having 3 to 20 carbon atoms, particularly preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably For 2-ethylhexyl. When R 26 is such a group, a color filter with little generation of impurities can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1+為+N(R27)4、Na+或K+，較佳為+N(R27)4。 Z1 + is + N(R 27 ) 4 , Na + or K + , preferably + N(R 27 ) 4 .

前述+N(R27)4，於4個R27中，較佳係至少2個為碳數5至20之1價的飽和烴基。此外，4個R27的合計碳數較佳為20至80，尤佳為20至60。於化合物(2a)中存在有+N(R27)4時，從含有R27為此等基的化合物(2a)之本發明之著色硬化性樹脂組成物，可形成雜質的產生少之彩色濾光片。 In the aforementioned + N(R 27 ) 4 , among the four R 27 , at least two of them are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, the total carbon number of the four R 27s is preferably from 20 to 80, particularly preferably from 20 to 60. When + N(R 27 ) 4 is present in the compound (2a), the colored curable resin composition of the present invention containing the compound (2a) in which R 27 is such a group can form a color filter with less generation of impurities. light sheet.

m1較佳為1至4，尤佳為1或2。 m1 is preferably 1 to 4, particularly preferably 1 or 2.

化合物(1a)的較佳例子，可列舉出以式(3a)所表示之化合物及該互變異構物(以下有時將此等總稱為「化合物(3a)」)。使用化合物(3a)時，二苯并哌喃染料(Aa)中之化合物(3a)的含量，較佳為50質量%以上，尤佳為70質量%以上，更佳為90質量%以上。 Preferable examples of the compound (1a) include the compound represented by the formula (3a) and the tautomer (hereinafter, these may be collectively referred to as "compound (3a)"). When the compound (3a) is used, the content of the compound (3a) in the dibenzopyran dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more.

Figure 106134182-A0202-12-0030-31
Figure 106134182-A0202-12-0030-31

[式(3a)中，R31及R32互為獨立地表示碳數1至10之1價的飽和烴基，該飽和烴基所含有之氫原子，可經碳數6至10的芳香族烴基、或鹵素原子所取代，該芳香族烴基所含有之氫原子，可經碳數1至3的烷氧基所取代，前述飽和烴基所含有之-CH2-，可經-O-、-CO-或-NR11-置換；R33與R34互為獨立地表示碳數1至4的烷基、碳數1至4的烷基氫硫基或碳數1至4的烷基磺醯基；R31與R33可成為一體而形成含有氮原子之環，R32與R34可成為一體而形成含有氮原子之環；p及q互為獨立地表示0至5的整數；p為2以上時，複數個R33可為相同或相異，q為2以上時，複數個R34可為相同或相異；R11表示與上述相同涵義] [In formula (3a), R 31 and R 32 each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group can be converted to an aromatic hydrocarbon group having 6 to 10 carbon atoms, Or halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group can be substituted by an alkoxy group with 1 to 3 carbon atoms, the -CH 2 - contained in the aforementioned saturated hydrocarbon group can be replaced by -O-, -CO- or -NR 11 -replacement; R 33 and R 34 independently represent an alkyl group with 1 to 4 carbon atoms, an alkyl hydrogen thio group with 1 to 4 carbon atoms or an alkylsulfonyl group with 1 to 4 carbon atoms; R 31 and R 33 may be integrated to form a ring containing a nitrogen atom, R 32 and R 34 may be integrated to form a ring containing a nitrogen atom; p and q independently represent an integer from 0 to 5; p is 2 or more When , a plurality of R 33 can be the same or different, and when q is 2 or more, a plurality of R 34 can be the same or different; R 11 represents the same meaning as above]

R31及R32之1價的飽和烴基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等之直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、2-乙基己基等之分枝鏈狀烷基；環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等之碳數3至10的脂環式飽和烴基。 The monovalent saturated hydrocarbon group of R 31 and R 32 includes straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. ; Branched chain alkyl of isopropyl, isobutyl, isoamyl, neopentyl, 2-ethylhexyl, etc.; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as tricyclodecyl.

可具有之取代基之芳香族烴基，可列舉出與R1中的芳香族烴基為相同之基。 The aromatic hydrocarbon group which may have a substituent includes the same groups as the aromatic hydrocarbon group in R 1 .

碳數1至3的烷氧基，可列舉出甲氧基、乙氧基、丙氧基等。 Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R31及R32，較佳係互為獨立地為碳數1至3之1價的飽和烴基。 Preferably, R 31 and R 32 are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

表示R33及R34之碳數1至4的烷基，可列舉出甲基、乙基、丙基、丁基、異丙基、異丁基、二級丁基、三級丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms representing R 33 and R 34 include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, and tertiary butyl.

R33及R34之碳數1至4的烷基氫硫基，可列舉出甲基氫硫基、乙基氫硫基、丙基氫硫基、丁基氫硫基及異丙基氫硫基等。 R33 and R34 have 1 to 4 alkyl hydrogen sulfhydryl groups, such as methyl sulfhydryl, ethyl sulfhydryl, propyl sulfhydryl, butyl sulfhydryl, and isopropyl sulfhydryl Base et al.

R33及R34之碳數1至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、丁基磺醯基及異丙基磺醯基等。 The alkylsulfonyl groups having 1 to 4 carbon atoms in R 33 and R 34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl Base et al.

R33及R34較佳為碳數1至4的烷基，尤佳為甲基。 R 33 and R 34 are preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.

p及q較佳為0至2的整數，尤佳為0或1。 p and q are preferably an integer of 0 to 2, particularly preferably 0 or 1.

化合物(1a)，例如可列舉出分別以式(1-1)至式(1-42)或式(1-21')所表示之化合物。式中，R26表示碳數1至20之1價的飽和烴基，較佳為碳數6至12的分枝鏈狀烷基，更佳為2-乙基己基。以式(1-1)至式(1-29)、式(1-21')所表示之化合物，相當於化合物(2a)，以式(1-30)至式(1-42)所表示之化合物，相當於化合物(3a)。 As the compound (1a), for example, compounds represented by formula (1-1) to formula (1-42) or formula (1-21′), respectively, can be exemplified. In the formula, R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl. Compounds represented by formula (1-1) to formula (1-29) and formula (1-21') are equivalent to compound (2a), and are represented by formula (1-30) to formula (1-42) The compound corresponds to compound (3a).

Figure 106134182-A0202-12-0032-32
Figure 106134182-A0202-12-0032-32

Figure 106134182-A0202-12-0033-33
Figure 106134182-A0202-12-0033-33

Figure 106134182-A0202-12-0034-34
Figure 106134182-A0202-12-0034-34

Figure 106134182-A0202-12-0035-35
Figure 106134182-A0202-12-0035-35

Figure 106134182-A0202-12-0036-36
Figure 106134182-A0202-12-0036-36

Figure 106134182-A0202-12-0037-37
Figure 106134182-A0202-12-0037-37

此等當中，較佳為C.I.酸性紅289的碸醯胺化物、C.I.酸性紅289的四級銨鹽、C.I.酸性紫102的碸醯胺化物或C.I.酸性紫102的四級銨鹽。此化合物可列舉出以式(1-1)至式(1-8)、式(1-11)及式(1-12)所表示之化合物等。 Among these, the amide compound of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the amide compound of C.I. Acid Violet 102, or the quaternary ammonium salt of C.I. Acid Violet 102 are preferable. Examples of the compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

從對有機溶劑之溶解性優異之點來看，較佳為以式(1-30)至式(1-39)所表示之化合物。 Compounds represented by formula (1-30) to formula (1-39) are preferred from the viewpoint of being excellent in solubility in organic solvents.

二苯并哌喃染料(Aa2)，亦可為市售之二苯并哌喃染料(例如中外化成股份有限公司製的「Chugai Aminol Fast Pink R-H/C」、田岡化學工業股份有限公司製的「Rhodamin 6G」)。亦可以市售之二苯并哌喃染料為起始原料，參考日本特開2010-32999號公報來合成。 Dibenzopyran dye (Aa2), or commercially available dibenzopyran dye (such as "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd., "Chugai Aminol Fast Pink R-H/C" manufactured by Tianoka Chemical Industry Co., Ltd. Rhodamin 6G”). Commercially available dibenzopyran dyes can also be used as starting materials to synthesize with reference to Japanese Patent Laid-Open No. 2010-32999.

(蒽醌染料(Aa3)) (Anthraquinone dye (Aa3))

蒽醌染料(Aa3)可為一般所知的物質。蒽醌染料 (Aa3)，例如可列舉出：C.I.溶劑黃117(以下省略C.I.溶劑黃的記載，僅記載號碼。)、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.媒染藍等。蒽醌染料較佳為溶解於有機溶劑者。蒽醌染料，尤佳為藍色、紫色或紅色。 The anthraquinone dye (Aa3) may be a generally known substance. Examples of the anthraquinone dye (Aa3) include: C.I. Solvent Yellow 117 (C.I. Solvent Yellow 117 is omitted below, and only the number is given), 163, 167, 189, C.I. Solvent Orange 77, 86, C.I. Solvent Red 111, 143 , 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. 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, C.I. Solvent Green 3, 28, 29, 32, 33, C.I. Acid Red 80, C.I. Acid Green 25, 27, 28, 41, C.I. Acid Violet 34, C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. Disperse Yellow 51, C.I. Disperse Violet 26, 27, C.I. Disperse Blue 1, 14, 56, 60 , C.I. Direct Blue 40, C.I. Mordant Red 3, 11, C.I. Mordant Blue, etc. The anthraquinone dye is preferably dissolved in an organic solvent. Anthraquinone dyes, particularly preferably blue, violet or red.

蒽醌染料(Aa3)，較佳為以式(1b)所表示之化合物(以下有時稱為「化合物(1b)」)。 The anthraquinone dye (Aa3) is preferably a compound represented by formula (1b) (hereinafter sometimes referred to as "compound (1b)").

Figure 106134182-A0202-12-0039-38
Figure 106134182-A0202-12-0039-38

[式(1b)中，R91及R92互為獨立地表示氫原子、可具有取代基之碳數1至10的脂肪族烴基、可具有取代基之碳數3至10的脂環式烴基或以式(1b')所表示之基] [In formula (1b), R 91 and R 92 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or the base represented by formula (1b')]

Figure 106134182-A0202-12-0039-39
Figure 106134182-A0202-12-0039-39

[式(1b')中，R93表示碳數1至6的烷基、鹵素原子、-SO3H、-CO2H、-CO2R94、-NHCOR94、-SO3R94、或-SO2NR94R95；R94表示可經鹵素原子、羥基或胺基所取代之碳數1至10的飽和烴基、或可經鹵素原子、羥基或胺基所取代之碳數3至10的脂環式烴基；R95表示氫原子、或碳數1至10的飽和烴基；r表示0至5的整數；r為2以上時，複數個R93可為相同或相異；X91表示單鍵或碳數1至6的烷二基] [In formula (1b'), R 93 represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO 3 H, -CO 2 H, -CO 2 R 94 , -NHCOR 94 , -SO 3 R 94 , or -SO 2 NR 94 R 95 ; R 94 represents a saturated hydrocarbon group with 1 to 10 carbon atoms which may be substituted by a halogen atom, a hydroxyl group or an amine group, or a saturated hydrocarbon group with 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amine group alicyclic hydrocarbon group; R 95 represents a hydrogen atom, or a saturated hydrocarbon group with a carbon number of 1 to 10; r represents an integer from 0 to 5; when r is 2 or more, a plurality of R 93 may be the same or different; X 91 represents single bond or alkanediyl having 1 to 6 carbon atoms]

當化合物(1b)具有-SO3H及/或-CO2H時，此等可形成鹽(例如鈉鹽或鉀鹽)。 When compound (1b) has -SO3H and/or -CO2H , these can form salts (eg, sodium or potassium salts).

以R91及R92所表示之脂肪族烴基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、異丙基、異丁基、二級丁基、三級丁基、異戊 基、新戊基、2-乙基己基等之碳數1至10的烷基。 The aliphatic hydrocarbon group represented by R 91 and R 92 includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isopropyl Alkyl groups having 1 to 10 carbon atoms such as butyl, tertiary butyl, tertiary butyl, isopentyl, neopentyl, 2-ethylhexyl and the like.

此等脂肪族烴基可具有之取代基，可列舉出羥基、鹵素原子等。 As a substituent which these aliphatic hydrocarbon groups may have, a hydroxyl group, a halogen atom, etc. are mentioned.

以R91、R92及R94所表示之脂環式烴基，可列舉出環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等之碳數3至10的環烷基。 Alicyclic hydrocarbon groups represented by R 91 , R 92 and R 94 include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and the like, and have 3 to 10 carbon atoms cycloalkyl.

此等脂環式烴基可具有之取代基，可列舉出羥基、鹵素原子等。 As a substituent which these alicyclic hydrocarbon groups may have, a hydroxyl group, a halogen atom, etc. are mentioned.

以R93所表示之烷基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、異丁基、二級丁基、三級丁基、異戊基、新戊基等。 The alkyl group represented by R 93 includes methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tertiary butyl, tertiary butyl, and isopentyl. , Neopentyl, etc.

以R94及R95所表示之飽和烴基，可列舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等之碳數1至10的烷基。 Saturated hydrocarbon groups represented by R 94 and R 95 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like having 1 to 10 carbon atoms the alkyl group.

-CO2R94，可列舉出甲氧羰基、乙氧羰基、丙氧羰基、三級丁氧羰基、己氧羰基及二十氧羰基等。 -CO 2 R 94 includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, hexyloxycarbonyl, and eicosoxycarbonyl.

-NHCOR94，可列舉出N-乙醯基胺基、N-丙醯基胺基、N-丁醯基胺基、N-異丁醯基胺基、N-三甲基乙醯基胺基等。 -NHCOR 94 , N-acetylamino, N-propionylamino, N-butyrylamino, N-isobutyrylamino, N-trimethylacetylamino, etc. are mentioned.

-SO3R94，可列舉出甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、三級丁氧基磺醯基、己氧基磺醯基及二十氧基磺醯基等。 -SO 3 R 94 , such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary butoxysulfonyl, hexyloxysulfonyl, and eicosoxy Sulfonyl etc.

-SO2NR94R95，可列舉出N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N- 丁基胺磺醯基、N-異丁基胺磺醯基、N-二級丁基胺磺醯基、N-三級丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-環己基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N-(3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基、N-(5-胺基戊基)胺磺醯基等之N-1取代胺磺醯基；N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-三級丁基甲基胺磺醯基、N,N-丁基乙基胺磺醯基、N,N-雙(1-甲基丙基)胺磺醯基、N,N-庚基甲基胺磺醯基等之N,N-2取代胺磺醯基等。 -SO 2 NR 94 R 95 , N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl sulfamoyl, N-isopropyl sulfamoyl, N- Butyl sulfamoyl, N-isobutyl sulfamoyl, N-tertiary butyl sulfamoyl, N-tertiary butyl sulfamoyl, N-pentyl sulfamoyl, N- (1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) sulfamoyl, N -(2,2-Dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl) sulfamoyl, N-( 3-Methylbutyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-cyclohexyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) base) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N- (1,4-Dimethylpentyl) sulfamoyl, N-octyl sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethyl) N-1 substituted sulfamoyl such as hexyl sulfamoyl, N-(1,1,2,2-tetramethylbutyl) sulfamoyl, N-(5-aminopentyl) sulfamoyl, etc. Sulfonyl; N,N-dimethylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfanyl Sulfonyl, N,N-isopropylmethylsulfamoyl, N,N-tertiary butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1 -N,N-2-substituted sulfamoyl group such as -methylpropyl) sulfamoyl group, N,N-heptyl methyl sulfamoyl group, etc.

表示X91之烷二基，可列舉出亞甲基、伸乙基、丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、乙烷-1,1-二基、丁烷-1,3-二基、2-甲基丙烷-1,3-二基、2-甲基丙烷-1,2-二基、戊烷-1,4-二基、2-甲基丁烷-1,4-二基等。 Alkanediyl representing X 91 includes methylene, ethylidene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane- 1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, etc.

化合物(1b)，可列舉出以式(3-1)至式(3-11)所表示之化合物。 As the compound (1b), compounds represented by the formula (3-1) to the formula (3-11) can be exemplified.

Figure 106134182-A0202-12-0042-40
Figure 106134182-A0202-12-0042-40

蒽醌染料(Aa3)，尤佳為C.I.溶劑藍45。為此等蒽醌染料時，不僅可形成更高對比的塗膜或圖案，並且可形成雜質的產生少且耐光性優異之塗膜或圖案。 Anthraquinone dye (Aa3), particularly preferably C.I. Solvent Blue 45. In the case of an anthraquinone dye such as this, a coating film or pattern with higher contrast can be formed, and a coating film or pattern with less generation of impurities and excellent light resistance can be formed.

(染料(Aa4)) (Dye (Aa4))

染料(Aa4)，只要是與三芳基甲烷著色劑(Aa1)、二苯 并哌喃染料(Aa2)、以及蒽醌染料(Aa3)為不同之染料即可，並無特別限定。染料(Aa4)，可列舉出油溶性染料、酸性染料、鹼性染料、直接染料、媒染染料、酸性染料的胺鹽或酸性染料的碸醯胺衍生物等之染料。具體可列舉出於色彩指數(The Society of Dyers and Colourists出版)中分類為染料，亦即分類為顏料以外之化合物，或是記載於染色記事本(色染公司)之一般所知的染料。根據化學結構，可列舉出偶氮染料、花青(Cyanine)染料、酞菁染料、萘醌(Naphthoquinone)染料、苯醌亞胺(Quinoneimine)染料、次甲基染料、偶氮次甲基染料、方酸(Squarylium)染料、吖啶(Acridine)染料、苯乙烯基染料、香豆素染料及硝基染料等。此等當中，較佳為有機溶劑可溶性染料。 The dye (Aa4) is not particularly limited as long as it is different from the triarylmethane colorant (Aa1), the dibenzopyran dye (Aa2), and the anthraquinone dye (Aa3). The dye (Aa4) includes dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfamide derivatives of acid dyes. Specifically, the dyes classified as dyes in the color index (published by The Society of Dyers and Colourists), that is, compounds classified as other than pigments, or generally known dyes described in dyeing notebooks (color dyeing companies) can be mentioned. According to chemical structures, azo dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, Squarylium dyes, acridine dyes, styryl dyes, coumarin dyes and nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred.

具體可列舉出：C.I.溶劑黃4、14、15、23、24、38、62、63、68、82、94、98、99、162；C.I.溶劑紅125、130；C.I.溶劑橙2、7、11、15、26、56；C.I.溶劑藍37、67、70、90；C.I.溶劑綠34、35等之C.I.溶劑染料；C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、 232、235、238、240、242、243、251；C.I.酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、57、66、73、80、88、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、422、426；C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173；C.I.酸性紫6、7；C.I.酸性藍18、29、59、60、70、72、74、82、87、92、102、113、117、120、126、130、131、142、147、151、154、158、161、166、167、168、170、171、184、187、192、199、210、229、234、236、242、243、256、259、267、285、296、315、335；C.I.酸性綠58、63、65、80、104、105、106、109等之C.I.酸性染料；C.I.直接黃2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141；C.I.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、 184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250；C.I.直接橙34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107；C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104；C.I.直接藍1、2、6、8、15、22、25、57、71、76、78、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、120、137、149、150、153、155、156、158、159、160、161、162、163、164、165、166、167、168、170、171、172、173、188、189、190、192、193、194、195、196、198、199、200、201、202、203、207、209、210、212、213、214、222、225、226、228、229、236、237、238、242、243、244、245、246、247、248、249、250、251、252、256、257、259、260、268、274、275、293；C.I.直接綠25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等之C.I.直接染料；C.I.鹼性藍3、9、19、24、25、28、29、40、41、54、58、59、64、65、66、67、68；C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65；C.I.媒染紅2、3、4、9、11、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、 43、45、46、48、53、56、63、71、74、85、86、88、90、94、95；C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48；C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58；C.I.媒染藍2、7、9、12、13、15、16、19、20、21、22、26、30、31、39、40、41、43、44、49、53、61、74、77、83、84；C.I.媒染綠1、4、5、10、15、26、29、33、34、35、41、43、53等之C.I.媒染染料等。 Specific examples include: C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; C.I. Solvent Red 125, 130; C.I. Solvent Orange 2, 7, 11, 15, 26, 56; C.I. Solvent Blue 37, 67, 70, 90; C.I. Solvent Dye of C.I. Solvent Green 34, 35; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31 , 34, 35, 37, 42, 44, 57, 66, 73, 80, 88, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182 , 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312 , 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6, 7; C.I. Acid Blue 18, 29, 59, 60, 70, 72, 74, 82, 87, 92, 102, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; C.I. acid dyes of C.I. Acid Green 58, 63, 65, 80, 104, 105, 106, 109, etc.; C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C.I. direct red , 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95 , 96, 103, 104; C.I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 C.I. Direct Dyes, etc.; C.I. Basic Blue 3, 9, 19, 24, 25, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; C.I. Mordant Yellow 5, 8 , 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant Red 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24 , 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; C.I. Mordant Blue 2, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40 , 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green 1, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. The C.I. Mordant Dyes, etc.

(顏料(Ab)) (Pigment (Ab))

本發明之著色硬化性樹脂組成物，可含有顏料(Ab)。顏料(Ab)並無特別限定，可使用一般所知的顏料，例如可列舉出於色彩指數(The Society of Dyers and Colourists出版)中分類為顏料之顏料。 The colored curable resin composition of the present invention may contain a pigment (Ab). The pigment (Ab) is not particularly limited, and generally known pigments can be used, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colourists).

顏料(Ab)，可列舉出：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、137、138、139、147、148、150、153、154、166、173、194、214等之黃色顏料；C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等之澄色顏料； 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等之紅色顏料；C.I.顏料藍15、15：3、15：4、15：6、60等之藍色顏料；C.I.顏料紫1、19、23、29、32、36、38等之紫色顏料；C.I.顏料綠7、36、58等之綠色顏料；C.I.顏料棕23、25等之棕色顏料；C.I.顏料黑1、7等之黑色顏料等。 Pigment (Ab), C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51 ,55,59,61,64,65,71,73, etc , 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment Violet 1, Purple pigments of 19, 23, 29, 32, 36, 38, etc.; green pigments of C.I. Pigment Green 7, 36, 58, etc.; brown pigments of C.I. Pigment Brown 23, 25, etc.; black pigments of C.I. Pigment Black 1, 7, etc. Wait.

顏料(Ab)，較佳為藍色顏料，尤佳為酞菁顏料及二噁嗪(Dioxazine)顏料，更佳為選自由C.I.顏料藍15：6及C.I.顏料紫23所組成之群組的至少一種。 Pigment (Ab), preferably blue pigment, especially phthalocyanine pigment and dioxazine pigment, more preferably at least one selected from the group consisting of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 A sort of.

顏料(Ab)，可視需要施以松香處理、使用導入有酸性基或鹼性基之顏料衍生物等之表面處理、依據高分子化合物等對顏料表面所進行之接枝處理、依據硫酸微粒化法所進行之微粒化處理、或是用以去除雜質之有機溶劑或水等所進行之洗淨處理、依據離子性雜質的離子交換法等所進行之去除處理等。顏料的粒徑，較佳係分別為均一。 Pigment (Ab), if necessary, subject to rosin treatment, surface treatment using pigment derivatives introduced with acid groups or basic groups, etc., grafting treatment on the surface of the pigment according to polymer compounds, etc., according to the sulfuric acid micronization method Micronization treatment, washing treatment with organic solvent or water for removing impurities, removal treatment according to ion exchange method of ionic impurities, etc. The particle diameters of the pigments are preferably uniform, respectively.

顏料，係可藉由含有顏料分散劑來進行分散處理，於顏料分散劑溶液中形成為均一的分散狀態之顏料分散液。顏料，可分別單獨進行分散處理，或混合複數種進行分散處理。 Pigments can be dispersed in a pigment dispersant solution by containing a pigment dispersant to form a uniformly dispersed pigment dispersion liquid in a pigment dispersant solution. Pigments can be dispersed individually, or a plurality of them can be mixed and dispersed.

前述顏料分散劑，可列舉出陽離子系、陰離 子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等之顏料分散劑。此等顏料分散劑，可單獨使用或組合2種以上而使用。顏料分散劑，可列舉出商品名稱為KP(信越化學工業股份有限公司製)、Fluorene(共榮社化學股份有限公司製)、Solsperse(Zeneca股份有限公司製)、EFKA(BASF股份有限公司製)、Ajisper(Ajinomoto Fine Techno股份有限公司製)、Disperbyk(BYK Chemie股份有限公司製)等。 The aforementioned pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants can be used alone or in combination of two or more. Pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Fluorene (manufactured by Kyōeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by BASF Co., Ltd.) , Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemie Co., Ltd.), etc.

使用顏料分散劑時，該用量相對於顏料100質量份，較佳為100質量份以下，尤佳為5質量份以上50質量份以下。顏料分散劑的用量位於前述範圍時，乃具有得到均一的分散狀態之顏料分散液之傾向。 When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, particularly preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the aforementioned range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

本說明書中，例示作為各成分之化合物，在無特別言明時，可單獨使用或組合複數種而使用。 In this specification, the compound as each component is exemplified, and unless otherwise specified, it can be used alone or in combination of plural kinds.

著色硬化性樹脂中之著色劑(A)的含有率，相對於固體成分的總量，較佳為5質量%以上70質量%以下，尤佳為5質量%以上60質量%以下，更佳為5質量%以上50質量%以下。著色劑(A)的含有率位於前述範圍內時，可得到期望之分光或色濃度。 The content rate of the colorant (A) in the colorable curable resin is preferably 5 mass % or more and 70 mass % or less, more preferably 5 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less. When the content rate of the colorant (A) is within the aforementioned range, a desired spectral or color density can be obtained.

本說明書中所謂「固體成分的總量」，意指從本發明之著色硬化性樹脂組成物中扣除溶劑(E)之成分的合計量。固體成分的總量及相對於此之各成分的含量，例如可藉由液相層析或氣相層析等之一般所知的手段來測定。 In this specification, "total amount of solid content" means the total amount of the component which subtracted the solvent (E) from the coloring curable resin composition of this invention. The total amount of solid components and the content of each component relative thereto can be measured by a generally known means such as liquid chromatography or gas chromatography, for example.

著色劑(A)中，各染料的含有率，可因應期望 之分光來適當地選擇，惟從可形成高對比的塗膜或圖案之點來看，較佳為以下範圍。 In the colorant (A), the content of each dye can be appropriately selected according to the desired light distribution, but the following ranges are preferred from the viewpoint of forming a high-contrast coating film or pattern.

著色劑(A)中之三芳基甲烷著色劑(Aa1)的含有率，較佳為0.5質量%以上98質量%以下，尤佳為61質量%以上97質量%以下，更佳為81質量%以上96質量%以下。 The content of the triarylmethane colorant (Aa1) in the colorant (A) is preferably 0.5 mass % or more and 98 mass % or less, more preferably 61 mass % or more and 97 mass % or less, more preferably 81 mass % or more 96% by mass or less.

著色劑(A)中之二苯并哌喃染料(Aa2)的含有率，較佳為0.1質量%以上80質量%以下，尤佳為0.5質量%以上40質量%以下，更佳為1質量%以上20質量%以下。 The content of the dibenzopyran dye (Aa2) in the colorant (A) is preferably 0.1 mass % or more and 80 mass % or less, more preferably 0.5 mass % or more and 40 mass % or less, more preferably 1 mass % More than 20 mass % or less.

著色劑(A)中之蒽醌染料(Aa3)的含有率，較佳為0.1質量%以上，尤佳為0.5質量%以上，更佳為1.0質量%以上。蒽醌染料(Aa3)的含有率，較佳為50質量%以下，尤佳為30質量%以下，更佳為10質量%以下。 The content of the anthraquinone dye (Aa3) in the colorant (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The content of the anthraquinone dye (Aa3) is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass or less.

著色劑(A)中，蒽醌染料(Aa3)的含量，相對於三芳基甲烷著色劑(Aa1)100質量份，較佳為0.5至50質量份，尤佳為1.0至35質量份，更佳為1.0至13.5質量份，特佳為1.2至13.1質量份。藉由使蒽醌染料(Aa3)的含量位於上述範圍內，可形成更高對比的塗膜或圖案。 In the colorant (A), the content of the anthraquinone dye (Aa3) is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the triarylmethane colorant (Aa1), more preferably 1.0 to 35 parts by mass, more preferably It is 1.0 to 13.5 parts by mass, particularly preferably 1.2 to 13.1 parts by mass. By making the content of the anthraquinone dye (Aa3) within the above range, a higher contrast coating film or pattern can be formed.

〈樹脂(B)〉 <Resin (B)>

樹脂(B)並無特別限定，較佳為鹼可溶性樹脂(B)。鹼可溶性樹脂(B)(以下有時稱為「樹脂(B)」)，為含有來自選自由不飽和羧酸及不飽和羧酸酐所組成之群組的至少一種單體(a)之結構單位之共聚物。 The resin (B) is not particularly limited, but is preferably an alkali-soluble resin (B). Alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)") is a structural unit containing at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride the copolymer.

此樹脂(B)，可列舉出以下樹脂[K1]至[K6]等。 As this resin (B), the following resins [K1] to [K6] etc. are mentioned.

樹脂[K1]選自由不飽和羧酸及不飽和羧酸酐所組成之群組的至少一種單體(a)(以下有時稱為「(a)」)，與具有碳數2至4的環狀醚結構及乙烯性不飽和鍵之單體(b)(以下有時稱為「(b)」)之共聚物；樹脂[K2](a)與(b)與可和(a)共聚合之單體(c)(惟與(a)及(b)不同)(以下有時稱為「(c)」)之共聚物；樹脂[K3](a)與(c)之共聚物；樹脂[K4]使(b)反應於(a)與(c)之共聚物之樹脂；樹脂[K5]使(a)反應於(b)與(c)之共聚物之樹脂；樹脂[K6]使(a)反應於(b)與(c)之共聚物，然後進一步使羧酸酐反應之樹脂。 Resin [K1] At least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a ring having 2 to 4 carbon atoms A copolymer of a monomer (b) with an ether-like structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); resin [K2] (a) and (b) can be copolymerized with (a) Copolymer of monomer (c) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); resin [K3] Copolymer of (a) and (c); resin [K4] Resin for reacting (b) to the copolymer of (a) and (c); Resin [K5] Resin for reacting (a) to the copolymer of (b) and (c); Resin [K6] for (a) Resin which is reacted with the copolymer of (b) and (c), and then further reacted with carboxylic acid anhydride.

(a)，具體可列舉出：丙烯酸、甲基丙烯酸、巴豆酸(Crotonic Acid)、鄰-、間-、對-乙烯基苯甲酸等之不飽和單羧酸；順丁烯二酸、反丁烯二酸、檸康酸(Citraconic Acid)、中康酸(Mesaconic Acid)、伊康酸(Itaconic Acid)、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、1,4-環己烯二羧酸等之不飽和二羧酸；甲基-5-降莰烯-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、5-羧基-6-乙基雙環[2.2.1]庚 -2-烯等之含有羧基之雙環不飽和化合物；順丁烯二酸酐、檸康酸酐、伊康酸酐、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、5,6-二羧基雙環[2.2.1]庚-2-烯酐等之不飽和二羧酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等之2元以上的多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯；α-(羥甲基)丙烯酸般之於同一分子中含有羥基及羧基之不飽和丙烯酸酯等。 (a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, etc.; maleic acid, fumaric acid, etc. Oleic acid, Citraconic Acid, Mesaconic Acid, Itaconic Acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4, Unsaturation of 5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc. Dicarboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2- 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- Bicyclic unsaturated compounds containing carboxyl groups such as methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc.; maleic anhydride, citrate Aconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[ Unsaturated mono[(( Meth) acryloxyalkyl] ester; α-(hydroxymethyl) acrylic acid is like an unsaturated acrylate containing hydroxyl and carboxyl groups in the same molecule.

此等當中，從共聚合反應性之點或所得到之樹脂對鹼性水溶液之溶解性之點來看，較佳為丙烯酸、甲基丙烯酸、順丁烯二酸酐等。 Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity or the point of solubility to an alkaline aqueous solution of the resin obtained.

(b)，意指例如具有碳數2至4的環狀醚結構(例如選自由環氧乙烷(Oxirane)環、氧呾(Oxetane)環及四氫呋喃環所組成之群組的至少1種)及乙烯性不飽和鍵之聚合性化合物。 (b) means, for example, 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 polymerizable compounds with ethylenically unsaturated bonds.

(b)，較佳為具有碳數2至4的環狀醚與(甲基)丙烯醯氧基之單體。 (b), preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

本說明書中，所謂「(甲基)丙烯酸」，表示選自由丙烯酸及甲基丙烯酸所組成之群組的至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等之記號，亦具有同樣的涵義。 In this specification, "(meth)acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Symbols such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

(b)，例如可列舉出具有環氧乙烷基及乙烯性不飽和鍵之單體(b1)(以下有時稱為「(b1)」)、具有氧呾基 及乙烯性不飽和鍵之單體(b2)(以下有時稱為「(b2)」)、以及具有四氫呋喃基及乙烯性不飽和鍵之單體(b3)(以下有時稱為「(b3)」)等。 (b), for example, a monomer (b1) (hereinafter sometimes referred to as "(b1)") having an oxirane group and an ethylenically unsaturated bond, a monomer having an oxyethylene group and an ethylenically unsaturated bond, Monomer (b2) (hereinafter sometimes referred to as "(b2)"), monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuran group and an ethylenically unsaturated bond, and the like.

(b1)，例如可列舉出具有直鏈狀或分枝鏈狀的脂肪族不飽和烴經環氧化之結構之單體(b1-1))(以下有時稱為「(b1-1)」)、以及具有脂環式不飽和烴經環氧化之結構之單體(b1-2))(以下有時稱為「(b1-2)」)。 (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is 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 sometimes referred to as "(b1-2)").

(b1-1)，可列舉出(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸β-甲基環氧丙酯、(甲基)丙烯酸β-乙基環氧丙酯、環氧丙基乙烯基醚、鄰-乙烯基苯甲基環氧丙基醚、間-乙烯基苯甲基環氧丙基醚、對-乙烯基苯甲基環氧丙基醚、α-甲基-鄰-乙烯基苯甲基環氧丙基醚、α-甲基-間-乙烯基苯甲基環氧丙基醚、α-甲基-對-乙烯基苯甲基環氧丙基醚、2,3-雙(環氧丙基氧基甲基)苯乙烯、2,4-雙(環氧丙基氧基甲基)苯乙烯、2,5-雙(環氧丙基氧基甲基)苯乙烯、2,6-雙(環氧丙基氧基甲基)苯乙烯、2,3,4-三(環氧丙基氧基甲基)苯乙烯、2,3,5-三(環氧丙基氧基甲基)苯乙烯、2,3,6-三(環氧丙基氧基甲基)苯乙烯、3,4,5-三(環氧丙基氧基甲基)苯乙烯、2,4,6-三(環氧丙基氧基甲基)苯乙烯等。 (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl (meth)acrylate, etc. Ethyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, alpha-methyl-o- -Vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)benzene Ethylene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(epoxymethyl)styrene Propyloxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-Tris(glycidoxymethyl)styrene, etc.

(b1-2)，可列舉出乙烯基環己烯一氧化物、1,2-環氧基-4-乙烯基環己烯(例如Celloxide 2000；Daicel股份有限公司製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如Cyclomer A400；Daicel股份有限公司製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如Cyclomer M100；Daicel股份有 限公司製)、以式(II)所表示之化合物及以式(III)所表示之化合物等。 (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexene (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester (for example, Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.) , a compound represented by formula (II), a compound represented by formula (III), and the like.

Figure 106134182-A0202-12-0053-41
Figure 106134182-A0202-12-0053-41

[式(II)及式(III)中，Ra及Rb表示氫原子或碳數1至4的烷基，該烷基所含有之氫原子可經羥基所取代；Xa及Xb表示單鍵、-Rc-、*-Rc-O-、*-Rc-S-或*-Rc-NH-；Rc表示碳數1至6的烷二基；*表示與O之鍵結鍵] [In formula (II) and formula (III), R a and R b 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 represent Single bond, -R c -, *-R c -O-, *-R c -S- or *-R c -NH-; R c represents an alkanediyl group with 1 to 6 carbon atoms; * represents a combination with O bond key]

碳數1至4的烷基，可列舉出甲基、乙基、正丙基、異丙基、正丁基、二級丁基、三級丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, and tertiary butyl.

氫原子經羥基所取代之烷基，可列舉出羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of alkyl groups in which hydrogen atoms are substituted with hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl -1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

Ra及Rb較佳可列舉出氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基，尤佳可列舉出氫原子、甲基。 R a and R b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and particularly preferably a hydrogen atom and a methyl group.

碳數1至6的烷二基，可列舉出亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Alkanediyl having 1 to 6 carbon atoms, such as methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane Alkane-1,5-diyl, hexane-1,6-diyl, etc.

Xa及Xb較佳可列舉出單鍵、亞甲基、伸乙基、*-CH2-O-及*-CH2CH2-O-，尤佳可列舉出單鍵、*-CH2CH2-O-(*表示與O之鍵結鍵)。 Preferred examples of X a and X b include single bond, methylene group, ethylidene group, *-CH 2 -O- and *-CH 2 CH 2 -O-, and particularly preferred examples include single bond, *-CH 2 CH 2 -O- (* indicates a bond with O).

以式(II)所表示之化合物，可列舉出以式(II-1)至式(II-15)中任一種所表示之化合物等。當中較佳為以式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)至式(II-15)所表示之化合物，尤佳為以式(II-1)、式(II-7)、式(II-9)或式(II-15)所表示之化合物。 As a compound represented by formula (II), the compound etc. which are represented by any one of formula (II-1) to formula (II-15) are mentioned. Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II) are preferred The compound represented by -15) is particularly preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

Figure 106134182-A0202-12-0054-42
Figure 106134182-A0202-12-0054-42

以式(III)所表示之化合物，可列舉出以式(III-1)至式(III-15)中任一種所表示之化合物等。當中較佳為以式(III-1)、式(III-3)、式(III-5)、式(III-7)、式(III-9)或式(III-11)至式(III-15)所表示之化合物，尤佳為以式 (III-1)、式(III-7)、式(III-9)或式(III-15)所表示之化合物。 The compound represented by formula (III) includes the compound represented by any one of formula (III-1) to formula (III-15), and the like. Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III) are preferred The compound represented by -15) is particularly preferably a compound represented by formula (III-1), formula (III-7), formula (III-9) or formula (III-15).

Figure 106134182-A0202-12-0055-43
Figure 106134182-A0202-12-0055-43

以式(II)所表示之化合物及以式(III)所表示之化合物，可分別單獨使用，或是併用以式(II)所表示之化合物及以式(III)所表示之化合物。併用此等時，以式(II)所表示之化合物及以式(III)所表示之化合物之含有比率，以莫耳基準計，較佳為5：95至95：5，尤佳為10：90至90：10，更佳為20：80至80：20。 The compound represented by the formula (II) and the compound represented by the formula (III) may be used independently, or the compound represented by the formula (II) and the compound represented by the formula (III) may be used in combination. When these are used together, the content ratio of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably 5:95 to 95:5 on a molar basis, more preferably 10: 90 to 90:10, more preferably 20:80 to 80:20.

(b2)，尤佳為具有氧呾基與(甲基)丙烯醯氧基 之單體。(b2)，可列舉出3-甲基-3-甲基丙烯醯氧基甲基氧呾、3-甲基-3-丙烯醯氧基甲基氧呾、3-乙基-3-甲基丙烯醯氧基甲基氧呾、3-乙基-3-丙烯醯氧基甲基氧呾、3-甲基-3-甲基丙烯醯氧基乙基氧呾、3-甲基-3-丙烯醯氧基乙基氧呾、3-乙基-3-甲基丙烯醯氧基乙基氧呾、3-乙基-3-丙烯醯氧基乙基氧呾等。 (b2), a monomer having an oxo group and a (meth)acryloyloxy group is particularly preferred. (b2), 3-methyl-3-methacryloyloxymethyl oxo, 3-methyl-3-acryloyloxymethyl oxo, 3-ethyl-3-methyl oxo Acryloyloxymethyloxygen, 3-ethyl-3-propenyloxymethyloxygen, 3-methyl-3-methacryloyloxyethyloxygen, 3-methyl-3- Acryloyloxyethyloxygen, 3-ethyl-3-methacryloyloxyethyloxygen, 3-ethyl-3-propenyloxyethyloxygen, and the like.

(b3)，尤佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。(b3)，具體可列舉出丙烯酸四氫呋喃甲酯(例如Viscoat #150、大阪有機化學工業股份有限公司製)、甲基丙烯酸四氫呋喃甲酯等。 (b3), the monomer which has a tetrahydrofuranyl group and a (meth)acryloyloxy group is especially preferable. (b3), tetrahydrofuran methyl acrylate (for example, Viscoat #150, the product made by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, etc. are mentioned specifically,.

(b)，從可提高所得到之彩色濾光片的耐熱性、耐藥品性等之可靠度之點來看，較佳為(b1)。此外，從著色硬化性樹脂組成物的保存穩定性優異之點來看，尤佳為(b1-2)。 (b), (b1) is preferable from the viewpoint that the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter can be improved. Moreover, (b1-2) is especially preferable from the point which is excellent in the storage stability of a colored curable resin composition.

(c)，例如可列舉出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷酯、(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-酯(該技術領域中，慣用名稱被稱為「(甲基)丙烯酸二環戊酯」。此外，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-酯(該技術領域中，慣用名稱被稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二 環戊氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯甲酯等之(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等之含有羥基之(甲基)丙烯酸酯；順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等之二羧酸二酯；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-羥甲基雙環[2.2.1]庚-2-烯、5-(2'-羥乙基)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(羥甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥乙基)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-羥甲基-5-甲基雙環[2.2.1]庚-2-烯、5-三級丁氧基羰基雙環[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(三級丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等之雙環不飽和化合物；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞 胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等之二羰基醯亞胺衍生物；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、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tertiary butyl (meth)acrylate, tributyl (meth)acrylate Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[ 5.2.1.02.6 ]decane-8-ester (meth)acrylate (in this technical field, commonly used The name is "dicyclopentyl (meth)acrylate". In addition, it may be called "tricyclodecyl (meth)acrylate"), (meth)acrylate tricyclo[5.2.1.0 2.6 ]decene -8-ester (in this technical field, the common name is called "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate , adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzene (meth)acrylate (Meth)acrylates such as methyl ester; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; Dicarboxylic acid diesters of ethyl ester, diethyl fumarate, diethyl itconate, etc.; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2- 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- alkene, 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-dihydroxybicyclo[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-diethoxy bicyclo[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-tertiary butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy ylcarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1 ] Hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, N-succinimide group -3-Maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-malei Dicarbonyl imidate, N-succinimidyl hexanoate, N-succinimidyl-3-maleimidopropionate, N-(9-acridyl)maleimide, etc. Amine derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride , vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

此等當中，從共聚合反應性及耐熱性之點來看，較佳為苯乙烯、乙烯基甲苯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸三環[5.2.1.02.6]癸烷-8-酯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、雙環[2.2.1]庚-2-烯。 Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth)acrylate, and tricyclo[5.2.1.0 2.6 ]decane (meth)acrylate are preferred Alkyl-8-ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]heptane -2-ene.

樹脂[K1]中，來自各個之結構單位的比率，於構成樹脂[K1]之全部結構單位中，較佳為：來自(a)之結構單位；2至60莫耳% In the resin [K1], the ratio of the structural unit derived from each of the total structural units constituting the resin [K1] is preferably: the structural unit derived from (a); 2 to 60 mol %

來自(b)之結構單位；40至98莫耳% Structural unit from (b); 40 to 98 mol%

尤佳為：來自(a)之結構單位；10至50莫耳% Especially preferred: structural units from (a); 10 to 50 mol%

來自(b)之結構單位；50至90莫耳%。 Structural unit from (b); 50 to 90 mol%.

當樹脂[K1]之結構單位的比率位於上述範圍時，著色硬化性樹脂組成物的保存穩定性、形成著色圖案時之顯影性、以及所得到之彩色濾光片的耐溶劑性，有變得優異之傾向。 When the ratio of the structural unit of the resin [K1] is in the above-mentioned range, the storage stability of the colored curable resin composition, the developability when forming the colored pattern, and the solvent resistance of the obtained color filter are reduced. Tendency to excellence.

樹脂[K1]，例如可參考文獻「高分子合成的實驗法」(大津隆行著 發行所 化學同人股份有限公司 第1版第1刷 1972年3月1日發行)所記載之方法及該文獻所記載之引用文獻來製造。 For resin [K1], for example, reference can be made to the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing House Chemical Doujin Co., Ltd. 1st Edition, March 1, 1972) and the methods described in this document. Manufactured from the cited references.

具體而言，可列舉出將(a)及(b)的既定量、聚合起始劑及溶劑等裝入反應容器中，例如藉由氮氣來取代氧氣以形成脫氧環境，並且一面攪拌一面進行加熱及保溫之方法。上述聚合起始劑及溶劑等並無特別限定，可使用該領域中一般所使用者。聚合起始劑，例如可列舉出偶氮化合物(2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯等)，溶劑，只要是可溶解各單體者即可，可列舉出後述溶劑等作為本發明之著色硬化性樹脂組成物的溶劑(E)等。 Specifically, the predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are put into a reaction vessel, for example, nitrogen gas is used to replace oxygen gas to form a deoxidized atmosphere, and heating is performed while stirring. and methods of keeping warm. The above-mentioned polymerization initiator, solvent, etc. are not particularly limited, and those generally used in this field can be used. Examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides As the solvent (E) of the colored curable resin composition of the present invention, the solvent (E) of the colored curable resin composition of the present invention, etc., may be used as long as it can dissolve each monomer.

所得到之共聚物，可直接使用反應後的溶液，或是使用經濃縮或稀釋後之溶液，或是使用以再沉澱等方法形所取出之固體(粉體)者。尤其，藉由使用本發明之著色硬化性樹脂組成物所含有之溶劑作為此聚合時之溶劑，可將反應後的溶液直接使用在本發明之著色硬化性樹脂組成物的調製中，所以可簡化本發明之著色硬化性樹脂組成物的製造步驟。 The obtained copolymer can be directly used as the solution after the reaction, or as the solution after concentration or dilution, or as the solid (powder) taken out by methods such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during the polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention, so that the simplification can be achieved. The manufacturing process of the colored curable resin composition of this invention.

樹脂[K2]中，來自各個之結構單位的比率，於構成樹脂[K2]之全部結構單位中，較佳為：來自(a)之結構單位；2至45莫耳% In the resin [K2], the ratio of the structural unit derived from each of the total structural units constituting the resin [K2] is preferably: the structural unit derived from (a); 2 to 45 mol%

來自(b)之結構單位；2至95莫耳% Structural unit from (b); 2 to 95 mol%

來自(c)之結構單位；1至65莫耳% Structural unit from (c); 1 to 65 mol%

尤佳為：來自(a)之結構單位；5至40莫耳% Especially preferred: structural units from (a); 5 to 40 mol %

來自(b)之結構單位；5至80莫耳% Structural unit from (b); 5 to 80 mol%

來自(c)之結構單位；5至60莫耳%。 Structural unit from (c); 5 to 60 mol%.

當樹脂[K2]之結構單位的比率位於上述範圍時，著色硬化性樹脂組成物的保存穩定性、形成著色圖案時之顯影性、以及所得到之彩色濾光片的耐溶劑性、耐熱性及機械強度，有變得優異之傾向。 When the ratio of the structural unit of the resin [K2] is within the above-mentioned range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and The mechanical strength tends to be excellent.

樹脂[K2]，例如可與記載作為樹脂[K1]的製造方法之方法相同而製造。 The resin [K2] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

樹脂[K3]中，來自各個之結構單位的比率，於構成樹脂[K3]之全部結構單位中，較佳為：來自(a)之結構單位；2至60莫耳% In the resin [K3], the ratio of the structural unit derived from each of the total structural units constituting the resin [K3] is preferably: the structural unit derived from (a); 2 to 60 mol %

來自(c)之結構單位；40至98莫耳% Structural unit from (c); 40 to 98 mol%

尤佳為：來自(a)之結構單位；10至50莫耳% Especially preferred: structural units from (a); 10 to 50 mol%

來自(c)之結構單位；50至90莫耳%。 Structural unit from (c); 50 to 90 mol%.

樹脂[K3]，例如可與記載作為樹脂[K1]的製造方法之方法相同而製造。 The resin [K3] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

樹脂[K4]，可藉由得到(a)與(c)之共聚物，並將(b)所具有之碳數2至4的環狀醚加成於(a)所具有之羧酸及/或羧酸酐而製造。 The resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms possessed by (b) to the carboxylic acid and/or the carboxylic acid possessed by (a) or carboxylic acid anhydride.

首先，與記載作為樹脂[K1]的製造方法之方 法相同來製造(a)與(c)之共聚物。此時，來自各個之結構單位的比率，較佳為與樹脂[K3]所列舉者為相同之比率。 First, the copolymer of (a) and (c) was produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each is preferably the same ratio as that listed in the resin [K3].

接著使(b)所具有之碳數2至4的環狀醚，反應於前述共聚物中之來自(a)之羧酸及/或羧酸酐的一部分。 Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is allowed to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer.

接著於(a)與(c)之共聚物的製造後，將燒瓶內的環境氣體從氮氣取代為空氣，並將(b)、羧酸或羧酸酐與環狀醚之反應觸媒(三(二甲基胺基甲基)酚等)、以及聚合抑制劑(氫醌等)等裝入燒瓶內，例如在60至130℃下反應1至10小時，藉此可製造樹脂[K4]。 Next, after the production of the copolymer of (a) and (c), the ambient gas in the flask was replaced from nitrogen to air, and the reaction catalyst (tri(b), carboxylic acid or carboxylic acid anhydride and cyclic ether) was replaced with air. dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (hydroquinone, etc.), etc., are put into a flask, and the resin [K4] can be produced by reacting at 60 to 130° C. for 1 to 10 hours, for example.

(b)的用量，相對於(a)100莫耳，較佳為5至80莫耳，尤佳為10至75莫耳。藉由設為此範圍，著色硬化性樹脂組成物的保存穩定性、形成圖案時之顯影性、以及所得到之圖案的耐溶劑性、耐熱性、機械強度及靈敏度的均衡，有變得良好之傾向。由於環狀醚的反應性高，不易殘存未反應的(b)，所以樹脂[K4]所使用之(b)，較佳為(b1)，更佳為(b1-1)。 The amount of (b) is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By setting this range, the storage stability of the colored curable resin composition, the developability during pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern can be improved. tendency. Since the cyclic ether has high reactivity and does not easily remain unreacted (b), the (b) used for the resin [K4] is preferably (b1), more preferably (b1-1).

前述反應觸媒的用量，相對於(a)、(b)及(c)的合計量100質量份，較佳為0.001至5質量份。前述聚合抑制劑的用量，相對於(a)、(b)及(c)的合計量100質量份，較佳為0.001至5質量份。 The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c).

裝入方法、反應溫度及時間等之反應條件，可考量到製造設備或因聚合所產生之散熱量等來適當地調整。與聚合條件相同，可考量到製造設備或因聚合所產生之散熱量等，來適當地調整裝入方法或反應溫度。 The reaction conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production facility, the amount of heat generated by the polymerization, and the like. Similar to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

樹脂[K5]，第一階段，係以與上述樹脂[K1]的製造方法相同，得到(b)與(c)之共聚物。與上述相同，所得到之共聚物，可直接使用反應後的溶液，或是使用經濃縮或稀釋後之溶液，或是使用以再沉澱等方法形所取出之固體(粉體)者。 Resin [K5], in the first stage, obtained the copolymer of (b) and (c) in the same manner as in the production method of the above-mentioned resin [K1]. In the same way as above, the obtained copolymer can be directly used as the solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) extracted by methods such as reprecipitation.

來自(b)與(c)之結構單位的比率，相對於構成前述共聚物之全部結構單位的合計莫耳數，較佳分別為：來自(b)之結構單位；5至95莫耳% The ratios of the structural units derived from (b) and (c), relative to the total moles of all the structural units constituting the aforementioned copolymer, are preferably respectively: structural units derived from (b); 5 to 95 mol%

來自(c)之結構單位；5至95莫耳% Structural unit from (c); 5 to 95 mol%

尤佳為：來自(b)之結構單位；10至90莫耳% Especially preferred: structural units from (b); 10 to 90 mol%

來自(c)之結構單位；10至90莫耳%。 Structural unit from (c); 10 to 90 mol%.

再者，以與樹脂[K4]的製造方法相同之條件，使(a)所具有之羧酸或羧酸酐，反應於(b)與(c)之共聚物所具有之來自(b)之環狀醚，藉此可得到樹脂[K5]。 Furthermore, under the same conditions as in the production method of resin [K4], the carboxylic acid or carboxylic acid anhydride contained in (a) is allowed to react with the ring derived from (b) contained in the copolymer of (b) and (c). form ether, thereby obtaining resin [K5].

反應於前述共聚物之(a)的用量，相對於(b)100莫耳，較佳為5至80莫耳。由於環狀醚的反應性高，不易殘存未反應的(b)，所以樹脂[K5]所使用之(b)，較佳為(b1)，更佳為(b1-1)。 The amount of (a) to be reacted to the aforementioned copolymer is preferably 5 to 80 mol relative to 100 mol of (b). Since the cyclic ether has high reactivity and is unlikely to remain unreacted (b), the (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

樹脂[K6]，為使羧酸酐進一步反應於樹脂[K5]之樹脂。係使羧酸酐反應於因環狀醚與羧酸或羧酸酐之反應所產生之羥基。 Resin [K6] is the resin which made carboxylic anhydride react with resin [K5] further. The carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

羧酸酐，可列舉出順丁烯二酸酐、檸康酸酐、伊康酸酐、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、5,6-二羧基雙環[2.2.1]庚-2-烯酐等。羧酸酐的用量，相對於(a)的用量1莫耳，較佳為0.5至1莫耳。 Carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene Anhydride etc. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol relative to 1 mol of the amount of (a).

樹脂(B)，具體可列舉出：(甲基)丙烯酸3,4-環氧基環己基甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯/(甲基)丙烯酸共聚物等之樹脂[K1]；(甲基)丙烯酸環氧丙酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、(甲基)丙烯酸3,4-環氧基三環[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)丙烯醯氧基甲基氧呾/(甲基)丙烯酸/苯乙烯共聚物等之樹脂[K2]；(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸苯甲酯/(甲基)丙烯酸三環癸酯/(甲基)丙烯酸共聚物等之樹脂[K3]；使(甲基)丙烯酸環氧丙酯加成於(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物之樹脂、使(甲基)丙烯酸環氧丙酯加成於(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物之樹脂、使(甲基)丙烯酸環氧丙酯加成於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物之樹脂等之樹脂[K4]；使(甲基)丙烯酸反應於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸環氧丙酯之共聚物之樹脂、使(甲基)丙烯酸反應於(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙 烯酸環氧丙酯之共聚物之樹脂等之樹脂[K5]；對於使(甲基)丙烯酸反應於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸環氧丙酯之共聚物所得到之樹脂，進一步使四氫鄰苯二甲酸酐反應而成之樹脂等之樹脂[K6]等。 Specific examples of the resin (B) include (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[ 5.2.1.0 2.6 ] Resin [K1] of decyl ester/(meth)acrylic acid copolymer, etc.; Glycidyl meth)acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[ 5.2.1.02.6 ]decyl ester/(meth)acrylic acid/N -Cyclohexylmaleimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[ 5.2.1.02.6 ]decyl ester/(meth)acrylic acid/vinyltoluene copolymer, 3- Resin [K2] of methyl-3-(meth)acryloyloxymethyloxy/(meth)acrylic acid/styrene copolymer; benzyl (meth)acrylate/(meth)acrylic acid copolymer resin [K3], such as styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid tricyclodecyl/(meth)acrylic acid copolymer, etc.; ) Resin in which glycidyl acrylate is added to benzyl (meth)acrylate/(meth)acrylic acid copolymer, and glycidyl (meth)acrylate is added to tricyclodecyl (meth)acrylate /Styrene/(meth)acrylic copolymer resin, adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylate Resin [K4] of acrylic copolymer resin, etc.; resin of (meth)acrylic acid reacting with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymer, (meth)acrylic acid Resin [K5] in which acrylic acid is reacted with a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate, etc.; Resin [K6] etc., such as the resin obtained by the copolymer of tricyclodecyl acrylate/(meth)acrylate glycidyl, further reacted with tetrahydrophthalic anhydride.

樹脂(B)，較佳係選自由樹脂[K1]、樹脂[K2]及樹脂[K3]所組成之群組的一種，尤佳係選自由樹脂[K2]及樹脂[K3]所組成之群組的一種。為此等樹脂時，著色硬化性樹脂組成物的顯影性優異。從著色圖案與基板之密著性之觀點來看，更佳為樹脂[K2]。 Resin (B), preferably one selected from the group consisting of resin [K1], resin [K2] and resin [K3], more preferably selected from the group consisting of resin [K2] and resin [K3] A kind of group. In the case of such resins, the developability of the colored curable resin composition is excellent. Resin [K2] is more preferable from a viewpoint of the adhesiveness of a colored pattern and a board|substrate.

樹脂(B)之經聚苯乙烯換算的重量平均分子量(Mw)，較佳為3,000至100,000，尤佳為5,000至50,000，更佳為5,000至30,000。重量平均分子量(Mw)位於前述範圍時，從含有此之著色硬化性樹脂組成物所形成之塗膜的硬度提升，該殘膜率亦高，未曝光部對顯影液之溶解性良好，著色圖案的解析度有提升之傾向。 The polystyrene-converted weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 30,000. When the weight-average molecular weight (Mw) is in the aforementioned range, the hardness of the coating film formed from the coloring curable resin composition containing it is improved, the residual film rate is also high, the solubility of the unexposed part to the developing solution is good, and the coloring pattern is obtained. The resolution tends to improve.

樹脂(B)的分散度「重量平均分子量(Mw)/數量平均分子量(Mn)」，較佳為1.1至6，尤佳為1.2至4。 The degree of dispersion "weight average molecular weight (Mw)/number average molecular weight (Mn)" of the resin (B) is preferably 1.1 to 6, particularly preferably 1.2 to 4.

樹脂(B)的酸值，較佳為50至170mg-KOH/g，尤佳為60至150mg-KOH/g，更佳為70至135mg-KOH/g。在此，酸值係作為將樹脂(B)1g中和所需之氫氧化鉀的量(mg)所測定之值，例如可使用氫氧化鉀水溶液進行滴定而求取。 The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, more preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

樹脂(B)的含量，相對於固體成分的總量，較佳為7至65質量%，尤佳為13至60質量%，更佳為17至 55質量%。當樹脂(B)的含量位於前述範圍時，可形成著色圖案，並且著色圖案的解析度及殘膜率有提升之傾向。 The content of the resin (B) is preferably from 7 to 65 mass %, more preferably from 13 to 60 mass %, more preferably from 17 to 55 mass % with respect to the total amount of solid content. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to improve.

〈聚合性化合物(C)〉 <Polymerizable compound (C)>

聚合性化合物(C)，為可藉由從聚合起始劑(D)所產生之活性自由基及/或酸而聚合之化合物。聚合性化合物(C)，可列舉出具有聚合性的乙烯性不飽和鍵之化合物等，較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D). As a polymerizable compound (C), the compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned, Preferably it is a (meth)acrylate compound.

具有1個乙烯性不飽和鍵之聚合性化合物，可列舉出丙烯酸壬基苯基卡必醇酯、丙烯酸2-羥基-3-苯氧基丙酯、丙烯酸2-乙基己基卡必醇酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯啶酮等，以及上述(a)、(b)及(c)。 The polymerizable compound having one ethylenically unsaturated bond includes nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and (a), (b) and (c) above.

具有2個乙烯性不飽和鍵之聚合性化合物，可列舉出(甲基)丙烯酸1,6-己二醇酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸三乙二醇酯、雙酚A的雙(丙烯醯氧基乙基)醚、二(甲基)丙烯酸3-甲基戊二醇酯等。 Polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol (meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl di(meth)acrylate. Alcohol ester, triethylene glycol di(meth)acrylate, bis(acrylooxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

聚合性化合物(C)，較佳為具有3個以上的乙烯性不飽和鍵之聚合性化合物。此聚合性化合物，可列舉出三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸新戊四醇酯、四(甲基)丙烯酸新戊四醇酯、五(甲基)丙烯酸二新戊四醇酯、六(甲基)丙烯酸二新戊四醇酯、八(甲基)丙烯酸三新戊四醇酯、七(甲基)丙烯酸三新戊四醇酯、十(甲基)丙烯酸四新戊四醇酯、九(甲基)丙烯酸四新戊四醇酯、異三聚 氰酸三(2-(甲基)丙烯醯氧基乙基)酯、經乙二醇變性之四(甲基)丙烯酸新戊四醇酯、經乙二醇變性之六(甲基)丙烯酸二新戊四醇酯、經丙二醇變性之四(甲基)丙烯酸新戊四醇酯、經丙二醇變性之六(甲基)丙烯酸二新戊四醇酯、經己內酯變性之四(甲基)丙烯酸新戊四醇酯、經己內酯變性之六(甲基)丙烯酸二新戊四醇酯等，當中較佳為五(甲基)丙烯酸二新戊四醇酯及六(甲基)丙烯酸二新戊四醇酯。 The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, and penta(meth)acrylate. Dipiveaerythritol acrylate, Dipiveaerythritol hexa(meth)acrylate, Tripivalerythritol octa(meth)acrylate, Tripivalerythritol hepta(meth)acrylate, Ten(meth)acrylate base) tetrapiotaerythritol acrylate, tetrapiotaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, denatured with ethylene glycol Tetra(meth)acrylate neotaerythritol, ethylene glycol denatured hexa(meth)acrylate dipeutaerythritol, propylene glycol denatured tetra(meth)acrylate neotaerythritol, propylene glycol denatured Denatured hexa(meth)acrylate dipivoerythritol, caprolactone denatured tetra(meth)acrylate neotaerythritol, caprolactone denatured hexa(meth)acrylate dipivoerythritol Esters, etc., among them, dipeutaerythritol penta(meth)acrylate and dipeutaerythritol hexa(meth)acrylate are preferable.

聚合性化合物(C)的重量平均分子量，較佳為150以上2,900以下，尤佳為250至1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, particularly preferably 250 to 1,500 or less.

聚合性化合物(C)的含量，相對於固體成分的總量，較佳為7至65質量%，尤佳為13至60質量%，更佳為17至55質量%。 The content of the polymerizable compound (C) is preferably from 7 to 65 mass %, more preferably from 13 to 60 mass %, more preferably from 17 to 55 mass % with respect to the total amount of solid content.

樹脂(B)與聚合性化合物(C)之含量比[樹脂(B)：聚合性化合物(C)]，以質量基準計，較佳為20：80至80：20，尤佳為35：65至80：20。 The content ratio of the resin (B) to the polymerizable compound (C) [resin (B):polymerizable compound (C)], on a mass basis, is preferably 20:80 to 80:20, particularly preferably 35:65 to 80:20.

當聚合性化合物(C)的含量位於前述範圍內時，著色圖案形成時的殘膜率及彩色濾光片的耐藥品性有提升之傾向。 When the content of the polymerizable compound (C) is within the aforementioned range, the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to improve.

〈聚合起始劑(D)〉 <Polymerization initiator (D)>

聚合起始劑(D)，只要是可藉由光或熱的作用來產生活性自由基、酸等而開始進行聚合之化合物即可，並無特別限定，可使用一般所知的聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and generally known polymerization initiators can be used. .

聚合起始劑(D)，可列舉出O-醯基肟化合物、 烷基苯基酮化合物、雙咪唑化合物、三嗪化合物、及醯基膦氧化物化合物等。 The polymerization initiator (D) includes an O-acyl oxime compound, an alkyl phenyl ketone compound, a bisimidazole compound, a triazine compound, an acyl phosphine oxide compound, and the like.

前述O-醯基肟化合物，為具有以式(d1)所表示之結構之化合物。以下，*表示鍵結鍵。 The aforementioned O-acyl oxime compound is a compound having a structure represented by formula (d1). Hereinafter, * represents a bond key.

Figure 106134182-A0202-12-0067-44
Figure 106134182-A0202-12-0067-44

前述O-醯基肟化合物，可列舉出N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)-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基氧基)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、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-亞胺等。亦可使用Irgacure OXE01、OXE02(以上為BASF股份有限公司製)、N-1919(ADEKA股份有限公司製)等之市售品。當中，O-醯基肟化合物，較佳係選自由N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺及N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺所組成之群組的至少1種，尤佳為N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1- 酮-2-亞胺。如為此等O-醯基肟化合物時，乃具有可得到高明亮度的彩色濾光片之傾向。 The aforementioned O-acyl oxime compound includes N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1 -1-(4-Phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentane Propane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethyl Alkyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane ylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl) benzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2- methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01 and OXE02 (the above are manufactured by BASF Co., Ltd.) and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyl Ethyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3 -At least one of the group consisting of cyclopentylpropane-1-one-2-imine, particularly preferably N-benzyloxy-1-(4-phenylthiophenyl)octane- 1-keto-2-imine. In the case of such an O-acyl oxime compound, there is a tendency that a color filter with high brightness can be obtained.

前述烷基苯基酮化合物，例如為具有以式(d2)所表示之結構或以式(d3)所表示之結構之化合物。此等結構中，苯環可具有取代基。 The aforementioned alkyl phenyl ketone compound is, for example, a compound having a structure represented by formula (d2) or a structure represented by formula (d3). In these structures, the benzene ring may have a substituent.

Figure 106134182-A0202-12-0068-46
Figure 106134182-A0202-12-0068-46

具有以式(d2)所表示之結構之化合物，可列舉出2-甲基-2-N-嗎福林基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎福林基苯基)-2-苯甲基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎福林基)苯基]丁烷-1-酮等。亦可使用Irgacure 369、907、379(以上為BASF股份有限公司製)等之市售品。 Compounds having a structure represented by formula (d2) include 2-methyl-2-N-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene yl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as Irgacure 369, 907, and 379 (the above are manufactured by BASF Corporation) can also be used.

具有以式(d3)所表示之結構之化合物，可列舉出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-酮之低聚物、α,α-二乙氧基苯乙酮、二苯乙二酮(benzil)二甲基縮酮等。 Compounds having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one The oligomer, α, α-diethoxyacetophenone, benzophenone (benzil) dimethyl ketal and so on.

從感度之點來看，烷基苯基酮化合物較佳為具有以式(d2)所表示之結構之化合物。 From the viewpoint of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a structure represented by formula (d2).

前述雙咪唑化合物，例如為以式(d5)所表示之化合物。 The aforementioned bisimidazole compound is, for example, a compound represented by the formula (d5).

Figure 106134182-A0202-12-0069-47
Figure 106134182-A0202-12-0069-47

[式(d5)中，R13至R18表示可具有取代基之碳數6至10的芳基] [In formula (d5), R 13 to R 18 represent optionally substituted aryl groups having 6 to 10 carbon atoms]

碳數6至10的芳基，可列舉出苯基、甲苯基、二甲苯基、乙基苯基及萘基等，較佳可列舉出苯基。 Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and the like, and a phenyl group is preferably used.

取代基，可列舉出鹵素原子、碳數1至4的烷氧基等。鹵素原子可列舉出氟原子、氯原子、溴原子、碘原子等，較佳可列舉出氯原子。碳數1至4的烷氧基，可列舉出甲氧基、乙氧基、丙氧基、丁氧基等，較佳可列舉出甲氧基。 The substituents include halogen atoms, alkoxy groups having 1 to 4 carbon atoms, and the like. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom, Preferably a chlorine atom is mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, and a methoxy group is preferably used.

雙咪唑化合物，可列舉出2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基雙咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基雙咪唑(參考日本特開平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(烷氧基苯基)雙咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)雙咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)雙咪唑(參考日本特公昭48-38403號公報、日本特開昭62-174204號公報等)、4,4',5,5'-位的苯基經碳烷氧基所取代之咪唑化合物(參考日本特開平7-10913號公報等)等。當中較佳為以下述式所表示之化合物及此等之混合物。 Bisimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl) Phenyl)-4,4',5,5'-tetraphenylbisimidazole (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'-tetra(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (refer to Japan Japanese Patent Publication No. Sho 48-38403, Japanese Patent Publication No. Sho 62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted with a carboalkoxy group (refer to Japanese Patent Laid-Open No. 7 - Bulletin No. 10913, etc.) and so on. Among them, compounds represented by the following formulae and mixtures thereof are preferred.

Figure 106134182-A0202-12-0070-48
Figure 106134182-A0202-12-0070-48

前述三嗪化合物，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-向日葵基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)次乙基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)次乙基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)次乙基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧苯基)乙烯基]-1,3,5-三嗪等。 The aforementioned triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-sunenyl-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)ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene Ethyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethylene] -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

前述醯基膦氧化物化合物，可列舉出2,4,6-三甲基苯甲醯基二苯基膦氧化物等。 As said acylphosphine oxide compound, 2,4,6- trimethylbenzyldiphenylphosphine oxide etc. are mentioned.

再者，聚合起始劑(D)，可列舉出安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等之安息香化合物；二苯基酮、鄰-苯甲醯基苯甲酸甲酯、4-苯基二苯基酮、4-苯甲醯基-4'-甲基二苯基硫化物、3,3',4,4'-四(三級丁基過氧羰基)二苯基酮、2,4,6-三甲基二苯基酮等之二苯基酮化合物；9,10-菲醌(9,10-Phenanthrenequinone)、2-乙基蒽醌、樟腦醌等之醌化合物；10-丁基-2-氯吖啶酮、二苯乙二酮(benzil)、苯基乙醛酸甲酯、二茂鈦(Titanocene)化合物等。 Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone, o-benzyl benzoic acid Methyl ester, 4-phenyldiphenyl ketone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl) Diphenyl ketone compounds such as benzophenone, 2,4,6-trimethyl benzophenone, etc.; 9,10-phenanthrenequinone (9,10-Phenanthrenequinone), 2-ethylanthraquinone, camphorquinone, etc. The quinone compound; 10-butyl-2-chloroacridone, benzophenone (benzil), methyl phenylglyoxylate, titanocene (Titanocene) compound and so on.

此等，較佳係與後述聚合起始輔助劑(D1)(尤其是胺化合物)組合使用。 These are preferably used in combination with a polymerization initiation adjuvant (D1) (especially an amine compound) described later.

聚合起始劑(D)，較佳係含有選自由烷基苯基酮化合物、三嗪化合物、醯基膦氧化物化合物、O-醯基肟化合物及雙咪唑化合物所組成之群組的至少一種之聚合起始劑，尤佳為含有O-醯基肟化合物之聚合起始劑。 The polymerization initiator (D) preferably contains at least one selected from the group consisting of alkyl phenyl ketone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and bisimidazole compounds The polymerization initiator is particularly preferably a polymerization initiator containing an O-acyl oxime compound.

聚合起始劑(D)的含量，相對於樹脂(B)及聚合性化合物(C)的合計量100質量份，較佳為0.1至40質量份，尤佳為1至30質量份。 The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

〈聚合起始助劑(D1)〉 <Polymerization Initiating Auxiliary (D1)>

聚合起始助劑(D1)，為用以促進藉由聚合起始劑而開始聚合之聚合性化合物的聚合所使用之化合物，或增敏劑。含有聚合起始助劑(D1)時，通常與聚合起始劑(D)組合使用。 The polymerization initiator (D1) is a compound used for accelerating the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator, or a sensitizer. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

聚合起始助劑(D1)，可列舉出胺化合物、烷氧基蒽化合物、噻噸酮(Thioxanthone)化合物及羧酸化合物等。 The polymerization initiator (D1) includes an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, and the like.

前述胺化合物，可列舉出三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯基酮(通稱米其勒酮(Michler's ketone))、4,4'-雙(二乙基胺基)二苯基酮、 4,4'-雙(乙基甲基胺基)二苯基酮等，當中較佳為4,4'-雙(二乙基胺基)二苯基酮。亦可使用EAB-F(保土谷化學工業股份有限公司製)等之市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-bis(dimethylamino)diphenyl ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis (Ethylmethylamino)diphenyl ketone, etc. Among them, 4,4'-bis(diethylamino)diphenyl ketone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

前述烷氧基蒽化合物，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、2-乙基-9,10-二丁氧基蒽等。 The aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

前述噻噸酮化合物，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、1-氯-4-丙氧基噻噸酮等。 The aforementioned thioxanthone compound includes 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

前述羧酸化合物，可列舉出苯基硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲基乙基苯基硫基乙酸、二甲基苯基硫基乙酸、甲氧基苯基硫基乙酸、二甲氧基苯基硫基乙酸、氯苯基硫基乙酸、二氯苯基硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫乙酸、N-萘基甘胺酸、萘氧基乙酸等。 The aforementioned carboxylic acid compound includes phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methylphenylthioacetic acid Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid , N-naphthylglycine, naphthyloxyacetic acid, etc.

使用此等聚合起始助劑(D1)時，該含量相對於樹脂(B)及聚合性化合物(C)的合計量100質量份，較佳為0.1至30質量份，尤佳為1至20質量份。當聚合起始助劑(D1)的量位於此範圍內時，能夠以更高感度來形成著色圖案，彩色濾光片的生產性有提升之傾向。 When these polymerization initiators (D1) are used, the content is preferably 0.1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). parts by mass. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

〈溶劑(E)〉 <Solvent (E)>

溶劑(E)並無特別限定，可使用該領域中通常所使用之 溶劑。溶劑(E)，可列舉出，酯溶劑(於分子內含有-COO-且不含-O-之溶劑)、醚溶劑(於分子內含有-O-且不含-COO-之溶劑)、醚酯溶劑(於分子內含有-COO-與-O-之溶劑)、酮溶劑(於分子內含有-CO-且不含-COO-之溶劑)、醇溶劑(於分子內含有OH且不含-O-、-CO-及-COO-之溶劑)、芳香族烴溶劑、醯胺溶劑及二甲基亞碸等。 The solvent (E) is not particularly limited, and those commonly used in this field can be used. Examples of the solvent (E) include ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecules), ethers Ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- and no -COO- in the molecule), alcohol solvent (containing OH in the molecule and not - O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl methylene, etc.

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、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、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、環己醇乙酸酯及γ丁內酯等。 The ester solvent includes methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl Propionate, Isopropyl Butyrate, Ethyl Butyrate, Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Cyclohexyl Alcohol acetate and γ-butyrolactone, etc.

醚溶劑，可列舉出乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫哌喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二乙二醇二丙醚、二乙二醇二丁醚、甲氧苯、乙氧苯及甲基甲氧苯等。 The ether solvent includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl butanol, tetrahydrofuran , tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethyl ether Butyl ether, methoxybenzene, ethoxybenzene and methyl methoxybenzene, etc.

醚酯溶劑，可列舉出甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、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、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯及二丙二醇甲醚乙酸酯等。 The ether ester solvent includes methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, 2-methoxypropionate propyl, 2-ethoxypropionate methyl ester, 2-ethoxypropionate ethyl ester, 2-methoxy-2-methyl propionate methyl ester, 2-ethyl propionate Ethyl oxy-2-methylpropionate, 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 ester and dipropylene glycol methyl ether acetate, etc.

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、環己酮及異佛爾酮等。 Ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone ketone, cyclopentanone, cyclohexanone and isophorone, etc.

醇溶劑，可列舉出甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及丙三醇等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

芳香族烴溶劑，可列舉出苯、甲苯、二甲苯及三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

醯胺溶劑，可列舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等。 The amide solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

此等溶劑可單獨使用或併用2種以上。 These solvents may be used alone or in combination of two or more.

當中，較佳為丙二醇單甲醚乙酸酯、二丙二醇甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺及N-甲基吡咯啶酮等，尤佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、乙二醇單丁醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁 基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯及N-甲基吡咯啶酮。 Among them, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol are preferred Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl- 2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., especially 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, 3-ethoxyethyl propionate and N-methylpyrrolidone.

溶劑(E)的含有率，相對於著色硬化性樹脂組成物的總量，較佳為70至95質量%，尤佳為75至92質量%。換言之，著色硬化性樹脂組成物的固體成分，較佳為5至30質量%，尤佳為8至25質量%。當溶劑(E)的含有率位於前述範圍時，塗佈著色硬化性樹脂組成物時之平坦性良好，此外，於形成彩色濾光片時，色濃度不會不足，所以有顯示特性變得良好之傾向。 The content of the solvent (E) is preferably 70 to 95% by mass, particularly preferably 75 to 92% by mass, with respect to the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, particularly preferably 8 to 25% by mass. When the content rate of the solvent (E) is within the above-mentioned range, the flatness at the time of coating the colored curable resin composition is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics become good. tendency.

〈勻染劑(F)〉 <Leveling agent (F)>

勻染劑(F)，可列舉出聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑等。此等可於側鏈具有聚合性基。 The leveling agent (F) includes polysiloxane-based surfactants, fluorine-based surfactants, and polysiloxane-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

聚矽氧系界面活性劑，可列舉出於分子內具有矽氧烷鍵之界面活性劑等。具體可列舉出Toray Silicone DC3PA、同SH7PA、同DC11PA、同SH21PA、同SH28PA、同SH29PA、同SH30PA、同SH8400(Toray Dow Corning股份有限公司製)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452及TSF4460(Momentive Performance Materials Japan有限責任合資公司製)等。 The polysiloxane-based surfactants include those having a siloxane bond in the molecule, and the like. Specifically, Toray Silicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

前述氟系界面活性劑，可列舉出於分子內具 有氟碳鏈之界面活性劑等。具體上可列舉出Fluorad(註冊商標)FC430、同FC431(Sumitomo 3M股份有限公司製)、Megafac(註冊商標)F142D、同F171、同F172、同F173、同F177、同F183、同F554、同R30、同RS-718-K(DIC股份有限公司製)、F-Top(註冊商標)EF301、同EF303、同EF351、同EF352(Mitsubishi Material Electronics Chemicals股份有限公司製)、Surflon(註冊商標)S381、同S382、同SC101、同SC105(Asahi Glass股份有限公司製)及E5844(Daikin Fine Chemical研究所製)等。 The aforementioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Fluorad (registered trademark) FC430, the same FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554, the same R30 , same as RS-718-K (manufactured by DIC Co., Ltd.), F-Top (registered trademark) EF301, same as EF303, same as EF351, same as EF352 (manufactured by Mitsubishi Material Electronics Chemicals Co., Ltd.), Surflon (registered trademark) S381, The same as S382, the same as SC101, the same as SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

前述具有氟原子之聚矽氧系界面活性劑，可列舉出於分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體可列舉出Megafac(註冊商標)R08、同BL20、同F475、同F477及同F443(DIC股份有限公司製)等。 The above-mentioned polysiloxane-based surfactant having a fluorine atom includes a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, Megafac (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (manufactured by DIC Co., Ltd.), etc. are mentioned.

含有勻染劑(F)時，該含有率相對於著色硬化性樹脂組成物的總量，較佳為0.001質量%以上0.2質量%以下，尤佳為0.002質量%以上0.1質量%以下，更佳為0.005質量%以上0.07質量%以下。當勻染劑(F)的含有率位於前述範圍時，可使彩色濾光片的平坦性達到良好。 When the leveling agent (F) is contained, the content is preferably 0.001 mass % or more and 0.2 mass % or less, more preferably 0.002 mass % or more and 0.1 mass % or less, with respect to the total amount of the colored curable resin composition. It is 0.005 mass % or more and 0.07 mass % or less. When the content rate of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be made favorable.

〈抗氧化劑(H)〉 <Antioxidant (H)>

從提升著色劑的耐熱性及耐光性之觀點來看，較佳係單獨使用或組合2種以上的抗氧化劑而使用。抗氧化劑，只要是工業上一般所使用之抗氧化劑即可，並無特別限定，可使用酚系抗氧化劑、磷系抗氧化劑及硫系抗氧化劑 等。 From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use alone or in combination of two or more kinds of antioxidants. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like can be used.

前述酚系抗氧化劑，可列舉出Irganox 1010(Irganox 1010：新戊四醇四[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、BASF股份有限公司製)、Irganox 1076(Irganox 1076：十八烷基-3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、BASF股份有限公司製)、Irganox 1330(Irganox 1330：3,3',3",5,5',5"-六(三級丁基)-a,a',a"-(三甲苯-2,4,6-三基)三-對甲酚、BASF股份有限公司製)、Irganox 3114(Irganox 3114：1,3,5-三(3,5-二(三級丁基)-4-羥基苯甲基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、BASF股份有限公司製)、Irganox 3790(Irganox 3790：1,3,5-三((4-三級丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、BASF股份有限公司製)、Irganox 1035(Irganox 1035：硫二伸乙基雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、BASF股份有限公司製)、Irganox 1135(Irganox 1135：苯丙酸、3,5-雙(1,1-二甲基乙基)-4-羥基、C7-C9側鏈烷酯、BASF股份有限公司製)、Irganox 1520L(Irganox 1520L：4,6-雙(辛基硫甲基)-鄰甲酚、BASF股份有限公司製)、Irganox 3125(Irganox3125、BASF股份有限公司製)、Irganox 565(Irganox 565：2,4-雙(正辛基硫基)-6-(4-羥基-3,5-二(三級丁基苯胺基)-1,3,5-三嗪、BASF股份有限公司製)、ADK Stab AO-80(ADK Stab AO-80：3,9-雙(2-(3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯基氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、ADEKA股份有限公司製)、Sumilizer BHT(Sumilizer BHT：住友化學股份有限公司製)、Sumilizer GA-80(Sumilizer GA-80：住友化學股份有限公司製)、Sumilizer GS(Sumilizer GS：住友化學股份有限公司製)、Cyanox 1790(Cyanox 1790：Cytec股份有限公司製)及維生素E(Eisai股份有限公司製)等。 Examples of the aforementioned phenolic antioxidant include Irganox 1010 (Irganox 1010: neopentaerythritol tetrakis[3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate], BASF Co., Ltd. Company), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate], BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa(tertiary butyl)-a,a',a"-(trimethylbenzene-2,4,6-triyl)tris - p-cresol, manufactured by BASF Co., Ltd.), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-bis(tertiary butyl)-4-hydroxybenzyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tertiarybutyl- 3-Hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: thiodieneethylbis[3-(3,5-bis(tert-butyl)-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.), Irganox 1135 (Irganox 1135: Phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6- Bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio) -6-(4-Hydroxy-3,5-bis(tertiary butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd.), ADK Stab AO-80 (ADK Stab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2, 4,8,10-Tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT: manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80: Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS: Sumitomo Chemical Co., Ltd.) Co., Ltd.), Cyanox 1790 (Cyanox 1790: Cytec Co., Ltd.), and vitamin E (Eisai Co., Ltd.), etc.

前述磷系抗氧化劑，可列舉出Irgafos 168(Irgafos 168：三(2,4-二(三級丁基)苯基)亞磷酸酯、BASF股份有限公司製)、Irgafos 12(Irgafos 12：三[2-[[2,4,8,10-四(三級丁基)二苯并[d,f][1,3,2]二氧雜膦-6-基]氧基]乙基]胺、BASF股份有限公司製)、Irgafos 38(Irgafos 38：雙(2,4-雙(1,1-二甲基乙基)-6-甲基苯基)乙酯亞磷酸、BASF股份有限公司製)、ADK Stab 329K(ADEKA股份有限公司製)、ADK Stab PEP36(ADEKA股份有限公司製)、ADK Stab PEP-8(ADEKA股份有限公司製)、Sandstab P-EPQ(Clariant公司製)、Weston 618(Weston 618、GE公司製)、Weston 619G(Weston 619G、GE公司製)、Ultranox 626(Ultranox 626、GE公司製)及Sumilizer GP(Sumilizer GP：6-[3-(3-三級丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四(三級丁基)二苯并[d,f][1,3,2]二氧雜磷雜庚烷)(住友化學股份有限公司製)等。 The aforementioned phosphorus-based antioxidants include Irgafos 168 (Irgafos 168: tris(2,4-bis(tertiary butyl)phenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: tris[ 2-[[2,4,8,10-Tetrakis(tertiarybutyl)dibenzo[d,f][1,3,2]dioxaphosphoran-6-yl]oxy]ethyl]amine , BASF Co., Ltd.), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Co., Ltd. ), ADK Stab 329K (manufactured by ADEKA Co., Ltd.), ADK Stab PEP36 (manufactured by ADEKA Co., Ltd.), ADK Stab PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant Co., Ltd.), Weston 618 ( Weston 618 (manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), and Sumilizer GP (Sumilizer GP: 6-[3-(3-tertiarybutyl-4) -Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra(tertiarybutyl)dibenzo[d,f][1,3,2]dioxaphospha Heptane) (manufactured by Sumitomo Chemical Co., Ltd.), etc.

前述硫系抗氧化劑，可列舉出硫二丙酸二月桂酯、二肉荳蔻基或二硬脂基等之硫二丙酸二烷酯化合物及四[亞甲基(3-十二烷基硫基)丙酸酯]甲烷等之多元醇的β-烷基巰基丙酸酯化合物等。 The aforementioned sulfur-based antioxidants include dilauryl thiodipropionate, dialkyl thiodipropionate compounds such as dimyristyl or distearyl, and tetrakis[methylene(3-dodecyl sulfide]. β-Alkyl mercaptopropionate compounds of polyhydric alcohols such as methane and the like.

〈其他成分〉 <Other ingredients>

本發明之著色硬化性樹脂組成物，可視需要含有填充劑、其他高分子化合物、密著促進劑、光穩定劑、鏈轉移劑等之該技術領域中一般所知的添加劑。 The colored curable resin composition of the present invention may optionally contain additives generally known in the technical field such as fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents.

〈著色硬化性樹脂組成物的製造方法〉 <Method for producing colored curable resin composition>

本發明之著色硬化性樹脂組成物，可藉由混合著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)、及溶劑(E)，以及視需要所使用之勻染劑(F)、聚合起始助劑(D1)、抗氧化劑(H)及其他成分而調製。 The coloring curable resin composition of the present invention can be prepared by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and as needed The used leveling agent (F), polymerization initiation aid (D1), antioxidant (H) and other components are prepared.

含有顏料(Ab)時，較佳係預先與溶劑(E)的一部分或全部混合，並使用珠磨機等進行分散直到顏料的平均粒徑成為0.2μm以下。此時，可視需要調配前述顏料分散劑、樹脂(B)的一部分或全部。然後將剩餘的成分，以成為既定濃度之方式混合於如此得到之顏料分散液，藉此可調製出目的之著色硬化性樹脂組成物。 When a pigment (Ab) is contained, it is preferable to mix with a part or all of the solvent (E) in advance, and to disperse|distribute using a bead mill etc. until the average particle diameter of a pigment becomes 0.2 micrometer or less. At this time, a part or all of the said pigment dispersing agent and resin (B) can be mix|blended as needed. Then, the remaining components are mixed with the pigment dispersion liquid thus obtained so as to have a predetermined concentration, whereby the intended coloring curable resin composition can be prepared.

關於著色劑(A)，染料較佳係預先溶解於溶劑(E)的一部分或全部以調製出溶液。較佳係以孔徑約0.01至1μm的過濾器來過濾該溶液。 About a coloring agent (A), it is preferable to prepare a solution by dissolving a part or all of the dye in the solvent (E) in advance. Preferably, the solution is filtered through a filter having a pore size of about 0.01 to 1 μm.

較佳係以孔徑約0.01至10μm的過濾器來過濾混合後的著色硬化性樹脂組成物。 Preferably, the mixed colored curable resin composition is filtered with a filter having a pore size of about 0.01 to 10 μm.

〈彩色濾光片的製造方法〉 <Manufacturing method of color filter>

可從本發明之著色硬化性樹脂組成物來製造著色圖案。該著色圖案的製造方法，可列舉出微影法、噴墨法、印刷法等，較佳可列舉出微影法。 A colored pattern can be produced from the colored curable resin composition of the present invention. As the manufacturing method of this coloring pattern, a lithography method, an inkjet method, a printing method, etc. are mentioned, Preferably, a lithography method is mentioned.

微影法，係將前述著色硬化性樹脂組成物塗佈於基板，進行乾燥而形成著色組成物層，然後隔著光罩使該著色組成物層曝光，並進行顯影之方法。微影法中，於曝光時不使用光罩及/或不進行顯影，可形成上述著色組成物層的硬化物之著色塗膜。如此形成之著色圖案或著色塗膜，為本發明之彩色濾光片。 The lithography method is a method of applying the coloring curable resin composition to a substrate, drying it to form a coloring composition layer, and exposing the coloring composition layer through a photomask and developing the coloring composition layer. In the lithography method, a colored coating film of the cured product of the colored composition layer described above can be formed without using a photomask and/or without performing development during exposure. The colored pattern or colored coating film thus formed is the color filter of the present invention.

所製作之彩色濾光片的膜厚並無特別限定，可因應目的或用途等來適當地調整，例如為0.1至30μm，較佳為0.1至20μm，更佳為0.5至6μm。 The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose or use, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

基板，可使用：石英玻璃、硼矽酸玻璃、鋁矽酸鹽玻璃、表面經二氧化矽塗覆之鈉鈣玻璃等之玻璃板；或是聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等之樹脂板；矽；或於前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。於此等基板上，可形成有其他的彩色濾光片層、樹脂層、電晶體、電路等。由微影法所進行之各色像素的形成，可在一般或慣用的裝置或條件下進行。例如可如下述般地製作。 The substrate can be used: quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface, etc.; or polycarbonate, polymethyl methacrylate, polymethyl methacrylate Resin plates such as ethylene phthalate; silicon; or those with aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the aforementioned substrate. On these substrates, other color filter layers, resin layers, transistors, circuits, and the like may be formed. The formation of pixels of various colors by lithography can be performed under general or conventional apparatus or conditions. For example, it can be produced as follows.

首先，將著色硬化性樹脂組成物塗佈於基板上，並藉由加熱乾燥(預烘烤)及/或減壓乾燥來去除溶劑等的揮發成分並乾燥，而得到平滑的著色組成物層。 First, a colored curable resin composition is applied on a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure, and then dried to obtain a smooth colored composition layer.

塗佈方法，可列舉出旋轉塗佈法、狹縫塗佈 法、狹縫及旋轉塗佈法等。 The coating method includes spin coating, slit coating, slit and spin coating, and the like.

進行加熱乾燥時之溫度，較佳為30至120℃，尤佳為50至110℃，此外，加熱時間較佳為10秒至60分鐘，尤佳為30秒至30分鐘。 The temperature during heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C, and the heating time is preferably 10 seconds to 60 minutes, particularly preferably 30 seconds to 30 minutes.

進行減壓乾燥時，較佳是在50至150Pa的壓力下，於20至25℃的溫度範圍內進行。 When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150Pa.

著色組成物層的膜厚並無特別限定，可因應目的之彩色濾光片的膜厚來適當地選擇。 The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the intended color filter.

接著，著色組成物層，係隔著用以形成目的之著色圖案之光罩來進行曝光。該光罩上的圖案並無特別限定，可使用因應目的之用途之圖案。 Next, the coloring composition layer is exposed through a photomask for forming the intended coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the purpose can be used.

曝光所使用之光源，較佳為發出250至450nm的波長光之光源。例如，可將未達350nm的光，使用去除該波長區域之濾波器來去除，或是將436nm附近、408nm附近、365nm附近的光，使用擷取此等波長區域之帶通濾波器而選擇性地擷取。具體而言，光源可列舉出汞燈、發光二極體、金屬鹵化物燈、鹵素燈等。 The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, the light below 350nm can be removed by using a filter that removes this wavelength region, or the light around 436nm, 408nm, and 365nm can be selectively selected using a bandpass filter that captures these wavelength regions to capture. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned as a light source.

由於可將平行光線均一地照射至曝光面全體，或是進行光罩與形成有著色組成物層之基板之正確的對位，故較佳係使用光罩對準器及步進器等之曝光裝置。 Since the entire exposure surface can be uniformly irradiated with parallel light, or the mask and the substrate on which the coloring composition layer is formed can be accurately aligned, it is preferable to use a mask aligner, a stepper, or the like for exposure. device.

使曝光後的著色組成物層接觸顯影液以進行顯影，藉此於基板上形成著色圖案。藉由顯影，使著色組成物層的未曝光部溶解於顯影液而去除。顯影液，較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等之鹼 性化合物的水溶液。此等鹼性化合物於水溶液中的濃度，較佳為0.01至10質量%，尤佳為0.03至5質量%。再者，顯影液可含有界面活性劑。顯影方法，可為槳葉式法、浸泡法及噴霧法等中任一種。此外，顯影時可將基板傾斜為任意角度。顯影後，較佳係進行水洗。 A colored pattern is formed on the substrate by contacting the exposed colored composition layer with a developing solution for development. By developing, the unexposed portion of the colored composition layer is dissolved in a developing solution and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, particularly preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The developing method may be any of the paddle method, the immersion method, and the spray method. In addition, the substrate can be inclined at any angle during development. After development, it is preferable to wash with water.

此外，較佳係對所得到之著色圖案進行後烘烤。後烘烤溫度較佳為150至250℃，尤佳為160至235℃。後烘烤時間較佳為1至120分鐘，尤佳為10至60分鐘。 In addition, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, particularly preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, particularly preferably 10 to 60 minutes.

藉由本發明之著色硬化性樹脂組成物，可製造高對比的彩色濾光片。該彩色濾光片，係有用於作為顯示裝置(液晶顯示裝置、有機EL裝置、電子紙等)以及固體攝像元件所使用之彩色濾光片。 With the colored curable resin composition of the present invention, a high-contrast color filter can be produced. This color filter is a color filter used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state imaging element.

[實施例][Example]

以下藉由實施例來更詳細說明本發明之著色硬化性樹脂組成物。例中的「%」及「份」，在無特別記載下，為質量%及質量份。 The colored curable resin composition of the present invention will be described in more detail below by way of examples. "%" and "part" in the example are mass % and mass part unless otherwise specified.

[合成例1：三芳基甲烷著色劑(A-I-18)的合成] [Synthesis Example 1: Synthesis of Triarylmethane Colorant (A-I-18)]

以下的反應係在氮氣環境下進行。將N-甲基苯胺(東京化成工業股份有限公司製)15.3份及N,N-二甲基甲醯胺60份加入於具備冷卻管及攪拌裝置之燒瓶後，將混合溶液冰冷。於冰冷下，於30分鐘間以每次些許之方式加入60%氫化鈉(東京化成工業股份有限公司製)5.7份後，一面升溫 至室溫一面攪拌1小時。以每次些許之方式將4,4'-二氟二苯基酮(東京化成工業股份有限公司製)10.4份加入於反應液，於室溫下攪拌24小時。以每次些許之方式將反應液加入於冰水200份後，於室溫下靜置15小時，藉由傾析來去除水，而得到作為殘渣之黏稠固體。將甲醇60份加入於此黏稠固體後，於室溫下攪拌15小時。過濾所析出之固體後，藉由層析法精製。將精製後的淡黃色固體於減壓下、60℃下進行乾燥，而得到以式(C-I-18)所表示之化合物9.8份。 The following reactions were carried out in a nitrogen atmosphere. After adding 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide to the flask equipped with a cooling pipe and a stirring device, the mixed solution was ice-cooled. Under ice-cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added a little at a time for 30 minutes, followed by stirring for 1 hour while warming up to room temperature. 10.4 parts of 4,4'- difluorodiphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the reaction liquid in small portions, and the mixture was stirred at room temperature for 24 hours. After adding the reaction solution to 200 parts of ice water a little at a time, it was left to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to the viscous solid, the mixture was stirred at room temperature for 15 hours. After filtering the precipitated solid, it was purified by chromatography. The purified pale yellow solid was dried under reduced pressure at 60°C to obtain 9.8 parts of a compound represented by formula (C-I-18).

Figure 106134182-A0202-12-0083-49
Figure 106134182-A0202-12-0083-49

以下的反應係在氮氣環境下進行。將以式(B-I-7)所表示之化合物8.2份、以式(C-I-18)所表示之化合物10份以及甲苯20份加入於具備冷卻管及攪拌裝置之燒瓶後，加入***12.2份，並於95至100℃攪拌3小時。接著將反應混合物冷卻至室溫後，以異丙醇170份來稀釋。接著將稀釋後的反應溶液注入於飽和食鹽水300份中後，加入甲苯100份並攪拌30分鐘。然後停止攪拌，靜置30分鐘使有機層與水層分離。以分液操作移除水層後，以飽和食鹽水300份洗淨有機層。將適量的芒硝加入於有機層並攪拌30分鐘後，進行過濾而得到乾燥後的有機層。以蒸發器將所得到之有機層進行溶劑餾除，而得到青紫色固體。然後，將青紫色固體於減壓下、60℃下進行乾燥，而 得到以式(A-II-18)所表示之化合物18.4份。 The following reactions were carried out in a nitrogen atmosphere. After adding 8.2 parts of the compound represented by the formula (B-I-7), 10 parts of the compound represented by the formula (C-I-18), and 20 parts of toluene to a flask equipped with a cooling pipe and a stirring device, 12.2 parts of phosphorus oxychloride was added portion, and stirred at 95 to 100 °C for 3 hours. Then, after cooling the reaction mixture 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, followed by stirring for 30 minutes. Then, stirring was stopped, and the organic layer was separated from the aqueous layer by standing for 30 minutes. After removing the aqueous layer by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was solvent-distilled with an evaporator, and the blue-purple solid was obtained. Then, the blue-violet solid was dried under reduced pressure at 60°C to obtain 18.4 parts of the compound represented by the formula (A-II-18).

Figure 106134182-A0202-12-0084-50
Figure 106134182-A0202-12-0084-50

以下的反應係在氮氣環境下進行。將以式(A-II-18)所表示之化合物8份、甲醇396份加入於具備冷卻管及攪拌裝置之燒瓶後，於室溫下攪拌30分鐘，而調製出藍色溶液。接著將水396份加入於藍色溶液後，更於室溫下攪拌30分鐘而得到反應溶液。 The following reactions were carried out in a nitrogen atmosphere. After adding 8 parts of the compound represented by formula (A-II-18) and 396 parts of methanol to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes to prepare a blue solution. Next, after adding 396 parts of water to the blue solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

於燒杯中投入於水53份，接著將Keggin型磷鎢酸(Aldrich公司製)11.8份及甲醇53份投入於該水中，於室溫下混合而調製出磷鎢酸溶液。 53 parts of water were put into a beaker, then 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and mixed at room temperature to prepare a phosphotungstic acid solution.

將所得到之磷鎢酸溶液，以1小時滴入於先前所調製之反應溶液中。然後於室溫下攪拌30分鐘後，進行過濾而得到藍色固體。將所得到之藍色固體加入於甲醇200份中並進行分散1小時後，重複進行2次的過濾操作。將藉由該操作所得到之藍色固體投入於水200份並進行分散1小時後，重複進行2次的過濾操作。將藉由該操作所得到之藍色固體於減壓下、60℃下進行乾燥，而得到以式(A-I-18)所表示之三芳基甲烷著色劑(A-I-18)17.1份。 The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. Then, after stirring at room temperature for 30 minutes, it was filtered to obtain a blue solid. The obtained blue solid was added to 200 parts of methanol and dispersed for 1 hour, and then the filtration operation was repeated twice. After the blue solid obtained by this operation was put into 200 parts of water and dispersed for 1 hour, the filtration operation was repeated twice. The blue solid obtained by this operation was dried at 60 degreeC under reduced pressure, and 17.1 parts of triarylmethane colorants (A-I-18) represented by formula (A-I-18) were obtained.

Figure 106134182-A0202-12-0085-51
Figure 106134182-A0202-12-0085-51

[合成例2：二苯并哌喃染料(1-38)的合成] [Synthesis Example 2: Synthesis of Dibenzopyran Dye (1-38)]

於遮光條件下混合以式(1x)所表示之化合物20份與N-丙基-2,6-二甲基苯胺(和光純藥工業股份有限公司製)200份，將所得到之溶液於110℃攪拌6小時。將所得到之反應液冷卻至室溫後，添加於水800份、35重量%鹽酸50份的混合液中，並於室溫下攪拌1小時，使結晶析出。取得所析出之結晶作為抽吸過濾的殘渣後進行乾燥，得到以式(1-38)所表示之二苯并哌喃染料(1-38)。 20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was added to 110 °C was stirred for 6 hours. After cooling the obtained reaction solution to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% by weight hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystal was obtained as a residue of suction filtration, and then dried to obtain a dibenzopyran dye (1-38) represented by the formula (1-38).

Figure 106134182-A0202-12-0085-52
Figure 106134182-A0202-12-0085-52

[合成例3：樹脂B1的合成] [Synthesis Example 3: Synthesis of Resin B1]

於具備迴流冷卻器、滴漏斗及攪拌機之燒瓶內，使氮氣適量地流入以構成氮氣環境，裝入乳酸乙酯305份，一面攪拌一面加熱至70℃並保溫。接著將丙烯酸46份、以 及丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯(以莫耳比50：50混合以式(I-1)所表示之化合物及以式(II-1)所表示之化合物者)240份溶解於乳酸乙酯185份而調製出溶液，並使用滴漏斗，於4小時內將該溶解液滴入於保溫在70℃之燒瓶內。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen gas was allowed to flow in an appropriate amount to form a nitrogen atmosphere, 305 parts of ethyl lactate was charged, and the mixture was heated to 70° C. while stirring and kept at the temperature. Next, 46 parts of acrylic acid and 3,4-epoxy tricyclo[5.2.1.0 2.6 ]decyl acrylate (in a molar ratio of 50:50) were mixed with the compound represented by the formula (I-1) and the compound represented by the formula (II) -1) 240 parts of compounds represented by ethyl lactate were dissolved in 185 parts of ethyl lactate to prepare a solution, and using a dropping funnel, the solution was dropped into a flask kept at 70°C for 4 hours.

Figure 106134182-A0202-12-0086-53
Figure 106134182-A0202-12-0086-53

另一方面，使用其他滴漏斗，以4小時將使聚合起始劑的2,2'-偶氮雙(2,4-二甲基戊腈)30份溶解於乳酸乙酯225份後之溶液滴入於燒瓶內。結束聚合起始劑溶液的滴入後，於70℃保持4小時，然後冷卻至室溫，而得到重量平均分子量(Mw)為9.1×103、分散度為2.1、固體成分26質量%、固體成分酸值120mg-KOH/g之樹脂B1溶液。樹脂B1具有以下所示之結構單位。 On the other hand, a solution obtained by dissolving 30 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 225 parts of ethyl lactate over 4 hours using another dropping funnel Drop into the flask. After finishing the dropping of the polymerization initiator solution, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a weight-average molecular weight (Mw) of 9.1×10 3 , a degree of dispersion of 2.1, a solid content of 26% by mass, and a solid Resin B1 solution with component acid value of 120 mg-KOH/g. Resin B1 has the structural unit shown below.

Figure 106134182-A0202-12-0086-54
Figure 106134182-A0202-12-0086-54

[合成例4：樹脂B2的合成] [Synthesis Example 4: Synthesis of Resin B2]

於具備迴流冷卻器、滴漏斗及攪拌機之燒瓶內，使氮氣適量地流入以構成氮氣環境，裝入丙二醇單甲醚乙酸酯371份，一面攪拌一面加熱至85℃。接著將丙烯酸54份、丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯(以莫耳比50：50混 合以式(I-1)所表示之化合物及以式(II-1)所表示之化合物者)225份、乙烯基甲苯(異構物混合物)81份、以及丙二醇單甲醚乙酸酯80份的混合溶液，以4小時滴入。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen gas was allowed to flow in an appropriate amount to form a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85°C while stirring. Next, 54 parts of acrylic acid and 3,4-epoxy tricyclo[5.2.1.0 2.6 ]decyl acrylate (in a molar ratio of 50:50) were mixed with the compound represented by the formula (I-1) and the compound represented by the formula (II- 1) A mixed solution of 225 parts of the compound represented by), 81 parts of vinyltoluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.

另一方面，將使2,2'-偶氮雙(2,4-二甲基戊腈)30份溶解於丙二醇單甲醚乙酸酯160份後之混合溶液，以5小時滴入。滴入結束後，於同一溫度保持4小時後冷卻至室溫，而得到B型黏度(23℃)246mPas、固體成分37.5質量%、溶液酸值43mg-KOH/g之共聚物(樹脂B2)。樹脂B2的重量平均分子量(Mw)為1.1×104、分散度為2.01。樹脂B2具有以下所示之結構單位。 On the other hand, a mixed solution obtained by dissolving 30 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the dropping was completed, the same temperature was maintained for 4 hours and then cooled to room temperature to obtain a copolymer (resin B2) having a B-type viscosity (23° C.) of 246 mPas, a solid content of 37.5% by mass, and a solution acid value of 43 mg-KOH/g. Resin B2 had a weight average molecular weight (Mw) of 1.1×10 4 and a degree of dispersion of 2.01. Resin B2 has the structural unit shown below.

Figure 106134182-A0202-12-0087-55
Figure 106134182-A0202-12-0087-55

合成例3、4中所得到之樹脂的重量平均分子量(Mw)及數量平均分子量(Mn)的測定，係使用GPC法，於以下條件下進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins obtained in Synthesis Examples 3 and 4 was performed under the following conditions using the GPC method.

裝置；K2479(島津製作所股份有限公司製) Installation; K2479 (manufactured by Shimadzu Corporation)

管柱；SHIMADZU Shim-pack GPC-80M String; SHIMADZU Shim-pack GPC-80M

管柱溫度；40℃ Column temperature; 40℃

溶劑；THF(四氫呋喃) Solvent; THF (tetrahydrofuran)

流速；1.0mL/min Flow rate; 1.0mL/min

檢測器；RI detector; RI

校正用標準物質；TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(Tosoh股份有限公司製) Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

將上述所得到之經聚苯乙烯換算的重量平均分子量(Mw)及數量平均分子量(Mn)之比(Mw/Mn)設為分散度。 The ratio (Mw/Mn) of the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) obtained above was taken as the degree of dispersion.

[調製例1：分散液(1)的調製] [Preparation Example 1: Preparation of Dispersion Liquid (1)]

將合成例1中所得到之三芳基甲烷著色劑(A-I-18)10份、分散劑(BYK(註冊商標)-LPN6919(BYK Chemie公司製))2份、合成例4中所得到之樹脂B2(固體成分換算)4份、以及丙二醇單甲醚乙酸酯84份混合，使用珠磨機將三芳基甲烷著色劑(A-I-18)充分地分散，藉此得到分散液(1)。 10 parts of triarylmethane colorant (A-I-18) obtained in Synthesis Example 1, 2 parts of a dispersant (BYK (registered trademark)-LPN6919 (manufactured by BYK Chemie)), and Resin B2 obtained in Synthesis Example 4 4 parts (in terms of solid content) and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the triarylmethane colorant (A-I-18) was sufficiently dispersed using a bead mill to obtain a dispersion liquid (1).

[調製例2：分散液(2)的調製] [Preparation Example 2: Preparation of Dispersion Liquid (2)]

將顏料(C.I.顏料藍15：6)12份、丙烯酸系顏料分散劑2份、以及丙二醇單甲醚乙酸酯80.5份混合，使用珠磨機將顏料充分地分散，藉此得到分散液(2)。 12 parts of pigment (C.I. Pigment Blue 15:6), 2 parts of acrylic pigment dispersant, and 80.5 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion liquid (2 ).

[實施例1至8、比較例1至3] [Examples 1 to 8, Comparative Examples 1 to 3]

(著色硬化性樹脂組成物的調製) (Preparation of Colored Curable Resin Composition)

以表3所示之份數，混合：‧分散液(1)(含有10質量%的三芳基甲烷著色劑(A-I-18))、‧二苯并哌喃染料(1-38)、‧蒽醌染料(C.I.溶劑藍45；Savinyl Blue RS；Clariant公司製)、‧分散液(2)、 ‧(B)樹脂：樹脂B1、‧(C)聚合性化合物：六丙烯酸二新戊四醇酯(Kayarad(註冊商標)DPHA；日本化藥股份有限公司製)、‧(D)聚合起始劑：N-苯甲醯氧基-1-(4-苯基氫硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE 01；BASF股份有限公司製)、‧(F)勻染劑：經聚醚變性之聚矽氧油(Toray Silicone SH8400；Toray Dow Corning股份有限公司製)、‧(E)溶劑：乳酸乙酯(EL)、‧(E)溶劑：丙二醇單甲醚乙酸酯(PGMEA)，而得到著色硬化性樹脂組成物。 In the parts shown in Table 3, mix: ‧Dispersion liquid (1) (containing 10% by mass of triarylmethane colorant (A-I-18)), ‧Dibenzopyran dye (1-38), ‧Anthracene Quinone dye (C.I. Solvent Blue 45; Savinyl Blue RS; manufactured by Clariant), ‧Dispersion (2), ‧(B) Resin: Resin B1, ‧(C) Polymerizable compound: Dipivalerythritol hexaacrylate ( Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.), ‧(D) Polymerization initiator: N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1 - Keto-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Co., Ltd.), ‧(F) Leveling agent: polyether-denatured polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd. Company), ‧(E) solvent: ethyl lactate (EL), ‧(E) solvent: propylene glycol monomethyl ether acetate (PGMEA), and a colored curable resin composition was obtained.

Figure 106134182-A0202-12-0090-56
Figure 106134182-A0202-12-0090-56

〈著色圖案的製作〉 <Creation of coloring patterns>

藉由旋轉塗佈法將著色硬化性樹脂組成物塗佈於5cm見方的玻璃基板(Eagle 2000；Corning公司製)上後，於100℃進行3分鐘的預烘烤而得到著色組成物層。放置冷卻後，將形成有著色組成物層之基板與石英玻璃製光罩之間的間隔設為100μm，使用曝光機(TME-150RSK；Topcon股份有限公司製)，於大氣環境下以150mJ/cm2的曝光量(365nm基準)進行光照射。光罩，係使用形成有100μm的線與空間圖案者。將光照射後的著色組成物層，於24℃下浸漬在含有非離子系界面活性劑0.12%與氫氧化鉀0.04%之水系顯影液以進行顯影，水洗後，於烤爐中以230℃進行30分鐘的後烘烤，而得到著色圖案。 After applying the colored curable resin composition on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, prebaking was performed at 100° C. for 3 minutes to obtain a colored composition layer. After standing to cool, the interval between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to expose the light to 150 mJ/cm in the atmosphere. Light irradiation was performed at an exposure amount of 2 (365 nm reference). As the photomask, one formed with a 100 μm line and space pattern was used. The light-irradiated coloring composition layer was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24°C for development, washed with water, and then carried out in an oven at 230°C A 30-minute post-bake results in a colored pattern.

〈膜厚測定〉 <Film thickness measurement>

對所得到之著色圖案，使用膜厚測定裝置(DEKTAK3；日本真空技術股份有限公司製)來測定膜厚。結果如表4所示。表4中，對於以表3所示之份數所混合得到之著色硬化性樹脂組成物中所含有之著色劑(A)，係顯示以使著色劑(A)的總量成為100之方式所換算之各成分的含量。 The film thickness of the obtained coloring pattern was measured using a film thickness measuring apparatus (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 4. In Table 4, the coloring agent (A) contained in the coloring curable resin composition obtained by mixing the parts shown in Table 3 is shown so that the total amount of the coloring agent (A) is 100. Convert the content of each component.

〈色度評估〉 <Evaluation of chromaticity>

對所得到之著色圖案，使用測色機(OSP-SP-200；Olympus股份有限公司製)來測定分光，使用C光源的特性 函數來測定CIE的XYZ表色系中之xy色度座標(x、y)與三刺激值Y。Y值愈大，表示明亮度愈大。結果如表4所示。 The obtained coloring pattern was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) for spectroscopic measurement, and the xy chromaticity coordinates (x) in the XYZ colorimetric system of CIE were measured using the characteristic function of the C light source. , y) and the tristimulus value Y. The larger the Y value, the greater the brightness. The results are shown in Table 4.

〈對比評估〉 <Comparative Evaluation>

除了於曝光時不使用光罩之外，其他進行與著色圖案的製作為相同之操作，而製作著色塗膜。對所得到之著色塗膜，使用對比計(CT-1；壺坂電機公司製、色彩色差計BM-5A；Topcon公司製、光源：F-10、偏光膜；壺坂電機股份有限公司製)，將空白值設為30000並測定對比。著色塗膜中的對比愈高，於著色圖案中亦同樣可視為達到高對比。結果如表4所示。 Except that the photomask was not used during exposure, the same operation as the production of the colored pattern was performed to prepare a colored coating film. A contrast meter (CT-1; manufactured by Tsusaka Electric Co., Ltd., colorimeter BM-5A; manufactured by Topcon Corporation, light source: F-10, polarizing film; manufactured by Tsusaka Electric Co., Ltd.) was used for the obtained colored coating film. , set the blank value to 30000 and measure the comparison. The higher the contrast in the colored coating film, the higher the contrast in the colored pattern can also be considered. The results are shown in Table 4.

Figure 106134182-A0202-12-0093-57
Figure 106134182-A0202-12-0093-57

根據實施例1至3及比較例2之著色硬化性樹脂組成物，y的色度座標為0.095，x的色度座標為0.136至0.139，可得到接近色度的著色圖案。此外，於實施例1至3中，與比較例2相比，可得到高明亮度的著色圖案，再者，可得到顯示高對比之著色塗膜。 According to the coloring curable resin compositions of Examples 1 to 3 and Comparative Example 2, the chromaticity coordinates of y are 0.095, and the chromaticity coordinates of x are 0.136 to 0.139, and a coloring pattern close to the chromaticity can be obtained. Moreover, in Examples 1-3, compared with the comparative example 2, the coloring pattern of high brightness was obtained, and also the coloring coating film which showed high contrast was obtained.

根據實施例4至8及比較例1、3之著色硬化性樹脂組成物，y的色度座標為0.095，x的色度座標為0.150至0.153，可得到接近色度的著色圖案。此外，於實施例4至8中，與比較例1、3相比，可得到高明亮度的著色圖案，再者，可得到顯示高對比之著色塗膜。 According to the coloring curable resin compositions of Examples 4 to 8 and Comparative Examples 1 and 3, the chromaticity coordinate of y is 0.095, and the chromaticity coordinate of x is 0.150 to 0.153, and a coloring pattern close to the chromaticity can be obtained. Furthermore, in Examples 4 to 8, compared with Comparative Examples 1 and 3, a colored pattern with high brightness was obtained, and further, a colored coating film showing high contrast was obtained.

從以上內容中，可得知從本發明之著色硬化性樹脂組成物中，能夠製作高對比的著色圖案。從本發明之著色硬化性樹脂組成物所得到之彩色濾光片，該顯示特性優異，可作為液晶顯示裝置的材料使用。 From the above, it can be seen that a high-contrast colored pattern can be produced from the colored curable resin composition of the present invention. The color filter obtained from the colored curable resin composition of the present invention is excellent in the display properties, and can be used as a material for a liquid crystal display device.

Claims (5)

一種著色硬化性樹脂組成物，其係含有：著色劑、樹脂、聚合性化合物及聚合起始劑；前述著色劑，含有：三芳基甲烷著色劑、二苯并哌喃染料、以及蒽醌染料，前述著色劑中之前述二苯并哌喃染料的含有率為1質量%以上、13.5質量%以下。 A coloring curable resin composition containing: a colorant, a resin, a polymerizable compound and a polymerization initiator; the colorant, containing: a triarylmethane colorant, a dibenzopyran dye, and an anthraquinone dye, The content rate of the said dibenzopyran dye in the said coloring agent is 1 mass % or more and 13.5 mass % or less. 如申請專利範圍第1項所述之著色硬化性樹脂組成物，其中前述蒽醌染料的含量，相對於前述三芳基甲烷著色劑100質量份為0.5至50質量份。 The colorable curable resin composition according to claim 1, wherein the content of the anthraquinone dye is 0.5 to 50 parts by mass relative to 100 parts by mass of the triarylmethane colorant. 如申請專利範圍第2項所述之著色硬化性樹脂組成物，其中前述蒽醌染料的含量，相對於前述三芳基甲烷著色劑100質量份為1.0至13.5質量份。 The colorable curable resin composition according to claim 2, wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass relative to 100 parts by mass of the triarylmethane colorant. 一種彩色濾光片，其係由申請專利範圍第1至3項中任一項所述之著色硬化性樹脂組成物所形成。 A color filter, which is formed of the coloring curable resin composition described in any one of claims 1 to 3 of the scope of application. 一種顯示裝置，其係包含申請專利範圍第4項所述之彩色濾光片。 A display device comprising the color filter described in item 4 of the patent application scope.
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