TWI682002B - Colored curable resin composition - Google Patents

Abstract

The present invention provides a colored curable resin composition comprising a coloring agent, a resin, a polymeric compound and a polymerization initiator; wherein, the coloring agent comprises at least one selected from the group consisting of yellow dye and yellow pigment, and blue dye and green pigment.

Description

著色硬化性樹脂組成物 Colored curable resin composition

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.

著色硬化性樹脂組成物係用在液晶顯示裝置、電致發光顯示裝置及電漿顯示器等顯示裝置所使用之濾色器的製造上。以降低顯示裝置的耗電為目的，要求一種穿透率高且高亮度的濾色器。就用以製造濾色器的著色硬化性樹脂組成物而言，日本特開2013-231165號公報中係記載一種含有鹵化酞菁顏料及香豆素(coumarin)染料作為著色劑之著色硬化性樹脂組成物。 The colored curable resin composition is used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. For the purpose of reducing power consumption of the display device, a color filter with high transmittance and high brightness is required. Regarding the color-curing resin composition used for manufacturing the color filter, Japanese Patent Application Laid-Open No. 2013-231165 describes a color-curing resin containing halogenated phthalocyanine pigment and coumarin dye as a colorant Composition.

本發明係包含下列發明： The present invention includes the following inventions:

[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；該著色劑係含有：選自由黃色染料及黃色顏料所組成群組之至少一種、藍色染料、以及綠色顏料。 [1] A color-curing resin composition containing: a colorant, a resin, a polymerizable compound, and a polymerization initiator; the colorant contains: at least one selected from the group consisting of yellow dyes and yellow pigments, Blue dye and green pigment.

[2]如[1]所述之著色硬化性樹脂組成物，其中，相對於著色 劑的合計含量，藍色染料的含有率為0.1質量%以上、20質量%以下。 [2] The color-curing resin composition according to [1], wherein In the total content of the agent, the content of the blue dye is 0.1% by mass or more and 20% by mass or less.

[3]如[1]或[2]所述之著色硬化性樹脂組成物，其中，藍色染料為選自由式(Ab1)所示之化合物、次甲基染料及次甲基偶氮染料所組成群組之至少一種染料。 [3] The color-curing resin composition according to [1] or [2], wherein the blue dye is selected from the group consisting of a compound represented by formula (Ab1), a methine dye, and a methine azo dye At least one dye forming a group.

[式中，R^1A至R^8A係分別獨立地表示氫原子、鹵原子、硝基、羥基、碳數1至20之烷基(於構成該烷基的碳原子之間可***氧原子)。R^4A與R^5A可彼此鍵結而形成-NH-、-S-或-SO₂-。 [In the formula, R ^1A to R ^8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 20 carbon atoms (an oxygen atom may be inserted between carbon atoms constituting the alkyl group). R ^4A and R ^5A may be bonded to each other to form -NH-, -S-, or -SO ₂ -.

R^9A至R^12A係分別獨立地表示氫原子、可被胺基或被鹵原子取代之碳數1至20之烷基(於構成該烷基的碳原子之間可***氧原子)、可被取代之芳烷基、或可被取代之芳基。R^9A與R^10A係鍵結而可與該等所鍵結的氮原子一同形成環，R^11A與R^12A係鍵結而可與該等所鍵結的氮原子一同形成環。 R ^9A to R ^12A independently represent a hydrogen atom, a C 1-20 alkyl group which may be substituted by an amine group or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group), and may be Substituted aralkyl, or aryl which may be substituted. R ^9A and R ^10A are bonded to form a ring together with the bonded nitrogen atoms, and R ^11A and R ^12A are bonded to form a ring together with the bonded nitrogen atoms.

A表示可被取代之芳香族烴基、或可被取代之芳香族雜環基。 A represents an aromatic hydrocarbon group which may be substituted, or an aromatic heterocyclic group which may be substituted.

G^g-表示相對陰離子(counter ion)。 G ^g- represents a counter anion (counter ion).

g表示0或任意的自然數。當g為0時，表示不具有相對陰離子]。 g represents 0 or any natural number. When g is 0, it means there is no relative anion].

[4]如[1]至[3]中任一項所述之著色硬化性樹脂組成物，其中，聚合起始劑含有O-醯基肟化合物。 [4] The color-curable resin composition according to any one of [1] to [3], wherein the polymerization initiator contains an O-acyl oxime compound.

[5]一種濾色器，其係由[1]至[4]中任一項所述之著色硬化性樹脂組成物所形成。 [5] A color filter formed of the color-curing resin composition according to any one of [1] to [4].

[6]一種顯示裝置，其係含有[5]所述之濾色器。 [6] A display device including the color filter described in [5].

依據本發明的著色硬化性樹脂組成物，可形成亮度優異的濾色器。 According to the coloring hardenable resin composition of the present invention, a color filter excellent in brightness can be formed.

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)，其中，著色劑(A)係含有選自由黃色染料及黃色顏料所組成群組之至少一種、藍色染料、以及綠色顏料。 The color-curing resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) contains a dye selected from the group consisting of yellow dyes At least one of the group consisting of yellow pigments, blue dyes, and green pigments.

本發明之著色硬化性樹脂組成物，較佳係更含有溶劑(E)及/或調平劑(F)。 The color-curing resin composition of the present invention preferably further contains a solvent (E) and/or a leveling agent (F).

本發明之著色硬化性樹脂組成物，亦可含有聚合起始助劑(D1)及/或硫醇化合物(T)。 The color-curing resin composition of the present invention may contain a polymerization initiation aid (D1) and/or a thiol compound (T).

於本說明書中，各成分所例示的化合物只要沒有特別的聲明，就可以單獨或組合複數種類來使用。 In this specification, the compounds exemplified for each component can be used alone or in combination of plural types unless otherwise stated.

<著色劑(A)> <Colorant (A)>

著色劑(A)係含有藍色染料(A1)、綠色顏料(A2)、以及選自由黃色染料及黃色顏料所組成群組之至少一種(以下，有時稱為「黃色著色劑(A3)」)。 The colorant (A) contains a blue dye (A1), a green pigment (A2), and at least one selected from the group consisting of yellow dyes and yellow pigments (hereinafter, sometimes referred to as "yellow colorant (A3)" ).

於本發明中，藍色染料(A1)係指於580nm以上、650nm以下的範圍具有極大吸收波長，較佳為於600nm以上、645nm以下的範圍，且係可溶於溶劑的色素。 In the present invention, the blue dye (A1) refers to a dye having a maximum absorption wavelength in a range of 580 nm or more and 650 nm or less, preferably in a range of 600 nm or more and 645 nm or less, and is a solvent-soluble dye.

藍色染料(A1)可列舉酞菁染料、式(Ab1)所示之化合物、二芳基甲烷染料、蒽醌染料、次甲基染料、次甲基偶氮染料等。其中，較佳為酞菁染料、式(Ab1)所示之化合物、次甲基染料、以及次甲基偶氮染料，更佳為式(Ab1)所示之化合物、次甲基染料、以及次甲基偶氮染料。 Examples of the blue dye (A1) include phthalocyanine dyes, compounds represented by formula (Ab1), diarylmethane dyes, anthraquinone dyes, methine dyes, and methine azo dyes. Among them, phthalocyanine dyes, compounds represented by formula (Ab1), methine dyes, and methine azo dyes are preferred, and compounds represented by formula (Ab1), methine dyes, and methine are more preferred Methyl azo dye.

酞菁染料(Aa)為含有於分子內具有酞菁骨架的化合物之染料。酞菁染料(Aa)可列舉色料索引(colour index)(The Society of Dyers and Colourists出版)所記載之C.I.溶劑藍67、70；C.I.直接藍86、87、189、199；C.I.酸性藍249；C.I.媒染藍77；日本特開平5-333207號公報、日本特開平6-51115號公報、日本特開平6-194828號公報所記載之染料等。 The phthalocyanine dye (Aa) is a dye containing a compound having a phthalocyanine skeleton in the molecule. Phthalocyanine dyes (Aa) include CI solvent blue 67, 70 described in the color index (published by The Society of Dyers and Colourists); CI direct blue 86, 87, 189, 199; CI acid blue 249; CI mordant blue 77; dyes described in Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. 6-194828, etc.

式(Ab1)所示之化合物(以下，有時稱為「化合物(Ab1)」。)係包含：色料索引(The Society of Dyers and Colourists出版)所記載之C.I.溶劑藍2、4、5、43、124；C.I.鹼性藍1、5、7、26；C.I.酸性藍1、3、5、7、9、11、13、15、17、22、24、26、34、48、75、83、86、88、90、91、99、100、103、104、108、109、110、119、123、147、213、269及日本專利第4492760號公報所記載之染料等。 The compound represented by formula (Ab1) (hereinafter, sometimes referred to as "compound (Ab1)") includes: Color Index (The Society of Dyers and Published by Colourists) CI Solvent Blue 2, 4, 5, 43, 124; CI Basic Blue 1, 5, 7, 26; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 48, 75, 83, 86, 88, 90, 91, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269 and Japanese patents Dyes, etc. described in No. 4492760.

式(Ab1)中、R^1A至R^8A係分別獨立地表示氫原子、鹵原子、硝基、羥基、碳數1至20的烷基(於構成該烷基的碳原子之間可***氧原子)。R^4A與R^5A可彼此鍵結而形成-NH-、-S-、或-SO₂-。 In formula (Ab1), R ^1A to R ^8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and a C 1-20 alkyl group (an oxygen atom may be inserted between carbon atoms constituting the alkyl group) ). R ^4A and R ^5A may be bonded to each other to form -NH-, -S-, or -SO ₂ -.

R^9A至R^12A係分別獨立地表示可被胺基或被鹵原子取代之碳數1至20的烷基(於構成該烷基的碳原子之間可***氧原子)、可被取代之芳烷基、或可被取代之芳基、或氫原子，較佳為氫原子、可被胺基或鹵原子取代之碳數1至20的烷基(於構成該烷基的碳原子之間可***氧原子)、或可被取代之芳基。R^9A與R^10A係鍵結而可與該等所鍵結的氮原子一同形成環，R^11A與R^12A係鍵結而可與該等所鍵結的氮原子一同形成環。 R ^9A to R ^12A independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) and an aromatic group which may be substituted An alkyl group, or an aryl group which may be substituted, or a hydrogen atom, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group or a halogen atom (between the carbon atoms constituting the alkyl group) Insert an oxygen atom), or an aryl group which may be substituted. R ^9A and R ^10A are bonded to form a ring together with the bonded nitrogen atoms, and R ^11A and R ^12A are bonded to form a ring together with the bonded nitrogen atoms.

A表示可被取代之芳香族烴基、或可被取代 之芳香族雜環基。 A represents an aromatic hydrocarbon group which may be substituted, or may be substituted Of aromatic heterocyclic groups.

G^g-表示相對陰離子。 G ^g- represents a relative anion.

g表示0或任意的自然數。當g為0時，表示不具有相對陰離子。 g represents 0 or any natural number. When g is 0, it means there is no relative anion.

式(Ab1)所示之化合物中，亦包含其互變異構物。 Compounds represented by formula (Ab1) also include tautomers.

R^1A至R^8A係分別獨立，較佳為氫原子、及碳數1至20的烷基。於R^1A至R^8A中，就碳數1至20的烷基而言，較佳為甲基、乙基、丙基、丁基等碳數1至4的烷基。 R ^1A to R ^8A are each independently, preferably a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. In R ^1A to R ^8A , the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl.

於R^9A至R^12A中，就碳數1至20的烷基而言，較佳為甲基、乙基、丙基、丁基等碳數1至4的烷基。可被取代之芳基可列舉鹵原子、可被硝基或羥基取代之苯基。於R^9A至R^12A中，芳烷基可列舉苯甲基、苯乙基等。可被取代之芳烷基可列舉可具有-SO₃ ^-或-SO₃J(J表示陽離子)作為取代基之芳烷基。 In R ^9A to R ^12A , the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. Examples of the aryl group which may be substituted include a halogen atom, and a phenyl group which may be substituted by a nitro group or a hydroxyl group. In R ^9A to R ^12A , the aralkyl group includes benzyl, phenethyl and the like. Examples of the aralkyl group which may be substituted include aralkyl groups which may have -SO ₃ ^- or -SO ₃ J (J represents a cation) as a substituent.

R^9A至R^12A係分別獨立，較佳為氫原子、碳數1至20的烷基、及可被取代之苯甲基。 R ^9A to R ^12A are each independently, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a benzyl group which may be substituted.

於A中，芳香族烴基可列舉苯基、萘基、甲苯甲醯基、二甲苯基等碳數6至10的芳香族烴基。芳香族雜環基可列舉含有吡咯基、

唑基、咪唑基、噻唑基、吲哚基(indolyl)等包含氧、窒或硫之5員環的雜環之芳香族雜環基。 In A, the aromatic hydrocarbon group includes an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as phenyl, naphthyl, tolyl, and xylyl. Examples of the aromatic heterocyclic group include pyrrolyl,

Aromatic heterocyclic groups such as oxazolyl, imidazolyl, thiazolyl, and indolyl containing a 5-membered heterocyclic ring of oxygen, sulfur, or sulfur.

於A中，芳香族烴基及芳香族雜環基可具有之取代基，可列舉鹵原子、可被取代之胺基、羥基、磺酸基、-SO₃ ^-、-SO₃J(J表示陽離子)等。 In A, the substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have include halogen atoms, amine groups which may be substituted, hydroxyl groups, sulfonic acid groups, -SO ₃ ^- and -SO ₃ J (J represents a cation )Wait.

上述胺基中之取代基，可列舉碳數1至4的烷基；可具碳數1至4的烷氧基作為取代基之芳基；可具有-SO₃ ^-或-SO₃J作為取代基之苯甲基等。 Examples of the substituent in the above amine group include an alkyl group having 1 to 4 carbon atoms; an aryl group having 1 to 4 carbon atoms as a substituent; and -SO ₃ ^- or -SO ₃ J as a substituent The base of benzyl and so on.

J可列舉無機陽離子或有機陽離子。無機陽離子可列舉鹼金屬陽離子、銨陽離子。有機陽離子可列舉例如有機銨陽離子、下述式的陽離子等咪唑鎓陽離子。 J can be an inorganic cation or an organic cation. Examples of inorganic cations include alkali metal cations and ammonium cations. Examples of the organic cation include imidazolium cations such as organic ammonium cations and cations of the following formula.

G^g-可列舉式(y1)、式(y2)或式(y3)所示之陰離子。 G ^g- may include anions represented by formula (y1), formula (y2) or formula (y3).

式中，R^B1表示1價有機基。該有機基可列舉甲基、乙基、丙基、丁基等碳數1至20的脂肪族烴基；苯基、萘基、甲苯甲醯基等碳數6至20的芳香族烴基，該脂肪族烴基及該芳香族烴基所含有之氫原子可被鹵原子等取代。 In the formula, R ^B1 represents a monovalent organic group. Examples of the organic group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, and butyl; aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, and toluoyl groups. The hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with halogen atoms or the like.

R^B2及R^B3表示鹵原子或鹵化烴基，R^B2及R^B3係彼此鍵結而形成含有-SO₂-N^--SO₂-之環。前述鹵化烴基較佳為氟化烴基，更佳為碳數1至4的氟化烷基，再更佳為全氟烷基。 R ^B2 and R ^B3 represent a halogen atom or a halogenated hydrocarbon group, and R ^B2 and R ^B3 are bonded to each other to form a ring containing -SO ₂ -N ^-- SO ₂ -. The aforementioned halogenated hydrocarbon group is preferably a fluorinated hydrocarbon group, more preferably a fluorinated alkyl group having 1 to 4 carbon atoms, and still more preferably a perfluoroalkyl group.

R^B4及R^B5表示2價有機基。該有機基較佳為2價芳香族基。該芳香族基可列舉伸苯基、萘二基等2價 之碳數6至10的芳香族烴基，該芳香族烴基所含有之氫原子可被羥基等取代。 R ^B4 and R ^B5 represent a divalent organic group. The organic group is preferably a divalent aromatic group. Examples of the aromatic group include divalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as phenylene and naphthalenediyl groups, and the hydrogen atoms contained in the aromatic hydrocarbon group may be substituted with hydroxyl groups or the like.

M表示鋁原子或硼原子。 M represents an aluminum atom or a boron atom.

式(y1)所示之陰離子，可列舉甲基磺酸陰離子、甲苯基磺酸陰離子、十二基苯磺酸陰離子、三氟甲基磺酸陰離子、全氟丁基磺酸陰離子等。 Examples of the anion represented by the formula (y1) include methanesulfonic acid anion, tolylsulfonic acid anion, dodecylbenzenesulfonic acid anion, trifluoromethylsulfonic acid anion, and perfluorobutylsulfonic acid anion.

式(y2)所示之陰離子可列舉下述式的陰離子等。 Examples of the anion represented by formula (y2) include the following anions.

式(y3)所示之陰離子可列舉下述式的陰離子等。 Examples of the anion represented by formula (y3) include the following anions.

再者，G^g-可列舉鹵化物離子、矽鎢酸陰離子、具有磺酸陰離子之樹脂、參(全氟烷基磺醯基)甲基化酸(tris(perfluoroalkylsulfonyl)methide acid)陰離子等。 In addition, G ^g- may include a halide ion, a silicotungstic acid anion, a resin having a sulfonic acid anion, a tris (perfluoroalkylsulfonyl)methide acid anion, and the like.

G^g-較佳為鹵化物離子、或是式(y2)或式(y3)所示之陰離 子，更佳為鹵化物離子及式(y2)所示之陰離子。 G ^{g- is} preferably a halide ion or an anion represented by formula (y2) or formula (y3), more preferably a halide ion and an anion represented by formula (y2).

於式(Ab1)中之A為芳香族烴基時，化合物(Ab1)可列舉例如下述式的化合物。於下述式中之J係與上述相同意義。 When A in the formula (Ab1) is an aromatic hydrocarbon group, the compound (Ab1) may, for example, be a compound of the following formula. J in the following formula has the same meaning as above.

化合物(Ab1)較佳為式(Ab2)所示之化合物(以下，有時稱為「化合物(Ab2)」。)。式(Ab2)所示之化合物 中，亦包含其互變異構物。 The compound (Ab1) is preferably a compound represented by the formula (Ab2) (hereinafter, sometimes referred to as "compound (Ab2)."). Compound represented by formula (Ab2) It also includes its tautomers.

式(Ab2)中，m表示任意的自然數。 In formula (Ab2), m represents an arbitrary natural number.

X表示氧原子、-NR⁵⁶-或硫原子。 X represents an oxygen atom, -NR ⁵⁶ -or a sulfur atom.

[Y]^m-表示m價陰離子。 [Y] ^m- represents an m-valent anion.

R⁵⁶表示氫原子或碳數1至10的烷基。 R ⁵⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R⁴¹至R⁴⁶係分別獨立地表示可被胺基或鹵原子取代之碳數1至20的烷基(於構成該烷基的碳原子之間可***氧原子)、可被取代之芳烷基、可被取代之芳基、或氫原子，較佳為可被胺基或鹵原子取代之碳數1至20的烷基(於構成該烷基的碳原子之間可***氧原子)、可被取代之芳基、或氫原子。R⁴¹與R⁴²係鍵結而可與該等所鍵結的氮原子一同形成環，R⁴³與R⁴⁴係鍵結而可與該等所鍵結的氮原子一同形成環，R⁴⁵與R⁴⁶係鍵結而可與該等所鍵結的氮原子一同形成環。 R ⁴¹ to R ⁴⁶ independently represent a C 1-20 alkyl group which may be substituted by an amine group or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group), and an aralkyl group which may be substituted Group, an aryl group which may be substituted, or a hydrogen atom, preferably an alkyl group having 1 to 20 carbon atoms which may be substituted by an amine group or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group), An aryl group which may be substituted, or a hydrogen atom. R ⁴¹ and R ⁴² are bonded to form a ring with these bonded nitrogen atoms, R ⁴³ and R ⁴⁴ are bonded to form a ring with these bonded nitrogen atoms, R ⁴⁵ and R ⁴⁶ is bonded and can form a ring together with these bonded nitrogen atoms.

R⁴⁷至R⁵⁴係份別獨立地表示氫原子、鹵原子、硝基、羥基、碳數1至8的烷基(於構成該烷基的碳原子之間可***氧原子)。R⁴⁸與R⁵²可彼此鍵結而形成-NH-、-S-或-SO₂-。 The R ⁴⁷ to R ⁵⁴ series independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms (an oxygen atom may be inserted between carbon atoms constituting the alkyl group). R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO ₂ -.

R⁵⁵表示氫原子、碳數1至20的烷基、或可被取代之芳基。 R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

此外，於1分子中含有複數個

時，該等可為相同結構或相異結構。 In addition, it contains a plurality of in one molecule

At the time, these may be the same structure or different structures.

R⁴¹至R⁴⁶係分別獨立，較佳為可被取代之苯甲基、碳數1至20的烷基或可被取代之芳基、或是與上述的氮原子一同形成之環，更佳為碳數1至20的烷基或可被取代之芳基，或是與上述的氮原子一同形成之環。 R ⁴¹ to R ⁴⁶ are independently, preferably benzyl which may be substituted, alkyl having 1 to 20 carbons or aryl which may be substituted, or a ring formed with the above nitrogen atom, more preferably It is an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted, or a ring formed with the above-mentioned nitrogen atom.

於R^41A至R^46A中，碳數1至20的烷基，較佳為甲基、乙基、丙基、丁基等碳數1至4的烷基。 In R ^41A to R ^46A , the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl.

於R^41A至R^46A中，芳基較佳為苯基、甲苯甲醯基等碳數6至10的芳基。 In R ^41A to R ^46A , the aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group and a tolyl group.

於R^41A至R^46A中，可被取代之苯甲基可列舉可具有-SO₃ ^-或-SO₃J(J表示陽離子)作為取代基之苯甲基。 In R ^41A to R ^46A , the benzyl group which may be substituted includes a benzyl group which may have -SO ₃ ^- or -SO ₃ J (J represents a cation) as a substituent.

R⁴⁷至R⁵⁴係分別獨立，較佳為氫原子及碳數1至4的烷基。 R ⁴⁷ to R ⁵⁴ are each independently, preferably a hydrogen atom and a C 1-4 alkyl group.

R⁵⁵較佳為氫原子、碳數1至4的烷基、或可被取代之苯基。該苯基中之取代基可列舉鹵原子、甲基、碳數1至 4的烷基磺醯基、三氟甲基等。 R ^{55 is} preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted. Examples of the substituent in the phenyl group include a halogen atom, a methyl group, an alkylsulfonyl group having 1 to 4 carbon atoms, and trifluoromethyl group.

式(Ab2)的陽離子部分可列舉於表1所示之式(Ab2-0)所示之陽離子1至陽離子15等。表中，*表示鍵結鍵。 The cation portion of the formula (Ab2) can be exemplified by the cation 1 to the cation 15 represented by the formula (Ab2-0) shown in Table 1. In the table, * indicates a bond key.

其中，式(Ab2)的陽離子部分，較佳為陽離子1至陽離子6、陽離子8、陽離子11、或陽離子12，特佳為陽離子1、陽離子2、陽離子8或陽離子12。 Among them, the cation portion of the formula (Ab2) is preferably cation 1 to cation 6, cation 8, cation 11, or cation 12, and particularly preferably cation 1, cation 2, cation 8, or cation 12.

[Y]^m-可列舉習知的陰離子。以耐熱性的觀點來看，較佳的[Y]^m-為含硼之陰離子、含鋁之陰離子、含氟之陰離子、以及含有選自由鎢、鉬、矽及磷所組成群組之至少1種元 素與氧作為必要元素之陰離子。 [Y] ^{m- can} include conventional anions. From the viewpoint of heat resistance, the preferred [Y] ^m- is an anion containing boron, an anion containing aluminum, an anion containing fluorine, and containing at least 1 selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus Various elements and oxygen are anions of essential elements.

化合物(Ab2)可列舉例如下述式所示之化合物。 The compound (Ab2) may, for example, be a compound represented by the following formula.

化合物(Ab2)可藉由使式(B-I)所示之化合物與式(C-I)所示之化合物反應而製造。該反應可在有機溶劑的存在下進行，亦可在無溶劑下進行。 The compound (Ab2) can be produced by reacting the compound represented by the formula (B-I) with the compound represented by the formula (C-I). This reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[式(B-I)及式(C-I)中，各符號係分別表示與前述相同的意義。] [In formula (B-I) and formula (C-I), each symbol system has the same meaning as described above. ]

化合物(Ab2)亦可藉由使式(B-II)所示之化合物與式(C-II)所示之化合物及式(C-II’)所示之化合物反應而製造。該反應可在有機溶劑的存在下進行，亦可在無溶劑下進行。 Compound (Ab2) can also be produced by reacting the compound represented by formula (B-II) with the compound represented by formula (C-II) and the compound represented by formula (C-II'). This reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[式(B-II)、式(C-II)及式(C-II’)中，各符號係分別表示與上述相同的意義。] [In formula (B-II), formula (C-II) and formula (C-II'), each symbol system has the same meaning as described above. ]

就化合物(B-I)及化合物(B-II)的製造方法而言，可列舉習知的各種方法，例如西德專利申請P3928243.0號所記載之方法。 The methods for producing compound (B-I) and compound (B-II) include various conventional methods, for example, the method described in West German Patent Application No. P3928243.0.

化合物(C-I)及化合物(C-II)可用習知的各種方法來製造，亦可為從市售品取得的化合物。 The compound (C-I) and the compound (C-II) can be produced by various conventional methods, and may be a compound obtained from a commercially available product.

將任意的化合物(Ab2)藉由進一步進行陰離子交換，可製造所欲之化合物(Ab2)。陰離子交換係例如藉由將於上述的方法中所製造之化合物(Ab2)與所欲之[Y]^m-的鹼金屬鹽在溶劑中混合而製造。 By further subjecting any compound (Ab2) to anion exchange, the desired compound (Ab2) can be produced. The anion exchange is produced, for example, by mixing the compound (Ab2) produced in the above method and the desired [Y] ^m- alkali metal salt in a solvent.

鹼金屬可列舉鋰、鈉及鉀。 Examples of alkali metals include lithium, sodium, and potassium.

就[Y]^m-的鹼金屬鹽而言，可列舉日本專利第4097704號或日本專利第4341251號及Journal of The Electrochemical Society，第148卷第1期、2001年、國際公開2008/075672號或日本特開2010-280586號公報所記載之鹼金屬鹽。 As for the alkali metal salt of [Y] ^m- , Japanese Patent No. 4097704 or Japanese Patent No. 4341251 and Journal of The Electrochemical Society, Volume 148, No. 1, 2001, International Publication No. 2008/075672 or The alkali metal salt described in Japanese Patent Laid-Open No. 2010-280586.

次甲基染料係含有具有二個基以奇數個次甲基鏈來連接的結構之化合物之染料，該二個基之至少一個為雜環或芳香環(該次甲基染料亦稱為「聚次甲基染料」)。 A methine dye is a dye containing a compound having a structure in which two groups are connected by an odd number of methine chains. At least one of the two groups is a heterocyclic ring or an aromatic ring (the methine dye is also called "poly Methylene dye").

上述化合物，具體而言，可列舉具有Xa-CH(=CH-CH)_x=Xb所示之結構之化合物(Xa及Xb係分別表示任意的基。x為0以上的整數)。 The above-mentioned compounds specifically include compounds having a structure represented by Xa-CH (=CH-CH) _x = Xb (Xa and Xb each represent an arbitrary group. x is an integer of 0 or more).

次甲基偶氮染料係指前述次甲基鏈中之1個或2個以上的次甲基被氮原子取代者。 The methine azo dyes refer to those in which one or more methine groups in the methine chain are replaced by nitrogen atoms.

次甲基染料及次甲基偶氮染料(以下，有時統稱為「次甲基染料(Ac)」)，較佳為具有上述二個基以1個次甲基或1個亞胺基來連接之結構之化合物，更佳為式(Ac1)所示之化合物。 Methylene dyes and methine azo dyes (hereinafter, sometimes collectively referred to as "methine dyes (Ac)"), preferably having the above-mentioned two groups with one methine group or one imine group The compound of the connected structure is more preferably a compound represented by formula (Ac1).

[式(Ac1)中、X⁶¹表示氮原子或CH。 [In formula (Ac1), X ⁶¹ represents a nitrogen atom or CH.

R⁶¹表示氫原子或碳數1至4的烷基。 R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R⁶²表示氫原子、氰基、胺甲醯基、羧基或碳數1至4的烷氧基羰基。 R ⁶² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group, or an alkoxycarbonyl group having 1 to 4 carbon atoms.

R⁶³表示氧原子、C(CN)₂、C(CN)CO₂L¹或C(CO₂L¹)₂。L1表示碳數1至8的烷基，構成該烷基的亞甲基單元之1個或2個可被氧原子取代。 R ⁶³ represents an oxygen atom, C(CN) ₂ , C(CN)CO ₂ L ¹ or C(CO ₂ L ¹ ) ₂ . L1 represents an alkyl group having 1 to 8 carbon atoms, and one or two methylene units constituting the alkyl group may be substituted with an oxygen atom.

R⁶⁴至R⁶⁶係分別獨立地表示可被胺基或鹵原子取代之碳數1至20的烷基、可被取代之胺基、可被取代之芳基、氫原子、或羥基，於構成該烷基的碳原子之間可***氧原子。] R ⁶⁴ to R ⁶⁶ independently represent a C 1-20 alkyl group which may be substituted by an amine group or a halogen atom, an amine group which may be substituted, an aryl group which may be substituted, a hydrogen atom, or a hydroxyl group, in An oxygen atom may be inserted between the carbon atoms of the alkyl group. ]

X⁶¹較佳為氮原子。 X ^{61 is} preferably a nitrogen atom.

R⁶¹較佳為碳數1至3的烷基，更佳為甲基。 R ^{61 is} preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

R⁶²較佳為氰基。 R ^{62 is} preferably a cyano group.

R⁶³較佳為氧原子。 R ^{63 is} preferably an oxygen atom.

R⁶⁴較佳為甲基、乙基或-CH(L²)(L³)。於-CH(L²)(L³)中，L²及L³係分別獨立地表示烷基，L²及L³的合計碳數為2至19，更佳為2至9。又，L²及L³較佳為直鏈狀烷基。 R ^{64 is} preferably methyl, ethyl or -CH(L ² )(L ³ ). In -CH(L ² )(L ³ ), L ² and L ³ each independently represent an alkyl group, and the total carbon number of L ² and L ³ is 2 to 19, more preferably 2 to 9. In addition, L ² and L ^{3 are} preferably linear alkyl groups.

R⁶⁵較佳為被2個碳數1至10的烷基(更佳為碳數3至6的烷基)取代之胺基，更佳為N,N-二異丙基胺基、N,N-二正丁基胺基、N,N-二正戊基胺基、N,N-二正己基胺基。 R ^{65 is} preferably an amine group substituted with 2 alkyl groups having 1 to 10 carbon atoms (more preferably, alkyl groups having 3 to 6 carbon atoms), more preferably N,N-diisopropylamino group, N, N-di-n-butylamino, N,N-di-n-pentylamino, N,N-di-n-hexylamino.

R⁶⁶較佳為氫原子、直鏈狀或分枝鏈狀之碳數1至8的烷基、萘基、苯基或具有1個以上的鹵原子(較佳為氟原子、氯原子)之苯基，更佳為氫原子、碳數3至5之分枝鏈狀烷基(較佳為異丙基、異戊基、第三丁基)、苯基或氯苯基。 R ^{66 is} preferably a hydrogen atom, a linear or branched chain alkyl group having 1 to 8 carbon atoms, a naphthyl group, a phenyl group, or one having at least one halogen atom (preferably a fluorine atom or a chlorine atom) The phenyl group is more preferably a hydrogen atom, a branched chain alkyl group having 3 to 5 carbon atoms (preferably isopropyl group, isopentyl group, and third butyl group), phenyl group, or chlorophenyl group.

就式(Ac1)所示之化合物而言，可列舉例如以下的化合物。式(Ac1)所示之化合物可藉由例如日本特開平3-166268號公報所記載之方法來製造。 Examples of the compound represented by formula (Ac1) include the following compounds. The compound represented by formula (Ac1) can be produced by, for example, the method described in Japanese Patent Laid-Open No. 3-166268.

於本發明中，綠色顏料(A2)意指於650nm以上、700nm以下的範圍具有極大吸收波長，並不溶或難溶於水或有機溶劑等溶劑之色素。可列舉例如於色料索引 (The Society of Dyers and Colourists出版)分類為顏料(pigment)之顏料。 In the present invention, the green pigment (A2) means a pigment that has a maximum absorption wavelength in the range of 650 nm or more and 700 nm or less, and is insoluble or hardly soluble in solvents such as water or organic solvents. For example, in the color index (Published by The Society of Dyers and Colourists) Pigments classified as pigments.

綠色顏料可列舉：C.I.顏料綠7、36、58、59，日本特開2004-70342號公報、日本特開2008-19383號公報、日本特開2007-320986號公報所記載之綠色顏料等鹵化酞菁顏料。較佳為C.I.顏料綠7、36、58、59。 Examples of green pigments include CI pigment green 7, 36, 58, 59, halogenated phthalides such as the green pigments described in JP 2004-70342, JP 2008-19383, and JP 2007-320986. Cyanine pigment. It is preferably C.I. Pigment Green 7, 36, 58, 59.

黃色著色劑(A3)為選自由黃色染料及黃色顏料所組成群組之至少一種。於本發明中，黃色著色劑(A3)意指於400nm以上、470nm以下的範圍具有極大吸收波長，較佳為於430nm以上、470nm以下的範圍具有極大吸收波長之色素。 The yellow colorant (A3) is at least one selected from the group consisting of yellow dyes and yellow pigments. In the present invention, the yellow colorant (A3) means a dye having a maximum absorption wavelength in the range of 400 nm or more and 470 nm or less, preferably a dye having a maximum absorption wavelength in the range of 430 nm or more and 470 nm or less.

黃色染料可列舉偶氮染料、金屬錯鹽染料、次甲基染料、香豆素染料、苯乙烯染料。其中，較佳為香豆素染料。 Examples of yellow dyes include azo dyes, metal salt dyes, methine dyes, coumarin dyes, and styrene dyes. Among them, coumarin dye is preferred.

香豆素染料為含有於分子內具有香豆素骨架的化合物之染料。香豆素染料可列舉色料索引(The Society of Dyers and Colourists出版)所記載之C.I.Acid酸性黃227、250，C.I.分散黃82、184，C.I.溶劑橘112，C.I.溶劑黃160、172，日本專利第1299948號公報所記載之香豆素染料等。該香豆素染料係以溶解於有機溶劑為較佳。 Coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. Examples of coumarin dyes include CIAcid Acid Yellow 227, 250, CI Disperse Yellow 82, 184, CI Solvent Orange 112, CI Solvent Yellow 160, 172 described in the Color Index (published by The Society of Dyers and Colourists), Japanese Patent Coumarin dyes and the like described in Gazette No. 1299948. The coumarin dye is preferably dissolved in an organic solvent.

此等之中，香豆素染料較佳為式(Ad1)或式(Ad2)所示之化合物(以下有時分別稱為「化合物(Ad1)」、「化合物(Ad2)」)。 Among these, the coumarin dye is preferably a compound represented by formula (Ad1) or formula (Ad2) (hereinafter sometimes referred to as "compound (Ad1)" and "compound (Ad2)", respectively).

[式(Ad1)中，Q^1B及Q^2B係分別獨立地表示氫原子或-CO₂M^1B，惟，Q^1B及Q^2B中任一者係表示-CO₂M^1B。 [In formula (Ad1), Q ^1B and Q ^2B independently represent a hydrogen atom or -CO ₂ M ^1B , however, either Q ^1B and Q ^2B represent -CO ₂ M ^1B .

R^1B至R^4B係分別獨立地表示氫原子或碳數1至20的1價烴基、或R^1B及R^3B一同與相隣的苯環上之碳原子及相隣的氮原子一同形成環、R^2B及R^4B一同與相隣的苯環上之碳原子及相隣的氮原子一同形成環、或是R^1B及R^2B鍵結而與相隣的氮原子一同形成環。構成該1價烴基的亞甲基可被氧原子、硫原子、-N(R^5B)-、磺醯基或羰基取代，該1價烴基所含有之氫原子亦可被鹵原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO₃M^1B、-CO₂M^1B、羥基或胺基取代。 R ^1B to R ^4B independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ^1B and R ^3B together form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, R ^2B and R ^4B together form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, or R ^1B and R ^2B bond to form a ring with an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be substituted by an oxygen atom, a sulfur atom, -N(R ^5B )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent hydrocarbon group may also be replaced by a halogen atom, a cyano group, Nitro, carbamoyl, sulfamoyl, -SO ₃ M ^1B , -CO ₂ M ^1B , hydroxyl or amine substitution.

R^5B表示氫原子或碳數1至20的1價烴基。R^5B存在複數個時，該等為相同或相異。 R ^5B represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When there are multiple R ^5Bs , these are the same or different.

M^1B表示氫原子或鹼金屬原子。] M ^1B represents a hydrogen atom or an alkali metal atom. ]

R^1B及R^2B係分別獨立，較佳為碳數1至10的1價脂肪族烴基，更佳為乙基、丁基、己基、2-乙基己基或辛基，再更佳為乙基、丁基、己基及2-乙基己基。 R ^1B and R ^2B are each independently, preferably a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably ethyl, butyl, hexyl, 2-ethylhexyl or octyl, and still more preferably ethyl , Butyl, hexyl and 2-ethylhexyl.

R^3B及R^4B較佳為氫原子。 R ^3B and R ^{4B are} preferably hydrogen atoms.

R^1B及R^3B一同而形成含有該等所鍵結的氮原子及碳原子之環時，或R^2B及R^4B一同而形成含有該等所鍵結的氮原 子及碳原子之環時，-R^1B-R^3B-及-R^2B-R^4B-可列舉-CH₂-CH₂-、-CF₂-CF₂-或-CH₂-C(CH₃)₂-等，較佳為-CH₂-CH₂-或-CH₂-C(CH₃)₂-，更佳為-CH₂-C(CH₃)₂-。 When R ^1B and R ^3B together form a ring containing these bonded nitrogen and carbon atoms, or R ^2B and R ^4B together form a ring containing these bonded nitrogen and carbon atoms,- R ^1B -R ^3B - and -R ^2B -R ^4B - include _{-CH 2 -CH 2 -, - CF} 2 -CF 2 - or _{-CH 2 -C (CH 3) 2} - and the like, preferably -CH ₂ -CH ₂ -or -CH ₂ -C(CH ₃ ) ₂ -, more preferably -CH ₂ -C(CH ₃ ) ₂ -.

就R^1B及R^2B鍵結而與相隣的氮原子一同形成環時的-R^1B-R^2B-而言，可列舉-(CH₂)₂-、-(CH₂)₃-、-(CH₂)₄-、-(CH₂)₅-、-(CH₂)₆-、-(CH₂)₇-、-(CF₂)₂-、-(CF₂)₃-、-(CF₂)₄-、-(CF₂)₅-、-(CF₂)₆-、-(CF₂)₇-等，較佳為-(CH₂)₄-、-(CH₂)₅-、-(CH₂)₆-、-(CF₂)₄-、-(CF₂)₅-或-(CF₂)₆-，更佳為-(CH₂)₄-、-(CH₂)₅-或-(CH₂)₆-，再更佳為-(CH₂)₄-或-(CH₂)₅-。 Examples of -R ^1B -R ^2B -when R ^1B and R ^{2B are} bonded to form a ring with an adjacent nitrogen atom include -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, and -( CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CF ₂ ) ₂ -, -(CF ₂ ) ₃ -, -(CF ₂ ) ₄ -, -(CF ₂ ) ₅ -, -(CF ₂ ) ₆ -, -(CF ₂ ) ₇ -etc., preferably -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -( CH ₂ ) ₆ -, -(CF ₂ ) ₄ -, -(CF ₂ ) ₅ -or -(CF ₂ ) ₆ -, more preferably -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -or- (CH ₂ ) ₆ -, even more preferably-(CH ₂ ) ₄ -or-(CH ₂ ) ₅ -.

M^1B較佳為水素原子、鈉原子或鉀原子，更佳為氫原子。 M ^{1B is} preferably a hydrogen atom, a sodium atom or a potassium atom, more preferably a hydrogen atom.

化合物(Ad1)可列舉例如下述式的化合物及日本特開2013-231165號公報所記載之化合物。 Examples of the compound (Ad1) include compounds of the following formula and compounds described in Japanese Patent Laid-Open No. 2013-231165.

式(Ad2)中，L^c表示碳數1至20的2價烴基或磺醯基，該烴基所含有之氫原子可被氟原子取代。 In formula (Ad2), L ^c represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and the hydrogen atom contained in the hydrocarbon group may be replaced by a fluorine atom.

X^C表示氧原子或硫原子。 X ^C represents an oxygen atom or a sulfur atom.

R^1C及R^2C係分別獨立地表示可具有取代基之苯基或碳數1至20的烷基，於構成該烷基的碳原子之間可***氧原子。 R ^1C and R ^2C independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom may be inserted between carbon atoms constituting the alkyl group.

R^7C至R^13C係分別獨立地表示氫原子、鹵原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO₃M^C、-CO₂M^C、羥基、甲醯基、胺基、碳數1至20的1價烴基，於構成該烴基的碳原子之間可***氧原子、硫原子、-N(R^14C)-、磺醯基或羰基，該烴基所含有之氫原子可被鹵原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO₃M^C、-CO₂M^C、羥基、甲醯基或胺基取代。 The R ^7C to R ^13C systems independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aminomethyl group, a sulfamoyl group, -SO ₃ M ^C , -CO ₂ M ^C , a hydroxyl group, a methyl group, An amine group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, -N(R ^14C )-, a sulfonyl group or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group, and the hydrogen contained in the hydrocarbon group The atom may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M ^C , -CO ₂ M ^C , a hydroxy group, a amide group, or an amine group.

R^14C表示氫原子或碳數1至20的1價烴基，R^14C存在複數個時，該等可為相同或相異。 R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of R ^14C , these may be the same or different.

M_C表示氫原子或鹼金屬原子。 M _C represents a hydrogen atom or an alkali metal atom.

就R^1C及R^2C的苯基可具有之取代基而言，可列舉鹵原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO₃M^C、-CO₂M^C、羥基、甲醯基、胺基、碳數1至20的1價烴基等。 Examples of the substituents that the phenyl group of R ^1C and R ^2C may have include halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, -SO ₃ M ^C , -CO ₂ M ^C , Hydroxyl group, formyl group, amine group, monovalent hydrocarbon group having 1 to 20 carbon atoms, etc.

L^C較佳為可被氟原子取代之碳數1至5的2價烴基或磺醯基，更佳為丙烷-2,2-二基、六氟丙烷-2,2-二基或磺醯 基。 L ^{C is} preferably a ^C 1 to 5 divalent hydrocarbon group or sulfonyl group which may be substituted with a fluorine atom, more preferably propane-2,2-diyl, hexafluoropropane-2,2-diyl or sulfonyl base.

X^C較佳為氧原子。 X ^{C is} preferably an oxygen atom.

化合物(Ad2)可列舉例如下式所示之化合物。 Examples of the compound (Ad2) include compounds represented by the following formula.

黃色顏料可列舉色料索引(The Society of Dyers and Colourists出版)所記載之C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、129、137、138、139、147、148、150、153、154、166、173、180、185、194、214等。其中，較佳為C.I.顏料黃129、138、139、150。 Examples of yellow pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86 described in the Color Index (published by The Society of Dyers and Colourists). 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, etc. Among them, C.I. Pigment Yellow 129, 138, 139, and 150 are preferred.

黃色著色劑(A3)較佳為黃色染料。當黃色著色劑(A3)為黃色染料時，會有可減少黃色著色劑(A3)的含量之傾向，故可增加著色硬化性樹脂組成物中之樹脂(B)或聚合性化合物(C)的含量，並可提升所得之濾色器的耐熱性、耐藥品性等耐久性。 The yellow colorant (A3) is preferably a yellow dye. When the yellow colorant (A3) is a yellow dye, there is a tendency to reduce the content of the yellow colorant (A3), so that the resin (B) or the polymerizable compound (C) in the colored curable resin composition can be increased Content, and can improve the durability of the resulting color filter such as heat resistance and chemical resistance.

著色劑(A)係在不損及本案著色硬化性樹脂組成物的性能之程度下，可更含有其他的染料及/或顏料。其他的染料可列舉於色料索引(The Society of Dyers and Colourists出版)中分類為顏料以外的具有色相之染料之化合物、或染色筆記(色染社)所記載之習知的染料中之藍色染料(A1)及黃色著色劑(A3)以外的染料。若依據化學結構，則可列舉：偶氮染料、酞菁染料、蒽醌染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、方酸菁染料、吖啶染料、苯乙烯基染料、喹啉染料及硝基染料等。 The colorant (A) may contain other dyes and/or pigments to the extent that the performance of the coloring hardenable resin composition in this case is not impaired. Other dyes can be listed in the Color Index (The Society of Dyers and Colourists Publishing) is classified as a compound of a dye having a hue other than a pigment, or a dye other than a blue dye (A1) and a yellow colorant (A3) among the conventional dyes described in Dyeing Notes (Dyeing Corporation). According to the chemical structure, it may include: azo dye, phthalocyanine dye, anthraquinone dye, cyanine dye, naphthoquinone dye, quinone imine dye, methine dye, squarylium dye, acridine dye, styrene Basic dyes, quinoline dyes and nitro dyes.

其他的顏料只要是除了綠色顏料(A2)、黃色著色劑(A3)的黃色顏料以外之顏料，就無特別限制，可使用習知的顏料，例如色料索引(The Society of Dyers and Colourists出版)中分類為顏料(pigment)之顏料。 Other pigments are not particularly limited as long as they are other than the green pigment (A2) and the yellow pigment (A3) yellow pigments, and conventional pigments can be used, such as the pigment index (published by The Society of Dyers and Colourists) Pigments classified as pigments.

顏料可列舉C.I.顏料橘13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橘色顏料；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等紅色顏料；C.I.顏料藍15、15：3、15：4、15：6、60等藍色顏料；C.I.顏料紫1、19、23、29、32、36、38等紫色顏料等。 Pigments include CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122 , 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15 : 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments.

著色劑(A)中，藍色染料(A1)、綠色顏料(A2)及黃色著色劑(A3)的含有率係分別在以下的範圍內為較佳。 Among the colorants (A), the content of the blue dye (A1), the green pigment (A2), and the yellow colorant (A3) are preferably within the following ranges.

藍色染料(A1)；0.1質量%以上、20質量%以下(更佳為0.5質量%以上15質量%以下，再更佳為1質量%以上、10質量%以下) Blue dye (A1); 0.1% by mass or more and 20% by mass or less (more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less)

綠色顏料(A2)；30質量%以上、85質量%以下(更佳為45質量%以上、75質量%以下，再更佳為50質量%以上、 70質量%以下) Green pigment (A2); 30% by mass or more, 85% by mass or less (more preferably 45% by mass or more, 75% by mass or less, and even more preferably 50% by mass or more, 70% by mass or less)

黃色著色劑(A3)；5質量%以上、60質量%以下(更佳為10質量%以上、50質量%以下，再更佳為15質量%以上、45質量%以下) Yellow colorant (A3); 5 mass% or more, 60 mass% or less (more preferably 10 mass% or more, 50 mass% or less, and even more preferably 15 mass% or more, 45 mass% or less)

相對於綠色顏料(A2)的含量100質量份，藍色染料(A1)的含量較佳為0.2質量份以上、100質量份以下，更佳為0.4質量份以上、50質量份以下，再更佳為0.6質量份以上、20質量份以下。 The content of the blue dye (A1) is preferably 0.2 parts by mass or more and 100 parts by mass or less, more preferably 0.4 parts by mass or more, and 50 parts by mass or less relative to 100 parts by mass of the green pigment (A2). It is 0.6 mass parts or more and 20 mass parts or less.

相對於綠色顏料(A2)的含量100質量份，黃色著色劑(A3)的含量較佳為10質量份以上、200質量份以下，更佳為20質量份以上、150質量份以下，再更佳為30質量份以上、120質量份以下。 The content of the yellow colorant (A3) is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more, and 150 parts by mass or less relative to 100 parts by mass of the green pigment (A2). 30 parts by mass or more and 120 parts by mass or less.

藍色染料(A1)的含有率於前述的範圍內時，所得之濾色器的亮度會有進一步提高之傾向，故為較佳。 When the content of the blue dye (A1) is within the aforementioned range, the brightness of the obtained color filter tends to be further improved, which is preferable.

著色劑(A)中，藍色染料(A1)、綠色顏料(A2)及黃色著色劑(A3)的組合之較佳為酞菁染料(Aa)/C.I.顏料綠7/香豆素染料、酞菁染料(Aa)/C.I.顏料綠58/香豆素染料、酞菁染料(Aa)/C.I.顏料綠7/偶氮染料、酞菁染料(Aa)/C.I.顏料綠58/偶氮染料、式(Ab1)所示之化合物/C.I.顏料綠7/香豆素染料、式(Ab1)所示之化合物/C.I.顏料綠36/香豆素染料、式(Ab1)所示之化合物/C.I.顏料綠58/香豆素染料、式(Ab1)所示之化合物/C.I.顏料綠7/偶氮染料、式(Ab1)所示之化合物/C.I.顏料綠7/C.I.顏料黃129、式(Ab1)所示之化合物/C.I.顏料綠7/C.I.顏料黃138、式(Ab1)所示之化合物 /C.I.顏料綠58/C.I.顏料黃129、式(Ab1)所示之化合物/C.I.顏料綠58/C.I.顏料黃138、式(Ab1)所示之化合物/C.I.顏料綠58/偶氮染料、次甲基染料(Ac)/C.I.顏料綠7/香豆素染料、次甲基染料(Ac)/C.I.顏料綠36/香豆素染料、次甲基染料(Ac)/C.I.顏料綠58/香豆素染料、次甲基染料(Ac)/C.I.顏料綠7/偶氮染料、次甲基染料(Ac)/C.I.顏料綠58/偶氮染料、次甲基染料(Ac)/C.I.顏料綠7/C.I.顏料黃129、次甲基染料(Ac)/C.I.顏料綠7/C.I.顏料黃138、次甲基染料(Ac)/C.I.顏料綠58/C.I.顏料黃129、次甲基染料(Ac)/C.I.顏料綠58/C.I.顏料黃138，再更佳為式(Ab1)所示之化合物/C.I.顏料綠7/香豆素染料、式(Ab1)所示之化合物/C.I.顏料綠58/香豆素染料、次甲基染料(Ac)/C.I.顏料綠7/香豆素染料、次甲基染料(Ac)/C.I.顏料綠58/香豆素染料。 Among the colorants (A), the combination of blue dye (A1), green pigment (A2) and yellow colorant (A3) is preferably phthalocyanine dye (Aa)/CI pigment green 7/coumarin dye, phthalocyanine Cyanine dye (Aa)/CI pigment green 58/coumarin dye, phthalocyanine dye (Aa)/CI pigment green 7/azo dye, phthalocyanine dye (Aa)/CI pigment green 58/azo dye, formula ( Ab1) Compounds/CI Pigment Green 7/ Coumarin Dyes, Compounds of Formula (Ab1)/CI Pigment Green 36/ Coumarin Dyes, Compounds of Formula (Ab1)/CI Pigment Green 58/ Coumarin dye, compound represented by formula (Ab1)/CI Pigment Green 7/azo dye, compound represented by formula (Ab1)/CI Pigment Green 7/CI Pigment Yellow 129, compound represented by formula (Ab1) /CI Pigment Green 7/CI Pigment Yellow 138, compound represented by formula (Ab1) /CI Pigment Green 58/CI Pigment Yellow 129, compound represented by formula (Ab1)/CI Pigment Green 58/CI Pigment Yellow 138, compound represented by formula (Ab1)/CI Pigment Green 58/azo dye, secondary A Base dye (Ac)/CI pigment green 7/coumarin dye, methine dye (Ac)/CI pigment green 36/coumarin dye, methine dye (Ac)/CI pigment green 58/coumarin Dyes, methine dyes (Ac)/CI Pigment Green 7/azo dyes, methine dyes (Ac)/CI Pigment Green 58/azo dyes, methine dyes (Ac)/CI Pigment Green 7/CI Pigment Yellow 129, methine dye (Ac)/CI Pigment Green 7/CI Pigment Yellow 138, methine dye (Ac)/CI Pigment Green 58/CI Pigment Yellow 129, methine dye (Ac)/CI Pigment Green 58/CI Pigment Yellow 138, better still compound represented by formula (Ab1)/CI Pigment Green 7/coumarin dye, compound represented by formula (Ab1)/CI Pigment Green 58/coumarin dye, Methylene dye (Ac)/CI pigment green 7/coumarin dye, methine dye (Ac)/CI pigment green 58/coumarin dye.

綠色顏料(A2)等顏料視需要可施以：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；藉由高分子化合物等對於顏料表面之接枝處理；藉由硫酸微粒化法等之微粒化處理；或是藉由用以去除雜質之有機溶劑或水等之洗淨處理；藉由離子性雜質的離子交換法等之去除處理等。 Pigments such as green pigments (A2) may be subjected to rosin treatment as needed; surface treatment using pigment derivatives with acidic or basic groups introduced; grafting treatment of the pigment surface by polymer compounds, etc.; Particulate treatment such as sulfuric acid pulverization method; or cleaning treatment by organic solvent or water for removing impurities; removal treatment by ion exchange method for ionic impurities, etc.

顏料係粒徑均勻為較佳。藉由使含有顏料分散劑來進行分散處理，可得到顏料在溶液中呈均勻分散的狀態之顏料分散液。 It is preferable that the pigment-based particle size is uniform. By carrying out the dispersion treatment by containing the pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

前述的顏料分散劑可列舉陽離子系、陰離子系、非離子系、兩性、聚酯系、聚胺系、丙烯酸系等界面活性劑等。 該等顏料分散劑可單獨或組合2種以上使用。顏料分散劑可列舉商品名為KP(信越化學工業股份有限公司製)、Flowlen(共榮社化學股份有限公司製)、SOLSPERSE(Zeneca股份有限公司製)、EFKA(BASF公司製)、Ajispur(味之素Fine-Techno股份有限公司製)、Disperbyk(BYK公司製)等。 Examples of the aforementioned pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants can be used alone or in combination of two or more. Examples of pigment dispersants include KP (made by Shin-Etsu Chemical Co., Ltd.), Flowlen (made by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (made by Zeneca Co., Ltd.), EFKA (made by BASF), and Ajispur (flavor Zinsu Fine-Techno Co., Ltd.), Disperbyk (by BYK), etc.

使用顏料分散劑時，相對於顏料的總量而言，其使用量較佳為1質量%以上、100質量%以下，更佳為5質量%以上、50質量%以下。顏料分散劑的使用量於前述的範圍內時，則有得到均勻的分散狀態之顏料分散液之傾向。 When a pigment dispersant is used, its use amount is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less relative to the total amount of pigment. When the amount of the pigment dispersant used is within the aforementioned range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.

相對於固形成分的總量而言，著色劑(A)的含量較佳為5至65質量%，更佳為8至60質量%，再更佳為10至55質量%。著色劑(A)的含量於前述的範圍時，作為濾色器時的色濃度充分，且可使組成物中含有需要量的樹脂或聚合性化合物，故可形成機械性強度充分的圖案。 The content of the colorant (A) is preferably 5 to 65% by mass, more preferably 8 to 60% by mass, and still more preferably 10 to 55% by mass relative to the total amount of solid content. When the content of the colorant (A) is in the aforementioned range, the color density when used as a color filter is sufficient, and the required amount of resin or polymerizable compound can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed.

在此，本說明書中之「固形成分的總量」係指從著色硬化性樹脂組成物的總量減去溶劑的含量之量。固形成分的總量及相對於此之各成分的含量，可用例如液相層析法或氣相層析法等習知的分析方法來測定。 Here, the "total amount of solid content" in this specification refers to the amount minus the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by a conventional analysis method such as liquid chromatography or gas chromatography.

<樹脂(B)> <Resin (B)>

樹脂(B)較佳為鹼性可溶性樹脂。樹脂(B)可列舉以下的樹脂[K1]至[K6]等。 The resin (B) is preferably an alkaline soluble resin. The resin (B) includes the following resins [K1] to [K6] and the like.

樹脂[K1]；選自由不飽和羧酸及不飽和羧酸酐所組成群組之至少1種(a)(以下有時稱為「(a)」)與具有碳數2至 4的環狀醚結構與乙烯性不飽和鍵的單體(b)(以下有時稱為「(b)」)之共聚物；樹脂[K2]；(a)與(b)及可與(a)共聚合的單體(c)(惟，(a)及(b)為相異)(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(a)與(c)的共聚物與(b)反應之樹脂；樹脂[K5]；使(b)與(c)的共聚物與(a)反應之樹脂；樹脂[K6]；使(b)與(c)的共聚物與(a)反應，再與羧酸酐反應之樹脂。 Resin [K1]; at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)") and having a carbon number of 2 to 4 copolymer of cyclic ether structure and ethylenically unsaturated bond monomer (b) (sometimes referred to as "(b)" below); resin [K2]; (a) and (b) and ( a) Copolymerized monomer (c) (however, (a) and (b) are different) (hereinafter sometimes referred to as "(c)") copolymer; resin [K3]; (a) and ( c) copolymer; resin [K4]; resin that reacts the copolymer of (a) and (c) with (b); resin [K5]; copolymer of (b) and (c) and (a) Resin for reaction; resin [K6]; resin for reacting the copolymer of (b) and (c) with (a), and then reacting with carboxylic anhydride.

作為(a)，具體而言，可列舉丙烯酸、甲基丙烯酸、巴豆酸、鄰-、間-、對-乙烯基苯甲酸等不飽和單羧酸類；順丁烯二酸、反丁烯二酸、檸康酸(citraconic acid)、中康酸、伊康酸、3-乙烯基苯二甲酸、4-乙烯基苯二甲酸、3,4,5,6-四氫苯二甲酸、1,2,3,6-四氫苯二甲酸、二甲基四氫苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸；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-乙烯基苯二甲酸酐、4-乙烯基苯二甲酸酐、3,4,5,6-四氫苯二甲酸酐、1,2,3,6-四氫苯二甲酸酐、二甲基四氫苯二甲酸 酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等不飽和二羧酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上的多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯；如α-(羥甲基)丙烯酸之於同一分子中含有羥基及羧基之不飽和丙烯酸酯等。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid and fumaric acid , Citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2 , Unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norcamene-2,3- Dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1 ]Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy -6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4- Vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic acid Unsaturated dicarboxylic anhydrides such as anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; mono[2-(meth)acryloyloxyethyl]succinate, phthalic acid mono Unsaturated mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids such as [2-(meth)acryloyloxyethyl] esters; such as α-(hydroxymethyl)acrylic acid For unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

此等之中，從共聚合反應性的觀點或所得之樹脂對於鹼性水溶液之溶解性的觀點來看，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 viewpoint of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b)為具有碳數2至4的環狀醚結構(例如選自由氧雜環丙烷環、氧雜環丁烷環及四氫呋喃環所組成群組之至少1種)與乙烯性不飽和鍵之單體。(b)較佳為具有碳數2至4的環狀醚結構與(甲基)丙烯醯氧基之單體。 (b) is a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond monomer. (b) A monomer having a cyclic ether structure with 2 to 4 carbon atoms and (meth)acryloyloxy group is preferred.

此外，於本說明書中，「(甲基)丙烯酸」表示選自由丙烯酸及甲基丙烯酸所組成群組之至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等標記亦具有相同的意義。 In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Symbols such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

(b)可列舉：具有氧雜環丙烷基與乙烯性不飽和鍵之單體(b1)(以下有時稱為「(b1)」)；具有氧雜環丁烷基與乙烯性不飽和鍵之單體(b2)(以下有時稱為「(b2)」)；具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)(以下有時稱為「(b3)」)等。 (b) Examples include monomers (b1) having an oxepanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"); having an oxetanyl group and an ethylenically unsaturated bond Monomer (b2) (hereinafter sometimes referred to as "(b2)"); monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

(b1)可列舉：具有直鏈狀或分枝鏈狀的脂肪族不飽和烴經環氧化的結構之單體(b1-1)(以下有時稱為 「(b1-1)」)；具有脂環式不飽和烴經環氧化的結構之單體(b1-2)(以下有時稱為「(b1-2)」)。 (b1) A monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (b1-1) (hereinafter sometimes referred to as "(B1-1)"); a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b1-2)").

(b1-1)可列舉(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸-β-甲基縮水甘油酯、(甲基)丙烯酸-β-乙基縮水甘油酯、乙烯基縮水甘油醚、鄰乙烯基苯甲基縮水甘油醚、間乙烯基苯甲基縮水甘油醚、對乙烯基苯甲基縮水甘油醚、α-甲基-鄰乙烯基苯甲基縮水甘油醚、α-甲基-間乙烯基苯甲基縮水甘油醚、α-甲基-對乙烯基苯甲基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-參(縮水甘油氧基甲基)苯乙烯、2,3,5-參(縮水甘油氧基甲基)苯乙烯、2,3,6-參(縮水甘油氧基甲基)苯乙烯、3,4,5-參(縮水甘油氧基甲基)苯乙烯、2,4,6-參(縮水甘油氧基甲基)苯乙烯等。 (b1-1) include (meth)acrylic acid glycidyl ester, (meth)acrylic acid-β-methyl glycidyl ester, (meth)acrylic acid-β-ethyl glycidyl ester, vinyl glycidyl ether, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-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 (glycidyloxy) Ylmethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-ginseng (glycidyloxy) Methyl) styrene, 2,3,5-ginseng (glycidoxymethyl) styrene, 2,3,6-ginseng (glycidoxymethyl) styrene, 3,4,5-ginseng (Glycidoxymethyl) styrene, 2,4,6-ginseng (glycidoxymethyl) styrene, etc.

(b1-2)可列舉：一氧化乙烯基環己烯、1,2-環氧基-4-乙烯基環己烷(例如Celloxide(註冊商標)2000；股份有限公司Daicel製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如Cyclomer(註冊商標)A400；股份有限公司Daicel製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如Cyclomer(註冊商標)M100；股份有限公司Daicel製)、式(I)所示之化合物及式(II)所示之化合物等。 (b1-2) Examples include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), (methyl ) 3,4-epoxycyclohexyl methyl acrylate (eg Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (eg Cyclomer (registered Trademark) M100; Daicel Co., Ltd.), the compound represented by formula (I), the compound represented by formula (II), etc.

[式(I)及式(II)中，R^a及R^b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被羥基取代。

[In Formula (I) and Formula (II), 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 with a hydroxyl group.

X^a及X^b表示單鍵、-R^c-、*-R^c-O-、*-R^c-S-或*-R^c-NH-。 X ^a and X ^b represents a single ^{bond, -R c -, * - R} c -O -, * - R c -S- or * -R ^c -NH-.

R^c表示碳數1至6的烷二基。 R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

*表示與O的鍵結鍵。] * Indicates a bond with O. ]

碳數1至4的烷基可列舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl groups.

就氫原子被羥基取代之烷基而言，可列舉羥甲基、1-羥乙基、2-羥乙基、1-羥丙基、2-羥丙基、3-羥丙基、1-羥基-1甲基乙基、2-羥基-1-甲基乙基、1-羥丁基、2-羥丁基、3-羥丁基、4-羥丁基等。 Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- Hydroxy-1methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R^a及R^b可列舉較佳為氫原子、甲基、羥甲基、1-羥乙基、2-羥乙基，更佳為氫原子、甲基。 R ^a and R ^b may preferably be a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

烷二基可列舉亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、庚烷-1,5-二基、己烷-1,6-二基等。 Examples of alkanediyl include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, heptane-1,5-diyl , Hexane-1,6-diyl and so on.

X^a及X^b可列舉較佳為單鍵、亞甲基、伸乙基、*-CH₂-O-及*-CH₂CH₂-O-，更佳為單鍵、*-CH₂CH₂-O-(*表示與O的鍵結鍵)。 X ^a and X ^{b are} preferably single bonds, methylene, ethylidene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably single bonds, *-CH ₂ CH ₂ -O-(* indicates a bonding bond with O).

式(I)所示之化合物可列舉式(I-1)至式(I-15)中任一者所示之化合物等。其中，較佳為式(I-1)、式(I-3)、 式(I-5)、式(I-7)、式(I-9)或式(I-11)至式(I-15)所示之化合物，更佳為式(I-1)、式(I-7)、式(I-9)或式(I-15)所示之化合物。 Examples of the compound represented by formula (I) include compounds represented by any one of formula (I-1) to formula (I-15). Among them, formula (I-1), formula (I-3), The compound represented by formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) is more preferably formula (I-1), formula The compound represented by (I-7), formula (I-9) or formula (I-15).

式(II)所示之化合物可列舉式(II-1)至式(II-15)中任一者所示之化合物等。其中，較佳為式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)至式(II-15)所示之化合物，更佳為式(II-1)、式(II-7)、式(II-9)或式(II-15)所示之化合物。 Examples of the compound represented by formula (II) include compounds represented by any one of formula (II-1) to formula (II-15). 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 more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

式(I)所示之化合物及式(II)所示之化合物可分別單獨使用亦可併用2種以上。將式(I)所示之化合物及式(II)所示之化合物併用時，此等的含有比例[式(I)所示之化合物：式(II)所示之化合物]以莫耳基準，較佳為5：95至95：5，更佳為20：80至80：20。 The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is on a molar basis, It is preferably 5:95 to 95:5, and more preferably 20:80 to 80:20.

(b2)係更佳為具有氧雜環丁烷基與(甲基)丙烯醯氧基之單體。(b2)可列舉3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、 3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。 (b2) is more preferably a monomer having an oxetanyl group and (meth)acryloyloxy group. (b2) 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl- 3-methacryloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methacryloxyethyl Oxetane, 3-methyl-3-propenyl oxyethyl oxetane, 3-ethyl-3-methyl propenyl oxyethyl oxetane, 3-ethyl-3-propene acetyl oxetane Ethyl ethyl oxetane and so on.

(b3)係更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。(b3)具體而言，可列舉丙烯酸四氫呋喃甲酯(例如Viscoat V#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) is more preferably a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group. (b3) Specifically, tetrahydrofuran methyl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, and the like can be mentioned.

就(b)而言，從可更提高所得之濾色器的耐熱性、耐藥品性等可靠性之觀點來看，較佳為(b1)。再者，從著色硬化性樹脂組成物的保存安定性優異之觀點來看，更佳為(b1-2)。 From the viewpoint of (b), from the viewpoint of further improving the reliability of the obtained color filter such as heat resistance and chemical resistance, (b1) is preferable. In addition, from the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

(c)可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十二酯、(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[5.2.1.0^2,6]癸烷-8-酯(在該技術領域中，以慣用名稱「二環戊基(甲基)丙烯酸酯」稱之。又，有時稱為「(甲基)丙烯酸三環癸酯」)、(甲基)丙烯酸三環[5.2.1.0^2,6]癸烯-8-酯(在該技術領域中，以慣用名稱「(甲基)丙烯酸二環戊烯酯」稱之)、(甲基)丙烯酸二環戊基氧乙酯、(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(甲 基)丙烯酸酯；(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯等含有羥基之(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-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己基氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己基氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物；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、氯化亞乙烯、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) Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (Meth)acrylic acid-2-ethylhexyl, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth) Group) cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-ester (meth)acrylate (in this technical field, It is commonly known as the "dicyclopentyl (meth)acrylate". It is sometimes called "tricyclodecyl (meth)acrylate"), tricyclo (meth)acrylate [5.2.1.0 ^2,6 ]Decene-8-ester (in this technical field, it is commonly known as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, (methyl) Isocamphor acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) (Meth)acrylates such as benzyl acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and the like (meth)acrylates containing hydroxyl groups; cis Dicarboxylic acid diesters such as diethyl oxalate, diethyl fumarate, and diethyl iconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1 ]Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept -2-ene, 5-(2'-hydroxyethyl) bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo [2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene , 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6- Diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-third butoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5- Cyclohexyloxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(third butoxycarbonyl)bicyclo[ 2.2.1] Bicyclic unsaturated compounds such as hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl) bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide , N-cyclohexyl maleimide diimide, N-benzyl maleimide diimide, N-succinimide-3-cis Butene diimide benzoate, N-succinimide-4-maleimide diimide butyrate, N-succinimide-6-maleimide diimide Dicarbonyl amide imine derivatives such as acid ester, N-succinimide-3-maleimide propionate, N-(9-acridinyl) maleimide diimide; benzene Ethylene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic Amine, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

此等之中，從共聚合反應性及耐熱性的觀點來看，較佳為苯乙烯、乙烯基甲苯、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-烯等。 Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenyl maleimide diimide, N-cyclohexyl maleimide diimide are preferred Amine, N-benzyl maleic diimide, bicyclo[2.2.1]hept-2-ene, etc.

於樹脂[K1]中，來自各個結構單元之比率，在構成樹脂[K1]的總結構單元中，較佳為來自(a)的結構單元：2至60莫耳%來自(b)的結構單元：40至98莫耳%；更佳為來自(a)的結構單元：10至50莫耳%來自(b)的結構單元：50至90莫耳%。 In the resin [K1], the ratio derived from each structural unit, among the total structural units constituting the resin [K1], is preferably the structural unit from (a): 2 to 60 mol% from the structural unit from (b) : 40 to 98 mol %; more preferably the structural unit from (a): 10 to 50 mol% structural unit from (b): 50 to 90 mol %.

樹脂[K1]的結構單元之比率於上述的範圍時，係有著色硬化性樹脂組成物的保存安定性、形成著色圖案時的顯影性、以及所得之濾色器的耐溶劑性優異之傾向。 When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent.

樹脂[K1]可參考例如文獻「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)所記載之方法及參照該文獻所記載之引用文獻而製造。 The resin [K1] can refer to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing House Chemical Dojin Co., Ltd., 1st edition, 1st brush, issued on March 1, 1972) and reference to this document. Manufactured from the cited documents.

具體而言，可列舉將預定量的(a)及(b)、聚合起始劑及溶劑等加入反應容器中，而例如藉由以氮來取代氧而形成脫氧環境，一邊攪拌一邊加熱及保溫之方法。此外，在此所使用的聚合起始劑及溶劑等並無特別限制，可使用該領域中一般所使用者。例如就聚合起始劑而言，可列舉偶氮化合物(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)，就溶劑而言，只要是溶解各單體者即可，可列舉後述的溶劑之本發明之著色硬化性樹脂組成物的溶劑(E)等。 Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to the reaction vessel, and for example, a nitrogen is substituted for oxygen to form a deoxygenated environment, while heating and keeping warm while stirring Method. In addition, the polymerization initiator and solvent used here are not particularly limited, and can be used by users generally used in this field. For example, as for the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The peroxide (benzoyl peroxide, etc.) may be any solvent as long as it dissolves each monomer, and examples thereof include the solvent (E) of the color-curable resin composition of the present invention and the like described below.

又，所得之共聚物可直接使用反應後的溶液，亦可使用經濃縮或稀釋的溶液，也可使用以再沉澱等方法作為固體(粉體)而取出者。特別是，就此聚合時之溶劑而言，藉由使用本發明之著色硬化性樹脂組成物所含有之溶劑，可將反應後的溶液直接使用於本發明之色硬化性樹脂組成物的調製，故可簡化本發明之著色硬化性樹脂組成物的製造步驟。 In addition, the obtained copolymer may be used as it is after the reaction, or it may be a concentrated or diluted solution, or it may be taken out as a solid (powder) by a method such as reprecipitation. In particular, as for the solvent at the time of polymerization, by using the solvent contained in the color-curable resin composition of the present invention, the solution after the reaction can be directly used for the preparation of the color-curable resin composition of the present invention. The manufacturing process of the color-curing resin composition of the present invention can be simplified.

於樹脂[K2]中，來自各個結構單元之比率，在構成樹脂[K2]的總結構單元中，較佳為來自(a)的結構單元：2至45莫耳%來自(b)的結構單元：2至95莫耳%來自(c)的結構單元：1至65莫耳%；更佳為來自(a)的結構單元：5至40莫耳%來自(b)的結構單元：5至80莫耳% 來自(c)的結構單元：5至60莫耳%。 In the resin [K2], the ratio derived from each structural unit, among the total structural units constituting the resin [K2], is preferably the structural unit from (a): 2 to 45 mole% from the structural unit from (b) : 2 to 95 mol% structural unit from (c): 1 to 65 mol%; more preferably structural unit from (a): 5 to 40 mol% structural unit from (b): 5 to 80 Mole% Structural unit from (c): 5 to 60 mol%.

樹脂[K2]的結構單元之比率於上述範圍時，有著色硬化性樹脂組成物的保存安定性、形成著色圖案時的顯影性、以及所得之濾色器的耐溶劑性、耐熱性及機械強度優異之傾向。 When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting color filter Excellent tendency.

樹脂[K2]例如可依與樹脂[K1]的製造方法所記載之方法相同的方式來製造。 The resin [K2] can be manufactured in the same manner as the method described in the manufacturing method of the resin [K1], for example.

於樹脂[K3]中，來自各個結構單元之比率，在構成樹脂[K3]的總結構單元中，較佳為來自(a)的結構單元：2至60莫耳%來自(c)的結構單元：40至98莫耳%；更佳為來自(a)的結構單元：10至50莫耳%來自(c)的結構單元：50至90莫耳%。 In the resin [K3], the ratio derived from each structural unit is preferably the structural unit derived from (a) among the total structural units constituting the resin [K3]: 2 to 60 mol% of the structural unit derived from (c) : 40 to 98 mol%; more preferably, structural units from (a): 10 to 50 mol%; structural units from (c): 50 to 90 mol%.

樹脂[K3]例如可依與樹脂[K1]的製造方法中所記載之方法相同的方式來製造。 The resin [K3] can be manufactured in the same manner as the method described in the manufacturing method of the resin [K1], for example.

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

首先，以與樹脂[K1]的製造方法中所記載之方法相同的方式來製造(a)與(c)之共聚物。此時，來自各個結構單元之比率，較佳為與在樹脂[K3]所列舉者相同的比率。 First, the copolymer of (a) and (c) is manufactured in the same manner as the method described in the manufacturing method of the resin [K1]. In this case, the ratio derived from each structural unit is preferably the same as that exemplified in the resin [K3].

其次，使前述共聚物中來自(a)之羧酸及/或羧酸酐的一部分與(b)所具有之碳數2至4的環狀醚反應。 Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the aforementioned copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms (b).

於(a)與(c)之共聚物的製造後，接著使燒瓶內氣體環境由氮氣取代為空氣，將(b)、羧酸或羧酸酐與環狀醚之反應催化劑(參(二甲基胺基甲基)苯酚等)及聚合抑制劑(對苯二酚等)等加入燒瓶內，在60至130℃反應1至10小時，藉此可製造樹脂[K4]。 After the production of the copolymer of (a) and (c), the gas environment in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (see (dimethyl Aminomethyl)phenol, etc.) and polymerization inhibitors (hydroquinone, etc.) are added to the flask and reacted at 60 to 130°C for 1 to 10 hours, whereby resin [K4] can be produced.

相對於(a)100莫耳而言，(b)的使用量較佳為5至80莫耳，更佳為10至75莫耳。藉由設在此範圍，著色硬化性樹脂組成物的保存安定性、形成圖案時的顯影性、以及所得之圖案的耐溶劑性、耐熱性、機械強度及靈敏度的平衡有變佳之傾向。從環狀醚的反應性高及不易殘留未反應的(b)來看，樹脂[K4]所使用的(b)中較佳為(b1)，更佳為(b1-1)。 Relative to (a) 100 mols, (b) is preferably used in an amount of 5 to 80 mols, more preferably 10 to 75 mols. By setting in this range, the balance of the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tends to be improved. From the viewpoint of (b) which has high reactivity of the cyclic ether and hardly remains unreacted, (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).

相對於(a)、(b)及(c)的合計含量100質量份而言，前述反應催化劑的使用量較佳為0.001至5質量份。相對於(a)、(b)及(c)的合計含量100質量份而言，前述聚合抑制劑的使用量較佳為0.001至5質量份。 The use amount of the reaction catalyst is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total content of (a), (b) and (c). The use amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total content of (a), (b), and (c).

加入方法、反應溫度及時間等反應條件，可考量製造設備或聚合造成的發熱量等而作適當調整。又，可與聚合條件同樣地考量製造設備或聚合造成的發熱量等來適當調整加入方法或反應溫度。 The reaction conditions such as the addition method, reaction temperature and time can be appropriately adjusted in consideration of the heat generated by the manufacturing equipment or polymerization. In addition, the addition method or reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like in the polymerization conditions.

樹脂[K5]就第一階段而言，係依與上述的樹脂[K1]之製造方法相同的方式得到(b)與(c)之共聚物。與上述同樣地，所得之共聚物可直接使用反應後的溶液，亦可使用濃縮或稀釋過的溶液，也可使用以再沉澱等方法作為 固體(粉體)而取出者。 Resin [K5] For the first stage, the copolymers of (b) and (c) are obtained in the same manner as the above-mentioned manufacturing method of the resin [K1]. In the same manner as above, the obtained copolymer can be used as it is after the reaction, or a concentrated or diluted solution can be used, or a method such as reprecipitation can be used. Take out the solid (powder).

相對於構成前述的共聚物之總結構單元位的合計莫耳數而言，來自(b)及(c)的結構單元之比率較佳係分別為來自(b)的結構單元：5至95莫耳%來自(c)的結構單元：5至95莫耳%；更佳為來自(b)的結構單元：10至90莫耳%來自(c)的結構單元：10至90莫耳%。 The ratio of the structural units derived from (b) and (c) relative to the total number of moles constituting the total structural unit positions of the aforementioned copolymer is preferably the structural units derived from (b): 5 to 95 Ear% comes from (c) structural unit: 5 to 95 mol %; more preferably comes from (b) structural unit: 10 to 90 mol% structural unit from (c): 10 to 90 mol %.

再者，在與樹脂[K4]的製造方法相同的條件下，藉由使來自(b)與(c)之共聚物所具有的(b)之環狀醚與(a)所具有的羧酸或羧酸酐反應，可得到樹脂[K5]。 Furthermore, the cyclic ether of (b) and the carboxylic acid of (a) contained in the copolymer derived from (b) and (c) under the same conditions as the production method of resin [K4] Or react with carboxylic anhydride to obtain resin [K5].

相對於(b)100莫耳而言，使前述的共聚物反應之(a)的使用量較佳為5至80莫耳。從環狀醚的反應性高及不易殘留未反應的(b)來看，樹脂[K5]所使用的(b)較佳為(b1)，更佳為(b1-1)。 The amount of (a) used to react the aforementioned copolymer with respect to (b) 100 moles is preferably 5 to 80 moles. From the viewpoint of (b), which has high reactivity of cyclic ethers and hardly remains unreacted, (b) used for resin [K5] is preferably (b1), more preferably (b1-1).

樹脂[K6]為使樹脂[K5]再與羧酸酐反應之樹脂。係使由環狀醚與羧酸或羧酸酐之反應所產生的羥基與羧酸酐反應。 Resin [K6] is a resin that reacts resin [K5] with carboxylic anhydride. The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or carboxylic anhydride reacts with a carboxylic anhydride.

羧酸酐可列舉順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基苯二甲酸酐、4-乙烯基苯二甲酸酐、3,4,5,6-四氫苯二甲酸酐、1,2,3,6-四氫苯二甲酸酐、二甲基四氫苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等。相對於(a)的使用量1莫耳而言，羧酸酐的使用量較佳為0.5 至1莫耳。 Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride , 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The use amount of carboxylic anhydride is preferably 0.5 relative to the use amount of (a) 1 mole To 1 mol.

樹脂(B)具體而言，可列舉(甲基)丙烯酸3,4-環氧基環己基甲酯/(甲基)丙烯酸共聚物、丙烯酸3,4-環氧基三環[5.2.1.0^2,6]癸酯/(甲基)丙烯酸共聚物等樹脂[K1]；(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、丙烯酸3,4-環氧基三環[5.2.1.0^2,6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2]；(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物等樹脂[K3]；使(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯之樹脂、使(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯之樹脂、使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯之樹脂等樹脂[K4]；使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯的共聚物與(甲基)丙烯酸反應之樹脂、使(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯的共聚物與(甲基)丙烯酸反應之樹脂等樹脂[K5]；使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯的共聚物與(甲基)丙烯酸反應之樹脂，再使該樹脂與四氫苯二甲酸酐反應之樹脂等樹脂[K6]等。 The resin (B) specifically includes 3,4-epoxycyclohexyl methyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricycloacrylate [5.2.1.0 ^{2 ,6} ]Decyl ester/(meth)acrylic acid copolymer and other resins [K1]; (meth)acrylic acid glycidyl ester/(meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl ester/styrene/(meth)acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl maleic diene Acetylene imide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer and other resins [K2]; (meth)acrylic acid Phenylmethyl ester/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer and other resins [K3]; Adding (meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer (meth) )Glycidyl acrylate resin, tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer added to glycidyl (meth)acrylate resin, trimethy (meth)acrylate Decyl ester/benzyl (meth)acrylate/(meth)acrylic acid copolymer addition resins such as glycidyl (meth)acrylate resin [K4]; tricyclodecyl (meth)acrylate/(A Base) a resin in which a copolymer of glycidyl acrylate reacts with (meth)acrylic acid, a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate and (meth)acrylic acid Resin and other resins [K5]; a resin that reacts a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, and then the resin and tetrahydrobenzene Resins such as formic anhydride reaction [K6], etc.

其中，樹脂(B)較佳為樹脂[K1]、樹脂[K2]及樹脂[K3]，更佳為樹脂[K1]及樹脂[K2]。 Among them, the resin (B) is preferably resin [K1], resin [K2] and resin [K3], more preferably resin [K1] and resin [K2].

樹脂(B)的聚乙烯換算重量平均分子量較佳為3,000至100,000，更佳為5,000至50,000，再更佳為5,000至30,000。分子量於前述的範圍內時，濾色器的硬度提升、殘膜率高及未曝光部對於顯影液之溶解性優良，而著色圖案的解析度有提升之傾向。 The weight average molecular weight in terms of polyethylene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the aforementioned range, the hardness of the color filter increases, the residual film rate is high, and the unexposed portion has excellent solubility in the developer, and the resolution of the coloring pattern tends to increase.

樹脂(B)的分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1至6，更佳為1.2至4。 The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

樹脂(B)的酸價較佳為50至170mg-KOH/g，更佳為60至150mg-KOH/g，再更佳為70至135mg-KOH/g。在此的酸價為以中和樹脂(B)1g所需要的氫氧化鉀之量(mg)而測定之值，例如可藉由使用氫氧化鉀水溶液滴定而求出。 The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g. The acid value here is a value measured with the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titration using an aqueous potassium hydroxide solution, for example.

相對於固形成分的總量而言，樹脂(B)的含量較佳為7至65質量%，更佳為13至60質量%，再更佳為17至55質量%。樹脂(B)的含量於前述的範圍內時，可形成著色圖案，而且有著色圖案的解析度及殘膜率提升之傾向。 The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass relative 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 the residual film rate of the colored pattern tend to increase.

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

聚合性化合物(C)為可藉由聚合起始劑(D)產生的活性自由基及/或酸而聚合之化合物，可列舉例如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 the active radical and/or acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenic unsaturated bond, etc., preferably (Meth) acrylate compounds.

其中，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。就此種聚合性化合 物而言，可列舉例如三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、參(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯、乙二醇改質季戊四醇四(甲基)丙烯酸酯、乙二醇改質二季戊四醇六(甲基)丙烯酸酯、丙二醇改質季戊四醇四(甲基)丙烯酸酯、丙二醇改質二季戊四醇六(甲基)丙烯酸酯、己內酯改質季戊四醇四(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯等。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. On this polymerizable compound In terms of substances, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, four season pentaerythritol deca(meth)acrylate, four season pentaerythritol nine(meth)acrylate, ginseng ( 2-(meth)acryloyloxyethyl)trimer isocyanate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol Tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified di pentaerythritol hexa (meth) acrylate, etc. .

其中，較佳為二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。 Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

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，更佳為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, and more preferably 250 to 1,500 or less.

相對於固形成分之總量而言，聚合性化合物(C)的含量較佳為7至65質量%，更佳為13至60質量%，再更佳為17至55質量%。聚合性化合物(C)的含量於前述的範圍內時，形成著色圖案時之殘膜率及濾色器的耐藥品性有提升之傾向。 The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass relative to the total amount of solid components. When the content of the polymerizable compound (C) is within the aforementioned range, the residual film rate when forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<聚合起始劑(D)> <polymerization initiator (D)>

聚合起始劑(D)只要係可藉由光或熱的作用來產生活性自由基、酸等而開始聚合之化合物即無特別限制，可使 用習知的聚合起始劑。就產生活性自由基的聚合起始劑而言，可列舉例如O-醯基肟化合物、烷基苯酮(alkylphenone)化合物、三

化合物、醯基膦氧化物及聯咪唑化合物。 The polymerization initiator (D) is not particularly limited as long as it can generate active radicals, acids, etc. to initiate polymerization by the action of light or heat, and a conventional polymerization initiator can be used. Examples of polymerization initiators that generate active radicals include, for example, O-acyl oxime compounds, alkylphenone compounds, and

Compounds, acylphosphine oxides and biimidazole compounds.

前述O-醯基肟化合物為具有式(d1)所示之部分結構之化合物。以下，*表示鍵結鍵。 The aforementioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * indicates a bonding key.

就前述O-醯基肟化合物而言，N-苯甲基氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲基氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二

環戊烯基甲基氧基)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-苯甲醯基氧基-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。可使用IRGACURE(註冊商標)OXE01、OXE02(以上為BASF公司製)、N-1919(ADEKA公司製)等市售品。其中，O-醯基肟化合物較佳為選自由N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺及N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺所組成群組之至少1 種，更佳為N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺。若為此等O-醯基肟化合物，則有得到高亮度的濾色器之傾向。 As for the aforementioned O-acyl oxime compounds, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy Yl-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- Yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di

(Cyclopentenylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6 -(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as IRGACURE (registered trademark) OXE01, OXE02 (above manufactured by BASF), N-1919 (made by ADEKA) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzene Methyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanyl At least one of the group consisting of phenyl)-3-cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanyl Phenyl)octan-1-one-2-imine. If such an O-acyl oxime compound is used, there is a tendency to obtain a high-brightness color filter.

前述烷基苯酮化合物為具有式(d2)所示之部分結構或式(d3)所示之部分結構之化合物。該等的部分結構中，苯環可具有取代基。 The aforementioned alkyl benzophenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

就具有式(d2)所示之部分結構之化合物而言，可列舉2-甲基-2-嗎啉基-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎啉基苯基)-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-嗎啉基)苯基]丁烷-1-酮、IRGACURE(註冊商標)369、907、379(以上為BASF公司製)，就具有式(d3)所示之部分結構之化合物而言，可列舉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-羥基環己基苯基甲酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮的低聚物、α,α-二乙氧基苯乙酮、苯甲基二甲基縮酮等。 Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propane-1-one, 2- Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl )Methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one, IRGACURE (registered trademark) 369, 907, 379 (above manufactured by BASF), having the formula (d3 ) Partially structured compounds shown include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl Ethoxy)phenyl]propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl) propane-1-one Polymer, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc.

就前述三

化合物而言，可列舉2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯 基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 As mentioned above

Compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-sunflower group-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

就前述醯基膦氧化物而言，可列舉2,4,6-三甲基苯甲醯基二苯基膦氧化物等。可使用IRGACURE(註冊商標)819(BASF公司製)等市售品。 Examples of the aforementioned acylphosphine oxide include 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like. Commercial products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can be used.

就前述聯咪唑化合物而言，可列舉2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基聯咪唑(參照日本特開平6-75372號公報、日本特開平6-75373號公報等)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)聯咪唑(參照日本特公昭48-38403號公報、日本特開昭62-174204號公報等)、4,4’,5,5’-位的苯基被烷氧羰基取代之咪唑化合物(參照日本特開平7-10913號公報等)等。 Examples of the aforementioned biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra( (Alkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204 Etc.), an imidazole compound in which the phenyl group in 4,4',5,5'-position is substituted with an alkoxycarbonyl group (refer to Japanese Patent Laid-Open No. 7-10913, etc.), etc.

再者，就聚合起始劑(D)而言，可列舉安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等安息香化合物；二苯基甲酮、鄰苯甲醯基安息香酸甲酯、4-苯基二苯基甲酮、4-苯甲醯基-4’-甲基二苯基硫化物、3,3’,4,4’-四(第三丁基過氧化羰基)二苯基甲酮、2,4,6-三甲基二苯基甲酮等二苯基甲酮化合物； 9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物；10-丁基-2-吖啶酮、二苯甲醯(benzil)、苯基乙醛酸甲酯、二茂鈦化合物等。此等係與後述的聚合起始助劑(D1)(特別是胺)組合而使用為較佳。 Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; diphenyl ketone, o-benzoyl benzoin Methyl acid ester, 4-phenyldiphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (third butyl peroxide (Carbonyl) diphenyl ketone, 2,4,6-trimethyldiphenyl ketone and other diphenyl ketone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-acridone, benzil, methyl phenylglyoxylate, titanocene Compounds etc. These systems are preferably used in combination with a polymerization initiation aid (D1) (especially amine) described later.

就酸產生劑而言，4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基甲基苯甲基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽等鎓鹽，或甲苯磺酸硝基苯甲酯、安息香甲苯磺酸酯等。 In terms of acid generators, 4-hydroxyphenyldimethylammonium p-toluenesulfonate, 4-hydroxyphenyldimethylammonium hexafluoroantimonate, 4-acetoxyphenyldimethylammonium pair Tosylate, 4-acetoxyphenylmethylbenzyl alkane hexafluoroantimonate, triphenylammonium p-toluenesulfonate, triphenylammonium hexafluoroantimonate, diphenyl oxonium para Onium salts such as tosylate, diphenylphosphonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, etc.

就聚合起始劑(D)而言，較佳為含有選自由O-醯基肟化合物、烷基苯酮化合物、三

化合物、醯基膦氧化物及聯咪唑化合物所組成群組之至少1種之聚合起始劑，更佳為含有O-醯基肟化合物之聚合起始劑。 The polymerization initiator (D) preferably contains a compound selected from the group consisting of O-acyl oxime compounds, alkyl benzophenone compounds, and

At least one polymerization initiator of the group consisting of a compound, an acylphosphine oxide and a biimidazole compound is more preferably a polymerization initiator containing an O-acyloxime compound.

相對於樹脂(B)及聚合性化合物(C)的合計含量100質量份而言，聚合起始劑(D)的含量較佳為0.1至30質量份，更佳為1至20質量份。聚合起始劑(D)的含量於前述的範圍內時，會高靈敏度化而有縮短曝光時間之傾向，故會提升濾色器的生產性。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total content of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the aforementioned range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

<聚合起始助劑(D1)> <Polymerization Initiator (D1)>

聚合起始助劑(D1)係為了促進藉由聚合起始劑而開始聚合的聚合性化合物之聚合而使用的化合物或增敏劑。含有聚合起始助劑(D1)時，通常會與聚合起始劑(D)組合而使 用。 The polymerization start aid (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound that starts polymerization by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually combined with the polymerization initiator (D) to make use.

就聚合起始助劑而言，可列舉胺化合物、烷氧基蒽化合物、氧硫雜蒽酮化合物及羧酸化合物等。 Examples of the polymerization start adjuvant include amine compounds, alkoxyanthracene compounds, oxaanthrone compounds, and carboxylic acid compounds.

就前述胺化合物而言，可列舉三乙醇胺、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)二苯基甲酮(一般稱為米其勒酮(michler's ketone))、4,4’-雙(二乙基胺基)二苯基甲酮、4,4’-雙(乙基甲基胺基)二苯基甲酮等，其中，較佳為4,4’-雙(二乙基胺基)二苯基甲酮。亦可使用EAB-F(保土谷化學工業股份有限公司製)等市售品。 Examples of the aforementioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-diethylaminobenzoate. Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylp-toluidine , 4,4'-bis (dimethylamino) diphenyl ketone (commonly known as micheler's ketone), 4,4'-bis (diethylamino) diphenyl methyl Ketones, 4,4'-bis(ethylmethylamino)diphenyl ketone, etc. Among them, 4,4'-bis(diethylamino) diphenyl ketone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Industry Co., Ltd.) can also be used.

就前述烷氧基蒽化合物而言，可列舉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。 Examples of the aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethane Base-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

就前述氧硫雜蒽酮化合物而言，可列舉2-異丙基氧硫雜蒽酮、4-異丙基氧硫雜蒽酮、2,4-二乙基氧硫雜蒽酮、2,4-二氯氧硫雜蒽酮、1-氯-4-丙氧基氧硫雜蒽酮等。 Examples of the oxathioxanthone compounds include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2, 4-Dichloroxanthene, 1-chloro-4-propoxyxanthone, etc.

就前述羧酸化合物而言，可列舉苯基硫烷基乙酸、甲基苯基硫烷基乙酸、乙基苯基硫烷基乙酸、甲基乙基苯基硫烷基乙酸、二甲基苯基硫烷基乙酸、甲氧基苯基硫烷基乙酸、二甲氧基苯基硫烷基乙酸、氯苯基硫烷 基乙酸、二氯苯基硫烷基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘硫乙酸、N-萘基甘氨酸、萘氧基乙酸等。 Examples of the aforementioned carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylbenzene Sulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfane Acetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthalenethioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

使用此等的聚合起始助劑(D1)時，其含量相對於樹脂(B)及聚合性化合物(C)的合計含量100質量份而言，較佳為0.1至30質量份，更佳為1至20質量份。聚合起始助劑(D1)的量於該範圍內時，可以更高靈敏度來形成著色圖案，有提升濾色器的生產性之傾向。 When using these polymerization initiation aids (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass relative to the total content of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, which tends to improve the productivity of the color filter.

<硫醇化合物(T)> <thiol compound (T)>

硫醇化合物(T)為分子內具有硫烷基(-SH)之化合物。 The thiol compound (T) is a compound having a thioalkyl group (-SH) in the molecule.

就分子內具有1個硫烷基之化合物而言，可列舉例如2-硫烷基

唑、2-硫烷基噻唑、2-硫烷基苯並咪唑、2-硫烷基苯并噻唑、2-硫烷基苯并

唑、2-硫烷基菸鹼酸、2-硫烷基吡啶、2-硫烷基吡啶-3-醇、2-硫烷基吡啶-N-氧化物、4-胺基-6-羥基-2-硫烷基嘧啶、4-胺基-6-羥基-2-硫烷基嘧啶、4-胺基-2-硫烷基嘧啶、6-胺基-5-亞硝基-2-硫脲嘧啶、4,5-二胺基-6-羥基-2-硫烷基嘧啶、4,6-二胺基-2-硫烷基嘧啶、2,4-二胺基-6-硫烷基嘧啶、4,6-二羥基-2-硫烷基嘧啶、4,6-二甲基-2-硫烷基嘧啶、4-羥基-2-硫烷基-6-甲基嘧啶、4-羥基-2-硫烷基-6-丙基嘧啶、2-硫烷基-4-甲基嘧啶、2-硫烷基嘧啶、2-硫脲嘧啶、3,4,5,6-四氫嘧啶-2-硫醇、4,5-二苯基咪唑-2-硫醇、2-硫烷基咪唑、2-硫烷基-1-甲基咪唑、4-胺基-3-肼基-5-硫烷基-1,2,4-***、3-胺基-5-硫烷基-1,2,4-***、2-甲基-4H-1,2,4-***-3-硫醇、4-甲基 -4H-1,2,4-***-3-硫醇、3-硫烷基1H-1,2,4-***-3-硫醇、2-胺基-5-硫烷基-1,3,4-噻二唑、5-胺基-1,3,4-噻二唑-2-硫醇、2,5-二硫烷基-1,3,4-噻二唑、(呋喃-2-基)甲基硫醇、2-硫烷基-5-噻唑酮、2-硫烷基噻唑啉、2-硫烷基-4(3H)-喹唑啉酮、1-苯基-1H-四唑-5-硫醇、2-喹啉硫醇、2-硫烷基-5-甲基苯并咪唑、2-硫烷基-5-硝基苯并咪唑、6-胺基-2-硫烷基苯并噻唑、5-氯-2-硫烷基苯并噻唑、6-乙氧基-2-硫烷基苯并噻唑、6-硝基-2-硫烷基苯并噻唑、2-硫烷基萘并咪唑、2-硫烷基萘并

唑、3-硫烷基-1,2,4-***、4-胺基-6-硫烷基吡唑并[2,4-d]吡啶、2-胺基-6-嘌呤硫醇、6-硫烷基嘌呤、4-硫烷基-1H-吡唑并[2,4-d]嘧啶等。 Compounds having one sulfanyl group in the molecule include, for example, 2-sulfanyl groups

Azole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzimidazole

Azole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy- 2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiourea Pyrimidine, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine , 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy- 2-sulfanyl-6-propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2 -Thiol, 4,5-diphenylimidazole-2-thiol, 2-thioalkylimidazole, 2-thioalkyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfur Alkyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3- Mercaptan, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino- 5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4 -Thiadiazole, (furan-2-yl)methyl mercaptan, 2-sulfanyl-5-thiazolone, 2-sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazoline Ketone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzo Imidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2 -Sulfanyl benzothiazole, 2-sulfanyl naphthymidazole, 2-sulfanyl naphtho

Azole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine, etc.

就分子內具有2個以上硫烷基之化合物而言，可列舉己烷二硫醇、癸烷二硫醇、1,4-雙(甲基硫烷基)苯、丁二醇雙(3-硫烷基丙酸酯)、丁二醇雙(3-硫烷基乙酸酯)、乙二醇雙(3-硫烷基乙酸酯)、三羥甲基丙烷參(3-硫烷基乙酸酯)、丁二醇雙(3-硫烷基丙酸酯)、三羥甲基丙烷參(3-硫烷基丙酸酯)、三羥甲基丙烷參(3-硫烷基乙酸酯)、季戊四醇肆(3-硫烷基丙酸酯)、季戊四醇肆(3-硫烷基乙酸酯)、參羥基乙基參(3-硫烷基丙酸酯)、季戊四醇肆(3-硫烷基丁酸酯)、1,4-雙(3-硫烷基丁基氧基)丁烷等。 Examples of compounds having two or more sulfanyl groups in the molecule include hexane dithiol, decane dithiol, 1,4-bis(methylsulfanyl)benzene, and butanediol bis(3- (Sulfanyl propionate), butanediol bis (3-sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane ginseng (3-sulfanyl Acetate), butanediol bis(3-sulfanyl propionate), trimethylolpropane ginseng (3-sulfanyl propionate), trimethylolpropane ginseng (3-sulfanyl propane ginate) Ester), pentaerythritol (3-sulfanyl propionate), pentaerythritol (3-sulfanyl acetate), hydroxyethyl ginseng (3-sulfanyl propionate), pentaerythritol (3 -Sulfanyl butyrate), 1,4-bis(3-sulfanylbutyloxy)butane, etc.

相對於聚合起始劑(D)100質量份而言，硫醇化合物(T)的含量較佳為0.5至20質量份，更佳為1至15質量份。硫醇化合物(T)的含量於此範圍內時，會有靈敏度變高、顯影性變優良之傾向。 The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass relative to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be excellent.

<溶劑(E)> <Solvent (E)>

溶劑(E)係不受特別限制，可使用該領域一般所使用的溶劑。該溶劑可列舉酯溶劑(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、二甲基亞碸等。 The solvent (E) is not particularly limited, and solvents generally used in this field can be used. Examples of the solvent include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), and ether ester solvents (in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule and not containing -O-, -CO -And -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

就酯溶劑而言，可列舉乳酸甲酯、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。 Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutyric acid methyl ester, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isopentyl acetate Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Cyclohexanol acetate and γ-butyrolactone etc.

就醚溶劑而言，可列舉乙二醇單甲醚、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、四氫吡喃、1,4-二

烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲***、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***及甲基苯甲醚等。 Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene 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-methylbutanol , Tetrahydrofuran, tetrahydropyran, 1,4-di

Alkanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methylbenzene Ether, etc.

就醚酯溶劑而言，可列舉甲氧基乙酸甲酯、 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-乙氧基丙酸乙酯、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***乙酸酯及二乙二醇單丁醚乙酸酯等。 Examples of ether ester solvents include methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, propyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-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 Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.

就酮溶劑而言，可列舉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。 Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -Pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

就醇溶劑而言，可列舉甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及丙三醇等。 Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

就芳香族烴溶劑而言，可列舉苯、甲苯、二甲苯及均三甲苯等。 Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene and the like.

就醯胺溶劑而言，可列舉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。 Examples of the acetamide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

上述的溶劑之中，從塗佈性、乾燥性的觀點來看，較佳為在1atm的沸點為120℃以上、180℃以下之有機溶劑。溶劑中較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單***、4-羥基-4-甲基-2-戊酮 及N,N-二甲基甲醯胺，更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、乳酸乙酯及4-羥基-4-甲基-2-戊酮。 Among the above-mentioned solvents, an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm is preferred from the viewpoint of coatability and dryness. The solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone.

相對於本發明之著色硬化性樹脂組成物的總量而言，溶劑(E)的含量較佳為70至95質量%，更佳為75至92質量%。換言之，著色硬化性樹脂組成物的固形成分之總量較佳為5至30質量%，更佳為8至25質量%。溶劑(E)的含量於前述的範圍內時，塗佈時的平坦性變優良，而且因為形成濾色器時之色濃度不會不足，而有顯示特性變優良之傾向。 The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass relative to the total amount of the color-curing resin composition of the present invention. In other words, the total amount of solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the aforementioned range, the flatness during coating becomes excellent, and since the color density at the time of forming the color filter is not insufficient, there is a tendency that the display characteristics become excellent.

<調平劑(F)> <Leveling agent (F)>

就調平劑(F)而言，可列舉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。此等於側鏈可具有聚合性基。 Examples of the leveling agent (F) include polysiloxane-based surfactants, fluorine-based surfactants, and polysiloxane-based surfactants having fluorine atoms. This means that the side chain may have a polymerizable group.

就聚矽氧系界面活性劑而言，可列舉分子內具有矽氧烷鍵之界面活性劑等。具體而言，可列舉Toray Silicone DC3PA、同系列之SH7PA、同系列之DC11PA、同系列之SH21PA、同系列之SH28PA、同系列之SH29PA、同系列之SH30PA、同系列之SH8400(商品名為Dow Corning Toray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合同會社製)等。 Examples of polysiloxane-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA in the same series, DC11PA in the same series, SH21PA in the same series, SH28PA in the same series, SH29PA in the same series, SH30PA in the same series, SH8400 in the same series (trade name Dow Corning) Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan Contract Co., Ltd.) etc.

就前述的氟系界面活性劑而言，可列舉分子內具有氟碳鏈之界面活性劑等。具體而言，可列舉Fluorad(註冊商標)FC430、同系列之FC431(住友3M股份有限公司製)、Megafac(註冊商標)F142D、同系列之F171、同系列之F172、同系列之F173、同系列之F177、同系列之F183、同系列之F554、同系列之R30、同系列之RS-718-K(DIC股份有限公司製)、EFTOP(註冊商標)EF301、同系列之EF303、同系列之EF351、同系列之EF352(三菱Material電子化成股份有限公司製)、Surflon(註冊商標)S381、同系列之S382、同系列之SC101、同系列之SC105(旭硝子股份有限公司製)及E5844(Daikin Fine Chemical研究所股份有限公司製)等。 Examples of the aforementioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, it includes Fluorad (registered trademark) FC430, the same series FC431 (made by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177, F183 of the same series, F554 of the same series, R30 of the same series, RS-718-K of the same series (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303 of the same series, EF351 of the same series , The same series of EF352 (Mitsubishi Material Electronics Co., Ltd.), Surflon (registered trademark) S381, the same series of S382, the same series of SC101, the same series of SC105 (made by Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Research Institute Co., Ltd.).

就具有前述的氟原子之聚矽氧系界面活性劑而言，可列舉分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體而言，可列舉Megafac(註冊商標)R08、同系列之BL20、同系列之F475、同系列之F477及同系列之F443(DIC股份有限公司製)等。 Examples of the polysiloxane-based surfactant having the aforementioned fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20 in the same series, F475 in the same series, F477 in the same series, and F443 (made by DIC Co., Ltd.) in the same series, etc. can be mentioned.

相對於著色硬化性樹脂組成物之總量而言，調平劑(F)的含量較佳為0.001質量%以上、0.2質量%以下，較佳為0.002質量%以上、0.1質量%以下，更佳為0.01質量%以上、0.05質量%以下。此外，此含量不包括前述顏料分散劑的含量係。調平劑(F)的含量於前述的範圍內時，可使濾色器的平坦性為優良。 The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less relative to the total amount of the colored curable resin composition It is 0.01% by mass or more and 0.05% by mass or less. In addition, this content does not include the content system of the aforementioned pigment dispersant. When the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be made excellent.

<其他的成分> <other ingredients>

本發明之著色硬化性樹脂組成物視需要，可含有填充劑、其他的高分子化合物、密合促進劑、抗氧化劑、光安定劑、鏈轉移劑等在該技術領域所習知的添加劑。 The color-curable resin composition of the present invention may contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as needed.

<著色硬化性樹脂組成物的製造方法> <Manufacturing method of colored curable resin composition>

本發明之著色硬化性樹脂組成物，例如可藉由將著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)以及視需要而使用之溶劑(E)、調平劑(F)、聚合起始助劑(D1)、硫醇化合物(T)及其他的成分進行混合而調製。 The color-curable resin composition of the present invention can be obtained, for example, by combining a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) as needed , Leveling agent (F), polymerization initiation aid (D1), thiol compound (T) and other components are mixed and prepared.

綠色顏料(A2)等顏料較佳為預先與溶劑(E)的一部分或全部進行混合，並使用珠磨機等予以分散以使顏料的平均粒徑成為0.2μm以下左右為止。此時，視需要可調配前述顏料分散劑、樹脂(B)的一部分或全部。於依此種方式所得之顏料分散液中，以使剩餘的成分成為預定的濃度之方式來進行混合，藉此可調製目標的著色硬化性樹脂組成物。 The pigment such as the green pigment (A2) is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like so that the average particle diameter of the pigment becomes approximately 0.2 μm or less. At this time, part or all of the aforementioned pigment dispersant and resin (B) may be blended as necessary. The pigment dispersion liquid obtained in this way is mixed in such a manner that the remaining components have a predetermined concentration, whereby the target color-curing resin composition can be prepared.

藍色染料(A1)等染料亦分別溶解於溶劑(E)的一部分或全部而預先調製溶液。將該溶液以孔徑0.01至1μm左右的濾網進行過濾為較佳。 Dyes such as the blue dye (A1) are also dissolved in part or all of the solvent (E) to prepare a solution in advance. The solution is preferably filtered through a filter with a pore size of about 0.01 to 1 μm.

混合後的著色硬化性樹脂組成物，係以孔徑0.01至10μm左右的濾網進行過濾為較佳。 After mixing, the color-curing resin composition is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

<濾色器的製造方法> <Manufacturing method of color filter>

本發明之濾色器係由本發明之著色硬化性樹脂組成物所形成。該濾色器可藉由使該著色硬化性樹脂組成物硬化而形成。 The color filter of the present invention is formed of the color-curing resin composition of the present invention. The color filter can be formed by curing the colored curable resin composition.

就由本發明之著色硬化性樹脂組成物製造著色圖案之方法而言，可列舉光蝕刻法、噴墨法、印刷法等。其中，較佳為光蝕刻法。光蝕刻法係將前述著色硬化性樹脂組成物塗佈於基板，並使之乾燥以形成著色組成物層，再隔著光罩將該著色組成物層進行曝光而顯影之方法。 Examples of the method for producing a colored pattern from the color-curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, the photoetching method is preferred. The photo-etching method is a method of applying the aforementioned colored curable resin composition to a substrate, and drying it to form a colored composition layer, and then exposing and developing the colored composition layer through a photomask.

於光蝕刻法中，藉由曝光時不使用光罩及/或不顯影，可形成上述著色組成物層的硬化物之著色塗膜。以此方式形成的著色圖案或著色塗膜為本發明之濾色器。 In the photoetching method, by not using a photomask during exposure and/or not developing, a colored coating film of the hardened product of the coloring composition layer can be formed. The colored pattern or colored coating film formed in this way is the color filter of the present invention.

所製作的濾色器之膜厚係不受特別限制，可視目的或用途等作適當調整，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 manufactured color filter is not particularly limited, and can be appropriately adjusted depending on the purpose or application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

基板係使用石英玻璃、硼矽酸玻璃、鋁矽酸鹽玻璃、表面塗覆有二氧化矽的鈉鈣玻璃等之玻璃板，或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等之樹脂板，矽，於前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。於該等基板上亦可形成其他的濾色層、樹脂層、電晶體、電路等。 The substrate is a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica, or polycarbonate, polymethyl methacrylate, polyterephthalic acid Resin plates such as ethylene glycol, silicon, and aluminum, silver, silver/copper/palladium alloy films, etc. are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

以光蝕刻法形成著色圖案，可以習知或慣用的裝置或條件進行。例如可依下述方式製作。 The coloring pattern is formed by photoetching method, which can be carried out by conventional or conventional equipment 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，進行加熱乾燥(預烤(pre-bake))及/或減壓乾燥，藉此去除溶劑等揮發成分而乾燥，得到平滑的著色組成物層。 First, apply the colored curable resin composition to the base On the board, heat drying (pre-bake) and/or drying under reduced pressure is performed to remove volatile components such as a solvent and dry, thereby obtaining a smooth colored composition layer.

就塗佈方法而言，可列舉旋轉塗佈法、狹縫式塗佈法、狹縫旋轉塗佈法等。 Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method.

進行加熱乾燥時的溫度較佳為30至120℃，更佳為50至110℃。又，加熱時間較佳為10秒至60分鐘，更佳為30秒至30分鐘。 The temperature during heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

進行減壓乾燥時，較佳為在50至150Pa的壓力下、20至25℃的溫度範圍進行。 When drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

著色組成物層的膜厚係不受特別限制，視目標的濾色器之膜厚作適當選擇即可。 The film thickness of the coloring composition layer is not particularly limited, and it may be appropriately selected depending on the film thickness of the target color filter.

其次，著色組成物層係隔著用以形成目標的著色圖案之光罩來進行曝光。該光罩上的圖案係不受特別限制，可使用對應目標用途之圖案。 Secondly, the colored composition layer is exposed through a mask used to form a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

曝光所使用的光源，較佳為產生250至450nm的波長之光之光源。例如可使用阻斷未達350nm的光之濾光片，以將此波長區域的光予以阻斷；或使用取出436nm附近、408nm附近、365nm附近的光之帶通濾光片，以將此等波長區域的光選擇性地取出。具體而言，可列舉水銀燈、發光二極體、金屬鹵素燈、鹵素燈等。 The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a filter that blocks light up to 350 nm can be used to block light in this wavelength range; or a bandpass filter that takes out light near 436 nm, near 408 nm, or near 365 nm can be used The light in the wavelength region is selectively extracted. Specifically, a mercury lamp, a light emitting diode, a metal halogen lamp, a halogen lamp, etc. are mentioned.

為了可於曝光面整體均勻地照射平行光線、將光罩與形成有著色組成物層之基板進行正確的對位，較佳係使用光罩對準機(mask aligner)及步進機(stepper)等曝光裝置。 In order to irradiate parallel light uniformly on the entire exposure surface and accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use a mask aligner and a stepper Wait for the exposure device.

使曝光後的著色組成物層接觸顯影液而進行顯影，藉此於基板上形成著色圖案。藉由顯影，著色組成物層的未曝光部分會溶解於顯影液而被去除。 The exposed coloring composition layer is contacted with a developing solution and developed, thereby forming a coloring pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer solution and removed.

顯影液較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物的水溶液。此等鹼性化合物之水溶液中的濃度較佳為0.01至10質量%，更佳為0.03至5質量%。再者，顯影液可含有界面活性劑。 The developer is preferably an aqueous solution of basic compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

顯影方法可為覆液(paddle)法、浸漬法及噴霧法等中之任一者。亦可在顯影時將基板以任意的角度傾斜。 The development method may be any of a paddle method, a dipping method, a spray method, and the like. It is also possible to tilt the substrate at an arbitrary angle during development.

顯影後，係以進行水洗為較佳。 After development, washing with water is preferred.

再者，係以對所得之著色圖案進行後烤(post-bake)為較佳。後烤溫度較佳為150至250℃，更佳為160至235℃。後烤時間較佳為1至120分鐘，更佳為10至60分鐘。 Furthermore, it is better to post-bake the obtained coloring pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

藉由本發明之著色硬化性樹脂組成物，可製作亮度特別優異之濾色器。該濾色器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)及固體攝影元件所使用之濾色器。其中，係有用於作為液晶顯示裝置用濾色器，特別是有用於作為以LED作為背光之液晶顯示裝置用的濾色器。 The color-curing resin composition of the present invention can produce a color filter with particularly excellent brightness. The color filter is used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state imaging element. Among them, it is used as a color filter for liquid crystal display devices, and particularly as a color filter for liquid crystal display devices using LEDs as backlights.

(實施例) (Example)

以下，藉由實施例更詳細地說明本發明之著色硬化性樹脂組成物。例子中之「%」及「份」只要沒 有特別的註明，即為質量%及質量份。 Hereinafter, the color-curing resin composition of the present invention will be described in more detail by examples. As long as the "%" and "parts" in the example are not Special notes indicate mass% and mass parts.

於以下的合成例中，化合物係藉由質量分析(LC；Agilent製1200型、MASS；Agilent製LC/MSD型)或元素分析(VARIO-EL；(Elementar股份有限公司製))來進行鑑定。 In the following synthesis examples, the compounds were identified by mass analysis (LC; Model 1200 manufactured by Agilent, MASS; LC/MSD model manufactured by Agilent) or elemental analysis (VARIO-EL; (manufactured by Elementar Corporation)).

[合成例1] [Synthesis Example 1]

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入硫氰酸鉀36.3份及丙酮160份後，於室溫下攪拌30分鐘。其次，以10分鐘滴下苯甲醯氯(東京化成股份有限公司製)50份。滴下結束後，再於室溫下攪拌2小時。其次，使反應混合物冰冷後，滴下N-乙基-鄰甲苯胺(東京化成股份有限公司製)45.7份。滴下結束後，再於室溫下攪拌30分鐘。其次，使反應混合物冰冷後，滴下30%氫氧化鈉水溶液34.2份。滴下結束後，再於室溫下攪拌30分鐘。其次，於室溫下滴下氯乙酸35.3份。滴下結束後，在加熱回流下攪拌7小時。其次，將反應混合物放冷至室溫後，將反應溶液注入於自來水120份中後，加入甲苯200份攪拌30分鐘。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將有機層以1當量的鹽酸200份來進行洗淨，接著以自來水200份來進行洗淨，最後以飽和食鹽水200份來進行洗淨。於有機層加入適當量的芒硝並攪拌30分鐘後，進行過濾而得到去除水分的有機層。將所得之有機層以蒸發器餾除溶劑， 得到淡黃色液體。將所得之淡黃色液體以管柱層析法進行精製。將精製過的淡黃色液體在減壓下以60℃乾燥，得到式(B-I-1)所示之化合物52份。產率為50%。 The following reaction is carried out under a nitrogen atmosphere. After adding 36.3 parts of potassium thiocyanate and 160 parts of acetone to the flask equipped with a cooling tube and a stirring device, it stirred at room temperature for 30 minutes. Next, 50 parts of benzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 10 minutes. After the dropping, the mixture was stirred at room temperature for 2 hours. Next, after cooling the reaction mixture in ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. Next, after ice-cooling the reaction mixture, 34.2 parts of a 30% sodium hydroxide aqueous solution was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. Next, 35.3 parts of chloroacetic acid was dropped at room temperature. After the dropping, the mixture was stirred under heating and reflux for 7 hours. Next, after cooling the reaction mixture to room temperature, the reaction solution was poured into 120 parts of tap water, and 200 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 200 parts of 1 equivalent of hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which moisture was removed. The resulting organic layer was distilled off the solvent with an evaporator, A light yellow liquid is obtained. The resulting light yellow liquid was purified by column chromatography. The purified light yellow liquid was dried at 60° C. under reduced pressure to obtain 52 parts of the compound represented by formula (B-I-1). The yield is 50%.

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入式(B-I-1)所示之化合物9.3份、4,4’-雙(二乙基胺基)二苯基甲酮(東京化成股份有限公司製)10份及甲苯20.0份後，其次，加入***14.8份並在95至100℃攪拌3小時。其次，使反應混合物冷卻至室溫後，以異丙醇170份來進行稀釋。其次，將稀釋過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。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將有機層以飽和食鹽水300份來進行洗淨。於有機層加入適當量的芒硝並攪拌30分鐘後，進行過濾而得到去除水分的有機層。將所得之有機層以蒸發器餾除溶劑，得到藍紫色固體。再將藍紫色體在減壓下以60℃乾燥，得到式(A-II-1)所示之化合物19.8份。產率為100%。 The following reaction is carried out under a nitrogen atmosphere. 9.3 parts of the compound represented by formula (BI-1), 4,4'-bis(diethylamino)diphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 were put in a flask equipped with a cooling tube and a stirring device. After 1 part and 20.0 parts of toluene, next, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. Next, after the diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which moisture was removed. The resulting organic layer was distilled off with an evaporator to obtain a blue-purple solid. The blue-purple body was dried under reduced pressure at 60°C to obtain 19.8 parts of the compound represented by formula (A-II-1). The yield is 100%.

式(A-II-1)所示之化合物的鑑定(質量分析)離子化模式=ESI+：m/z=601.3[M-Cl]⁺精確質量(Exact Mass)：636.3 Identification (mass analysis) of the compound represented by formula (A-II-1) Ionization mode = ESI+: m/z = 601.3 [M-Cl] ⁺ exact mass (Exact Mass): 636.3

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入式(A-II-1)所示之化合物10份、雙(三氟甲磺醯基)醯亞胺鋰(東京化成股份有限公司製)4.5份及N,N-二甲基甲醯胺100份後，在50至60℃攪拌3小時。其次，使反應混合物冷卻至室溫後，一邊攪拌1小時一邊進行滴下至自來水2000份中，會得到深藍色懸浮液。將所得之懸浮液予以過濾，得到藍綠色固體體。再將藍綠色固體在減壓下以60℃乾燥，得到式(Ab2-1)所示之化合物11.3份。產率為82%。 The following reaction is carried out under a nitrogen atmosphere. Put 10 parts of the compound represented by formula (A-II-1), 4.5 parts of lithium bis(trifluoromethanesulfonyl)imide (made by Tokyo Chemical Industry Co., Ltd.) and N in a flask equipped with a cooling tube and a stirring device After 100 parts of N-dimethylformamide was stirred at 50 to 60°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was dripped into 2000 parts of tap waters with stirring for 1 hour, and a dark blue suspension was obtained. The resulting suspension was filtered to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60°C to obtain 11.3 parts of the compound represented by formula (Ab2-1). The yield was 82%.

將式(Ab2-1)所示之化合物0.35g溶解於三氯甲烷而成體積250cm³，再將其中的2cm³以離子交換水稀釋而成體積100cm³(濃度為0.028g/L)，使用分光光度計(石英管、光程長；1cm)來測定吸收光譜。此化合物係在極大吸收波長λ max=628nm顯示吸光度2.9(任意單位)。 0.35g compound of formula (Ab2-1) dissolved in chloroform from FIG volume 250cm ^3, then 2cm ³ wherein the ion-exchanged water diluting volume 100cm ³ (at a concentration of 0.028g / L), using Spectrophotometer (quartz tube, optical path length; 1cm) to measure the absorption spectrum. This compound shows an absorbance of 2.9 (arbitrary units) at the maximum absorption wavelength λ max = 628 nm.

[合成例2] [Synthesis Example 2]

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入硫氰酸鉀11份及丙酮39.4份後，於室溫下攪拌30分鐘。其次，以10分鐘滴下苯甲醯氯13份。滴下結束後，再於室溫下攪拌2小時。其次，使反應溶液冰冷後，滴下二(2-乙基己基)胺23份。滴下結束後，再於室溫下攪拌30分鐘。其次，使反應溶液冰冷後，滴下30%氫氧化鈉水溶液30份。滴下結束後，再於室溫下攪拌30分鐘。其次，於室溫下滴下氯乙酸9.2份。滴下結束後，在加熱回流下攪拌7小時。其次，將反應溶液放冷至室溫後，將反應溶液注入於自來水13份中後，加入乙酸乙酯26份並攪拌30分鐘。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將有機層以1當量的鹽酸13份來進行洗淨，接著以自來水13份來進行洗淨，最後以飽和食鹽水13份來進行洗淨。於有機層加入適當量的芒硝並攪拌30分鐘後，進行過濾而得到去除水分的有機層。將所得之有機層以蒸發器餾除溶劑，得到淡黃色液體。再將淡黃色液體在減壓下以60℃乾燥，得到式 (B-I-2)所示之化合物14份。產率為48%。 The following reaction is carried out under a nitrogen atmosphere. After adding 11 parts of potassium thiocyanate and 39.4 parts of acetone to the flask equipped with a cooling tube and a stirring device, it stirred at room temperature for 30 minutes. Next, 13 parts of benzyl chloride were dropped in 10 minutes. After the dropping, the mixture was stirred at room temperature for 2 hours. Next, after cooling the reaction solution in ice, 23 parts of bis(2-ethylhexyl)amine was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. Next, after ice-cooling the reaction solution, 30 parts of 30% sodium hydroxide aqueous solution was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. Next, 9.2 parts of chloroacetic acid was dropped at room temperature. After the dropping, the mixture was stirred under heating and reflux for 7 hours. Next, after cooling the reaction solution to room temperature, after pouring the reaction solution into 13 parts of tap water, 26 parts of ethyl acetate was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 13 equivalents of hydrochloric acid, followed by 13 parts of tap water, and finally 13 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which moisture was removed. The obtained organic layer was distilled off with an evaporator to obtain a pale yellow liquid. The light yellow liquid was dried under reduced pressure at 60°C to obtain the formula 14 parts of the compound shown by (B-I-2). The yield is 48%.

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入正戊醇1000份、3-胺基巴豆腈133份及N-胺基乙醯基-N’-(2-乙基己醯基)肼250份後，在加熱回流下攪拌2小時。其次，加入氯化鋅166.4份後，再於加熱回流下攪拌4小時。其次，滴下濃鹽酸225份。滴下結束後，一同餾除正戊醇與水蒸氣。將殘留的懸浮液予以抽氣過濾，再將殘留物以水來進行洗淨，得到淡黃色固體。再將淡黃色固體在減壓下以60℃乾燥，得到式(C-II-1)所示之化合物215份。產率為71%。 The following reaction is carried out under a nitrogen atmosphere. After putting 1000 parts of n-amyl alcohol, 133 parts of 3-aminocrotononitrile and 250 parts of N-aminoethyl acetyl-N'-(2-ethylhexyl) hydrazine in a flask equipped with a cooling tube and a stirring device, Stir for 2 hours with heating under reflux. Next, after adding 166.4 parts of zinc chloride, it was stirred under heating and reflux for 4 hours. Next, drop 225 parts of concentrated hydrochloric acid. After the dropping, n-pentanol and water vapor were distilled together. The remaining suspension was suction filtered, and the residue was washed with water to obtain a pale yellow solid. The light yellow solid was dried under reduced pressure at 60°C to obtain 215 parts of the compound represented by formula (C-II-1). The yield was 71%.

以下的反應係在氮氣環境下進行。於具備 冷卻管及攪拌裝置的燒瓶投入式(C-II-1)所示之化合物120份、冰醋酸1200份及濃鹽酸1200份後，於室溫下攪拌30分鐘。其次，使反應溶液冰冷後，加入23%亞硝酸鈉水溶液28.5份並攪拌3小時，得到紅褐色懸浮液。將所得之紅褐色懸浮液予以抽氣過濾後，將殘留物以水來進行洗淨，得到紅褐色固體。再將紅褐色固體在減壓下以60℃乾燥，得到式(C-I-1)所示之化合物120份。產率為90%。 The following reaction is carried out under a nitrogen atmosphere. Yu You After 120 parts of the compound represented by the formula (C-II-1), 1200 parts of glacial acetic acid, and 1200 parts of concentrated hydrochloric acid were put into the flask of the cooling tube and the stirring device, the mixture was stirred at room temperature for 30 minutes. Next, after ice-cooling the reaction solution, 28.5 parts of 23% sodium nitrite aqueous solution was added and stirred for 3 hours to obtain a reddish brown suspension. After the resulting red-brown suspension was suction filtered, the residue was washed with water to obtain a red-brown solid. The reddish brown solid was dried under reduced pressure at 60°C to obtain 120 parts of the compound represented by formula (C-I-1). The yield is 90%.

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入濃鹽酸2份、乙酸7份及式(C-I-1)所示之化合物1.5份並於室溫攪拌30分鐘。其次，於反應溶液加入式(B-I-2)所示之化合物1.6份及水0.5份後、於室溫攪拌30分鐘。其次，於反應溶液加入磺醯胺0.05份後，於室溫攪拌20分鐘。其次，於反應溶液加入30%氫氧化鈉水溶液7份後，於60℃攪拌4小時。其次，將反應溶液放冷至室溫後，將反應溶液注入於自來水15份中後，加入乙酸乙酯15份並攪拌30分鐘。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將所得之有機層以蒸發器餾除溶劑，得到藍綠色 固體。再將藍綠色固體以管柱層析法進行精製，得到式(Ac1-7)所示之化合物1.2份。產率為36%。 The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 2 parts of concentrated hydrochloric acid, 7 parts of acetic acid, and 1.5 parts of the compound represented by formula (C-I-1) were put in and stirred at room temperature for 30 minutes. Next, after adding 1.6 parts of the compound represented by formula (B-I-2) and 0.5 part of water to the reaction solution, the mixture was stirred at room temperature for 30 minutes. Next, after adding 0.05 part of sulfonamide to the reaction solution, it was stirred at room temperature for 20 minutes. Next, after adding 7 parts of 30% sodium hydroxide aqueous solution to the reaction solution, it was stirred at 60°C for 4 hours. Next, after cooling the reaction solution to room temperature, the reaction solution was poured into 15 parts of tap water, then 15 parts of ethyl acetate was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After discarding the water layer by liquid separation operation, the resulting organic layer was distilled off the solvent with an evaporator to obtain a blue-green color solid. The blue-green solid was purified by column chromatography to obtain 1.2 parts of the compound represented by formula (Ac1-7). The yield was 36%.

將式(Ac1-7)所示之化合物0.35g溶解於三氯甲烷而成體積250cm³，再將其中的2cm³以離子交換水稀釋而成體積100cm³(濃度為0.028g/L)，使用分光光度計(石英管、光程長；1cm)來測定吸收光譜。此化合物係在λ max=621nm顯示吸光度2.6(任意單位)。 Dissolve 0.35g of the compound represented by formula (Ac1-7) in chloroform to make a volume of 250cm ³ , and then dilute 2cm ^{3 of it} with ion exchanged water to make a volume of 100cm ³ (concentration 0.028g/L), use Spectrophotometer (quartz tube, optical path length; 1cm) to measure the absorption spectrum. This compound showed an absorbance of 2.6 (arbitrary units) at λ max = 621 nm.

式(Ac1-7)所示之化合物的鑑定 Identification of the compound represented by formula (Ac1-7)

(質量分析)離子化模式=ESI+：m/z=684.4[M+H]⁺精確質量：683.4 (Mass analysis) ionization mode=ESI+: m/z=684.4[M+H] ⁺ accurate mass: 683.4

[合成例3] [Synthesis Example 3]

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入2-溴-3’-硝基苯乙酮(東京化成股份有限公司製)5份及50%異丙醇水溶液50份後，於室溫下攪拌30分鐘。其次，以10分鐘添加硫氰酸鉀3份。滴下結束 後，再於室溫下攪拌3小時。其次，滴下自來水50份。滴下結束後，再於室溫下攪拌30分鐘。將析出的黃色固體濾出後，將所得之黃色固體以管柱層析法進行精製。將精製過的黃色固體在減壓下以60℃乾燥，得到式(B-II-21)所示之化合物4.2份。產率為92%。 The following reaction is carried out under a nitrogen atmosphere. Put 5 parts of 2-bromo-3'-nitroacetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 parts of 50% isopropyl alcohol aqueous solution into a flask equipped with a cooling tube and a stirring device, and stir at room temperature for 30 minutes . Next, 3 parts of potassium thiocyanate was added in 10 minutes. Dripping end After that, it was stirred at room temperature for 3 hours. Next, drop 50 parts of tap water. After the dropping, the mixture was stirred at room temperature for 30 minutes. After filtering out the precipitated yellow solid, the obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60°C to obtain 4.2 parts of the compound represented by formula (B-II-21). The yield was 92%.

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入式(B-II-13)所示之化合物5份及乙醇50份後，於室溫下攪拌30分鐘。其次，以10分鐘分別滴下哌啶(東京化成股份有限公司製)2.9份及冰醋酸1.4份。滴下結束後，再於加熱回流下攪拌2小時。將反應溶液放冷至室溫後，滴下自來水70份。滴下結束後，再於室溫下攪拌30分鐘。將析出的黃色固體濾出後，將所得之黃色固體以管柱層析法進行精製。將精製過的黃色固體在減壓下以60℃乾燥，得到式(B-I-21)所示之化合物4.2份。產率為64%。 The following reaction is carried out under a nitrogen atmosphere. After putting 5 parts of the compound represented by formula (B-II-13) and 50 parts of ethanol into a flask equipped with a cooling tube and a stirring device, it was stirred at room temperature for 30 minutes. Next, 2.9 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.4 parts of glacial acetic acid were dropped over 10 minutes. After the dropping, the mixture was stirred under heating and refluxing for 2 hours. After the reaction solution was cooled to room temperature, 70 parts of tap water was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. After filtering out the precipitated yellow solid, the obtained yellow solid was purified by column chromatography. The purified yellow solid was dried under reduced pressure at 60°C to obtain 4.2 parts of the compound represented by formula (B-I-21). The yield was 64%.

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入式(B-I-21)所示之化合物10.4份、4,4’-雙(二乙基胺基)二苯基甲酮(東京化成股份有限公司製)10份及甲苯20.0份後，其次，加入***14.8份並在95至100℃攪拌3小時。其次，使反應混合物冷卻至室溫後，以異丙醇170份稀釋。其次，將稀釋過的反應溶液注入飽和食鹽水300份中後，加入甲苯100份並攪拌30分鐘。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將有機層以飽和食鹽水300份來進行洗淨。於有機層加入適當量的芒硝並攪拌30分鐘後，進行過濾而得到去除水分的有機層。將所得之有機層以蒸發器餾除溶劑，得到藍紫色固體。將所得之藍紫色固體以管柱層析法進行精製。將精製過的藍紫色固體在減壓下以60℃乾燥。得到式(A-II-21)所示之化合物10.2份。產率為52%。 The following reaction is carried out under a nitrogen atmosphere. Put 10.4 parts of the compound represented by formula (BI-21), 4,4'-bis(diethylamino)diphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) in a flask equipped with a cooling tube and a stirring device 10 After 1 part and 20.0 parts of toluene, next, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. Next, after the diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which moisture was removed. The resulting organic layer was distilled off with an evaporator to obtain a blue-purple solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried at 60°C under reduced pressure. 10.2 parts of the compound represented by formula (A-II-21) was obtained. The yield is 52%.

式(A-II-21)所示之化合物的鑑定 Identification of the compound represented by formula (A-II-21)

(質量分析)離子化模式=ESI+：m/z=596.3[M-Cl]⁺精確質量：631.3 (Mass analysis) ionization mode=ESI+: m/z=596.3[M-Cl] ⁺ accurate mass: 631.3

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入式(A-II-21)所示之化合物10份、雙(三氟甲磺醯基)醯亞胺鋰(東京化成股份有限公司製)5.9份及N,N-二甲基甲醯胺30份後，在40℃攪拌3小時。其次，使反應混合物冷卻至室溫後，一邊攪拌1小時一邊進行滴下至自來水500份中，得到深藍色懸浮液。將所得之懸浮液予以過濾，得到藍綠色固體。再將藍綠色固體在減壓下以60℃乾燥，得到式(Ab2-21)所示之化合物11.5份。產率為83%。 The following reaction is carried out under a nitrogen atmosphere. Put 10 parts of the compound represented by formula (A-II-21), bis (trifluoromethanesulfonyl) lithium imide (made by Tokyo Chemical Industry Co., Ltd.) 5.9 parts and N in a flask equipped with a cooling tube and a stirring device After 30 parts of N-dimethylformamide, it was stirred at 40°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was dripped into 500 parts of tap waters, stirring for 1 hour, and the dark blue suspension was obtained. The resulting suspension was filtered to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60°C to obtain 11.5 parts of the compound represented by formula (Ab2-21). The yield was 83%.

將式(Ab2-21)所示之化合物0.35g溶解於三氯甲烷而成體積250cm³，再將其中的2cm³以離子交換水稀釋而成體積100cm³(濃度為0.028g/L)，使用分光光度計(石英管、光程長；1cm)來測定吸收光譜。此化合物係在λ max=634nm顯示吸光度3.0(任意單位)。 0.35g compound of formula (Ab2-21) dissolved in chloroform from FIG volume 250cm ^3, then 2cm ³ wherein the ion-exchanged water diluting volume 100cm ³ (at a concentration of 0.028g / L), using Spectrophotometer (quartz tube, optical path length; 1cm) to measure the absorption spectrum. This compound showed an absorbance of 3.0 (arbitrary unit) at λ max = 634 nm.

[合成例4] [Synthesis Example 4]

以下的反應係在氮氣環境下進行。於具備冷卻管及攪拌裝置的燒瓶投入硫氰酸鉀33份及丙酮160份後，在室溫 下攪拌30分鐘。其次，以10分鐘滴下2-甲基苯甲醯氯(東京化成股份有限公司製)50份。滴下結束後，再於室溫下攪拌2小時。其次，使反應混合物冰冷後，滴下N-乙基-鄰甲苯胺(東京化成股份有限公司製)41.6份。滴下結束後，再於室溫下攪拌30分鐘。其次，使反應混合物冰冷後，滴下30%氫氧化鈉水溶液34.2份。滴下結束後，再於室溫下攪拌30分鐘。其次，在室溫下滴下氯乙酸32.1份。滴下結束後，在加熱回流下攪拌7小時。其次，將反應混合物放冷至室溫後，將反應溶液注入於自來水120份中後，加入甲苯200份並攪拌30分鐘。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將有機層以1當量的鹽酸200份來進行洗淨，接著以自來水200份來進行洗淨，最後以飽和食鹽水200份來進行洗淨。於有機層加入適當量的芒硝並攪拌30分鐘後，進行過濾而得到去除水分的有機層。將所得之有機層以蒸發器餾除溶劑，得到淡黃色液體。將所得之淡黃色液體以管柱層析法進行精製。將精製過的淡黃色液體在減壓下以60℃乾燥，得到式(B-I-9)所示之化合物40.5份。產率為41%。 The following reaction is carried out under a nitrogen atmosphere. After adding 33 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a cooling tube and a stirring device, at room temperature Stir for 30 minutes. Next, 50 parts of 2-methylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 10 minutes. After the dropping, the mixture was stirred at room temperature for 2 hours. Next, after cooling the reaction mixture in ice, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. Next, after ice-cooling the reaction mixture, 34.2 parts of a 30% sodium hydroxide aqueous solution was dropped. After the dropping, the mixture was stirred at room temperature for 30 minutes. Next, 32.1 parts of chloroacetic acid was dropped at room temperature. After the dropping, the mixture was stirred under heating and reflux for 7 hours. Next, after cooling the reaction mixture to room temperature, the reaction solution was poured into 120 parts of tap water, then 200 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 200 parts of 1 equivalent of hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which moisture was removed. The obtained organic layer was distilled off with an evaporator to obtain a pale yellow liquid. The resulting light yellow liquid was purified by column chromatography. The purified light yellow liquid was dried at 60° C. under reduced pressure to obtain 40.5 parts of the compound represented by formula (B-I-9). The yield was 41%.

以下的反應係在氮氣環境下進行。於具備 冷卻管及攪拌裝置的燒瓶投入式(B-I-9)所示之化合物9.7份、4,4’-雙(二乙基胺)二苯基甲酮(東京化成股份有限公司製)10份及甲苯20份後，其次，加入***14.8份並在95至100℃攪拌3小時。其次，使反應混合物冷卻至室溫後，以異丙醇170份進行稀釋。其次，將稀釋過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。接著停止攪拌，靜置30分鐘後分離為有機層與水層。以分液操作棄除水層後，將有機層以飽和食鹽水300份來進行洗淨。於有機層加入適當量的芒硝並攪拌30分鐘後，進行過濾而得到去除水分的有機層。將所得之有機層以蒸發器餾除溶劑，得到藍紫色固體。將所得之藍紫色固體以管柱層析法進行精製。將精製過的藍紫色固體在減壓下以60℃乾燥，得到式(A-II-9)所示之化合物15.1份。產率為75%。 The following reaction is carried out under a nitrogen atmosphere. Yu You The cooling tube and the flask of the stirring device were charged with 9.7 parts of the compound represented by formula (BI-9), 10 parts of 4,4'-bis(diethylamine)diphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene After 20 parts, next, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. Next, after the diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which moisture was removed. The resulting organic layer was distilled off with an evaporator to obtain a blue-purple solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 15.1 parts of the compound represented by formula (A-II-9). The yield is 75%.

式(A-II-9)所示之化合物的鑑定 Identification of the compound represented by formula (A-II-9)

(質量分析)離子化模式=ESI+：m/z=615.4[M-Cl]⁺精確質量：650.3 (Mass analysis) ionization mode=ESI+: m/z=615.4[M-Cl] ⁺ accurate mass: 650.3

以下的反應係在氮氣環境下進行。於具備 冷卻管及攪拌裝置的燒瓶投入式(A-II-9)所示之化合物10份、雙(三氟甲磺醯基)醯亞胺鋰(東京化成股份有限公司製)5.7份及N,N-二甲基甲醯胺30份後，在40℃攪拌3小時。其次，使反應混合物冷卻至室溫後，一邊攪拌1小時一邊進行滴下至自來水500份中，得到深藍色懸浮液。將所得之懸浮液予以過濾，得到藍綠色固體。再將藍綠色固體在減壓下以60℃乾燥，得到式(Ab2-9)所示之化合物13.2份。產率為96%。 The following reaction is carried out under a nitrogen atmosphere. Yu You The cooling tube and the flask of the stirring device were charged with 10 parts of the compound represented by formula (A-II-9), 5.7 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and N,N -After 30 parts of dimethylformamide, it was stirred at 40°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was dripped into 500 parts of tap waters, stirring for 1 hour, and the dark blue suspension was obtained. The resulting suspension was filtered to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60°C to obtain 13.2 parts of the compound represented by formula (Ab2-9). The yield was 96%.

將式(Ab2-9)所示之化合物0.35g溶解於三氯甲烷而成體積250cm³，再將其中的2cm³以離子交換水進行稀釋而成體積100cm³(濃度為0.028g/L)，使用分光光度計(石英管、光程長；1cm)來測定吸收光譜。此化合物係在λ max=627nm顯示吸光度2.7(任意單位)。 0.35g compound of formula (Ab2-9) dissolved in chloroform from FIG volume 250cm ^3, then 2cm ³ wherein the ion-exchanged water for diluting the volume of 100cm ³ (at a concentration of 0.028g / L), A spectrophotometer (quartz tube, optical path length; 1 cm) was used to measure the absorption spectrum. This compound showed an absorbance of 2.7 (arbitrary units) at λ max = 627 nm.

[合成例5] [Synthesis Example 5]

將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製)10份、4-(二乙基胺基)水楊醛(東京化成工業股份有限公 司製)12.8份、苯甲酸(東京化成工業股份有限公司製)2.73份、1-戊醇(東京化成工業股份有限公司製)157份及氰基乙酸乙酯(東京化成工業股份有限公司製)7.43份予以混合，在120℃攪伴3小時。加入氰基乙酸乙酯(東京化成工業股份有限公司製)7.46份、苯甲酸(東京化成工業股份有限公司製)2.79份、1-戊醇(東京化成工業股份有限公司製)49.8份及4-(二乙基胺基)水楊醛(東京化成工業股份有限公司製)12.7份，在120℃攪伴14小時。加入氰基乙酸乙酯(東京化成工業股份有限公司製)3.76份、苯甲酸(東京化成工業股份有限公司製)1.41份、1-戊醇(東京化成工業股份有限公司製)52.5份及4-(二乙基胺基)水楊醛(東京化成工業股份有限公司製)6.35份，在120℃攪伴8小時。使上述的反應液冷卻至室溫後，抽氣過濾而得到為殘留物之析出的結晶。於該殘留物加入四氫呋喃140份，在70℃攪拌1小時後，抽氣過濾而得到為殘留物之不溶物。於該殘留物加入四氫呋喃120份，在70℃攪拌1小時後，抽氣過濾而得到為殘留物之不溶物。於該殘留物加入N,N-二甲基甲醯胺340份，加熱至90℃而使之溶解後，靜置在0℃至5℃。抽氣過濾而得到為殘留物析出的結晶。將該殘留物在60℃減壓乾燥，得到式(Ad1-1)所示之化合物5.69份。以¹H-NMR確認結構。 10 parts of 4-amino-3-hydroxybenzoic acid (made by Tokyo Chemical Industry Co., Ltd.), 12.8 parts of 4-(diethylamino) salicylaldehyde (made by Tokyo Chemical Industry Co., Ltd.), benzoic acid ( Tokyo Chemical Industry Co., Ltd.) 2.73 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 157 parts and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 7.43 parts were mixed, and stirred at 120 ℃ With 3 hours. Add ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 7.46 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 2.79 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 49.8 parts and 4- 12.7 parts of (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120°C for 14 hours. Add ethyl cyanoacetate (made by Tokyo Chemical Industry Co., Ltd.) 3.76 parts, benzoic acid (made by Tokyo Chemical Industry Co., Ltd.) 1.41 parts, 1-pentanol (made by Tokyo Chemical Industry Co., Ltd.) 52.5 parts and 4- (Diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.35 parts, and stirred at 120°C for 8 hours. After cooling the above reaction liquid to room temperature, suction filtration was performed to obtain crystals precipitated as residues. 140 parts of tetrahydrofuran was added to the residue, and after stirring at 70°C for 1 hour, suction filtration was performed to obtain an insoluble substance as a residue. 120 parts of tetrahydrofuran was added to the residue, and after stirring at 70°C for 1 hour, suction filtration was performed to obtain an insoluble substance as a residue. To this residue, 340 parts of N,N-dimethylformamide was added, heated to 90°C to dissolve it, and allowed to stand at 0°C to 5°C. Suction filtration was performed to obtain crystals precipitated as residues. The residue was dried under reduced pressure at 60°C to obtain 5.69 parts of the compound represented by formula (Ad1-1). The structure was confirmed by ¹ H-NMR.

<式(Ad1-1)所示之化合物的鑑定> <Identification of compound represented by formula (Ad1-1)>

¹H-NMR(500MHz,DMSO-d6)：1.14(6H,t),3.47(4H,q),6.57(1H,d),6.78(1H,dd),7.68(1H,d),7.79(1H,d),7.96(1H,dd),8.15(1H,d),8.80(1H,s),13.11(1H,s). ¹ H-NMR (500MHz, DMSO-d6): 1.14 (6H, t), 3.47 (4H, q), 6.57 (1H, d), 6.78 (1H, dd), 7.68 (1H, d), 7.79 (1H , d), 7.96 (1H, dd), 8.15 (1H, d), 8.80 (1H, s), 13.11 (1H, s).

[合成例6] [Synthesis Example 6]

將間苯二酚(東京化成工業股份有限公司製)275份與正己胺(東京化成工業股份有限公司製)101份予以混合，一邊將生成的水去除一邊在150至155℃攪拌20小時。放冷後，將反應混合物溶解於甲苯433份，將此甲苯溶液以40℃的溫水1000份進行洗淨3次。於此甲苯溶液加入無水硫酸鎂50份並進行攪拌後，過濾之。將濾液的溶劑餾除而得到粗生成物。將該粗生成物溶解於甲苯234份，在0℃以下進行攪拌，藉由將晶析物過濾來回收。將該晶析物在50℃減壓乾燥，得到式(pt1)所示之化合物95.7份。 275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and stirred at 150 to 155°C for 20 hours while removing the generated water. After cooling, the reaction mixture was dissolved in 433 parts of toluene, and this toluene solution was washed three times with 1000 parts of warm water at 40°C. After adding 50 parts of anhydrous magnesium sulfate to this toluene solution and stirring it, it was filtered. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene, stirred at 0° C. or lower, and recovered by filtering the crystals. The crystals were dried under reduced pressure at 50°C to obtain 95.7 parts of the compound represented by formula (pt1).

<式(pt1)所示之化合物的鑑定> <Identification of compound represented by formula (pt1)>

(質量分析)離子化模式=ESI+：m/z=[M+H]⁺ 194.2精確質量：193.2 (Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 194.2 accurate mass: 193.2

將式(pt1)所示之化合物95.3份與水48.0份予以混合，在80℃進行攪拌。接著，一邊加入1-溴-2-乙基己烷(東京化成工業股份有限公司製)107份，一邊在80℃攪拌3小時後，加入48%氫氧化鈉水溶液22.4份。將此混合物在110℃攪拌18小時。放冷後，將反應混合物使用10%氫氧化鈉水溶液調整pH至5，加入甲苯130份並進行攪拌，萃取甲苯層。將甲苯萃取液以溫水500份進行洗淨2次，加入無水硫酸鎂25份並進行攪拌，過濾之。將濾液的溶劑予以餾除，得到含有以式(pt2)所示之化合物為主成分之殘留物154份。 95.3 parts of the compound represented by formula (pt1) and 48.0 parts of water were mixed, and it stirred at 80 degreeC. Next, while adding 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirring at 80°C for 3 hours, 22.4 parts of a 48% sodium hydroxide aqueous solution was added. The mixture was stirred at 110°C for 18 hours. After cooling, the reaction mixture was adjusted to pH 5 using 10% aqueous sodium hydroxide solution, 130 parts of toluene was added and stirred, and the toluene layer was extracted. The toluene extract was washed twice with 500 parts of warm water, 25 parts of anhydrous magnesium sulfate was added and stirred, and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing the compound represented by formula (pt2) as a main component.

<式(pt2)所示之化合物的鑑定> <Identification of the compound represented by formula (pt2)>

(質量分析)離子化模式=ESI+：m/z=[M+H]⁺ 306.3精確質量：305.3 (Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 306.3 accurate mass: 305.3

將含有所得到之式(pt2)所示之化合物作為主成分之殘留物154份與N,N-二甲基甲醯胺597份予以混合，在-6℃至3℃進行攪拌。對該混合物，一邊將液溫維 持在-6℃至3℃，一邊加入***(和光純藥工業股份有限公司製)258份。將此混合物在室溫攪拌1小時後，在60℃攪拌4小時。放冷後，將反應混合物加入於冰水1500份，使用48%氫氧化鈉水溶液進行中和。對於此加入甲苯867份，萃取甲苯層。將此甲苯萃取液以15%氯化鈉水溶液1200份進行洗淨2次。於此甲苯萃取液加入無水硫酸鎂60份並進行攪拌後，過濾之。將濾液的溶劑餾除而得到殘留物。將該殘留物以管柱層析法進行精製，得到式(pt3)所示之化合物94.4份。 154 parts of the residue containing the obtained compound represented by formula (pt2) as a main component and 597 parts of N,N-dimethylformamide were mixed and stirred at -6°C to 3°C. For this mixture, While maintaining at -6°C to 3°C, 258 parts of phosphorus oxychloride (made by Wako Pure Chemical Industries, Ltd.) was added. After the mixture was stirred at room temperature for 1 hour, it was stirred at 60°C for 4 hours. After cooling, the reaction mixture was added to 1500 parts of ice water, and neutralized with 48% aqueous sodium hydroxide solution. For this, 867 parts of toluene was added, and the toluene layer was extracted. This toluene extract was washed twice with 1200 parts of 15% sodium chloride aqueous solution. To this toluene extract, 60 parts of anhydrous magnesium sulfate was added and stirred, and then filtered. The solvent of the filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 94.4 parts of the compound represented by formula (pt3).

<式(pt3)所示之化合物的鑑定> <Identification of the compound represented by formula (pt3)>

(質量分析)離子化模式=ESI+：m/z=[M+H]⁺ 334.3精確質量：333.3 (Mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 334.3 accurate mass: 333.3

將雙(3-胺基-4-羥基苯基)碸(東京化成工業股份有限公司製)10.6份、式(pt3)所示之化合物25.3份、苯甲酸(東京化成工業股份有限公司製)3.2份、1-戊醇(東京化成工業股份有限公司製)184份及氰基乙酸乙酯(東京化成工業股份有限公司製)8.59份予以混合，在120℃攪拌3小時。於此反應溶液將式(pt3)所示之化合物25.4份、安息香酸(東京化成工業股份有限公司製)3.21份、1-戊醇(東京 化成工業股份有限公司製)90份及氰基乙酸乙酯(東京化成工業股份有限公司製)8.59份予以混合，在120℃攪拌12小時。使上述的反應液冷卻至室溫後，加入甲醇1800份，抽氣過濾而得到為殘留物之析出的結晶。將該殘留物以管柱層析法進行精製，得到式(Ad2-10)所示之化合物20.6份。以¹H-NMR確認結構。 10.6 parts of bis(3-amino-4-hydroxyphenyl) ash (made by Tokyo Chemical Industry Co., Ltd.), 25.3 parts of the compound represented by formula (pt3), and benzoic acid (made by Tokyo Chemical Industry Co., Ltd.) 3.2 1 part, 184 parts of 1-pentanol (made by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (made by Tokyo Chemical Industry Co., Ltd.) were mixed, and it stirred at 120 degreeC for 3 hours. In this reaction solution, 25.4 parts of the compound represented by formula (pt3), 3.21 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate 8.59 parts of ester (made by Tokyo Chemical Industry Co., Ltd.) were mixed, and it stirred at 120 degreeC for 12 hours. After cooling the above reaction liquid to room temperature, 1800 parts of methanol was added, and suction filtration was performed to obtain crystals precipitated as a residue. The residue was purified by column chromatography to obtain 20.6 parts of the compound represented by formula (Ad2-10). The structure was confirmed by ¹ H-NMR.

<式(Ad2-10)所示之化合物的鑑定> <Identification of the compound represented by formula (Ad2-10)>

¹H-NMR(500MHz,DMSO-d₆)：0.85(6H,t),0.87(6H,t),0.87(6H,t),1.20至1.40(28H),1.56(4H,tt),1.75(2H,ttt),3.34(4H,d),3.43(4H,t),6.55(2H,d),6.79(2H,dd),7.64(2H,d),7.91(2H,d),8.01(2H,dd),8.36(2H,d),8.73(2H,s) ¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.85 (6H, t), 0.87 (6H, t), 0.87 (6H, t), 1.20 to 1.40 (28H), 1.56 (4H, tt), 1.75 ( 2H, ttt), 3.34 (4H, d), 3.43 (4H, t), 6.55 (2H, d), 6.79 (2H, dd), 7.64 (2H, d), 7.91 (2H, d), 8.01 (2H ,dd),8.36(2H,d),8.73(2H,s)

[合成例7] [Synthesis Example 7]

於具備回流冷卻器、滴下漏斗及攪拌機的燒瓶內取代為將流通適量氮氣的氮氣環境，加入丙二醇單甲醚乙酸酯371份，一邊進行攪拌一邊加熱至85℃。其次，將令丙烯酸54份、丙烯酸3,4-環氧基三環[5.2.1.0^2,6]癸烷-8-基酯及丙烯酸3,4-環氧基三環[5.2.1.0^2,6]癸烷-9-基酯之混合物(含量比以莫耳比為50：50)225份、乙烯基甲苯(異構物的混合物)81份溶解於丙二醇單甲醚乙酸酯80份而調製之混合 溶液以4小時滴下於燒瓶內。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, instead of a nitrogen atmosphere in which an appropriate amount of nitrogen flows, 371 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85°C while stirring. Secondly, 54 parts of acrylic acid, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] A mixture of decane-9-yl ester (content ratio is 50:50 in molar ratio) 225 parts, vinyl toluene (mixture of isomers) 81 parts dissolved in 80 parts of propylene glycol monomethyl ether acetate to prepare The mixed solution was dropped into the flask in 4 hours.

另一方面，將令聚合起始劑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份之溶液以5小時進行滴下。起始劑溶液的滴下結束後，維持在85℃ 4小時後，冷卻至室溫，得到共聚物(樹脂Ba)溶液。樹脂Ba溶液的固形成分為37%，以B型黏度計(23℃)所測定之黏度為246mPa．s。樹脂Ba的重量平均分子量為1.06×10⁴，固形成分換算酸價為115mg-KOH/g，分子量分佈為2.01。樹脂Ba係具有以下的結構單元。 On the other hand, a solution in which 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the starter solution was dropped, the temperature was maintained at 85°C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ba) solution. The solid content of the resin Ba solution is 37%, and the viscosity measured by a B-type viscometer (23°C) is 246 mPa. s. The weight average molecular weight of the resin Ba is 1.06×10 ⁴ , the acid value in terms of solid content is 115 mg-KOH/g, and the molecular weight distribution is 2.01. The resin Ba system has the following structural units.

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法並以以下的條件進行。 The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin are measured under the following conditions using the GPC method.

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

管柱；SHIMADZU Shim-pack GPC-80M Column; 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/分鐘 Flow rate; 1.0mL/min

偵測器；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) Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (TOSOH Corporation system)

將上述所得之聚苯乙烯換算重量平均分子量及數量平均分子量之比例(Mw/Mn)作為分子量分佈。 The ratio (Mw/Mn) of the weight-average molecular weight and the number-average molecular weight in terms of polystyrene obtained above was used as the molecular weight distribution.

<顏料分散液的調製> <Preparation of pigment dispersion liquid>

調製例1 Modulation example 1

綠色顏料(A2)：C.I.顏料綠7(顏料；λ max=660nm) 27份、丙烯酸系顏料分散劑 12份、樹脂(B)：甲基丙烯酸/甲基丙烯酸苯甲酯共聚物(共聚合比(質量比)；30/70、Mw；1.2×10⁴)(固形成分換算) 9.5份、以及溶劑(E)：丙二醇單甲醚乙酸酯 180份 Green pigment (A2): CI Pigment Green 7 (pigment; λ max=660 nm) 27 parts, acrylic pigment dispersant 12 parts, resin (B): methacrylic acid/benzyl methacrylate copolymer (copolymerization ratio (Mass ratio); 30/70, Mw; 1.2×10 ⁴ ) (solid content conversion) 9.5 parts, and solvent (E): 180 parts of propylene glycol monomethyl ether acetate

將上述成分予以混合，並使用珠磨機使顏料充分地分散，藉此調製顏料分散液1。 The above components are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby preparing pigment dispersion liquid 1.

調製例2 Modulation example 2

除了以C.I.顏料綠7(顏料)取代C.I.顏料綠58(顏料；λ max=675nm)以外，其餘則進行與調製例1相同的操作來調製顏料分散液2。 Except that C.I. Pigment Green 7 (pigment) was substituted for C.I. Pigment Green 58 (pigment; λ max=675 nm), the same operation as in Preparation Example 1 was carried out to prepare Pigment Dispersion Liquid 2.

實施例1至8及比較例1至2 Examples 1 to 8 and Comparative Examples 1 to 2

<著色硬化性樹脂組成物的調製> <Preparation of colored curable resin composition>

混合表2的各成分而得到綠色著色硬化性樹脂組成物。表2中，樹脂的份數係表示固形成分換算值。 The components of Table 2 were mixed to obtain a green colored curable resin composition. In Table 2, the part number system of the resin represents the converted value of the solid content.

<藍色染料(A1)> <Blue dye (A1)>

Aa；式(Ab2-1)所示之化合物(λ max=628nm) Aa; compound represented by formula (Ab2-1) (λ max = 628 nm)

Ab；式(Ac1-7)所示之化合物(λ max=621nm) Ab; compound represented by formula (Ac1-7) (λ max=621 nm)

Ac；式(Ab2-21)所示之化合物(λ max=634nm) Ac; compound represented by formula (Ab2-21) (λ max = 634 nm)

Ad；式(Ab2-9)所示之化合物(λ max=627nm) Ad; compound represented by formula (Ab2-9) (λ max=627 nm)

Ae；C.I.酸性藍1(λ max=639nm) Ae; C.I. Acid Blue 1 (λ max=639nm)

Af；式(Ad1-1)所示之化合物(λ max=453nm) Af; compound represented by formula (Ad1-1) (λ max=453 nm)

Ag；式(Ad2-10)所示之化合物(λ max=455nm) Ag; compound represented by formula (Ad2-10) (λ max=455nm)

<樹脂(B)> <Resin (B)>

Ba；樹脂Ba Ba; resin Ba

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

二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥股份有限公司製) Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

<聚合起始劑(D)> <polymerization initiator (D)>

N-苯甲基氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺(IRGACURE(註冊商標)OXE-01；BASF公司製；O-醯基肟化合物) N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE-01; manufactured by BASF; O-acyl Oxime compound)

<溶劑(E)> <Solvent (E)>

Ea；丙二醇單甲醚乙酸酯 Ea; propylene glycol monomethyl ether acetate

Eb；乳酸乙酯 Eb; ethyl lactate

Ec；4-羥基-4-甲基-2-戊酮 Ec; 4-hydroxy-4-methyl-2-pentanone

<調平劑(F)> <Leveling agent (F)>

聚醚改質聚矽氧油(Toray Silicone SH8400；Dow Corning Toray股份有限公司製) Polyether modified polysiloxane oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

<著色圖案的製作> <Creation of coloring pattern>

於5cm見方的玻璃基板(Eagle 2000；康寧公司製)上，將著色硬化性樹脂組成物以旋轉塗佈法予以塗佈後，在100℃預烤3分鐘而形成著色組成物層。放冷後，將形成有著色組成物層的基板與石英玻璃製的光罩之間隔設為100μm，並使用曝光機(TME-150RSK；TOPCON股份有限 公司製)在大氣壓下以光量(365nm基準)進行光照射。光罩係使用形成有100μm線寬/線距圖案(line & space pattern)者。將光照射後的著色組成物層於含有非離子系界面活性劑0.12%與氫氧化鉀0.04%之水系顯影液在24℃浸漬顯影60秒，進行水洗後，在烤爐中，於210℃進行後烤30分鐘。 On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), the colored curable resin composition was applied by a spin coating method, and prebaked at 100° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the reticle made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; TOPCON Co., Ltd. was used Co., Ltd.) Irradiation of light at atmospheric pressure with a light quantity (365 nm reference). For the photomask system, a line width/line pattern of 100 μm is used. The coloring composition layer after light irradiation was immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, washed with water, and then carried out in an oven at 210°C After baking for 30 minutes.

由實施例1至8及比較例1的著色硬化性樹脂組成物得到著色圖案。在比較例2的著色硬化性樹脂組成物中，藉由顯影之著色組成物層未曝光部分之去除並未充分地進行，而未得到著色圖案。表3中之圖案形成欄中，有得到著色圖案時記錄為○，未得到時則記錄為×。 The colored patterns were obtained from the coloring curable resin compositions of Examples 1 to 8 and Comparative Example 1. In the coloring curable resin composition of Comparative Example 2, removal of the unexposed portion of the coloring composition layer by development was not sufficiently performed, and a colored pattern was not obtained. In the pattern formation column in Table 3, when a colored pattern is obtained, it is recorded as ○, and when it is not obtained, it is recorded as ×.

<膜厚測定> <Measurement of film thickness>

對於所得之著色圖案係使用膜厚測定裝置(DEKTAK3；日本真空技術股份有限公司製))來測定膜厚。 For the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.).

<色度評估> <colorimetric evaluation>

對於所得之著色圖案係使用測色機(OSP-SP-200；Olympus股份有限公司製)來測定分光，並使用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值愈大則表示亮度愈高。結果顯示於表3。 For the obtained coloring pattern, a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectrophotometry, and the characteristic function of the C light source was used to determine the xy chromaticity coordinates (x , Y) and tristimulus value Y. The larger the Y value, the higher the brightness. The results are shown in Table 3.

(產業上之可利用性) (Industry availability)

若依據本發明之著色硬化性樹脂組成物，可製造亮度優異的濾色器。 According to the coloring curable resin composition of the present invention, a color filter with excellent brightness can be manufactured.

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；該著色劑含有：選自由黃色染料及黃色顏料所組成群組之至少一種、藍色染料及綠色顏料；相對於固形分的總量，著色劑為5至65質量%，樹脂為7至65質量%，聚合性化合物為7至65質量%；相對於樹脂及聚合性化合物的合計量100質量份，聚合起始劑為0.1至30質量份；其中，藍色染料為選自由式(Ab1)所示之化合物、次甲基染料及次甲基偶氮染料所組成群組之至少一種染料，

式(Ab1)中，R^1A至R^8A係分別獨立地表示氫原子、鹵原子、硝基、羥基、碳數1至20之烷基(於構成該烷基的碳原子之間可***氧原子)；R^4A與R^5A可彼此鍵結而形成-NH-、-S-或-SO₂-；R^9A至R^12A係分別獨立地表示可被胺基或鹵原子取 代之碳數1至20之烷基(於構成該烷基的碳原子之間可***氧原子)、可被取代之芳烷基、可被取代之芳基或氫原子；R^9A與R^10A係鍵結而可與該等所鍵結的氮原子一同形成環，R^11A與R^12A係鍵結而可與該等所鍵結的氮原子一同形成環；A表示可被取代之芳香族雜環基；G^g-表示相對陰離子；g表示0或任意的自然數；當g為0時，表示不具有相對陰離子。 A coloring hardenable resin composition comprising: a colorant, a resin, a polymerizable compound and a polymerization initiator; the colorant contains: at least one selected from the group consisting of yellow dyes and yellow pigments, blue dyes and Green pigment; relative to the total solid content, the colorant is 5 to 65% by mass, the resin is 7 to 65% by mass, the polymerizable compound is 7 to 65% by mass; relative to the total amount of resin and polymerizable compound is 100% Parts, the polymerization initiator is 0.1 to 30 parts by mass; wherein the blue dye is at least one dye selected from the group consisting of a compound represented by formula (Ab1), a methine dye, and a methine azo dye,

In formula (Ab1), R ^1A to R ^8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and a C 1-20 alkyl group (an oxygen atom may be inserted between carbon atoms constituting the alkyl group) ); R ^4A and R ^5A can be bonded to each other to form -NH-, -S- or -SO ₂ -; R ^9A to R ^12A independently represent the number of carbons 1 to 20 that can be substituted by an amine group or a halogen atom An alkyl group (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), an aralkyl group which may be substituted, an aryl group which may be substituted, or a hydrogen atom; R ^9A and R ^10A are bonded to The nitrogen atoms to be bonded together form a ring, R ^11A and R ^12A are bonded to form a ring with the nitrogen atoms to be bonded together; A represents an aromatic heterocyclic group which may be substituted; G ^g- represents Relative anion; g means 0 or any natural number; when g is 0, it means there is no relative anion. 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，相對於著色劑的合計含量，藍色染料的含有率為0.1質量%以上、20質量%以下。 The coloring curable resin composition as described in item 1 of the patent application, wherein the content of the blue dye is 0.1% by mass or more and 20% by mass or less relative to the total content of the colorant. 如申請專利範圍第1項或第2項所述之著色硬化性樹脂組成物，其中，聚合起始劑含有O-醯基肟化合物。 The color-curing resin composition as described in item 1 or item 2 of the patent application scope, wherein the polymerization initiator contains an O-acyl oxime compound. 一種濾色器，其係由申請專利範圍第1項或第2項所述之著色硬化性樹脂組成物所形成。 A color filter formed of the color-curing resin composition described in item 1 or 2 of the patent application. 一種顯示裝置，其係含有申請專利範圍第4項所述之濾色器。 A display device containing the color filter described in item 4 of the patent application.