TW202043311A - Colored curable resin composition - Google Patents

Abstract

A colored curable resin composition including a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colored curable resin composition also includes a phenolic antioxidant (E), and the resin (B) includes a resin (B1) including a structural unit (b1-1) represented by formula (1b) [the symbols in the formula are as defined in the specification.].

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, and various resin compositions have been developed. For example, Patent Document 1 describes a resin composition for color filters, which contains: a solvent, a reactive diluent, a photopolymerization initiator, a colorant, and a copolymer containing a structural unit represented by formula (1) Things.

[化1]

[The definition of the symbol in formula (1) is as described in Patent Document 1] [Prior Art Literature] [Patent Literature]

[Patent Document 1] WO 2018/110097 A1

[The problem to be solved by the invention] As a method of forming a color filter using a colored curable resin composition, for example, a photolithography method and a method using an inkjet device can be cited. The photolithography method usually includes the following steps: coating a colored curable resin composition on a substrate, and forming a composition layer by heat drying (pre-baking) and/or reduced pressure drying to remove volatile components such as solvents , The composition layer is irradiated (exposed) with light, and the developer is brought into contact with the exposed composition layer to form (develop) a colored pattern or a colored coating film. After this development, post-baking of heating the colored pattern is often performed.

In the conventional colored curable resin composition, the thickness of the colored pattern or colored coating film may be greatly reduced by post-baking. The present invention is made focusing on this situation, and its object is to provide a colored curable resin composition that can suppress the decrease in the colored pattern or the thickness of the colored coating film caused by heating (especially post-baking).

[Means to solve the problem] The present invention that can achieve the object is as follows. [1] A colored curable resin composition, which is a colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and The colored curable resin composition further contains a phenolic antioxidant (E), and The resin (B) contains the resin (B1) containing the structural unit (b1-1) represented by the formula (1b).

[化2]

[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 carbons, or an alkoxy group having 1 to 6 carbons, and n represents 1 An integer of -10, and * indicate a bonding position, wherein at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbons]. [2] The colored curable resin composition according to the above [1], wherein the resin (B1) is a structural unit (b1) containing a structural unit (b1-1) derived from a polymerizable unsaturated compound having an acidic group -2) A copolymer with other structural units (b1-3), and the amount of structural unit (b1-1) when the total of all structural units in the copolymer is 100 mol% is 1 mol% to 50 mol%. [3] The colored curable resin composition according to [1] or [2], wherein the weight average molecular weight of the resin (B1) is 1,000 to 50,000. [4] The colored curable resin composition according to any one of [1] to [3], wherein the content of the resin (B1) is 5 parts by weight relative to 100 parts by weight of the polymerizable compound (C) ~400 parts by weight. [5] The colored curable resin composition according to any one of [1] to [4], wherein the content of the phenolic antioxidant (E) is relative to 100 parts by weight of the polymerizable compound (C) 0.1 parts by weight to 25 parts by weight. [6] The colored curable resin composition according to any one of [1] to [5], wherein the colorant (A) contains a dye (A1) and a pigment (A2). [7] The colored curable resin composition according to any one of [1] to [6], wherein the polymerizable compound (C) is a radical polymerizable compound, and the polymerization initiator (D) is Light radical polymerization initiator. [8] The colored curable resin composition according to any one of [1] to [7], wherein the colorant (A) contains a compound selected from the group consisting of a compound represented by formula (A3-1) and formula ( At least one compound (A3) in the group consisting of the compounds represented by A3-2).

[化3]

[In the formula (A3-1), R ^41a and R ^42a each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, 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-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atom, R ^43a and R ^44a each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or an optionally substituted carbon number 7 to 30 Aralkyl, or R ^43a and R ^44a are bonded to form a 3-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atoms, and R ^47a to R ^54a each independently represent a hydrogen atom, a halogen atom, nitro, _{^{hydroxy, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or a substituted alkyl group having a carbon number of 1 to 8, R ^f represents a fluoroalkyl group having a carbon number 1 to 12 , Ring T ^1a represents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted 5-membered to 10-membered aromatic heterocyclic ring, and the saturated hydrocarbon group having 1 to 20 carbon atoms may have The substituent is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, and an amino group, and the substituent that the aromatic hydrocarbon group having 6 to 14 may have is selected from a halogen atom and a nitro group , hydroxy, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - group -SO ₂ -R ^f, and may have a substituent alkyl having 1 to 8 group consisting of at least one of the 7 to 30 carbon atoms, said aralkyl group may have a substituent group selected from the group consisting of halogen atom, nitro, hydroxy, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, and may be At least one of the group consisting of a substituted alkyl group having 1 to 8 carbons, and the substituents that the aromatic hydrocarbon ring having 6 to 14 may have are selected from halogen atoms, nitro groups, hydroxyl groups, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - group -SO ₂ -R ^f, and the alkyl group may have a substituent having a carbon number of 1 to 8, consisting of at least one of the five 3-10-membered aromatic heterocyclic group may have a substituent selected from the group consisting of halogen atom, nitro, hydroxy, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, and may have a substituent At least one of the group consisting of an alkyl group having 1 to 8 carbon atoms, and the substituent group that the alkyl group having 1 to 8 carbon may have is selected from halogen atoms, hydroxyl groups, methanoyl groups and amino groups. At least one of the group consisting of, when the saturated hydrocarbon group having 1 to 20 carbons is a saturated hydrocarbon group having 2 to 20 carbons, -CH ₂ -contained in the saturated hydrocarbon 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, The -CH ₂ -contained in the alkyl group may be substituted with -O- or -CO-, r represents an integer of 1 or more, and M ^{r +} represents a hydrogen ion, an r-valent metal ion, or N ⁺ (R ^55a ) ₄ , the four R ^55a may be the same or different, R ^55a represents a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons or an aralkyl group with 7 to 10 carbons, and k represents the anion represented by the formula (A3-1a) The sum of the numbers of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f is an integer of 2 or more,

[化4]

[In formula (A3-1a), ring T ^1a , R ^41a to R ^44a, and R ^47a to R ^54a each have the same meaning as described above] When r is an integer of 2 or more, the formula (A3-1a) the anion represented plurality may be the same or different, and at k-1 is an integer of 2 or greater, the plurality of M ^{r +} may be the same or different]

[化5]

[In formula (A3-2), R ^41b and R ^42b each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, Or an aralkyl group having 7 to 30 carbon atoms that may have a substituent, or R ^41b and R ^42b are bonded to form a 3-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atom, R ^43b and R ^44b each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbons which may have a substituent, or a carbon 7-30 which may have a substituent Aralkyl, or R ^43b and R ^44b are bonded to form a 3- to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atoms, R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, A nitro group, a hydroxyl group, or an optionally substituted alkyl group having 1 to 8 carbons, and ring T ^1b represents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted 5 to 10 member The substituent of the saturated hydrocarbon group with 1 to 20 carbon atoms may be at least one selected from the group consisting of a halogen atom, a hydroxyl group, a methanoyl group and an amino group, and the carbon number is 6 The substituent that the aromatic hydrocarbon group of to 14 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 optionally substituted alkyl group having 1 to 8 carbons, The substituents that the aralkyl group having 7 to 30 carbons may have are 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 carbons that may have a substituent At least one of the substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is selected from halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted alkyl groups having 1 to 8 carbon atoms. At least one of the group consisting of a group, the substituent that the 5-membered to 10-membered aromatic heterocyclic ring may have is selected from a halogen atom, a nitro group, a hydroxyl group, a methanoyl group, and a carbon that may have a substituent At least one of the group consisting of an alkyl group having 1 to 8, and the substituent that the alkyl group having 1 to 8 may have is selected from the group consisting of a halogen atom, a hydroxyl group, a methanoyl group, and an amino group At least one of the group, when the saturated hydrocarbon group having 1 to 20 carbons is a saturated hydrocarbon group having 2 to 20 carbons, the -CH ₂ -contained in the saturated hydrocarbon 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 -, m represents an integer of 1 or more, [Y] ^m- represents an anion of m valence, and when m is an integer of 2 or more, multiple cations represented by formula (A3-2c) may be the same or different;

[化6]

[In formula (A3-2c), ring T ^1b , R ^41b to R ^44b, and R ^47b to R ^54b have the same meaning as described above, respectively]]. [9] The colored curable resin composition according to [8], wherein the colorant (A) contains a dye (A1) different from the compound (A3).

[Effects of the invention] If the colored curable resin composition of the present invention is used, it is possible to suppress the decrease in the colored pattern or the thickness of the colored coating film caused by heating (especially post-baking).

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a phenolic antioxidant (E). Furthermore, resin (B) contains resin (B1) containing the structural unit (b1-1) represented by said formula (1b). Hereinafter, each component of the colored curable resin composition of the present invention will be described in order.

As long as there is no special description, each component described in this specification and the raw material for producing each component can be used only one kind, or two or more kinds can be used in combination.

＜Colorant (A)＞ The colorant (A) is classified into a solvent-soluble dye (A1) and a solvent-insoluble pigment (A2). In one aspect of the present invention, the colorant (A) includes both the dye (A1) and the pigment (A2).

The dye (A1) preferably includes at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes, and coumarin dyes. In the case of using at least one dye selected from the group, 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 relative to the entire dye (A1). % By weight or less, more preferably 5% by weight or more and 100% by weight or less.

The dye (A1) more preferably contains a xanthene dye. In the case of using a xanthene dye, 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, and still more preferably 5% by weight relative to the entire dye (A1) Weight% or more and 100 weight% or less, preferably 100 weight%. That is, the dye (A1) is most preferably composed of xanthene dye.

The xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes include: CI acid red 51 (hereinafter, the description of CI acid red is omitted and only the number is described; the same applies to other dyes), 52, 87, 92, 94, 289, 388 ; CI acid violet 9, 30, 102; CI basic red 1 (rhodamine 6G), 2, 3, 4, 8; CI basic red 10, 11; CI alkali Basic violet 10 (rose red B), 11; CI solvent red (solvent red) 218; CI mordant red (mordant red) 27; CI reactive red (reactive red) 36 (rose bengal) B ); acid rose red (sulforhodamine) G; xanthene dyes described in JP 2010-32999 A, xanthene dyes described in JP 4492760, etc. The xanthene dye is preferably a dye dissolved in an organic solvent.

As a preferable xanthene dye, the compound represented by Formula (1a) (Hereinafter, it may be described as "compound (1a)"). Compound (1a) may also be its tautomer. In the case of using the compound (1a), its content is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more with respect to the entire xanthene dye. It is particularly preferable to use only the compound (1a) as the xanthene dye.

[化7]

[In formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbons, and an optionally substituted monovalent aromatic group with 6 to 10 carbons Hydrocarbyl group or a group represented by *-R ¹² -Si(R ¹³ ) ₃ (in the formula, * represents the bonding position to the nitrogen atom), the -CH ₂ -contained in the saturated hydrocarbon group may be through -O -, - CO- or -NR ¹¹ - substituted, 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, 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 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 5, when m is 2 or more, multiple R ⁵ 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 ⁺ , the four R ¹¹ may be the same or different, and R ⁸ represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbons, and -CH ₂ -contained in the saturated aliphatic hydrocarbon group may be controlled by -O-,- Substitution with CO-, -NH- or -NR ⁸ -, R ⁹ and R ¹⁰ may be bonded to each other to form a 3-membered to 10-membered heterocyclic ring containing a nitrogen atom. R ¹¹ represents a hydrogen atom and has 1 to 20 carbon atoms The monovalent saturated hydrocarbon group or the aralkyl group having 7 to 10 carbons, R ¹² represents an alkanediyl group having 1 to 10 carbons, and the -CH ₂ -contained in the alkanediyl group may be controlled by -O-, -CO -, -NR ⁸ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- substituted, and R ¹³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbons or a carbon number of 1 to The alkoxy group of 4 and the plurality of R ¹³ may be the same or different, respectively, wherein, in the case where there is -SO ₃ ^- in the form of an ion in formula (1a), the number is one]

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

Examples of the aromatic hydrocarbon group may have a substituent group, include: halogen ^{atoms, -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 . The plurality of, preferably _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ^10, more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ^10. As -SO ₃ ^- Z ^{+ in} this case, -SO ₃ ^- N ⁺ (R ¹¹ ) _{4 is} preferable.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ may be linear, branched, or cyclic. Examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl , Isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl and other alkyl groups with 1 to 20 carbons; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl , C3-20 alicyclic saturated hydrocarbon groups such as tricyclodecyl.

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 hydrocarbon group in R ⁹ and R ¹⁰ may have include a hydroxyl group and a halogen atom.

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

[化8]

Examples of -OR ⁸ include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and di Decaalkoxy and so on.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tertiary butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of -SR ⁸ include methyl mercapto, ethyl mercapto, butyl mercapto, hexyl mercapto, decyl mercapto, and eicosyl mercapto. Examples of -SO ₂ R ⁸ include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl. Examples of -SO ₃ R ⁸ include: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, and oxacin Alkoxysulfonyl and the like.

As -SO ₂ NR ⁹ R ¹⁰ , for example, the following groups can be cited: sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, N-iso Propyl sulfasulfonyl, N-butyl sulfasulfonyl, N-isobutyl sulfasulfonyl, N-second butyl sulfasulfonyl, N-third butyl sulfasulfonyl, N- Pentylsulfasulfonyl, N-(1-ethylpropyl)sulfasulfonyl, N-(1,1-dimethylpropyl)sulfasulfonyl, N-(1,2-dimethyl Propyl)sulfasulfonyl, N-(2,2-dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl) )Sulfasulfonyl, N-(3-methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethylbutyl) Group) sulfasulfonyl, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N- (1,4-Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethyl) N-1 substituted sulfasulfonyl such as hexylsulfasulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl; N,N-dimethylsulfasulfonyl, N ,N-Ethyl Methylsulfamate, N,N-Diethylsulfamethine, N,N-Propyl Methylsulfamate, N,N-Isopropyl Methylsulfamate , N,N-tertiary butyl methyl sulfasulfonyl, N,N-butyl ethyl sulfasulfonyl, N,N-bis(1-methylpropyl)sulfasulfonyl, N,N-heptane N, N-2 substituted sulfamoyl and the like.

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, more preferably SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ . m is preferably 1-4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbons in R ⁶ and R ⁷ include groups having 1 to 6 carbons in the alkyl groups 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 R ¹² include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and isopropylidene. , Isobutylene, 2-methyltrimethylene, isopentyl, isohexyl, isooctyl, 2-ethylhexyl, 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 a methoxy group, an ethoxy group, a propoxy group, and a tertiary butoxy group. R ^{13 is} preferably methyl, ethyl, methoxy, or ethoxy, more preferably methoxy or ethoxy.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ . As the N ⁺ (R ¹¹ ) ₄ , it is preferable that at least two of the four R ¹¹ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of the four R ¹¹ is preferably 20 to 80, more preferably 20 to 60. In the case where N ⁺ (R ¹¹ ) ₄ is present in the compound (1a), if R ^{11 is} these groups, a color filter with less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (1a) Light film.

The compound (1a) is preferably a compound represented by formula (2a) (hereinafter, it may be described as "compound (2a)"). Compound (2a) may also be its tautomer.

[化9]

[In formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons which may have a carboxyl group, and a monovalent aromatic hydrocarbon group having 6 to 10 carbons which may have a substituent Or a group represented by *-R ¹² -Si(R ¹³ ) ₃ (in the formula, * represents the bonding position to a nitrogen atom), R ²¹ and R ²² can form a ring containing a nitrogen atom together, 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, m is 2 or more in When, multiple R ²⁵ may be the same or different, a represents an integer of 0 or 1, X represents a halogen atom, R ²⁶ represents a monovalent saturated hydrocarbon group with 1 to 20 carbons, Z1 ⁺ represents N ⁺ (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , the four R ²⁷ may be the same or different, and R ²⁷ represents a monovalent saturated hydrocarbon group with 1 to 20 carbons or a benzyl group, wherein there is -SO _{3 in the} form of an ion in formula (2a) ^-In the case of one, the number is one]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbons in R ²¹ to R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group of R ¹ to R ⁴ . Examples of the aromatic hydrocarbon group may have a substituent group, examples thereof _{^{include: -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, -SO 3 R 26 or -SO ₂ NHR ^26. The description of the group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ²¹ to R ²⁴ is the same as described above.

As the combination of R ²¹ - R ^24, preferably R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a divalent aromatic hydrocarbon group having a carbon number of 6 to 10, said aromatic hydrocarbon by -SO ₃ ^-, -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ substituted. 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 carbons, and the aromatic hydrocarbon groups are through -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ Superseder. If R ²¹ to R ^{24 are} these groups, a color filter excellent in heat resistance can be formed from the coloring curable resin composition of the present invention containing the compound (2a).

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

[化10]

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 saturated hydrocarbon groups in R ⁸ to R ¹¹ . When R ²¹ to R ²⁴ are a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms that may have a carboxyl group, R ²¹ to R ^{24 are} preferably each independently a methyl group that may have a carboxyl group or an ethyl group that may have a carboxyl group. Or propyl group which may have a carboxyl group. Further, -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in R ^26, preferred is a branched chain alkyl group having a carbon number of 3 to 20, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, and further Preferably it is 2-ethylhexyl. If R ^{26 is} these groups, the coloring curable resin composition of the present invention containing the compound (2a) can be used to form a color filter with little foreign matter generation.

Z1 ⁺ is N ⁺ (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ²⁷ ) ₄ . As the N ⁺ (R ²⁷ ) ₄ , it is preferable that at least two of the four R ²⁷ are monovalent saturated hydrocarbon groups having 5 to 20 carbons. In addition, the total carbon number of the four R ²⁷ is preferably 20 to 80, more preferably 20 to 60. In the case where N ⁺ (R ²⁷ ) ₄ is present in the compound (2a), if R ^{27 is} these groups, the coloring and curable resin composition of the present invention containing the compound (2a) can form less foreign matter Color filters. m is preferably 1-4, more preferably 1 or 2.

In addition, the compound (1a) is also preferably a compound represented by formula (3a) (hereinafter, it may be described as "compound (3a)"). Compound (3a) may also be its tautomer.

[化11]

[In the formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon 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 with the nitrogen atom), the saturated hydrocarbon group may be substituted by a monovalent aromatic hydrocarbon group having 6 to 10 carbons, a halogen atom or a carboxyl group, and the -CH ₂ -contained in the saturated hydrocarbon group may be substituted by -O -, -CO- or -NR ¹¹ -substituted, the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbons, R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbons, and the number of carbons 1 to 4 alkyl mercapto groups or C 1 to 4 alkyl sulfonyl groups, R ³¹ and R ³³ together can form a ring containing a nitrogen atom, R ³² and R ³⁴ can together form a ring containing a nitrogen atom, and p and q each independently represents an integer from 0 to 5. When p is 2 or more, multiple R ³³ may be the same or different; when q is 2 or more, multiple R ³⁴ may be the same or different, and R ¹¹ is Stated as the same meaning]

The monovalent saturated hydrocarbon having 1 to 10 carbons in R ³¹ and R ³² may be linear, branched, or cyclic. Examples thereof include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, isopentyl, new Alkyl groups having 1 to 10 carbon atoms such as pentyl and 2-ethylhexyl; saturated alicyclic hydrocarbon groups having 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The explanation of 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 hydrocarbon group having 6 to 10 carbon atoms that R ³¹ and R ³² may have as a substituent include a phenyl group. Examples of the alkyl group having 1 to 3 carbon atoms which the aromatic hydrocarbon group may have as a substituent include a methyl group, an ethyl group, and a propyl group. Examples of the alkoxy group having 1 to 3 carbon atoms that the aromatic hydrocarbon group may have as a substituent include a methoxy group, an ethoxy group, and a propoxy group. The explanation of the group represented by *-R ¹² -Si(R ¹³ ) ₃ in R ³¹ and R ³² is the same as described above. Preferably, R ³¹ and R ³² are 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, second butyl, and tertiary butyl. Wait. Examples of the alkyl mercapto group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl mercapto, ethyl mercapto, propyl mercapto, butyl mercapto, isopropyl mercapto, and the like. Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropyl Sulfonyl and so on. R ³³ and R ^{34 are} preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

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

Examples of the compound (1a) include compounds represented by formula (1-1) to formula (1-45). In addition, R ⁴⁰ in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbons, preferably a branched chain alkyl group having 6 to 12 carbons, and more preferably 2-ethylhexyl. In addition, R ²⁶ in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms as described above.

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The xanthene dye is preferably 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, the compound represented by Formula (1-1)-Formula (1-8), Formula (1-11), or Formula (1-12) is mentioned, for example. In addition, in terms of excellent solubility in organic solvents, any of formula (1-24) to formula (1-33), formula (1-44), and formula (1-45) is also preferred Those represented by the compound.

As the xanthene dye, commercially available xanthene dyes can be used (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Chugai Chemical Co., Ltd., and "Rodan manufactured by Taoka Chemical Industry Co., Ltd." Ming (Rhodamin) 6G”). In addition, it is also possible to synthesize commercially available xanthene dyes as starting materials with reference to a known technique (for example, Japanese Patent Laid-Open No. 2010-32999).

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

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[In the 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 hydrocarbon group with 1 to 20 carbons, where the saturated hydrocarbon group has 2 to 20 carbons In this case, -CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O- or -CO-, and R ^9A to R ^12A each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbon atoms, and may have substitution The aromatic hydrocarbon group having 6 to 20 carbons or the aralkyl group having 7 to 30 carbons which may have substituents, and the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, the -CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O- or -CO-, and R ^9A and R ^10A may also be bonded to these The bonded nitrogen atoms form a ring together, and R ^11A and R ^12A may also bond to form a ring together with the bonded nitrogen atoms. R ^13A represents an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, [ G] ^g- represents any g-valent counter anion, and g represents 0 or any natural number. When g is a natural number of 2 or more, multiple cations in formula (4a) may be the same or different ]

Coumarin dyes are dyes containing compounds having a coumarin skeleton in the molecule. Examples of coumarin dyes include: CI acid yellow (acid yellow) 227, 250; CI disperse yellow (disperse yellow) 82, 184; CI solvent orange (solvent orange) 112; CI solvent yellow (solvent yellow) 160, 172; Coumarin dyes described in Japanese Patent No. 1299948, etc. It is preferably a dye dissolved in an organic solvent.

Examples of dyes other than the above-mentioned dyes include dyes and dyeing notes (shikisensha) described in the Color Index (published by The Society of Dyers and Colourists). The dyes described in. In addition, examples of dyes include azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, and squaraine dyes. , Acridine dyes, styryl dyes, quinoline dyes and nitro dyes. Among these, dyes dissolved in organic solvents are preferred.

As specific examples of dyes, the following dyes can be cited. (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; CI 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 (solvent violet) 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI 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 1, 3, 5, 28, 29, 32, 33, etc.

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

(3) C.I. Basic Dyes C.I. Basic green 1 etc.

(4) C.I. Reactive Dyes C.I. Reactive yellow (reactive yellow) 2, 76, 116; C.I. Reactive orange 16 etc.

(5) C.I. Direct dye CI 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 (disperse violet) 26, 27; C.I. Disperse blue 1, 14, 56, 60, etc.

(7) C.I. Medium dye C.I. Mordant yellow (mordant yellow) 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI medium orange (mordant orange) 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 Wait.

(8) C.I. Vat Dyes C.I. Vat green 1 etc.

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

As the pigment (A2), for example, the following pigments can be cited: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129 , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI pigment red (pigment red) 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 Red pigment C.I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. purple pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38; 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 black pigments, etc.

The pigment (A2) is preferably a red pigment or a blue pigment. The red pigment preferably has absorption in a wavelength region of 580 nm or less, and more preferably has absorption in a wavelength region of 480 nm or more and 560 nm or less. In addition, the red pigment is preferably a pigment that transmits light in a wavelength region of 610 nm or more.

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

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

Specific examples of preferable red pigments include: CI 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 the compound represented by formula (P) described in JP 2013-014750. Among these, CI Pigment Red 177, 208, 242, 254, 269, and the compound represented by the formula (P) described in JP 2013-014750 are more preferred, and CI Pigment Red 177, 254, And the compound represented by formula (P) described in JP 2013-014750.

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

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

Specifically, CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 is preferred, CI Pigment Blue 15, 15:3, 15:4, 15:6 is more preferred, and CI is particularly preferred Pigment Blue 15:6. By using the blue pigment, the transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter become better.

For pigments, if necessary, rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc., grafting treatment on the surface of the pigment with polymer compounds, etc., and sulfuric acid micronization method, etc. Micronization treatment for removing impurities, or cleaning treatment with organic solvents or water for removing impurities, treatment for removing ionic impurities by ion exchange methods, etc. The particle size of the pigment is preferably uniform.

By performing the dispersion treatment using a dispersant, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

As a dispersing agent, surfactant is mentioned, for example. The surfactant may be any of cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants. Examples of the surfactant include polyester-based surfactants, polyamine-based surfactants, and acrylic-based surfactants. Examples of commercially available dispersants include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (Jie Li (Made by zeneca), EFKA (made by BASF), Ajisper (registered trademark) (made 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 with respect to 100 parts by weight of the pigment (A2). If the content of the dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

The content of the colorant (A) relative to the total solid content 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 still more preferably 5% by weight or more and 50% by weight. Weight% or less. The "total amount of solid content" in this specification refers to the amount after removing the solvent content from the total amount of the colored curable resin composition. If the content of the colorant (A) is within the above range, a color filter with sufficient color density can be obtained. In addition, if the content of the coloring agent (A) is within the above-mentioned range, a necessary amount of resin or polymerizable compound can be contained in the composition, so a color filter with sufficient mechanical strength can be formed. The total amount of solid content and the content of each component with respect to it can be measured by well-known analysis means such as liquid chromatography or gas chromatography, for example.

In the case of using the dye (A1), its content relative to the total solid 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 still more preferably 55% by weight %the following. If the content of the dye (A1) is in the above range, a coloring curable resin composition having good developability with respect to an alkaline developer can be obtained.

In the case of using the pigment (A2), its content relative to the total solid 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, more 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.

In the case of using dyes (A1) and pigments (A2), the weight ratio of dyes (A1) to pigments (A2) (dye (A1): pigment (A2)) is preferably 1:99 to 99:1, more Preferably, it is 1:99 to 95:5, particularly preferably 5:95 to 90:10.

In one aspect of the present invention, the colorant (A) includes one selected from the formula (A3-1):

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

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

The compound (A3) (ie, the compound (A3-1) and the compound (A3-2)) is formed according to its structure (for example, the types of (M ^{r +} ) ^k-1 and [Y] ^m- as counter ions) "Solvent-soluble dyes" or "solvent-insoluble pigments". That is, the range of the compound (A3) includes both a compound as a dye and a compound as a pigment.

First, the definition of the group etc. in the compound (A3) will be explained. Unless otherwise stated, the groups in the compound (A3) have the following definitions. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

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

The alkyl group may be either linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include groups having 1 to 10 carbon atoms in the examples of the alkyl group having 1 to 20 carbon atoms. Examples of other alkyl groups with different carbon numbers are also the same. In addition, examples of groups other than the alkyl group and groups having different carbon numbers are also the same. For example, examples of saturated hydrocarbon groups having 2 to 20 carbons include groups having 2 to 20 carbons in the examples of saturated hydrocarbon groups having 1 to 20 carbons.

The alkanediyl group may be either linear or branched. Examples of the alkanediyl group having 1 to 10 carbon atoms include: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, isopropylidene, and isobutylene Group, 2-methyltrimethylene, isopentyl, isohexyl, isooctyl, 2-ethylhexyl, etc.

The fluoroalkyl group may be either linear or branched. Examples of fluoroalkyl groups 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, perfluorobutyl.

The alkoxy group may be either linear or branched. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, isopropoxy, isobutoxy, and iso Pentyloxy, neopentyloxy.

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

Examples of the aralkyl group 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 the 3-member to 10-member nitrogen-containing heterocyclic ring include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

The aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring having 6 to 14 carbon atoms may be any of a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

The aromatic heterocyclic ring may be either a monocyclic ring or a condensed ring. Examples of the 5-member to 10-member aromatic heterocyclic ring include: pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, thiazole ring, furan ring, thiophene ring, pyridine ring, pyrimidine ring, pyridazine ring, pyridine ring Azine ring, indole ring, benzimidazole ring, benzothiazole ring, quinoline ring, benzofuran ring, etc.

Next, the basis etc. in formula (A3-1) will be explained. R ^41a and R ^42a in the formula (A3-1) each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbons, 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 nitrogen-containing heterocyclic ring of 3 to 10 members together with the bonded nitrogen atom.

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

In the case where the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. Here, the -CH ₂ - and does not contain a nitrogen atom bonded to -CH ₂ - and terminal methyl, as the saturated hydrocarbon group of -CH ₂ -. In addition, -CH ₂ -CH ₂ -contained in the saturated hydrocarbon group will not be substituted with -OO- or -CO-CO-.

Carbon atoms (A3-1) in the aromatic hydrocarbon group having 6 to 14 of formula may have a substituent group selected from the group consisting of halogen atom, nitro, hydroxy, methyl ^{_{acyl, -SO 3 -, -SO 2 -N}} - -SO At least one of _2- R ^f and a C1-C8 alkyl group which may have a substituent.

Carbon atoms (A3-1) in the formula aralkyl group having 7 to 30 may have a substituent group selected from the group consisting of halogen atom, nitro, hydroxy, methyl ^{_{acyl, -SO 3 -, -SO 2 -N}} - -SO At least one of _2- R ^f and a C1-C8 alkyl group which may have a substituent. R ^f in the formula (A3-1) represents a fluoroalkyl group having 1 to 12 carbon atoms.

The substituent that the C1-C8 alkyl group in formula (A3-1) 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.

In the case where the alkyl group having 1 to 8 carbon atoms in the formula (A3-1) is an alkyl group having 2 to 8 carbon atoms, the -CH ₂ -contained in the alkyl group may be substituted with -O- or -CO-. Here, -CH ₂ -in the methyl group that is the terminal of the alkyl group is not included in the -CH ₂ -. In addition, -CH ₂ -CH ₂ -contained in the alkyl group will not be substituted with -OO- or -CO-CO-.

R ^{41a is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and still more preferably an alkyl group having 1 to 4 carbons. 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 carbons and -SO ₃ ^- , and more preferably has one or two carbon numbers of 1 to 8 The alkyl group of as a substituent may have a -SO ₃ ^- phenyl group, and it is more preferable to have one or two C 1 to 4 alkyl groups as a substituent and may have a -SO ₃ ^- phenyl group.

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

R ^{43a is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and still more preferably an alkyl group having 1 to 4 carbons. 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 carbons and -SO ₃ ^- , and more preferably has one or two carbon numbers of 1 to 8 The alkyl group of as a substituent may have a -SO ₃ ^- phenyl group, and it is more preferable to have one or two C 1 to 4 alkyl groups as a substituent and may have a -SO ₃ ^- phenyl group.

In formula (A3-1) R ^47a ~ R ^54a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or may have a substituent The group is an alkyl group having 1 to 8 carbon atoms. R ^47a ~ R ^54a are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a -SO ₃ ^-, more preferably a hydrogen atom or -SO ₃ ^-.

The ring T ^1a in the formula (A3-1) represents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted 5- to 10-member aromatic heterocyclic ring.

Carbon atoms in the formula (A3-1) aromatic hydrocarbons having 6 to 14 ring may have a substituent group selected from the group consisting of halogen atom, nitro, hydroxy, methyl ^{_{acyl, -SO 3 -, -SO 2 -N}} - - At least one of SO ₂ -R ^f and an optionally substituted alkyl group consisting of 1 to 8 carbon atoms.

In formula (A3-1) 5 - 10 membered aromatic heterocyclic group may have a substituent selected from the group consisting of halogen atom, nitro, hydroxy, methyl ^{_{acyl, -SO 3 -, -SO 2 -N}} - - At least one of SO ₂ -R ^f and an optionally substituted alkyl group consisting of 1 to 8 carbon atoms.

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

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R ^45a and R ^46a in formula (1t) each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or The substituent is an aralkyl group having 7 to 30 carbon atoms, or R ^45a and R ^46a are bonded to form a 3-member to 10-member nitrogen-containing heterocyclic ring together with these bonded nitrogen atoms.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1t) 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.

The number of carbon atoms (1T) aromatic hydrocarbon group having 6 to 14 may have a substituent selected from the group consisting of halogen atom, nitro, hydroxy, methyl ^{_{acyl, -SO 3 -, -SO 2 -N}} - -SO 2 - R ^f and at least one of the group consisting of an optionally substituted alkyl group having 1 to 8 carbon atoms.

The number of carbon atoms (1T) of formula aralkyl group having 7 to 30 may have a substituent group selected from the group consisting of halogen atom, nitro, hydroxy, methyl ^{_{acyl, -SO 3 -, -SO 2 -N}} - -SO 2 - R ^f and at least one of the group consisting of an optionally substituted alkyl group having 1 to 8 carbon atoms.

The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (1t) 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.

R ^{45a is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and still more preferably an alkyl group having 1 to 4 carbons.

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 carbons and -SO ₃ ^- , and more preferably has one or two carbon numbers of 1 to 8 The alkyl group of as a substituent may have a -SO ₃ ^- phenyl group, and it is more preferable to have one or two C 1 to 4 alkyl groups as a substituent and may have a -SO ₃ ^- phenyl group.

R ^56a in the formula (1t) represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or an optionally substituted carbon number 7 ～30 aralkyl group.

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 ^- , and more preferably has one or two halogen atoms A phenyl group that may have -SO ₃ ^- as a substituent, and more preferably a phenyl group that has one or two fluorine atoms as a substituent and may have -SO ₃ ^- .

L ^1a in the formula (1t) 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.

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

R in Formula (A3-1) represents an integer of 1 or more. r is preferably 2. When r is an integer of 2 or more, a plurality of anions represented by formula (A3-1a) may be the same or different.

[化24]

[In formula (A3-1a), ring T ^1a , R ^41a to R ^44a, and R ^47a to R ^54a respectively have the same meaning as described above] Hereinafter, the anion represented by formula (A3-1a) may be described as "anion (A3-1a)". The multiple anions (A3-1a) are preferably the same.

K in the formula (A3-1) represents the total number of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f of the anion (A3-1a), and is an integer of 2 or more. k is preferably 2.

M ^r in formula (A3-1) ⁺ represents a hydrogen ion, monovalent metal ion or R & lt N ⁺ (R ^55a) _4, four R ^55a may be the same or different. R ^55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. K-1 in the case where in formula (A3-1) is an integer of 2 or more, a plurality of M ^{r +} may be the same or different.

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

M ^{r + is more} preferably a divalent metal ion, further preferably an alkaline earth metal ion, particularly preferably a barium ion (Ba ²⁺ ).

The compound (A3-1) is preferably a compound (hereinafter, sometimes referred to as "compound (A3-1')") in which R ^41a and R ^43a are each independently a hydrogen atom or carbon number 1. The alkyl group of ~8, 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 carbons and -SO ₃ ^- , and R ^47a ~ R ^54a each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a -SO ₃ ^-, ring T ^1a of the formula (1T) Central [formula (1T) represented by, R ^45a is a hydrogen atom or An alkyl group having 1 to 8 carbons, 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 carbons and -SO ₃ ^- , and R ^56a is an optional A free halogen atom, an alkyl group having 1 to 8 carbon atoms, and a phenyl group of at least one substituent of the group consisting of -SO ₃ ^- , L ^1a is a sulfur atom, and * represents the bonding position with the carbocation], r to 2, k represents an anion (A3-1a) has the -SO ₃ ^- and the total number is 2, two anions (A3-1a) the same, as well as M ^{r +} Ba ^2+.

In the compound (A3-1'), R ^41a and R ^{43a are more} preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and more preferably an alkyl group having 1 to 4 carbons; R ^42a and R ^44a are each independently It is more preferable to have one or two alkyl groups having 1 to 8 carbons as a substituent, and may have a -SO ₃ ^- phenyl group, and it is further preferable to have one or two alkyl groups having 1 to 4 carbons as a substituent , and may have -SO ₃ ^- phenyl; R ^47a ~ R ^54a is 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 further having a carbon number of good The alkyl group of 1 to 4, R ^{46a is more} preferably one or two alkyl groups having 1 to 8 carbons as a substituent, and may have a -SO ₃ ^- phenyl group, and more preferably has one or two carbon numbers The alkyl group of 1 to 4 is a substituent and may have a -SO ₃ ^- phenyl group; and R ^{56a is more} preferably a phenyl group that has one or two halogen atoms as a substituent and may have -SO ₃ ^- , and further It is preferably a phenyl group which has one or two fluorine atoms as a substituent and may have -SO ₃ ^- .

Among the compounds (A3-1), a compound represented by the following formula (A3-1-1) (hereinafter, sometimes referred to as "compound (A3-1-1)") is particularly preferred. Further, the following formula (A3-1-1), two "-SO ₃ ^-" means that each of the described anions having -SO ₃ ^- group as a substituent, and each of the anionic -SO ₃ ^- number The total of is 2 (that is, the total of the number of -SO ₃ ^- in the two anions is 4).

[化25]

Compound (A3-1) can be based on a known method (for example, the method described in "Journal of Organic Chemistry" ((1994), vol. 59, #11, pp. 3232-3236), Japanese patent The method described in JP 2018-127596 A) is produced.

Next, the basis etc. in the formula (A3-2) will be described. R ^41b and R ^42b in the formula (A3-2) each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbons, 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 bonded nitrogen atom.

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

When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) is a saturated hydrocarbon group having 2 to 20 carbon atoms, the -CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. Here, the -CH ₂ - and does not contain a nitrogen atom bonded to -CH ₂ - and terminal methyl, as the saturated hydrocarbon group of -CH ₂ -. In addition, -CH ₂ -CH ₂ -contained in the saturated hydrocarbon group will not be substituted with -OO- or -CO-CO-.

The substituents that the aromatic hydrocarbon group having 6 to 14 carbons in the formula (A3-2) may have are selected from halogen atoms, nitro groups, hydroxyl groups, methanols, and optionally substituted alkyls with 1 to 8 carbons. At least one of the group of bases.

The substituents that the aralkyl group having 7 to 30 carbons in the formula (A3-2) may have are selected from halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted alkyls having 1 to 8 carbons. At least one of the group of bases.

The substituent that the C1-C8 alkyl group in the formula (A3-2) 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 alkyl group having 1 to 8 carbon atoms in the formula (A3-2) is an alkyl group having 2 to 8 carbon atoms, -CH ₂ -contained in the alkyl group may be substituted with -O- or -CO-. Here, -CH ₂ -in the methyl group that is the terminal of the alkyl group is not included in the -CH ₂ -. In addition, -CH ₂ -CH ₂ -contained in the alkyl group will not be substituted with -OO- or -CO-CO-.

R ^{41b is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and still more preferably an alkyl group having 1 to 4 carbons. 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 still more preferably a phenyl group.

R ^43b and R ^44b in the formula (A3-2) each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 14 carbons, 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-member to 10-member nitrogen-containing heterocyclic ring together with the bonded nitrogen atom.

R ^{43b is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and still more preferably an alkyl group having 1 to 4 carbons. 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 still more preferably a phenyl group.

R ^47b to R ^54b in formula (A3-2) each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an optionally substituted alkyl group having 1 to 8 carbons.

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

The ring T ^1b in the formula (A3-2) represents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted 5- to 10-member aromatic heterocyclic ring.

The substituents that the aromatic hydrocarbon ring having 6 to 14 carbons in the formula (A3-2) may have are selected from the group consisting of halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted carbon 1-8 At least one member of the group consisting of alkyl groups.

The substituents that the 5-membered to 10-membered aromatic heterocyclic ring in formula (A3-2) may have are selected from halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted carbon number 1-8 At least one member of the group consisting of alkyl groups.

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

[化26]

R ^45b and R ^46b in formula (2t) each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or The substituent is an aralkyl group having 7 to 30 carbon atoms, or R ^45b and R ^46b are bonded to form a 3-member to 10-member nitrogen-containing heterocyclic ring together with the bonded nitrogen atom.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2t) 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.

The substituents that the aromatic hydrocarbon group having 6 to 14 carbons in the formula (2t) may have are selected from halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted alkyl groups having 1 to 8 carbons. At least one of the group of.

The substituents that the aralkyl group having 7 to 30 carbons in the formula (2t) may have are selected from halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted alkyl groups having 1 to 8 carbons. At least one of the group of.

The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (2t) 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.

R ^{45b is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and still more preferably an alkyl group having 1 to 4 carbons.

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 a substituent, and more preferably one or two alkyl groups. A phenyl group having an alkyl group having 1 to 4 carbon atoms as a substituent.

R ^56b in the formula (2t) represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, or an optionally substituted carbon number 7 ～30 aralkyl group.

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 benzene having one or two halogen atoms as a substituent The group is more preferably a phenyl group having one or two fluorine atoms as a substituent.

L ^1b in the formula (2t) 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. * In the formula (2t) represents the bonding position with the carbocation.

M in Formula (A3-2) represents an integer of 1 or more. m is preferably an integer of 1-20, more preferably an integer of 2-14, still more preferably an integer of 2-8, particularly preferably 3. When m is an integer of 2 or more, a plurality of cations represented by formula (A3-2c) may be the same or not.

[化27]

[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] Hereinafter, the cation represented by formula (A3-2c) may be described as "cation (A3-2c)". The plurality of cations (A3-2c) are preferably the same.

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

The compound (A3-2) is preferably a compound (hereinafter, sometimes referred to as "compound (A3-2')") in which 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) [formula ( In 2t), R ^45b is a hydrogen atom or an alkyl group having 1 to 8 carbons, R ^46b is a phenyl group which may have an alkyl group having 1 to 8 carbons, and R ^56b is a phenyl group which may have a halogen atom and a carbon number of 1 to 8 The phenyl group of at least one substituent in the group consisting of the alkyl group of 8, L ^1b is a sulfur atom, and * represents the bonding position with the carbocation], m is 3, and the three cations (A3-2c) are the same , And [Y] ^m- is [PW ₁₂ O ₄₀ ] ^3- .

In the 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 more preferably It is an alkyl group having 1 to 4 carbons; R ^42b and R ^44b are each independently more preferably a phenyl group which may have an alkyl group having 1 to 4 carbons, and more preferably a phenyl group; R ^47b to R ^54b are each independently more Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom; R ^{45b 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 ^{46b is more} preferably a phenyl group having one or two alkyl groups having 1 to 8 carbons as a substituent, and still more preferably a phenyl group having one or two alkyl groups having 1 to 4 carbons as a substituent; and R ^56b More preferred is a phenyl group having one or two halogen atoms as a substituent, and still more preferred is a phenyl group having one or two fluorine atoms as a substituent.

Among the compounds (A3-2), particularly preferred is a compound represented by the following formula (A3-2-1) (hereinafter, sometimes referred to as "compound (A3-2-1)").

[化28]

The compound (A3-2) can be produced according to a known method (for example, the method described in JP 2015-28121 A).

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

In the case where a dispersant is included in the dispersion of the compound (A3), its content is preferably 1 part by weight or more and 500 parts by weight or less, more preferably 5 parts by weight or more with respect to 100 parts by weight of the compound (A3). 300 parts by weight or less. If the content of the dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

In the case of using the compound (A3), its content relative to the total solid 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, more preferably 50% by weight or less.

When using the compound (A3), it is preferable to use a dye (A1) different from the compound (A3). That is, in a preferred aspect of the present invention, the colorant (A) includes a dye (A1) and a compound (A3) that are different from the compound (A3). The description of the type and content of the dye (A1) in this aspect is as described above.

In the case of using the dye (A1) and the compound (A3), the weight ratio of the dye (A1) to the compound (A3) (dye (A1): compound (A3)) is preferably 0.5:99.5 to 99:1, more Preferably, it is 0.5:99.5 to 95:5, particularly preferably 0.5:95 to 90:10.

＜Resin (B)＞ The resin (B) used in the present invention contains the resin (B1) containing the structural unit (b1-1) represented by the formula (1b) (hereinafter, sometimes referred to as "structural unit (b1-1)").

[化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 carbons, or an alkoxy group having 1 to 6 carbons, and n represents 1 An integer of ～10, and * indicates the bonding position, wherein at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbons] In the resin (B1), the structural unit (b1-1) may contain only one type , Can also contain two or more. By using the resin (B1), it is possible to suppress the reduction of the colored pattern or the thickness of the colored coating film caused by heating (especially post-baking).

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, Neopentyl.

Examples of the alkoxy group having 1 to 6 carbon atoms in R ^2B to R ^4B include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, and isopropoxy , Isobutoxy, isopentoxy, neopentoxy.

R ^2B to R ^4B are each independently preferably methoxy, ethoxy or propoxy, more preferably methoxy or ethoxy. n is preferably an integer of 1-6, more preferably an integer of 1-3.

The resin (B1) preferably contains a structural unit (b1-1) and a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter, may be described as "structural unit (b1-2) ") and other structural units (b1-3) (hereinafter, sometimes referred to as "structural unit (b1-3)") copolymers. Here, the other structural unit (b1-3) refers to a structural unit different from the structural unit (b1-1) and the structural unit (b1-2). In the resin (B1) which is a copolymer, the structural unit (b1-1), the structural unit (b1-2), and the structural unit (b1-3) may contain only one type, and may contain two or more types.

As an acidic group which a structural unit (b1-2) has, a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfo group (-S(=O) ₂ OH) are mentioned, for example. Among these, a carboxyl group is preferred.

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

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

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

From the viewpoint of developability, 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 polystyrene conversion using Gel Permeation Chromatography (GPC).

From the viewpoints of thermal decomposition resistance, thermal yellowing resistance, and solvent resistance, the silane equivalent of the resin (B1) is preferably 400 to 4,000, more preferably 500 to 3,000. When the silane equivalent of the resin (B1) is 400 or more, it is effective for further improving the heat decomposition resistance and heat yellowing resistance of the colored pattern or the colored coating film. Furthermore, the silane equivalent of resin (B1) is a value calculated according to the following formula: Silyl group equivalent = weight average molecular weight of resin (B1) / average number of silyl groups per molecule. The silyl group 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 structural unit (b1-2), from the viewpoint of developability, the acid value of the resin (B1) is preferably 20 mgKOH/g to 300 mgKOH/g, and more Preferably it is 30 mgKOH/g～200 mgKOH/g. Furthermore, the acid value of the resin (B1) is a value measured in accordance with Japanese Industrial Standards (JIS) K6901 5.3 and using a mixed indicator of bromothymol blue and phenol red, which is The value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B1) can be determined, for example, by titration using an aqueous potassium hydroxide solution.

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

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

[化30]

[The meaning of the symbol in formula (2b) is as described above]

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

The resin (B1), which is a copolymer containing the structural unit (b1-1), the structural unit (b1-2), and the structural unit (b1-3), can be manufactured by the following method: in the presence of a solvent, according to a known The radical polymerization method contains a compound (m1-1), a polymerizable unsaturated compound having an acidic group (m1-2) (hereinafter, sometimes referred to as "compound (m1-2)"), and other polymerizable unsaturated compounds The monomer mixture of compound (m1-3) (hereinafter, sometimes referred to as "compound (m1-3)") is copolymerized. 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 structural unit (b1-1) is derived from the compound (m1-1), the structural unit (b1-2) is derived from the compound (m1-2), and the structural unit (b1-3) is derived from the compound (m1-3).

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

As the compound (m1-1), for example, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethyl Oxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylethyldiethoxysilane, 3-(methyl) Yl)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, etc. Among these, in terms of availability and reactivity, 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyl are preferred.基三ethoxysilane. Here, the "3-(meth)acryloyloxypropylmethyldimethoxysilane" refers to a group selected from 3-propenyloxypropylmethyldimethoxysilane and 3- At least one of methacryloxypropylmethyldimethoxysilane. Other identical descriptions also have the same meaning.

Examples of the acidic group that the compound (m1-2) has include a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfo group (-S(=O) ₂ OH). Among these, a carboxyl group is preferred.

As the compound (m1-2), for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-acrylic acid Oxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. Among these, (meth)acrylic acid is preferable from the viewpoint of availability and reactivity.

Examples of the compound (m1-3) include the following compounds: butadiene; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate , Butyl (meth)acrylate, second butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth) Neopentyl acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate Ester, lauryl (meth)acrylate, lauryl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate , Ethyl cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, (methyl) ) 5-methyl norbornyl acrylate, 5-ethyl norbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth) 1,1,1-trifluoroethyl acrylate, perfluoroethyl (meth)acrylate, perfluoro-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, (meth)acrylic acid Triphenyl methyl ester, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butanetriol Mono(meth)acrylate, pentanetriol mono(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, isobornyl (meth)acrylate Base ester, adamantyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, ( Glycidyl meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, (3-ethyloxetan-3-yl) methyl (meth)acrylate, (methyl) ) 2-isocyanatoethyl acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato(meth)acrylate -1-Methyl ethyl, 2-isocyanato-1,1-dimethyl ethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, by using end-blocking A blocked isocyanate obtained by blocking the isocyanate group of the (meth)acrylate having an isocyanate group (for example, 2-isocyanatoethyl (meth)acrylate) (Meth)acrylate, (meth)acrylate N,N-dimethylaminoethyl, (meth)acrylate N,N-diethylaminoethyl, (meth)acrylate N- Tertiary butylamino ethyl, tetramethylpiperidinyl (meth)acrylate, hexamethylpiperidinyl (meth)acrylate; amide (meth)acrylate, N (meth)acrylate, N-dimethyl amide, (meth) acrylic acid N, N-diethyl amide, (meth) acrylic acid N, N-dipropyl amide, (Meth) acrylic acid N,N-diisopropylamide, (meth)acrylic acid anthrylamide, N-isopropyl (meth)acrylamide, (meth)acrylic morpholine, diacetone ( (Methyl)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] dodeca-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve 3-ene, 8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6] dec -8-ene, tricyclic [5.2.1.0 ^2,6 ] dec-3-ene, tricyclic [4.4.0.1 ^2,5 ] undec-3-ene, tricyclic [6.2.1.0 ^1,8 ] ten One carbon-9-ene, tricyclic [6.2.1.0 ^1,8 ] undec-4-ene, tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodecano-3 - ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, 8-ethylidene tetracyclo [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, pentacyclic [6.5 .1.1 ^3,6 .0 ^2,7 .0 ^9,13] pentadec-4-ene, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] pentadeca -3- Alkene, 5-norbornene-2,3-dicarboxylic anhydride, (meth)acrylic acid aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride Ethylene, vinyl pyridine, vinyl acetate, vinyl toluene; styrene and its derivatives; diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate; Maleic anhydride, itaconic anhydride, citraconic anhydride.

From the viewpoint of availability and reactivity, the compound (m1-3) is preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate Base ester, dicyclopentyl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (methyl) ) N,N-diethylamino ethyl acrylate, N,N-dimethyl amide (meth)acrylate, morpholine (meth)acrylate, styrene, vinyl toluene and norbornene, more preferably It is methyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid (3-ethyloxy) Etidine-3-yl) methyl ester, styrene and vinyl toluene.

From the viewpoints of thermal decomposition resistance and thermal yellowing resistance, the compound (m1-3) is preferably alkyl (meth)acrylate, more preferably methyl (meth)acrylate and benzyl (meth)acrylate Base ester, dicyclopentyl (meth)acrylate.

From the viewpoint of solvent resistance, the compound (m1-3) preferably has a functional group that reacts with an acidic group (for example, a glycidyl group, an oxetanyl group, an isocyanate group, and a blocked isocyanate group). The polymerizable compound of cyanate group) is more preferably glycidyl (meth)acrylate and (3-ethyloxetan-3-yl)methyl methacrylate.

As the blocking agent used in the blocking of the isocyanate group, for example, the following blocking agents can be cited: ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam and other end-blocking agents; Methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol and other alcohol-based blocking agents ； Phenol, cresol, xylenol, ethyl phenol, o-isopropyl phenol, p-tertiary butyl phenol and other butyl phenol, p-tertiary octyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol , Oxybenzoic acid esters, regenol, p-naphthol, p-nitrophenol, p-chlorophenol and other phenolic blocking agents; Active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, methyl acetylacetate, ethyl acetylacetate, and acetone acetone; Mercaptan-based blocking agents such as butyl mercaptan, thiophenol, and tertiary dodecyl mercaptan; Diphenylamine, phenylnaphthylamine, aniline, carbazole and other amine-based blocking agents; Acetanilide (acetanilide), methoxy acetanisidide (acetanisidide), acetamide, benzamide and other acid amide blocking agents; Succinic acid imine, maleic acid imine and other acid imine blocking agents; Imidazole-based blocking agents such as imidazole, 2-methylimidazole and 2-ethylimidazole; Urea-based blocking agents such as urea, thiourea, and ethylene urea; Carbamate-based blocking agents such as phenyl N-phenylcarbamate and 2-oxazolidinone; Imine-based blocking agents such as ethylene imine and polyethylene imine; Oxime series blocking agents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, etc.; Bisulfite-based blocking agents such as sodium bisulfite and potassium bisulfite.

In order to control the weight molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the resin (B1) within a preferable range, and to suppress gelation during polymerization, the solvent used in the polymerization preferably contains carbon Number of 3-10 solvents containing hydroxyl groups. Examples of the hydroxyl-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and benzyl alcohol; 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 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, tripropylene glycol monomethyl ether, etc. (poly) Alkanediol monoalkyl ethers.

The solvent used in the polymerization may include solvents other than the hydroxyl group-containing solvent having 3 to 10 carbon atoms. Examples of the solvent include (poly)alkylene glycol monomers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Alkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptan Ketones, 3-heptanone and other ketones; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Ethoxy ethyl acetate, hydroxy ethyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate Ester, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl 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 and other esters; aromatics such as toluene and xylene Group hydrocarbons; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and other carboxylic acid amines. Among these, from the viewpoint of reactivity, (poly)alkylene glycol monoalkyl ether acetates are preferred.

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 carbons relative to the entire solvent used in the polymerization is preferably 10 weight. % To 100% by weight, more preferably 20% to 100% by weight.

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

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

The resin (B1) is preferably a copolymer of (meth)acrylic acid, 3-(meth)acryloxypropyltrimethoxysilane, and methyl (meth)acrylate. In the case of using the compound (A3), the resin (B1) is preferably (meth)acrylic acid, 3-(meth)acryloyloxypropyltriethoxysilane, and (meth)acrylic acid dicyclopentane Copolymers of alkyl esters.

The resin (B) may contain a resin (B2) different from the resin (B1). The resin (B2) is preferably an alkali-soluble resin, and is preferably a polymer containing structural units derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides Body (hereinafter, sometimes referred to as "single body (m2-1)"). In the polymer, the structural unit may include only one type or two or more types.

The resin (B2) more preferably contains a structural unit derived from a monomer (m2-1) and a monomer derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, there are When described as "monomer (m2-2)") a copolymer of structural units. The copolymer may also include other structural units. As other structural units, for example, a monomer derived from a monomer (m2-1) and a monomer (m2-2) different from the monomer (m2-2) (hereinafter, sometimes referred to as "monomer (m2-3)" ), a structural unit having an ethylenically unsaturated bond, etc. In the copolymer, the structural unit may include only one type, or may include two or more types.

As a single body (m2-1), for example, the following single body: Acrylic acid, methacrylic acid, crotonic acid, ortho-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid and other unsaturated monocarboxylic acids; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as dicarboxylic 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-dicarboxybicyclo[2.2.1]hept-2-ene, Bicyclic unsaturated compounds containing carboxyl groups such as 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 other than fumaric acid and mesaconic acid; Succinic acid mono[2-(meth)acryloyloxyethyl] ester and phthalic acid mono[2-(meth)acryloyloxyethyl] ester and other polycarboxylic acids with more than two valence Unsaturated mono[(meth)acryloxyalkyl] esters; α-(hydroxymeth)acrylic acid and other unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

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

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

As a monomer (m2-2), for example, a monomer having an oxocyclopropyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (m2-2-1)") , Monomers with oxetanyl and ethylenically unsaturated bonds (hereinafter sometimes referred to as "monomers (m2-2-2)") and monomers with tetrahydrofuranyl and ethylenically unsaturated bonds Body (hereinafter sometimes referred to as "single body (m2-2-3)") etc.

As the monomer (m2-2-1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes described as "mono Weight body (m2-2-1a)”) and a monomer having a structure formed by epoxidation of alicyclic unsaturated hydrocarbons (hereinafter, sometimes referred to as “monomer (m2-2-1b)”) .

The monomer (m2-2-1a) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. As a single body (m2-2-1a), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate , Glycidyl vinyl ether, vinyl benzyl glycidyl ether, α-methyl vinyl benzyl 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-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl) Styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2,4,6-tris(glycidyloxymethyl)styrene, etc.

As the monomer (m2-2-1b), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (Celloxide) ( Registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel) ), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel), compounds represented by formula (BI) and formula (BII) The compound etc. represented.

[化31]

[In formula (BI) and formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons which may be substituted by a hydroxyl group, and X ^a and X ^b each independently represent a single bond ^{, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-, R ^c is a C 1-6 alkanediyl group, and * represents O, Bond position]

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

[化32]

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

[化33]

In addition, the compound represented by formula (BI) and the compound represented by formula (BII) may be used alone, respectively, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. In the case of using these 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 calculated , Preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and still 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, second (meth)acrylate Butyl ester, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Stearyl ester, cyclopentyl (meth)acrylate, tricyclic (meth)acrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, tricyclic (meth)acrylate [5.2.1.0 ^{2, 6} ]Decane-9-yl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene-8-yl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene -9-yl ester, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate , (Meth)acrylates such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate; (meth)acrylic acid Hydroxy-containing (meth)acrylates such as 2-hydroxyethyl and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid such as diethyl maleate, diethyl fumarate and diethyl itaconate Acid diester; 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 Ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept- 2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene , 5,6-Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1]Hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2 -Ene, 5-tertiary butoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[ 2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2 .1] Bicyclic unsaturated compounds such as hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide 3-maleimide benzoate, N-succinimidyl -4-maleimidin butyrate, N-succinimidyl-6-maleimidin caproate, N-succinimidyl-3-maleimidin propionate and N-(9-acridinyl)maleimines and other dicarbonylimines derivatives; vinyl-containing aromatics such as styrene, α-methylstyrene, vinyl toluene, and p-methoxystyrene Compounds; (meth)acrylonitrile and other vinyl-containing nitriles; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth)acrylamide and other vinyl-containing amides; vinyl acetate and other esters; 1, Dienes such as 3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

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

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The resin (B2) having such a structural unit can be obtained by the following method: For a polymer containing a structural unit derived from a monomer (m2-1) and a structural unit derived from a monomer (m2-2) , Addition has a monomer having a group capable of reacting with the group of the structural unit and an ethylenically unsaturated bond.

As the structural unit having an ethylenically unsaturated bond, for example, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit; and a structural unit obtained by adding (formaldehyde) to a maleic anhydride unit Base) a structural unit obtained from 2-hydroxyethyl acrylate; and a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit; by adding a structural unit having a hydroxyl group Structural units etc. obtained by carboxylic anhydride.

A polymer containing a structural unit derived from a monomer (m2-1) can be produced by, for example, making the monomer of the structural unit of the polymer in a solvent in the presence of a polymerization initiator polymerization. The polymerization initiator, solvent, etc. are not particularly limited, and those generally 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 Oxide (benzyl peroxide, etc.). The solvent is not particularly limited as long as it dissolves each monomer. For example, the solvent (H) described later can be cited. Furthermore, the obtained polymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by methods such as reprecipitation can also be used.

In the production of a polymer containing a structural unit derived from a monomer (m2-1), a carboxylic acid anhydride having an ethylenically unsaturated bond may be used as the monomer. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetra Hydrogen phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]heptan-2- Acrylic anhydride and so on.

As the resin (B2), for example, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic (meth)acrylate [5.2. 1.0 ^2,6 ]decyl ester/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate /Styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleic acid Amine copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/(meth)acrylic acid 2 -Hydroxyethyl copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/vinyl toluene copolymer, (meth)acrylic acid 3, 4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/(meth)acrylate 2-ethylhexyl copolymer, (meth)acrylic acid 3,4-epoxy tricyclic [5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decenyl ester/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3 -Methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, (meth)acrylic acid benzyl ester/(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.

In the case of using a combination of two or more resins (B2), the combination preferably contains 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] decyl (meth)acrylate/( (Meth) acrylic acid copolymer, (meth) acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/(methyl) )2-hydroxyethyl acrylate copolymer, (meth)acrylate 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl/(meth)acrylic acid/vinyltoluene copolymer, and (meth)acrylic acid/vinyltoluene copolymer ) At least one of the group consisting of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl 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 still more preferably 5,000 to 30,000. The molecular weight distribution (Mw/Mn) (that is, the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn)) of the resin (B2) is preferably 1.1-6, more preferably 1.2-4. Here, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin (B2) are values calculated by polystyrene conversion using gel permeation chromatography (GPC).

The acid value (solid content conversion value) of the resin (B2) is preferably 10 mgKOH/g～300 mgKOH/g, more preferably 20 mgKOH/g～250 mgKOH/g, and still more preferably 20 mgKOH/g～200 mgKOH/ g, still more preferably 20 mgKOH/g～170 mgKOH/g, still more preferably 30 mgKOH/g～170 mgKOH/g, particularly preferably 50 mgKOH/g～150 mgKOH/g, and even more preferably 60 mgKOH/ g～140 mgKOH/g, the best is 60 mgKOH/g～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 it can be determined, 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 still more preferably 10 parts by weight Parts ~ 800 parts by weight.

In the case of using resin (B2), its content relative to the total solid content is preferably 1% by weight to 50% by weight, more preferably 1% by weight to 45% by weight, and still more preferably 1% by weight to 40% by weight % By weight, preferably 1% by weight to 30% by weight.

＜Polymerizable compound (C)＞ The polymerizable compound (C) is a compound that can be polymerized by a living radical and/or acid generated from the polymerization initiator (D). The polymerizable compound (C) is preferably a radical polymerizable compound. Examples of the radically polymerizable compound include a polymerizable compound having an ethylenically unsaturated bond. The radically polymerizable compound is preferably (meth)acrylates.

Examples of the polymerizable compound (C) include the following compounds: Nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. An ethylenically unsaturated bond compound; 1,6-Hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Compounds with two ethylenically unsaturated bonds, such as bis(acryloxyethyl) ether of bisphenol A and 3-methylpentanediol di(meth)acrylate; Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, etc. have three ethylenic properties Compounds with saturated bonds; Pentaerythritol tetra (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, etc. Compounds with four ethylenically unsaturated bonds; Compounds with five ethylenically unsaturated bonds such as dipentaerythritol penta(meth)acrylate; Dipentaerythritol hexa(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate Acrylates and other compounds with six ethylenically unsaturated bonds; Tripentaerythritol hepta (meth)acrylate, tripentaerythritol octa (meth)acrylate, pentaerythritol nona (meth)acrylate, pentaerythritol deca (meth)acrylate, etc. have more than seven ethylenically unsaturated bonds compound of.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having five or six ethylenically unsaturated bonds. Specifically, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable. As commercially available products of the polymerizable compound (C), for example, KAYARAD (registered trademark) DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin Nakamura Chemical Industry Co., Ltd.), and A9550 (Xin Nakamura Chemical Industry Company), etc.

The molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less. In addition, the molecular weight of the polymerizable compound (C) of 1,000 or more is a weight average molecular weight (Mw) calculated by polystyrene conversion using gel permeation chromatography (GPC).

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

In addition, the weight ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35:65 to 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. by the action of light or heat and initiate polymerization, 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 photo-radical polymerization initiator (that is, the colored curable resin composition of the present invention is a photo-curable resin composition物).

The photoradical polymerization initiator is preferably at least one selected from the group consisting of O-acyl oxime compounds, phenalkyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, and biimidazole compounds, more preferably For O- oxime compounds.

The O-acetoxime compound is a compound having a partial structure represented by the formula (d1) (in the following formula, * represents a bonding position).

[化34]

Examples of the O- oxime compound include: N-benzyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzyloxy 1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane -1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane- 1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane Methyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl Benzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-(2- Hydroxyethyloxy)phenylmercaptophenyl]propane-1-one-2-imine and the like. Can also use 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 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) and other commercially available products. Among them, the O- 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 (above, manufactured by BASF), N-benzyloxy-1-(4-phenylmercapto Phenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine and N-benzyl At least one of the group consisting of acyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropan-1-one-2-imine, more preferably selected from TR-PBG327( Changzhou Qiangli Electronic New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) ) (Registered trademark) OXE04 (above, made by BASF) and N-benzyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine At least one of the group. If these O-acetoxime compounds are used, there is a tendency to obtain a high-brightness color filter.

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

[化35]

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholinyl-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Irgacure (registered trademark) 369, Irgacure (registered trademark) 907, Irgacure (registered trademark) 379 (above, made by BASF), etc. can also be used. For sale. As a compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Ketone oligomers, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc. In terms of sensitivity, the phenalkyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloro Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-〔 2-(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

As an acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide etc. are mentioned, for example. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent 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'-tetra(dialkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open Sho 62-174204), a biimidazole compound in which the phenyl group at the 4, 4', 5, 5'-position is substituted with an alkoxycarbonyl group (carboalkoxy) (for example, refer to Japanese Patent Laid-Open No. 7-10913).

Examples of other polymerization initiators (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthalate , 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)diphenyl Benzophenone compounds such as methyl ketone and 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2- Chloracridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the polymerization initiation aid (F) (especially amines) described later.

As an acid generator, for example, 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl Alumium p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzyl alumium hexafluoroantimonate, triphenyl alumium p-toluenesulfonate, triphenyl alumium hexafluoroantimonate, diphenyl Onium salts such as p-toluene sulfonate, diphenyl hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

The content of the polymerization initiator (D) is preferably 0.1 parts by weight to 30 parts by weight, and more preferably 1 part by weight to 20 parts by weight with respect 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-mentioned range, the sensitivity of the colored curable resin composition of the present invention tends to be improved and the exposure time is shortened, so the productivity of the color filter is improved.

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

In this specification, the "phenolic antioxidant" refers to an antioxidant having a phenolic hydroxyl group. Therefore, in this specification, for example, antioxidants containing both phenolic hydroxyl groups and phosphorus atoms are classified as phenolic antioxidants rather than phosphorus antioxidants. In addition, the phenolic antioxidant in this specification also includes an antioxidant having a protected phenolic hydroxyl group (hereinafter, it may be described as a "protected phenolic antioxidant").

Examples of phenolic antioxidants include the following antioxidants: (1) Alkylthiomethylphenol 2,4-dioctylthiomethyl-6-tertiary butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethyl Phenol, 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 hydrosulfide Acetate, 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 Hydrosulfanyl acetate.

(4) Hydroxybenzylated malonate derivatives Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl) 4-hydroxy-5-methylbenzyl)malonate, di-dodecylhydrothioethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxyl Benzyl)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-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-th Tributyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(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) Yl)isocyanurate, tris[2-(3',5'-di-tert-butyl-4'-hydroxycinnamyloxy)ethyl]isocyanurate.

(7) Benzyl phosphonate derivatives Dimethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di- Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphine Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester.

(8) Amino phenol derivatives 4-hydroxylauric acid aniline, 4-hydroxystearic acid aniline, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

(9) β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the following monohydric alcohol or polyhydric alcohol ester Methanol, ethanol, octanol, stearyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol , Diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl) glufamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxane Heterobicyclo[2,2,2]octane.

(10) β-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and the following monohydric alcohol or polyhydric alcohol ester Methanol, ethanol, octanol, stearyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol , Diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl) glufamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxane Heterobicyclo[2,2,2]octane.

(11) β-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionic acid and the following monohydric alcohol or polyhydric alcohol ester Methanol, ethanol, octanol, stearyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol , Diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl) glufamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxane Heterobicyclo[2,2,2]octane.

(12) Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, stearyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol , Diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl) glufamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxane Heterobicyclo[2,2,2]octane.

(13) The 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-tertiary butyl-4'-hydroxyphenyl)propanyl]hexamethylene diamine, N,N'-bis[3-(3',5'-di-tert-butyl- 4'-Hydroxyphenyl)propanyl]trimethylene diamine.

Those obtained by protecting the phenolic hydroxyl group of the exemplified phenolic antioxidant with a protecting group can also be used as the phenolic antioxidant in the present invention. Examples of the protecting group include ether-based protecting groups, acetal-based protecting groups, acyl-based protecting groups, and silyl ether-based protecting groups. Examples of ether-based protective groups include methyl, benzyl, p-methoxybenzyl, and tertiary butyl. Examples of acetal protecting groups include methoxymethyl, 2-tetrahydropyranyl, and ethoxyethyl. Examples of the acyl group-based protecting group include acetyl group, trimethyl acetyl group, and benzyl group. As the silyl ether-based protecting group, for example, a trimethylsilyl group, a triethylsilyl group, a tertiary butyldimethylsilyl group, a triisopropylsilyl group, and a tertiary butyldiphenylsilyl group can be cited. In addition, as the protective group, a tertiary butoxycarbonyl (Boc) group may also be used. The protecting group of the phenolic hydroxyl group is preferably a Boc group.

Commercially available phenolic antioxidants can be used. As commercially available products of phenolic antioxidants, for example, Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.), Adekastab (registered trademark) AO series (Aidi (Made by ADEKA). As a commercial product of the protected phenol-based antioxidant, for example, Adeka arkls (registered trademark) GPA-5001 (manufactured by ADEKA) can be cited.

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

＜Polymerization initiator (F)＞ The colored curable resin composition of the present invention may further include a polymerization initiation assistant (F). The polymerization initiation auxiliary (F) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. As a polymerization start auxiliary agent (F), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned, for example.

Examples of amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4' -Bis(ethylmethylamino)benzophenone and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred. As the amine compound, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used.

As the alkoxyanthracene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

As the thioxanthone compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothio Heteroanthrone, 1-chloro-4-propoxythioxanthone, etc.

As the carboxylic acid compound, for example, thioglycolic acid, methyl thioglycolic acid, ethyl thioglycolic acid, methyl ethyl thioglycolic acid, dimethyl thioglycolic acid, methoxybenzene thioglycolic acid, dimethoxy Thioglycolic acid, chlorobenzene thioglycolic acid, dichlorobenzene thioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

The polymerization initiation assistant (F) is preferably a thioxanthone compound, more preferably 2,4-diethylthioxanthone.

In the case of using the polymerization initiator (F), the content relative to 100 parts by weight of the total of the resin (B) and the polymerizable compound (C) is preferably 0.1 to 30 parts by weight, and more preferably 1 Parts by weight ~ 20 parts by weight. In addition, when the 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. Parts by weight, more preferably 15 parts by weight to 55 parts by weight. If the amount of the polymerization initiation assistant (F) is within the above-mentioned 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 include a thiol compound (G). The thiol compound (G) is a compound having a mercapto group (-SH).

Examples of compounds having one mercapto group include: 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptonicotinic acid , 2-mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-6-hydroxy-2- Mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4,6 -Diamino-2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4- Hydroxy-2-mercapto-6-methylpyrimidine, 4-hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3,4 ,5,6-Tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3- Hydrazine-5-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole- 3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-mercapto-1H-1,2,4-triazole-3-thiol, 2-amino -5-Mercapto-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole Azole, (furan-2-yl) methyl mercaptan, 2-mercapto-5-thiazolidinone, 2-mercaptothiazolinone, 2-mercapto-4(3H)-quinazolinone, 1-phenyl-1H- Tetrazole-5-thiol, 2-quinolinethiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole , 5-Chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthimidazole, 2-mercaptonaphthoxazole Azole, 3-mercapto-1,2,4-triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purine thiol, 6-mercaptopurine , 4-Mercapto-1H-pyrazolo[2,4-d]pyrimidine, etc.

Examples of compounds having two or more mercapto groups include hexane dithiol, decane dithiol, 1,4-bis(methylmercapto)benzene, butanediol bis(3-mercaptopropionate), Butanediol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane tris(3-mercaptoacetate), butanediol bis(3-mercaptopropane) Acid ester), trimethylolpropane tris(3-mercaptopropionate) (alias "trimethylolpropane tris(3-hydrothiopropionate)"), trimethylolpropane tris(3-mercapto Acetate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptoacetate), trihydroxyethyl tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate) ), 1,4-bis(3-mercaptobutyloxy)butane, etc.

The thiol compound (G) is preferably a compound having two or more mercapto groups, and more preferably trimethylolpropane tris(3-mercaptopropionate).

In the case of using the thiol compound (G), the content is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the polymerizable compound (C). If the content of the thiol compound (G) is within this range, the sensitivity becomes higher and the developability tends to become better.

＜Solvent (H)＞ The colored curable resin composition of the present invention may further include a solvent (H). The solvent (H) is not particularly limited, and solvents generally used in this field can be used. As the solvent (H), for example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule and no -O-,- CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc. 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 the ester solvent include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, Cyclohexanol acetate and γ-butyrolactone, etc.

As the ether solvent, for example, 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, two Ethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropane Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, 2-methoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-methoxy-2-methylpropionate, 2 -Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate and dipropylene glycol methyl ether acetate, etc.

As the ketone solvent, for example, 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, etc.

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

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

As the solvent (H), an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm is preferable in terms of coatability and drying properties. The solvent (H) is preferably 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, more preferably It is 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol and ethyl 3-ethoxypropionate.

In the case of using the solvent (H), its content is preferably 35% to 95% by weight, and more preferably 40% to 92% by weight with respect to the entire colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5% by weight to 65% by weight, more preferably 8% by weight to 60% by weight. If the content of the solvent (H) is within the above-mentioned range, the flatness during application becomes good, and the color density is not insufficient when forming a color filter, so the display characteristics tend to become good.

＜Leveling agent (I)＞ The colored curable resin composition of the present invention may also contain a leveling agent (I). As a leveling agent (I), a silicone type surfactant, a fluorine type surfactant, etc. are mentioned, for example. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule, and the like. As its commercially available products, for example, Toray Silicone (Toray Silicone) DC3PA, Toray Silicone (Toray Silicone) SH7PA, Toray Silicone (Toray Silicone) DC11PA, Toray Silicone (Toray Silicone) SH21PA, Toray Silicone (Toray Silicone) SH28PA, Toray Silicone (Toray Silicone) SH29PA, Toray Silicone (Toray Silicone) SH30PA, Toray Silicone (Toray Silicone) SH8400 (manufactured by Toray Dow 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 (Momentive Performance Materials Japan) Co., Ltd.), etc.

The silicone-based surfactant may have a fluorine atom. Examples of silicone-based surfactants having fluorine atoms include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac (Megafac) F443 (manufactured by DIC), etc.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule, and the like. As its commercially available products, for example, Fluorad (registered trademark) FC430, Fluorad (Fluorad) FC431 (manufactured by Sumitomo 3M Corporation); Megafac (registered trademark) F142D, Megafac (registered trademark) Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac ) RS-718-K (manufactured by DIC); 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 Company) And E5844 (manufactured by Daikin Fine Chemical Research Institute (stock)), 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, relative to the entire colored curable resin composition, More preferably, it is 0.01 weight% or more and 0.05 weight% or less. In addition, the content of the dispersant used in the production of the pigment dispersion is not included in this content. 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 contain fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and other additives known in the art as necessary.

<Method for manufacturing colored curable resin composition> The colored curable resin composition of the present invention can be prepared, for example, by combining the colorant (A), resin (B) (resin (B1) and resin (B2) as necessary), and polymerizable compound (C) , Polymerization initiator (D) and phenolic antioxidant (E), as well as solvent (H), leveling agent (I), polymerization initiator (F), thiol compound (G) and other The ingredients are mixed.

When the pigment (A2) is used, it is preferable to mix part or all of the pigment (A2) with the solvent (H) in advance, and use a bead mill to disperse the pigment (A2) until the average of the pigment (A2) The particle diameter is about 0.2 μm or less to prepare a pigment dispersion. At this time, a part or all of the dispersant and the resin (B) (especially the resin (B2)) can be adjusted as needed. By mixing the remaining components in the pigment dispersion liquid obtained in this way so as to have a predetermined concentration, the target colored curable resin composition can be prepared.

When the dye (A1) is used, the dye (A1) may be dissolved in part or all of the solvent (H) in advance to prepare a dye solution. It is preferable to filter the solution with a filter with a pore diameter of about 0.01 μm to 1 μm. In addition, it is preferable to filter the colored curable resin composition obtained by mixing the components with a filter having a pore diameter of about 0.01 μm to 10 μm.

<Color filter and manufacturing method of liquid crystal display device> As a method of forming a color filter using the colored curable resin composition of the present invention, for example, a photolithography method and a method using an inkjet device can be cited. The photolithography method usually includes the following steps: coating a colored curable resin composition on a substrate, and then heat drying (pre-baking) and/or vacuum drying to remove volatile components such as solvents to form a composition In the layer, the composition layer is irradiated (exposed) with light through the mask, and the developer is brought into contact with the exposed composition layer to form (develope) a colored pattern. After the development, post-baking of heating the colored pattern is often performed. In the photolithography method, by not using a photomask and/or not performing development during exposure, a colored coating film as a hardened product of the composition layer can be formed. The colored pattern and colored coating film thus obtained can be used as a color filter.

Examples of the substrate include a glass plate, a resin plate, and a silicon plate. 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. may 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 application, etc., for example, 0.1 μm to 30 μm, preferably 1 μm to 20 μm, and more preferably 1 μm to 6 μm.

The formation of the colored pattern (pixel) by the photolithography method can be performed by a known or customary device or condition. For example, the colored pattern can be formed as follows.

First, a colored curable resin composition is coated on a substrate, and volatile components such as a solvent are removed by heat drying (pre-baking) and/or reduced-pressure drying to obtain a smooth composition layer. Examples of the coating method include spin coating, slit coating, slit and spin coating, and the like.

Next, the composition layer is irradiated (exposed) with light through a photomask for forming the target colored pattern. In order to uniformly irradiate the entire exposure surface with parallel light, or to accurately align the mask and the substrate on which the composition layer is formed, it is preferable to use a mask aligner and a stepper. Wait for the exposure device.

By contacting the exposed composition layer with the developer, a colored pattern can be formed (developed) on the substrate. The unexposed part of the composition layer is dissolved in the developing solution and removed by development. The developer is preferably an aqueous solution of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide. The development method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate may be inclined at any angle during development. It is preferable to wash with water after development.

The color filter manufactured from the colored curable resin composition of the present invention is used as a color filter used in display devices (for example, liquid crystal display devices, organic electroluminescence (EL) devices, electronic paper, etc.) and solid-state imaging devices Light film is useful. [Example]

Hereinafter, examples are given to explain the present invention more specifically, but the present invention is not limited by the following examples at all, and can also be implemented with appropriate changes within the scope that can be adapted to the above-mentioned and following gist. It is included in the technical scope of the present invention. In addition, in the following, unless otherwise specified, "parts" means "parts by weight", and "%" other than thickness retention means "% by weight".

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

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the production example was performed under the following conditions using GPC. Device: K2479 (manufactured by Shimadzu Corporation) String: SHIMADZU Shim-pack GPC-80M Column temperature: 40℃ Solvent: THF (tetrahydrofuran) Flow rate: 1.0 mL/min Detector: RI Standard materials for calibration: TSK Standard Polystyrene (TSK STANDARD POLYSTYRENE) F-40, F-4, F-228, A-2500, A-500 (manufactured by Tosoh) The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above is defined as a molecular weight distribution.

<Production Example 1: Production of resin (B1-1)> In a flask including a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 750.0 g of 3-methoxybutanol was placed, and the mixture was stirred while replacing with nitrogen, and the temperature was raised to 80°C. Secondly, from the dropping funnel, the following materials were dropped into the flask. The materials contained 25.6 g (0.30 mol) of methacrylic acid and 146.4 g of 3-methacryloxypropyl trimethoxysilane. (0.50 mol) and 49.2 g (0.49 mol) of methyl methacrylate and 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) 28.8 g becomes. After the dripping, 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 ).

<Production example 2: Production of resin (B1-2)> In a flask including a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 750.0 g of propylene glycol monomethyl ether was placed, and the mixture was stirred while replacing with nitrogen, and the temperature was raised to 80°C. Secondly, from the dropping funnel, the following substances were dropped into the flask. The substances contained 39.2 g (0.46 mol) of methacrylic acid, and 132.0 g (0.46 mol) of 3-methacryloyloxypropyltriethoxysilane. g (0.46 mol) and 50.1 g (0.23 mol) of dicyclopentyl methacrylate are added to the monomer mixture with 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization Starter) 28.8 g. After the dripping, 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, silyl group equivalent: 550) ).

<Production Example 3: Production of Resin (B2-1)> In a flask including a reflux cooler, a dropping funnel, and a stirrer, the atmosphere was replaced with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was placed and stirred while Heat to 80°C. Then, 38 parts of acrylic acid, acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester and acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ² ] were added dropwise over 5 hours. ^,6 ] A mixed solution of 289 parts of a mixture of decane-9-yl esters (containing a ratio of 1:1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained 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 dropwise addition, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin) with a solid content of 35.1% and a viscosity of 125 mPa·s measured with a B-type viscometer (23°C). (B2-1)) Solution. 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. The resin (B2-1) has the following structural units (in the following formula, * represents a bonding position).

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<Production Example 4: Production of Red Pigment Dispersion Liquid> 50.6 parts of red pigment synthesized in the following manner, dispersant (BYKLPN-6919 manufactured by BYK; propylene glycol monomethyl ether acetate 60% solution) 10.1 parts, resin (B2 -1) 20.3 parts (calculated based on solid content), 64.5 parts of propylene glycol monomethyl ether and 216.0 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.4 μm zirconia beads are added, and paint conditioner is used. (Manufactured by LAU Corporation) The obtained mixture was shaken for 1 hour. After that, the zirconia beads were removed by filtration to obtain a dispersion liquid of the red pigment.

The red pigment used in the production of the dispersion liquid of the red pigment is synthesized as follows. 174 g of tertiary amyl alcohol and 22.2 g of metallic sodium were reacted under a nitrogen atmosphere at 130° C. to synthesize tertiary amyl alcohol sodium. Heat it to 60°C, add 91.0 g of 4-bromobenzonitrile, 71.05 g of di-tertiary amyl succinate, and 108.9 g of tertiary amyl alcohol, so that the temperature of the obtained suspension is below 85°C Stir the suspension for 2 hours. The suspension was directly stirred at 85°C for more than 18 hours, and then added to a mixed solution 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 was completed, the obtained mixture was stirred for 5 hours while maintaining the temperature at 0°C to complete the reaction, and then the solid matter was recovered by filtration. Use methanol and water to alternately clean the recovered solid matter. This washing is repeated until the coloration of methanol and water used in washing disappears and the precipitation of salt disappears. The washed solid matter was dried for 18 hours with a vacuum dryer at 80°C to obtain a red pigment.

<Production Example 5: Production of Blue Pigment Dispersion Liquid> Combine CI Pigment Blue 15:6 19.2 parts, dispersant (BYKLPN-6919 manufactured by BYK; propylene glycol monomethyl ether acetate 60% solution) 6.7 parts, resin (B2- 1) 7.7 parts (calculated in terms of solid content), 14.6 parts of ethyl lactate and 143.8 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.4 μm zirconia beads are added, and the coating regulator (made by LAU) The obtained mixture was shaken for 1 hour. After that, the zirconia beads were removed by filtration to obtain a blue pigment dispersion.

<Production Example 6: Production of compound (A3-1-1)> The compound represented by the following formula (A3-1-1) was produced by the method described in Example 7 of JP 2018-127596 A.

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<Production Example 7: Production of Compound (A3-2-1)> The compound represented by the following formula (A3-2-1) was produced by the method described in Synthesis Example 19 of JP 2015-38201 A.

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<Production Example 8: Production of dispersion liquid of compound (A3-1-1)> 7 parts of compound (A3-1-1), dispersant (DISPERBYK (registered trademark) manufactured by BYK-Chemie)-2050; propylene glycol monomethyl ether acetate 52% Solution) 3 parts, 3 parts of resin (B2-1) (calculated based on solid content), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads. Use paint A conditioner (manufactured by LAU) shakes the obtained mixture for 3 hours. After that, the zirconia beads were removed by filtration to produce a dispersion liquid of the compound (A3-1-1). Furthermore, although the compound (A3-1-1) is a dye soluble in diacetone alcohol, in order to improve the reliability of the compound (A3-1-1) related to heat resistance and light resistance, propylene glycol monomethyl ether is used Acetate is used to prepare a dispersion liquid of the compound (A3-1-1), and use the dispersion liquid.

<Production Example 9: Production of dispersion liquid 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), resin ( B2-1) (calculated based on solid content) 6 parts, 74 parts of propylene glycol monomethyl ether acetate, 4 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads are mixed, using a paint conditioner (made by LAU) The obtained mixture was shaken for 3 hours. After that, the zirconia beads were removed by filtration to produce a dispersion liquid of the compound (A3-2-1). Furthermore, although the compound (A3-2-1) is a dye dissolved in diacetone alcohol, in order to improve the reliability of the compound (A3-2-1) related to heat resistance and light resistance, propylene glycol monomethyl ether is used Acetate is used to prepare a dispersion liquid of the compound (A3-2-1), and use the dispersion liquid.

Example 1 to Example 16 and Comparative Example 1 to Comparative Example 5 (1) Manufacture of colored curable resin composition Each component was mixed so that it might become a composition shown in following Table 1-Table 3, and the colored curable resin composition was obtained.

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 JP 2016-27075 (A1-2): A dye represented by the following formula (A1-2) obtained by the method described in Example 2 of JP 2017-226814 (A1-3): A dye represented by the following formula (A1-3) obtained by the method described in Synthesis Example 2 of JP 2016-176075

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<Pigment (A2) dispersion> Red pigment dispersion: the dispersion obtained in Production Example 4 Blue pigment dispersion: the dispersion obtained in Production Example 5

<Dispersion liquid of compound (A3)> Compound (A3-1-1) dispersion: the dispersion obtained in Production Example 8 Compound (A3-2-1) dispersion: the dispersion obtained in Production Example 9

＜Resin (B)＞ (B1-1): Resin (B1-1) obtained in Production Example 1 (B1-2): Resin obtained in Production Example 2 (B1-2) (B2-1): The resin (B2-1) obtained in Production Example 3 (used in the production of a dispersion liquid of the pigment (A2), the production of a dispersion liquid 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): A compound represented by the following formula (D-1) ("TR-PBG327" manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) (D-2): "Irgacure (registered trademark) 907" manufactured by BASF

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＜Phenolic antioxidant (E)＞ (E-1): 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldi Benzo[d,f][1.3.2] dioxaphosphapine ("Sumilizer (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd.) (E-2): "Adeka arkls (registered trademark) GPA-5001" manufactured by ADEKA (E-3): "Adekastab (registered trademark) AO-60" manufactured by ADEKA

＜Phosphorus antioxidants＞ TPP: Triphenyl phosphite (Adekastab (registered trademark) TPP, manufactured by ADEKA)

＜Polymerization initiator (F)＞ (F-1): 2,4-Diethylthioxanthone ("KAYACURE (registered trademark) DETX-S" manufactured by Nippon Kayaku Co., Ltd.)

＜Thiol compound (G)＞ (G-1): Trimethylolpropane tris(3-hydrothiopropionate) (manufactured by SC Organic Chemical Company)

＜Solvent (H)＞ (H-1): 3-Methoxy-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 158°C) (H-2): Diacetone alcohol (manufactured 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 (KHneochem), boiling point 121°C)

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

(2) The color filter (colored coating film) is formed on a 2-inch square glass substrate (eagle 2000; manufactured by Corning), and the colored curable resin is coated by spin coating The composition is then prebaked at 100°C for 3 minutes to form a composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon) was used to irradiate the composition layer with light at an exposure amount of 60 mJ/cm ² (365 nm standard) in an atmospheric environment. After light irradiation, post-baking was performed in an oven at 230°C for 20 minutes, thereby obtaining 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 Japan Vacuum Technology Co., Ltd.), and the result was 3.0 μm.

(3) Evaluation of thickness retention The thickness of the formed colored coating film before and after post-baking was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and the thickness retention rate was calculated according to the following equation. Thickness retention rate (%)=(thickness after post-baking/thickness before post-baking)×100 The results are shown in Tables 1 to 3.

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Dyestuff (A1-1) (parts) 8 8 8 7 8 Red pigment dispersion (parts) 362 362 371 352 362 Resin (B1-1) (parts) 30 30 29 30 30 Polymeric compound (C-1) (parts) 50 50 50 50 50 Polymerization initiator (D) (parts) (D-1) 10 10 10 (D-2) 5 10 Phenolic antioxidant (E) (parts) (E-1) 3 (E-2) 3 1 Phosphorus antioxidants (parts) TPP 3 Polymerization initiation assistant (F-1) (parts) 3 Thiol compound (G-1) (parts) 7 Solvent (H) (parts) (H-1) 124 124 126 126 124 (H-2) 266 266 259 259 266 (H-3) 216 216 205 205 216 Leveling agent (I-1) (parts) 0.2 0.2 0.2 0.2 0.2 Film thickness retention rate 82% 81% 79% 67% 76%

[Table 2] Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 3 Comparative example 4 Dyestuff (A1) (parts) (A1-2) 2 (A1-3) 2 2 2 2 2 2 2 2 Blue pigment dispersion (parts) 192 192 192 192 189 185 198 187 189 Resin (B) (parts) (B1-1) 52 52 52 52 53 52 53 (B1-2) 52 (B2-1) 52 Polymeric compound (C-1) (parts) 40 40 40 40 40 40 40 40 40 Polymerization initiator (D-1) (parts) 10 10 10 10 10 10 10 10 10 Phenolic antioxidant (E) (parts) (E-1) 3 (E-2) 3 3 3 0.2 8 3 (E-3) 3 Solvent (H) (parts) (H-1) 217 217 217 217 211 209 218 (H-2) 8 8 8 10 6 6 6 8 6 (H-3) 305 305 305 303 317 302 340 290 526 (H-4) 209 Leveling agent (I-1) (parts) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Film thickness retention rate 80% 80% 82% 83% 78% 79% 79% 67% 76%

[table 3] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative example 5 Dyestuff (A1) (parts) (A1-2) 0.6 (A1-3) 0.4 1.9 0.4 0.4 0.5 0.4 Compound (A3) dispersion liquid (parts) (A3-1-1) 302 298 302 294 315 294 (A3-2-1) 197 Resin (B) (parts) (B1-1) 49 50 49 50 49 50 (B1-2) 49 Polymeric compound (C-1) (parts) 40 40 40 40 40 40 40 Polymerization initiator (D-1) (parts) 10 10 10 10 10 10 10 Phenolic antioxidant (E-2) (parts) 3 3 3 3 0.2 8 Solvent (H) (parts) (H-1) 199 199 197 200 197 200 (H-2) 1 9 6 1 1 1 1 (H-3) 240 234 363 241 228 261 227 (H-4) 198 Leveling agent (I-1) (parts) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Film thickness retention rate 82% 83% 82% 86% 81% 83% 77%

As is clear from the results shown in Tables 1 to 3, Examples 1 to 16 using phenolic antioxidants and resin (B1) (ie, resin (B1-1) or resin (B1-2)) The colored curable resin composition and the comparative example 1, comparative example 3 and comparative example 5 without using antioxidant, or the comparative example 2 using phosphorus antioxidant instead of phenolic antioxidant, and the comparative example not using resin (B1) Compared with the colored curable resin composition of 4, the decrease in the thickness of the colored coating film caused by post-baking can be suppressed. [Industrial availability]

If the colored curable resin composition of the present invention is used, it is possible to suppress the decrease in the colored pattern or the thickness of the colored coating film caused by heating (especially post-baking). The color filter manufactured from the coloring curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

no

no

Claims (9)

A colored curable resin composition, which is a colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and a colored curable resin composition The substance further contains a phenolic antioxidant (E), and the resin (B) contains a resin (B1) containing the structural unit (b1-1) represented by the formula (1b),

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 carbons, or an alkoxy group having 1 to 6 carbons, and n represents 1 to An integer of 10 and * indicate a bonding position, wherein at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbons. The colored curable resin composition according to claim 1, wherein the resin (B1) is a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group and the resin (b1-1), and others The copolymer of the structural unit (b1-3), and the amount of the structural unit (b1-1) when the total of all the structural units in the copolymer is 100 mol% is 1 mol% to 50 mol%. The colored curable resin composition according to claim 1 or 2, wherein the weight average molecular weight of the resin (B1) is 1,000 to 50,000. The colored curable resin composition according to any one of claims 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). The colored curable resin composition according to any one of claims 1 to 4, wherein the content of the phenolic antioxidant (E) is 0.1 to 25 parts by weight relative to 100 parts by weight of the polymerizable compound (C) Parts by weight. The colored curable resin composition according to any one of claims 1 to 5, wherein the colorant (A) includes a dye (A1) and a pigment (A2). The colored curable resin composition according to any one of claim 1 to claim 6, wherein the polymerizable compound (C) is a radical polymerizable compound, and the polymerization initiator (D) is a photo-radical polymerization initiator Beginner. The colored curable resin composition according to any one of claims 1 to 7, wherein the colorant (A) contains a compound selected from the group consisting of a compound represented by formula (A3-1) and a compound represented by formula (A3-2) At least one compound (A3) in the group consisting of the indicated compounds,

In the formula (A3-1), R ^41a and R ^42a each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbons, 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-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atom, R ^43a and R ^44a each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 14 carbons, or an optionally substituted aromatic hydrocarbon group with 7 to 30 carbons. Alkyl group, or R ^43a and R ^44a are bonded to form a 3-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atoms, and R ^47a to R ^54a each independently represent a hydrogen atom, a halogen atom, or a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or a substituent having a carbon number of alkyl group having 1 to 8, R ^f represents a fluoroalkyl group having a carbon number 1 to 12, Ring T ^1a represents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted 5-membered to 10-membered aromatic heterocyclic ring, wherein the saturated hydrocarbon group having 1 to 20 carbon atoms may have substitution The group is at least one selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, and an amino group, and the substituent that the aromatic hydrocarbon group having 6 to 14 may have is selected from halogen atoms, nitro groups, hydroxy, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - group -SO ₂ -R ^f, and may have a substituent alkyl having 1 to 8 group consisting of at least one of said 7 to 30 carbon atoms, an aralkyl group may have a substituent group selected from the group consisting of halogen atom, nitro, hydroxy, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, and may have The substituent is at least one of the group consisting of an alkyl group having 1 to 8 carbon atoms, and the substituent group of the aromatic hydrocarbon ring having 6 to 14 carbon atoms may be selected from the group consisting of halogen atoms, nitro groups, hydroxyl groups, and methyl groups. _{^{acyl, -SO 3 -, -SO 2 -N}} - group -SO ₂ -R ^f, and may have a substituent alkyl having 1 to 8 group consisting of at least one of a 5 ~ 10 aromatic heterocyclic group may have a substituent selected from the group consisting of halogen atom, nitro, hydroxy, methyl _{^{acyl, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, and may have a substituent group At least one of the group consisting of an alkyl group having 1 to 8 carbon atoms, wherein the substituent group that the alkyl group having 1 to 8 carbon atoms may have is selected from halogen atoms, hydroxyl groups, methanoyl groups, and amino groups At least one of the group of, when the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ -contained in the saturated hydrocarbon 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, The -CH ₂ -contained in the alkyl group may be substituted with -O- or -CO-, r represents an integer of 1 or more, and M ^{r +} represents a hydrogen ion, an r-valent metal ion or N ⁺ (R ^55a ) ₄ , The four R ^55a may be the same or different, R ^55a represents a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons or an aralkyl group with 7 to 10 carbons, and k represents the anion represented by the formula (A3-1a) The total number of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f is an integer of 2 or more,

In formula (A3-1a), ring T ^1a , R ^41a to R ^44a, and R ^47a to R ^54a have the same meaning as described above; when r is an integer of 2 or more, it is represented by formula (A3-1a) anion at a plurality of the same or different, and at k-1 is an integer of 2 or greater, the plurality of M ^{r +} may be the same or different;

In the formula (A3-2), R ^41b and R ^42b each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, 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-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atom, R ^43b and R ^44b each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 14 carbons, or an optionally substituted aromatic hydrocarbon group with 7 to 30 carbons. Alkyl group, or R ^43b and R ^44b are bonded to form a 3-member to 10-member nitrogen-containing heterocyclic ring with the bonded nitrogen atoms, and R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, or a nitrate A group, a hydroxyl group, or an optionally substituted alkyl group having 1 to 8 carbons, and ring T ^1b represents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted 5 to 10 member In an aromatic heterocyclic ring, the substituent that the saturated hydrocarbon group having 1 to 20 carbon 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, and the carbon number is 6 to The substituent that the aromatic hydrocarbon group of 14 may have is at least one selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a methanoyl group, and an optionally substituted alkyl group having 1 to 8 carbons, so The substituent that the aralkyl group having 7 to 30 carbons may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an optionally substituted alkyl group having 1 to 8 carbons. At least one of the substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is selected from halogen atoms, nitro groups, hydroxyl groups, methanoyl groups, and optionally substituted alkyl groups having 1 to 8 carbon atoms At least one of the group consisting of, 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 methanoyl group, and the number of carbon atoms that may have a substituent At least one of the group consisting of an alkyl group of 1-8, and the substituent that the alkyl group of 1-8 may have is selected from the group consisting of a halogen atom, a hydroxyl group, a methanoyl group and an amino group At least one of them, when the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ -contained in the saturated hydrocarbon 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- , M represents an integer of 1 or more, [Y] ^m- represents an anion of m valence, and when m is an integer of 2 or more, multiple cations represented by formula (A3-2c) may be the same or different;

In the formula (A3-2c), rings T ^1b , R ^41b to R ^44b and R ^47b to R ^54b have the same meanings as described above. The colored curable resin composition according to claim 8, wherein the colorant (A) contains a dye (A1) different from the compound (A3).