TWI840555B - Colored hardening resin composition - Google Patents

Abstract

The present invention provides a coloring curable resin composition that can suppress the reduction in thickness of a coloring pattern or a coloring coating film caused by heating (particularly post-baking). A coloring curable resin composition comprising a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the coloring curable resin composition further comprises a phenolic antioxidant (E), and the resin (B) comprises a resin (B1) comprising a constituent unit (b1-1) represented by formula (1b) [the symbols in the following formula are defined as described in the specification].

Description

Colored hardening resin composition

The present invention relates to a colored curable resin composition.

Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and a variety of resin compositions have been developed. For example, Patent Document 1 describes a resin composition for a color filter, which contains: a solvent, a reactive diluent, a photopolymerization initiator, a colorant, and a copolymer containing a constituent unit represented by formula (1).

[The definitions of symbols in formula (1) are as described in patent document 1]

[Prior art literature]

[Patent Literature]

[Patent Document 1] WO 2018/110097 A1

As a method of forming a color filter using a colored curable resin composition, for example, photolithography and a method using an inkjet device can be cited. In the photolithography method, the following steps are generally included: the colored curable resin composition is applied to a substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and/or reduced pressure drying to form a composition layer, and the composition layer is irradiated (exposed) with light, so that the developer contacts the exposed composition layer to form (develop) a colored pattern or a colored coating film. After the development, the colored pattern is often post-baked by heating.

In existing coloring curable resin compositions, the thickness of the coloring pattern or the coloring coating film is sometimes greatly reduced due to post-baking. The present invention is made with this in mind, and its purpose is to provide a coloring curable resin composition that can suppress the reduction in the thickness of the coloring pattern or the coloring coating film caused by heating (especially post-baking).

The present invention that can achieve the above-mentioned purpose is as follows.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colored curable resin composition further comprises a phenolic antioxidant (E), and the resin (B) comprises a resin (B1) comprising a constituent unit (b1-1) represented by formula (1b).

[In formula (1b), R ^1B represents a hydrogen atom or a methyl group, R ^2B to R ^4B each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n represents an integer of 1 to 10, and * represents a bonding position, wherein at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbon atoms].

[2] The colored curable resin composition as described in [1], wherein the resin (B1) is a copolymer comprising a constituent unit (b1-1), a constituent unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and other constituent units (b1-3), and the amount of the constituent unit (b1-1) is 1 mol% to 50 mol% when the total of all the constituent units in the copolymer is taken as 100 mol%.

[3] The colored curable resin composition as described in [1] or [2], wherein the weight average molecular weight of the resin (B1) is 1,000 to 50,000.

[4] A colored curable resin composition as described in any one of [1] to [3], wherein the content of the resin (B1) is 5 parts by weight to 400 parts by weight relative to 100 parts by weight of the polymerizable compound (C).

[5] The colored curable resin composition as described in any one of [1] to [4], wherein the content of the phenolic antioxidant (E) is 0.1 parts by weight to 25 parts by weight relative to 100 parts by weight of the polymerizable compound (C).

[6] The colored curable resin composition as described in any one of [1] to [5], wherein the coloring agent (A) comprises a dye (A1) and a pigment (A2).

[7] The colored curable resin composition as described in any one of [1] to [6], wherein the polymerizable compound (C) is a radical polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator.

[8] The colored curable resin composition as described in any one of [1] to [7], wherein the coloring agent (A) comprises at least one compound (A3) selected from the group consisting of compounds represented by formula (A3-1) and compounds represented by formula (A3-2).

[In the formula (A3-1), R ^41a and R ^42a each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded, R 43a and R 44a each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43a and R ^44a each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43a and R R ^47a to R 54a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atoms to which they are bonded, R ^47a to R ^54a are independently hydrogen atoms, halogen atoms, nitro groups, hydroxyl groups, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an alkyl group having 1 to 8 carbon atoms which may have a substituent, R ^f is a fluoroalkyl group having 1 to 12 carbon atoms, and the ring T ^1a represents an aromatic alkyl ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocyclic ring having 5 to 10 members which may have a substituent, the saturated alkyl group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, the aromatic alkyl group having 6 to 14 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent, and the aralkyl group having 7 to 30 carbon atoms may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent, the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have a substituent selected from a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent, the 5-membered to 10-membered aromatic heterocyclic ring may have a substituent selected from a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent, the alkyl group having 1 to 8 carbon atoms which may have a substituent is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, when the saturated alkyl group having 1 to 20 carbon atoms is a saturated alkyl group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated alkyl group may be substituted with -O- or -CO-, when the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-, r represents an integer greater than 1, Mr ⁺ represents a hydrogen ion, an r-valent metal ion or N ⁺ (R ^55a ) ₄ , four R ^{55a s} may be the same or different, R ^55a represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; k represents the total number of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f possessed by the anion represented by formula (A3-1a), and is an integer greater than or equal to 2; [Chemical 4]

[In formula (A3-1a), ring ^T1a , ^R41a to ^R44a and ^R47a to ^R54a have the same meanings as described above]

When r is an integer greater than 2, the multiple anions represented by formula (A3-1a) may be the same or different, and when k-1 is an integer greater than 2, the multiple Mr ⁺ may be the same or different.]

[In the formula (A3-2), R ^41b and R ^42b each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded, R 43b and R 44b each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43b and R ^44b each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^{43b and R 44b} each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, R ^47b to R 54b are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atoms to which they are bonded, R ^47b to R ^54b are independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and the ring T ^1b represents an aromatic alkyl ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocyclic ring having 5 to 10 members which may have a substituent, the saturated alkyl group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, the aromatic alkyl group having 6 to 14 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent, and the aralkyl group having 7 to 30 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent , the aromatic alkyl ring having 6 to 14 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a methyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent, the aromatic heterocyclic ring having 5 to 10 members may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a methyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent, the alkyl group having 1 to 8 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and an amino group, and when the saturated alkyl group having 1 to 20 carbon atoms is a saturated alkyl group having 2 to 20 carbon atoms, the -CH ₂ - may be substituted with -O- or -CO-, when the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-, m represents an integer greater than 1, [Y] ^m- represents an m-valent anion, and when m is an integer greater than 2, the multiple cations represented by formula (A3-2c) may be the same or different;

[In formula (A3-2c), ring T ^1b , R ^41b to R ^44b and R ^47b to R ^54b have the same meanings as described above]].

[9] The colored curable resin composition as described in [8], wherein the coloring agent (A) contains a dye (A1) different from the compound (A3).

If the colored curable resin composition of the present invention is used, the reduction in thickness of the colored pattern or colored coating film caused by heating (especially post-baking) can be suppressed.

The coloring curable resin composition of the present invention comprises: a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a phenolic antioxidant (E). Furthermore, the resin (B) contains a resin (B1) comprising a constituent unit (b1-1) represented by the formula (1b). The components of the coloring curable resin composition of the present invention are described below in sequence.

Unless otherwise specified, each component and the raw materials used to produce each component described in this manual may be used alone or in combination of two or more.

<Colorant (A)>

Colorants (A) are classified into dyes (A1) soluble in solvents and pigments (A2) insoluble in solvents. In one embodiment of the present invention, colorants (A) include both dyes (A1) and pigments (A2).

The dye (A1) preferably includes at least one dye selected from the group consisting of oxanthracene dyes, triarylmethane dyes and coumarin dyes. When at least one dye selected from the group is used, the total amount thereof is preferably 1% by weight or more and 100% by weight or less, more preferably 2% by weight or more and 100% by weight or less, and further preferably 5% by weight or more and 100% by weight or less, relative to the whole dye (A1).

The dye (A1) preferably contains an oxyanthracene dye. When an oxyanthracene dye is used, its content is preferably 1% by weight or more and 100% by weight or less, more preferably 2% by weight or more and 100% by weight or less, further preferably 5% by weight or more and 100% by weight or less, and most preferably 100% by weight, relative to the whole dye (A1). That is, the dye (A1) is preferably composed of an oxyanthracene dye.

The oxanthracene dye is a dye including a compound having an oxanthracene skeleton in the molecule. Examples of oxyanthracene dyes include C.I. acid red 51 (hereinafter, C.I. acid red is omitted and only the number is recorded; the same applies to other dyes), 52, 87, 92, 94, 289, 388; C.I. acid violet 9, 30, 102; C.I. basic red 1 (rhodamine 6G), 2, 3, 4, 8; C.I. basic red 10, 11; C.I. basic violet 10 (rose red B), 11; C.I. solvent red 218; C.I. mordant red 27; C.I. reactive red 36 (rose Bengal) bengal) B); acid rose red (sulforhodamine) G; oxyanthracene dyes described in Japanese Patent Publication No. 2010-32999 and oxyanthracene dyes described in Japanese Patent Publication No. 4492760, etc. As oxyanthracene dyes, dyes that are soluble in organic solvents are preferred.

As a preferred oxyanthracene dye, a compound represented by formula (1a) (hereinafter, sometimes described as "compound (1a)") can be listed. Compound (1a) may also be a tautomer. When compound (1a) is used, its content is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more relative to the total oxyanthracene dye. It is particularly preferred to use only compound (1a) as the oxyanthracene dye.

[In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a group represented by *-R ¹² -Si(R ¹³ ) ₃ (in the above formula, * represents a bonding position to a nitrogen atom), -CH ₂ - contained in the above saturated hydrocarbon group may be substituted by -O-, -CO-, or -NR ¹¹ -, R ¹ and R ² may form a ring containing a nitrogen atom together, R ³ and R ⁴ may form a ring containing a nitrogen atom together, and R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ , or -SO ₂ NR ⁹ R ¹⁰ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R ^5's may be the same or different, a represents an integer of 0 or 1, X represents a halogen atom, Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^11's may be the same or different, R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a halogen atom, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be substituted by -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring including a nitrogen atom, R ¹¹ represents a hydrogen atom, a monovalent saturated alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, R ¹² represents an alkanediyl group having 1 to 10 carbon atoms, wherein -CH ₂ - contained in the alkanediyl group may be substituted by -O-, -CO-, -NR ⁸ -, -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO-, and R ¹³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ¹³ may be the same or different, wherein, when -SO ₃ ^- in ionic form is present in formula (1a), the number thereof is one]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent in R ¹ to R ⁴ include phenyl, tolyl, xylyl, mesityl, propylphenyl, and butylphenyl.

Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among these, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are preferred, and -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are more preferred. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^- N ⁺ (R ¹¹ ) ₄ .

The monovalent saturated alkyl group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ may be in any of a linear, branched or cyclic form. Examples thereof include: alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, and the like; and alicyclic saturated alkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

Examples of the substituent that the saturated hydrocarbon group in R ¹ to R ⁴ may have include an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, and a carboxyl group.

Examples of the substituent that the saturated alkyl group in ^R9 and ^R10 may have include a hydroxyl group and a halogen atom.

Examples of the ring formed by ^R1 and ^R2 together and the ring formed by ^R3 and ^R4 together include the following rings.

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy.

Examples of -CO ₂ R ⁸ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

Examples of -SR ⁸ include methylbenzene, ethylbenzene, butylbenzene, hexylbenzene, decylbenzene and eicosylbenzene.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an eicosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a t-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosyloxysulfonyl group.

As -SO ₂ NR ⁹ R ¹⁰ , for example, the following groups can be cited: sulfonylamine; N-methylsulfonylamine, N-ethylsulfonylamine, N-propylsulfonylamine, N-isopropylsulfonylamine, N-butylsulfonylamine, N-isobutylsulfonylamine, N-sec-butylsulfonylamine, N-tert-butylsulfonylamine, N-pentylsulfonylamine, N-(1-ethylpropyl)sulfonylamine, N-(1,1-dimethylpropyl)sulfonylamine, N-(1,2-dimethylpropyl)sulfonylamine, N-(2,2-dimethylpropyl)sulfonylamine, propyl) amine sulfonyl, N-(1-methylbutyl) amine sulfonyl, N-(2-methylbutyl) amine sulfonyl, N-(3-methylbutyl) amine sulfonyl, N-cyclopentyl amine sulfonyl, N-hexyl amine sulfonyl, N-(1,3-dimethylbutyl) amine sulfonyl, N-(3,3-dimethylbutyl) amine sulfonyl, N-heptyl amine sulfonyl, N-(1-methylhexyl) amine sulfonyl, N-(1,4-dimethylpentyl) amine sulfonyl, N-octyl amine sulfonyl, N-(2- The invention also includes N-1-substituted sulfonylamines such as N-(1,5-dimethyl)hexylsulfonylamine, N-(1,1,2,2-tetramethylbutyl)sulfonylamine; and N,N-2-substituted sulfonylamines such as N,N-dimethylsulfonylamine, N,N-ethylmethylsulfonylamine, N,N-diethylsulfonylamine, N,N-propylmethylsulfonylamine, N,N-isopropylmethylsulfonylamine, N,N-tert-butylmethylsulfonylamine, N,N-butylethylsulfonylamine, N,N-bis(1-methylpropyl)sulfonylamine, and N,N-heptylmethylsulfonylamine.

R ⁵ is preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ , and more preferably SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ .

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

Examples of the alkyl group having 1 to 6 carbon atoms in ^R6 and ^R7 include the alkyl groups having 1 to 6 carbon atoms listed above.

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

Examples of the alkanediyl group having 1 to 10 carbon atoms in ^R12 include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, isopropylene, isobutylene, 2-methyltrimethylene, isopentylene, isohexylene, isooctylene, 2-ethylhexylene, etc. Among these, an alkanediyl group having 1 to 6 carbon atoms is preferred, and an alkanediyl group having 1 to 4 carbon atoms is more preferred.

Examples of the alkyl group having 1 to 4 carbon atoms in R ¹³ include methyl, ethyl, propyl and butyl.

Examples of the alkoxy group having 1 to 4 carbon atoms in R ¹³ include methoxy, ethoxy, propoxy, and tert-butoxy.

R ¹³ is preferably methyl, ethyl, methoxy or ethoxy, more preferably methoxy or ethoxy.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .

As the N ⁺ (R ¹¹ ) ₄ , at least two of the four R ^11s are preferably monovalent saturated alkyl groups having 5 to 20 carbon atoms. The total carbon number of the four R ^11s is preferably 20 to 80, more preferably 20 to 60. When N ⁺ (R ¹¹ ) ₄ is present in the compound (1a), if R ¹¹ is any of these groups, a color filter having less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (1a).

As compound (1a), a compound represented by formula (2a) (hereinafter, sometimes described as "compound (2a)") is preferred. Compound (2a) may also be a tautomer thereof.

[In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxyl group, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a group represented by *-R ¹² -Si(R ¹³ ) ₃ (in the above formula, * represents a bonding position to a nitrogen atom), R ²¹ and R ²² may together form a ring containing a nitrogen atom, R ²³ and R ²⁴ may together form a ring containing a nitrogen atom, R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ , m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R ²⁵ may be the same or different, a represents an integer of 0 or 1, X represents a halogen atom, R wherein Z1 ⁺ represents N ⁺ ( ^R27 ) ₄ , Na ⁺ or K ⁺ , the four ^R27s may be the same or different, and ^R27 represents ^a monovalent saturated alkyl group having 1 to 20 carbon atoms or a benzyl group, wherein ^when _-SO3- in ionic form exists in formula (2a), the number thereof is one]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include the same groups as those listed as the aromatic hydrocarbon groups for R ¹ to R ^4. Examples of the substituent that the aromatic hydrocarbon group may have include -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

The explanation of the group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ²¹ to R ²⁴ is the same as described above.

As a combination of R ²¹ to R ²⁴ , it is preferred that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbon groups are substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ , or -SO ₂ NHR ^26. A further preferred combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbon groups are substituted by -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ^26. When R ²¹ to R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing compound (2a).

Examples of the ring containing a nitrogen atom formed by R ²¹ and R ²² together, and the ring containing a nitrogen atom formed by R ²³ and R ²⁴ together include the same rings as those formed by R ¹ and R ² together. Among them, an aliphatic heterocyclic ring is preferred. Examples of the aliphatic heterocyclic ring include the following rings.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²¹ to R ²⁴ , R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are monovalent saturated alkyl groups having 1 to 20 carbon atoms which may have a carboxyl group, R ²¹ to R ²⁴ are preferably independently methyl groups which may have a carboxyl group, ethyl groups which may have a carboxyl group, or propyl groups which may have a carboxyl group. In addition, R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ is preferably a branched chain alkyl group having 3 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, and further preferably a 2-ethylhexyl group. When R ²⁶ is any of these groups, a color filter having less generation of foreign substances can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is N ⁺ ( ^R27 ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ ( ^R27 ) ₄ . As the N ⁺ ( ^R27 ) ₄ , at least two of the four ^R27 are preferably monovalent saturated alkyl groups having 5 to 20 carbon atoms. The total carbon number of the four ^R27 is preferably 20 to 80, more preferably 20 to 60. When N ⁺ ( ^R27 ) ₄ is present in compound (2a), if ^R27 is any of these groups, a color filter with less generation of foreign matter can be formed from the colored curable resin composition of the present invention containing compound (2a).

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

In addition, as compound (1a), a compound represented by formula (3a) (hereinafter, sometimes described as "compound (3a)") is also preferred. Compound (3a) may also be a tautomer thereof.

[In the formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated alkyl group having 1 to 10 carbon atoms, or a group represented by *-R ¹² -Si(R ¹³ ) ₃ (in the formula, * represents the bonding position to the nitrogen atom), the saturated alkyl group may be substituted by a monovalent aromatic alkyl group having 6 to 10 carbon atoms, a halogen atom or a carboxyl group, the -CH ₂ - contained in the saturated alkyl group may be substituted by -O-, -CO- or -NR ¹¹ -, the aromatic alkyl group may be substituted by an alkoxy group having 1 to 3 carbon atoms, R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms, R ³¹ and R ³³ may form a ring containing a nitrogen atom together, and R ³² and R R ³⁴ may together form a ring containing a nitrogen atom, and p and q each independently represent an integer of 0 to 5, when p is 2 or more, a plurality of R ³³ may be the same or different, when q is 2 or more, a plurality of R ³⁴ may be the same or different, and R ¹¹ has the same meaning as described above]

The monovalent saturated alkyl group having 1 to 10 carbon atoms in R ³¹ and R ³² may be in a linear, branched or cyclic form. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, isopentyl, neopentyl and 2-ethylhexyl; and alicyclic saturated alkyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

The group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ³¹ and R ³² is the same as described above.

Examples of the monovalent aromatic alkyl group having 6 to 10 carbon atoms which may be substituted for R ³¹ and R ³² include phenyl.

Examples of alkyl groups having 1 to 3 carbon atoms that may be present as substituents in aromatic hydrocarbon groups include methyl, ethyl, and propyl.

Examples of alkoxy groups having 1 to 3 carbon atoms that may be present as substituents on aromatic hydrocarbon groups include methoxy, ethoxy, propoxy, etc.

The group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ³¹ and R ³² is the same as described above.

R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms which may have a carboxyl group.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, t-butyl and the like.

Examples of the alkyl group having 1 to 4 carbon atoms in ^R33 and ^R34 include methyl, ethyl, propyl, butyl and isopropyl groups.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl.

R ³³ and R ³⁴ are preferably alkyl groups having 1 to 4 carbon atoms, more preferably methyl groups.

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

As compound (1a), for example, compounds represented by formula (1-1) to formula (1-45) can be listed. In the following formula, ^R40 represents a monovalent saturated alkyl group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. In addition, ^R26 in the following formula represents a monovalent saturated alkyl group having 1 to 20 carbon atoms as described above.

[Chemistry 12]

[Chemistry 13]

[Chemistry 14]

[Chemistry 15]

[Chemistry 17]

[Chemistry 19]

As the oxyanthracene dye, preferably, it is a sulfonamide of C.I. Acid Red 289, a quaternary ammonium salt of C.I. Acid Red 289, a sulfonamide of C.I. Acid Violet 102, or a quaternary ammonium salt of C.I. Acid Violet 102. As such a compound, for example, compounds represented by formula (1-1) to formula (1-8), formula (1-11) or formula (1-12) can be cited.

In addition, in terms of excellent solubility in organic solvents, compounds represented by any one of formula (1-24) to formula (1-33), formula (1-44) and formula (1-45) are also preferred.

Oxygenated anthracene dyes can be commercially available oxyanthracene dyes (e.g., "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd., "Rhodamin 6G" manufactured by Tagoka Chemical Industry Co., Ltd.). In addition, commercially available oxyanthracene dyes can be used as starting materials and synthesized with reference to known techniques (e.g., Japanese Patent Publication No. 2010-32999).

The triarylmethane dye is preferably a compound represented by formula (4a).

[In formula (4a), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a saturated alkyl group having 1 to 20 carbon atoms. When the saturated alkyl group has 2 to 20 carbon atoms, the -CH ₂ - contained in the saturated alkyl group may be substituted by -O- or -CO-. R ^9A to R ^12A each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms, an aromatic alkyl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. The saturated alkyl group may be substituted by a substituted or unsubstituted amino group or a halogen atom. When the saturated alkyl group has 2 to 20 carbon atoms, the -CH _{2 -} contained in the saturated alkyl group may be substituted by -O- or -CO-. - may be substituted by -O- or -CO-, R ^9A and R ^10A may also be bonded to form a ring together with the nitrogen atoms to which they are bonded, R ^11A and R ^12A may also be bonded to form a ring together with the nitrogen atoms to which they are bonded, R ^13A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, [G] ^g- represents any g-valent counter anion, and g represents 0 or any natural number, and when g is a natural number greater than 2, the multiple cations in formula (4a) may be the same or different]

Coumarin dyes are dyes containing compounds with a coumarin skeleton in the molecule. Examples of coumarin dyes include: C.I. Acid Yellow 227, 250; C.I. Disperse Yellow 82, 184; C.I. Solvent Orange 112; C.I. Solvent Yellow 160, 172; coumarin dyes described in Japanese Patent No. 1299948, etc. Preferably, the dye is soluble in an organic solvent.

As dyes other than the above dyes, for example, dyes listed in the Color Index (published by The Society of Dyers and Colourists) and dyes listed in the Dyeing Notes (Shikisensha) can be listed. In addition, as dyes, for example, azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azoformine dyes, squarylium dyes, acridine dyes, styryl dyes, quinoline dyes, and nitro dyes can be listed. Among these, dyes that are soluble in organic solvents are preferred.

As specific examples of dyes, the following dyes can be listed.

(1) C.I. solvent dye

C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C.I. Solvent Violet C.I. violet) 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. solvent blue (solvent blue) 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. solvent green (solvent green) 1, 3, 5, 28, 29, 32, 33, etc.

(2) C.I. Acid dyes

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160 、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251；C.I. Acid Orange Orange) 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Acid Red 73, 80, 91, 97, 138, 151, 211, 274; C.I. Acid Green (acid green) 3, 5, 9, 25, 27, 28, 41; C.I. Acid Violet 34, 120; C.I. Acid Blue (acid blue) 25, 27, 40, 45, 78, 80, 112, etc.

(3) C.I. Alkaline dyes

C.I. Basic green 1, etc.

(4) C.I. reactive dyes

C.I. reactive yellow 2, 76, 116; C.I. reactive orange 16, etc.

(5) C.I. Direct dyes

C.I. Direct yellow: 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I. Direct orange: 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct blue: 40, etc.

(6) C.I. Disperse Dyes

C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse Blue 1, 14, 56, 60, etc.

(7) C.I. mordant dyes

C.I. mordant yellow: 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; 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, etc.

(8) C.I. reduced dyes

C.I. Vat green 1, etc.

The pigment (A2) is not particularly limited, and known pigments can be used, for example, pigments listed in the Dye Index (published by The Society of Dyers and Colourists).

As the pigment (A2), for example, the following pigments can be cited: yellow pigments such as C.I. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; and red pigments such as C.I. pigment red. C.I. pigment blue (pigment blue) 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. pigment violet (pigment violet) 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. pigment green (pigment green) 7, 36, 58 and other green pigments; C.I. pigment brown (pigment brown) 23, 25 and other brown pigments; C.I. pigment black (pigment black) 1, 7 and other black pigments, etc.

The pigment (A2) is preferably a red pigment or a blue pigment.

The red pigment preferably has absorption in the wavelength region below 580nm, and more preferably has absorption in the wavelength region above 480nm and below 560nm. In addition, the red pigment is preferably a pigment that transmits light in the wavelength region above 610nm.

As the red pigment, known pigments can be used, for example, pigments listed in the Dye Index (published by The Society of Dyers and Colourists).

Among red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, and diketopyrrolopyrrole pigments are preferred, and anthraquinone pigments and diketopyrrolopyrrole pigments are more preferred.

Specific examples of preferred red pigments include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, and compounds represented by formula (P) described in Japanese Patent Laid-Open No. 2013-014750. Among these, C.I. Pigment Red 177, 208, 242, 254, 269 and compounds represented by formula (P) described in Japanese Patent Laid-Open No. 2013-014750 are more preferred, and C.I. Pigment Red 177, 254 and compounds represented by formula (P) described in Japanese Patent Laid-Open No. 2013-014750 are further preferred.

The blue pigment preferably has absorption in the wavelength region below 700nm, and more preferably has absorption in the wavelength region above 580nm and below 650nm. In addition, the blue pigment is preferably a pigment that transmits light in the wavelength region above 400nm.

The blue pigment is preferably a phthalocyanine pigment, more preferably a copper phthalocyanine pigment and/or a zinc phthalocyanine pigment, further preferably a copper phthalocyanine halide pigment and/or a zinc phthalocyanine halide pigment, and particularly preferably a copper phthalocyanine halide pigment.

Specifically, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 are preferred, C.I. Pigment Blue 15, 15:3, 15:4, 15:6 are more preferred, and C.I. Pigment Blue 15:6 is particularly preferred. By using the above blue pigment, it is easy to optimize the transmitted spectrum, and the light resistance and chemical resistance of the color filter become good.

For the pigment, rosin treatment, surface treatment using pigment derivatives with acidic or alkaline groups, grafting treatment on the pigment surface using polymer compounds, micronization treatment using sulfuric acid micronization method, or cleaning treatment using organic solvents or water to remove impurities, or treatment to remove ionic impurities using ion exchange method, etc. can be performed as needed. The particle size of the pigment is preferably uniform.

By using a dispersant for dispersion treatment, a pigment dispersion in which the pigment is evenly dispersed in the solution can be obtained.

As the dispersant, for example, a surfactant can be cited. The surfactant can be any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. As the surfactant, for example, polyester-based surfactants, polyamine-based surfactants, acrylic-based surfactants, etc. can be cited. Examples of commercially available dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno), DISPERBYK (registered trademark) (manufactured by BYK-Chemie), BYKLPN (manufactured by BYK), etc.

When a dispersant is included in the pigment dispersion, its content is preferably 1 part by weight or more and 500 parts by weight or less, and more preferably 5 parts by weight or more and 300 parts by weight or less, relative to 100 parts by weight of the pigment (A2). If the content of the dispersant is within the above range, a uniformly dispersed pigment dispersion tends to be obtained.

The content of the colorant (A) relative to the total amount of solid components is preferably 1% by weight or more and 60% by weight or less, more preferably 3% by weight or more and 55% by weight or less, and even more preferably 5% by weight or more and 50% by weight or less. The so-called "total amount of solid components" in this specification refers to the amount after deducting the content of the solvent from the total amount of the colored curable resin composition. If the content of the colorant (A) is within the above range, a color filter with sufficient color concentration can be obtained. In addition, if the content of the colorant (A) is within the above range, the composition can contain a necessary amount of resin or polymerizable compound, thereby forming a color filter with sufficient mechanical strength. The total amount of solid components and the content of each component relative to it can be measured using known analytical methods such as liquid chromatography or gas chromatography.

When the dye (A1) is used, its content is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably 60% by weight or less, and further preferably 55% by weight or less relative to the total amount of the solid component. If the content of the dye (A1) is within the above range, a colored curable resin composition having good developability with an alkaline developer can be obtained.

When the pigment (A2) is used, its content relative to the total amount of solid components is preferably 1% by weight or more, more preferably 1.5% by weight or more, and preferably 60% by weight or less, more preferably 55% by weight or less, and further preferably 50% by weight or less. If the content of the pigment (A2) is within the above range, a color filter with good chromaticity can be obtained.

When dye (A1) and pigment (A2) are used, the weight ratio of dye (A1) to pigment (A2) (dye (A1): pigment (A2)) is preferably 1:99~99:1, more preferably 1:99~95:5, and particularly preferably 5:95~90:10.

In one aspect of the present invention, the coloring agent (A) comprises a coloring agent selected from the formula (A3-1):

The compound represented by (hereinafter, sometimes referred to as "compound (A3-1)") and formula (A3-2):

At least one compound (A3) in the group consisting of the compounds represented (hereinafter, sometimes described as "compound (A3-2)").

Compound (A3) (i.e., compound (A3-1) and compound (A3-2)) is a "solvent-soluble dye" or a "solvent-insoluble pigment" depending on its structure (e.g., the types of (M ^r+ ) ^k-1 and [Y] ^m- as counter ions). That is, the scope of compound (A3) includes both compounds that are dyes and compounds that are pigments.

First, the definitions of the groups in compound (A3) are explained. Unless otherwise specified, the groups in compound (A3) have the following definitions.

Examples of halogen atoms include fluorine atom, chlorine atom, bromine atom, and iodine atom.

The saturated alkyl group may be any of a straight chain, a branched chain, and a ring. Examples of saturated alkyl groups having 1 to 20 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, and other alkyl groups having 1 to 20 carbon atoms; and alicyclic saturated alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

The alkyl group may be a straight chain or a branched chain. As examples of alkyl groups having 1 to 10 carbon atoms, the groups having 1 to 10 carbon atoms in the examples of alkyl groups having 1 to 20 carbon atoms can be cited. The examples of alkyl groups having different carbon atoms are the same. In addition, regarding groups other than alkyl groups, the examples of groups having different carbon atoms are the same. For example, as examples of saturated alkyl groups having 2 to 20 carbon atoms, the groups having 2 to 20 carbon atoms in the examples of saturated alkyl groups having 1 to 20 carbon atoms can be cited.

The alkanediyl group may be either a straight chain or a branched chain. Examples of alkanediyl groups having 1 to 10 carbon atoms include methylene, ethyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, isopropyl, isobutyl, 2-methyltrimethylene, isopentyl, isohexyl, isooctyl, and 2-ethylhexyl.

The fluoroalkyl group may be a straight chain or a branched chain. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, and perfluorobutyl.

The alkoxy group may be either a straight chain or a branched chain. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy, isopentyloxy, and neopentyloxy.

Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, and 9-anthryl.

Examples of aralkyl groups having 7 to 30 carbon atoms include benzyl, phenethyl, naphthylmethyl, and 3-phenylpropyl.

The nitrogen-containing heterocyclic ring may be either a monocyclic ring or a condensed ring. Examples of nitrogen-containing heterocyclic rings having 3 to 10 members include: pyrrolidine ring, morpholine ring, piperidine ring, and piperazine ring.

The aromatic hydrocarbon ring may be a single ring or a condensed ring. The aromatic hydrocarbon ring with 6 to 14 carbon atoms may be a benzene ring, a naphthalene ring, a phenanthrene ring, or an anthracene ring.

Aromatic heterocyclic rings may be either monocyclic or condensed rings. Examples of 5- to 10-membered aromatic heterocyclic rings include pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, thiazole ring, furan ring, thiophene ring, pyridine ring, pyrimidine ring, oxazine ring, pyrazine ring, indole ring, benzimidazole ring, benzothiazole ring, quinoline ring, benzofuran ring, etc.

Next, the bases etc. in formula (A3-1) are explained.

R ^41a and R ^42a in formula (A3-1) each independently 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 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded.

The saturated alkyl group having 1 to 20 carbon atoms in formula (A3-1) may have a substituent which is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and an amino group.

When the saturated alkyl group having 1 to 20 carbon atoms in formula (A3-1) is a saturated alkyl group having 2 to 20 carbon atoms, _-CH2- contained in the saturated alkyl group may be substituted with -O- or -CO-. Here, the _-CH2- does not include _-CH2- bonded to a nitrogen atom and _-CH2- in a methyl group at the end of the saturated alkyl group. In addition, _-CH2 - _CH2- contained in the saturated alkyl group may not be substituted with -OO- or -CO-CO-.

The substituent that the aromatic alkyl group having 6 to 14 carbon atoms in formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The aralkyl group having 7 to 30 carbon atoms in formula (A3-1) may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

^Rf in formula (A3-1) represents a fluoroalkyl group having 1 to 12 carbon atoms.

The alkyl group having 1 to 8 carbon atoms in formula (A3-1) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and an amino group.

When the alkyl group having 1 to 8 carbon atoms in formula (A3-1) is an alkyl group having 2 to 8 carbon atoms, _-CH2- contained in the alkyl group may be substituted with -O- or -CO-. Here, the _-CH2- does not include _-CH2- in the methyl group at the end of the alkyl group. In addition, the _-CH2 - _CH2- contained in the alkyl group may not be substituted with -OO- or -CO-CO-.

R ^41a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

R ^42a is preferably a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , more preferably a phenyl group which may have -SO ₃ ^- and may have one or two alkyl groups having 1 to ⁸ carbon atoms as substituents, and further preferably a phenyl group which may have -SO ₃ - and may have one or two alkyl groups having 1 to 4 carbon atoms as substituents.

R ^43a and R ^44a in formula (A3-1) each independently represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43a and R ^44a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded.

R ^43a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

R ^44a is preferably a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , more preferably a phenyl group which may have -SO ₃ ^- and may have one or two alkyl groups having 1 to ⁸ carbon atoms as substituents, and further preferably a phenyl group which may have -SO ₃ - and may have one or two alkyl groups having 1 to 4 carbon atoms as substituents.

R ^47a to R ^54a in formula (A3-1) each independently represents 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 which may have a substituent. R ^47a to R ^54a each independently represent preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or -SO ₃ ^- , and more preferably a hydrogen atom or -SO ₃ ^- .

Ring ^T1a in Formula (A3-1) represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent, or an aromatic heterocyclic ring having 5 to 10 members which may have a substituent.

The substituent that the aromatic hydrocarbon ring having 6 to 14 carbon atoms in formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The 5- to 10-membered aromatic heterocyclic ring in formula (A3-1) may have a substituent which is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

The ring T ^1a is preferably a ring represented by the formula (1t).

R ^45a and R ^46a in formula (1t) each independently represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^45a and R ^46a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded.

The saturated alkyl group having 1 to 20 carbon atoms in formula (1t) may have a substituent which is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and an amino group.

The substituent that the aromatic alkyl group having 6 to 14 carbon atoms in formula (1t) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The aralkyl group having 7 to 30 carbon atoms in formula (1t) may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

The alkyl group having 1 to 8 carbon atoms in formula (1t) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group and an amino group.

R ^45a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

R ^46a is preferably a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , more preferably a phenyl group which may have -SO ₃ ^- and may have one or two alkyl groups having 1 to ⁸ carbon atoms as substituents, and further preferably a phenyl group which may have -SO ₃ - and may have one or two alkyl groups having 1 to 4 carbon atoms as substituents.

R ^56a in formula (1t) represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

R ^56a is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , more preferably a phenyl group which may have -SO ₃ ^- and further preferably a phenyl group which may have -SO ₃ ^- and one or two fluorine atoms as substituents.

In formula (1t), L ^1a represents a sulfur atom, an oxygen atom or -NR ^57a -. R ^57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ^{L 1a} is preferably a sulfur atom.

The * in formula (1t) indicates the bonding position with the carbon cation. In other words, -* in formula (1t) indicates bonding. -* in other formulas also indicates bonding in the same way.

In formula (A3-1), r represents an integer greater than 1. Preferably, r is 2. When r is an integer greater than 2, the multiple anions represented by formula (A3-1a) may be the same or different.

[Chemistry 24]

[In formula (A3-1a), ring ^T1a , ^R41a to ^R44a and ^R47a to ^R54a have the same meanings as described above]

In the following, the anion represented by formula (A3-1a) is sometimes described as "anion (A3-1a)". It is preferred that a plurality of anions (A3-1a) are the same.

In the formula (A3-1), k represents the total number of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f possessed by the anion (A3-1a), and is an integer greater than or equal to 2. Preferably, k is 2.

Mr ⁺ in formula (A3-1) represents a hydrogen ion, an r-valent metal ion or N ⁺ ( ^R55a ) ₄ , and four ^R55a may be the same or different. ^R55a represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. When k-1 in formula (A3-1) is an integer greater than 2, multiple Mr ⁺ may be the same or different.

Mr ⁺ is preferably an r-valent metal ion. Examples of r-valent metal ions include alkaline metal ions such as lithium ion, sodium ion, potassium ion; alkaline earth metal ions such as palladium ion, magnesium ion, calcium ion, strontium ion, barium ion; transition metal ions such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion; and typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, and bismuth ion.

Mr ⁺ is more preferably a divalent metal ion, further preferably an alkali earth metal ion, and particularly preferably a barium ion (Ba2 ⁺ ).

The compound (A3-1) is preferably a compound (hereinafter sometimes described as "compound (A3-1')"), wherein R ^41a and R ^43a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ^42a and R ^44a are each independently a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , R ^47a to R ^54a are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or -SO ₃ ^- , and ring T ^1a is a ring represented by the formula (1t) [in the formula (1t), R ^45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ^46a is a phenyl group which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and -SO ₃ ^- , R ^56a is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 8 carbon atoms, and -SO ₃ ^- , L ^1a is a sulfur atom, and * represents a bonding position with a carbon cation], r is 2, k represents the total number of -SO ₃ ^- contained in the anion (A3-1a) and is 2, the two anions (A3-1a) are the same, and Mr ⁺ is Ba ²⁺ .

In compound (A3-1'), R ^41a and R ^43a are more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms; R ^42a and R ^44a are each independently more preferably a phenyl group having one or two alkyl groups having 1 to 8 carbon atoms as substituents and optionally having -SO ₃ ^- , and more preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as substituents and optionally having -SO ₃ ^- ; R ^47a to R ^54a are more preferably a hydrogen atom or -SO ₃ ^- ; R ^45a is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms; R ^46a is more preferably a phenyl group having one or two alkyl groups having 1 to 8 carbon atoms as substituents and optionally having -SO ₃ -. ^-phenyl , further preferably phenyl having one or two alkyl groups of 1 to 4 carbon atoms as substituents and optionally having -SO ₃ ^- ; and R ^56a is more preferably phenyl having one or two halogen atoms as substituents and optionally having -SO ₃ ^- , further preferably phenyl having one or two fluorine atoms as substituents and optionally having -SO ₃ ^- .

Among the compounds (A3-1), particularly preferred are compounds represented by the following formula (A3-1-1) (hereinafter, sometimes described as "compound (A3-1-1)"). In the following formula (A3-1-1), the description of two "-SO ₃ ^- " means that each anion has -SO ₃ ^- as a substituent, and the total number of -SO ₃ ^- in each anion is 2 (that is, the total number of -SO ₃ ^- in the two anions is 4).

Compound (A3-1) can be produced according to a known method (for example, the method described in "Journal of Organic Chemistry" ((1994), vol.59, #11, pp.3232-3236), and the method described in Japanese Patent Publication No. 2018-127596).

Next, the bases etc. in formula (A3-2) are explained.

R ^41b and R ^42b in formula (A3-2) each independently represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded.

The saturated alkyl group having 1 to 20 carbon atoms in formula (A3-2) may have a substituent which is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, and an amino group.

When the saturated alkyl group having 1 to 20 carbon atoms in formula (A3-2) is a saturated alkyl group having 2 to 20 carbon atoms, _-CH2- contained in the saturated alkyl group may be substituted with -O- or -CO-. Here, the _-CH2- does not include _-CH2- bonded to a nitrogen atom and _-CH2- in a methyl group at the end of the saturated alkyl group. In addition, _-CH2 - _CH2- contained in the saturated alkyl group may not be substituted with -OO- or -CO-CO-.

The substituent that the aromatic alkyl group having 6 to 14 carbon atoms in formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The substituent that the aralkyl group having 7 to 30 carbon atoms in formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The alkyl group with 1 to 8 carbon atoms in formula (A3-2) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group and an amino group.

When the alkyl group having 1 to 8 carbon atoms in formula (A3-2) is an alkyl group having 2 to 8 carbon atoms, _-CH2- contained in the alkyl group may be substituted with -O- or -CO-. Here, the _-CH2- does not include _-CH2- in the methyl group at the end of the alkyl group. In addition, _-CH2 - _CH2- contained in the alkyl group may not be substituted with -OO- or -CO-CO-.

R ^41b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

R ^42b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and further preferably a phenyl group.

R ^43b and R ^44b in formula (A3-2) each independently represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43b and R ^44b are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atoms to which they are bonded.

R ^43b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

R ^44b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and further preferably a phenyl group.

In formula (A3-2), R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent.

R ^47b to R ^54b are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom.

Ring T ^1b in formula (A3-2) represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent, or an aromatic heterocyclic ring having 5 to 10 members which may have a substituent.

The substituent that the aromatic hydrocarbon ring having 6 to 14 carbon atoms in formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The 5- to 10-membered aromatic heterocyclic ring in formula (A3-2) may have a substituent that is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The ring T ^1b is preferably a ring represented by the formula (2t).

R ^45b and R ^46b in formula (2t) each independently represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^45b and R ^46b are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded.

The saturated alkyl group having 1 to 20 carbon atoms in formula (2t) may have a substituent which is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group and an amino group.

The substituent that the aromatic hydrocarbon group having 6 to 14 carbon atoms in formula (2t) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a methyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The substituent that the aralkyl group having 7 to 30 carbon atoms in formula (2t) may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.

The alkyl group having 1 to 8 carbon atoms in formula (2t) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group and an amino group.

R ^45b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

R ^46b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group having one or two alkyl groups having 1 to 8 carbon atoms as substituents, and further preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as substituents.

R ^56b in formula (2t) represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

R ^56b is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group having one or two halogen atoms as substituents, and further preferably a phenyl group having one or two fluorine atoms as substituents.

In formula (2t), L ^1b represents a sulfur atom, an oxygen atom or -NR ^57b -. R ^57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L ^1b is preferably a sulfur atom.

The * in formula (2t) represents the bonding position with the carbon cation.

In formula (A3-2), m represents an integer greater than 1. m is preferably an integer of 1 to 20, more preferably an integer of 2 to 14, further preferably an integer of 2 to 8, and particularly preferably 3. When m is an integer greater than 2, the multiple cations represented by formula (A3-2c) may be the same or different.

[In formula (A3-2c), ring ^T1b , ^R41b to ^R44b and ^R47b to ^R54b have the same meanings as described above]

Hereinafter, the cation represented by formula (A3-2c) may be referred to as "cation (A3-2c)". It is preferred that the plurality of cations (A3-2c) are the same.

[Y] ^m- in formula (A3-2) represents an m-valent anion. [Y] ^m- is preferably a polyanion containing a tungsten atom, more preferably [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [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- , [SiW ₉ O ₃₄ ] ^10- , [SiW ₁₀ O ₃₆ ] ^8- , [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- or [WO ₄ ] ^2- , and preferably [PW ₁₂ O ₄₀ ] ^3- .

The compound (A3-2) is preferably a compound (hereinafter sometimes described as "compound (A3-2')"), wherein R ^41b , R ^43b and R ^47b to R ^54b are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ^42b and R ^44b are each independently a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, and ring T ^1b is a ring represented by formula (2t) [in formula (2t), R ^45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ^46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, and R ^56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms, and L ^1b is a sulfur atom, and * indicates a bonding position with a carbon cation], m is 3, the three cations (A3-2c) are the same, and [Y] ^m- is [PW ₁₂ O ₄₀ ] ^3- .

In compound (A3-2'), R ^41b and R ^43b are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms; R ^42b and R ^44b are each independently more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and further preferably a phenyl group; R ^47b to R ^54b are each independently more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom; R ^45b is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms; R ^46b is more preferably a phenyl group having one or two alkyl groups having 1 to 8 carbon atoms as substituents, and further preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as substituents; and R ^56b is more preferably a phenyl group having one or two halogen atoms as substituents, and further preferably a phenyl group having one or two fluorine atoms as substituents.

Among the compounds (A3-2), the compounds represented by the following formula (A3-2-1) are particularly preferred (hereinafter, sometimes described as "compound (A3-2-1)").

Compound (A3-2) can be produced according to a known method (for example, the method described in Japanese Patent Publication No. 2015-28121).

The compound (A3) is preferably mixed with a solvent that does not dissolve it and used as a dispersion of the compound (A3). When preparing the dispersion of the compound (A3), it is preferred to use a dispersant. As the dispersant, for example, the dispersants described for the pigment dispersion can be cited.

When a dispersant is included in the dispersion of compound (A3), its content is preferably 1 part by weight or more and 500 parts by weight or less, and more preferably 5 parts by weight or more and 300 parts by weight or less, relative to 100 parts by weight of compound (A3). If the content of the dispersant is within the above range, a uniformly dispersed pigment dispersion tends to be obtained.

When compound (A3) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, and preferably 60% by weight or less, more preferably 55% by weight or less, and further preferably 50% by weight or less relative to the total amount of solid components.

When using compound (A3), it is preferred to use a dye (A1) different from compound (A3). That is, in a preferred embodiment of the present invention, the coloring agent (A) contains a dye (A1) different from compound (A3) and compound (A3). The type and content of the dye (A1) in this embodiment are as described above.

When dye (A1) and compound (A3) are used, the weight ratio of dye (A1) to compound (A3) (dye (A1): compound (A3)) is preferably 0.5:99.5~99:1, more preferably 0.5:99.5~95:5, and particularly preferably 0.5:99.5~90:10.

<Resin (B)>

The resin (B) used in the present invention contains a resin (B1) containing a constituent unit (b1-1) represented by formula (1b) (hereinafter, sometimes described as "constituent unit (b1-1)").

[Chemistry 29]

[In formula (1b), R ^1B represents a hydrogen atom or a methyl group, R ^2B to R ^4B each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n represents an integer of 1 to 10, and * represents a bonding position, wherein at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbon atoms]

In the resin (B1), the constituent unit (b1-1) may include only one type or two or more types. By using the resin (B1), the reduction in thickness of the coloring pattern or the coloring coating film caused by heating (especially post-baking) can be suppressed.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^2B to R ^4B include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl and neopentyl.

Examples of the alkoxy group having 1 to 6 carbon atoms in R ^2B to R ^4B include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy, isopentyloxy and neopentyloxy.

R ^2B to R ^4B are each independently preferably methoxy, ethoxy or propoxy, more preferably methoxy or ethoxy.

n is preferably an integer between 1 and 6, and more preferably an integer between 1 and 3.

The resin (B1) is preferably a copolymer comprising a constituent unit (b1-1), a constituent unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter, sometimes described as "constituent unit (b1-2)"), and other constituent units (b1-3) (hereinafter, sometimes described as "constituent unit (b1-3)"). Here, the so-called other constituent unit (b1-3) refers to a constituent unit different from the constituent unit (b1-1) and the constituent unit (b1-2). In the resin (B1) as a copolymer, the constituent unit (b1-1), the constituent unit (b1-2), and the constituent unit (b1-3) may each contain only one kind or two or more kinds.

Examples of the acidic group contained in the constituent unit (b1-2) include a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfonic acid group (-S(=O) ₂ OH). Among these, a carboxyl group is preferred.

From the viewpoint of solvent resistance, the amount of the constituent unit (b1-1) when the total of all constituent units in the copolymer is set to 100 mol% is preferably 1 mol% to 50 mol%, more preferably 5 mol% to 40 mol%, and even more preferably 10 mol% to 30 mol%.

From the viewpoint of developing properties, the amount of the constituent unit (b1-2) when the total of all constituent units in the copolymer is set to 100 mol% is preferably 10 mol% to 50 mol%, more preferably 15 mol% to 45 mol%, and even more preferably 20 mol% to 40 mol%.

From the viewpoint of developing properties and solvent resistance, the amount of the constituent unit (b1-3) when the total of all constituent units in the copolymer is set to 100 mol% is preferably 1 mol% to 89 mol%, more preferably 15 mol% to 80 mol%, and even more preferably 30 mol% to 70 mol%.

From the perspective of developing properties, the weight average molecular weight (Mw) of the resin (B1) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 3,000 to 30,000. The weight average molecular weight (Mw) is a value calculated by gel permeation chromatography (GPC) and converted to polystyrene.

From the viewpoint of thermal decomposition resistance, thermal yellowing resistance and solvent resistance, the silyl equivalent of resin (B1) is preferably 400 to 4,000, and more preferably 500 to 3,000. If the silyl equivalent of resin (B1) is 400 or more, it is effective for further improving the thermal decomposition resistance and thermal yellowing resistance of the colored pattern or colored coating. In addition, the silyl equivalent of resin (B1) is a value calculated according to the following formula: Silyl equivalent = weight average molecular weight of resin (B1) / average number of silyl groups in one molecule.

The silyl equivalent can be calculated from the input amount of the monomer used in the production of the resin (B1).

When the resin (B1) is a copolymer containing the constituent unit (b1-2), the acid value of the resin (B1) is preferably 20 mgKOH/g to 300 mgKOH/g, and more preferably 30 mgKOH/g to 200 mgKOH/g from the viewpoint of developing properties. The acid value of the resin (B1) is a value measured in accordance with Japanese Industrial Standards (JIS) K6901 5.3 using a mixed indicator of bromothymol blue and phenol red, and is a value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B1), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

From the perspective of forming a good pattern without defects and peeling after alkali development, the content of the resin (B1) is preferably 5 to 400 parts by weight, more preferably 7.5 to 375 parts by weight, and further preferably 10 to 350 parts by weight, relative to 100 parts by weight of the polymerizable compound (C).

The resin (B1) can be produced by copolymerizing only the compound (m1-1) represented by the following formula (2b) (hereinafter, sometimes described as "compound (m1-1)") or a monomer mixture containing the compound (m1-1) and other compounds in the presence of a solvent according to a known free radical polymerization method.

[The meanings of the symbols in formula (2b) are as described above]

The copolymer resin (B1) can be produced, for example, by dissolving the compound (m1-1) and other compounds as needed in a solvent, preparing a solution, adding a polymerization initiator to the solution, and reacting at 50°C to 130°C for 1 hour to 20 hours.

The resin (B1) which is a copolymer comprising the constituent unit (b1-1), the constituent unit (b1-2) and the constituent unit (b1-3) can be produced by copolymerizing a monomer mixture comprising the compound (m1-1), a polymerizable unsaturated compound (m1-2) having an acidic group (hereinafter, sometimes described as "the compound (m1-2)") and other polymerizable unsaturated compounds (m1-3) (hereinafter, sometimes described as "the compound (m1-3)") in the presence of a solvent according to a known free radical polymerization method. Here, the other polymerizable unsaturated compound (m1-3) refers to a polymerizable unsaturated compound different from the compound (m1-1) and the compound (m1-2). In addition, the constituent unit (b1-1) is derived from the compound (m1-1), the constituent unit (b1-2) is derived from the compound (m1-2), and the constituent unit (b1-3) is derived from the compound (m1-3).

The copolymer resin (B1) can be produced, for example, by dissolving compound (m1-1), compound (m1-2) and compound (m1-3) in a solvent, preparing a solution, adding a polymerization initiator to the solution, and reacting at 50°C to 130°C for 1 hour to 20 hours.

Examples of compound (m1-1) include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylethyldiethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane. Among these, 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane are preferred in terms of availability and reactivity. Here, "3-(meth)acryloxypropylmethyldimethoxysilane" refers to at least one selected from 3-acryloxypropylmethyldimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane. Other identical descriptions have the same meaning.

Examples of the acidic group contained in compound (m1-2) include a carboxyl group, a phosphate group (—OP(═O)(OH) ₂ ), and a sulfone group (—S(═O) ₂ OH). Among these, a carboxyl group is preferred.

As compound (m1-2), for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. Among them, (meth)acrylic acid is preferred from the viewpoint of ease of acquisition and reactivity.

As the compound (m1-3), for example, the following compounds can be cited: butadiene; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, Ethyl cyclohexyl acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butanetriol mono(meth)acrylate, pentatriol mono(meth)acrylate Acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxycyclobutane-3-yl)methyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-diisocyanatopropyl (meth)acrylate ethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, a (meth)acrylate having a blocked isocyanate group obtained by blocking the isocyanate group of the (meth)acrylate having an isocyanate group (e.g., 2-isocyanatoethyl (meth)acrylate) using a blocking agent, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, hexamethylpiperidyl (meth)acrylate; (meth)acrylic acid amide, N,N-dimethyl (meth)acrylate amide, N,N-diethyl (meth)acrylate amide, N,N-dipropyl (meth)acrylate amide, (meth) N,N-diisopropyl acrylate, anthracenyl (meth)acrylate, N-isopropyl (meth)acrylamide, morpholine (meth)acrylate, diacetone (meth)acrylamide; norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene, tricyclo[4.4.0.1 ^2,5 ]undec-3-ene, tricyclo[6.2.1.0 ^1,8 ]undec-9-ene, tricyclo[6.2.1.0 ^1,8 ]undec-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,12 ] dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodec-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadeca-4-ene, pentacyclo[7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic anhydride, (meth)acrylic anilide, (meth)acrylic nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, vinyltoluene; styrene and its derivatives; diethyl citric acid, diethyl maleate, diethyl fumarate, diethyl itaconate; maleic anhydride, itaconic anhydride, citric anhydride.

From the viewpoint of ease of acquisition and reactivity, as compound (m1-3), methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, glyceryl (meth)acrylate, (3-ethyloxycyclobutane-3-yl)methyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylamide (meth)acrylate, benzoline (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, and methyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, glyceryl (meth)acrylate, (3-ethyloxycyclobutane-3-yl)methyl (meth)acrylate, styrene and vinyltoluene are more preferred.

From the viewpoint of heat decomposition resistance and heat yellowing resistance, the compound (m1-3) is preferably an alkyl (meth)acrylate, and more preferably methyl (meth)acrylate, benzyl (meth)acrylate, or dicyclopentanyl (meth)acrylate.

From the viewpoint of solvent resistance, the compound (m1-3) is preferably a polymerizable compound having a functional group that reacts with an acidic group (e.g., glycidyl, cyclobutylene oxide, isocyanate, blocked isocyanate), and more preferably glycidyl (meth)acrylate or (3-ethylcyclobutylene oxide)methyl methacrylate.

As the blocking agent used for blocking the isocyanate group, for example, the following blocking agents can be cited: ε-caprolactam, δ-valerolactamide, γ-butyrolactam, β-propiolactamide and other lactam-based blocking agents; methanol, ethanol, propanol, butanol, ethylene glycol, methyl solvent, butyl solvent, methyl carbitol, benzyl alcohol, phenyl solvent, furfuryl alcohol, cyclohexanol and other alcohol-based blocking agents; phenol, cresol, xylenol, ethylphenol, etc. Phenol-based end-capping agents such as butylphenol, o-isopropylphenol, tert-butylphenol, tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid esters, daphneol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; active methylene-based end-capping agents such as dimethyl malonate, diethyl malonate, methyl acetylacetate, ethyl acetylacetate, acetylacetone, etc.; butanethiol (butyl Mercaptan), thiophenol, tertiary-dodecyl mercaptan and other thiol-based capping agents; diphenylamine, phenylnaphthylamine, aniline, carbazole and other amine-based capping agents; acetanilide, acetanisidide, acetamide, benzamide and other acid amide-based capping agents; succinimide, maleic imide and other acid imide-based capping agents Agent; imidazole-based end-capping agents such as imidazole, 2-methylimidazole, and 2-ethylimidazole; urea-based end-capping agents such as urea, thiourea, and ethyleneurea; aminocarbamate-based end-capping agents such as N-phenylaminophenyl ester and 2-oxazolidinone; imine-based end-capping agents such as ethyleneimine and polyethyleneimine; oxime-based end-capping agents such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, and cyclohexanone oxime; bisulfite-based end-capping agents such as sodium bisulfite and potassium bisulfite.

In order to control the molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the resin (B1) within a preferred range and to suppress gelation during polymerization, the solvent used in the polymerization is preferably a solvent containing a hydroxyl group having 3 to 10 carbon atoms. As solvents containing hydroxyl groups having 3 to 10 carbon atoms, for example, monoalcohols such as propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and benzyl alcohol; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether.

The solvent used in the polymerization may also contain solvents other than the solvent containing a hydroxyl group having 3 to 10 carbon atoms. Examples of the solvent include (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxylate, ethyl hydroxylate, 3-methyl- Esters such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc. Among these, (poly)alkylene glycol monoalkyl ether acetates are preferred from the viewpoint of reactivity.

From the viewpoint of controlling the weight molecular weight and molecular weight distribution (Mw/Mn) of the resin (B1), the content of the solvent containing a hydroxyl group having 3 to 10 carbon atoms relative to the total amount of the solvent used in the polymerization is preferably 10 wt% to 100 wt%, more preferably 20 wt% to 100 wt%.

The amount of the solvent used in the polymerization is not particularly limited, but is preferably 30 to 1,000 parts by weight, and more preferably 50 to 800 parts by weight, relative to 100 parts by weight of the total amount of compound (m1-1), compound (m1-2) and compound (m1-3).

The polymerization initiator that can be used in the polymerization is not particularly limited, and examples thereof include: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyric acid) dimethyl ester, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, etc. The amount of the polymerization initiator used is not particularly limited, and is preferably 0.5 to 20 parts by weight, and more preferably 1.0 to 10 parts by weight, relative to 100 parts by weight of the total amount of compound (m1-1), compound (m1-2), and compound (m1-3).

The resin (B1) is preferably a copolymer of (meth)acrylic acid, 3-(meth)acryloxypropyltrimethoxysilane and methyl (meth)acrylate. When compound (A3) is used, the resin (B1) is preferably a copolymer of (meth)acrylic acid, 3-(meth)acryloxypropyltriethoxysilane and dicyclopentanyl (meth)acrylate.

Resin (B) may also contain a resin (B2) different from resin (B1). Resin (B2) is preferably an alkali-soluble resin, and is preferably a polymer containing the following constituent units, wherein the constituent units are derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, sometimes described as "monomer (m2-1)"). In the polymer, the constituent units may include only one type or two or more types.

Resin (B2) is preferably a copolymer containing constituent units derived from monomer (m2-1) and constituent units derived from a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenic unsaturated bond (hereinafter, sometimes described as "monomer (m2-2)"). The copolymer may also contain other constituent units. As other constituent units, for example, constituent units derived from a monomer different from monomer (m2-1) and monomer (m2-2) (hereinafter, sometimes described as "monomer (m2-3)"), constituent units having an ethylenic unsaturated bond, etc. can be listed. In the copolymer, the constituent units may include only one kind or two or more kinds.

Examples of the monomer (m2-1) include the following monomers: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, liraconic 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, and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6- Bicyclic unsaturated compounds containing carboxyl groups such as dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxymethylbicyclo[2.2.1]hept-2-ene and 5-carboxyethylbicyclo[2.2.1]hept-2-ene; carboxylic anhydrides such as anhydrides of the unsaturated dicarboxylic acids mentioned above except fumaric acid and mesaconic acid; unsaturated mono[(meth)acryloxyalkyl] esters of polycarboxylic acids having a valence of more than two such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule such as α-(hydroxymethyl)acrylic acid.

As the monomer (m2-1), acrylic acid, methacrylic acid and maleic anhydride are preferred in terms of reactivity or solubility of the obtained resin in alkaline aqueous solution.

The monomer (m2-2) refers to a polymerizable compound having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenic unsaturated bond. The monomer (m2-2) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloyloxy group. Examples of the cyclic ether structure with 2 to 4 carbon atoms include: an oxycyclopropane ring, an oxycyclobutane ring, and a tetrahydrofuran ring.

Examples of the monomer (m2-2) include a monomer having an oxocyclopropyl group and an ethylenic unsaturated bond (hereinafter, sometimes described as "monomer (m2-2-1)"), a monomer having an oxocyclobutyl group and an ethylenic unsaturated bond (hereinafter, sometimes described as "monomer (m2-2-2)"), and a monomer having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter, sometimes described as "monomer (m2-2-3)"), etc.

Examples of monomers (m2-2-1) include monomers having a structure formed by epoxidation of aliphatic unsaturated hydrocarbons in a straight chain or branched chain (hereinafter, sometimes described as "monomer (m2-2-1a)") and monomers having a structure formed by epoxidation of alicyclic unsaturated hydrocarbons (hereinafter, sometimes described as "monomer (m2-2-1b)"). As monomers (m2-2-1a), monomers having a glycerol group and an ethylenic unsaturated bond are preferred. Examples of the monomer (m2-2-1a) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α-methylvinylbenzyl 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-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene and 2,4,6-tri(glycidyloxymethyl)styrene, etc.

Examples of monomers (m2-2-1b) include vinylcyclohexene oxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide (registered trademark) 2000; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) M100; manufactured by Daicel), compounds represented by formula (BI) and compounds represented by formula (BII), etc.

[Chemistry 31]

[In formula (BI) and formula (BII), ^Ra and ^Rb each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, ^Xa and ^Xb each independently represent a single bond, * ^-Rc- , *-Rc ^- O-, *-Rc ^- S- or *-Rc ^- NH-, ^Rc represents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bonding position with O]

As the compound represented by formula (BI), for example, compounds represented by any one of formula (I-1) to formula (I-15) can be listed. Among them, compounds represented by any one of formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11) to formula (I-15) are preferred, and compounds represented by any one of formula (I-1), formula (I-7), formula (I-9) and formula (I-15) are more preferred.

[Chemistry 32]

As the compound represented by formula (BII), for example, there can be listed compounds represented by any one of formula (II-1) to formula (II-15). Among them, preferably, it is a compound represented by any one of formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15), and more preferably, it is a compound represented by any one of formula (II-1), formula (II-7), formula (II-9) and formula (II-15).

[Chemistry 33]

In addition, the compound represented by formula (BI) and the compound represented by formula (BII) can be used separately or in combination. When used in combination, the molar ratio of the compound represented by formula (BI) and the compound represented by formula (BII) (compound represented by formula (BI) : compound represented by formula (BII)) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

Examples of the monomer (m2-3) include the following monomers: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] (meth)acrylates such as decen-9-yl ester, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, fumaric acid Diethyl ester and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1] Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(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-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate and N-(9-acridinyl)maleimide and other dicarbonyl acyl groups. Amine derivatives; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene; nitriles containing vinyl groups such as (meth)acrylonitrile; halides such as vinyl chloride and vinylidene chloride; amides containing vinyl groups such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

In terms of reactivity and heat resistance, the monomer (m2-3) is preferably styrene, vinyltoluene, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and benzyl (meth)acrylate.

The constituent unit having an ethylenic unsaturated bond is preferably a constituent unit having a (meth)acryl group. The resin (B2) having such a constituent unit can be obtained by adding a monomer having a group that can react with the group possessed by the constituent unit and an ethylenic unsaturated bond to a polymer comprising a constituent unit derived from a monomer (m2-1) and a constituent unit derived from a monomer (m2-2).

As constituent units having ethylenic unsaturated bonds, for example, there can be listed: constituent units obtained by adding glycidyl (meth)acrylate to a (meth)acrylate unit; constituent units obtained by adding 2-hydroxyethyl (meth)acrylate to a maleic anhydride unit; constituent units obtained by adding (meth)acrylic acid to glycidyl (meth)acrylate units; constituent units obtained by adding carboxylic anhydride to constituent units having a hydroxyl group, etc.

A polymer containing constituent units derived from a monomer (m2-1) can be produced, for example, by polymerizing monomers constituting constituent units of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator and the solvent are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.). As for the solvent, there is no particular limitation if it is a solvent that dissolves each monomer, and examples thereof include the solvent (H) described later. Furthermore, the obtained polymer can be used directly as a solution after the reaction, or as a concentrated or diluted solution, or can be taken out in a solid (powder) form by re-precipitation or other methods.

In the production of a polymer containing a constituent unit derived from the monomer (m2-1), a carboxylic anhydride having an ethylenic unsaturated bond may also be used as a monomer. Examples of the carboxylic anhydride include maleic anhydride, conic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6- dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

Examples of the resin (B2) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid copolymers, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymers, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymers, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer ^, ] decenyl ester/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxycyclobutane/(meth)acrylic acid/styrene copolymer, benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, and resins described in Japanese Patent Laid-Open No. 9-106071, Japanese Patent Laid-Open No. 2004-29518, and Japanese Patent Laid-Open No. 2004-361455.

When a combination of two or more resins (B2) is used, the combination preferably comprises at least one selected from the group consisting of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/2-ethylhexyl(meth)acrylate copolymer.

The weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. The molecular weight distribution (Mw/Mn) of the resin (B2) (i.e., the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) is preferably 1.1 to 6, and more preferably 1.2 to 4. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (B2) are values calculated by gel permeation chromatography (GPC) and converted to polystyrene.

The acid value (solid content conversion value) of the resin (B2) is preferably 10 mgKOH/g to 300 mgKOH/g, more preferably 20 mgKOH/g to 250 mgKOH/g, further preferably 20 mgKOH/g to 200 mgKOH/g, further preferably 20 mgKOH/g to 170 mgKOH/g, further preferably 30 mgKOH/g to 170 mgKOH/g, particularly preferably 50 mgKOH/g to 150 mgKOH/g, further particularly preferably 60 mgKOH/g to 140 mgKOH/g, and most preferably 60 mgKOH/g to 135 mgKOH/g. The acid value of the resin (B2) is a value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B2), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

When the resin (B2) is used, its content relative to 100 parts by weight of the colorant (A) is preferably 1 part by weight to 1,200 parts by weight, more preferably 5 parts by weight to 1,000 parts by weight, and even more preferably 10 parts by weight to 800 parts by weight.

When resin (B2) is used, its content relative to the total amount of solid components is preferably 1% to 50% by weight, more preferably 1% to 45% by weight, further preferably 1% to 40% by weight, and most preferably 1% to 30% by weight.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active free radicals and/or acids generated from the polymerization initiator (D). The polymerizable compound (C) is preferably a free radical polymerizable compound. Examples of free radical polymerizable compounds include polymerizable compounds having ethylenic unsaturated bonds. Free radical polymerizable compounds are preferably (meth)acrylates.

Examples of the polymerizable compound (C) include compounds having one ethylenically unsaturated bond, such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone; compounds having one ethylenically unsaturated bond, such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Compounds having two ethylenically unsaturated bonds, such as trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-(meth)acryloxyethyl) isocyanurate, etc.; compounds having three ethylenically unsaturated bonds, such as pentaerythritol tetra(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(acryloyloxyethyl) ether, and 3-methylpentanediol di(meth)acrylate; compounds having three ethylenically unsaturated bonds, such as trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-(meth)acryloyloxyethyl) isocyanurate; Compounds with four ethylenic unsaturated bonds, such as ethylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, and caprolactone modified pentaerythritol tetra(meth)acrylate; Compounds with five ethylenic unsaturated bonds, such as dipentaerythritol penta(meth)acrylate; Compounds with six ethylenic unsaturated bonds, such as dipentaerythritol hexa(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, and caprolactone modified dipentaerythritol hexa(meth)acrylate; Compounds with seven or more ethylenic unsaturated bonds, such as tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, four-season pentaerythritol nona(meth)acrylate, and four-season pentaerythritol deca(meth)acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds, and more preferably a polymerizable compound having five or six ethylenic unsaturated bonds. Specifically, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred. Commercially available products of the polymerizable compound (C) include, for example: KAYARAD (registered trademark) DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd.), and A9550 (Shin-Nakamura Chemical Co., Ltd.).

The 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 molecular weight of the polymerizable compound (C) of 1,000 or more is the weight average molecular weight (Mw) calculated by gel permeation chromatography (GPC) and converted to polystyrene.

The content of the polymerizable compound (C) relative to the total amount of the solid component is preferably 7% to 65% by weight, more preferably 13% to 60% by weight, and further preferably 17% to 55% by weight. If the content of the polymerizable compound (C) is within the above range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to be improved.

In addition, the weight ratio of resin (B) to polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80~80:20, and more preferably 35:65~80:20.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. and initiate polymerization by the action of light or heat, and a known polymerization initiator can be used. The polymerization initiator (D) is preferably a photoradical polymerization initiator. More preferably, the polymerizable compound (C) is a radical polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator (that is, the coloring curable resin composition of the present invention is a photocurable resin composition).

The photo-radical polymerization initiator is preferably at least one selected from the group consisting of O-acyl oxime compounds, phenyl alkyl ketone compounds, triazine compounds, acyl phosphine oxide compounds and biimidazole compounds, and is more preferably an O-acyl oxime compound.

O-acyl oxime compounds are compounds having a partial structure represented by formula (d1) (in the following formula, * represents a bonding position).

[Chemistry 34]

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3- dimethyl-2,4-dioxolanecyclopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-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, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylphenyl]propane-1-one-2-imine, and the like. Commercially available products such as TR-PBG327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (all manufactured by BASF), and N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyl oxime compound is preferably selected from TR-PBG327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (all manufactured by BASF), N-benzoyloxy-1-(4-phenylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylphenyl)octane-1-one-2-imine and N-benzoyloxy- At least one of the group consisting of 1-(4-phenylphenyl)-3-cyclopentylpropane-1-one-2-imine, more preferably at least one of the group consisting of TR-PBG327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (all manufactured by BASF) and N-benzoyloxy-1-(4-phenylphenyl)octane-1-one-2-imine. If these O-acyl oxime compounds are used, a color filter with high brightness tends to be obtained.

The phenyl alkyl ketone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3) (in the following formula, * represents a bonding position). In these partial structures, the benzene ring may also have a substituent.

Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-oxo-1-(4-oxo-phenyl)propane-1-one, 2-dimethylamino-1-(4-oxo-phenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methyl phenyl)methyl]-1-[4-(4-oxo-phenyl)phenyl]butane-1-one. Commercially available products such as Irgacure (registered trademark) 369, Irgacure (registered trademark) 907, and Irgacure (registered trademark) 379 (all manufactured by BASF) can also be used.

Examples of compounds having a partial structure represented by formula (d3) include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-〔4-(2-hydroxyethoxy)phenyl〕propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc.

In terms of sensitivity, the phenylalkyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl〕-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-〔2-(furan-2-yl)vinyl〕-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-〔2-(4-diethylamino-2-methylphenyl)vinyl〕-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-〔2-(3,4-dimethoxyphenyl)vinyl〕-1,3,5-triazine, etc.

As the acylphosphine oxide compound, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide can be listed. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. 6-75372 and Japanese Patent Laid-Open No. 6-75373), 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'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted by carboalkoxy groups (for example, see Japanese Patent Publication No. 7-10913), etc.

As other polymerization initiators (D), for example, there can be listed: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzoyl, methyl phenylglyoxylate, and titaniumocene compounds. These are preferably used in combination with the polymerization initiator aid (F) (especially amines) described later.

Examples of acid generators include onium salts such as 4-hydroxyphenyl dimethyl zirconia p-toluenesulfonate, 4-hydroxyphenyl dimethyl zirconia hexafluoroanticorate, 4-acetoxyphenyl dimethyl zirconia p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzyl zirconia hexafluoroanticorate, triphenyl zirconia p-toluenesulfonate, triphenyl zirconia hexafluoroanticorate, diphenyl iodine p-toluenesulfonate, diphenyl iodine hexafluoroanticorate, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, and more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the total of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity of the colored curable resin composition of the present invention tends to be improved and the exposure time is shortened, thereby improving the productivity of the color filter.

<Phenolic antioxidant (E)>

One of the characteristics of the coloring curable resin composition of the present invention is that it contains a phenolic antioxidant (E). By using a phenolic antioxidant (E), the thickness reduction of the coloring pattern or the coloring coating film caused by heating (especially post-baking) can be suppressed. In addition, by using a phenolic antioxidant (E), the heat resistance of the coloring pattern or the coloring coating film can be improved.

In this manual, the so-called "phenolic antioxidant" refers to an antioxidant having a phenolic hydroxyl group. Therefore, in this manual, for example, an antioxidant containing both a phenolic hydroxyl group and a phosphorus atom is classified as a phenolic antioxidant rather than a phosphorus antioxidant. In addition, the phenolic antioxidant in this manual also includes an antioxidant having a protected phenolic hydroxyl group (hereinafter, sometimes described as a "protected phenolic antioxidant").

As phenolic antioxidants, for example, the following antioxidants can be listed:

(1) Alkylthiomethylphenol

2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Di-dodecylthiomethyl-4-nonylphenol.

(2) Tocopherols

α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol.

(3) O-benzyl derivatives, N-benzyl derivatives and S-benzyl derivatives

3,5,3',5'-Tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl hydrothioacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) disulfide terephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl hydrothioacetate.

(4) Hydroxybenzylated malonate derivatives

Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylthioethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

(5) Aromatic hydroxybenzyl derivatives

1,3,5-Trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tri(3,5-tert-butyl-4-hydroxybenzyl)phenol.

(6) Triazine derivatives

2,4-Bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-tert-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-phenoxy)-1,3,5-triazine, tris(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris[2-(3',5'-di-tert-butyl-4'-hydroxycinnamyloxy)ethyl] isocyanurate.

(7) Benzylphosphonate derivatives

Dimethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

(8) Acylaminophenol derivatives

4-Hydroxylauric acid anilide, 4-Hydroxystearic acid anilide, Octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

(9) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trihydroxymethylpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

(10) Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trihydroxymethylpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

(11) Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and the following monohydric or polyhydric alcohols

Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trihydroxymethylpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

(12) Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and the following monohydric alcohols or polyhydric alcohols

Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trihydroxymethylpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

(13) Amide of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

N,N'-Bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]trimethylenediamine.

The phenolic antioxidants in the present invention may be formed by protecting the phenolic hydroxyl groups of the exemplified phenolic antioxidants with protecting groups. Examples of the protecting groups include ether protecting groups, acetal protecting groups, acyl protecting groups, and silyl ether protecting groups. Examples of ether protecting groups include methyl, benzyl, p-methoxybenzyl, and tert-butyl. Examples of acetal protecting groups include methoxymethyl, 2-tetrahydropyranyl, and ethoxyethyl. Examples of acyl protecting groups include acetyl, trimethylacetyl, and benzoyl. As silyl ether protecting groups, for example, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, and tert-butyldiphenylsilyl can be listed. In addition, tert-butyloxycarbonyl (Boc) can also be used as a protecting group. As a protecting group for phenolic hydroxyl groups, the Boc group is preferred.

Commercially available phenolic antioxidants can be used. Examples of commercially available phenolic antioxidants include Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.) and Adekastab (registered trademark) AO series (manufactured by ADEKA Corporation). Examples of commercially available protected phenolic antioxidants include Adeka Arkls (registered trademark) GPA-5001 (manufactured by ADEKA Corporation).

From the viewpoint of suppressing the reduction of the coloring pattern or the thickness of the coloring film caused by heating and obtaining a good coloring pattern after alkali development, the content of the phenolic antioxidant (E) is preferably 0.1 to 25 parts by weight, more preferably 0.2 to 20 parts by weight, further preferably 0.5 to 20 parts by weight, and particularly preferably 3 to 10 parts by weight, relative to 100 parts by weight of the polymerizable compound (C).

<Polymerization initiation aid (F)>

The colored curable resin composition of the present invention may further contain a polymerization initiator (F). The polymerization initiator (F) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that starts polymerization by the polymerization initiator. Examples of the polymerization initiator (F) include amine compounds, alkoxyanthracene compounds, thioxanthrone compounds, and carboxylic acid compounds.

As amine compounds, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. As amine compounds, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

Examples of thioxanthrone compounds include 2-isopropylthioxanthrone, 4-isopropylthioxanthrone, 2,4-diethylthioxanthrone, 2,4-dichlorothioxanthrone, and 1-chloro-4-propoxythioxanthrone.

Examples of carboxylic acid compounds include: phenylacetic acid, methylphenylacetic acid, ethylphenylacetic acid, methylethylphenylacetic acid, dimethylphenylacetic acid, methoxyphenylacetic acid, dimethoxyphenylacetic acid, chlorophenylacetic acid, dichlorophenylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

The polymerization initiation aid (F) is preferably a thioxanthrone compound, more preferably 2,4-diethylthioxanthrone.

When a polymerization initiator (F) is used, its content relative to 100 parts by weight of the total of the resin (B) and the polymerizable compound (C) is preferably 0.1 parts by weight to 30 parts by weight, and more preferably 1 part by weight to 20 parts by weight. In addition, when a polymerization initiator (F) is used, its content relative to 100 parts by weight of the polymerization initiator (D) is preferably 5 parts by weight to 80 parts by weight, more preferably 10 parts by weight to 60 parts by weight, and further preferably 15 parts by weight to 55 parts by weight. If the amount of the polymerization initiator (F) is within the above range, a colored pattern can be formed with high sensitivity, and the productivity of the color filter tends to be improved.

<Thiol compound (G)>

The colored curable resin composition of the present invention may further contain a thiol compound (G). The thiol compound (G) is a compound having a styryl group (-SH).

Examples of the compound having one alkyl group include 2-alkyl oxazole, 2-alkyl thiazole, 2-alkyl benzimidazole, 2-alkyl benzothiazole, 2-alkyl benzoxazole, 2-alkyl nicotinic acid, 2-alkyl pyridine, 2-alkyl pyridine-3-ol, 2-alkyl pyridine-N-oxide, 4-amino-6-hydroxy-2-alkyl pyrimidine, 4-amino-2-alkyl pyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-alkyl pyrimidine, 4,6-diamino-2-alkyl pyrimidine, 2,4-diamino- 6-Alkylopyrimidine, 4,6-dihydroxy-2-alkynylpyrimidine, 4,6-dimethyl-2-alkynylpyrimidine, 4-hydroxy-2-alkynyl-6-methylpyrimidine, 4-hydroxy-2-alkynyl-6-propylpyrimidine, 2-alkynyl-4-methylpyrimidine, 2-alkynylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-alkynylimidazole, 2-alkynyl-1-methylimidazole, 4-amino-3-hydrazino-5-alkynyl-1,2,4-triazole, 3-amino-5-alkynyl-1,2,4-triazole triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-butyl-1H-1,2,4-triazole-3-thiol, 2-amino-5-butyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dibutyl-1,3,4-thiadiazole, (furan-2-yl) methyl mercaptan, 2-butyl-5-thiazolidinone, 2-butylthiazoline, 2-butyl-4 (3H)-quinazolinone, 1-phenyl-1H-tetrazolyl-5-thiophene Alcohol, 2-quinolinethiol, 2-hydroxy-5-methylbenzimidazole, 2-hydroxy-5-nitrobenzimidazole, 6-amino-2-hydroxybenzothiazole, 5-chloro-2-hydroxybenzothiazole, 6-ethoxy-2-hydroxybenzothiazole, 6-nitro-2-hydroxybenzothiazole, 2-hydroxynaphthoimidazole, 2-hydroxynaphthooxazole, 3-hydroxy-1,2,4-triazole, 4-amino-6-hydroxypyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-hydroxypurine, 4-hydroxy-1H-pyrazolo[2,4-d]pyrimidine, etc.

Examples of compounds having two or more alkyl groups include hexanedithiol, decanedithiol, 1,4-di(methylalkyl)benzene, butanediol bis(3-alkylpropionate), butanediol bis(3-alkyl acetate), ethylene glycol bis(3-alkyl acetate), trihydroxymethylpropane tris(3-alkyl acetate), butanediol bis(3-alkyl propionate), trihydroxymethylpropane tris(3 -Benzyl propionate) (also known as "trihydroxymethylpropane tris (3-hydrogenthiopropionate)"), trihydroxymethylpropane tris (3-benzylacetate), pentaerythritol tetra (3-benzylacetate), pentaerythritol tetra (3-benzylacetate), trihydroxyethyl tris (3-benzylacetate), pentaerythritol tetra (3-benzylacetate), 1,4-bis (3-benzybutyloxy) butane, etc.

The thiol compound (G) is preferably a compound having two or more hydroxyl groups, and more preferably trihydroxymethylpropane tris(3-hydroxypropionate).

When a thiol compound (G) is used, its content is preferably 0.5 to 20 parts by weight, and more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the polymerizable compound (C). If the content of the thiol compound (G) is within this range, the sensitivity tends to be higher and the developing property tends to be better.

<Solvent (H)>

The colored curable resin composition of the present invention may further contain a solvent (H). The solvent (H) is not particularly limited, and a solvent commonly used in the art may be used. Examples of the solvent (H) include: ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (solvents containing OH and not containing -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. Furthermore, the concept of "-O-" does not include the "-O-" in "-COO-", and the concept of "-CO-" does not include the "-CO-" in "-COO-".

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexanol acetate, and γ-butyrolactone.

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

As ether ester solvents, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate, etc.

Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, diacetone alcohol, cyclopentanone, cyclohexanone and isophorone.

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

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

Examples of amide solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

As the solvent (H), in terms of coating properties and drying properties, an organic solvent having a boiling point of 120°C or higher and 180°C or lower at 1 atm is preferred. As the solvent (H), 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred, and 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol and ethyl 3-ethoxypropionate are more preferred.

When a solvent (H) is used, its content is preferably 35% to 95% by weight, and more preferably 40% to 92% by weight, relative to the entire coloring curable resin composition of the present invention. In other words, the total amount of solid components of the coloring curable resin composition is preferably 5% to 65% by weight, and more preferably 8% to 60% by weight. If the content of the solvent (H) is within the above range, the flatness during coating becomes good, and in addition, the color concentration will not be insufficient when forming a color filter, so there is a tendency for the display characteristics to become good.

<Leveling agent (I)>

The colored curable resin composition of the present invention may also contain a leveling agent (I). Examples of the leveling agent (I) include silicone-based surfactants and fluorine-based surfactants. These may also have polymerizable groups in the side chains.

Examples of silicone-based surfactants include surfactants having siloxane bonds in the molecule. Examples of commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning) and Toray Silicone SH8400. Corning); 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 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

Silicone-based surfactants may also have fluorine atoms. Examples of silicone-based surfactants having fluorine atoms include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).

Examples of fluorine-based surfactants include surfactants having a fluorine-carbon chain in the molecule. Examples of commercially available products include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co.); Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac R40, Megafac R555, Megafac R60, Megafac R70, Megafac R80, Megafac R90, Megafac R100, Megafac R110, Megafac R111, Megafac R112, Megafac R113, Megafac R114, Megafac R115, Megafac R116, Megafac R117, Megafac R118, Megafac R119, Megafac R120, Megafac R121, Megafac R122, Megafac R123, Megafac R124, Megafac R125, Megafac R126, Megafac R127, Megafac R128, Megafac R129, Megafac R130, Megafac R131, Megafac R132, Megafac R133, Megafac R134, Megafac R135, Megafac R136, Megafac R137, Megafac R138, Megafac R139, Megafac R140, Megafac R141, Megafac R142 fac) RS-718-K (manufactured by DIC Corporation); Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Ltd.), etc.

When the leveling agent (I) is used, its content is preferably 0.001% by weight or more and 0.2% by weight or less, more preferably 0.002% by weight or more and 0.1% by weight or less, and further preferably 0.01% by weight or more and 0.05% by weight or less, relative to the entire coloring curable resin composition. Furthermore, this content does not include the content of the dispersant used in the manufacture of the pigment dispersion. If the content of the leveling agent (I) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored curable resin composition of the present invention may also contain fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents and other additives known in the art as needed.

<Method for producing a colored curable resin composition>

The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant (A), a resin (B) (resin (B1) and optionally a resin (B2)), a polymerizable compound (C), a polymerization initiator (D) and a phenolic antioxidant (E), and optionally a solvent (H), a leveling agent (I), a polymerization initiator aid (F), a thiol compound (G) and other components.

When using the pigment (A2), it is preferred to mix the pigment (A2) with a part or all of the solvent (H) in advance, and disperse the pigment (A2) using a bead mill or the like until the average particle size of the pigment (A2) is about 0.2 μm or less, thereby preparing a pigment dispersion. At this time, a part or all of the dispersant and the resin (B) (especially the resin (B2)) may be prepared as needed. By mixing the remaining components in the thus obtained pigment dispersion in a manner to obtain a predetermined concentration, the target coloring curable resin composition may be prepared.

When the dye (A1) is used, the dye (A1) may be dissolved in part or all of the solvent (H) to prepare a dye solution. The solution is preferably filtered using a filter having a pore size of about 0.01 μm to 1 μm. In addition, the colored curable resin composition obtained by mixing the above components is preferably filtered using a filter having a pore size of about 0.01 μm to 10 μm.

<Color filter and liquid crystal display device manufacturing method>

As a method of forming a color filter using the colored curable resin composition of the present invention, for example, photolithography and a method using an inkjet device can be cited. In the photolithography method, the following steps are generally included: the colored curable resin composition is applied to a substrate, volatile components such as a solvent are removed by heat drying (pre-baking) and/or reduced pressure drying to form a composition layer, the composition layer is irradiated (exposed) with light through a photomask, and a developer is brought into contact with the exposed composition layer to form (develop) a colored pattern. After the development, a post-baking of heating the colored pattern is often performed. In the photolithography method, a colored coating film as a cured product of the composition layer can be formed by not using a photomask during exposure and/or not performing development. The colored pattern and colored coating thus obtained can be used as a color filter.

As the substrate, for example, glass plates, resin plates, silicon plates, etc. can be listed. Aluminum, silver, silver/copper/palladium alloy thin films, etc. can also be formed on the substrate. Furthermore, other color filter layers, resin layers, transistors, circuits, etc. can also be formed on the substrate.

The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the target use, for example, 0.1μm~30μm, preferably 1μm~20μm, and more preferably 1μm~6μm.

The formation of a colored pattern (pixel) using photolithography can be performed by known or conventional devices or conditions. For example, a colored pattern can be formed as follows.

First, a colored curable resin composition is applied to a substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and/or reduced pressure drying to obtain a smooth composition layer. Examples of coating methods include spin coating, slit coating, slit and spin coating, etc.

Next, the component layer is irradiated (exposed) with light through a photomask for forming the target coloring pattern. In order to evenly irradiate the entire exposure surface with parallel light or to accurately align the photomask with the substrate on which the component layer is formed, it is preferred to use an exposure device such as a mask aligner and a stepper.

By bringing the exposed component layer into contact with a developer, a colored pattern can be formed (developed) on the substrate. The unexposed portion of the component layer is dissolved in the developer and removed by development. As a developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, etc. is preferred. The developing method may be any of a coating method, an immersion method, and a spray method. Furthermore, the substrate may be tilted at any angle during development. It is preferred to wash with water after development.

The color filter produced from the colored curable resin composition of the present invention is useful as a color filter used in display devices (e.g., liquid crystal display devices, organic electroluminescence (EL) devices, electronic paper, etc.) and solid-state imaging devices.

[Implementation example]

The following examples are given to more specifically illustrate the present invention, but the present invention is not limited to the following examples at all, and can be implemented with appropriate changes within the scope of the above and the following purposes, all of which are included in the technical scope of the present invention. In addition, below, unless otherwise specified, "parts" means "parts by weight", and "%" other than thickness retention rate means "% by weight".

The structures of the compounds below were confirmed by mass spectrometry (LC; 1200 model manufactured by Agilent, MASS; LC/MSD model manufactured by Agilent).

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained in the production example were measured using GPC under the following conditions.

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI

Standard materials for calibration: TSK standard polystyrene F-40, F-4, F-228, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the obtained polystyrene-converted weight average molecular weight to the number average molecular weight (Mw/Mn) is defined as the molecular weight distribution.

<Manufacturing Example 1: Manufacture of Resin (B1-1)>

Place 750.0 g of 3-methoxybutanol in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, stir while replacing the atmosphere with nitrogen, and heat to 80°C.

Next, the following substance was added dropwise into the flask from the dropping funnel. The substance was prepared by adding 28.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) to a monomer mixture containing 25.6 g (0.30 mol) of methacrylic acid, 146.4 g (0.50 mol) of 3-methacryloyloxypropyltrimethoxysilane, and 49.2 g (0.49 mol) of methyl methacrylate.

After the addition was completed, the mixture was stirred at 80°C for 5 hours and copolymerized to obtain resin (B1-1) (weight average molecular weight (Mw): 5,500, acid value: 82 mgKOH/g, silane equivalent: 500).

<Manufacturing Example 2: Manufacture of Resin (B1-2)>

Place 750.0 g of propylene glycol monomethyl ether in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, stir while replacing the atmosphere with nitrogen, and heat to 80°C.

Next, the following substance was added dropwise into the flask from the dropping funnel. The substance was prepared by adding 28.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) to a monomer mixture containing 39.2 g (0.46 mol) of methacrylic acid, 132.0 g (0.46 mol) of 3-methacryloyloxypropyltriethoxysilane and 50.1 g (0.23 mol) of dicyclopentyl methacrylate.

After the addition was completed, the mixture was stirred at 80°C for 5 hours and copolymerized to obtain resin (B1-2) (weight average molecular weight (Mw): 4,000, acid value: 135 mgKOH/g, silane equivalent: 550).

<Production Example 3: Production of Resin (B2-1)>

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, a nitrogen atmosphere was replaced, 280 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 80°C while stirring. Subsequently, a mixed solution of 38 parts of acrylic acid, 289 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (containing ratio of 1:1 in molar ratio), and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was completed, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B2-1)) solution having a solid content of 35.1% and a viscosity of 125 mPa.s measured by a B-type viscometer (23°C). The weight average molecular weight (Mw) of the obtained copolymer was 9.2×10 ³ , the molecular weight distribution (Mw/Mn) was 2.08, and the acid value (solid content conversion value) was 77 mgKOH/g. Resin (B2-1) has the following structural units (in the following formula, * indicates the bonding position).

<Production Example 4: Production of red pigment dispersion>

50.6 parts of the red pigment synthesized in the following manner, 10.1 parts of a dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), 20.3 parts of a resin (B2-1) (calculated as solid content), 64.5 parts of propylene glycol monomethyl ether, and 216.0 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the obtained mixture was vibrated for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion of the red pigment.

The red pigment used in the preparation of the red pigment dispersion is synthesized as follows.

174 g of tert-amyl alcohol and 22.2 g of metallic sodium were reacted at 130° C. in a nitrogen atmosphere to synthesize sodium tert-amyl alcohol. The mixture was heated to 60° C., 91.0 g of 4-bromobenzonitrile, 71.05 g of di-tert-amyl succinate, and 108.9 g of tert-amyl alcohol were added, and the suspension was stirred for 2 hours so that the temperature of the obtained suspension was 85° C. or less. The suspension was stirred at 85° C. for more than 18 hours, and then added to a mixture of 200 g of methanol, 1000 g of water, and 49.21 g of sulfuric acid cooled to -10° C. After the addition of the suspension is completed, the obtained mixture is stirred for 5 hours while being kept at 0°C to complete the reaction, and then the solid matter is recovered by filtration. The recovered solid matter is washed alternately with methanol and water. The washing is repeated until the coloring of the methanol and water used in the washing disappears and the precipitation of the salt disappears. The washed solid matter is dried in a vacuum dryer at 80°C for 18 hours to obtain a red pigment.

<Production Example 5: Production of a blue pigment dispersion>

19.2 parts of C.I. Pigment Blue 15:6, 6.7 parts of dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), 7.7 parts of resin (B2-1) (calculated as solid content), 14.6 parts of ethyl lactate and 143.8 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4μm zirconia beads were added, and the obtained mixture was vibrated for 1 hour using a paint conditioner (manufactured by LAU). Afterwards, the zirconia beads were removed by filtration to obtain a dispersion of blue pigment.

<Production Example 6: Production of Compound (A3-1-1)>

The compound represented by the following formula (A3-1-1) was prepared by the method described in Example 7 of Japanese Patent Publication No. 2018-127596.

<Production Example 7: Production of Compound (A3-2-1)>

The compound represented by the following formula (A3-2-1) was prepared by the method described in Synthesis Example 19 of Japanese Patent Publication No. 2015-38201.

<Production Example 8: Production of a dispersion of compound (A3-1-1)>

7 parts of compound (A3-1-1), 3 parts of dispersant (DISPERBYK (registered trademark)-2050 manufactured by BYK-Chemie; 52% solution of propylene glycol monomethyl ether acetate), 3 parts of resin (B2-1) (calculated as solid content), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol, and 300 parts of 0.2 mm zirconia beads were mixed, and the obtained mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to prepare a dispersion of compound (A3-1-1). Furthermore, although compound (A3-1-1) is a dye soluble in diacetone alcohol, in order to improve the reliability of compound (A3-1-1) related to heat resistance and light resistance, propylene glycol monomethyl ether acetate is used to prepare a dispersion of compound (A3-1-1), and the dispersion is used.

<Production Example 9: Production of a dispersion of compound (A3-2-1)>

14 parts of compound (A3-2-1), 2 parts of dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), 6 parts of resin (B2-1) (calculated as solid content), 74 parts of propylene glycol monomethyl ether acetate, 4 parts of diacetone alcohol, and 300 parts of 0.2 mm zirconia beads were mixed, and the obtained mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to prepare a dispersion of compound (A3-2-1). Furthermore, although compound (A3-2-1) is a dye soluble in diacetone alcohol, in order to improve the reliability of compound (A3-2-1) related to heat resistance and light resistance, propylene glycol monomethyl ether acetate is used to prepare a dispersion of compound (A3-2-1), and the dispersion is used.

Example 1 to Example 16 and Comparative Example 1 to Comparative Example 5

(1) Production of coloring curable resin composition

The components are mixed in such a manner as to form the compositions shown in Tables 1 to 3 below to obtain a colored curable resin composition.

The components used in the production of the colored curable resin composition are as follows.

<Dye (A1)>

(A1-1): A dye represented by the following formula (A1-1) obtained by the method described in Example 1 of Japanese Patent Laid-Open No. 2016-27075

(A1-2): A dye represented by the following formula (A1-2) obtained by the method described in Example 2 of Japanese Patent Laid-Open No. 2017-226814

(A1-3): A dye represented by the following formula (A1-3) obtained by the method described in Synthesis Example 2 of Japanese Patent Laid-Open No. 2016-176075

<Dispersion of pigment (A2)>

Red pigment dispersion: the dispersion obtained in Preparation Example 4

Blue pigment dispersion: the dispersion obtained in Preparation Example 5

<Dispersion of compound (A3)>

Dispersion of compound (A3-1-1): the dispersion obtained in Preparation Example 8

Dispersion of compound (A3-2-1): the dispersion obtained in Preparation Example 9

<Resin (B)>

(B1-1): Resin (B1-1) obtained in Production Example 1

(B1-2): Resin (B1-2) obtained in Production Example 2

(B2-1): Resin (B2-1) obtained in Preparation Example 3 (used in the preparation of the dispersion of the pigment (A2), the preparation of the dispersion of the compound (A3), and Comparative Example 4)

<Polymerizable compound (C)>

(C-1): Dipentaerythritol hexaacrylate ("KAYARAD (registered trademark) DPHA" manufactured by Nippon Kayaku Co., Ltd.)

<Polymerization initiator (D)>

(D-1): The compound represented by the following formula (D-1) ("TR-PBG327" manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

(D-2): "Irgacure (registered trademark) 907" manufactured by BASF

[Chemistry 40]

<Phenolic antioxidant (E)>

(E-1): 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxophosphine ("Sumilizer (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd.)

(E-2): "Adeka arkls (registered trademark) GPA-5001" manufactured by ADEKA Corporation

(E-3): "Adekastab (registered trademark) AO-60" manufactured by ADEKA Corporation

<Phosphorus antioxidants>

TPP: Triphenylphosphite ("Adekastab (registered trademark) TPP" manufactured by ADEKA)

<Polymerization initiation aid (F)>

(F-1): 2,4-diethylthioxanthrone ("KAYACURE (registered trademark) DETX-S" manufactured by Nippon Kayaku Co., Ltd.)

<Thiol compound (G)>

(G-1): Trihydroxymethylpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals)

<Solvent (H)>

(H-1): 3-methoxy-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 158°C)

(H-2): Diacetone alcohol (produced by Tokyo Chemical Industry Co., Ltd., boiling point 168°C)

(H-3): Propylene glycol monomethyl ether acetate (manufactured by KHneochem, 146°C)

(H-4): Propylene glycol monomethyl ether (manufactured by KHneochem, boiling point 121°C)

<Leveling agent (I)>

(I-1): Silicone-based surfactant ("Toray Silicone SH8400" manufactured by Toray Dow Corning)

(2) Formation of color filter (colored coating)

A colored curable resin composition was applied to a 2-inch square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then pre-baked at 100°C for 3 minutes to form a composition layer. After cooling, the composition layer was irradiated with light at an exposure dose of 60mJ/ ^cm2 (365nm reference) in an atmospheric environment using an exposure machine (TME-150RSK; manufactured by Topcon). After light irradiation, post-baking was performed in an oven at 230°C for 20 minutes to obtain a colored coating film. After being left to cool, the thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and the result was 3.0 μm.

(3) Evaluation of thickness retention rate

The thickness of the formed colored coating before and after post-baking was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.), and the thickness retention rate was calculated according to the following formula.

Thickness retention rate (%) = (thickness after post-baking/thickness before post-baking) × 100

The results are shown in Tables 1 to 3.

[Table 2]

As is clear from the results shown in Tables 1 to 3, the coloring curable resin compositions of Examples 1 to 16 using a phenolic antioxidant and resin (B1) (i.e., resin (B1-1) or resin (B1-2)) can suppress the reduction in thickness of the coloring coating film caused by post-baking, compared with the coloring curable resin compositions of Comparative Examples 1, 3, and 5 that do not use an antioxidant, or Comparative Example 2 that uses a phosphorus antioxidant instead of a phenolic antioxidant, and Comparative Example 4 that does not use resin (B1).

[Industrial availability]

If the coloring curable resin composition of the present invention is used, the reduction in thickness of the coloring pattern or the coloring coating film caused by heating (especially post-baking) can be suppressed. The color filter produced from the coloring curable resin composition of the present invention is useful as a color filter used in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

Claims (8)

A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colored curable resin composition further comprises a phenolic antioxidant (E), and the resin (B) contains a resin (B1) comprising a constituent unit (b1-1) represented by formula (1b), the resin (B1) is a copolymer comprising the constituent unit (b1-1), a constituent unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and other constituent units (b1-3), and the amount of the constituent unit (b1-1) when the total of all the constituent units in the copolymer is taken as 100 mol % is 1 mol % to 50 mol %.

In formula (1b), R ^1B represents a hydrogen atom or a methyl group, R ^2B to R ^4B each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n represents an integer of 1 to 10, and * represents a bonding position, wherein at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbon atoms. The colored curable resin composition as described in claim 1, wherein the weight average molecular weight of the resin (B1) is 1,000 to 50,000. The colored curable resin composition as described in claim 1 or claim 2, wherein the content of the resin (B1) is 5 parts by weight to 400 parts by weight relative to 100 parts by weight of the polymerizable compound (C). The colored curable resin composition as described in claim 1 or claim 2, wherein the content of the phenolic antioxidant (E) is 0.1 parts by weight to 25 parts by weight relative to 100 parts by weight of the polymerizable compound (C). A colored curable resin composition as described in claim 1 or claim 2, wherein the coloring agent (A) comprises a dye (A1) and a pigment (A2). A colored curable resin composition as described in claim 1 or claim 2, wherein the polymerizable compound (C) is a free radical polymerizable compound, and the polymerization initiator (D) is a photo-free radical polymerization initiator. The colored curable resin composition according to claim 1 or claim 2, wherein the coloring agent (A) comprises at least one compound (A3) selected from the group consisting of compounds represented by formula (A3-1) and compounds represented by formula (A3-2),

In formula (A3-1), R ^41a and R ^42a each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded, R 43a and R 44a each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43a and R ^44a each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43a and R R ^47a to R 54a are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atoms to which they are bonded, R ^47a to R ^54a are independently hydrogen atoms, halogen atoms, nitro groups, hydroxyl groups, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an alkyl group having 1 to 8 carbon atoms which may have a substituent, R ^f is a fluoroalkyl group having 1 to 12 carbon atoms, and the ring T ^1a represents an aromatic alkyl ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocyclic ring having 5 to 10 members which may have a substituent, the saturated alkyl group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, the aromatic alkyl group having 6 to 14 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent, and the aralkyl group having 7 to 30 carbon atoms may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent, the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have a substituent selected from a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent, the 5-membered to 10-membered aromatic heterocyclic ring may have a substituent selected from a halogen atom, a nitro group, a hydroxyl group, a formyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , and at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms which may have a substituent, the substituent that the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, when the saturated alkyl group having 1 to 20 carbon atoms is a saturated alkyl group having 2 to 20 carbon atoms, -CH ₂ - contained in the saturated alkyl group may be substituted with -O- or -CO-, when the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH ₂ - contained in the alkyl group may be substituted with -O- or -CO-, r represents an integer greater than 1, Mr ⁺ represents a hydrogen ion, an r-valent metal ion or N ⁺ (R ^55a ) ₄ , four R ^{55a s} may be the same or different, R ^55a represents a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; k represents the total number of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f possessed by the anion represented by formula (A3-1a), and is an integer greater than or equal to 2;

In formula (A3-1a), ring ^T1a , ^R41a ~ ^R44a and ^R47a ~ ^R54a have the same meanings as described above; when r is an integer greater than 2, the multiple anions represented by formula (A3-1a) may be the same or different, and when k-1 is an integer greater than 2, the multiple Mr ⁺ may be the same or different;

In formula (A3-2), R ^41b and R ^42b each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to form a 3-membered to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded, R 43b and R 44b each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43b and R ^44b each independently represent a hydrogen atom, a saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^43b and R R ^47b to R 54b are bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atoms to which they are bonded, R ^47b to R ^54b are independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and the ring T ^1b represents an aromatic alkyl ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocyclic ring having 5 to 10 members which may have a substituent, the saturated alkyl group having 1 to 20 carbon atoms which may have a substituent selected from at least one of the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, the aromatic alkyl group having 6 to 14 carbon atoms which may have a substituent selected from at least one of the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent, the aralkyl group having 7 to 30 carbon atoms which may have a substituent selected from at least one of the group consisting of a at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent; the substituent that the aromatic alkyl ring having 6 to 14 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent; the substituent that the 5-membered to 10-membered aromatic heterocyclic ring may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent; The alkyl group having 1 to 8 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group; when the saturated alkyl group having 1 to 20 carbon atoms is a saturated alkyl group having 2 to 20 carbon atoms, _-CH2- contained in the saturated alkyl group may be substituted with -O- or -CO-; when the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, _-CH2- contained in the alkyl group may be substituted with -O- or -CO-; m represents an integer greater than 1; [Y] ^m- represents an m-valent anion; and when m is an integer greater than 2, the plurality of cations represented by formula (A3-2c) may be the same or different;

In formula (A3-2c), ring T ^1b , R ^41b to R ^44b and R ^47b to R ^54b have the same meanings as described above. A colored curable resin composition as described in claim 7, wherein the coloring agent (A) contains a dye (A1) different from the compound (A3).