TWI738797B - Compound, colored curable resin composition, color filter and display device - Google Patents

Abstract

。 The use of the coloring curable resin composition containing the compound of the present invention can provide a color filter and a display device with good brightness. The compound of the present invention is represented by formula (I) and satisfies at least one of (i) to (vi): (i) R ¹ is a saturated hydrocarbon group with -COOM, and at least one of ^{R 2} to R ^{4 is aromatic} (Ii) R ¹ and R ³ are aromatic hydrocarbon groups with -COOM; (iii) R ¹ is an aromatic hydrocarbon group with -COOM, and R ³ is a saturated hydrocarbon group with -COOM (Iv) R ¹ is a saturated hydrocarbon group with -COOM, R ³ is a saturated hydrocarbon group with -COOM; (v) R ¹ is a saturated hydrocarbon group, R ² is an aromatic hydrocarbon group with -COOM; (vi) R ¹ and R ² is a hydrogen atom or a saturated hydrocarbon group, ^{at least one of R 3} and R ⁴ is an aromatic hydrocarbon group having -COOM,

.

Description

Compound, colored curable resin composition, color filter and display device

Field of the Invention The present invention relates to a compound and a colored curable resin composition.

BACKGROUND OF THE INVENTION Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays are manufactured using a colored curable resin composition. As such a colored curable resin composition, a colored curable resin composition containing a compound represented by the following formula or the like is known:

。 現有技術文獻 專利文獻【化1】

. Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent Application Publication No. 2010-32999

SUMMARY OF THE INVENTION Problems to be Solved by the Invention The lightness of a color filter formed from a coloring curable resin composition containing the above-mentioned compound known in the past is sometimes not sufficiently satisfactory. Means to solve the problem

[式（I）中，R¹ ~R⁴ 相互獨立表示氫原子、可具有取代基的碳數1~20的飽和烴基、或者可具有取代基的碳數6~10的芳香族烴基，該飽和烴基中所含的-CH₂ -可被-O-、-CO-或-NR¹¹ -替換。R¹ 和R² 可一起形成含有氮原子的環，R³ 和R⁴ 可一起形成含有氮原子的環。 R⁶ 和R⁷ 相互獨立地表示氫原子或碳數1~6的烷基。 R¹¹ 表示氫原子、碳數1~20的飽和烴基或碳數7~10的芳烷基。 不過，使由式（I）表示的化合物滿足必要條件（i）~（vi）中的至少1個： （i）R¹ 為具有-COOM的碳數1~20的飽和烴基，R² ~R⁴ 中的至少1個為可具有取代基的碳數6~10的芳香族烴基，並且在1分子中所含的-COOM為1個。 （ii）R¹ 和R³ 為具有-COOM的碳數6~10的芳香族烴基。 （iii）R¹ 為具有-COOM的碳數6~10的芳香族烴基，R³ 為具有-COOM的碳數1~20的飽和烴基。 （iv）R¹ 為具有-COOM的碳數3~20的飽和烴基，R³ 為具有-COOM的碳數1~20的飽和烴基。 （v）R¹ 為可具有取代基的碳數1~20的飽和烴基，R² 為具有-COOM的碳數6~10的芳香族烴基。 （vi）R¹ 和R² 為氫原子或可具有取代基的碳數1~20的飽和烴基，R³ 和R⁴ 中的至少1個為具有-COOM的碳數6~10的芳香族烴基。 （i）~（vi）中，M表示氫原子、Na⁺ 、K⁺ 、或⁺ N（R¹² ）₄ ，4個R¹² 可以相同也可不同。 R¹² 表示氫原子、碳數1~20的飽和烴基或碳數7~10的芳烷基。] [2] 著色固化性樹脂組合物，其包含：[1]所述的化合物、樹脂（B）、聚合性化合物（C）和聚合引發劑（D）。 [3] 濾色器，其由[2]所述的著色固化性樹脂組合物形成。 [4] 顯示裝置，其包含[3]所述的濾色器。 發明的效果The present invention includes the following inventions. [1] The compound represented by formula (I). 【化2】

[In formula (I), R ¹ to R ⁴ independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or an aromatic hydrocarbon group with 6 to 10 carbons which may have a substituent, the saturated _{-CH 2} -contained in the hydrocarbon group may be replaced by -O-, -CO- or -NR ¹¹ -. R ¹ and R ² can together form a ring containing a nitrogen atom, and R ³ and R ⁴ can together form a ring containing a nitrogen atom. R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. However, the compound represented by the formula (I) should satisfy at least one of the necessary conditions (i) to (vi): (i) R ¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms with -COOM, and R ² to R ^4, at least one carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 10, -COOM and contained in one molecule is one. (Ii) R ¹ and R ³ are aromatic hydrocarbon groups having 6 to 10 carbon atoms having -COOM. (Iii) R ¹ is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM, and R ³ is a saturated hydrocarbon group having 1 to 20 carbons having -COOM. (Iv) R ¹ is a saturated hydrocarbon group with 3 to 20 carbons having -COOM, and R ³ is a saturated hydrocarbon group with 1 to 20 carbons having -COOM. (V) R ¹ is an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 2} is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM. (Vi) R ¹ and R ² are hydrogen atoms or optionally substituted saturated hydrocarbon groups of 1 to 20 carbons, ^{and at least one of R 3} and R ⁴ is an aromatic hydrocarbon group of 6 to 10 carbons with -COOM . In (i) ~ (vi), M represents a hydrogen atom, Na ⁺ , K ⁺ , or ⁺ N (R ¹² ) ₄ , and the four R ¹² may be the same or different. R ¹² represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ] [2] A colored curable resin composition comprising: the compound described in [1], the resin (B), the polymerizable compound (C), and the polymerization initiator (D). [3] A color filter formed of the coloring curable resin composition described in [2]. [4] A display device including the color filter described in [3]. The effect of the invention

The coloring curable resin composition containing the compound of the present invention can form a color filter excellent in lightness.

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention is represented by formula (I). It should be noted that the compounds of the present invention also include tautomers, stereoisomers, and salts thereof. In addition, each component and functional group exemplified below can be used alone or in combination.

【化3】

[In formula (I), R ¹ to R ⁴ independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or an aromatic hydrocarbon group with 6 to 10 carbons which may have a substituent, the _{-CH 2} -contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom. R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. However, the compound represented by the formula (I) satisfies at least one of the necessary conditions (i) to (vi): (i) R ¹ is a saturated hydrocarbon group with a carbon number of 1 to 20 having -COOM, and R ² to R ⁴ At least one of them is an aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent, and there is one -COOM contained in one molecule. (Ii) R ¹ and R ³ are aromatic hydrocarbon groups having 6 to 10 carbon atoms having -COOM. (Iii) R ¹ is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM, and R ³ is a saturated hydrocarbon group having 1 to 20 carbons having -COOM. (Iv) R ¹ is a saturated hydrocarbon group with 3 to 20 carbons having -COOM, and R ³ is a saturated hydrocarbon group with 1 to 20 carbons having -COOM. (V) R ¹ is an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 2} is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM. (Vi) R ¹ and R ² are hydrogen atoms or optionally substituted saturated hydrocarbon groups of 1 to 20 carbons, ^{and at least one of R 3} and R ⁴ is an aromatic hydrocarbon group of 6 to 10 carbons with -COOM . In (i) ~ (vi), M represents a hydrogen atom, Na ⁺ , K ⁺ , or ⁺ N (R ¹² ) ₄ , and the four R ¹² may be the same or different. R ¹² represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a mesitylene group, a propylphenyl group, and a butylphenyl group.

Examples of substituents that the aromatic hydrocarbon group may have include halogen atoms, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -COOM, -CO ₂ R ⁸ , and- SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ , and these substituents are preferably substituted with hydrogen atoms contained in the aromatic hydrocarbon group. Among these, as the substituent, -SO ₃ H, -SO ₃ ^- Z ^+, and -SO ₂ NR ⁹ R ¹⁰ are preferred, and -SO ₃ ^- Z ⁺ , -COOM, and -SO ₂ NR ⁹ R ^{10 are} more preferred. As -SO ₃ ^- Z ^{+ in} this case, -SO ₃ ^-+ N(R ¹¹ ) ₄ is preferable. When the aromatic hydrocarbon group contains —COOM as a substituent, —COOM is preferably bonded to the meta position or the para position with respect to the bonding end. If R ¹ to R ⁴ are these groups, the coloring curable resin composition of the present invention containing the compound (I) can form a color filter with little foreign matter generation and excellent heat resistance.

R ⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom. R ⁹ and R ¹⁰ independently represent a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms which may have a substituent. The -CH ₂ -contained in the saturated aliphatic hydrocarbon group may be replaced by -O-, -CO-,- NH- or -NR ⁸ -replacement, R ⁹ and R ¹⁰ can be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

Examples of saturated hydrocarbon groups having 1 to 20 carbons in R ¹ to R ⁴ and R ⁸ to R ¹² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl and other branches Chain alkyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbons. The carbon number of the saturated hydrocarbon group is more preferably 1-10. The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to R ⁴ may be substituted with -COOM as a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, for example. In addition, in ^{the saturated hydrocarbon group represented by R 1} to R ⁴ , it is preferable that the hydrogen atom bonded to the terminal carbon atom (primary carbon atom) is substituted with a substituent. Examples of the aromatic hydrocarbon group having 6 to 10 carbons that can be ^{substituted by the hydrogen atom of the saturated hydrocarbon group of R 1} to R ⁴ include the groups exemplified as the aromatic hydrocarbon group of 6 to 10 carbons in ^{R 1} to R ⁴ The same group. The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted by, for example, a hydroxyl group or a halogen atom as a substituent.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following rings. * Indicates the bonding end.

【化4】

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and diethylhexyloxy. Alkoxy groups such as decaalkoxy and the like.

Examples of -CO ₂ R ⁸ include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

Examples of -SR ⁸ include alkylsulfanes such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl, and eicosylsulfanyl. Base and so on. Examples of -SO ₂ R ⁸ include alkyl groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl. Sulfonyl and so on. Examples of -SO ₃ R ⁸ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosane Alkoxysulfonyl groups such as oxysulfonyl groups and the like.

Examples of -SO ₂ NR ⁹ R ¹⁰ include sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, and N-isopropyl Sulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentyl Sulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl) ) Sulfamoyl, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl) Sulfamoyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1 ,4-Dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethylhexyl)amine Sulfonamide, N-(1,1,2,2-tetramethylbutyl)sulfamoyl and other N-1 substituted sulfamoyl groups; N,N-dimethylsulfamoyl, N,N -Ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N ,N-tert-Butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethyl N, N-2 substituted sulfamoyl and the like.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include alkyl groups having 1 to 6 carbon atoms among the alkyl groups exemplified above. Among them, as R ⁶ and R ⁷ , a hydrogen atom is preferred.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ to R ^{12 include benzyl, phenylethyl, and phenylbutyl.}

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . As the above-mentioned ⁺ N(R ¹¹ ) ₄ , it is preferable ^{that at least two of the four R 11} are saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, ^{the total carbon number of the four R 11} is preferably 20 to 80, and more preferably 20 to 60.

However, the compound represented by the formula (I) satisfies at least one of the necessary conditions (i) to (vi), and preferably satisfies at least one of the necessary conditions (i), (ii), (iv), and (v) : (I) R ¹ is a saturated hydrocarbon group having 1 to 20 carbons with -COOM, ^{at least one of R 2} to R ⁴ is an optionally substituted aromatic hydrocarbon group with 6 to 10 carbons, and in 1 molecule The included -COOM is one. (Ii) R ¹ and R ³ are aromatic hydrocarbon groups having 6 to 10 carbon atoms having -COOM. (Iii) R ¹ is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM, and R ³ is a saturated hydrocarbon group having 1 to 20 carbons having -COOM. (Iv) R ¹ is a saturated hydrocarbon group with 3 to 20 carbons having -COOM, and R ³ is a saturated hydrocarbon group with 1 to 20 carbons having -COOM. (V) R ¹ is an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 2} is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM. (Vi) R ¹ and R ² are hydrogen atoms or optionally substituted saturated hydrocarbon groups of 1 to 20 carbons, ^{and at least one of R 3} and R ⁴ is an aromatic hydrocarbon group of 6 to 10 carbons with -COOM . In (i) ~ (vi), M represents a hydrogen atom, Na ⁺ , K ⁺ , or ⁺ N (R ¹² ) ₄ , and the four R ¹² may be the same or different. R ¹² represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons.

M is particularly preferably a hydrogen atom. R ¹² is preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a benzyl group.

In the necessary condition (i), it is preferable that R ¹ is a saturated hydrocarbon group with COOM having 1 to 20 carbons (preferably a saturated hydrocarbon group with 1 to 10 carbons), and at least two of ^{R 2} to R ^{4 may be substituted} Aromatic hydrocarbon group with 6 to 10 carbon atoms. In addition, it is more preferable that R ¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably a saturated hydrocarbon group having 1 to 10 carbon atoms) having COOM, and R ² and R ³ are optionally substituted aromatic hydrocarbon groups having 6 to 10 carbon atoms. .

In the requirement (ii), it is preferable that R ² and R ⁴ are a hydrogen atom or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms.

In the requirement (iv), it is preferable that R ² and R ⁴ are an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. In addition, it is preferable that R ² is a saturated hydrocarbon group having 3 to 20 carbon atoms having COOM, and it is more preferable that R ¹ and R ² are saturated hydrocarbon groups having 3 to 10 carbon atoms having COOM.

In the requirement (v), it is more preferable that R ³ is a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, and R ⁴ is an aromatic hydrocarbon group having 6 to 10 carbons which has COOM.

As the compound (I), a compound represented by formula (Ia) (hereinafter may be referred to as “compound (Ia)”) is preferred. Compound (Ia) may be its tautomer.

【化5】

[In formula (Ia), R ²¹ to R ²⁴ independently represent a hydrogen atom, -R ^26, or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. R ²¹ and R ²² may together form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may together form a ring containing a nitrogen atom. R ²⁶ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have COOM. M represents a hydrogen atom, Na ⁺ , K ⁺ , or ⁺ N (R ¹² ) ₄ , and the four R ¹² may be the same or different. R ¹² represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. However, the compound represented by formula (Ia) satisfies at least one of the necessary conditions (ia) to (via): (ia) ^{at least one of R 21} is a saturated hydrocarbon group with COOM and carbon number of 1-20, R ^{At least one of 22} to R ²⁴ is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbons, and one -COOM is contained in one molecule. (Iia) R ²¹ and R ²³ are an aromatic hydrocarbon group having a carbon number of 6 to 10 having COOM. (Iiia) R ²¹ is an aromatic hydrocarbon group with 6 to 10 carbons having COOM, and R ²³ is a saturated hydrocarbon group with 1 to 20 carbons having COOM. (Iva) R ²¹ is a saturated hydrocarbon group with 3 to 20 carbons having COOM, and R ²³ is a saturated hydrocarbon group with 1 to 20 carbons having COOM. (Va) R ²¹ is an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 22} is an aromatic hydrocarbon group having 6 to 10 carbons and having COOM. (Via) R ²¹ and R ²² are a hydrogen atom or an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 23} is an aromatic hydrocarbon group having 6 to 10 carbons having COOM. ]

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include the same groups as those exemplified as the above-mentioned aromatic hydrocarbon group of ^{R 1} to R ^4. A hydrogen atom contained in the aromatic hydrocarbon group may be _{^{-COOM, -SO 3 -, -SO 3}} H, -SO 3 - Z1 +, or a substituted -SO ₃ R ²⁵ -SO ₂ NHR ^25. When the hydrogen atom contained in the aromatic hydrocarbon group is substituted by -COOM, it is preferable that -COOM is bonded to the meta position or the para position with respect to the bonding end. Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . R ²⁵ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. As the combination of R ²¹ - R ^24, preferably R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is an aromatic hydrocarbon group having a carbon number of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group is -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ instead. A more preferred combination is: R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are aromatic hydrocarbon groups with 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO ₃ ^- Z1 ^{+ or-} Replaced by SO ₂ NHR ^26.

Examples of the nitrogen atom-containing ring formed by R ²¹ and R ²² together and the nitrogen atom-containing ring formed by R ²³ and R ²⁴ together include the same ring as the ring formed by ^{R 1} and R ^{2 together.} Among them, aliphatic heterocycles are preferred. As this aliphatic heterocyclic ring, the following aliphatic heterocyclic ring can be mentioned, for example. * Indicates the bonding end.

【化6】

Examples of the saturated hydrocarbon groups having 1 to 20 carbon atoms in R ²⁵ to R ²⁷ include the same groups as those exemplified as saturated hydrocarbon groups in ^{R 8} to R ^11. When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is preferably each independently a methyl group or an ethyl group. When R ²¹ to R ²⁴ are -R ²⁶ and R ²⁶ has -COOM, it is preferable that the hydrogen atom bonded to the terminal carbon atom (primary carbon atom) of ^{-R 26 is replaced by -COOM.} Further, -SO ₂ NHR ^26, and ²⁶ of R -SO ₃ R ^26, preferably branched chain alkyl group having a carbon number of 3 to 20 carbon atoms, more preferably branched chain alkyl group having 6 to 12, more preferably 2 Ethylhexyl.

As the above-mentioned ⁺ N(R ²⁷ ) ₄ , it is preferable ^{that at least two of the four R 27} are saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, the total carbon number of R 4 is preferably 20 to ²⁷ 80, more preferably 20 to 60. ^{When +} N(R ²⁷ ) ₄ is present in the compound (Ia), R ²⁷ may be the same or different.

However, the compound represented by formula (Ia) satisfies at least one of the necessary conditions (ia) to (via), and preferably satisfies at least one of the necessary conditions (ia), (iia), (iva), and (va) : (Ia) R ²¹ is a saturated hydrocarbon group with 1 to 20 carbons with -COOM, ^{at least one of R 22} to R ²⁴ is an optionally substituted aromatic hydrocarbon group with 6 to 10 carbons, and in 1 molecule The included -COOM is one. (Iia) R ²¹ and R ²³ are aromatic hydrocarbon groups with 6 to 10 carbon atoms having -COOM. (Iiia) R ²¹ is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM, and R ²³ is a saturated hydrocarbon group having 1 to 20 carbons having -COOM. (Iva) R ²¹ is a saturated hydrocarbon group having 3 to 20 carbons having -COOM, and R ²³ is a saturated hydrocarbon group having 1 to 20 carbons having -COOM. (Va) R ²¹ is an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 22} is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM. (Via) R ²¹ and R ²² are hydrogen atoms or optionally substituted saturated hydrocarbon groups of 1 to 20 carbons, ^{and at least one of R 23} and R ²⁴ is an aromatic hydrocarbon group of 6 to 10 carbons with -COOM .

M is particularly preferably a hydrogen atom. R ¹² is preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a benzyl group.

In the requirement (ia), R ²¹ is preferably a saturated hydrocarbon group with 1 to 20 carbons (preferably a saturated hydrocarbon group with 1 to 10 carbons) with -COOM, and at least two of ^{R 22} to R ^{24 may be substituted} Aromatic hydrocarbon group with 6 to 10 carbon atoms. Preferably, R ²¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably a saturated hydrocarbon group having 1 to 10 carbon atoms) having -COOM, and R ²² and R ²³ are optionally substituted aromatic hydrocarbon groups having 6 to 10 carbon atoms.

In the requirement (iia), it is preferable that R ²² and R ²⁴ are a hydrogen atom or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms.

In the requirement (iva), R ²² and R ²⁴ are preferably an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. In addition, it is preferable that R ²² is a saturated hydrocarbon group having 3 to 20 carbons having -COOM, and it is more preferable that R ²¹ and R ²² be a saturated hydrocarbon group having 3 to 10 carbons having -COOM.

In the requirement (va), it is more preferable that R ²³ is an optionally substituted saturated hydrocarbon group ^{having 1 to 20 carbons, and R 24} is an aromatic hydrocarbon group having 6 to 10 carbons having -COOM.

In addition, as the compound (I), a compound represented by formula (Ib) (hereinafter may be referred to as "compound (Ib)") is also preferable. Compound (Ib) may be its tautomer.

【化7】

[In formula (Ib), R ³¹ and R ³² independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group of ^{R 31} and R ^{32 can be replaced by -COOM and 6 to 10 carbon atoms.} The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -COOM or an alkoxy group having 1 to 3 carbon atoms. The saturated hydrocarbon group contained in the ^{above-mentioned R 31} and R ^{32 contains -CH} ₂ -can be replaced by -O-, -CO- or -NR ¹¹ -. R ³³ and R ³⁴ independently represent -COOM, an alkyl group having 1 to 4 carbons, an alkylsulfanyl group having 1 to 4 carbons, or an alkylsulfonyl group having 1 to 4 carbons. R ³¹ and R ³³ may together form a ring containing a nitrogen atom, and R ³² and R ³⁴ may together form a ring containing a nitrogen atom. p and q represent an integer from 0 to 5 independently of each other. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different. R ¹¹ has the same meaning as above. M represents a hydrogen atom, Na ⁺ , K ⁺ , or ⁺ N (R ¹² ) ₄ , and the four R ¹² may be the same or different. R ¹² represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. However, the compound represented by the formula (Ib) satisfies at least one of the necessary conditions (ib) to (ivb): (ib) R ³¹ is a saturated hydrocarbon group with a carbon number of 1 to 20 with -COOM, contained in one molecule The -COOM is 1. (Iib) At least one of ^{R 33} and R ^{34 is -COOM.} (Iiib) R ³¹ is a saturated hydrocarbon group with a carbon number of 1 to 20 having -COOM, and R ³⁴ is -COOM. (Ivb) R ³¹ is a saturated hydrocarbon group having 3 to 20 carbons having -COOM, and R ³² is a saturated hydrocarbon group having 1 to 20 carbons having -COOM. ]

Examples of the saturated hydrocarbon group having 1 to 10 carbons in R ³¹ and R ³² include groups having 1 to 10 carbons in the saturated hydrocarbon group of ^{R 8.} Examples of the optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include the same groups as the aromatic hydrocarbon group in ^{R 1.} In addition, ^{when the saturated hydrocarbon group represented by R 31} and R ³² is substituted by -COOM, it is preferable that the hydrogen atom bonded to the terminal carbon atom (primary carbon atom) is substituted by -COOM. As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example. R ³¹ and R ^{32 are} preferably a saturated hydrocarbon group having 1 to 3 carbon atoms independently of each other.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ^{34 include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropyl.} Sulfuryl and so on. Examples of the alkylsulfonyl groups having 1 to 4 carbon atoms in R ³³ and R ^{34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropyl.} Sulfonyl and so on. As R ³³ and R ³⁴ , -COOM or an alkyl group having 1 to 4 carbon atoms is preferable, and -COOM or a methyl group is more preferable. In addition, when R ³³ and R ³⁴ are -COOM, it is preferable that -COOM is bonded to the meta position or the para position with respect to the carbon atom bonded to N.

p and q are preferably an integer of 0-2, preferably 1 or 2.

However, the compound represented by the formula (Ib) preferably satisfies at least one of the requirements (ib) to (ivb), and preferably satisfies at least one of the requirements (ib), (iib), and (ivb). (Ib) R ³¹ is a saturated hydrocarbon group with a carbon number of 1 to 20 having -COOM, and there is one -COOM contained in one molecule. (Iib) At least one of ^{R 33} and R ^{34 is -COOM.} (Iiib) R ³¹ is a saturated hydrocarbon group with a carbon number of 1 to 20 having -COOM, and R ³⁴ is -COOM. (Ivb) R ³¹ is a saturated hydrocarbon group having 3 to 20 carbons having -COOM, and R ³³ is a saturated hydrocarbon group having 1 to 20 carbons having -COOM.

M is particularly preferably a hydrogen atom. R ¹² is preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a benzyl group.

In the requirement (iib), it is preferable that both R ³³ and R ³⁴ are -COOM.

In the requirement (ivb), R ³³ is preferably a saturated hydrocarbon group having 3 to 20 carbon atoms having -COOM, and R ³³ and R ^{34 are} more preferably a saturated hydrocarbon group having 3 to 10 carbon atoms having -COOM.

Examples of the compound (I) include compounds represented by formula (Aa-1) to formula (Aa-52).

【化8】

【化9】

【化10】

【化11】

【化12】

【化13】

【化14】

The colored curable resin composition of the present invention contains a compound (I) as a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

In the colored curable resin composition of the present invention, the content of the compound (I) relative to the total solid content of the colored curable resin composition is preferably 0.1-20% by mass, more preferably 0.5-10% by mass. More preferably, it is 0.5-5 mass %.

<Coloring agent (A)> The coloring agent (A) may contain a dye (A1) and a pigment (A2) in addition to the compound (I).

The dye (A1) is not particularly limited, and well-known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as substances having hue in addition to pigments in the Excellent Index (published by The Society of Dyers and Colourists), and well-known dyes described in the dyeing notes (Sei Dyers Co., Ltd.). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azo Methine dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred. It should be noted that the compound (I) is contained in the dye (A1).

Specifically, CI Solvent Yellow 4 (hereinafter the description of CI Solvent Yellow is omitted, and only the serial number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227 , 230, 245, 247; CI solvent orange 2, 7, 11, 15, 26, 56, 77, 86; CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48 , 51, 59, 60; CI solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32 , 33, 34, 35 and other CI solvent dyes, CI 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; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52 , 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151 , 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270 , 274, 277, 280, 281, 289, 308, 312, 315, 316 , 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25 , 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Green 1 , 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, 104, 105 , 106, 109 and other CI acid dyes, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176 , 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C. I. Direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 3 , 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93 , 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159 , 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201 , 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250 , 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, CI direct dyes such as 77, 79, 82, CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue 1, 14, 56, 60 and other CI Disperse Dyes, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic Red 9; CI Basic Dyes such as CI Basic Green 1, CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI reactive dyes such as CI Reactive Red 36 CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C. I. Mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant Purple 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30 , 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes, CI vat green 1, etc. CI vat dyes, etc. These dyes can be appropriately selected according to the spectroscopic spectrum of the desired color filter.

In the dye (A1), the content of the compound (I) relative to the total amount of the dye (A1) is preferably 1 to 99% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass.

The dye (A1) preferably contains an anthraquinone dye (Ad).

As the anthraquinone dye (Ad), a known substance can be used. Examples of anthraquinone dyes (Ad) include CI Solvent Yellow 117, 163, 167, 189, CI Solvent Orange 77, 86, CI Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169 , 172, 175, 181, 207, 222, 227, 230, 245, 247, CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111 , 112, 122, 128, 132, 136, 139, CI Solvent Green 3, 28, 29, 32, 33, CI Acid Red 80, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112 CI Disperse Yellow 51, CI Disperse Violet 26, 27, CI Disperse Blue 1, 14, 56, 60, CI Direct Blue 40, CI Mordant Red 3, 11, CI Mordant Blue 8 etc. The anthraquinone dye (Ad) is preferably dissolved in an organic solvent, and cyan, purple or red anthraquinone dyes are more preferable.

Among these, as the anthraquinone dye (Ad), a compound represented by formula (1d) (hereinafter may be referred to as "compound (1d)") is preferred.

【化15】

[In formula (1d), R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 10 carbons, an optionally substituted alicyclic hydrocarbon group with 3 to 10 carbons, Or by formula (1d')

【化16】

(In formula (1d'), R ⁹³ represents an alkyl group with 1 to 6 carbon atoms, a halogen atom, -SO ₃ H, -CO ₂ H, -CO ₂ R ⁹⁴ , -NHCOR ⁹⁴ , -SO ₃ R ^{94 or-} SO ₂ NR ⁹⁴ R ^95. R ⁹⁴ represents an aliphatic hydrocarbon group with 1 to 10 carbons, or an alicyclic hydrocarbon group with 3 to 10 carbons, and the hydrogen atoms contained in the aliphatic hydrocarbon group or alicyclic hydrocarbon group may be halogenated Substitution by atom, hydroxyl or amino group. R ⁹⁵ represents a hydrogen atom and a saturated hydrocarbon group with 1 to 10 carbon atoms. r represents an integer of 0 to 5. When r is 2 or more, a plurality of R ⁹³ may be the same or different. X ⁹¹ represents a single bond or an alkylene group having 1 to 6 carbon atoms.) represents a group. ]

When the compound (1d) has -SO ₃ H and/or -CO ₂ H, they may form a salt (for example, Na salt, K salt).

In R ⁹¹ and R ⁹² , R ⁹⁴ and R ⁹⁵ , examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Base, nonyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 2-ethylhexyl, etc. Examples of the substituent that these aliphatic hydrocarbon groups may have include a hydroxyl group, a halogen atom, or an amino group, and a hydroxyl group or a halogen atom is preferable.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ⁹¹ , R ⁹² and R ⁹⁴ include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, etc. . Examples of the substituent that these alicyclic hydrocarbon groups may have include a hydroxyl group, a halogen atom, or an amino group, and the hydroxyl group or a halogen atom is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁹³ include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. Base, isopentyl, neopentyl, etc.

Examples of -CO ₂ R ⁹⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, an eicosyloxycarbonyl group, and the like.

Examples of -NHCOR ⁹⁴ include N-acetylamino, N-propanylamino, N-butyrylamino, N-isobutyrylamino, N-neopentylamino, and the like.

Examples of -SO ₃ R ⁹⁴ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosanyloxy Sulfonyl and so on.

Examples of -SO ₂ NR ⁹⁴ R ⁹⁵ include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N -Butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N-( 1-Ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) sulfamoyl, N- (2,2-Dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N-(3 -Methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-cyclohexylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl) ) Sulfamoyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-( 1,4-Dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexyl N-1 substituted sulfamoyl groups such as sulfamoyl, N-(1,1,2,2-tetramethylbutyl)sulfamoyl, and N-(5-aminopentyl)sulfamoyl; N,N-dimethylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methyl Propyl) sulfamoyl, N,N-heptylmethylsulfamoyl, etc. N,N-2 substituted sulfamoyl, etc.

In X ⁹¹ , examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, and butane-1,4 -Diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane- 1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, etc.

R ⁹³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO ₃ R ⁹⁴ , -SO ₂ NR ⁹⁴ R ⁹⁵ , more preferably -SO ₂ NR ⁹⁴ R ⁹⁵ , and even more preferably -SO ₂ NHR ⁹⁴ ( In each formula, R ⁹⁴ and R ⁹⁵ are the same as defined above).

Examples of the compound (1d) include compounds represented by formula (3-1) to formula (3-11).

【化17】

The anthraquinone dye (Ad) is preferably a compound represented by formula (1d) in which R ⁹¹ and R ⁹² are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group which may have a halogen atom, and a compound represented by formula (1d' The compound represented by any one of the groups represented by) is more preferably a compound represented by formula (3-4) and formula (3-11).

When the anthraquinone dye (Ad) is contained, the content of the dye (A1) is preferably 1 to 99% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass relative to the total amount of the dye (A1).

The pigment (A2) is not particularly limited, and well-known pigments can be used. For example, pigments classified as pigments in the Excellent Index (published by The Society of Dyers and Colourists) can be used. Examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; 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 cyan pigments; CI Pigment Violet 1, 19, 23, 29, 32 , 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

As the pigment, cyan pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60 are preferred; purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred, and CI pigments are more preferred Blue 15:3, 15:6 and CI Pigment Violet 23, more preferably CI Pigment Blue 15:6. By including the above-mentioned pigment, the optimization of the transmission spectrum is easy, and the light resistance and chemical resistance of the color filter become good.

For pigments, if necessary, resin treatment, surface treatment using pigment derivatives introduced with acidic groups or basic groups, etc., grafting treatment to the surface of the pigment using polymer compounds, etc., and sulfuric acid micronization method Micronization treatment such as, or cleaning treatment using organic solvents, water, etc. for removing impurities, removal treatment of ionic impurities using ion exchange methods, etc. The pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, it is possible to obtain a pigment dispersion in a state where the pigment is uniformly dispersed in the solution.

Examples of the above-mentioned pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surfactants. These pigment dispersants may be used alone or in combination of two or more kinds. As a pigment dispersant, it is represented by a trade name, and it includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Cerusbes (manufactured by Zebeka Co., Ltd.), and EFKA (manufactured by CIBA Co., Ltd.) ), Ajispa (manufactured by Ajinomoto Fyntec Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), etc. In the case of using a pigment dispersant, the amount used 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 with respect to the total amount of the pigment (A2). If the amount of the pigment dispersant used is within the above-mentioned range, there is a tendency to obtain a pigment dispersion in a uniform dispersion state.

In the colorant (A), the content ratio of the dye (A1) to the pigment (A2) (dye (A1)/pigment (A2)) on a mass basis, usually 1/99~99/1, preferably 3/97 ~40/60, more preferably 5/95~30/70.

The content rate of the coloring agent (A) relative to the total amount of solids is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass. If the content of the coloring agent (A) is within the above-mentioned range, the color density at the time of making a color filter is sufficient, and the composition can contain the necessary amount of resin and polymerizable compound, so that a pattern with sufficient mechanical strength can be formed. Here, the "total amount of solid content" in this specification refers to the amount after removing the solvent content from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component with respect to it can be measured by, for example, known analysis means such as liquid chromatography or gas chromatography.

<Resin (B)> The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6] and the like. Resin [K1]: It has a structural unit derived from at least one selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)") and a structure derived from a ring having 2 to 4 carbon atoms A copolymer of structural units of monomer (b) (hereinafter sometimes referred to as "(b)") with a crystalline ether structure and ethylenically unsaturated bond; resin [K2]: having structural units derived from (a) and ( The structural unit of b) and the copolymerization of the structural unit derived from the monomer (c) which can be copolymerized with (a) (However, it is different from (a) and (b).) (hereinafter sometimes referred to as "(c)") Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a structural unit having a structural unit derived from (b) and a structural unit derived from (a) Copolymer with the structural unit derived from (c); Resin [K5]: Copolymer with the structural unit added to the structural unit from (b) and the structural unit derived from (c); Resin [K6 ]: A copolymer having a structural unit derived from (a) and a structural unit derived from (b), and further a carboxylic anhydride is added, and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid; maleic acid, fumaric acid, and citracan Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6 -Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid 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-vinyl Phthalic 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 and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2-(meth)propenoxyethyl] ester, phthalic acid mono[ Unsaturated mono[(meth)acryloxyalkyl] esters of polycarboxylic acids with two or more valences, such as 2-(meth)acryloxyethyl] ester; such as α-(hydroxymeth)acrylic acid The unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(B) For example, it refers to a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymeric compound. (B) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred. In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

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

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

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2, 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Cerocoid 2000; manufactured by Daicel Co., Ltd.), (methyl ) 3,4-epoxycyclohexyl methyl acrylate (for example, Seikromam A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Seikromam M100; ( Co., Ltd.), the compound represented by the formula (BI), the compound represented by the formula (BII), and the like.

【化18】

[In the formula (BI) and the formula (BII), R ^a and R ^b represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group may be substituted with a hydroxyl group. X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-. R ^c represents an alkylene group having 1 to 6 carbon atoms. * Indicates the bonding end with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. 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, and 1-hydroxy -1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. As R ^a and R ^b , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are exemplified, and more preferably, a hydrogen atom and a methyl group are exemplified.

Examples of alkylene include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, hexane-1,6-diyl, etc. X ^a and X ^b preferably include single bonds, methylene, ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more preferably single bonds, *- CH ₂ CH ₂ -O- (* indicates the bonding end with O).

As a compound represented by formula (BI), the compound etc. which are represented by any one of formula (BI-1)-formula (BI-15) are mentioned. Among them, the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI-9) or the formula (BI-11) ~ the formula (BI- The compound represented by 15) is more preferably a compound represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15).

【化19】

【化20】

As a compound represented by Formula (BII), the compound etc. which are represented by any one of Formula (BII-1)-Formula (BII-15) etc. are mentioned. Among them, the formula (BII-1), the formula (BII-3), the formula (BII-5), the formula (BII-7), the formula (BII-9) or the formula (BII-11) ~ the formula (BII- The compound represented by 15) is more preferably a compound represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15).

【化21】

【化22】

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used individually, or two or more of them may be used in combination. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratio [compound represented by formula (BI): compound represented by formula (BII)] is expressed on a molar basis, It is preferably 5:95 to 95:5, and more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxy Ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methylpropenyloxyethyl oxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

As (b3), a monomer having a tetrahydrofuran group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), (b1) is preferable from the point which can further improve the reliability of the heat resistance, chemical resistance, etc. of the color filter obtained. Furthermore, (b1-2) is more preferable in the point that the storage stability of a colored curable resin composition is excellent.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. Esters, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field In, as a common name, it is called "dicyclopentyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate".), tricyclo (meth)acrylate [5.2.1.0 ^2,6 ] Decene-8-yl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name.), dicyclopentyloxyethyl (meth)acrylate, ( Isobornyl methacrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate , (Meth)acrylates such as benzyl (meth)acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptan -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-diethyl Oxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept- 2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyl Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2. 1]Hept-2-ene, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N- Cyclohexylmaleimide, N-benzylmaleimide, N-succinate Amino-3-maleimidin benzoate, N-succinimidino-4-maleimidin butyrate, N-succinimidino-6-maleimihexanoic acid Salt, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide and other dicarbonylimine derivatives; styrene, α-methyl Styrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methyl Allylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide are preferred. Amine, bicyclo[2.2.1]hept-2-ene, etc.

In the resin [K1], the ratio of the structural unit derived from each monomer is preferably the structural unit derived from (a): 2-60 mol% of the structural unit derived from (b) among all the structural units constituting the resin [K1] : 40 to 98 mol%, more preferably a structural unit derived from (a): 10 to 50 mol%, a structural unit derived from (b): 50 to 90 mol%. If the ratio of the structural unit of the resin [K1] is within the above-mentioned range, there is a tendency that 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 are excellent.

For the resin [K1], for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition First Printing Issued on March 1, 1972) and the document Manufactured by the cited literature.

Specifically, the prescribed amounts of (a) and (b), polymerization initiator, solvent, etc. are charged into the reaction vessel, for example, oxygen is replaced with nitrogen to form a deoxygenated atmosphere, and heating and keeping warm while stirring. In addition, the polymerization initiator, solvent, etc. used here are not particularly limited, and those generally used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides As the solvent (benzyl peroxide, etc.), it is sufficient to dissolve each monomer. As the solvent (E) of the coloring curable resin composition of the present invention, the solvents described below can be cited.

In addition, for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a product taken out as a solid (powder) by a method such as reprecipitation may be used. In particular, during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the reacted solution can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of this invention can be simplified.

In the resin [K2], the ratio of the structural unit derived from each monomer is preferably the structural unit derived from (a): 2 to 45 mol% of the structural unit derived from (b) among all the structural units constituting the resin [K2] : 2~95 mol% structural unit derived from (c): 1~65 mol%, more preferably structural unit derived from (a): 5-40 mol% structural unit derived from (b): 5~80 mol% derived (C) Structural unit: 5-60 mol%. If the ratio of the structural units of the resin [K2] is within the above-mentioned range, the storage stability of the colored curable resin composition, the developability when the colored pattern is formed, and the solvent resistance, heat resistance and mechanical properties of the resulting color filter are present. Tendency to be excellent in strength.

The resin [K2] can be manufactured in the same manner as the method described as the manufacturing method of the resin [K1], for example.

In the resin [K3], the ratio of the structural unit derived from each monomer is preferably the structural unit derived from (a): 2-60 mol% of the structural unit derived from (c) among all the structural units constituting the resin [K3] : 40 to 98 mol%, more preferably a structural unit derived from (a): 10 to 50 mol%, a structural unit derived from (c): 50 to 90 mol%. The resin [K3] can be manufactured in the same manner as the method described as the manufacturing method of the resin [K1], for example.

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether with 2 to 4 carbon atoms in (b) to the carboxylic acid and/or carboxylic anhydride of (a) . First, the copolymer of (a) and (c) is manufactured in the same manner as the method described as the manufacturing method of resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably the same ratio as the ratio listed in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above-mentioned copolymer. Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris(dimethylaminomethyl) Base) phenol, etc.) and polymerization inhibitors (for example, hydroquinone, etc.) are placed in the flask, and reacted at 60 to 130°C for 1 to 10 hours, for example, to produce resin [K4]. The use amount of (b) is preferably 5 to 80 moles, and more preferably 10 to 75 moles relative to 100 moles of (a). By setting it to this range, 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 tend to become good. Since the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, as (b) used for the resin [K4], (b1) is preferred, and (b1-1) is more preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c). The reaction conditions such as the feeding method, reaction temperature, and time can be appropriately adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, as with the polymerization conditions, it is possible to appropriately adjust the feeding method and the reaction temperature in consideration of the manufacturing equipment, the heat generated by the polymerization, and the like.

Regarding the resin [K5], as the first stage, the copolymer of (b) and (c) was obtained in the same manner as the above-mentioned method for producing the resin [K1]. In the same manner as described above, the resulting copolymer may be used as it is after the reaction, a concentrated or diluted solution, or a product taken out as a solid (powder) by a method such as reprecipitation. The ratio of the structural units derived from (b) and (c) is preferably a structural unit derived from (b): 5 to 95 mol% relative to the total moles of all the structural units constituting the above-mentioned copolymer: Structural unit of: 5 to 95 mol%, more preferably structural unit derived from (b): 10 to 90 mol% Structural unit derived from (c): 10 to 90 mol%.

Furthermore, under the same conditions as the production method of resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) is reacted with the cyclic ether derived from (b) contained in the copolymer of (b) and (c). , Which can obtain resin [K5]. The amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 moles relative to 100 moles of (b). Since the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, as (b) used for the resin [K5], (b1) is preferred, and (b1-1) is more preferred.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride and resin [K5]. The carboxylic acid anhydride is reacted with the hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride. Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The usage amount of carboxylic anhydride is preferably 0.5 to 1 mol relative to 1 mol of the usage amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0 ^2.6 ]Decyl ester/(meth)acrylic acid copolymer and other resins [K1]; (meth)acrylic acid/(meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/vinyl toluene copolymer , Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, acrylic acid 3,4 -Epoxy tricyclo [5.2.1.0 ^2.6 ] decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxy Etidine/(meth)acrylic acid/styrene copolymer and other resins [K2]; (meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer and other resins[K2] K3]; Resin made by adding glycidyl (meth)acrylate and benzyl (meth)acrylate/(meth)acrylic acid copolymer to make glycidyl (meth)acrylate and (meth)acrylic acid Resin made by addition of tricyclodecyl ester/styrene/(meth)acrylic acid copolymer, combining glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/ Resins such as resins made by addition of (meth)acrylic acid copolymers [K4]; made by reacting (meth)acrylic acid with a copolymer of (meth)acrylic acid tricyclodecyl ester/(meth)acrylic acid glycidyl ester Resins such as (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester/styrene/(meth)acrylic acid glycidyl ester copolymers are reacted [K5]; make (meth) Resins [K6] and other resins formed by reacting acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate and further reacted with tetrahydrophthalic anhydride. Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K2] is particularly preferable.

The weight average molecular weight in terms of polystyrene 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. If the molecular weight is within the above-mentioned range, the hardness of the color filter increases, the residual film rate is high, the solubility of the unexposed part to the developer is good, and the resolution of the colored pattern tends to increase. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

In terms of solid content, 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. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) relative to the total amount of solids is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. If the content of the resin (B) is within the above-mentioned range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to increase.

<Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized using living radicals and/or acid generated by the polymerization initiator (D), and examples thereof include polymerizable ethylenic unsaturated bonds The compound, etc., is preferably a (meth)acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Esters, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol non(meth)acrylate Ester, tris(2-(meth)acryloyloxyethyl) isocyanurate, glycol modified pentaerythritol tetra(meth)acrylate, glycol modified dipentaerythritol hexa(meth)acrylic acid Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa( Meth) acrylate etc. Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) relative to the total amount of solids is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. If the content rate of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to increase.

<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating living radicals, acids, etc. by the action of light and heat, and known polymerization initiators can be used . Examples of polymerization initiators that generate living radicals include alkyl phenyl ketone compounds, triazine compounds, phosphine oxide compounds, O-oxime compounds, and biimidazole compounds.

The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents the bonding end.

【化23】

Examples of the above-mentioned O-acetoxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine Acetyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl) -3-cyclopentylpropan-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- Dioxolylmethoxy)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-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as IRGACURE OXE01, OXE02 (manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can be used. Among them, the O- oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine. In the case of these O-acetoxime compounds, a color filter with high brightness tends to be obtained.

The above-mentioned alkyl phenyl ketone 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.

【化24】

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]butan-1-one and so on. Commercial products such as IRGACURE 369, 907, and 379 (the above are made by BASF) can be used. As a compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Oligomers of ketones, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc. In terms of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(tris Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri Oxazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) ) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

As the above-mentioned acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. are mentioned. Commercial products such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62 -174204, etc.), imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913, etc.).

Furthermore, as the polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like can be mentioned. Compounds; benzophenone, o-benzophenone methyl benzoate, 4-phenylbenzophenone, 4-benzophenone-4'-methyl diphenyl sulfide, 3,3', Benzophenone compounds such as 4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the polymerization initiator (D1) (particularly amines) described later.

As the acid generator, for example, 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxy phenyl dimethyl P-toluene sulfonate, 4-acetoxyphenylmethyl benzyl hexafluoroantimonate, triphenyl sulfonate p-toluenesulfonate, triphenyl sulfonate hexafluoroantimonate, two Onium salts such as phenyl iodonium p-toluenesulfonate, diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound is preferable, and it is more preferable A polymerization initiator containing an O-acetoxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above-mentioned range, there is a tendency to increase the sensitivity and shorten the exposure time, and therefore the productivity of the color filter improves.

<Polymerization initiation adjuvant (D1)> The polymerization initiation adjuvant (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the above-mentioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis( Dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the above-mentioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone, etc.

Examples of the above-mentioned carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenyl Sulfuryl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

In the case of using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of resin (B) and polymerizable compound (C) share. If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to increase.

<Solvent (E)> The solvent (E) is not particularly limited, and solvents 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 molecule), ether ester solvents Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule, no -O-,- CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc. These solvents may be used alone or in combination of two or more kinds.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and Diethylene glycol monobutyl ether acetate, etc.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, 1,3,5-trimethylbenzene, and the like.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above-mentioned solvents, organic solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferable from the viewpoints of coatability and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether are preferred. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl 2-pentanone, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate.

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 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 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes good, and since the color density is not insufficient when the color filter is formed, there is a tendency for the display characteristics to become good.

<Leveling agent (F)> As the leveling agent (F), organosilicon surfactants, fluorine surfactants, organosilicon surfactants having fluorine atoms, and the like can be cited. These may have a polymerizable group in the side chain. Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule, and the like. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by MOM ティティブ・パフォーママンパンジズパンジズ).

Examples of the above-mentioned fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Flourado (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megofack (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (Manufactured by DIC Co., Ltd.), Eftup (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electron Chemicals Co., Ltd.), Sofron (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) Manufacturing) and E5844 (manufactured by Diinkin Fumikaru Research Institute (Co.)) and so on.

Examples of the above-mentioned organosilicon surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megofack (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Co., Ltd.) and the like can be cited.

When the leveling agent (F) is contained, relative to the total amount of the colored curable resin composition, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less , More preferably, it is 0.01 mass% or more and 0.05 mass% or less. In addition, the content rate of the said pigment dispersing agent is not included in this content rate. If the content rate of the leveling agent (F) is within the above-mentioned range, the flatness of the color filter can be improved.

<Other components> The colored curable resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as required, which are known in the technical field. additive.

<The manufacturing method of the colored curable resin composition> The colored curable resin composition of the present invention can be obtained, for example, by adding a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and It is prepared by mixing the solvent (E), leveling agent (F) and other ingredients to be used. When using a pigment (A2), it is preferable to mix part or all of the solvent (E) in advance, and to disperse it using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, a part or all of the above-mentioned pigment dispersant and resin (B) can be blended as needed. By mixing the remaining components in the pigment dispersion liquid obtained in this way so as to have a predetermined concentration, the target coloring curable resin composition can be prepared. The dye (A1) is preferably dissolved in a part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution with a filter with a pore diameter of about 0.01 to 1 μm. It is preferable to filter the mixed colored curable resin composition with a filter having a pore diameter of about 0.01 to 10 μm.

<The manufacturing method of a color filter> As a method of manufacturing a colored pattern from the coloring curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film as a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way can be used as the color filter of the present invention. The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, use, etc., and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface, polycarbonate, polymethyl methacrylate, and poly-p-phenylene can be used. Resin plates such as ethylene dicarboxylate, silicon, aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of pixels of each color by photolithography can be performed under known or customary equipment and conditions. For example, it can be produced as follows. First, the colored curable resin composition is coated on a substrate, and dried by heating (pre-baking) and/or under reduced pressure to remove volatile components such as the solvent and dry to obtain a smooth colored composition layer. As the coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. can be cited. The temperature at the time of heat drying is preferably 30 to 120°C, and 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. In the case of 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. The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use can be used. As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, a filter that cuts off light below 350 nm may be used to cut off the wavelength range, or a band pass filter that cuts light near 436 nm, near 408 nm, and near 365 nm may be used to selectively extract these wavelength ranges. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be cited. Since it is possible to uniformly irradiate the entire exposure surface with parallel light and perform accurate alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use exposure devices such as a mask aligner and a stepper.

The coloring composition layer after exposure is brought into contact with a developing solution for development, thereby forming a coloring pattern on the substrate. By development, the unexposed part of the coloring composition layer is dissolved and removed in the developer. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The development method may be any of the rotary immersion method, the dipping method, and the spray method. Furthermore, the substrate can be inclined at an arbitrary angle during development. It is preferable to wash with water after development.

Furthermore, it is preferable to post-bak the obtained colored 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.

Using the coloring curable resin composition of the present invention, a color filter having particularly excellent lightness can be manufactured. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements. Example

The following examples are given to illustrate the present invention more specifically. Of course, the present invention is not limited by the following examples. Of course, it can also be implemented with appropriate changes within the scope that can be adapted to the subject matter described above and below. All of them are included in the present invention. Within the scope of technology. It should be noted that as long as there is no special description below, "parts" means "parts by mass" and "%" means "% by mass".

In the following examples, the structure of the compound was confirmed by mass analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD type).

[Example 1]

【化25】

In a flask with a cooling tube and a stirring device, 3 parts of a compound represented by formula (X) (manufactured by Nakawai Kasei), 21 parts of N-methylpyrrolidone and 1.3 parts of potassium hydroxide were added, and the mixture was stirred at room temperature for 1 hour. , Adding 2.3 parts of ethyl acrylate, stirring at the same temperature for 2 hours. The obtained reaction liquid was added to 105 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 3.5 parts of the compound represented by the formula (Aa-1-IM).

【化26】

Identification (mass analysis) of the compound represented by the formula (Aa-1-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 675.3 Accurate mass: 674.3

1 part of the compound represented by formula (Aa-1-IM), 7 parts of methanol, and 3.0 parts of 8% sodium hydroxide aqueous solution were added to a flask having a cooling tube and a stirring device, and the mixture was stirred at room temperature for 9 and a half hours. The obtained reaction liquid was added to 35 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 0.9 parts of the compound represented by the formula (Aa-1).

【化27】

Identification (mass analysis) of the compound represented by formula (Aa-1) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 647.5 Accurate mass: 646.2

[Example 2] 1 part of the compound represented by formula (X) (manufactured by Nakawai Kasei), 7 parts of N-methylpyrrolidone, 1.0 part of potassium carbonate, and 4-bromobutyric acid were added to a flask with a cooling tube and a stirring device 2.0 parts of ethyl esters were stirred at 100°C for 7 and a half hours. After allowing to cool, 20 parts of 2N hydrochloric acid was added to the obtained reaction solution, and the mixture was extracted twice with 45 parts of chloroform. The chloroform layers were put together, washed with saturated brine, and dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and dried under reduced pressure at 60°C to obtain 4.1 parts of a crude compound represented by formula (Aa-33-IM).

【化28】

Identification (mass analysis) of the compound represented by the formula (Aa-33-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 803.5 Accurate mass: 802.3

4.1 parts of the compound represented by formula (Aa-33-IM), 9.8 parts of methanol, and 3.5 parts of 8% sodium hydroxide aqueous solution were added to a flask having a cooling tube and a stirring device, and the mixture was stirred at room temperature for 6 hours. The obtained reaction liquid was added to 30 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 1.0 part of the compound represented by formula (Aa-33).

【化29】

Identification (mass analysis) of the compound represented by the formula (Aa-33) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 747.5 Accurate mass: 746.3

[Example 3] 3 parts of the compound represented by formula (X) (manufactured by Nakawai Kasei), 21 parts of N-methylpyrrolidone and 1.7 parts of tert-butoxy potassium were added to a flask with a cooling tube and a stirring device. After stirring at room temperature for 30 minutes, 1.6 parts of 1-bromopropane was added, and stirring was carried out at the same temperature for 1 hour. The obtained reaction liquid was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 1 hour. As a result, crystals precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 3.0 parts of the compound represented by the formula (Aa-8-IM1).

【化30】

Identification (mass analysis) of the compound represented by the formula (Aa-8-IM1) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 617.5 Accurate mass: 616.2

Add 1 part of the compound represented by the formula (Aa-8-IM1), 7 parts of N-methylpyrrolidone, 0.45 parts of potassium carbonate and 0.95 parts of ethyl 4-bromobutyrate into a flask with a cooling tube and a stirring device. Stirred at 100°C for 5 and a half hours. The obtained reaction liquid was added to 35 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 1.2 parts of the compound represented by the formula (Aa-8-IM2).

【化31】

Identification (mass analysis) of the compound represented by the formula (Aa-8-IM2) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 731.5 Accurate mass: 730.3

1 part of the compound represented by formula (Aa-8-IM2), 7 parts of methanol, and 2.7 parts of 8% sodium hydroxide aqueous solution were added to a flask equipped with a cooling tube and a stirring device, and the mixture was stirred at room temperature for 3 and a half hours. The obtained reaction liquid was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 0.9 parts of a compound represented by formula (Aa-8).

【化32】

Identification (mass analysis) of the compound represented by the formula (Aa-8) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 703.5 Accurate mass: 702.3

[Example 4] Into a flask with a cooling tube and a stirring device, 0.5 parts of a compound represented by the formula (Aa-1-IM), 3.5 parts of N-methylpyrrolidone, 0.26 parts of potassium carbonate, and 2.3 parts of 1-bromopropane were added , Stir at room temperature for 80 hours. The obtained reaction liquid was added to 70 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 0.5 part of the compound represented by the formula (Aa-4-IM2).

【化33】

Identification (mass analysis) of the compound represented by the formula (Aa-4-IM2) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 717.5 Accurate mass: 716.3

0.5 parts of the compound represented by formula (Aa-4-IM2), 3.4 parts of methanol, and 1.3 parts of 8% sodium hydroxide aqueous solution were added to a flask equipped with a cooling tube and a stirring device, and the mixture was stirred at room temperature for 2 hours. The obtained reaction liquid was added to 70 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 0.4 parts of the compound represented by formula (Aa-4).

【化33】

Identification (mass analysis) of the compound represented by the formula (Aa-4) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 689.5 Accurate mass: 688.3

[Example 5] Into a flask with a cooling tube and a stirring device, 1.5 parts of a compound represented by formula (X) (manufactured by Nakawai Kasei), 10.5 parts of N-methylpyrrolidone, 1.1 parts of potassium carbonate, and 4-bromobutyric acid were added 0.5 part of ethyl ester was stirred at 90°C for 4 and a half hours. The obtained reaction liquid was added to 52.5 parts of ion-exchanged water and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60°C. The obtained bold was purified by silica gel column chromatography (mobile phase: chloroform/methanol-10/1) to obtain 0.2 part of the compound represented by the formula (Aa-5-IM).

【化35】

Identification (mass analysis) of the compound represented by the formula (Aa-5-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 689.5 Accurate mass: 688.3

0.2 parts of the compound represented by formula (Aa-5-IM), 1.6 parts of methanol, and 1.0 part of 8% sodium hydroxide aqueous solution were added to a flask having a cooling tube and a stirring device, and the mixture was stirred at room temperature for 2 and a half hours. The obtained reaction liquid was added to 16 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 0.2 parts of the compound represented by the formula (Aa-5).

【化36】

Identification (mass analysis) of the compound represented by the formula (Aa-5) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 661.5 Accurate mass: 660.3

[Example 6]

【化37】

Add 5 parts of 3,6-dichlorosulfofluorescein represented by formula (XX) (manufactured by Zhongwai Kasei), 35 parts of N-methylpyrrolidone, and 3-amino-4 in a flask equipped with a cooling tube and a stirring device 12.2 parts of methyl methyl benzoate were stirred at 130°C for 7 hours. After allowing to cool, the obtained reaction liquid was added to an aqueous solution of 7.5 parts of concentrated hydrochloric acid and 70 parts of ion-exchanged water, and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 6.6 parts of a compound represented by formula (Aa-41-IM).

【化38】

Identification (mass analysis) of the compound represented by the formula (Aa-41-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 663.5 Accurate mass: 662.2

Into a flask with a cooling tube and a stirring device, 6 parts of the compound represented by the formula (Aa-41-IM), 42 parts of N-methylpyrrolidone, 5.0 parts of potassium carbonate and 6.6 parts of 1-bromopropane were added at 90°C Stirred for 6 hours. After allowing to cool, the obtained reaction liquid was added to 210 parts of ion-exchanged water and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 5.9 parts of the compound represented by the formula (Aa-44-IM).

【化39】

Identification (mass analysis) of the compound represented by the formula (Aa-44-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 747.8 Accurate mass: 746.3

3 parts of the compound represented by formula (Aa-44-IM), 21 parts of methanol, and 8.0 parts of 8% sodium hydroxide aqueous solution were added to a flask equipped with a cooling tube and a stirring device, and the mixture was stirred at room temperature for 8 hours. The obtained reaction liquid was added to 105 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 2.5 parts of a compound represented by formula (Aa-44).

【化40】

Identification (mass analysis) of the compound represented by the formula (Aa-44) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 719.5 Accurate mass: 718.2

[Example 7]

【化41】

Add 5 parts of 3,6-dichlorosulfofluorescein represented by formula (XX) (manufactured by Zhongwai Kasei), 35 parts of N-methylpyrrolidone, and 4-amino-3 into a flask with a cooling tube and a stirring device. 12.2 parts of methyl methyl benzoate were stirred at 130°C for 16 hours. After allowing to cool, the obtained reaction liquid was added to an aqueous solution of 7.5 parts of concentrated hydrochloric acid and 70 parts of ion-exchanged water, and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 6.5 parts of the compound represented by the formula (Aa-45-IM).

【化42】

Identification (mass analysis) of the compound represented by the formula (Aa-45-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 663.8 Accurate mass: 662.2

Add 6 parts of the compound represented by formula (Aa-45-IM), 42 parts of N-methylpyrrolidone, 5.0 parts of potassium carbonate and 6.6 parts of 1-bromopropane into a flask with a cooling tube and a stirring device, at 90°C Stirred for 8 hours. After allowing to cool, the obtained reaction liquid was added to 210 parts of ion-exchanged water and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 6.0 parts of the compound represented by the formula (Aa-48-IM).

【化43】

Identification (mass analysis) of the compound represented by the formula (Aa-48-IM) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 747.8 Accurate mass: 746.3

3 parts of the compound represented by formula (Aa-48-IM), 21 parts of methanol, and 8.0 parts of 8% sodium hydroxide aqueous solution were added to a flask equipped with a cooling tube and a stirring device, and the mixture was stirred at room temperature for 8 and a half hours. The obtained reaction liquid was added to 105 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes. As a result, crystals precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 2.0 parts of the compound represented by formula (Aa-48).

【化44】

Identification (mass analysis) of the compound represented by the formula (Aa-48) Ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 719.5 Accurate mass: 718.2

[Synthesis Example 1] Into a flask equipped with a reflux cooler, a dropping funnel and a stirrer, an appropriate amount of nitrogen was poured into it, replaced with a nitrogen atmosphere, and 371 parts of 1-methoxy-2-propyl acetate were put in and stirred. While heating to 85°C. Next, 54 parts of acrylic acid, acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 or/and a mixture of 9-yl ester (trade name A mixed solution of 225 parts of "E-DCPA" manufactured by Daicel Co., Ltd., 81 parts of vinyl toluene (isomer mixture), and 80 parts of 1-methoxy-2-propyl acetate. On the other hand, 30 parts of 2,2-azobis(2,4-dimethylvaleronitrile), a polymerization initiator, was dropped over 5 hours to dissolve 160 parts of 1-methoxy-2-propyl acetate. Solution in part. After the dripping of the initiator solution is finished, it is kept at the same temperature for 4 hours and then cooled to room temperature. The viscosity measured by the B-type viscosity (23°C) is 246 mPas. The solid content of the resin (B-1) solution was 37.5% by weight, and the acid value in terms of solid content was 115 mg-KOH/g. The weight average molecular weight Mw of the resulting copolymer was 10600, and the molecular weight distribution (Mw/Mn) was 2.01. The resin (B-1) has the following structural units.

【化45】

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out under the following conditions by the GPC method. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF Flow rate: 1.0 mL/min Solid content concentration of the tested liquid: 0.001~0.01 mass% Injection volume: 50 μL detector : RI calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio of the number average molecular weight (Mw/Mn) is taken as the molecular weight distribution.

[Example 8] (Preparation of colored curable resin composition) (A) colorant: CI Pigment Blue 15:6 (pigment) 27 parts acrylic pigment dispersant 9.5 parts propylene glycol monomethyl ether acetate 222 parts Mix, use a bead mill to fully disperse the pigment, and then add (A) colorant: 1.2 parts of the compound represented by formula (Aa-1) (A) colorant: CI solvent blue 45 1.5 parts (B) resin: Resin B1 (calculated as solid content) 60 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kabradd (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts (D) Polymerization initiator: N-benzyl Oxyoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE 01; manufactured by BASF Corporation) 9 parts (F) leveling agent: Polyether modified silicone oil (TORAY SILICONE SH8400: Toray-Dow Corning Co., Ltd.) 0.15 parts (E) solvent: 4-hydroxy-4-methyl-2-pentanone 156 parts (E) solvent: propylene glycol monomethyl 401 parts of ether acetate were mixed to obtain a colored curable resin composition.

[Comparative Example 1] (A) Colorant: CI Pigment Blue 15:6 (pigment) 29 parts of acrylic pigment dispersant 10.1 parts of propylene glycol monomethyl ether acetate 236 parts were mixed, and a bead mill was used to make the pigment sufficiently Disperse, then, (A) colorant: dye (Aa-x) 1.4 parts (A) colorant: CI solvent blue 45 1.6 parts (B) resin: resin B1 (in terms of solid content) 60 parts (C) polymerizable Compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 40 parts (D) Polymerization initiator: N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1 -Keto-2-imine (IRGACURE (registered trademark) OXE 01; manufactured by BASF) 9 parts (F) leveling agent: polyether modified silicone oil (TORAY SILICONE SH8400: manufactured by Toray-Dow Corning Co., Ltd.) 0.15 parts (E) Solvent: 156 parts of 4-hydroxy-4-methyl-2-pentanone (E) Solvent: 397 parts of propylene glycol monomethyl ether acetate were mixed to obtain a colored curable resin composition. In addition, the dye (Aa-x) is a mixture of compounds represented by the following formulas (A2-2-1) to (A2-2-8). 【化46】

Examples 9-14, Comparative Example 1 Except having used the composition shown in Table 1, the same operation as Example 8 was performed, and the colored curable resin composition was obtained.

【Table 1】

It should be noted that in Table 1, "A2-1 ¹⁾ " is prepared by mixing and pre-dispersing acrylic pigment dispersant and propylene glycol monomethyl ether acetate in the amount described in the ^{"E-1 3)" column} . The "E-1 ²⁾ " column shows the total content of propylene glycol monomethyl ether acetate. In Table 1, each component has the following meaning. Moreover, resin (B) shows the mass part in solid content conversion. Compound (I): Compound (Aa-1) Compound (I): Compound (Aa-33) Compound (I): Compound (Aa-8) Compound (I): Compound (Aa-4) Compound (I): Compound (Aa-5) Compound (I): Compound (Aa-44) Compound (I): Compound (Aa-48) Anthraquinone Dyes (Ad): Ad-1: CI Solvent Blue 45 (Savinyl Blue RS; manufactured by Clarianto) ) Pigment (A2): A2-1: CI Pigment Blue 15: 6 Resin (B): B-1: Resin B1 Polymerizable compound (C): Dipentaerythritol hexaacrylate (Kaburado (registered trademark) DPHA; Nippon Kayaku (Manufactured by Co., Ltd.) Polymerization initiator (D): D-1: N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (IRGACURE (Registered trademark) OXE 01; manufactured by BASF; O-acetoxime compound) Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: 4-hydroxy-4- Methyl-2-pentanone leveling agent (F): polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray-Dow Corning Co., Ltd.)

The colored curable resin compositions of Examples 8 to 14 and Comparative Example 1 obtained as described above were evaluated.

<Preparation of the colored pattern> After applying the colored curable resin composition by spin coating on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning), it was pre-baked at 100°C for 3 minutes to obtain a colored composition layer . After leaving to cool, the distance between the substrate on which the coloring composition layer was formed and the quartz glass photomask was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used at 150 mJ/cm ^{2 in an air atmosphere.} The exposure amount (365nm standard) was irradiated with light. As the photomask, a photomask in which a pattern of 100 μm lines and gaps was formed was used. The light-irradiated coloring composition layer was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds. After washing with water, it was carried out in an oven at 230°C. Bake after 20 minutes to obtain a colored pattern.

<Measurement of film thickness> With respect to the obtained colored pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Chromaticity evaluation> For the obtained coloring pattern, the spectroscopy was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the characteristic function of the C light source was used to measure the CIE XYZ color system Xy chromaticity coordinates (x, y) and stimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

【Table 2】

It was confirmed that the coating film obtained using the colored curable resin composition of the example showed high lightness. This shows that the colored coating film and the colored pattern obtained from the colored curable resin composition of the present invention can be used as a high-brightness color filter, and the liquid crystal display device including the color filter has excellent display characteristics. Industrial availability

The coloring curable resin composition of the present invention can form a high-brightness color filter. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

(without)

Claims (4)

A compound represented by formula (I) used to prepare a coloring curable resin composition with high brightness:

In the formula (I), R ¹ to R ⁴ independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons that may have a substituent, or an aromatic hydrocarbon group having 6 to 10 carbons that may have a substituent. _{The -CH 2} -contained in the hydrocarbon group can be replaced by -O-, -CO- or -NR ¹¹ -, R ¹ and R ² can together form a ring containing a nitrogen atom, and R ³ and R ⁴ can together form a nitrogen atom containing R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group with 1 to 6 carbons, and R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons or an aralkyl group with 7 to 10 carbons, but , The compound represented by formula (I) satisfies at least one of the necessary conditions (i), (iii), (iv) and (vi): (i) R ¹ is saturated with -COOM and carbon number 1-20 Hydrocarbyl group, ^{at least one of R 2} to R ⁴ is an aromatic hydrocarbon group with 6 to 10 carbon atoms that may have a substituent, and there is one -COOM contained in one molecule, (iii) R ¹ has -COOM The aromatic hydrocarbon group with 6 to 10 carbons, R ³ is a saturated hydrocarbon group with 1 to 20 carbons having -COOM, (iv) R ¹ and R ³ are saturated hydrocarbon groups with 3 to 20 carbons having -COOM, ( vi) R ¹ and R ² are hydrogen atoms or optionally substituted saturated hydrocarbon groups of 1 to 20 carbons, ^{and at least one of R 3} and R ⁴ is an aromatic hydrocarbon group of 6 to 10 carbons with -COOM, In (i), (iii), (iv) and (vi), M represents a hydrogen atom, Na ⁺ , K ⁺ , or ⁺ N(R ¹² ) ₄ , the four R ¹² may be the same or different, R ¹² Represents a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, or an aralkyl group with 7 to 10 carbons. A colored curable resin composition comprising the compound described in claim 1, a resin (B), a polymerizable compound (C), and a polymerization initiator (D). A color filter formed of the coloring curable resin composition according to claim 2. A display device including the color filter according to claim 3.