TWI766152B

TWI766152B - Colored curable resin composition, color filter, and display device

Info

Publication number: TWI766152B
Application number: TW108108812A
Authority: TW
Inventors: 中山智博; 髙石悠
Original assignee: 南韓商東友精細化工有限公司
Priority date: 2018-03-19
Filing date: 2019-03-15
Publication date: 2022-06-01
Also published as: JP7063663B2; KR20200123092A; WO2019182315A1; CN111868630A; CN111868630B; TW201938692A; JP2019163370A; KR102609109B1

Abstract

本發明提供一種著色硬化性樹脂組合物、彩色濾光片及顯示裝置，上述著色硬化性樹脂組合物包含著色劑、樹脂、聚合性化合物及聚合起始劑，著色劑包含式（I）所表示之化合物及紅色顏料（但，式（I）所表示之化合物除外），並且相對於著色劑總量，紅色顏料之含有率為10質量%以上且95質量%以下。The present invention provides a coloring curable resin composition, a color filter, and a display device, wherein the coloring curable resin composition includes a colorant, a resin, a polymerizable compound and a polymerization initiator, and the colorant includes a colorant represented by formula (I) The compound and the red pigment (except the compound represented by the formula (I)), and the content of the red pigment is 10% by mass or more and 95% by mass or less with respect to the total amount of the colorant.

Description

著色硬化性樹脂組合物、彩色濾光片及顯示裝置Colored curable resin composition, color filter, and display device

本發明係關於一種著色硬化性樹脂組合物、彩色濾光片及顯示裝置。The present invention relates to a colored curable resin composition, a color filter, and a display device.

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、CCD（Charge Coupled Device，電荷耦合元件）或CMOS（Complementary Metal-Oxide Semiconductor，互補金屬氧化物半導體）感測器等之固體攝像元件中所使用之彩色濾光片係由著色硬化性樹脂組合物製造。作為此種著色硬化性樹脂組合物，已知有包含下述式所表示之化合物作為著色劑之組合物（專利文獻1）。

Solid-state imaging devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, and solid-state imaging devices such as CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) sensors The color filter used in this is manufactured from a coloring curable resin composition. As such a colorable curable resin composition, a composition containing a compound represented by the following formula as a colorant is known (Patent Document 1).

[先前技術文獻] [專利文獻] [專利文獻1]日本專利申請案特開2015-60154號公報[Prior Art Literature] [Patent Literature] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-60154

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

由歷來已知的上述著色硬化性樹脂組合物所形成之彩色濾光片的明度係無法令人滿意。 [解決問題之手段]The lightness of the color filter formed from the conventionally known coloring curable resin composition mentioned above is unsatisfactory. [means to solve the problem]

本發明之要旨係如以下所述。The gist of the present invention is as follows.

[1] 一種著色硬化性樹脂組合物，其包含著色劑、樹脂、聚合性化合物及聚合起始劑，其中著色劑包含式（I）所表示之化合物及紅色顏料（但，式（I）所表示之化合物除外），且相對於著色劑總量，紅色顏料之含有率為10質量%以上且95質量%以下，

[式（I）中， R¹ 至R¹¹ 各自獨立地表示氫原子、鹵素原子、碳數1至8之飽和烴基或碳數6至20之芳基，該飽和烴基及該芳基中所含之氫原子可經鹵素原子取代； R¹² 至R¹⁵ 各自獨立地表示羥基、鹵素原子、氰基、硝基、碳數1至8之飽和烴基、苯基或苄基，該飽和烴基中所含之氫原子可經鹵素原子取代，該苯基及該苄基中所含之氫原子可經碳數1至4之烷基、鹵素原子、氰基或乙烯基取代； R¹ 與R¹³ 、R² 與R¹² 、R⁴ 與R¹⁵ 以及R⁵ 與R¹⁴ 可各自連結而形成包含氮原子之六員環，R¹² 與R¹³ 以及R¹⁴ 與R¹⁵ 可各自連結而形成包含氮原子之三至六員環之雜環； A^q- 表示q價之陰離子，q表示1或2； p表示式（I）所表示之化合物將電荷保持為中性之係數]。[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a compound represented by the formula (I) and a red pigment (but, the formula (I) excluding the compounds indicated), and the content of the red pigment is 10% by mass or more and 95% by mass or less relative to the total amount of colorants,

[In formula (I), R ¹ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the saturated hydrocarbon group and the aryl group contained in the The hydrogen atom of the hydrogen atom may be substituted by a halogen atom; R ¹² to R ¹⁵ each independently represent a hydroxyl group, a halogen atom, a cyano group, a nitro group, a saturated hydrocarbon group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and the saturated hydrocarbon group contained in the The hydrogen atom of the phenyl group and the benzyl group can be substituted by a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group can be substituted by an alkyl group with 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group; R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ , and R ⁵ and R ¹⁴ can each be linked to form a six-membered ring containing nitrogen atoms, and R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ can each be linked to form three containing nitrogen atoms. Heterocycle to six-membered ring; A ^q- represents an anion of q-valence, q represents 1 or 2; p represents the coefficient of the compound represented by formula (I) to keep the charge neutral].

[2] 如[1]所述之著色硬化性樹脂組合物，其中著色劑進一步包含黃色顏料（但，式（I）所表示之化合物除外）。[2] The colored curable resin composition according to [1], wherein the colorant further contains a yellow pigment (except for the compound represented by the formula (I)).

[3] 一種彩色濾光片，其係由如[1]或[2]所述之著色硬化性樹脂組合物形成。[3] A color filter formed from the colored curable resin composition according to [1] or [2].

[4] 一種顯示裝置，其包含如[3]所述之彩色濾光片。 [發明效果][4] A display device comprising the color filter described in [3]. [Inventive effect]

利用本發明之著色硬化性樹脂組合物，可形成明度優異之彩色濾光片。Using the coloring curable resin composition of the present invention, a color filter excellent in lightness can be formed.

本發明之著色硬化性樹脂組合物係包含著色劑（以下有時稱為著色劑（A））、樹脂（以下有時稱為樹脂（B））、聚合性化合物（以下有時稱為聚合性化合物（C））、以及聚合起始劑（以下有時稱為聚合起始劑（D））。The colored curable resin composition of the present invention contains a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), and a polymerizable compound (hereinafter sometimes referred to as a polymerizable compound) compound (C)), and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).

著色劑（A）係包含式（I）所表示之化合物及紅色顏料（但，式（I）所表示之化合物除外），相對於著色劑總量，紅色顏料之含有率為10質量%以上且95質量%以下。The colorant (A) contains the compound represented by the formula (I) and the red pigment (except for the compound represented by the formula (I)), and the content of the red pigment is 10% by mass or more with respect to the total amount of the colorant. 95% by mass or less.

本發明之著色硬化性樹脂組合物較佳進一步包含溶劑。The colored curable resin composition of the present invention preferably further contains a solvent.

本發明之著色硬化性樹脂組合物亦可包含調平劑。The colored curable resin composition of the present invention may also contain a leveling agent.

於本說明書中，只要無特別說明，則作為各成分而例示之化合物可單獨或將複數種組合使用。In this specification, unless otherwise specified, the compounds exemplified as the respective components can be used alone or in combination of plural kinds.

＜著色劑（A）＞＜Colorant (A)＞

著色劑（A）係包含式（I）所表示之化合物及紅色顏料（式（I）所表示之化合物除外）。The colorant (A) contains the compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).

式（I）所表示之化合物係如以下所述。

[式（I）中， R¹ 至R¹¹ 各自獨立地表示氫原子、鹵素原子、碳數1至8之飽和烴基或碳數6至20之芳基，該飽和烴基及該芳基中所含之氫原子可經鹵素原子取代； R¹² 至R¹⁵ 各自獨立地表示羥基、鹵素原子、氰基、硝基、碳數1至8之飽和烴基、苯基或苄基，該飽和烴基中所含之氫原子可經鹵素原子取代，該苯基及該苄基中所含之氫原子可經碳數1至4之烷基、鹵素原子、氰基或乙烯基取代； R¹ 與R¹³ 、R² 與R¹² 、R⁴ 與R¹⁵ 以及R⁵ 與R¹⁴ 可各自連結而形成包含氮原子之六員環，R¹² 與R¹³ 以及R¹⁴ 與R¹⁵ 可各自連結而形成包含氮原子之三至六員環之雜環； A^q- 表示q價之陰離子，q表示1或2； p表示式（I）所表示之化合物將電荷保持為中性之係數。]The compound represented by formula (I) is as follows.

[In formula (I), R ¹ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the saturated hydrocarbon group and the aryl group contained in the The hydrogen atom of the hydrogen atom may be substituted by a halogen atom; R ¹² to R ¹⁵ each independently represent a hydroxyl group, a halogen atom, a cyano group, a nitro group, a saturated hydrocarbon group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and the saturated hydrocarbon group contained in the The hydrogen atom of the phenyl group and the benzyl group can be substituted by a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group can be substituted by an alkyl group with 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group; R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ , and R ⁵ and R ¹⁴ can each be linked to form a six-membered ring containing nitrogen atoms, and R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ can each be linked to form three containing nitrogen atoms. A heterocyclic ring to a six-membered ring; A ^q- represents an anion of q-valence, and q represents 1 or 2; p represents the coefficient with which the compound represented by the formula (I) keeps the charge neutral. ]

表示R¹ 至R¹⁵ 之碳數1至8之飽和烴基可為直鏈狀、支鏈狀及環狀中之任一種。作為直鏈狀或支鏈狀之飽和烴基，可列舉：甲基、乙基、丙基、丁基、戊基、己基、辛基等直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、2-乙基己基等支鏈狀烷基等。該飽和烴基之碳數較佳為1至6，更佳為1至4。The saturated hydrocarbon group having 1 to 8 carbon atoms representing R ¹ to R ¹⁵ may be any of linear, branched and cyclic. Examples of linear or branched saturated hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl; isopropyl, isobutyl, isopropyl, Branched alkyl groups such as pentyl, neopentyl, 2-ethylhexyl, etc. The carbon number of the saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 4.

環狀之飽和烴基可為單環，亦可為多環。作為該環狀之飽和烴基，可列舉：環丙基、環丁基、環戊基、環己基等環烷基。該環狀之飽和烴基之碳數較佳為3至8，更佳為6至8。The cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3 to 8, more preferably 6 to 8.

其中，較佳為直鏈狀飽和烴基，特別佳為甲基、乙基、丙基。Among them, a linear saturated hydrocarbon group is preferable, and a methyl group, an ethyl group, and a propyl group are particularly preferable.

作為R¹ 至R¹¹ 之碳數6至20之芳基，可列舉：苯基、甲苯基、茬基、萘基、蒽基、菲基、聯苯基、聯三苯基等；較佳為苯基、萘基、甲苯基、茬基；特別佳為苯基。該芳基為碳數6至20，較佳為碳數6至15、更佳為碳數6至12。Examples of the aryl groups having 6 to 20 carbon atoms in R ¹ to R ¹¹ include phenyl, tolyl, sulfanyl, naphthyl, anthracenyl, phenanthryl, biphenyl, triphenyl and the like; preferably Phenyl, naphthyl, tolyl, stubble; particularly preferred is phenyl. The aryl group has 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms.

前述飽和烴基及前述芳基中所含之氫原子可經鹵素原子取代。The hydrogen atom contained in the aforementioned saturated hydrocarbon group and the aforementioned aryl group may be substituted with a halogen atom.

作為鹵素原子，可列舉氟、氯、溴、碘等。又，於鹵素原子為氟原子之情形時，較佳為鹵素原子以形成三氟甲基單元、五氟乙基單元、七氟丙基單元等全氟烷基單元之方式進行取代。As a halogen atom, fluorine, chlorine, bromine, iodine, etc. are mentioned. Moreover, when a halogen atom is a fluorine atom, it is preferable that a halogen atom is substituted so that a perfluoroalkyl unit, such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit, may be formed.

式（I）所表示之化合物較佳具有一個以上且五個以下之鹵素原子，更佳具有一個以上且三個以下之鹵素原子，尤佳具有一個或二個鹵素原子。該鹵素原子亦可包含氫原子經取代者。The compound represented by the formula (I) preferably has one or more and five or less halogen atoms, more preferably one or more and three or less halogen atoms, and particularly preferably has one or two halogen atoms. The halogen atom may also include a hydrogen atom substituted.

其中，較佳為R¹ 至R¹¹ 中之至少一者為鹵素原子，更佳為R⁷ 至R¹¹ 中之至少一者為鹵素原子，尤佳為R⁷ 至R¹¹ 中之任一者為鹵素原子。又，於R¹ 至R¹¹ 中之二者為鹵素原子之情形時，尤佳為R⁷ 與R⁸ 、R⁷ 與R⁹ 、R⁷ 與R¹⁰ 、R⁷ 與R¹¹ 、R⁸ 與R⁹ 、R⁸ 與R¹⁰ 、R⁸ 與R¹¹ 、R⁹ 與R¹⁰ 、R⁹ 與R¹¹ 、或者R¹⁰ 與R¹¹ 為鹵素原子。其中，進一步更佳為R⁷ 、R⁷ 與R⁸ 、R⁷ 與R⁹ 、R⁹ 與R¹¹ 為鹵素原子，特別佳為R⁷ 、R⁷ 與R⁸ 、R⁹ 與R¹¹ 為鹵素原子。Among them, preferably at least one of R ¹ to R ¹¹ is a halogen atom, more preferably at least one of R ⁷ to R ¹¹ is a halogen atom, especially preferably any one of R ⁷ to R ¹¹ is halogen atom. Moreover, when both of R ¹ to R ¹¹ are halogen atoms, R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁷ and R ¹⁰ , R ⁷ and R ¹¹ , R ⁸ and R are particularly preferred. ⁹ , R ⁸ and R ¹⁰ , R ⁸ and R ¹¹ , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are halogen atoms. Among them, it is more preferable that R ⁷ , R ⁷ and R ⁸ , R ⁷ and R ⁹ , and R ⁹ and R ¹¹ are halogen atoms, particularly preferably R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹¹ are halogen atoms .

作為鹵素原子，可列舉氟、氯、溴、碘等，最佳為氯。As a halogen atom, fluorine, chlorine, bromine, iodine etc. are mentioned, and chlorine is the most preferable.

於R¹² 至R¹⁵ 中，苯基及苄基中所含之氫原子可經碳數1至4之烷基、鹵素原子、氰基或乙烯基取代。In R ¹² to R ¹⁵ , the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with an alkyl group having 1 to 4 carbons, a halogen atom, a cyano group or a vinyl group.

可用於取代R¹² 至R¹⁵ 之苯基及苄基中所含之氫原子的碳數1至4之烷基可列舉前述碳數1至8之飽和烴基中與碳數1至4者相同者。The alkyl group having 1 to 4 carbon atoms which can be used to replace the hydrogen atom contained in the phenyl group and the benzyl group of R ¹² to R ¹⁵ can be the same as those having 1 to 4 carbon atoms among the aforementioned saturated hydrocarbon groups having 1 to 8 carbon atoms. .

R¹ 與R¹³ 、R² 與R¹² 、R⁴ 與R¹⁵ 、R⁵ 與R¹⁴ 可各自連結而形成包含氮原子之六員環。R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ , and R ⁵ and R ¹⁴ may each be linked to form a six-membered ring including a nitrogen atom.

作為該六員環，可列舉四氫吡啶環、吡啶環、嘧啶環、喹啉環、異喹啉環等。Examples of the six-membered ring include a tetrahydropyridine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, and the like.

R¹² 與R¹³ 、R¹⁴ 與R¹⁵ 可各自連結而形成包含氮原子之三至六員環之雜環。R ¹² and R ¹³ , R ¹⁴ and R ¹⁵ may each be linked to form a three- to six-membered heterocyclic ring containing a nitrogen atom.

作為該三至六員環之雜環，可列舉吡咯啶環、嗎福林環、哌啶環、哌嗪環、硫代嗎福林環、吡咯環、咪唑環、咪唑啶環、吡唑啶環、異四氫噻唑環等含氮雜環，較佳可列舉吡咯啶環、哌啶環等僅具有一個氮原子作為雜原子之含氮脂肪族雜環。Examples of the heterocyclic ring of the three- to six-membered ring include a pyrrolidine ring, a morpholin ring, a piperidine ring, a piperazine ring, a thiomorpholin ring, a pyrrole ring, an imidazole ring, an imidazolium ring, and a pyrazolidine ring. The nitrogen-containing heterocyclic ring such as a ring and an isotetrahydrothiazole ring is preferably a nitrogen-containing aliphatic heterocyclic ring having only one nitrogen atom as a heteroatom, such as a pyrrolidine ring and a piperidine ring.

較佳為，R¹ 至R⁶ 均為氫原子，R⁷ 至R¹¹ 中之至少一者為鹵素原子，R¹² 至R¹⁵ 各自獨立地為碳數1至8之飽和烴基；更佳為，R¹ 至R⁶ 均為氫原子，R⁷ 至R¹¹ 中之一者或二者為鹵素原子，R¹² 至R¹⁵ 各自獨立地為碳數1至8之直鏈狀飽和烴基；尤佳為，R¹ 至R⁶ 均為氫原子；R⁷ 至R¹¹ 中之任一者為鹵素原子，或者R⁷ 與R⁸ 、R⁷ 與R⁹ 、R⁷ 與R¹⁰ 、R⁷ 與R¹¹ 、R⁸ 與R⁹ 、R⁸ 與R¹⁰ 、R⁸ 與R¹¹ 、R⁹ 與R¹⁰ 、R⁹ 與R¹¹ 、或R¹⁰ 與R¹¹ 為鹵素原子；R¹² 至R¹⁵ 各自獨立地為碳數1至4之烷基。Preferably, R ¹ to R ⁶ are all hydrogen atoms, at least one of R ⁷ to R ¹¹ is a halogen atom, and R ¹² to R ¹⁵ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms; more preferably, R ¹ to R ⁶ are all hydrogen atoms, one or both of R ⁷ to R ¹¹ is a halogen atom, and R ¹² to R ¹⁵ are each independently a straight-chain saturated hydrocarbon group having 1 to 8 carbon atoms; particularly preferably , R ¹ to R ⁶ are all hydrogen atoms; any one of R ⁷ to R ¹¹ is a halogen atom, or R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁷ and R ¹⁰ , R ⁷ and R ¹¹ , R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁸ and R ¹¹ , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are halogen atoms; R ¹² to R ¹⁵ are each independently carbon An alkyl group of numbers 1 to 4.

較佳為表示鹵素原子以外之R⁷ 至R¹¹ 均為氫原子。It is preferable that R ⁷ to R ¹¹ other than the halogen atom are all hydrogen atoms.

A^q- 表示q價之陰離子，q表示1或2。A ^q- represents an anion of q-valence, and q represents 1 or 2.

p表示式（I）所表示之化合物將電荷保持為中性之係數。具體而言，p較佳為1至14，更佳為1至6，尤佳為1至4，進一步更佳為1至3，特別佳為1或2。p represents the coefficient by which the compound represented by the formula (I) keeps the charge neutral. Specifically, p is preferably 1 to 14, more preferably 1 to 6, particularly preferably 1 to 4, still more preferably 1 to 3, particularly preferably 1 or 2.

作為上述陰離子，可列舉鹵化物陰離子、其他無機陰離子、有機羧酸根陰離子、有機磺酸根陰離子、有機磷酸根陰離子、有機醯亞胺酸根陰離子、有機甲基化酸根陰離子、有機鉻酸根陰離子等。Examples of the anions include halide anions, other inorganic anions, organic carboxylate anions, organic sulfonate anions, organic phosphate anions, organic imidate anions, organic methylate anions, organic chromate anions, and the like.

作為鹵化物陰離子，可列舉氯化物離子、溴化物離子、碘化物離子、氟化物離子等。As a halide anion, a chloride ion, a bromide ion, an iodide ion, a fluoride ion, etc. are mentioned.

作為無機陰離子，可列舉過氯酸根離子、氯酸根離子、硫氰酸根離子、六氟磷酸根離子（以下有時稱為「陰離子（VII）」）、六氟銻酸根離子、四氟硼酸根離子等。Examples of the inorganic anions include perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion (hereinafter sometimes referred to as "anion (VII)"), hexafluoroantimonate ion, and tetrafluoroborate ion Wait.

又，作為無機陰離子，可列舉含有由鎢、鉬、矽及磷所組成之群組中所選之至少一個原子與氧原子的陰離子。就耐熱性之觀點而言，較佳為含有鎢原子與氧原子之陰離子。Moreover, as an inorganic anion, the anion containing at least one atom and an oxygen atom selected from the group which consists of tungsten, molybdenum, silicon, and phosphorus is mentioned. From the viewpoint of heat resistance, an anion containing a tungsten atom and an oxygen atom is preferred.

作為含有由鎢、鉬、矽及磷所組成之群組中所選之至少一個原子與氧原子的陰離子，可列舉：α-[PW₁₂ O₄₀ ]^3- （以下有時稱為「陰離子（IX）」）等Keggin型磷鎢酸根離子；α-[P₂ W₁₈ O₆₂ ]^6- 、β-[P₂ W₁₈ O₆₂ ]^6- 等Dawson型磷鎢酸根離子；α-[SiW₁₂ O₄₀ ]^4- 、β-[SiW₁₂ O₄₀ ]^4- 、γ-[SiW₁₂ O₄₀ ]^4- 等Keggin型矽鎢酸根離子；[P₂ W₁₇ O₆₁ ]^10- 、[P₂ W₁₅ O₅₆ ]^12- 、[H₂ P₂ W₁₂ O₄₈ ]^12- 、[NaP₅ W₃₀ O₁₁₀ ]^14- 、α-[SiW₉ O₃₄ ]^10- 、γ-[SiW₁₀ O₃₆ ]^8- 、α-[SiW₁₁ O₃₉ ]^8- 、β-[SiW₁₁ O₃₉ ]^8- ；[W₆ O₁₉ ]^2- 、[W₁₀ O₃₂ ]^4- 、WO₄ ^2- 等含鎢之同素聚合酸根離子；矽酸根離子；磷酸根離子等。Examples of anions containing at least one atom and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus include α-[PW ₁₂ O ₄₀ ] ^3- (hereinafter sometimes referred to as "anion ( IX)") and other Keggin-type phosphotungstate ions; α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- and other Dawson-type phosphotungstate ions; α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- and other Keggin silicotungstic acid ions; [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- ; [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and other tungsten-containing The homotopy polymer acid ion; Silicate ion; Phosphate ion, etc.

作為有機羧酸根陰離子，可列舉乙酸根離子、草酸根離子、苯甲酸根離子等。As an organic carboxylate anion, acetate ion, oxalate ion, benzoate ion etc. are mentioned.

作為有機磺酸根陰離子，可列舉甲磺酸根離子、十二烷基磺酸根離子、苯磺酸根離子、甲苯磺酸根離子、萘磺酸根離子、二苯基胺-4-磺酸根離子、2-胺基-4-甲基-5-氯苯磺酸根離子、2-胺基-5-硝基苯磺酸根離子、酞菁磺酸根離子、具有聚合性取代基之磺酸根離子、苯二磺酸根陰離子、萘二磺酸根陰離子等。Examples of the organic sulfonate anion include methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, tosylate ion, naphthalenesulfonate ion, diphenylamine-4-sulfonate ion, 2-amine 4-methyl-5-chlorobenzenesulfonate ion, 2-amino-5-nitrobenzenesulfonate ion, phthalocyanine sulfonate ion, sulfonate ion with polymerizable substituent, benzenedisulfonate anion , naphthalene disulfonate anion, etc.

作為有機磷酸根陰離子，可列舉辛基磷酸根離子、十二烷基磷酸根離子、十八烷基磷酸根離子、苯基磷酸根離子、壬基苯基磷酸根離子、2,2'-亞甲基雙（4,6-二-三級丁基苯基）膦酸根離子等。Examples of the organic phosphate anion include octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-idene Methyl bis (4,6-di-tertiary butylphenyl) phosphonate ion, etc.

作為有機鉻酸根陰離子，可列舉雙[2-[（4,5-二氫-3-甲基-5-側氧-1-苯基-1H-吡唑-4-基）偶氮]苯甲酸根基]鉻酸根離子（以下有時稱為「陰離子（VIII）」）等。Examples of the organic chromate anion include bis[2-[(4,5-dihydro-3-methyl-5-oxy-1-phenyl-1H-pyrazol-4-yl)azo]benzoic acid Root group] chromate ion (hereinafter sometimes referred to as "anion (VIII)") and the like.

其中，A^q- 較佳為無機陰離子、有機羧酸根陰離子、有機磺酸根陰離子、有機醯亞胺酸根陰離子、有機甲基化酸根陰離子，更佳為六氟磷酸根離子、含氟有機羧酸根陰離子、含氟有機磺酸根陰離子、含氟有機醯亞胺酸根陰離子、含氟有機甲基化酸根陰離子（以下亦將該等總稱而稱為含氟陰離子）。Among them, A ^q- is preferably inorganic anion, organic carboxylate anion, organic sulfonate anion, organic imidate anion, organic methylate anion, more preferably hexafluorophosphate ion, fluorine-containing organic carboxylate anion , fluorine-containing organic sulfonate anion, fluorine-containing organic imide anion, fluorine-containing organic methylate anion (hereinafter also collectively referred to as fluorine-containing anion).

作為含氟陰離子，例如可列舉CF₃ CO₂ ^- 以及式（III）、（IV）、（V）或（VI）所表示之陰離子。

[式（III）中，W³ 及W⁴ 相互獨立地表示氟原子或碳數1至4之氟化烷基，或者W³ 與W⁴ 一併表示碳數1至4之氟化烷二基。]

[式（IV）中，W⁵ 至W⁷ 相互獨立地表示氟原子或碳數1至4之氟化烷基。]

[式（V）中，Y¹ 表示碳數1至4之氟化烷二基。]

[式（VI）中，Y² 表示碳數1至4之氟化烷基。]As a fluorine _- containing anion, _CF3CO2- ^and the anion represented by formula (III), (IV), (V) or (VI) are mentioned, for example.

[In formula (III), W ³ and W ⁴ independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent a fluorinated alkanediyl group having 1 to 4 carbon atoms . ]

[In formula (IV), W ⁵ to W ⁷ independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

[In formula (V), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

[In formula (VI), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

在式（III）、（IV）及（VI）中，碳數1至4之氟化烷基較佳為全氟烷基。作為該全氟烷基，可列舉：-CF₃ 、-CF₂ CF₃ 、-CF₂ CF₂ CF₃ 、-CF(CF₃ )₂ 、-CF₂ CF₂ CF₂ CF₃ 、-CF₂ CF(CF₃ )₂ 、-C(CF₃ )₃ 等。In the formulae (III), (IV) and (VI), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C(CF ₃ ) ₃ and the like.

在式（III）及（V）中，碳數1至4之氟化烷二基較佳為全氟烷二基，可列舉：-CF₂ -、-CF₂ CF₂ -、-CF₂ CF₂ CF₂ -、-C(CF₃ )₂ -、-CF₂ CF₂ CF₂ CF₂ -等。In formulas (III) and (V), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples thereof include -CF ₂ -, -CF ₂ CF ₂ -, and -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ - and the like.

作為式（III）所表示之陰離子（以下有時稱為「陰離子（III）」），可列舉分別由式（III-1）至式（III-6）所表示之陰離子（以下有時稱為「陰離子（III-1）」至「陰離子（III-6）」）。

Examples of the anion represented by formula (III) (hereinafter sometimes referred to as "anion (III)") include anions represented by formula (III-1) to (III-6), respectively (hereinafter sometimes referred to as "anion (III)"). "Anion (III-1)" to "Anion (III-6)").

作為式（IV）所表示之陰離子（以下有時稱為「陰離子（IV）」），可列舉式（IV-1）所表示之陰離子（IV-1）。

The anion (IV-1) represented by formula (IV-1) can be mentioned as an anion (it may be hereafter called "anion (IV)") represented by Formula (IV).

作為式（V）所表示之陰離子（以下有時稱為「陰離子（V）」），可列舉分別由式（V-1）至式（V-4）所表示之陰離子（以下有時稱為「陰離子（V-1）」至「陰離子（V-4）」）。

Examples of the anion represented by formula (V) (hereinafter sometimes referred to as "anion (V)") include anions represented by formula (V-1) to formula (V-4) respectively (hereinafter sometimes referred to as "anion (V)"). "Anion (V-1)" to "Anion (V-4)").

作為式（VI）所表示之陰離子（以下有時稱為「陰離子（VI）」），可列舉分別由式（VI-1）至式（VI-4）所表示之陰離子（以下有時稱為「陰離子（VI-1）」至「陰離子（VI-4）」）。

Examples of the anion represented by formula (VI) (hereinafter sometimes referred to as "anion (VI)") include anions represented by formula (VI-1) to (VI-4), respectively (hereinafter sometimes referred to as "anion (VI)"). "Anion (VI-1)" to "Anion (VI-4)").

含氟陰離子亦可為由CF₃ CO₂ ^- 、陰離子（III）、陰離子（IV）、陰離子（V）及陰離子（VI）所組成之群組中所選的至少一種陰離子。其中，較佳為CF₃ CO₂ ^- 、陰離子（III-1）、陰離子（III-2）、陰離子（III-6）、陰離子（IV-1）、陰離子（V-1）、陰離子（VI-1）、陰離子（VI-2）、陰離子（VI-3），更佳為CF₃ CO₂ ^- 、陰離子（III-2）、陰離子（IV-1）、陰離子（VI-1）。The fluorine-containing anion may also be at least one anion selected from the group consisting of CF ₃ CO ₂ ⁻ , anion (III), anion (IV), anion (V), and anion (VI). Among them, CF ₃ CO ₂ ^- , anion (III-1), anion (III-2), anion (III-6), anion (IV-1), anion (V-1), anion (VI- 1), anion (VI-2), anion (VI- ₃ ), more preferably CF3CO2-, anion (III ^- ₂ ), anion (IV-1), anion (VI-1).

式（I）所表示之化合物較佳為式（I-A）所表示之化合物。

（式（I-A）中，R⁷ 至R¹⁵ 、p、q、A^q- 係與前述為相同含義。）The compound represented by the formula (I) is preferably a compound represented by the formula (IA).

(In formula (IA), R ⁷ to R ¹⁵ , p, q, and A ^q- have the same meanings as described above.)

在以下之表1至8中，Me表示甲基，Et表示乙基，III-1至III-6、VI-1、VII表示上述式（III-1）至式（III-6）所表示之陰離子、式（VI-1）所表示之陰離子、陰離子（VII）。In Tables 1 to 8 below, Me represents a methyl group, Et represents an ethyl group, and III-1 to III-6, VI-1, and VII represent those represented by the above formulae (III-1) to (III-6) Anion, anion represented by formula (VI-1), anion (VII).

式（I-A）所表示之化合物較佳為式（I-1）至式（I-480）所表示之化合物。The compound represented by formula (I-A) is preferably a compound represented by formula (I-1) to formula (I-480).

[表1]

[Table 1]

[表2]

[Table 2]

[表3]

[table 3]

[表4]

[Table 4]

[表5]

[table 5]

[表6]

[Table 6]

[表7]

[Table 7]

[表8]

[Table 8]

其中，較佳為式（I-1）至式（I-240）所表示之化合物，更佳為式（I-121）至式（I-240）所表示之化合物，尤佳為式（I-136）至式（I-150）所表示之化合物、式（I-226）至式（I-240）所表示之化合物，特別佳為式（I-136）、式（I-141）、式（I-142）、式（I-149）、式（I-226）所表示之化合物，最佳為式（I-136）、式（I-141）、式（I-149）、式（I-226）所表示之化合物。Among them, compounds represented by formula (I-1) to formula (I-240) are preferable, compounds represented by formula (I-121) to formula (I-240) are more preferable, and compounds represented by formula (I-240) are especially preferable -136) to the compound represented by the formula (I-150), the compound represented by the formula (I-226) to the formula (I-240), particularly preferably the formula (I-136), the formula (I-141), Compounds represented by formula (I-142), formula (I-149), and formula (I-226), preferably formula (I-136), formula (I-141), formula (I-149), formula The compound represented by (I-226).

相對於著色劑總量，式（I）所表示之化合物的含有率較佳為5質量%以上且90質量%以下，更佳為5質量%以上且40質量%以下，尤佳為5質量%以上且30質量%以下。The content of the compound represented by the formula (I) is preferably 5 mass % or more and 90 mass % or less, more preferably 5 mass % or more and 40 mass % or less, particularly preferably 5 mass %, relative to the total amount of the colorant. more than 30 mass % or less.

相對於固體成分總量，式（I）所表示之化合物的含有率較佳為0.5質量%以上且20質量%以下，更佳為1質量%以上且15質量%以下，尤佳為2質量%以上且12質量%以下。The content of the compound represented by the formula (I) is preferably 0.5 mass % or more and 20 mass % or less, more preferably 1 mass % or more and 15 mass % or less, and particularly preferably 2 mass % with respect to the total solid content. More than 12 mass % or less.

此處，本說明書中之「固體成分總量」，係指從著色硬化性樹脂組合物總量中去除溶劑之含量後所得的量。固體成分總量以及相對其之各成分的含量可利用例如液相層析法或者氣相層析法等習知之分析方法來測定。Here, "the total amount of solid content" in this specification means the amount obtained by excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid components and the content of each component relative thereto can be measured by a known analytical method such as liquid chromatography or gas chromatography.

＜紅色顏料＞＜Red Pigment＞

作為本發明之著色硬化性樹脂組合物中所含之紅色顏料，可使用習知之顏料，例如可列舉於染料索引（Colour Index）（英國染色與色料師學會（The Society of Dyers and Colourists）出版）中被分類為顏料（pigment）之顏料中被分類為紅色者。亦可將二種以上加以組合。但，式（I）所表示之化合物除外。As the red pigment contained in the colorable curable resin composition of the present invention, known pigments can be used, and examples are listed in the Colour Index (published by The Society of Dyers and Colourists). ) is classified as red among the pigments classified as pigments. Two or more kinds may be combined. However, the compounds represented by the formula (I) are excluded.

具體而言，可列舉：C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、179、180、192、202、209、215、216、224、242、254、255、264、265、266、268、269、273等紅色顏料。Specifically, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments.

在紅色顏料中，較佳為蒽醌顏料、偶氮顏料、喹吖酮顏料、苝顏料、二酮基吡咯并吡咯顏料，更佳為C.I.顏料紅177、179、202、208、242、254、269、溴化二酮基吡咯并吡咯顏料，更佳為C.I.顏料紅177、254、溴化二酮基吡咯并吡咯顏料。Among the red pigments, preferably anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, more preferably C.I. Pigment Red 177, 179, 202, 208, 242, 254, 269. Brominated diketopyrrolopyrrole pigments, more preferably C.I. Pigment Red 177, 254, brominated diketopyrrolopyrrole pigments.

相對於著色劑總量，紅色顏料之含有率為10質量%以上且95質量%以下，較佳為30質量%以上且90質量%以下，更佳為50質量%以上，尤佳為60質量%以上。The content of the red pigment is 10% by mass or more and 95% by mass or less, preferably 30% by mass or more and 90% by mass or less, more preferably 50% by mass or more, and particularly preferably 60% by mass, relative to the total amount of colorants above.

於本發明之著色硬化性樹脂組合物包含後述的著色劑（A1）之情形時，相對於著色劑總量，式（I）所表示之化合物與紅色顏料之合計含有率較佳為30質量%以上，更佳為40質量%以上，尤佳為50質量%以上，且較佳為99質量%以下，更佳為95質量%以下。When the colorable curable resin composition of the present invention contains a colorant (A1) described later, the total content of the compound represented by the formula (I) and the red pigment is preferably 30% by mass with respect to the total amount of the colorant. Above, more preferably 40 mass % or more, particularly preferably 50 mass % or more, and preferably 99 mass % or less, more preferably 95 mass % or less.

相對於固體成分總量，紅色顏料之含有率較佳為1質量%以上且60質量%以下，更佳為2質量%以上且50質量%以下。The content of the red pigment is preferably 1% by mass or more and 60% by mass or less, more preferably 2% by mass or more and 50% by mass or less, with respect to the total solid content.

本發明之著色硬化性樹脂組合物亦可包含式（I）所表示之化合物及紅色顏料以外之著色劑（以下有時稱為著色劑（A1））來作為著色劑（A）。著色劑（A1）中亦可包含一種或者二種以上之著色劑。The coloring curable resin composition of this invention may contain the compound represented by Formula (I) and the coloring agent other than a red pigment (it may be hereafter called a coloring agent (A1)) as a coloring agent (A). The coloring agent (A1) may contain one or two or more coloring agents.

著色劑（A1）可為染料，亦可為顏料。作為染料，可列舉染料索引（英國染色與色料師學會出版）以及染色筆記（色染公司）中所記載之習知染料。又，依據化學結構，可列舉：偶氮染料、蒽醌染料、三苯基甲烷染料、二苯并哌喃（xanthene）染料（但，式（I）所表示之化合物除外）、花青染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料、方酸菁（squarylium）染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料、硝基染料及酞菁染料等。該等中，有機溶劑可溶性染料係較佳的。該等染料可併用二種以上。The colorant (A1) may be a dye or a pigment. Examples of dyes include conventional dyes described in Dyestuff Index (published by the British Institute of Dyeing and Colorists) and Dyeing Notes (Dyeing Company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran (xanthene) dyes (except compounds represented by formula (I)), cyanine dyes, Naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and phthalocyanine dyes. Among these, organic solvent-soluble dyes are preferred. These dyes may be used in combination of two or more.

具體而言，可列舉以下所述之染料索引（C.I.）編號之染料。 C.I.溶劑黃14、15、23、24、25、38、62、63、68、79、81、82、83、89、94、98、99、162； C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251； C.I.活性黃2、76、116； C.I.直接黃2、4、28、33、34、35、38、39、43、44、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、132、136、138、141； C.I.分散黃51、54、76； C.I.溶劑橙2、7、11、15、26、41、54、56、99； C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、149、162、169、173； C.I.活性橙16； C.I.直接橙26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107； C.I.溶劑紅24、49、90、91、111、118、119、122、124、125、127、130、132、143、145、146、150、151、155、160、168、169、172、175、181、207、218、222、227、230、245、247； C.I.酸性紅73、80、91、92、97、138、151、211、274、289； C.I.酸性紫34、102； C.I.分散紫26、27； C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60； C.I.溶劑藍14、18、35、36、45、58、59、59：1、63、68、69、78、79、83、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139； C.I.酸性藍25、27、40、45、78、80、112； C.I.直接藍40； C.I.分散藍1、14、56、60； C.I.溶劑綠1、3、5、28、29、32、33； C.I.酸性綠3、5、9、25、27、28、41； C.I.鹼性綠1； C.I.還原綠1等。Specifically, the dyes of the dye index (C.I.) number described below can be mentioned. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Active Yellow 2, 76, 116; C.I. Direct Yellow 2,4,28,33,34,35,38,39,43,44,47,50,54,58,68,69,70,71,86,93,94,95,98,102 , 108, 109, 129, 132, 136, 138, 141; C.I. Disperse Yellow 51, 54, 76; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Active Orange 16; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175 , 181, 207, 218, 222, 227, 230, 245, 247; C.I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; C.I. Acid Violet 34, 102; C.I. Disperse Violet 26, 27; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111 , 112, 122, 128, 132, 136, 139; C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112; C.I. Direct Blue 40; C.I. Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Vat Green 1, etc.

作為顏料，可使用習知之顏料，例如可列舉於染料索引（染色家協會出版）中分類為顏料之顏料。亦可將二種以上加以組合。但，式（I）所表示之化合物除外。As a pigment, a well-known pigment can be used, for example, the pigment classified as a pigment in the Dyestuff Index (published by the Association of Dyers) is exemplified. Two or more kinds may be combined. However, the compounds represented by the formula (I) are excluded.

具體而言可列舉：C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、129、137、138、139、147、148、150、153、154、166、173、185、194、214等黃色顏料； C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料； 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； C.I.顏料綠7、36、58、59等綠色顏料。Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 , 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green 7, 36, 58, 59 and other green pigments.

著色劑（A1）較佳為黃色顏料，更佳為C.I.顏料黃138、139、150、185。The colorant (A1) is preferably a yellow pigment, more preferably C.I. Pigment Yellow 138, 139, 150, and 185.

於包含黃色顏料之情形時，相對於著色劑總量，黃色顏料之含有率較佳為1質量%以上且50質量%以下，更佳為2質量%以上且40質量%以下，尤佳為5質量%以上且35質量%以下。When the yellow pigment is contained, the content of the yellow pigment is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 40% by mass or less, and particularly preferably 5% by mass relative to the total amount of the colorant. mass % or more and 35 mass % or less.

相對於固體成分總量，黃色顏料之含有率較佳為1質量%以上且25質量%以下，更佳為2質量%以上且20質量%以下，尤佳為3質量%以上且15質量%以下。The content rate of the yellow pigment is preferably 1 mass % or more and 25 mass % or less, more preferably 2 mass % or more and 20 mass % or less, particularly preferably 3 mass % or more and 15 mass % or less, relative to the total solid content. .

式（I）所表示之化合物、紅色顏料以及著色劑（A1）中之顏料（以下有時稱為顏料等）亦可視需要而實施：松香處理；使用導入有酸性基或鹼性基之著色劑衍生物等的表面處理；利用高分子化合物等對顏料等表面之接枝處理；利用硫酸微粒化法等之微粒化處理；用以去除雜質之利用有機溶劑或水等之洗滌處理；利用離子性雜質之離子交換法等的去除處理等。顏料等之粒徑較佳為各自大致均勻。顏料等係藉由含有分散劑而進行分散處理，從而成為於分散液中均勻分散之狀態。The compound represented by the formula (I), the red pigment and the pigment in the coloring agent (A1) (hereinafter sometimes referred to as pigment, etc.) can also be implemented as needed: rosin treatment; using a coloring agent introduced with an acidic group or a basic group Surface treatment of derivatives, etc; Removal treatment of impurities such as ion exchange method, etc. It is preferable that the particle diameters of a pigment etc. are each substantially uniform. Pigments and the like are dispersed uniformly in the dispersion liquid by containing a dispersant and performing dispersion treatment.

作為分散劑，可列舉界面活性劑等，可為陽離子系、陰離子系、非離子系及兩性中之任一種界面活性劑。具體而言可列舉聚酯系、多胺系及丙烯酸系等之界面活性劑等。其他分散劑亦可使用後述之樹脂（B）。該等分散劑可單獨使用或將二種以上組合使用。作為分散劑，若以商品名表示，則可列舉：KP（信越化學工業股份有限公司製造）、Flowlen（共榮社化學股份有限公司製造）、Solsperse（註冊商標）（捷利康（Zeneca）股份有限公司製造）、EFKA（註冊商標）（巴斯夫（BASF）公司製造）、Ajisper（註冊商標）（味之素精細化學股份有限公司製造）以及Disperbyk（註冊商標）（畢克化學公司製造）、BYK（註冊商標）（畢克化學公司製造）等。As a dispersing agent, surfactant etc. are mentioned, and it may be any of a cationic type, an anionic type, a nonionic type, and an amphoteric surfactant. Specifically, surfactants, such as polyester type, polyamine type, and acrylic type, etc. are mentioned. The resin (B) mentioned later can also be used for other dispersing agents. These dispersants may be used alone or in combination of two or more. As a dispersant, if it is represented by a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyeisha Chemical Co., Ltd.), Solsperse (registered trademark) (Zeneca Co., Ltd.) Company), EFKA (registered trademark) (BASF Corporation), Ajisper (registered trademark) (Ajinomoto Fine Chemicals Co., Ltd.) registered trademark) (manufactured by BYK Chemicals), etc.

於使用分散劑之情形時，相對於顏料等100質量份，分散劑之使用量較佳為100質量份以下，更佳為5質量份以上且70質量份以下。若分散劑之使用量處於前述範圍內，則存在有可獲得更均勻之分散狀態之著色劑含有液之傾向。When a dispersant is used, the usage-amount of the dispersant is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 70 parts by mass or less, with respect to 100 parts by mass of the pigment or the like. When the usage-amount of a dispersing agent is in the said range, there exists a tendency for the coloring agent containing liquid of a more uniform dispersion state to be obtained.

在著色硬化性樹脂組合物中，於固體成分總量中，著色劑（A）之含量通常為20質量%以上且80質量%以下，較佳為30質量%以上且70質量%以下，更佳為40質量%以上且60質量%以下。In the colored curable resin composition, the content of the colorant (A) is usually 20% by mass or more and 80% by mass or less, preferably 30% by mass or more and 70% by mass or less, more preferably in the total solid content. It is 40 mass % or more and 60 mass % or less.

＜樹脂（B）＞＜Resin (B)＞

樹脂（B）並無特別限定，較佳為鹼可溶性樹脂，更佳為具有源自從不飽和羧酸及不飽和羧酸酐所組成之群組中所選之至少一種單體（a）（以下有時稱為「（a）」）的結構單元之樹脂。較佳地，樹脂（B）進一步具有從以下結構單元所組成之群組中所選的至少一種結構單元：源自具有碳數2至4之環狀醚結構及乙烯性不飽和鍵之單體（b）（以下有時稱為「（b）」）的結構單元、源自可與（a）共聚合之單體（c）（但，與（a）及（b）不同）（以下有時稱為「（c）」）的結構單元、以及於側鏈上帶有乙烯性不飽和鍵的結構單元。The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one monomer (a) (below) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. Sometimes referred to as "(a)") structural unit resin. Preferably, the resin (B) further has at least one structural unit selected from the group consisting of the following structural units: derived from a monomer having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (b) Structural unit (hereinafter sometimes referred to as "(b)"), derived from monomer (c) (but, different from (a) and (b)) which can be copolymerized with (a) (hereinafter there are The structural unit referred to as "(c)") and the structural unit with an ethylenically unsaturated bond on the side chain.

作為（a），具體而言，例如可列舉：丙烯酸、甲基丙烯酸、馬來酸酐、伊康酸酐、3,4,5,6-四氫鄰苯二甲酸酐、琥珀酸單[2-（甲基）丙烯醯氧基乙基]酯等，較佳為丙烯酸、甲基丙烯酸、馬來酸酐。Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-( Meth)acryloyloxyethyl]ester, etc., preferably acrylic acid, methacrylic acid, maleic anhydride.

此外，在本說明書中，「（甲基）丙烯酸」係表示選自丙烯酸及甲基丙烯酸所組成之群組中的至少一種。「（甲基）丙烯醯基」及「（甲基）丙烯酸酯」等表述亦具有相同含義。In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

（b）較佳為具有碳數2至4之環狀醚結構（例如由環氧乙烷環、氧呾環及四氫呋喃環所組成之群組中所選的至少一種）及（甲基）丙烯醯氧基之單體。(b) preferably has a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxo ring and a tetrahydrofuran ring) and (meth)propylene Monomer of alkoxy group.

作為（b），例如可列舉：（甲基）丙烯酸縮水甘油酯、乙烯基苄基縮水甘油醚、（甲基）丙烯酸-3,4-環氧基三環[5.2.1.0^2,6 ]癸酯、3-乙基-3-（甲基）丙烯醯氧基甲基氧呾、（甲基）丙烯酸四氫糠酯等，較佳為（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸-3,4-環氧基三環[5.2.1.0^2,6 ]癸酯、3-乙基-3-（甲基）丙烯醯氧基甲基氧呾。As (b), for example, glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, (meth)acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane are mentioned. esters, 3-ethyl-3-(meth)acryloyloxymethyl oxalate, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (meth)acrylic acid -3,4-Epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester, 3-ethyl-3-(meth)acryloyloxymethyloxygen.

作為（c），例如可列舉：（甲基）丙烯酸甲酯、（甲基）丙烯酸丁酯、（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-8-基酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸-2-羥基乙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、苯乙烯、乙烯基甲苯等，較佳為苯乙烯、乙烯基甲苯、（甲基）丙烯酸-2-羥基乙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺等。(c), for example, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (meth)acrylate base) tricyclo[5.2.1.0 ^2,6 ]dec-8-yl acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene, etc., preferably styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and the like.

具有於側鏈上帶有乙烯性不飽和鍵之結構單元的樹脂可藉由於（a）與（c）之共聚物中加成（b），或於（b）與（c）之共聚物中加成（a）而製造。該樹脂亦可為於（b）與（c）之共聚物中加成（a）並進一步使羧酸酐進行反應而成之樹脂。The resin having a structural unit with an ethylenically unsaturated bond in the side chain can be added to the copolymer of (a) and (c) by adding (b), or to the copolymer of (b) and (c) Manufactured by adding (a). The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting a carboxylic anhydride.

樹脂（B）之聚苯乙烯換算之重量平均分子量較佳為3,000至100,000，更佳為5,000至50,000，尤佳為5,000至30,000。The polystyrene-converted weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000.

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

以固體成分換算計，樹脂（B）之酸值較佳為50至170 mg-KOH/g（毫克-KOH／公克），更佳為60至150 mg-KOH/g，尤佳為70至135 mg-KOH/g。此處，酸值係作為將1公克的樹脂（B）中和所必需之氫氧化鉀之量（毫克）而測定的值，例如可藉由使用氫氧化鉀水溶液進行滴定而求出。In terms of solid content, the acid value of the resin (B) is preferably 50 to 170 mg-KOH/g (mg-KOH/gram), more preferably 60 to 150 mg-KOH/g, particularly preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

相對於固體成分總量，樹脂（B）之含有率較佳為1至60質量%，更佳為5至50質量%，尤佳為7至40質量%。The content of the resin (B) is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 7 to 40% by mass relative to the total solid content.

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

聚合性化合物（C）係可利用由聚合起始劑（D）所產生之活性自由基及／或酸而進行聚合之化合物，例如可列舉具有聚合性之乙烯性不飽和鍵的化合物等，較佳為（甲基）丙烯酸酯化合物。The polymerizable compound (C) is a compound that can be polymerized using active radicals and/or acids generated by the polymerization initiator (D), for example, compounds having a polymerizable ethylenically unsaturated bond, etc. Preferably it is a (meth)acrylate compound.

其中，聚合性化合物（C）較佳為具有三個以上之乙烯性不飽和鍵之聚合性化合物。作為此種聚合性化合物，例如可列舉：三羥甲基丙烷三（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯等。Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, Pentaerythritol penta(meth)acrylate, dipivaloerythritol hexa(meth)acrylate, etc.

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

相對於固體成分總量，聚合性化合物（C）之含有率較佳為1質量%以上且小於30質量%，更佳為3質量%以上且28質量%以下，尤佳為5質量%以上且20質量%以下。The content of the polymerizable compound (C) is preferably 1 mass % or more and less than 30 mass %, more preferably 3 mass % or more and 28 mass % or less, particularly preferably 5 mass % or more, with respect to the total solid content. 20 mass % or less.

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

聚合起始劑（D）若為可利用光或熱之作用而產生活性自由基、酸等來引發聚合之化合物，則無特別限定，可使用習知之聚合起始劑。作為產生活性自由基之聚合起始劑，例如可列舉： N-苯甲醯氧基-1-（4-苯基氫硫基苯基）丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-（4-苯基氫硫基苯基）-3-環戊基丙烷-1-酮-2-亞胺、2-甲基-2-嗎福林基-1-（4-甲基氫硫基苯基）丙烷-1-酮、2-二甲基胺基-1-（4-嗎福林基苯基）-2-苄基丁烷-1-酮、1-羥基環己基苯基酮、2,4-雙（三氯甲基）-6-向日葵基-1,3,5-三嗪、2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙（2-氯苯基）-4,4',5,5'-四苯基聯咪唑等。The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and conventional polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include: N-Benzyloxy-1-(4-phenylhydrogenthiophenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylhydrogensulfide phenyl) octane-1-one-2-imine, N-benzyloxy-1-(4-phenylhydrogenthiophenyl)-3-cyclopentylpropan-1-one-2 -Imine, 2-methyl-2-morpholinyl-1-(4-methylhydrogenthiophenyl)propan-1-one, 2-dimethylamino-1-(4-morpholino) Linylphenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-sunenyl-1,3,5-tris oxazine, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole Wait.

聚合起始劑較佳為包含選自以下群組之至少一者的聚合起始劑：三嗪化合物、醯基氧化膦化合物、烷基苯酮化合物、O-醯基肟化合物及聯咪唑化合物；更佳為包含O-醯基肟化合物之聚合起始劑。The polymerization initiator is preferably a polymerization initiator comprising at least one selected from the group consisting of triazine compounds, acylphosphine oxide compounds, alkyl phenone compounds, O-acyl oxime compounds and biimidazole compounds; More preferably, it is a polymerization initiator containing an O-acyl oxime compound.

相對於樹脂（B）及聚合性化合物（C）之合計量100質量份，聚合起始劑（D）之含量較佳為0.1至30質量份，更佳為1至20質量份。若聚合起始劑（D）之含量處於前述範圍內，則存在有高感度化而曝光時間縮短之傾向，因此彩色濾光片之生產性提高。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 amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the aforementioned range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

相對於聚合起始劑（D）之總量，O-醯基肟化合物之含有率較佳為50質量%以上，更佳為80質量%以上，尤佳為90質量%以上，特別佳為95質量%以上。若O-醯基肟化合物之含有率處於前述範圍內，則於形成著色圖案時之感度或顯影性、著色劑含有率高之情況下，亦存在有可製作高明度之彩色濾光片之傾向。The content of the O-acyl oxime compound is preferably 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and particularly preferably 95% by mass relative to the total amount of the polymerization initiator (D). mass % or more. When the content rate of the O-acyl oxime compound is within the above-mentioned range, when the sensitivity, developability, and colorant content rate at the time of forming a colored pattern are high, there is a tendency that a high-brightness color filter can be produced. .

本發明之著色硬化性樹脂組合物亦可包含聚合起始助劑。The colored curable resin composition of the present invention may also contain a polymerization initiator.

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

聚合起始助劑（D1）係為了促進由聚合起始劑來引發聚合的聚合性化合物之聚合而使用之化合物、或者係增感劑。於包含有聚合起始助劑（D1）之情形時，通常與聚合起始劑（D）組合使用。The polymerization initiator (D1) is a compound used for accelerating the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator, or a sensitizer. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

作為聚合起始助劑（D1），可列舉：4,4'-雙（二甲基胺基）二苯甲酮（通稱米其勒酮）、4,4'-雙（二乙基胺基）二苯甲酮、9,10-二甲氧基蒽、2,4-二乙基硫氧雜蒽酮、N-苯基甘胺酸等。Examples of the polymerization initiator (D1) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino) ) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.

於使用該等聚合起始助劑（D1）之情形時，相對於樹脂（B）及聚合性化合物（C）之合計量100質量份，聚合起始助劑（D1）之含量較佳為0.1至30質量份，更佳為1至20質量份。若聚合起始助劑（D1）之量處於該範圍內，則可以更高感度來形成著色圖案，存在有彩色濾光片之生產性提高之傾向。When these polymerization initiators (D1) are used, the content of the polymerization initiator (D1) is preferably 0.1 with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

本發明之著色硬化性樹脂組合物較佳為包含溶劑。The colored curable resin composition of the present invention preferably contains a solvent.

＜溶劑（E）＞<Solvent (E)>

溶劑（E）並無特別限定，可使用該領域中通常使用之溶劑。例如可列舉：酯溶劑（分子內包含-COO-且不含-O-之溶劑）、醚溶劑（分子內包含-O-且不含-COO-之溶劑）、醚酯溶劑（分子內包含-COO-及-O-之溶劑）、酮溶劑（分子內包含-CO-且不含-COO-之溶劑）、醇溶劑（分子內包含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、二丙酮醇等。The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecules), ether ester solvents (containing - COO- and -O- solvent), ketone solvent (solvent containing -CO- in the molecule and no -COO-), alcohol solvent (containing OH in the molecule and not containing -O-, -CO- and -COO- solvent), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, diacetone alcohol, etc.

作為溶劑，可列舉：乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸正丁酯、丁酸乙酯、丁酸丁酯、丙酮酸乙酯、乙醯乙酸甲酯、環己醇乙酸酯及γ-丁內酯等酯溶劑（分子內包含-COO-且不含-O-之溶劑）；乙二醇單丁醚、二乙二醇單甲醚、丙二醇單甲醚、3-甲氧基-1-丁醇、二乙二醇二甲醚、二乙二醇甲基***等醚溶劑（分子內包含-O-且不含-COO-之溶劑）； 3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸-3-甲氧基丁酯、丙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯等醚酯溶劑（分子內包含-COO-及-O-之溶劑）； 4-羥基-4-甲基-2-戊酮、庚酮、4-甲基-2-戊酮、環己酮等酮溶劑（分子內包含-CO-且不含-COO-之溶劑）；丁醇、環己醇、丙二醇等醇溶劑（分子內包含OH且不含-O-、-CO-及-COO-之溶劑）；甲苯、二甲苯等芳香族烴溶劑；二丙酮醇等。可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等醯胺溶劑。Examples of the solvent include ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, Esters such as hexyl acetate and γ-butyrolactone (solvents containing -COO- and no -O- in the molecule); ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether , 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ether and other ether solvents (solvents that contain -O- and do not contain -COO- in the molecule); Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Ether ester solvents such as alcohol monoethyl ether acetate (solvents containing -COO- and -O- in the molecule); 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone and other ketone solvents (solvents that contain -CO- and do not contain -COO- in the molecule); Alcohol solvents such as butanol, cyclohexanol and propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-); aromatic hydrocarbon solvents such as toluene and xylene; diacetone alcohol, etc. Examples thereof include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

作為溶劑，更佳為：丙二醇單甲醚乙酸酯、丙二醇單甲醚、乳酸乙酯、環己酮、二丙酮醇及3-乙氧基丙酸乙酯。As a solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, diacetone alcohol, and 3-ethoxy ethyl propionate are more preferable.

溶劑較佳為包含丙二醇單甲醚乙酸酯之混合溶劑。作為與丙二醇單甲醚乙酸酯組合之溶劑，較佳為：乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、二乙二醇單甲醚、二乙二醇單***、二丙二醇甲醚乙酸酯、乙酸-3-甲氧基丁酯、3-甲氧基-1-丁醇、二丙酮醇、及4-羥基-4-甲基-2-戊酮；更佳為丙二醇單甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、乙酸-3-甲氧基丁酯、3-甲氧基-1-丁醇、二丙酮醇及3-乙氧基丙酸乙酯；尤佳為乳酸乙酯、二丙酮醇。The solvent is preferably a mixed solvent containing propylene glycol monomethyl ether acetate. The solvent to be combined with propylene glycol monomethyl ether acetate is preferably ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether , Dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, diacetone alcohol, and 4-hydroxy-4-methyl-2-pentanone; more Preferred are propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, diacetone alcohol and 3-ethoxypropane ethyl acetate; especially preferred are ethyl lactate and diacetone alcohol.

相對於溶劑總量，與丙二醇單甲醚乙酸酯組合之溶劑的合計含有率較佳為0.1質量%以上且50質量%以下，更佳為0.3質量%以上且40質量%以下，尤佳為0.5質量%以上。The total content of the solvent combined with propylene glycol monomethyl ether acetate is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.3% by mass or more and 40% by mass or less, particularly preferably 0.3% by mass or more and 40% by mass or less with respect to the total amount of the solvent 0.5 mass % or more.

於包含有溶劑（E）之情形時，相對於本發明之著色硬化性樹脂組合物總量，溶劑（E）之含有率較佳為65至95質量%，更佳為70至92質量%。換言之，著色硬化性樹脂組合物之固體成分總量較佳為5至35質量%，更佳為8至30質量%。若溶劑（E）之含有率處於前述範圍內，則塗佈時之平坦性變得良好，又，形成彩色濾光片時色濃度不會不足，因此存在有顯示特性變得良好之傾向。When the solvent (E) is contained, the content of the solvent (E) is preferably 65 to 95% by mass, more preferably 70 to 92% by mass, with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 35% by mass, more preferably 8 to 30% by mass. When the content rate of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes favorable, and the color density does not become insufficient when forming a color filter, so there is a tendency that the display characteristics become favorable.

＜其他成分＞＜Other ingredients＞

本發明之著色硬化性樹脂組合物亦可視需要而包含：調平劑、填充劑、其他高分子化合物、黏接促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域中習知之添加劑。The colored curable resin composition of the present invention may also include, as required, leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other known additives in the technical field. .

＜著色硬化性樹脂組合物之製造方法＞<The manufacturing method of the colored curable resin composition>

本發明之著色硬化性樹脂組合物可藉由將著色劑（A）、樹脂（B）、聚合性化合物（C）、聚合起始劑（D）、視需要之溶劑（E）及其他成分混合而製備。The colored curable resin composition of the present invention can be obtained by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), an optional solvent (E) and other components while preparing.

＜彩色濾光片之製造方法＞<Manufacturing method of color filter>

作為利用本發明之著色硬化性樹脂組合物而製造著色圖案之方法，可列舉：光刻法、噴墨法、印刷法等。其中，較佳為光刻法。在光刻法中，藉由於曝光時不使用光罩，以及／或者不進行顯影，可形成作為上述著色組合物層之硬化物的著色塗膜。以上述方式形成之著色圖案或著色塗膜即為本發明之彩色濾光片。As a method of producing a colored pattern using the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. In the photolithography method, a colored coating film which is a cured product of the above-mentioned colored composition layer can be formed by not using a mask and/or developing during exposure. The colored pattern or colored coating film formed in the above-mentioned manner is the color filter of the present invention.

本發明之著色硬化性樹脂組合物可製作明度優異之彩色濾光片。該彩色濾光片可作為顯示裝置（例如液晶顯示裝置、有機EL（electroluminescence，電致發光）裝置、電子紙等）及固體攝像元件中所使用之彩色濾光片而使用。The colored curable resin composition of the present invention can produce a color filter excellent in lightness. The color filter can be used as a color filter used in display devices (eg, liquid crystal display devices, organic EL (electroluminescence) devices, electronic paper, etc.) and solid-state imaging elements.

[實施例][Example]

以下，藉由實施例對本發明之著色硬化性樹脂組合物進行更詳細之說明。只要無特別說明，則例中之「%」及「份」為質量%及質量份。Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "parts" in the examples are % by mass and parts by mass.

＜製造例1：化合物1之合成＞<Production Example 1: Synthesis of Compound 1>

於冰浴中，向硫酸（40.2份）中添加N,N-二乙基胺基苯酚（18.9份）及2,4-二氯苯甲醛（10.0份），於125°C下攪拌2天。反應結束後，於冰浴中，將反應液注入氫氧化鈉水溶液中，將析出之紫色結晶進行過濾。將所獲得之紫色結晶以管柱層析法進行分離純化，獲得16.1份（產率為60.0%）之下述化合物1。

In an ice bath, N,N-diethylaminophenol (18.9 parts) and 2,4-dichlorobenzaldehyde (10.0 parts) were added to sulfuric acid (40.2 parts), and the mixture was stirred at 125° C. for 2 days. After the reaction was completed, the reaction solution was poured into an aqueous sodium hydroxide solution in an ice bath, and the precipitated purple crystals were filtered. The obtained purple crystals were separated and purified by column chromatography to obtain 16.1 parts (yield: 60.0%) of the following compound 1.

＜製造例2：化合物2之合成＞<Production Example 2: Synthesis of Compound 2>

將製造例1之2,4-二氯苯甲醛變更為2,3-二氯苯甲醛，進行同樣之操作，以產率63.0%獲得下述化合物2。

The following compound 2 was obtained at a yield of 63.0% by changing the 2,4-dichlorobenzaldehyde of Production Example 1 to 2,3-dichlorobenzaldehyde and performing the same operation.

＜製造例3：化合物3之合成＞<Production Example 3: Synthesis of Compound 3>

將製造例1之2,4-二氯苯甲醛變更為2-氯苯甲醛，進行同樣之操作，以產率61.0%獲得下述化合物3。

The following compound 3 was obtained at a yield of 61.0% by performing the same operation by changing the 2,4-dichlorobenzaldehyde of Production Example 1 to 2-chlorobenzaldehyde.

＜製造例4：化合物4之合成＞<Production Example 4: Synthesis of Compound 4>

將製造例1之2,4-二氯苯甲醛變更為2,6-二氯苯甲醛，進行同樣之操作，以產率30.0%獲得下述化合物4。

The following compound 4 was obtained at a yield of 30.0% by changing the 2,4-dichlorobenzaldehyde of Production Example 1 to 2,6-dichlorobenzaldehyde, and performing the same operation.

＜製造例5：化合物（I-149）之合成＞<Production Example 5: Synthesis of Compound (I-149)>

將上述化合物1（6.5份）及氯醌（5.5份）溶解於乙腈（33.6份）中，於室溫下攪拌3小時。將反應液用氯仿稀釋，添加氫氧化鈉水溶液。將析出之固體過濾後，將濾液用氯仿進行萃取，以水、雙（三氟甲磺醯基）醯亞胺鉀水溶液、水之順序進行洗滌。濃縮後，利用甲醇對殘渣進行晶析，以紫色結晶之形式獲得4.76份（產率為42.5%）之下述化合物（I-149）[式（I-149）所表示之化合物]。

The above-mentioned compound 1 (6.5 parts) and chloranil (5.5 parts) were dissolved in acetonitrile (33.6 parts), and the mixture was stirred at room temperature for 3 hours. The reaction solution was diluted with chloroform, and an aqueous sodium hydroxide solution was added. After the precipitated solid was filtered, the filtrate was extracted with chloroform, and washed with water, an aqueous solution of potassium bis(trifluoromethanesulfonyl)imide, and water in this order. After concentration, the residue was crystallized from methanol to obtain 4.76 parts (yield: 42.5%) of the following compound (I-149) [compound represented by formula (I-149)] as purple crystals.

＜製造例6：化合物（I-141）之合成＞<Production Example 6: Synthesis of Compound (I-141)>

將製造例5之化合物1變更為化合物2，進行同樣之操作，以產率34.9%獲得下述化合物（I-141）[式（I-141）所表示之化合物]。

The following compound (I-141) [compound represented by formula (I-141)] was obtained at a yield of 34.9% by changing the compound 1 of Production Example 5 to the compound 2 and performing the same operation.

＜製造例7：化合物（I-136）之合成＞<Production Example 7: Synthesis of Compound (I-136)>

將製造例5之化合物1變更為化合物3，進行同樣之操作，以產率44.0%獲得下述化合物（I-136）[式（I-136）所表示之化合物]。

The following compound (I-136) [a compound represented by formula (I-136)] was obtained in a yield of 44.0% by changing the compound 1 of Production Example 5 to the compound 3 and performing the same operation.

＜製造例8：化合物（I-226）之合成＞<Production Example 8: Synthesis of Compound (I-226)>

將製造例5之化合物1變更為化合物3，將雙（三氟甲磺醯基）醯亞胺鉀水溶液變更為六氟磷酸鉀水溶液，進行同樣之操作，以產率53.0%獲得下述化合物（I-226）[式（I-226）所表示之化合物]。

The following compound ( I-226) [the compound represented by the formula (I-226)].

＜製造例9：化合物（I-142）之合成＞<Production Example 9: Synthesis of Compound (I-142)>

將製造例5之化合物1變更為化合物4，進行同樣之操作，以產率41.8%獲得下述化合物（I-142）[式（I-142）所表示之化合物]。

The following compound (I-142) [compound represented by formula (I-142)] was obtained at a yield of 41.8% by changing the compound 1 of Production Example 5 to the compound 4 and performing the same operation.

＜¹ H-NMR＞< ¹ H-NMR>

將上述所獲得之各化合物分別溶解於氘代溶劑（CDCl₃ ）中，測定¹ H-NMR（Bruker公司製造之AVANCE（註冊商標）IIIHD400）。Each of the compounds obtained above was dissolved in a deuterated solvent (CDCl ₃ ) and measured by ¹ H-NMR (AVANCE (registered trademark) IIIHD400 manufactured by Bruker).

將結果示於表9中。The results are shown in Table 9.

[表9]

[Table 9]

對於上述所獲得之各化合物，以下述程序進行最大吸收波長（λmax）、莫耳吸光係數（ε）之評價。將結果示於表10中。For each compound obtained above, the evaluation of the maximum absorption wavelength (λmax) and the molar absorption coefficient (ε) was performed by the following procedure. The results are shown in Table 10.

＜最大吸收波長（λmax）及莫耳吸光係數（ε）＞<Maximum absorption wavelength (λmax) and Molar absorption coefficient (ε)>

稱取10毫克之試樣（各化合物），放入100毫升之量瓶中，於其中添加氯仿至標線，以超音波使其振盪10分鐘，獲得均勻化之溶液。從所獲得之溶液中，用定量吸管取出2毫升，放入空的50毫升之量瓶中後，於其中添加氯仿至標線，製備測定樣品。Weigh 10 mg of the sample (each compound), put it into a 100-ml volumetric flask, add chloroform to the mark, and shake it with ultrasonic waves for 10 minutes to obtain a homogenized solution. From the obtained solution, 2 ml was taken out with a quantitative pipette, put into an empty 50 ml measuring flask, and then chloroform was added to the mark to prepare a measurement sample.

對於上述測定樣品，利用日本分光製造之U-3900來進行下述測定。亦即，測定氯仿之基線後，將上述測定樣品放入光程長為1公分之石英槽中，以0.5奈米之間隔且以300奈米／分鐘（nm/min）對800至300奈米之可見光區域進行吸光度測定，將於600至400奈米下成為最大吸光度之波長設為λmax。又，根據λmax之吸光度及其分子量，使用朗伯-比爾定律（Lambert-Beer's law），來計算莫耳吸光係數ε。For the above-mentioned measurement sample, the following measurement was performed using U-3900 manufactured by JASCO Corporation. That is, after measuring the baseline of chloroform, the above-mentioned measurement sample is placed in a quartz cell with an optical path length of 1 cm, at 0.5 nanometer intervals and at 300 nanometers per minute (nm/min) for 800 to 300 nanometers. Absorbance measurement was performed in the visible light region, and the wavelength at which the maximum absorbance was obtained at 600 to 400 nm was set as λmax. In addition, from the absorbance of λmax and its molecular weight, the Mohr absorption coefficient ε is calculated using the Lambert-Beer's law.

[表10]

[Table 10]

紅色顏料合成例Red Pigment Synthesis Example

使174份之三級戊醇及22.2份之金屬鈉於氮氣環境下及130°C下進行反應而合成三級戊醇鈉。將其加熱至60°C，添加91.0份之4-溴苯甲腈、71.05份之琥珀酸二-三級戊酯、108.9份之三級戊醇，以液溫為85°C以下之方式攪拌2小時。將該懸浮液進一步攪拌18小時以上，然後，添加於冷卻至-10°C之200份之甲醇、1000份之水與49.21份之硫酸的混合液中。懸浮液之添加結束後，保持為0°C，攪拌5小時而使反應結束後，將固體成分過濾。將固體成分利用甲醇及水交替地反覆洗滌，直至濾液之著色消失且鹽不再析出為止。然後，將固體成分於80°C之真空乾燥機中乾燥18小時，獲得目標之紅色顏料1。所獲得之量為107份。Sodium tertiary pentoxide was synthesized by reacting 174 parts of tertiary pentanol and 22.2 parts of metallic sodium under nitrogen atmosphere at 130°C. It was heated to 60°C, 91.0 parts of 4-bromobenzonitrile, 71.05 parts of di-tertiary pentyl succinate, 108.9 parts of tri-pentyl alcohol were added, and the liquid temperature was stirred so that the liquid temperature was below 85°C. 2 hours. The suspension was further stirred for 18 hours or more, and then added to a mixed solution of 200 parts of methanol, 1000 parts of water and 49.21 parts of sulfuric acid cooled to -10°C. After the addition of the suspension was completed, the temperature was maintained at 0° C., and the solid content was filtered after stirring for 5 hours to complete the reaction. The solid content was washed alternately and repeatedly with methanol and water until the coloring of the filtrate disappeared and the salt no longer precipitated. Then, the solid content was dried in a vacuum dryer at 80° C. for 18 hours to obtain the target red pigment 1. The amount obtained was 107 parts.

樹脂合成例1Resin Synthesis Example 1

於具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內流通適量之氮氣而置換為氮氣環境，加入141份之乳酸乙酯、178份之丙二醇單甲醚乙酸酯，一面攪拌一面加熱至85°C。接著，耗費5小時滴加以下之混合溶液：38份之丙烯酸、25份之丙烯酸-3,4-環氧基三環[5.2.1.0^2,6 ]癸-8-基酯與丙烯酸-3,4-環氧基三環[5.2.1.0^2,6 ]癸-9-基酯之混合物（含有率為1：1）、137份之環己基馬來醯亞胺、50份之甲基丙烯酸-2-羥基乙酯、338份之丙二醇單甲醚乙酸酯。另一方面，耗費6小時滴加將5份之2,2-偶氮雙異丁腈溶解於88份之丙二醇單甲醚乙酸酯中而成之混合溶液。滴加結束後，於85°C下保持4小時後，冷卻至室溫，獲得固體成分為25.6%之共聚物（樹脂（B-1））溶液。所生成之共聚物之重量平均分子量Mw為8000，分散度為2.1，固體成分換算之酸值為111 mg-KOH/g。樹脂（B-1）具有下述結構單元。

A proper amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and heated to 85° while stirring. C. Next, the following mixed solution was added dropwise over 5 hours: 38 parts of acrylic acid, 25 parts of acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-8-yl ester and acrylic acid-3, A mixture of 4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-9-yl ester (content ratio 1:1), 137 parts of cyclohexylmaleimide, 50 parts of methacrylic acid- 2-hydroxyethyl ester, 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the solution was kept at 85° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution with a solid content of 25.6%. The weight-average molecular weight Mw of the resulting copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH/g. Resin (B-1) has the following structural unit.

樹脂合成例2Resin Synthesis Example 2

於具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內流通適量之氮氣而設為氮氣環境，加入280份之丙二醇單甲醚乙酸酯，一面攪拌一面加熱至80°C。繼而，於該燒瓶內，使用滴加泵，耗費約5小時滴加以下之溶液：將38份之丙烯酸、289份之丙烯酸-3,4-環氧基三環[5.2.1.0^2,6 ]癸-8-基酯與丙烯酸-3,4-環氧基三環[5.2.1.0^2,6 ]癸-9-基酯之混合物（含有率為1：1）溶解於125份之丙二醇單甲醚乙酸酯中而成之溶液。另一方面，利用另一滴加泵，耗費約6小時，於燒瓶內滴加將33份之聚合起始劑2,2-偶氮雙（2,4-二甲基戊腈）溶解於235份之丙二醇單甲醚乙酸酯中而成之溶液。滴加結束後，於80°C下保持4小時後，冷卻至室溫，獲得固體成分為35.1%之共聚物（樹脂（B-2））溶液。所生成之共聚物之重量平均分子量Mw為9200，分散度為2.08，固體成分換算之酸值為77 mg-KOH/g。樹脂（B-2）具有下述結構單元。

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, an appropriate amount of nitrogen was circulated to set it as a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 80° C. while stirring. Then, in the flask, the following solution was added dropwise over about 5 hours using a dropping pump: 38 parts of acrylic acid, 289 parts of acrylic acid-3,4-epoxy tricyclic [5.2.1.0 ^2,6 ] The mixture of dec-8-yl ester and 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-9-yl acrylate (content ratio 1:1) was dissolved in 125 parts of propylene glycol monomethyl ether acetate solution. On the other hand, 33 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts by dropwise addition in the flask over about 6 hours using another dripping pump. of propylene glycol monomethyl ether acetate. After the dropwise addition, the solution was kept at 80° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution with a solid content of 35.1%. The weight-average molecular weight Mw of the resulting copolymer was 9200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin (B-2) has the following structural unit.

樹脂之重量平均分子量（Mw）以及數量平均分子量（Mn）之測定係使用GPC（Gel Permeation Chromatography，凝膠滲透層析）法，於以下條件下進行。裝置：K2479（島津製作所股份有限公司製造）管柱：SHIMADZU Shim-pack GPC-80M 管柱溫度：40°C 溶劑：THF（tetrahydrofuran，四氫呋喃）流速：1.0 毫升／分鐘（mL/min）檢測器：RI 校正用標準物質：TSK STANDARD POLYSTYRENE（標準聚苯乙烯）F-40、F-4、F-288、A-2500、A-500（東曹股份有限公司製造）The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of the resin were measured using GPC (Gel Permeation Chromatography) under the following conditions. Device: K2479 (manufactured by Shimadzu Corporation) String: SHIMADZU Shim-pack GPC-80M Column temperature: 40°C Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1.0 milliliters per minute (mL/min) Detector: RI Standard material for calibration: TSK STANDARD POLYSTYRENE (standard polystyrene) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

將上述所獲得之聚苯乙烯換算之重量平均分子量及數量平均分子量的比（Mw/Mn）作為分散度。The ratio (Mw/Mn) of the weight-average molecular weight and the number-average molecular weight in terms of polystyrene obtained above was taken as the degree of dispersion.

[分散液1之製作][Preparation of Dispersion 1]

將28份之紅色顏料1、7份之分散劑（BYK公司製造之BYKLPN-6919，固體成分換算）、6份之樹脂（B-2）（固體成分換算）、及159份之丙二醇單甲醚乙酸酯進行混合，添加600份之0.4微米直徑之氧化鋯珠，使用塗料調和器（LAU公司製造）來振盪1小時。然後，藉由過濾而去除氧化鋯珠，獲得分散液1。28 parts of red pigment 1, 7 parts of dispersant (BYKLPN-6919 manufactured by BYK company, in terms of solid content), 6 parts of resin (B-2) (in terms of solid content), and 159 parts of propylene glycol monomethyl ether Acetate was mixed, 600 parts of zirconia beads with a diameter of 0.4 μm were added, and the mixture was shaken for 1 hour using a paint mixer (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration, and a dispersion liquid 1 was obtained.

[分散液2之製作][Preparation of Dispersion 2]

將24份之C.I.顏料黃138、11份之分散劑（BYK公司製造之BYKLPN-6919，固體成分換算）、5份之樹脂（B-2）（固體成分換算）、及160份之丙二醇單甲醚乙酸酯進行混合，添加600份之0.4微米直徑之氧化鋯珠，使用塗料調和器（LAU公司製造）來振盪1小時。然後，藉由過濾而去除氧化鋯珠，獲得分散液2。24 parts of C.I. Pigment Yellow 138, 11 parts of dispersant (BYKLPN-6919 manufactured by BYK, in terms of solid content), 5 parts of resin (B-2) (in terms of solid content), and 160 parts of propylene glycol monomethyl The ether acetate was mixed, 600 parts of zirconia beads with a diameter of 0.4 μm were added, and the mixture was shaken for 1 hour using a paint mixer (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration, and a dispersion liquid 2 was obtained.

[分散液3之製作][Preparation of Dispersion 3]

將20份之C.I.顏料黃185、14份之分散劑（BYK公司製造之BYKLPN-6919，固體成分換算）、8份之樹脂（B-2）（固體成分換算）、158份之丙二醇單甲醚乙酸酯進行混合，添加600份之0.4微米直徑之氧化鋯珠，使用塗料調和器（LAU公司製造）來振盪1小時。然後，藉由過濾而去除氧化鋯珠，獲得分散液3。20 parts of C.I. Pigment Yellow 185, 14 parts of dispersant (BYKLPN-6919 manufactured by BYK, in terms of solid content), 8 parts of resin (B-2) (in terms of solid content), 158 parts of propylene glycol monomethyl ether Acetate was mixed, 600 parts of zirconia beads with a diameter of 0.4 μm were added, and the mixture was shaken for 1 hour using a paint mixer (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration, and a dispersion liquid 3 was obtained.

[實施例1至7、比較例1][Examples 1 to 7, Comparative Example 1]

[著色硬化性樹脂組合物之製備][Preparation of Colored Curable Resin Composition]

將表11所示之成分進行混合，獲得各種著色硬化性樹脂組合物。The components shown in Table 11 were mixed to obtain various colored curable resin compositions.

[表11]

樹脂（B）：樹脂（B-1）（固體成分換算）聚合性化合物（C）：二新戊四醇六丙烯酸酯（新中村化學工業股份有限公司製造之「A9550」，固體成分換算）聚合起始劑（D）：N-苯甲醯氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（Irgacure（註冊商標）OXE 01，巴斯夫公司製造）溶劑（E）：E-1：丙二醇單甲醚乙酸酯溶劑（E）：E-2：乳酸乙酯溶劑（E）：E-3：二丙酮醇調平劑（F）：聚醚改質矽油（固體成分換算）（Toray Silicone SH8400，東麗道康寧股份有限公司製造）[Table 11]

Resin (B): Resin (B-1) (in terms of solid content) Polymerizable compound (C): Dipionaerythritol hexaacrylate (“A9550” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., in terms of solid content) Polymerization Initiator (D): N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Manufacturing) Solvent (E): E-1: Propylene Glycol Monomethyl Ether Acetate Solvent (E): E-2: Ethyl Lactate Solvent (E): E-3: Diacetone Alcohol Leveler (F): Polyethylene Ether-modified silicone oil (solid content conversion) (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

＜彩色濾光片之製作＞＜Production of color filter＞

於5公分見方之玻璃基板（Eagle 2000；康寧公司製造）上，利用旋轉塗佈法來塗佈著色硬化性樹脂組合物後，於100°C下預烘烤3分鐘而形成著色組合物層。放置冷卻後，使用曝光機（TME-150RSK，拓普康股份有限公司製造），於大氣環境下以60毫焦耳／平方公分（mJ/cm² ）之曝光量（365奈米基準），對著色組合物層進行光照射。然後，於烘箱中，以230°C進行20分鐘的後烘烤，獲得彩色濾光片。The colored curable resin composition was applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Corporation) by a spin coating method, and then pre-baked at 100° C. for 3 minutes to form a colored composition layer. After standing to cool, use an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.) to colorize at an exposure dose of 60 millijoules/square centimeter (mJ/cm ² ) (365 nm reference) in an atmospheric environment. The composition layer is irradiated with light. Then, post-baking was performed at 230° C. for 20 minutes in an oven to obtain a color filter.

[膜厚測定][Film thickness measurement]

對於所獲得之彩色濾光片，使用膜厚測定裝置（DEKTAK3，日本真空技術股份有限公司製造）來測定膜厚。將結果示於表12中。The film thickness of the obtained color filter was measured using a film thickness measuring apparatus (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 12.

[色度評價][Chroma evaluation]

對於所獲得之玻璃基板上之彩色濾光片，使用測色儀（OSP-SP-200，奧林巴斯股份有限公司製造）來測定分光，使用C光源之顏色匹配函數來測定CIE之XYZ表色系中的xy色度座標（x、y）及刺激值Y。Y之值越大，表示明度越高。將結果示於表12中。For the obtained color filter on the glass substrate, a colorimeter (OSP-SP-200, manufactured by Olympus Co., Ltd.) was used to measure the light spectrum, and the color matching function of the C light source was used to measure the XYZ table of CIE The xy chromaticity coordinates (x, y) and the stimulus value Y in the color system. The larger the value of Y, the higher the brightness. The results are shown in Table 12.

[表12]

[Table 12]

無none

Claims

一種著色硬化性樹脂組合物，其包含著色劑、樹脂、聚合性化合物及聚合起始劑，其中著色劑包含式(I)所表示之化合物及紅色顏料(但，式(I)所表示之化合物除外)，且相對於著色劑總量，紅色顏料之含有率為10質量%以上且95質量%以下，

於式(I)中，R¹至R¹¹各自獨立地表示氫原子、鹵素原子、碳數1至8之飽和烴基或碳數6至20之芳基，該飽和烴基及該芳基中所含之氫原子可經鹵素原子取代；R⁷至R¹¹的至少一者為鹵素原子；R¹²至R¹⁵各自獨立地表示羥基、鹵素原子、氰基、硝基、碳數1至8之飽和烴基、苯基或苄基，該飽和烴基中所含之氫原子可經鹵素原子取代，該苯基及該苄基中所含之氫原子可經碳數1至4之烷基、鹵素原子、氰基或乙烯基取代；R¹與R¹³、R²與R¹²、R⁴與R¹⁵以及R⁵與R¹⁴可各自連結而形成包含氮原子之六員環，R¹²與R¹³以及R¹⁴與R¹⁵可各自連結而形成包含氮原子之三至六員環之雜環；A^q-表示q價之陰離子，q表示1或2；p表示式(I)所表示之化合物將電荷保持為中性之係數。 A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a compound represented by formula (I) and a red pigment (but, a compound represented by formula (I) excluding), and the content of the red pigment is 10% by mass or more and 95% by mass or less relative to the total amount of colorants,

In formula (I), R ¹ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the saturated hydrocarbon group and the aryl group contained in the aryl group The hydrogen atom can be substituted by a halogen atom; at least one of R ⁷ to R ¹¹ is a halogen atom; R ¹² to R ¹⁵ each independently represent a hydroxyl group, a halogen atom, a cyano group, a nitro group, a saturated hydrocarbon group with 1 to 8 carbon atoms , phenyl or benzyl, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, the hydrogen atom contained in the phenyl and the benzyl group may be replaced by an alkyl group with 1 to 4 carbon atoms, a halogen atom, a cyano group group or vinyl substitution; R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ , and R ⁵ and R ¹⁴ can each be linked to form a six-membered ring containing a nitrogen atom, R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ can each be linked to form a three- to six-membered heterocyclic ring containing a nitrogen atom; A ^q- represents an anion of q valence, and q represents 1 or 2; p represents the compound represented by formula (I) to keep the charge as Neutral coefficient.

如請求項1所述之著色硬化性樹脂組合物，其中著色劑進一步包含黃色顏料(但，式(I)所表示之化合物除外)。 The colored curable resin composition according to claim 1, wherein the colorant further contains a yellow pigment (except for the compound represented by the formula (I)).

一種彩色濾光片，其係由如請求項1或2所述之著色硬化性樹脂組合物所形成。 A color filter formed from the coloring curable resin composition according to claim 1 or 2.

一種顯示裝置，其包含如請求項3所述之彩色濾光片。 A display device comprising the color filter of claim 3.