TW202018019A - Colored curable resin composition, color filter, and display device - Google Patents

Abstract

A conventionally known colored curable resin composition was not sufficiently soluble in a developing solution at the time of manufacturing a color filter. The present invention relates to a colored curable resin composition, and a color filter and a display device each formed using same, the colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and a compound containing cobalt (III), wherein the colorant contains triarylmethane lake and the maximum value of the molar absorption coefficient in the visible region of the compound containing cobalt (III) is smaller than the maximum value of the molar absorption coefficient in the visible region of the colorant.

Description

Colored curable resin composition, color filter, and display device

The present invention relates to a color-curing resin composition, a color filter, and a display device.

Solid-state imaging such as liquid crystal display devices, electroluminescence display devices, plasma displays and other display devices, or CCD (Charge Coupled Device), CMOS (Complementary Metal-Oxide Semiconductor) sensors, etc. The color filter used in the device is made of a color-curing resin composition. As such a color-curing resin composition, a composition containing a dye as a colorant and containing a compound containing cobalt (II) for the purpose of improving light resistance (Patent Document 1) is known. Patent Document 1 describes that the above composition is excellent in resistance to a developing solution and has a high development residual film rate.

[Prior Technical Literature] [Patent Literature] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-295116

[Problems to be solved by the invention]

The above-mentioned coloring curable resin composition has not been known to sufficiently satisfy the solubility of the developing solution when manufacturing the color filter. [Means for solving problems]

The present invention includes the following inventions.

[1] A color-curing resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and a compound containing cobalt (III), wherein the colorant includes a triarylmethane lake ), the maximum value of the molar absorption coefficient of the compound containing cobalt (III) in the visible light region is smaller than the maximum value of the molar absorption coefficient of the colorant in the visible light region.

[式（I）中， R¹¹ 至R¹⁴ 係各自獨立表示氫原子、碳數1至20的飽和烴基、可具有取代基之碳數6至20的芳香族烴基、或可具有取代基之碳數7至30的芳烷基，於該碳數1至20的飽和烴基中，該飽和烴基所包含之氫原子係可被經或未經取代之胺基或者鹵素原子置換，在該飽和烴基的碳數為2至20的情況下，該飽和烴基所包含之亞甲基係可被氧原子或-CO-置換。但，於該碳數2至20的飽和烴基中，不存在相鄰的亞甲基同時被氧原子置換的情況。R¹¹ 與R¹² 可鍵結並與該等所鍵結之氮原子一起形成環，R¹³ 與R¹⁴ 可鍵結並與該等所鍵結之氮原子一起形成環。 R¹⁷ 至R²⁴ 係各自獨立表示氫原子、鹵素原子、硝基、羥基、碳數1至8的烷基，構成該烷基的亞甲基係可被氧原子或-CO-置換。R¹⁸ 與R²² 可互相鍵結而形成-NH-、-O-、-S-或-SO₂ -。 環T¹ 係表示可具有取代基之碳數3至10的芳香族雜環或可具有取代基之碳數6至10的芳香族烴環。 [Y]^m- 係表示含有由鎢、鉬、矽、及磷所組成之群組中所選之至少一種元素及氧的任意m價陰離子。 m係表示任意的自然數。 再者，在1分子中含有複數個由下列式所表示之結構的情況下，該等可為相同結構亦可為不同結構。

[式中，環T¹ 、R¹¹ 至R¹⁴ 及R¹⁷ 至R²⁴ 係各自與前述具有相同含義。]]

[式（II）中， R⁴¹ 至R⁴⁴ 係各自獨立表示氫原子、碳數1至20的飽和烴基、可具有取代基之碳數6至20的芳香族烴基、或可具有取代基之碳數7至30的芳烷基，該芳香族烴基與該芳烷基所可能具有之取代基係可為-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f ，該飽和烴基所包含之氫原子係可被經或未經取代之胺基或者鹵素原子置換，在該飽和烴基的碳數為2至20的情況下，該飽和烴基所包含之亞甲基係可被氧原子或-CO-置換。但，於該碳數2至20的飽和烴基中，不存在相鄰的亞甲基同時被氧原子置換的情況。R⁴¹ 與R⁴² 可鍵結並與該等所鍵結之氮原子一起形成環，R⁴³ 與R⁴⁴ 可鍵結並與該等所鍵結之氮原子一起形成環。 R⁴⁷ 至R⁵⁴ 係各自獨立表示氫原子、鹵素原子、硝基、羥基、-SO₃ ^- 、-SO₂ -N^- -SO₂ -R^f 、或碳數1至8的烷基，構成該烷基之亞甲基係可被氧原子或-CO-置換，R⁴⁸ 與R⁵² 可互相鍵結而形成-NH-、-S-或-SO₂ -。 但，於該烷基中，不存在相鄰的亞甲基同時被氧原子置換的情況。 環T² 係表示碳數3至10的芳香族雜環或碳數6至10的芳香族烴環，該芳香族雜環與該芳香族烴環係可具有碳數1至20的飽和烴基、經或非經取代之胺基或者可具有取代基之碳數6至20的芳香族烴基。該芳香族烴基所可能具有之取代基係可為-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f 。 M^r+ 係表示r價的金屬離子。 k係表示R⁴¹ 至R⁴⁴ 、R⁴⁷ 至R⁵⁴ 與環T² 所具有之-SO₃ ^- 的個數以及-SO₂ -N^- -SO₂ -R^f 的個數之和。 r係表示1以上之整數。 R^f 係表示碳數1至12的氟烷基。 但，R⁴¹ 至R⁴⁴ 、R⁴⁷ 至R⁵⁴ 與環T² 係具有至少一個-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f 。 再者，在1分子中含有複數個由下列式所表示之結構的情況下，該等可為相同結構亦可為不同結構。

[式中，環T² 、R⁴¹ 至R⁴⁴ 及R⁴⁷ 至R⁵⁴ 係各自與前述具有相同含義。]][2] The color-curable resin composition described in [1], wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by formula (I) and a formula (II) Of compounds.

[In formula (I), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. The aralkyl group of 7 to 30, in the saturated hydrocarbon group of 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by an amine group or halogen atom which may be substituted or unsubstituted. When the carbon number is 2 to 20, the methylene group included in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. R ¹¹ and R ¹² may be bonded and form a ring together with the nitrogen atoms to which they are bonded, and R ¹³ and R ¹⁴ may be bonded and form a ring together with the nitrogen atoms to which they are bonded. Each of R ¹⁷ to R ²⁴ independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms, and the methylene system constituting the alkyl group may be replaced by an oxygen atom or -CO-. R ¹⁸ and R ²² may be bonded to each other to form -NH-, -O-, -S- or -SO ₂ -. The ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent. [Y] ^m- means an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen. The m system represents any natural number. In addition, in the case where one molecule contains a plurality of structures represented by the following formulas, these may be the same structure or different structures.

[In the formula, the rings T ¹ , R ¹¹ to R ¹⁴ and R ¹⁷ to R ²⁴ each have the same meaning as described above. ]]

[In formula (II), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. The aralkyl group of 7 to 30, the aromatic hydrocarbon group and the aralkyl group may have a substituent may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the saturated hydrocarbon group contains The hydrogen atom system may be replaced by an unsubstituted or substituted amine group or a halogen atom. In the case where the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene system contained in the saturated hydrocarbon group may be replaced by an oxygen atom or- CO-replacement. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. R ⁴¹ and R ⁴² may be bonded and form a ring together with the bonded nitrogen atoms, and R ⁴³ and R ⁴⁴ may be bonded and form a ring together with the bonded nitrogen atoms. R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom-based, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or alkyl having 1 to 8, constituting the The methylene group of the alkyl group may be replaced by an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO ₂ -. However, in this alkyl group, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. The ring T ² system represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms. The aromatic heterocyclic ring and the aromatic hydrocarbon ring system may have a saturated hydrocarbon group having 1 to 20 carbon atoms. A substituted or unsubstituted amine group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The possible substituents of the aromatic hydrocarbon group may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . The M ^r+ system represents r-valent metal ions. k represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² have. r represents an integer of 1 or more. R ^f represents a C 1-12 fluoroalkyl group. However, R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² system have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . In addition, in the case where one molecule contains a plurality of structures represented by the following formulas, these may be the same structure or different structures.

[In the formula, the ring T ² , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ each have the same meaning as described above. ]]

[3] The color-setting curable resin composition according to [1] or [2], further comprising a pigment different from the triarylmethane lake.

[4] A color filter formed from the color-curing resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter described in [4]. [Effect of invention]

According to the coloring curable resin composition of the present invention, when forming a color filter, the solubility in a developing solution is excellent, and further, a peeling sheet derived from a colored curable resin composition does not easily remain in the developing solution .

The color-curable resin composition of the present invention includes a colorant (hereinafter, sometimes referred to as a colorant (A)), a resin (hereinafter, sometimes referred to as a resin (B)), and a polymerizable compound (hereinafter, Sometimes referred to as a polymerizable compound (C)), a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)), and a compound containing cobalt (III) (hereinafter, sometimes referred to as a compound) (G)).

The colorant (A) contains triarylmethane lake (hereinafter, also referred to as colorant (A1)).

The color-curable resin composition of the present invention preferably further contains a solvent.

The color-curable resin composition of the present invention may also contain a leveling agent.

In this specification, unless otherwise specified, the compounds exemplified as each component may be used alone or in combination.

>Colorant (A)>

The triarylmethane lake refers to a pigment that has a triarylmethane skeleton and is insoluble or poorly soluble in an organic solvent (preferably the solvent included in the color-curable resin composition of the present invention).

The skeleton of triarylmethane refers to a skeleton in which three aromatic rings are bonded to one carbon, preferably in three aromatic rings, both of which are aromatic hydrocarbon rings and one is an aromatic heterocyclic skeleton.

The triarylmethane lake is preferably at least one selected from the following group: a compound represented by formula (I) (hereinafter, also referred to as compound (I)) and a compound represented by formula (II) (below In the text, it is also called compound (II)).

[式（I）中， R¹¹ 至R¹⁴ 係各自獨立表示氫原子、碳數1至20的飽和烴基、可具有取代基之碳數6至20的芳香族烴基、或可具有取代基之碳數7至30的芳烷基，於該碳數1至20的飽和烴基中，該飽和烴基所包含之氫原子係可被經或未經取代之胺基或者鹵素原子置換，在該飽和烴基的碳數為2至20的情況下，該飽和烴基所包含之亞甲基係可被氧原子或-CO-置換。但，於該碳數2至20的飽和烴基中，不存在相鄰的亞甲基同時被氧原子置換的情況。R¹¹ 與R¹² 可鍵結並與該等所鍵結之氮原子一起形成環，R¹³ 與R¹⁴ 可鍵結並與該等所鍵結之氮原子一起形成環。 R¹⁷ 至R²⁴ 係各自獨立表示氫原子、鹵素原子、硝基、羥基、碳數1至8的烷基，構成該烷基的亞甲基係可被氧原子或-CO-置換。R¹⁸ 與R²² 可互相鍵結而形成-NH-、-O-、-S-或-SO₂ -。 環T¹ 係表示可具有取代基之碳數3至10的芳香族雜環或可具有取代基之碳數6至10的芳香族烴環。 [Y]^m- 係表示含有由鎢、鉬、矽、及磷所組成之群組中所選之至少一種元素及氧的任意m價陰離子。 m係表示任意的自然數。 再者，在1分子中含有複數個由下列式所表示之結構的情況下，該等可為相同結構亦可為不同結構。

[式中，環T¹ 、R¹¹ 至R¹⁴ 及R¹⁷ 至R²⁴ 係各自與前述具有相同含義。]]>The compound represented by formula (I)>

[In formula (I), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. The aralkyl group of 7 to 30, in the saturated hydrocarbon group of 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by an amine group or halogen atom which may be substituted or unsubstituted. When the carbon number is 2 to 20, the methylene group included in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. R ¹¹ and R ¹² may be bonded and form a ring together with the nitrogen atoms to which they are bonded, and R ¹³ and R ¹⁴ may be bonded and form a ring together with the nitrogen atoms to which they are bonded. Each of R ¹⁷ to R ²⁴ independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms, and the methylene system constituting the alkyl group may be replaced by an oxygen atom or -CO-. R ¹⁸ and R ²² may be bonded to each other to form -NH-, -O-, -S- or -SO ₂ -. The ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent. [Y] ^m- means an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen. The m system represents any natural number. In addition, in the case where one molecule contains a plurality of structures represented by the following formulas, these may be the same structure or different structures.

[In the formula, the rings T ¹ , R ¹¹ to R ¹⁴ and R ¹⁷ to R ²⁴ each have the same meaning as described above. ]]

The aromatic heterocyclic ring system of the ring T ¹ may be a single ring or a condensed ring.

Examples of possible substituents of the aromatic heterocycle of the ring T ¹ include a halogen atom, a cyano group, a C 1-20 alkyl group which may have a substituent, and a C 6-20 aromatic group which may have a substituent Group hydrocarbon group, optionally substituted amine group, etc. Ring T ¹ preferably has an amine group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.

Among them, the aromatic heterocyclic ring system of the ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a five-membered aromatic heterocyclic ring containing a nitrogen atom.

[R²⁶ 係表示氫原子、碳數1至20的飽和烴基、或可具有取代基之芳香族烴基。 X1係表示氧原子、-NR²⁷ -或硫原子。 R²⁷ 係表示氫原子或碳數1至10的烷基。 R¹⁵ 及R¹⁶ 係各自獨立表示可具有取代基之碳數1至20的飽和烴基、為碳數2至20的烷基而該烷基中所包含之亞甲基可被氧原子置換的基團、可具有取代基之芳香族烴基、可具有取代基之芳烷基、或者氫原子。R¹⁵ 及R¹⁶ 可鍵結並與該等所鍵結之氮原子一起形成環。 但，不存在相鄰的亞甲基同時被氧原子置換的情況，另外，不存在與N鍵結之亞甲基被氧原子置換的情況。 *係表示與碳陽離子的鍵結端。]Furthermore, the ring T ¹ is particularly preferably a ring represented by the formula (Ab2-y1).

[R ²⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent. X1 represents an oxygen atom, -NR ²⁷ -or a sulfur atom. R ²⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ¹⁵ and R ¹⁶ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 2 to 20 carbon atoms, and the methylene group included in the alkyl group may be replaced by an oxygen atom Group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ¹⁵ and R ¹⁶ may be bonded and form a ring together with these bonded nitrogen atoms. However, there is no case where adjacent methylene groups are replaced by oxygen atoms at the same time, and there is no case where methylene groups bonded to N are replaced by oxygen atoms. * Indicates the bonding end with carbocation. ]

Examples of the aromatic hydrocarbon ring of ring T ¹ include a benzene ring and a naphthalene ring.

Examples of the substituents that the aromatic hydrocarbon ring of the ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aromatic group having 6 to 20 carbon atoms which may have a substituent Group hydrocarbon group, optionally substituted amine group, etc.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ to R ¹⁶ and R ²⁶ may be linear, branched, or cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and di Linear alkyl groups such as decayl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ¹¹ to R ¹⁶ and R ²⁶ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

The saturated hydrocarbon groups of R ¹¹ to R ¹⁶ and R ²⁶ may be substituted with halogen atoms or substituted with substituted amine groups. Examples of the amine group which may be substituted include, for example, amine groups; alkylamine groups such as methylamino groups, dimethylamino groups, and diethylamino groups. In addition, examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. In addition, when the halogen atom is a fluorine atom, it is preferable that the halogen atom is substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit.

Examples of the alkyl groups having 1 to 8 carbon atoms represented by R ¹⁷ to R ^{24 include} those having 1 to 8 carbon atoms in the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon groups represented by R ¹¹ . group.

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ²⁷ include a linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ¹¹ , and groups having 1 to 10 carbon atoms. .

When the saturated hydrocarbon group represented by R ¹¹ to R ¹⁶ (preferably an alkyl group) has a carbon number of 2 or more, the methylene system contained in the saturated hydrocarbon group (preferably an alkyl group) may be oxygenated The atom or -CO- is preferably replaced by an oxygen atom. The carbon number of the saturated hydrocarbon group (preferably an alkyl group) is preferably 2 to 10, more preferably 2 to 8. In addition, when the methylene group is replaced by an oxygen atom or -CO-, the carbon number system between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is, for example, 1 To 5, preferably 2 to 3, more preferably 2. However, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms.

In addition, as the aromatic hydrocarbon group which may have a substituent represented by R ¹¹ to R ¹⁶ and R ²⁶ , it is preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, further preferably 6 to 6 carbon atoms 12. Examples of the aromatic hydrocarbon group include aromatic groups such as phenyl, tolyl, succinyl, naphthyl, anthracenyl, phenanthryl, biphenyl, and terphenyl, and preferably phenyl, naphthyl, tolyl 3. Stubble base, particularly preferably phenyl. In addition, the aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; and carbon numbers such as methoxy group and ethoxy group. 1 to 6 alkoxy; hydroxyl; sulfamoyl; sulfamoyl; methyl sulfonyl and other alkyl sulfonyl with 1 to 6 carbons; methoxycarbonyl, ethoxycarbonyl and other carbons with 1 to 6 carbons 6 alkoxycarbonyl and so on.

Examples of the aralkyl group which may have a substituent represented by R ¹¹ to R ¹⁶ include carbon groups such as methylene, ethylidene, and propylene bonded to the groups described above as aromatic hydrocarbon groups. 1 to 5 alkanediyl groups.

As a ring formed by R ¹¹ and R ¹² bonded together with the bonded nitrogen atoms, a ring formed by R ¹³ and R ¹⁴ bonded together with the bonded nitrogen atoms, and R ¹⁵ The ring formed by bonding to R ¹⁶ together with the nitrogen atom to which they are bonded may include a nitrogen-containing non-aromatic 4-membered ring such as pyrrolidine ring, morpholin ring, piperidine ring, piperazine ring, etc. The 7-membered ring preferably includes a 4-membered to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring and a piperidine ring.

Among them, R ¹¹ to R ¹⁴ and R ²⁶ are preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and more preferably a saturated hydrocarbon group each having 1 to 8 carbon atoms or A group represented by the following formula. In the following formula, * represents the bond end with the nitrogen atom.

R ¹⁵ to R ¹⁶ are each preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a group having an oxygen atom inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent, Or R ¹⁵ and R ^{16 are} bonded and form a ring together with the nitrogen atoms to which they are bonded. More preferably, R ¹⁵ to R ¹⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ¹⁵ and R ^{16 are} bonded to form only having A nitrogen atom acts as a heteroatom ring with 4 to 7 members. In the following formula, * represents the bonding end with a nitrogen atom.

In addition, examples of the groups in which the methylene groups of the alkyl groups having 1 to 8 carbon atoms and the alkyl groups having 2 to 8 carbon atoms represented by R ¹⁷ to R ²⁴ are replaced by oxygen atoms or -CO- can be exemplified from the foregoing Among the groups corresponding to R ¹¹ to R ¹⁶ , a group having 8 or less carbon atoms is selected.

From the viewpoint of ease of synthesis, R ¹⁷ to R ²⁴ are preferably each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom atom.

X1 is preferably a sulfur atom.

As the cation portion of the formula (I), as shown in Table 1 below, the cation 1 to the cation 14 represented by the formula (Ia) can be cited.

[Table 1]

In Table 1, Ph1 to Ph9 represent groups represented by the following formulas. In the formula, * represents the bonding end.

Among them, as the cation portion of the formula (I), cation 1 to cation 6 and cation 11 to cation 14 are preferred, and cation 1, cation 2 or cation 12 to 14 are particularly preferred, and cation 12 is most preferred.

[Y] ^{m- is} preferably any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen. Compounds containing such anions tend to have good heat resistance and solvent resistance.

The m series is more preferably 1 to 20, further preferably 1 to 10, and still more preferably 2 to 6.

The anion system is preferably an anion of heteropoly acid and isopoly acid containing tungsten, and anions of phosphotungstic acid, silicotungstic acid, and tungsten homopolymer acid.

Examples of the anions of heteropolymeric acid and homopolymeric acid containing tungsten include: Keggin-type phosphotungstic acid ions α-[PW ₁₂ O ₄₀ ] ^3- and Dawson-type phosphotungstic acid ions α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type silicotungstic acid ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ -[SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures of these.

The anion is also preferably an anion formed by at least one element selected from the group consisting of silicon and phosphorus and oxygen.

Examples of the anion formed by at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ^2- and PO ₄ ^3- .

From the ease of synthesis and post-treatment, it is preferably: phosphotungstic acid anions such as Keggin-type phosphotungstic acid ions and Dawson-type phosphotungstic acid ions; silicotungstic acid anions such as Keggin-type tungstosilicate ions; [W ₁₀ O ₃₂ ] ^4- Tungsten-based homopolymeric acid anions. Among them, phosphotungstic acid anions and tungsten homopolymeric acid anions are particularly preferred.

Examples of the compound (I) include compounds represented by the following formulas.

[Table 2]

[table 3]

The compound (I) is preferably a compound represented by formula (I-41) to formula (I-44), more preferably a compound represented by formula (I-41).

The compound represented by formula (I) can be manufactured according to the method described in Japanese Patent Application Laid-Open No. 2015-28121.

[式（II）中， R⁴¹ 至R⁴⁴ 係各自獨立表示氫原子、碳數1至20的飽和烴基、可具有取代基之碳數6至20的芳香族烴基、或可具有取代基之碳數7至30的芳烷基，該芳香族烴基與該芳烷基所可能具有之取代基係可為-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f ，該飽和烴基所包含之氫原子係可被經或未經取代之胺基或者鹵素原子置換，在該飽和烴基的碳數為2至20的情況下，該飽和烴基所包含之亞甲基係可被氧原子或-CO-置換。但，於該碳數2至20的飽和烴基中，不存在相鄰的亞甲基同時被氧原子置換的情況。R⁴¹ 與R⁴² 可鍵結並與該等所鍵結之氮原子一起形成環，R⁴³ 與R⁴⁴ 可鍵結並與該等所鍵結之氮原子一起形成環。 R⁴⁷ 至R⁵⁴ 係各自獨立表示氫原子、鹵素原子、硝基、羥基、-SO₃ ^- 、-SO₂ -N^- -SO₂ -R^f 、或碳數1至8的烷基，構成該烷基之亞甲基係可被氧原子或-CO-置換，R⁴⁸ 與R⁵² 可互相鍵結而形成-NH-、-S-或-SO₂ -。 但，於該烷基中，不存在相鄰的亞甲基同時被氧原子置換的情況。 環T² 係表示碳數3至10的芳香族雜環或碳數6至10的芳香族烴環，該芳香族雜環與該芳香族烴環係可具有碳數1至20的飽和烴基、經或非經取代之胺基或者可具有取代基之碳數6至20的芳香族烴基。該芳香族烴基所可能具有之取代基係可為-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f 。 M^r+ 係表示r價的金屬離子。 k係表示R⁴¹ 至R⁴⁴ 、R⁴⁷ 至R⁵⁴ 與環T² 所具有之-SO₃ ^- 的個數以及-SO₂ -N^- -SO₂ -R^f 的個數之和。 r係表示1以上之整數。 R^f 係表示碳數1至12的氟烷基。 但，R⁴¹ 至R⁴⁴ 、R⁴⁷ 至R⁵⁴ 與環T² 係具有至少一個-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f 。 再者，在1分子中含有複數個由下列式所表示之結構的情況下，該等可為相同結構亦可為不同結構。

[式中，環T² 、R⁴¹ 至R⁴⁴ 及R⁴⁷ 至R⁵⁴ 係各自與前述具有相同含義。]]>The compound represented by formula (II)>

[In formula (II), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. The aralkyl group of 7 to 30, the aromatic hydrocarbon group and the aralkyl group may have a substituent may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the saturated hydrocarbon group contains The hydrogen atom system may be replaced by an unsubstituted or substituted amine group or a halogen atom. In the case where the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene system contained in the saturated hydrocarbon group may be replaced by an oxygen atom or- CO-replacement. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. R ⁴¹ and R ⁴² may be bonded and form a ring together with the bonded nitrogen atoms, and R ⁴³ and R ⁴⁴ may be bonded and form a ring together with the bonded nitrogen atoms. R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom-based, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or alkyl having 1 to 8, constituting the The methylene group of the alkyl group may be replaced by an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO ₂ -. However, in this alkyl group, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. The ring T ² system represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms. The aromatic heterocyclic ring and the aromatic hydrocarbon ring system may have a saturated hydrocarbon group having 1 to 20 carbon atoms. A substituted or unsubstituted amine group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The possible substituents of the aromatic hydrocarbon group may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . The M ^r+ system represents r-valent metal ions. k represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² have. r represents an integer of 1 or more. R ^f represents a C 1-12 fluoroalkyl group. However, R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² system have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . In addition, in the case where one molecule contains a plurality of structures represented by the following formulas, these may be the same structure or different structures.

[In the formula, the ring T ² , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ each have the same meaning as described above. ]]

The aromatic heterocyclic ring system represented by the ring T ² may be a single ring or a condensed ring. The carbon number of the aromatic heterocyclic ring represented by the ring T ² is preferably 3 to 10, more preferably 3 to 8. In addition, the aromatic heterocyclic ring system is preferably a 5-membered ring to a 10-membered ring, and more preferably a 5-membered ring to a 9-membered ring. Examples of monocyclic aromatic heterocycles include five-membered rings containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; the furan ring and the thiophene ring do not contain nitrogen 5-membered ring of atom; 6-membered ring containing nitrogen atom such as pyridine ring, pyrimidine ring, pyrazine ring, pyrazine ring, etc. Examples of the aromatic heterocyclic ring of the condensed ring include: a condensed ring containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; and a condensed ring containing no nitrogen atom such as a benzofuran ring. .

Examples of possible substituents of the aromatic heterocyclic ring of the ring T ² include a halogen atom, a cyano group, a C 1-20 saturated hydrocarbon group which may have a substituent, a substituted or unsubstituted amine group, or may have Aromatic hydrocarbon groups having 6 to 20 carbon atoms for the substituent, etc., preferably, a saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted amine group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent Hydrocarbyl. The ring T ² preferably has an amine group which may have a substituent, and the substituent which the amine group may have is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic group having 6 to 10 carbon atoms which may have a substituent Group hydrocarbon group, aralkyl group having 7 to 30 carbon atoms which may have a substituent, and the like.

Among them, the aromatic heterocycle of the ring T ² is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a 5-membered ring aromatic heterocycle containing a nitrogen atom.

[式（t1）中， R⁵⁶ 係表示氫原子、碳數1至20的飽和烴基、或者可具有取代基之碳數6至20的芳香族烴基。 X2係表示-O-、-N(R⁵⁷ )-或-S-。 R⁵⁷ 係表示氫原子或碳數1至10的烷基。 R⁴⁵ 及R⁴⁶ 係各自獨立表示氫原子、可具有取代基之碳數1至20的飽和烴基、可具有取代基之碳數6至20的芳香族烴基、或者可具有取代基之碳數7至30的芳烷基，在該飽和烴基的碳數為2至20的情況下，該飽和烴基所包含之亞甲基係可被氧原子或-CO-置換。但，於該碳數2至20的飽和烴基中，不存在相鄰的亞甲基同時被氧原子置換的情況。R⁴⁵ 與R⁴⁶ 可鍵結並與該等所鍵結之氮原子一起形成環。 *係表示與碳陽離子的鍵結端。]The ring T ² is preferably a ring represented by formula (t1).

[In formula (t1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. X2 represents -O-, -N(R ⁵⁷ )- or -S-. R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or 7 carbon atoms which may have a substituent In the case of an aralkyl group of up to 30, when the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene system included in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. R ⁴⁵ and R ⁴⁶ may be bonded and form a ring together with the nitrogen atoms to which they are bonded. * Indicates the bonding end with carbocation. ]

[式（t2-1）中， R⁶⁰ 係表示氫原子、碳數1至20的飽和烴基、或者可具有取代基之碳數6至20的芳香族烴基。 R⁶¹ 係表示氫原子、-SO₃ ^- 、或-SO₂ -N^- -SO₂ -R^f 。 R⁵⁹ 係表示氫原子、可具有取代基之碳數1至20的飽和烴基、可具有取代基之碳數6至20的芳香族烴基、或者可具有取代基之碳數7至30的芳烷基。 *係表示與碳陽離子的鍵結端。]The ring T ² system is further preferably a ring represented by formula (t2-1).

[In formula (t2-1), R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. R ⁶¹ represents a hydrogen atom, -SO ₃ ^- , or -SO ₂ -N ^-- SO ₂ -R ^f . R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an arane having 7 to 30 carbon atoms which may have a substituent base. * Indicates the bonding end with carbocation. ]

Examples of the aromatic hydrocarbon ring represented by the ring T ² include a benzene ring and a naphthalene ring.

Examples of the substituents that the aromatic hydrocarbon ring represented by the ring T ² may have include the substituents that the aromatic heterocyclic ring may have.

The saturated hydrocarbon groups of 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the saturated hydrocarbon groups of 1 to 20 carbon atoms that may be substituted for the amine group of ring T ² may be Any of straight chain, branched chain, and ring. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and hexadecyl Straight-chain alkyl groups such as alkyl and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The carbon number of the saturated hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 8, and even more preferably from 1 to 6.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the cyclic saturated hydrocarbon group that the amine group that ring T ² may have may have a single ring or many ring. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3 to 10, more preferably 6 to 10.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the amine group that ring T ² may have are preferably a saturated hydrocarbon group that is preferably methyl, ethyl, isopropyl, or propylene Group, butyl, pentyl, hexyl, isobutyl, 2-ethylhexyl, cyclohexyl, adamantyl and the like.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the amine group which ring T ² may have may have a saturated hydrocarbon group which may have a substituted or unsubstituted amine group or a halogen atom as Substituents. Examples of the substituted amine group include alkylamine groups such as methylamino group, dimethylamino group, and diethylamino group. In addition, examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. In addition, when the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as trifluoromethyl, perfluoroethyl, and perfluoropropyl.

Examples of the alkyl groups having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include the groups having 1 to 8 carbon atoms in the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon groups represented by R ⁴¹ . group.

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include groups having 1 to 10 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ .

When the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ has a carbon number of 2 to 20, the methylene system included in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no case where adjacent methylene groups are simultaneously replaced by oxygen atoms. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (that is, a straight chain or branched chain alkyl group) Is a linear alkyl). The preferable carbon number of the saturated hydrocarbon group in which the methylene group can be replaced by an oxygen atom or -CO- is 2 to 10, more preferably 2 to 8. In addition, when the methylene group is replaced with an oxygen atom or -CO-, the carbon number system between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is preferably 1 to 5, more preferably 2 to 3, and still more preferably 2.

In addition, the aromatic hydrocarbon group which may have a substituent represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the aromatic hydrocarbon group which the amine group which ring T ² may have may have (but the aromatic hydrocarbon group It may have a substituent.) The carbon number system is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 12. Examples of the aromatic hydrocarbon group include phenyl, tolyl, succinyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and triphenylene. Phenyl, naphthyl, tolyl, and succinyl are preferred. , Particularly preferably phenyl. In addition, the aromatic hydrocarbon group may have one or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; sulfamoyl group; methyl group Alkylsulfonyl groups with 1 to 6 carbon atoms such as sulfonyl; alkoxycarbonyl groups with 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; -SO ₃ ^- ; -SO ₂ -N ^-- SO ₂ -R ^f and the like may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . However, -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f are preferably aromatic hydrocarbon rings directly bonded to the aromatic hydrocarbon group, that is, the hydrogen atoms bonded to the aromatic hydrocarbon ring are replaced .

As specific examples of the aromatic hydrocarbon group which may have a substituent, for example, a group represented by the following formula can be cited. In the following formula, * represents the bonding end with a nitrogen atom.

As the aralkyl group which may have a substituent represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ and the aralkyl group which the amine group which ring T ² may have (but the aralkyl group may have a substituent.), Examples include the groups described above as aromatic hydrocarbon groups in which a C1 to C10 (preferably C1 to C5) alkanediyl group is bonded to methylene, ethylidene, propylidene, etc. group. The carbon number of the aralkyl group is preferably from 7 to 30, more preferably from 7 to 20, and even more preferably from 7 to 17.

As a ring formed by R ⁴¹ and R ⁴² bonded together with these bonded nitrogen atoms, a ring formed by R ⁴³ and R ⁴⁴ bonded together with these bonded nitrogen atoms, and R ⁴⁵ The ring formed by bonding with R ⁴⁶ and the nitrogen atom to which they are bonded may include a nitrogen-containing non-aromatic 4-membered ring such as pyrrolidine ring, morpholin ring, piperidine ring, piperazine ring, etc. The 7-membered ring preferably includes a 4-membered to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring and a piperidine ring.

R ^{58 is} preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁶ , R ⁵⁸ to R ^{60 are} preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and more preferably each independently has 1 to 8 carbon atoms. Saturated hydrocarbon group or a group represented by the following formula. R ⁵⁶ and R ⁵⁸ to R ⁶⁰ are further preferably represented by the following formula. In the following formula, * represents the bonding end with a nitrogen atom.

R ⁴⁵ to R ⁴⁶ are each preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which the methylene group constituting the alkyl group having 2 to 20 carbon atoms is replaced by an oxygen atom or -CO-, or may have a substituent Aromatic hydrocarbon groups, or R ⁴⁵ and R ^{46 are} bonded and form a ring together with these bonded nitrogen atoms. R ⁴⁵ to R ⁴⁶ are more preferably each a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ^{46 are} bonded to form only one nitrogen A 4-membered to 7-membered ring in which the atom is a heteroatom; further preferably each is a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula. In the following formula, * represents the bonding end with a nitrogen atom.

In addition, as a group represented by R ⁴⁷ to R ⁵⁴ , a methylene group constituting an alkyl group having 2 to 8 carbon atoms is replaced by an oxygen atom or -CO- (however, in this alkyl group, there is no adjacent When the methylene group is replaced by an oxygen atom at the same time), the carbon atoms in the group represented by R ⁴¹ to R ^46, which constitute the alkyl group having 2 to 20 carbon atoms, are replaced by an oxygen atom or -CO- Groups under the number 8.

R ⁴⁷ to R ⁵⁴ are each preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

In addition, R ^{57 is} preferably a hydrogen atom or a C 1-5 alkyl group.

R ^{61 is} preferably a hydrogen atom.

Examples of r-valent metal ions represented by M ^r+ include: alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as beryllium ions, magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, Zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion and other transition metal ions; zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion and other typical metal ions, etc. . The r system is, for example, 1 or more, preferably 2 or more, and preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less.

As Mr ⁺ , it is more preferably alkaline earth metal ions, typical metal ions, etc., further preferably alkaline earth metal ions, zinc ions, and very preferably alkaline earth metal ions.

In formula (II), the number of Mr ⁺ is (k-1)/r. At this time, the compound (II) has a valence of 0, that is, an electrically neutral compound.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, and tetrafluoro Ethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluoro Butyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl, etc. Among them, the fluoroalkyl group represented by R ^f is preferably a perfluoroalkyl group. In addition, the carbon number of the fluoroalkyl group represented by R ^f is preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3.

In formula (II), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . The sum (k) of the numbers of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f possessed by R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² is preferably 1 to 7 , More preferably 2 to 7, further preferably 2 to 4, further preferably 2 or 3, and very preferably 2.

-SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f preferably satisfy at least one or more conditions selected from the following (Ia) to (Id), and more preferably satisfy the requirements selected from (Ia) and ( Ib) at least one or more conditions. (Ia) It is ^bonded to any one of the foregoing by including R ⁴⁷ to R ⁵⁴ (Ib) and any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴ (Ic) Bonding (Id) to any of the C 7 to C 30 aralkyl groups which may have a substituent represented by R ⁴¹ to R ⁴⁴ and replacing the hydrogen atom of the aromatic heterocyclic ring represented by T ² Bonding of any aromatic hydrocarbon group with 6 to 20 carbon atoms

However, when -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is bonded to the aromatic hydrocarbon group or aralkyl group, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f It is preferably an aromatic hydrocarbon ring directly bonded to an aromatic hydrocarbon group or an aralkyl group. In other words, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f preferably replaces the hydrogen atom bonded to the aromatic hydrocarbon ring.

Representing R ⁴¹ to R ⁴⁴ may be the substituent group having a carbon number of 6 to 20 aromatic hydrocarbon group or represents R ⁴¹ to R ⁴⁴ may be the group having a carbon number of aromatic hydrocarbon ring substituted aralkyl group having 7 to 30 in (For example, a benzene ring), -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is preferably bonded to the para-position with respect to the bonding position of the nitrogen atom.

When the compound (II) contains a plurality of -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , a plurality of -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f Although it can also be bonded to the same aromatic hydrocarbon ring, it is preferably bonded to a different aromatic hydrocarbon ring.

The compound (II) preferably does not have an ethylenically unsaturated bond.

[式（II-1）中， R⁸¹ 至R⁹⁰ 係各自獨立表示氫原子、碳數1至20的飽和烴基、鹵素原子、-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f 。 k1係表示R⁴¹ 、R⁴³ 、R⁴⁷ 至R⁵⁴ 、R⁸¹ 至R⁹⁰ 及環T² 所具有之-SO₃ ^- 的個數及-SO₂ -N^- -SO₂ -R^f 的個數的和。 R⁴¹ 、R⁴³ 、R⁴⁷ 至R⁵⁴ 、T² 、M^r+ 、r、R^f 係與上述有相同含義。 但，R⁴¹ 、R⁴³ 、R⁴⁷ 至R⁵⁴ 、R⁸¹ 至R⁹⁰ 及環T² 係具有至少一個-SO₃ ^- 或-SO₂ -N^- -SO₂ -R^f 。]The compound (II) is preferably a compound represented by the following formula (II-1) (hereinafter, sometimes referred to as "compound (II-1)").

[In formula (II-1), R ⁸¹ to R ⁹⁰ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . k1 represents the number of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f in R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ⁹⁰ and ring T ² And. R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , T ² , Mr ⁺ , r, and R ^f have the same meanings as described above. However, R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ⁹⁰ and ring T ² system have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . ]

Examples of the saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁸¹ to R ⁹⁰ include the same groups as those exemplified as the saturated hydrocarbon group represented by R ⁴¹ . R ⁸¹ to R ⁹⁰ are preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , more preferably a hydrogen atom, -SO ₃ ^- or _{^{-SO 2 -N - -SO 2 -R f}} .

-SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f preferably satisfies at least one or more conditions selected from (Ie) to (Ig), and more preferably satisfies one selected from (If) and (Ig) At least one or more of the conditions further satisfy the condition of (If). (Ie) Included by any one of R ⁴⁷ to R ⁵⁴ (If) Included by any one of R ⁸¹ to R ⁹⁰ (Ig) and the carbon number of the hydrogen atom replacing the aromatic heterocyclic ring represented by T ² 6 to 20 aromatic hydrocarbon bond

-SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is very good to satisfy the condition of (If'). (If') included by either or both of R ⁸⁶ and R ⁸⁹

In the formula (II-1), R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ⁹⁰ and -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f possessed by the ring T ² The sum (k1) of the number of is preferably 1 to 7, more preferably 1 to 4, and even more preferably 1 or 2.

As the compound (II-1), compounds represented by the following (compounds represented by formulas (AI-1) to (AI-13)) and the like can be cited.

Among them, formula (A-I-7) is particularly good.

Coloring dispersion

When producing the color-curable resin composition of the present invention, the colorant (A1) is preferably dispersed in a solvent to prepare a color-dispersed liquid. The coloring dispersion liquid may include a coloring agent (A1), a solvent, a dispersing agent, and a resin if necessary, and the coloring dispersion liquid may be combined with the resin (B), a polymerizable compound (C), and a polymerization initiator (D), etc. Mix to prepare a color-curing resin composition.

As the solvent, any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. For example, examples of the solvent include ether ester solvents described below.

In the coloring dispersion liquid, the content of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 12 parts by mass relative to 1 part by mass of the coloring agent (A1).

For dispersing the colorant (A1) in a solvent to prepare a coloring dispersion liquid, a dispersant is preferably used. As the dispersant, conventional pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersant systems may be used alone or in combination of two or more. As the pigment dispersant, the product name indicates KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), and EFKA ( BASF (made by BASF), Ajisper (made by Ajinomoto Fine Chemical Co., Ltd.), Disperbyk (made by BYK), BYK (made by BYK), etc.

In the coloring dispersion liquid, the content of the dispersing agent is, for example, 1 to 1000 parts by mass, preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the coloring agent (A1). Particularly preferably, it is 10 to 80 parts by mass.

When the coloring agent (A1) is dispersed in a solvent to prepare a coloring dispersion liquid, the coloring and dispersing agent system may include a part or all of the resin (B) contained in the color curable resin composition in advance, preferably in advance It contains a part of the resin (B) contained in the colored curable resin composition. By containing the resin (B) in advance, the dispersion stability when forming the color-curing resin composition can be further improved. The content of the resin (B) in the colored dispersion is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass relative to 100 parts by mass of the coloring agent (A1).

Of the total amount of the colorant (A), the content of the colorant (A1) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass %the above.

The content of the coloring agent (A1) in the total solid content of the colored curable resin composition is preferably 2 to 60% by mass, more preferably 4 to 55% by mass, and still more preferably 6 to 50% by mass .

In addition, in this specification, "the total amount of solid content" means the total amount of the components after removing the solvent from the coloring hardenable resin composition of this invention. The total amount of solid components and the content of each component relative thereto can be measured by, for example, conventional analysis means such as liquid chromatography or gas chromatography.

The colorant (A) preferably further contains a colorant different from the colorant (A1) (hereinafter, also referred to as colorant (A2)).

The colorant (A2) may be either a dye or a pigment.

As dyes, for example, compounds classified as substances having a hue other than pigments in the Colour Index (published by The Society of Dyers and Colourists), and in The conventional dyes described in the dyeing notes (Dyeing Company). The xanthene dye system is particularly preferred.

The dibenzopiperan dye is a dye containing a compound having a dibenzopiperan skeleton in the molecule. Examples of the dibenzopiperan dye include CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to other cases.), 52, 87, 92, 94 , 289, 388; CI Acid Violet 9, 30, 102; CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, 10, 11; CI Basic Violet 10 (Rose Red B) 11, 11; CI Solvent Red 218; CI Mordant Red 27; CI Reactive Red 36 (Bengal Rose Red (Bengal Rose) B); Acid Rose Red (sulforhodamine) G; Japanese Patent Application Publication No. 2010-32999 Dibenzopiperan dye and the dibenzopiperan dye described in Japanese Patent No. 4492760. Dyes that are soluble in organic solvents are preferred.

[式（1a）中，R^a1 至R^a4 係各自獨立表示氫原子、可具有取代基之碳數1至20的1價飽和烴基、或可具有取代基之碳數6至10的1價芳香族烴基，該飽和烴基所包含之亞甲基係可被-O-、-CO-或-NR^a11 -置換。R^a1 與R^a2 可一起形成含有氮原子的環，R^a3 與R^a4 可一起形成含有氮原子的環。 R^a5 係表示-OH、-SO₃ ^- 、-SO₃ H、-SO₃ ^- Z⁺ 、-CO₂ H、-CO₂ ^- Z⁺ 、-CO₂ R^a8 、-SO₃ R^a8 或-SO₂ NR^a9 R^a10 。 R^a6 與R^a7 係各自獨立表示氫原子或碳數1至6的烷基。 m係表示0至5之整數。當m為2以上時，複數個R^a5 係可相同亦可不同。 a係表示0或1之整數。 X係表示鹵素原子。 Z⁺ 係表示⁺ N(R^a11 )₄ 、Na⁺ 或K⁺ ，四個R^a11 係各自可相同亦可不同。 R^a8 係表示碳數1至20的1價飽和烴基，該飽和烴基中所包含之氫原子係可被鹵素原子置換。 R^a9 及R^a10 係各自獨立表示氫原子或可具有取代基之碳數1至20的1價飽和烴基，該飽和烴基所包含之亞甲基係可被-O-、-CO-、-NH-或-NR^a8 -置換，R^a9 及R^a10 係可互相結合而形成含有氮原子之3員環至10員環的雜環。 R^a11 係表示氫原子、碳數1至20的1價飽和烴基、或碳數7至10的芳烷基。]Among these, the dibenzopiperan dye is preferably a dye containing a compound represented by formula (1a) (hereinafter, sometimes referred to as "compound (1a)"). Compound (1a) can also be its tautomer. When the compound (1a) is used, the content of the compound (1a) in the dibenzopiperan dye is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the dibenzopiperan dye, it is preferred to use only the compound (1a).

[In formula (1a), R ^a1 to R ^a4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms which may have a substituent Group hydrocarbon group, the methylene group contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ^a11 -. R ^a1 and R ^a2 may form a ring containing a nitrogen atom together, and R ^a3 and R ^a4 may form a ring containing a nitrogen atom together. R ^a5 are diagrams _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R a8, -SO 3 R a8 or -SO ₂ NR ^a9 R ^a10 . R ^a6 and R ^a7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is an integer from 0 to 5. When m is 2 or more, plural R ^a5 may be identical or different lines. a represents an integer of 0 or 1. X series represents a halogen atom. Z ⁺ system means ⁺ N(R ^a11 ) ₄ , Na ⁺ or K ⁺ , and each of the four R ^a11 systems may be the same or different. R ^a8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced with a halogen atom. R ^a9 and R ^a10 each independently represent a hydrogen atom or a C 1 to 20 monovalent saturated hydrocarbon group which may have a substituent, and the methylene group included in the saturated hydrocarbon group may be substituted by -O-, -CO-, or -NH ^-Or -NR ^a8 -substitution, R ^a9 and R ^a10 can combine with each other to form a heterocyclic ring containing a 3-membered ring to a 10-membered ring containing a nitrogen atom. R ^a11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

In formula (1a), in the presence of -SO ₃ ^- , the number is preferably one.

Examples of monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms in R ^a1 to R ^a4 include phenyl, tolyl, stubble, 2,4,6-trimethylphenyl, propylphenyl, And butyl phenyl and so on.

Examples of the aromatic hydrocarbon group may have the substituent include a halogen ^{atom, R a8, -OH, -OR a8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, - CO ₂ R ^a8 , -SR ^a8 , -SO ₂ R ^a8 , -SO ₃ R ^a8 or -SO ₂ NR ^a9 R ^a10 . Among these, as a substituent group, is preferably based _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ^a9 R ^a10, more preferably -SO ₃ ^- Z ⁺ and - SO ₂ NR ^a9 R ^a10 . In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^-+ N(R ^a11 ) ₄ . If R ^a1 to R ^{a4 are} such groups, a color filter with little foreign matter generation and excellent heat resistance can be formed from the coloring curable resin composition of the present invention containing the compound (1a).

Examples of the C 1-20 monovalent saturated hydrocarbon groups in R ^a1 to R ^a4 and R ^a8 to R ^a11 include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl Straight-chain alkyl such as yl, octyl, nonyl, decyl, dodecyl, hexadecyl, icosyl; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl Equi-branched alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms.

The hydrogen atom contained in the saturated hydrocarbon group in R ^a1 to R ^a4 may be replaced with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, for example.

The hydrogen atom contained in the saturated hydrocarbon group in R ^a9 and R ^a10 may be replaced with a hydroxyl group or a halogen atom, for example.

As the ring formed by R ^a1 and R ^a2 together, and the ring formed by R ^a3 and R ^a4 together, for example, the following rings may be mentioned. In the formula, * represents the bonding end.

As -OR ^a8 , for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethyl Hexyloxy, eicosyloxy, etc.

Examples of -CO ₂ R ^a8 include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

Examples of -SR ^a8 include methylsulfanyl, ethylsulfuryl, butylsulfuryl, hexylsulfuryl, decylsulfuryl, and eicosylsulfuryl. Wait.

Examples of -SO ₂ R ^a8 include methylsulfonyl, ethylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl.醯基等.

As -SO ₃ R ^a8 , for example, methoxysulfonyl (methoxysulfonyl), ethoxysulfonyl, propoxysulfonyl, tertiary butoxysulfonyl, hexyloxysulfon Acyl, and eicosyloxysulfonyl, etc.

Examples of -SO ₂ NR ^a9 R ^a10 include: sulfamoyl; N-methylsulfamoyl (N-methylsulfamoyl), N-ethylsulfamoyl, N-propylsulfamoyl Acyl, N-isopropylamine sulfonamide, N-butylamine sulfonamide, N-isobutylamine sulfonamide, N-secondary butylamine sulfonamide, N-tertiary butylamine Sulfonyl, N-pentylamine sulfonamide, N-(1-ethylpropyl) sulfonamide, N-(1,1-dimethylpropyl) sulfonamide, N-(1 ,2-dimethylpropyl) sulfamoyl, N-(2,2-dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-( 2-methylbutyl) sulfa amide, N-(3-methylbutyl) sulfa amide, N-cyclopentyl sulfa amide, N-hexyl sulfa amide, N-(1, 3-dimethylbutyl) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) amine Sulfonyl, N-(1,4-dimethylpentyl) sulfonamide, N-octyl sulfonamide, N-(2-ethylhexyl) sulfonamide, N-(1, 5-Dimethyl)hexyl sulfamoyl, N-(1,1,2,2-tetramethylbutyl) sulfamoyl and other N-1 substituted sulfamoyl; N,N-dimethyl Sulfasalamide, N,N-ethylmethylsulfaminyl, N,N-diethylsulfaminyl, N,N-propylmethylsulfaminyl, N,N-isopropyl Methylsulfamidyl, N,N-tertiary butylmethylsulfamoyl, N,N-butylethylaminosulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl , N,N-heptylmethylsulfamoyl, etc. N,N-2 substituted sulfamoyl, etc.

R ^a5 system is preferably ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R a8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ^a9, more preferably _{^{-SO 3 -, -SO 3 - Z}} +, -SO 3 H or -SO ₂ NHR ^a9.

m is preferably 1 to 4, more preferably 1 or 2.

Examples of the alkyl groups having 1 to 6 carbon atoms in ^Ra6 and ^Ra7 include the alkyl groups having 1 to 6 carbon atoms in the alkyl groups listed above.

As the number of carbon atoms in R ^a11 7-10 aralkyl groups include benzyl, phenylethyl, phenylbutyl and the like.

Z ⁺ system ⁺ N(R ^a11 ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^a11 ) ₄ .

As the aforementioned ⁺ N(R ^a11 ) ₄ , among the four R ^a11 , it is preferable that at least two of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of the four ^Ra11 is preferably 20 to 80, more preferably 20 to 60. In the case where ⁺ N(R ^a11 ) ₄ is present in the compound (1a), if R ^{a11 is} such a group, it is possible to generate less foreign matter from the color-curable resin composition of the present invention containing the compound (1a) Color filters.

[式（3a）中，R^a31 及R^a32 係各自獨立表示碳數1至10的1價飽和烴基，該飽和烴基所包含之氫原子係可被碳數6至10的芳香族烴基或鹵素原子置換，該芳香族烴基所包含之氫原子係可被碳數1至3的烷氧基置換，前述飽和烴基中所包含之亞甲基係可被-O-、-CO-或-NR^a11 -置換。 R^a33 及R^a34 係各自獨立表示碳數1至4的烷基、碳數1至4的烷基氫硫基、或碳數1至4的烷基磺醯基。 R^a31 及R^a33 係可一起形成含有氮原子的環，R^a32 及R^a34 係可一起形成含有氮原子的環。 p及q係各自獨立表示0至5的整數。當p為2以上時，複數個R^a33 係可相同亦可不同。當q為2以上時，複數個R^a34 係可相同亦可不同。 R^a11 係與上述表示相同含義。]In addition, the compound (1a) is preferably a compound represented by the formula (3a) (hereinafter, sometimes referred to as "compound (3a)"). Compound (3a) can also be its tautomer.

[In formula (3a), R ^a31 and R ^a32 each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. Replacement, the hydrogen atom contained in the aromatic hydrocarbon group may be replaced by an alkoxy group having 1 to 3 carbon atoms, and the methylene group contained in the aforementioned saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ^a11- Replace. R ^a33 and R ^a34 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl hydrosulfide group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. The R ^a31 and R ^a33 systems can form a ring containing a nitrogen atom together, and the R ^a32 and R ^a34 systems can form a ring containing a nitrogen atom together. p and q independently represent integers from 0 to 5. When p is 2 or more, a plurality of ^Ra33 systems may be the same or different. When q is 2 or more, a plurality of ^Ra34 systems may be the same or different. R ^a11 has the same meaning as described above. ]

^Examples of the C 1 to C 10 monovalent saturated hydrocarbon groups in R ^a31 and R ^a32 include C 1 to C 10 groups among the groups in R ^a8 .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that can be used as a substituent include the same groups as those in R ^a1 .

Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, and propoxy.

R ^a31 and R ^a32 are each preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the C 1-4 alkyl groups in Ra ³³ and Ra ³⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, secondary butyl, and tertiary butyl.

Examples of the C 1-4 alkyl hydrosulfide groups in Ra ³³ and Ra ³⁴ include methyl hydrosulfide, ethyl hydrosulfide, propyl hydrosulfide, butyl hydrosulfide, and isopropyl Hydrogen sulfide and so on.

Examples of the alkyl sulfonyl groups having 1 to 4 carbon atoms in Ra ³³ and Ra ³⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and isopropyl Sulfonyl and so on.

R ^a33 and R ^a34 are preferably C 1-4 alkyl groups, more preferably methyl groups.

p and q are preferably integers from 0 to 2, more preferably 0 or 1.

As the compound (1a), for example, compounds represented by formula (1-1) to formula (1-13) can be cited.

In addition, from the viewpoint of excellent solubility in an organic solvent, a compound represented by any one of formula (1-1) to formula (1-10) is also preferable.

Dibenzopiperan dyes can use commercially available dibenzopiperan dyes (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Chugai Chemicals Co., Ltd. and "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd. ). In addition, as a starting material of a commercially available dibenzopiperan dye, it can be synthesized by referring to Japanese Patent Application Laid-Open No. 2010-32999.

As other dyes, azo dyes, cyanine dyes, triphenylmethane dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinoline yellow dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes can also be used , Methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes, etc. Dyes can be used.

As such a dye, specifically, CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted and only the number is described.), 14, 15, 23, 24, 38, 62, 63, 68, 82 , 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; C.I. 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; C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. 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, 57, 66, 73, 76, 80, 88 , 91, 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, 308, 312, 315, 316, 339 , 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6B, 7, 15, 16, 17, 19, 21, 23, 24, 25, 34, 38, 49, 72; 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; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; 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; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. Direct dyes, C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. disperse blue 1, 14, 56, 60, etc. C.I. disperse dyes, 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; C.I. Basic Violet 2; C.I. Basic Red 9; C.I. Basic Green 1 and other C.I. Basic dyes, C.I. Reactive Yellow 2, 76, 116; C.I. Active Orange 16; C.I. Reactive Red 36 and other C.I. reactive dyes, C.I. 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, 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 violet 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; C.I. mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 etc. C.I. mordant dye, C.I. Vat Green 1, etc. C.I. Vat dyes, etc.

As the pigment, for example, a pigment classified as a pigment (but different from the compound (I) and the compound (II)) in the Dye Index (published by the British Society of Dyeing and Colorist Society) can be cited, and can be exemplified The following pigments. Green pigment: C.I. Pigment Green 7, 36, 58 etc. Yellow Pigment: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc. Orange pigment: C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. Red pigment: C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Blue pigment: C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. Violet pigment: C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc.

These pigments may use one kind of pigment or plural kinds of pigments for various color systems, and may combine pigments of various colors.

Among them, the aforementioned pigment system is preferably a blue pigment or a purple pigment, more preferably C.I. Pigment Blue 15:3, 15:6 or C.I. Pigment Violet 23.

Pigments can also be subjected to the following treatments as needed: rosin treatment; surface treatment using pigment derivatives with an acidic or basic group introduced; grafting treatment of the surface of the pigment with a polymer compound; the use of sulfuric acid micronization method, etc. Micronization treatment; washing treatment using organic solvent or water to remove impurities; removal treatment using ion exchange method using ionic impurities, etc. The particle size of the pigment is preferably substantially uniform. The pigment is dispersed by containing a pigment dispersant to obtain a pigment dispersion liquid in a uniformly dispersed state in the pigment dispersant solution. The pigment system may be individually dispersed, or a plurality of kinds may be mixed to perform dispersion.

Examples of the pigment dispersant include the same as described above.

In the case of using a pigment dispersant, the amount of the pigment dispersant used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 180 parts by mass or less, relative to 100 parts by mass of the pigment. It is preferably 20 parts by mass or more and 160 parts by mass or less. If the amount of the pigment dispersant is within the aforementioned range, when two or more pigments are used, there is a tendency that a more uniform dispersion state of the pigment dispersion liquid can be obtained.

When the colorant (A) contains the colorant (A2), the content of the colorant (A2) in the total amount of the colorant (A) is preferably 1 to 40% by mass, more preferably 1 To 30% by mass, further preferably 1 to 10% by mass.

The content of the coloring agent (A) in the colored curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 7% by mass or more and 65% by mass or less relative to the total amount of solid content. It is more preferably 10% by mass or more and 60% by mass or less, and particularly preferably 12% by mass or more and 57% by mass or less. If the content of the aforementioned compound is within the aforementioned range, the desired spectral and color density can be obtained more easily.

The coloring agent (A) is preferably a compound represented by the formula (I) or a compound represented by the formula (II), preferably a compound represented by the formula (I) and a blue pigment or dibenzopiperan dye The combination of is preferably a combination of a compound represented by formula (II) and a blue pigment or dibenzopiperan dye.

>Resin (B)>

Although the resin (B) is not particularly limited, it is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6] and the like. Resin [K1]: having a structure derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter, sometimes referred to as "(a)") A copolymer of a unit and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b)"); Resin [K2]: having a structural unit derived from (a) and a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (but, and (a) and (b ) Different) (hereinafter, sometimes referred to as "(c)") copolymer of structural units; Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b), further adding a carboxylic acid anhydride, and a structural unit derived from (c).

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 , 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; Methyl-5-norcamene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1] Hept-2-ene, 5-carboxy-6-ethyl bicyclo[2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as acid anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. Monovalent [2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate and other polyvalent carboxylic acids of 2 or more Saturated mono[(meth)acryloyloxyalkyl] esters; Similar to α-(hydroxymethyl) acrylic acid, unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule, etc.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(B) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring ) A polymerizable compound bonded to ethylenic unsaturation. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

As (b), for example, a monomer (b1) having an ethylene oxide (oxiranyl) and ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having oxygen, and Monomer (oxetanyl) and ethylenically unsaturated bond monomer (b2) (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuran group and ethylenically unsaturated bond (b3) (hereinafter Sometimes called "(b3)") etc.

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

Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, and glycidyl ethylene. 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 (Glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3, 4-ginseng (glycidyloxymethyl) styrene, 2,3,5-ginseng (glycidyloxymethyl) styrene, 2,3,6-ginseng (glycidyloxymethyl) Styrene, 3,4,5-ginseng (glycidyloxymethyl) styrene, 2,4,6-ginseng (glycidyloxymethyl) styrene, etc.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000, manufactured by Daicel Corporation), (methyl) -3,4-epoxycyclohexylmethyl acrylate (for example, CYCLOMER A400, manufactured by Daicel Corporation), -3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER M100, Daicel Corporation), (meth)acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester, (meth)acrylic acid-3,4-epoxy tricyclo[5.2 .1.0 ^2,6 ]decyloxyethyl ester etc.

As (b2), the system is more preferably a monomer having an oxo group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloxymethyloxyx, 3-methyl-3-propenyloxymethyloxyx, and 3-ethyl-3- Methacryloyloxymethyloxyxyl, 3-ethyl-3-propenyloxymethyloxyxyl, 3-methyl-3-methylpropenyloxyethyloxyxyl, 3- Methyl-3-propenyloxyethyloxy, 3-ethyl-3-methacryloxyoxyethyloxy, 3-ethyl-3-propenyloxyethyloxy Wait.

As (b3), the system is more preferably a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group. 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), from the viewpoint of further improving the reliability of the obtained color filter such as heat resistance and chemical resistance, it is preferably (b1). Further, from the viewpoint of excellent storage stability of the colored curable resin composition, the system is more preferably (b1-2).

Examples of (c) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and secondary butyl (meth)acrylate , Tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, hard (meth)acrylate Fatty ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo (meth)acrylate [5.2.1.0 ^{2, 6} ] Decane-8-yl ester (in the technical field to which the present invention belongs, as a common name, it is called "(meth)acrylic acid dicyclopentyl (pentanyl) ester". In addition, it is sometimes called "( Tricyclodecyl methacrylate”), tricyclo[meth.acrylic acid] [5.2.1.0 ^2,6 ]decene-8-yl ester (in the technical field of the present invention, it is called as a common name "Dicyclopentenyl (meth)acrylate".), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate Ester, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. ( Methacrylic acid esters; (meth)acrylic acid 2-hydroxyethyl esters, (meth)acrylic acid 2-hydroxypropyl esters, etc. (meth)acrylic acid esters containing hydroxyl groups; diethyl maleate Diethyl dicarboxylates such as esters, diethyl fumarate and diethyl ester of itaconic acid; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2- Ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1] Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6- Bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo [2.2.1]Hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene , 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonyl Bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl) bicyclo[2.2.1]hept -2-ene, 5,6-bis(cyclohexyloxycarbonyl ) Bicyclic [2.2.1] hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N -Succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-male Dicarbonyl amide imine derivatives such as imidate caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloromethylene Ethylene, propylene amide, methacryl amide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzyl are preferred Based on maleimide, bicyclo[2.2.1]hept-2-ene, etc.

In the resin [K1], among all the structural units constituting the resin [K1], the ratio of the structural units derived from each is preferably: Structural unit derived from (a): 2 to 60 mol%, Structural unit derived from (b): 40 to 98 mole %; Better yet: Structural unit derived from (a): 10 to 50 mol%, Structural unit derived from (b): 50 to 90 mol%.

If the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that the following properties are excellent: the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the resulting color The solvent resistance of the filter.

Resin [K1] refers to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki, Chemical Tongren Publishing House Co., Ltd., first edition, first brush, issued on March 1, 1972) and It is manufactured by citing the documents described in this document.

Specifically, the following methods may be mentioned: a prescribed amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, for example, by replacing oxygen with nitrogen to form a deoxygenated atmosphere, while stirring Under heating and heat preservation. In addition, the polymerization initiator and the solvent used here are not particularly limited, and those generally used in the technical field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and Organic peroxide (benzoyl peroxide, etc.); as the solvent, as long as it is a substance that can dissolve each monomer, examples of the solvent (E) that is described later as the solvent (E) of the colored curable resin composition of the present invention.

Furthermore, the obtained co-polymer can be used directly as the solution after the reaction, the concentrated solution or the diluted solution can also be used, or a solid (powder) by reprecipitation or the like can be used. The substance removed. In particular, as the solvent at the time of polymerization, by using the solvent contained in the color-curable resin composition of the present invention, the solution after the reaction can be directly used for the formulation of the color-curable resin composition of the present invention, thereby The preparation steps of the color-curing resin composition of the present invention can be simplified.

In the resin [K2], among all the structural units constituting the resin [K2], the ratio of the structural units derived from each is preferably: Structural unit derived from (a): 2 to 45 mol%, Structural unit derived from (b): 2 to 95 mol%, Structural unit derived from (c): 1 to 65 mol%; Better yet: Structural unit derived from (a): 5 to 40 mol%, Structural unit derived from (b): 5 to 80 mol%, Structural unit derived from (c): 5 to 60 mol%.

If the ratio of the structural unit of the resin [K2] is within the above range, there is a tendency that the following properties are excellent: the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the resulting color The solvent resistance, heat resistance and mechanical strength of the filter.

The resin [K2] can be produced, for example, by the method described as the production method of the resin [K1].

In the resin [K3], among all the structural units constituting the resin [K3], the ratio of the structural units derived from each is preferably: Structural unit derived from (a): 2 to 60 mol%, Structural unit derived from (c): 40 to 98 mole %; Better yet: Structural unit derived from (a): 10 to 50 mol%, Structural unit derived from (c): 50 to 90 mol%.

The resin [K3] can be produced, for example, by the method described as the production method of the resin [K1].

The resin [K4] can be produced as follows: a copolymer of (a) and (c) is obtained, and a cyclic ether having 2 to 4 carbon atoms (b) is added to the carboxylic acid and (a) /Or carboxylic anhydride.

First, the copolymers of (a) and (c) are manufactured in the same manner as described for the manufacturing method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio listed in the resin [K3].

Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the aforementioned copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms that (b) has.

Continuing with the production of the copolymers (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (such as Methylaminomethyl)phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are added to the flask, and reacted at 60°C to 130°C for 1 to 10 hours, for example, to produce resin [K4].

The amount of (a) and (b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles. By controlling the amount of use in this range, there is a tendency that the following properties become good: 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 , Heat resistance, mechanical strength and balance of sensitivity. From the viewpoint that the cyclic ether has high reactivity and unreacted (b) does not easily remain, the (b) used in the resin [K4] is preferably (b1), more preferably (b1-1) .

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 preparation method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization. In addition, similar to the polymerization conditions, the preparation method and the reaction temperature can be appropriately adjusted in consideration of the manufacturing equipment, the amount of heat generated by the polymerization, and the like.

Regarding the resin [K5], as the first stage, the production method of the resin [K1] described above can be followed to obtain the copolymer of (b) and (c). In the same way as above, the obtained copolymer can be used directly in the state of the solution after the reaction, and the concentrated solution or the diluted solution can also be used, or it can be used as a solid (powder) by a method such as reprecipitation. The substance removed.

With respect to the total number of moles of all the structural units constituting the aforementioned copolymer, the ratios of the structural units derived from (b) and (c) are each preferably: Structural unit derived from (b): 5 to 95 mol%, Structural unit derived from (c): 5 to 95 mol%; Better yet: Structural unit derived from (b): 10 to 90 mol%, Structural unit derived from (c): 10 to 90 mol%.

Furthermore, the cyclic ether of (b) and the carboxylic acid of (a) which the copolymer of (b) and (c) has, under the same conditions as the manufacturing method of resin [K4] Carboxylic anhydride reacts to obtain resin [K5].

The amount of (a) reacted with the aforementioned copolymer is preferably 5 to 80 moles relative to 100 moles of (b). From the viewpoint that the cyclic ether has high reactivity and unreacted (b) does not easily remain, the (b) used in the resin [K5] is preferably (b1), more preferably (b1-1) .

Resin [K6] is a resin obtained by further reacting resin [K5] with carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or 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, 1,2,3 ,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of carboxylic anhydride is preferably 0.5 to 1 mole relative to the amount of (a) used in 1 mole.

Specific examples of the resin (B) include: (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, acrylic acid-3,4-epoxytricyclo[ 5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic copolymer and other resins [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic copolymer, (Meth)acrylic acid glycidyl ester/styrene/(meth)acrylic acid copolymer, acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N- Cyclohexylmaleimide copolymer, acrylic-3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/(meth Group) Acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3-(meth)acryloyloxymethyloxybenzene/(meth)acrylic acid/styrene copolymer and other resins [K2]; Resin such as benzyl (meth)acrylate/(meth)acrylic copolymer, styrene/(meth)acrylic copolymer [K3]; in benzyl (meth)acrylate/(meth)acrylic copolymer A resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer and adding glycidyl (meth)acrylate to The obtained resin, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, and tricyclodecyl (meth)acrylate /Styrene/(meth)acrylic acid copolymer of glycidyl ester and (meth)acrylic acid resin and other resins [K5]; Trimethydecyl (meth)acrylate/(meth)acrylic acid shrinkage The resin obtained by reacting the copolymer of glyceride with (meth)acrylic acid and the resin obtained by further reacting with tetrahydrophthalic anhydride [K6], etc.

Among them, the resin (B) is preferably resin [K1] and resin [K2], and particularly preferably resin [K2].

The polystyrene-equivalent weight average molecular weight 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 in the aforementioned range, the resolution of the colored pattern tends to be improved based on the following: the hardness of the color filter is improved, the residual film rate is high, and the unexposed portion has good solubility in the developer.

The degree of dispersion of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

In terms of solid content conversion, the acid value of the resin (B) is preferably 50 mg-KOH/g (mg-KOH/g) to 170 mg-KOH/g, more preferably 60 mg-KOH/g to 150 mg -KOH/g, further preferably 70 mg-KOH/g to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 gram of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

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

>Polymer compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by the active radical and/or acid generated from the polymerization initiator (D), and examples thereof include a polymerizable compound having an ethylenic unsaturated bond, etc. Jia Ke is 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 a polymerizable compound include trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, Dipentaerythritol penta (meth) acrylate, di neopentaerythritol hexa (meth) acrylate, tri neopentaerythritol octa (meth) acrylate, tri neopentaerythritol hexa (meth) acrylate Ester, tetra neopentaerythritol deca(meth)acrylate, tetra neopentaerythritol nona (meth)acrylate, ginseng (2-(meth)acryloyloxyethyl) isocyanurate, Ethylene glycol modified neopentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified neopentaerythritol tetra(meth)acrylate, Propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified neopentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate Wait.

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 solid content 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 aforementioned range, there is a tendency that the residual film rate when forming the colored pattern is improved and the chemical resistance of the color filter is improved.

>Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it can generate active radicals, acids, etc. by the action of light or heat to start polymerization, and a conventional polymerization initiator can be used. Examples of the polymerization initiator that generates active radicals include alkyl phenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

The aforementioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * means the bonding end.

Examples of the aforementioned O-acyl oxime compounds include N-benzyloxy-1-(4-phenylhydrothiophenyl)butane-1-one-2-imine, N -Benzyloxy-1-(4-phenylhydrothiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylhydrogen Thiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)- 9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl -2,4-dioxolylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[ 9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1 -[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as IRGACURE OXE01, IRGACURE OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among them, the O-acyl oxime compound is preferably at least one selected from the group consisting of: N-benzyloxy-1-(4-phenylhydrothiophenyl)butane-1-one- 2-imine, N-benzyloxy-1-(4-phenylhydrothiophenyl)octan-1-one-2-imine, and N-benzyloxy-1 -(4-phenylhydrothiophenyl)-3-cyclopentylpropane-1-one-2-imine; more preferably N-benzyloxy-1-(4-phenylhydrosulfide Phenyl)octan-1-one-2-imine. In the case of such O-acyl oxime compounds, there is a tendency that color filters with high brightness can be obtained.

The aforementioned alkyl benzophenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In some of these structures, the benzene ring may also have a substituent.

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-N-morpholino-1-(4-methylhydrothiophenyl) Propane-1-one, 2-dimethylamino-1-(4-N-morpholinylphenyl)-2-benzylbutane-1-one, 2-(dimethylamino)- 2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one and the like. Commercial products such as IRGACURE 369, IRGACURE 907, and IRGACURE 379 (above, manufactured by BASF) can also be used.

As the compound having a partial structure represented by 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 Oligomers of 1-one, α,α-diethoxyacetophenone, dimethylacetophenone, etc.

From the viewpoint of sensitivity, the alkyl benzophenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the aforementioned triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis (Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-sunflower-1,3,5 -Triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-methylfuran-2-yl)ethenyl] -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-( Furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2- Methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl) Vinyl (ethenyl)]-1,3,5-triazine, etc.

Examples of the aforementioned acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like. Commercial products such as IRGACURE (registered trademark) 819 (made by BASF) can also be used.

As the aforementioned biimidazole compound, for example, 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 Application 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 Application No. 48-38403 Gazette, Japanese Unexamined Patent Publication No. 62-174204, etc.), 4,4',5,5'-position phenyl substituted biimidazole compounds (carboalkoxy) (for example, see Japanese Patent Application Laid-Open 7-10913, etc.) etc.

Furthermore, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Affinity compounds; benzophenone, methyl phthaloyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3' ,4,4'-tetrakis (tertiary butyl carbonyl peroxide) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2- Quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiation aid (D1) (especially amines) described later.

Examples of acid-generating polymerization initiators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4- Acetyloxyphenyl dimethylsulfonium p-toluenesulfonate, 4-ethynyloxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonate Sulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and other onium salts; or nitrobenzyl tosylate, benzoin toluene Sulfonates, etc.

As the polymerization initiator (D), it is preferably a polymerization initiator including at least one selected from the group consisting of an alkyl benzophenone compound, a triazine compound, an acylphosphine oxide compound, and an O-acyl group Oxime compounds and biimidazole compounds; more preferably, polymerization initiators containing O-acyl oxime compounds.

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

>Polymerization Initiator (D1)>

The polymerization start aid (D1) is a compound for promoting the polymerization of the polymerizable compound that starts polymerization by the polymerization initiator, or is a sensitizer. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization start adjuvant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the aforementioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl aminobenzoate, 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(ethyl Methylmethylamino) benzophenone and the like; among them, 4,4′-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the aforementioned 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 compounds include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichlorothia Anthrone, 1-chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylhydrothioacetic acid, methylphenylhydrothioacetic acid, ethylphenylhydrothioacetic acid, methylethylphenylhydrothioacetic acid, and dimethylphenylhydrogen Thioacetic acid, methoxyphenylhydrothioacetic acid, dimethoxyphenylhydrothioacetic acid, chlorophenylhydrothioacetic acid, dichlorophenylhydrothioacetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

In the case of using the polymerization initiation aid (D1), the content of the polymerization initiation aid (D1) is preferably relative to the total amount of 100 parts by mass of the resin (B) and the polymerizable compound (C) It is 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. If the content of the polymerization initiation aid (D1) is within the aforementioned range, there is a tendency to further form a colored pattern with high sensitivity, and the productivity of the color filter can be improved.

>Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in related fields can be used. For example, ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (intramolecular Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (molecules containing OH but not -O-, -CO- and- COO-solvent), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutyric acid methyl ester, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl Alcohol 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, diethylene glycol monoethyl ether, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran , Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol di Butyl ether, phenyl methyl ether (anisole), phenyl ethyl ether (phenetole), methyl phenyl methyl ether, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethyl Ethoxy-2-methylpropionic acid ethyl ester, 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 Ester etc.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentan Ketone, 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, mesitylene 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, from the viewpoint of coating properties and drying properties, organic solvents having a boiling point of 1 atm (atm) of 120°C or more and 180°C or less are preferable. 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, diethyl ether Ethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate And 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 color-curing resin composition of the present invention. In other words, the 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 aforementioned range, the flatness during coating becomes good, and the color density is not insufficient when forming a color filter, so there is a tendency that the display characteristics become good.

>Leveling agent (F)>

Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may also have a polymerizable group on the side chain.

Examples of polysiloxane-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, there may be listed: TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade name, manufactured by Toray Dow Corning Co., Ltd.) ; KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Maito Advanced Materials Japan contract Manufactured by the company), etc.

Examples of the aforementioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, it may include: FLOURAD (registered trademark) FC430, FLOURAD (registered trademark) FC431 (made by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) F142D, MEGAFAC (registered trademark) F171, MEGAFAC (registered trademark) F172, MEGAFAC (registered trademark) F173, MEGAFAC (registered trademark) F177, MEGAFAC (registered trademark) F183, MEGAFAC (registered trademark) F554, MEGAFAC (registered trademark) R30, MEGAFAC (registered trademark) RS-718-K (DIC Corporation) Manufacturing); EFTOP (registered trademark) EF301, EFTOP (registered trademark) EF303, EFTOP (registered trademark) EF351, EFTOP (registered trademark) EF352 (manufactured by Mitsubishi Materials Materials Corporation); SURFLON (registered trademark) S381, SURFLON (Registered trademark) S382, SURFLON (registered trademark) SC101, SURFLON (registered trademark) SC105 (manufactured by AGC Co., Ltd. (old Asahi Glass Co., Ltd.)); and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), etc.

Examples of the above-mentioned polysiloxane-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC (registered trademark) BL20, MEGAFAC (registered trademark) F475, MEGAFAC (registered trademark) F477, and MEGAFAC (registered trademark) F443 (manufactured by DIC Corporation) and the like can be cited.

The content of the leveling agent 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, even more preferably 0.01% by mass with respect to the total amount of the colored curable resin composition. % Or more and 0.05% or less by mass. In addition, this content rate is a content rate which does not contain the said pigment dispersant. If the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter may be improved.

>Compound (G)>

The color-curable resin composition of the present invention contains a compound containing cobalt (III). The compound (G) contains carbon atoms, and the maximum value of the molar absorption coefficient of the compound containing cobalt (III) in the visible region is smaller than the maximum value of the molar absorption coefficient of the colorant in the visible region. By containing the compound containing cobalt (III), the solubility in the developer can be improved, and the residual property of the release sheet can be improved.

The compound containing cobalt (III) may be a metal complex, a metal salt, etc., or it may be a substance soluble in an organic solvent.

Furthermore, although the color-curable resin composition of the present invention preferably does not contain a compound containing cobalt (II), it may also contain the compound under conditions that show solubility in a developer and an effect of suppressing the generation of a peeling sheet. A coloring agent containing cobalt.

The maximum value of the molar absorption coefficient ε of the compound containing cobalt (III) in the visible region (wavelength 400 nm to 780 nm) can be obtained as follows: 0.1 g of the compound containing cobalt (III) is propylene glycol mono Diethyl ether acetate was diluted to 0.100 L and formulated into a solution. The absorption spectrum of the solution was measured using an ultraviolet-visible spectrophotometer and calculated using Lambert-Beer law.

The maximum value of the molar absorption coefficient ε of the compound containing cobalt (III) in the visible light region is less than the maximum value of the molar absorption coefficient ε of the coloring agent contained in the color-curable resin composition of the present invention in the visible light region, It is preferably 0 or more and 1000 or less, and more preferably 0 or more and 500 or less.

If the maximum value of the Mohr absorption coefficient ε of the compound containing cobalt (III) in the visible light range is 1000 or less, there is a tendency that the brightness of the color filter becomes higher, which is preferable.

The maximum value of the mole absorption coefficient ε of the coloring agent in the visible light range can be obtained as follows: 0.01 g of the coloring agent is diluted with propylene glycol monomethyl ether acetate to 0.100 L and formulated into a solution, using ultraviolet light and visible light spectrophotometry The absorption spectrum of the solution is measured by a meter and calculated using Lambert-Beer law.

The maximum value of the molar absorption coefficient ε of the colorant (preferably triarylmethane lake, more preferably the compound represented by formula (I) or the compound represented by formula (II)) in the visible light range is, for example, more than 1000 and 500,000 or less, preferably 5,000 or more and 300,000 or less, more preferably 7,000 or more and 200,000 or less, still more preferably 9,000 or more and 150,000 or less.

[式（F1）至式（F3）中，X¹ 及X² 係各自獨立表示氧原子或硫原子，Z¹ 係表示碳原子或硫原子。 R¹ 係表示氫原子可經鹵素原子置換的碳數1至20的1價脂肪族烴基、或可具有1價取代基的胺基。 R² 及R³ 係各自獨立表示碳數1至20的1價脂肪族烴基、或碳數6至20的1價芳香族烴基。 X³ 及X⁴ 係各自獨立表示氧原子、氮原子或含有羰基的基團。 R⁴ 至R⁷ 係各自獨立表示碳數1至8的1價脂肪族烴基。另外，R⁴ 及R⁵ 、或R⁵ 及R⁶ 、或R⁶ 及R⁷ 之相鄰的取代基亦可閉環而形成環。 M¹ 至M³ 係表示鈷(III)。 a、b及d係表示整數3。在a為整數3的情況下，複數個R¹ 係可相同亦可不同；在b為整數3的情況下，複數個R² 及R³ 係可相同亦可不同；在d為整數3的情況下，複數個R⁴ 至R⁷ 係可相同亦可不同。c係表示0至6的整數。]From the viewpoint of improving solubility, the compound containing cobalt (III) is preferably a compound represented by formula (F1) to formula (F3).

[In Formula (F1) to Formula (F3), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and Z ¹ represents a carbon atom or a sulfur atom. R ¹ represents a C 1-20 monovalent aliphatic hydrocarbon group in which a hydrogen atom can be replaced by a halogen atom, or an amine group which may have a monovalent substituent. R ² and R ³ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. X ³ and X ⁴ independently represent an oxygen atom, a nitrogen atom, or a group containing a carbonyl group. R ⁴ to R ⁷ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. In addition, the adjacent substituents of R ⁴ and R ⁵ , or R ⁵ and R ⁶ , or R ⁶ and R ⁷ may be closed to form a ring. M ¹ to M ³ represent cobalt (III). The a, b, and d systems represent the integer 3. When a is an integer 3, plural R ¹ systems may be the same or different; when b is an integer 3, plural R ² and R ³ systems may be the same or different; when d is an integer 3 Below, the plural R ⁴ to R ⁷ series may be the same or different. c is an integer from 0 to 6. ]

The above-mentioned aliphatic hydrocarbon group in R ¹ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. Examples of the halogen atom in R ¹ include fluorine atom, chlorine atom, bromine atom and iodine atom.

R ¹ is preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the amine group represented by R ¹ include monoalkylamine groups and dialkylamine groups. Examples of the alkyl group in the monoalkylamine group and the dialkylamine group include alkyl groups having 1 to 8 carbon atoms (methyl, ethyl, propyl, butyl, etc.).

The aliphatic hydrocarbon group in R ² and R ³ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.

The aromatic hydrocarbon groups in R ² and R ³ are preferably phenyl and naphthyl.

R ² and R ³ are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably a carbon number 1 to 6 alkyl groups. R ² and R ³ may be the same or different.

c is preferably 0 to 1, more preferably 0.

Examples of the carbonyl group-containing groups represented by X ³ and X ⁴ include -(CO) _m1 -(O) _m2 -(CH ₂ ) _m3 -[m1 and m2 represent 0 or 1, m3 represents 0 to An integer of 4. However, the total of m1, m2, and m3 represents an integer of 1 to 6, and -(CO) _m1 -is bonded to the benzene ring. ], -(O) _m4 -(CO) _m5 -(CH ₂ ) _m6 -[m4 and m5 represent 0 or 1, m6 represents an integer from 0 to 4. However, the total of m4, m5, and m6 represents an integer of 1 to 6, and -(O) _m4 -is bonded to the benzene ring. ]Wait.

X ³ and X ⁴ are each independently -CO-O- or -O-.

Examples of the ring formed by bonding two adjacent substituents among R ⁴ to R ⁷ include a benzene ring, a naphthalene ring, and a cycloalkane ring.

Examples of the aliphatic hydrocarbon groups represented by R ⁴ to R ⁷ include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.

Among them, the compound containing cobalt (III) is particularly preferably a compound represented by formula (F2).

The maximum value of the molar absorption coefficient ε mentioned above is related to the structure (eg molecular weight) of the compound. If the molecular weight becomes larger, the molar absorption coefficient tends to become larger.

The molecular weight of the compound containing cobalt (III) is preferably 260 or more, more preferably 270 or more, and still more preferably 295 or more. The upper limit of the molecular weight is not particularly limited, and may be, for example, about 5000 or less, 3000 or less, or 1000 or less.

The other compound containing cobalt (III) may be a complex compound in which cobalt (III) is coordinated with an amine group (preferably ammonia), or a salt of the complex compound.

From the viewpoint of improving the light resistance of the obtained cured film, the compound containing cobalt (III) preferably has a single-tooth ligand and a double-tooth ligand.

Examples of the ligand-containing cobalt (III)-containing compound include cobalt (III) hexaammonium chloride (III), ginseng (2,4-pentanedionato) cobalt (III), and the like.

Only one type of compound containing cobalt (III) may be used, or two or more types may be used in combination.

The content of the compound containing cobalt (III) is preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15 with respect to the total solid content of the colored curable resin composition The mass% is very preferably 1 to 10 mass %. If the content of the compound containing cobalt (III) is within the aforementioned range, the solubility in the developer can be significantly improved, and the generation of peeling sheets can be suppressed.

In addition, when the total amount of the colorant is 100 parts by mass, the content of the compound containing cobalt (III) is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 17 parts by mass, and still more preferably 0.5 to 15 parts by mass.

>Other ingredients>

The color-curing resin composition of the present invention may contain additives known in related technical fields such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary.

>Manufacturing method of colored curable resin composition>

The color-curable resin composition of the present invention can be obtained by combining the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the compound (G), and if necessary, for example The used solvent (E), leveling agent (F) and polymerization initiation aid (D1) are mixed with other ingredients to prepare.

The colorant (A) is preferably prepared using the above-mentioned coloring dispersion liquid or pigment dispersion liquid. The remaining components are mixed in the colored dispersion liquid or the pigment dispersion liquid so as to form a specified concentration, whereby the target coloring curable resin composition can be formulated.

In the case of containing dyes, the dyes can be pre-dissolved in part or all of the solvent (E) to prepare a solution. Preferably, the solution can be filtered with a filter having a pore size of about 0.01 to 1 micrometer.

Preferably, the mixed color-curing resin composition can be filtered with a filter having a pore size of about 0.01 to 10 microns.

>Manufacturing method of color filter>

As a method of manufacturing a colored pattern from the color-curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. may be mentioned. Among them, the photolithography method is preferred. The photolithography method is a method of applying the above-mentioned colored curable resin composition on a substrate, drying it to form a coloring composition layer, exposing the colored composition layer through a photomask, and developing it. In the photolithography method, by not using a photomask during exposure and/or not developing, a colored coating film, that is, a hardened product of the above-mentioned colored composition layer can be formed. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the manufactured color filter is not particularly limited, and can be adjusted appropriately according to the purpose and application, for example, it can be 0.1 to 30 microns, preferably 0.1 to 20 microns, and more preferably 0.5 to 6 microns.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface; or polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used Resin plates such as diesters; silicon; thin films of aluminum, silver, silver/copper/palladium alloy formed on the aforementioned substrate. Other color filter layers, resin layers, transistors, circuits, etc. may also be formed on these substrates.

The formation of pixels of various colors by photolithography can be performed by conventional or commonly used equipment and conditions. For example, it can be produced in the following manner.

First, a colored curable resin composition is applied on a substrate, and heat drying (pre-baking) and/or drying under reduced pressure is performed to remove and dry volatile components such as a solvent to obtain a smooth coloring composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit and a spin coating method, and the like.

In the case of heating and drying, the temperature is preferably 30°C to 120°C, more preferably 50°C 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 Pa (Pa) to 150 Pa and a temperature range of 20°C to 25°C.

The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected according to the target film thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask used to form a target color coating. The pattern on the photomask is not particularly limited, and a pattern according to the intended use can be used.

The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light with a wavelength of less than 350 nanometers can be cut using a filter that cuts off the wavelength range; light near 436 nanometers, near 408 nanometers, or near 365 nanometers can also be used to extract these wavelength ranges Bandpass filter to selectively remove. Specifically, mercury lamps, light-emitting diodes, metal halogen lamps, halogen lamps, and the like can be mentioned.

Since parallel light can be uniformly irradiated to the entire exposure surface, or the photomask and the substrate on which the colored composition layer is formed can be accurately aligned, it is preferable to use a photomask to align the exposure machine and stepper ( stepper) and other exposure devices.

A colored pattern is formed on the substrate by contacting and developing the colored composition layer after exposure to a developing solution. Through development, the unexposed portion of the coloring composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred. The concentration of the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. Further, the substrate can be tilted to an arbitrary angle during development.

After development, it is preferably washed with water.

Further, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150°C to 250°C, more preferably 160°C to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the color-curable resin composition of the present invention, the solubility in the developing solution is particularly excellent, and the peeling sheet does not easily remain, thereby making it possible to produce a color filter having fewer defects originating from the peeling sheet. The color filter can be used as a color filter used in a display device (for example, a liquid crystal display device, an organic EL (electroluminescence) device, electronic paper, etc.) and a solid-state imaging element.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. In the example, it indicates the% or part of the content or dosage. Unless otherwise stated, they are all quality standards.

In the following, the structure of the compound is confirmed by mass analysis (LC; Model 1200 manufactured by Agilent, MASS; Model LC/MSD manufactured by Agilent).

[Synthesis Example 1]

The following reaction system is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 50 parts of the compound represented by the formula (CI-2) and 188 parts of N,N-dimethylformamide and stir in an ice bath while cooling for 30 minute. 40 parts of tertiary potassium butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into the flask, and the mixture was further stirred for 1 hour while cooling in an ice bath. Keeping the reaction solution ice-cold, 55.6 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the reaction solution was heated to 35°C with an oil bath and stirred for 5 hours, it was left to cool to room temperature. In another flask equipped with a stirring device, 1000 parts of a 10% aqueous solution of sodium chloride was put, and the reaction solution was added dropwise while stirring. After stirring for 30 minutes, filtration was performed to obtain a solid. The obtained solid was washed 3 times in 500 parts of ion-exchanged water and dried under reduced pressure at 60°C to obtain 53.0 parts of the compound represented by formula (BP-2) (yield 93.5%).

The following reaction system is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were charged, and the mixture was stirred at room temperature for 30 minutes. After 40.0 parts of 2,6-difluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, it was stirred at room temperature for 1 hour. After 30.6 parts of N-methyl o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the aforementioned flask over 30 minutes, it was stirred at room temperature for 1 hour. Into the aforementioned flask, an aqueous solution obtained by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchanged water was added, and after 60.4 parts of a 30% sodium hydroxide aqueous solution was added, it was stirred at room temperature for 18 hours. After further adding 600 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the yellow-white solid precipitated was filtered out. After washing the obtained yellow-white solid in 120 parts of acetonitrile, it was washed in 560 parts of ion-exchanged water. In a flask equipped with a stirring device, put the washed yellow-white solid, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene at room temperature Stir for 2 hours. Here, after adding 80.8 parts of 30% sodium hydroxide aqueous solution dropwise over 10 minutes, it was stirred for 5 minutes, and the water layer was removed by a liquid separation operation. After 156 parts of ion-exchanged water was added to the obtained organic layer and separated and washed, 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added and separated and washed. After the obtained organic layer was concentrated in a distiller, it was dried at 35° C. under reduced pressure to obtain a compound represented by formula (BI-2) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

The following reaction system is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 13.2 parts of the compound represented by the formula (BP-2), 19.0 parts of the compound represented by the formula (BI-2), and 38 parts of toluene are added, followed by addition Phosphorus trichloride 9.2 parts was stirred at 100°C for 7 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of a 35% aqueous hydrochloric acid solution was poured into the diluted reaction mixture, and the water layer was removed through a liquid separation operation. After distilling off the solvent of the obtained organic layer with a distiller, it dried under reduced pressure at 60 degreeC, and obtained the compound represented by Formula (X0) as a blue-violet solid. The yield of blue-purple solids was 39.4 parts.

The following reaction system is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 38.4 parts of the compound represented by formula (X0) and 112 parts of dichloromethane were put in and stirred for 30 minutes. The reaction solution was cooled with ice to maintain the internal temperature at 10° C. After adding 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), the reaction solution was warmed to room temperature and stirred for 9 hours. Next, the reaction solution was cooled with ice to maintain the internal temperature at 10°C, and the reaction solution was diluted in a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion-exchanged water. After the diluted reaction solution was poured into 1120 parts of toluene, it was stirred for 30 minutes and a viscous solid precipitated. After the oil layer was discharged by decantation, 320 parts of toluene was added to the obtained viscous solid and stirred for 30 minutes. The oil layer was discharged by decantation, and 832 parts of 20% saline was added to the obtained viscous solid and stirred for 1 hour, and the blue solid was filtered out through filtration. The obtained blue solid was washed in 576 parts of 20% saline and dried under reduced pressure at 35°C. The obtained solid and 128 parts of methanol were put into a flask equipped with a stirring device, stirred for 30 minutes, and then filtered to separate the solid and the filtrate. This filtrate was named filtrate A3. The solid taken out by filtration was washed in 192 parts of methanol, and the solid and the filtrate were separated by filtration. This filtrate was named filtrate B3. The filtrate A3 and the filtrate B3 were mixed, and after removing the solvent in the distiller, the mixture was dried under reduced pressure at 40°C to obtain the compound represented by the formula (X1) as a blue-violet solid. The yield of blue-purple solids was 38.3 parts.

由式（a2）表示之化合物的鑑定 （質量分析）離子化模式=ESI-: m/z=949.5[M-Ba+2H]^- 精確質量（Exact Mass）[M-Ba]：947.28In a flask equipped with a condenser and a stirring device, add 28.0 parts of the compound represented by formula (X1), 43.2 parts of barium chloride dihydrate and 356 parts of ion-exchanged water, and stir at 40°C for 2 hours After that, the reaction suspension was filtered. Into a flask equipped with a stirring device, the solid taken out by filtration and 350 parts of ion-exchanged water were put, and after stirring for 30 minutes, the suspension was filtered. After washing the obtained solid in 280 parts of ion-exchanged water, it was dried at 60° C. under reduced pressure to obtain a compound represented by formula (a2) as a blue-violet solid. The yield was 24.5 parts and the yield was 81.7%.

The identified represented by the formula (a2) a compound (mass spectrometry) ionization mode = ESI-: m / z = 949.5 [M-Ba + 2H] - Exact mass (Exact Mass) [M-Ba ]: 947.28

[Synthesis Example 2]

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

[Synthesis Example 3]

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux condenser, a dropping funnel, and a stirrer and replaced with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was placed and heated to 80°C while stirring. Next, in the flask, using a dropping pump, the following solution was added dropwise over approximately 5 hours: 38 parts of acrylic acid and 289 parts of acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2,6 ] A mixture of dec-8-yl ester and acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-9-yl ester (containing a ratio of 1:1) dissolved in 125 parts of propylene glycol monomethyl A solution made from ether acetate. On the other hand, using another drop-adding pump for about 6 hours, 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts Solution of propylene glycol monomethyl ether acetate. After the dropwise addition, the solution was kept at the same temperature for 4 hours and cooled to room temperature to obtain a copolymer (resin (B-2)) solution with a solid content of 35.1%. The weight average molecular weight Mw of the resulting copolymer was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin (B-2) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin are measured using the GPC (Gel Permeation Chromatography) method under the following conditions. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1.0 ml/min (mL/min) The concentration of the detected liquid solid content: 0.001% by mass to 0.01% by mass Injection volume: 50 microliters (μL) Detector: RI Standard material for calibration: TSK STANDARD POLYSTYRENE (standard polystyrene) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the weight-average molecular weight and the number-average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.

[Preparation of colored dispersion 1]

51.2 parts of the compound represented by formula (a1) (synthesized according to the method described in Japanese Patent Application Laid-Open No. 2015-38201), 21.4 parts of dispersant (manufactured by BYK, BYKLPN-6919; propylene glycol monomethyl ether Acetate 60% solution), 20.5 parts of resin (B-2) (solid content conversion), 334 parts of propylene glycol monomethyl ether acetate, add 600 parts of 0.4 micron diameter zirconia beads, use paint to blend Shaker (made by LAU) for 1 hour. Thereafter, the zirconia beads were removed by filtration to obtain colored dispersion liquid 1.

[Preparation of Coloring Dispersion 2]

21.3 parts of the compound represented by the formula (a2), 26.7 parts of the dispersant (manufactured by BYK, BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution), and 5.3 parts of the resin (B-2) (solid content (Converted), 26.7 parts of diacetone alcohol, 187 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 micron diameter zirconia beads were added, and shaken for 1 hour using a paint blender (manufactured by LAU). After that, the zirconia beads were removed by filtration to obtain a colored dispersion liquid 2.

[Production of Pigment Dispersion 3]

Mix 26.2 parts of CI Pigment Blue 15:6 (pigment), 9.2 parts of acrylic pigment dispersant (solid content conversion), 197 parts of propylene glycol monomethyl ether acetate, and 20 parts of ethyl lactate, using a bead mill A bead mill fully disperses the pigment to obtain pigment dispersion 3.

[Examples 1 to 6, Comparative Example 1]

[Preparation of colored curable resin composition]

・樹脂（B）：樹脂（B-1）（固體成分換算） ・聚合性化合物（C）：二新戊四醇六丙烯酸酯（KAYARAD（註冊商標）DPHA，日本化藥股份有限公司製造） ・聚合起始劑（D）：N-苯甲醯氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（IRGACURE（註冊商標）OXE 01，巴斯夫製造） ・溶液（E）： 溶液（E-1）：乳酸乙酯 溶液（E-2）：丙二醇單甲醚乙酸酯 ・調平劑（F）：聚醚改質矽油（固體成分換算）（Toray Silicone SH8400，東麗道康寧股份有限公司製造） ・化合物（G）： 化合物（G-1）：參（2,4-戊二酮酸根）鈷(III)；東京化成工業股份有限公司製造 化合物（g-1）：雙（2,4-戊二酮酸根）鈷(II)；東京化成工業股份有限公司製造The components shown in Table 4 were mixed to obtain respective color-curing resin compositions.・Colorant (A-4): compound represented by formula (3-44) (compound synthesized according to the method described in Japanese Patent Application Laid-Open No. 2013-68941)

・Resin (B): Resin (B-1) (solid content conversion) ・Polymer compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) ・Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE 01, BASF Manufacturing) • Solution (E): Solution (E-1): Ethyl lactate solution (E-2): Propylene glycol monomethyl ether acetate • Leveling agent (F): Polyether modified silicone oil (solid content conversion) (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) ・Compound (G): Compound (G-1): Ginseng (2,4-pentanedione acid) cobalt (III); Compound manufactured by Tokyo Chemical Industry Co., Ltd. (G-1): bis(2,4-pentanedione acid) cobalt (II); manufactured by Tokyo Chemical Industry Co., Ltd.

[Table 4]

[Calculation of Mohr Absorption Coefficient]

In a measuring flask, weigh 0.1 g of the compound (G-1) shown in Table 4 and put it in, and then dilute with propylene glycol monomethyl ether acetate to form 0.10 L. Similarly, the compounds represented by the formulas (a1) and (a2) were weighed at 0.01 g and put in, and then diluted with diacetone alcohol to form 0.10 L. For these solutions, an ultraviolet-visible spectrophotometer (V-650DS, manufactured by Japan Spectroscopy Co., Ltd.) (quartz cell, optical path distance: 1 cm) was used to measure the absorption spectrum, and Lambert-Beer was used. According to the law, the maximum value of the molar absorption coefficient ε in the visible light region (wavelength 400 nm to 780 nm) is calculated. The results are shown in Table 5.

[table 5]

>Solubility Evaluation of Developer>

On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), after applying the colored curable resin composition by a spin coating method, the film thickness after baking is 2.0 microns, and then pre-baked at 100°C Bake for 3 minutes to form a composition layer.

In a petri dish containing 50 ml of an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide, immerse and develop the substrate on which the aforementioned composition layer is formed at 24°C. The time when the dissolution of the 20 mm center part of the substrate ends is defined as the development time.

In addition, when the developer after immersion was visually observed, the case where no release sheet derived from the colored curable resin composition could not be confirmed in the developer was determined to be ○, and the case where the release sheet could be confirmed was determined Is ×. If it can be confirmed that there is a release sheet derived from the colored curable resin composition in the developer, it will adhere to the pattern as a foreign substance and cause defects, which is undesirable. The results are shown in Table 4.

no

no

Claims (5)

A color-curing resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and a compound containing cobalt (III), wherein the colorant includes a triarylmethane lake (triarylmethane lake), the The maximum value of the molar absorption coefficient of the compound containing cobalt (III) in the visible region is smaller than the maximum value of the molar absorption coefficient of the colorant in the visible region. The color-curable resin composition according to claim 1, wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II),

In the formula (I), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent The aralkyl group of 7 to 30, in the saturated hydrocarbon group of 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by an amine group or halogen atom which may be substituted or unsubstituted. When the carbon number is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-; however, in the saturated hydrocarbon group having 2 to 20 carbon atoms, there is no adjacent sub-group The methyl group is replaced by an oxygen atom at the same time; R ¹¹ and R ¹² can be bonded and form a ring together with the nitrogen atoms to which they are bonded, R ¹³ and R ¹⁴ can be bonded and bonded to the nitrogen atoms to which they are bonded Together, they form a ring; R ¹⁷ to R ²⁴ independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms. The methylene system constituting the alkyl group may be replaced by an oxygen atom or -CO- Substitution; R ¹⁸ and R ²² may be bonded to each other to form -NH-, -O-, -S- or -SO ₂ -; ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent Or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent; [Y] ^m- means any one containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen m-valent anion; m represents an arbitrary natural number; moreover, in the case where a molecule contains a plurality of structures represented by the following formulas, these may be the same structure or different structures,

In the formula, the ring T ¹ , R ¹¹ to R ¹⁴ and R ¹⁷ to R ²⁴ each have the same meaning as described above;

In the formula (II), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent The aralkyl group of 7 to 30, the aromatic hydrocarbon group and the aralkyl group may have a substituent may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the saturated hydrocarbon group contains The hydrogen atom system may be replaced by an unsubstituted or substituted amine group or a halogen atom. In the case where the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene system contained in the saturated hydrocarbon group may be replaced by an oxygen atom or- CO-replacement; however, in the saturated hydrocarbon group of 2 to 20 carbons, there is no case where adjacent methylene groups are replaced by oxygen atoms at the same time; R ⁴¹ and R ⁴² can be bonded and bonded to these Nitrogen atoms form a ring together, R ⁴³ and R ⁴⁴ can be bonded and form a ring together with these bonded nitrogen atoms; R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO _{^{3 -, -SO 2 -N - -SO}} 2 -R f, or an alkyl group having 1 to 8 carbon atoms constituting the alkyl group of methylene-based can be replaced with an oxygen atom or a -CO-, R ⁴⁸ and R ⁵² Can be bonded to each other to form -NH-, -S- or -SO ₂ -; however, in this alkyl group, there is no case where adjacent methylene groups are replaced by oxygen atoms at the same time; Ring T ² represents carbon number 3 to 10 aromatic heterocyclic ring or 6 to 10 carbon aromatic hydrocarbon ring, the aromatic heterocyclic ring and the aromatic hydrocarbon ring system may have 1 to 20 carbon saturated hydrocarbon group, substituted or unsubstituted amine Group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; the substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f ; M ^r+ Represents r-valent metal ion; k represents ^R41 to ^R44 , ^R47 to ^R54 and the number of -SO ₃ ^- possessed by ring T ² and -SO ₂ -N ^-- SO ₂ -R ^f The sum of the numbers; r represents an integer of 1 or more; R ^f represents a fluoroalkyl group having 1 to 12 carbons; however, R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ² have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f ; Furthermore, in the case where a molecule contains a plurality of structures represented by the following formulas, these may be the same structure or different structures,

In the formula, the ring T ² , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ each have the same meaning as described above. The color-setting curable resin composition according to claim 1 or 2, further comprising a pigment different from the triarylmethane lake. A color filter formed from the color-curing resin composition described in claim 1 or 2. A display device comprising the color filter according to claim 4.